135 PERP0607 6 (1) Benzene-Toluene Nexant

PERP Report
Benzene/Toluene
06/07-6
July 2007
44 South Broadway, White Plains, New York 10601, USA

Tel: +1 914 609 0300 Fax: +1 914 609 0399
Copyright by Nexant, Inc. 2007
This Report was prepared by Nexant, Inc. (Nexant) and is part of ChemSystems Process Evaluation/Research Planning
(PERP) Program. Except where specifically stated otherwise in this Report, the information contained herein is prepared on the
basis of information that is publicly available, and contains no confidential third party technical information to the best
knowledge of Nexant. The aforesaid information has not been independently verified or otherwise examined to determine its
accuracy, completeness, or feasibility.
Neither Nexant, Subscriber, nor any person acting on behalf of either assumes any liabilities with respect to the use of, or for
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of the Report.
Contents
Section
1
Executive Summary .................................................................................................
1.1
INTRODUCTION .........................................................................................
1.2
PRODUCTION OF REFORMATE ..............................................................
1.2.1
Conventional ......................................................................................
1.2.2
Production of Aromatic via Non-Conventional Routes.....................
1.3
PRODUCTION FROM PYROLYSIS GASOLINE......................................
1.4
AROMATICS EXTRACTION .....................................................................
1.5
DEALKYLATION ........................................................................................
1.6
ECONOMICS ................................................................................................
1.6.1
Reformate...........................................................................................
1.6.2
Benzene/Toluene................................................................................
COMMERCIAL ANALYSIS........................................................................
10
1.7.1
United States ......................................................................................
10
1.7.2
Western Europe..................................................................................
10
1.7.3
Asia/Pacific ........................................................................................
11
CONCLUSIONS............................................................................................
11
Current Commercial Technology...........................................................................
13
2.1
INTRODUCTION .........................................................................................
13
2.2
CATALYTIC REFORMING ........................................................................
15
2.2.1
Chemistry...........................................................................................
16
2.2.2
Catalyst ..............................................................................................
20
2.2.3
Process Variables ...............................................................................
21
2.2.4
Reformer Types .................................................................................
24
2.2.5
Feed Preparation ................................................................................
25
2.2.6
Reformer Operation ...........................................................................
31
2.2.7
Yields and Utilities ............................................................................
32
2.2.8
Commercial Technology....................................................................
34
2.3
PRODUCTION FROM PYROLYSIS GASOLINE......................................
35
2.4
AROMATICS EXTRACTION .....................................................................
37
1.7
1.8
2
Page
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Contents
2.4.1
Introduction........................................................................................
37
2.4.2
BTX Extraction Processes .................................................................
39
2.4.3
Single Aromatics Extraction Processes .............................................
45
DEALKYLATION PROCESSES .................................................................
48
2.5.1
Introduction........................................................................................
48
2.5.2
Hydrodealkyation...............................................................................
48
2.5.3
Toluene Disproportionation ...............................................................
54
2.6
PRODUCTION FROM COKE OVEN LIGHT OIL.....................................
57
2.7
PRODUCTION OF AROMATICS VIA NONCONVENTIONAL ROUTES
58
2.7.1
Asahi Chemicals Alpha Process .......................................................
58
2.7.2
BP/UOPs Cyclar Process ...............................................................
59
2.7.3
CP Chems Aromax Process............................................................
64
2.5
2.7.4
UOPs RZ Platforming ....................................................................
66
2.7.5
Summary of Non-conventional Routes..............................................
68
Developing Technologies .........................................................................................
70
3.1
METHANOL TO AROMATICS ..................................................................
70
3.2
METHANE TO BENZENE ..........................................................................
71
3.3
PATENTS OF INTEREST ............................................................................
72
3.3.1
Axens (IFP) and SK Corporation.......................................................
72
3.3.2
Chevron Phillips Chemical Company (CPChem)..............................
75
3.3.3
China Petroleum and Chemical Corporation (CPCC) & Sinopec .....
76
3.3.4
ExxonMobil .......................................................................................
77
3.3.5
Fina Technology Inc. .........................................................................
78
3.3.6
Institut Francais DuPetrole (IFP) .......................................................
78
3.3.7
SABIC................................................................................................
79
3.3.8 UOP....................................................................................................
79
Economic Analysis ...................................................................................................
80
4.1
BASIS ............................................................................................................
80
4.1.1
Pricing Basis ......................................................................................
80
4.1.2
Investment Basis ................................................................................
81
4.1.3
Cost of Production Basis....................................................................
81
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ii
Contents
4.2
ECONOMICS ................................................................................................
82
4.2.1
Investment..........................................................................................
82
4.2.2
Cost of Production of Reformate .......................................................
82
4.2.3
Cost of Production of Benzene ..........................................................
89
4.2.4
Sensitivity ..........................................................................................
102
CONCLUSIONS............................................................................................
106
Market Analysis .......................................................................................................
108
5.1
APPLICATIONS ...........................................................................................
108
5.1.1
Benzene..............................................................................................
108
5.1.2
Toluene ..............................................................................................
113
UNITED STATES .........................................................................................
114
5.2.1
Consumption ......................................................................................
114
5.2.2
Supply ................................................................................................
115
5.2.3
Supply, Demand and Trade................................................................
117
WESTERN EUROPE ....................................................................................
117
5.3.1
Consumption ......................................................................................
117
5.3.2
Supply ................................................................................................
118
5.3.3
121
ASIA PACIFIC..............................................................................................
121
5.4.1
Consumption ......................................................................................
121
5.4.2
Supply ................................................................................................
122
5.4.3
126
4.3
5
5.2
5.3
5.4
Appendix
Page
Elements of Nexant's ChemSystems Capital Cost Estimates................................
A-1
PERP Program Title Index .....................................................................................
B-1
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iii
Contents
Figure
Page
1.1 Aromatics Distribution in Non-Conventional Routes................................................
1.2 Effect of Steam Cracker Feedstock on Aromatics Yield ...........................................
1.3 Effect of Severity on Aromatics Yields for a Full Range Naphtha Feed...................
1.4 Cost of Production of Reformate ...............................................................................
1.5 Benzene Cost of Production.......................................................................................
1.6 Benzene to Toluene Price Delta.................................................................................
12
2.1 Semi-regenerative Reformer Process Flow Diagram ...............................................
26
2.2 Continuous Catalytic Reforming Process Flow Diagram.........................................
27
2.3 Cyclic Catalytic Reformer Process Flow Diagram....................................................
28
2.4 Naphtha Hydrotreater Process Flow Diagram ...........................................................
30
2.5 Effect of Steam Cracker Feedstock on Aromatics Yield ...........................................
35
2.6 Effect of Severity on Aromatics Yields for a Full Range Naphtha Feed...................
36
2.7 Shell/UOP Sulfolane Process.....................................................................................
41
2.8 Aromatics Fractionation Section................................................................................
43
2.9 BTX Recovery Block Flow Diagram ........................................................................
44
2.10 Morphylane Extractive Distillation Process Flow Diagram ....................................
47
2.11 Detol Unit Simplified Flowsheet .............................................................................
51
2.12 Litol Unit Simplified Flowsheet ..............................................................................
53
2.13 Toluene Disproportionation Typical Flowsheet .......................................................
56
2.14 Alpha Process Flow Diagram ....................................................................................
60
2.15 UOP/BP Cyclar Aromatization Process Flow Diagram .......................................
62
2.16 Aromax (Chevron Phillips ) Paraffins to BTX Process Flow Diagram....................
65
2.17 UOP RZ-Platforming Process Flow Diagram............................................................
67
2.18 Aromatics Distribution in Non-Conventional Routes................................................
69
3.1 Historical C9 Aromatics, LPG and Benzene Raffinate Pricing (USGC) ...................
73
3.2 Integrated APU/Pyrolysis Unit Block Flow Diagram ...............................................
75
4.1 Reformate Cost of Production ...................................................................................
83
4.2 Benzene Cost of Production.......................................................................................
89
4.3 Cost of Production of Reformate Sensitivity to Pricing .........................................
102
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Contents
4.4 Cost of Production of Benzene Sensitivity to Pricing ............................................
103
4.5 Sensitivity of Cost of Production of Reformate to Feed Price...................................
104
4.6 Sensitivity of Cost of Production of Benzene to Feed Price......................................
105
4.7 Sensitivity of Cost of Production via TDP to Mixed Xylenes Price..........................
105
4.8 Benzene to Toluene Price Delta.................................................................................
106
5.1 U.S. Benzene End-Use Pattern ..................................................................................
115
5.2 Western Europe Benzene End-Use Pattern................................................................
118
5.3 Asia Pacific Benzene End-Use Pattern ......................................................................
122
Table
Page
1.1 Typical BTX Composition from Pygas and Reformate.............................................
1.2 Basic Relationships in Catalytic Reforming ..............................................................
1.3 U.S. Benzene Supply, Demand and Trade.................................................................
10
1.4 Western Europe Benzene Supply, Demand and Trade..............................................
10
1.5 Asia Pacific Benzene Supply, Demand and Trade ....................................................
11
1.6 Reformate Process Selection......................................................................................
12
2.1 Typical BTX Composition from Pygas and Reformate.............................................
13
2.2 Licensors of Aromatics Technology..........................................................................
15
2.3 Basic Relationships in Catalytic Reforming ..............................................................
17
2.4 Reformer Yield From Medium Quality Full Range Naphtha....................................
32
2.5 Typical Yields of UOPs Reforming Processes.........................................................
33
2.6 Typical Yields of Axens Reforming Processes ........................................................
33
2.7 Typical Utilities of UOP and Axens Reforming Processes .......................................
34
2.8 Pyrolysis Gasoline Analysis ......................................................................................
37
2.9 Extractive Distillation: Effect of N-Formylmorpholine Solvent on Boiling

Temperatures at One Atmosphere, F........................................................................
38
2.10 Properties of Extraction Distillation Solvents............................................................
39
2.11 BTX Recovery Material Balance (Pygas)..................................................................
42
2.12 BTX Recovery Material Balance (Reformate) ..........................................................
45
2.13 Benzene Product Quality from the Octenar Process................................................
48
2.14 Hydrodealkylation Processes .....................................................................................
48
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Contents
2.15 Typical Composition of Benzole ...............................................................................
57
2.16 Aromax Reforming Design Parameters ...................................................................
66
2.17 Aromax Product Mix versus Feed Cut Point ...........................................................
66
3.1 APU Yields and Products ..........................................................................................
72
3.2 APU Yields ................................................................................................................
74
4.1 Price and Utility Basis ...............................................................................................
80
4.2 Capacities and Investment .........................................................................................
82
4.3 Cost of Production Estimate for: Reformate

Process: Continuous Catalyst Regeneration Reformer (includes Hydrotreater).......
84

Process: RZ Platforming ........................................................................................
86

Process: Cyclar.......................................................................................................
87

Process: Aromax ......................................................................................................
88

Process: Alpha ...........................................................................................................
90
4.8 Cost of Production Estimate for: Benzene

Process: Reformate Extraction (Sulfolane) plus BTX Distillation ............................
92

Process: Solvent Extraction of Pygas ........................................................................
93

Process: Extractive Distillation of Pygas...................................................................
95

Process: Bulk Dealkylation of Pygas.........................................................................
96

Process: Litol Process (from coke oven light oil)......................................................
97

Process: Toluene Hydrodealkylation (THDA) ..........................................................
99

Process: Toluene Disproportionation (TDP) .............................................................
100

Process: Selective Toluene Disproportionation (STDP)............................................
101
4.16 Reformate Process Selection Matrix..........................................................................
107
5.1 U.S. Benzene and Toluene Capacity, 2006................................................................
116
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Contents
5.2 U.S. Benzene Supply, Demand and Trade.................................................................
117
5.3 Western Europe Benzene and Toluene Capacity, 2006.............................................
120
5.4 Western Europe Benzene Supply, Demand and Trade..............................................
121
5.5 Asia Pacific Benzene and Toluene Capacity, 2006 ...................................................
123
5.6 Asia Pacific Benzene Supply, Demand and Trade ....................................................
126
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vii
Section 1
1.1
Executive Summary
INTRODUCTION
Aromatics are produced as coproducts in refinery catalytic reformers, olefins plants, coal tar
processing, and toluene disproportionation (TDP) units. In addition, on-purpose supplies of
benzene are produced via toluene hydrodealkylation (THDA) units. THDA units are the swing
source and used when benzene supply is tight and prices get high enough to justify the
economics of those plants.
About 70 percent of the global production of benzene is by extraction from either reformate or
pyrolysis gasoline (pygas). Reformate is formed in the catalytic reforming of naphtha, a
technology primarily directed at the production of high octane gasoline components. Pygas is a
liquid byproduct formed in the production of olefins by steam cracking liquid feeds, such as
naphtha or gas oil. Ethylene plants typically operate near full capacity, but the feedstock slate
may vary depending on market conditions. Extraction from reformate and pygas are the most
economical sources of benzene.
The composition of BTX (benzene, toluene and xylenes) depends on the source. Table 1.1
compares BTX from pygas and reformate. Pygas is typically rich in benzene, whereas xylenes
and toluene are the main components of reformate.
Table 1.1
Typical BTX Composition from Pygas and Reformate
(Weight Percent)
Pygas
BTX content
Benzene
Toluene
Xylenes
Reformate
Standard
Severity
Medium
Severity
CCR
SR
58
48
33
19
42
44
31
25
51
17
39
44
42
14
39
47
Typical
Demand
Split
49
23
28
Based on cracking full range naphtha

Continuous catalytic regenerative reformer
Semi-regenerative reformer
Table 1.1 also very roughly shows the global demand for BTX products. In general, benzene is
present in the main feedstocks in proportions lower than market demand, whereas toluene is in
considerable excess, as are xylenes. To some extent this imbalance is corrected by their relative
values as gasoline components because refiners have the option of extracting BTX as chemical
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Section 1
Executive Summary
products or blending them in fuel. Xylenes and toluene are more valuable as blendstocks than
benzene, and the benzene content in gasoline is restricted for environmental reasons.
1.2
PRODUCTION OF REFORMATE
The term "reforming" is used to designate a process by which the molecular structure of naphtha
is changed, with the intent of lessening the knocking tendency (i.e. raising the octane number) of
naphtha intended for use in internal combustion engines. Octane rating of unleaded gasoline is
related to the chemical structure of its constituent hydrocarbons. Aromatics and heavily
branched paraffins have the highest octane. Since most straight-run naphtha is low in aromatics
(5 to 10 percent) and octane (about 50 (RON + MON)/2), the chemical composition needs to be
changed, by reforming, to increase the yield of aromatics. The process is also widely used for
synthesizing aromatics for the chemical industry from selected naphtha fractions.
1.2.1
Conventional
Essentially all of the benzene, toluene and mixed xylenes (BTX) recovered in an oil refinery is
produced in the catalytic reforming unit (both continuous catalytic regenerative (CCR) and semiregenerative (SR) types). In a refinery which is not integrated into petrochemical production, the
reformate product, or C5+ stream, containing benzene and heavier aromatics, is utilized as a high
octane gasoline blendstock. In recent years, the utilization of benzene in the U.S. gasoline pool
has decreased as a result of the limits placed on benzene content in gasoline by environmental
regulations. Many U.S. refineries that are not integrated with aromatics production remove the
benzene precursors upstream of the reforming unit, which minimizes benzene levels in
reformate. The benzene precursors are typically utilized as isomerization unit feedstock for
incorporation into the gasoline pool. Conversely, refineries that are integrated with aromatics
production maximize the production of benzene in the reformer unit.
Benzene production can vary based on reformer operating rates and seasonal demand for
gasoline, feedstock slate and severity of the operations. Production from this source is expected
to grow tracking gasoline consumption growth. The only difference in operations for aromatics
production and motor fuel production is in the choice of operating parameters (especially
feedstock selection) to maximize the yields of BTX.
In a typical reforming process, the reactions include dehydrogenation, dehydrocyclization,
isomerization and hydrocracking. The dehydrogenation reaction typically will be the
dehydroisomerization of alkylcyclopentanes to aromatics, the dehydrogenation of paraffins to
olefins, the dehydrogenation of cyclohexanes to aromatics, and the dehydrocyclization of
paraffins to aromatics. The aromatization of the normal paraffins to aromatics is generally
considered to be the most important because of the high octane of the resulting aromatic product
compared to the low octane ratings for normal paraffins. The isomerization reactions include
isomerization of normal paraffins to isoparaffins and the isomerization of substituted aromatics.
The hydrocracking reactions include the hydrocracking of paraffins and hydrodesulfurization of
any sulfur that is remaining in the feedstock.
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Executive Summary
The reaction kinetics are such that naphthene dehydrogenation is the fastest and paraffin
dehydrocyclization is the slowest. While operating within these boundaries hydrocracking of
paraffins and naphthenes also occurs. However, for a given catalyst, lower operating pressures
will deemphasize hydrocracking, and thus make it possible to achieve better yields.
The maximum potential yields of aromatics that could be obtained from naphthenes and
paraffins if hydrocracking could be suppressed are determined by the thermodynamic equilibria
for aromatization reactions. These data show, first, that corresponding aromatic yields from the
various classes of compounds follow the order (from highest to lowest) alkylcyclohexanes,
alkylcyclopentanes, paraffins. Second, aromatic yields increase with the number of carbon
atoms per molecule; benzene from C6 paraffin has a lower yield than toluene from C7 paraffin.
Third, for a given reactant, the potential aromatics yield increases as the hydrogen partial
pressure is decreased.
As the catalyst ages, it is necessary to change the process operating conditions to maintain the
reaction severity and to suppress undesired reactions. The basic relationships are shown in
Table 1.2.
Table 1.2
Basic Relationships in Catalytic Reforming
Reaction
Reaction rate
Heat effect
Hydrocracking
Slowest
Exothermic
Isomerization
Rapid
Mildly
Exothermic
Dehydrocyclization
Slow
Mildly
Endothermic
Aids
Aids
Hinders
None
Aids
Hinders
Hinders
Aids
Hinders
Absorb
Increase
Decrease
Varies
Increase
None
Increase
Decrease
Increase
Increase
Evolves
Decrease
Increase
Decrease
Increase
Naphthene
Isomerization Dehydrogenation
Rapid
Fastest
Mildly
Quite
Exothermic
Endothermic
Effect of:
High pressure
High temperature
High space velocity
None
Aids
Hinders
Hinders
Aids
Hinders
None
Decrease
Increase
Increase
Decrease
Evolves
Decrease
Increase
Decrease
Increase
Effect on:
Hydrogen production
RVP
Density
Volume yield
Octane
1.2.2
Production of Aromatic via Non-Conventional Routes
There exist several nonconventional routes to convert low value refinery byproducts to benzene,
toluene, and xylenes. These have been developed and commercialized by various companies
over the past several years and include:
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Section 1
Executive Summary
Asahi Chemicals Alpha Process, which has been operating at the companys Mizushima
complex in Okayama, Japan, since 1993, employing an olefinic feed (licensed by Stone
& Webster).
The first commercial operation of BP/UOPs CyclarTM Process was in 1999 at Saudi
Basic Industries Corporation (SABIC).
CP Chems Aromax Process, which is operating at its Pascagoula refinery, at Saudi

Chevron Phillips Chemical using a second generation Aromax catalyst and at CEPSA,
Spain.
UOPs RZ PlatformingTM process started up its first commercial unit in the second
quarter of 1998.
Each of the technologies is described briefly in the report that follows. The BTX distribution for
each of the non-conventional routes is compared with a conventional CCR reformate
(RON=102) distribution in Figure 1.1. As can be seen in the figure, benzene production from the
Aromax process is significantly more than from the Alpha process (i.e. 65 percent versus 30
percent). The benzene production from the CyclarTM and RZ PlatformingTM processes is similar
and lower than these two processes. The CCR route produces the least amount of benzene at the
suggested conversion.
Figure 1.1
Aromatics Distribution in Non-Conventional Routes
100%
80%
60%
40%
20%
0%
CCR
CYCLAR
Benzene
Toluene
RZ
AROMAX
PLATFORMING
Mixed Xylenes C9+ Aromatics
ALPHA
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1.3
Executive Summary
PRODUCTION FROM PYROLYSIS GASOLINE
Pyrolysis gasoline or pygas is produced as a byproduct of olefins production by the steam

cracking of naphtha or gas oil feedstocks. Pygas contains a high proportion of aromatics,
primarily benzene and toluene, and a smaller amount of mixed xylenes which themselves can
contain up to 40 percent ethylbenzene.
Pygas also contains significant quantities of diolefinic materials, which tend to form gum on
standing for any period of time, even at ambient conditions. These diolefinic materials are
removed (by reaction to olefins and paraffins) by a first stage hydrotreatment, which for this
analysis is assumed to be included in the olefins unit itself. A second stage of hydrotreatment is
necessary before the pygas is suitable for aromatics extraction; the costs of this downstream
processing are more properly borne by the produced aromatics.
Yields of pygas are determined by the severity of the cracking operation, and the composition of
the feedstocks. Both of these factors are themselves determined by the overall economics of the
plant with aromatics production of secondary importance. The effect of the various feeds on the
aromatics yields is shown in Figure 1.2. In general the heavier the feed, the more aromatics are
produced.
Figure 1.2
Effect of Steam Cracker Feedstock on Aromatics Yield
Ton Per Ton of Ethylene
0.60
0.50
0.40
0.30
0.20
0.10
0.00
ethane
propane
n-butane
BENZENE
light
full range light AGO
naphtha
naphtha
TOLUENE XYLENES OTHER
HVGO
Q207_00101.0007.4106_char t s.xls
The effect of increasing severity of the cracker operation is to increase the yield of aromatics.
This is shown in Figure 1.3 for a full range naphtha (FRN) feedstock. The severity (defined by
the propylene to ethylene ratio) is varied from a high severity operation (P/E=0.48) to a medium
severity (P/E=0.59). The BTX content is lowered from 69 to 42 percent of the pygas and the
Benzene/Toluene
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Section 1
Executive Summary
benzene drops from 39 to 19 percent. As the yield of ethylene is also increasing, the ratio of
aromatics to ethylene falls and then rises.
Figure 1.3
Effect of Severity on Aromatics Yields for a Full Range Naphtha Feed
1.2
P/E=0.590
1.0
P/E=0.540
0.8
P/E=0.516
P/E=0.478
0.6
0.4
0.2
0.0
HIGH
STANDARD
BENZENE
INTERMEDIATE
TOLUENE
XYLENES
MEDIUM
OTHER
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1.4
AROMATICS EXTRACTION
It is necessary to use a solvent extraction technique to recover BTX products of commercial

quality, since aromatics and nonaromatics may have similar boiling points and form azeotropes.
After extraction, the BTX products can be separated, if necessary, by distillation. There are three
basic types of solvent extraction systems:
Azeotropic distillation, which uses a low boiling point solvent with an affinity for
nonaromatics. The solvent is distilled overhead with the nonaromatic raffinate.
Extractive distillation (ED), which employs a high boiling point solvent with an affinity
for aromatics. The influence that a solvent has on the boiling temperature of the various
components is significant. For benzene the boiling temperature increases by almost
100F, whereas for cyclohexane the delta is about 13F. Thus, the nonaromatics can be
distilled overhead, whereas the bottoms product will consist of solvent loaded with
aromatics. The aromatics can then be separated from the solvent by distillation. In the
ED step, the light nonaromatics are preferentially removed because of their lower boiling
point, although this can be partly compensated for by a high light/heavy selectivity of the
solvent. As a result, the aromatics product contains relatively small quantities of light
nonaromatics. This means that a benzene of reasonable quality may be obtained from C6-
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Section 1
Executive Summary
C8 cut, but the toluene and xylenes would be poorer quality. For this reason, ED is
normally used when the feed is a heart cut of the appropriate boiling range.
Liquid/liquid solvent extraction (LLE), which uses solvents that form a separate liquid
phase. Aromatics are considerably more soluble than nonaromatics in the solvents
employed. The aromatics are extracted from the feed stream in a liquid/liquid contactor,
and the extract stream is stripped to recover the aromatic product and the solvent. In this
case, the aromatic product would tend to be more contaminated by the light nonaromatics
that are preferentially stripped off in the second stage. For liquid/liquid extraction, a low
light/heavy selectivity is required (i.e. fewer light nonaromatics pass into the solvent).
Within each type, there are a number of solvents available. However, for a given process design
the solvent type is not replaceable. LLE is usually employed where recovery of benzene and
toluene are important with respect to yield and quality. ED is usually employed where the key
product is benzene and/or the yield is not so critical.
The complementary features of the ED and the liquid/liquid extraction systems are often
combined when extraction of the full BTX range is required. In this case, the extract from the
liquid/liquid stage passes to an ED column, where nonaromatics and some aromatics are
removed as overheads product, which recycles to the liquid/liquid extraction stage. The bottoms
product from the ED column passes to a stripper to separate the purified aromatics and the
solvent.
In general LLE processes are more capital intense and have higher utility requirements, but
produce a higher product yield and are suitable for BTX separation. ED processes have lower
capital requirements and lower utility requirements. The ED processes tend to give a lower
product yield and are suitable for benzene separation. LLE is normally selected where there is a
need for high quality, high yield of toluene, particularly for subsequent conversion (e.g. TDP).
1.5
DEALKYLATION
The market demand for benzene, as a proportion of total BTX, is higher than the proportion of
benzene in typical BTX products. Conversion of toluene and, to a lesser extent, xylenes, is
practiced by two basic techniques:
Hydrodealkylation involves stripping the methyl groups from toluene or xylenes to

produce benzene and methane.
Although not purely dealkylation, the topic of toluene disproportionation is also included
under this heading as a discretionary method of producing benzene. The toluene is
converted to benzene and xylenes in this process.
Benzene/Toluene
PERP 06/07-6
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Section 1
Executive Summary
1.6
ECONOMICS
1.6.1
Reformate
The costs of production for the various technologies for producing reformate have been
developed at a world scale plant capacity of 500 kta. Of the five types of technologies reviewed
herein, we have shown that the economics can vary widely. This range of economic
performance is clearly seen in Figure 1.4, where all five processes are viewed on a side-by-side
basis. Aromax is the low cost process which is consistent with previous PERP reports (02/035). CCRTM and RZ PlatformingTM have essentially the same low cost of production. CyclarTM is
the highest cost route to reformate, which confirms the results from Nexants previous PERP
report (02/03-5). If a 30 percent discount is applied to the LPG feedstock price (pricing one
might find in the Middle East), the CyclarTM economics are competitive with the low cost
technologies.
It is important to note that the economics presented herein are in essence a snapshot in time.
In Figure 1.4 we have tried to mitigate this by comparing the fourth quarter 2006 costs with the
five-year historical averages for feed and product prices. In each analysis the results show
similar, but lower costs of production when using the 5-year average.
Figure 1.4
Cost of Production of Reformate
(500 kta USGC)
3.00
Dollars Per Gallon
2.50
2.00
1.50
1.00
0.50
0.00
AROMAX
CCR
RZ
ALPHA
PLATFORMING
4Q2006 5 Yr Avg
CYCLAR
Q207_00101.0007.4106_char t s.xls
1.6.2
Benzene/Toluene
The costs of production of benzene from various sources employing different technologies are
summarized in Figure 1.5. The 2006 costs range from a low of $2.09 per gallon ($626 per metric
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
Section 1
Executive Summary
ton) for selective toluene disproportionation (STDP) to a high of $3.12 per gallon ($934 per
metric ton) for bulk dealkylation of pyrolysis gasoline. It is important to note that the economics
presented herein are in essence a snapshot in time. In Figure 1.5 we have tried to mitigate this
by comparing the fourth quarter 2006 costs with the five-year historical averages for feed and
product prices. In each analysis the results show similar, but lower costs of production when
using the 5-year average.
Figure 1.5
Benzene Cost of Production
(334 kta, USGC)
3.50
Dollars Per Gallon
3.00
2.50
2.00
1.50
1.00
0.50
0.00
SE
SE Pygas ED Pygas Dealky
Litol
Reformate
Pygas
4Q2006 5 Yr Avg
THDA
TDP
STDP
Q207_00101.0007.4106_chart s.xls
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
Section 1
Executive Summary
1.7
COMMERCIAL ANALYSIS
1.7.1
United States
With limited plans for new aromatics capacity in the future, the United States is expected to
remain the largest net importer in the region. Operating rates have recovered from the hurricanes
of 2005. The United States supply and demand balance is shown in Table 1.3.
Table 1.3
U.S. Benzene Supply, Demand and Trade
(Thousand metric tons)
2001
2002
2003
2004
2005
2006
2007
2008
2009
2010
Firm Capacity
Speculative Capacity
Total Capacity
9,872
0
9,872
9,754
0
9,754
9,753
0
9,753
9,680
0
9,680
9,543
0
9,543
9,654
0
9,654
9,654
151
9,805
9,680
250
9,930
9,654
301
9,954
9,654
501
10,154
Production
Operating Rate
6,844
69%
7,398
76%
7,898
81%
7,960
82%
7,326
77%
7,962
82%
8,037
82%
8,070
81%
7,984
80%
8,101
80%
Net Exports
Consumption
(939)
7,783
(1,236)
8,633
(1,211)
9,110
(1,237)
9,197
(1,538)
8,864
(1,293)
9,266
(1,426)
9,470
(1,440)
9,519
(1,513)
9,513
(1,349)
9,465
1.7.2
Western Europe
Western Europe has been a net importer of benzene in recent years. With the start-up of
numerous styrene and cumene plants in Asia and the Middle East, Western European demand for
benzene is expected to decline in the near term allowing Western Europe to become selfsufficient in benzene for a few years. The Western Europe supply and demand balance is shown
in Table 1.4.
Table 1.4
Western Europe Benzene Supply, Demand and Trade
2001
2002
2003
2004
2005
2006
2007
2008
2009
2010
Firm Capacity
Total Capacity
9,437
0
9,437
9,532
0
9,532
10,033
0
10,033
10,130
0
10,130
10,121
0
10,121
10,297
0
10,297
10,571
0
10,571
10,662
100
10,762
10,632
100
10,732
10,632
(10)
10,622
Production
Operating Rate
7,635
81%
7,884
83%
8,242
82%
8,430
83%
8,456
84%
8,901
86%
9,091
86%
9,134
85%
9,066
84%
8,746
82%
Net Exports
Consumption
(156)
7,791
(8)
7,892
(182)
8,424
(566)
8,996
(648)
9,104
76
8,832
(17)
9,112
74
9,059
47
9,022
(57)
8,805
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
10
Section 1
1.7.3
Executive Summary
Asia/Pacific
Since the late 1900s the Asia Pacific region has been close to a balanced position in benzene,
with Taiwan and Indonesia the major importers and Japan, South Korea and Thailand providing
most of the exports within the region. In the last several years high benzene prices in other parts
of the world, especially the U.S. and surplus capacity in China provided opportunities for exports
to flow out of the region. For most of the outlook period, Asia Pacific is expected to be a small
net importer and occasionally a net exporter when opportunities arise. The Asia Pacific supply
and demand balance is shown in Table 1.5.
Table 1.5
Asia Pacific Benzene Supply, Demand and Trade
2001
2002
2003
2004
2005
2006
2007
2008
2009
2010
Firm Capacity
Total Capacity
14,716
0
14,716
15,123
0
15,123
15,614
0
15,614
15,927
0
15,927
16,505
0
16,505
17,883
0
17,883
18,707
200
18,907
19,550
531
20,082
20,116
662
20,778
20,465
1,032
21,497
Production
Operating Rate
11,446
78%
11,814
78%
12,764
82%
14,100
89%
15,167
92%
14,821
83%
15,967
84%
16,826
84%
17,121
82%
17,406
81%
Net Exports
Consumption
(78)
11,524
(271)
12,085
(354)
13,118
434
13,666
367
14,799
(387)
15,220
(252)
16,245
(74)
16,917
(262)
17,418
(578)
18,010
1.8
CONCLUSIONS
Whether or not TDP or THDA units operate economically will not only depend on pricing
conditions (e.g., alternative value for toluene), but also on market position. Because THDA is
often the most expensive route for producing benzene, merchant THDA facilities tend to operate
only when the price of benzene exceeds the cost of production via THDA. Captive THDA units,
in contrast, usually serve to balance internal requirements for benzene and are run independently
of merchant market conditions. Historically the delta between the price of benzene and toluene
has been about 32 cents per gallon ($96 per metric ton) as shown in Figure 1.6. However, in the
past few years this delta has varied greatly. For the fourth quarter of 2004 it was almost $1.65
per gallon ($500 per metric ton), while for the second quarter of 2006 it was negative 8 cents per
gallon (-24 per metric ton). Currently (4th quarter 2006) this delta is about $1.10 per gallon
($332 per metric ton) while the cost of toluene hydrodealkylation is 23 cents per gallon ($68 per
metric ton).
Benzene/Toluene
PERP 06/07-6
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11
Section 1
Executive Summary
Figure 1.6
Benzene to Toluene Price Delta
600
Delta Benzene - Toluene, $/T
500
400
300
200
100
0
-100
1982-Q1 1984-Q1 1986-Q1 1988-Q1 1990-Q1 1992-Q1 1994-Q1 1996-Q1 1998-Q1 2000-Q1 2002-Q1 2004-Q1 2006-Q1
Q207_00101.0007.4106_chart s.xls
In addition to the economics, a variety of other issues must also be considered when choosing
process technology. Some of these considerations are listed below:
Access to feedstock
Outlet for byproducts
Investment requirements
Revamp and integration potential or strategy
Feedstock/product price fluctuations/forecasts
Technology availability/licensing terms
Technology risk
Security of supply/strategic importance
Table 1.6 summarizes Nexants view with respect to some of the strategic issues. In the final
analysis, the selection of any of these aromatic technologies will have to be based on a careful
case by case assessment.
Table 1.6
Reformate Process Selection
Feedstock
Sensitivity to feed price
Investment requirement
Technology availability
Commercially proven units
CCRTM
Naphtha
Low
Low
Yes
Numerous
Rz PlatformingTM
Naphtha
Low
Low
Yes
Numerous
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
CyclarTM
LPG
Moderate
High
Yes
One
Aromax
Naphtha
High
Low
Yes
Several
Alpha
C5/C6
Moderate
Moderate
Yes
One
12
Section 2
2.1
Current Commercial Technology
INTRODUCTION
Aromatics are produced as coproducts in refinery catalytic reformers, olefins plants, coal tar
processing, and toluene disproportionation (TDP) units. In addition, on-purpose supplies of
benzene are produced via toluene hydrodealkylation (THDA) units. THDA units are the swing
source and used when benzene supply is tight and prices get high enough to justify the
economics of those plants.
About 70 percent of the global production of benzene is by extraction from either reformate or
pyrolysis gasoline (pygas). The former is formed in the catalytic reforming of naphtha, a
technology primarily directed at the production of high octane gasoline components. The latter
is a liquid byproduct formed in the production of olefins by steam cracking liquid feeds, such as
naphtha or gas oil. Ethylene plants typically operate near full capacity, but the feedstock slate
may vary depending on market conditions. Extraction from reformate and pygas are the most
economical sources of benzene.
The composition of BTX (benzene, toluene and xylenes) depends on the source. Table 2.1
compares BTX from pygas and reformate. Pygas is typically rich in benzene, whereas xylenes
and toluene are the main components of reformate.
Table 2.1
Typical BTX Composition from Pygas and Reformate
(Weight percent)
Pygas
Standard Medium
Severity Severity
BTX content
58
42
Benzene
48
44
Toluene
3
31
Xylenes
19
25
Reformate
CCR
51
17
39
44
SR
42
14
39
47
Typical
Demand Split
49
49
23
28
Based on cracking full range naphtha

Continuous catalytic regenerative reformer
Semi-regenerative reformer
Table 2.1 also very roughly shows the global demand for BTX products. In general, benzene is
present in the main feedstocks in proportions lower than market demand, whereas toluene is in
considerable excess, as are xylenes. To some extent this imbalance is corrected by their relative
values as gasoline components because refiners have the option of extracting BTX as chemical
products or blending them in fuel. Xylenes and toluene are more valuable as blendstocks than
benzene, and the benzene content in gasoline is restricted for environmental reasons.
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
13
Section 2
Essentially all of the BTX recovered in an oil refinery is produced in the catalytic reforming unit
(both continuous catalytic regenerative and semi-regenerative types). In a refinery which is not
integrated into petrochemical production, the reformate product, or C5+ stream, containing
benzene and heavier aromatics, is utilized as a high octane gasoline blendstock. In recent years,
the utilization of benzene in the U.S. gasoline pool has decreased as a result of the limits placed
on benzene content in gasoline by environmental regulations. Many U.S. refineries that are not
integrated with aromatics production remove the benzene precursors upstream of the reforming
unit, which minimizes benzene levels in the reformate. The benzene precursors are typically
utilized as isomerization unit feedstock for incorporation into the gasoline pool. Conversely,
refineries that are integrated with aromatics production maximize the production of benzene in
the reformer unit.
Benzene production can vary based on reformer operating rates and seasonal demand for
gasoline, feedstock slate and severity of the operations. Production from this source is expected
to grow tracking gasoline consumption growth.
Benzene and higher aromatics are produced in varying amounts in olefin plants. Benzene may
be recovered by extraction from the pygas coproduct stream. The quantity and composition of
the pygas varies with the feedstock cracked and cracker severity. Lighter feedstocks produce
little pygas, but there may be sufficient benzene content in pygas from liquids crackers to justify
extraction.
The slight trend toward heavier steam cracker feedstocks will result in higher benzene
production within the pygas and result in growth of benzene from pygas exceeding the overall
ethylene production growth.
A third source of BTX is light oil produced during the coking of coal. Although this was once
the only source of aromatics, it is now a minor contributor to the total supply amounting to only
6-7 percent of the global capacity (mostly in the Former Soviet Union and Eastern Europe).
Benzene extraction from coal tar operations is not expected to grow, since the output of the steel
industry has been essentially level for some years. Clean Air Act emission regulations restrict
output from this source.
Benzene may be produced from toluene by hydrodealkylation (THDA) or disproportionation
(TDA). Hydrodealkylation removes a methyl group from the toluene molecule and replaces it
with a hydrogen atom to form benzene and methane. Toluene disproportionation converts
toluene to mixed xylenes and benzene by removing a methyl group from one toluene molecule
(creating benzene) and replacing it onto a second toluene molecule (creating xylenes). Both
conventional (TDP) and selective (STDP) technologies are available for license.
In this section, technologies based on extraction and dealkylation are described, along with a
discussion of each major feedstock and estimates of reformate and benzene production costs. A
discussion of non-conventional routes to BTX is also included. The emphasis of the economic
analysis is placed on benzene because of its importance as a chemical product. A list of the
foremost licensors of aromatics technology is provided in Table 2.2.
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
14
Section 2
Table 2.2
Licensors of Aromatics Technology
Technology
Licensor
Process
Reforming
UOP
CCR Platforming, RZ Platforming,

Cyclar
Aromizing, Octanizing, Dualforming
Aromax
Alpha Process
HDA
Detol, Litol, Pyrotol
Hydeal
HDA
THD
MHC
THDA
XylenesPlus
Hydrodealkylation
Toluene
Disproportionation/
Transalkylation
Other
Axens
Chevron Phillips
S&W
Lyondell
Lummus
UOP/Marathon Ashland Petroleum
HRI/Axens
Gulf
Mitsubishi
UOP
Lyondell
UOP
Axens
GTC Technology Inc.
SK Corp
Shanghai Research Institute of
Petrochemical Technology (SRIPT)
UOP
Axens
2.2
Tatoray, PX-Plus, TAC9

MTDP-3, HDA, TransPlusSM, PxMaxSM
GT-STDPSM, GT-TolAlkSM, GT-TransAlkSM
ATA
S-TDT
MX Sorbex, Olefins Reduction Process
(ORP)
Advanced Pygas Upgrading (APU)
CATALYTIC REFORMING
Modern catalytic reforming using platinum was first commercialized in 1949 by UOP for use by
the petroleum industry; The term "reforming" is used to designate a process by which the
molecular structure of naphtha is changed, with the intent of lessening the knocking tendency
(i.e. raising the octane number) of naphtha intended for use in internal combustion engines.
Octane rating of unleaded gasoline is related to the chemical structure of their constituent
hydrocarbons. Aromatics and heavily branched paraffins have the highest octane. Since most
straight-run naphtha is low in aromatics (5 to 10 percent) and octane (about 50 (RON +
MON)/2), the chemical composition needs to be changed, by reforming, to increase the yield of
aromatics. The process is also widely used for synthesizing aromatics for the chemical industry
from selected naphtha fractions.
The catalytic reforming process is used in the production of gasoline of desired octane number,
aromatics (benzene, toluene, mixed xylenes including ethyl benzene) and hydrogen for plant use
(e.g. hydrotreating of the naphtha feed). The only difference in operations for aromatics
production and motor fuel production is in the choice of operating parameters (especially
feedstock selection) to maximize the yields of benzene, toluene and mixed xylenes (BTX).
Benzene/Toluene
PERP 06/07-6
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15
Section 2
2.2.1
Chemistry
In a typical reforming process, the reactions include dehydrogenation, dehydrocyclization,

isomerization and hydrocracking. The dehydrogenation reaction typically will be the
dehydroisomerization of alkylcyclopentanes to aromatics, the dehydrogenation of paraffins to
olefins, the dehydrogenation of cyclohexanes to aromatics, and the dehydrocyclization of
paraffins to aromatics. The aromatization of the normal paraffins to aromatics is generally
considered to be the most important because of the high octane of the resulting aromatic product
compared to the low octane ratings for normal paraffins. The isomerization reactions include
isomerization of normal paraffins to isoparaffins and the isomerization of substituted aromatics.
The hydrocracking reactions include the hydrocracking of paraffins and hydrodesulfurization of
any sulfur that is remaining in the feedstock.
It is important to note the simultaneous production of hydrogen when aromatics are
manufactured by catalytic reforming. In the United States, this hydrogen is used as feedstock for
hydrotreating and hydrocracking. Of the light hydrocarbons made in catalytic reforming,
propane finds its way into LPG; isobutane goes to alkylation units; and n-butane is used to adjust
the vapor pressure of finished gasoline. Only small yields of methane and ethane go to plant
fuel.
The reaction kinetics are such that naphthene dehydrogenation is the fastest and paraffin
dehydrocyclization is the slowest. While operating within these boundaries hydrocracking of
paraffins and naphthenes also occurs. However, for a given catalyst, lower operating pressures
will deemphasize hydrocracking, and thus make it possible to achieve better yields.
The maximum potential yields of aromatics that could be obtained from naphthenes and
paraffins if hydrocracking could be suppressed are determined by the thermodynamic equilibria
for aromatization reactions. These data show, first, that corresponding aromatic yields from the
various classes of compounds follow the order (from highest to lowest) alkylcyclohexanes,
alkylcyclopentanes, paraffins. Second, aromatic yields increase with the number of carbon
atoms per molecule; benzene from C6 paraffin has a lower yield than toluene from C7 paraffin.
Third, for a given reactant, the potential aromatics yield increases as the hydrogen partial
pressure is decreased.
As the catalyst ages, it is necessary to change the process operating conditions to maintain the
reaction severity and to suppress undesired reactions. The basic relationships are shown in
Table 2.3.
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
16
Section 2
Table 2.3
Basic Relationships in Catalytic Reforming
Reaction
Reaction rate
Heat effect
Hydrocracking
Slowest
Exothermic
Isomerization
Rapid
Mildly
Exothermic
Dehydrocyclization
Slow
Mildly
Endothermic
Naphthene
Isomerization Dehydrogenation
Rapid
Fastest
Mildly
Quite
Exothermic
Endothermic
Aids
Aids
Hinders
Non
Aids
Hinders
Hinders
Aids
Hinders
None
Aids
Hinders
Hinders
Aids
Hinders
Absorb
Increase
Decrease
Varies
Increase
None
Increase
Decrease
Increase
Increase
Evolves
Decrease
Increase
Decrease
Increase
None
Decrease
Increase
Increase
Decrease
Evolves
Decrease
Increase
Decrease
Increase
Effect of:
High pressure
High temperature
High space velocity
Effect on:
Hydrogen production
RVP
Density
Volume yield
Octane
On a mole basis, naphthene conversion to aromatics is about 98 percent with the number of
carbon atoms in the precursor being retained in the product as follows:
methylcyclopentane
cyclohexane
dimethylcyclopentane
methylcycloheptane
dimethylcyclohexane
cycloheptane
produces
produces
produces
produces
produces
produces
benzene
benzene
toluene
toluene
xylene
xylene
For paraffins the following moles of aromatics are produced from one mole of paraffins having
the indicated number of carbon atoms:
1 mole of a six carbon paraffin yields 0.05 moles of a six carbon aromatic
1 mole of a seven carbon paraffin yields 0.10 moles of a seven carbon aromatic
1 mole of an eight carbon paraffin yields 0.25 moles of an eight carbon aromatic
1 mole of a nine carbon paraffin yields 0.45 moles of a nine carbon aromatic
1 mole of a ten carbon paraffin yields 0.45 moles of a ten carbon aromatic
2.2.1.1
Dehydrogenation Reactions
The dehydrogenation of naphthenes (either an alkylcyclohexane or an alkylcyclopentane) occurs

at extremely fast reaction rates and is highly endothermic. The result is the need for fired heaters
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
17
Section 2
between the catalyst beds in order to maintain the reaction temperatures. The dehydrogenation
reaction of alkylcyclohexane to aromatics is represented below by the reaction of
methylcyclohexane to toluene.
CH3
CH3
+ 3H2
Methylcyclohexane
Toluene
Hydrogen
Q207_00101.0007.4106.cdx
All cyclohexanes dehydrogenate very rapidly and completely to aromatics. The cyclopentanes
react at a much slower rate and undergo both isomerization to form the corresponding
cyclohexanes and ring opening to form paraffins.
The dehydrogenation of cyclohexane derivatives is a much faster reaction than that of the
dehydrocyclization of paraffins represented below by the reaction of normal heptane to toluene.
Although the latter is also endothermic, it proceeds via multiple steps and at a relatively slow
reaction rate. It is the most difficult reforming reaction to promote. For instance, the reaction
rate for dehydrocyclization of hexane is only one-third that of hydrocracking. Thus, the fraction
of the normal hexane converted to benzene is relatively low.
CH3
+ 4H2
n-C7H16
n-Heptane
Toluene
Hydrogen
Q207_00101.0007.4106.cdx
On the other hand, normal heptane hydrocracks at about the same rate as normal hexane, so the
faster rate of dehydrocyclization (about four times that of hexane) leads to significantly greater
fractional conversion to aromatics for normal heptane in comparison with hexane.
A third reaction necessary to obtain the high aromatic concentrations needed in the product to
produce a high octane is the dehydroisomerization of an alkylcyclopentane to an
alkylcyclohexane and then to an aromatic. These reaction steps are highly dependent on the
processing conditions. The reaction of methylcyclopentane to benzene via cyclohexane is as
follows:
Benzene/Toluene
PERP 06/07-6
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18
Section 2
CH3
Methylcyclopentane
Cyclohexane
+ 3H2
Benzene
Hydrogen
Q207_00101.0007.4106.cdx
Aromatics have a higher liquid density than paraffins or naphthenes with the same number of
carbon atoms so one volume of paraffins produces only about 0.77 volume of aromatics and one
volume of naphthenes produces about 0.87 volume of aromatics. At the same time the aromatics
production increases the gasoline end point of the naphtha. To summarize, aromatics yield is
increased by high temperature, low pressure, low space velocity, and low hydrogen-tohydrocarbon mole ratios. With reference to the latter, a sufficient hydrogen partial pressure must
be maintained to avoid excessive coke formation.
2.2.1.2
Isomerization of Paraffins and Naphthenes
The isomerization of paraffins occurs readily in commercial reforming operations, but at typical
operating temperatures the thermodynamic equilibrium is in favor of the more desirable (higher
octane) branched isomers. Pressure has only a slight effect. In gasoline blending these reactions
make a significant contribution to the octane improvement of the naphtha. The reactions are fast
and mildly exothermic. The isomerization of an alkylcyclopentane to cyclohexanes plus
subsequent conversion to benzene is described above. The reaction below represents a typical
isomerization of a normal paraffin.
CH3
CH3CH2CH2CH2CH2CH3
n-Hexane
CH3CHCH2CH2CH3
iso-Hexane
Q207_00101.0007.4106.cdx
Isomerization yield is increased by high temperature, low space velocity, and low pressure.
2.2.1.3
Hydrocracking
Paraffin hydrocracking is slower than the isomerization reaction and is exothermic.

Hydrocracking yields are increased by high temperature, high pressure, and low space velocity.
The disappearance of paraffins from the gasoline boiling range via hydrocracking does
concentrate aromatics in the product, and thus contributes to octane improvement. The reaction
consumes hydrogen and results in lower yields. Hydrocracking is represented below by the
reaction of normal hexane to butane and ethane.
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19
Section 2
Most operators prefer to minimize hydrocracking within the reformer reactors in order to
minimize the light naphtha (C5s) and LPG make (C3 and C4). Thus, careful control of the
operating conditions (i.e., temperature) is needed in order to obtain high product quality and
yields.
CH3CH2CH2CH2CH2CH3 + H2
n-Hexane
Hydrogen
CH3CH2CH2CH3 + CH3CH3
Butane
Ethane
Q207_00101.0007.4106.cdx
2.2.1.4
Miscellaneous Reactions
Demethylation reactions generally occur only at conditions of high temperature, high pressure,
and in the presence of a super active catalyst (typically found during startup following catalyst
replacement or regeneration). The reaction is highly exothermic and could lead to disastrous
results (e.g., catalyst meltdown). Strict attention to procedures is required during these
operations. The dealkylation of aromatics is similar to aromatic demethylation differing only in
the size of the fragment removed from the ring.
2.2.2
Catalyst
All of the reforming catalysts in general use today contain platinum (0.2-0.75 weight percent)
supported on a silica or silica-aluminum base. In most cases rhenium (0.2-0.78 weight percent)
is combined with platinum to form a more stable catalyst that permits operation at lower
pressure. Iridium and tin have also been used in place of rhenium. Chlorine (0.9-1.2 weight
percent) is often added as a promoter and to maintain the platinum well dispersed over the
catalyst surface. The catalyst shape may be cylindrical, spherical, or triple in sizes from oneeighteenth to one-eighth inch in diameter. The density for extruded catalyst is between 37 and
48 pounds per cubic foot and for spherical catalyst is between 32 and 45 pounds per cubic foot.
Since a typical throughput limitation for a reformer unit is the amount of coke that can be burned
in the CCR regenerator, one method for increasing throughput and, thus, increase aromatics
production is to replace older generation catalyst (e.g., UOPs R-134) with the latest generation
catalyst (e.g., UOPs R-264). That is, newer generation catalyst should provide higher activity
and produce less coke.
Platinum is thought to serve as the catalytic site for hydrogenation and dehydrogenation
reactions and chlorinated alumina provides an acid site for isomerization, cyclization, and
hydrocracking reactions. Rhenium or iridium act as coke inhibitors. In early reforming units
employing a monometallic platinum catalyst high sulfur levels in the feedstock led to the need
for high metal content (0.6 to 0.75 weight percent platinum).
The advent of the
platinum/rhenium catalyst (bimetallic) required that the sulfur level in the feed be reduced to less
than one wppm.
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20
Section 2
Reforming catalyst activity is a function of surface area, pore volume, and active platinum and
chlorine content. Catalyst activity is reduced during operation by coke deposition and chloride
loss. Noble metal catalysts lose activity in the presence of sulfur or nitrogen compounds and are
poisoned by metals such as arsenic and lead at concentrations of far less than 1 ppm. The first
deactivation is reversible, whereas the second is irreversible.
For a semi-regeneration operation (high pressure) up to 200 barrels of charge can be processed
per pound of catalyst before regeneration is required. The activity of the catalyst can be restored
by high temperature oxidation of the carbon followed by chlorination. The activity of the
catalyst decreases during the on stream period and the reaction temperature is increased as the
catalyst ages to maintain the desired operating severity. The catalyst can normally be
regenerated at least three times before it has to be replaced and returned to the manufacturer for
reclamation. Regenerations may be required in cycles anywhere from 3 to 24 months.
2.2.3
2.2.3.1
Process Variables
Pressure
Pressure (defined as average reactor pressure), especially hydrogen partial pressure, has a major
effect on catalyst deactivation. Because of side reactions, coke is deposited on the catalyst.
Higher pressure results in less carbon because the hydrogen-lean residues on the catalyst are
hydrogenated. At lower pressures, this capability is no longer present, and conventional
platinum-on-alumina catalysts rapidly decrease in activity and yields of aromatics and hydrogen.
Selectivity deteriorates because the ratio of hydrocracking to aromatization increases as the
catalyst is deactivated. Thus, the early versions of the catalytic reforming process emphasized
relatively high pressures (500-800 psi) and high hydrogen recycle rates (6,000 to 10,000 SCF per
barrel of feed). However, the realization of better yields at lower pressure became the driving
force for further catalyst development.
Modern continuous reformers are being designed for pressures in the range of 50 to 100 psig. In
general, as reactor pressure is decreased, catalyst requirements decrease, gasoline yields increase,
and catalyst deactivation increases.
2.2.3.2
Temperature
Reactor bed temperature is the primary variable available to control product quality. Two
expressions are commonly used to define reactor temperature. Weighted average inlet
temperature (WAIT) is the fraction of catalyst in each reactor bed multiplied by its inlet
temperature. Weighted average bed temperature (WABT) is the fraction of catalyst in each bed
multiplied by the average of its inlet and outlet temperatures. Each feedstock has its own
temperature/octane relationship. By raising or lowering the reactor temperature, the plant
engineer can raise or lower the product octane number. As temperature is increased the catalyst
requirement is decreased, the gasoline yield increases, and catalyst deactivation increases.
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Section 2
2.2.3.3
Feedstock Quality
Naphtha quality has the most influence on the reformate quantity and reformer design. The
relationship between naphtha and the resulting reformate stream is complex. Hydrocarbon types
by paraffin, naphthenes and aromatics (PNA) and ASTM distillation ranges are the minimum
required to characterize a charge stock. Although these analyses do not completely describe the
charge stock and its effect on yields, activity, and stability, they serve as a basis for selectivity
and stability evaluation. A lean naphtha is defined as one in which the paraffin content of the
feed is typically above 65 weight percent.
2.2.3.4
Feed Boiling Range
General guidelines suggest a link between the initial boiling point (IBP) of the naphtha and the
aromatics level in the resulting reformate. The IBP is designed to exclude pentane and lighter
materials and is established at the hydrotreater back end fractionator or stripper. A plant operator
will generally control the IBP to include in the feed those components that will reform to
benzene (i.e., methylcyclopentane and cyclohexane boiling at 161.3F and 177.3F,
respectively). Full range naphtha (FRN) will typically contain C5 components boiling as low as
82F (isopentane). Light naphtha (80-150F cut) is separated upstream by distillation and either
isomerized or sent directly to the gasoline pool. Heavy naphtha (160+F) is sent to the reformer.
For maximum benzene production, the typical IBP is between 167F and 176F. To minimize
benzene production, the IBP is typically around 212F to 221F.
The final boiling point or ASTM distillation end point (EP) is designed to exclude coke
precursors and is established at the crude fractionator or pipestill. The EP is usually set at 400F
in order to eliminate the hydrocarbons, which form polycyclic aromatics. These latter aromatics
are responsible for carbon laydown on the catalyst and shortened cycle life. Decreasing the end
point will have the effect of increasing the catalyst requirement, decreasing the mogas yield and
decreasing catalyst deactivation.
The reformate product has a higher EP and a lower IBP than the feedstock. Thus, higher boiling
point hydrocarbons are present in the final reactor where the operating severity is the highest and
coking is most likely to occur. Because of extension of the IBP and EP during the reforming
process, some operators hold the feedstock EP well below the 400F limit.
2.2.3.5
Naphtha Quality (Naphthenic versus Paraffinic)
The relationship of paraffins, naphthenes, and aromatics in naphtha to the resulting reformate
quality is much harder to define. The method used by most operators to estimate catalyst
performance is the naphthenes and aromatics content in the feed, expressed as liquid volume
percent equal to naphthenes plus aromatics (N+A). A feedstock with a composition of 60
percent paraffins, 33 percent naphthenes, and 7 percent aromatics (N+A = 40) is more difficult to
reform than a feedstock with a composition of 34 percent paraffins, 29 percent naphthenes, and
37 percent aromatics (N+A = 66). Increasing the naphthenes plus aromatics in the feed has the
effect of decreasing the catalyst requirement, increasing the C5+ yield, as well as the octane yield
(octane number times C5+ yield) and increasing the catalyst deactivation.
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22
Section 2
2.2.3.6
Impurities
Cracker stocks (thermal cracker, cat cracker, and coker naphthas) containing a significant
amount of olefins need to be hydrotreated as described below.
The active material in most catalytic reforming catalysts is platinum. Certain metals (lead, iron,
arsenic, etc.) as well as sulfur compounds, nitrogen compounds, chlorine, olefins, water, and
oxygen will cause catalyst deactivation. Hydrotreating of the feed is usually sufficient to remove
these materials. Hydrogen for the hydrotreater reactions is supplied from the downstream
catalytic reformer. A discussion of the hydrotreating process is presented in Section 2.2.5 Feed
Preparation.
2.2.3.7
Space Velocity
Space velocity is a measure of the contact time between the feedstock (i.e., naphtha) and the
catalyst (i.e., amount of naphtha processed over a certain amount of catalyst for a set period of
time). If volumes are used the term is liquid hourly space velocity (LHSV) and if weights are
used the term is weight hourly space velocity (WHSV). Volumes (typically barrels) are
established at 60F and 14.7 psia (petroleum industry standards).
The space velocity will determine the limits of product quality (i.e., octane number). The greater
the space velocity, the lower the limit or maximum octane possible. Reactor temperatures are
interchangeable with LHSV, and the two together determine product quality. Within normal
reforming design parameters, space velocity has little effect on catalyst stability (on a barrel per
pound basis). Higher LHSV results in a lower severity; conversely, lower LHSV results in a
higher severity.
2.2.3.8
Hydrogen to Hydrocarbon Ratio
The hydrogen to hydrocarbon (H2/HC) ratio is defined as the moles of recycle hydrogen per
mole of naphtha charged to the unit. The recycle hydrogen is necessary for the purposes of
catalyst stability (i.e., to protect the catalyst from rapid coking). It has the effect of sweeping the
reaction products and condensable materials from the catalyst and supplying the catalyst with
readily available hydrogen.
An increase in the H:HC ratio will move the naphtha feed through the reactor at a faster rate and
supply a greater heat sink for the endothermic heat of reaction. It also increases the hydrogen
partial pressure and, therefore, the catalyst stability with little effect on product quality or yields.
On the other hand, lower ratios save energy (i.e., compression costs) and favor the naphthene
dehydrogenation and dehydrocyclization reactions.
At the low pressure levels designed for modern reformers, the typical H:HC ratio is in the range
of 2 to 5. Older high pressure units operate in the range of eight to ten. Increasing the recycle
rate will decrease the catalyst requirement, the gasoline yield and the catalyst deactivation.
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23
Section 2
2.2.4
Reformer Types
Reforming processes are classified as continuous, cyclic or semi-regenerative depending upon

the frequency of catalyst regeneration.
2.2.4.1
Semi-regenerative
The semi-regenerative (SR) unit has the advantage of low capital costs. Regeneration requires
the unit to be taken off line. Depending on the severity of operation, regeneration is required at
intervals of three to six months. High hydrogen recycle rates and operating pressures are utilized
to minimize coke laydown and consequent loss of catalyst activity.
A process flow diagram is shown in Figure 2.1. The pretreated feed and recycle hydrogen are
heated to between 925 and 975F before entering the first reactor. In the first reactor, the major
reaction is the dehydrogenation of naphthenes to aromatics, and since this is strongly
endothermic, a large drop in temperature occurs. To maintain the reaction rate, the gases are
reheated before being passed over the catalyst in the second reactor. As the charge proceeds
through the reactors, the reaction rates decrease and the reactors become larger and less reheat is
needed. Three reactors are usually sufficient to provide the desired degree of reaction and
heaters are needed before each reactor to bring the mixture up to reaction temperature. In
practice, either separate heaters can be used or one heater can contain several separate coils. The
reaction mixture from the last reactor is cooled and the liquid products condensed. The
hydrogen-rich gases are separated from the liquid phase in a separator and the liquid from the
separator is sent to a fractionator to be debutanized.
The hydrogen-rich gas stream is split into a hydrogen recycle stream and a net hydrogen
byproduct used in hydrotreating or hydrocracking operations or as fuel.
The operating pressure is typically in the range of 100 to 350 psig and uses a hydrogen rate of
4,000 to 8,000 SCF/bbl of fresh feed. LHSV is in the range of 2 to 3.
2.2.4.2
Continuous Catalyst Regeneration (CCR)
The equipment for the continuous process is designed to permit the removal and replacement of
catalyst during normal operation. As a result, the catalyst can be regenerated continuously and
maintained at a high activity. Because coke laydown and thermodynamic equilibrium yields of
reformate are both favored by low pressure operation, the ability to maintain high catalyst
activities by continuous catalyst regeneration is the major advantage of the continuous type of
unit. This advantage has to be evaluated with respect to the higher capital costs and possible
lower operating costs due to lower hydrogen recycle rates and pressures needed to keep coke
laydown at an acceptable level.
A process flow diagram of UOP's CCR Platforming process scheme is shown in Figure 2.2.
The catalyst flows by gravity from the last (bottom) reactor in to a catalyst collector vessel,
which maintains uniform catalyst withdrawal. After depressuring and purging, the catalyst is
lifted to a catalyst hopper. Catalyst then flows to the regeneration tower, where the carbon is
burned off and the catalyst chloride level is adjusted. Net regeneration gas is vented.
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24
Section 2
Regenerated catalyst is then returned to the first (top) reactor. In this scheme the reactor operates
only in its primary function, providing the catalytic environment for the reforming reactions; thus
it is not exposed to the severe regeneration conditions. The Axens flow scheme (not shown)
employs a "smooth-flowing," moving bed process. The Axens reactors are not stacked and the
catalyst moves from one vessel to another.
The second generation of UOP's CCR process is the result of still lower operating pressure and
development of improved catalyst. The typical operating conditions of UOP's second generation
CCR are a reactor pressure of 50 psig, a space velocity of 1.7, and a H:HC ratio of less than 2.5.
The system continuously regenerates up to 4,500 pounds per hour of catalyst. The Axens
continuous design also operates at the lower pressure of 50 psig.
Axens proposes a modified regeneration system, RegenC, which includes a primary burn zone
equipped with a dry burn loop to minimize the moisture level during combustion; a finishing
burn zone; an oxychlorination zone with an independent gas loop; and a calcination zone. The
dry burn loop has been found to extend catalyst life in industrial units by reducing surface area
loss during coke burning.
Most new grass roots aromatics projects involve the continuous reforming technologies of either
UOP or Axens.
2.2.4.3
Cyclic
The cyclic process is a compromise between the semi-regenerative and the continuous process
described above. It is characterized by having a swing reactor in addition to those on stream, as
shown in Figure 2.3. The catalyst in a cyclic unit can be regenerated without shutting the unit
down as required for a semi-regenerative unit. When the activity of the catalyst in one of the on
stream reactors drops below the desired level, this reactor is isolated from the system and
replaced by the swing reactor. The catalyst in the replaced reactor is then regenerated by
admitting hot air into the reactor to burn the carbon off the catalyst. After regeneration it is used
to replace the next reactor needing regeneration.
The cyclic design is more expensive then the semi-regenerative scheme. All the reactors in the
cyclic process are the same size. A complete spare reactor is required as well as a complex
piping manifold. Regeneration is typically performed on a 24 or 48 hour cycle. On the plus side
the cyclic process offers the advantage of a lower pressure operation then the semi-regenerative
process and higher yields of reformate at the same severity.
2.2.5
Feed Preparation
The active material in most catalytic reforming catalysts is platinum. As mentioned above, the
presence of certain compounds and elements will cause the catalyst to deactivate. Feed
pretreatment, in the form of hydrotreating (H/T), is usually employed to remove these materials.
The hydrotreater employs a cobalt/molybdenum catalyst to desulfurize, denitrogenate,
deoxygenate, and demetallate the feedstock.
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25
Hydrotreated
Naphtha Feed
HYDROGEN
RECYCLE
COMPRESSOR
Steam
FIRED
HEATERS
Benzene/Toluene
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HYDROGEN
SEPARATOR
Net
Hydrogen
REBOILER
REACTORS
Reformate
LPG
Figure 2.1
Semi-regenerative Reformer
Process Flow Diagram
Q207_00101.0007.4106.vsd
STABILIZER
Gas
Section 2
26
Q207_00101.0007.4106
Drying Zone
Benzene/Toluene
PERP 06/07-6
Lift
Gas
Air
Chlorination
Zone
Combustion
{
Zone
LOCK
HOPPER
#1
Hydrodesulfurization Unit
Naphtha feed from
Spent Catalyst
LOCK
HOPPER
#2
Regeneration
Section
(simplified)
REACTORS
HEATER
Reformate
to Stabilizer
Net Gas
High pressure
Recontactor
Q207_00101.0007.4106.vsd
Figure 2.2
Continuous Catalytic Reforming
Recycle Hydrogen
Low pressure
Separation
Section 2
27
Benzene/Toluene
PERP 06/07-6
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Hydrotreated
Naphtha Feed
PREHEAT
FURNACE
REACTOR (A)
RECYCLE GAS
COMPRESSOR
FIRST
HEATER
THIRD
HEATER
REACTOR (C)
FLUE GAS RECYCLE

COMPRESSOR
DRIER
Reformate
to Stabilizer
SEPARATOR
DRUM
Figure 2.3
Cyclic Catalytic Reformer
SWING
REACTOR
REACTOR (D)
FLUE GAS
PREHEATER
Q207_00101.0007.4106.vsd
High Purity Hydrogen

Tail Gas
LOWER REGENERATION HEADER
LOWER REACTION HEADER
SECOND
HEATER
REACTOR (B)
UPPER REACTION HEADER
UPPER REGENERATION HEADER
Air or
Flue Gas
Purge
Section 2
28
Section 2
In the hydrotreater the sulfur and nitrogen compounds are converted to hydrogen sulfide and
ammonia and easily removed via stripping of the hydrotreated stream. Olefins are saturated to
paraffins. The metals in the feed are retained on the hydrotreater catalyst. Finally, a small
amount of cracking occurs in the hydrotreater and the light hydrocarbons, which are produced
must be removed in the stabilizer in order to establish the initial boiling point as described above.
A process flow diagram for a naphtha hydrotreater is presented in Figure 2.4. The feed is usually
taken from a naphtha splitter where the light portion (C5/C6) is distilled off and sent to an
isomerization unit or directly to the gasoline pool. The heavy portion is directed to the
hydrotreater where the feed is pumped to operating pressure and heated with the reactor effluent
before final heating is done in a fired heater.
The reactor inlet usually has some sort of receptor to collect scale and fines. A downflow or
radial flow reactor can be employed. Only one reactor is typically needed for virgin naphtha
service. The reactions are exothermic so there is a small temperature increase across the reactor.
The effluent is cooled first against the fresh feed and then against air and/or water. The
condensed product is pumped to the stabilizer where the hydrogen sulfide, ammonia, and light
gasses are stripped out.
The hydrogen is recycled from the high pressure separator back to the front end of the unit. A
small purge is removed in order to limit the buildup of inerts and fresh hydrogen. Makeup from
the reformer is added in order to maintain the hydrogen partial pressure within the reactor.
The two main concerns with the operation of the hydrotreater are catalyst deactivation and
pressure drop. Hydrotreaters are typically designed to run one to two years before the catalyst
must be regenerated (usually to coincide with a plant turnaround). Pressure drop increases over
the run due to scale, catalyst fines, coke, and polymer deposits at the top of the reactor bed
(downflow reactor). The top of the catalyst bed can usually be skimmed via an inert entry
procedure with minimal downtime. At the same time fresh catalyst is installed to replace the
catalyst skimmed off during the procedure.
The operating conditions within the hydrotreater reactor depend upon the particular feed and
impurities. They are typically 525F to 850F at a pressure of 400 to 800 psig. The space
velocity (LHSV) is in the range of 2 to 6 per hour. The hydrogen partial pressure is maintained
above 100 psia in the reactor in order to assure complete hydrotreating. Hydrogen consumption
is in the range of 50 to 150 SCF per barrel for a low sulfur virgin naphtha, but can be several
times this value for a cracked naphtha containing a significant amount of olefins and diolefins.
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29
NAPHTHA
FEED
MAKE-UP
HYDROGEN
Reactor
effluent-to-feed
exchanger
HEATER
Recycle hydrogen
SEPARATOR
COOLER
REACTOR
COMPRESSOR
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STABILIZER
Hydrotreated
product to
reformer
Stabilizer
overhead gas
Q207_00101.0007.4106.vsd
Figure 2.4
Naphtha Hydrotreater
Pure gas
Section 2
30
Section 2
2.2.6
Reformer Operation
Process variables need to be checked daily (and adjusted as required) to produce and maintain
the maximum yield of desired products. At the same time the plant operator must meet product
quality and do both within the limits of acceptable catalyst life.
2.2.6.1
Gasoline Mode
Daily checks should include the reactor inlet temperature, reactor bed delta temperatures, reactor
bed outlet temperatures, reactor pressure, H:HC ratio, and space velocity as well as checking a
rough material balance. Delta temperature is an indication of catalyst activity. Outlet
temperature gives an indication of reforming reaction (i.e. too low of a temperature may indicate
very little reforming reaction taking place in the bottom of the reactor).
A plant operator has two ways to change the severity of reforming: reactor inlet temperature
(WAIT) and reactor charge rate (LHSV). If a higher octane reformate is required, the reactor
inlet temperatures can be raised. If unit limitations do not allow a temperature increase, a boost
in octane number can still be achieved by reducing the charge rate, and thus lowering space
velocity.
2.2.6.2
BTX Operation
Operating a catalytic reformer to produce aromatics (BTX) differs little from reforming to raise
the octane for motor fuel blending. That is, reformates with high octane numbers have high
concentrations of aromatics.
The two major differences in the operation to produce octane and to produce BTX are the
operating pressure and the feedstock selection. The pressure of a reformer operating with a low
endpoint feed (as described below) can be lower, thus maximizing the aromatics yield.
The naphtha feed can have a lower endpoint for producing BTX because the high boiling (i.e.
heavier) components can be eliminated. That is, C9+ components (those boiling above 350F)
show less selectivity to produce BTX. In addition, by feeding a naphtha with a lower endpoint,
the coking tendency of the system is reduced.
Other feedstock related variations that can be used to maximize BTX production are:
Dehydrocyclization of paraffins is favored more by lowering pressure than by raising

temperature.
The boiling range of the precursors are an indication of the type of aromatics produced.
Thus, benzene precursors are in the 160-180F boiling range; toluene precursors are in
the range of 180-250F boiling range; and xylene precursors boil between 250 and 350F.
Cracked naphthas are premium feedstock for BTX production (i.e., rich sources of
aromatics and naphthenes).
The higher the aromatic content of the feed to a reformer, the higher the yield of aromatic
based on feed.
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31
Section 2
2.2.7
Yields and Utilities
The quantity and composition of the reformate depends on the feedstock, the conditions of
operation, and the type of reformer system. Table 2.4 compares reformate from two typical
reformers. One is a semi-regenerative unit using a bimetallic catalyst at a low severity of 96
RON (research octane number). The move to lead free gasoline has forced refiners to introduce
high severity reformers that incorporate CCR technology. The second typical reformer in the
table is a CCR unit operating at 102 RON. The higher severity reformers produce higher
quantities of total aromatics, and within the BTX fraction the proportion of benzene is also
higher.
Table 2.4
Reformer Yield From Medium Quality Full Range Naphtha
(weight percent)
Catalyst
A
Semi-regenerative Unit,
Bimetallic Catalyst
25 Bar, 96 RON
Hydrogen
Gases
LPG
C5 reformate
Total
1.7
4.5
12.8
81.0
100.0
B
Continuous
Regeneration Unit
High Stability
9 Bar, 102 RON
3.0
3.8
9.8
83.4
100.0
Reformate quality
Nonaromatics (C5-C8)
Benzene
Toluene
Xylenes
C9
Total
45.4
5.8
16.9
20.6
11.3
100.0
29.3
9.0
21.0
23.7
17.0
100.0
(1)
P/N/A:60/25/15, nominal range 70 to 170C. (158 to 338F)

Yield structure A is typical of the least rich reformates, likely to be used for BTX extraction;
yield B is typical of the richest reformates.
(3)
The data are based on actual unit performance; the quality of naphtha in B is very similar
to, but slightly heavier than that in A.
(2)
When reforming for aromatics only, the naphtha may be prefractionated to produce a reformer
feedstock of appropriate composition, depending on which BTX products are required. Another
process scheme involves the use of a blocked reformer. A light cut passes to the aromatics
section of the reformer for production of aromatics and gasoline, whereas the heavier cut is fed
to a gasoline-only part of the reformer. Fractionation and associated tanks would not be needed
to produce gasoline alone, so their cost, if used, should be assigned to the recovered aromatics.
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32
Section 2
Typical yields for UOP's and Axens reforming processes are presented in Table 2.5 and 2.6,
respectively. Typical utilities for UOP are compared with Axens in Table 2.7.
Table 2.5
Typical Yields of UOPs Reforming Processes
Reformer Type
Feed, IBP, F
Feed, EP, F
Average pressure, psig
RONC (C5+)
C5+RVP, psi
Yields, LV%
C5+
Benzene
Toluene
Xylenes
Hydrogen, SCFB
(1)
FRN
SR
Cut(1)
CCR
Cut(1)
CCR
FRN
CCR
180
380
300
100
4.2
215
380
50
92
2.1
215
380
50
102
2.2
180
380
50
102
2.8
74.2
2.8
9.7
15.7
790
87.7
0.21
7.4
13.9
1,190
84.0
0.37
9.6
18.2
1,620
81.8
2.4
9.1
16.8
1,710
Benzene precursors removed
Table 2.6
Typical Yields of Axens Reforming Processes
Operation
Reformer Type
Feed
IBP, F
EP, F
P, vol%
N, vol%
A, vol%
Pressure
RONC (C5+)
Product
Benzene, wt%
Toluene, wt%
Xylenes wt%
C5+ yield, wt%
Hydrogen, wt%
Gasoline
Continuous
BTX Operation
Continuous
194
338
65
26
9
50
102
176
302
57
37
6
50
-
88
3.8
8.5
26.3
26.1
87
4.1
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Section 2
Table 2.7
Typical Utilities of UOP and Axens Reforming Processes
(per barrel)
UOP
Axens
Electrical power
kW
0.900
1.008
Steam-600
Thousand lb
0.042
0.033
Boiler feed water
Thousand lb
0.066
0.072
Fuel fired
Million Btu
0.252
0.274
Nitrogen
Thousand SCF
0.002
0.004
(1)
CCR Platforming unit operating at 50 psig average reactor pressure, 102 C5+ RONC with
a 1,500 lb/hr catalyst regeneration section (excluding recontacting utilities that are dependent
on battery limits pressure)
(2)
Average of gasoline and aromatics operations
Although most new continuous reformers designed for gasoline production produce reformate
with a RON of about 102, reformers designed for BTX production produce reformate with a
RON of at least 104 and some as high as 108. Older SR reformers produce reformate with a
RON of about 96 to 100. It is important to understand that a high octane reformate stream will
contain low levels of C8 paraffins, such that a simpler and less costly recovery flow scheme is
required. A low C8 paraffin concentration allows the C8+ portion of the reformate to be separate
by distillation. High levels of C8 paraffins will require an extraction process.
2.2.8
2.2.8.1
Commercial Technology
UOP
UOP has designed and licensed more than 600 fixed bed plus 154 operating CCR Platforming
units throughout the world ranging in size from 15,000 to 63,000 BPSD. UOP first introduced
its Platforming process using the first commercial platinum catalyst in 1949. The first generation
continuous catalyst regeneration (CCR) reformer was commercialized in 1971. The second
generation CCR technology characterized by very low pressure operation (approximately 50
psig) has been available since 1990, and a low platinum catalyst (R-34) version of UOPs
standard reforming catalyst, R-32, is also available. UOPs R-134 catalyst is its standard in
this area. The second generation CCR was commercialized toward the end of 1988 and has had
numerous units designed since.
2.2.8.2
Axens
Axens is the only other licensor to offer a continuous catalyst regeneration reformer. Its
Octanizing and Aromizing processes are well tested with over 50 licenses awarded. The
Aromizing process (Aromatics mode) is a high severity process that uses a specially tailored
catalyst to produce chemical grade aromatics.
Axens latest innovation is the dry burn loop, and advanced regenerator design (RegenC).
This new regenerator is claimed to provide longer catalyst life and reduced catalyst costs of 30 to
70 percent. Axens latest catalyst, CR 401, has demonstrated improved C5+ and hydrogen yield
and lower attrition levels.
Benzene/Toluene
PERP 06/07-6
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34
Section 2
2.2.8.3
Other
Semi-regenerative reformer designs are available for license from ExxonMobil (Powerforming)
and Engelhard (Magnaforming) as well as UOP and Axens. The Englehard (Magnaforming)
technology and technical service to these units has been transferred to Axens. ExxonMobil also
offers its cyclic reforming technology.
Chevron Phillips and BP are not presently licensing their reforming technology (Rheniforming
and Ultraforming, respectively).
2.3
PRODUCTION FROM PYROLYSIS GASOLINE
Pyrolysis gasoline (pygas), a byproduct of olefins production by steam cracking naphtha of gas
oil feedstocks, contains a high proportion of aromatics, primarily benzene and toluene, and a
smaller amount of C8 aromatics that contain up to 40 percent ethylbenzene.
Pyrolysis gasoline yields are determined by the severity of the cracking operation and the
composition of feedstocks. Pygas is only a byproduct of an olefin unit, so these two factors are
determined by the overall economics of the plant. The effects of feedstock on BTX yields are
summarized in Figures 2.5.
Figure 2.5
Effect of Steam Cracker Feedstock on Aromatics Yield
0.60
0.50
0.40
0.30
0.20
0.10
0.00
Ethane
Propane
n-Butane
Benzene
Light
Full Range Light AGO
Naphtha Naphtha
Propane n-Butane Light Naphtha
HVGO
Q207_00101.0007.4106_char t s.xls
The effect of increasing severity of the cracker operation is to increase the yield of aromatics.
This is shown in Figure 2.6 for a full range naphtha (FRN) feedstock. The severity (defined by
the propylene to ethylene ratio) is varied from a high severity operation (P/E=0.48) to a medium
Benzene/Toluene
PERP 06/07-6
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35
Section 2
severity (P/E=0.59). The BTX content is lowered from 69 to 42 percent of the pygas and the
benzene drops from 39 to 19 percent. As the yield of ethylene is also increasing, the ratio of
aromatics to ethylene falls and then rises.
Figure 2.6
Effect of Severity on Aromatics Yields for a Full Range Naphtha Feed
1.2
P/E=0.590
1.0
P/E=0.540
0.8
P/E=0.516
P/E=0.478
0.6
0.4
0.2
0.0
High
Standard
Benzene
Toluene
Intermediate
Xylenes
Medium
Other
Q207_00101.0007.4106_chart s.xls
Pyrolysis gasoline contains significant quantities of diolefinic materials that, when left standing
for any period of time, tend to form gum, even at ambient conditions. The stream is therefore
hydrogenated prior to addition to the gasoline pool. This hydrotreater uses nickel or palladium
catalysts and requires a hydrogen source. The diolefins are converted to primary olefins, and the
product from the first stage hydrotreater is of motor gasoline quality.
If chemical grade aromatics are required, all olefins must be removed from the feed prior to
aromatics extraction. This necessitates a second stage hydrotreater operating under more severe
conditions to ensure complete saturation of the olefins. There are a number of possible
configurations of the two hydrotreatment stages and the two distillation columns, whose
selection depends on factors such as the cost of hydrogen and the destination of the other product
streams. In any case, the second hydrotreatment stage is needed only if aromatics are to be
extracted and the costs of this processing should be properly borne by the aromatic products.
A representative analysis for a first stage hydrotreated pyrolysis gasoline derived from naphtha is
given in Table 2.8.
Benzene/Toluene
PERP 06/07-6
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36
Section 2
Table 2.8
Pyrolysis Gasoline Analysis
(weight percent)
Composition
C4s
Benzene
Toluene
Xylenes
Ethylbenzene
Styrene
Properties
Diene value
Existing gum
Gravity
Boiling range
IBP
50 Percent
FBP
RVP
Viscosity
Bromine number
RON
Sulfur
2.4
AROMATICS EXTRACTION
2.4.1
Introduction
Minimum
0.0
27.0
15.0
4.0
1.0
0.0
Maximum
1.0
35.0
25.0
9.0
1.5
0.5
2 max
4 mg/100mL max
0.75-0.82 gm/cc
40-60C
80-100C
170-200C
0.4-0.6 kgm/cc
0.7-0.8 cP
20 gm Br/100 gm
10
0.1 max
It is necessary to use a solvent extraction technique to recover BTX products of commercial

quality, since aromatics and nonaromatics may have similar boiling points and form azeotropes.
After extraction, the BTX products can be separated, if necessary, by distillation. There are three
basic types of solvent extraction systems:
Azeotropic distillation, which uses a low boiling point solvent with an affinity for
nonaromatics. The solvent is distilled overhead with the nonaromatic raffinate.
Extractive distillation (ED), which employs a high boiling point solvent with an affinity
for aromatics. The influence that a solvent has on the boiling temperature of the various
components is shown in Table 2.9. The effect of the aromatics is significant. For
benzene the boiling temperature increases by almost 100F, whereas for cyclohexane the
delta is about 13F. Thus, the nonaromatics can be distilled overhead, whereas the
bottoms product will consist of solvent loaded with aromatics. The aromatics can then be
separated from the solvent by distillation. In the ED step, the light nonaromatics are
preferentially removed because of their lower boiling point, although this can be partly
compensated for by a high light/heavy selectivity of the solvent. As a result, the
aromatics product contains relatively small quantities of light nonaromatics. This means
that a benzene of reasonable quality may be obtained from C6-C8 cut, but the toluene and
Benzene/Toluene
PERP 06/07-6
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37
Section 2
xylenes would be poorer quality. For this reason, ED is normally used when the feed is a
heart cut of the appropriate boiling range.
Table 2.9
Extractive Distillation: Effect of N-Formylmorpholine Solvent on
Boiling Temperatures at One Atmosphere, F
Aromatics
Benzene
Toluene
Naphthenes
Cyclohexane
Methylcyclohexane
trans-1,2-Dimethylcyclopentane
cis-1,4-Dimethylcyclohexane
Paraffins
n-Heptane
n-Octane
2-Methylheptane
Olefins
4-Methyl-1-hexene
1-Hexene
1-Heptene
1-Octene
N-Formylmorpholine (NFM)
Pure Component
15% Component/
85% Solvent
C6H6
C7H8
176.27
231.16
275.82
321.27
C6H12
C7H14
C7H14
C8H16
177.34
213.71
197.32
255.80
190.17
225.52
209.49
266.48
C7H16
C8H18
C8H18
209.91
258.17
243.77
218.65
132.46
256.06
C7H14
C6H12
C7H14
C8H16
188.12
145.20
200.57
250.25
204.22
148.90
218.38
275.47
Liquid/liquid solvent extraction (LLE), which uses solvents that form a separate liquid
phase. Aromatics are considerably more soluble than nonaromatics in the solvents
employed. The aromatics are extracted from the feed stream in a liquid/liquid contactor,
and the extract stream is stripped to recover the aromatic product and the solvent. In this
case, the aromatic product would tend to be more contaminated by the light nonaromatics
that are preferentially stripped off in the second stage. For liquid/liquid extraction, a low
light/heavy selectivity is required (i.e. fewer light nonaromatics pass into the solvent).
Within each type, there are a number of solvents available. However, for a given process design
the solvent type is not replaceable. LLE is usually employed where recovery of benzene and
toluene are important with respect to yield and quality. ED is usually employed where the key
product is benzene and/or the yield is not so critical. Properties of various solvents are shown in
Table 2.10.
The complementary features of the ED and the liquid/liquid extraction systems are often
combined when extraction of the full BTX range is required. In this case, the extract from the
liquid/liquid stage passes to an ED column, where nonaromatics and some aromatics are
removed as overheads product, which recycles to the liquid/liquid extraction stage. The bottoms
product from the ED volume passes to a stripper to separate the purified aromatics and the
solvent.
Benzene/Toluene
PERP 06/07-6
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38
Section 2
Table 2.10
Properties of Extraction Distillation Solvents
Sulfolane
Formula
Molecular weight
bp @ 1.0 Kg/Cm2, C
Freezing point, C
Flash point, C
Miscible with water
Smell/odor
Stability
Boiling point difference(1)
Operating Conditions
Temperature, C
Pressure, bar
Ratio of solvent to raw material
(1)
C4H8O2S
120.6
287
27
177
Yes
Oil-like
Good
71
N-Methylpyrrolidone
(NMP)
C5H9NO
99.13
205
-25
91
Yes
Faintly ominous
Very good
14
Dimethysulfoxide
(DMS)
H3CSOCH3
78.13
189
19
89
Yes
None
Decomp @ 190C
--
N-Formylmorpholine
(NFM)
C5H9NO2
115.13
243
23
119
Yes
Very faint
Very good
26
100
2
3-6:1
20-40
1
4-5:1
20-30
1
3-5:1
180-200
1
5-6:1
Benzene boiling point methylcyclohexane bp (in the presence of solvent)
In general LLE processes are more capital intense and have higher utility requirements, but
produce a higher product yield and are suitable for BTX separation. ED processes have lower
capital requirements and lower utility requirements. The ED processes tend to give a lower
product yield and are suitable for benzene separation. LLE is normally selected where there is a
need for high quality, high yield of toluene, particularly for subsequent conversion (e.g., TDP).
2.4.2
BTX Extraction Processes
A number of processes are available for the extraction of BTX. LLE technologies are available
from UOP (Sulfolane and Carom), Axens (Sulfolane), and Lurgi (Arosolvan). Most of the
processes capable of producing all three aromatics at commercial quality from a wide boiling
range feedstock are based on a water or monoethylene glycol or diethylene glycol extractant.
This process has been commercial since the combination of liquid/liquid extraction and
extractive distillation.
Lurgis ArosolvanTM process for the recovery of BTX aromatics is such a system. The solvent is
a mixture of N-methylpyrrolidone (NMP) and water or monoethylene glycol or diethylene
glycol. This process has been commercial since the late 1950s.
UOP developed the UdexTM process jointly with Dow Chemical in the early 1950s. It used a
mixture of liquid/liquid extraction and distillation with solvents based on glycol.
In the early 1960s, UOP entered an exclusive licensing deal with Shell for a process based on
Sulfolane, or tetrahydrothiophene-1,1-dioxide. Some of Sulfolanes advantages are its high
selectivity and high yield. The disadvantage of thermal instability at its boiling point is
Benzene/Toluene
PERP 06/07-6
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39
Section 2
countered by the addition of small quantities of water to depress the boiling point. More than 90
new Sulfolane units and eight conversions to Udex have been licensed to date, with a total
capacity in excess of 0.95 million barrels per day of feed.
Where only two components, such as benzene and toluene, are desired, there is the option of
cutting to a C6 and a C7 fraction and sending each to a separate ED system. Krupp Uhde offers
this approach via its Morphylane process, based on N-formylmorpholine (NFM). For full BTX
extraction, however, Krupp Uhde offers a combined liquid/liquid plus ED process called
MorphylexTM based on the same solvent. Krupp Uhde has applied divided-wall column (DWC)
technology to its ED process and claims an energy savings of up to 35 percent and capital
savings up to 20 percent. (A dividing-wall in a vertical column permits two distillation steps to
be performed in one piece of equipment, with a reduced number of heat exchangers and
peripheral equipment items).
Reformate and pygas can be treated together in a BTX extraction unit. In the case of reformate,
a full C6+ cut is often treated, allowing recovery of xylenes. For pygas, a C6-C7 cut may be used
as feedstock because of the high proportion of less desirable ethylbenzene in the C8 aromatics.
The Sulfolane process is described as an example of a widely used technology, and a typical
flowsheet for a Sulfolane unit is shown in Figure 2.7. The capital investment requirements and
utility consumption for a sulfolane extraction unit is directly linked to the feedstock composition
and the particular needs of the client.
The reformate feedstock may be prefractionated if the purpose of the system is to remove only
selected aromatics, although, as described previously, the system is designed for full BTX
removal. The feed cut enters the extractor, which is typically a rotating disc contactor. The feed
flows upward countercurrent to a stream of Sulfolane solvent, where aromatic hydrocarbons are
selectively dissolved. Undissolved hydrocarbons, comprising mainly nonaromatics, are removed
from the top of the extractor as the raffinate phase.
The extract phase, or rich solvent, flows from the bottom of the extractor to the extract stripper.
This is the extractive distillation step, where light nonaromatics are stripped. Light nonaromatics
are condensed and returned as a reflux to the extractor since they contain some aromatics
unavoidably volatilized in the extract stripper. This extractive distillation step is a product purity
control; the light reflux, which displaces heavy nonaromatics from the solvents, is also
beneficial.
One of the features of the process is the ability to use a secondary solvent. Instead of all
solvent passing through the liquid/liquid extracting column, a portion of recycled solvent can be
bypassed to extractive distillation. This permits the promotion of high volatility nonaromatics in
extractive distillation while taking advantage of relatively high hydrocarbon loading in
liquid/liquid extraction.
The bottoms stream from the extract stripper contains the net aromatics product and the
Sulfolane solvent. This passes to the recovery column, where the aromatics are stripped from the
high boiling solvent. A light reflux reduces solvent carryover with the aromatics. High purity
aromatics are recovered as product, and the solvent is recycled. The aromatics product is clay
treated to remove residual contaminants that may affect the acid wash color test.
Benzene/Toluene
PERP 06/07-6
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40
Solvent
Depentanized
Feed
EXTRACTOR
C.W.
RAFFINATE
WATER WASH
COLUMN
Raffinate
MP
Stm.
STRIPPER
WATER
STRIPPER
CONDENSER
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
EXTRACT
Figure 2.7
Shell/UOP Sulfolane Process
HP
Stm.
HP
Stm.
Q207_00101.0007.4106.vsd
REGENERATOR
HP
Stm.
RECOVERY
COLUMN
Clean Condensate M/U

CONDENSER
Section 2
41
Section 2
Raffinate from the top of the extractor requires a water wash to recover dissolved solvent. It is
washed countercurrently with solvent free water before export. The solvent is recovered from
the water in a water stripper where the heat of evaporation is provided by indirect exchange with
hot lean solvent. Steam generated in the stripper supplies the extract recovery column. This is a
key feature of the heat integration of the process. Sulfolane degradation, primarily related to
oxidation loss, can be minimized by using proper gas blanketed feed and by reducing equipment
leakage. Intermittently, a regenerator distills solvent overhead and retains degraded material for
discharge.
The aromatics product stream passes to a distillation system to separate the benzene, toluene, and
xylenes products, as shown in Figure 2.8.
A block flow diagram for BTX recovery in conjunction with a liquid/liquid solvent extraction
unit is shown in Figure 2.11. The corresponding material balances for pygas and reformate feeds
are given in Tables 2.11 and 2.12, respectively. The one case (pygas) has a high benzene (34
percent) and low xylenes (13 percent) concentration. The other case (reformate) has a low
benzene (less than 6 percent) concentration and a high xylenes concentration (almost 20 percent),
typical of a reformer operating in a gasoline mode. The basis for the pygas is typical production
for a steam cracker employing a naphtha feed at standard severity (approximately 0.5 pounds of
propylene per pound of ethylene) at ethylene capacity of 1 billion pounds per year. The
optimum BTX fractionation design is based on work done by Chung et al.
Table 2.11
BTX Recovery Material Balance (Pygas)
Stream Number
Stream Name
Feed
DeC5
Ovhd
Raffinate
Extract
Bz Drag
Benzene
Toluene
Xylenes
C9+
aromatics
104
72.5
0.0
977
81,426
1,651
105
30.0
0.0
268
18,253
440
105
140.0
0.0
45
4,391
105
105
140.0
0.0
665
58,783
1,109
178.1
15.0
1.0
8
601
12
120
45.0
0.0
351
27,416
517
120
55.0
0.0
166
15,431
295
120
20.0
0.0
101
10,717
203
120
45.0
0.0
39
4,621
88
22.2%
5.9%
34.2%
18.9%
13.2%
5.6%
98.9%
1.0%
0.2%
0.0%
0.0%
0.0%
0.6%
99.4%
0.0%
0.0%
0.0%
0.0%
0.0%
0.4%
47.3%
26.2%
18.3%
7.7%
0.0%
35.1%
64.9%
0.0%
0.0%
0.0%
0.0%
0.1%
99.9%
0.1%
0.0%
0.0%
0.0%
0.1%
0.1%
99.8%
0.1%
0.0%
0.0%
0.0%
0.0%
0.1%
99.8%
0.1%
0.0%
0.0%
0.0%
0.0%
1.6%
98.4%
Properties
Temperature, F
Pressure, psia
Vapor Fraction
Mole Flow, Lb mol/hr
Mass Flow, Lb/hr
Volume Flow, cu. ft./hr
Composition, wt pct
C5 C6-C8 non aromatics
Benzene
Toluene
Xylenes
C9 +
Benzene/Toluene
PERP 06/07-6
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42
Extract From
Sulfolane Unit
HP
Stm.
XYLENES
COLUMN
CLAY
TREATER
CLAY TREATER
CHARGE TANK
Mixed Xylenes
BENZENE
COLUMN
Heavy Aromatics
MP
Stm.
CONDENSER
Benzene
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
HP
Stm.
Toluene
Figure 2.8
Aromatics Fractionation Section
TOLUENE
COLUMN
Q207_00101.0007.4106.vsd
Water To
Sour Water
Stripper
Benzene Drag
CONDENSER
Section 2
43
Feed
H/T
DEPENTANIZER
EXTRACTION
SOLVENT
C5-
Raffinate
Bz Drag
BENZENE
COLUMN
TOLUENE
COLUMN
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
C9+ Aromatics
Xylenes
Benzene
Q207_00101.0007.4106.vsd
Figure 2.9
BTX Recovery Block Flow Diagram
XYLENES
COLUMN
Toluene
Section 2
44
Section 2
Table 2.12
BTX Recovery Material Balance (Reformate)
Stream Number
Stream Name
Feed
2
DeC5
Ovhd
Extract
5
Bz
Drag
Benzene
Toluene
Xylenes
9
C9+
aromatics
Raffinate
104
72.5
0.0
1,457
133,342
2,846
105
30.0
0.0
268
18,294
440
105
140.0
0.0
45
45,396
105
105
140.0
0.0
665
69,669
1,109
178.1
15.0
1.0
5
391
8
120
45.0
0.0
90
7,062
133
120
55.0
0.0
219
20,356
389
120
20.0
0.0
245
26,034
494
120
45.0
0.0
132
15,823
302
19.1%
28.7%
5.6%
15.2%
19.7%
11.6%
99.1%
0.9%
0.0%
0.0%
0.0%
0.0%
16.3%
83.7%
0.0%
0.0%
0.0%
0.0%
0.0%
0.1%
10.7%
29.2%
37.8%
22.2%
0.0%
0.5%
99.5%
0.0%
0.0%
0.0%
0.0%
0.1%
99.9%
0.0%
0.0%
0.0%
0.0%
0.1%
0.1%
99.7%
0.0%
0.0%
0.0%
0.1%
0.0%
0.1%
99.8%
0.0%
0.0%
0.0%
0.0%
0.0%
2.2%
97.8%
Properties
Temperature, F
Pressure, psia
Vapor Fraction
Mole Flow, Lb mol/hr
Mass Flow, Lb/hr
Volume Flow, cu. ft./hr
Composition, wt pct
C5 C6-C8 non aromatics
Benzene
Toluene
Xylenes
C9 +
2.4.3
Single Aromatics Extraction Processes
Many producers extract all three components of BTX from reformate, with the impetus for the
extraction the demand for xylenes for isomer separation. In some cases, only benzene, and to a
lesser extent toluene, are required. The feed is then prefractionated to give a benzene or a
benzene/toluene heart cut, with the balance typically sent to the gasoline pool. Licensors of ED
technology include Axens (DMF), Lurgi (Distapex), Krupp Uhde (Morphylane), and GTC
Technology Inc. (GT-BTX).
As noted previously, extractive distillation is often more appropriate for the extraction of a single
aromatic product from a heart cut than is liquid/liquid extraction. One distinct advantage that ED
has over LLE is that only two major towers (extractive distillation column and aromatics
recovery column) are required instead of four towers (extractor, wash column, stripper, and
recovery). Also, since a heart cut (C6/C7) is usually fed to an ED facility, the unit throughput is
usually less.
Lurgi, for example, offers its combined liquid/liquid and ED processes, Arosolvan, for full BTX
extraction; and its ED process, Distapex, for single aromatic components. The solvent used is
the same in both: N-methylpyrrolidone (NMP). Distapex is appropriate when the aromatics
component has a high concentration (e.g., 60-70 percent) in the feedstock cut. This makes it
suitable for the recovery of benzene or toluene from pygas. An ED system, such as Distapex, is
also suitable for extraction of aromatics from coke oven light oil, following a hydrorefining step
to remove impurities such as sulfur, nitrogen, and oxygen.
Benzene/Toluene
PERP 06/07-6
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45
Section 2
As described in Section 2.2, Krupp Uhde also offers its Morphylane process, based on the
solvent N-formylmorpholine (NFM). This is aimed at feedstocks with high aromatics
concentrations. Others include UDEXTM (licensed by UOP) and GT-BTX (licensed by GTC
Technology Corp).
The Morphylane extractive distillation process has been modified for the recovery of aromatics
from catalytic reformate. This process, called Octenar, can be used in a number of applications.
To upgrade the octane value of reformate, the Octenar process can be used to separate an
aromatics-rich stream containing BTX. This stream is of lower purity than that of a system such
as Sulfolane, but is intended as a high octane blending component. Another variant involves
taking a portion of the benzene overhead from the extractive distillation column; the extract
passing to the stripper is high in aromatics and low in benzene, and is suitable for gasoline
blending.
In designing an extraction system, there are a number of options relating to whether and how the
reformate feed is precut which will impact the need for fractionation after extraction to take a
benzene product stream. The process described here is a typical Octenar system for extracting
an aromatics concentrate from a (C6-) reformate cut.
Figure 2.10 shows a simplified process flowsheet. The feedstock reformate is charged to the
extractive distillation column, and lean cool solvent enters the top. The nonaromatics leave in
the column overheads product, together with a small amount of aromatics and solvents.
The bottoms product from the ED column consists primarily of solvent and aromatics. This
flows by pressure differential to the aromatics recovery column, where the aromatics are
separated by distillation under vacuum. A portion of the condensed aromatics is refluxed to
achieve purity and reduce solvent carryover.
The overhead stream from the ED column is condensed and some is returned to the column as
reflux. No water wash is applied to the raffinate. A solvent recovery column is not included in
this design. The total solvent loss by all means is quoted as approximately 22 ppm, expressed on
the benzene steam.
Extensive use is made of the heat content of the hot solvent from the stripped column. It
provides part of the heat load for the ED column and the stripper column itself.
A side stream of hot lean solvent is intermittently fed to a solvent regeneration unit, where it is
distilled from high boiling decomposition products under vacuum before being returned to the
solvent circuit. A solvent drum, supply pump, and drain tank are also required, although not
shown on the diagram.
Benzene quality, as predicted by Krupp Uhde, is shown in Table 2.13.
Benzene/Toluene
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C7+ Fraction
LP
Stm
Reformate
COLUMN
PREFRACTIONATION
MP
Stm
EXTRACTIVE
DISTILLATION
COLUMN
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Figure 2.10
Morphylane Extractive Distillation
HP
Steam
AROMATICS
RECOVERY
COLUMN
Benzene
Nonaromatics
Section 2
47
Section 2
Table 2.13
Benzene Product Quality from the Octenar Process
Color (platinum/cobalt scale)
Distillation range
Solidification point
Acid wash color
Acidity
Hydrogen sulfide and sulfur dioxide
Thiophene
Copper corrosion
Nonaromatics
2.5
DEALKYLATION PROCESSES
2.5.1
Introduction
20 max
1C
Min/4.85C anhydrous
2 max
No free acid
None
Varies with reformate
Pass
500 max w/w ppm
The market demand for benzene, as a proportion of total BTX, is higher than the proportion of
benzene in typical BTX products. Conversion of toluene and, to a lesser extent, xylenes, is
practiced by two basic techniques:
Hydrodealkylation involves stripping the methyl groups from toluene or xylenes to

produce benzene and methane.
Although not purely dealkylation, the topic of toluene disproportionation is also included
under this heading as a discretionary method of producing benzene. The toluene is
converted to benzene and xylenes in this process.
2.5.2
Hydrodealkyation
A summary of hydrodealkylation processes is shown in Table 2.14.

Table 2.14
Hydrodealkylation Processes
Company
UOP/Marathon Ashland Petroleum
Houdry(1)
HRI/Axens
Gulf
Houdry(1)
Mitsubishi
Houdry(1)
UOP
(1)
Process
Name
Hydeal
Detol
HDA
THD
Pyrotol
MHC
Litol
THDA
Process
Type
Catalytic
Catalytic
Thermal
Thermal
Catalytic
Thermal
Catalytic
Catalytic
Feedstock
Toluene/higher aromatics
Pygas/reformate
Pygas/reformate
Light oil
Licensing rights held by ABB Lummus Global

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Section 2
All the commercial processes involve the same basic chemistry. For toluene, the reaction is as
follows:
C6H5CH3 + H2
C6H6 + CH4
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Similar reactions occur with higher alkylated benzenes. Xylenes dealkylate in two steps,
whereas ethylbenzene dealkylates directly to benzene and ethane. Side reactions result in the
formation of diphenyls or polymers. These are normally burnt as fuel with the offgas. Around
83 percent of the toluene is ultimately converted to benzene product, and the balance is lost to
fuel. No solvent extraction of benzene is necessary and high purity benzene may be recovered
by simple distillation. Small quantities of sulfur compounds are eliminated; the hydrogen sulfide
leaves in the gaseous effluent.
Dealkylation processes may be catalytic or thermal. Typical operating conditions for the
catalytic type are 575C to 650C and 25-60 bar. A higher temperature, of up to 760C, is used
in the thermal processes. The basic process flowsheet is similar for both. Hydrogen-rich gas is
recycled to control the temperature in the exothermic reaction stage. The liquid product is
stabilized with the removal of light ends, clay treated, and fractionated to produce the benzene
product. Toluene and heavies are recycled.
ARCO and Hydrocarbon Research developed the HDA thermal process, operating at low
concentrations to give greater benzene yields. The THD process developed by Gulf is similar.
These processes are suitable for the conversion of process streams that consist substantially of
aromatics such as toluene from BTX separation.
Bulk dealkylation is also practiced. In the Houdry Pyrotol process, the nonaromatics content of
the feed can be up to 30 percent. The process uses a pretreatment reactor for the selective
hydrogenation of olefinics. Pyrotol can be used for the bulk dealkylation of pyrolysis gasoline.
It requires more hydrocracking of the non-aromatics than the Litol process (see below), but a
smaller amount of desulfurization, as well as a comparable amount of hydrodealkylation.
The Mitsubishi MHC process is a thermal process that also handles feeds with significant
nonaromatics components. Hydrogen of relatively low purity may be used, reducing the makeup
requirements.
Another variation is required for recovery of benzene from coke oven light oil. The Houdry
Litol process uses a pretreatment reactor in a fashion similar to the Pyrotol process, and
produces a polymer residue stream. Another important requirement is to hydrogenate sulfur and
nitrogen impurities that are present in higher quantities than in other feedstocks.
To illustrate the technology employed, the three Houdry dealkylation processes are briefly
described. The economics of dealkylation of pyrolysis gasoline and coke oven light oil are
included in the sections on economics later in this report.
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Section 2
2.5.2.1
Detol Process
The Detol process is shown in simplified form in Figure 2.11.

Catalytic Reactor Section
Fresh feed and recycle aromatics from the benzene tower are pumped to system pressure. The
total liquid feed is combined with makeup gas and hydrogen-rich recycle gas from the recycle
gas compressor and is then heated by exchange with hot reactor effluent and brought to reactor
temperature in a fired heater.
The heated mixture flows through the first reactor where a portion of the dealkylation reaction
occurs. Since the net effect of the reaction is a temperature rise in the reactor, the first reactor
effluent is quenched by a portion of cold recycle gas before it is sent to the second reactor. In
large plants, additional reactors are employed in order to maximize catalyst utilization.
The effluent from the last reactor is cooled by exchange with reactor feed and stabilizer feed, and
is used to supply reboiler heat to the stabilizer and benzene tower. Final cooling and partial
condensation of the effluent is done in the air cooled condenser.
High Pressure Gas Treatment
After condensation, the reactor effluent gas and liquid are separated in a high pressure flash
drum. The recycle gas from the flash drum is split into two streams. One stream flows directly
to the recycle compressor knockout drum, whereas the remainder is sent to a hydrogen
purification unit. In this unit, BTX is recovered by scrubbing the feed gas with a slip stream of
recycle aromatics from the benzene tower bottoms and a 90 percent purity hydrogen stream is
obtained. The recovered aromatics along with the flash drum liquid are sent to the stabilizer.
The purified hydrogen recombines with the bypassed portion of recycle gas and flows to the
compressor knockout drum. After compression, the recycle gas is divided into two streams. The
major portion is combined with makeup hydrogen plus the liquid feed and charged to the first
reactor. The remainder is used to cool the first reactor effluent as previously described.
Stabilization and Clay Treatment
High pressure flash liquid is preheated with reactor effluent before being charged to the stabilizer
tower. The stabilizer serves to reject overhead all components lighter than benzene while
retaining benzene and heavier components in the bottoms product. Reboiler heat is provided to
the tower by exchange with reactor effluent.
The overheads gas from the stabilizer is chilled so that benzene is recovered and returned to the
stabilizer reflux drum. The remaining vapor is vented.
The stabilizer bottoms product is pumped directly to the clay treaters. These vessels contain clay
beds, which, through polymerization and adsorption, serve to remove trace impurities from the
aromatics product. Two reactors are provided to be run in either parallel or series flow. Each
reactor can be dumped and reloaded while the other treater remains on stream.
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HEAVIER
RECYCLE
TOLUENE
AND
FRESH
FEED
CHILLER
FUEL
GAS
STABILIZER
MAKEUP
HYDROGEN
BFW
CLAY TREATERS
REACTOR
STEAM
TOWER
BENZENE
UNIT
PRODUCT
BENZENE
PURIFICATION
GAS
FUEL
COMPRESSOR
GAS
RECYCLE
Figure 2.11
Detol Unit Simplified Flowsheet
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DRUM
FLASH
CONDENSOR
REACTOR
Section 2
51
Section 2
Product Recovery
The clay treated aromatics are charged to the benzene tower. This tower produces a high purity
overheads benzene product, a toluene and heavier bottoms product that also contains crude
diphenyl, and a small amount of benzene. The overheads benzene product stream is cooled and
pumped to storage. Most of the bottoms stream is recycled to extinction; a small part is used in
the hydrogen purification unit.
Catalyst Regeneration
Catalyst regeneration is required occasionally to restore the catalyst to its original activity.
Regeneration of the reactors occurs in an inert atmosphere, with air bled into an inert
recirculating stream at a controlled rate to control temperature in the reactors. The unit is
offstream during these periods. In addition to the equipment common to normal operation,
regeneration requires a source of nitrogen for purging and a source of compressed air or oxygen
for the regeneration itself.
2.5.2.2
Litol Process
The Litol process was developed by Houdry and Bethlehem Steel to produce pure benzene from
aromatic light oil obtained as a byproduct from the coking of coal. A simplified flowsheet is
shown in Figure 2.12.
The light oil is first prefractionated to remove material heavier than C8 aromatics. The top
product has a nominal end point of 150C. The aromatics recovered from the stabilizer
overheads product are added to this cut. The total feed is pumped to reactor pressure, preheated,
and passed to the vaporizer.
In the vaporizer, a part of the preheated hydrogen recycle stream is used to vaporize the feed. A
small amount of high boiling polymer is formed, returned to the prefractionator tower, and leaves
with the bottoms product. Vaporized feed is mixed with the remaining recycle hydrogen and
enters the pretreatment reactor, which hydrogenates materials that would form coke and severely
reduce the onstream life of the catalyst in subsequent reactors.
The pretreated feed stream is combined with recycle from the bottoms product of the benzene
tower and brought to dealkylation reaction temperature in a fired heater. The heater effluent
flows through the first reactor, thus purifying the aromatics through conversion of sulfur and
nitrogen compounds to hydrogen sulfide and ammonia, and by hydrocracking the nonaromatics.
In this reactor some benzene is formed from a portion of the higher homologs (e.g. toluene, C8
aromatics) that are dealkylated. Since the net effect of the reactions results in a temperature rise,
the effluent from the first reactor is quenched by a cold hydrogen recycle gas stream from the
high pressure flash drum (via the recycle gas compressor). The effluent then flows to the second
reactor where similar heat release occurs due primarily to the dealkylation reactions. The reactor
inlet temperatures are increased gradually through the cycle to maintain the desired production
rates and product purity.
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Benzene/Toluene
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TREATER
CAUSTIC
PRODUCT
BENZENE
BOTTOMS
PREFRAC
OIL
LIGHT
CAUSTIC
TOWER
BENZENE
TOWER
CLAY TREATERS
PREFRACTIONATOR
CHILLER
FUEL
GAS
STABILIZER
VAPORIZER
TO ATMOS
PRETREATMENT
REACTOR
DRUM
FLASH
RECYCLE
BFW
COMPRESSOR
HYDROGEN
STEAM
HP
REACTOR
MAKE UP
H
2
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Figure 2.12
Litol Unit Simplified Flowsheet
GAS
VENT
COMPRESSOR
REACTOR
Section 2
53
Section 2
Heat is recovered from the hot reactor effluent by raising steam and by several process heat
exchangers before being partly condensed and flashed. Part of the flashed vapor is taken as an
effluent to remove hydrogen sulfide and light hydrocarbons from the circuit. There may be
recovery of aromatics from this purge stream. The remaining vapor is mixed with compressed
hydrogen; some is used to cool the effluent from the first reactor and the remainder is mixed with
the feed to the pretreatment reactor.
As with the Detol process, the liquid from the flash drum is stabilized and the overheads
product is chilled to recover benzene. The stabilizer bottoms product is clay treated and sent to
the benzene tower. The bottoms product from the benzene tower is recycled and added to the
pretreated reactor feed.
The product benzene is treated with dilute sodium hydroxide to wash out trace sulfur
contaminants.
Catalyst regeneration is required occasionally, as in the Detol process.
2.5.2.3
Pyrotol
Houdrys Pyrotol process is primarily aimed at the dealkylation of aromatics within a pyrolysis
gasoline stream.
The flowsheet of the Pyrotol process fed by raw pyrolysis gasoline is very similar to that of the
Litol process, with feed prefractionation as necessary.
The feed is prefractionated to depentanize and to remove at least part of the C9+ components.
The feed cut is vaporized and passed to a pretreatment reactor where dienes, cyclodiolefins, and
styrene are selectively hydrogenated. In the Pyrotol reactors, aromatics are dealkylated to
benzene. Other reactions include the cracking of nonaromatics to light hydrocarbons, primarily
C1 to C3, and desulfurizing. Unreacted toluene and heavier aromatics are recycled to the reaction
stage.
2.5.3
Toluene Disproportionation
Toluene may be disproportionated to benzene and xylenes as follows:

CH3
CH3
+
CH3
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Some processes also accept C9 feedstock, from which xylenes are produced via transalkylation.
The advantage of disproportionation lies in its high conversion to liquid products and its low
consumption of hydrogen compared to dealkylation. It also provides a means of producing
Benzene/Toluene
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54
Section 2
xylenes from feedstocks such as pyrolysis gasoline, where the C8 cut is relatively small and has a
high proportion of ethylbenzene.
Processes have been available for licensing since the early 1970s, but most are now licensed by
either UOP (TatorayTM) or Axens (ExxonMobils MTDP-3); the latter is available for license
only in grassroots aromatics complexes. Revamps and individual units are still licensed through
ExxonMobil.
The efficiency of toluene conversion is typically 42 to 48 percent per pass.
Although ExxonMobil's MTDP-3 process can handle C9 aromatics on a limited basis, UOP
claims that its Tatoray process can handle up to 100 percent C9 aromatics and has operated
commercially with up to 10 percent C10 aromatics in the feed. ExxonMobil has developed and
commercialized a heavy aromatics transalkylation process, TransPlusSM, which can handle up to
100 percent C9+ with up to 25 percent C10 aromatics. This process was developed with CPC of
Taiwan and commercialized in June 1997. UOP and Toray have entered into an agreement to
further commercialize the latters TAC-9 process. This technology produces a high yield of
mixed xylenes from feeds containing up to 100 percent C9 and C10 aromatics. Pilot work by
Atofina on its T2BX process indicates that this unit also could run with heavy aromatics in the
feed, at up to 25 percent.
Increasing the content of heavier aromatics in the feed increases the formation of heavy products,
which reduces the overall yield of benzene and xylenes. It does increase, however, the yield of
xylenes relative to benzene, and the optimum C9 aromatics concentration ranges from 40 to 60
percent of the feedstock depending on economics.
One of the disadvantages of toluene disproportionation is that the xylenes product is usually an
equilibrium mix of isomers, which does not correspond to the split of market demand. Both
UOP and ExxonMobil offer Selective Toluene Disproportionation processes, which produce a
xylenes stream with around 90 percent of para-xylene, the desired isomer. Details of these
technologies were discussed in PERP report 05/06-8, Xylenes.
The toluene disproportionation processes of the different licensors are similar. A typical process
is shown in Figure 2.13 and described below.
Dry toluene feed with recycle gas is preheated by indirect heat exchange with reactor effluent,
and by a fired heater, before entering the catalytic reactor. The reactor product is cooled and sent
to a phase separator. Most of the hydrogen-rich vapor phase is recycled with a small purge to
maintain the appropriate hydrogen partial pressure in the reactor. The separator liquid is
stabilized to remove minor quantities of light ends and is clay treated to remove trace olefins.
The reactor conditions vary with the proprietary process, but are typically 40-45 bar and 320350C. The ExxonMobil Selective Toluene Disproportionation process operates at 22-35 bar
and 400-470C with initial coking pretreatment at higher temperature and pressure.
Benzene/Toluene
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Benzene/Toluene
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FEEDSTOCK
TOLUENE
FEED
DRYERS
FIRED
HEATER
RECYCLE
COMPRESSOR
REACTOR
CW
SEPARATOR
Purge
Gas
CLAY
TREATER
Product
Stream
Gas
Ends
Q207_00101.0007.4106.vsd
Figure 2.13
Toluene Disproportionation
Typical Flowsheet
Steam
STABILIZER
CW
Light
Section 2
56
Section 2
2.6
PRODUCTION FROM COKE OVEN LIGHT OIL
In the early 1950s coal derived aromatics accounted for a significant portion of the world
benzene/toluene supply. However, this supply could not keep pace with the chemical industrys
expanding demand for aromatics, and today accounts for less than 5 percent of total supply
within Western Europe and the United States.
Light oil arises as a byproduct in the coking of coal, largely to provide a carbon source in steel
making. To make coke, coal is pyrolyzed at around 1,000C; temperatures vary widely in
practice. About 70 percent of the product is solid coke, consisting primarily of carbon. The
remainder is volatilized, and leaves through the top of the coke ovens. This gaseous stream is
fractionated, and its cuts are used in various ways:
A light hydrocarbon gas, around 20 percent of the product, is recycled to fire the coke
ovens.
Ammonia is less than 0.5 percent of the product.
Coal tars, around 4 percent of the product, are separated and refined to yield polycyclic
compounds such as naphthalene, anthracene, pyridine, and phenanthrene.
Crude benzole, or coke oven light oil, is about 1 percent of the product.
Crude benzole is recovered by washing the gaseous stream, already cooled to 25-35C (7795F), with a petroleum fraction with a boiling point of 300-350C (572-662F). The petroleum
wash is then recovered by steam distillation and recycled.
A typical composition of benzole is shown in Table 2.15.
Table 2.15
Typical Composition of Benzole
(Weight percent)
60-70
Benzene
Toluene
12-16
Xylenes
4-8
Styrene
2-4
C5-C8 nonaromatics
5-9
Carbon disulfide
0.4-0.6
Sulfur compounds
0.5-0.7
C9 hydrocarbons
2-3
Coke Oven Light Oil (COLO) is a byproduct of coke manufacture from coal. The oil derived is
a foul smelling amber liquid composed of mononuclear aromatic hydrocarbons, olefins, styrene,
sulfur, and nitrogen compounds, etc. The Lyondell process requires: (1) two-stage hydrotreating
reaction, which saturates of diolefins, styrene, mono-olefins and converts sulfur nitrogen
compounds to H2S, NH3 respectively. (2) Fractionation removes light ends, produces a
concentrated aromatics stream for downstream aromatics extraction. This unique process
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Section 2
operates at lower temperature and pressure than competitors and recovers the maximum possible
quantity of benzene from COLO, with minimum aromatics loss due to saturation.
2.7
PRODUCTION OF AROMATICS VIA NONCONVENTIONAL ROUTES
There exist several nonconventional routes to convert low value refinery byproducts to benzene,
toluene, and xylenes. These have been developed and commercialized by various companies
over the past several years and include:
Asahi Chemicals Alpha Process, which has been operating at the companys Mizushima
complex in Okayama, Japan, since 1993, employing an olefinic feed (licensed by Stone
& Webster).
The first commercial operation of BP/UOPs CyclarTM Process was in 1999 at Saudi
Basic Industries Corporation (SABIC).
CP Chems Aromax Process, which is operating at its Pascagoula refinery, at Saudi

Chevron Phillips Chemical using a second generation Aromax catalyst and CEPSA,
Spain.
UOPs RZ PlatformingTM process started up its first commercial unit in second quarter
1998.
Each of the technologies is described briefly in the sections that follow.

2.7.1
Asahi Chemicals Alpha Process
Asahi Chemical Industry Co., Ltd. and its subsidiary, Sanyo Petrochemical Company, have
jointly developed and commercialized the Alpha Process (licensed by Stone and Webster) for the
production of aromatic hydrocarbons starting from low valued light olefinic hydrocarbons. This
process has been evaluated in PERP Report 97/98S1, Aromatics from Light Olefins. The
following discussion provides an overview of the process. The process is unique in that it
handles olefinic and paraffinic feeds. It was originally developed to upgrade C4 and C5 raffinate
from the steam cracking of naphtha at Asahis petrochemical complex in Okayama, Japan.
2.7.1.1
Chemistry
The proposed reaction mechanism has light olefins such as pentenes, butenes, and propylene
forming from paraffinic material by dehydrogenation and/or cracking. This is followed by
oligomerization, cyclization, and dehydrogenation to aromatics. Along with oligomerization, the
olefins disproportionate rapidly and redistribute to an equilibrium composition. Therefore,
almost the same BTX distribution is obtained in the product irrespective of the feed composition.
Temperature is more of a factor in determining the BTX distribution. The rate controlling step in
these reactions is the dehydrogenation and cracking of paraffins that require a large amount of
energy.
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Section 2
Olefins are the preferred feedstock although paraffins can be handled. An olefinic feed allows a
simpler design. The more paraffins in the feed, the more catalyst and energy required. Diolefins
promote coking and deactivation. Thus, selective dehydrogenation of the feed may be required
upstream.
2.7.1.2
Process Description
Figure 2.14 provides a simple flow diagram of the Alpha Process. A pair of fixed bed swing
reactors are used for the Alpha Process. For a typical feed with greater than 50 percent olefins, a
single reactor is applicable. The catalyst activity deteriorates gradually over the normal
operation (500-550C (932-1022F), 3-7 kg /cm (g), and WHSV of 2-4 w/w/h). Activity is
easily recovered by a periodic, conventional inert air regeneration. More paraffinic feeds may
require additional reactor beds (or vessels) and reheating the streams between reactor beds.
The feed is preheated in the feed/effluent heat exchanger. Final reactor inlet temperature is
obtained by a fired heater. The reactor effluent is cooled first against feed, followed by water
and refrigerant. The liquid product is then separated and sent to a stabilizer column, where the
C5 and lighter hydrocarbons are separated from the BTX components. No further treatment is
required before feeding the BTX to an aromatics plant. The light hydrocarbon byproducts (C5-)
are almost pure paraffins and are very good steam cracker feedstocks.
The first commercial plant with a capacity of 3,500 BPD has been operating since July, 1993 at
Sanyos Mizushima plant in Okayama. The feed is a C4/C5 raffinate, which is approximately 50
percent olefins.
2.7.2
BP/UOPs CyclarTM Process
The CyclarTM process can produce petrochemical grade aromatics from C3 and C4 alkanes (i.e.
LPG). UOP indicates that the distribution of the butane species in the C4 feedstock is
inconsequential. Components lighter than propane should be minimized since they act as inert
diluents. C5 and C6 components should be limited to less than 20 and 2 weight percent,
respectively, to minimize coke formation in the process. C3 and C4 olefins can be included in the
feed but should be limited to less than 10 percent. Butane feedstocks produce a product that is
leaner in benzene and richer in xylenes than that produced from propane. The aromatics yield is
slightly higher with an all-butane feed as opposed to an all-propane feed.
The catalyst is a sphere consisting of a proprietary zeolite incorporated with a non-noble metal
promoter in an inert binder. The zeolitic component in the catalyst provides acidity, and the
metal promoter combines with the zeolite to provide dehydrogenation activity. The inert binder
and shape-selective properties of the zeolite retard the formation of coke. UOP claims that 30
percent less catalyst is required with second generation catalyst.
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500550C
Benzene/Toluene
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Feed
CATALYST
REGENERATOR
FIXED HEATERS
3-7
kg/cm2
Refrigerant
C.W.
FEED/EFFLUENT
HEAT
EXCHANGERS
REACTORS
Aromatics
Light
Paraffin
Q207_00101.0007.4106.vsd
Figure 2.14
Alpha Process Flow Diagram
STABILIZER
C.W.
Fuel Gas
Section 2
60
Section 2
The process is best described as dehydrocyclodimerization and is thermodynamically favored at

temperatures above 425C (800F). The dehydrogenation of light paraffins to olefins is the rate
limiting step. The olefins oligomerize to form larger intermediates that rapidly cyclize to
naphthenes. The final reaction step is the dehydrogenation of the naphthenes to their
corresponding aromatics. The reactions are shown as follows:
Paraffins
Oligomers
Olefins
By-products
Naphthenes
Aromatics + Hydrogen
Q207_00101.0007.4106-1.cdx
UOP offers two alternative designs: the low pressure design that produces the maximum
aromatics yield; and high pressure design (but still less than 100 psig) that requires only half the
catalyst and therefore has a lower investment (approximately 25 percent less) and lower
operating costs. However, the high pressure design produces about 20 percent less aromatics
product than the low pressure design. UOPs Continuous Catalyst Regeneration (CCR)
technology is employed for the reactor design. A process flow diagram for the CyclarTM Process
is shown in Figure 2.15.
Fresh feed is combined with a small recycle stream consisting of unconverted feed. After being
heated to the required reactor inlet temperature, the stream is converted to aromatics in a series
of four reactors with interstage heating. This configuration allows high conversion despite the
highly endothermic nature of the CyclarTM reaction. The reactors are low pressure drop, radial
flow, and stacked to allow gravity flow of the catalyst between reactors, as in the UOP
Platforming process and the CCR system. The effluent from the fourth reactor exchanges heat
with the combined feed, is cooled, and partly condensed. Liquid form the low pressure separator
is recovered and fed to a stripper where C6 and heavier aromatics are recovered as a bottoms
product.
Aromatics from the stripper bottoms are sent to a conventional, three tower BTX distillation train
where individual cuts of benzene, toluene, and mixed xylenes are distilled overhead. C9+
aromatics are recovered from the xylenes tower bottoms. The combined toluene and C9s could
be sent to a toluene disproportionation (e.g. Tatoray) unit, which would convert these to mixed
xylenes. The mixed xylenes could further be processed in a Parex-type unit to produce paraxylene.
Vapor from the low pressure separator is compressed and sent to a gas recovery section where
hydrogen and light byproducts are separated from the unconverted feed. The unconverted feed is
recycled to the reactors along with the stripper overheads. The small amount of aromatics that
are recovered in the gas separation section are also sent to the stripper.
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61
CHARGE AND INTERHEATERS
STACKED
REACTORS
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LPG
C.W.
From
Reactor
LP
SEPARATOR
Recycl e To R eactor
CONTINUOUS CATALYST
REGENERATION SECTION
STRIPPER
Produc t
C6+
Aromatic
RECOVERY
SECTION
GAS
Net
Fuel Gas
Q207_00101.0007.4106.vsd
Figure 2.15
UOP/BP CyclarTM Aromatization
BOOSTER
COMPRESSOR
Hydrogen
Section 2
62
Section 2
The hydrogen stream could be recovered in several ways, depending on the purity desired, and
the economics:
An absorber/stripper system producing a 65 mole percent hydrogen product
A cold box producing 95 mole percent hydrogen
An absorber/stripper system combined with a Pressure Swing Absorption (PSA) unit,

producing 99 mole percent hydrogen
A cold box combined with a PSA unit is usually more attractive if large quantities of 99+
mole percent hydrogen are desired
Catalyst flowing from the final reactor is transferred by lift gas to the top of the regeneration
tower where it is separated from the lift gas and proceeds by gravity flow through the
regenerator. Operating conditions that fully restore catalyst performance and protect the catalyst
from hydrothermal damage are established. Regenerator catalyst inventory is limited to a small
fraction of what is required in the reactor.
The regenerated catalyst proceeds through small transfer lines into flow control and surge
hoppers and finally into the regenerator lock hopper. Lift gas then transports the catalyst back to
the top of the first reactor in the stack, thus completing the catalyst circuit. Catalyst movement is
very gradual, with the rate controlled at the outlet of the regeneration tower. From this control
point, level control devices regulate all catalyst transfers. The catalyst from the fourth reactor
allows a constant and high level of catalyst activity and selectivity to be maintained in the
reactors. This steady-state catalyst condition eliminates the need for changes in process
temperatures to compensate for catalyst deactivation that might be typical of a semiregenerative
type reformer.
The desired conversion level, yield, and product quality are continuously maintained. The
regenerator section is sized to be compatible with a wide range of plant capacities while
maintaining the desired optimal steady state catalyst quality in the reactor.
The reactor and regenerator are independent. Each operates at its own ideal set of conditions.
Individual reactors do not cycle between reaction and regeneration conditions. This simplifies
metallurgy, heater sizing, and hydraulics since these can be designed for specific duties.
Although the aromatization reaction sequence involves some exothermic steps, the
preponderance of dehydrogenation and cracking reactions causes the overall reaction to be
highly endothermic. The reaction product is separated into hydrogen and light byproduct (for
fuel) with unconverted alkanes recycled to extinction. In this example the hydrogen purity of the
net hydrogen stream is 95 percent (via a cold box). The aromatics product is very rich in BTX.
Typically, the level of nonaromatics is less than 0.1 percent. This means that solvent extraction
is not needed to meet most product specifications.
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Section 2
2.7.3
CP Chems Aromax Process
The Aromax process is very similar to conventional catalytic reforming, with the exception of
extra sulfur removal facilities and the high paraffinicity of the feedstock. Aromax was
specifically developed to take advantage of low-quality feedstocks in order to make more
valuable benzene product. The proprietary catalyst is an L-type zeolite synthesized in such a
way as to have a high proportion (greater than 80 percent) of large crystals (i.e. larger than 1,000
angstroms). The typical pore size for this type of zeolite is 7 to 9 angstroms. The catalyst is very
sensitive to sulfur and water; thus, more sophisticated sulfur removal facilities have been
included in the flow scheme. The second generation Aromax catalyst provides superior
performance with heavier feedstocks and is claimed to have lower capital and operating costs.
One of the major drawbacks of this process is the high yield of toluene, which is of the lowest
commercial value of the three major aromatics. The toluene could be further processed in a
disproportionation unit to produce benzene and mixed xylenes. The mixed xylenes could further
be processed in a separation unit to produce the desired end product, para-xylene.
A general flow scheme for an Aromax unit is shown in Figure 2.16. The feed must be very
effectively desulfurized to ensure that catalyst activity is maintained throughout the run. A
typical residual sulfur level of less than 0.1 ppm is cited by Chevron Phillips Chemical (CP
Chem).
CP Chem has developed a two stage proprietary sulfur and water control system that is shown
inside the dotted box in the figure.
The first stage absorber, containing a supported cupric oxide adsorbent, operates at about 300F
to adsorb residual hydrogen sulfide form the stripped feed; the second stage reactor/absorber
operates at a high temperature in the presence of recycle hydrogen to remove the last traces of
sulfur-containing species from the feed naphtha.
The reforming section is a fixed bed design requiring on site regeneration once per year. The
refrigeration section has been added to reduce benzene losses in the separator drum overhead gas
to an acceptable level. Countercurrent liquid extraction could also be used for this step. The low
pressure operation (100 psig reactor outlet pressure), narrow boiling range of the feedstock, and
high hydrogen yield make liquid benzene recovery more difficult. The recycle gas dryer is
assumed to also contain a portion of sulfur adsorbent material to keep the sulfur content in the
recycle to a very low level.
Recycle gas is circulated by a centrifugal compressor that compresses the gas to suitable pressure
for recontacting in the upstream absorber/deethanizer for BTX and LPG recovery. The separator
liquid is sent to a debutanizer where the C4 material is separated and sent overhead to the
absorber/deethanizer for LPG recovery. A C5-rich side stream may also be withdrawn here to
purge out any accumulation of C5 material that may be present either because it was not
recovered in the upstream fractionation facilities or generated via cracking reactions in the
reaction section.
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64
Lt.
Naphtha
SULFUR
ABSORBER
FEED
PREHEATER
SULFUR
CONTROL
REACTOR
C.W.
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Refrig.
PRODUCT
SEPARATOR
CONDENSERS
FEED/EFFLUENT
EXCHANGER
REFORMING
REACTORS
AND
FURNACES
RECYCLE GAS
DRYER/SULFUR
TRAP
RECYCLE/MAKE GAS
COMPRESSOR
Raffinate Recycle
from BTX Extraction
BTX
Product
Q207_00101.0007.4106.vsd
Figure 2.16
Aromax (Chevron Phillips ) Paraffins to
BTX Process Flow Diagram
DEBUTANIZER
C5 To
Gasoline Blending
( If Required )
C4 & Lighter
To Absorber /
Deethanizer
Hydrogen
Rich Gas To
Absorber /
Deethanizer
Section 2
65
Section 2
The debutanizer bottoms stream is routed to the BTX extraction unit where product is extracted
and unconverted paraffins are recovered for recycle to the Aromax reformer.
A summary of the design parameters for the Aromax process is shown in Table 2.16.
The product mix depends on the feedstock. Feeds containing C6 through C7 components will
produce benzene and toluene, whereas a C6 through C8 feed will produce xylenes as well. The
feed cut points and resulting product mix are shown in Table 2.17.
Table 2.16
Aromax Reforming Design Parameters
Average reactor pressure, psig
Reactor temperature, F
Recycle gas rate, SCF/bbl
Recycle gas ratio, H2:HC
LHSV, hr-1
(1)
150
850-950
6,300(1)
5:1
1.5
Based on total feed.

Table 2.17
Aromax Product Mix versus Feed Cut Point
Cut Point Range, C

50-80
50-115
50-150
50-170
2.7.4
Product Mix
Benzene
BT
BTX
BTX + C9s
UOPs RZ PlatformingTM
The RZ PlatformingTM catalyst is a fixed bed, regenerable catalyst system that UOP has worked
on for over ten years. It has the ability to convert C6 and C7 paraffins to aromatics, and is
particularly well suited for producers requiring large amounts of benzene.
Feedstocks to the reforming unit using the RZ-100 catalyst can range from extraction unit
raffinates to BTX naphthas. Most streams will require hydrotreating and rerunning to remove
the C5s before processing in the RZ-100 unit. Although the RZ-100 catalyst is similar in many
ways to conventional reforming catalyst, it differs greatly in the production of benzene and
toluene. The selectivity of RZ-100 for these light aromatics is greatly improved over
conventional catalyst.
Figure 2.17 shows a process flow diagram of the UOPs RZ PlatformingTM process.
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Raffinate &
Hydrotreated
Naphtha C 6+ Feed
From Depentanizer
Steam
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HYDROGEN
RECYCLE
COMPRESSOR
REACTORS
HYDROGEN
SEPARATOR
Net
Hydrogen
FIRED HEATERS
REBOILER
STABILIZER
Q207_00101.0007.4106.vsd
Figure 2.17
UOP RZ-Platforming Process
Flow Diagram
C6+ Aromatics
LPG
Fuel
Gas
Section 2
67
Section 2
An RZ PlatformingTM unit can be used in parallel with a second conventional reforming unit to
optimize the production of desired aromatics by processing different fractions of the hydrotreated
feed. In such cases, the conventional reformer can be dedicated to processing the heavier feed
fraction, taking advantage of its ability to produce xylenes.
A light naphtha stream, which is rich in C6 and C7 components, can be routed to the RZ
PlatformingTM unit, where selectivity for converting light paraffins to benzene and toluene is
greater. A reformer raffinate stream could also be recycled to the RZ unit.
The RZ process is identical to other semi-regenerative (SR) reformer processes. Feed from the
hydrotreater and raffinate from the sulfolane unit are treated in a sulfur guard bed. The feed is
then combined with recycle hydrogen, preheated by exchange with reactor effluent, heated to
reaction temperature by a charge heater, and passed to the first reactor.
Since endothermic reactions cause the temperature to decrease, the effluent is reheated to
reaction temperature and sent to the second reactor. Effluent from the second reactor is reheated
and sent to the third reactor and so on. Effluent from the last reactor is cooled before being
passed to the products separator drum.
Products separator gas, which is hydrogen-rich, is compressed and combined with fresh feed to
the unit. Net gas is taken from the products separator and compressed in a two stage
countercurrent recontacting scheme that maximizes recovery of C5+ liquids to the fractionation
section. This also increases the purity of the byproduct hydrogen stream.
Unstabilized reformate from the countercurrent recontacting section is preheated by exchange
with debutanizer column bottoms before being fed to the debutanizer column. The debutanizer
column is reboiled by the fired heater convection section and a fired trim heater. Overheads
from the column are partly condensed in the debutanizer condenser and collected in the
debutanizer overhead receiver. Uncondensed vapors are recycled to the recontacting section.
Some of the liquid is returned to the column as reflux and the remaining overhead liquid product
is sent to the battery limits for recovery of LPG. The stabilized reformate product bottoms are
cooled against the column feed and the products cooler before being sent to the battery limits.
2.7.5
Summary of Non-conventional Routes
The BTX distribution for each of the non-conventional routes is compared with a conventional
CCR reformate (RON=102) distribution in Figure 2.18. However, as can be seen in the figure,
benzene production from the Aromax process is significantly more than from the Alpha process
(i.e. 65 percent versus 30 percent). The benzene production from the CyclarTM and RZ
PlatformingTM processes is similar and lower than these two processes. The CCR route produces
the least amount of benzene at the suggested conversion.
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Section 2
Figure 2.18
Aromatics Distribution in Non-Conventional Routes
100%
80%
60%
40%
20%
0%
CCR
CYCLAR
Benzene
Toluene
RZ
AROMAX
PLATFORMING
Mixed Xylenes C9+ Aromatics
ALPHA
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Section 3
Developing Technologies
Since the last PERP report on this subject there have been numerous patents and patent
applications dealing with the production of aromatics. A majority of these have been awarded to
the two major licensors of aromatics technology, namely UOP and IFP (Axens). Nexant has
reviewed the recent developments for the production of benzene and toluene. The more
interesting developments are discussed in this section.
3.1
METHANOL TO AROMATICS
The desire to receive value for "stranded" gas is stimulating research around the world to develop
catalysts and process technology for converting natural gas to transportable commercial
products. A. Wu and C. Drake of Phillips Petroleum (now Chevron Phillips Chemical
Company) have patented a novel catalyst combination that converts methanol (MeOH) to
aromatics (MTA) and especially xylenes. Methanol to aromatics was first found in Mobil's New
Zealand methanol to gasoline (MTG) pilot process operated in the 1980s.
The invention is based on exposing methanol to two catalyst compositions in sequence: A
silicoaluminophosphate (SAPO) followed by a zeolite containing zinc and metals from Group
IIIA and Group VIB. The most preferred catalysts are SAPO-34 and HZSM-5, respectively.
In their patents (U.S. Patent 6,372,680 and 6,489,528), 10 g of SAPO-34 was mixed with 10 g of
colloidal silica solution and the mixture extruded into 1/16"-diam pellets and dried at room
temperature. The dried pellets were then calcined at 538C (1000F) for 6 hours. For the
second-stage catalyst, 28 g of HZSM-5 was mixed with 2.8 g of zinc hexaborate and 32.4 g of
colloidal silica solution. The mixture was then extruded into 1/16"-diam pellets, dried, and
steamed for 650C (1202F) for 4 hours.
To demonstrate the requirement to use the two catalysts in sequence, runs using each catalyst
alone were performed first. A MeOHH2O feedstock (20:80 mole ratio) was passed through a
stainless steel tube reactor containing the SAPO-34 catalyst at 450C (842F) and 0 psig at a rate
of 25 mL/h. After 7.2 hours on stream it was found that MeOH was 100 percent converted, but
no aromatics were formed. A similar experiment was performed using only the zeolite catalyst.
Again, 100 percent conversion of the MeOH was achieved, but with only ~1 percent selectivity
to aromatics.
A third experiment was run with both catalysts placed in sequence in the tubular reactor (SAPO34 was the upper catalyst) and run under the conditions described above. This time, dramatically
different results were obtained. With 100 percent MeOH conversion, 31.3 wt percent selectivity
to aromatics was achieved with a very high 81 percent of the aromatics being xylenes.
Interestingly, if the two catalysts are physically mixed, then only about 10 wt percent selectivity
to aromatics is achieved. It should be kept in mind that MeOH "contains" 56 wt percent water
and only 44 wt percent hydrocarbons. Thus, the maximum weight yield of aromatics that could
be achieved is ~42 percent.
Unfortunately, the patent does not give enough information to truly understand the mechanism of
this unusual catalysis. For instance, in the runs that used only the individual catalysts, the patent
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Section 3
does not reveal what products are formed from the complete conversion of the MeOH. It can be
surmised that the likely products are mostly olefins because SAPO-34 is the key catalyst in the
UOP/Hydro Methanol to olefins (MTO) process. Then, exposure of the formed olefins to the
zeolite catalyst could convert them to aromatics la Mobil's MTG process that used ZSM-5.
3.2
METHANE TO BENZENE
Direct catalytic conversion of methane to higher hydrocarbons and specifically to aromatics

(e.g., such as benzene) has received extensive attention in the news recently:
Japans Mitsui Chemicals Inc. said it will open a research and development center on
Singapores Jurong Island to develop a catalyst to produce benzene from natural gas.
The company aims to produce at least 600 kta of benzene from gas after about 5 years of
R&D.
Mitsubishi Chemical has established an industrial process for producing benzene and
hydrogen from coke oven gas (COG) and carbon dioxide (CO2) contained in plant waste
gas. The company plans to start constructing a 150-250 kta benzene plant based on the
process as early as 2008.
Details about the Mitsui and Mitsubishi technologies are not yet available. However, Conoco
Phillips Company was awarded a patent (U.S. patent 6,552,243) for a catalyst and process for
producing aromatics from methane. This patent comprises an invention for the non-oxidative
aromatization of methane using a crystalline aluminosilicate molecular sieve catalyst exhibiting a
high conversion and a high selectivity to aromatics hydrocarbons such as benzene, toluene,
xylene and naphthalene.
The catalyst exhibits the MFI crystal structure (e.g., ZSM-5) and has a silica-to-alumina ratio of
about 50:1. In addition the crystalline aluminosilicate has the external surface acidity selectively
passivated by means of an amorphous silica layer.
The process comprises a one or multiple fixed-bed reactors in series that contacts a methane feed
stream with the catalyst at the preferred temperature of 675-750C (1247-1382F), at a preferred
pressure of between 0.5 and 2 bar and a preferred weight hourly space velocity (WHSV) of 0.1-4
hr-1. In the multi-stage design the products are recovered by means of an intermediate separation
step between the reactors. At the same time hydrogen is removed from the intermediate stream
in order to drive the reaction toward completion. Low molecular weight hydrocarbons can be
recycled to extinction. Hydrogen can also be recycled.
The patent examples show methane conversions as high as 25 percent and aromatic yields (C6C10) as high as 15 percent, but only for short periods. After about an hour the conversion and
yields drop significantly to 15-20 percent and 7-8 percent, respectively.
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Section 3
3.3
PATENTS OF INTEREST
3.3.1
Axens (IFP) and SK Corporation
Axens is licensing a new technology developed and patented by SK Corp. for upgrading
pyrolysis gasoline (re. U.S. patent 6,635,792). This selective catalytic technology converts the
C9+ material (via hydrodealkylation) and C6-C8 non-aromatics (via cracking and hydrogenation)
contained in pygas to BTX and LPG. The economics will be very dependent on the values of the
raffinate, C9 aromatics and LPG. On-spec benzene can be produced via distillation and, thus, it
eliminates or replaces the solvent extraction process. The LPG could be recycled to the steam
cracker for additional ethylene and propylene production. The catalyst is comprised either of
platinum/tin or platinum/lead.
The yields from an Advanced Pygas Upgrading Unit (APU) are compared with those from an
extraction unit in Table 3.1. A quick analysis shows that the gain in BTX is about 6.5 weight
percent when employing the APU technology.
Table 3.1
APU Yields and Products
(kmta)
Unit
Feeds
Products
APU
Pygas
Hydrogen
Total In
Benzene
Toluene
Xylenes
Raffinate (Bz)
Fuel Oil
LPG
Fuel Gas
Total Out
400
11
411
180
92
22
6
4
72
36
411
Extraction
400
0
400
170
66
40
76
48
0
0
400
The historical pricing of benzene raffinate, C9 aromatics (equal to its mogas blending value) and
LPG is shown in Figure 3.1 for the USGC. This shows that historically LPG has had a lower
value than C9 aromatics and is about equal in value to benzene raffinate. (The latter can also be
recycled to the steam cracker for additional ethylene and propylene productions although the
yield of ethylene and propylene is lower than for LPG). Based on this pricing data, it is
uncertain whether adding an APU unit will improve the economics of an aromatics facility. The
application of the APU technology will be very site specific depending very much on the values
applied to the products in question.
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Section 3
Figure 3.1
Historical C9 Aromatics, LPG and Benzene Raffinate Pricing (USGC)
(US dollars per metric ton)
1,200
1,000
$/MT
800
600
400
200
0
2000
2001
2002
2003
C9 AROMATICS
2004
LPG
2005
2006
Raffinate (Bz)
Q207_00101.0007.4106_char t s.xls
SK Corporation has taken the APU process a step further and integrated it with a pyrolysis unit
(re. U.S. patent application 2006/0287561). The latest invention produces increased aromatics
by processing the pygas in the APU and recycling the LPG to the pyrolysis unit to improve the
productivity of light olefins.
A block flow diagram of the invention is shown in Figure 3.2. The significant features of this
integration scheme are:
the pygas from the steam cracker is recycled to the APU unit
the hydrogen from the steam cracker cold box is recycle to the APU unit
the reformer grade hydrogen (60-75 mol percent) and LPG from the APU unit is recycle
to the steam cracker
the non-aromatics from the APU unit are recycled to the steam cracker
Within the APU unit the flow is much like a hydrotreater. Pygas from the steam cracker is
combined with hydrogen. The hydrogen is recycled from the steam cracker and make-up
hydrogen (H2 MU) is added to maintain the hydrogen purity. The feed mix is preheated with
reactor effluent before reaching the final reactor inlet temperature in a fired heater. Within the
reactor several reactions take place: dealkylation, transalkylation and hydrogenation. The
catalyst is 10-95 wt percent zeolites which at least one selected from the group consisting of
mordenite, a beta type of zeolite and a ZSM-5 type of zeolite and which has a silica/alumina
molar ratio of 200 or less. This is mixed with 5-90 wt. percent inorganic binder to produce a
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Section 3
support and either platinum/tin or platinum/lead is supported on the mixture. Typical yields for
the APU unit are provided in Table 3.2.
Table 3.2
APU Yields
(weight percent)
Feed
Hydrogen
Methane
Ethane
LPG
C5+ non aromatics
Benzene
Toluene
Ethylbenzene
Xylenes
C9+ aromatics
APU Effluent
Extraction plus
C8+ HDA
0.7
6.6
17.7
1.4
44.4
22.5
0.5
5.2
1.0
5.5
2.5
0.0
19.0
55.0
16.3
0.0
0.0
1.7
19.2
42.3
16.5
5.9
4.0
12.1
hydrogen to APU=1.0 wt%; hydrogen to extraction & HDA=1.1 wt%
The reactor effluent is cooled first by preheating the feed and then finally by air and/or cooling
water to about 30-50C (86-122F). The resulting mixed phase is separated and the liquid sent to
a conventional fractionation system where the aromatic components (benzene, toluene and
xylenes) are separated and recovered. The gas, which is 60-75 mol percent hydrogen and 25-40
mol percent hydrocarbon (methane, ethane, LPG) is sent to the steam cracker compression
section for recovery of the LPG and recycle of the hydrogen. The LPG is recovered via
fractionation and recycled to the pyrolysis furnaces as additional feed. Since the example used
herein is a naphtha cracker, the LPG would normally be recycled to separate pyrolysis furnaces
for optimum cracking.
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Section 3
Figure 3.2
Integrated APU/Pyrolysis Unit Block Flow Diagram
Gas (60-75 mol% hydrogen)
H2 MU
Separator
Benzene
Toluene
Furnace
Fractionation
Section
Xylenes
Reactor
C9+ aromatics
Hydrogen
APU
Non-aromatics
Pygas
Steam Cracker
Ethylene
Naphtha
Pryolysis
Furnaces
Compression
Section
Propylene
Cold Box
Fractionation
Section
Pyrolysis Fuel Oil

C2, C3, C4 recycle
Q207_00101.0007.4106.ppt
3.3.2
Chevron Phillips Chemical Company (CPChem)
Chevron Chemical Company (now Chevron Phillips Chemical Company) has been awarded a
patent (U.S. patent 6,143,166) in which reforming/aromatization of hydrocarbons occurs in two
parallel reformers in order to maximize the benzene and para-xylene production. In the first
reformer hydrocarbons comprising a C6-C7 cut are passed over a monofunctional, non-acidic
aromatization catalyst at reforming conditions to form a reformate comprising benzene and a
hydrogen rich gas having a purity of at least 88 mol percent. The second parallel reformer feeds
a portion of the hydrogen rich gas from the first reformer and a hydrocarbon feed comprising a
C8+ cut over a bifunctional, acidic reforming catalyst, under reforming conditions to form a
xylenes product. Use of such a processing scheme allows an increase in the hydrogen purity
reaching the bifunctional reformer catalyst while minimizing the total gas flow rate to the
reformer and minimizing the compressor horsepower. The higher purity hydrogen reduces
coking and increases the life of the bifunctional catalyst. The reforming in both reactors is
carried out in the presence of hydrogen at a pressure adjusted to favor the dehydrocyclization
reaction thermodynamically and to limit undesirable hydrocracking reactions. Operating
conditions are typically 40 to 150 psig, 400 to 600C (752 to 1112F), and a hydrogen to
hydrocarbon ratio between 2:1 and 6:1. Below 400C the reaction speed is insufficient and
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Section 3
consequently the yield is too low for industrial purposes. Operating above 600C reduces the
yield due to interference from secondary reactions such as hydrocracking and coking.
3.3.3
China Petroleum and Chemical Corporation (CPCC) & Sinopec
CPCC and Sinopec have developed a new composite solvent (U.S. patent 7,078,580) for
extractive distillation (ED) of aromatics. The composite is made up of a solvent, a solutizer and
a modifier. The solutizer is selected from any one (or mixture of any two) of C8-C11 aromatics
having different number of carbon atoms where the number of carbon atoms of the lowest
aromatic in the solutizer should be greater than that of the highest aromatic in the aromatics to be
separated. The solvent and modifier (0.01-10 weight percent) are independently selected from
sulfolane derivatives, N-formylmorpholine (NFM) and N-methylpyrrolidone (NMP).
The acidity and basicity of the modifier are opposite to those of the main solvent. Addition of
the modifier into the composite solvent can solve the deviation of the separated aromatics from
neutrality caused by the main solvent. For instance, when sulfolane is used as a main solvent,
the separated aromatic product is also weakly acidic as sulfolane is weakly acidic per se.
Therefore, a post treatment of the product is needed to neutralize its acidity. Similarly when
weakly basic N-formylmorpholine or N-methylpyrrolidone is used as the main solvent, the
separated product is also weakly basic. Therefore, an acid treatment of the product is needed to
neutralize the basicity thereof.
The process for separating aromatics by extractive distillation using the composite according to
this invention is:
Introducing the lean composite solvent to the upper portion of the ED column.
Introducing the hydrocarbon mixture to the middle of the Ed column.
Withdrawing the non-aromatics from the top of the ED column.
Passing the rich composite solvent containing the aromatics from the bottom of the ED
column to the middle of a solvent recovery column.
Recovering the aromatics (benzene or benzene/toluene mixture) from the top of the
recovery column.
Recovering the lean composite solvent from the bottom of the recovery column and
sending it to the top of the ED column.
The operating conditions are:
Top pressure, MPa
Inlet temperature (lean/rich solvent), C
Bottom temperature, C
Solvent to feed ratio
Reflux ratio
Theoretical trays
ED Column
0.10-0.30
80-130
130-180
3.0-7.0
0.1-3.0
10-40
Benzene/Toluene
PERP 06/07-6
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Recovery Column
0.04-0.10
125-175
160-190
0.5-2.5
10-25
76
Section 3
Due to the addition of the solutizer, the composite solvent enhances the solubility enabling the
composite solvent to have sufficiently high recovery rates when used to recover aromatics from
feedstock with low aromatic content, thus, expanding the applicable area of the device. The
addition of the modifier ensures the neutrality of the aromatic product and thereby reduces or
omits the post treatment.
3.3.4
ExxonMobil
U.S. patent 6,864,203 proposes a bound zeolite catalyst for use in alkylation, transalkylation or
isomerization of aromatic hydrocarbons. Synthetic zeolites are normally prepared by the
crystallization of zeolites from a supersaturated synthesis mixture. The resulting crystalline
product is then dried and calcined to produce a zeolite powder. Although the zeolite powder has
good adsorptive properties, its practical applications are severely limited because it is difficult to
operate fixed beds with zeolite powder. Therefore, prior to using the powder in commercial
processes, the zeolite crystals are usually bound. This is typically done by forming a zeolite
aggregate such as a pill, sphere, or extrudate. The extrudate is usually formed by extruding the
zeolite in the presence of a non-zeolitic binder and drying and calcining the resulting extrudate.
The binder materials used are resistant to the temperatures and other conditions (e.g., mechanical
attrition) which occur in various hydrocarbon conversion processes. Examples of binder
materials include amorphous materials such as alumina, silica, titania and various types of clays.
The performance of the zeolite catalyst (e.g., activity, selectivity, activity maintenance, or
combinations thereof), can be reduced because of the binder. For example, since the binder is
typically present in an amount of up to about 50 weight percent of the zeolite, the binder dilutes
the adsorption properties of the zeolite aggregate and may block access to the pores of the
zeolite, thus, slowing the rate of mass transfer and the effectiveness. Finally the binder may
affect the chemical reactions that are taking place or may catalyze undesirable reactions. The
bound zeolite catalyst of this patent comprises crystals of a large pore first zeolite and a binder
comprising smaller crystals of a second zeolite. This provides a means of controlling
undesirable reactions taking place in or near the external surface of the first zeolite crystals and
can improve the mass transfer of reactants by providing access to and from the pores of the first
zeolite. In addition, the second zeolite binding crystals can have catalyst activity. The patent
examples show a higher activity and higher xylene selectivity than an alumina bound mordenite
catalyst.
U.S. patent application 2006/0149104 by Mohr et al of ExxonMobil describes a process for
methylating benzene, toluene, or both present in the reformate to produce a product having a
higher xylenes content than the reformate. In this case a methylation unit is located inside the
reforming loop with reformate methylation carried out without interstage separation. In
conventional aromatics facilities, the reformate is usually first separated from the other
hydrocarbons present in the reformate by fractionation and extraction. Methanol is the preferred
methylating agent. Toluene present in the reformate is methylated to form xylenes. Benzene
present in the reformate can be methylated to form toluene, which in turn can be methylated to
form xylenes. Depending on the composition of the reformate, other reactions may also occur
(e.g., ethylbenzene can be methylated to form para-ethyl-methylbenzene or dealkylated to form
Benzene/Toluene
PERP 06/07-6
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77
Section 3
benzene). In addition the amount of para-xylene produced in the patent examples was greater
than equilibrium.
3.3.5
Fina Technology Inc.
Fina has been awarded a number of patents dealing with toluene disproportionation and
transalkylation of heavy aromatics.
U.S. patents 6,504,076 and 6,846,964 provide a method for conversion of heavy
alkylaromatic compounds, particularly those in the C8-C12 range, into more valuable
aromatics (BTX) utilizing a toluene disproportionation (TDP) unit containing a nickel,
palladium or platinum-modified mordenite catalyst. This invention allows a large
amount of heavy alkylaromatic compounds to be processed without adversely affecting
the catalyst activity or catalyst life. The feed can be a mix of toluene and heavy
aromatics or heavy aromatics alone.
U.S. patent 6,706,937 offers a metal modified zeolite transalkylation catalyst. The
temperature is progressively increased while continuing the operation of the
transalkylation zone to maintain a condition of constant reaction severity.
U.S. patent 6,803,493 presents a catalyst (nickel-promoted mordenite) and a process for
the disproportionation of less than pure toluene (80-90 percent pure), the rest being C6-C8
non-aromatics. The non-aromatics are cracked to LPG in the process. Catalyst activity
was shown to be enhanced by increasing the temperature, reactor pressure, the hydrogen
to oil ratio and by decreasing the space velocity. By appropriate adjustment of these
factors, a feedstock having a diluted toluene content can be employed to effectively
disproportionate the toluene to benzene and xylenes accompanied by cracking of the
substantial non-aromatic content of the feed to produce lower molecular weight
hydrocarbons.
U.S. patent 6,897,346 provides a process for the transalkylation of polyalkylated aromatic
compounds over a high porosity zeolite-Y molecular sieve having a surface of no more
than 500 m2/g.
3.3.6
Institut Francais DuPetrole (IFP)
U.S. patent 6,864,400 awarded to IFP uses a catalyst which contains at least one zeolite with
structure type NES, preferably NU-87, comprising silicon and at least one element T selected
from the group formed by aluminum, iron, gallium and boron. Preferably, element T has been
extracted so that the overall Si/T atomic ratio is more than 20. This zeolite is at least partially in
its acid form. The binder is preferably alumina. The catalyst also contains at least one metal
selected from the group formed by group VIIB, group VIB and iridium, preferably rhenium.
Finally, the catalyst optionally also contains at least one metal selected from the group formed by
elements from groups III and IV of the periodic table, preferably indium or tin. The performance
of the catalyst of this invention based on rhenium was substantially improved over that of prior
art (nickel-based catalyst). It was particularly active with a higher overall conversion for half as
much metal. Further the benzene plus xylene yield increased and the lower ethylbenzene yield
Benzene/Toluene
PERP 06/07-6
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78
Section 3
facilitated para-xylene separation. Finally the yield of light compounds (C1-C4) increased to the
detriment of the heavy compound yield which favors the stability of the catalyst and was due to
the dealkylating properties of this novel catalyst.
In U.S. patent 6,605,566, IFP has discovered a catalyst with substantially improved properties
with respect to previous reforming catalyst. This novel supported bimetallic catalyst comprises a
group VIII metal such as platinum or tin, a portion of which interacts strongly with the group
VIII metal with the catalyst in the reduced state. In particular it is noted that the presence of a
large quantity (greater than 10 percent) of a reduced tin species with oxidation state 0 and closely
associated with a group VIII metal in a bimetallic catalyst that is partially oxidized (by oxidation
carried out under perfectly controlled conditions with discontinuous injection of oxygen), reveals
a strong interaction in the reduced state of the catalyst between the group VIII metal and at least
a fraction of the tin, guaranteeing a beneficial bimetallic effect on the performance of the
hydrocarbon transformation units, such as catalyst reforming units, in terms of activity and
stability. Better activity and better stability increase the aromatics yield, the target products of
catalytic reforming. In the case of reforming, the catalyst of this invention results in a better
quality of reformate having a higher RON and deactivates more slowly than know catalysts.
3.3.7
SABIC
With respect to the CyclarTM process (re. Section 2.7.2), SABIC has been awarded several
patents (U.S. patents 6,784,333, 7,186,871 and 7,186,872) for improvements to the process and
catalyst. The catalyst is a crystalline zeolite on which platinum has been deposited, specifically a
platinum containing ZSM-5. The catalyst demonstrates a correlation between platinum loading
and selectivity to ethane. As the platinum loading is lowered the selectivity to BTX is lower as
well. An advantage to this catalyst is that the fuel gas produced has a higher content of ethane
relative to methane. Whereas a methane-rich fuel gas would primarily be used for its heat value,
an ethane-rich stream could be used as feed to a steam cracker after recovering the ethane.
3.3.8
UOP
UOP has developed a new family of zeolites (re. U.S. patent 7,091,390) identified as UZM-8 and
UZM-8HS which have unique x-ray diffraction patterns. These zeolites can be used in
alkylation of aromatics, transalkylation of aromatics, isomerization of aromatics and alkylation
of isoparaffins. The UZM-8 compositions are alumino-silicates having Si/Al molar ratio from
about 6.5 to about 35. Although UZM-8 compositions have some similarities to a layered
material identified as MCM-56, there are sufficient differences that UZM-8 compositions are
structurally different from MCM-56 materials and, thus, are unique new zeolite structures.
The reader is referred to PERP report 05/06-S6, Optimizing Aromatics Production, for a
discussion and analysis of UOPs patented flow scheme for the production of aromatics (re. U.S.
patents 6,740,788, 7,169,368, and 7,179,434).
Benzene/Toluene
PERP 06/07-6
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79
Section 4
Economic Analysis
4.1
BASIS
4.1.1
Pricing Basis
The pricing basis for the economics analysis that follows is summarized in Table 4.1 for the
USGC fourth quarter 2006.
Table 4.1
Price and Utility Basis
(USGC, fourth quarter 2006)
Feedstock/Byproducts
Naphtha
LPG
C5-C6
Propane
Butanes
Raffinate (Bz extraction)
Reformate
Pyrolysis gasoline
Hydrogen (reformer grade)
Benzene
Toluene, contract value
Toluene, mogas value
Mixed xylenes, contract value
Mixed xylenes, mogas value
C9 Aromatics
Utilities
Power, purchased
Cooling water
LP Steam
MP Steam
HP Steam
Boiler Feed Water
Inert Gas
Fuel
Manpower
Operators
Foremen
Supervisor
Units
$/Unit
Gallon
Gallon
Gallon
Gallon
Gallon
Gallon
Gallon
Gallon
Thousand SCF
Gallon
Gallon
Gallon
Gallon
Gallon
Gallon
1.364
1.013
1.323
0.950
1.120
1.323
1.860
1.810
3.383
3.653
2.511
2.087
2.570
2.151
2.223
kWh
Thousand Gal
Thousand Lb
Thousand Lb
Thousand Lb
Thousand Gal
Thousand SCF
Million Btu
0.059
0.108
10.149
10.310
11.622
1.956
1.706
6.436
$/Year
$/Year
$/Year
44,681
50,716
61,199
Benzene/Toluene
PERP 06/07-6
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80
Section 4
4.1.2
Economic Analysis
Investment Basis
A process plant can be viewed as consisting of two types of facilities. The first is the
manufacturing area, containing all process equipment needed to convert the raw materials into
the product. The capital costs of these facilities are commonly referred to as the inside battery
limits (ISBL). The second group of facilities contains the outside battery limits (OSBL) or
offsites. These include general utilities (e.g., instrument and utility air, nitrogen, fire water, etc.),
administrative buildings, steam generation facilities, cooling water system, electrical distribution
systems, waste disposal facilities, etc. In addition to the plant capital, the owner usually has
other costs associated with a project such as project management, start-up, etc.
For all the cases considered, investment costs assume "instantaneous" construction or
implementation in the designated year. This is a simplification because initiation, design, and
construction can take several years to complete. In order to undertake the instantaneous analysis,
phased investment costs and associated financial charges are consolidated into a single overall
project cost. The elements of Nexant ChemSystems capital cost estimates are presented in the
Appendix. All investments are for the U.S. Gulf Coast (USGC) for the fourth quarter 2006.
The buildup of the installed (direct) cost is developed starting with the purchased equipment cost
and using historical factors to estimate the bulk equipment costs (piping, electrical,
instrumentation and communication, paint and insulation, civil and structural), as well as labor.
The indirect costs are added also using historical factors. These include prorateable costs (fringe
benefits; burdens; insurance), field expenses (consumables; small tools; equipment rental; field
services; temporary construction facilities; field construction supervisor) and home office costs
plus fees (engineering plus incidentals; purchasing; construction management). The sum of the
direct and indirect equals the total installed cost (TIC).
Working capital is calculated to reflect raw materials, byproducts and supplies inventories,
accounts receivable, cash requirements, etc. with credit for accounts payable.
4.1.3
Cost of Production Basis
Labor costs are based on typical manpower rates for the USGC, while direct overhead and
maintenance costs are at normal industry levels (e.g. 45 percent of labor costs and 2-4 percent of
ISBL, respectively, for the USGC). Maintenance costs on the USGC are typically split 50-50
between labor and materials. Other costs included in the analysis - general overhead, insurance
and property taxes and environmental costs - are also based on typical industry levels (e.g. 60
percent of fixed cost, 1 percent of total plant capital and 0.5 percent of total plant capital,
respectively, for the USGC).
The detailed economics analysis which follows can be separated into two discrete categories:
Variable costs - raw material (e.g., naphtha, LPG), including catalysts and chemicals;
utilities, such as purchased electricity, cooling water, natural gas and boiler feedwater
(BFW); and byproducts.
Benzene/Toluene
PERP 06/07-6
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81
Section 4
Economic Analysis
Fixed costs - direct operating costs, such as labor, maintenance, and direct overheads;
allocated costs, such as general plant overhead, insurance, environmental and taxes.
Utilities and byproduct credits are considered variable costs since they are, to a large extent,
dependent on the plant's operating rate or rate of fuel consumption. Fixed operating and
allocated costs, as their title indicates, are largely independent of the operating rate. The sum of
variable and fixed costs is termed the "total cash cost of production." This is the out-of-pocket
expense and owner incurs before including working capital, capital investment depreciation and
any return on capital employed (ROCE). Depreciation is assumed to be 20 years for OSBL and
10 years for ISBL including the capitalized other project costs (OPC). The return on capital
employed (ROCE) is assumed to be 10 percent unless otherwise noted. The on-stream factor
assumed for this evaluation is based on operating for 8,000 hours per year.
4.2
ECONOMICS
4.2.1
Investment
The capacities and ISBL investment for the various reforming technologies discussed herein are
presented in Table 4.2. Capacities are based on a world scale capacity of 500 kta. Investment is
for the USGC in the fourth quarter of 2006. The lowest cost investment source of reformate is
either via CCRTM or RZ PlatformingTM. The highest capital investment per ton of reformate
product is for the CyclarTM process.
Table 4.2
Capacities and Investment
(USGC, fourth quarter 2006)
Technology
CCRTM
Aromax
RZ PlatformingTM
Alpha
CyclarTM
4.2.2
Capacity, kta
500
500
500
500
500
ISBL Investment, million

US$
65.5
72.6
64.3
95.9
158.3
US$/metric ton
of reformate
131
145
129
192
317
Cost of Production of Reformate
The costs of production for the various technologies for producing reformate have been
developed at a world scale plant capacity of 500 kta. Of the five types of technologies reviewed,
we have shown that the economics can vary widely. This range of economic performance is
clearly seen in Figure 4.1, where all five processes are viewed on a side-by-side basis. Aromax
is the low cost process which is consistent with previous PERP reports (02/03-5). CCRTM and
RZ PlatformingTM have essentially the same low cost of production. CyclarTM is the highest cost
route to reformate, which confirms the results from Nexants previous PERP report (02/03-5).
Benzene/Toluene
PERP 06/07-6
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82
Section 4
Economic Analysis
If a 30 percent discount is applied to the LPG feedstock price (pricing one might find in the
Middle East), the CyclarTM economics are competitive with the low cost technologies. The
individual process costs are discussed in the sections which follow and the sensitivities of these
economics are noted in Section 4.2.4.
Figure 4.1
Reformate Cost of Production
(500 kta, USGC, fourth quarter 2006)
3.00
Dollars Per Gallon
2.50
2.00
1.50
1.00
0.50
0.00
AROMAX
CCR
RZ
PLATFORMING
ALPHA
CYCLAR
NET RAW MATERIALS
UTILITIES
DIRECT FIXED COSTS
ALLOCATED FIXED COSTS
DEPRECIATION
ROCE
Q207_00101.0007.4106_char t s.xls
4.2.2.1
CCRTM Reforming
The cost of production estimate for producing reformate from naphtha in a 500 thousand metric
ton per year CCRTM unit is shown in Table 4.3. Net raw materials are estimated to be $1.49 per
gallon ($495 per metric ton). Utility costs add 8.9 cents per gallon ($30 per metric ton) bringing
the variable cost to $1.58 per gallon ($525 per metric ton). After adding in the fixed costs, the
total cash cost is estimated to be $1.63 per gallon ($542 per metric ton). Depreciation of 10
percent of ISBL, 5 percent of OSBL and other project costs adds another 6.3 cents per gallon
($21 per metric ton) to the cost of production. Return on total capital employed of 10 percent
adds 9.4 cents per gallon ($31 per metric ton). The final cost of production including return on
investment is estimated to be $1.79 per gallon ($594 per metric ton).
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
83
Section 4
Economic Analysis
Table 4.3
Cost of Production Estimate for: Reformate
Process: Continuous Catalyst Regeneration Reformer (includes Hydrotreater)
Plant start-up
Analysis date
Location
Capacity
4Q2006
USGC
166
500
100
166
Operating rate
Throughput
CAPITAL COST
ISBL
OSBL
Total Plant Capital
Other Project Costs
Total Capital Investment
Working capital
Million gallons/yr
Thousand metric tons/yr
percent
Million gallons/yr
UNITS
Per Gal
Product
PRODUCTION COST SUMMARY

RAW MATERIALS
Naphtha
gallons
Catalyst & Chemicals
TOTAL RAW MATERIALS
BY-PRODUCT CREDITS
Fuel Gas
MM Btu
LPG
gallons
Hydrogen - reformer grade kSCF
TOTAL BY-PRODUCT CREDITS
NET RAW MATERIALS
UTILITIES
Power
kwh
Cooling Water
M Gal
Natural Gas
MM Btu
Steam, HP
M Lbs
Steam, LP
M Lbs
Boiler Feedwater
M Gal
TOTAL UTILITIES
NET RAW MATERIALS & UTILITIES
PRICE
U.S. $
/Unit
1.2684
1.0000
1.3640
0.0020
(0.0008)
(0.0777)
(0.0457)
6.4359
1.0348
3.3833
0.1800
0.0103
0.0116
0.0001
0.0000
0.0004
0.0589
0.1080
6.4359
11.6220
10.1488
1.9560
VARIABLE COST
DIRECT FIXED COSTS
Labor,
30 Men
44.68
Foremen,
5 Men
50.72
Super.,
1 Men
61.20
Maint., Material & Labor
3
Direct Overhead
45
TOTAL DIRECT FIXED COSTS
General Plant Overhead
60
Insurance, Property Tax
1
Environmental
0.5
TOTAL ALLOCATED FIXED COSTS
TOTAL CASH COST
Depreciation @
10 % for ISBL & OPC
Thousand U.S. $
Thousand U.S. $
Thousand U.S. $
% of ISBL
% Labor & Supervision
% Direct Fixed Costs
% Total Plant Capital
5 % for OSBL
COST OF PRODUCTION
RETURN ON TOTAL CAPITAL INVESTMENT (Incl. WC) @
COST OF PRODUCTION + ROI
10 Percent
MILLION U.S. $
65.5
29.8
95.3
23.8
119.1
37.5
156.6
U.S. $
Per Gal
ANNUAL
COST MM
U.S. $
U.S. $
Per MT
1.730
0.002
1.732
(0.005)
(0.080)
(0.154)
(0.240)
1.492
0.011
0.001
0.075
0.002
0.000
0.001
0.089
1.581
287.21
0.33
287.55
(0.89)
(13.34)
(25.65)
(39.88)
247.67
1.76
0.18
12.44
0.26
0.03
0.12
14.80
262.47
1.581
262.47
525
0.008
0.002
0.000
0.012
0.004
0.026
0.016
0.006
0.003
0.024
1.632
1.34
0.25
0.06
1.97
0.74
4.37
2.62
0.95
0.48
4.05
270.88
8
542
0.063
10.42
21
1.695
281.30
563
0.094
15.66
31
1.789
296.97
594
575
(530)
495
30
525
Q207_00101.0007.4106_COP-tables.xls
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
84
Section 4
4.2.2.2
Economic Analysis
RZ PlatformingTM
The cost of production estimate for producing reformate via RZ PlatformingTM with a capacity of
500 thousand metric ton per year is shown in Table 4.4. Net raw materials are estimated to be
$1.52 per gallon ($506 per metric ton). Utility costs add 5.6 cents per gallon ($19 per metric ton)
bringing the variable cost to $1.58 per gallon ($525 per metric ton). After adding in the fixed
costs, the total cash cost is estimated to be $1.63 per gallon ($542 per metric ton). Depreciation
of 10 percent of ISBL, 5 percent of OSBL, and other project costs adds another 6.3 cents per
gallon ($21 per metric ton) to the cost of production. Return on total capital employed of 10
percent adds 9.5 cents per gallon ($31 per metric ton). The final cost of production including
return on investment is estimated to be $1.79 per gallon ($594 per metric ton).
4.2.2.3
CyclarTM
The cost of production estimate for producing reformate from LPG using UOPs CyclarTM
technology in a 500 thousand metric ton per year unit is shown in Table 4.5. Net raw materials
are estimated to be $1.96 per gallon ($652 per metric ton). Utility costs add 28.7 cents per gallon
($95 per metric ton) bringing the variable cost to $2.25 per gallon ($748 per metric ton). After
adding in the fixed costs, the total cash cost is estimated to be $2.34 per gallon ($778 per metric
ton). Depreciation of 10 percent of ISBL, 5 percent of OSBL, and other project costs adds
another 15.5 cents per gallon ($51 per metric ton) to the cost of production. Return on total
capital employed of 10 percent adds 21.3 cents per gallon ($71 per metric ton). The final cost of
production including return on investment is estimated to be $2.71 per gallon ($900 per
metric ton).
4.2.2.4
Aromax
The cost of production estimate for producing reformate via Aromax employing a unit with a
capacity of 500 thousand metric ton per year is shown in Table 4.6. Net raw materials are
estimated to be $1.30 per gallon ($432 per metric ton). Utility costs add 16.3 cents per gallon
metric ton).
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
85
Section 4
Economic Analysis
Table 4.4
Process: RZ PlatformingTM
Plant start-up
Analysis date
Location
Capacity
4Q2006
USGC
166
500
100
166
Operating rate
Throughput
CAPITAL COST
ISBL
OSBL
Total Plant Capital
Other Project Costs
Working capital
Million gallons/yr
percent
Million gallons/yr
UNITS
Per Gal
Product

RAW MATERIALS
Naphtha
gallons
gallons
TOTAL RAW MATERIALS
BY-PRODUCT CREDITS
Fuel Gas
MM Btu
NET RAW MATERIALS
UTILITIES
Power
kwh
Cooling Water
M Gal
Natural Gas
MM Btu
Steam, HP
M Lbs
TOTAL UTILITIES
PRICE
U.S. $
/Unit
1.1129
0.1539
1.0000
1.3640
1.3233
0.0154
(0.0032)
(0.0565)
6.4359
3.3833
0.0417
0.0589
0.0012
0.1080
0.0125
6.4359
(0.0023) 11.6220
VARIABLE COST
DIRECT FIXED COSTS
Labor,
30 Men
44.68
Foremen,
5 Men
50.72
Super.,
1 Men
61.20
3
Direct Overhead
45
60
1
Environmental
0.5
TOTAL CASH COST
Depreciation @
10 % for ISBL & OPC
Thousand U.S. $
Thousand U.S. $
Thousand U.S. $
% of ISBL
5 % for OSBL
COST OF PRODUCTION
10 Percent
MILLION U.S. $
64.3
33.1
97.4
24.3
121.7
35.4
157.2
U.S. $
Per Gal
ANNUAL
COST MM
U.S. $
U.S. $
Per MT
1.518
0.204
0.015
1.737
(0.020)
(0.191)
(0.212)
1.525
0.002
0.000
0.081
(0.027)
0.056
1.582
252.01
33.81
2.56
288.38
(3.40)
(31.75)
(35.15)
253.24
0.41
0.02
13.37
(4.44)
9.36
262.60
(467)
506
1.582
262.60
525
0.008
0.002
0.000
0.012
0.004
0.026
0.016
0.006
0.003
0.024
1.632
1.34
0.25
0.06
1.93
0.74
4.33
2.60
0.97
0.49
4.06
270.98
8
542
0.063
10.52
21
1.696
281.50
563
0.095
15.72
31
1.790
297.22
594
577
19
525
Q207_00101.0007.4106_COP-tables.xls
Benzene/Toluene
PERP 06/07-6
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86
Section 4
Economic Analysis
Table 4.5
Process: CyclarTM
Plant start-up
Analysis date
Location
Capacity
4Q2006
USGC
166
500
100
166
Operating rate
Throughput
CAPITAL COST
ISBL
OSBL
Total Plant Capital
Other Project Costs
Working capital
Million gallons/yr
percent
Million gallons/yr
UNITS
Per Gal
Product

RAW MATERIALS
Propane
gallons
Butane
gallons
TOTAL RAW MATERIALS
BY-PRODUCT CREDITS
Fuel Gas
MM Btu
NET RAW MATERIALS
UTILITIES
Power
kwh
Cooling Water
M Gal
Natural Gas
MM Btu
Steam, HP
M Lbs
Steam, LP
M Lbs
Boiler Feedwater
M Gal
TOTAL UTILITIES
PRICE
U.S. $
/Unit
1.4280
1.2636
1.0000
0.9496
1.1204
0.0064
(0.0669)
(0.1133)
6.4359
3.3833
0.5570
0.0172
0.0283
0.0061
0.0000
0.0000
0.0589
0.1080
6.4359
11.6220
10.1488
1.9560
VARIABLE COST
DIRECT FIXED COSTS
Labor,
30 Men
44.68
Foremen,
5 Men
50.72
Super.,
1 Men
61.20
3
Direct Overhead
45
60
1
Environmental
0.5
TOTAL CASH COST
Depreciation @
10 % for ISBL & OPC
Thousand U.S. $
Thousand U.S. $
Thousand U.S. $
% of ISBL
5 % for OSBL
COST OF PRODUCTION
10 Percent
MILLION U.S. $
158.3
79.1
237.4
59.3
296.7
56.9
353.7
U.S. $
Per Gal
ANNUAL
COST MM
U.S. $
U.S. $
Per MT
1.356
1.416
0.006
2.778
(0.431)
(0.383)
(0.814)
1.964
0.033
0.002
0.182
0.070
0.000
0.000
0.287
2.252
225.11
235.03
1.05
461.20
(71.50)
(63.62)
(135.12)
326.08
5.45
0.31
30.24
11.70
0.00
0.00
47.70
373.78
2.252
373.78
748
0.008
0.002
0.000
0.029
0.004
0.043
0.026
0.014
0.007
0.047
2.342
1.34
0.25
0.06
4.75
0.74
7.15
4.29
2.37
1.19
7.85
388.78
14
16
778
0.155
25.72
51
2.497
414.50
829
0.213
35.37
71
2.710
449.86
900
922
(1,794)
652
95
748
Q207_00101.0007.4106_COP-tables.xls
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
87
Section 4
Economic Analysis
Table 4.6
Process: Aromax
Plant start-up
Analysis date
Location
Capacity
4Q2006
USGC
166
500
100
166
Operating rate
Throughput
CAPITAL COST
ISBL
OSBL
Total Plant Capital
Other Project Costs
Working capital
Million gallons/yr
percent
Million gallons/yr
UNITS
Per Gal
Product

RAW MATERIALS
lt. naphtha
gallons
TOTAL RAW MATERIALS
BY-PRODUCT CREDITS
Fuel Gas
MM Btu
C5
gallons
NET RAW MATERIALS
UTILITIES
Power
kwh
Cooling Water
M Gal
Natural Gas
MM Btu
Steam, HP
M Lbs
Steam, LP
M Lbs
Boiler Feedwater
M Gal
TOTAL UTILITIES
PRICE
U.S. $
/Unit
1.3230
1.0000
1.3233
0.0064
(0.0143)
(0.1035)
(0.0100)
6.4359
3.3833
1.3233
0.7205
0.0874
0.0022
0.0058
0.0029
0.0000
0.0589
0.1080
6.4359
11.6220
10.1488
1.9560
VARIABLE COST
DIRECT FIXED COSTS
Labor,
30 Men
44.68
Foremen,
5 Men
50.72
Super.,
1 Men
61.20
3
Direct Overhead
45
60
1
Environmental
0.5
TOTAL CASH COST
Depreciation @
10 % for ISBL & OPC
Thousand U.S. $
Thousand U.S. $
Thousand U.S. $
% of ISBL
5 % for OSBL
COST OF PRODUCTION
10 Percent
MILLION U.S. $
72.6
36.3
109.0
27.2
136.2
39.7
175.9
U.S. $
Per Gal
ANNUAL
COST MM
U.S. $
U.S. $
Per MT
1.751
0.006
1.757
(0.092)
(0.350)
(0.013)
(0.455)
1.302
0.042
0.009
0.014
0.068
0.030
0.000
0.163
1.465
290.63
1.05
291.69
(15.28)
(58.13)
(2.20)
(75.62)
216.07
7.05
1.57
2.32
11.27
4.92
0.00
27.12
243.19
1.465
243.19
486
0.008
0.002
0.000
0.013
0.004
0.028
0.017
0.007
0.003
0.026
1.519
1.34
0.25
0.06
2.18
0.74
4.58
2.75
1.09
0.54
4.38
252.15
9
504
0.071
11.80
24
1.590
263.96
528
0.106
17.59
35
1.696
281.55
563
583
(1,004)
432
54
486
Q207_00101.0007.4106_COP-tables.xls
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
88
Section 4
4.2.2.5
Economic Analysis
Alpha Process
The cost of production estimate for producing reformate via S&Ws alpha process is shown in
Table 4.7 for a 500 kta unit. Net raw materials are estimated to be $180 per gallon ($596 per
metric ton). Utility costs add 10.2 cents per gallon ($34 per metric ton) bringing the variable
cost to $190 per gallon ($630 per metric ton). After adding in the fixed costs, the total cash cost
is estimated to be $1.96 per gallon ($650 per metric ton). Depreciation of 10 percent of ISBL, 5
percent of OSBL, and other project costs adds another 8.3 cents per gallon ($27 per metric ton)
to the cost of production. Return on total capital employed of 10 percent adds 12.2 cents per
gallon ($41 per metric ton). The final cost of production including return on investment is
estimated to be $2.16 per gallon ($718 per metric ton).
4.2.3
Cost of Production of Benzene
The costs of production of benzene from various sources employing different technologies are
summarized in Figure 4.2. The costs range from a low of $2.09 per gallon ($626 per metric ton)
for selective toluene disproportionation (STDP) to a high of $3.12 per gallon ($934 per metric
ton) for bulk dealkylation of pyrolysis gasoline.
Figure 4.2
Benzene Cost of Production
(334 kta, USGC)
3.50
3.00
Dollars Per Gallon
2.50
2.00
1.50
1.00
0.50
0.00
SE (1)
SE (2)
Reformate Pygas
(1)
(2)
ED (2)
Pygas
Dealky
Pygas
Litol
THDA
TDP
STDP
NET RAW MATERIALS
UTILITIES
DIRECT FIXED COSTS
DEPRECIATION
ROCE
Solvent Extraction
Extractive Distillation
Q207_00101.0007.4106_char t s.xls
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
89
Section 4
Economic Analysis
Table 4.7
Process: Alpha
Plant start-up
Analysis date
Location
Capacity
4Q2006
USGC
166
500
100
166
Operating rate
Throughput
CAPITAL COST
ISBL
OSBL
Total Plant Capital
Other Project Costs
Working capital
Million gallons/yr
percent
Million gallons/yr
UNITS
Per Gal
Product

RAW MATERIALS
C5-C6
gallons
TOTAL RAW MATERIALS
BY-PRODUCT CREDITS
Fuel Gas
MM Btu
LPG
gallons
NET RAW MATERIALS
UTILITIES
Power
kwh
Cooling Water
M Gal
Natural Gas
MM Btu
Steam, MP
M Lbs
Inert Gas
kSCF
Refrigeration
MM Btu
TOTAL UTILITIES
PRICE
U.S. $
/Unit
1.9997
1.0000
1.3233
0.0064
(0.0257)
(0.5498)
(0.0397)
6.4359
1.0134
3.3833
0.2431
0.1374
0.0031
0.0025
0.0001
0.0022
0.0589
0.1080
6.4359
10.3095
1.7055
12.0000
VARIABLE COST
DIRECT FIXED COSTS
Labor,
30 Men
44.68
Foremen,
5 Men
50.72
Super.,
1 Men
61.20
3
Direct Overhead
45
60
1
Environmental
0.5
TOTAL CASH COST
Depreciation @
10 % for ISBL & OPC
Thousand U.S. $
Thousand U.S. $
Thousand U.S. $
% of ISBL
5 % for OSBL
COST OF PRODUCTION
10 Percent
MILLION U.S. $
95.9
23.0
118.9
29.7
148.6
54.1
202.8
U.S. $
Per Gal
ANNUAL
COST MM
U.S. $
U.S. $
Per MT
2.646
0.006
2.653
(0.166)
(0.557)
(0.134)
(0.857)
1.796
0.014
0.015
0.020
0.026
0.000
0.027
0.102
1.898
439.29
1.05
440.34
(27.48)
(92.49)
(22.28)
(142.25)
298.09
2.38
2.46
3.33
4.33
0.03
4.40
16.93
315.02
1.898
315.02
630
0.008
0.002
0.000
0.017
0.004
0.032
0.019
0.007
0.004
0.030
1.959
1.34
0.25
0.06
2.88
0.74
5.28
3.17
1.19
0.59
4.95
325.25
11
10
650
0.083
13.71
27
2.042
338.96
678
0.122
20.28
41
2.164
359.24
718
881
(1,889)
596
34
630
Q207_00101.0007.4106_COP-tables.xls
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
90
Section 4
4.2.3.1
Economic Analysis
Benzene from Reformate Extraction (Sulfolane) including BTX Distillation
The cost of production estimate for producing benzene via extraction from a conventional
reformate (i.e., employing the Sulfolane process) is shown in Table 4.8 for a 334 kta (100 million
gallon per year) unit. Toluene and mixed xylenes are taken as byproducts and priced at their
mogas blending value. Net raw materials are estimated to be $1.93 per gallon ($579 per metric
ton). Utility costs add 40.3 cents per gallon ($121 per metric ton) bringing the variable cost to
$2.34 per gallon ($699 per metric ton). After adding in the fixed costs, the total cash cost is
estimated to be $2.44 per gallon ($730 per metric ton). Depreciation of 10 percent of ISBL, 5
4.2.3.2
Benzene Recovery from Pygas
The cost of production for benzene recovered from a typical pygas has been analyzed in various
ways. These technologies included liquid/liquid (solvent) extraction (LLE), extractive
distillation (ED), and bulk dealkylation of pygas. For comparison purposes the same size plant
was used for each of the three technologies: 334 kta (100 million gallon per year).
Solvent Extraction (LLE) of Pygas
The cost of production estimate for producing benzene via solvent extraction (LLE) of pygas is
shown in Table 4.9. Net raw materials are estimated to be $1.53 per gallon ($457 per metric
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
91
Section 4
Economic Analysis
Table 4.8
Cost of Production Estimate for: Benzene
Process: Reformate Extraction (Sulfolane) plus BTX Distillation
Plant start-up
Analysis date
Location
Capacity
4Q2006
USGC
100
334
100
100
Operating rate
Throughput
CAPITAL COST
ISBL
OSBL
Total Plant Capital
Other Project Costs
Working capital
Million gallons/yr
percent
Million gallons/yr
UNITS
Per Gal
Product

RAW MATERIALS
Reformate
gallon
TOTAL RAW MATERIALS
BY-PRODUCT CREDITS
C5-C6
gallon
gallon
Toluene - mogas value
gallon
Mixed xylenes -mogas value gallon
C9 Aromatics
gallon
NET RAW MATERIALS
UTILITIES
Power
kwh
Cooling Water
M Gal
Steam, MP
M Lb
Fuel
MM Btu
TOTAL UTILITIES
PRICE
U.S. $
/Unit
9.8968
1.0000
1.8603
0.0029
(0.9200)
(1.4987)
(2.7245)
(2.6014)
(0.9002)
1.3233
1.3233
2.0866
2.1509
2.2233
0.4173
0.2757
0.0050
0.0462
0.0589
0.1080
10.3095
6.4359
VARIABLE COST
DIRECT FIXED COSTS
Labor,
10 Men
44.68
Foremen,
5 Men
50.72
Super.,
1 Men
61.20
3
Direct Overhead
45
60
1
Environmental
0.5
TOTAL CASH COST
Depreciation @
10 % for ISBL & OPC
Thousand U.S. $
Thousand U.S. $
Thousand U.S. $
% of ISBL
5 % for OSBL
COST OF PRODUCTION
10 Percent
MILLION U.S. $
122.2
42.9
165.1
41.3
206.3
175.3
381.6
U.S. $
Per Gal
18.411
0.003
18.414
(1.217)
(1.983)
(5.685)
(5.595)
(2.002)
(16.482)
1.932
0.025
0.030
0.052
0.297
0.403
2.335
ANNUAL
COST MM
U.S. $
1,840.86
0.29
1,841.15
(121.72)
(198.30)
(568.42)
(559.44)
(200.12)
(1,648.02)
193.13
2.46
2.98
5.15
29.74
40.33
233.47
U.S. $
Per MT
5,516
(36,337)
579
121
699
2.335
233.47
699
0.004
0.003
0.001
0.037
0.003
0.048
0.029
0.017
0.008
0.053
2.436
0.45
0.25
0.06
3.67
0.34
4.77
2.86
1.65
0.83
5.34
243.57
14
16
730
0.185
18.49
55
2.621
262.06
785
0.382
38.16
114
3.003
300.23
899
Q207_00101.0007.4106_COP-tables.xls
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
92
Section 4
Economic Analysis
Table 4.9
Process: Solvent Extraction of Pygas
Plant start-up
Analysis date
Location
Capacity
4Q2006
USGC
100
334
100
100
Operating rate
Throughput
CAPITAL COST
ISBL
OSBL
Total Plant Capital
Other Project Costs
Working capital
Million gallons/yr
percent
Million gallons/yr
UNITS
Per Gal
Product

RAW MATERIALS
Pygas
gallon
TOTAL RAW MATERIALS
BY-PRODUCT CREDITS
gallon
C5-C6
gallon
C9 Aromatics
gallon
Toluene - contract
gallon
Mixed xylenes
gallon
Benzene drag
MM Btu
NET RAW MATERIALS
UTILITIES
Power
kwh
Cooling Water
M Gal
Steam, MP
M Lb
TOTAL UTILITIES
PRICE
U.S. $
/Unit
3.2005
0.0236
1.0000
1.8104
3.3833
0.0096
(0.2105)
(0.9281)
(0.1699)
(0.5706)
(0.3968)
(0.0032)
1.3233
1.3233
2.2233
2.5109
2.5701
6.4359
0.2203
0.1034
0.0231
0.0589
0.1080
10.3095
VARIABLE COST
DIRECT FIXED COSTS
Labor,
10 Men
44.68
Foremen,
5 Men
50.72
Super.,
1 Men
61.20
3
Direct Overhead
45
60
1
Environmental
0.5
TOTAL CASH COST
Depreciation @
10 % for ISBL & OPC
Thousand U.S. $
Thousand U.S. $
Thousand U.S. $
% of ISBL
5 % for OSBL
COST OF PRODUCTION
10 Percent
MILLION U.S. $
59.8
31.3
91.1
22.8
113.8
61.5
175.3
U.S. $
Per Gal
ANNUAL
COST MM
U.S. $
U.S. $
Per MT
5.794
0.080
0.010
5.884
(0.279)
(1.228)
(0.378)
(1.433)
(1.020)
(0.021)
(4.358)
1.526
0.013
0.011
0.238
0.262
1.788
579.35
7.97
0.96
588.28
(27.85)
(122.80)
(37.77)
(143.25)
(101.97)
(2.06)
(435.70)
152.58
1.30
1.12
23.82
26.24
178.82
1.788
178.82
536
0.004
0.003
0.001
0.018
0.003
0.029
0.017
0.009
0.005
0.031
1.848
0.45
0.25
0.06
1.79
0.34
2.90
1.74
0.91
0.46
3.10
184.82
1,762
(9,607)
457
79
536
9
554
0.098
9.82
29
1.947
194.64
583
0.175
17.53
53
2.122
212.17
636
Q207_00101.0007.4106_COP-tables.xls
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
93
Section 4
Economic Analysis
Extractive Distillation (ED) of Pygas

The cost of production estimate for producing benzene via extraction distillation of pygas is
shown in Table 4.10. Net raw materials are estimated to be $2.52 per gallon ($755 per metric
Bulk Dealkylation of Pygas
The cost of production estimate for producing benzene via bulk dealkylation of pygas is shown
in Table 4.11. Net raw materials are estimated to be $2.57 per gallon ($771 per metric ton).
Utility costs add 18.2 cents per gallon ($55 per metric ton) bringing the variable cost to $2.75 per
gallon ($825 per metric ton). After adding in the fixed costs, the total cash cost is estimated to
be $2.82 per gallon ($845 per metric ton). Depreciation of 10 percent of ISBL, 5 percent of
OSBL, and other project costs adds another 11.4 cents per gallon ($34 per metric ton) to the cost
of production. Return on total capital employed of 10 percent adds 18.0 cents per gallon ($54
per metric ton). The final cost of production including return on investment is estimated to be
$3.12 per gallon ($934 per metric ton).
4.2.3.3
Benzene via the Litol Process
The cost of production estimate for producing benzene from coke oven light oil via the Litol
process is shown in Table 4.12 for a 334 kta (100 million gallon per year) unit. Net raw
materials are estimated to be $1.80 per gallon ($536 per metric ton). Utility costs add 13.4 cents
per gallon ($40 per metric ton) bringing the variable cost to $1.92 per gallon ($576 per metric
ton). After adding in the fixed costs, the total cash cost is estimated to be $2.03 per gallon ($608
per metric ton). Depreciation of 10 percent of ISBL, 5 percent of OSBL, and other project costs
adds another 16.3 cents per gallon ($49 per metric ton) to the cost of production. Return on total
metric ton).
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
94
Section 4
Economic Analysis
Table 4.10
Process: Extractive Distillation of Pygas
Plant start-up
Analysis date
Location
Capacity
4Q2006
USGC
100
334
100
100
Operating rate
Throughput
CAPITAL COST
ISBL
OSBL
Total Plant Capital
Other Project Costs
Working capital
Million gallons/yr
percent
Million gallons/yr
UNITS
Per Gal
Product

RAW MATERIALS
Pygas
gallon
TOTAL RAW MATERIALS
BY-PRODUCT CREDITS
gallon
C5-C6
gallon
C7/C9 cut, Lb
gallon
Benzene drag
MM Btu
NET RAW MATERIALS
UTILITIES
Power
kwh
Cooling Water
M Gal
Steam, MP
M Lb
TOTAL UTILITIES
PRICE
U.S. $
/Unit
3.2005
0.0236
1.0000
1.8104
3.3833
0.0284
(0.2105)
(0.9281)
(1.1373)
(0.0032)
1.3233
1.3233
1.6294
6.4359
0.1829
0.0322
0.0103
0.0589
0.1080
10.3095
VARIABLE COST
DIRECT FIXED COSTS
Labor,
10 Men
44.68
Foremen,
5 Men
50.72
Super.,
1 Men
61.20
3
Direct Overhead
45
60
1
Environmental
0.5
TOTAL CASH COST
Depreciation @
10 % for ISBL & OPC
Thousand U.S. $
Thousand U.S. $
Thousand U.S. $
% of ISBL
5 % for OSBL
COST OF PRODUCTION
10 Percent
MILLION U.S. $
79.7
27.9
107.6
26.9
134.5
63.2
197.7
U.S. $
Per Gal
ANNUAL
COST MM
U.S. $
U.S. $
Per MT
5.794
0.080
0.028
5.902
(0.279)
(1.228)
(1.853)
(0.021)
(3.380)
2.522
0.011
0.003
0.106
0.120
2.642
579.35
7.97
2.84
590.16
(27.85)
(122.80)
(185.29)
(2.06)
(337.99)
252.16
1.08
0.35
10.62
12.05
264.21
2.642
264.21
792
0.004
0.003
0.001
0.024
0.003
0.035
0.021
0.011
0.005
0.037
2.715
0.45
0.25
0.06
2.39
0.34
3.50
2.10
1.08
0.54
3.71
271.42
10
11
813
0.121
12.06
36
2.835
283.47
849
0.198
19.77
59
3.033
303.24
908
1,768
(7,452)
755
36
792
Q207_00101.0007.4106_COP-tables.xls
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
95
Section 4
Economic Analysis
Table 4.11
Process: Bulk Dealkylation of Pygas
Plant start-up
Analysis date
Location
Capacity
4Q2006
USGC
100
334
100
100
Operating rate
Throughput
CAPITAL COST
ISBL
OSBL
Total Plant Capital
Other Project Costs
Working capital
Million gallons/yr
percent
Million gallons/yr
UNITS
Per Gal
Product

RAW MATERIALS
Pyrolysis Gasoline
Gallon
TOTAL RAW MATERIALS
BY-PRODUCT CREDITS
Fuel Gas
MM Btu
C5-C6
Gallon
C9 Aromatics
Gallon
NET RAW MATERIALS
UTILITIES
Power
kwh
Cooling Water
M Gal
Steam, HP
M Lb
Fuel
MM Btu
TOTAL UTILITIES
PRICE
U.S. $
/Unit
2.2931
0.0456
1.0000
1.8104
3.3833
0.0550
(0.0787)
(0.3945)
(0.3418)
6.4359
1.3233
2.2233
0.4005
0.0442
0.0007
0.0226
0.0589
0.1080
11.6220
6.4359
VARIABLE COST
DIRECT FIXED COSTS
Labor,
10 Men
44.68
Foremen,
5 Men
50.72
Super.,
1 Men
61.20
3
Direct Overhead
45
60
1
Environmental
0.5
TOTAL CASH COST
Depreciation @
10 % for ISBL & OPC
Thousand U.S. $
Thousand U.S. $
Thousand U.S. $
% of ISBL
5 % for OSBL
COST OF PRODUCTION
10 Percent
MILLION U.S. $
71.6
32.3
103.9
26.0
129.9
50.3
180.1
U.S. $
Per Gal
ANNUAL
COST MM
U.S. $
U.S. $
Per MT
4.152
0.154
0.055
4.361
(0.506)
(0.522)
(0.760)
(1.788)
2.573
0.024
0.005
0.009
0.145
0.182
2.755
415.10
15.44
5.50
436.03
(50.63)
(52.19)
(75.98)
(178.80)
257.23
2.36
0.48
0.86
14.54
18.23
275.46
2.755
275.46
825
0.004
0.003
0.001
0.021
0.003
0.033
0.020
0.010
0.005
0.035
2.823
0.45
0.25
0.06
2.15
0.34
3.25
1.95
1.04
0.52
3.51
282.23
10
11
845
0.114
11.37
34
2.936
293.60
880
0.180
18.01
54
3.117
311.61
934
1,306
(3,942)
771
55
825
Q207_00101.0007.4106_COP-tables.xls
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
96
Section 4
Economic Analysis
Table 4.12
Process: Litol Process (from coke oven light oil)
Plant start-up
Analysis date
Location
Capacity
4Q2006
USGC
50
167
100
50
Operating rate
Throughput
CAPITAL COST
ISBL
OSBL
Total Plant Capital
Other Project Costs
Working capital
Million gallons/yr
percent
Million gallons/yr
UNITS
Per Gal
Product

RAW MATERIALS
Coke oven light oil

pound
TOTAL RAW MATERIALS
BY-PRODUCT CREDITS
Fuel
MM Btu
Light/heavy ends (fuel value) MM Btu
NET RAW MATERIALS
UTILITIES
Power
kwh
Cooling Water
M Gal
Steam, HP
M Lb
Fuel
MM Btu
TOTAL UTILITIES
PRICE
U.S. $
/Unit
1.0900
0.0471
1.0000
1.6944
3.3833
0.0550
(0.0204)
(0.0219)
6.4359
6.4359
0.2737
0.0589
0.0539
0.1080
(0.0016) 11.6220
0.0204
6.4359
VARIABLE COST
DIRECT FIXED COSTS
Labor,
10 Men
44.68
Foremen,
5 Men
50.72
Super.,
1 Men
61.20
3
Direct Overhead
45
60
1
Environmental
0.5
TOTAL CASH COST
Depreciation @
10 % for ISBL & OPC
Thousand U.S. $
Thousand U.S. $
Thousand U.S. $
% of ISBL
5 % for OSBL
COST OF PRODUCTION
10 Percent
MILLION U.S. $
51.4
23.2
74.6
18.6
93.2
15.9
109.1
U.S. $
Per Gal
ANNUAL
COST MM
U.S. $
U.S. $
Per MT
1.847
0.159
0.055
2.061
(0.131)
(0.141)
(0.272)
1.789
0.016
0.006
(0.019)
0.131
0.134
1.923
92.34
7.96
2.75
103.05
(6.55)
(7.05)
(13.60)
89.45
0.81
0.29
(0.94)
6.56
6.72
96.17
(600)
536
1.923
96.17
576
0.009
0.005
0.001
0.031
0.007
0.053
0.032
0.015
0.007
0.054
2.030
0.45
0.25
0.06
1.54
0.34
2.65
1.59
0.75
0.37
2.71
101.52
16
16
608
0.163
8.17
49
2.194
109.69
657
0.218
10.91
65
2.412
120.60
723
617
40
576
Q207_00101.0007.4106_COP-tables.xls
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
97
Section 4
4.2.3.4
Economic Analysis
Benzene via Toluene Hydrodealkylation (THDA)
The cost of production estimate for producing benzene via toluene hydrodealkylation (THDA) is
shown in Table 4.13 for a 334 kta (100 million gallon per year) unit. Net raw materials are
production including return on investment is estimated to be $2.77 per gallon ($831 per metric
ton).
4.2.3.5
Benzene via Toluene Disproportionation (TDP)
The cost of production estimate for producing benzene via conventional toluene
disproportionation (TDP) is shown in Table 4.14 for a 334 kta (100 million gallon per year) unit.
Mixed xylenes are considered a byproduct for this analysis. Net raw materials are estimated to
be $2.06 per gallon ($618 per metric ton). Utility costs add 43.9 cents per gallon ($131 per
metric ton) bringing the variable cost to $2.50 per gallon ($750 per metric ton). After adding in
the fixed costs, the total cash cost is estimated to be $2.56 per gallon ($768 per metric ton).
Depreciation of 10 percent of ISBL, 5 percent of OSBL, and other project costs adds another 9.6
cents per gallon ($29 per metric ton) to the cost of production. Return on total capital employed
of 10 percent adds 16.6 cents per gallon ($50 per metric ton). The final cost of production
including return on investment is estimated to be $2.83 per gallon ($846 per metric ton).
The cost of production estimate for producing benzene via selective toluene disproportionation
(TDP) is shown in Table 4.15 for a 334 kta (100 million gallon per year) unit. para-Xylenes are
considered a byproduct for this analysis and valued at their market price. Net raw materials are
production including return on investment is estimated to be $2.09 per gallon ($626 per metric
ton).
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
98
Section 4
Economic Analysis
Table 4.13
Process: Toluene Hydrodealkylation (THDA)
Plant start-up
Analysis date
Location
Capacity
4Q2006
USGC
100
334
100
100
Operating rate
Throughput
CAPITAL COST
ISBL
OSBL
Total Plant Capital
Other Project Costs
Working capital
Million gallons/yr
percent
Million gallons/yr
UNITS
Per Gal
Product

RAW MATERIALS

Gallons
TOTAL RAW MATERIALS
BY-PRODUCT CREDITS
Fuel Gas
pound
NET RAW MATERIALS
UTILITIES
Power
kwh
Cooling Water
M Gal
Steam, HP
M Lb
Steam, MP
M Lb
Boiler Feedwater
M Gal
Fuel
MM Btu
TOTAL UTILITIES
PRICE
U.S. $
/Unit
1.2200
0.0442
1.0000
2.0866
3.3833
0.0020
(0.0425)
6.4359
0.3076
0.0589
0.0100
0.1080
(0.0007) 11.6220
0.0024 10.3095
0.0002
1.9560
0.0074
6.4359
VARIABLE COST
DIRECT FIXED COSTS
Labor,
10 Men
44.68
Foremen,
5 Men
50.72
Super.,
1 Men
61.20
3
Direct Overhead
45
60
1
Environmental
0.5
TOTAL CASH COST
Depreciation @
10 % for ISBL & OPC
Thousand U.S. $
Thousand U.S. $
Thousand U.S. $
% of ISBL
5 % for OSBL
COST OF PRODUCTION
10 Percent
MILLION U.S. $
51.0
26.1
77.1
19.3
96.4
31.8
128.1
U.S. $
Per Gal
ANNUAL
COST MM
U.S. $
U.S. $
Per MT
2.546
0.149
0.002
2.697
(0.273)
(0.273)
2.424
0.018
0.001
(0.009)
0.025
0.000
0.048
0.084
2.508
254.53
14.94
0.20
269.66
(27.33)
(27.33)
242.34
1.81
0.11
(0.86)
2.50
0.04
4.78
8.40
250.73
2.508
250.73
751
0.004
0.003
0.001
0.015
0.003
0.026
0.016
0.008
0.004
0.027
2.561
0.45
0.25
0.06
1.53
0.34
2.63
1.58
0.77
0.39
2.74
256.11
8
767
0.083
8.33
25
2.645
264.44
792
0.128
12.81
38
2.773
277.25
831
808
(603)
726
25
751
Q207_00101.0007.4106_COP-tables.xls
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
99
Section 4
Economic Analysis
Table 4.14
Process: Toluene Disproportionation (TDP)
Plant start-up
Analysis date
Location
Capacity
4Q2006
USGC
100
334
100
100
Operating rate
Throughput
CAPITAL COST
ISBL
OSBL
Total Plant Capital
Other Project Costs
Working capital
Million pounds/yr
percent
Million pounds/yr
UNITS
Per Gal
Product

RAW MATERIALS

Gallons
Hydrogen - pure
Pounds
TOTAL RAW MATERIALS
BY-PRODUCT CREDITS
Fuel Gas, MM Btu
MM Btu
C9 Aromatics, Gal
Gallons
Mixed xylenes, Gal
Gallons
NET RAW MATERIALS
UTILITIES
Power
kwh
Cooling Water
M Gal
Steam, HP
M Lb
Steam, MP
M Lb
Fuel
MM Btu
TOTAL UTILITIES
PRICE
U.S. $
/Unit
2.3856
0.0650
1.0000
2.0866
2.9061
0.0193
(0.0301)
(0.2278)
(0.9435)
6.4359
2.2081
2.5701
0.6839
0.1026
0.0000
0.0205
0.0274
0.0589
0.1080
11.6220
10.3095
6.4359
VARIABLE COST
DIRECT FIXED COSTS
Labor,
10 Men
44.68
Foremen,
5 Men
50.72
Super.,
1 Men
61.20
3
Direct Overhead
45
60
1
Environmental
0.5
TOTAL CASH COST
Depreciation @
10 % for ISBL & OPC
Thousand U.S. $
Thousand U.S. $
Thousand U.S. $
% of ISBL
5 % for OSBL
COST OF PRODUCTION
10 Percent
MILLION U.S. $
62.0
24.8
86.8
21.7
108.4
57.6
166.1
U.S. $
Per Gal
ANNUAL
COST MM
U.S. $
U.S. $
Per MT
4.978
0.189
0.019
5.186
(0.194)
(0.503)
(2.425)
(3.122)
2.064
0.040
0.011
0.000
0.212
0.176
0.439
2.503
497.71
18.88
1.93
518.51
(19.37)
(50.29)
(242.46)
(312.12)
206.39
4.03
1.11
0.00
21.15
17.60
43.89
250.28
2.503
250.28
750
0.004
0.003
0.001
0.019
0.003
0.030
0.018
0.009
0.004
0.031
2.564
0.45
0.25
0.06
1.86
0.34
2.96
1.78
0.87
0.43
3.08
256.32
9
768
0.096
9.60
29
2.660
265.92
797
0.166
16.61
50
2.826
282.53
846
1,553
(6,882)
618
131
750
Q207_00101.0007.4106_COP-tables.xls
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
100
Section 4
Economic Analysis
Table 4.15
Process: Selective Toluene Disproportionation (STDP)
Plant start-up
Analysis date
Location
Capacity
4Q2006
USGC
100
334
100
100
Operating rate
Throughput
CAPITAL COST
ISBL
OSBL
Total Plant Capital
Other Project Costs
Working capital
Million pounds/yr
percent
Million pounds/yr
UNITS
Per Gal
Product

RAW MATERIALS

Gallons
Hydrogen - pure
Pounds
TOTAL RAW MATERIALS
BY-PRODUCT CREDITS
Fuel Gas, MM Btu
MM Btu
C9 Aromatics, Gal
Gallons
Mixed xylenes, Gal
Gallons
para-xylene
Pounds
NET RAW MATERIALS
UTILITIES
Power
kwh
Cooling Water
M Gal
Steam, LP
M Lb
Steam, MP
M Lb
Fuel
MM Btu
TOTAL UTILITIES
PRICE
U.S. $
/Unit
2.3219
0.0903
1.0000
2.0866
2.9061
0.0029
(0.0253)
(0.0454)
(0.0375)
(6.0204)
6.4359
2.2081
2.5701
0.5350
0.3709
0.0205
0.0001
0.0065
0.0144
0.0589
0.1080
10.1488
10.3095
6.4359
VARIABLE COST
DIRECT FIXED COSTS
Labor,
10 Men
44.68
Foremen,
5 Men
50.72
Super.,
1 Men
61.20
3
Direct Overhead
45
60
1
Environmental
0.5
TOTAL CASH COST
Depreciation @
10 % for ISBL & OPC
Thousand U.S. $
Thousand U.S. $
Thousand U.S. $
% of ISBL
5 % for OSBL
COST OF PRODUCTION
10 Percent
MILLION U.S. $
60.2
54.4
114.6
28.6
143.2
52.2
195.5
U.S. $
Per Gal
ANNUAL
COST MM
U.S. $
U.S. $
Per MT
4.845
0.262
0.003
5.110
(0.163)
(0.100)
(0.096)
(3.221)
(3.580)
1.530
0.022
0.002
0.001
0.067
0.093
0.185
1.715
484.43
26.24
0.29
510.96
(16.27)
(10.01)
(9.64)
(322.05)
(357.98)
152.98
2.19
0.22
0.07
6.70
9.30
18.47
171.45
1.715
171.45
514
0.004
0.003
0.001
0.018
0.003
0.029
0.017
0.011
0.006
0.035
1.779
0.45
0.25
0.06
1.81
0.34
2.91
1.75
1.15
0.57
3.47
177.83
10
533
0.116
11.60
35
1.895
189.43
568
0.195
19.55
59
2.090
208.98
626
1,531
(7,893)
458
55
514
Q207_00101.0007.4106_COP-tables.xls
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
101
Section 4
4.2.4
4.2.4.1
Economic Analysis
Sensitivity
Five-Year Average Pricing
It is important to note that the economics presented herein are in essence a snapshot in time.
In Figures 4.3 and 4.4 we have tried to mitigate this by using five-year historical averages for
feed and product prices. The results of this sensitivity are shown in Figure 4.3 for the reformate
cases and Figure 4.4 for the benzene cases. In each analysis the results show similar, but lower
costs of production when using the 5-year average.
Figure 4.3
Cost of Production of Reformate Sensitivity to Pricing
(500 kta, USGC)
3.00
Dollars Per Gallon
2.50
2.00
1.50
1.00
0.50
0.00
AROMAX
CCR
RZ
ALPHA
PLATFORMING
4Q2006 5 Yr Avg
CYCLAR
Q207_00101.0007.4106_char t s.xls
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
102
Section 4
Economic Analysis
Figure 4.4
Cost of Production of Benzene Sensitivity to Pricing
(334 kta, USGC)
3.50
Dollars Per Gallon
3.00
2.50
2.00
1.50
1.00
0.50
0.00
SE
SE Pygas ED Pygas
Reformate
Dealky
Pygas
4Q2006
Litol
THDA
TDP
STDP
5 Yr Avg
Q207_00101.0007.4106_chart s.xls
4.2.4.2
Feed Price
The sensitivity of the costs of production to feed price is shown in Figure 4.5 for the costs of
production of reformate and Figure 4.6 for the costs of production of benzene. Figure 4.5 shows
that the CyclarTM process is the most sensitive to feedstock pricing while RZ PlatformingTM and
CCRTM reforming are the least sensitive.
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
103
Section 4
Economic Analysis
Figure 4.5
Sensitivity of Cost of Production of Reformate to Feed Price
4.00
3.50
Dollars Per Gallon
3.00
2.50
2.00
1.50
1.00
0.50
0.00
60%
70%
80%
90%
100%
110%
120%
130%
140%
Percent of Base Case Feed Price

CCR
ALPHA
CYCLAR
RZ PLATFORMING
AROMAX
Q207_00101.0007.4106_chart s.xls
Figure 4.6 shows that producing benzene via recovery from reformate employing liquid/liquid
extraction (Sulfolane) is the most sensitive to feedstock pricing while the Litol process is the
least sensitive followed closely by THDA. As toluene prices increase THDA is more
economical than TDP. However, TDP economics are also a function of the credit derived from
the mixed xylene byproduct and is therefore, a function of mixed xylene pricing as well. This
sensitivity is shown in Figure 4.7. As the price of mixed xylenes is varied by plus or minus 30
percent the cost plus return of benzene via TDP varies by plus or minus 73 cents per gallon
($218 per metric ton).
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
104
Section 4
Economic Analysis
Figure 4.6
Sensitivity of Cost of Production of Benzene to Feed Price
9.00
8.00
7.00
Dolars Per Gallon
6.00
5.00
4.00
3.00
2.00
1.00
0.00
60%
70%
80%
90%
100%
110%
120%
130%
140%
Percent of Base Case Feed Price

SULFOLANE
LITOL
SE PYGAS
THDA
ED PYGAS
TDP
DEALKYL PYGAS
STDP
Q207_00101.0007.4106_chart s.xls
Figure 4.7
Sensitivity of Cost of Production via TDP to Mixed Xylenes Price
4.00
3.50
Dollars Per Gallon
3.00
2.50
2.00
1.50
1.00
0.50
0.00
60%
70%
80%
90%
100%
110%
120%
130%
140%
Percent of Base Case Mixed Xylenes Price

Q207_00101.0007.4106_chart s.xls
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
105
Section 4
4.3
Economic Analysis
CONCLUSIONS
Whether or not TDP or THDA units operate economically will not only depend on pricing
conditions (e.g., alternative value for toluene), but also on market position. Because THDA is
often the most expensive route for producing benzene, merchant THDA facilities tend to operate
only when the price of benzene exceeds the cost of production via THDA. Captive THDA units,
in contrast, usually serve to balance internal requirements for benzene and are run independently
of merchant market conditions. Historically the delta between the price of benzene and toluene
has been about 32 cents per gallon ($96 per metric ton) as shown in Figure 4.8. However, in the
past few years this delta has varied greatly. For the fourth quarter of 2004 it was almost $1.65
per gallon ($500 per metric ton), while for the second quarter of 2006 it was negative 8 cents per
gallon (-24 per metric ton). Currently (4th quarter 2006) this delta is about $1.10 per gallon
($332 per metric ton) while the cost of toluene hydrodealkylation is 23 cents per gallon ($68 per
metric ton).
Figure 4.8
Benzene to Toluene Price Delta
600
Delta Benzene - Toluene, $/T
500
400
300
200
100
0
-100
1982-Q1 1984-Q1 1986-Q1 1988-Q1 1990-Q1 1992-Q1 1994-Q1 1996-Q1 1998-Q1 2000-Q1 2002-Q1 2004-Q1 2006-Q1
Q207_00101.0007.4106_chart s.xls
In addition to the economics, a variety of other issues must also be considered when choosing
process technology. Some of these considerations are listed below:
Access to feedstock
Outlet for byproducts
Investment requirements
Revamp and integration potential or strategy
Feedstock/product price fluctuations/forecasts
Technology availability/licensing terms

Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
106
Section 4
Economic Analysis
Technology risk
Security of supply/strategic importance
Table 4.16 summarizes Nexants view with respect to some of the strategic issues. In the final
analysis, the selection of any of these aromatic technologies will have to be based on a careful
case by case assessment.
Table 4.16
Reformate Process Selection Matrix
CCR
Naphtha
Low
Rz
PlatformingTM
Naphtha
Low
CyclarTM
LPG
Moderate
Aromax
Naphtha
High
Alpha
C5/C6
Moderate
Investment
requirement
Low
Low
High
Low
Moderate
Technology
availability
Yes
Yes
Yes
Yes
Yes
Numerous
Numerous
One
Several
One
TM
Feedstock
sensitivity to
feed price
Commercially
proven units
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
107
Section 5
5.1
APPLICATIONS
5.1.1
Benzene
5.1.1.1
Market Analysis
Introduction
One of the major uses of benzene is as a gasoline component. It is contained within streams that
contribute to the gasoline pool, primarily catalytic reformate. For non-fuel benzene applications,
it is extracted or otherwise produced as described in Section 2. This market analysis is
concerned only with the non-fuel uses of benzene.
Benzene has many uses, and demand continues to grow despite increasing restrictions and
environmental regulations. Creation of styrene monomer is the largest use of benzene, followed
by cumene/phenol, cyclohexane, and nitrobenzene. Those derivatives are used to produce a wide
range of plastics, fibers, resins and films. Benzene is also an excellent solvent for waxes, resins,
rubber and various other organic materials, but toxicological properties greatly limit use.
5.1.1.2
Ethylbenzene/Styrene
Over half of the world's benzene production is used in ethylbenzene (EB) and styrene monomer
(SM) production. The dominant route involves the alkylation of benzene with ethylene,
followed by direct dehydrogenation to styrene. This route has been operated commercially since
the 1930s, although it has undergone considerable improvement and modifications since then.
The alkylation can be effected in either the liquid phase or the vapor phase. The ethylbenzene is
dehydrogenated to styrene and hydrogen over a catalyst in the presence of steam. Both benzene
and toluene are formed as byproducts; this is one of the minor sources of toluene.
Styrene is also produced from ethylbenzene by indirect dehydrogenation, using the OXIRANE
process. In this process ethylbenzene is converted to a hydroperoxide by direct air oxidation,
and the hydroperoxide is converted to an alcohol in an epoxidation reaction with propylene.
Finally, the alcohol is dehydrated to styrene. Propylene oxide is a coproduct of this process.
Some ethylbenzene is also removed from the C8 fraction of BTX aromatics, but this is a small
quantity in comparison to synthesis from benzene.
About two thirds of the styrene in the United States, Western Europe, and Japan is used to
produce polystyrene. The polymer is produced in a number of forms. The pure homopolymer
(crystal grade) is transparent and has a high refractive index that gives it a sparkling appearance.
Polystyrene can be made less brittle by incorporating 5 to 10 percent of rubbery polymers into
the material during polymerization. This results in high impact polystyrene (HIPS), which
accounts for about two thirds of polystyrene production. Foamed polystyrene is produced by
blending crystal polystyrene with a low boiling point hydrocarbon. The blend is extruded and a
foam is produced as the solvent volatilizes. Expanded polystyrene (EPS) is different from the
foamed product, since it is made from beads impregnated with blowing agents and has very
different properties.
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Market Analysis
Polystyrene applications include the use of general purpose and high impact grades in moldings
and extruded sheet. Their good appearance and rigidity make them suitable for attractive
packaging and displays, housewares, appliances, furniture applications, toys, and miscellaneous
other applications. Foamed polystyrene is used in packaging, insulation, building, and furniture.
Expanded polystyrene is used mainly as insulation in construction and as packaging.
Styrene is also used to produce a number of other polymers including:
ABS - acrylonitrile butadiene styrene
SAN - styrene acrylonitrile
SB latex and SBR - styrene butadiene elastomers
Unsaturated polyester
All the polymer products compete on price and performance with other materials, but it is
anticipated that styrenics will largely hold their position. One potentially significant trend is the
increasing regulatory requirement for recycling of polymers in the United States and Western
Europe. Depending on specific future regulations, the demand growth rate of polystyrene and
other styrenics will be reduced somewhat, but not to the extent that a market decline will result.
5.1.1.3
Cumene/Phenol
Benzene consumption in the production of cumene is the second largest market, accounting for
around 21 percent of global demand. Cumene is made by the vapor phase alkylation of benzene
with propylene. It is important to also consider phenol as well as cumene. Virtually all cumene
is used to produce phenol, and most phenol production is derived from cumene.
Phenol is a chemical intermediate produced from cumene by peroxidation in which the
hydroperoxide is formed and subsequently split under acid cleavage conditions to give phenol
and coproduct acetone.
Solutia has developed a direct route to phenol that uses nitrous oxide, a byproduct of adipic acid
production, to oxidize benzene to phenol. No acetone is produced in this route. Shell is
considering a world-scale phenol plant to be built in Singapore using a new technology based on
benzene and butenes, producing methyl ethyl ketone (MEK) as a coproduct and less byproduct
acetone than in traditional processes. (re. PERP report 04/05-S12).
Three of the main outlets for phenol are phenolic resins, bisphenol A, and caprolactam. Phenolic
resins such as phenol/formaldehyde are mature products used in applications such as wood glues
and molded electrical equipment. The demand in developed countries is growing at less than
GNP due to competition with newer polymers and some environmental concerns relating to
formaldehyde.
Bisphenol A is used in polycarbonate production. Another bisphenol A use is in epoxy resin
production. Polycarbonate applications have shown strong growth in recent years; this is
expected to continue.
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Section 5
Market Analysis
The third main product from phenol is caprolactam, which is used primarily as an intermediate in
producing nylon fibers, and to a lesser extent film. Caprolactam can also be produced from
cyclohexane. Nylon demand in the three main industrial regions remains flat.
Acetone is coproduced with phenol. A large volume of acetone is used as a solvent. This is a
highly fragmented market, in which the pharmaceutical sector is increasing in importance. The
largest single acetone use is in the production of methyl methacrylate, which is polymerized to
products such as Perspex. Acetone is also used with phenol in bisphenol A production and in the
manufacture of a number of other derivatives.
Although important to the economics of phenol production, acetone demand is unlikely to dictate
production rates since it can also be produced from isopropanol.
5.1.1.4
Cyclohexane
Cyclohexane is a basic nylon intermediate that is produced from benzene by hydrogenation.

Producers are usually back integrated to benzene. The process is simple and can be switched on
and off to use surplus benzene and hydrogen.
Cyclohexane is used as a feedstock in one of the routes to caprolactam production. This route is
competitive with that derived from phenol and is more economical than toluene based processes.
The other important cyclohexane derivative is adipic acid, a precursor to nylon 6,6. The use of
cyclohexane in adipic acid and caprolactam accounts for 95 percent of demand.
5.1.1.5
Nitrobenzene
Nitrobenzene refers to a single product, a benzene ring with an NO2 group attached. Benzene is
nitrated in a reaction with nitric acid in the presence of concentrated sulfuric acid. The
technology is well proven and licensed by three vendors.
Nitrobenzene is mainly consumed as a feedstock to make aniline, which in turn is used primarily
to produce methylene diisocyanate (MDI) used primarily in polyurethane foams. The rest goes
into production of hydroquinone, acetaminophen, and other low volume products. Nitrobenzene
is not exported; it is scarcely traded. Trade is conducted in aniline.
About three quarters of aniline is used as a feedstock in the polyurethane manufacturing process.
The aniline is reacted with formaldehyde to yield diphenylmethane diamine and this is reacted
with phosgene to yield para-, para-methylene diphenyldiisocyanate (MDI). In practice, a
mixture of MDI isomers is produced and referred to as polymeric MDI (PMDI) or sometimes
as polyisocyanate. The mixture is subsequently polymerized to polyurethane.
Aniline can also be produced from phenol, but this route is less economical and is not widely
practiced.
Aniline is also consumed in the production of rubber chemicals, dyes, pharmaceutical products,
agricultural products, and other chemicals.
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Section 5
Market Analysis
Nitrobenzene demand is heavily dependent on polyurethane demand, which has shown strong
historical growth rates. Polyurethane consumption in the automotive and construction sectors is
linked to economic growth.
5.1.1.6
Chlorobenzene
The term chlorobenzene applies to the chlorinated benzene derivatives. The primary commercial
products
are
monochlorobenzene,
ortho-dichlorobenzene,
para-dichlorobenzene,
trichlorobenzene, and tetrachlorobenzene. Benzene is chlorinated in the presence of a ferric
chloride catalyst or via oxychlorination using hydrochloric acid. As reaction temperature and the
proportion of chlorine is increased, so does the percentage of polychloro derivatives in the
product.
Monochlorobenzene used to be an intermediate for phenol and was a feedstock for the pesticide
DDT, but cumene has displaced chlorobenzene in the former instance and DDT has been banned.
Monochlorobenzene is still used to make nitrochlorobenzene and other fine chemicals, and it has
solvent uses as well. Dichlorobenzene is a feedstock for polyphenylene sulfide (PPS), has
solvent applications, and is a component of flame retardants. Trichlorobenzene is used as a
dyestuff carrier. All of the chlorobenzenes are used as feedstocks for pesticides.
PPS is chlorobenzene's high growth sector. Demand is gaining 10-15 percent per year.
Production is concentrated in Japan and the United States, but new capacity is unlikely in
Western Europe during the 1990s.
Otherwise, chlorobenzene demand is either static or in decline. Chlorinated products in general
are being displaced because they are believed to be too toxic and chemically stable (i.e. not
easily enough degraded). Underlying growth in these sectors is unimpressive. Solvents
applications are growing at rates similar to the general economy; pesticides are expanding at a
slower rate. Agricultural markets are depressed, and the worldwide debt crisis has forced many
buyer nations to scale back purchases.
5.1.1.7
Alkylbenzene
Alkylbenzene is the term for three commercial products, linear alkylbenzene (LAB),
dodecylbenzene (DDB), and dialkylbenzene. DDB is known by at least two other names,
branched alkylbenzene and hard alkylbenzene.
LAB is, as its name suggests, a benzene ring with a linear alkyl group attached. The alkyl group
varies slightly in length - an average of C12. DDB is a benzene ring with a branched C12 group
attached. LAB is the most significant of the three products, constituting over 90 percent of
commercial alkylbenzene.
LAB is used to make linear alkylbenzene sulfonate (LAS), an anionic surfactant. LAS is the
largest volume anionic, with applications in liquid and powder detergents and household
cleaners. It is not consumed in personal care products, which use surfactants based on natural
products.
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Section 5
Market Analysis
LAS's portion of the detergent market is expected to be static. On the one hand, demand for
anionics will be stimulated by the introduction of concentrated detergent powders, which already
are gaining market share in the Far East. On the other hand, detergent formulators are likely to
avoid LAS and choose competing anionics when possible, because of questions about its
degradability and image problems associated with benzene in consumer products.
DDB is used to make alkylbenzene sulfonate, another anionic surfactant and an isomer of LAS.
Alkylbenzene sulfonate consumption has declined steadily for about two decades. Starting in the
United States, one country after another has banned its use in detergents because of its poor
biodegradability. The ban is complete throughout the developed world (including Western
Europe) and is widely spread among the less developed countries. The switch from ABS to LAS
has largely run its course, and there is little substitution potential remaining.
Dialkylbenzene is a small volume product, used as a lubricant, plasticizer, and heat transfer fluid
additive.
5.1.1.8
Maleic Anhydride
Maleic anhydride is produced by the oxidation of benzene or n-butane and as a byproduct of

phthalic anhydride production. New fluidized bed reactor technology has been developed for nbutane oxidation enabling larger plant sizes to be built. Coupled with the switch to less
expensive n-butane feedstock, greater economies of scale can be enjoyed, making the benzene
based route to maleic anhydride look increasingly less economical. Since feedstock costs
account for half of the production cash cost, many maleic anhydride producers will convert old
benzene based units to n-butane even with the slight reduction in output the change brings.
End uses for maleic anhydride are largely mature. The main use is in unsaturated polyester resin,
which is used with glass fiber for boat building, construction, and electrical applications, and in
synthetic marble. Other established uses are the production of food acids and agricultural
chemicals. New uses for maleic anhydride are butanediol, a chemical intermediate used in
polyurethanes, polybutylene terephthalate, and tetrahydrofuran production.
Maleic anhydride is not made from benzene in the United States, and production by this route is
expected to be displaced by n-butane oxidation in the rest of the world. Globally, there will be a
significant drop in consumption of benzene for maleic anhydride production in coming years.
5.1.1.9
Other
Other uses of benzene include the production of resorcinol, which is a benzene ring with two
hydroxyl groups in the ortho-configuration. Most resorcinol is consumed in the manufacture of
high performance adhesive used in tires and laminated beams. The rest is used in pharmaceutical
and dye manufacturing.
Benzene is also used in making a variety of other products such as biphenyl and triphenyl. Some
benzene is used as a solvent, but this application has declined because of health concerns relating
to benzene's carcinogenic properties.
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Section 5
5.1.2
5.1.2.1
Market Analysis
Toluene
Introduction
Toluene is primarily used as a component in gasoline, and is extracted from reformate or other
sources. Controls on the total aromatics content in gasoline will be less stringent than those
relating to benzene; the blending value of toluene is around 10 percent higher than benzene's.
Of the toluene extracted or otherwise produced, the largest single use is for the production of
benzene by dealkylation or the production of both benzene and xylenes by disproportionation.
The other toluene applications are outlined below.
5.1.2.2
Solvents
Toluene, a powerful organic solvent, is used in many applications including paints and coatings,
adhesives and sealants, printing inks, metal cleaners, and pesticides.
There is a general trend away from the use of organic solvents, particularly aromatics because of
direct health concerns and curbs on VOC emissions.
5.1.2.3
Toluene Diisocyanate
Toluene diisocyanate (TDI) is produced by the dinitration of toluene with nitric acid in the
presence of sulfuric acid, followed by catalytic hydrogenation and reaction with phosgene. TDI,
empirical formula CH3C6H5(NCO)2, is normally produced as a mixture of isomers, although pure
2,4-TDI can be made if required.
TDI is the basic raw material of polyurethane foam production. The polyurethane is produced by
the reaction of TDI with glycerol, polypropylene oxide, with a reaction product of
trimethylolpropane and propylene oxide, or other appropriate polyols. Water is often used as the
foaming agent because it generates carbon dioxide and amines in reaction with TDI.
The main demand is for flexible urethane foams, followed by elastomeric foams and rigid foams
for appliances such as refrigerators.
5.1.2.4
Phenol
Phenol, for the most part, is produced from cumene. A small quantity is derived from toluene.
The toluene is first oxidized to benzoic acid, then undergoes decarboxylation with oxygen to
form phenol and carbon dioxide.
5.1.2.5
Caprolactam
Caprolactam is produced by a number of routes, including those based on phenol and

cyclohexane. The process based on toluene includes oxidation to benzoic acid, followed by
hydrogenation to cyclohexane and carboxylic acid. Caprolactam is then produced by reaction
with nitrosylsulfuric acid.
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Section 5
Market Analysis
Nylon demand, and thus caprolactam demand, is declining in the main industrial regions. The
toluene based production processes are likely to close first.
5.1.2.6
Other
Other uses of toluene include the production of:
Benzoic acid, an intermediate in the production of benzoyl chloride and plasticizers such
as butyl benzoate
Benzyl chloride, which can be produced directly by chlorination of toluene and which is
used as an intermediate in the production of various plasticizers, and in soaps, perfumes,
and flavoring agents
Vinyltoluene, produced by alkylation with ethylene followed by dehydrogenation, and

used as a resin modifier in unsaturated polyester resins
Toluenesulfonic acid, used mainly for conversion to para-cresol, from which antioxidants
are produced
Toluenesulfonyl chloride
5.2
UNITED STATES
5.2.1
Consumption
Approximately 45 percent of the benzene in the United States is consumed in the production of
ethylbenzene for styrene. Its growth is modest due to low polystyrene production growth and a
projected reduction in styrene exports. Cumene is the next largest benzene derivative in the
United States and makes up about 28 percent of the total consumption. Cyclohexane,
nitrobenzene and LAB consume most of the rest of the benzene within the United States. United
States benzene consumption is shown in Figure 5.1.
More than 75 percent of the toluene chemical use is for benzene and xylenes (para-xylene)
production via dealkylation, disproportionation and transalkylation. The next largest chemical
usage for toluene is TDI. Toluene is also used as a solvent, but this end use has been declining
due to more stringent air quality regulation.
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Section 5
Market Analysis
Figure 5.1
U.S. Benzene End-Use Pattern
LAB/BAB
2%
Nitrobenzene
10%
Cyclohexane
13%
Styrene
45%
Others
2%
Cumene
28%
Q207_00101.0007.4106_chart s.xls
5.2.2
Supply
The benzene and toluene capacity within the United States has been essentially flat since the late
1990s reflecting a lack of new naphtha cracking complexes for ethylene production and
investment in new refineries, the two main sources of benzene production. Furthermore rising
gasoline prices and weak para-xylene margins over the past few years have discouraged
investment in alternative sources. There are currently no firm plans to add benzene or toluene
production capacity and net imports have been rising.
A list of the United States benzene and toluene capacities is shown in Table 5.1.
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Section 5
Market Analysis
Table 5.1
U.S. Benzene and Toluene Capacity, 2006
Company
Location
Alon
ATOFINA
ATOFINA
BASF FINA
BP
BP
BP
BP
BP
BP Amoco
BP Amoco
BP Amoco
Chalmette Refining
Chalmette Refining
Chevron
Chevron Phillips
Chevron Phillips
Chevron Phillips
Chevron Phillips
Chevron Phillips
Chevron Texaco
Citgo
Citgo
Citgo
Citgo
Citgo
Coastal
Coastal
Coastal
ConocoPhillips
ConocoPhillips
ConocoPhillips
ConocoPhillips
Dow
Dow
Dow
El Paso Energy
El Paso Energy
El Paso Energy
Equilon
Equistar
Equistar
Equistar
Equistar
ExxonMobil
ExxonMobil
ExxonMobil
ExxonMobil
ExxonMobil
ExxonMobil
ExxonMobil
ExxonMobil
Flint Hills Resources
Frontier Oil
Hovensa
Hovensa
Huntsman
Koch Industries
Koch Industries
Koch Industries
Koch Industries
Lyondell-CITGO Refining
Lyondell-CITGO Refining
Marathon Ashland
Marathon Ashland
Motiva
NOVA Chemicals
Phillips
Phillips
Premcor
Premcor
Shell
Shell
Sunoco
Sunoco
Sunoco
Sunoco
Sunoco
Tosco
Tosco
Total Petrochemicals
Ultramar Diamond Shamrock
Valero
Valero
Valero
Valero
TOTAL
Big Spring, TX
Port Arthur, TX
Port Arthur, TX
Port Arthur, TX
Decatur, AL
Texas City, TX
Texas City, TX
Texas City, TX
Texas City, TX
Texas City, TX
Texas City, TX
Texas City, TX
Chalmette, LA
Chalmette, LA
Richmond, CA
Guayama, PR
Pascagoula, MS
Port Arthur, TX
Sweeny, TX
Guayama, PR
Richmond, CA
Lemont, IL
Corpus Christi, TX
Lake Charles, LA
Lemont, IL
Corpus Christi, TX
Corpus Christi, TX
Corpus Christi, TX
Westville, NJ
Alliance, LA
Alliance, LA
Sweeny, TX
Wood River, IL
Plaquemine, LA
Freeport, TX
Plaquemine, LA
Corpus Christi, TX
Corpus Christi, TX
Westville, NJ
Wood River, IL
Corpus Christi, TX
Channelview, TX
Chocolate Bayou, TX
Corpus Christi, TX
Baton Rouge, LA
Baytown, TX
Beaumont, TX
Baton Rouge, LA
Baytown, TX
Beaumont, TX
Baytown, TX
Beaumont, TX
Corpus Christi, TX
Corpus Christi, TX
Corpus Christi, TX
Corpus Christi, TX
El Dorado, KS
St. Croix, VI
St. Croix, VI
Port Arthur, TX
Corpus Christi, TX
Corpus Christi, TX
Corpus Christi, TX
Corpus Christi, TX
Houston, TX
Houston, TX
Catlettsburg, KY
Texas City, TX
Delaware City, DE
Bayport, TX
Alliance, LA
Alliance, LA
Lima, OH
Lima, OH
Deer Park, TX
Deer Park, TX
Marcus Hook, PA
Philadelphia, PA
Toledo, OH
Westville, NJ
Marcus Hook, PA
Alliance, LA
Alliance, LA
Port Arthur, TX
Port Arthur, TX
Three Rivers, TX
Lima, OH
Corpus Christi, TX
Lima, OH
Three Rivers, TX
Capcity, kta
Benzene
Toluene
47
165
0
0
117
62
53
39
85
20
267
718
344
0
0
0
67
150
82
0
0
510
174
0
0
0
135
363
67
167
449
216
623
20
56
68
0
0
0
177
90
198
90
242
200
577
397
260
267
33
0
0
0
0
100
283
90
333
240
217
200
33
66
166
479
317
853
250
672
84
317
167
150
403
184
495
267
50
134
193
557
60
69
0
0
0
0
134
360
40
183
105
23
66
47
112
50
0
0
0
0
306
306
823
200
300
66
178
57
247
50
144
33
0
0
100
289
83
0
266
50
134
120
108
56
45
9,523
10,582
Process
Reformate extraction
TDP
Pygas extraction
Isomerization and fractionation
Pygas extraction
Selective TDP
Pygas extraction
Selective TDP
Selective TDP
Aromax
Aromax
TDP
Coal tar
TDP
HDA
HDA
HDA
Pygas extraction
Pygas extraction
HDA
HDA
Pygas extraction
Pygas extraction
Pygas extraction
Pygas extraction
Pygas extraction
Pygas extraction
Selective TDP
Selective TDP
HDA
Selective TDP
TDP
Pygas extraction
HDA
Selective TDP
TDP
HDA
HDA
HDA
Pygas extraction
TDP
HDA
TDP
HDA
Q207_00101.0007.4106_tables.xls
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Section 5
5.2.3
Market Analysis
Supply, Demand and Trade
With limited plans for new aromatics capacity in the future, the United States is expected to
remain the largest net importer in the region. Operating rates have recovered from the hurricanes
of 2005. The United States supply and demand balance is shown in Table 5.2.
Table 5.2
U.S. Benzene Supply, Demand and Trade
(thousand metric tons)
Firm Capacity
Total Capacity
2001
9,872
0
9,872
2002
9,754
0
9,754
2003
9,753
0
9,753
2004
9,680
0
9,680
2005
9,543
0
9,543
2006
9,654
0
9,654
2007
9,654
151
9,805
2008
9,680
250
9,930
2009
9,654
301
9,954
2010
9,654
501
10,154
Production
Operating Rate
6,844
69%
7,398
76%
7,898
81%
7,960
82%
7,326
77%
7,962
82%
8,037
82%
8,070
81%
7,984
80%
8,101
80%
Net Exports
Consumption
(939)
7,783
(1,236)
8,633
(1,211)
9,110
(1,237)
9,197
(1,538)
8,864
(1,293)
9,266
(1,426)
9,470
(1,440)
9,519
(1,513)
9,513
(1,349)
9,465
5.3
WESTERN EUROPE
5.3.1
Consumption
About 49 percent of the benzene in Western Europe is consumed by the production of

ethylbenzene (for styrene) followed by cumene (23 percent). Nitrobenzene and cyclohexane
account for most of the remaining demand (12 and 11 percent, respectively). Overall
consumption is expected to show mature growth rates throughout the outlook period. The enduse pattern for benzene within Western Europe is shown in Figure 5.2.
Toluene is produced in greater quantities than required for chemical uses and is therefore
consumed as a gasoline blendstock and converted into benzene and xylenes.
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Section 5
Market Analysis
Figure 5.2
Western Europe Benzene End-Use Pattern
Nitrobenzene
12%
LAB/BAB
2%
Cyclohexane
11%
Styrene
49%
Others
3%
Cumene
23%
Q207_00101.0007.4106_chart s.xls
5.3.2
Supply
There are numerous sources of aromatics production in Western Europe and each aromatics
complex is unique. Traditionally, a significant quantity of the aromatics produced in European
reformers has been blended into gasoline. This practice has been restricted under the European
Auto Oil legislation. However, the effect of the 35 percent upper aromatics limit in gasoline is
not expected to be dramatic, as most producers have already moved to within a few percent of
the limit. Gasoline producers operating fluid catalytic cracker (FCC) units normally have no
problem in meeting the 35 percent aromatics limit, and can blend in a proportion of aromatic
streams as long as they do not contain significant quantities of benzene. Aromatics raffinate
streams typically have a high octane rating, and are low in sulfur, and therefore are attractive to
gasoline blenders. Smaller refineries without FCC units typically use significant quantities of
reformate to reach the required octane level. The second phase of the aromatics reduction is
leading to more MTBE, an alternate octane enhancer, being blended into gasoline. In 2005, high
gasoline prices and refinery disruption along the USGC caused by severe hurricanes led to record
high prices for gasoline blend components including MTBE and aromatics. However, MTBE
supplies are expected to increase as the U.S. phases out MTBE use and the Middle East invests
in new capacity. The next phase of gasoline legislation changes will be driven by the European
Unions initiative toward renewable sources of energy and biodiesel fuels such as ethanol and
ETBE.
Benzene production in Western Europe is heavily influenced by ethylene production, which
generates the pygas byproduct and is the major source of benzene in Europe. As the benzene in
pygas can no longer be blended into gasoline in significant quantities, incremental ethylene
production normally necessitates the production of a proportionate quantity of benzene.
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Section 5
Market Analysis
Production of benzene from benzole has enjoyed a small revival as its economics are more
attractive in periods of high oil/benzene pricing. The market price of benzole is flexible
however, so much of the benefit from the recent high benzene prices is believed to have gone to
the coke/benzole producers.
For most producers of aromatics, toluene is surplus to chemical requirements, and dealkylation is
available as an alternative to blending toluene back into gasoline.
There are several benzene expansion planned in the next few years. In 2006 CEPSA started up a
new aromatics plant employing Chevrons Aromax technology at its existing refinery in
Huelva, Spain. The benzene will be used to feed a new cumene/phenol plant by the companys
petrochemical subsidiary Ertisa. Also in 2006, in Tarragona, Spain Repsol YPF has
commissioned a benzene extraction unit to feed the companys POSM unit. The additional
benzene will be extracted from both pygas and reformate sources. In Antwerp BASF is adding a
new furnace to its naphtha cracker for commissioning in late 2007. With this investment, an
increase in benzene extraction capacity is also expected.
A list of the Western Europre benzene and toluene capacities is shown in Table 5.3.
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Section 5
Market Analysis
Table 5.3
Western Europe Benzene and Toluene Capacity, 2006
Country
Company
Location
Belgium
Belgium
Belgium
Belgium
Belgium
Belgium
Belgium
Finland
France
France
France
France
France
France
France
France
France
France
France
France
France
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Germany
Italy
Italy
Italy
Italy
Italy
Italy
Italy
Italy
Italy
Italy
Italy
Italy
Italy
Italy
Italy
Italy
Italy
Italy
Netherlands
Netherlands
Netherlands
Netherlands
Netherlands
Netherlands
Netherlands
Netherlands
Portugal
Spain
Spain
Spain
Spain
Spain
Spain
Spain
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
United Kingdom
TOTAL
BASF
BP
BP Amoco
Fina Antwerp Olefins
Rutgers
TOTALFINAELF
Borealis
AP Feyzin
ATOFINA
ATOFINA
ATOFINA
ATOFINA
Gexaro
Shell
TOTALFINAELF
Aral Aromatics
BASF
BASF
BP Koln
BSL Olefinverbund
BSL Olefinverbund
DEA
DEA
DEA
Erdoelchemie
Holborn
Ineos
Innovene Koln
OMV
PCK
Ruhr Oel
Ruhr Oel
Ruhr Oel
Ruhr Oel
Shell
Shell
Shell
Shell
Shell
Shell
Shell & DEA Oil
Shell & DEA Oil
Shell & DEA Oil
Wintershall
Wintershall
Wintershall
EniChem
EniChem
EniChem
EniChem
EniChem
EniChem
EniChem
EniChem
EniChem
Polimeri Europa
Polimeri Europa
Polimeri Europa
Polimeri Europa
Polimeri Europa
Polimeri Europa
Syndial
Syndial
Syndial
Dow
Dow
DSM
ExxonMobil
ExxonMobil
SABIC Europe
Shell
TOTALFINAELF
Petrogal
CEPSA
CEPSA
CEPSA
CEPSA
CEPSA
Repsol YPF
Repsol YPF
Bitmac
BP
BP
BP Amoco
BP Amoco
Conoco
Conoco
ConocoPhillips
ConocoPhillips
HIH
HIH
HIH
Huntsman
Huntsman
Huntsman
Huntsman
Ineos
Ineos
Innovene
Innovene
SABIC UK
SABIC UK
SABIC UK
SABIC UK
Shell
Shell
Antwerp
Geel
Geel
Antwerp
Zelzate
Antwerp
Antwerp
Porvoo
Feyzin
Carling
Carling
Carling
Gonfreville
Lavera
Berre
Carling
Carling
Carling
Gonfreville
Gonfreville
Gonfreville
Gelsenkirchen
Mannheim
Mannheim
Dormagen
Bohlen
Bohlen
Wesseling
Heide
Wesseling
Dormagen
Hamburg
Dormagen
Dormagen
Burghausen
Schwedt
Gelsenkirchen
Gelsenkirchen
Gelsenkirchen
Gelsenkirchen
Godorf
Godorf
Wesseling
Godorf
Heide
Wesseling
Wesseling
Heide
Wesseling
Lingen
Lingen
Mannheim
Porto Torres
Priolo
Porto Marghera
Porto Torres
Priolo
Priolo
Sarroch
Priolo
Porto Torres
Priolo
Porto Marghera
Priolo
Priolo
Sarroch
Priolo
Porto Torres
Porto Torres
Porto Torres
Terneuzen
Terneuzen
Geleen
Botlek
Botlek
Geleen
Moerdijk
Vlissingen
Oporto
Huelva
Huelva
Algeciras
Huelva
Algeciras
Puertollano
Tarragona
Llanwern
Grangemouth
Grangemouth
Grangemouth
Grangemouth
Immingham
Immingham
Immingham
Immingham
North Tees
North Tees
North Tees
North Tees
North Tees
North Tees
North Tees
Grangemouth
Grangemouth
Grangemouth
Grangemouth
North Tees
North Tees
North Tees
North Tees
Stanlow
Stanlow
Capcity, kta
Benzene
Toluene
258
65
60
0
170
64
250
0
148
110
40
0
0
0
0
240
0
50
95
185
200
160
430
0
250
30
150
150
80
0
117
200
0
0
0
0
65
175
360
0
120
100
80
120
235
64
172
0
145
305
70
145
100
180
80
120
323
43
0
0
0
45
30
60
105
0
0
0
0
0
0
0
0
0
75
110
50
112
59
20
60
50
80
85
85
29
30
300
600
0
300
300
190
350
500
190
80
215
230
94
120
245
659
30
125
50
125
180
484
0
0
0
0
0
0
0
95
120
323
0
0
0
250
80
0
0
195
155
160
30
100
150
10,326
215
90
260
100
4,953
Process
Pygas extraction
Pygas extraction
Coal tar
Pygas extraction
Pygas extraction
Coal tar
HDA
Pygas extraction
Pygas extraction
Pygas extraction
Pygas extraction
Coal tar
HDA
Pygas extraction
Pygas extraction
Coal tar
HDA
Pygas extraction
Pygas extraction
HDA
Pygas extraction
Pygas extraction
Pygas extraction
Pygas extraction
Pygas extraction
Pygas extraction
HDA
Pygas extraction
HDA
Pygas extraction
Pygas extraction
Pygas extraction
HDA
HDA
HDA
Pygas extraction
Pygas extraction
Pygas extraction
Selective TDP
TDP
HDA
Pygas extraction
Pygas extraction
Selective TDP
HDA
Pygas extraction
TDP
HDA
Pygas extraction
Pygas extraction
Pygas extraction
Pygas extraction
Pygas extraction
Aromax
HDA
Selective TDP
Bulk HDA
Coal tar
Pygas extraction
Pygas extraction
HDA
HDA
Pygas extraction
TDP
Pygas extraction
TDP
Transalkylation
Pygas extraction
Pygas extraction
Pygas extraction
TDP
Transalkylation
Pygas extraction
Q207_00101.0007.4106_tables.xls
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
120
Section 5
5.3.3
Market Analysis
Western Europe has been a net importer of benzene in recent years. With the start-up of
numerous styrene and cumene plants in Asia and the Middle East, Western European demand for
benzene is expected to decline in the near term allowing Western Europe to become selfsufficient in benzene for a few years. The Western Europe supply and demand balance is shown
in Table 5.4.
Table 5.4
Western Europe Benzene Supply, Demand and Trade
Firm Capacity
Total Capacity
2001
9,437
0
9,437
2002
9,532
0
9,532
2003
10,033
0
10,033
2004
10,130
0
10,130
2005
10,121
0
10,121
2006
10,297
0
10,297
2007
10,571
0
10,571
2008
10,662
100
10,762
2009
10,632
100
10,732
2010
10,632
(10)
10,622
Production
Operating Rate
7,635
81%
7,884
83%
8,242
82%
8,430
83%
8,456
84%
8,901
86%
9,091
86%
9,134
85%
9,066
84%
8,746
82%
Net Exports
Consumption
(156)
7,791
(8)
7,892
(182)
8,424
(566)
8,996
(648)
9,104
76
8,832
(17)
9,112
74
9,059
47
9,022
(57)
8,805
5.4
ASIA PACIFIC
5.4.1
Consumption
Benzene demand in Asia has increased sharply as the region continues to expand and broaden its
derivative base. While styrene via ethylbenzene continues to consume the largest share of
benzene (55 percent), cumene, a precursor for polycarbonates, grew the most rapidly with the
start-up of several new plants in the region. Cyclohexane is the third largest consumer of
benzene in the region. While there is a good deal of potential for growth in nylon production in
the region, there are few plans for new cyclohexane capacity. Nitrobenzene has historically
represented a small share of the total benzene consumption. However, this derivative will show
strong growth from a relatively small base over the next few years.
Currently Japan is the largest consumer of benzene in the region, but China is expected to take
the lead by 2008. India and Thailand are expected to show rapid growth from a much smaller
base. Overall benzene consumption is expected to show moderate growth rates during the
outlook period. Asia Pacific benzene consumption is shown in Figure 5.3.
More than 50 percent of the toluene consumed in Asia for chemical use is used in the production
of benzene and xylenes via toluene disproportionation and for on-purpose benzene production
via toluene hydrodealkylation. The second largest use is for solvents, which is expected to show
moderate growth.
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
121
Section 5
Market Analysis
Figure 5.3
Asia Pacific Benzene End-Use Pattern
Others
28%
Styrene
55%
Cumene
17%
Q207_00101.0007.4106_chart s.xls
5.4.2
Supply
Most new major aromatics capacity additions will come on-line in Asia and the Middle East in
the outlook period. The massive ethylene demand growth in China has given rise to several new
large scale liquid based crackers in China with extraction facilities to recover benzene. Several
new additions were added in 2005/2006 (BASF-YPC, Jilin Chemical, Secco, and Maoming
Petrochemical). Others will be added between 2007 and 2009 (CNOOC/Shell and Fujian
Refinery & Chemical). This trend will continue in the forecast period and China will continue to
be nearly self-sufficient in benzene. In addition Zhenhai Refining, Fujian Refinery and LG
Chem are adding benzene from reformate extraction in China during the same timeframe.
Additional benzene will be extracted from Zhenhai Refinings planned cracker complex slated
for 2010.
In Japan Idemitsu Petrochemical restarted its mothballed HDA unit in Chiba in 2006. Nippon
Oil has announced plans to add benzene extraction capacity from reformate at the Sendai
refinery in 2008. Similarly Kashima Aromatics is adding 170 kta of benzene extraction capacity
from reformate at its plant.
In South Korea, Samsung Total is continuing its expansion by adding an additional 150 kta of
benzene from reformate by 2008. SK Corp started-up its BTX facility in 2006 (80 kta).
Reliance (India), FCFC (Taiwan), Aromatics Thailand and Thai Oil (Thailand), and TPPI
(Indonesia) are adding or have recently added new capacity. In summary Asia Pacific is
expected to add over 3 million tons per year of new capacity between 2006 and 2010.
A list of the Asia Pacific benzene and toluene capacities is shown in Table 5.5.
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
122
Section 5
Market Analysis
Table 5.5
Asia Pacific Benzene and Toluene Capacity, 2006
Country
Company
Location
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
China
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Baling Petrochemical
BASF-YPC
CNOOC
CNOOC
CSPC
Dalian Petrochemical
Daqing General
Daqing General
Dushanzi Petrochemical
Fujian Refinery & Chemical
Fushun Petrochemical
Gaoqiao Petrochemical
Guangzhou Petrochemical
Guangzhou Petrochemical
Jilin Chemical
Jilin Chemical
Jilin Chemical
Jilin Chemical
Jinling Petrochemical
Jinxi Refinery
Jinzhou Petrochemical
Jiujiang Petrochemical
Lanzhou Petrochemical
Lanzhou Petroleum
Liaoyang Petrochemical
Luoyang Petrochemical
Maoming Petrochemical
Maoming Petrochemical
Qilu Petrochemical
Qilu Petrochemical
Qilu Petrochemical
Qilu Petrochemical
Qingdao Lidong
Secco
Shanghai Petrochemical
Shijiazhuang Refinery
Taiyuan Chemical
Tianjin Petrochemical
Urumqi Petrochemical
Various China
Wuhan Petrochemical
Yangzi Petrochemical
Yanhua Petrochemical
Zhenhai Refining
Zhenhai Refining
Zhenhai Refining
Zhenhai Refining
Zhongyuan Petrochemical
Adchemco
Cosmo Matsuyama
Fuji Oil
Fuji Oil
Idemitsu Petrochemical
Baling, Hunan
Nanjing, Jiangsu
Dongfang, Hainan
Huizhou, Guangdong
Huizhou, Guangdong
Dalian, Liaoning
Daqing, Heilongjiang
Daqing, Heilongjiang
Karamay, Xinjiang
Fuzhou, Fujian
Fuzhou, Fujian
Fuzhou, Fujian
Fushun, Liaoning
Fushun, Liaoning
Fushun, Liaoning
Pudong, Shanghai
Guangzhou, Guangdong
Guangzhou, Guangdong
Jilin, Jilin
Jilin, Jilin
Jilin, Jilin
Jilin, Jilin
Nanjing, Jiangsu
Jinxi, Liaoning
Jinzhou, Liaoning
Jiujiang, Jiangxi
Lanzhou, Gansu
Lanzhou, Gansu
Liaoyang, Liaoning
Liaoyang, Liaoning
Liaoyang, Liaoning
Liaoyang, Liaoning
Luoyang, Henan
Maoming, Guangdong
Maoming, Guangdong
Zibo, Shandong
Zibo, Shandong
Zibo, Shandong
Zibo, Shandong
Qingdao, Shandong
Caojing, Shanghai
Jinshanwei, Shanghai
Shijiazhuang, Hebei
Tiayuan, Shanxi
Dagang, Tianjin
Tianjin, Tianjin
Tianjin, Tianjin
Urumqi, Xinjiang
Urumqi, Xinjiang
Urumqi, Xinjiang
Various China, China
Wuhan, Hubei
Nanjing, Jiangsu
Nanjing, Jiangsu
Nanjing, Jiangsu
Nanjing, Jiangsu
Beijing, Beijing
Beijing, Beijing
Beijing, Beijing
Ningbo, Zhejiang
Ningbo, Zhejiang
Ningbo, Zhejiang
Ningbo, Zhejiang
Puyang, Henan
Fukuyama
Matsuyama, Ehime
Chiba
Chiba
Chiba
Tokuyama, Yamaguchi
Chiba
Tokuyama, Yamaguchi
Chiba
Tokuyama, Yamaguchi
Capcity, kta
Benzene
Toluene
38
102
128
10
27
0
226
45
121
120
15
40
65
0
0
0
0
37
100
30
30
35
15
20
160
45
39
105
45
121
25
67
15
40
10
27
30
37
100
9
20
42
113
100
105
282
157
40
108
3
185
50
134
15
50
538
180
10
240
40
9
24
42
0
120
323
22
2
25
67
10
556
24
42
34
190
85
229
108
40
142
10
27
0
57
153
100
269
30
52
0
96
258
100
75
202
126
80
80
100
302
812
100
269
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
Process
Pygas extraction
Pygas extraction
Pygas extraction
Pygas extraction
Pygas extraction
Transalkylation
Pygas extraction
TDP
Pygas extraction
Pygas extraction
Pygas extraction
HDA
Pygas extraction
Pygas extraction
Pygas extraction
Pygas extraction
TDP
Pygas extraction
Pygas extraction
TDP
Pygas extraction
Pygas extraction
TDP
Coal tar
Pygas extraction
TDP
TDP
Coal tar
Pygas extraction
TDP
HDA
Pygas extraction
Pygas extraction
TDP
Pygas extraction
Coal tar
HDA
HDA
HDA
Pygas extraction
Pygas extraction
123
Section 5
Market Analysis
Table 5.5
Asia Pacific Benzene and Toluene Capacity, 2006 (contd)
Country
Company
Location
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
Japan
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
Japan Energy
Japan Energy
Japan Energy
Japan Energy
JFE Chemical
JFE Chemical
Kashima Aromatics
Kashima Aromatics
Kawasaki Steel
Kyokuto Oil
Kyushu Aromatics
Maruzen Petrochemical
Maruzen Petrochemical
Mitsubishi Chemical
Mitsubishi Chemical
Mitsubishi Chemical
Mitsui
Nippon Mitsubishi Oil
Nippon Oil
Nippon Oil
Nippon Oil
Nippon Oil
Nippon Oil
Nippon Oil
Nippon Oil
Nippon Petrochemicals
Nippon Steel Chemical
Osaka Petrochemical
Sanyo Petrochemicals
Sanyo Petrochemicals
Seibu Oil
Showa Yokkaichi
Sumitomo
Taiyo Oil
Taiyo Oil
Toa Oil
Tonen Chemical
Tonen Chemical
Tonen General Sekiyu
Tosoh Corporation
Ukishima Aromatics
DC Chemical
GS-Caltex
GS-Caltex
GS-Caltex
GS-Caltex
GS-Caltex
Honam
Honam
Hyundai Oil
Hyundai Oil
Hyundai Oilbank
Hyundai Oilbank
Hyundai Petrochemical
Inchon Oil
Inchon Oil
Kohap
Kohap
Korea Steel Chemical
KP Chemical
KP Chemical
LG Daesan
LG Daesan
Mizushima
Nagoya
Mizushima
Nagoya
Chiba
Fukuyama
Kashima, Ibaraki
Kashima, Ibaraki
Chiba
Chiba
Oita City, Oita
Chiba
Chiba
Kashima, Ibaraki
Kashima, Ibaraki
Mizushima
Chiba
Mizushima
Muroran
Negishi
Mizushima
Marifu
Marifu
Mizushima
Muroran
Negishi
Sendai, Miyagi
Mizushima
Kawasaki
Hirohata
Oita City, Oita
Oita City, Oita
Osaka, Osaka
Mizushima
Mizushima
Yamaguchi
Yokkaichi, Mie
Chiba
Ehime
Ehime
Kawasaki
Kawasaki
Wakayama
Sakai, Osaka
Kawasaki
Sakai, Osaka
Wakayama
Yokkaichi, Mie
Kawasaki
Kwangyang
Yeochon
Yeochon
Yeochon
Yeochon
Yeochon
Yeochon
Yeochon
Daesan
Daesan
Daesan
Daesan
Daesan
Daesan
Daesan
Inchon
Inchon
Ulsan
Ulsan
Kwangyang
Ulsan
Ulsan
Daesan
Daesan
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
Capcity, kta
Benzene
Toluene
65
100
35
94
67
180
122
64
8
0
0
72
194
100
150
250
85
180
282
210
145
0
0
0
0
100
105
282
210
565
106
285
172
463
0
218
78
107
69
180
80
158
425
130
170
142
40
108
90
242
122
230
160
431
55
148
0
0
10
80
215
42
180
115
309
154
65
60
110
19
150
403
114
307
380
50
180
90
78
0
0
62
167
38
0
0
0
12
4
0
0
0
30
81
70
50
90
Process
HDA
HDA
Coal tar
Coal tar
Coal tar
Transalkylation
HDA
Pygas extraction
HDA
Pygas extraction
Pygas extraction
Pygas extraction
Selective TDP
HDA
Selective TDP
Pygas extraction
Coal tar
HDA
Pygas extraction
HDA
Pygas extraction
Pygas extraction
HDA
Pygas extraction
Transalkylation
Coal tar
Selective TDP
TDP
Pygas extraction
Transalkylation
Transalkylation
HDA
Pygas extraction
Pygas extraction
TDP
TDP
Coal tar
TDP
HDA
Pygas extraction
124
Section 5
Market Analysis
Table 5.5
Asia Pacific Benzene and Toluene Capacity, 2006 (contd)
Country
Company
Location
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
South Korea
Taiwan
Taiwan
Taiwan
Taiwan
Taiwan
Taiwan
Taiwan
Taiwan
Taiwan
Taiwan
Taiwan
Taiwan
Taiwan
Australia
India
India
India
India
India
India
India
India
India
India
India
India
India
India
India
India
India
India
India
India
Indonesia
Indonesia
Indonesia
Indonesia
Malaysia
Malaysia
Malaysia
Malaysia
Singapore
Singapore
Singapore
Singapore
Singapore
Singapore
Singapore
Thailand
Thailand
Thailand
Thailand
Thailand
Thailand
Thailand
Thailand
Thailand
Thailand
Thailand
Thailand
TOTAL
Samsung Total
Samsung Total
Samsung Total
SK Corp
SK Corp
SK Corp
SK Corp
SK Incheon Oil
SK Incheon Oil
YNCC
YNCC
YNCC
CPC
CPC
CPC
CPC
CPC
FCFC
FCFC
FCFC
FCFC
FCFC
FCFC
FCFC
FCFC
Huntsman
Bharat Petroleum
Bokharo Steel
Bongaigaon Refineries
Haldia
Hindustan Steel
Indian Oil Corp.
Indian Oil Corp.
Indian Oil Corp.
IPCL
Kochi Refineries
Mangalore Refinery
NOCIL
ONGC
ONGC
Oswal Agro
Reliance
Reliance
Reliance
Reliance
Reliance
Pertamina
Pertamina
TPPI
TPPI
Aromatics Malaysia
Aromatics Malaysia
Titan Petchem
Titan Petrochemicals
ExxonMobil
ExxonMobil
ExxonMobil
PCS Singapore
Shell
Singapore Aromatics
Singapore Aromatics
Aromatics (Thailand)
ExxonMobil
IRPC
Map Ta Phut Olefins
Rayong Olefins
Thai Oil
Thai Oil
TPI
Daesan
Daesan
Daesan
Ulsan
Ulsan
Ulsan
Ulsan
Inchon
Inchon
Yeochon
Yeochon
Yeochon
Kaohsiung City
Kaohsiung City
Linyuan
Linyuan
Kaohsiung City
Mailiao
Mailiao
Mailiao
Mailiao
Mailiao
Mailiao
Mailiao
Mailiao
West Footscray
Mumbai
Bokharo
Bongaigaon
Haldia, West Bengal
Various India
Koyali
Panipat
Panipat
Vadodara, Gujarat
Kochi, Kerala
Mangalore
Thane, Maharashtra
Dahej, Gujarat
Mangalore
Thrombay
Hazira, Gujarat
Jamnagar, Gujarat
Patalganga
Jamnagar, Gujarat
Patalganga
Cilicap
Cilicap
Tuban
Tuban
Kerteh
Kerteh
Pasir Gudang
Pasir Gudang
Jurong
Jurong
Jurong
Jurong Island
Pulau Bukom
Jurong Island
Jurong Island
Map Ta Phut
Map Ta Phut
Map Ta Phut
Map Ta Phut
Map Ta Phut
Sriracha
Rayong
Map Ta Phut
Map Ta Phut
Map Ta Phut
Sriracha
Rayong
Capcity, kta
Benzene
Toluene
180
484
140
0
60
150
130
270
40
250
63
21
146
111
110
90
90
78
100
159
84
226
63
180
0
90
180
484
0
64
172
0
110
87
85
229
33
19
48
85
30
48
129
33
525
472
40
87
234
114
290
0
0
0
10
140
264
1,311
80
215
130
36
75
202
52
181
726
34
130
350
50
110
0
60
300
807
50
270
0
21
90
242
150
200
538
0
134
0
70
188
29
130
0
160
70
472
0
76
17,684
20,293
Process
Selective TDP
TDP
HDA
Pygas extraction
TDP
Pygas extraction
Pygas extraction
TDP
HDA
Pygas extraction
Pygas extraction
Transalkylation
Pygas extraction
Pygas extraction
Pygas extraction
TDP
Transalkylation
Coal tar
Coal tar
Pygas extraction
Coal tar
Pygas extraction
Pygas extraction
Pygas extraction
Pygas extraction
Pygas extraction
TDP
TDP
TDP
TDP
TDP
Pygas extraction
Pygas extraction
Pygas extraction
TDP
Pygas extraction
Pygas extraction
Pygas extraction
Selective TDP
TDP
Pygas extraction
Steam cracker - naphtha
Pygas extraction
Pygas extraction
Q207_00101.0007.4106_tables.xls
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
125
Section 5
5.4.3
Market Analysis
Since the late 1900s the Asia Pacific region has been close to a balanced position in benzene,
with Taiwan and Indonesia the major importers and Japan, South Korea and Thailand providing
most of the exports within the region. In the last several years high benzene prices in other parts
of the world, especially the U.S., and surplus capacity in China provided opportunities for
exports to flow out of the region. For most of the outlook period, Asia Pacific is expected to be a
small net importer and occasionally a net exporter when opportunities arise. The Asia Pacific
supply and demand balance is shown in Table 5.6.
Table 5.6
Asia Pacific Benzene Supply, Demand and Trade
Firm Capacity
Total Capacity
2001
14,716
0
14,716
2002
15,123
0
15,123
2003
15,614
0
15,614
2004
15,927
0
15,927
2005
16,505
0
16,505
2006
17,883
0
17,883
2007
18,707
200
18,907
2008
19,550
531
20,082
2009
20,116
662
20,778
2010
20,465
1,032
21,497
Production
Operating Rate
11,446
78%
11,814
78%
12,764
82%
14,100
89%
15,167
92%
14,821
83%
15,967
84%
16,826
84%
17,121
82%
17,406
81%
Net Exports
Consumption
(78)
11,524
(271)
12,085
(354)
13,118
434
13,666
367
14,799
(387)
15,220
(252)
16,245
(74)
16,917
(262)
17,418
(578)
18,010
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
126
Appendix A
Elements of Nexant's ChemSystems Capital Cost Estimates
Elements of Nexants ChemSystems Capital Cost Estimates

Process Evaluation/Research Planning, 2007
Costs typically included in Nexants ChemSystems capital cost estimates are defined as follows:
A.1
INSIDE BATTERY LIMITS INVESTMENT
The inside battery limits (ISBL) portion of a plant can be thought of as a boundary over which
are imported raw materials, catalysts and chemicals, and utility supply streams. In a like manner,
main products, byproducts, and spent utility return streams are exported over this boundary.
ISBL investment includes the cost of the main processing blocks of the chemical plant necessary
to manufacture products. It represents an "instantaneous" investment (i.e., no escalation) for a
plant ordered from a contractor and built on a prepared site with normal load-bearing and
drainage characteristics of a developed country.
Battery limits investment includes the installed cost of the following major items:
Process equipment: vessels and internals, heat exchangers, pumps and compressors,
drivers, solids handling
Major spare equipment/parts (e.g., spare rotor for turbine or compressor)
Building housing process units
Process and utility pipes and supports within the major process areas
Instruments, including computer control systems
Electrical wires and hardware
Foundations and pads
Structures and platforms
Insulation
Paint/corrosion protection
Process sewers
Fire water pipes and monitors
Utility stations
The installed cost also includes construction overhead: fringe benefits, payroll burdens, field
supervision, equipment rentals, small tools (expendables), field office expenses, site support
services, temporary facilities, etc.
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
A-1
Appendix A
A.2
OUTSIDE BATTERY LIMITS INVESTMENT
Outside battery limits (OSBL) investment includes the plant investment items that are required in
addition to the main processing units within the battery limits. These auxiliary items are
necessary to the functioning of the production unit, but perform in a supporting role rather than
being directly involved in production. A distinguishing characteristic is the potential for sharing
offsite facilities among several production units in a large plant, in which case investment cost
would be allocated or prorated.
OSBL investment includes the installed cost of the following major items:
Storage for feeds, products, byproducts, including tanks/silos, dikes, inerting, process
warehouse, and bagging/palletizing equipment
Steam generation units
Cooling water systems, including cooling towers and circulation pumps
Process water treatment systems and supply pumps
Boiler feed water treatment systems and supply pumps
Refrigeration systems, including chilled water/brine circulating pumps
Heat transfer medium systems, including organic vapor, hot oil, molten salts
Electrical supply, transformers, and switchgear
Loading and unloading arms, pumps, conveyors, lift trucks, including those to handle
barge, tank/hopper car, and tank/hopper/other truck traffic; weigh scales
Auxiliary buildings, including all services, furnishings, and equipment:
Central control room

Maintenance
Stores warehouse
Laboratory
Garages/fire station
Change house/cafeteria
Medical/safety
Administration
General utilities, including plant air, instrument air, inert gas, stand-by electrical
generator, fire water pumps
Site development, including roads and walkways, parking, railroad sidings, electrical
main substation, lighting, water supply, fuel supply, clearing and grading, drainage,
fencing, sanitary and storm sewers, and communications
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
A-2
Appendix A
Yard pipes, including lines for cooling water, process water, boiler feed water, fire water;
fuel; plant air, instrument air, inert gas; collection of organic wastes, aqueous wastes, and
flare/incinerator feeds; and process tie-ins to storage
A.3
CONTRACTOR CHARGES
These charges are typically 15 to 25 percent of installed ISBL and OSBL costs and are included
proportionately in the ISBL and the OSBL investments. Contractor charges include the
following major items:
Detailed design and engineering, including process and offsites design and general
engineering, equipment specifications, plant layout, drafting, cost engineering, scale
models
Administrative charges, including project management, engineering supervision,

procurement, expediting, inspection, travel and living, home office construction
expenses, general home office overhead
Contractor profit
A.4
PROJECT CONTINGENCY ALLOWANCE
A project contingency allowance is typically 15 to 25 percent of installed ISBL and OSBL costs
and is included proportionately in the ISBL and the OSBL investments.
A project contingency allowance is applied to the total of the above costs to take into account
unknown elements of the process being estimated. For well-defined processes where primary
input has come from engineering contractors, a contingency of 10 to 20 percent would be typical.
At the other end of the spectrum, a capital estimate for a speculative process developed from
patent and literature data alone might warrant a contingency of 20 to as much as 50 percent in
extreme cases.
A.5
OTHER PROJECT COSTS
These costs are very site/project specific; however, they typically range from 20 to 40 percent of
installed ISBL + OSBL costs. A norm value of 25 percent will be used in the absence of more
specific information.
For the purpose of our study, other project costs normally include startup/commissioning costs,
miscellaneous owners costs, etc. They are described below:
Startup/Commissioning Costs
Extra operating manpower
Owner's technical manpower
Startup services
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
A-3
Appendix A
Licensor representatives
Contractor personnel
Equipment supplier/other vendor representatives
Operating manuals and training programs
Modifications and maintenance during startup
Operating expenses to the extent that they do not result in saleable product
Miscellaneous Owner's Costs
Licensing/royalty/expertise fees: basic process and engineering design package
Jetties, marine terminals, docks, etc.
Long distance pipelines for raw material/products
Land, rights of way, permits, surveys, and fees
Piling, soil compaction/dewatering, unusual foundation requirements
Sales, use, and other taxes
Freight, insurance in transit, and import duties (equipment, pipe, steel, instruments, etc.)
Escalation/inflation of costs over time, assuming instantaneous construction
Interest on construction loan, assuming instantaneous construction
Overtime pay during construction
Construction workers' housing, canteen, other infrastructure for remote site
Field insurance
Project team, including preliminary planning studies, HAZOP studies, environmental

reviews, design, engineering, estimating, inspection, accounting, auditing, legal,
construction management, travel, and living
Initial charges of raw materials, catalysts, chemicals, and packaging materials
Initial stock of maintenance, laboratory, operating, and office supplies
Transport equipment, including barges, railcars, tank trucks, bulk shipping containers,
plant vehicles
Provisions for temporary shutdown expenses
Owner's scope contingency allowance
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
A-4
Appendix A
A.6
WORKING CAPITAL
Working capital typically includes the following items:
Accounts receivable (products and byproducts shipped but not paid by customer),
typically one month's gross cost of production (COP)
Cash on hand (short-term operating funds), typically one week's gross COP minus
depreciation
Minor spare equipment and parts inventory, percentage of replacement BL capital
Credit for accounts payable (feedstocks, catalysts, chemicals, and packaging materials
received but not paid to supplier), typically one month's delivered cost
Value of product and byproduct inventories, typically two weeks' gross COP
Value of raw material inventory, typically two weeks' delivered cost
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
A-5
Appendix B
PERP Program Title Index

PERP Program Title Index (1997/1998 2006/2007)
This index is intended to be a handy and convenient tool for quickly identifying PERP reports of
interest. It should be noted, however, that this is a title index only. For a more complete search,
dating back to 1972, the full subject indices should be used. See your local technical information
service department for the PERP subject indices or contact Nexant. To browse all Nexant
ChemSystems reports, please visit: www.chemsystems.com
Title
Report
Date
Title
Report
Date
ABS Resins
06/07S8
08/07
Ammonia
05/06S11
02/07
Acetic Acid
06/07-1
Aniline/Nitrobenzene
02/03-2
06/03
Acetic Acid
02/03-1
09/03
Aromatics from Light Olefins
97/98S1
04/99
Acetic Acid/Acetic Anhydride
97/98-1
01/99
Aromatics Production, Optimizing
05/06S6
02/07
Acetic Acid via Ethane Oxidation
99/00S5
01/01
Ascorbic Acid and Sorbitol
97/98S11
03/99
Acetic Anhydride/Cellulose Acetate
03/04S1
06/04
Barrier Monomers for PET
02/03S12
12/03
Acetone/Phenol/Cumene
05/06-4
03/07
Benefits of Refinery/Petrochemical Integration 06/07S7
09/07
Acetone/Phenol/Cumene
01/02-2
10/02
Benzene, Styrene from Ethane and
05/06S3
11/06
Acetylene-Based VCM
05/06S4
02/07
Benzene/Toluene
06/07-6
07/07
Acetylene Production Technologies
05/06S9
04/07
Benzene/Toluene
02/03-5
04/03
Acrylamide
01/02S10
11/02
Benzene/Toluene
98/99-6
05/99
Acrylic Acid
04/05-6
02/06
Biodesulfurization of Petroleum Fractions
98/99S7
01/00
Acrylic Acid
00/01-7
05/01
Biodiesel
02/03S2
12/03
Acrylonitrile
05/06-2
10/06
Biogasoline
05/06S1
12/06
Acrylonitrile
00/01-6
03/02
Biomass Gasification
06/07S5
Adipic Acid
03/04-3
11/04
Biotech Route to Lactic Acid/Polylactic Acid
00/01S3
05/02
Adipic Acid
98/99-3
07/99
Biotransformation Routes to 1,3-Propanediol
97/98S4
09/98
Advances in LNG Technologies
03/04S10
10/04
Bisphenol A
06/07-7
Aliphatic Diisocyanates
98/99S11
09/99
Bisphenol A
01/02-6
09/02
Alkylbenzene, Linear (LAB)
01/02S8
05/03
Bisphenol A
97/98-4
05/98
Alkyl Vinyl Ethers
97/98S6
07/98
Butadiene/Butylenes
05/06-5
01/07
Alpha Olefins, Developments in

Production Technology
Butadiene/Butylenes
01/02-3
02/03
97/98S14
01/99
Butadiene/Butylenes
97/98-2
06/98
Alpha Olefins
06/07-5
*
Butadiene, Chemicals from
99/00S13
01/01
Alpha Olefins
02/03-4
01/04
Butadiene, Oxo Alcohols from
98/99S13
01/00
Alpha Olefins
98/99-7
12/99
Alternative Uses for MTBE Facilities
99/00-7
03/01
Butadiene Rubber/Styrene Butadiene

Rubber (SBR/BR)
02/03S1
12/03
Ammonia
97/98-6
08/98
Butanediol, 1,4-/THF
02/03-7
01/04
Amorphous High Temperature ETPs
03/04S12
12/04
Butanediol/THF
98/99S1
09/99
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
B-1
Appendix B
Title
Report
Date
Butanediol/THF
06/07-4
Butyl Acetate/Ethyl Acetate
97/98S5
08/98
Butylenes/Butadiene
05/06-5
01/07
Butylenes/Butadiene
01/02-3
02/03
Butylenes/Butadiene
97/98-2
Caprolactam
Title
Report
Date
Dimethyl Carbonate Production

Technology: Developments in
99/00S6
05/00
Dimethyl Ether (DME)
97/98S8
03/99
Dimethylnaphthalene, (2,6-)
99/00S7
06/00
EDC/VCM
03/04-6
12/04
06/98
EDC/VCM
99/00-3
04/00
04/05-3
02/06
EPDM
04/05S2
05/05
Caprolactam
99/00-4
03/01
Epichlorohydrin
99/00S11
07/00
Catalytic Ethane Dehydrogenation,

Ethylene via
Epoxy Resins
04/05S11
12/05
98/99S9
04/99
Elastomers, Polyolefin
05/06S7
02/07
Cellulose Acetate/Acetic Anhydride
03/04S1
06/04
Chemicals from Butadiene
99/00S13
01/01
Ethane Dehydrogenation, Ethylene

via Catalytic
98/99S9
04/99
Chlor Alkali
01/02S4
03/03
Ethane Oxidation, Acetic Acid via
99/00S5
01/01
Coal Gasification Technologies
03/04S11
01/05
Ethane Partial Oxidation, Ethylene via

Catalytic
03/04S2
07/04
Coal to Olefins
05/06S5
04/07
Ethane and Benzene, Styrene from
05/06S3
11/06
Compounding, Polypropylene
04/05S6
12/05
Ethanol
04/05-8
01/06
Copolyester and Copolyamide Elastomers,

Thermoplastic
02/03S9
10/03
Ethanol
99/00-8
08/01
Cost/Performance of Fuel Oxygenates
99/00S3
09/00
Ethanolamines
01/02S2
08/02
Crystalline High Temperature Polymers
04/05S3
02/06
ETBE/MTBE Update
06/07S12
Cumene/Phenol/Acetone
05/06-4
03/07
Ethyl Acetate/Butyl Acetate
97/98S5
08/98
Cumene/Phenol/Acetone
01/02-2
10/02
03/04-8
11/04
Curtailing Coke Formation in Ethylene

Furnace Tubes
99/00-6
08/00
02/03S10
06/03
Ethylene
04/05-7
09/05
Desulfurization Technologies, Novel
00/01S8
10/02
Ethylene Oxide/Ethylene Glycol
04/05-5
01/06
Detergent Alcohols
98/99S5
01/02
Ethylene Oxide/Ethylene Glycol
00/01-2
11/01
Developments in Alpha Olefin Production

Technology
97/98S14
01/99
Ethylene, Propylene
00/01-4
06/01
Developments in Dimethyl Carbonate

Production Technology
99/00S6
05/00
Ethylene via Catalytic Ethane

Dehydrogenation
98/99S9
04/99
Developments in Non-Phosgene Polycarbonate Technology
02/03S8
10/03
Ethylene via Catalytic Ethane Partial

Oxidation
03/04S2
07/04
Developments in PET Recycling
99/00S4
07/00
Extending the Methane Value Chain
99/00S9
10/00
Developments in Propylene Oxide

Technology
Fiber Spinning Technology, Nylon
04/05S5
12/05
00/01S12
11/01
Fiber Spinning Technology, PET
03/04S8
08/04
Developments in PTA Production

Technologies
00/01S7
02/02
Fiber Spinning Technology, PET
97/98S13
02/00
Developments in Syngas Technology
03/04S4
02/05
Fischer-Tropsch Liquids as Steam

Cracker Feedstocks
01/02S9
12/02
Developments in Thermoplastic Elastomers
98/99S12
11/99
Fluidized Bed Vinyl Acetate Process
98/99S3
02/00
Dicyclopentadiene and Derivatives
97/98S7
08/98
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
B-2
Appendix B
Title
Report
Date
Title
Report
Date
Formaldehyde
00/01-8
04/01
LNG Receiving Terminals
05/06S12
01/07
Formaldehyde and Derivatives
04/05S10
01/06
LNG Technologies, Advances in
03/04S10
10/04
Fuel Cells for Transportation
02/03S5
12/03
Maleic Anhydride
03/04-7
02/05
Fuel Oxygenates, Cost/Performance of
99/00S3
09/00
Maleic Anhydride
99/00-5
06/00
Fuel Switching with NGLs/Small Scale LNG
04/05S1
08/05
Managing Technology Development in

the Chemical Industry
97/98S2
06/99
Gasification, Biomass
06/07S5
*
MDI/TDI
98/99S8
09/99
Gasification Technologies, Coal
03/04S11
Medium Quality Terephthalic Acid
03/04S6
10/04
01/05
Gas Processing and NGL Extraction: Natural

Gas Conditioning
04/05S8
03/06
MEK/Phenol Co-Product Process
04/05S12
02/06
Glycerin
00/01S4
11/01
Methane Value Chain, Extending the
99/00S9
10/00
Glycerin Conversion to Propylene Glycol
06/07S4
10/07
Methanol
03/04-4
12/04
Glycol Ethers
01/02S6
08/02
Methanol
98/99-4
05/00
Green Polyethylene
06/07S11
Methanol to Olefins
00/01S9
01/02
Heavy Oils, Unconventional
04/05S9
11/05
Methyl Methacrylate
04/05-2
03/06
HDPE
05/06-3
12/06
Methyl Methacrylate
99/00-2
09/01
High Density Polyethylene
01/02-1
12/02
Modified Polyphenylene Oxide (MPPO)
02/03S3
03/03
High Temperature ETPs, Amorphous
03/04S12
12/04
MTBE/ETBE Update
06/07S12
High Temperature Polymers, Crystalline
04/05S3
02/06
MTBE Facilities, Alternative Uses of
99/00-7
03/01
High Temperature Thermoplastic Nylons
01/02S3
06/02
MTBE Phaseout on Chemical Markets,

Impact of
00/01S2
06/01
Hydrocarbon Resins
99/00S10
03/01
Nanocomposites, Thermoplastic
00/01S11
09/01
Hydrogen Peroxide
03/04-5
10/04
Hydrogen Peroxide
98/99-8
09/99
NGL Extraction and Gas Processing:

Natural Gas Conditioning:
04/05S8
03/06
Hydrogen Peroxide-Based Propylene Oxide
06/07S2
NGL Extraction Technologies
06/07S10
Hydrogen Production in Refineries
06/07S1
10/07
NGLs/Small Scale LNG, Fuel Switching with
04/05S1
08/05
Impact of Supply Chain IT Applications on

The Refining Industry
Nitric Acid
97/98S12
10/98
04/05S4
04/06
Nitrobenzene/Aniline
02/03-2
06/03
Non-Phosgene Polycarbonate Technology,

Developments in
02/03S8
10/03
Novel Desulfurization Technologies
00/01S8
10/02
Nylon 6/Nylon 6,6
99/00S1
04/00
Nylon Fiber Spinning Technology
04/05S5
12/05
Nylons, High Temperature Thermoplastic
01/02S3
06/02
Octene-1, On-Purpose
05/06S10
04/07
Iron and Cobalt Based Olefin Polymerization Catalysts
97/98S9
09/99
Isoprene
98/99S2
09/99
Lactic Acid/Polylactic Acid, Biotech Route to
00/01S3
05/02
LDPE
04/05-1
06/05
LDPE
00/01-5
04/01
LDPE Copolymers, Specialty
03/04S9
12/04
Light Olefins, Aromatics from
97/98S1
04/99
Linearalkylbenzene (LAB)
01/02S8
05/03
Olefin Polymerization Catalysts, Iron and

Cobalt Based
97/98S9
09/99
Liquid Crystal Polymers
00/01S10
09/01
Olefins, Coal to
05/06S5
04/07
LLDPE
03/04-1
01/05
Olefins, Methanol to
00/01S9
01/02
LLDPE
99/00-1
06/00
Oleochemicals
99/00S12
05/01
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
B-3
Appendix B
Title
Report
Date
On-Purpose N2O Production for Phenol

Manufacture
98/99S14
09/99
On-Purpose Octene-1
05/06S10
04/07
Optimizing Aromatics Production
05/06S6
02/07
Options for Refinery C5's
98/99S4
09/99
Oxo Alcohols
06/07-8
07/07
Oxo Alcohols
01/02-8
04/03
Oxo Alcohols from Butadiene
98/99S13
01/00
PET Fiber Spinning Technology
03/04S8
08/04
PET Fiber Spinning Technology
97/98S13
02/00
PET Manufacture, Reducing Costs in
04/05S7
07/05
PET Recycling, Developments in
99/00S4
Petroleum Coke Utilization Options
Title
Report
Date
Polypropylene
02/03-3
08/03
Polypropylene
98/99-1
01/00
Polypropylene Compounding
04/05S6
12/05
Polystyrene
04/05-4
02/06
Polystyrene/ABS
00/01-1
06/01
Polytrimethylene Terephthalate (PTT)
01/02S7
10/02
Polyurethanes, Thermoplastic (TPUs)
02/03S7
05/03
Polyvinyl Alcohol
01/02S5
11/02
Polyvinyl Chloride (PVC)
03/04-2
03/04
Polyvinyl Chloride
98/99-2
04/99
07/00
Propanediol, (1,3-), Biotransformation

Routes to
97/98S4
09/98
97/98S10
03/99
Propionic Acid
98/99S10
06/99
Phenol/Acetone/Cumene
05/06-4
03/07
Propylene
06/07-3
Phenol/Acetone/Cumene
01/02-2
10/02
Propylene, Ethylene
00/01-4
06/01
Phenol Manufacture, On-Purpose N2O

Production for
Propylene Oxide
02/03-8
11/03
98/99S14
10/99
Propylene Oxide
97/98-7
12/98
Phenol/MEK Co-Product Process
04/05S12
02/06
Phthalic Anhydride
06/07S6
08/07
Propylene Oxide Technology, Developments in
00/01S12
11/01
Plants as Plants
00/01S6
12/02
Propylene Refineries
03/04S7
01/05
Plastic Beer Bottles
00/01S1
04/02
Propylene, Routes to
97/98S3
02/00
Plasticizers, Trends in
05/06S8
03/07
PTA Production Technologies, Developments in
00/01S7
02/02
Polyacetal
01/02S12
10/02
PTMEG/Spandex
01/02S11
12/02
Polyaramids
06/07S9
Polybutylene Terephthalate
98/99S6
07/99
Pyromellitic Dianhydride/Trimellitic
Anhydride
99/00S8
07/00
Polycarbonate
05/06-7
07/06
Reducing Costs in PET Manufacture
04/05S7
07/05
Polycarbonates
01/02-5
07/02
Refineries, Hydrogen Production in
06/07S1
10/07
Polycarbonates
97/98-8
10/98
Refineries, Propylene
03/04S7
01/05
Polyether Polyols
03/04S5
10/04
Refinery of the Future as Shaped by

Environmental Issues
02/03S11
12/03
Polyethylene Terephthalate
02/03-6
09/03
Polyethylene Terephthalate
98/99-5
01/00
Refining Industry, Impact of Supply

Chain IT Applications on
04/05S4
04/06
Polylactic Acid/Lactic Acid, Biotech Route to
00/01S3
10/02
Receiving Terminals, LNG
05/06S12
01/07
Polymers, Super Absorbent (SAP)
03/04S3
04/04
Routes to Propylene
97/98S3
02/00
Polymer Compounding
99/00S2
04/00
Silicones
00/01S5
05/02
Polyolefin Elastomers
05/06S7
02/07
Sorbitol and Ascorbic Acid
97/98S11
03/99
Polyphenylene Oxide, Modified (MPPO)
02/03S3
03/03
Spandex/PTMEG
01/02S11
12/02
Polyphenylene Sulfide (PPS)
02/03S4
04/03
Specialty LDPE Copolymers
03/04S9
12/04
Polypropylene
06/07-2
11/07
Stationary Fuel Cells
02/03S6
11/03
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
B-4
Appendix B
Title
Report
Date
Steam Cracker Feedstocks, FischerTropsch Liquids as
01/02S9
12/02
Title
Report
Date
Titanium Dioxide
99/00S14
08/00
Toluene/Benzene
06/07-6
07/07
Styrene Butadiene Rubber/Butadiene

Rubber (SBR/BR)
02/03S1
12/03
Toluene/Benzene
02/03-5
04/03
Styrene/Ethylbenzene
03/04-8
11/04
Toluene/Benzene
98/99-6
05/99
Styrene/Ethylbenzene
99/00-6
08/00
Trends in Plasticizers
05/06S8
03/07
Styrene from Ethane and Benzene
05/06S3
11/06
Trimellitic Anhydride/Pyromellitic
Dianhydride
99/00S8
07/00
Sulfide, Polyphenylene (PPS)
02/03S4
04/03
Unconventional Heavy Oils
04/05S9
11/05
Super Absorbent Polymers (SAP)
03/04S3
04/04
Urea
06/07S3
10/07
Supply Chain IT Applications on the

Refining Industry, Impact of
04/05S4
04/06
Utilization Options, Petroleum Coke
97/98S10
03/99
Syngas Technology, Developments in
03/04S4
02/05
VCM, Acetylene-Based
05/06S4
02/07
TDI/MDI
98/99S8
09/99
VCM/EDC
03/04-6
12/04
Technology Management, Managing, in

the Chemical Industry
VCM/EDC
99/00-3
04/00
97/98S2
06/99
Vinyl Acetate
05/06-1
08/06
Terephthalic Acid
05/06-6
12/06
Vinyl Acetate
00/01-3
02/02
Terephthalic Acid
01/02-4
12/02
Vinyl Acetate Process, Fluidized Bed
98/99S3
02/00
Terephthalic Acid
97/98-5
02/99
Wood Composites
05/06S2
04/07
Terephthalic Acid, Medium Quality
03/04S6
10/04
Thermoplastic Copolyester and Copolyamide

Elastomers
Xylenes
05/06-8
08/06
02/03S9
10/03
Xylenes
01/02-7
05/02
Thermoplastic Elastomers, Developments in
98/99S12
11/99
Xylenes
97/98-3
07/98
Thermoplastic Nanocomposites
00/01S11
09/01
Thermoplastic Polyolefin (TPO) and

Vulcanizate (TPV) Elastomers
01/02S1
07/02
Thermoplastic Polyurethanes (TPUs)
02/03S7
05/03
* To be published
Benzene/Toluene
PERP 06/07-6
Q207_00101.0007.4106
B-5

135 PERP0607 6 (1) Benzene-Toluene Nexant

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135 PERP0607 6 (1) Benzene-Toluene Nexant

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PERP Report

44 South Broadway, White Plains, New York 10601, USA

Executive Summary .................................................................................................

PRODUCTION OF REFORMATE ..............................................................

Production of Aromatic via Non-Conventional Routes.....................

PRODUCTION FROM PYROLYSIS GASOLINE......................................

AROMATICS EXTRACTION .....................................................................

United States ......................................................................................

Current Commercial Technology...........................................................................

CATALYTIC REFORMING ........................................................................

Process Variables ...............................................................................

Reformer Types .................................................................................

Feed Preparation ................................................................................

Reformer Operation ...........................................................................

Yields and Utilities ............................................................................

PRODUCTION FROM PYROLYSIS GASOLINE......................................

AROMATICS EXTRACTION .....................................................................

BTX Extraction Processes .................................................................

Single Aromatics Extraction Processes .............................................

DEALKYLATION PROCESSES .................................................................

Toluene Disproportionation ...............................................................

PRODUCTION FROM COKE OVEN LIGHT OIL.....................................

PRODUCTION OF AROMATICS VIA NONCONVENTIONAL ROUTES

Asahi Chemicals Alpha Process .......................................................

BP/UOPs Cyclar Process ...............................................................

CP Chems Aromax Process............................................................

UOPs RZ Platforming ....................................................................

Summary of Non-conventional Routes..............................................

Developing Technologies .........................................................................................

METHANOL TO AROMATICS ..................................................................

METHANE TO BENZENE ..........................................................................

PATENTS OF INTEREST ............................................................................

Axens (IFP) and SK Corporation.......................................................

Chevron Phillips Chemical Company (CPChem)..............................

China Petroleum and Chemical Corporation (CPCC) & Sinopec .....

Fina Technology Inc. .........................................................................

Institut Francais DuPetrole (IFP) .......................................................

Economic Analysis ...................................................................................................

Pricing Basis ......................................................................................

Investment Basis ................................................................................

Cost of Production Basis....................................................................

Cost of Production of Reformate .......................................................

Cost of Production of Benzene ..........................................................

Market Analysis .......................................................................................................

UNITED STATES .........................................................................................

Supply, Demand and Trade................................................................

WESTERN EUROPE ....................................................................................

Supply, Demand and Trade................................................................

Supply, Demand and Trade................................................................

Elements of Nexant's ChemSystems Capital Cost Estimates................................

PERP Program Title Index .....................................................................................

1.1 Aromatics Distribution in Non-Conventional Routes................................................

1.2 Effect of Steam Cracker Feedstock on Aromatics Yield ...........................................

1.4 Cost of Production of Reformate ...............................................................................

1.5 Benzene Cost of Production.......................................................................................

1.6 Benzene to Toluene Price Delta.................................................................................

2.1 Semi-regenerative Reformer Process Flow Diagram ...............................................

2.2 Continuous Catalytic Reforming Process Flow Diagram.........................................

2.3 Cyclic Catalytic Reformer Process Flow Diagram....................................................

2.4 Naphtha Hydrotreater Process Flow Diagram ...........................................................

2.5 Effect of Steam Cracker Feedstock on Aromatics Yield ...........................................

2.7 Shell/UOP Sulfolane Process.....................................................................................

2.8 Aromatics Fractionation Section................................................................................