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ABSTRACT.............................................................................................................................vii
WORK PLAN............................................................................................................................ix
1.INTRODUCTION.................................................................................................................10
2.MARKET ANALYSIS...........................................................................................................11
3.PROCESSES DESCRIPTIONS............................................................................................13
3.2.1.Block diagram..............................................................................................................20
3.3.Enichem Process.............................................................................................................23
3.3.1.Block Diagram.............................................................................................................25
3.4.1.Block diagram..............................................................................................................28
3.4.3.Catalytc Distillation....................................................................................................40
3.4.4.Vacuum Distillation.....................................................................................................42
5.CONCLUSION......................................................................................................................51
6.REFERENCES......................................................................................................................53
7.APPENDIX............................................................................................................................55
Table.2. Overall process material balance after Dow - Kellog technology ........................................15
Table 4. Comparison of MCM-22 and zeolite beta catalysts for cumene synthesis..............................19
Table10. Selectivity and DIPB distribution at different temperature and propylene conversions.........29
Table 14. Cdtech Process Stream Summary Table In The Product Purification...................................46
Remember the interoffice letter on the request of cumene production search .Cumene is the
common name for isopropylbenzene (IPB), is an aromatic hydrocarbon. It is an important
chemical in the present industrial world and its uses are steadily increasing. It is an
intermediate for the production of of phenol and its co-product acetone and there is a demand
for the cumene with a purity of 98.5%.
The possibly formed triisopropylbenzene(TIPB) also react with benzene yielding cumene and
DIPB.
There is also the prospect for increased demand for some of the cuemene by-products such as
DIPB. The production of diphenols from DIPB is important for synthesis of resorcinol (from
m-DIPB) and hydroquinone(from DIPB).
Well the cumeen formation reaction can be occured in liquid and gas phases, but high
conversion values are obtained at gas phase reactions using catalyst. Early years virtually all
cumene was produced using either solid phosphoric acid(SPA). The SPA catalyst consist of a
complex mixture of orthosiliconphosphate, pyrosiliconphospate, and polyphosphoric acid
supported on kieselguhr. SPA process conditions include pressures that range from 3.0 to 4.1
Mpa, (29-40 bar) temparetures that range from 1800C to 2300C, benzene to propylene ratio
from 5 to 7, and weight hourly space velocities(WHSVs) between 1 and 2. To maintain the
desired level of activity, small amounts of water continuously fed inti the reactor. The water
continually liberates H3PO4 causing some downstream corrosion. Approximately 4-5 wt.% of
the product consist of di- and tri- isopropylbenzenes.
2
In the early 1980s, a process catalyzed by AlCl3 based on the same chemistry used in the
ethyl benzene process was introduced. This process can be at lower benzene to propylene
ratio than the SPA process because AlCl3 can transalkylate the polyalkylated benzenes back to
cumene. The process also operates at temperatures lower than the SPA process because the
more highly acidic anhydrous AlCl3 tends to produce significantly more undesired n-
propylbenzene at equivalent temperatures.
Since the mid-1990s cumene producers have begun to convert to the more environmentally
friendly and more efficent zeolite-based processes operating around 25 atm pressure. In
addition to the reduced maintanence cost, success most of the di- soprophylbenzene(DIPB)
by-product is converted to cumene in seperate transalkylation processes, this process produces
higher cumene yields than the previous conventional processes. The recycle DIPB combines
with a portion of the recycle benzene and is also chard downflow through the transalkylation
reactor and DIPB and unreacted benzene are converted to more cumene with the following
reaction;
The catalytic exothermic alylation reaction is held in either shell and tube reactors or packed
fixed bed reactors under temperature control. The propylene feed may either be pure or
contain a substantial amount of propane, which can come from a refinery fluid catalytic
cracking operation. however, the feed must be essentially free of ethylene and buthylenes to
avoid contamination of the product wwith ethyl and buthyl benzenes. Current zeolite catalyst
already operate at process temperatures that require minimal external heat addition. heat
integration and heat management will be of increasing concern at the lower benzene - to -
propylene ratios because the cumene synthesis reaction is so highly exothermic. Recycle
particularly in the alkylation reactor is likely to become increasingly important as a heat
management strategy. Since manufacturers prefer cheaper and consequently lower quality
feed stocks, how to limit build-up of by-products and feed impurities in these recycle loops is
important parameter.
3
The current zeolite-based processes allow for significant debottlenecking of SPA plants with
little additional capital. Although the zeolite processes have been able to produce cumene with
purities that cannot be approached by either the SPA or the AlCl3 process additional
researches have undoubtly been directed towards identifiying improved alkylation and
transalkylation catalysts. Alkylation catalysts that operate at benzene-to-propylene ratios of 3
or possibly even lower are desirable because they greatly reduce the need for costly seperation
capacity. Transalkylation and alkylation catalyst that produce even lower by-product
concentration at low benzene to propylene levels are likely to be preferable.
The Mobil-Badger cumene process commercialized in 1994, consist of a fixed bed alkylator, a
fixed bed transalkylator and the separation section. The high cumene purity around 99.97wt.%
at 99.7wt% yield is primarily attributable to the high monoalkylation selectiviy of the mcm-22
catalyst with low benzene- to - propylene ratios in the range of 2-4M. Ethyl benzene , prophyl
benzene and buthylbenzene levels are an order of magnitude lower than those obtained with
the SPA catalyst process. commercially the catalys has demonstrated cycle lengths in excess
of 2 years with an ultimate catalyst life in excess of 5 years.
The flow scheme of UOP's Q-Max process commercialized in 1996 is uses MgAPSO-31
catalyst that is very active and selective for cumene reportedly eliminated the formation of n-
propylbenzene.
Dow's 3-DDm cumene process uses a highly deluminated mordenite catalyst in a two stage
fixed bed alkylation and transalkylation process operating with a lower benzene-to-propylene
ratios than the conventional SPA process. The mordenite-based transalkylation stage of this
process has operated commercially since 1992. Dow's mordenite compenent corresponding to
a zeolite with a low acid side density which reduces the rates of hydrogen transfer and
propylene oligomerization, but high acid side strength which allows the reaction to be run at
lower temperatures (below 1700C). In transalkylation p-IPB are transalkylated with benzene at
a reactor temperature of approximately 1500 C. DIPB conversions of up to 65% with greater
than 90% selectivity toward cumene have been reported.
4
CDTech's CD cumene process has the effect of rising the benzene-to-propylene ratio in the
bulk phase surrounding the catalyst. Cumene yields in excess of 99% are claimed for this dual
operations alkylation is carried out isothermally at relativelly low temperatures and pressures
of approximately 5 bar in the overhead. The mild reaction conditions are reported to produce
cumene of very high purity with the maine impurities as ethylbenzene(220ppm) and n-
propylbenzene(350ppm). Cd Tech's patents refer to zeolites Y, omega and beta.
Current zeolite catalysts already operate at process temperatures that require minimal external
heat addition. Heat integration and heat management will be of increasing concern at the
lower benzene-to-propylene raitos because the cumene synthesis reaction is so highly
exothermic(Hf= -98 kj/mol). Recycle, particularly in the alkylation reactor is likely to
become increasingly important as management strategy. The key will be how to limit the
build-up of by-products and feed impurities in these recycle loops, particularly as
manufacturers seek cheaper and consequently lower quality feedstocks.
The last semester you carried out preliminary study to gain rough estimate on the suitability of
construction of cumene cumene producing plant in Turkey and decision on the capacity. You
mainly focused on the process with the fixed bed alkylation reactor using the zeolite-based
catalyst for the cumene production and carried out the design of some equipments for this
process. Now you are rudely say something about economical suitability of construction of
the plant. However, due to lack of time you skipped the "process analysis", "market analysis"
anad "detailed feasibilty search" for the selecting most suitable pathway. Your job in this
semester is the complete design of a cumene plant. You are responsible for selecting the
production route in addition to capacity selection and plant location. In the deciding all, you
must also concentrated on the product, raw materials and by-product specifications. In your
design stdy you must consider (i) environmental problems, waste disposal and suggested
precuations, (ii) safety and health concerns and (iii) process controllability and flexibility (iv)
energy recovery and preserving the sources. The main objective of your study is to carry out
complete economical analysis(manufacturing cost and profitability analysis).
5
For the final decision of the company about the construction, the report will be posted at the
end of the january, so please report me no later than 4 january, 2013. The success of a design
study needs good timing. In the time period allocated to cumene plant design you are
expected to subdevidethe work to several phases. You will be requesteed to submit writeen
reports on the production pathway selection. We will have a discussiion meeting on october
19, 2012 to decide on the process flow sheeting. You will submit an informal report
summarizing the result of production path way selection. In your report, you should give the
process description and the detailed flow sheet with the necessary summary tables. now you
are requested planning the work packages to complete this particular project till
september, 28, 2012. please be ready for the discussion of time-table (both for the first
report and the whole design study) on next lecture and also prepare the design basis.
6
ABSTRACT
This study focus on deciding the suitable production pathway and deciding the
flowsheet of the choosen Cumene production process. Today, the cumene is used almost
exclusively for manufacturing phenol and acetone. The global demand for phenol has been
steadily increasing over the last 10 years. In 2000, global phenol demand stood at 6,000,000
tons, before increasing to 8,000,000 tons in 2010. Those phenol production companies want
the purity of cumene at least %99,5. All cumene production processes checked for this market
analysis which helped to decide capacity and purity. The most using processes are Mobile-
Badger cumene process, Enichem cumene process, 3-DDM cumene process and CDCumene
process. In this case all investigations were searched for those four processes.
The Mobil Badger Process; high cumene purity is primarily attributable to the high
monoalkylation selectivity of the MCM-22 catalyst. But MCM-22 is the most expensive one
comparing to Other types of catalysts (Beta Zeolite, Zeolite Y, etc). MCM-22 ensures high
selectivity of cumene/DIPB however Additonally operational conditions includes high
pressures and temperatures and it causes extra risks.
The Enichem Process operates at a benzene to propylene ratio of 4:1. Cumene yields
and selectivities are both greater than 99%. This benzene to propylene ratio brings extra raw
material and extra utilities with those benefits. Enichems process uses a modified beta
catalyst. Beta catalyst is not much expensive but it causes more side reactions
(oligomerization, nPB like TIPB...). Besides propylene conversion is lower with beta catalyst.
7
The energy spent for benzene recycling can be reduced considerably by heat
integration, namely by double - effect distillation. In addition, the heat developed by reaction
can be advantageously recovered as medium - pressure steam.
Profitability guess of CD-Tech Cumene Process is done with using raw materials cost
as outcomes and product price as incomes. Profitability is 36 % of Cumene sales. As a
conclusion studies shows that CD Tech Cumene Process is the most suitable process.
8
WORK PLAN
WORK PACKAGE WORK TO BE DONE OUTPUT TIME
SECOND REPORT FIRST REPORT (19.10.2012)
Market Analysis Manufacturing cost and capital cost calculation Capacity selection 04.10.2012
Choosing the true production pathway Process selection Process name 11.10.2012
Design Basis Process Flow Diagram
Process Flow Sheeting Operational conditions 16.10.2012
Utility Equipment size and operational safety risks Equipment summary table
Material and energy balance calculation Determined phase and compositions Stream summary table
Product, raw materials and by-product Preparing of specification sheet according to ending Raw material versus product cost 18.10.2012
Utility Cost
specifications calculation data
Plant Layout Equipment distances were determined Land Requirement 08.11.2012
Specification Sheets of
Detailed Equipment design Survey of the Plant Layout Standards equipments 26.11.2012
FINAL REPORT
9
1.INTRODUCTION
Cumene process is an industrial process for developing phenol and acetone which are
important for the chemical industry from benzene and propylene. In this report, it has been
done process analysis, market analysis and detailed feasibility report for cumene process.
There are different processes about production of cumene like Mobil-Badger, 3-DDM Dow,
EniChem, CD-Tech. All of them these process have the same reactions which are reacts in
alkylation reactor and transalkylation reactor. However operating conditions and flow
diagrams are different. This report including comparison of these processes about capacities,
product purities, operational conditions, as a result of material balance mass flow rate of raw
materials, energy recovery, total annulized cost, risk factors and also catalyst. The alkylation
of benzene with propylene to produce cumene, a starting material for the production of
acetone and phenol ,is very important in hydrocarbon processes. Traditionally, some mineral
acids including AlCl3 and others are employed, which present good catalytic performance ,
while raising serious environmental problems such as corrosion and waste disposal. In order
to overcome some drawbacks of the traditional mineral acid catalysts, technologies such as
the Mobil-Badger process using MCM-22,the CD-Tech and EniChem process using Y and
Beta zeolites and the 3-DDM Dow process using Mordenite have made great progress in
recent years.
This report presents as a result of comparison these four processes cause of highest
Energy recovery, ultra high purity cumene using a proprietary zeolite catalyst that is non-
corrosive and environmentally, and also Alkylation reactor has operational benefit like
catalytic distillation reactor that involves a combination of catalysis and distillation in a single
column decided to produce cumene with CD-Tech Cumene process. CD-Tech Cumene
process is seen as most economical processes for producing cumene, but there are some
limitations for using CD-Tech Cumene Process. Catalyst price, catalyst life and process
control of Alkylation reactor is most important factor in catalytic distillation reactor. Because
deactivation of catalyst is higher in CDCumene, there are two works which are distillation and
reaction and it effects to heat of reaction.
10
2.MARKET ANALYSIS
Worldwide cumene market analyzed to learn customers of cumene and decide capacity
and product properties. In market cumene is used with at least purity %99:
1. As feed back for the production of Phenol and its co-product acetone
2. The cumene oxidation process for phenol synthesis has been growing in popularity since
the 1960s and is prominent today. The first step of this process is the formation of cumene
hydroperoxide. The hydroperoxide is then selectively cleaved to Phenol and acetone.
3. Phenol in its various formaldehyde resins to bond construction materials like plywood and
composition board (40% of the phenol produced) for the bisphenol A employed in making
epoxy resins and polycarbonate (30%) and for caprolactum, the starting material for nylon-6
(20%). Minor amounts are used for alkylphenols and pharmacuticals.
4. The largest use for acetone is in solvents although increasing amounts are used to make
bisphenol A and methylacrylate.
6. Cumene in minor amounts is used as a thinner for paints, enamels and lacquers and to
produce acetophenone, the chemical intermediate dicumylperoxide and diiso propyl benzene.
Essentially, all world cumene is consumed for the production of phenol and acetone.
As a result, demand for cumene is strongly tied to the phenol market. Trade in cumene
accounts for only 4% of world production. The largest exporters of cumene are the United
States (to Germany) and Japan (to the Republic of Korea). Taiwan also imports large volumes
of cumene for phenol production.
11
restricted phenol exports to Europe and higher-demand regions such as Asia and South
America.
Increased demand for bisphenol A and phenolic resins will result in strong demand for
phenol, particularly in Asia (excluding Japan). As a result, consumption of cumene for phenol
is forecast to grow at approximately 8% per year in the region. China alone is expected to add
over a million metric tons of cumene capacity during 20112015 (with most capacity coming
onstream in 2013) to supply its phenol/acetone plants that are slated to come onstream during
that period.
CAPACITY(ton/year) COMPANY
CDTech Process [2] 270,000 Formosa Chemicals and Fibre Corporation Taiwan
Dow Process [1] 144,000 USA Noveon
Mobil Badger Process [3] 200,000 LG Chemical LTD
Enichem Process[7] 130,000 Polimeri Europa
12
3.PROCESSES DESCRIPTIONS
At this Process; benzene and propylene are reacted in the alkylation reactor in a large
excess of benzene (more than 5:1 molar ratio) at sufficiently high pressure that ensures only
one liquid phase at the reaction temperature, usually between 160 and 240 C in the presence
of (3DDM) zeolite catalyst to produce cumene. Some DIPB are also formed; very little tri-
isopropylbenzes and by-products are formed due to the shape- selectivity of the catalyst. The
DIPB's are recovered in the distillation section and recycled to the reaction section for
transalkylation with benzene to form additional cumene.
The reactor section effluent, consisting of unreacted benzene, cumene, and DIPB's is
fractionated in four distillation columns operating in series. Light components, present in the
propylene feed, are removed; unreacted benzene is recovered and recycled; pure cumene is
separated as a product, and finally the DIPB's are recovered and recycled to the transalkylator.
A small heavies purge is taken to fuel. [10]
13
3.1.1. 3-DDM Block diagram
R 1: alkykation, R 2: transalkylation,
The following reactor performance in recycle is the aim: over 99.9% per/pass
propylene conversion over 88% cumene selectivity, adiabatic temperature rise below 70 C,
but a maximum catalyst temperature of 250 C. The inlet pressure should be sufficiently high
to ensure only one liquid phase. Thermodynamic calculations at 35 bar indicate bubble
temperatures of 198 and 213 C for propylene/ benzene ratios of 1/4 and 1/7, respectively. At
the reactor outlet the reaction mixture has a temperature of 230 C and a pressure of 34 bar,
the molar composition being 86.6% benzene, 12.6% cumene and 0.8% DIPB. Other
components are lights, in this case the propane entered with the feed, and heavies, lumped as
tri-propylbenzene.
14
The first separation (C-1) is the depropanizer column. A pressure of 12 bar is
convenient for (C-1) because it gives a bottoms temperature below 200 C and a condenser
temperature of 34C. The pressure is selected so as to ensure the condensation of the top
product by air cooling. The following configuration ensures a high recovery of propane with
less than 100 ppm benzene: 16 theoretical stages with feed on 5 and a temperature of 150 C,
and a reflux of 4300 kg/h.
Next, follows the separation of the ternary mixture benzene/IPB/DIPB. The recovery
of benzene takes place in the column (C-2). The recycle column(C-2) has high recovery of
benzene in top is desirable (over 99.9%) but small amounts of cumene are tolerated.
If follows the separation cumene/DIPB in the column (C-3), this time operated under
vacuum and constrained by the reboiler temperature. The column (C-3) for cumene
distillation operates under vacuum to avoid an excessive bottom temperature. A number of 30
stages and a reflux ratio of 1.2 are sufficient to ensure good - purity cumene with less than
100 ppm benzene.
DIPB recovered from heavies in the vacuum distillation column (C-4) is sent to the
transalkylation, together with an appropriate amount of recycled benzene.
LPG Variable
15
known for some time but not commercialised because of two disadvantages that the mordenite
zeolite overcomes: the tendency to form hard-to-remove impurities such as ethylbenzene and
butylbenzene via disproportionation reactions, and the tendency of the catalyst to deactivate
rapidly.
A further advantage of the zeolite system over the acid catalysts is the ability to
transalkylate the byproduct diisopropylbenzene (DIPB) back into cumene more easily.
The optimization variable is the flow rate of the recycled benzene. As a constraint, the
outlet reactor temperature is limited at 250C. The alkylation reactions are exothermic so
temperature have to control above 250 C continuosly, it occurs extra cost. [11]
16
3.1.3. 3-DDM DOW PROCESS EQUIPMENT SUMMARY TABLE
Table 3. DDM Dow Process Equipment Summary Table
Operational Operation
Name Code Function temperature al pressure Type Risk Precaution
(0C) (atm)
*Choosing true zeolit cataliyst
Alkylation reactor To produce cumene Fixed bed *nonregenerable and of posing catalyst (mordanite) instead of solid
R-1 from propylene and 160-250 25-35 reactor *hard-to-remove impurities cataliyst to large excess of benzene
benzene (more than 5 : 1 molar ratio)
Transalkylation To produce cumene
reactor R-2 from DIPB and 150 15 Fixed bed - -
benzene reactor
To seperate propan Distillation
Depropanizer C-1 from the feed T:200 12 column - -
B: 34
To seperate
benzene from - 1,2 Distillation Higher load to reboiler or condenser Charge drum is placed after the
Benzene column C-2 cumene and column catalytic reactor and condenser
DIPBTo purificate
freshbenzene feed
Cumene column To seperate cumene Distillation
C-3 from DIPB - 1,2 column *excessive bottom temperature. *vacuum distillation column
17
3.2.Mobil Badger Process
The production of cumene by alkylation of benzene with propylene has, in the past,
been carried out commercially over two catalyst systems: solid phosphoric acid (SPA) or
aluminum chloride (AlCl3). Both SPA and AlCl3 present severe environmental problems; SPA
catalyst is wet, corrosive, and might contain hydrocarbons, while waste AlCl 3 is a corrosive
liquor that also might contain hydrocarbons. Both are classified as hazardous wastes. The
Mobil/Badger Cumene process uses a new zeolite catalyst developed by Mobil (MCM-22),
tested by Badger, and first commercialized in 1996.
The MobilBadger process produces very pure cumene, 99.97 wt.% at 99.7 wt.%
yield. The high cumene purity is primarily attributable to the high monoalkylation selectivity
of the MCM-22 catalyst. This catalyst is unique in its ability to
minimize propyleneoligomerization while still exhibiting very high activity for
benzene alkylation. Commercially, the catalyst has demonstrated cycle lengths in excess of 2
years. Ultimate catalyst life is in excess of 5 years.
18
The selectivity of the MCM-22 catalyst reduces the size requirements for the
fractionation section, and also reduces the coke forming reactions, which tend to shorten the
cycle length. A key result of the catalysts low oligomerization selectivity is the ability to
design for low benzene-to-propylene ratios in the range of 24M.Table 4 compares the
selectivities and activities of MCM-22 and zeolite beta zeolites in single pass alkylation of
benzene with propylene. The zeolite beta catalyst produces significantly more propylene
oligomer, but has a slightly lower selectivity for PIPB.
Table 4. Comparison of MCM-22 and zeolite beta catalysts for cumene synthesis
Although the conventional catalysts are effective for alkylation, they suffer some
important disadvantages. Firstly, they are corrosive which implies that the reactor section of
the process must be constructed of special materials. Secondly the use of such catalyst results
in wate disposal problems. Although the Mobil-Badger process has the advantages mentioned
above, it has suffered the disadvantage of rather rapid catalyst deactivation(weeks) due to
coke deposition. This problem has been overcome in later version of the process.Recently a
new liquid phase alkylation process based on a very selective zeolit called MCM-22 was
developed .The catalyst is reported to be highly active for alkylation but inactive for
oligomerization, permitting operation at low benzene:propyene ratios, while achieving the
highest yield and product purity. However experience with this process is limited and
information rather scarce. [12]
19
3.2.1.Block diagram
R 1: alkykation, R 2: transalkylation,
C 1: propane column, C 2: benzene recycle column,
C 3: cumene column, C 4: polyispropylbenzenes column.
The process is based on ExxonMobils proprietary MCM22 catalyst and was jointly de
veloped by the ExxonMobil and the Washington Group. The process includes a xed bed
alkylation reactor, a xed bed transalkylation reactor, anda distillation section. Propylene and
benzene are premixed and fed to the alkyla-tion reactor where propylene is completely reacted
in the liquid phase. The alkylator efuent ows to the depropanizer where nonreactive
propane is recoveredas LPG. The depropanizer bottoms ows to the recycle column where
excess benzene is recovered and recycled to the reactors. The crude cumene from the benzene
column bottoms ows to the cumene column where high purity cumene product is recovered
overhead. The cumene column bottoms is sent to the PIPB column where PIPB is recovered
and sent to the transalkylator. In the transalkylator PIPB reacts with benzene to form
additional cumene. The transalkylation effulent joins the depropanizer bottoms and flows to
the recycle colum.
20
The plant consists of a fixed bed alkylation reactor, fixed bed transalkylation reactor
and a distillation section. Liquid propylene and fresh and recycle benzene are premixed before
being fed to the alkylation reactor where the propylene is completely reacted. Separately,
recycled poly-isopropyl-benzene (PIPB) is pre-mixed with benzene and fed to the
transalkylation reactor where the PIPB reacts with the benzene to form additional cumene.
[13]
LPG Variable
21
3.2.3.MOBIL BADGER PROCESS EQUIPMENT SUMMARY TABLE
Table 6. Mobil Badger Process Equipment Summary Table
Operational Operational
0
Name Code Function temperature( C) pressure (atm) Type Risk Precaution
*Low B/P ratio in reactor *Increase recycle Benzene flow
To produce cumene Fixed bed feed to reactor
Alkylation reactor R-1 from propylene and 200 35 reactor *catalyst deactivation isnt *choosing very selective and
benzene well so coke deposition active cataliyst
To produce cumene *side product is produced
Transalkylation R-2 from DIPB and - - Fixed bed in Transalkylator because *Reduce temp in
reactor benzene reactor of high temperature Transalkylator.
22
3.3.Enichem Process
The Enichem cumene process was announced in 1995 and then commercialized at
Enichems Porto Torres, Sardinia plant in March 1996. First industrial application dates back
to March 1996 when, at Porto Torres site (Sardinia, Italy), a first industrial test-run based on
an initial cumene capacity of 70 kt/y was done. In 1997 the new zeolite based technology was
extended to 130 kt/y cumene capacity. In 2000, following four years of continuous trouble-
free test-run operation, the fully proven technology was applied to the revamp of the existing
cumene plant for a total of 400 kt/y cumene capacity at Syndial (a subsidiary of Eni SpA)
Porto Torres site.
Polimeri Europa, a wholly owned subsidiary of the Italian oil company Eni, operates
in the business of olefins and aromatics, basic intermediate products, chlorine derivatives,
polyethylene, polystyrene and elastomers.[14]
23
Table 7. Enichem process Features and Benefits [15]
3.3.1.Block Diagram
24
Figure 5. Enichem Process of Block Diagram
Cumene is made by the alkylation of benzene with propylene, which yields a mixture
of alkylated and polyalkylated benzenes. Excess benzene is used so propylene reacts
completely. Propylene is injected before each catalyst bed to improve catalyst selectivity and
enhance its activity and stability. The mixture of alkylated and polyalkylated benzenes is sent
to a distillation train that consists of a benzene column, cumene column and poly-
isopropylbenzene (PIPB) column. The polyalkylated benzenes recovered in the PIPB column
are transalkylated with benzene to produce additional cumene for maximum cumene yield.
The alkylation and transalkylation effluents are fed to the benzene column, where the excess
benzene is taken as the overhead product for recycle to the reactors.
The benzene column bottoms goes to the cumene column, where product cumene
(isopropylbenzene) is taken as the overhead product. The cumene column bottoms is sent to
the PIPB column, where overhead PIPB is recycled back to the transalkylation reactor. The
bottoms of the PIPB column is composed of a small amount of high boilers that can be used
as fuel. Propane and other non-condensables contained in the propylene feed pass through the
process unreacted and are recovered as propane product or as fuel. The cumene unit has
considerable flexibility to meet a variety of local site conditions (i.e., utilities) in an efficient
manner.
25
The process operates at a benzene to propylene ratio of 1:1. Cumene yields and
selectivities are both greater than 99%. Cumene purity was founded 99.95 wt.%.
Enichems process uses a modified beta catalyst(PBE-1 zeolite catalyst) and The process is
reported to be readily retrofit into existing cumene units. Few additional details about
this process have been released.
LPG Variable
The CD Techs Cumene process 270,000 Ton /per year Cumene capacity.
The CD Cumene process, marketed by ABB, produces ultra high purity cumene using
a proprietary zeolite Y catalyst that is non-corrosive and environmentally. The CDCumene
technology is one of a family of process technologies developed and commercialized by
Catalytic Distillation Technologies.
26
The performance indices of the conceptual design based on literature data are in agreement
with the best technologies.
The alkylation reaction is promoted by acid - type catalysts. The synthesis can be
performed in gas or liquid phase. Before 1990 gas phase alkylation processes dominated,
but today liquid - phase processes with zeolite catalysts prevail. Recent developments make
use of reactive distillation.
Propylene is dissolved in a large excess of benzene (more than 5:1 molar ratio) at suffi
ciently high pressure that ensures only one liquid phase at the reaction temperature, usually
between 160 and 240 C.
3.4.1.Block diagram
27
Figure 6. CDTech Process of Block Diagram
Types of zeolites are the most applied like; beta, Y, MCM - 22 and mordenite. These
catalysts are characterized by large pore opening necessary for achieving high selectivity.
Since industrial catalysts are employed as pellets, the mass - and heat transfer effects
can play an important role. The internal diffusion is often the critical step controlling the
overall process rate.
Table 8 presents some global yield data, including transalkylation. Zeolite beta is often
mentioned among the best suited for fixed - bed operation, with selectivity in cumene around
90%.
Table 9. Selectivity obtained with different zeolite catalysts in cumene synthesis [8]
28
Other studies prefer MCM - 22 because of better stability against deactivation. As
Table 8 shows, the selectivities of zeolite - beta and MCM - 22 are similar in the range of
temperature of 180220 C and benzene/propylene ratios of 3.5 7.2. Modified Y - type
zeolites were found capable of selectivity over 97% at lower temperature, and are therefore
recommended for catalytic distillation. Recent patents show that the new superactive zeolite
catalysts are suitable for both alkylation and transalkylation reactions.[8]
Table 10. Selectivity and DIPB distribution at different temperature and propylene
conversions [8]
Process Features
1. Catalytic distillation structures provide efficient vapor liquid contacting, and combine
reaction and fractionation in a single unit operation
2. Proprietary zeolite catalyst
3. Controlled low and constant alkylation temperature.
4. Simple, low pressure operation
5. Improved heat integration and heat recovery
6. Adaptable to processing chemical and refinery grade propylene feed-stocks [16]
Advantages
29
2. Meets evolving environmental requirements;
continuous operation
transalkylation capability maximizes yield
Eliminates corrosive acidic effluents and associated disposal problems
lower maintenance costs
6. Improves economics;
plants can be custom
designed to process specific feedstocks, including the less expensive feedstocks [16]
DESIGN BASIS
Catalyst, Zeolite-Y
30
Pressure, bar 14
Conversion, % :
Propylene %100
Benzene % 55
Catalyst Zeolite-Y
Temperature, C 140-150
Seperations Units:
Benzene column:
Cumene column:
31
Operational Conditions : Tin : 124 0C Tbottom: 172 0C Ttop: 1100C
32
Basis: 110 kmole/ h Cumene is producing in Alkylation and Transalkylation reactors.
Degrees of Freedom
-1 Equations (m1+m2=m3)
Degrees of Freedom = +1 so problem is not soluble. Calculations are made for alkylation and
transalkylation reactors with Cumene production rate basis.
SYSTEM=ALKYLATION REACTOR
In alkylation reactor there are two reactions. One is main reaction and other is side reaction.
We know that selectivity of cumene per DIPB 8:1. So when x mole DIPB produced,
8*x cumene produced in main reaction.
SYSTEM=TRANSALKYLATION REACTOR
33
In transalkylation reactor, cumene produce with DIPB which is coming from alkylation
reactor.
For x mole DIBP coming from alkylation reactor, x mole Cumene will be produced.
34
Propylene required for Cumene is 9*x.
Propylene required for DIPB is x.
Conversion of Propylene is %100 in Alkylation Reactor.
Total propylene required= 10*x=10*11=110 kmol/h
Benzene required for Cumene is equal to produced Cumene in main reaction.
Required Benzene = 110 kmol/h
%60 excess benzene so total benzene: 110/0,6 = 180 kmol/h
SYSTEM=BENZENE COLUMN
35
Benzene :81,37 kmole / h
Cumene :88 kmole / h
DIPB :11 kmole / h
Top:
Bottom:
SYSTEM=CUMENE COLUMN
36
Outlet of the Cumene Column:
Top:
Bottom:
The bottom stream of the cumene column which includes DIPB, is going to Transalkylation
reactor.
Transalkylation Reactor
Outlet of the Cumene column is going to Transalkylation Reactor. Molar ratio of Benzene to
DIPB to send Transalkylation Reactor is about 5,2.
Outlet of the Benzene columns top feed merge with fresh benzene then split for going to
Alkylation reactor and Transalkylation reactor.
37
Divider sending %39 of recyled benzene to transalkylation reactor which is 115,86 kmole/h
Benzene.
So the other part of recyled benzene, %61 is being sended to alkylation reactor.
296*0,61=180,4 kmole / h
Inputs:
Outputs:
38
Table 11. Overall Material Balance
MT/MT
Cumene Product
Feeds
Propylene (100% basis) 0.352
Benzene (100% basis) 0.652
Products
Cumene 1.00
Heavy residue 0.004
Propane *
Purity 99.97 wt %
Specific gravity 20 / 20 C 0.864
Distillation range
Including 152.5 C < 1 C
Bromine index <2
3.4.3.Catalytc Distillation
About CDTECH cumene process Alkylation reactor has operational benefit like
catalytic distillation reactor that involves a combination of catalysis and distillation in a
single column.
39
Figure 7. Catalytic Distillation Reactor
The mixture after reaction is further treated in the columns (C - 1) for separating the excess of
benzene and in (C - 2) for separating the cumene and DIPB. Both columns operate under
vacuum at about 0.3 bar. The top temperature is at 198 C while the bottom temperature
climbs to 242 C.
40
concentration of propylene in the reactor, because unreacted benzene is seperated from the
liquid product mixture in the stripper section and returned to the reactor section [17].
The heat of the highly exotrhermic alkylation reaction is now used directly in the
distillation of reactants and products: benzene evaporates from the liquid mixture. The vapor
is then condensed in the overhead condenser and returned to the reactor.It is claimed that this
process requires only half the amount of enrgy compared to other process, while the
investment costs are reduced by 25% . Furthermore, due to the internal recirculation of
excess benzene, there is no need to recycle large amounts of benzene, reducing the operating
costs of the process. The major advantages of the zeolite-based vapor-phase are the absence of
aqueous waste streams and the fact thar no corrosive substances are used, so that high alloy
materials and brick linings are not required. Furthermore, equipment for catalyst recovery and
waste treatment is eliminated. On the other hand, due to the larger benzene/propylene ratio,
the costs for benzene recovery and recirculation are higher [17].
Catalytic distillation column for cumene synthesis. Here, the product IPB is much
heavier than the reactants, benzene and propylene, making possible easy separation in
bottoms. On the other hand, propylene is much lighter than benzene, which should be used in
large excess for better selectivity. It is desirable that the propylene reacts completely to avoid
a new separation problem. Therefore, the column should keep only two sections, reaction and
stripping. Benzene and propylene are fed at the top and at the bottom of the reaction section
creating a countercurrent fl ow of reactants. The reaction takes place in the liquid phase in the
presence of a zeolite catalyst. This time, the minimum refl ux rate is dictated not by the
separation but by the amount of benzene that must be condensed to remove the heat of
reaction. From the heat recovery viewpoint the pressure should be selected to get the highest
possible temperature in top.
If, from the heat - saving viewpoint the advantage of reactive distillation over fixed -
bed reactor technology seems obvious, from reaction - engineering viewpoint there are some
physical constraints that may be seen as disadvantages:
Firstly, when a reactant is highly volatile the driving force for reaction in the liquid
phase is diminished by the vapor liquid equilibrium. This is the case with the propylene.
Secondly, the flow of reactants and products in the countercurrent favors the formation
of secondary polyalkylation species. This negative effect on selectivity is amplified by the fact
41
that in a RD setup the amount of benzene is limited by the optimum reflux rate needed for
heat integration.
3.4.4.Vacuum Distillation
Parts of crude oil boiling at atmospheric pressure over 360 C distillation of products in this
section is subject to degradation due to high temperature causes. In order to prevent this, the
person in question is subjected to distillation under vacuum. As mentioned previously,
vacuum, reduced pressure is reduced to atmospheric pressure. In addition, the boiling point
substances is reduced on the pressure drops. Taking advantage of these factors atmospheric
column looking at extremely high temperatures under vacuum decomposition of heavy
decomposed materials.
One tool to reduce the number of stages needed is to utilize vacuum distillation.
Vacuum distillation increases the relative volatility of the key components in many
applications. Lower pressure increase relative volatilities in most system.
Vacuum distillation is the reduced temperature requirement at lower pressures For
many systems the products degrade or polymerize at elevated temperature
Increasing capacity, purity and yield
Fractional distillation under vacuum leads to easier separation of components of
a mixture.
Change in position of the azeotropic point at reduced pressure. This enables separation
under reduced pressure / vacuum of hard to separate materials
For high boiling products when distillation at atmospheric pressure causes difficulties
with respect to energy losses and availability of construction material
Distillations operated under vacuum, yield even lower.
The most important parameter is height of sluice about tray design. Increases yield of
tray by increases height of sluice but in this way pressure drop and liquid entrainment
occurs so this mean extra cost.
Benzene and Cumene Distillation columns (at CD-Tech Cumene Process ) operational
pressure is 0,3 bar and it is very low pressure to provide this pressure, columns has
operational benefits like vacuuming.
42
3.4.3.CD TECH PROCESS EQUIPMENT SUMMARY TABLE
Table 13. CDTech Process Equipment Summary Table
Operational Operational
0
Name Code Function temperature( C) pressure(atm) Type Risk Precaution
To produce cumene from *Deactivitaion
Catalytic propylene and benzene Catalytic of catalyst *Long-lived
distillation reactor RD-1 To seperate unreacted 200 14 distillation reactor * benzene is Catalyst
components from product limited by the * heat
optimum reflux integration
rate
43
3.4.5.Process Flow Sheet
44
STREAM SUMMARY TABLE IN THE PRODUCT PURIFICATION
Table 14. Cdtech Process Stream Summary Table In The Product Purification
Steam Code Temperature (C) Pressure (atm) Phase Vapor Fraction Components Flow rate (kg/h)
ST 1 200 14 Vapor 1 Propylene 4629
ST 2 25 1.5 Liquid 0 Benzene 14534
ST 3 200 14 Vapor 1 Benzene 14089
ST 4 242 14.5 Vapor 1 Benzene,cumene 18718
45
CD-TECH ENICHEM MOBIL-BADGER 3-DDM DOW
Capacity(ton/year) 270,000 130,000 200,000 144,000
Cumene purity(%) 99.97 99 99.7 98.5
Firstly Aluminium Chloride Firstly Aluminium Chloride
Catalyst Zeolit Y Zeolit Beta Now MCM-22 Now Mordenite
Catalyst life 6 5
Transalkylation Reactor Alkylation Reactor
46
4.1.Comparison of Catalysts
According to the published literature, all the zeolite-based processes commercially
offered have comparable functioning (cumene yield above 99.5%, product purity as high as
99.95%).
While 3-DDM Dow cumene process using Mordenite zeolite catalysts have been
claimed to be useful in the propylation of benzene to cumene, no mordenite zeolit based
propylation process is in the commercial practice today. This is because of certain limitation
of the above mention Zeolites in the process for the propylation of benzene to cumene. These
limitations are ;
(1)fast deactivation of the above mentioned Zeolites in the process tor propylation due to coke
formation leading to low cycle lengths of less than six months,
(2)low tolerence of Zeolites like Faujasites and Mordenites to even very low levels of water
usually present in the propylene feedstock and
MOBIL Apart from the obvious disadvantages of corrosion, the need to remove the
catalyst from yhe product and the production of polluting waste the benzene feed must be
virtually free of water in order to prevent destruction of the catalyst complex, which requires
an additional drying step. Furthermore the catalyst complex needs to be prepared seperately.
Both steps add to investment and operation cost [18].
In the CD CUMENE process, CD Tech catalyst bales are filled with an acidic, wide-
pore zeolite catalyst, for example, zeoliteY. The bales are stacked in the middle of a
distillation column. The propene concentration in the reaction zone is held fairly low to slow
down a side reaction in which diisopropylbenzene (DIPB) and triisopropylbenzene (TIPB) are
formed. The cumene product with impurities of ethylbenzene and n-propylbenzene, is taken
from the bottom of the column.
47
The advantages of CD technology in cumene synthesis are lower formation of oligo-
isopropylbenzenes (DIPB and TIPB), higher catalyst lifetime, and a higher conversion of
benzene [20].
Since the incoming reaction gases in most cases must be heated to the ignition
temperature of the catalytic reaction, adiabatic reaction control is often coupled with heat
exchange between the incoming and exiting reaction gas resulting in so-called auto thermal
reaction control. T. Reactions with a large heat of reaction as well as reactions that are
extremely temperature-sensitive are carried out in reactors in which indirect heat exchange
occurs via a circulating heat transfer medium integrated in the fixed bed.
3) For repeated heating and cooling of the circulating matenal to the reaction temperature
and the temperature of the separating device
4) Due to loss of product resulting from the need to remove part of the circulatmg
material to limit the amount of mert substances or byproducts in the recycle stream (bleed
stream).
Some of the reasons that catalytic distillation has proven to be commercially attractive are
[22],
Higher conversion
48
Capital cost are reduced by combining catalytic reaction with distillation within the
same piece of equipment, often reducing the need for a seperate reactor.
For some equilibrium limited reactions, using catalytic distillation enables conversions
well in excess of fixed bed equilibrium limitations. Cd tech process conversions in excess of
99.9% are achievable with fixed bed reaction step an done distillation step compared to 96-
97% for fixed bed process using two reactors [22].
49
5.CONCLUSION
Variety of features were examined in the end of comprasion of these four different
cumene production processes (CD-Tech, Mobil-Badger, EniChem, 3-DDM Dow) to select the
true production pathway. Market analysis was done for products properties and processes
capacity was searched to capacity selection. According to market analysis and industrial
applications, product purity is at least %99 and 110 kmol/h Cumene capacity is logical.
Processes are using same raw materials for producing Cumene with Alkylation and
Transalkylation reactions in different reactor types with different operating conditions and
catalysts. All processes are manufacturing of cumene by the alkylation of benzene by making
use of zeolite catalysts. In literature survey, with H-Zeolite-Y catalyst of CD-Tech, indicate a
relatively low yield when compared to the -zeolite of Enichem, around half of the predicted
maximum yield. MCM-22 zeolite of Mobile-Badger include a low benzene/propylene ratio,
clean reactions in simple and small reactors, simple distillation, nearly stoichiometrical yield,
maximum feedstock exibility, and minimal environmental impact. Although the Mobil-
Badger process has the advantages mentioned above, it has suffered the disadvantage of rather
rapid catalyst deactivation(weeks) due to coke deposition.
Although very high yields are seen with the two most acidic -zeolites whereas higher
temperatures are required to obtain a good cumene yield with the -zeolite of EniChem;
catalytic distillation becomes economically interesting only if a suitable catalyst is available
like Zeolit-Y of CD-Tech.
CD-Tech process has catalytic distillation reactor where is benzene alkylation and
seperating unreacted propylene to reactor, it has benzene reflux. In addition, there is no need
to depropanizer column and DIPB column. Benzene alkylation is exothermic reaction, it
generates heat and is using for distillation in catalytic distillation to energy recovery. In other
processes, generated heat is transferring to seperating columns with utility. CD-Tech process
is 2 times cheaper about energy requirment and 2.4 times cheaper about capital invesment
with these differences, values shown in Table-16 Consequently, CD-Tech process has the
advantages about operating cost and equipment cost.
50
Table 16. Manufacturing Costs [23]
Profitability guess of CD-Tech Cumene Process is done with using raw materials cost as
outcomes and product price as incomes. Profitability is 36 % of Cumene sales.
As a result of material balances amount of raw materials and market analysis were proved that
CD-Tech was a sustainable process. So we were decided that continue this project with CD-
Tech cumene process.
6.REFERENCES
51
[1]K Weissermel,H.-J. Arpe Industrial Organic Chemistry Fourth,Completely,Revised Edition
[2] http//www.cdtech.com/indexset.html
[3]http://www.businesswire.com/news/home/20110921005269/en/Badger-Licensing-Provide-
Cumene-BPA-Licenses-LG
[4]http://www.sbioinformatics.com/design_thesis/Cumene/Cumene_Properties&uses.pdf
[5]http://www.dequi.eel.usp.br/~barcza/Fenol%20UOP.pdf
[6]http://www.primaryinfo.com/projects/cumene.htm
[7]http://www.icis.com/v2/companies/9146114/polimeri-europa.html)
[10]http:// ip.com/IPCOM/000217241
[11]http://www.icis.com/Articles/1994/04/04/35102/kelloggdow-detail-new-route-to-
cumene.html
[12]Chemical process technology Jacob A.Moulijn Michiel Makeee Annelies Van Diepen
page/279-281
[13]http://www.icis.com/Articles/1997/12/08/51748/mobilbadger-make-the-most-of-catayst-
use.html
[14]http://www.icis.com/v2/companies/9146114/polimeri-europa.html
[15]www.Lummus.CBI.com
[17]Chemical process technology Jacob A. Moulijn Michiel Makeee Annelies Van Diepen
[18]http://www.surechem.org/index.php?
Action=document&docId=267794&db=EPA&tab=desc&lang=&db_query=0%3A%3A0%3A
%3A0%3A&markupType=all
52
[19]Energy Efficient Catalytic Reaction and Production of Cumene, Russell L.Jarek,Steven
M. Thornberg, Stacia Barrow, Daniel E. Trudell, and Tina M.Neroff.
[20](Ullmans Encycloepedia of Chemical Technology , Wiley - VCH, Weinheim, Germany ,
2003)
[21]http://www.cbi.com/images/uploads/tech_sheets/MTBE_Sheet_R-3.pdf
7.APPENDIX
LPG EXPLOSION LIMIT
53
FIRE AND EXPLOSION HAZARD DATA
A critical issue in reactor design is exploiting at best the high exothermicity of the
alkylation reaction. Note that the thermal effect corresponds roughly to the evaporation of
3.67 moles benzene. A measure of exothermicity is the adiabatic temperature rise illustrated in
Figure 8 as a function of the molar ratio benzene/propylene with the inlet temperature as a
parameter.
Higher dilution with benzene can make it fall signifi cantly, from 120 C to less than
60 C; the inlet temperature plays a minor role. On the other hand, higher benzene/propylene
ratio gives better selectivity, but increases the cost of separations. As a result, the ratio
54
benzene/propylene is a key optimization variable. Other measures for better temperature
control could be employed, such as a series of reactors with intermediate cooling, or injection
of a cold inert. The simulation shows that these methods have no signifi cant effects on the
overall yields, although they may offer a better protection of the catalyst in long time
operation.
55