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 Case 4:
Sulfuric Acid Alkylation
Abstract
Computer flowsheet simulation of plant processes has become a
widely accepted design and optimization tool in today's refinery.
Because most refinery processes have a high degree of thermal
integration and material recycle, process simulation is often the
only way to quantify how different unit operations interrelate in the
overall flowsheet environment.
The H2SO4 alkylation plant is used in this paper as a vehicle to
demonstrate how a modern flowsheet simulator, PRO/II, may be
used to evaluate process alternatives, which include parametric
studies of flowsheet variables and changes in flowsheet
configuration. Three flowsheet variables are perturbed to study the
effect on economically sensitive flowsheet parameters. Two key
flowsheet configuration design decisions are explored:
Effluent refrigeration vs. auto refrigeration, and
De-isobutanizer vs. iso-stripper operation.
This work does not make definitive judgments on the merits of
these options, but rather demonstrates how these design choices
may be evaluated by the process engineer using modern simulation
technology.

PRO/II Case Book Sulfuric Acid Alkylation 4-1

Sulfuric Acid Alkylation
Market Position
Alkylate is a high octane component in gasoline blends. It is
composed primarily of iso-octanes and iso-heptanes which make a
very small contribution to the overall vapor pressure, and no
contribution to the aromatic or olefin content. These have become
key issues in refinery planning since implementation of the Clean
Air Act Amendments of 1990.[4-1],[4-2].Increasing alkylate
production can partially offset the need to reduce reforming
severities to meet aromatic targets. Alkylation can also be used to
reduce olefin content in gasoline.
Table 4-1 shows the octane and vapor pressure characteristics of the
principal reactants and products of an alkylation plant. This
demonstrates that, although the octane numbers of alkylation feeds
are suitable for gasoline production, the vapor pressures are
excessive.
Table 4-1: Octane and Vapor Pressure Characteristics of
Alkylate Reactants and Products[4-3]
Vapor Pressure
Octane at 100F
Reactants Motor Research psia
Isobutane 97.6 100.1 72.6
Propylene 84.9 100.2 227.6
Isobutylene na na 64.6
* *
2-Butylenes 83.5 100.0 47.8*
1-butylene 80.8 97.4 63.2
2-Methylbutylenes 83* 99* 16.4*
Products (partial list) 20.4
Isopentane 90.3 92.3 3*
Dimethylpentanes 88* >100
*
Trimethylpentanes 98 >100 1*
C9s 98* 100* >0.5
* approximate average

Reactor products have excellent octane as well as vapor pressure

characteristics. Sulfuric acid alkylation is a highly complementary
process for refineries that are considering on-site MTBE
production.[4-4] The MTBE process selectively reacts isobutylene

4-2 Sulfuric Acid Alkylation March 5, 2014

 from the olefin stream, permitting 1- and 2-butylene to pass through
for alkylation. Isobutylene produces lower quality alkylate, while 1-
and 2-butylene produce superior alkylate.

Comparison to HF Alkylation
The relative advantages of hydrofluoric acid (HF) to H2SO4
alkylation have been vigorously debated in the open literature and
in the marketplace for years.[4-5] From about 1960 through the
1980s, HF alkylation was preferred to H2SO4 alkylation in new
plants. The advantages of HF include superior product when the
olefin content is high in propylene and isobutylene, and reduced
catalyst cost. Also, HF alkylation does not require refrigeration or
acid regeneration so it is marginally better in that respect.
More recently, preferences have shifted toward H2SO4 alkylation.
This is due in part to the high corrosive nature of the HF acid, which
requires exotic materials of construction. The process is also much
more hazardous due to the HF acid, and is not readily acceptable
environmentally. Safety and liability considerations, together with a
reduction in isobutylene content in the olefin feed (due to the
MTBE plant), are additional factors. Also, the more recent
development of the wet sulphuric acid process (described briefly
in Appendix 4-C) ameliorates may of the disadvantages previously
incurred by H2SO4 alkylation. Together, all these factors are
changing the economics to favor H2SO4 alkylation. Several
refiners, particularly those near major population centers, are
considering revamping their HF alkylation facitlities to H2SO4
alkylation.

Chemistry
The primary purpose of the alkylation reactor is to join isobutane
and a light olefin to form branched alkylates.[4-6]
acid
iC 4 + C 3 C 7 + heat
(4-1)
acid
iC 4 + C 4 C 8 + heat

Disproportionation reactions contribute to a distribution of alkylate

products from iC5 to C12+; e.g.,
2C 8 C 7 + C 9 (4-2)

PRO/II Case Book Sulfuric Acid Alkylation 4-3

 Olefin polymerization is undesirable and is usually minimized by
proper mixing, low reaction temperatures and high isobutane
concentrations.

2C 3 H 6 C 6 H 12
(4-3)
C n H 2n + C m H 2m C n + m H 2 m + n

The polymers form acid-soluble oils that foul the sulfuric acid
catalyst, resulting in excessive purge and makeup requirements. As
the acid strength weakens, an acid runaway, characterized by low
octane and increased acid consumption, may occur.

Simulation Scope and Objectives

The objective is to model the overall basic sulfuric acid alkylation
process in a manner that permits the process engineer to analyze
virtually all flowsheeting issues. The flowsheet models presented
here allow the following questions to be answered with few or no
changes to the input description:
How is the process affected if more propane is circulated in the
depropanizer-refrigeration recycle?
How is the process affected if more isobutane is recycled from
the de-isobutanizer?
What are the optimum feed tray locations for each of the four
distillation columns?
How do the utility requirements change for changes in
feed-stock?
What are the total reboiler steam requirements for all four
distillation columns?
What is the total refrigeration duty?
If supplemental isobutane is available, where is the optimum
place in the flowsheet to introduce this feed?
For a given reactor volume, what is the space velocity?
What are the differences if the deisobutanizer is operated as an
isostripper instead of a conventional tower?
How is the refrigeration duty affected if effluent regrigeration
rather than autorefrigeration is chosen?

4-4 Sulfuric Acid Alkylation March 5, 2014

 How much reboiler duty is saved if the debutanizer is
elimi-nated by drawing a normal butane?rich side stream off of
the deisobutanizer? How is the isobutane recycle affected?
The simulation makes the following simplifying assumptions:
Feed pretreatment is not included. When the amine towers
are working correctly, their operation has no effect on the
flowsheet.
Caustic treatment is not considered. The reactor products
generally run through a caustic wash to neutralize acid
carry-over and ester formation. When the acid settler is
working correctly, the caustic wash has little effect on the
heat or hydrocarbon balance, so it may be safely deleted
from the simulation.
The stoichiometry is fixed for each isobutane-olefin
reaction pair, and each olefin reacts to extinction. The
REACTOR MODEL section clarifies this further.
Sulfuric acid is assumed to be 100% pure and totally
immiscible with the process hydrocarbon. In reality,
circulating sulfuric acid is generally maintained at 85 to 96
weight percent.
The trace amount of hydrocarbon absorbed by the acid is
disposed of by the acid purge and may usually be ignored in
the hydrocarbon balance. Acid entrained or absorbed in the
reactor hydrocarbon effluent is neutralized by caustic wash,
and does not normally have a significant effect on the
hydrocarbon balance. For flowsheet simulation purposes,
the only effect of having a sulfuric acid circulation is to
correctly account for the flowing heat capacity.

Reactor Modelling
Reaction Stoichiometry
A fixed stoichiometry for each pair of reacting components is
derived from the work of Cupit, et al.[4-7] This reference provides
reaction yields on a volumetric basis. PRO/II was used to normalize
the products to mass balance with the feeds. Note that, although it is
necessary to adjust the stoichiometry to mass balance, it is not
necessary to normalize the stoichiometry to integer coefficients.
Table 4-2 lists the coefficients used in this simulation. Heat of

PRO/II Case Book Sulfuric Acid Alkylation 4-5

 reaction data need not be supplied. PRO/II automatically accounts
for reaction enthalpy via pure component heat of formation data
adjusted for temperature and pressure.
Table 4-2: Stoichiometric Coefficients for Alkylating
Pairs of Components
Olefin Propylene Isobytylene 2-Butylenes 1-Butylene
Reactant
olefin 12.3008 8.5683 10.9924 11.5763
isobutane 12.3461 10.5445 11.3223 9.9587
Products
isopentene 0.5541 1.2706 0.6346 0.6877
2,3-dimethylbutane 0.5553 0.5925 0.6261 0.5870
2,4-dimethylpentane 2.3756 0.3827 0.2832 0.3016
2,2,4-trimethylpentane 5.9539 0.2638 0.1703 0.1730
2,4-dimethylhexane 0.4574 2.5703 3.3018 3.1778
2,3-dimethylhexane 0.0731 0.3627 0.4360 0.5271
2,3,4-trimethyl pentane 0.3969 2.1523 4.6514 4.2314
2,2,5-trimethylhexane 0.0821 0.3998 0.1852 0.1686
C9s (nbp=280, mw=128) 0.0594 0.2074 0.0782 0.0984
C10s (nbp=325, mw=142) 0.6688 0.2754 0.0891 0.0720
C11s (nbp=365, mw=156) 0.4325 0.2134 0.799 0.0761
C12s (nbp=395, mw=170) 0.0468 0.5173 .02831 0.2674
C13+ (nbp=425,mw=184) 0.0315 0.0239 0.0000 0.0079

Reactor Configurations
In the auto-refrigeration flowsheets considered by this paper, the
reaction vessel is divided into four reaction chambers. Flashing
occurs in each chamber to balance the exothermic heat of reaction.
In the flowsheet where effluent refrigeration is considered, the
reaction takes place in a single reaction chamber under sufficient
pressure to suppress vapor flashing. This work assumes the reaction
is maintained at 45 F. Temperatures significantly above 45 F result
in excessive acid consumption and lower octane. Temperatures
significantly below 45 F increase the refrigeration load. Liquid
hydrocarbon and acid phases coexist in the reactor.

4-6 Sulfuric Acid Alkylation March 5, 2014

 The reactor could be modeled with a reactor unit operation using
conventional two phase equilibrium models, followed by a three
phase flash. This has one disadvantage in that the reactor is nested
two levels deep in controller and recycle loops, and rigorous three
phase flashes add to the calculation overhead. In this paper, a
stream calculator unit operation replaces the three-phase flash. This
allows the user to mathematically manipulate stream separation.
One other solution for modeling a three phase reactor is to declare
the acid as a solid component. It thus carries with it a fixed heat
capacity, but no vapor pressure. This strategy is not used in the
simulations presented here, but has been proven in preliminary runs
for this work.

Thermodynamic Models
The Soave modification to the Redlich?Kwong equation of state is
used for all unit operations in the flowsheet for the calculation of
equilibrium, enthalpy and entropy. [4-8]

Sulfuric Acid Alkylation Flowsheet

The flowsheet for the sulfuric acid alkylation plant with auto-
refrigeration and isostripper design is shown in Figure 4-1.
Treated saturated feed is combined with recycle from the
refrigeration circuit and depropanized in column DEC3. The
overhead enters the deethanizer DEC2 and leaves the flowsheet as
fuel gas and HD5 propane product. The bottoms are cooled to 100 F
and enter the economizer together with condensed propane rich
re-frigeration and supplemental isobutane feed. Evaporation in the
economizer cools the stream to 55 F. The pressure is then let down
to 30 psia as it enters the first reaction chamber together with
sulfuric acid and recycle isobutane.
Acid and hydrocarbon are cascaded into each of four reaction
chambers in sequence. Olefin feed enters the tube side of the
economizer where it is cooled to 65 F.
The stream is split into four equal parts, each of which enters a
separate reaction chamber. Olefin reacts to extinction with
isobutane in each chamber to form alkylate.

PRO/II Case Book Sulfuric Acid Alkylation 4-7

 Figure 4-1: H2SO4 Alkylation Plant

Vaporization in each chamber approximately compensates for the

heat of reaction to maintain the reactor at about 45 F throughout.
All of the vapor is collected and recycled to the refrigeration circuit.
Acid is settled and decanted. Part of the acid is purged for on?site or

4-8 Sulfuric Acid Alkylation March 5, 2014

 off?site regeneration. The hydrocarbon enters the isostripper DIC4
where normal butane and alkylate product is separated from the
isobutane rich recycle. The alkylate is then stabilized to an RVP of
12 psi in the debu-tanizer DEC4. The hydrocarbon feeds to the
flowsheet are shown in Table 4-3.
Table 4-3: Feed Hydrocarbon Conditions
Component Rates, standard liq. vol, bbl/hr
Saturated Olefin Supplemental
Feed Feed Isobutane
Stream ID 1 2 3
methane 2.0 - -
ethane 10.1 - -
propane 100.0 9.0 -
Isobutane 187.5 95.0 36.0
normal butane 100.0 50.0 9.0
propylene - 9.0 -
isobutylene - 14.0 -
2-butylene - 75.0 -
2-butylene - 56.0 -
Isopentane - 5.0 -
Total 399.5 413.0 45.0
Temperature, F 100 100 100
Pressure, psia 400 215 400

The supplemental isobutane feed has been included here to

demon-strate that alternate sources of isobutane with varying
compositions and thermal conditions may be processed.
Table 4-4: Acid Feed to Reactor
Stream Property Property Value
Feed Stream ID SA1
Stream ID SA1
Acid rate, 106 lb/hr 1.00
Temperature, F 45
Pressure, psig 40

The optimum flowsheet feed location for this stream may or may
not be the same as for the bulk of the isobutane feed. The effects of
alternate feed locations may be quickly tested via simulation.

PRO/II Case Book Sulfuric Acid Alkylation 4-9

RUN #1 Auto-Refrigeration and Iso-Stripper Operation
Simulation Strategy
The success of the simulation convergence depends on which
flow-sheet variables have assumed values, and which are calculated
by the program. Assumed values may be investigated through
sensitivity analyses and optimization techniques. Referring to the
flowsheet in Figure 4-1, convergence stability is enhanced by fixing
flowrates at least once in each of the recycle circuits. Thus, the
bottoms of depropanizer DEC3 is specified to contain a fixed value
of 50 mole/hr of propane, and the overhead rate from
deisobutanizer is fixed at 1000 bbl/hr.
The economizer H2 is operated in a manner that fixes the outlet
temperature of both sides of the exchanger. Normally, there are only
enough degrees of freedom to specify one outlet temperature of a
heat exchanger; however, the upstream pressure on the saturates
side is varied by controller C1 until both temperature specifications
are met. This control loop is embedded in another control loop as
well as a recycle loop. It is thus essential that the tolerance is
tightened, enabling the external loops to see clean derivatives. Since
this is the innermost loop, a good practice is to set this tolerance just
barely loose enough to ensure convergence on each pass. An
absolute tolerance of 0.0001 F is used in this demonstration.
The reactor RX1A effluent temperature is controlled at 45 F by
adjusting splitter S1. This has the effect of circulating more or less
refrigerant through the autorefrigeration circuit and thus cooling the
reactor to a greater or lesser extent. The number of control iterations
is limited to 5 as it is not necessary to solve this recycle to
completion on each recycle pass. This permits the recycle and
control loop to converge simultaneously, reducing CPU time. An
absolute tolerance of 0.0002 F is used.
Effluent processing includes two-stage compression followed by an
after-cooler condenser. To speed up recycle calculations, all these
unit operations are replaced by single flash drum MCOM.
Following the successful convergence of all recycle loops, detailed
effluent calculations are performed once by solving two
compressors and a heat exchanger (see Figure 4-2). Although the
compressors do not require excessive amounts of CPU, the number
of passes through this loop make it well worthwhile to reduce the
two P-S (constant pressure - constant entropy) compressors and one

4-10 Sulfuric Acid Alkylation March 5, 2014

 P-T (constant pressure - constant temperature) heat exchanger to the
single P-T flash unit MCOM.

Figure 4-2: Detailed Effluent Processing Model of Flash MCOM

The case study feature of PRO/II may used to study the effects of
increased propane to the refrigeration circuit, increased isobutane
recycle, and a change in feed composition to include more normal
butane. However, this must be run as a batch execution because the
PROVISION Graphical User Interface still does not fully support
all features of Casestudy.

Input Description
Appendix 4-A lists the PRO/II keyword input file for the auto-
refrigeration/isostripper batch run. This is revision 2 that is
compatible with PRO/II versions 8 and 9. An electronic copy of the
file is available in the %P2Install% \manual\casebook\inputs\
directory, where %P2Install% is the directory where PRO/II is
installed.

Results
Key operating conditions for the base case and case studies are
summarized in Table 4-5, including total reboiler duties, reactor
effluent flowrates and isobutane content, refrigeration loads, and
product flows. These parameters form the basis for calculating
operating expenses.

PRO/II Case Book Sulfuric Acid Alkylation 4-11

 Table 4-5: Key Flowsheet Parameters
Run #1 - Auto-refrigeration and Isostripper Operation
Base More C3 More iC4 More nC4
Case Recycle Recycle in Feed
Input Flow Parameters
C3 in de-propanizer
50 100 50 50
bottoms, moles/hr
Recycle from
2525 2525 2600 2525
isostripper, bbl/hr
Additional normal
butane in saturates 0 0 0 50
feed, bbl/hr
Calculated Flow Parameters
Reboiler duties, 106 Btu/hr
De-ethanizer DEC2 1.00 1.00 1.00 1.00
De-propanizer DEC3 28.24 29.02 28.40 28.46
Iso-stripper DIC4 80.69 80.69 82.73 80.36
De-butanizer DEC4 9.09 9.08 9.10 11.73
Total reboiler duties 119.02 119.79 121.23 122.05

HC liquid reactor effluent
Hot volume rate, gpm 2180 2180 2232 2214
isobutane content, liq
64.0 64.0 64.0 58.4
vol %

Compressor shaft power, hp

Stage 1 996 995 977 1044
Stage 2 2005 2005 2005 2069
Total compressor duty 3001 3000 2982 2113

Product flowrates at standard conditions

Gas products, mscfh
Fuel gas 17.42 17.41 17.42 17.44
Liquid products, bbl/hr
Liquid propane 111.1 111.1 111.0 110.8
Normal butane 118.9 118.6 118.9 168.7
12 RVP alkylate 522.3 522.3 522.3 522.6

4-12 Sulfuric Acid Alkylation March 5, 2014

 Table 4-6 illustrates one approach to summarizing the results.

Table 4-6: Significance of Simulation Results for Run #1

Case Observation
More C3 in
Increases depropanizer reboiler
depropanizer
duty
bottoms
Increases isobutane
concentration in reactor.
Reduces reactor and settler
residence time due to increased
More iC4 reactor throughput.
recycle
Increases isostripper reboiler
duty.
Reduces first stage compressor
load.
Reactor iso-butane concentration
decreases.
Reactor throughput increases.
More nC4 in The debutanizer reboiler rate
feed increases in proportion to
increases in product butane.
The refrigeration load
requirement decreases.
Conclusion
Profitability is improved when
propane in depropanizer bottoms
is minimized.
Increase in octane and decrease
in acid consumption due to iso-
butane content, together with
reduced compressor loading,
more than compensates for
increase in reboiler duty. If the
iso-stripper hydraulics and
reactor residence time
requirements are not limiting,
profitability improves as iso-
butane recycle increases.
Although normal butane is an
inert copmponent in the reactor,
it adversely affects plant
profitability. In particular, the
decrease in reactor iso-butane
concentration translates to a
significant drop in octane and
increase in acid consumption.

Runs #2 and #3 - Deisobutanizer with Auto-thermal

Refrigeration and Deisobutanizer with
effluent Refrigeration
Appendix 4-B provides listings of differences in key word files
from run 1 to runs 2 and 3. Figure 2-3 illustrates the difference in
configuration between the isostripper and the deisobutanizer in the
flowsheet.

PRO/II Case Book Sulfuric Acid Alkylation 4-13

 Figure 4-3: Iso-stripper vs. De-butanizer Configuration

The deisobutanizer overhead constitutes the isobutane rich recycle

to the reactor. Based on the recycle rate chosen, the reflux and feed
tray location is optimized in a separate run constrained by an 80
percent of flood specification. The larger the recycle, the smaller
the reflux with the limiting case being the isostripper design
demonstrated by Run #1.
In the flowsheet for the effluent refrigeration process, the reactions
occur under pressure with cooling coils sufficient to keep all
hydrocarbons in the liquid state.
After decanting the acid, the hydrocarbon reactor effluent is let
down and passed through the tube side of the reactor. A 10 F hot-
out/cold-out approach is assumed to be sufficient to cool the
reactor, thus the tube side outlet is assumed to be at 35 F.

4-14 Sulfuric Acid Alkylation March 5, 2014

 Input Description
The changes required in the input file are shown in Appendix 4-B.

Results
Key operating conditions for all three configurations studied are
summarized in Table 4-7.
Table 4-7: Comparison of Key Flowsheet Parameters for Alternate Configurations
Refrigeration circuit Auto- Auto- Effluent
Refrigeration Refrigeration Refrigeration
Deisobutanizer Isostripper Deisobutanize Deisobutnaize
configuration r r
Calculated Flow Parameters
Reboiler duties, 106 Btu/hr
De-ethanizer DEC2 1.00 1.00 1.00
De-propanizer DEC3 28.24 27.11 27.20
Iso-stripper DIC4 80.69 80.03 80.03
De-butanizer DEC4 9.09 9.10 9.10
Total reboiler duties 119.02 117.24 117.33

HC liquid reactor effluent

Hot volume rate, gpm 2180 1131 1120
isobutane, liq vol % 64.0 50.7 50.2
Compressor shaft power, hp
Stage 1 996 1454 1706
Stage 2 2005 2016 2086
Total compressor duty 3001 3470 3792
Product flowrates at standard conditions
Gas products, mscfh
Fuel gas 17.42 17.46 17.48
Liquid products, bbl/hr
Liquid propane 111.1 111.0 110.9
Normal butane 118.9 119.0 119.0
12 RVP alkylate 522.3 522.3 522.3

PRO/II Case Book Sulfuric Acid Alkylation 4-15

 The significance of these results can be summarized as follows:

Table 4-8: Significance of Results for Runs #2 and #3

Comparison Observation Conclusion
Isostripper vs. Debutanizer operation decreases The isostripper operation
deisobutanizer substantially the isobutane requires a substantially larger
content in the reactor. capital investment for increased
The deisobutanizer operation reactor and settler volumes. The
substantially decreases the benefit to this is a substantially
reactor volumetric throughput. improved octane and lower acid
The deisobutanizer operation consumption due to the higher
decreases the depropanizer duty, reactor isobutane concentration.
but increases refrigeration load.
Auto vs. effluent Autorefrigeration requires less Based on the operating
refrigeration refrigeration. parameters considered here,
autorefrigeration operation is
more economical.
Licensors of autorefrigeration alkylation point out that the lower
temperatures required on the tube side of effluent refrigeration
reactors accounts for the higher compression requirements.[4-9] Note,
however, that the two reactor designs are fundamentally different.
Other considerations, not included here, such as capital costs and
mixing utilities, have an important impact.

Conclusions
Steady state process simulation technology has matured to the point
where large scale highly integrated process plants are simulated
routinely to answer "what if" questions ranging from small
parametric changes to changes in plant configuration. PRO/II has
been used to demonstrate this capability in solving a sulfuric acid
alkylation flowsheet which has a high degree of recycle and thermal
integration. Typical process questions regarding this flowsheet have
been posed and answered.

4-16 Sulfuric Acid Alkylation March 5, 2014

References
4-1 Masters, K.R., "Alkylation's Role in Reformulated Gasoline", pre-
sented at 1991 Spring National Meeting AIChE.

4-2 Unzelman, G.H., "U.S. Clean Air Act Expands Role for Oxygen-
ates", Oil & Gas Journal, April 15, 1991.

4-3 API, Technical Data Book ? Petroleum Refining, Volume 1 (1987).

4-4 Chapin, L.E., Liolios, G.C. and Robertson, T.M., "Which Alkyla-
tion? HF or H2SO4?", Hydrocarbon Processing, September 1985,
pg. 67?71.

4-5 Myer, D.W., Chapin, L.E. and Muir, R.F., "Cost Benefits of Sulfuric
Acid Alkylation," Chem. Eng. Progress, 79, 8, pg. 59?65 (1983).

4-6 Lee, L. and Harriott, P., "The Kinetics of Isobutane Alkylation in

Sulfuric Acid," I&EC Process Design Dev., 16, 3 (1977).

4-7 Cupit, C.R., Gwyn, J.E. and Jernigan, E.C., "Special Report Cata-
lytic Alkylation", Petroleum and Chemical Engineering, 33, 47,
1961 and 34, 49, (1962).

4-8 Soave, G., "Equilibrium Constants from a Modified Redlich?Kwong

Equation of States," Chem. Eng. Sci., 27, 1177?1203 (1972).

4-9 Lerner, H. and Citarella, V.A., "Exxon Research and Engineering

Sulfuric Acid Alkylation Technology", presented at 1991 NPRA
Annual Meeting.

PRO/II Case Book Sulfuric Acid Alkylation 4-17

4-18 Sulfuric Acid Alkylation March 5, 2014
 Appendix 4-A Keyword Input

Input File
TITLE PROJ=CaseBook, PROB=H2SO4 ALKY,USER=SIMSCI
DESC 12,000 BPSD H2SO4 Alkylation plant.
PRINT RATE=M,LV,STREAM=PART,INPUT=ALL
CALC TRIALS=40 ,RECYCLE=TEAR
DIME LIQV=BBL,XDENS=SPGR
OUTD SI
SEQU FX,HT3 ,FB2,DEC3, FB2X &
PC1,S1,V1, H2,C1, &
OLSP,RX1A,F1X,RX1B,F1Y,RX1C,F1Z,RX1D, &
F1ZZ,SETL,VAPR,C2,MCOM, P2, &
DIC4,FT1, P1,DEC4,FB4,CL4, &
P3,DEC2,FB1,CL1, &
SCTN,CMP1,CMP2,AFTR
tole duty=0.005,misc=0.01

COMP DATA

LIBID 1,C1 /2,C2 /3,C3 /4,IC4 /5,NC4 /&

6,PROPENE/7,ISOBUTENE/8,T2BUTENE,,2BUTENE /9, 1BUTENE / &
10,IC5 /11,23DMB /12,24MP /13,23MP /&
14,224MPN /15,24HX /16,23HX /17,234MP /18,225MHX
PETRO 19,C9s, 128.26, 0.73, 280 / &
20,C10s, 142.28, 0.74, 325 / &
21,C11s, 156.31, 0.75, 365 / &
22,C12s, 170.34, 0.76, 395 / &
23,C13s, 184.36, 0.77, 425
LIBID 24,H2SO4,BANK=SIMSCI
TC(K) 24,924
PC(BAR) 24,64
$ VISC(L) CORR=1,DATA=24,,,1
VISC(V) CORR=1,DATA=24,,,1
COND(V) CORR=1,DATA=24,,,1
$ COND(L) CORR=1,DATA=24,,,1

THERMODYNAMIC DATA

METHOD SYSTEM=SRK,TRANSPORT=PURE,SET=SRK
ENTHALPY ALPHA=SIMSCI
SA06 24,1.81341,1.25196,0.566576

STREAM DATA

$ SATURATE FEED
PROP STREAM=1,TEMP=100,PRES=400, &
COMP(LV)=1,2 / 2,10 / 3,100 / 4,187.5 / 5,100.

PRO/II Case Book Sulfuric Acid Alkylation 4-19

 $ OLEFIN FEED
PROP STREAM=2,TEMP=100,PRES=215, &
COMP(LV)=3,9 / 4,95 / 5,50 / 6,9 / 7,14/ 8,175 /9,56 / 10,5

$ MAKE-UP
PROP STREAM=3,TEMP=100,PRES=400,RATE(LV)=45, &
COMP(LV)=4,80 / 5,20

$ MAKEUP N-BUTANE FOR CASE STUDY ANALYSIS

PROP STREAM=1NB,TEMP=100,PRES=400,COMP(LV)=5,1,RATE=0.00001

$ ACID FEED
PROP STREAM=SA1, TEMP=45, PRES=40, COMP(WT,LB/HR)=24,1000000

$ DEIC4 FEED
PROP STREAM=253X,TEMP=110,PRES=115,REFSTREAM=251

$ DEC2 FEED
PROP STREAM=11B,TEMP=140,REFSTREAM=11A

$ RECYCLE STREAM DATA ESTIMATES

PROP STREAM=27P,NAME=RCY_SAT,PHASE=L,PRES=400, &

COMP=3,80 / 4,280 / 5,50

PROP STREAM=26,NAME=SRG_DRUM,PHASE=L,PRES=73, &

COMP=3,1100 / 4,3500 / 5,620

PROP STREAM=30R,NAME=RCY_IC4,TEMP=62,PRES=200, &

COMP=3,210 / 4, 3000 / 5,300

NAME 1,SATURATED FEED/2,OLEFIN FEED/3,MAKEUP IC4/ &

10,DEC3 FEED/11,PROPANE TO DEC2/12,DEC3 BOTTOMS/ &
20, OLEFIN TO RXN/21,IC4 TO RXN/24, RXN VAPORS/&
25, RXN LIQUIDS/26, COMP SURGE DRUM LIQ/27, RCY TO DEC3/&
30, DEIC4 OVHD/ 30R, IC4 RCY/32, BUTANE/332,ALKYLATE/&
40, FUEL GAS/41B, HD5 PROPANE

OUTPUT FORMAT=VOLSUM, STREAMS=1,2,3,DESCRIPTION=FEED

STREAMS
OUTPUT FORMAT=VOLSUM, STREAMS=40,41B,32,332, &
DESCRIPTION=PRODUCT STREAMS
OUTPUT FORMAT=VOLSUM, STREAMS=25, &
DESCRIPTION=REACTOR EFFLUENT

FORMAT ID=VOLSUM, NAME, LINE, TEMP, PRES, LINE, &

LRATE(LV,1,2,BBL/DAY)=C2+, LRATE(LV,3,BBL/DAY)=PROPANE,&
LRATE(LV,4,BBL/DAY)=I-BUTANE, LRATE(LV,5,BBL/DAY)=N-BUTANE,&
LRATE(LV,6,BBL/DAY)=PROPENE, LRATE(LV,7,9,BBL/DAY)=BUTENES,&
LRATE(LV,10,BBL/DAY)=PENTANE, LRATE(LV,11,23,BBL/DAY)=C6+,LINE,&
RATE(LV,BBL/DAY), RATE(LV,BBL/HR), &

4-20 Sulfuric Acid Alkylation March 5, 2014

 RATE(LV,M3/HR), LINE, &
ARATE(LV,GAL/MIN), ARATE(LV,L/MIN), LINE, &
RATE(GV,FT3/HR), RATE(GV,M3/HR), LINE, CPCT(LV,4)
RXDATA

RXSET ID=RS1
REACTION ID=RX1
$ PROPENE - ISOBUTENE REACTION
STOIC 4, -12.3461/ 6, -12.3008/ &
10, 0.5541/ 11, 0.5553/ 12, 2.3756/ 13, 5.9539/ 14, 0.4574/ &
15, 0.0731/ 16, 0.1062/ 17, 0.3969/ 18, 0.0821/ 19, 0.0594/ &
20, 0.6688/ 21, 0.4325/ 22, 0.0468/ 23, 0.0315

REACTION ID=RX2
$ ISOBUTENE - ISOBUTANE REACTION
STOIC 4, -8.5683/ 7, -10.5445/ &
10, 1.2706/ 11, 0.5925/ 12, 0.3827/ 13, 0.2638/ 14, 2.5703/ &
15, 0.3627/ 16, 0.5101/ 17, 2.1523/ 18, 0.3998/ 19, 0.2074/ &
20, 0.2754/ 21, 0.2134/ 22, 0.5173/ 23, 0.0239

REACTION ID=RX3
$ 2-BUTENE - ISOBUTANE REACTION
STOIC 4,-10.9924/ 8, -11.3233/ &
10, 0.6347/ 11, 0.6261/ 12, 0.2832/ 13, 0.1703/ 14, 3.3018/ &
15, 0.4360/ 16, 0.5566/ 17, 4.6514/ 18, 0.1852/ 19, 0.0782/ &
20, 0.0891/ 21, 0.0799/ 22, 0.2831

REACTION ID=RX4
$ 1-BUTENE - ISOBUTANE REACTION
STOIC 4,-11.5763/ 9, -9.9587/ &
10, 0.6877/ 11, 0.5870/ 12, 0.3016/ 13, 0.1730/ 14, 3.1778/ &
15, 0.5271/ 16, 0.6466/ 17, 4.2314/ 18, 0.1686/ 19, 0.0984/ &
20, 0.0720/ 21, 0.0761/ 22, 0.2674/ 23, 0.0079

UNIT OPERATION

FLASH UID=FX,NAME=OLEFIN FD
$ THIS SIMULATES THE OLEFIN FEED FROM THE BOTTOM OF THE
$ OLEFIN DEPROPANIZER (WHICH WILL BE ADDED AT A LATER DATE
FEED 2
PROD L=2A
BUBB TEMP=200

FLASH UID=HT3, NAME=PRECHILLER

$ PRECOOLS OLEFIN FEED TO 100 F
FEED 2A
PROD L=2B
ISO TEMP=100,DP=5

HX UID=FB2
OPERATION CTEMP=170

PRO/II Case Book Sulfuric Acid Alkylation 4-21

 COLD FEED=1,1NB,27P,L=10

COLUMN UID=DEC3, NAME=SAT DEC3

FEED 10,20
PROD OVHD=11,60,BTMS=12
CONDENSER TYPE=BUBB,PRES=310
PARA TRAY=40
SPEC REFLUX,VALUE=4000
SPEC STREAM=12,COMP=3,RATE,VALUE=50.0
ESTI MODEL=CONVENTIONAL,RRATIO=9.0
DUTY 1,1/2,40
VARY DUTY=1,2
PSPEC PTOP=315,DPCOL=10
PRINT PROP=BRIEF
TRATE SECTION=2,39,SIEVE,PASSES=2, &
SPACING(TRAY,IN)=24, DIAMETER(TRAY,FT)=10.0

HX UID=FB2X
HOT FEED=12,L=121,DP=5
OPERATION
COLD FEED=1,1NB,27P,L=10X
CONFIG U=80
DEFINE DUTY AS HX=FB2, DUTY

HX UID=PC1, NAME=ECON PRECOOL

HOT FEED=121,L=122,DP=5
OPERATION HTEMP=100
CONFIG U=100
UTIL WATER TIN=70,TEMP=80

SPLITTER UID=S1
FEED 26
PROD L=27,L=28
SPEC STREAM=27,RATE(LV),VALUE=75

VALVE UID=V1
FEED 28
PROD M=28V
OPERATION DP=30

HX UID=H2, NAME=ECONOMIZER
HOT FEED=2B,L=20,DP=3
COLD FEED=122,3,28V,DP=1,L=21,V=29
CONFIG U=80
OPERATION HTEMP=65

CONTROLLER UID=C1
SPEC STREAM=21,TEMP,VALUE=55,ATOL=0.0001
VARY VALVE=V1,DP,MAXI=70

4-22 Sulfuric Acid Alkylation March 5, 2014

 $$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$
$ REACTOR SECTION
SPLITTER UID=OLSP,NAME=OLEFIN_SPLITTER
FEED 20
PROD V=20A, V=20B, V=20C, V=20D
SPEC STREAM=20A,RATE,RATIO, REFF, VALUE=0.25
SPEC STREAM=20B,RATE,RATIO, REFF, VALUE=0.25
SPEC STREAM=20C,RATE,RATIO, REFF, VALUE=0.25

CONREACTOR UID=RX1A, NAME=1ST_STAGE

FEED 20A,21,30R,SA1
PROD M=24X
OPERATION PRES=30,ADIABATIC
RXCALC MODEL=STOIC $,REFPHASE=L,REFTEMP=45
RXSTOIC RXSET=RS1
REACTION RX1
BASE COMPONENT=6
CONVERSION 1
REACTION RX2
BASE COMPONENT=7
CONVERSION 1
REACTION RX3
BASE COMPONENT=8
CONVERSION 1
REACTION RX4
BASE COMPONENT=9
CONVERSION 1

STCALC UID=F1X,NAME=3_PHASE
FEED 24X
OVHD V=24A,L=25A
BTMS STREAM=25AX
FOVHD 1,23,1.0/24,0.0

CONREACTOR UID=RX1B, NAME=2ND_STAGE

FEED 20B,25A,25AX
PROD M=24Y
OPERATION PRES=29,ADIABATIC
RXCALC MODEL=STOIC $,REFPHASE=L,REFTEMP=45
RXSTOIC RXSET=RS1
REACTION RX1
BASE COMPONENT=6
CONVERSION 1
REACTION RX2
BASE COMPONENT=7
CONVERSION 1
REACTION RX3
BASE COMPONENT=8
CONVERSION 1
REACTION RX4
BASE COMPONENT=9

PRO/II Case Book Sulfuric Acid Alkylation 4-23

 CONVERSION 1

STCAL UID=F1Y, NAME=3_PHASE

FEED 24Y
OVHD V=24B,L=25B
BTMS STREAM=25BX
FOVHD 1,23,1.0/24,0.0

CONREACTOR UID=RX1C, NAME=3RD_STAGE

FEED 20C,25B,25BX
PROD M=24Z
OPERATION PRES=28,ADIABATIC
RXCALC MODEL=STOIC $,REFPHASE=L,REFTEMP=45
RXSTOIC RXSET=RS1
REACTION RX1
BASE COMPONENT=6
CONVERSION 1
REACTION RX2
BASE COMPONENT=7
CONVERSION 1
REACTION RX3
BASE COMPONENT=8
CONVERSION 1
REACTION RX4
BASE COMPONENT=9
CONVERSION 1

STCALC UID=F1Z,NAME=3_PHASE
FEED 24Z
OVHD V=24C,L=25C
BTMS STREAM=25CX
FOVHD 1,23,1.0/24,0.0

CONREACTOR UID=RX1D, NAME=4TH_STAGE

FEED 20D,25C,25CX
PROD M=24ZZ
OPERATION PRES=27,ADIABATIC
RXCALC MODEL=STOIC $,REFPHASE=L,REFTEMP=45
RXSTOIC RXSET=RS1
REACTION RX1
BASE COMPONENT=6
CONVERSION 1
REACTION RX2
BASE COMPONENT=7
CONVERSION 1
REACTION RX3
BASE COMPONENT=8
CONVERSION 1
REACTION RX4
BASE COMPONENT=9
CONVERSION 1

4-24 Sulfuric Acid Alkylation March 5, 2014

 STCALC UID=F1ZZ,NAME=3_PHASE
FEED 24ZZ
OVHD V=24D,L=25D
BTMS L=25DX
FOVHD 1,23,1.0/24,0.0

STCALC UID=SETL,NAME=ACID_SETTLER
FEED 25D/25DX
OVHD V=24E,L=25,PRES=26
BTMS STREAM=SA2,PRES=26
FOVHD 1,23,1.0/24,0.0

MIXER UID=VAPR, NAME=RXN_VAPORS

FEED 24A,24B,24C,24D,24E
PROD V=24

CONTROLLER UID=C2
SPEC STREAM=25,TEMP,VALUE=45,ATOL=0.0002
VARY SPLITTER=S1,SPEC,MINI=1,MAXI=1000,STEP=20
CPARAMETER ITER=5

$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$
$ REFRIGERATION CIRCUIT

FLASH UID=MCOM $ SIMULATED IN DETAIL OUTSIDE THE

FEED 24,29 $ RECYCLE LOOPS WITH CMP1, CMP2 AND AFTR
BUBB TEMP=100 $ PRES=73
PROD L=26

$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$
$ PRODUCT PURIFICATION CIRCUIT

PUMP UID=P2,NAME=EFFL_PUMP
FEED 25
PROD L=251
OPERATION PRES=120

$
$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$
$ After first run, substitute first insert in Appendix 4-B for Column DIC4
COLUMN UID=DIC4, NAME=ISO-STRIPPER
PARA SURE=20, TRAYS=42
FEED 253X, 1
PROD OVHD=30, BTMS=31, 1300
DUTY 1, 42

$ The next line sets the iC4 recycle rate

SPEC STREAM=30, RATE(LV),VALUE=2525

PRO/II Case Book Sulfuric Acid Alkylation 4-25

 VARY DUTY=1
ESTIMATE MODEL=CONVENTIONAL
PRESSURE 1,90 / 42,95
PRINT PROP=BRIEF
TRATE SECTION=2,42,SIEVE,PASSES=4, &
SPACING(TRAY,IN)=24, DIAMETER(TRAY,FT)=13

$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$

HX UID=FT1,NAME=EFFL_RECL
COLD FEED=251,L=252,DP=5
HOT FEED=30,L=30R,DP=5
OPER HTEMP=62
CONFIG U(BTU/HR)=90

PUMP UID=P1
FEED 27
PROD L=27P
OPER PRES=400

$ THE DEBUTANIZER CIRCUIT IS SOLVED OUTSIDE THE LOOP

COLUMN UID=DEC4,NAME=DEBUTANIZER
PARA TRAYS=30,ERRINC=1.05
FEED 31,15
PROD OVHD=32,350,BTMS=33
COND TYPE=TFIX,TEMP=100,PRES=80
DUTY 1,1/2,30
SPEC STREAM=33, RVP,VALUE=12.0
SPEC STREAM=32, COMP=10, PERCENT(LV), VALUE=2.0
VARY DUTY=1,2
ESTIMATE MODEL=CONVENTIONAL
PRESSURE 2,85/30,90
PRINT PROP=BRIEF
TRATE SECTION=2,29,SIEVE,PASSES=1, &
SPACING(TRAY,IN)=24, DIAMETER(TRAY,FT)=5

HX UID=FB4,NAME=EFFL_ALKY
COLD FEED=252,L=253,DP=5
HOT FEED=33,L=331,DP=5
OPER CTEMP=110

HX UID=CL4,NAME=ALKY_CLR
HOT FEED=331,L=332,DP=5
UTIL WATER TIN=70,TEMP=80
OPER HTEMP=100

$ THE DEETHANIZER IS SOLVED OUTSIDE THE LOOP

PUMP UID=P3
FEED 11

4-26 Sulfuric Acid Alkylation March 5, 2014

 PROD L=11A
OPERATION PRES=600

COLUMN UID=DEC2, NAME=DEETHANIZER

FEED 11B,5
PROD OVHD=40,40,BTMS=41
CONDENSER TYPE=PART,PRES=420
PARA TRAY=20
SPEC TRAY=1,TEMP,VALUE=100.0
SPEC STREAM=41,TVP(PSIG),VALUE=203 $ HD5 SPEC IS 208 MAX
ESTI MODEL=CONVENTIONAL,RRATIO=2.0
DUTY 1,1/2,20
VARY DUTY=1,2
PSPEC PTOP=425,DPCOL=10
PRINT PROP=BRIEF
TSIZE SIEVE

HX UID=FB1
COLD FEED=11A,L=11B,DP=5
HOT FEED=41,L=41A,DP=5
OPERATION HOCO=5

HX UID=CL1
HOT FEED=41A,L=41B,DP=5
UTIL WATER TIN=70,TOUT=80
OPERATION HTEMP=100

$ THE COMPRESSOR REQUIREMENTS CAN BE CALCULATED AFTER

$ THE RECYCLE LOOPS ARE SOLVED

VALVE UID=SCTN, NAME=SUCTION

FEED 24
PROD V=240
OPERATION PRES=23

COMPRESSOR UID=CMP1, NAME=1ST STAGE

FEED 240
PROD V=241
OPERATION CALC=GPSA,EFF=80
DEFINE PRESSURE AS STREAM=29 PRESSURE MINUS 1

COMPRESSOR UID=CMP2, NAME=2ND STAGE

FEED 241,29
PROD V=260
OPER CALC=GPSA
DEFINE PRESSURE AS STREAM=26,PRESSURE,PLUS 5.0

FLASH UID=AFTR, NAME=AFT_COOL

FEED 260
PROD L=261
BUBB DP=5

PRO/II Case Book Sulfuric Acid Alkylation 4-27

 $ -----------------------------------------------------
RECYCLE

LOOP NO=1, START=FB2, END=P1, TOLE=0.0025

LOOP NO=2,START=DEC2,END=FB1, WEGS, TOLE=0.0005

$ -----------------------------------------------------

CASESTUDY OLDCASE=BASECASE,NEWCASE=MORE_C3
CHANGE COLUMN=DEC3,SPEC(2),VALUE=100
DESC INCREASE C3 IN THE BOTTOMS OF THE
DESC SATURATE DEPROPANIZER.

CASESTUDY OLDCASE=BASECASE,NEWCASE=MORE_IC4
CHANGE COLUMN=DIC4,SPEC,VALUE=2600
DESC INCREASE IC4 RECYCLE

CASESTUDY OLDCASE=BASECASE,NEWCASE=MORE_NC4
CHANGE STREAM=1NB,RATE(LV),VALUE=50
DESC INCREASE NC4 IN SATURATE FEED

END

4-28 Sulfuric Acid Alkylation March 5, 2014

 Appendix 4-B
Input Changes for Runs 2 and 3

Keyword Input File Inserts

Run 2 (De-isobutanizer Configuration) and
Run 3(Effluent Refrigeration Configuration)
Substitute these file inserts for the corresponding sections if input
listed in Appendix 4-B.

Insert 1: Debutanizer
Original input to discard:
COLUMN UID=DIC4, NAME=ISO-STRIPPER
PARA SURE=20, TRAYS=42
FEED 253X, 1
PROD OVHD=30, BTMS=31, 1300
DUTY 1, 42

$ The next line sets the iC4 recycle rate

SPEC STREAM=30, RATE(LV),VALUE=2525

VARY DUTY=1
ESTIMATE MODEL=CONVENTIONAL
PRESSURE 1,90 / 42,95
TRATE SECTION=2,42,SIEVE,PASSES=4, &
SPACING(TRAY,IN)=24, DIAMETER(TRAY,FT)=13
PRINT PROP=BRIEF

Changed input to insert:

COLUMN UID=DIC4, NAME=Debutanizer
PARAMETER TRAY=43
FEED 253X, 20
PROD OVHD=30, BTMS=31, 1300
DUTY 1, 1 / 2, 43
SPEC STREAM=30, RATE(LV), VALUE=1000

$ The next statements set the IC4 recycle

SPEC REFLUX(LV), VALUE=1600
VARY DUTY=1, 2
ESTIMATE MODEL=CONVENTIONAL
PRESSURE1, 85 / 2, 90 / 43, 95
TRATESECTION=2,42 SIEVE, PASSES=4, &
SPACING(TRAY, IN)=24, DIAMETER(TRAY, FT)=13

PRO/II Case Book Sulfuric Acid Alkylation 4-29

 PRINT PROP=BRIEF

Insert 2: Effluent Refrigeration

Changed input to be inserted.
Replace CONREACTOR RX1A with:
PUMP UID=P4, NAME=Sats Pump
FEED 21
PROD L=21X
OPERATION PRES=80

REACTOR UID=RX, NAME=1st_stage

FEED 20, 21X, 30R, SA1
PROD M=25X
OPERATION PRES=80, ISPTHERMAL, TEMP=45
RXCALC CONV $ RefPhase=L, RefTemp=45
$ PROPENE - ISOBUTENE REACTION
REACTION RX1
BASE COMPONENT=6
CONVERSION 1
$ ISOBUTENE - ISOBUTANE REACTION
REACTION RX2
BASE COMPONENT=7
CONVERSION 1
$ 2-BUTENE - ISOBUTANE REACTION
REACTION RX3
BASE COMPONENT=8
CONVERSION 1
$ 1-BUTENE - ISOBUTANE REACTION
REACTION RX4
BASE COMPONENT=9
CONVERSION 1

STCALC UID=ACST, NAME=Acid Settler

FEED 25X
OVHD L=25Y, DP=2
BTMS STREAM=SA1, DP=0
FOVHD 1,23, 1.0 / 24, 0.0
$
$ Simulates
$ dP across valve,
$ dP across tubes,
$ heat exchange and separation in one unit
$
$FLASH UID=TUBE, NAME=Cooling Tubes
FEED 25Y
PROD V=24, L=25
ADIA TEMP=35, PEST=20
DEFINE DUTY AS REACT=RX, DUTY, MULTIPLY, -1.0

4-30 Sulfuric Acid Alkylation March 5, 2014

 Appendix 4-C :
Wet Sulfuric Acid Process

The availability of a suitable catalyst is also an important factor in

deciding whether to building an alkylation plant. When sulfuric
acid is used, significant volumes are needed. Access to a suitable
plant is required for the supply of fresh acid and the disposition of
spent acid. If a sulfuric acid plant must be constructed specifically
to support an alkylation unit, such construction will have a
significant impact on both the initial requirements for capital and
ongoing costs of operation.
Alternatively it is possible to install a WSA Process unit to
regenerate the spent acid. The WSA process is the ideal choice for
regeneration of spent sulphuric acid. No drying of the gas takes
place. This means that there will be no loss of acid, no acidic waste
material and no heat is lost in process gas reheating. The selective
condensation in the WSA condenser ensures that the regenerated
fresh acid will be 98% w/w even with the humid process gas. It will
be possible to combine spent acid regeneration with disposal of
hydrogen sulphide by using hydrogen sulphide as fuel.[A-5].
The wet sulfuric acid process (WSA process) is one out of many gas
desulfurization processes on the market today. Since its
introduction in the 1980s, where it was patented by the Danish
catalyst company Haldor Topse A/S, it has been recognised as an
efficient process for recovering sulfur from various process gasses
in the form of commercial quality sulfuric acid (H2SO4). The WSA
process is applied in all industries where removal of sulfur is an
issue.
Wet catalysis processes differ from other contact sulfuric acid
processes in that the feed gas still contains moisture when it comes
into contact with the catalyst. The sulfur trioxide formed by
catalytic oxidation of the sulfur dioxide reacts instantly with the
moisture to produce sulfuric acid in the vapour phase to an extent
determined by the temperature. Liquid acid is subsequently formed
by condensation of the sulfuric acid vapour and not by absorption of
the sulfur trioxide in concentrated sulfuric acid, as is the case in
contact processes based on dry gases. The concentration of the

PRO/II Case Book Sulfuric Acid Alkylation 4-31

 product acid depends on the H2O/SO3 ratio in the catalytically
converted gases and on the condensation temperature. [A-5] [A-6]
The wet catalysis process is especially suitable for processing the
wet gasses obtained by the combustion of hydrogen sulfide (H2S)
containing off-gasses.[A-7] The combustion gasses are merely
cooled to the converter inlet temperature of about 420-440 C. To
process these wet gasses in a conventional cold-gas contact process
(DCDA) plant would necessitate cooling the gas to an economically
unacceptable extent to remove the large excess of moisture.
Therefore in many cases Wet catalysis processes is a more cost-
efficient way of treating hydrogen sulfide containing off-gases.
Description of the wet sulfuric acid process (WSA)
In the first step, sulfur is burned to produce sulfur dioxide.
S (s) + O2 (g) --> SO2 (g) (4-4)
or Hydrogen sulfide H2S gas is incinerated to SO2 gas.
H2S + 3/2O2 --> H2O + SO2 + 518KJ/mole (4-5)
This is then oxidized to sulfur trioxide using oxygen in the presence
of a vanadium (V) oxide catalyst.
2 SO2 + O2 --> 2 SO3 + 99KJ/mole (in presence of V2O5) (4-6)
The sulfur trioxide is hydrated into sulfuric acid H2SO4.
SO3 + H2O --> H2SO4 (g) + 101 KJ/mole (4-7)
The last step is the condensation of the sulfuric acid to liquid 97-
98% H2SO4
H2SO4 (g) + 0.17H2O (g) --> H2SO4(l) + 69 KJ/mole

Appendix 4-C References

A-5 Sulphur recovery; (2007) The Process Principles, details advances
in sulphur recovery by the WSA process. Denmark: Jens Kristen
Laursen, Haldor Topse A/S. Reprinted from Hydrocarbon Engi-
neering August 2007

A-6 U.H.F Sander, H. Fischer, U. Rothe, R. Kola (1984). Sulphur, Sul-

phur Dioxide and Sulphuric Acid (1st Edition ed.). The British Sul-
phur Corporation Limited. ISBN 0902777645.

A-7 Gary, J.H. and Handwerk, G.E. (1984). Petroleum Refining Technol-
ogy and Economics (2nd Edition ed.). Marcel Dekker, Inc. ISBN
0824771508.

4-32 Sulfuric Acid Alkylation March 5, 2014

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