PRO/II Casebook

Sulfuric Acid Alkylation Plant

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
inte- gration and material recycle, process simulation is often the
only way to quantify how different unit operations interrelate in the
over- all 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.

Copyright Notice
Case book #2
Alkylation Plant
Rev. 2 July, 2009

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2-1 Sulfuric
PRO/II Acid
Case Alkylation
Book
Plant

Sulfuric Acid Alkylation

August 5 2009
Plant 2-1

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2-2 Sulfuric
PRO/II Acid
Case Alkylation
Book
Plant

Sulfuric Acid Alkylation

August 5 2009
Plant 2-2

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 1990.1, 2 Increasing alkylate production
can par- tially offset the need to reduce reforming severities to
meet aro- matic targets. Alkylation can also be used to reduce
olefin content in gasoline.
Table 2-1 shows the octane and vapor pressure characteristics of
the principal reactants and products of an alkylation plant. This
demon- strates that, although the octane numbers of alkylation
feeds are suitable for gasoline production, the vapor pressures are
excessive. Reactor products have excellent octane as well as vapor
pressure characteristics.

Table 2-1: Octane and Vapor Pressure Characteristics of

Alkylate Reactants and Products3

Reactants

Vapor
Pressure at
100F
psia

Motor

Research

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*
20.4

Isopentane

90.3

92.3

Dimethylpentanes

88*

>100

Trimethylpentanes

98*

>100

Products (partial list)

C9s

98
*

100

approximate average

>0.5

Sulfuric acid alkylation is a highly complementary process for

refineries that are considering on-site MTBE production.4 The
MTBE process selectively reacts isobutylene 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.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 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.6

acid
iC 4 + C 3 C 7 + heat

(2-1)

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

(2-2)

Olefin polymerization is undesirable and is usually minimized by

proper mixing, low reaction temperatures and high isobutane concentrations.
(2-3)
2C H C H
3

12

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?

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 reac-

tion 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 cor- rectly 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.7 This reference provides
reac- tion 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 nec- essary to normalize the stoichiometry to integer
coefficients. Table
2-2 lists the coefficients used in this simulation. Heat of 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 2-2: Stoichiometric Coefficients for Alkylating

Pairs of Components
Propylene Isobytylene 2-Butylenes 1-Butylene
Olefin
Reactant
olefin
isobutane

12.3008
12.3461

8.5683
10.5445

10.9924
11.3223

11.5763
9.9587

0.5541
0.5553
2.3756
5.9539
0.4574
0.0731
0.3969
0.0821
0.0594
0.6688
0.4325
0.0468
0.0315

1.2706
0.5925
0.3827
0.2638
2.5703
0.3627
2.1523
0.3998
0.2074
0.2754
0.2134
0.5173
0.0239

0.6346
0.6261
0.2832
0.1703
3.3018
0.4360
4.6514
0.1852
0.0782
0.0891
0.799
.02831
0.0000

0.6877
0.5870
0.3016
0.1730
3.1778
0.5271
4.2314
0.1686
0.0984
0.0720
0.0761
0.2674
0.0079

Products
isopentene
2,3-dimethylbutane
2,4-dimethylpentane
2,2,4-trimethylpentane
2,4-dimethylhexane
2,3-dimethylhexane
2,3,4-trimethylpentane
2,2,5-trimethylhexane
C9s (nbp=280, mw=128)
C10s (nbp=325, mw=142)
C11s (nbp=365, mw=156)
C12s (nbp=395, mw=170)
C13+ (nbp=425, mw=184)

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
reac-

tion 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.
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
sim- ulations 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.8

Sulfuric Acid Alkylation Flowsheet

The flowsheet for the sulfuric acid alkylation plant with auto-refrigeration and isostripper design is shown in Figure 2-1.
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
econo- mizer where it is cooled to 65 F.

Figure 2-1: H2SO4 Alkylation Plant

The stream is split into four equal parts, each of which enters a
sep- arate reaction chamber. Olefin reacts to extinction with
isobutane in each chamber to form alkylate. 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 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
2-3.

Table 2-3: Feed Hydrocarbon Conditions

Component Rates, standard liq. vol, bbl/hr
Saturated
Olefin
Supplemental
Feed
Feed
Isobutane
1
2
3
Stream ID
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

399.5

413.0

45.0

Temperature, F

100

100

100

Pressure, psia

400

215

400

Total

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 2-4: Acid Feed to Reactor

Property
Stream Property Value
Feed Stream ID

Stream ID
Acid rate, 106 lb/hr
Temperature, F
Pressure, psig

SA1
SA1
1.00
45
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.

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 2-1, 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 tight- ened, 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 abso- lute 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 comple- tion on each recycle pass. This permits the recycle and
control loop to converge simultaneously, reducing CPU time. An
absolute toler- ance 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.
Follow- ing the successful convergence of all recycle loops,
detailed effluent calculations are performed once by solving two
2-11PRO/II
SulfuricCase
AcidBook
Alkylation Plant

Sulfuric Acid Alkylation

August 5 Plant
2009 2-

compressors and a heat exchanger (seeFigure 2-2). Although the

compressors do not

2-12PRO/II
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AcidBook
Alkylation Plant

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August 5 Plant
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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 P-T (constant
pressure - constant temperature) heat exchanger to the single P-T
flash unit MCOM.
Figure 2-2: 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 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
avail- able 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 2-5, including total reboiler duties, reactor
effluent flowrates and isobutane content, refrigeration loads, and
product flows. These parameters form the basis for calculating
operating expenses.

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Table 2-5: Key Flowsheet Parameters

Run #1 - Auto-refrigeration and Isostripper Operation
Base Case

More C3
Recycle

More iC4
Recycle

More nC4
in Feed

50

100

50

50

2525

2525

2600

2525

50

1.00
28.24
80.69
9.09
119.02

1.00
29.02
80.69
9.08
119.79

1.00
28.40
82.73
9.10
121.23

1.00
28.46
80.36
11.73
122.05

2180
64.0

2180
64.0

2232
64.0

2214
58.4

996
2005
3001

995
2005
3000

977
2005
2982

1044
2069
2113

17.41

17.42

17.44

111.1
118.6
522.3

111.0
118.9
522.3

110.8
168.7
522.6

Input Flow Parameters

C3 in de-propanizer
bottoms, moles/hr
Recycle from isostripper,
bbl/hr
Additional normal butane
in saturates feed, bbl/hr

Calculated Flow Parameters

Reboiler duties, 106 Btu/hr
De-ethanizer DEC2
De-propanizer DEC3
Iso-stripper DIC4
De-butanizer DEC4
Total reboiler duties

HC liquid reactor effluent

Hot volume rate, gpm
isobutane content, liq vol %
Compressor shaft power, hp
Stage 1
Stage 2
Total compressor duty

Product flowrates at standard conditions

Gas products, mscfh
Fuel gas
17.42
Liquid products, bbl/hr
Liquid propane
111.1
Normal butane
118.9
12 RVP alkylate
522.3

The significance of these results can be summarized as follows:

Table 2-6: Significance of Simulation Results for Run #1

Case

Observation

Conclusion

More C3 in
depropanizer
bottoms

Increases depropanizer reboiler

duty

Profitability is improved when

propane in depropanizer bottoms
is minimized.

More iC4
recycle

Increases isobutane concentration in reactor.

Reduces reactor and settler residence time due to increased
reactor throughput.
Increases isostripper reboiler
duty.
Reduces first stage compressor
load.

Increase in octane and decrease

in acid consumption due to isobutane 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.

More nC4 in
feed

Reactor iso-butane concentration

decreases.
Reactor throughput increases.
The debutanizer reboiler rate
increases in proportion to
increases in product butane.
The refrigeration load requirement decreases.

Although normal butane is an

inert copmponent in the reactor,
it adversely affects plant profitability. In particular, the
decrease in reactor iso-butane
concentra- tion translates to a
significant drop in octane and
increase in acid consumption.

2-14 Sulfuric Acid Alkylation Plant

August 5 2009

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

Refrigeration and Deisobutanizer with effluent
Refrigeration
Appendix 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.
Figure 2-3: 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
demon- strated by Run #1.

2-15PRO/II
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Alkylation Plant

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August 5 Plant
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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.

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After decanting the acid, the hydrocarbon reactor effluent is let

down and passed through the tube side of the reactor. A 10 F hotout/cold-out approach is assumed to be sufficient to cool the reactor, thus the tube side outlet is assumed to be at 35 F.

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

Results

Key operating conditions for all three configurations studied are

summarized in Table 2-7.

Table 2-7: Comparison of Key Flowsheet Parameters for Alternate

Configurations
Refrigeration circuit

AutoRefrigeration

AutoRefrigeration

Effluent
Refrigeration

Deisobutanizer configuration

Isostripper

Deisobutanizer

Deisobutnaizer

Calculated Flow Parameters

Reboiler duties, 106 Btu/hr
De-ethanizer DEC2
De-propanizer DEC3
Iso-stripper DIC4
De-butanizer DEC4
Total reboiler duties

HC liquid reactor effluent

Hot volume rate, gpm

isobutane content, liq vol %
Compressor shaft power, hp
Stage 1
Stage 2
Total compressor duty

1.00
28.24
80.69
9.09
119.02

1.00
27.11
80.03
9.10
117.24

1.00
27.20
80.03
9.10
117.33

2180
64.0

1131
50.7

1120
50.2

996
2005
3001

1454
2016
3470

1706
2086
3792

17.46

17.48

111.0
119.0
522.3

110.9
119.0
522.3

Product flowrates at standard conditions

Gas products, mscfh
Fuel gas
17.42
Liquid products, bbl/hr
Liquid propane
111.1
Normal butane
118.9
12 RVP alkylate
522.3

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The significance of these results can be summarized as follows:

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

Comparison

Observation

Conclusion

Isostripper vs.
deisobutanizer

Debutanizer operation decreases

substantially the isobutane content in the reactor.
The deisobutanizer operation
substantially decreases the reactor volumetric throughput.
The deisobutanizer operation
decreases the depropanizer duty,
but increases refrigeration load.

The isostripper operation

requires a substantially larger
capital investment for increased
reactor and settler volumes. The
benefit to this is a substantially
improved octane and lower acid
consumption due to the higher
reactor isobutane concentration.

Auto vs. effluent

refrigeration

Autorefrigeration requires less

refrigeration.

Based on the operating

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.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.

References
1
2
3
4

6
7

Masters, K.R., "Alkylation's Role in Reformulated Gasoline",

presented at 1991 Spring National Meeting AIChE.
Unzelman, G.H., "U.S. Clean Air Act Expands Role for Oxygenates", Oil & Gas Journal, April 15, 1991.
API, Technical Data Book ? Petroleum Refining, Volume
1 (1987).
Chapin, L.E., Liolios, G.C. and Robertson, T.M., "Which
Alkylation? HF or H2SO4?", Hydrocarbon Processing, September 1985, pg. 67?71.
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).
Lee, L. and Harriott, P., "The Kinetics of Isobutane
Alkylation in Sulfuric Acid," I&EC Process Design Dev., 16,
3Cupit,
(1977).
C.R., Gwyn, J.E. and Jernigan, E.C., "Special Report
Catalytic Alkylation", Petroleum and Chemical Engineering,
33, 47, 1961 and 34, 49, (1962).
Soave, G., "Equilibrium Constants from a Modified
Redlich?Kwong Equation of States," Chem. Eng. Sci., 27,
1177?1203 (1972).
Lerner, H. and Citarella, V.A., "Exxon Research and
Engineer- ing Sulfuric Acid Alkylation Technology",
presented at 1991
NPRA Annual Meeting.

Appendix 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.

$ 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
(100F),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), &
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
COLD FEED=1,1NB,27P,L=10

2-21PRO/II
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Sulfuric Acid Alkylation

August 5 Plant
2009 2-

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 n v
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

2-22PRO/II
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Alkylation Plant

Sulfuric Acid Alkylation

August 5 Plant
2009 2-

$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$
$
$
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
2-23PRO/II
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Alkylation Plant

Sulfuric Acid Alkylation

August 5 Plant
2009 2-

REACTION RX4
BASE COMPONENT=9
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
2-24PRO/II
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AcidBook
Alkylation Plant

Sulfuric Acid Alkylation

August 5 Plant
2009 2-

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 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
VARY DUTY=1
ESTIMATE MODEL=CONVENTIONAL
PRESSURE 1,90 / 42,95
2-25PRO/II
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2009 2-

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
PROD L=11A
OPERATION PRES=600
2-26PRO/II
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COLUMN UID=DEC2, NAME=DEETHANIZER

2-27PRO/II
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2009 2-

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

2-28PRO/II
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2009 2-

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

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2009 2-

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

2-30PRO/II
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2009 2-

Appendix B:
Input Changes for Runs 2 and 3
Keyword Input File Inserts for Run 2 (De-isobutanizer Configuration) and Run 3(Effluent Refrigeration Configuration)
Substitute these file inserts for the corresponding sections if input
listed in Appendix A.

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
PRESSURE 1, 85 / 2, 90 / 43, 95
TRATE
SECTION=2,42 SIEVE, PASSES=4, &
SPACING(TRAY, IN)=24, DIAMETER(TRAY,
FT)=13
PRINT PROP=BRIEF

2-31PRO/II
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Alkylation Plant

Sulfuric Acid Alkylation

August 5 Plant
2009 2-

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

2-32PRO/II
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Appendix 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
condensa- tion in the WSA condenser ensures that the regenerated
fresh acid will be 98% w/w even with the humid process gas. It will
be possi- ble to combine spent acid regeneration with disposal of
hydrogen sulphide by using hydrogen sulphide as fuel.[A1].
The wet sulfuric acid process (WSA process) is one out of many
gas desulfurization processes on the market today. Since its
introduc- tion in the 1980s, where it was patented by the Danish
catalyst com- pany 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 pro- cess 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 conden- sation of the sulfuric acid vapour and not by absorption
of the sulfur trioxide in concentrated sulfuric acid, as is the case in
contact pro- cesses based on dry gases. The concentration of the
product acid depends on the H2O/SO3 ratio in the catalytically
converted gases and on the condensation temperature. [A1] [A2]

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The wet catalysis process is especially suitable for processing the

wet gasses obtained by the combustion of hydrogen sulfide (H2S)
containing off-gasses.[A3] 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. There- fore 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)
or Hydrogen sulfide H2S gas is incinerated to SO2 gas.
H2S + 3/2O2 --> H2O + SO2 + 518KJ/mole
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)
The sulfur trioxide is hydrated into sulfuric acid H2SO4.
SO3 + H2O --> H2SO4 (g) + 101 KJ/mole
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 C References
A1

A2

A3

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 Engineering August 2007
U.H.F Sander, H. Fischer, U. Rothe, R. Kola (1984).
Sulphur, Sulphur Dioxide and Sulphuric Acid (1st Edition
ed.). The British Sulphur Corporation Limited. ISBN
0902777645.
Gary, J.H. and Handwerk, G.E. (1984). Petroleum Refining
Technology and Economics (2nd Edition ed.). Marcel
Dekker, Inc. ISBN 0824771508.

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