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Design and Control of a Modified Vinyl Acetate Monomer Process

William L. Luyben*

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Publication Date (Web): August 17, 2011 | doi: 10.1021/ie201131m

Department of Chemical Engineering, Lehigh University, Bethlehem, Pennsylvania 18015, United States
ABSTRACT: The vinyl acetate monomer (VAM) process presents several challenging design problems because of the many design
optimization variables and several important constraints. The process features a cooled tubular reactor, both gas and liquid recycle
streams, two absorbers, and two distillation columns, one involving heterogeneous azeotropic distillation. The major design
variables are reactor temperature, reactor size, reactor pressure, ethylene gas recycle and acetic acid liquid recycle. The major
constraints are a maximum oxygen ammability limit, a maximum internal reactor temperature limit, and the need to stay above
dewpoint temperatures in the reactor. This paper develops an economic optimum owsheet based on the conditions and parameters
provided by M. L. Luyben and B. D. Tyreus over a decade ago as a challenge problem for the academic community for design and
control studies (Comput. Chem. Eng. 1998, 22, 867
877). The conceptual design developed produces 18% more VAM product for
the same oxygen fresh feed ow rate used in the original design. Compared to the original nonoptimized design, the modied design
has a reactor that is twice as large with reactor inlet conditions showing lower oxygen concentrations and higher acetic acid
concentrations. Operating pressure is lower, liquid acetic acid recycle is larger, and gas ethylene recycle is smaller. A plantwide
control scheme that provides eective disturbance rejection and is signicantly dierent than the structure used in the original design
is developed.

1. INTRODUCTION
The industrial challenge problem presented by Luyben and
Tyreus1 has received only limited attention by the academic
community despite its rich mixture of important steady-state
design and dynamic control features and issues. Three plantwide control studies were reported. All of these control studies
are based on the original owsheet presented in the challenge
problem. Luyben et al2 demonstrated that eective plantwide
control could be achieved using a conventional PI control
structure. Chen et al3 developed a nonlinear dynamic model in
Matlab and studied alternative control structures. Olsen et al4
presented other alternative control structures.
There was no claim in the original paper that the process
design had been optimized from the standpoint of economics.
The original owsheet used a reactor with 622 tubes, 0.037 m in diameter and 10 m in length. The gas recycle was large (939 kmol/h)
and the liquid acetic acid recycle was small (84.2 kmol/h). With a
fresh oxygen feed of 31.26 kmol/h, the vinyl acetate monomer
(VAM) product was 49.56 kmol/h.
A conceptual design is developed in this paper that nds the
economic optimum equipment sizes and operating conditions,
which are signicantly dierent than the original design. The
basic unit operations are the same as in the original design, but
equipment sizes and operating conditions are quite dierent.
The most signicant improvement in performance is an 18%
increase in the production of VAM for the identical fresh feed
ow rate of oxygen. A bigger reactor is required, but the
dominant economic value of the product should easily justify
the increase in capital investment.
There are three very important and interacting constraints in
this process. The vital safety constraint is to keep the oxygen
concentration below the ammability limit. The largest oxygen
concentration occurs at the reactor inlet. In the original design,
this concentration was reported as 7.4 mol % oxygen. In the
r 2011 American Chemical Society

proposed owsheet, the oxygen concentration is only 2.6 mol %,

far below the maximum safety limit. The lower oxygen concentrations improve the selectivity since the combustion reaction is
lowered.
The second constraint is a maximum reactor temperature of
455 K to prevent catalyst degradation. Since the reactor is cooled,
the maximum temperature occurs partway down the reactor.
With a xed coolant temperature on the shell side of the reactor
tubes and xed reactor size, this constraint can be maintained by
adjusting the ow rate of gas recycle, which is mostly ethylene.
The higher the gas recycle, the lower the peak temperature. Of
course, higher gas recycle means higher gas compression costs in
terms of both capital and energy.
The third important constraint is the need to guarantee that
there is no liquid in the reactor since the reactions occur in the gas
phase. Liquid can form if the temperatures in the reactor are too
low, if the pressure is too high, or if the concentration of the highboiling acetic acid is too high.
Low reactor temperatures improve selectivity (more VAM
and less CO2) because the activation energy of the VAM reaction
is lower than that of the combustion reaction, as discuss in the
next section. Reactor temperatures are aected by the coolant
temperature and the gas recycle. At low coolant temperatures, it
is sometimes necessary to increase gas recycle beyond that
required to limit the peak reactor temperature in order to keep
above dewpoint temperatures.
Although selectivity is reduced by running at higher reactor
temperatures, there is an important advantage of being able to
recover the exothermic heats of reaction through generation of
Received: May 25, 2011
Accepted: August 6, 2011
Revised:
July 25, 2011
Published: August 07, 2011
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Figure 1. Modied owsheet.

steam in the reactor, which is an energy credit. If the cooling

medium temperature on the shell side of the cooled reactor
can be operated at 433 K, low-pressure steam can be produced
(6 bar) with a value of $7.78 per GJ (Turton6).
Higher acetic acid concentrations also improve selectivity and
can be achieved by increasing acetic acid recycle. However, more
gas recycle may be required to prevent the formation of liquid in
the reactor. In addition, energy consumption in the acetic acid
vaporizer and in the azeotropic distillation column increase.
All of these issues must be considered in the conceptual design of this very interesting and complex process. The modied
design has 1100 tubes instead of 622. The acetic acid recycle is
much larger, which results in a reactor inlet concentration of
30.28 mol % acetic acid compared to the original design of 11 mol
%. The operating pressure is reduced from 8.7 to 6.5 atm. The
reboiler duty of the azeotropic column is reduced from 4.65 to
3.47 MW.
The original design had a high concentration of the chemically
inert ethane (21.6 mol % C2H6) in the gas recycle loop, which
was assumed to build up. The ethane concentration in the
modied design based on steady-state Aspen Plus simulation is
found to be very small. There are only 0.05676 kmol/h of ethane
entering in the fresh ethylene feed (99.9 mol % C2H4). Most of
this leaves as small impurities in the organic product stream
(0.02639 kmol/h C2H4) and in the aqueous stream (0.02688
kmol/h C2H4) with trace amounts in the purge and decanter
vent streams. In the dynamic simulation discussed later in this
paper, a much larger purge ow rate is required to prevent the

buildup of the inert ethane since Aspen Dynamics predicts very

small concentrations of ethane in both products.

2. PROCESS DESCRIPTION
Figure 1 shows the modied design. In all the cases presented
in this paper, the ow rate of fresh oxygen is xed at 31.26 kmol/
h, which is the same as used in the original design. The conditions
shown in Figure 1 are the economic optimum as developed in a
later section in this paper.
Fresh acetic acid is combined with an acetic acid recycle
stream and fed into a vaporizer along with a gas stream, which is
the fresh ethylene feed plus a gas recycle stream. The vaporizer
operates at 6.6 atm and 423 K, which requires medium-pressure
steam (11 bar, 457 K, $8.22 per GJ). Vaporizer energy consumption is 3.88 MW.
The vapor stream is combined with fresh oxygen and enters
the cooled tubular reactor at 421 K with a concentration of 2.63
mol % oxygen and 30.28 mol % acetic acid, the remainder being
mostly ethylene. The reactor contains 1100 tubes, 0.037 m in
diameter and 10 m in length. The coolant temperature is 433 K,
and the heat removal in the reactor is 2.79 MW. The overall heattransfer coecient is that used in the original design (0.17 kW
m
2 K
1). Figure 2 gives temperature and composition proles
in the reactor. The maximum temperature is 455 K with the
coolant temperature of 433 K and a gas recycle ow rate of 744
kmol/h. Catalyst properties are taken from the Luyben and
Tyreus paper (0.8 void volume, 1935 kg/m3 particle density).
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Figure 2. (a) Reactor temperature prole; (b) reactor composition proles.

The per-pass conversion of ethylene is 7.3%, of acetic acid

is 15%,and of oxygen is 97.8%. The selectivity is 23 (ratio of VAM
formed in the reactor to CO2 formed in the reactor). It should be
noted that the selectivity of the original process is only 11, so a very
signicant improvement in the yield of VAM has been achieved.
The reactor euent is cooled to 323 K and fed to a ash drum.
The liquid stream is fed to the rst distillation column. The gas
stream is fed to an absorber in which VAM is recovered by an
acetic acid wash stream. The gas from the absorber goes to a
second absorber that removes carbon dioxide using a monoethanol amine solution. The gas from the top of the CO2
absorber is compressed and recycled to the vaporizer.
The liquid streams from separator and from the VAM absorber
are fed to a distillation column whose function is to remove the small

amount of ethylene contained in these streams. The de-ethanizer

column (D/E) operates at 27.2 atm. The reux-drum temperature
is 257 K, so refrigeration is required in the condenser. The easy
separation between ethylene and VAM is achieved using a 21-stage
column and a reux ratio of 1.
The bottoms from the D/E column is fed to the second
distillation column whose function is to recover the acetic acid for
recycle back to the vaporizer. A 21-stage column is assumed,
which is the same as that used in the original design. The ternary
system of VAM, water, and acetic acid is highly nonlinear with a
heterogeneous azeotrope formed. The overhead vapor from the
column is cooled to 310 K and forms two liquid phases in a
decanter. The aqueous phase is 99.45 mol % water. The organic
phase is 94.41 mol % VAM. A small vent stream leaves the top of
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Figure 3. T
xy diagram for ethylene/VAM at 27.2 atm.

the decanter. Reux to the top of the azeotropic column is a

portion of the organic phase from the decanter. This reux is
adjusted to maintain the VAM composition of the organic phase
in the decanter and varies as acetic acid recycle, reactor size, and
system pressure are varied.

3. KINETICS AND PHASE EQUILIBRIUM

The kinetic equations given by Luyben and Tyreus are not
easily implemented in Aspen simulations because they are not in
the convenient power-law form and would require writing and
compiling of a user kinetic subroutine. As a practical engineering
alternative, the approach taken was to t the performance results
(yield of VAM and CO2) for the reactor given in the original
design by selecting pre-exponential factors and activation energies for the two reactions.
1
C2 H4 CH3 COOH O2 f CHOCOCH3 H2 O
2
C2 H4 3O2 f 2CO2 2H2 O
1
The physical dimensions of the reactor and catalyst properties
were xed at those given in the original design (622 tubes, 0.037 m
in diameter and 10 m in length lled with 2590 kg of catalyst). The
coolant temperature (406 K) and overall heat-transfer coecient
(U = 0.17 kW m
2 K
1) were those used in the original design.
The reactor inlet conditions were set as those given in the original
design in terms of inlet temperature, pressure and all molar ow
rates. The ratio of the activation energies of the two competing gasphase irreversible reaction was set at 2.5, which is close to the ratio
given in the original design (E1 = 8000 kJ/kmol and E2 = 20000 kJ/
kmol). Then the values of the two pre-exponential factors (R1 and
R2) were varied by trial and error until the production rates of VAM
and CO2 in the reactor were close to those reported in the original
design. The kinetic relationships used in this paper are
R 1 R1 e
E1 =RT pE pHAc pO 0:5 5:8  10
18 e
8000=RT pE pHAc pO 0:5
R 2 R2 e
E2 =RT pE pO 6:7  10
15 e
20:000=RT pE pO

Overall reaction rates R n have units of kmol s
1 kg
1. Partial

pressures of components pj have units of Pascals. Note that the
combustion reaction is assumed to be rst-order in both oxygen and
ethylene partial pressures.
These simplied kinetics are compared in the following
paragraph with those given in the original paper that show more
complex composition dependence.
"

pE pHAc pO 1 1:7pW
1 0:583pO 1 1:7pW 1 6:8pHAc 
"
#
pO 1 0:68pW
R 2 1:9365  105 e
10116=T
1 0:76pO 1 068pW

R 1 0:1036e
3674=T

3
Overall reaction rates R n have units of mol min
1 g
1 in eq 3.
Partial pressures of components pj have units of psia. Using
the reactor inlet compositions, coolant temperature and reactor pressure in the original paper, the two reactions rates can
be calculated: R 1 = 3.203  10
4 and R 2 = 8.83  10
6 mol
min
1 g
1. These can be compared with those calculated using
the reactor conditions in the modied design shown in Figure 1:
R 1 = 3.089  10
4 and R 2 = 0.152  10
6 mol min
1 g
1. It is
clear that the reactor conditions in the modied design are more
favorable for the production of desired VAM. This demonstrates
that the simplied kinetics used in this study have been successful
in developing a process with a much higher selectivity, as
conrmed by the calculations using the rigorous kinetics.
The phase equilibrium in the VAM process is quite nonlinear
with a heterogeneous azeotrope formed in the ternary system of
VAM, acetic acid, and water. The Aspen NRTL phase equilibrium parameters are used in the simulations of the vaporizer,
reactor, absorber, de-ethanizer, and decanter. The UNIFHOC physical property package is used in the azeotropic column
to account for the association of acetic acid. The valid phases in
this column are VLL. The separation in the rst D/E column
between ethylene and VAM is fairly easy, as shown in the T
xy
diagram given in Figure 3 at the operating pressure of 27.2 atm.
A ternary diagram is given in Figure 4 for the principal
components in the azeotropic column: VAM, acetic acid, and
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Figure 4. Ternary diagram for VAM/water/acetic acid at 0.33 atm.

water. The pressure is 0.33 atm, which gives a heterogeneous

azeotropic temperature of 312 K that is close to the decanter
temperature. The bottoms from the column contains 5 mol %
water. The composition of the overhead vapor from the column
is close to the azeotropic composition. The column feed is 535.3
kmol/h and the organic reux is 390 kmol/h, giving the mix point
shown in Figure 4 between the feed composition and the organic
composition. The component balance line runs through the mix
point and connects the bottoms point and the overhead point.
The AMINES physical property package is used in the CO2
absorber. The MEA/water solvent fed to the top of the absorber
would come from the base of a stripping column, which is not
included in the simulation because the stripping column has little
economic eect on the major units of the process.

4. FLOWSHEET CONVERGENCE
It might be useful to say a few words about the issue of
owsheet convergence for this complex multiunit process. The
existence of two recycle streams can present signicant problems
in these types of processes. However, the two recycles were
successfully closed by employing the technique of xing the total
ows (fresh plus recycle) and permitting the makeup streams
to vary.
For example, the total ow rate of gas to the vaporizer (fresh
ethylene feed plus recycle gas) is held constant using an Aspen
Plus Flowsheet Design Specication that varied the ethylene fresh
feed. A second Aspen Plus Flowsheet Design Specication varied
the acetic acid fresh feed to maintain a specied total acetic acid
ow rate (fresh plus recycle) to the vaporizer. This convergence
method worked quite well and was successful in handling a wide
range of values of design variables.
5. EFFECT OF DESIGN VARIABLES
The four major design variables in the vinyl acetate monomer
process are reactor temperatures (set by the temperature of the

coolant and the ow rate of gas recycle that maintains a 455 K

peak temperature), the reactor size (set by the number of tubes),
the pressure in the gas loop (vaporizer, reactor, separator, and
absorbers), and the ow rate of the recycle acetic acid. An
iterative exhaustive enumeration of these four variables was used
to nd the optimum values of the design variables. The economic
objective function was incremental return on incremental investment. For example, as more tubes are used in the reactor, capital
investment increases due to the cost of the vessel (more heattransfer area) and the cost of the catalyst. Production of VAM
product increases as more tubes are added, but the increase is at
an increasingly smaller rate. The point that gives an incremental
ROI of at least 30% was selected.
The three constraints that must be satised are a maximum
peak temperature in the reactor, an upper limit on the oxygen
concentration of the feed to the reactor (assumed to be 7 mol %
oxygen), and the requirement that the material in the reactor is all
gas phase (temperature must be above the dewpoint temperature
of the mixture at all points in the reactor). Keep in mind that the
ow rate of fresh oxygen is xed for all cases.
5.1. Effect of Reactor Size. The catalyst in the VAM process is
quite expensive because it contains palladium. A catalyst cost of
$800 per kg is assumed (2.27 wt % palladium at $800 oz), which
favors small reactors to reduce capital investment.
A reactor coolant temperature of 433 K is initially selected so
that the steam generated in the reactor can be used elsewhere in
the plant as low-pressure steam. Operating with lower coolant
temperature is explored in a later section. The peak reactor
temperature is maintained at 455 K by varying gas recycle ow
rate using a Flowsheet Design Specication. The acetic acid recycle
is initially set at 375 kmol/h. Reactor inlet pressure is initially set
at 6.5 atm.
With these design variables xed, the eect of changing the
number of reactor tubes is shown in Figure 5. The production of
VAM and the consumption of reactants increase as more tubes
are used in the reactor, but these ow rates begin to level out for
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Figure 5. Eect of reactor size.

more than about 1200 tubes. Since the product is worth more
than the reactants, prot increases. But capital cost of the reactor
vessel and the catalyst increase linearly as more tubes are used.
The cost of the reactor vessel is based on the heat-transfer area.
The economic parameters for chemical costs given by Tyreus
and Luyben are used to assess the economics: VAM = $0.971 per
kmol, ethylene = $0.442 per kmol and acetic acid = $0.596 per
kmol. The cost of oxygen is not considered because the fresh
oxygen ow rate is the same in all cases. A pseudo-prot
parameter is dened as the value of the VAM produced minus the
cost of the ethylene and acetic acid reactants minus the energy
costs of the compressor, vaporizer, and azeotropic column
reboiler plus the value of the reactor steam:

Table 1. Eect of Reactor Sizea

Ntubes = 1000 Ntubes = 1100 Ntubes = 1200

profit$=h produce kmol=h$0:971

fresh ethylene kmol=h$0:442

fresh HAc kmol=h$0:596


3600 s=h
$16:8=GJ

compressor work kW
106 kW=GW


3600 s=h
$8:22=GJ

vaporizer energy MW
103 MW=GW


3600 s=h
$7:78=GJ

azeo column reboiler MW
103 MW=GW


3600 s=h
$7:88=GJ
4
reactor steam MW
103 MW=GW
The energy costs in the de-ethanizer (reboiler heat input and
condenser refrigeration) and in the absorbers remain essentially
the same as conditions in the reactor are changed, so they are not
considered.
Capital investment is the sum of the installed costs of the
reactor vessel, catalyst, vaporizer, and compressor. The capital
costs of all the other units remain essentially the same as
conditions in the reactor change. They are not considered in
the economics since an incremental return on investment is used

product
gastot

kmol/h
kmol/h

57.538
821.6

57.983
796.9

58.202
786.3

ethylene

kmol/h

56.27

56.61

56.79

acetic acid

kmol/h

55.15

55.57

55.77

organic reux kmol/h

369

371

372

Qvap

MW

3.833

3.807

3.801

Tvap

421.6

422.2

423

QRX

MW

2.724

2.784

2.824

QR2
compressor

MW
kW

2.638
266.3

2.658
257.2

2.668
253.3

yRXin

mol % O2

2.71

2.66

2.64

mol % C2H4

64.35

63.81

63.57

mol % HAc

29.03

29.66

29.94

xB2

mol % H2O

6.19

6.03

5.97

prot

106 $/y

14.606

14.761

14.841

capital

106 $

5.6159

6.0577

6.5096

Conditions: 6.5 atm; HAc total = 375 kmol/h; Tcool = 455 K; Tmax = 455 K.

to select the optimum values of design variables. Cost equations

from Douglas5 and Turton et al6 are used to calculate these
capital costs.
Figure 5 and Table 1 show that prot is increasing but capital
investment is also increasing as more reactor tubes are used. The
incremental return on investment decreases. Moving from 1000
to 1100 tubes gives an incremental return on investment of 35%.
Adding more tubes yields a lower incremental return on investment. Note that the required total gas recycle is set to achieve
a 455 K peak reactor temperature. Under these conditions, with
a 433 K reactor coolant temperature, the dewpoint limitation
is avoided (the process stream leaving the reactor has a vapor
fraction >1). Reactor inlet oxygen concentration (2.66 mol %) is
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Figure 6. Eect of HAc recycle.

Table 2. Eect of Acetic Acid Recyclea

HAc total =
375 kmol/h

HAc total =
385 kmol/h

HAc total =
395 kmol/h

product
gastot

kmol/h
kmol/h

57.983
796.9

58.188
800.6

58.388
804.3

ethylene

kmol/h

56.61

56.74

56.88

acetic acid

kmol/h

55.57

55.76

55.96

organic reux kmol/h

371

390

410

Qvap

MW

3.807

3.881

3.968

Tvap

422.2

423

423

QRX

MW

2.784

2.789

2.795

QR2
compressor

MW
kW

2.658
257.2

2.806
258.2

2.986
259.1

yRXin

mol % O2

2.66

2.63

2.59

mol % C2H4

63.81

63.41

63.02

mol % HAc

29.66

30.26

30.89

xB2

mol % H2O

6.03

5.29

4.69

prot

106 $/y

14.761

14.776

14.772

capital

106 $

6.0577

6.0601

6.0622

Conditions: 6.5 atm; Ntubes = 1100; Tcool = 455 K; Tmax = 455 K.

well below the ammability limit of 7 mol %. However, the eects

of other important design optimization variables must be considered. One of the most important is acetic acid recycle.
5.2. Effect of Acetic Acid Recycle. The kinetic relationships
indicate that higher acetic acid concentrations in the reactor feed
should promote the desired VAM reaction. However, more
acetic acid recycle means higher energy consumption in the
vaporizer. The azeotropic column energy consumption is also
higher because more organic reflux is required to maintain the
VAM purity of the organic phase in the decanter. In addition,
since acetic acid is the heaviest component in terms of volatility,
higher acetic acid concentration in the reactor raise the dewpoint

temperature, which could require either more gas recycle or

higher reactor coolant temperatures.
Figure 6 and Table 2 give results for a range of acetic acid
recycle ow rates. The abscissa in Figure 6 is the total acetic acid
(fresh feed plus recycle). The production of product VAM
increases, as does the consumption of reactants (ethylene and
acetic acid). Gas recycle ow rate increases to keep the 455 K
peak temperature, which increases compressor work. Naturally
vaporizer energy consumption increases, as does the required
organic reux (R2) to the azeotropic column.
Prot initially increases, but hits a maximum at a total acetic
acid ow rate of 385 kmol/h. Capital investment increases
steadily but quite slowly as acetic acid recycle is increased. Table 2
shows a large incremental return on an incremental investment in
going from 375 to 385 kmol/h. Prot increases by $15,000 per
year for a small $24,000 increase in capital investment.
It should be noted that the reactor inlet acetic acid composition
in the modied design (30.26 mol % HAc) is very signicantly
dierent than that in the original (11 mol % HAc) because of
the much larger acetic acid recycle ow rate (329.2 compared to
84.2 kmol/h). The higher acetic acid concentrations in the reactor
promote the desired VAM reaction.
In addition, the reactor inlet oxygen composition in the modied
design (2.63 mol % O2) is signicantly dierent than that in the
original (7.4 mol % O2). This inhibits the undesired combustion
reaction. Finally, the reactor size is signicantly dierent (1100
versus 622 tubes), which means higher capital investment in the
reactor vessel and catalyst. However, the valuable VAM produced is
much larger (58.19 versus 49.56 kmol/h), which can justify a
signicant increase in capital investment and energy consumption.
Note also that the vaporizer energy consumption is higher (3.88
MW in the modied design versus 1.5 MW). However, the azeotropic column reboiler duty is lower (2.806 MW in the modied versus 4.65 MW). Since the recycle gas ow rate is smaller in
the modied design, the compressor work is smaller (258 versus
350 kW).
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Figure 7. Eect of pressure.

Table 3. Eect of Pressurea

P = 6.0 atm

P = 6.5 atm

P = 7.0 atm

product

kmol/h

57.368

57.538

57.629

gastot
ethylene

kmol/h
kmol/h

676.0
56.03

821.6
56.27

966.1
56.37

acetic acid

kmol/h

55.00

55.15

55.24

organic reux

kmol/h

387

369

357

Qvap

MW

3.650

3.882

4.000

Tvap

423

422

420

QRX

MW

2.784

2.724

2.670

QR2

MW

2.804

2.638

2.529

compressor
yRXin

kW
mol % O2

233.2
3.21

266.3
2.71

294.3
2.36

mol % C2H4

63.81

64.35

65.02

mol % HAc

33.21

29.03

25.77

xB2

mol % H2O

6.03

6.19

7.09

prot

106 $/y

14.598

14.606

14.584

capital

106 $

5.5409

5.6159

5.6781

a
Conditions: HAc total = 375 kmol/h; Ntubes = 1000; Tcool = 455 K;
Tmax = 455 K.

5.3. Effect of Reactor Pressure. The reaction rates of both

reactions depend directly on pressure, so higher pressures increase
both reaction rates, as shown in the kinetics given in eq 2, which
should decrease reactor size for a given conversion. The undesirable
combustion reaction is assumed to have first-order dependence on
oxygen while the desirable VAM reaction is assumed to have a squareroot dependence. Therefore, lower pressure should favor the desired
reaction, and selectivity should improve lower pressures. Both fresh
gas streams are available at high pressure, so feed gas compression is
not required over the range of system pressures considered.

The results of running several pressures are shown in Figure 7

and Table 3. The other three design variables are xed at Tcool =
433 K, Ntubes = 1000 and HAc total = 375 kmol/h. The most
important eect of changing pressure is the ow rate of gas
recycle, which is set to maintain a peak reactor temperature of
455 K. The middle left graph in Figure 7 shows a very large
change in the Gastot required. As the pressure at the inlet of the
reactor is varied from 5.5 to 7 atm, the total gas increases by a
factor of 2.
The reactor heat removal changes only slightly, and the reactor
temperature proles are very similar at all pressures. The higher
reaction rates at higher pressure require more gas recycle so that
the maximum peak temperature in the reactor is not exceeded.
Naturally, the larger gas recycle increases compressor costs. Table 3
shows that vaporizer energy consumption also increases. Since the
gas recycle goes through the vaporizer in order to lower vaporizer
temperatures, more gas must be heated as gas recycle increases.
More product is produced as pressure is increased, but prot
hits a peak at 6.5 atm because of the increases in energy costs in
the compressor and the vaporizer.
5.4. Effect of Reactor Coolant Temperature. The kinetic
relationships indicate that lower reactor temperatures should
improve selectivity because the activation energy of the desired
VAM reaction is smaller than the activation energy of the
undesired combustion CO2 reaction. However, lower reactor
temperatures decrease conversion so bigger reactors are required. Lower reactor temperatures also require higher gas
recycle flow rate to keep from forming liquid in the reactor.
The optimum design involves an economic trade-off among
these various effects. Running the reactor hot enough to generate
steam would appear to be the best design, but several other
coolant temperatures were explored.
Figure 8 and Table 4 give results over a range of reactor coolant
temperatures. The other variables xed in these runs are 1100
tubes, 6.5 atm, and 385 kmol/h HAc total. In most cases the gas
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Figure 8. Eect of reactant coolant temperature.

Table 4. Eect of Reactor Coolant Temperaturea

Tcool = 430 K Tcool = 433 K Tcool = 435 K
product
gastot

kmol/h
kmol/h

58.801
665.8

58.188
800.6

57.564
919.3

ethylene

kmol/h

57.19

56.74

56.31

acetic acid

kmol/h

56.33

55.76

55.19

organic reux kmol/h

419

390

375

Qvap

MW

3.797

3.881

3.964

Tvap

427

423

420

QRX

MW

2.984

2.789

2.619

QR2
compressor

MW
kW

3.090
209.2

2.806
258.2

2.673
301.2

mol % O2

2.90

2.63

2.46

mol % C2H4

59.40

63.41

66.23

yRXin

mol % HAc

34.33

30.26

27.43

xB2

mol % H2O

3.90

5.39

6.35

prot

106 $/y

14.259

14.776

14.521

capital

106 $

5.948

6.0601

6.1553

Conditions: HAc total = 385 kmol/h; Ntubes = 1100; Tmax = 455 K; 6.5 atm.

recycle is set to maintain a 455 K peak reactor temperature, but at

low coolant temperatures the gas recycle must be increased to keep
the temperatures in the reactor above the dewpoint temperature.
The prot points shown in the left bottom graph in Figure 8 do
not include a credit for steam generated in the reactor for coolant
temperatures below 433 K. Gas recycle is set by the reactor peak
temperature limitation for coolant temperature down to 427 K.
Below this coolant temperature, the dewpoint limitation comes
into eect, which requires a higher gas recycle ow rate (second
left graph in Figure 8) and more compressor work (third right
graph in Figure 8).

Capital investment increases with reactor coolant temperature, but prot takes a jump up at 433 K because of the reactor
steam credit. The increase in prot in going from 430 to 433 K is
$517,000 per year. The corresponding reactor steam credit is
$684,000 per year. The incremental capital cost is $112,100,
which is easily justied.

6. PLANTWIDE CONTROL
Now that the modied owsheet has been determined, its
dynamic controllability is explored. Figure 9 gives the plantwide
control structure developed. It is signicantly dierent than those
proposed for the original design. Since the oxygen concentrations are well below the ammability limit, the ow rate of fresh
oxygen can be used as the throughput handle (sets the production rate of product).
The control structure has the following loops:
1. Fresh oxygen feed is ow controlled.
2. Total acetic acid is ratioed to the ow rate of fresh oxygen.
The ow rate of fresh acetic acid is manipulated to control the
total of the fresh and recycle acetic acid. This conguration
prevents snowballing problems in the liquid recycle loop.
3. Vaporizer level is controlled by manipulating heat input.
4. Pressure in the vaporizer (and thus the gas loop) is
controlled by manipulating the ow rate of fresh feed of
ethylene.
5. Reactor exit temperature is controlled by manipulating the
cooling medium temperature.
6. Separator temperature is controlled by manipulating heat
removal in the partial condenser.
7. Liquid level in the separator is controlled by manipulating
the exiting liquid stream.
8. The acetic acid wash stream to the top of the absorber is
ow controlled and its temperature is controlled by manipulating heat removal in the cooler.
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Figure 9. Plantwide control structure.

9. The liquid level in the base of the absorber is controlled by

manipulating the exiting liquid stream.
10. The MEA solvent to the top of the CO2 absorber is ow
controlled.
11. The liquid level in the base of the CO2 absorber is
controlled by manipulating the exiting liquid stream.
12. The ethane concentration in the purge stream is controlled by manipulating the ow rate of the purge.
13. The work of the recycle compressor is held constant.
14. The pressure in the D/E column is controlled by
manipulating the vapor distillate product from the
reux drum.
15. The reux ow rate is ow controlled.
16. Reux drum level is controlled by manipulating condenser heat removal.
17. Stage-8 temperature is controlled by manipulating reboiler heat addition.
18. Base level is controlled by manipulating the ow rate of
the bottoms.
19. The pressure in the azeotropic column is controlled by
the valve in the overhead line.
20. Organic reux is ratioed to column feed in the azeotropic
column.

21. Base level is controlled by manipulating bottoms ow rate.

22. Stage 7 temperature is controlled by manipulating
reboiler duty.
23. Decanter temperature is controlled by manipulating heat
removal in the condenser.
24. Decanter pressure is controlled by manipulating the ow
rate of the vent stream.
25. Interface level is controlled by manipulating the ow rate
of the aqueous product stream.
26. Organic level is controlled by manipulating the ow rate
of the VAM product stream.
The dynamic owsheet was converged to a steady state in Aspen
Dynamics and gave results quite similar to the steady-state Aspen
Plus results, with one exception. The major dierence is the ow rate
of the purge stream required to prevent the buildup of inert ethane.
The purge ow rate is increased from 0.143 to 1.055 kmol/h to
maintain an ethane concentration in the recycle gas of 3.89 mol %.
The reason for this dierence is thought to be the result of the
convergence inaccuracies in steady-state simulations of individual
units where the very minute concentrations of ethane can lead to
incorrect component balances. The higher purge ow rate gives a
greater loss of ethylene, so the VAM produced is reduced from 58.19
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Figure 10. Throughput changes.

to 57.73 kmol/h, which is still signicantly greater than the original

49.56 kmol/h.
The performance of the control structure was tested for throughput and feed composition disturbances. Figure 10 gives results for
15% step disturbances in the set point of the oxygen ow controller.
Solid lines are for an increase and dashed lines are for a decrease. The
disturbance is handled well with VAM product purity (third right
graph in Figure 10A) held very close to the desired purity. The other
two fresh feed streams eventually change in the appropriate direction (ethylene brought in to hold system pressure and acetic acid

brought in to hold the total acetic acid ow to the reactor, which is

ratioed to the oxygen ow rate).
Figure 10B shows that there are some dynamic changes in the
purge ow rate as the composition controller attempts to maintain the ethane composition in the recycle gas, but the nal
steady-state purge ow rate changes only slightly from the initial
steady-state value.
Figure 11 gives result when the ethane impurity in the fresh
ethylene feed undergoes a drastic change from 0.1 to 1 mol %.
The purge ow rate must increase to remove this 10-fold increase
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Figure 11. Ethane disturbances.

in inert entering the system. A proportional-only controller

(KC = 5) is used for this composition, so the ethane composition
increases to about 6.5 mol % and the purge ow rate increases to
almost 10 kmol/h. The increased loss of ethylene results in a
reduction the product formed and the fresh acetic acid fed. The
plantwide control structure provides eective regulatory control
of this complex process.

(5) Douglas, J. M. Conceptual Design of Chemical Processes; McGraw-Hill:

New York, 1988.
(6) Turton, R., Bailie, R. C., Whiting, W. B., Shaelwitz, J. A. Analysis,
Synthesis and Design of Chemical Processes, 2nd ed.; Prentice Hall: Upper
Saddle River, NJ, 2003.

7. CONCLUSION
A modied vinyl acetate owsheet has been developed
that looks very favorable from a steady-state economic point of
view. Selectivity is signicantly improved by lowering oxygen
concentrations and increasing acetic acid concentrations in the
reactor.
An eective plantwide control structure is developed that is
signicantly dierent than that proposed for the original process
and provides stable regulatory control in the face of large disturbances.
AUTHOR INFORMATION
Corresponding Author

*E-mail: WLL0@Lehigh.edu. Tel.: 610-758-4256. Fax: 610-758-5057.

REFERENCES
(1) Luyben, M. L.; Tyreus, B. D. An industrial design/control study
for the vinyl acetate monomer process. Comput. Chem. Eng. 1998,
22, 867877.
(2) Luyben, W. L., Tyreus, B. D., Luyben, M. L. Plantwide Process
Control; McGraw-Hill: New York, 1999.
(3) Chen, R.; Daves, K; McAvoy, T. J. A nonlinear dynamic model of
a vinyl acetate process. Ind. Eng. Chem. Res. 2003, 42, 44784487.
(4) Olsen, D, G; Svrcek, W. Y.; Young, B. R. Plantwide control study
of a vinyl acetate monomer process design. Chem. Eng. Commun. 2005,
192, 12431257.
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