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ARTICLE

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Design and Control of a Modified Vinyl Acetate Monomer Process


William L. Luyben*
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 flammability limit, a maximum internal reactor temperature limit, and the need to stay above
dewpoint temperatures in the reactor. This paper develops an economic optimum flowsheet 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, 867877). The conceptual design developed produces 18% more VAM product for
the same oxygen fresh feed flow rate used in the original design. Compared to the original nonoptimized design, the modified 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 effective disturbance rejection and is significantly different than the structure used in the original design
is developed.

1. INTRODUCTION proposed flowsheet, the oxygen concentration is only 2.6 mol %,


The industrial challenge problem presented by Luyben and far below the maximum safety limit. The lower oxygen concen-
Tyreus1 has received only limited attention by the academic trations improve the selectivity since the combustion reaction is
community despite its rich mixture of important steady-state lowered.
design and dynamic control features and issues. Three plant- The second constraint is a maximum reactor temperature of
wide control studies were reported. All of these control studies 455 K to prevent catalyst degradation. Since the reactor is cooled,
are based on the original flowsheet presented in the challenge the maximum temperature occurs partway down the reactor.
problem. Luyben et al2 demonstrated that effective plantwide With a fixed coolant temperature on the shell side of the reactor
control could be achieved using a conventional PI control tubes and fixed reactor size, this constraint can be maintained by
structure. Chen et al3 developed a nonlinear dynamic model in adjusting the flow rate of gas recycle, which is mostly ethylene.
Matlab and studied alternative control structures. Olsen et al4 The higher the gas recycle, the lower the peak temperature. Of
presented other alternative control structures. course, higher gas recycle means higher gas compression costs in
There was no claim in the original paper that the process terms of both capital and energy.
design had been optimized from the standpoint of economics. The third important constraint is the need to guarantee that
The original flowsheet used a reactor with 622 tubes, 0.037 m in dia- there is no liquid in the reactor since the reactions occur in the gas
meter and 10 m in length. The gas recycle was large (939 kmol/h) phase. Liquid can form if the temperatures in the reactor are too
and the liquid acetic acid recycle was small (84.2 kmol/h). With a low, if the pressure is too high, or if the concentration of the high-
fresh oxygen feed of 31.26 kmol/h, the vinyl acetate monomer boiling acetic acid is too high.
(VAM) product was 49.56 kmol/h. Low reactor temperatures improve selectivity (more VAM
A conceptual design is developed in this paper that finds the and less CO2) because the activation energy of the VAM reaction
economic optimum equipment sizes and operating conditions, is lower than that of the combustion reaction, as discuss in the
which are significantly different than the original design. The next section. Reactor temperatures are affected by the coolant
basic unit operations are the same as in the original design, but temperature and the gas recycle. At low coolant temperatures, it
equipment sizes and operating conditions are quite different. is sometimes necessary to increase gas recycle beyond that
The most significant improvement in performance is an 18% required to limit the peak reactor temperature in order to keep
increase in the production of VAM for the identical fresh feed above dewpoint temperatures.
flow rate of oxygen. A bigger reactor is required, but the Although selectivity is reduced by running at higher reactor
dominant economic value of the product should easily justify temperatures, there is an important advantage of being able to
the increase in capital investment. recover the exothermic heats of reaction through generation of
There are three very important and interacting constraints in
this process. The vital safety constraint is to keep the oxygen Received: May 25, 2011
concentration below the flammability limit. The largest oxygen Accepted: August 6, 2011
concentration occurs at the reactor inlet. In the original design, Revised: July 25, 2011
this concentration was reported as 7.4 mol % oxygen. In the Published: August 07, 2011

r 2011 American Chemical Society 10136 dx.doi.org/10.1021/ie201131m | Ind. Eng. Chem. Res. 2011, 50, 10136–10147
Industrial & Engineering Chemistry Research ARTICLE

Figure 1. Modified flowsheet.

steam in the reactor, which is an energy credit. If the cooling buildup of the inert ethane since Aspen Dynamics predicts very
medium temperature on the shell side of the cooled reactor small concentrations of ethane in both products.
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 2. PROCESS DESCRIPTION
can be achieved by increasing acetic acid recycle. However, more Figure 1 shows the modified design. In all the cases presented
gas recycle may be required to prevent the formation of liquid in in this paper, the flow rate of fresh oxygen is fixed at 31.26 kmol/
the reactor. In addition, energy consumption in the acetic acid h, which is the same as used in the original design. The conditions
vaporizer and in the azeotropic distillation column increase. shown in Figure 1 are the economic optimum as developed in a
All of these issues must be considered in the conceptual de- later section in this paper.
sign of this very interesting and complex process. The modified Fresh acetic acid is combined with an acetic acid recycle
design has 1100 tubes instead of 622. The acetic acid recycle is stream and fed into a vaporizer along with a gas stream, which is
much larger, which results in a reactor inlet concentration of the fresh ethylene feed plus a gas recycle stream. The vaporizer
30.28 mol % acetic acid compared to the original design of 11 mol operates at 6.6 atm and 423 K, which requires medium-pressure
%. The operating pressure is reduced from 8.7 to 6.5 atm. The steam (11 bar, 457 K, $8.22 per GJ). Vaporizer energy consump-
reboiler duty of the azeotropic column is reduced from 4.65 to tion is 3.88 MW.
3.47 MW. The vapor stream is combined with fresh oxygen and enters
The original design had a high concentration of the chemically the cooled tubular reactor at 421 K with a concentration of 2.63
inert ethane (21.6 mol % C2H6) in the gas recycle loop, which mol % oxygen and 30.28 mol % acetic acid, the remainder being
was assumed to build up. The ethane concentration in the mostly ethylene. The reactor contains 1100 tubes, 0.037 m in
modified design based on steady-state Aspen Plus simulation is diameter and 10 m in length. The coolant temperature is 433 K,
found to be very small. There are only 0.05676 kmol/h of ethane and the heat removal in the reactor is 2.79 MW. The overall heat-
entering in the fresh ethylene feed (99.9 mol % C2H4). Most of transfer coefficient is that used in the original design (0.17 kW
this leaves as small impurities in the organic product stream m2 K1). Figure 2 gives temperature and composition profiles
(0.02639 kmol/h C2H4) and in the aqueous stream (0.02688 in the reactor. The maximum temperature is 455 K with the
kmol/h C2H4) with trace amounts in the purge and decanter coolant temperature of 433 K and a gas recycle flow rate of 744
vent streams. In the dynamic simulation discussed later in this kmol/h. Catalyst properties are taken from the Luyben and
paper, a much larger purge flow rate is required to prevent the Tyreus paper (0.8 void volume, 1935 kg/m3 particle density).
10137 dx.doi.org/10.1021/ie201131m |Ind. Eng. Chem. Res. 2011, 50, 10136–10147
Industrial & Engineering Chemistry Research ARTICLE

Figure 2. (a) Reactor temperature profile; (b) reactor composition profiles.

The per-pass conversion of ethylene is 7.3%, of acetic acid amount of ethylene contained in these streams. The de-ethanizer
is 15%,and of oxygen is 97.8%. The selectivity is 23 (ratio of VAM column (D/E) operates at 27.2 atm. The reflux-drum temperature
formed in the reactor to CO2 formed in the reactor). It should be is 257 K, so refrigeration is required in the condenser. The easy
noted that the selectivity of the original process is only 11, so a very separation between ethylene and VAM is achieved using a 21-stage
significant improvement in the yield of VAM has been achieved. column and a reflux ratio of 1.
The reactor effluent is cooled to 323 K and fed to a flash drum. The bottoms from the D/E column is fed to the second
The liquid stream is fed to the first distillation column. The gas distillation column whose function is to recover the acetic acid for
stream is fed to an absorber in which VAM is recovered by an recycle back to the vaporizer. A 21-stage column is assumed,
acetic acid wash stream. The gas from the absorber goes to a which is the same as that used in the original design. The ternary
second absorber that removes carbon dioxide using a mono- system of VAM, water, and acetic acid is highly nonlinear with a
ethanol amine solution. The gas from the top of the CO2 heterogeneous azeotrope formed. The overhead vapor from the
absorber is compressed and recycled to the vaporizer. column is cooled to 310 K and forms two liquid phases in a
The liquid streams from separator and from the VAM absorber decanter. The aqueous phase is 99.45 mol % water. The organic
are fed to a distillation column whose function is to remove the small phase is 94.41 mol % VAM. A small vent stream leaves the top of
10138 dx.doi.org/10.1021/ie201131m |Ind. Eng. Chem. Res. 2011, 50, 10136–10147
Industrial & Engineering Chemistry Research ARTICLE

Figure 3. Txy diagram for ethylene/VAM at 27.2 atm.

the decanter. Reflux to the top of the azeotropic column is a Overall reaction rates R n have units of kmol s1 kg1. Partial
portion of the organic phase from the decanter. This reflux is pressures of components pj have units of Pascals. Note that the
adjusted to maintain the VAM composition of the organic phase combustion reaction is assumed to be first-order in both oxygen and
in the decanter and varies as acetic acid recycle, reactor size, and ethylene partial pressures.
system pressure are varied. These simplified kinetics are compared in the following
paragraph with those given in the original paper that show more
3. KINETICS AND PHASE EQUILIBRIUM complex composition dependence.
The kinetic equations given by Luyben and Tyreus are not " #
pE pHAc pO ð1 þ 1:7pW Þ
easily implemented in Aspen simulations because they are not in R 1 ¼ 0:1036e3674=T
½1 þ 0:583pO ð1 þ 1:7pW Þ½1 þ 6:8pHAc 
the convenient power-law form and would require writing and " #
compiling of a user kinetic subroutine. As a practical engineering pO ð1 þ 0:68pW Þ
R 2 ¼ 1:9365  105 e10116=T
alternative, the approach taken was to fit the performance results 1 þ 0:76pO ð1 þ 068pW Þ
(yield of VAM and CO2) for the reactor given in the original
design by selecting pre-exponential factors and activation en- ð3Þ
ergies for the two reactions.
Overall reaction rates R n have units of mol min1 g1 in eq 3.
1 Partial pressures of components pj have units of psia. Using
C2 H4 þ CH3 COOH þ O2 f CHOCOCH3 þ H2 O
2 the reactor inlet compositions, coolant temperature and re-
C2 H4 þ 3O2 f 2CO2 þ 2H2 O actor pressure in the original paper, the two reactions rates can
be calculated: R 1 = 3.203  104 and R 2 = 8.83  106 mol
ð1Þ min1 g1. These can be compared with those calculated using
The physical dimensions of the reactor and catalyst properties the reactor conditions in the modified design shown in Figure 1:
were fixed at those given in the original design (622 tubes, 0.037 m R 1 = 3.089  104 and R 2 = 0.152  106 mol min1 g1. It is
in diameter and 10 m in length filled with 2590 kg of catalyst). The clear that the reactor conditions in the modified design are more
coolant temperature (406 K) and overall heat-transfer coefficient favorable for the production of desired VAM. This demonstrates
(U = 0.17 kW m2 K1) were those used in the original design. that the simplified kinetics used in this study have been successful
The reactor inlet conditions were set as those given in the original in developing a process with a much higher selectivity, as
design in terms of inlet temperature, pressure and all molar flow confirmed by the calculations using the “rigorous kinetics”.
rates. The ratio of the activation energies of the two competing gas- The phase equilibrium in the VAM process is quite nonlinear
phase irreversible reaction was set at 2.5, which is close to the ratio with a heterogeneous azeotrope formed in the ternary system of
given in the original design (E1 = 8000 kJ/kmol and E2 = 20000 kJ/ VAM, acetic acid, and water. The Aspen NRTL phase equilib-
kmol). Then the values of the two pre-exponential factors (R1 and rium parameters are used in the simulations of the vaporizer,
R2) were varied by trial and error until the production rates of VAM reactor, absorber, de-ethanizer, and decanter. The UNIF-
and CO2 in the reactor were close to those reported in the original HOC physical property package is used in the azeotropic column
design. The kinetic relationships used in this paper are to account for the association of acetic acid. The valid phases in
this column are VLL. The separation in the first D/E column
R 1 ¼ R1 eE1 =RT pE pHAc ðpO Þ0:5 ¼ 5:8  1018 e8000=RT pE pHAc ðpO Þ0:5 between ethylene and VAM is fairly easy, as shown in the Txy
R 2 ¼ R2 eE2 =RT pE pO ¼ 6:7  1015 e20:000=RT pE pO diagram given in Figure 3 at the operating pressure of 27.2 atm.
A ternary diagram is given in Figure 4 for the principal
ð2Þ components in the azeotropic column: VAM, acetic acid, and
10139 dx.doi.org/10.1021/ie201131m |Ind. Eng. Chem. Res. 2011, 50, 10136–10147
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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 coolant and the flow rate of gas recycle that maintains a 455 K
azeotropic temperature of 312 K that is close to the decanter peak temperature), the reactor size (set by the number of tubes),
temperature. The bottoms from the column contains 5 mol % the pressure in the gas loop (vaporizer, reactor, separator, and
water. The composition of the overhead vapor from the column absorbers), and the flow rate of the recycle acetic acid. An
is close to the azeotropic composition. The column feed is 535.3 iterative exhaustive enumeration of these four variables was used
kmol/h and the organic reflux is 390 kmol/h, giving the mix point to find the optimum values of the design variables. The economic
shown in Figure 4 between the feed composition and the organic objective function was incremental return on incremental invest-
composition. The component balance line runs through the mix ment. For example, as more tubes are used in the reactor, capital
point and connects the bottoms point and the overhead point. investment increases due to the cost of the vessel (more heat-
The AMINES physical property package is used in the CO2
transfer area) and the cost of the catalyst. Production of VAM
absorber. The MEA/water solvent fed to the top of the absorber
product increases as more tubes are added, but the increase is at
would come from the base of a stripping column, which is not
included in the simulation because the stripping column has little an increasingly smaller rate. The point that gives an incremental
economic effect on the major units of the process. ROI of at least 30% was selected.
The three constraints that must be satisfied are a maximum
peak temperature in the reactor, an upper limit on the oxygen
4. FLOWSHEET CONVERGENCE concentration of the feed to the reactor (assumed to be 7 mol %
It might be useful to say a few words about the issue of oxygen), and the requirement that the material in the reactor is all
flowsheet convergence for this complex multiunit process. The gas phase (temperature must be above the dewpoint temperature
existence of two recycle streams can present significant problems of the mixture at all points in the reactor). Keep in mind that the
in these types of processes. However, the two recycles were flow rate of fresh oxygen is fixed for all cases.
successfully closed by employing the technique of fixing the total 5.1. Effect of Reactor Size. The catalyst in the VAM process is
flows (fresh plus recycle) and permitting the makeup streams quite expensive because it contains palladium. A catalyst cost of
to vary. $800 per kg is assumed (2.27 wt % palladium at $800 oz), which
For example, the total flow rate of gas to the vaporizer (fresh favors small reactors to reduce capital investment.
ethylene feed plus recycle gas) is held constant using an Aspen A reactor coolant temperature of 433 K is initially selected so
Plus Flowsheet Design Specification that varied the ethylene fresh that the steam generated in the reactor can be used elsewhere in
feed. A second Aspen Plus Flowsheet Design Specification varied the plant as low-pressure steam. Operating with lower coolant
the acetic acid fresh feed to maintain a specified total acetic acid temperature is explored in a later section. The peak reactor
flow rate (fresh plus recycle) to the vaporizer. This convergence temperature is maintained at 455 K by varying gas recycle flow
method worked quite well and was successful in handling a wide rate using a Flowsheet Design Specification. The acetic acid recycle
range of values of design variables. is initially set at 375 kmol/h. Reactor inlet pressure is initially set
at 6.5 atm.
With these design variables fixed, the effect of changing the
5. EFFECT OF DESIGN VARIABLES number of reactor tubes is shown in Figure 5. The production of
The four major design variables in the vinyl acetate monomer VAM and the consumption of reactants increase as more tubes
process are reactor temperatures (set by the temperature of the are used in the reactor, but these flow rates begin to level out for
10140 dx.doi.org/10.1021/ie201131m |Ind. Eng. Chem. Res. 2011, 50, 10136–10147
Industrial & Engineering Chemistry Research ARTICLE

Figure 5. Effect of reactor size.

more than about 1200 tubes. Since the product is worth more Table 1. Effect of Reactor Sizea
than the reactants, profit increases. But capital cost of the reactor
Ntubes = 1000 Ntubes = 1100 Ntubes = 1200
vessel and the catalyst increase linearly as more tubes are used.
The cost of the reactor vessel is based on the heat-transfer area. product kmol/h 57.538 57.983 58.202
The economic parameters for chemical costs given by Tyreus gastot kmol/h 821.6 796.9 786.3
and Luyben are used to assess the economics: VAM = $0.971 per ethylene kmol/h 56.27 56.61 56.79
kmol, ethylene = $0.442 per kmol and acetic acid = $0.596 per acetic acid kmol/h 55.15 55.57 55.77
kmol. The cost of oxygen is not considered because the fresh
organic reflux kmol/h 369 371 372
oxygen flow rate is the same in all cases. A “pseudo-profit”
Qvap MW 3.833 3.807 3.801
parameter is defined as the value of the VAM produced minus the
cost of the ethylene and acetic acid reactants minus the energy Tvap K 421.6 422.2 423
costs of the compressor, vaporizer, and azeotropic column QRX MW 2.724 2.784 2.824
reboiler plus the value of the reactor steam: QR2 MW 2.638 2.658 2.668
compressor kW 266.3 257.2 253.3
profitð$=hÞ ¼ ðproduce kmol=hÞð$0:971Þ yRXin mol % O2 2.71 2.66 2.64
 ðfresh ethylene kmol=hÞð$0:442Þ mol % C2H4 64.35 63.81 63.57
 ðfresh HAc kmol=hÞð$0:596Þ mol % HAc 29.03 29.66 29.94
  xB2 mol % H2O 6.19 6.03 5.97
3600 s=h
 ðcompressor work kWÞ ð$16:8=GJÞ
106 kW=GW
  profit 106 $/y 14.606 14.761 14.841
3600 s=h
 ðvaporizer energy MWÞ ð$8:22=GJÞ capital 106 $ 5.6159 6.0577 6.5096
103 MW=GW a
Conditions: 6.5 atm; HAc total = 375 kmol/h; Tcool = 455 K; Tmax = 455 K.
 
3600 s=h
 ðazeo column reboiler MWÞ ð$7:78=GJÞ
103 MW=GW to select the optimum values of design variables. Cost equations
  from Douglas5 and Turton et al6 are used to calculate these
3600 s=h
þ ðreactor steam MWÞ ð$7:88=GJÞ ð4Þ capital costs.
103 MW=GW
Figure 5 and Table 1 show that profit is increasing but capital
The energy costs in the de-ethanizer (reboiler heat input and investment is also increasing as more reactor tubes are used. The
condenser refrigeration) and in the absorbers remain essentially incremental return on investment decreases. Moving from 1000
the same as conditions in the reactor are changed, so they are not to 1100 tubes gives an incremental return on investment of 35%.
considered. Adding more tubes yields a lower incremental return on invest-
Capital investment is the sum of the installed costs of the ment. Note that the required total gas recycle is set to achieve
reactor vessel, catalyst, vaporizer, and compressor. The capital a 455 K peak reactor temperature. Under these conditions, with
costs of all the other units remain essentially the same as a 433 K reactor coolant temperature, the dewpoint limitation
conditions in the reactor change. They are not considered in is avoided (the process stream leaving the reactor has a vapor
the economics since an incremental return on investment is used fraction >1). Reactor inlet oxygen concentration (2.66 mol %) is
10141 dx.doi.org/10.1021/ie201131m |Ind. Eng. Chem. Res. 2011, 50, 10136–10147
Industrial & Engineering Chemistry Research ARTICLE

Figure 6. Effect of HAc recycle.

Table 2. Effect of Acetic Acid Recyclea temperature, which could require either more gas recycle or
higher reactor coolant temperatures.
HAc total = HAc total = HAc total =
Figure 6 and Table 2 give results for a range of acetic acid
375 kmol/h 385 kmol/h 395 kmol/h recycle flow rates. The abscissa in Figure 6 is the total acetic acid
product kmol/h 57.983 58.188 58.388 (fresh feed plus recycle). The production of product VAM
gastot kmol/h 796.9 800.6 804.3 increases, as does the consumption of reactants (ethylene and
ethylene kmol/h 56.61 56.74 56.88 acetic acid). Gas recycle flow rate increases to keep the 455 K
acetic acid kmol/h 55.57 55.76 55.96 peak temperature, which increases compressor work. Naturally
organic reflux kmol/h 371 390 410 vaporizer energy consumption increases, as does the required
Qvap MW 3.807 3.881 3.968 organic reflux (R2) to the azeotropic column.
Profit initially increases, but hits a maximum at a total acetic
Tvap K 422.2 423 423
acid flow rate of 385 kmol/h. Capital investment increases
QRX MW 2.784 2.789 2.795
steadily but quite slowly as acetic acid recycle is increased. Table 2
QR2 MW 2.658 2.806 2.986
shows a large incremental return on an incremental investment in
compressor kW 257.2 258.2 259.1
going from 375 to 385 kmol/h. Profit increases by $15,000 per
yRXin mol % O2 2.66 2.63 2.59
year for a small $24,000 increase in capital investment.
mol % C2H4 63.81 63.41 63.02 It should be noted that the reactor inlet acetic acid composition
mol % HAc 29.66 30.26 30.89 in the modified design (30.26 mol % HAc) is very significantly
xB2 mol % H2O 6.03 5.29 4.69 different than that in the original (11 mol % HAc) because of
the much larger acetic acid recycle flow rate (329.2 compared to
profit 106 $/y 14.761 14.776 14.772 84.2 kmol/h). The higher acetic acid concentrations in the reactor
capital 106 $ 6.0577 6.0601 6.0622 promote the desired VAM reaction.
a In addition, the reactor inlet oxygen composition in the modified
Conditions: 6.5 atm; Ntubes = 1100; Tcool = 455 K; Tmax = 455 K.
design (2.63 mol % O2) is significantly different than that in the
well below the flammability limit of 7 mol %. However, the effects original (7.4 mol % O2). This inhibits the undesired combustion
of other important design optimization variables must be con- reaction. Finally, the reactor size is significantly different (1100
sidered. One of the most important is acetic acid recycle. versus 622 tubes), which means higher capital investment in the
5.2. Effect of Acetic Acid Recycle. The kinetic relationships reactor vessel and catalyst. However, the valuable VAM produced is
indicate that higher acetic acid concentrations in the reactor feed much larger (58.19 versus 49.56 kmol/h), which can justify a
should promote the desired VAM reaction. However, more significant increase in capital investment and energy consumption.
acetic acid recycle means higher energy consumption in the Note also that the vaporizer energy consumption is higher (3.88
vaporizer. The azeotropic column energy consumption is also MW in the modified design versus 1.5 MW). However, the azeo-
higher because more organic reflux is required to maintain the tropic column reboiler duty is lower (2.806 MW in the modi-
VAM purity of the organic phase in the decanter. In addition, fied versus 4.65 MW). Since the recycle gas flow rate is smaller in
since acetic acid is the heaviest component in terms of volatility, the modified design, the compressor work is smaller (258 versus
higher acetic acid concentration in the reactor raise the dewpoint 350 kW).
10142 dx.doi.org/10.1021/ie201131m |Ind. Eng. Chem. Res. 2011, 50, 10136–10147
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Figure 7. Effect of pressure.

Table 3. Effect of Pressurea The results of running several pressures are shown in Figure 7
and Table 3. The other three design variables are fixed at Tcool =
P = 6.0 atm P = 6.5 atm P = 7.0 atm
433 K, Ntubes = 1000 and HAc total = 375 kmol/h. The most
product kmol/h 57.368 57.538 57.629 important effect of changing pressure is the flow rate of gas
gastot kmol/h 676.0 821.6 966.1 recycle, which is set to maintain a peak reactor temperature of
ethylene kmol/h 56.03 56.27 56.37 455 K. The middle left graph in Figure 7 shows a very large
acetic acid kmol/h 55.00 55.15 55.24 change in the Gastot required. As the pressure at the inlet of the
organic reflux kmol/h 387 369 357
reactor is varied from 5.5 to 7 atm, the total gas increases by a
factor of 2.
Qvap MW 3.650 3.882 4.000
The reactor heat removal changes only slightly, and the reactor
Tvap K 423 422 420
temperature profiles are very similar at all pressures. The higher
QRX MW 2.784 2.724 2.670 reaction rates at higher pressure require more gas recycle so that
QR2 MW 2.804 2.638 2.529 the maximum peak temperature in the reactor is not exceeded.
compressor kW 233.2 266.3 294.3 Naturally, the larger gas recycle increases compressor costs. Table 3
yRXin mol % O2 3.21 2.71 2.36 shows that vaporizer energy consumption also increases. Since the
mol % C2H4 63.81 64.35 65.02 gas recycle goes through the vaporizer in order to lower vaporizer
mol % HAc 33.21 29.03 25.77 temperatures, more gas must be heated as gas recycle increases.
xB2 mol % H2O 6.03 6.19 7.09 More product is produced as pressure is increased, but profit
hits a peak at 6.5 atm because of the increases in energy costs in
profit 106 $/y 14.598 14.606 14.584
the compressor and the vaporizer.
5.4. Effect of Reactor Coolant Temperature. The kinetic
capital 106 $ 5.5409 5.6159 5.6781
a relationships indicate that lower reactor temperatures should
Conditions: HAc total = 375 kmol/h; Ntubes = 1000; Tcool = 455 K; improve selectivity because the activation energy of the desired
Tmax = 455 K.
VAM reaction is smaller than the activation energy of the
undesired combustion CO2 reaction. However, lower reactor
5.3. Effect of Reactor Pressure. The reaction rates of both temperatures decrease conversion so bigger reactors are re-
reactions depend directly on pressure, so higher pressures increase quired. Lower reactor temperatures also require higher gas
both reaction rates, as shown in the kinetics given in eq 2, which recycle flow rate to keep from forming liquid in the reactor.
should decrease reactor size for a given conversion. The undesirable The optimum design involves an economic trade-off among
combustion reaction is assumed to have first-order dependence on these various effects. Running the reactor hot enough to generate
oxygen while the desirable VAM reaction is assumed to have a square- steam would appear to be the best design, but several other
root dependence. Therefore, lower pressure should favor the desired coolant temperatures were explored.
reaction, and selectivity should improve lower pressures. Both fresh Figure 8 and Table 4 give results over a range of reactor coolant
gas streams are available at high pressure, so feed gas compression is temperatures. The other variables fixed in these runs are 1100
not required over the range of system pressures considered. tubes, 6.5 atm, and 385 kmol/h HAc total. In most cases the gas
10143 dx.doi.org/10.1021/ie201131m |Ind. Eng. Chem. Res. 2011, 50, 10136–10147
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Figure 8. Effect of reactant coolant temperature.

Table 4. Effect of Reactor Coolant Temperaturea Capital investment increases with reactor coolant tempera-
ture, but profit takes a jump up at 433 K because of the reactor
Tcool = 430 K Tcool = 433 K Tcool = 435 K
steam credit. The increase in profit in going from 430 to 433 K is
product kmol/h 58.801 58.188 57.564 $517,000 per year. The corresponding reactor steam credit is
gastot kmol/h 665.8 800.6 919.3 $684,000 per year. The incremental capital cost is $112,100,
ethylene kmol/h 57.19 56.74 56.31 which is easily justified.
acetic acid kmol/h 56.33 55.76 55.19
organic reflux kmol/h 419 390 375
Qvap MW 3.797 3.881 3.964
6. PLANTWIDE CONTROL
Tvap K 427 423 420 Now that the modified flowsheet has been determined, its
QRX MW 2.984 2.789 2.619 dynamic controllability is explored. Figure 9 gives the plantwide
QR2 MW 3.090 2.806 2.673
control structure developed. It is significantly different than those
proposed for the original design. Since the oxygen concentra-
compressor kW 209.2 258.2 301.2
tions are well below the flammability limit, the flow rate of fresh
yRXin mol % O2 2.90 2.63 2.46
oxygen can be used as the throughput handle (sets the produc-
mol % C2H4 59.40 63.41 66.23 tion rate of product).
mol % HAc 34.33 30.26 27.43 The control structure has the following loops:
xB2 mol % H2O 3.90 5.39 6.35 1. Fresh oxygen feed is flow controlled.
2. Total acetic acid is ratioed to the flow rate of fresh oxygen.
profit 106 $/y 14.259 14.776 14.521 The flow rate of fresh acetic acid is manipulated to control the
capital 106 $ 5.948 6.0601 6.1553 total of the fresh and recycle acetic acid. This configuration
a
Conditions: HAc total = 385 kmol/h; Ntubes = 1100; Tmax = 455 K; 6.5 atm. 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
recycle is set to maintain a 455 K peak reactor temperature, but at controlled by manipulating the flow rate of fresh feed of
low coolant temperatures the gas recycle must be increased to keep ethylene.
the temperatures in the reactor above the dewpoint temperature. 5. Reactor exit temperature is controlled by manipulating the
The profit points shown in the left bottom graph in Figure 8 do cooling medium temperature.
not include a credit for steam generated in the reactor for coolant 6. Separator temperature is controlled by manipulating heat
temperatures below 433 K. Gas recycle is set by the reactor peak removal in the partial condenser.
temperature limitation for coolant temperature down to 427 K. 7. Liquid level in the separator is controlled by manipulating
Below this coolant temperature, the dewpoint limitation comes the exiting liquid stream.
into effect, which requires a higher gas recycle flow rate (second 8. The acetic acid wash stream to the top of the absorber is
left graph in Figure 8) and more compressor work (third right flow controlled and its temperature is controlled by manip-
graph in Figure 8). ulating heat removal in the cooler.
10144 dx.doi.org/10.1021/ie201131m |Ind. Eng. Chem. Res. 2011, 50, 10136–10147
Industrial & Engineering Chemistry Research ARTICLE

Figure 9. Plantwide control structure.

9. The liquid level in the base of the absorber is controlled by 21. Base level is controlled by manipulating bottoms flow rate.
manipulating the exiting liquid stream. 22. Stage 7 temperature is controlled by manipulating
10. The MEA solvent to the top of the CO2 absorber is flow reboiler duty.
controlled. 23. Decanter temperature is controlled by manipulating heat
11. The liquid level in the base of the CO2 absorber is removal in the condenser.
controlled by manipulating the exiting liquid stream. 24. Decanter pressure is controlled by manipulating the flow
12. The ethane concentration in the purge stream is con- rate of the vent stream.
trolled by manipulating the flow rate of the purge. 25. Interface level is controlled by manipulating the flow rate
13. The work of the recycle compressor is held constant. of the aqueous product stream.
14. The pressure in the D/E column is controlled by 26. Organic level is controlled by manipulating the flow rate
manipulating the vapor distillate product from the of the VAM product stream.
reflux drum. The dynamic flowsheet was converged to a steady state in Aspen
15. The reflux flow rate is flow controlled. Dynamics and gave results quite similar to the steady-state Aspen
16. Reflux drum level is controlled by manipulating conden- Plus results, with one exception. The major difference is the flow rate
ser heat removal. of the purge stream required to prevent the buildup of inert ethane.
17. Stage-8 temperature is controlled by manipulating re- The purge flow rate is increased from 0.143 to 1.055 kmol/h to
boiler heat addition.
maintain an ethane concentration in the recycle gas of 3.89 mol %.
18. Base level is controlled by manipulating the flow rate of
the bottoms. The reason for this difference is thought to be the result of the
19. The pressure in the azeotropic column is controlled by convergence inaccuracies in steady-state simulations of individual
the valve in the overhead line. units where the very minute concentrations of ethane can lead to
20. Organic reflux is ratioed to column feed in the azeotropic incorrect component balances. The higher purge flow rate gives a
column. greater loss of ethylene, so the VAM produced is reduced from 58.19
10145 dx.doi.org/10.1021/ie201131m |Ind. Eng. Chem. Res. 2011, 50, 10136–10147
Industrial & Engineering Chemistry Research ARTICLE

Figure 10. Throughput changes.

to 57.73 kmol/h, which is still significantly greater than the original brought in to hold the total acetic acid flow to the reactor, which is
49.56 kmol/h. ratioed to the oxygen flow rate).
The performance of the control structure was tested for through- Figure 10B shows that there are some dynamic changes in the
put and feed composition disturbances. Figure 10 gives results for purge flow rate as the composition controller attempts to main-
15% step disturbances in the set point of the oxygen flow controller. tain the ethane composition in the recycle gas, but the final
Solid lines are for an increase and dashed lines are for a decrease. The steady-state purge flow rate changes only slightly from the initial
disturbance is handled well with VAM product purity (third right steady-state value.
graph in Figure 10A) held very close to the desired purity. The other Figure 11 gives result when the ethane impurity in the fresh
two fresh feed streams eventually change in the appropriate direc- ethylene feed undergoes a drastic change from 0.1 to 1 mol %.
tion (ethylene brought in to hold system pressure and acetic acid The purge flow rate must increase to remove this 10-fold increase

10146 dx.doi.org/10.1021/ie201131m |Ind. Eng. Chem. Res. 2011, 50, 10136–10147


Industrial & Engineering Chemistry Research ARTICLE

Figure 11. Ethane disturbances.

in inert entering the system. A proportional-only controller (5) Douglas, J. M. Conceptual Design of Chemical Processes; McGraw-Hill:
(KC = 5) is used for this composition, so the ethane composition New York, 1988.
increases to about 6.5 mol % and the purge flow rate increases to (6) Turton, R., Bailie, R. C., Whiting, W. B., Shaelwitz, J. A. Analysis,
almost 10 kmol/h. The increased loss of ethylene results in a Synthesis and Design of Chemical Processes, 2nd ed.; Prentice Hall: Upper
Saddle River, NJ, 2003.
reduction the product formed and the fresh acetic acid fed. The
plantwide control structure provides effective regulatory control
of this complex process.

7. CONCLUSION
A modified vinyl acetate flowsheet has been developed
that looks very favorable from a steady-state economic point of
view. Selectivity is significantly improved by lowering oxygen
concentrations and increasing acetic acid concentrations in the
reactor.
An effective plantwide control structure is developed that is
significantly different than that proposed for the original process
and provides stable regulatory control in the face of large dis-
turbances.

’ 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, 867–877.
(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, 4478–4487.
(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, 1243–1257.

10147 dx.doi.org/10.1021/ie201131m |Ind. Eng. Chem. Res. 2011, 50, 10136–10147

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