Ind. Eng. Chem. Res.

2011, 50, 1453–1459 1453

Selective Hydrogenation of Methylacetylene and Propadiene in an Industrial

Process: A Multiobjective Optimization Approach
Wei Wu* and Yu-Lu Li
Department of Chemical and Materials Engineering, National Yunlin UniVersity of Science and Technology,
Douliou, Yunlin 64002, Taiwan, R.O.C.

An industrial selective hydrogenation process for methylacetylene (MA) and propadiene (PD) that is mainly
composed of two hydrogenation reactors, a separator drum, and a recycle design is presented. According to
the specific requirements on the product yield as well as degree of MAPD removal, the optimal operating
strategy depends on multiple conflicting objectives for the MAPD conversion and the propylene (PP) selectivity.
For the multiobjective optimization algorithm subject to prescribed process constraints, the Pareto-optimal
solution is obtained via the fuzzy-based membership function and two-phase procedure. Finally, the simulation
shows that the desired operating condition regarding ratios of H2 to MAPD at each reactor and the recycle
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ratio is determined.

1. Introduction the Pareto-optimal solution, the iterative programming integrated

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with fuzzy inference and the two-phase approach are presented.

For most naphtha-processing plants, propylene (C3-cut) stream
By virtue of computing material and energy balance equations,
usually contains more than 90% propylene (PP) and up to 6%
the feasible operating manner is successfully verified.
methylacetylene (MA) and propadiene (PD). The MAPD
removal mechanism was initially established in the gas-phase
2. Process Description
process.1,2 To reduce operating cost and increase competitive-
ness, the liquid-phase operation was often seen in current Consider the liquid-phase operation of the MAPD-selective
petrochemical industry.3,4 In general, the kinetic analysis of hydrogenation process, shown in Figure 1, that is mainly
selective hydrogenation of MAPD was usually addressed via composed of two hydrogenation reactors, a separator drum, and
the experimental setup, but the study of the selective hydrogena- a recycle design. The inlet MAPD stream is mixed with a recycle
tion of acetylene has been investigated in some kinds of stream from the vapor-liquid separator drum. The mixed feed
industrial reactors.5,6 Recently, Wang and Froment7 showed the flow with an inlet hydrogen stream is fed into the top of the
effect of catalyst deactivation for an industrial hydrogenation first reactor (I). For the typically exothermic hydrogenation
reactor, and Wu et al.8 introduced kinetic modeling and process, the temperature of outlet stream from the bottom of
simulation for the industrial MAPD converter. the first reactor is higher than the temperature of inlet stream,
In the past decades, the basic optimality criterion using the but the outlet concentration of MAPD is lower than the inlet
Pontryagin maximum principle has been carried out in fixed concentration of MAPD. By exploiting a coolant device and a
bed catalytic reactors.9 For exothermic hydrogenation reactions, separator drum, a split outlet stream from the first reactor flows
the traditional dynamic optimization algorithm could regulate back as a recycle stream and another stream with a split H2
the reactor temperature to prevent runways.10 When the produc- stream is fed into the top of the second reactor (II). In our
tion, yield, and selectivity are all considered in the process approach, the feasible operating manner would to be established
operation, the suitable operating strategies for an industrial step by step under the operating constraints and specifications
styrene reactor11 would allow performing the multiobjective for each industrial reactor. In the first step, the prescribed kinetic
optimization algorithm. In regard to different objective require- models for each reactor are described as follows.
ments, the multiobjective optimization technique can be applied
to the hybrid power system,12 the polygeneration energy system Assumed that the selective hydrogenation reactions including
design,13 and the fed-batch bioreactor.14 To obtain Pareto- the propylene formation reaction and the formation of oligomers
optimal (a set of equally good) solutions, several multiobjective (green oil) are shown by7
optimization problems were usually solved by the specific
genetic algorithm,15 the advanced evolutionary algorithm,16 and
the iterative programming integrated with fuzzy inference.17
On the basis of the same kinetic models, shown in Wu et
al.,8 for an industrial MAPD converter, the process operating
manner depends on ratios of H2 to MAPD at each reactor and
the recycle ratio. To address desired operating manner, the
MAPD conversion and the propylene (PP) selectivity are treated
as multiple and conflicting objectives such that the compromise
solutions among the objectives are determined by solving the
multiobjective optimization algorithm under prescribed process
constraints. To establish a rapid and simple approach for finding
* To whom correspondence should be addressed. E-mail: weiwu@
yuntech.edu.tw. Figure 1. Operation analysis of the MAPD converter process.

10.1021/ie100994j  2011 American Chemical Society

Published on Web 10/06/2010
1454 Ind. Eng. Chem. Res., Vol. 50, No. 3, 2011

the propylene formation reaction RPD, RPP, RPN, RC6, RC9]|s)I,II, and Rm represents the recycle ratio
for the recycle stream to the inlet stream of the second reactor.
rMA (ii) Assuming that each hydrogenation reactor is adiabatic,
MA 98 rPP the overall energy balances for each reactor are written as
+ H2 rPD propylene 98 propane (1)
PD 98 H2
Fr
reactor I: (T̂ - TI) )
Vr I,f
1
∑
r (-∆Hl) I
Fbcpm(Rm + 1) l∈N l
k
the oligomer formation reaction (8)
rMA-C rMA-C
6 9
98 C6 + MA 98 C9 Fr
2MA + H2 H2 H2 reactor II: (T - TII) )
Vr II,f
1
Fbcpm l∈N l∑
r (-∆Hl) II (9)
(2) k
2PD + H2 rPD-C
6
rPD-C
9
98 C6 + PD 98 C9
H2 H2 where TI and TII represent the temperature of the first reactor
and the second reactor, respectively. T̂If ) (Rm + 1)/(RmTref +
On the basis of the same kinetic model in Wu et al.,8 all TI,f) represents the mixed feed temperature in the first reactor,
reaction rates for each reactor (µ ) I, II) are described by and TI,f represents the feed temperature of the first reactor.
Thermodynamic and physical parameters, e.g., the specific heat
ri0(crs, Ts) ) ki(Ts)fi(crs, Ts, Kj), s ∈ {I, II}, i ∈ Nk, j ∈ NK
of bulk fluid cpm, bulk density Fb, and heat of reaction of reactant
(3)
∆Hl, are assumed to be constant if the variation of each reactor
where crs ) [cH2, cMA, cPD, cPP, cPN, cC6, cC9]|s)I,II, the reaction temperature is very small.
rate constant ki ) ki0 exp(-Ei/RTs), and the equilibrium constant Remark 1. All kinetic parameters and thermodynamic or
Kj ) Kj0 exp(Gj/RTs), Nk ) {MA, PD, PP, MA-C6, PD-C6, MA- physical parameters, e.g., specific heat, density of bulk fluid,
C9, PD-C9, C}, and NK ) {cat-MA, cat-PD, cat-PP, Η2, MA, and reaction heat, have been shown in Wu et al.8 According to
PD, PP, PN, C6, C9}. The nonlinear function for each reaction the mass and energy balances for each reactor by eqs 6-9, the
fi is based on the Langmuir-Hinshelwood/Hougen-Watson input-output model of this selective hydrogenation process is
(LHHW) kinetic model.1,7,8 If the rate of formation of the established. Moreover, the ratios of H2 to MAPD at each reactor,
deactivating agent is considered, then the original rate equation i.e. H2/MAPD|s)I and H2/MAPD|s)II, and the recycle ratio Rm
in eq 3 is modified as could affect the product amount of each reactor and indirectly
change the temperature of each reactor.
ri ) ri0 exp(-RiCc), i ∈ Nk (4)
3. Operating Characteristic Analysis
where Cc represents the amount of carbon per unit weight of
For an industrial hydrogenation process operation, the operat-
catalyst and Ri represents deactivation constant for hydrogena-
ing temperature for the first reactor usually ranges from about
tion reactions. Moreover, the net rates of formation for each
320 to 350 K, the operating temperatures for the second reactor
component are shown by
ranges from about 300 to 325 K, the pressure ranges from 2.4
RMA ) rMA + 2rMA-C6 + rMA-C9 to 2.6 bar, and space velocity ranges from 500 to 1000 h-1.
According to this industrial specification, the outlet concentration
RPD ) rPD + 2rPD-C6 + rPD-C9
of MAPD of the first reactor needs to be kept at 3000 ppm
RPP ) rMA + rPD - rPP (1000 ppm, and the outlet concentration of MAPD of the
RPN ) rPP second reactor should be less than 600 ppm. From those system
RC6 ) rMA-C6 + rPD-C6 - rMA-C9 - rPD-C9 (5) specifications and operating constraints, the desired operating
RC9 ) rMA-C9 + rPD-C9 condition with feasible input manipulation will be addressed
as follows.
RH2 ) rMA + rPD + rPP + 2rMA-C6 + 2rPD-C6+
Since the inlet concentration of MAPD for both reactors is
rMA-C9 + rPD-C9 changed by manipulating H2/MAPD|s)I, H2/MAPD|s)II, and Rm,
RC ) rC the systematic analysis of process operating condition depends
on normalized operating indexes, including the MAPD conver-
In the second step, the operating manner for both reactors sion (XMAPD), the propylene selectivity (SPP), and temperatures
and recycle design are introduced into the specific modeling. of the first reactor (NT1) and the second reactor (NT2).
(i) Assuming that each reactor is well-mixed and recycle time
delay is ignored, the mass balances for each composition at each inlet amount of MAPD - outlet amount of MAPD
XMAPD )
reactor are shown by inlet amount of MAPD
outlet amount of PP - inlet amount of PP
SPP )
Fr I RrI(crI, TI) inlet amount of MAPD - outlet amount of MAPD
reactor I: (ĉ - cr ) )
I
(6) outlet temperature at first reactor
Vr r,f Rm + 1 NT1 ≡
operating temperature at first reactor
outlet temperature at second reactor
Fr I NT2 ≡
reactor II: (c - crII) ) RrII(crII, TII) (7) operating temperature at second reactor
Vr r (10)

where Fr is the volumetric flow rate in the feed, Vr is volume Remark 2. On the basis of previous mass balances for both
of each reactor, cr,fI the feed concentration of the first reactor, reactors, the outlet amounts of MAPD and PP can be evaluated
and ĉr,fI ) cr,fI/(Rm + 1) is the mixed feed concentration of the at prescribed values of H2/MAPD at each reactor and recycle
first reactor. The reaction rate at each reactor is Rrs ) [RH2, RMA, ratio. Similarly, the temperature for both reactors can be

Figure 2. Steady-state operation: (a) XMAPD and SPP vs Rm and (b) NT1 and
NT2 vs Rm.
evaluated by energy balances for both reactors. By the normal-
ized operating indexes, the operating conditions for prescribed
bounds of ratios of H2 to MAPD at each reactor and the recycle
ratio from low to high are estimated via the following analyses.
When the added H2 amount is fixed, the recycle ratio Rm is
adjusted from low to high; Figure 2a shows that the increase of
recycle ratio can increase the MAPD conversion, but the
corresponding PP selectivity gradually decreases. The feed at
the first reactor is diluted by the large recycle ratio such that
the reaction rate of the first reactor becomes slow. Figure 2b
shows that the temperature of the first reactor becomes lower
compared to the second reactor while the recycle ratio increases.
Since the feed rate at the second reactor decreases due to the
increase of recycle ratio, the slow space velocity can improve
the conversion of reaction as well as increase the temperature
of the second reactor.
When the recycle ratio is fixed, Figure 3a shows that the PP
selectivity depends on different ratios of H2 to MAPD. By the
estimated bounds for 1 e H2/MAPD|s)I e 2 and 0 < H2/
MAPD|s)II e 0.5, the high PP selectivity can maximize the yield
of propylene. If the upper limits of outlet concentration of
MAPD for each reactor are considered, Figure 3b shows that
the highest MAPD conversion can be achieved by large ratios
of H2 to MAPD at each reactor. Figure 4a,b shows that each
temperature distribution of the reactors I and II depends on
different ratios of H2 to MAPD. Under the prescribed operating
limits, e.g., the outlet concentration of MAPD and operating
temperatures for each reactor, the constrained operating points
are found by symbolizing the cluster of black or green points
depicted in Figures 3 and 4, respectively.
Ind. Eng. Chem. Res., Vol. 50, No. 3, 2011 1455
Figure 3. Steady-state operation: (a) SMAPD vs H2/MAPD|s)I and H2/
MAPD|s)II and (b) XMAPD vs H2/MAPD|s)I and H2/MAPD|s)II.
Under the constant recycle ratio and the specified outlet
concentration of MAPD and temperatures of each reactor, the
feasible operating ranges for the manipulation of both ratios of
H2 to MAPD at each reactor can be found by the above figures.
According to the estimated bounds 1 e H2/MAPD|s)I, H2/
MAPD|s)II e 3, the corresponding MAPD conversion is close
to 0.99 and the PP selectivity is kept at approximately 0.5.
4. Fuzzy-Based Multiobjective Optimization
By above analyses of operating indexes vs input effects, the
feasible ranges of input manipulations can be found by
computing the input-output model, i.e.
q(x, u) ) 0 (11)
where the state x ) [crI, crII, TI, TII] and the input u ) [H2/
MAPD|s)I, H2/MAPD|s)II, Rm]. For an industrial MAPD hydro-
genation process, the MAPD conversion is expected to be
maximized, but the green oil should be minimized, i.e., the
highest PP selectivity. It implies that both specific indexes of
XMAPD and SPP need to be optimized by virtue of an adequate
optimization technique. It has been shown that both XMAPD and
SPP are conflicting objectives; thus, the multiobjective optimiza-
tion strategy would turn out to be a trade-off result in which
the determination of a compromise set of multiple objectives is
usually called the Pareto optimization. To establish a rapid and
simple method for solving the multiobjective optimization
algorithm, the application of fuzzy set theory is effective. In
our approach, the fuzzy membership function in terms of the
maximum and minimum values for each objective is shown by
1456 Ind. Eng. Chem. Res., Vol. 50, No. 3, 2011

q(x, u) ) 0
JS - Jmax
S
µJS ) max
JS - Jmin S
Jmax
X - JX
µJX ) (14)
Jmax
X - Jmin
X
1 e H2 /MAPD| s)I e 3
1 e H2 /MAPD| s)II e 3
Rm g 0

Step 2 (Phase II). Using the product operator for all fuzzy
objectives, the results of step 1 are examined by the following
formulation

max{µJS × µJX} (15)

u

subject to the following constraints

q(x, u) ) 0
µJi g µGmax, i ∈ {S, X}
1 e H2 /MAPD| s)I e 3 (16)
1 e H2 /MAPD| s)II e 3
Rm g 0

Remark 3. Using the fuzzy goals for multiple objectives,

Figure 4. Steady-state operation: (a) NT1 vs H2/MAPD|s)I and H2/MAPD|s)II
and (b) NT2 vs H2/MAPD|s)I and H2/MAPD|s)II.
the single objective maximization problem in terms of the
aggregation function is established in step 1. The two-phase
procedures of steps 1 and 2 aim to find a locally unique solution
through the minimum and product operators. Regarding the

{
Pareto optimality in terms of fuzzy objective combinations, it
1, JS g Jmax is shown that the Pareto-optimal solution u*, if and only if there
S
does not exist another u ∈ Ωu such that µJi(u) g µJi(u*) for all
JS - Jmax
S
µJS ) , Jmin < Ji < Jmax (12a) i and µJi(u) g µJi(u*) for at least one i.
S S
Jmax
S - Jmin
S When two of three input manipulations are fixed, the optimal
value for one of the inputs is found by using two-phase

{
0, JS e Jmin
S
procedures. The maximal fuzzy objective with respect to one
1, JX e JXmin of the input manipulations, H2/MAPD|s)I ) 2.39, is obtained
Jmax - JX and depicted in Figure 5a. The corresponding two objectives
X
µJX ) X < JX < JX
Jmin max
, (12b) JX and JS are shown in parts b and c of Figure 5, respectively.
JX - Jmin
max
X Obviously, the Pareto-optimal result is verified. In addition,
0, Ji g Jmax
X
Figure 6 shows that another optimal operating condition is
obtained while Rm ) 5.
When one of three input manipulations is fixed, the optimal
where the objectives JS ) SPP and JX ) XMAPD. The upper and
solution for two of three inputs is determined by using the two-
lower bounds for each objective are shown by Jmax
i ) maxu∈Ωu phase procedures. The three-dimenional profiles for the ag-
Ji and Jmin
i ) minu∈Ωu Ji, i ∈{X, S}. Ωu represents the physical gregation function µG with respect to prescribed inputs are
bounds for each input. µJS denotes a monotonic increasing shown in Figure 7, in which the optimal solution is pointed
membership function, and µJX denotes a monotonic decreasing with green symbol and the process constraints are covered by
membership function. Moreover, the fuzzy-based multiobjective black networks. When the input H2/MAPD|s)II is given, the
optimization algorithm is proceeded by utilizing the two-phase optimal solution for both ratios of H2/MAPD|s)I and Rm can be
procedure.17,18 found by Figure 7a. Similarly, different combinations for two
of three inputs are shown in parts b and c of Figure 7,
Step 1 (Phase I). Using the minimum operator for all fuzzy respectively.
objectives, an optimal solution set is found by maximizing the
aggregation function µG 5. Conclusions
The optimization and simulation of the industrial selective
µGmax ) max
u
min{µJS, µJX} hydrogenation process is addressed. The merits of our ap-
) max µG (13) proaches are summarized below:
u
(1) With regard to ratios of H2 to MAPD at each reactor and
the recycle ratio, the feasible operating manner is established.
(2) The MAPD conversion and the propylene selectivity are
subject to the following constraints treated as multiple conflicting objectives.
 Ind. Eng. Chem. Res., Vol. 50, No. 3, 2011 1457

Figure 6. Pareto optimality: (a) µG vs Rm, (b) XMAPD vs Rm, (c) SPP vs
Rm.
Figure 5. Pareto optimality: (a) µG vs H2/MAPD|s)I, (b) XMAPD vs H2/
MAPD|s)I, and (c) SPP vs H2/MAPD|s)I.

(3) The multiobjective optimization algorithm subject to

prescribed process constraints is solved by virtue of the iterative In this paper, the Pareto-optimal result can be effectively
programming integrated with fuzzy inference. achieved via the fuzzy-based membership function and the two-
(4) To establish a rapid and simple approach, the calculation phase procedure such that the optimal operating conditions are
using the two-phase procedure is adequate. easily verified via the graphic determination.
1458 Ind. Eng. Chem. Res., Vol. 50, No. 3, 2011

Figure 7. Pareto optimality: (a) µG vs H2/MAPD|s)I and Rm, (b) µG vs H2/MAPD|s)I and H2/MAPD|s)II, and (c) µG vs Rm and H2/MAPD|s)II.

Acknowledgment of the Republic of China for financially supporting this

The authors would like to thank the Chinese Petroleum research under Contracts No. EEA9715001 and NSC 98-
Corp. of the Republic of China and National Science Council 2622-E-224-025-CC3.

Notation
MA ) methylacetylene
PD ) propadiene
PP ) propylene
PN ) propane
GO ) green oil
crs ) molar concentration of reactant s at prescribed reactor,
kmol/m3
cr,f ) the feed concentration at prescribed reactor, kmol/m3
s operating strategies for an industrial selective hydrogenation process. Ind.
cpm ) specific heat of bulk fluid, kJ/(kg · K)
Ei ) activation energy of the ith reaction, kJ/kmol
Gj ) activation energy of the jth reaction, kJ/kmol
Fr ) volumetric flow rate, m3/h
ki ) reaction rate constant of the ith reaction
ki0 ) preexponential factor of the ith reactant
Kj ) equilibrium constant of species j
Kj0 ) preexponential factor for equilibrium constant of species j
Rm ) recycle ratio
Ts ) the temperature at prescribed reactor, K
Ts,f ) the feed temperature at prescribed reactor, K
Vr ) reactor volume, m3
Greek Symbols
Fb ) bulk density, kg/m3
∆Hl ) heat of the lth reaction, kJ/kmol
Rl ) deactivation constant of the lth reaction
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ReceiVed for reView April 30, 2010
ReVised manuscript receiVed August 19, 2010
Accepted September 14, 2010
IE100994J