2598 Ind. Eng. Chem. Res.

1991,30, 2598-2603
Literature Cited J. Am. Oil Chem. SOC.1973,50,31-38.
(9) Mark, H. F.; Othmer, D. F.; Overberger, C. G.; Seaborg, G. T.,
(1)Ahmed, M. U.;Hussian, S. K.; Ahmed, M.; Osman, S. M. Cy- Eds. Encyclopedia of Chemical Technology; Wiley Interscience:
clopropenoid fatty acids in seed oils of Sida acuta and Sida New York, 1978; pp 1-15.
rhombifolia (Malvaceae). J. Am. Oil Chem. Soc. 1976, 53, (10)Mark, H. F.;Othmer, D. F.; Overberger, C. G.; Seaborg, G. T.,
698-699. Eds. Encyclopedia of Chemical Technology; Wiley Interscience:
(2)Bharucha, K.E.; Gunstone, F. D. Vegetable oils IV-A new me- New York, 1978;pp 111-176.
thod of determining the component acids of oils containing epoxy (11)Official and Tentative Methods of American Oil Chemists’
and/or hydroxy acids. J. Sci. Food Agric. 1955,6,373-380. Society, 3rd ed.; AOCS: Champaign, IL, 1973;Vol. 11, Methods
(3)Bharucha, K.E.; Gunstone, F. D. Vegetable oils Part VI-The Da 15-48and Da 16-48.
Component acids of Ergot oil. J. Chem. Soc. 1957, Part 1, (12)Schneider, E. L.; Loke, S. P.; Hopkins, D.T. Gas liquid chro-
610-614. matographic analysis of cyclopropenoid acids. J. Am. Oil Chem.
(4)Daulatabad, C. D.; Hosamani, K. M.; Desai, V. A. Cyclopropenoid SOC.1968,45, 585-590.
fatty acids in the Plumbaginaceae plant family. Chem. Znd. 1987,
126-127.
(5) Davis, E. N.; Wallen, L. L.; Goodwin, J. C.; Rohwedder, W. K.; * To whom correspondence should be addressed.
Rhodes, R. A. Microbial Hydration of cis-9-Alkenoic Acids. Lip-
ids 1969,4,356-362. Chirag Mahmood Jehan D. Daulatabadl
(6)Fioriti, J. A.; Sims, R.J. A spray reagent for the identification Vijayaraj A. Desai, Kallappa M. Hosamani
of epoxides on thin layer plates. J. Chromatogr. 1968, 32, Department of Chemistry
761-763.
(7)Harris, J. A.; Magne, F. C.; Skau, E. L. Cyclopropenoidfatty acids Karnatak University
11-A step-wise hydrogen bromide titration method for cyclo- Dharwad 580 003, India
propenoid and epoxy derivatives. J. Am. Oil Chem. SOC.1963,40,
718-720. Received for review May 20, 1991
(8)Kleiman, R.;Spencer, G. F. Gas Chromatography-Mass Spec- Revised manuscript received September 3, 1991
trometry of methyl esters of unsaturated oxygenated fatty acids. Accepted September 16, 1991

Numerical Calculation of Simultaneous Absorption of H2S and C02 in

Aqueous Hydroxide Solutions
Simultaneous absorption of H2S and COPin aqueous hydroxide solutions is studied numerically,
considering reversibility effects of all reactions involved. A finite-difference scheme based on film
theory is developed, which exhibits excellent convergence characteristics. The effect of finite C02
reaction rate is examined, and the role of the second dissociation of C 0 2 in enhancing the kinetic
selectivity toward H2S absorption is demonstrated. Under certain conditions, forced desorption of
C 0 2 is predicted. The effect of temperature on the selectivity of the system a t hand is investigated.
It is shown that, as the temperature increases, the effect of the accelerated C 0 2 reaction is gradually
reversed by the increased COz back-pressure and by forced desorption effects. In fact, the results
suggest that the selectivity at temperatures around 200 “C may be significantly greater than that
attained a t room temperature.

Introduction this study is the selective removal of H2S, contained to-

The problem of simultaneous absorption of two gases gether with C02 in high-enthalpy geothermal steam, by
accompanied by chemical reaction was first considered by scrubbing input or output streams with an aqueous hy-
Roper, Hatch, and Pigford (1962). The special case studied droxide solution. Process simplicity and operational re-
involved irreversible, instantaneous reactions and was strictions (e.g., high temperatures in the case of H2S re-
analyzed based on the concept of the “reaction plane”. moval upstream of the turbines) do not favor the use of
Ramachandran (1971) considered the case when both re- alkanol amines, which is widespread in the chemical in-
actions are reversible and instantaneous while a number dustry.
of authors provided approximate solutions for the case of Absorption of H2S and C 0 2 in aqueous hydroxide solu-
irreversible reactions, one which occurs instantaneously tions was first studied by Astarita and Gioia (1965).
and the other which proceeds at a finite rate (Onda et al., Considering the reactions involved as irreversible, they
1970b; Goettler and Pigford, 1971; Ramachandran . and employed the notion of two reaction planes and showed
Sharma, 1971; Cornelisse et al., 1977). that the selectivity toward H2S is considerably higher than
Relatively recently it was numerically shown by Cor- expected on the basis of the Roper, Hatch, and Pigford
nelisse et al. (1980) that the inclusion of reversibility could theory. The key assumption made by Astarita and Gioia
lead to one component being desorbed under a driving was that the fast (but not instantaneous) reaction of C02
force positive for absorption. This phenomenon of forced does not take place at all, unless there exists a substantial
desorption was systematically analyzed by Astarita and concentration of OH- ions, in which case it is assumed to
Savage (1982) for the case of instantaneous reactions, by proceed to completion instantaneously.
considering the “shift reaction- between the two gases. An analysis of the H2S-C02-NaOH system, taking into
The simultaneous absorption of H a and C02in alkaline account reversibility effects of all reactions, has not been
solutions is a typical industrial operation where the above presented yet, to the best of our knowledge. It is indicative
analyses are applicable. The reaction of H2S is instanta- of the state of the art in absorption tower design that even
neous under all conditions, whereas C02 reacts at a finite comprehensive computer simulations such as those of De
rate. Selective H2S absorption is often highly desirable, Leye and Froment (1986) treat the C02 absorption as
as in the case of H2S removal to produce an environmen- irreversible. This can be attributed in part to the fact that
tally acceptable off-stream. The application motivating the system at hand is further complicated by the second
OSSS-5SS5/91/2630-2598$02.50/0 Q 1991 American Chemical Society
 Ind. Eng. Chem. Res., Vol. 30, No. 12, 1991 2599
dissociation reactions of C02 and H2S,which cannot be Mass-Transfer Model
neglected at the pH range of practical interest. The gas-phase resistance to mass transfer is considered
The complete set of reactions is considered in the negligible and only the liquid-side mass transfer is mod-
present work, and an efficient computational scheme is eled. In order to focus attention on the fundamental issues,
developed for its solution in the framework of film theory. the simplifying assumption of equal diffusivities is made.
The exact solution derived accounts for a variety of effects, This assumption permits an analysis based on the film
such as reversibility and finite reaction rate. Therefore, theory model, which leads to ordinary instead of partial
at the expense of a modest amount of computational time, differential equations.
it can be used with more confidence than the approximate A straightforward extension of the proposed computa-
approach of Astarita and Gioia (1965). The numerical tional scheme includes use of the correct diffusivities and
solution of the mass-transfer equations will be incorpo- application of the semiempirical correction of Chang and
rated, in future work, in a computer code for the design Rochelle (1982), to provide results similar to those of
of gas scrubbers. The use of film theory is, therefore, surface renewal theory. Indeed, Glasscock and Rochelle
preferred because of the shorter computation time involved (1989) show that the differences from unsteady-state
as compared with unsteady-state theories. models are negligible compared to the uncertainty in the
The occurrence of a shift reaction in the present chem- actual mass-transfer mechanism. Since, however, no
ical system leads to the manifestation of forced desorption quantitative comparison with data is attempted in the
phenomena, which have been repeatedly documented in present work, this alternative is not pursued *here.
the case of aqueous amine solutions (Cornelisseet al., 1980; The steady-state mass balances across the liquid film
Astarita and Savage, 1982; Al-Ghawas and Sandall, 1988). result in the following equations:
One original feature of the present contribution, however,
is the consideration of the more complex situation where carbon dioxide reaction balance
two gases are simultaneously absorbed, each by consecutive
reactions coupled at every level. Indeed, the second dis- d2[C021 k
sociation of C 0 2appears to significantly affect the kinetic
D - dx2 - (,,,,2l[OH-] - -[HC03-]
Kl
selectivity toward H2S for a wide range of conditions.
Finally, the effect of temperature on the selectivity of total carbon balance
the system at hand is investigated. Limited attention has
d2[C02] d2[HC03-]
been paid in the literature to this aspect, although it is
evident that results concerning single-gas absorption
+

dx2
+ d2[C032-]
dx2
cannot be safely extended to the more complex case of
multiple-gas absorption presently considered. total sulfur balance
d2[H2S]
Chemistry
When H2S and C02 are being absorbed in a hydroxide
+-d2[HS-]
dx2
solution, the following reversible reactions should be con-
sidered (Astarita and Gioia, 1965): total hydroxide balance
C02 + OH- HC03- (1) d2[OH-]
D-= R1+ Rz + R3 + R4
H2S + OH- + H2O
HS- (2) dx2

HC03- + OH- == C032-+ H 2 0

HS- + OH- + S2- + H 2 0
Equilibrium constants are denoted by K,, K2,K3,and K4,
(3)
(4)
dx2 dx2 -I
d2[C032-] d2[S2-]
dx2
where R1,R2, R3,and R4 represent the rates of reactions
1-4. The equilibrium of the instantaneous reactions
respectively. Reactions 2, 3, and 4 may be considered provides the following equations:
instantaneous when compared to the rate of diffusional
processes. The rate of reaction 1 is given (Astarita et al., [HS-] = K2 [H2S] [OH-] (11)
1983) by the relation

[S2-] = K4[HS-][OH-] (13)

with the rate constant k depending on the temperature T
and the ionic strength I in the following way: The bulk of the liquid is assumed to be in equilibrium
for a given loading of total carbon and sulfur (C= total
log k = 13.635 - 2895/T + 0.08I (5b) carbon concentration, S = total sulfur concentration, and
M = total metallic ion concentration are given). These
The occurrence of the shift reaction constraints, together with an equation representing the
H2S + HC03- + COP + HS- + H2O (6) electrical charge balance (negative charge concentration
= M), uniquely determine the liquid composition in the
is automatically accounted for by considering reactions 1 bulk. The boundary conditions at the edge of the liquid
and 2 as reversible. film, x = 0, equate the concentration of each component
As for the physicochemical data needed for the model, to its bulk value.
Henry's law is assumed to hold, with the dependence of [H2S1 = [H2Slb, IHS-1 = [HS-lb,
the constants on temperature taken from Astarita et al.
(1983). The equilibrium constants as functions of the [s2-] = [s2-]b, [OH-] = [OH-],, [coz] = [C02]b,
temperature are given by the above authors and are also [HC03-] = [HC03-]b, [c03'-] = [co32-]b
tabulated in Barber0 et al. (1982). on x = 0 (14)
2600 Ind. Eng. Chem. Res., Vol. 30, No. 12,1991

At the gas-liquid interface, x = 6, the following equations For given values, [H2S]iand [C021i,of the gas concen-
hold: tration on the interface, (7), (11)-(13), and (23)-(25) con-
stitute the system to be solved. The unknowns are the
7)
Nco, = -D( d[CO2l enhancement factors fi and f2 and the concentration of
i each component across the liquid film.

d[H2S] d[HS-] d[S2-] Numerical Method

- --
The equations are nondimensionalizedusing the metallic
~

dx dx
ion concentration, M, as the characteristic concentration
and the film thickness 6 as the characteristic length. The
=0 (17) fundamental dimensionless group appearing is the reac-
i
tion-diffusion parameter A, given by
A = kMa2/D (27)
where tD = a2/Dis the characteristic diffusion time. For

+
dx dx
-1
d[HCO3-] d[S2-]
-
i
(18)
a reasonably well mixed liquid, tD varies within a relatively
narrow range (Astarita et al., 1983):
4 x 10-3 < tD< 4 x io-* (28)
Relations 15 and 16 equate the transfer rates at the gas The system is solved numerically by discretizing the
and liquid sides for COPand H2S, respectively. Equation equations to N + 2 points across the liquid film. In this
17 states that no carbon-containing ions pass the interface, formulation, the unknowns are the concentrations of each
nor can they be converted infinitely fast into C02. of the seven species at the N + 1 points (point 1 is at the
Equation 18 is a budget of [OH-] ions at the interface and edge of the liquid film) and the two enhancement factors,
is the outcome of the following arguments Since no [OH-] a total of [7(N + 1)+ 21. Equations 11-13 and 23-25 are
ions cross the interface, the diffusion-induced flux and the applied to each point across the film, giving 6(N 1) +
surface rate of consumption at the interface s u m up to zero. equations. Two equations are provided by specifying the
H2Sand C02concentrations on the interface and another
N by applying (7) to the N interior points of the film. To
this end, the derivative in (7) is approximated by central
finite differences.
where Ril,Riz,Ri3,and Ri4are the surface rates of reactions The last equation needed is provided by applying (7) at
1,2,3, and 4 respectively, right on the interface. It is noted the point N + 2, right on the interface. Boundary con-
that the surface rate of consumption can be nonzero only dition 15 is discretized at point N + 2 by a central finite
for instantaneous reactions; therefore Ril = 0. The other difference formula, and the hypothetical concentration at
surface rates are calculated by writing down appropriate point N + 3, outside the gas-liquid interface, is used to
budgets at the interface for each instantaneous reaction derive the following expression for the second derivative
separately, as follows: on the interface:

The above computational scheme produces a system of

nonlinear algebraic equations, which is solved by Newton’s
method. The standard procedure is modified by including
in the algorithm a constraint which rejects negative values
of the concentration during the iteration, thus leading to
the physically significant solution. An additional im-
provement to the computational scheme involves the
unequal distribution of the discretization points across the
film in order to achieve finer resolution close to the in-
terface. The numerical method exhibits excellent con-
vergence characteristics and presents no stability problems
like the ones reported in the literature concerning solution
of similar systems by a shooting technique (Al-Ghawas and
Sandall, 1988).
Results
The accuracy of the present numerical scheme was
confirmed by successful computation of the analytically
tractable cases of absorption of a single component fol-
lowed either by instantaneous reversible reaction (Onda
et al., 1970a) or by irreversible reaction at finite rate (Van
Krevelen and Hoftijzer, 1948). The difference of the nu-
merical results from analytic expressions of the above
studies was less than 1% and 3%, respectively.
The simultaneous absorption of H2S and C02was con-
sidered next, focusing on the special case where the bulk
 Ind. Eng. Chem. Res., Vol. 30, No. 12, 1991 2601

Table I. Parameters Used To Study the Effect of Reaction

Rate

[HZSli,kmol/m3
[CO& kmol/m3
S, kmol/m3
25 OC
0.060
0.019
0.5
225 OC
0.060
0.019
0.5 E
20 11 J H2S

C, kmol/m3
M, kmol/m3
0.5
2.0
0.5
2.0 -
L
a 10

4.2 X lo7 6.2 x 103

1.0 x 107 2.1 x 104
4.5 x 103 3.8
2.1 1.0 x 10'

-IO1

-5 0 5 10 15

log(A/M)
" Figure 2. HzS and COSenhancement factors as a function of the
E
e
reaction-diffusion parameter, using the equilibrium constants at 225
O C and bulk concentrations indicated in Table I.

c
5

"Ea
0 5

log(AIM)
10 15
kB
Figure 1. H2S and COz enhancement factors as a function of the
t
b
reaction-diffusion parameter, using the equilibrium constants at 25
"C and bulk concentrations indicated in Table I.
f
8
liquid concentration of the reaction products is zero. This
permits comparison with the approximate analytical results
of Astarita and Gioia (1965). The outcome indicates that 0.0 0.3 0.6 0.9 1.2 15
the approximate model overestimates the absorption of
Xi6
C02, a discrepancy which diminishes as the C02reaction
rate approaches infinity. The most serious drawback of Figure 3. Concentration profiles across the film for parameter
that model, however, is its neglect of reversibility effects. values indicated in Table I (225 "C)and very fast COz reaction. The
Forced desorption cannot be predicted by the Astarita- concentrations are scaled by the factors indicated on the figure to
permit presentation on the same plot. A maximum in the COz con-
Gioia model, and it is under conditions favoring such centration close to the interface, indicative of forced desorption, is
phenomena that the model is expected to fail. observed.
Following the above comparisons, absorption into a
liquid with nonzero concentration of the reaction products takes over for values of A I M above lo8.
is considered and the effect of two parameters, reaction The effect of the second dissociation of CO, is illustrated
rate and temperature, is, studied in detail. by setting K3 = K4 = 0 and recalculating the enhancement
(a) Effect of t h e Rate of Reaction. To illustrate the factors. The results, which appear as dashed lines in
effect of the reaction-diffusion parameter, A , the following Figure 1, indicate that the second dissociation has a fa-
two cases are considered: The equilibrium constants used vorable effect on the selective absorption of H2S. For a
are those corresponding to the reactions taking place (case large range of reaction rates, inclusion of the second dis-
i) at 25 "C and (case ii) at 225 "C. These parameters, as sociation leads to an increase of the H2S enhancement
well as the bulk concentrations used, are given in Table factor with an even more significant decrease of the C 0 2
I. For the specific system and conditions considered the enhancement factor. This is expected, since in the absence
reaction-diffusion parameter is fully specified. The com- of C032- ions there is a single reaction plane for both gases
putations, however, are performed by varying A as a pa- defined by the depletion of OH-ions.
rameter in order to illustrate its effect on the absorption It is interesting to contrast this observation with the
-
rates. It should be noted that, in the limit of instantaneous
reactions (A a),selective absorption of CO, is favored
in case i and that of H2S is favored in case ii.
well-known negative effect of the CO2-ions on the ther-
modynamic selectivity of H2S (Astarita et al., 1983). This
is an example of the case where factors influencing the
The results for case i are presented in Figure 1. With thermodynamic selectivity in one way could have the op-
decreasing reaction rate, there is a transition from a posite effect on the kinetic selectivity.
thermodynamic selectivity favoring the absorption of CO, The results for case ii are presented in Figure 2. The
to a kinetically imposed selective absorption of H2S. It C02enhancement factor first increases with reaction rate,
is interesting to note that kinetic selectivity in favor of H2S reaching a maximum at some intermediate value. The Ha
is still dominant for values of A I M as high as lo6 (corre- enhancement factor exhibits a minimum in the same range
sponding to C 0 2 reaction rate constant of lo8 m3/(kmol of reaction rates and then asymptotically reaches a plateau,
s)) and thermodynamic selectivity in favor of COP only with CO, dipping to large negative values.
2602 Ind. Eng. Chem. Res., Vol. 30, No. 12,1991

Table 11. Enhancement Factors for H$3 and Cot here is incorporated in a computer code, which will be used
Absorption as a Function of Temperature in the interpretation of data from experiments already
temD. O C H,S enhancement CO, enhancement under way.
25 20.3 1.2
75 50.0 2.7 Acknowledgment
125 68.0 6.4
175 76.5 -23.1 Financial support for this work has been obtained from
225 80.6 -92.7 the European Economic Communities (program VALO-
REN), from the General Secretariat for Research and
The behavior in the limit of large values of the reac- Technology of Greece, and from the Greek Public Power
tion-diffusion parameter is an example of forced desorp- Corporation (PPC).
tion, discovered by Cornelisse et al. (1980)and analyzed
for irreversible reactions by Astarita and Savage (1982). Nomenclature
Indeed, the concentration of C02 in the bulk is much A = dimensionless reaction-diffusion parameter, A = kMa2/D
smaller than on the interface and an overall driving force C = total carbon concentration, kmol/m3
for absorption exists. Reversibility effects close to the D = molecular diffusivity, m2/s
interface, however, overshoot to COPconcentration above = enhancement factor of gas j
the interface value, leading to desorption. A concentration
profile for such a case is shown in Figure 3.
fi= ionic strength of solution, kion/m3
k = reaction rate constant, m3/(kmol s)
(b) Absorption at High Temperatures. Some con- K . = equilibrium constant of reaction j , m3/kmol
cern has been expressed in the literature (Hohlfeld, 1980) d = total metallic ion concentration in solution, kmol/m3
about the efficiency of selective absorption of H2S by Nj = molar flux of species j , kmol/(m2 s)
scrubbing with hydroxide solutions at elevated tempera- Rj = volume rate of reaction j , kmol/(m3 s)
tures, in view of the increased reaction rate of the com- R , = surface rate at the interface of reaction j, kmol/(m2s)
petitive absorption of COO. However, the above results S = total sulfur concentration in solution, kmol/m3
indicate that the process could still prove efficient. T = absolute temperature, K
To further investigate the effect of temperature on the x = distance, measured from the edge of film toward the
selectivity of the system at hand, a series of runs is carried interface, m
y, = COzconcentration at location j across the film, kmol/m3
out with bulk concentrations S = 0.5, C = 0.5, and M =
2.0 and temperatures ranging from 25 to 225 "C. The gas Greek Letters
phase is assumed to consist of H2S and C02,with partial 6 = film thickness, m
pressure of 0.5 atm each. The reaction rate constant, as Registry No. H@, 7783-06-4;C02, 124-389NaOH, 1310-73-2.
given by (5b), is used and the dependence of Henry's law
and equilibrium constants on temperature is also taken Literature Cited
into account. The results, which are presented for selected
temperatures in Table 11, indicate a monotonic increase Al-Ghawas, H.A.; Sandall, 0. C. Modeling the simultaneous trans-
in the H2S enhancement factor with temperature. The port of two acid gases in tertiary amines with reversible reactions.
Sep. Sci. Technol. 1988,23,1523-1540.
behavior of C02 is more interesting. An increase in the Astarita, G.; Gioia, F. Simultaneous absorption of hydrogen sulfide
enhancement factor with temperature is observed first, and carbon dioxide in aqueous hydroxide solutions. Ind. Eng.
attributable to the increase of the kinetic constant. At high Chem. Fundam. 1965,4,317-320.
temperatures, however, reversibility effects come into play Astarita, G.; Savage, D. W. Simultaneous absorption with reversible
and finally forced desorption of C02 occurs. Actual ab- instantaneous chemical reaction. Chem. Eng. Sci. 1982, 37,
sorption rates for C02 are adversely affected, as noted by 677-686.
Astarita, G.; Savage, D. W.; Bisio, A. L. Cas Treating with Chemical
Yu and Astarita (1987),even at lower temperatures by the Solvents; Wiley: New York, 1983;pp 36,93,and 253.
combined effects of the increase in C02 back-pressure and Barbero, J. A.; McCardy, K. G.; Tremaine, P. R. Apparent heat
Henry's law constant with temperature. On the basis of capacities and volumes of aqueous hydrogen sulfide and sodium
the results presented, it can be argued that the selectivity hydrogen sulfide near 25 "C. The temperature dependence of H a
in H2S absorption will initially deteriorate with tempera- ionization. Can. J. Chem. 1982,60,1872-1880.
ture, possibly reaching a minimum before 100 "C, but will Change, C. S.; Rochelle, G. T. Mass transfer enhanced by equilib-
rium reactions. Ind. Eng. Chem. Fundam. 1982,21, 379-385.
improve dramatically at higher temperatures. Cornelisse, R.; Beenackers, A. A. C. M.; Van Swaij, W. P. M. Si-
multaneous absorption of two gases in a reactive liquid, one gas
Conclusions reacting instantaneously. Chem. Eng. Sci. 1977,32,1532-1535.
Absorption of H2S and COPin aqueous hydroxide solu- Comelisse, R.; Beenackers, A. A. C. M.; Van Beckum, F. P. H.; Van
tions is studied numerically. A computational scheme is Swaij, W. P. M. Numerical calculation of simultaneous mass
transfer of two gases accompanied by complex reversible reac-
developed for this complex system, which is shown to tions. Chem. Eng. Sci. 1980,35,1245-1260.
converge for any possible value of the parameters involved. De Leye, L.; Froment, G.F. Rigorous simulation and design of col-
In particular, varying the reaction rate of the noninstan- umns for gas absorption and chemical reaction-I1 Plate columns.
taneous reaction over more than 15 orders of magnitude Comput. Chem. Eng. 1986,10,505-515.
causes no convergence problems and the correct asymptotic Glasscock, D. A.; Rochelle, G. T. Numerical simulation of theories
results (pure diffusion at one end and instantaneous re- for gas absorption with chemical reaction. AIChE J. 1989,35,
1271-1281.
action at the other) are recovered. This scheme can easily Goettler, L.A.; Pigford, R. L. Computational studies of the simul-
be adapted to a different set of reactions. taneous chemical absorption of two gases. AIChE J. 1971,17,
Kinetic selectivity toward H2S is observed for a wide 793-800.
range of values of the C02 reaction rate constant. It is Hohlfeld, R. W. Selective absorption of Ha from sour gas. J. Pet.
demonstrated that the second dissociation of C02further Technol. 1980,32, 1083-1089.
enhances this phenomenon. Finally, forced desorption of Onda, K.; Sada, E.; Kobayashi, T.; Fujine, M. Gas absorption ac-
companied by complex chemical reactions-I. Reversible chem-
COP,possibly leading to very high selectivity, is shown to ical reactions. Chem. Eng. Sci. 1970a,25,753-760.
become important at temperatures well above 100 "C. Onda, K.; Sada, E.; Kobayashi, T.; Fujine, M. Gas absorption ac-
In forthcoming work, the numerical scheme presented companied by complex chemical reactions-111. Parallel chemical
 Ind. Eng. Chem. Res., Vol. 30,No. 12,1991 2603
reactions. Chem. Eng. Sci. 1970b,25, 1023-1031. Yu, W.-C.; Astarita, G.Selective absorption of hydrogen sulfide in
Ramachandran, P. A. Simultaneoue absorption of two gases accom- tertiary amine solutions. Chem. Eng. Sci. 1987,42,419424.
panied by reversible htantaneouschemical reaction. Chem. Eng.
Sci. 1971,26, 349-355. Vasilis Bontozoglou, Anastasios J. Karabelas*
Ramachandran, P.A.;Sharma, M. M. Simultaneous absorption of Chemical F’rocess Engineering Research Institute
two gases. Trans. Inst. Chem. Eng. 1971,49,253. and Department of Chemical Engineering
Roper, G. H.;Hatch, T. F.; Pigford, R. L. Theory of absorption and Aristotle University of Thessaloniki
reaction of two gases in a liquid. Ind. Eng. Chem. Fundam. 1962, P.O. Box 1517, GR 54006 Thessaloniki, Greece
2 , 144-152.
Van Krevelen, D. W.; Hoftijzer, P. J. Kinetics of gas-liquid Received for review April 1, 1991
reactions-I. General theory. R e d . Trau. Chim. 1948, 67, Revised manuscript receiued September 17, 1991
563-586. Accepted September 27, 1991