5846 Ind. Eng. Chem. Res.

2004, 43, 5846-5853

KINETICS, CATALYSIS, AND REACTION ENGINEERING

Mass-Transfer Characteristics for Gas-Liquid Reaction of H2S and

Sulfuric Acid in a Packed Column
Hui Wang,† Ivo G. Dalla Lana, and Karl T. Chuang*
Department of Chemical and Materials Engineering, University of Alberta,
Edmonton, Alberta T6G 2G6, Canada

The mass-transfer characteristics of a gas-liquid reaction system in a packed column filled

with ceramic Raschig rings were studied using the reaction between hydrogen sulfide (H2S)
and sulfuric acid solutions. An analysis based on two-film theory shows that the mass-transfer
resistance consists of two consecutive steps: gas-side mass transfer and surface reaction. The
resistance from the liquid side was negligible because the concentration of sulfuric acid was
above stoichiometric and can be regarded as a constant. Onda et al.’s correlations (Onda, K.;
Takeuchi, H.; Okumoto, Y. J. Chem. Eng. Jpn. 1968, 1, 56) are able to estimate the effective
interfacial area as well as the mass-transfer coefficients for our reactor system. Because the
reaction between H2S and concentrated sulfuric acid is a pseudo-first-order reaction with respect
to H2S under the experimental conditions used, the approximate equality between the measured
overall mass-transfer coefficient and the reaction rate constant suggests the regime of reaction
rate control. In other words, the comparison between the rate constants and mass-transfer
coefficient is able to show the rate-controlling regimes in terms of operating conditions such as
acid concentration, temperature, and acid and gas flow rates. Tests were also carried out with
gaseous compounds often found in industrial H2S streams. No reaction was observed for methane,
carbon dioxide, carbonyl sulfide, and carbon disulfide. However, the conversion of ethylene was
about 20%, and those of mercaptan and thiophene were nearly 100%. This study provides useful
data that can facilitate scale-up calculations of this potential sulfur removal and recovery
technology.

Introduction interfacial area (mol s-1 m-2) for reactions 1 and 2,

A new sulfur removal and recovery technology is
being sought based on the gas-liquid reactions of H2S
and sulfuric acid, i.e., the reaction between H2S and
concentrated sulfuric acid, denoted as reaction 1, and
the reaction between H2S and sulfur dioxide (SO2),
which is produced in the former reaction, denoted as
reaction 2. The reaction kinetics of these two reactions
were studied separately using a gas-liquid batch reac-
tor under the extreme conditions where only one of the
reactions occurred at a time and the reaction rate was
controlling.1,2 The results suggested that the two reac-
tions predominantly occur at the interface between the
gas and liquid phases. The rate equations of the two
reactions per unit interfacial area are
rH2S,1 ) kP1PH2S (1)
rH2S,2 ) kP2PH2SPSO2 (2)
where rH2S,1 and rH2S,2 are the reaction rates per
* To whom correspondence should be addressed. Tel.:
(780) 492-4676. Fax: (780) 492-2881. E-mail: karlt.chaung@
ualberta.ca.
†
Present address: Department of Chemical Engineering,
University of Saskatchewan, Saskatoon, Saskatchewan S7N
5C5, Canada.
10.1021/ie030845u CCC: $27.50 © 2004 American Chemical Society
Published on Web 07/10/2004
respectively; kP1 and kP2 are the corresponding rate
constants; and PH2S and PSO2 are the partial pressures
of H2S and SO2, respectively. A column reactor packed
with ceramic Raschig rings is technically favored to
carry out these gas-liquid reactions when the technol-
ogy based on the kinetic results is developed. For scale-
up, two additional issues have to be taken into consid-
eration: the mass-transfer characteristics of this reaction
system in the packed column reactor and the reactivity
of the reaction agent, i.e, sulfuric acid, to possible species
contained in the to-be-treated gas streams. This paper
reports the results of a study of these two respects.
For the reaction between H2S and sulfuric acid, H2S
from the bulk gas and H2SO4 from the bulk liquid
diffuse to the interface, where they react. For the
reaction between H2S and SO2, after the latter has been
generated from the former reaction at the interface, SO2
must dissolve in the liquid phase to initiate the reaction
with H2S.2 However, when fresh concentrated (g90 wt
%) sulfuric acid is used, the reaction between H2S and
sulfuric acid is overwhelming, and the reaction between
H2S and SO2 is negligible. Meanwhile, when a dilute
H2S gas mixture (e5 mol %) is fed, sulfuric acid can be
considered to be present in excess, so that its concentra-
tion remains essentially constant during the course of
the reaction. As a result, the mass-transfer resistance
to the diffusion of H2SO4 in the liquid phase is also
 Ind. Eng. Chem. Res., Vol. 43, No. 18, 2004 5847

where y is the mole fraction of H2S, a is the gas-liquid

interface area per unit volume packing, P is the total
pressure of the gas phase, G is the superficial molar flow
rate of the gas, and z is the height of packing bed. To
use eq 8 to calculate KGa from experimental data, the
experiments have to be carried out such that the amount
of mass transport along the axial direction is negligible
compared to the amount of mass transported by convec-
tion and the acid concentration change resulting from
the reaction is insignificant. The first condition is
satisfied for almost all situations involving flow in
packed-column reactors,5 and so is the second if the
proper flow rates of H2S and sulfuric acid are chosen.
The prerequisite for using eq 8 to separate KG from
KGa is to have the value for the mass-transfer area per
unit volume of the packed bed, a. After comparing the
applicability of the available models to our reactor
system in terms of packing material and operating
conditions, we chose to use Onda et al.’s correlation (eq
9) for the estimation of this parameter. To further
confirm the validity of Onda et al.’s equations for the
packed-bed reactor that was used, the liquid-side mass-
Figure 1. Mass-transfer profile of the gas-liquid reaction of H2S transfer coefficient, kL, for the H2S-water system was
and H2SO4. measured and compared with the values estimated
according to eq 11. Subsequently, the gas-side mass-
negligible. According to the two-film model,3,4 the mass- transfer coefficient values calculated from the experi-
transfer profile, as shown in Figure 1, is that H2S mental data using eq 8 and that estimated from Onda
diffuses from gas phase to the gas-liquid interface, et al.’s correlation (eq 10) were compared, and the rate-
where it undergoes a pseudo-first-order reaction with controlling regime was determined from the comparison.
H2SO4. At steady state, the flux of H2S being trans- Onda et al.’s empirical equations6 are as follows
ported from the bulk gas to the interface is equal to the
reaction rate per unit surface area
aw/at ) 1 - exp[-1.45(σc/σ)0.75(L/atµL)0.1
i i
rH2S ) kG(PH2S - PH 2S
) ) kP1PH 2S
(3) (L2at/FL2g)-0.05(L2/FLσat)0.2] (9)
i
The partial pressure of H2S at the interface, PH 2S
, is kGRT/atDG ) c(G/atµG)0.7(µG/FGDG)1/3(atDp)-2.0 (10)
not as easily measured as the bulk partial pressure,
i
PH2S. To eliminate PH 2S
, solving eq 3 yields
kL(FL/µLg)1/3 ) 0.0051(L/awµL)2/3(µL/FLDL)-1/2(atDp)0.4
kGPH2S (11)
i
PH ) (4)
2S kG + kP1
where aw is the wetted surface area of the packing, m2
and the rate of reaction at the interface becomes m-3; at is the total surface area of the packing, m2 m-3;
σc is the critical surface tension of the packing material,
rH2S ) KGPH2S (5) dyn cm-1; σ is the surface tension, dyn cm-1; L is the
superficial mass velocity of the liquid, kg m-2 h-1; µL is
the viscosity of the liquid, kg m-1 h-1; FL is the density
where KG is the overall mass-transfer coefficient and
of the liquid, kg m3; g is the gravitational constant, m
can be defined as
h-2; kG is the gas-phase mass-transfer coefficient, kg-
1 1 1 mol m-2 h-1 atm-1; R is the gas constant, m3 atm kg-
) + (6) mol-1 K-1; T is the absolute temperature, K; G is the
KG kG kP1
superficial mass velocity of the gas, kg m-2 h-1; DG is
the diffusivity of H2S in the gas, m2 h-1; µG is the
for this reaction system. For the packed column reactor, viscosity of the gas, kg m-1 h-1; FG is the density of the
a steady-state mole balance on H2S in a differential gas, kg m-3; Dp is the nominal size of the packing, m;
segment of the bed along the axial direction of the and c is 5.23 for the larger packing and 2.00 for the
reactor results in the differential equation smaller (nominal size < 15 cm) packing.
In addition, to determine whether the developing
dy KGaP
) dz (7) technology would interact with the useful constituents
y G and other sulfides in possible to-be-treated sour gas
streams, this study also includes the reactions between
Integration of eq 7 from y1, the inlet mole fraction of
concentrated sulfuric acid and possible components in
H2S, to y2, the outlet mole fraction of H2S, gives rise to
sour gas streams: methane, ethylene, carbon dioxide,
the expression
carbonyl sulfide, carbon disulfide, mercaptan, and
y2 KGaPz thiophene. A semibatch reactor was used to measure
ln ) (8) the conversion and determine whether these compounds
y1 G react with sulfuric acid.
5848 Ind. Eng. Chem. Res., Vol. 43, No. 18, 2004
Physicochemical Properties
Some physicochemical properties of the gases and
liquids involved in this study are discussed as follows:
Density, Gravitational Constant, and Surface
Tension. The density of sulfuric acid solutions and
water was found from Perry’s Chemical Engineers’
Handbook.7 The value for a particular acid concentra-
tion and temperature was determined using interpola-
tion from the available data if it was not available in
the handbook. The density of the gas was calculated
using the equation of state for an ideal gas. The density
of water was calculated in terms of the temperature
used in the experiments. The gravitational constant is
9.807 m s-2. The critical surface tension, σc, of ceramic
rings is 56 dyn cm-1 from Table 18-11 of Perry’s
Chemical Engineers’ Handbook.7 The surface tensions,
σL, of water and sulfuric acid have been reported by
Myhre et al.8 Although the surface tension of a liquid
varies with temperature, the dependence is not signifi-
cant. For example, the surface tension of 96 wt %
sulfuric acid changes from 0.05544 N m-1 at 0 °C to
0.05308 N m-1 at 50 °C. The value of surface tension at
a particular temperature was estimated by interpolation
or extrapolation using the data available.
Viscosity. The viscosities of sulfuric acid solution and
water at a given temperature were chosen from the
nomograph for viscosities of liquids.7 The viscosities of
gases such as nitrogen can be found in CRC Handbook
of Chemistry and Physics.9
Diffusivity. The diffusivity of H2S in water was
calculated by the Wilke-Chang correlation10
T
DH2S,L ) 1.173 × 10-16(φML)0.5 (12)
µLVH2S0.6
where DH2S,L is the diffusivity of H2S diffusing through
water, m2 s-1; φ is the “association parameter” of the
solution, which is 2.6 for water, as suggested by Wilke
and Chang; ML is the molar molecular weight of water,
g mol-1; µL is the viscosity of the solution, Pa s or kg
m-1s-1; and VH2S is the molar volume of H2S at the
boiling point, 0.0329 L mol-1. Thus, eq 12 can be
simplified to read
T glass, which was heated to a preset temperature by a
DH2S,L ) 1.339 × 10-14 (13)
µL
The diffusivity of H2S in the liquid phase, DH2S,L, is
used for the calculation of kL, and a mass-transfer
resistance analysis indicates that the resistance in the
liquid can be negligible when reaction occurs between
a dilute H2S gas stream and a concentrated sulfuric acid
solution. Therefore, the calculation of DH2S,L in sulfuric
acid was unnecessary.
The diffusivity of H2S in the gas phase was deter-
mined using the Fuller equation10
1 × 10-7T 1.75(1/MA + 1/MB)1/2
DAB ) (14)
P[(∑vA)1/3 + (∑vB)1/3]2
where A represents H2S and B represents N2 for most
of the runs in this study; DAB is the diffusivity, m2 s-1;
T is the temperature, K; MA and MB are the molar
weights of A and B, respectively, g mol-1; P is the total
pressure, atm; and ∑vA and ∑vB are the sums of the
structural volumes of A and B, respectively. For the
binary system of H2S and N2
DAB ) 8.840 × 10-10T 1.75/P (15)
Experimental Method
A schematic diagram of the experimental setup is
shown in Figure 2. Because both liquid (sulfuric acid)
and gas (containing H2S) involved in this study are
corrosive, ceramic Raschig rings with a nominal size of
6 mm, which is the magnitude of the outside diameter
and ring height, were used as the packing. The column
was made of Pyrex glass with an inner diameter of 0.06
m and a height of 1 m. The bottom section of the column
consisted of a packing holder made of Teflon, a gas-
liquid separation chamber, a liquid outlet flow-control-
ling valve, and a gas inlet/outlet tube. The top section
consisted of a liquid inlet tube connected to a liquid
distributor and a gas inlet/outlet tube. The three sec-
tions were joined together by two standard joints and
sealed with Teflon gaskets. Curved aluminum blocks,
inside which the cartridge heaters were installed, were
placed around the column to protect the reactor and to
heat it as well. The temperature of the heaters was
controlled by an Omron temperature controller, model
E5CX (Omron Corporation, Tokyo, Japan) with 0.1 °C
resolution. In addition to the thermocouples that mea-
sured the temperature of the column skin, two other
thermocouples with glass covers were located in the
inlet and outlet acid solutions to monitor the tempera-
ture inside the column. Installing different amount of
packing allowed a change in the height of the packing
in the column. The position of the liquid distributor was
adjustable such that it could be positioned just above
the packing when the height of the packing was
changed. The gas stream was introduced into the
column either from the top or from the bottom so that
either co-current or countercurrent operation was pos-
sible. Most of the runs were carried out in co-current
flow. The flow rates of the cylinder gases were regulated
by mass flow controllers (Sierra Instruments, Inc.,
Monterey, CA), which were calibrated using a BIOS
primary air flow meter, model DryCal DC-2M (BIOS
International Corporation, Pompton Plains, NJ). The
fresh acid solution was stored in a 5-L tank of Pyrex
hot plate (model 200T, Fisher Scientific). The heated
acid solution was pumped into the column using a
variable-speed acid pump (Cole Parmer Instruments
Co., Chicago, IL). The preheater was located after the
pump if temperatures higher than 100 °C were required.
This is because the acid pump could not be operated
above 100 °C. The spent acid solution was collected in
another 5-L tank. For the sake of safety, the glass tanks
were placed into stainless steel pockets.
For a typical run, sulfuric acid solution of the desired
concentration was prepared and heated to a preset
temperature. The inlet gas mixture was prepared ac-
cording to the chosen composition and flow rate. The
composition was also analyzed using a GC equipped
with TCD and SCD.11 Then, the solution was pumped
into the column at a set flow rate. The gas mixture was
directed to the column once steady acid flow had been
established. After the reaction, both gas and liquid were
directed to the gas-liquid separation chamber below the
packing bed (for co-current flow). A valve was used to
control the liquid level in the chamber. When steady
state was reached, the composition of the effluent gas
 Ind. Eng. Chem. Res., Vol. 43, No. 18, 2004 5849

Figure 2. Schematic diagram of the experimental setup for the packed-bed column reactor: 1, mass flow controllers; 2, fresh acid storage
tank; 3, protecting pockets; 4, temperature controllers; 5, valves; 6, acid pump; 7, acid preheater; 8, heating-oil storage tank; 9, heating-
oil pump; 10, packed-bed column reactor; 11, temperature indicator; 12, gas-liquid separator; 13, acid flow control valve; 14, spent acid
storage tank; 15, pressure gauges; 16, 4-way valve; 17, needle valves; 18, GC coupled with TCD and SCD.

was analyzed three times during a run. Usually, it took overall liquid-side mass-transfer coefficient can be
15 min for the system to reach steady state. expressed as
Sulfuric acid solutions at various concentrations were
*
prepared by diluting ∼96 wt % sulfuric acid (Fisher rH2S ) KL(CH 2S
- CH2S) (16)
Scientific, Nepean, Ontario, Canada) with deionized
water. The 100 wt % acid was prepared by mixing 20% where
free SO3 fuming sulfuric acid (Acros Organics, Morris
Plains, NJ) with 96 wt % sulfuric acid solution. The 1 1 1
concentrations of the solutions were determined by ) + (17)
KL HkG kL
titration with a standard 0.1 N sodium hydroxide
solution (Fisher Scientific, Nepean, Ontario, Canada),
KL is the overall liquid-side mass-transfer coefficient;
using 0.1% methyl orange solution (Fisher Scientific, *
Fair Lawn, NJ) as an indicator. Cylinders of anhydrous CH 2S
is the H2S concentration in equilibrium with a
hydrogen sulfide (CP grade), SO2, and prepurified pressure of PH2S in the gas phase; CH2S is the H2S
nitrogen were provided by Praxair Products Inc. (Mis- concentration in the liquid phase; H is the Henry’s law
sissauga, Ontario, Canada). The specifications for other constant; and kG and kL are the gas-side and liquid-side
chemicals can be found in ref 11. mass-transfer coefficients, respectively. A molar balance
for a differential segment of the bed along the axial
direction of the reactor at steady state gives
Results and Discussion
L *
dCH2S ) KLa(CH - CH2S) dz (18)
Estimation of the Liquid-Side Mass-Transfer FL 2S

Coefficient. The H2S-water system was used to esti-

mate the liquid-side mass-transfer coefficient of our
packed-bed reactor. In such experiments, a high degree
of purity of the gas phase is usually used such that the
gas-side resistance is considered to be negligible in
comparison with the liquid-side resistance.12 However,
for safety reasons, these experiments employed a feed
gas containing H2S (1-5 mol %) and nitrogen (inert).
Thus, the H2S flux from gas to liquid in terms of the
where L is the superficial mass flow rate of the liquid,
FL is the density of the liquid phase, a is the effective
interfacial area, and z is the axial direction of the
column. L could be regarded as a constant because the
amount of H2S transferred from the gas phase to the
liquid phase was small. To easily integrate eq 18, the
experiments were carried out such that PH2S did not
*
change significantly (<10%) and, thus, CH 2S
could be
5850 Ind. Eng. Chem. Res., Vol. 43, No. 18, 2004

Table 1. Measured and Estimated Values of kL for the H2S-Water System

H2S in G L KLa KL kLa
run gas (%) (kg m-2 s-1) (kg m-2 s-1) (s-1) (m s-1) (m s-1)
MS-3c 0.988 0.00341 0.764 0.00549 1.31 × 10-5 1.47 × 10-5
MS-4a 0.988 0.00341 0.764 0.00588 1.33 × 10-5 1.47 × 10-5
MS-6 0.905 0.00682 0.764 0.00605 1.44 × 10-5 1.47 × 10-5
MS-7a 2.51 0.00682 0.764 0.00518 1.23 × 10-5 1.47 × 10-5
MS-5 0.988 0.00341 1.27 0.0101 2.12 × 10-5 1.90 × 10-5
a Values of kL in this column were calculated using eq 11.

regarded as a constant as well. KLa was consequently

computed from the integration of eq 18, i.e.

( )
*
L CH 2S
- CH2S,1
KLa ) ln * (19)
FL z CH2S - CH2S,2

where CH2S,1 and CH2S,1 are the H2S concentrations in

the water that enters and exits the reactor, respectively.
To separate KL from KLa, the wetted surface area, aw,
from eq 9 was used to replace the effective interfacial
area, a, and then KLa was divided by aw. The total
specific surface area of the packing, at, was estimated
by at ) 4.7/Dp for the Raschig rings.12
To determine whether the process is controlled by
liquid-side mass transfer, the effect of the gas and liquid
flow rates on KL was investigated. As shown in Table
1, the value of KL is significantly affected by the liquid Figure 3. KGa measurements at different heights of the packing
flow rate but insensitive to the gas flow rate. When the bed. Experimental conditions for the four points, respectively: bed
height ) 0.20, 0.40, 0.58, and 0.75 m; acid concentration ) 90.13,
superficial liquid flow rate was increased from 0.764 to 89.20, 89.20, and 89.60 wt %; temperature ) 24.2, 23.9, 24.7, and
1.27 kg m-2 s-1, KL increased from 1.33 × 10-5 to 2.12 23.9 °C.
× 10-5 m s-1. However, the KL value remained constant
when the gas flow rate was doubled. As a result, it can
be concluded that liquid-side mass transfer is the rate-
controlling step for H2S absorption by water in our
packed-bed reactor. KL can, therefore, be considered as
a close estimation of kL. This view is also supported by
the comparability between the value of KL from the
experiment and that of kL from eq 11. Table 1 shows
that the two values corresponding to the same set of
experimental conditions deviate from each other by
(11%, which falls within the possible error range of
(20% suggested by Onda et al.6 In summary, the
experiments using the H2S-water system show that eq
11 is able to estimate the liquid-side mass-transfer
coefficient and that eq 9 is able to estimate the effective
interfacial area for the packed-bed reactor used in our
experiments.
H2S Absorption Accompanied by Reaction. To Figure 4. Temperature dependence of estimated kG and kP1 and
ensure accurate measurements, lower acid concentra- measured KG. Experimental conditions for the four points, respec-
tions, e.g., 90 wt %, were chosen such that the conver- tively: bed height ) 0.20, 0.20, 0.20, and 0.20 m; acid concentra-
sions of H2S in the runs were no more than 50%. In the tion ) 90.13, 90.07, 90.09, and 90.10 wt %; temperature ) 24.2,
first series of experiments, the possibility of end effects 44.0, 61.0, and 75.5 °C.
was investigated by varying the packing height. At 25
°C, sulfuric acid of 90 wt % concentration was pumped by the wetted interfacial area, aw, which was calculated
at 130 mL/min into the column. It was dispersed at the from eq 9. The values of KG are shown in Figure 4. At
top of the packing through the liquid distributor. The the same time, the values of the reaction rate constant,
gas stream containing 1% H2S was directed into the top kP1, at the corresponding temperatures were calculated
of the column at 1.5L/min (STP). The H2S concentra- following the Arrhenius equation

( )
tions in the inlet and outlet gas streams were measured,
and KGa was calculated using eq 8. The KGa values are Ea
kP1 ) A0 exp - (20)
plotted against the packing height, z, in Figure 3, and RT
the results show that no significant end effects are
observed for these experiments. The fluctuation in KGa and these are shown in Figure 4 as well. We have
values can be attributed to the slight variations in the reported that A0 and Ea are functions of acid concentra-
acid concentration or temperature for various runs. tion and can be evaluated using regressed models.1 With
KGa values were also obtained at different tempera- the values of the regressed parameters in ref 1, A0 and
tures. The KG values were calculated by dividing KGa Ea were calculated, and then kP1 was obtained using eq

20. Figure 4 shows that the temperature dependence
behaviors of KG and kP1 follow the same pattern, which
is different from that of kG calculated from eq 10.
Comparing eqs 3 and 5, the values of KG and kP1
represent the H2S disappearance rate if the H2S partial
pressure is the same. In fact, if reaction controls the
i
process, mass transfer will be fast and PH 2S
) PH2S in
eq 3; conversely if mass transfer is controlling, eq 5 has
the same value of PH2S. Thus, the same pattern that
these two parameters KG and kP1 depend on tempera-
ture might suggest the regime of reaction rate control.
As discussed, at steady state
kP1aPH2S ) KGawPH2S (21)
Theoretically, if aw calculated from eq 9 is an exact
estimation of the true interfacial area, a, KG should be
equal to kP1. However, KG was found to be 10% less than
kP1, indicating that aw could be higher than the true
interfacial area, a, if we assume that the KGa values
from the experiments were more accurate. Although
Onda et al.6 pointed out that the estimation of a by aw
from eq 9 would bring about errors of (20%, what could
be the possible physical reasons that might cause true
real interfacial area to be less than the estimated value
in this study? First, liquid channeling through the
packing might occur in our small-diameter column.
Second, the packing surface might be covered to some
extent by the sulfur produced by the reaction, especially
when the production of sulfur is large and/or liquid flow
rate is small. We tried to reduce this effect to an
insignificant extent by ensuring high liquid flow rates
and low sulfur production. The molar ratio of our
highest sulfur production rate to the acid flow rate was
3.5 × 10-5. Under these circumstances, the coverage of
the interfacial area by solid sulfur was estimated using
the wetted area and the particle size of the sulfur. It is
known that the modification of sulfur is complex. Thus,
the particle size of the sulfur produced from the reaction
is difficult to estimate. However, the literature13 shows
that sulfur from the oxidation of H2S tends to keep S8
allotropy, which forms orthorhombic crystals with a unit
structure consisting of 128 sulfur atoms.14 Assuming
that all of the sulfur forms unit cells and that all of the
cells float at the surface of sulfuric acid solution,
calculation of the coverage of the liquid surface by sulfur
in terms of the wetted surface area, the liquid hold-up,
the liquid flow rate, the sulfur production rate, and the
average cross-sectional area of a unit cell gives a value
of 13.3%. This value could be much smaller because
larger sulfur crystals might form, which would make
the overall cross-sectional area of the sulfur particles
smaller, and sulfur colloids tend to stay in the liquid
phase, which would make the surface coverage smaller.
Our earlier paper1 showed that sulfur colloids stay in
the acid solution when visible amounts of sulfur are
formed in the reaction between pure H2S and concen-
trated sulfuric acid. In summary, poor liquid distribu-
tion on the packing surface and sulfur blocking might
render the true wetted surface smaller than that
estimated from eq 9; however, the difference still falls
in the error range suggested by Onda et al.6 Considering
the errors from the estimation of the interfacial area,
the above discussion leads to the conclusion that the
reaction rate constant, kP1, calculated from eq 20 is able
to approximate the overall mass-transfer coefficient, KG,
for this packed-bed reactor when the reaction rate
controls the process.
Ind. Eng. Chem. Res., Vol. 43, No. 18, 2004 5851
Figure 5. Analysis of rate-controlling regime for reaction with
96 wt % acid.
The rate of reaction of H2S with 96 wt % sulfuric acid
is greater than that with 90 wt % acid,1 resulting in
higher H2S conversions. Thus, this concentration is
favorable when the real process is conducted in a packed
column reactor. However, this higher conversion would
adversely affect the measurement accuracy of the mass-
transfer parameters. Even when the packing height was
reduced to 0.2 m, the conversion of H2S at room
temperature could reach as high as 90%. At tempera-
tures of g60 °C, the conversion was so high that the
concentration of H2S in the effluent gas was below the
detection limit of the analyzing instrument, even though
high gas flow rates and high H2S concentrations were
applied. Thus, no experimental data could be obtained
for calculating KG under such conditions. Nevertheless,
because the characteristics of mass-transfer resistance
are not altered by an increase in the acid concentration,
the same analysis as used in the case of 90 wt % acid
could result in the rate-controlling regime for the
reaction of 96 wt % acid. On the basis of this consider-
ation, the reaction rate constant, kP1, for 96 wt %
sulfuric acid and the gas-side mass-transfer coefficient,
kG, were calculated from eqs 20 and 10, respectively.
The values for these two constants are shown in Figure
5. Because the reaction with 96 wt % acid is also first-
order, a comparison of the magnitudes of kP1 and kG
indicates that, when the temperature is below ca. 60
°C, the process is controlled by reaction but, when the
temperature exceeds 60 °C, mass transfer becomes the
rate-controlling step. At room temperature, however, the
overall mass-transfer coefficient, KG, measured from the
experiment, shown as a dot in Figure 5, is close to the
value estimated from eq 20. Although we obtained one
experimental point for 96 wt % acid, the results of the
comparison with the calculated data should be believ-
able because Onda et al.’s correlations have been shown
to be valid in the estimation of mass-transfer charac-
teristics of packed-bed reactors.6
Onda et al.’s correlations (eqs 9-11) were developed
from experimental data using a packed column with
countercurrent flow.6 It is worth pointing out that the
valid use of these equations for a co-current flow system
in this study extended their applicability.
Reactions between Sulfuric Acid and Other
Components in Sour Gases. Using a semibatch
system in which the acid solution was charged into the
reactor and the gas mixture was passed through the
solution,14 the reactions of sulfuric acid at 96 and 80
wt % concentrations with other possible components in
5852 Ind. Eng. Chem. Res., Vol. 43, No. 18, 2004
sour gases, namely, methane (CH4), ethylene (C2H4),
carbon dioxide (CO2), carbonyl sulfide (COS), carbon
disulfide (CS2), mercaptan (C2H5SH), and thiophene
(C4H4S), were investigated. The acid solution was
heated to 120 °C in advance, and the gas mixture
contained 20 mol % CH4, CO2, COS, or CS2; 10 mol %
mercaptan or thiophene; and/or 5 mol % ethylene. The
components of the exiting gas and their concentrations
were measured by GC. No conversion was observed for
CH4, CO2, COS, and CS2. About 20% conversion was
observed for ethylene, resulting in 0.3-0.35% SO2 in
the exiting gas from 96 wt % acid but none from 80 wt
% acid. It is believed that the hydration of ethylene
might have occurred in both solutions and that SO2
might be produced by the reduction of sulfuric acid
molecules. For mercaptan and thiophene, complete
conversion was observed in 96 wt % acid, and above 99%
conversion was observed in 80 wt % acid. About 3.80-
5.31% of the mercaptan and a trace amount of the
thiophene were converted into SO2. Other products that
might stay in the liquid acid were not identified. The
detailed conversion and product distribution for each
component can be found in the literature.15
Conclusions
The mass-transfer characteristics of a gas-liquid
reaction in a packed column reactor are studied using
the reaction system of H2S and sulfuric acid and H2S-
water absorption. A “two-film” theory analysis shows
that, when H2S is transported from the gas phase to
the surface of concentrated sulfuric acid for reaction,
the overall mass transfer of H2S consists of two con-
secutive steps: gas-side mass transfer and surface
reaction. The liquid-side resistance can be negligible
when H2SO4 is present in stoichiometric excess. Onda
et al.’s correlation (eq 9) is capable of estimating the
effective gas-liquid interfacial area of the packed
column filled with ceramic Raschig rings. With this
interfacial area, the value of KL for the H2S-water
absorption system and that of KG for the H2S-sulfuric
acid reaction system were obtained from the data for
KLa and KGa measured experimentally. For H2S-water
absorption, the resulting KL value is close to the liquid-
side mass-transfer coefficient kL calculated by another
of Onda et al.’s correlation (eq 11). In addition, for the
H2S-sulfuric acid reaction system, the measured KG
value is approximately equal to the reaction rate
constant. Because the reaction between H2S and con-
centrated sulfuric acid is pseudo-first-order with respect
to H2S, the comparison between the reaction rate
constant and mass-transfer coefficient in terms of
magnitude reveals the rate-controlling regime. Sulfuric
acid does not interact with gas components such as CH4,
CO2, COS, and CS2. However, it consumes ethylene to
some extent, with the conversion depending on acid
concentration and temperature. The nearly complete
conversions of mercaptan and thiophene are beneficial
if these sulfur species are present and need to be
removed. The information acquired from this study is
useful for reactor scale-up and process design in devel-
oping a sulfur removal process from the reaction be-
tween H2S and sulfuric acid.
Acknowledgment
The authors acknowledge financial support from the
Natural Sciences and Engineering Research Council of
Canada and the Alberta Oilsands Technology and
Research Authority.
Nomenclature
a ) effective surface area, m2 m-3 or m-1
at ) total surface area of the packing, m2 m-3 or m-1
aw ) wetted surface area, m2 m-3 or m-1
C ) concentration in the liquid phase, mol m-3
c ) constant in eq 10; 5.23 for larger packing and 2.00 for
smaller packing
D ) diffusivity, m2 s-1 or m2 h-1
DG ) diffusivity in the gas phase, m2 s-1 or m2 h-1
DL ) diffusivity in the liquid phase, m2 s-1 or m2 h-1
Dp ) nominal size of the packing, m
G ) superficial mass flow rate of the gas, kg m-2 h-1 or
mol m-2 s-1
g ) gravitational constant, m h-2
H ) Henry’s law constant, m3 Pa mol-1
KG ) Overall mass-transfer coefficient in the gas phase mol
s-1 m-2 Pa-1
KL ) overall mass-transfer coefficient in the liquid phase,
m s-1
kG ) gas-phase mass-transfer coefficient, mol s-1 m-2 Pa-1
kL ) liquid-phase mass-transfer coefficient, m s-1
kP1 ) rate constant for reaction between H2S and H2SO4,
mol s-1 m-2 Pa-1
kP2 ) rate constant for reaction between H2S and SO2, mol
s-1 m-2 Pa-1
L ) superficial mass flow rate of the liquid, kg m-2 h-1
M ) molecular weight, g mol-1
P ) pressure or partial pressure, Pa
Pi ) pressure or partial pressure at the interfacial surface,
Pa
R ) gas constant, m3 Pa K-1 mol-1
r ) reaction rate or mass-transfer rate, mol s-1 m-2
T ) absolute temperature, K
V ) solute molar volume at the boiling point, L mol-1
v ) structural volume of a molecule
y ) mole fraction of a component in the gas phase
z ) height of the packing, m
Subscripts
A ) soluble gas component
B ) another soluble gas component
b ) bottom
c ) critical
G ) gas
L ) liquid
p ) packing units (rings, spheres, etc.)
t ) total, top
w ) wetted
1 ) related to the reaction between H2S and H2SO4
2 ) related to the reaction between H2S and SO2
Greek Letters
µ ) viscosity, Pa s or kg m-1 h-1
F ) density, kg m-1
σ ) surface tension, dyn cm-1 or kg h-2
φ ) association parameter
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Received for review November 21, 2003
Revised manuscript received March 26, 2004
Accepted May 12, 2004
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