Ind. Eng. Chem. Res.

1994, 33, 7-13 7

Modeling Reaction Quench Times in the Waste Heat Boiler of a Claus

Plant
Linda V. Nasato,+ Kunal Karan, Anil K. Mehrotra, and Leo A. Behie*
Department of Chemical and Petroleum Engineering, The University of Calgary,
Calgary, Alberta, Canada T2N 1N4

At the high temperatures found in the modified Claus reaction furnace, the thermal decomposition
and oxidation of H2S yields large quantities of desirable products, gaseous hydrogen (H2) and sulfur
(S2). However, as the temperature of the gas stream is lowered in the waste heat boiler (WHB)
located downstream of the furnace, the reverse reaction occurs leading to reassociation of H2 and
S2 molecules. To examine the reaction quenching capabilities of the WHB, a rigorous computer
model was developed incorporating recently published intrinsic kinetic data. A sensitivity study
performed with the model demonstrated that WHBs have a wide range of operation with gas mass
flux in the tubes from 4 to 24 kg/(m2«s). Most important, the model showed that it was possible
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to operate WHBs such that quench times could be decreased to 40 ms, which is a reduction by 60%
compared to a base case scenario. Furthermore, hydrogen production could be increased by over
20% simply by reconfiguring the WHB tubes.
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Introduction in the catalytic reactors. The unrecovered sulfur, in

The separation of sulfur compounds from natural gas
is usually accomplished by a selective absorption process
that produces an acid gas feed for a Claus sulfur recovery
unit. The acid gas contains as its major components, H2S,
CO, and H20; and as its minor components, hydrocarbons,
N2, and COS.
The basis of the modified Claus process is the production
of elemental sulfur via a two-step reaction. In the first
step or thermal stage, one-third of the H2S is completely
oxidized to S02 in the reaction furnace, located at the
front end of plant. A benefit that also occurs is the
production of significant quantities of elemental sulfur
(S2) from the thermal decomposition of H2S. In fact, the
sulfur produced in the furnace is 50-60 % of the total sulfur
condensed in the plant. Well-known equilibrium curves,
such as those published in the GPSA Data Book (1987)
or by Paskall (1979), show that the sulfur conversion
increases with flame temperature, from about 68 % at 926
°C to about 75% at 1260 °C. The main H2S oxidation
reaction is
H2S + 3/202 S02 + H20
—
(1)
Note that a number of other reactions occur in the furnace
(Paskall, 1979) including
s + h2o
H2S + V2Oj
—
elemental or combined form (H2S, COS, CS2), is combusted
to S02 in the tailgas incinerator which is then emitted to
the atmosphere. Tailgas clean-up units are added some-
times prior to incineration to increase the sulfur recovery
and minimize emissions.
Role of the WHB. The Claus furnace and the WHB
together are treated normally as a single unit. The Claus
furnace WHB is a shell and tube heat exchanger (see Figure
1) in which product gases from the furnace at 900-1300
°C are cooled to 250-300 °C in one or two tube passes and
high-pressure steam is generated on the shellside. The
Claus furnace product is a mixture of gases; in addition
to the expected sulfur compounds (S2, H2S, and S02),
combustion products (H20 and C02), and inerts (N2 and
Ar), four other compounds often appear (H2, CO, COS,
and CS2).
Field tests conducted at the Ultramar Refinery (Wilm-
ington, C A) by Sames et al. (1990) indicate that a reduction
in S2, H2, and CO contents and an increase in H2S and
COS contents of the product gas takes place along the
WHB tube. Hydrogen, although not present in the feed
gas to the furnace, was reported to be present at the outlet
of the single tube pass WHB. Its presence was attributed
to the thermal decomposition of H2S into H2 and S2. The
thermal decomposition of H2S is a reversible reaction for
which the forward reaction is favored at high temperatures
(2)

encountered in the Claus reaction furnace, while the reverse

+ 2H20 reaction or reassociation of H2 and S2 is favored at the
2H2S + S02
—
3/2S2 (3)
lower temperatures in the WHB. The disappearance of
+ 3H20 CO in the WHB tube is attributed to its reaction with S2
3H2S + 3/202 (4)
-
3/2S2
to form COS. The following two reactions are thus believed
The reaction furnace is followed by the waste heat boiler to occur in the WHB tubes:
(WHB), where heat is recovered by cooling the furnace
product gases. In the second step or the catalytic stage, h2 + V2s2 * h2s (6)
unreacted H2S is then combined with S02, produced via
eq 1, over an alumina catalyst to form elemental sulfur in CO + V2s2 cos (7)
fixed bed reactors by the following reaction:
Located just after the reaction furnace, the WHB plays
2H2S + S02 3/xS, + 2H20
s=t (5) an important role in the overall design of the Claus plant.
Sulfur formed in each stage of the Claus plant is The reactions given as eqs 6 and 7 had never been
condensed and recovered to achieve maximum conversion considered to occur in the WHB prior to the study by
Sames et al. (1990). In fact, the gas composition at the
* To whom correspondence may be addressed, inlet and the outlet of waste heat boiler have been assumed
t Present Address: Goar, Allison and Associates Inc., Tyler, to be the same for design purpose, leading to an incorrect
TX. and overly conservative design. Thus, it is not surprising

0888-5885/94/2633-0007$04.50/0 © 1994 American Chemical Society

8 Ind. Eng. Chem. Res., Vol. 33, No. 1, 1994

REACTION FURNACE WASTE HEAT BOILER (WHB)

PROCESS GAS TO
CONDENSER NO. 1
. HIGH PRESSURE
REFRACTORY _L STEAM
COMBUSTION LINING <
AIR ZL

FUEL GAS
(START-UP)
T BOILER
TO SEAL POT
Figure 1. Schematic diagram of a reaction furnace and the waste heat boiler (WHB).
that the primary aim of the WHB was considered to cool
or quench the gas and not to quench the two reactions
that occur in the tubes. However, an improved and
optimized design of a WHB, taking into account the two
reactions, can reduce the quench- time and increase the
production of potentially valuable H2 and S2.
Quenching of the H2-S2 reassociation reaction (eq 6) in
the WHB would result in an increase in available H2.
Hydrogen, although present only in small quantities, offers
several benefits to the overall process. A number of
commercially available tailgas clean-up processes require
the reduction of tailgas sulfur compounds (i.e. COS, CS2,
S, and S02) to produce H2S prior to further treatment.
Hydrogen is usually produced by the reforming of methane;
hence, it involves additional capital and operating costs
that become an integral part of the cost of the tailgas
treatment process. An increase in a continuous source of
hydrogen from the thermal stage, thus implies a reduction
in requirement of additional H2, and thus a lowering of
the capital investment.
The quenching of the H2S formation reaction would
also result in a decrease in H2S output from the WHB
outlet. In turn, this implies a reduction in the H2S/S02
ratio, which is to be maintained at a stoichiometric ratio
of 2:1 for the catalytic reactions that occur in the
downstream reactors. Maintaining this ratio would de-
crease the S02 output from the furnace. This will require
oxidizing a reduced amount of H2S in the furnace which
can be achieved by lower air or oxygen throughput to the
furnace. For air-based operations, this results in hydrau-
lically unloading the downstream sulfur recovery unit. In
oxygen-based operations, this results in a reduced oxygen
requirement for the furnace and consequently a lower cost
involved in its production.
Contrary to belief, most of the COS in the Claus process
is formed in the WHB and not in the reaction furnace.
The presence of COS in the product gases is undesirable
due to the difficulty of its hydrolysis to H2S in the
downstream catalytic reactors. The COS, although present
only in small quantities at the WHB exit, contributes
significantly to sulfur emissions if not hydrolyzed to H2S.
The quenching of the COS formation reaction will result
in a reduction of COS output from the WHB exit. This
FEED WATER
(Nasato, 1993). Plug flow is assumed in the WHB tubes,
implying negligible radial concentration and temperature
gradients. Other assumptions include steady-state op-
eration and ideal gas behavior. Finally, it has been
assumed that a constant tube-wall temperature is main-
tained as saturated water vaporizes to form high-pressure
steam on the shellside of the WHB. The effects of the
hydrodynamic and thermal entrance regions have been
neglected which Nighswander et al. (1989) found to be a
good assumption.
Although a number of reactions may occur in the WHB
tube, the reactions between H2 and S2 and CO and S2 were
considered to be most important. This is justfiable in
view of the findings by Sames et al. (1990). The reactions
given by eqs 6 and 7 are reversible, homogeneous gas-
phase reactions and are first order with respect to the
concentrations of the species involved, namely H2, CO, S2,
H2S, and COS.
Material Balance. The component mass balance
equations for j = 1, .... nc components and i = 1, ..., Nc
reactions are
dFj/Az
=
1.....nc
A^syr[;. j =
(8)
The main secondary sulfur species reactions are as follows
(Sames et al., 1990):
3S2
—*
S6 (9)
—*
4S2 S8 GO)
These reactions have been ignored for two reasons. First,
this paper establishes that the key chemical reaction is
quenched at a temperature (7'q)of900°Cnearthe entrance
of the WHB tube. Above a temperature of 900 °C, sulfur
vapor is present as S2. Secondly, no sulfur vapor condenses
in the WHB tube because the gas temperature is always
above the sulfur dew point temperature. Moreover, the
heat of reaction for the two reactions (eqs 9 and 10) is only
about 20 % of the total heat duty (GPSA Data Book, 1987).
Energy Balance. The energy balance equation is given
by
dT/dz =
[A{(-AHm)rl + (-zVffR2)r2|
-

implies a reduction in sulfur loss or an enhancement in D[/(T-Tw)]/[J>;.Cp;·] (11)

sulfur recovery.
Pressure Drop. The pressure drop is obtained from
momentum balance:
Model Development
Model Equations Development. A rigorous one- dP/dz = -2fG2/PD (12)
dimensional model of a WHB tube has been developed where f =
Fanning friction factor for tubes at Re > 5000,
 Ind. Eng. Chem. Res., Vol. 33, No. 1, 1994 9

which is calculated from and S2 to form COS may be written as

f =
0.079fie-°·025 (13) (_rco)
= ~~

Residence Time. Assuming ideal gas behavior, the
actual mean residence time in the tubular reactor is given
by
dtR/dz = {AP)(RT)~lC£jFjyl (14)
Heat Transfer. The overall heat-transfer coefficient,
U, is defined as follows:
*WD p Dff0
kmDu D0h0
where //¡ and ff0 are fouling factors and were obtained
from Perry et al. (1984) as 1.77 X 10"4 and 8.81 X 10"5
m2-K/W, respectively. Since U is in the range of 30-40
W/(m2-K), any uncertainty in the fouling factors, ff\ and
ff0, will be insignificant. The tube outside heat transfer
coefficient for steam generation, h0, is assumed to be large
in comparison to the inside coefficient, hi, making the
Ccos/K) (23)
Design Constraints. There are two major constraints
involved in the design of the Claus furnace WHB, the
pressure drop across the tubes and the heat flux.
i. Pressure Drop. The Claus plant operates at close
to atmospheric pressure which leaves little freedom in
terms of allowable pressure drop. The overall pressure
drop across the plant is restricted by the pressure of the
inlet stream, which is normally in the range of 160-175
kPa. Since the pressure at the plant outlet is atmospheric,
(15) the maximum possible pressure drop across the plant is
D0
generally in the range of 60-75 kPa. The maximum
allowable pressure drop across the WHB tubes is, thus, in
the range of 6-8 kPa. Although a typical value of pressure
drop is 4 kPa, the maximum allowable pressure drop for
the model simulation was set to 6 kPa.
ii. Heat Flux. The process of quenching, requiring
rapid removal of heat from the system, implies a high heat
flux, defined as U(T Tw). However, the maximum
-

fourth term of eq 15 negligible. possible value of heat flux in a system that involves boiling
The local inside heat transfer coefficient, hi, was of a liquid is restricted by the critical heat flux (CHF).
calculated from the Dittus-Boelter equation (Welty et Mechanical failures, in the form of tube burnout, can result
al., 1976): if the heat flux approaches the CHF. The CHF value is
a function of a number of parameters, the pressure of the
(Mg =
0.023(fie/8(Pg°·33 (16) boiling liquid (saturation pressure) being one of them.
The thermodynamic, physical, and transport properties Dykas and Jensen (1992) studied the CHF phenomenon
of gases were calculated rigorously using pure component in a bundle of horizontal tubes. They reported the CHF
values at zero steam quality for saturation pressures of
properties and appropriate mixture formulae, as summa-
rized in Appendix A. 150 and 500 kPa as 160 and 240 kW/m2, respectively. The
Reaction Kinetics. The rate expression for the re- CHF value increases with an increase in saturation
versible homogeneous gas-phase reaction between H2 and pressure. Since the minimum saturation pressure, for the
S2 (eq 6) is given by the following equation: purpose of model simulation, is 1740 kPa, which is more
than 500 kPa, the maximum allowable heat flux value of
= ~

(17) 175 kW/m2 can be safely assumed.

(— 2) ^iPh2Ps2 ^2Ph2s Model Simulation and Solution Method. Equations
The kinetic parameters for the reassociation reaction were 8,11,12, and 14 represent a system of first-order ordinary
derived from the work of Dowling et al. (1990) by modifying differential equations. The solution to these equations
their rate expression to a conveniently usable form (Nasato, was obtained through the use of a computer program
1993). written in the Advanced Continuous Simulation Language
(ACSL) installed on IBM 6000 RISC computer at The
=
(45.48 X io6)e(-26000/im (18) University of Calgary.

Results
k2
=
(3.779 X io9)eH800°/fi7’) (19)
The rate expression for the homogeneous gas-phase Definition of Quench Time. The time taken to
reaction between CO and S2 (eq 7) may be approximated quench a reaction such that its rate becomes insignificant
is termed the quench time. In order to determine the
as follows (Nasato, 1993):
quench time, the quench temperature (Tq) must be known
=
(20) first. The quench temperature is the temperature at which
(-rco) ^2^cos
-

feiCC0Cs2 the rate of reaction becomes relatively insignificant.

where (-rco) is the rate of disappearance of CO with units
kmol/(m3-s). Applying the first-order rate constant de-
veloped by Klemm and Davis (1974) to eq 20 results in the
rate constant for the reverse reaction as follows:
k2
=
(9.15 X io5)e(-3630/fiT)
The forward and reverse rate constants, k\ and ki,
respectively, are related by the equilibrium constant, K
(in m3/kmol), as follows (Bichowsky, 1936):
K = = ß(22500-36·0: )/ß'
k1/k2
Equation 22, as given by Bichowsky (1936), has been
modified slightly in order to predict the data more
accurately (Nasato, 1993). The final kinetic expression,
by combining eqs 20 and 22, for the reaction between CO
Hence, a dimensionless temperature, , is defined as
0 =
Cr-Tq)/(Tf-Tq) (24)
According to eq 24, 0 = 1 at T = T{ (at the tube inlet);
conversely, = 0 at T = Tq. For this study, the reactions
(21) are considered to be essentially ceased when the reaction
rates are decreased by 95 % of their values at the WHB
inlet. At the 95% level, almost 99% of the hydrogen
conversion is complete (Nasato, 1993). Therefore, the time
at which falls to zero is defined as the quench time.
(22) Base Case Conditions. A base case set of operating
conditions for the WHB were selected from Sames et al.
(1990) and are given in Table 1. The flow rate, inlet
composition, and temperature were obtained from Western
Research’s Ultramar Field Test 1, as shown in Table 2
(Sames et al., 1990). The feed composition was assumed
10 Ind. Eng. Chem. Res., Vol. 33, No. 1, 1994

Table 1. Base Case Conditions for the Ultramar Refinery

WHB (Sames et al., 1990)
feed temperature (TV), K 1594.0
tube-wall temperature (Tw), K 487.6
total molar flow rate, kmol/h 298.9
mass flux (G), kg/(m2-s) 6.7
feed pressure (P0), kPa 162
tube length, m 8.23
tube inside diameter (D), mm 43.99
tube outside diameter (D0), mm 50.80
number of tubes (single pass) 240

Table 2. Inlet Feed Molar Flow Rates to the WHB (Sames

et al., 1990)
molar flow rates (Fy), kmol/h
test 1 test 2 test 3 test 4 test 5
WHB feed temp (7V), °C 1321 1224 1208 1285 1488
Gas Temperature (°C)
h2 10.04 7.94 3.86 5.78 11.18
n2 134.10 146.10 88.67 92.52 113.00 Figure 2. Predicted molar flow rates for evaluation of the quench
CO 2.74 2.07 1.32 2.07 3.52 temperature in the WHB (base case conditions).
co2 6.43 5.88 4.80 6.34 6.60
h2s 10.31 9.66 6.37 9.82 11.52
cos 0.47 0.29 0.24 0.42 0.60
so2 5.67 4.30 3.28 4.11 6.17
h2o 95.30 82.78 45.60 61.47 121.40
S2 33.86 28.97 20.96 28.91 40.02

total 298.9 287.9 175.1 211.4 314.0

constant and oxygen-enriched air (32 %) was utilized. A

constant wall temperature was assumed since saturated
steam is produced on the shellside of the WHB.
The simulations were performed using the base case
parameters and data from the Ultramar Refinery Field
Test 1. Figure 2 represents a plot, for one WHB tube, of
the molar flow of H2 and H2S for the base case conditions
where the gases enter the WHB tube at 1320 °C and are
predicted to leave at 250 °C. The quench temperature is
approximately 900 °C (1173 K). Secondly, the axial
temperature profile inside the WHB tube is plotted in
Figure 3 and the actual residence time (eq 14) inside the
tube is plotted in Figure 4 for the base case conditions.
The results of the base case analyses indicate that the
reaction between H2 and S2 is quenched in 67 ms which
occurs in the first 1 m of the tube.
Discussion of Results
The effect of varying tube diameter, while maintaining
the mass flux (G) constant, on the temperature profile is
presented in Figure 5. The mass flux was maintained at
the base case condition of 6.7 kg/ (m2-s) by varying the
number of tubes. The results indicate that use of a smaller
tube diameter reduces the quench time. For example, a
tube diameter of 25.4 mm (1.0 in.) results in a decrease in
quench time from 67 to 25 ms, or a 63% reduction for the
reaction between H2 and S2. This corresponds to an
increase in H2 recovery of 21% and a decrease in H2S
production of 15%. Increasing the tube diameter to 3.0
in. results in an increase in residence time from 67 to 122
ms. This corresponds to only a 6.7 % reduction in H2 and
a 2.7% increase in H2S production.
Figure 6 shows that an increase in mass flux from 6.7
to 12.0 kg/(m2-s) results in approximately 35% decrease
in quench time from 67 to 44 ms. This corresponds to a
7.2% increase in H2 recovery and a decrease of 3.4% in
H2S production. For a reduction of mass flux to 4.0 kg/
(m2-s), the quench time increased by 53% from 67 to 104
ms. This corresponds to a 4.6 % reduction in H2 yield and
a 2.1% increase in H2S production. For a mass flux of
23.6 kg/(m2-s), the quench time decreased from 67 to 24
ms, which is a 65% reduction. For this case, the increase
Tube ..er.gth (m)
Figure 3. Predicted temperature profile in the WHB tube (base
case conditions).
in mass flux resulted in an increase of H2 production of
19.6% and a reduction in H2S production of 8.5%.
The pressure drop increases with the mass flux (eq 12);
however, within the range of mass flux evaluated, the
pressure drop did not exceed the maximum allowable value
of 6 kPa. Figure 7 illustrates the effect of mass flux on
the pressure profile through the WHB tube. The pressure
drop for a mass flux of 6.7 kg/(m2-s) is about 100 Pa, which
increases to about 500 Pa for the mass flux of 12.0 kg/
(m2-s). Finally, the pressure drop of 2000 Pa is predicted
for a mass flux of 23.6 kg/ (m2-s). Note that mass velocities
in the range 10-30 kg/(m2-s) are recommended for WHBs
by Goar (1990).
Another important variable that is affected by gas mass
flux is the heat flux. Figure 8 presents plots of heat flux
along the WHB tube for four values of gas mass flux. An
increase in the gas mass flux by a factor 3.5 leads to a
3-fold increase in maximum heat flux. This is due to the
fact that an increase in mass flux implies an increase in
Reynolds number and in turn an increase in h\ (eq 16).
Nonetheless, all of the heat flux values in Figure 8 are far
below the CHF of 175 kW/m2.
A plot of the molar flow rates of H2, H2S, CO, and COS,
as a function of the WHB tube length, is given as Figure
9. The results in Figure 9 illustrate that, as the hot effluent
gas stream from the reaction furnace enters the WHB and
begins to cool, the recombination of H2 and S2 to form
H2S is favored. As the gas stream cools in the WHB, the
forward and reverse reactions are quenched and the
composition remains essentially unchanged.

Figure 4. Predicted gas residence time in the WHB tube (base case
conditions).
Figure 5. Effect of tube diameter on quench time predictions at
mass flux of 6.7 kg/(m2-s) (base case conditions).
Figure 6. Effect of mass flux on quench time predictions for 43.99-
mm (2.0-in.) WHB tube diameter.
In Figure 10, the molar flow rates for all components
(H2, S2, H2S, CO, and COS) are compared with the
Ultramar Refinery field test data; the calculated results
agree fairly well with the measured data.
Design Recommendations
The results from the model presented here can be used
beneficially in the design and operation of a commercial
WHB. Within the physical limits of a typical WHB, three
Ind. Eng. Chem. Res., Vol. 33, No. 1,1994 11
Tube Length (m)
Figure 7. Effect of mass flux on pressure profile for 43.99-mm (2.0-
in.) WHB tube diameter.
Tube Length (m)
Figure 8. Effect of mass flux on local heat flux for 43.99-mm (2.0-
in.) WHB tube diameter.
Figure9. Variation of predicted molar flow rates of H2, H2S, CO,
and COS along the WHB tube (base case conditions).
variables may be adjusted to optimize the production of
the desirable components, H2 and S2 and, at the same
time, retard the production of the undesirable components,
H2S and COS. The three variables are the tube diameter,
the gas mass flux, and the pressure of the steam generated
on the shellside of the WHB. Each variable and the
resulting benefits are discussed below.
i. Tube Diameter. If a new unit is being designed, an
optimum tube diameter should be selected to allow for
rapid quenching of the reactions without exceeding the
allowable pressure drop. All other factors being equal, it
12 Ind. Eng. Chem. Res., Vol. 33, No. 1, 1994
Figure 10. Comparison of simulation results for the molar flow
rates of H2, S2, HgS, CO, and COS at the WHB outlet with measured
data from Ultramar Refinery Field Test 1 (Sames et al., 1990).
was shown that reducing the tube size from 2.0 to 1.0 in.,
for the Ultramar Refinery, results in approximately 60%
reduction in the reaction quench time, allowing for a 21 %
increase in H2 production. It is recommended the tube
size be dictated primarily by the pressure drop constraint
(i.e. a typical design pressure drop of 4 kPa). The tube
diameter should not be oversized, as this has the effect of
retarding the quenching of the reactions.
ii. Gas Mass Flux. For a new unit, it is possible to
adjust the gas mass flux by either increasing or decreasing
the number of tubes in the WHB. In an existing unit, the
mass flux can only be increased by decreasing the effective
number of tubes in the WHB. A higher mass flux allows
for a more rapid quenching of the reactions (faster by
21-42%); however, very large values of mass flux may be
limited by the CHF. Over the 10-30 kg/ (m2-s) range of
gas mass flux recommended for WHBs (Goar, 1990), the
CHF generally decreases with the steam quality (Dykas
and Jensen, 1992). Therefore, it is recommended that the
gas mass flux be set at an optimum level to allow for a
rapid quenching of the reactions without exceeding the
recommended mass flux. As was shown, increasing the
mass flux by a factor of 3.5 results in approximately 20 %
increase in H2 production without any significant effect
on the production of COS.
iii. Steam Pressure. The tube wall temperature is
set by the pressure of saturated steam generated on the
shellside of the WHB. It was determined that lower wall
temperatures, hence lower steam pressures, allow for more
rapid quenching of the reactions (Nasato, 1993). Within
the range of steam pressure analyzed, 345-3450 kPa (50-
500 psig), an increase or decrease in quench time does not
result in a significant change in H2, H2S, or COS production
(Nasato, 1993). The pressure of steam generated in the
WHB usually ranges between 2400-4100 kPa (350-600
psig). Normally, 345-520 kPa (50-75 psig) saturated steam
is produced in all sulfur condensers, except in the final
condenser, which may produce 100-140 kPa (15-20 psig)
steam (Goar, 1990). Therefore, it is recommended that
the steam pressure, hence the wall temperature, be dictated
by the plant utility steam requirements and not as a means
for promoting rapid quenching of the reactions.
Conclusions
A rigorous mathematical model has been developed for
the evaluation of kinetic and heat transfer characteristics
of a WHB in a modified Claus sulfur recovery unit. The
operating mass flux of 6.7 kg/(m2*s) (Sames et al., 1990)
is below the recommended range of 10-30 kg/(m2«s) (Goar,
1990). An enhancement in sulfur recovery can be achieved
by increasing the mass flux, possibly by plugging some of
the tubes in an existing WHB.
It is shown that quench times are in the range of 25 to
75 ms for the quenching of reaction furnace effluent gases
in the WHB. Reactions must be quenched rapidly in the
front end of the WHB to prevent the reassociation of
hydrogen and sulfur to produce hydrogen sulfide, and to
suppress the formation of undesirable carbonyl sulfide
from carbon monoxide and sulfur.
It was determined that the WHB in the Ultramar
Refinery is capable of quenching the reaction gases in a
time as low as 25 ms. For new designs, smaller tube
diameters and a higher mass flux should be investigated
within the constraints of the allowable pressure drop and
critical heat flux. Also, the production of lower pressure
steam on the shellside of the exchanger can provide a small
reduction in quench time.
The extent of the reassociation of H2 and S2 to form
H2S, and the reaction of CO and S2 to form COS depends
on the relative kinetics and the residence time/temperature
profile in the WHB, which would vary with the particular
design. Incorporating these considerations into the design
of a WHB reduces the potential for these reactions to
occur. This translates into a higher concentration of
potentially useful H2 in the tailgas, thus reducing the
requirement for H2 in commercial tailgas clean-up pro-
cesses. Eliminating the formation of COS in the WHB
will result in a significant decrease in sulfur emission from
the downstream incinerator. Also, an increase in the
overall sulfur conversion within the furnace results in a
higher efficiency for O2 usage in oxygen-enrichment
operations.
Acknowledgment
Financial support was provided by the Natural Sciences
and Engineering Research Council of Canada (NSERC).
Nomenclature
A cross-sectional area of the tube (=irD2/4), m2
=
Cp heat capacity at constant pressure, J/(kmol-K)
=
Cv = heat capacity at constant volume, J/(kmoVK)
D = tube diameter, m
Du = log-mean tube diameter, m
/ = Fanning friction factor for tubes
ff = tube fouling factor, (m2-K)/W
F molar flow rate, kmol/s
-
G = gas mass flux, kg/(m2-s)
h = heat transfer coefficient, W/(m2-K)
AHr = heat of reaction, J/kmol
K = equilibrium constant for COS formation reaction, m3/
kmol
forward rate constant, kmol/(m3-s-atm2)
ki =
k<i reverse rate constant, kmol/(m3-s-atm)
=
km = thermal conductivity of tube material, W/(m*K)
= molar mass, kg/kmol
Nu, = Nusselt number (=h¡D/\m)
p = partial pressure, Pa
P = pressure, Pa
Pr = Prandtl number
R = universal gas constant (=8314 J/(kmol-K))
Re = Reynolds number (=GD/#tm)
r = rate of reaction, kmol/(m3-s)
s¡j
=
stoichiometric coefficient of component j in reaction i
T = temperature, K
Tf = WHB feed gas temperature, K
Tq
=
quench temperature, K
 Ind. Eng. Chem. Res., Vol. 33, No. 1, 1994 13

T, reduced temperature (Cp); were obtained from Himmelblau (1982) with the
=

Tw tube-wall temperature, K
=
mixture heat capacity as (Cp)m = Zyj(Cp)j.
(r = gas residence time in tube, s Heat of Reaction. The standard heat of reaction data
U = overall heat transfer coefficient, W/(m2-K)
xw = tube-wall thickness, m
(-AHr) were obtained from Himmelblau (1982).
y = mole fraction
z = axial distance, m
Literature Cited
Greefc Letters
=
inverse of reduced viscosity, µ _1 Bichowsky, R. F. The International Critical Tables; Reinhold
6 = dimensionless quench temperature Publ.: New York, 1936; Vol. I..
p = mass
density, kg/m3 Dowling, N. I.; Hyne, J. B.; Brown, D. M. Kinetics of Reaction between
= thermal conductivity of gas, W/(m-K) Hydrogen and Sulfur Under High-Temperature Claus Furnace
µ = dynamic viscosity, Pa-s Conditions. Ind. Eng. Chem. Res. 1990, 29, 2327.
=
viscosity in eq Al, µ Dykas, S.; Jensen, . K. Critical Heat Flux on tube in a Horizontal
=
mixing parameter Tube Bundle. Exp. Therm. Fluid Sci. 1992, 5, 34.
Subscripts Gas Processors Suppliers Association (GPSA). Engineering Data
c = critical Book; GPSA: Tulsa, OK, 1987; Chapter 22.
i = inside Goar, B. G. Design Considerations for Modified-Claus Sulphur
i = ith reaction Recovery Plants. In Sulphur Recovery; Western Research: Cal-
j =
;th component gary, Alberta, Canada, 1990.
m = mixture Himmelblau, D. M. Basic Principles and Calculations in Chemical
o = outside Engineering, 4th ed.; Prentice-Hall: New Jersey, 1982.
z = local
Klemm, R. B.; Davis, D. D. A Flash Photolysis—Resonance Fluo-
rescence Kinetic Study of the Reaction S(3P)+OCS. J. Phys. Chem.
Appendix A 1974, 78, 1137.
Nasato, L. V. Modelling of Quench Times in the Waste Heat Boiler
Dynamic Viscosity. The corresponding states method, of a Modified Claus Plant. M. Eng. Thesis, Univ. of Calgary,
by Lucas, was used to estimate the pure component Calgary, Alberta, Canada, 1993.
viscosity (Reid et al., 1986):
Nighswander, J. A.; Huntrods, R. S.; Mehrotra, A. K.; Behie, L. A.
íj£ = -
0.357e_°'449T' + 0.340e"4058T' + 0.018 Quench Time Modelling in Propane Ultrapyrolysis. Can. J. Chem.
0.807T?·618
Eng. 1989, 67, 608.
(Al) Paskall, H.G. Capability of the Modified-Claus Process; Department
where = 0.176 ( ^ , 4)116. The gas mixture viscosity of Energy and Natural Resources: Edmonton, Alberta, Canada,
was calculated from Wilke’s method (Reid et al., 1986): 1979; Chapter IV.
Perry, R. H.; Green, D. W.; Maloney, J. O. Perry’s Chemical
Engineers' Handbook, 6th ed.; McGraw-Hill: New York, 1984.
=
·)·1] (A2)
Reid, R. C.; Prausnitz, J. M.; Poling, B. E. The Properties of Oases
1=1 7=1 and Liquids, 4th ed.; McGraw-Hill: New York, 1986.
where 0;;· , 1 = ( ;· Mr1)112, as given by Herning and
=
Sames, J. A.; Paskall, H.G.; Brown, D. M.; Chen, M. S. K.; Sulkowski
Zipperer (Reid et al., 1986). D. Field Measurements of Hydrogen Production in an Oxygen-
Thermal Conductivity. The pure component thermal Enriched Claus Furnace. Proceedings of Sulfur 1990 International
conductivities were calculated using a method by Steil Conference, Cancún, Mexico, April 1-4, Conference sponsor:
and Thodos (Reid et al., 1986): British Sulfur Corp. Ltd., 1990; pp 89-105.
Welty, J. R.; Wicks, C. E.; Wilson, R. E. Fundamentals of Momentum,
XM ,,,,2.03 (A3) Heat and Mass Transfer, 2nd ed.; John Wiley: New York, 1976.

Wilke’s method was used for the mixture thermal con- Received for review July 6,1993
ductivity (Reid et al., 1986): Revised manuscript received September 22, 1993
n n Accepted October 5, 1993·
K =
I> (£> 1]
1=1 7=1
(A4)
• Abstract published in Advance ACS Abstracts, December
Heat Capacity. The pure component heat capacities 1,1993.