4236 Ind. Eng. Chem. Res.

1997, 36, 4236-4242

Recovery of Calcium Carbonate and Hydrogen Sulfide from Waste

Calcium Sulfide

Mark W. Brooks† and Scott Lynn*

Department of Chemical Engineering and Lawrence Berkeley National Laboratory, University of California,
Berkeley, California 94720-1462

The removal of H2S from hot coal gas using a limestone-based sorbent generates a large quantity
of calcium sulfide waste (e.g., 67 tons/day from the gasification of 1000 tons/day of 3% S coal)
that cannot be landfilled because of potential H2S evolution and sulfide leaching. In the process
proposed here, the CaS is dissolved by reaction with H2S complexed with aqueous methyldi-
ethanolamine (MDEA) or other alkanolamines. In the second step, the highly soluble Ca(HS)2
reacts readily with CO2, also complexed with aqueous MDEA, to precipitate pure CaCO3 of
uniform crystal size and to form MDEA-complexed H2S in solution. The solution from step 2 is
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splitshalf is recycled to step 1 and half is sent to a stripper to recover H2S and from there to a
column where the needed CO2 is absorbed from a combustion gas.
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Introduction and Previous Work These characteristics make limestone an attractive

sorbent for H2S removal from coal gas. However, CaS
Currently, most of the coal consumed in power
cannot be placed in a landfill directly because of the
generation is burned to produce high-pressure steam,
danger of H2S evolution or leaching of the sulfide ions
which is expanded through a steam turbine system to
into the ground water. Practical possibilities for CaS
drive electric generators. The last few decades have
treatment include converting the sulfide back to CaCO3
seen intense research on cleaner and more efficient coal-
or CaO, thus regenerating the H2S sorbent, and direct
fired power generation. The technique of gasifying coal
oxidation of the sulfide to sulfate, which would allow
prior to combustion has received a great deal of this
safe disposal of the waste.
research attention.
Direct oxidation of the CaS with air produces CaO
A benefit of coal gasification at high temperature and
by the following reaction:
pressure is the greater ease of sulfur removal. The
sulfur is in the form of H2S and can be removed by a
solid sorbent with relatively little cooling of the gas. By 2CaS + 3O2 f 2CaO + 2SO2 (2)
contrast, following combustion the sulfur is in the form
of SO2, is greatly diluted, and is at near-atmospheric Unfortunately, if sulfate formation is to be prevented,
pressure. This combination increases cleaning costs. the reaction must be conducted above 1400 °C
Of the many possible solid sorbents, the least expen- (Schwerdtfeger and Barin, 1993). However, after five
sive is limestone. Fenouil and Lynn (1995a,b) found cycles their CaO retained only 15% of its initial H2S-
that limestone, which is typically about 97 wt % CaCO3, sorption capacity, probably as a result of sintering.
can reduce H2S to a level of 100-200 ppm, well below Keairns et al. (1974) proposed reversing the sorption
that mandated by the Clean Air Act, with conversion reaction at a lower temperature:
of 90+% of the calcium to CaS:
CaO + H2S f CaS + H2O (1) CaS + H2O + CO2 f CaCO3 + H2S (3)

The sorption is done in a separate step, just ahead of a
combustion turbine and within 25 °C of the calcination
temperature, which occurs at 800-900 °C and depends
on pressure and CO2 content. (Limestone is frequently
mixed with the coal in the gasifier, but there is a
significant loss in both calcium conversion and H2S
reduction and a corresponding increase in ash volume.)
Limestone is much cheaper than zinc-based sorbents
(even with allowance for recycling the latter). Moreover,
its optimal temperature being 200-300 °C higher allows
an improved thermal efficiency of power generation.
Even when the lower H2S level obtainable with zinc-
based sorbents is deemed essential (10-20 ppm), bulk
desulfurization with limestone followed by polishing
with a zinc-based sorbent may prove to be economically
attractive.
* Author to whom correspondence is addressed. Telephone:
(510) 642-1634. FAX: (510) 642-4778. E-mail: Lynn@
cchem.berkeley.edu.
† Present address: Exxon Research and Engineering, P.O.
However, they reported that, after 21 cycles, sintering
reduced the conversion of CaCO3 to CaS from 69% to
13%.
The argument could be made that the cost of lime-
stone is so small there is no need to regenerate the
sorbent. This may be the case, but CaS is considered
hazardous and must be rendered inert before disposal.
Schwerdtfeger and Barin (1993) studied oxidation to
CaSO4 but concluded that it was not possible to convert
CaS quantitatively to CaSO4 in a single-step process.
They found that at elevated temperatures (>1100 °C)
the sulfation reaction was fast but that some of the CaS
was converted to CaO with the release of SO2. Evolu-
tion of SO2 was avoided at lower temperatures, but the
oxidation was too slow for an industrial process.
Van der Ham et al. (1996) proposed a complex
reaction sequence that featured reaction (1) followed by
CaS + 2SO2 h CaSO4 + S2 (4)

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CaS + 3CaSO4 h 4CaO + 4SO2 (5)
in which sulfidation (reaction (1)) is best carried out
near 850 °C, reaction (4) near 700 °C, and reaction (5)
at 1100-1200 °C. They postulated that reaction (5)
occurs in the eutectic melt formed by CaS and CaSO4
above 1100 °C. Although such a mechanism would
normally lead to sintering, van der Ham et al. reported
a drop in capacity of only about 35% after eight cycles.
However, their equipment limited the temperature for
reaction (5) to 980 °C, so the loss in capacity may
thereby have been minimized.
All of the proposed regeneration and disposal schemes
described above produce dilute streams of SO2 requiring
further processing and/or encounter sintering problems
that hinder further cycles of regeneration. The produc-
tion of fresh CaCO3 crystals from an aqueous slurry of
CaS would eliminate both problems. As early as 1869,
Bechamp studied reaction (3) between CO2 and solid
CaS particles suspended in water (Gmelins Handbuch
der Anorganishen Chemie, 1957). However, the reaction
was incomplete due to the formation of a CaCO3 layer
around the CaS.
Neither CO2 nor CaS is very soluble in water.
Calcium sulfide has a solubility of less than 1 g/L at 25
°C, and CO2 at 1 atm of partial pressure has a solubility
of only 1.7 g/L at 20 °C (Perry and Green, 1984).
Reaction (3) occurs between the dissolved CO2 and solid
CaS at the liquid-solid interface and is limited by how
fast the CO2 can dissolve and diffuse. The production
of CaCO3 at this interface eventually encapsulates the
remaining CaS, preventing further reaction.
Biswas et al. (1976) achieved 98% carbonation of 150-
µm CaS particles in an aqueous slurry by controlling
the CO2 flow, bubble size, and slurry depth. By using
roughly 3 times the stoichiometric amount of CO2, they
produced a gas containing about 33% H2S, just high
enough for sulfur recovery in a Claus plant. They
proposed that a series of reactions occurs: reaction (3)
followed by
CaS + H2S f Ca(HS)2 (6)
and
Ca(HS)2 + CO2 + H2O f CaCO3 + 2H2S (7)
Thus, CaS reacts initially with CO2, with the formation
of aqueous H2S and the precipitation of CaCO3. The
aqueous H2S that does not escape into the gas phase
reacts with more CaS to form the highly soluble Ca-
(HS)2, which can then react in solution with CO2 to
precipitate CaCO3 and produce more H2S, perpetuating
the reaction. The rate at which Ca(HS)2 and CaCO3 are
formed is dictated by how fast the CO2 can dissolve and
diffuse to a reaction site and also by the concentration
of aqueous H2S that can be maintained. A process in
which the aqueous solubilities of both CO2 and H2S were
significantly increased would greatly improve the rates
of reactions (3), (6), and (7), the utilization of the CO2,
and the concentration of the product H2S gas.
In the research presented below, aqueous methyldi-
ethanolamine (MDEA) is used to increase the solubili-
ties of CO2 and H2S by forming the corresponding
substituted ammonium complexes. Since alkanol-
amines are weaker bases than CaS, solubilizing CO2
and H2S in this way does not inhibit their reactions with
CaS and Ca(HS)2. The reactions are as follows:
Ind. Eng. Chem. Res., Vol. 36, No. 10, 1997 4237
MDEA‚H2S + CaS f MDEA + Ca(HS)2 (8)
MDEA‚H2CO3 + MDEA + Ca(HS)2 f
2MDEA‚H2S + CaCO3 (9)
In reaction (8), MDEA has complexed H2S, keeping it
in solution and readily available for reaction with solid
CaS. The products of this liquid-solid reaction are free
MDEA and a solution of Ca(HS)2. (Calcium hydrosul-
fide is very soluble in water, 248.7 g/L at 20 °C (Seidell,
1940).) Carbon dioxide, bound in solution by MDEA as
the bicarbonate, then reacts in a separate step with the
aqueous Ca(HS)2 to precipitate CaCO3 and produce H2S,
which is complexed by the free MDEA. A portion of the
MDEA‚H2S stream is used to produce more Ca(HS)2 via
reaction (8), and the remaining portion is stripped to
produce a concentrated H2S gas, which may be con-
verted to elemental sulfur by known technology. The
stripped MDEA solution is reloaded with CO2 in an
absorber, with a combustion gas as the CO2 source, and
recycled. This system has several advantages compared
to other CaS-regeneration techniques:
(1) “Fresh” CaCO3 is obtained after each regeneration
cycle. This eliminates crystal-structure problems such
as sintering and attrition that are experienced in many
high-temperature sorption/regeneration cycles. Pure
CaCO3 has other uses as a product but is also a suitable
material for landfill.
(2) A concentrated stream of H2S is generated from
the stripping operation, which facilitates its conversion
to elemental sulfur. Utilization of CO2 is correspond-
ingly high.
(3) The higher H2S and CO2 solubilities increase
reaction rates and decrease reactor volumes.
(4) The formation of the highly soluble Ca(HS)2
eliminates CaS encapsulation during carbonation, re-
sulting in nearly stoichiometric conversion of CaS to
CaCO3.
The goal of this research was to study the critical
steps in this method for converting CaS into CaCO3 and
H2S. The effect of CaS particle size and prior CaS
oxidation on the kinetics of Ca(HS)2 generation, reaction
(8), was determined. Reaction (9) was studied by
determining the effects of MDEA‚H2CO3 and Ca(HS)2
concentrations on the crystal-size distribution of the
precipitated crystals and the amount of excess CO2
required for complete Ca(HS)2 conversion. The data
were then used to design a complete process for the
production of an enriched H2S stream and a relatively
pure (>95%) calcium carbonate product from waste CaS.
Experimental Equipment and Procedures
The limestone used in the experiments described
below was provided by Great Lakes Calcium Corp.,
Green Bay, WI; Table 1 shows the average chemical
composition. The MDEA was supplied by Union Car-
bide and had a purity of 99 wt %, with the balance being
water. The CaS was obtained from three sources. One
batch was made from limestone by the procedure
described below. The second was a sample of technical-
grade CaS supplied by Fisher Scientific Co. that had
been exposed to air periodically over a period of several
years. The third was a fresh sample of reagent-grade
(“Alpha”) CaS supplied by Johnson Mathey Co. Table
2 gives the chemical compositions of these calcium
sulfide samples.
4238 Ind. Eng. Chem. Res., Vol. 36, No. 10, 1997
Table 1. Limestone Composition (wt %) (Great Lakes
Calcium Corp., Green Bay, WI)
CaCO3 MgCO3 SiO2 Fe2O3 Al2O3
97.8 1.63 0.28 0.15 0.13
Table 2. Calcium Sulfide Compositions (wt %) and
Particle Sizes
source CaS CaSO4 CaCO3 MgCO3 SiO2 Fe2O3 Al2O3 size (µm)
Alfa 98 2 <0.1 <0.1 <0.1 <0.1
Towler 95 3 <1 1 <1 <1 <1
reactor 95 3 <1 1 <1 <1 <1
Fisher 74 12 5 5 2 1 1 74-88
Wet analytical techniques were used for the analysis
of solid CaS and to determine the concentrations of
MDEA, MDEA‚H2S, MDEA‚CO2, and Ca(HS)2 in solu-
tion. The purity of solid CaS and the concentration of
MDEA‚H2S solutions were determined by iodimetric
titration (Jeffery et al., 1989). The concentrations of the
separate Ca(HS)2 and MDEA solutions were determined
by acidimetric titration with 1 M HCl. Analyses of
MDEA, MDEA‚H2S, and Ca(HS)2 mixtures were deter-
mined by first analyzing for the total sulfur content
iodimetrically and then titrating a separate sample with
1 M HCl. Although three different basic compounds
were present, their pKa’s were sufficiently similar that
only one inflection point could be determined accurately.
This point occurred around a pH of 4.5. Since the
MDEA concentration in the samples was always known,
the excess acid required to reach the endpoint was due
to the presence of Ca(HS)2. The H2S concentration could
then be determined by the difference from the total
sulfur content. The amount of CO2 complexed with
MDEA in solution was determined gravimetrically by
reacting with excess aqueous Ba(OH)2 to form solid
BaCO3. The solid was filtered, dried, and weighed.
Differential Reactor. The differential quartz reac-
tor designed and built by Towler (1992) and described
by Fenouil and Lynn (1995a) was used for the high-
temperature production of CaS from limestone. The
design of the reactor allows a continuous flow of gas to
be heated to reactor temperature, to pass by the
limestone sample, and then to exit. The limestone was
first calcined to CaO at about 850 °C and then reacted
with H2S to form CaS. (Sulfidation occurs much more
rapidly and completely with CaO than with CaCO3
(Fenouil and Lynn, 1995a,b).)
In these experiments, roughly 10 g of millimeter-sized
limestone particles, contained in a small quartz con-
tainer, was placed in the quartz reactor. The position
of the limestone sample was located at the maximum
temperature of the reactor, which was then set to 850
°C, while a nitrogen flow of 0.55 mL/s was established.
The calcination temperature in an atmosphere of nitro-
gen is below 850 °C:
CaCO3 f CaO + CO2
Reaction was complete after 3 h at 850 °C; the stones
turned from gray to white. Weight measurements were
used to determine when conversion was complete.
After calcination, sulfidation was conducted by lower-
ing the reactor temperature to 800 °C and establishing
the flows of N2 and H2S at 0.55 and 0.45 mL/s,
respectively. The reaction could be monitored qualita-
tively by color change going from white to gray. A
sample was then taken and titrated iodimetrically to
determine the sulfur content quantitatively with a
precision of (0.2 wt %. After 8 h of sulfidation at 800
S
0.01
<43
74-88
1-2 mm
Figure 1. Bubble reactor flow sheet.
°C, the particles assayed 95 wt % CaS. Before the
sample was removed, the reactor was cooled to room
temperature under a purge of nitrogen.
Bubble Reactor. An experimental apparatus was
built to absorb the acid gases H2S and CO2 with MDEA.
The apparatus, illustrated in Figure 1, was constructed
of a 250-mL Erlenmeyer flask with a side arm. Ad-
ditional details are given by Brooks (1995).
In a typical experiment, 100 mL of a 60 wt % MDEA
solution was placed in the bubble reactor. The pH of
the solution was initially found to be 10.5. After purging
the reactor with nitrogen, a flow of acid gas was
established. The solution was gently mixed with a 2-cm
stirring bar. The flow rates were monitored by cali-
brated rotameters, and the effluent gas was scrubbed
with a 2 M NaOH solution as indicated in Figure 1. For
the CO2-loading case, the CO2 flow rate was established
at 2 mL/s. After 3 h, the pH reached a constant value
of 8.95. The time and flow correspond to 1.75 times the
stoichiometric amount of CO2 required for MDEA
saturation. A sample of the solution was then taken
and acid-titrated to determine how much water had
been lost from solution during CO2 bubbling. The
MDEA concentration would typically increase from 5.04
to 5.28 M. To determine the CO2 loading, a sample of
MDEA‚CO2 solution was reacted with Ba(OH)2 solution,
as noted above. The amount of CO2 in solution was
determined with a precision of (0.3%. At a typical CO2
loading, 21% of the MDEA was found to be complexed.
The procedure for loading the MDEA with H2S was
virtually identical to the loading with CO2. The nitro-
gen purge flow was replaced by an H2S flow of 0.6 mL/
s. As the reaction proceeded, the pH was monitored and
reached a constant of 8.05 after 7 h. The degree of H2S
loading was typically 70% of the MDEA and was
determined with a precision of (1.9%. The system was
(10) monitored for leaks continuously when using H2S.
These acid-gas-loaded solutions were stored in tightly
sealed bottles under a fume hood, but acid gas still
evolved upon opening. This required the loadings to be
redetermined before each set of experiments.
Calcium Hydrosulfide Generation. Calcium hy-
drosulfide was produced via the liquid-solid reaction
described in reaction (8). In a typical experiment, a CaS
sample of known purity and particle size was added to
3 mL of an MDEA‚H2S solution of known concentration
and loading in a 10-mL reactor flask. The CaS was kept
as the limiting reagent, with 35% excess H2S. After
capping the flask, the slurry was agitated vigorously on
 Ind. Eng. Chem. Res., Vol. 36, No. 10, 1997 4239
a magnetic stirrer. The reactor was placed in a ther-
mostated water bath kept at 20 °C. After a measured
amount of time, the reaction was stopped by vacuum
filtration of the unreacted CaS from the liquid. The CaS
was then washed, dried under nitrogen, and weighed,
and the sulfide content was determined with a precision
of (0.2 wt %. From this information the conversion of
CaS to Ca(HS)2 could be determined with a precision
of (0.5%. A check for experimental accuracy was done
by comparing the molar ratio of Ca(HS)2 found in the
filtrate to the decrease of CaS remaining in the solid.
The values ranged from 0.93 to 0.99.
Calcium Carbonate Precipitation. Experiments
to precipitate calcium carbonate via reaction (9) were
performed by mixing Ca(HS)2 and MDEA‚H2CO3 solu-
tions. The resulting CaCO3 crystals were separated
from the liquid, washed, and dried. The crystal size was
measured with an optical microscope.
In a typical experiment, 4 mL of an MDEA‚H2CO3
solution and 6 mL of a Ca(HS)2 solution were simulta-
neously added to a mixing flask at 22 °C. The concen-
trations of each solution were known, and Ca(HS)2 was
kept as the limiting reagent. Addition of these two
Figure 2. Effect of particle size on hydrosulfidation of CaS derived
solutions to the mixing flask was done in 2 min. from limestone.
Precipitation of CaCO3 crystals occurred immediately
upon mixing of the solutions. Gentle stirring of the
resulting CaCO3 slurry was continued for 5 min to
ensure complete reaction. The CaCO3 crystals were
then separated from solution by vacuum filtration,
washed, dried, and weighed. The conversion of Ca(HS)2
to CaCO3 was determined with a precision of (1.8%.
The crystal-size range of the CaCO3 product was
determined with a Cambridge Instruments Stereo Zoom
Light microscope. The structure of the crystals was also
analyzed with a scanning electron microscope. The
experiment was repeated for different Ca(HS)2 concen-
trations to determine if there was any effect on crystal
size. In addition, the amount of excess CO2 was reduced
to near-stoichiometric amounts to determine the effect
on Ca(HS)2 conversion.

Experimental Results
1. Effect of CaS Particle Size on Rate of Hydro-
sulfidation. Conversion-versus-time data were gath-
ered for 95 wt % CaS particles of two different particle
diameters. The CaS was made by the high-temperature
sulfidation of limestone. Figure 2 illustrates the data
for particles with diameters of 1-2 mm and also of 74-
88 µm. Figure 2 shows that the rate of CaS hydrosul-
fidation increases as the size of the particles decreases,
as would be expected from the increase in the external
surface area available for reaction. Particles in the size
range of 1-2 mm required 120 min to achieve a
fractional conversion of 0.85-0.90. This is in contrast
to particles in the size range of 74-88 µm, which
required only 15 min to reach the same conversion. The
porosities of the samples were not measured separately
but were assumed to be similar. No attempt was made
to model the dissolution process mathematically because
of the high fraction of CaS (∼95 wt %) in these particles.
The matrix of insoluble residue remaining after the CaS
was dissolved would be too irregular and variable for
such modeling to be either meaningful or useful.
A moving-bed sorption system would use millimeter-
sized limestone particles for H2S removal and produce
CaS particles of the same size. To produce CaCO3 from
waste CaS on an industrial scale, a CaS-crushing
operation (such as a ball mill) might be installed either
Figure 3. Effect of CaS oxidation on CaS hydrosulfidation.
prior to or as part of the CaS/H2S reactor to decrease
the reaction time for CaS digestion.
2. Effect of Prior CaS Oxidation on Hydrosul-
fidation Reaction. The effect of CaS oxidation and
impurities on conversion is illustrated in Figure 3. The
CaS particles had purities of 74, 95, and 98 wt %. Most
of the impurity was the result of oxidation of CaS to
the sulfate resulting from exposure to air. Some inerts
such as MgCO3 and SiO2 were also present. The
particles were reacted with a 3.5 M solution of
MDEA‚H2S; the conversion of CaS to Ca(HS)2 was
measured versus time. Figure 3 shows how the rate of
hydrosulfidation of CaS decreases as the purity of the
CaS decreases. It appears that the decrease in the rate
of conversion was caused by the encapsulation of inner
deposits of CaS by CaSO4. This is most evident in the
conversion of the 98 wt % CaS, which reached complete
conversion in 4 min. The high rate of reaction of this
material also reflects the smaller particle size. The 98
4240 Ind. Eng. Chem. Res., Vol. 36, No. 10, 1997
Figure 4. Calcium carbonate crystals.
wt % CaS was a freshly purchased storeroom chemical
with roughly half the particle size of the other CaS
particles tested. Because the quartz reactor was un-
available at the time, it was not possible to prepare
fresh, unoxidized CaS from limestone for these experi-
ments.
In an industrial process, the CaS content of the
material leaving the H2S-sorption step would be about
80 wt %. The impurities would consist mainly of
unreacted CaO, together with magnesium and silicon
compounds. The CaO would not hinder the hydrosul-
fidation reaction since CaO will also react with H2S to
form Ca(HS)2. The CaS stream would be cooled and
transported to the hydrosulfidation step while minimiz-
ing contact with the air to prevent excessive formation
of CaSO4 by oxidation. Using a liquid-flooded ball mill
as the reactor would eliminate any encapsulation of CaS
that does exist by simultaneously reacting the CaS and
crushing away the inert material.
3. Precipitation of Calcium Carbonate. Solu-
tions of Ca(HS)2 and MDEA‚H2CO3 were simulta-
neously added to a mixing flask at 22 °C. The quantities
and concentrations of each solution were known, and
MDEA‚H2CO3 was kept in excess. The CaCO3 precipi-
tated immediately upon mixing of the two solutions.
Initial experiments were conducted with a 0.67 M Ca-
(HS)2 solution and a 60 wt % MDEA solution that was
21% loaded with CO2. The ratio of the solutions gave a
35% excess of CO2 upon mixing. During these experi-
ments, the yield of CaCO3 was determined to be 0.96-
0.99; the loss was ascribed to experimental uncertainty
rather than slow kinetics. The photographic images of
crystals of CaCO3 were then measured and found to be
in the range of 5-10 µm.
Figure 4 shows the CaCO3 crystals as filmed with a
scanning electron microscope (SEM). The SEM photo-
graph shows two different CaCO3 crystal structures.
Most of the crystals have a roughly spherical shape with
diameters of 5-10 µm. The remaining crystals are
slightly smaller and have a rhombohedral crystal struc-
ture of about the same size as the spheroids. All of the
crystals have a relatively narrow size distribution.
There is a striking absence of very fine material. Both
crystal structures are suitable for separation by filtra-
tion. The known crystal structures of CaCO3 (calcite)
are hexagonal and rhombohedral. The presence of the
spheroidal particles may be caused by impurities in
solution. The SEM photograph has a magnification of
2800, and the white line is 3.57 µm long.
To determine the dependence of the conversion on the
amount of excess CO2 in solution, the CO2 was reduced
to an excess of only 4%. These experiments also
resulted in a yield of CaCO3 of about 0.96. Thus high
conversions could still be attained at near-stoichiometric
levels of CO2. The CaCO3 crystal size was measured
and found to remain in the range of 5-10 µm. Experi-
ments were also conducted with the addition of 5-10-
µm CaCO3 seed crystals. The molar quantity of seed
crystals added was equivalent to 25% of the Ca(HS)2 in
solution. It was reasoned that if there were CaCO3
crystals present, the fresh CaCO3 would prefer to
precipitate on the existing crystals rather than nucleate
fresh crystals. However, it was found that the addition
of seed crystals had no effect on the resulting range of
CaCO3 crystal sizes.
The next set of experiments was conducted with a
decrease in Ca(HS)2 concentration to 0.104 M; the
MDEA‚CO2 concentration remained constant. It was
thought that decreasing the Ca(HS)2 concentration
might decrease the rate of formation of CaCO3 crystals
and result in fewer but larger crystals. However, the
resulting crystal size again remained in the range of
5-10 µm.
The settling velocity of the CaCO3 crystals was
determined in water at 22 °C and found to be about 7.5
× 10-3 cm/s. This corresponds to a particle size of 9.5
µm according to Stokes’ law, which agrees approxi-
mately with the size found microscopically. At 20 °C
the nominal viscosities of water and a 60 wt % MDEA
solution are 1 and 23.7 mPa‚s, respectively (Bryan
Research and Engineering, 1994). Thus, the settling
velocity of the CaCO3 particles in the 60 wt % MDEA
solution should be of the order of 3 × 10-4 cm/s. Since
the lowest settling velocity recommended for separation
by sedimentation is 10-2 cm/s, separation by filtration
or centrifugation would be used.
Process Design and Evaluation. A process based
on the results above was designed to treat the CaS
waste from a coal-gasification plant processing 1000
metric tons of 3 wt % sulfur coal/day, i.e., 67 tons/day
of CaS. Assuming that 80% of the CaCO3 in the feed
forms CaS and the remainder is calcined, the flow of
CaO from the process would be 13 tons/day. As noted
above, this flow of CaO forms Ca(HS)2 upon reaction
with H2S, leading to the consumption of additional CO2
in the carbonation step. Inert material in the limestone
will pass through undissolved.
Figure 5 illustrates the process-flow diagram for the
CaS-treatment system. The simulation program
TSWEET (Bryan, 1995) was utilized for the design of
the absorber and stripper sections of this design.
Details of the process parameters used in the simulation
are given by Brooks (1995). The process starts with the
feed of hot (∼200 °C) millimeter-sized CaS waste
particles along with an 8 mol % excess of MDEA‚H2S
solution to CSTR 8, where a slurry forms and the
hydrosulfidation reaction begins. (Since the MDEA
solution also contains some complexed CO2, some Ca-
CO3 also forms in CSTR 8.) The residence time in CSTR
8 (and for CSTR’s 6 and 7 and Reactor 9) was set at 5
min, giving a volume for each of about 6.0 m3. The
partially reacted CaS slurry is then fed to a ball mill
(or other liquid-filled grinder), Reactor 9, where the
remaining CaS particles are simultaneously crushed
and reacted with MDEA‚H2S to form Ca(HS)2. Reactor
9 and CSTR 8 combine to achieve a 99% conversion of
CaS to Ca(HS)2. The assumption that freshly-formed
 Ind. Eng. Chem. Res., Vol. 36, No. 10, 1997 4241

Figure 5. Process configuration for recovery of H2S and CaCO3 from CaS.

CaS would react fully within the allotted residence time Table 3. Operating Parameters for Stripper
of 5 min in each of the two reactors would have to be ideal actual tray spacing diameter reboiler % H2S
demonstrated in a pilot plant. stages stages (m) (m) duty (kW) stripped
A fraction of the stream leaving Reactor 9 may be 10 20 0.61 0.63 1296 95.5
recycled through a cooler back to CSTR 8, if needed, for
temperature control. If one wishes to prevent inert Table 4. Operating Parameters for Absorber
solids from being mixed with the CaCO3 to be formed ideal actual tray spacing diameter gas flow % CO2
in CSTR 6, the slurry of those solids suspended in the stages stages (m) (m) rate (m3/h) absorbed
solution of Ca(HS)2 and free MDEA leaving Reactor 9 10 30 0.51 0.81 592 94
may be pumped to Filter 10. (The inert solids would
absorber. Typically, a combustion gas would be used
consist of small amounts of CaCO3 and CaS along with
as the source of CO2 for the process. This stream,
gangue such as MgO and SiO2 coming from the original
comprised of about 10% CO2, would be cooled and
limestone.)
compressed before being fed to the absorber. The
Either directly or by way of Filter 10, the solution of
absorption process benefits from operation at higher
Ca(HS)2 plus MDEA leaving Reactor 9 goes to CSTR 6,
pressures, so the operating pressure of the absorber is
where it reacts with MDEA‚H2CO3 solution and CaCO3
set by an optimization that will be site-specific. The
precipitates. The relative quantity of MDEA‚H2CO3
CO2 loading of the MDEA solution leaving the absorber
solution fed to CSTR 6 is a 5-10 mol % excess relative
was specified to be 30-35%, which requires operating
to Ca(HS)2 to ensure substantially complete precipita-
the absorber at the inlet pressure of the combustion
tion of calcium ion. The resulting CaCO3 slurry is then
turbine. This CO2-rich MDEA stream is fed to CSTR 6
fed to a second reactor, CSTR 7, where the reaction
for the CaCO3 precipitation reaction. Table 4 gives the
reaches completion before the slurry is pumped to Filter
operating parameters for the absorber. Operation of the
11 for CaCO3 recovery. The CaCO3 is filtered and
absorber at a relatively low pressure might lead to the
washed free of mother liquor using condensate from the
choice of diethanolamine (or another alkanolamine) as
stripper condenser. A system that includes Filter 10
sorbent to improve the kinetics of CO2 absorption.
would produce 116 tons of high-purity CaCO3/day from
Filter 11 for the flows above.
Conclusions
The solution leaving Filter 11 is free of Ca(HS)2 but
contains MDEA that is about 25% loaded with H2S and In the process described above, a stream of raw, solid
1-2% loaded with CO2 at a temperature of about 60 CaS is dissolved into an aqueous solution by reaction
°C. Roughly half of this solution is pumped to CSTR 8, with MDEA-complexed H2S. The Ca(HS)2 so formed is
and the remainder is pumped to a stripping column. The converted by reaction with MDEA-complexed CO2 into
stripper produces a concentrated gas stream (90-95% relatively pure CaCO3, regenerating MDEA-complexed
H2S) and a lean solution of MDEA. Operating param- H2S. Part of the latter is stripped, forming a concen-
eters for the stripper are given in Table 3. trated stream of H2S. The process utilizes MDEA (or
The MDEA stream coming from the bottom of the another alkanolamine) to increase the concentrations
stripper is cooled from 135 to 75 °C by heat exchange of CO2 and H2S that can be dissolved in an aqueous
with the H2S-rich feed. The MDEA is then cooled solution, thereby greatly improving the kinetics of both
further with cooling water before being fed to the reactions.
4242 Ind. Eng. Chem. Res., Vol. 36, No. 10, 1997
It was determined experimentally that the CaS
particle size and purity greatly influence the rate of CaS
hydrosulfidation. As the CaS particle size decreases
and the purity increases, the rate of hydrosulfidation
increases. As the purity of the CaS particles decreases
(particularly by partial oxidation to sulfate), the impuri-
ties encapsulate interior regions of CaS and slow the
hydrosulfidation reaction.
The precipitation of CaCO3 from the reaction between
Ca(HS)2 and MDEA‚CO2 occurs very rapidly, and reac-
tion is essentially complete with only a 5% stoichiomet-
ric excess of CO2. The CaCO3 crystals produced have a
relatively narrow crystal-size distribution centered at
5-10 µm, with a striking absence of fines. The addition
of seed crystals to this precipitation reaction had no
effect on the crystal size nor did varying the Ca(HS)2
concentration or the reactant stoichiometry.
The use to which the CaCO3 would be put will vary
with the circumstances. At worst it would form an
innoccuous landfill. Pelletization and reuse as sorbent
for H2S may prove practical. The highest value would
be derived from maximizing its purity and size charac-
teristics to generate a pigment or a chemical raw
material. Streams of raw SrS or BaS could be converted
to their respective carbonates by analogous chemistry.
Acknowledgment
This research was funded by the Morgantown Energy
Technology Center through the U.S. Department of
Energy under Contract DE-AC03-76SF00098.
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Received for review February 12, 1997
Revised manuscript received June 16, 1997
Accepted June 17, 1997X
IE970151J
X Abstract published in Advance ACS Abstracts, August 15,
1997.