REMOVAL OF H2S FROM COAL-DERIVED GASES

by

S. Lynn, R.M. Hix, D.W.Neumann, S.F. Sciamanna, and C.A. Stevens

Departmenl o f Chemical Engineering
Universily OJ CaliJornia, Berkeley. C A 94720
I n t roductioa

When coal is gasified most of the s u l f u r is converted to H2S a n d must be removed

before the gas can be used either as a fuel or as synthesis gas. The UCB S u l f u r Recovery
Process (UCBSRP) is being developed as a general method for removing H2S from gases.
T h e H2S is absorbed in a polyglycol ether, then reacted in the liquid phase with SO2 to
f o r m marketable elemental s u l f u r a n d water. T h e process allows high s p e c i f i c i t y and
flexibility; H2S can be reduced to the part-per-million level o r below in t h e presence of
C 0 2 and the other components of gasified coal. The C 0 2 may be left in the original gas
stream or it may be co-absorbed and recovered a s a separate, s u l f u r - f r e e product. The
process thus has application both to syngas a n d hydrogen p r o d u c t i o n f r o m 02-blown
gasifiers and to power production using a n air-blown gasifier.
Process Configurations
Figure 1 shows a flowsheet f o r t h e UCBSRP in a configuration t h a t gives maximum
s e l e c t i v i t y f o r H2S removal. In t h e p r i m a r y a b s o r b e r H,2S is removed p r i m a r i l y by
physical absorption. T h e stream of solvent leaving t h e absorber is nearly saturated with
all of the components of the gas being treated. A water wash a t the top of the primary
absorber prevents loss of solvent vapor in the treated gas.
Most of t h e solvent s t r e a m l e a v i n g the p r i m a r y a b s o r b e r t h e n e n t e r s a
r e a c t o r / c r y s t a l l i z e r t h a t operates a t t h e pressure of t h e p r i m a r y a b s o r b e r . A second
solvent stream containing SO2 is metered into the same reactor a t a r a t e t h a t keeps the
SO2 content within t h e reactor a few percent above stoichiometric relative t o the H2S.
(It is necessary to have a n excess of one reactant or the o t h e r in each reactor to avoid
excessive reactor volumes a n d the need f o r highly precise reactor control.) A clarified
o v e r f l o w f r o m t h e S 0 2 - r i c h r e a c t o r is pumped b a c k to t h e p r i m a r y a b s o r b e r . T h i s
solvent stream has been completely f r e e d of its H2S content but is still saturated with
respect to the other components in the gas being treated in t h e primary absorber. The
net co-absorption of these other gas components (such as C 0 2 ) is thus kept q u i t e small
a n d the e f f e c t i v e selectivity for H2S is of the order of 50 to 100. The SO2 content of
this solvent stream, although low, provides a chemical enhancement f o r the absorption of
the H2S on the upper trays of the primary absorber to facillitate meeting very stringent
H2S specifications i n the treated gas. (The temperature in the primary absorber is high
enough to prevent precipitation of t h e s u l f u r f o r m e d by t h i s reaction. Not shown in

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For presentation a t the symposium "Separation Processes for Coal Conversion"

Toronto Meeting, American Chemical Society, June, 1988.

300

Figure I , to avoid clutter, is provision for cooling both reactor/crystallizers with cooling
water so that the solvent is sub-saturated in sulfur a t all other points in t h e system.)
T h e underflow f r o m the SO2-rich reactor carries the sulfur a n d water formed in t h e
r e a c t i o n b e t w e e n H2S a n d S 0 2 . T h e f l o w of t h i s s t r e a m is sized t o k e e p t h e water
content of the solvent f r o m exceeding 5% and is directly proportional to the rate of H2S
removal - - the flow will typically be about 10% of the total flow of solvent through the
p r i m a r y absorber. S u f f i c i e n t H2S-rich solvent, from the primary absorber, is added to
the stream to leave a small excess of H2S a f t e r all of the residual SO2 has reacted. This
stream is then flashed to atmospheric pressure in the settler/surge tank,
T h e sulfur made in t h e process forms a slurry i n the underflow from the surge tank.
The sulfur is recovered a n d washed in a centrifuge. In most cases about one-third of the
s u l f u r will be burned in the furnace to make the SO2 needed i n the process. T h e energy
recovered i n t h e waste-heat boiler will usually supply a n d perhaps exceed t h e energy
required by the process.
T h e overflow streams from the surge tank a n d the centrifuge a r e combined a n d sent
to t h e solvent stripper. Boiling most of the water out of the solvent provides a stripping
vapor t h a t also removes unreacted H2S a n d co-absorbed gases such a s C 0 2 f r o m the
solvent. Most of t h e solvent leaving the solvent stripper is used in t h e SO2 scrubber
where i t absorbs the SO2 from the combustion gas leaving the furnace. T h e SO2 content
of this solvent is nil, a n d hence the SO2 content of the stack gas leaving the scrubber can
readily be reduced t o t h e part-per-million level. The remainder of the solvent from the
stripper is sent to the primary absorber, where i t prevents loss of SO2 in the treated gas.
Figure 2 shows a process configuration suitable f o r removing a n d recovering one or
more components (in a d d i t i o n to the H2S) from t h e gas being treated, such a s removing
C 0 2 from a synthesis gas ahead of a s h i f t reactor in a process f o r producing hydrogen.
T h e operation of this process is identical to t h a t described above in many respects. It
differs as follows:
At the bottom of t h e primary absorber is a short section in which much of the H2
and CO are stripped f r o m the solvent. T h e stripping gas is obtained by a partial flash of
t h e solvent i m m e d i a t e l y downstream of t h e p r i m a r y absorber. Most of t h e H2S-rich
solvent stream leaving t h e flash drum, together with a controlled flow of SO2 solution,
e n t e r s a n S 0 2 - r i c h reactor. T h e pressure of t h e SO2-rich solvent stream is reduced in
stages (only t w o a r e s h o w n ) to a b o u t one atmosphere. T h e o f f - g a s f r o m each stage is
recompressed t o the pressure desired f o r the C 0 2 product a n d i s contacted w i t h neat
solvent to remove traces of S 0 2 , then washed with water to recover solvent vapor. For
the case shown, in w h i c h a high degree of C 0 2 removal is not required, clarified H2Sf r e e solvent f r o m t h e atmospheric f l a s h can be pumped d i r e c t l y back to t h e primary
absorber.

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'

As i n the flow configuration designed f o r high H2S selectivity, t h e s u l f u r and water

formed i n the reaction a r e conveyed o u t o f the last SOZ-rich reactor in a stream that is
rendered H2S-rich w i t h by-passed H2S solution. As before, the f l o w of t h i s stream is
proportional to the rate of sulfur production.
Lynn, et al. (1987) compared conventional technology to the UCBSRP f o r removing
H2S f r o m the recycle gas of a c r u d e oil r e s i d u u m h y d r o d e s u l f u r i z a t i o n u n i t . T h e
UCBSRP has the potential for significantly reducing both the capital and operating costs
because of the reduction i n the number of processing steps and in utilities consumption.
L y n n a n d Sciamanna ( 1 9 8 8 ~ )f o u n d a similar a d v a n t a g e f o r t h e UCBSRP f o r treating

~~

Table 1:

Corrosion Rates of Steels in Process Solutions.

MEASURED RATES AND CONDITIONS

Metal
Carbon Steel
304 Stainless
316 Stainless

SOz:

@ 100C

@ 12OoC

0.6

1.7
1.5
4.8

0.7

1.3

H2S: @ 15OoC
0.05

0.02
0.01

* Mils/year in diethylene glycol methyl ether, 5% H20,

saturated with sulfur, 50
100 psi gas pressure.

302

Since 60OC i s t h e m a x i m u m t e m p e r a t u r e a t which SO2 is present ( o u t l e t of the SO2

absorber), carbon steel and 304 and 316 stainless steels should corrode a t rates much less
than I mil/year (0.02 mm/yr) under all process conditions.
S u l f u r Crystallization
A major potential advantage of the UCB Sulfur Recovery Process is the purity of the
crystalline s u l f u r t h a t is produced. T h e sulfur crystallizes from solution both as a result
of cooling and as a result of chemical reaction between H2S and S02. In the former case
t h e degree of s u p e r s a t u r a t i o n is relatively low because t h e solubility of s u l f u r in the
solvent varies only a f e w g r a m s per l i t e r over t h e t e m p e r a t u r e r a n g e of interest. A
substantially higher concentration of sulfur can result from the chemical reaction.

The crystallizer consists of a well-stirred 2-liter vessel. Hot saturated feed enters at
the top, and the vessel walls a r e cooled. Cold effluent exits a t the bottom of the vessel as
a sulfur/solvent slurry. A sample of the effluent slurry i s collected when the system is
at steady-state and t h e size distribution of the sulfur crystals is determined. analysis.
G a s Absorption with Chemical Reaction
Tray efficiency d a t a a r e needed f o r two process situations. In one, H2S a t very low
concentration is being absorbed by a chemically reactive solution of S 0 2 . In t h e other,
gaseous SO2 i n the low parts-per-million concentration range is absorbed by lean process
solvent. Both a r e of interest because one wishes to e f f e c t very stringent sulfur removal
with the UCBSRP. T h e equipment consists of a single seive tray (or section of packed
column) placed in a test section through which gas a n d liquid streams pass. Murphree
t r a y efficiencies a r e determined from the mass balances and previously obtained solubili t y data.
Work Required for Proof-of-Concept
The crystallizer is being modified to incorporate crystal size classification to retain
smaller c r y s t a l s a n d p r o d u c e a p r o d u c t of l a r g e r size. S u l f u r will be produced by
chemical reaction. Data obtained for absorption of H2S enhanced by the presence of SO2
in t h e solvent will b e used to develop a model t h a t incorporates the reaction kinetics
work done previously.
A c o m p u t e r model t h a t s i m u l a t e s a l l of t h e u n i t o p e r a t i o n s i n t h e process is
operational and facillitates process synthesis f o r specific applications. It will be used to
evaluate a n d f u r t h e r refine the process configurations shown in Figures I and 2 for the
purification of hydrogen derived from gasified coal.

Acknowledgement
This work was supported by the Assistant Secretary for Fossil Energy, Office of Coal
Utilization, Division of S u r f a c e Coal Gasification, of the US. Department of Energy
under contract DE-AC03-76SF00098.

303

References
Demyanovich, R.J. a n d Lynn, S. 1987. Vapor-Liquid E q u i l i b r i a of S u l f u r Dioxide in
Polar Organic Solvents. I&EC Research 26 548.
Lynn,

s., Neumann,

D.W., Sciamanna, S.F., and Vorhis, F.H.

1987. A Comparison of the

UCB S u l f u r R e c o v e r y Process w i t h C o n v e n t i o n a l S u l f u r R e c o v e r y Technology.

Environmental Progress 6 257.
Neumann, D.W. and Lynn, S. 1986. Kinetics of the Reaction of H2S and SO2 in Organic
Solvents. I&EC Proc. Des. & Dev. 25 248.
Sciamanna. S.F.and S. Lynn, 1988. Sulfur Solubility in Pure and Mixed Organic Solvents.
I. & E.C. Research (in press).
Sciamanna, S.F. a n d S. Lynn, 1988. S o l u b i l i t y of Hydrogen S u l f i d e , S u l f u r Dioxide,
Carbon Dioxide, Propane and n-Butane i n Polyglycol Ethers. I. & E.C. Research (in
press).
An I n t e g r a t e d Process f o r S i m u l t a n e o u s
S c i a m a n n a , S.F. a n d S. L y n n , 1988.
Desulfurization, Dehydration, a n d Recovery of Hydrocarbon Liquids f r o m Natural
Gas Streams. I. & E.C. Research (in press).

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Figure 1 HZS-Selective Process.

TREITED GAS

Pigure 2

Co-Absorption Process.

305