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Int. J. Hydrogen Energy, Vol. 7, No, 6, pp. 477--482, 1982. 0360-3199/82/060477-06 $03.

00/0
Printed in Great Britain. Pergamon Press Ltd.
International Association for Hydrogen Energy.

RECOVERY OF H Y D R O G E N FROM H Y D R O G E N S U L F I D E W I T H
METALS OR METAL SULFIDES
H. KIUCHt, T. NAKAMURA, K. FUNAKIand T. TANAKA
Hokkaido University, Sapporo, 060 Japan

(Receivedfor publication 5 August 1981)


Abstract--The following two types of reactions were investigated for the recovery of hydrogen from hydrogen
sulfide:
Type 1 HES--* H2 + Sv, Type 2 H2S + O2~ H2 + SO2.
Each type of reaction is constructed by a two-step cycle, in which H2S is reacted with metal or metal sulfide and
then the resulting sulfide undergoes thermal decomposition or oxidation. Ag2S, FeS, C09S8, Ni3S2,and the double
sulfide CuFeS2 were examined in the former type of reaction, while Ag, Cu, Ni, liquid Pb, and liquid Bi-Ag alloy
were used as an intermediate in the latter.

INTRODUCTION Overall reaction


Because of its physical and chemical properties, hydro- zH2S + zO2 ~ zH2 + zSO2. (6)
gen is highly valued as an energy source, a raw material
for the chemical industry, and as a reducing agent. The
recovery of hydrogen from hydrogen sulfide has recently EXPERIMENTAL
attracted attention for the following reasons. (1) A I. Treatment of H2S by Type 1 reaction
thermochemical process for water splitting has been
proposed and discussed, which incorporates the disso- In the cyclic continuous experiments, sul~rization
ciation of H2S or HI (more easily decomposed than and thermal decomposition were repeated alternately,
1-120) as a hydrogen evolution reaction. (2) Sour gas simply by changeovers of gases flowing thro~agh the
containing great amounts of H2S is known as a virgin fixed packed bed of metal sulfide powder. Therefore,
energy source. (3) In geothermal utilization, H2S is the decomposition behaviour of H2S into H2 a ad SOas
frequently contained in steam. (4) A great amount of an overall reaction can be understood by fi ~llowing
H2S is formed as a by-product from the hydrogen either behavior of the two reactions consisting tlle cycle.
reduction smelting and acid leaching of sulfide ore or The cyclic experiments started with the sulfuri~ ation of
the hydrodesulfurization of petroleum, a lower metal sulfide while passing H2S throlLgh at a
In this study, two kinds of treatment of hydrogen given flow rate. The concentrations of H2 an( H2S in
sulfide, shown in the following equation, are the outlet gas were determined by gas chromal ,graphy
investigated: on a given volume of gas withdrawn through a micro-
syringe. The cycle usually consisted of constituent
Type 1 reaction (M: metal) reactions for I h each. After the sulfurization, the pow-
Sulfurization der was heated to the thermal decomposition temper-
(M or MxSr) + zH2S --~ (MSz or M~Sy+z) + zH2 (1) ature while Ar was passed through, and then the sulfide
was decomposed under reduced pressure. The sulfur
Thermal decomposition gas formed was made to flow in one direction by leaking
(MSz or MxSy+z) ~ (M or MxSy) + zS ° (2) a given quantity of Ar gas during the vacuumi thermal
decomposition, which condensed and collectdd in the
trap. After decomposition for I h, the po,~der was
Overall reaction cooled to the sulfurization temperature while passing
Ar through. Such operations were repeated
zH2S ~ zH2 + zS ° (3) continuously.
Type 2 reaction (M: metal)
Sulfurization I1. Treatment of H2S by Type 2 reaction
M + zH2S ~ MSz + zH2 (4) The experiments consist of two parts: one is con-
Regeneration of metal cerned with H2 recovery from H2S and thel other is
concerned with regeneration of metal from metal sul-
MSz + zO2 ~ M + zSO2 (5) fide. For the former, metal was sulfurized and H2 gen-
eration behavior was investigated by the analysis of H2
477
478 H. KIUCHI, T. NAKAMURA, K. FUNAKI AND T. TANAKA

concentration in the outlet gas by gas chromatography Table 1. Sulfur contents of FeS~÷xafter sulfurization and
in the same manner as mentioned in the treatment of thermal decomposition
H2S by the Type 1 reaction. In the sulfurization of liquid
metal, HzS was bubbled into the melt or soft-blown at 1ottlce constant sulfur
the surface of the melt through a lance. For solid metal, reoct10n "C C (A) (et0m-Z)
metal powder was charged into an alumina boat and sulfurlzotlon 550 5.6790 55.12
then was sulfurized in a stream of H2S. For the latter, thermal decomposition 750 5.7253. 52.55
tests were conducted by oxidation of metal sulfide pow- 0t ambientpressure
der in an alumina boat under 02 flow or by mutual
reaction between metal sulfide and metal sulfate in an sulfurlzotlon 600 5.6808 54,96
alumina boat under A r flow. The rates of these reactions thermal
under decomposition
reducedpressure 750 5.7621 51.52
were determined by the analysis of SO2 in the exit gas.
The exit gases were absorbed in KI-KIO3 solutions and
they were continuously titrated during a test by sodium
thiosulfate solution. Figure 2 gives the equilibrium gas composition cor-
responding to the coexisting composition of Fe-FeS and
RESULTS A N D DISCUSSION FeSI+~-FeS2. The coexisting gas composition was deter-
mined by the data reported by Rosenqvist [4] and
I. Treatment of H2S by the Type 1 reaction
Kubaschewski and Evans [5] and the data on the solu-
For this reaction the cycle is composed of sulfurization bility of S in FeS~+x [6]. Figure 2 shows that the H2/H2S
of metals or metal sulfides with H2S and thermal decom- ratio fails rapidly as the reaction proceeds, even at true
position of the products. Based on thermodynamic con- equilibrium. Thus a large amount of sulfide must be
siderations, Bi [1] or FeS [2] has been suggested as a processed per mol of H2 formed. Attention should be
medium for the reaction. There are, however, few drawn to this advantage. Furthermore, the actual
reports containing conclusions based on experimental amounts of H2 evolved, however, were no more than
results. Sulfurization and thermal decomposition were 30% of theoretical amounts. This may be due to the
repeated alternately by using a fixed packed bed of diffusion resistance within the solid. Some indications
metal sulfide powder. Figure 1 shows the results with for the selection of the medium were obtained from
iron sulfide, in which two different sulfurization behav- these results. One is that y + z in equation (1) should
iors for cycles involving thermal decomposition at not be as large as x. In addition, the diffusion of metal
ambient pressure and under reduced pressure, are com- ion in the sulfide phase should occur easily. A cycle
pared at each optimum sulfurization temperature. The expressed in the change of Co453 ~ CoS or Ni3S2 ~ NiS
measurements of the composition change of iron sulfide for medium was thought to be reasonable.
during the cycle were also carried out by using iron The cycle with nickel sulfide was started by sulfuri-
sulfide powder in an alumina boat. The sulfur content zation of Ni3S2, and the thermal decomposition was
of iron sulfide after each reaction was determined by carried out under reduced pressure. The results are
measurement of the lattice constant (c) and by using
Turkdogan's report [3], and is listed in Table l.

50 , , 150
thermoI d., 750°C 2 !!
normol p. ~ I '
40 - - - 120 ' '
,,, -0.i
/ ~ FeSI+x
"/"' ~2^
600°C F~+

~ 30
F, ~(s°lf.)/_L , _ 9o e~ ;"= o ~-es 0.5 ~

> ~ 0,9 =~
20 60 III - v - 55o

~ ,,
[] 10 30 ,,,,
0 tll
-4
I I Jill I

0 0 48 50 52 54 56 58
20 40 60 SULFUR (atom-Z tn FeSI+ X)
TIME (minute)
Fig. 2. Sulfur content of iron sulfide as a function of
Fig. 1. Hz formation in the iron sulfide cycles. PHzs/PH2
RECOVERY OF HYDROGEN FROM HYDROGEN SULFIDE 479
i00 ] , -- 100
550°C Isulf' sulf. V 550°C
~ Ithermo] d, A 600
~I 750°C 0 650
~ 80 ~, reduced D, ~ 80 D 700
° \ °
E l 1st >
=
_o 60 ~2nd ~3 ~ 60-- --

L~ 40 ~ 40 I
o

=~ 2o =~ 20 the
850°C "II
, ~ reduced o. I
0 0 '
0 20 40 60 0 20 40 t~,
TIME (minute) TIME (minute)

Fig. 3. Effect of repeated cycling in the nickel sulfide cycle. Fig. 5. Effect of sulfurization temperature on H2 formmion for
the cobalt sulfide cycle involving thermal decomposition at
850°C under reduced pressure.
shown in Fig. 3. The figure shows that H2 evolution was
excellent in the first cycle but the behavior worsened
cycle by cycle. This may be attributed to sintering or
partial fusion of the medium. Depression of the fusing observed and the change of the medium in the cycle
point of nickel sulfide formed by thermal decomposition was found to be Ni3S2 ~,~ NiS from the identification by
may be suggested and this can be accounted for by the X-ray diffraction of the products after the sulfurization
phase diagram for the system Ni-S [6]. This not only of thermal decomposition.
disturbed desulfurization but also caused channelling In the cycle with cobalt sulfide, the mixture Of Co9S8
in the packed bed. and CoS obtained by sulfurization of metallic cobalt
Prevention of sintering was attempted by dispersing with H2S was used. The Co/S mole ratio was 0J83. The
nickel sulfide powder in an inert substance. As a result, experiments were repeated after thermal dec0mposi-
the cycle with the mixture of an equal amount of Ni3S2 tion. Since the melting point of cobalt sulfide iis high,
and MoS2 was found to give excellent results every time. the unfavorable effects of cyclic repetition Observed
Figure 4 shows the effects of sulfurization temperature with nickel sulfide did not occur. Figure 5 shows the
on the behavior. In the cycle with MoS2 only, H2 was effects of sulfurization temperature on the behavior.
not detected at 450°C. NiMoS4 is known as the double Though the optimum temperature lay between 600°C
sulfide of Ni and Mo, but this double sulfide was not and 700°C from the comparison of the maxirhum H:
concentration, the total volume of H2 evolved increased
with the decrease in temperature. It may be ipointed
out that in this cycle the effect of the sulfdrization
- - -- temperature is small compared to the effect in other
100 T ]thermol'd.,
I 800°C
sulfide cycles. According to Rosenqvist's report [4],
80 ~... reauceoD. the equilibrium H2 concentration of the H25-I~2 system
wherein C09S8 and CoS can co-exist increases with tem-
I t _ ~ perature at approx. 500-800°C. Although the expla-
6o nation of this rare phenomenon was not giyen, the
,~ Xx ' reason is due perhaps to the large temperature idepend-
ence of the composition variation of CoS~+x. For other
40
~ . . . . . .

~x~ sulfides, the equilibrium H: concentration increases


inversely with temperature. Actually, the reaction rate
I osulfurlzotlon
400oc of sulfurization for such cycles is optimum between 400
20 vt~ 450500 and 600°C, from the dependence rate on temperature,
whereas thermal decomposition is much better at higher
°o 2'0 -4o 60 80 temperature. The cobalt sulfide cycle may be charac-
TINE (minute) terized by a small difference in temperature ]between
Fig. 4. Effect of sulfurization temperature on H2 concentration sulfurization and thermal decomposition. Experimental
for the reaction between Ni3S2 and H2S in the presence of results obtained at the same two temperatures are shown
MoS2. in Fig. 6.
480 H. KIUCHI, T. NAKAMURA, K. FUNAKI AND T. TANAKA
100 I 250 Table 2. Fractional thermal decomposition of Ag2S powder
under reduced pressure (duration of reaction: 1 h)
-0- 850"C /
-43- 800 /,,
n 80 jAp S 200 ji eaulllbrlum PS2 aressure fractional reaction
0 ~ "C (rrmHg) (mmHg) (~I)
s p Ss
750 0.00347 2.5 15.0
60 150 -"
~ 780 0.00599 2,5 29.9
780 0,00599 1,0 50,0
~ 850 0.0209 1,0 93.7
~: 40 -- 100

taJ to be sintered at sulfurization temperatures higher than


20 , 50 600°C. The diffusion coefficient of Ag + in Ag2S is con-
sidered large, and the experimental result showed that
Ag was readily transformed to Ag2S at 600°C. The
00 20 40 60 0 thermal decomposition of Ag2S was examined by
TIME (minute) measurement of weight change for the powder sample
in an alumina boat (Table 2). Relatively easy decom-
Fig. 6. H2 concentration vs reaction time plot obtained from position was found under reduced pressure. The Ag
the experiments in which sulfurization temperature is the same formed was hair-like in shape. A cycle utilizing this
as that of thermal decomposition, feature may be possible and is now being examined.

Cycles involving natural chalcopyrite (CuFeS:-x) and II. Treatment of H2S by the Type 2 reaction
synthetic pentlandite (Ni4.sFe4.sSs) were also examined.
They are interesting as examples of the double sulfide, This type is composed of sulfurization of metal and
but in each case the behavior of H2 evolution was like regeneration of metal by oxidation of the sulfides. The
the iron sulfide cycle. SO2 can be recovered easily as sulfuric acid, in the same
The equilibrium H2 concentration of equation (1) manner as a non-ferrous extractive metallurgy, or as
with metal is generally very high. But the regeneration elemental sulfur by the Claus reaction with H2S.
of metal by equation (2) is difficult. Silver was chosen Similar to this cycle is the Shell process using Cu [8].
for investigation of this cycle. Figure 7 shows hydrogen The authors have proposed the application of liquid
evolution when A g powder was sulfurized in an alumina metal for the purpose of avoiding reaction hindrance
boat. According to Richardson and Jeffes [7] the equi- by the sulfide film formed on the surface of solid metal,
librium H2 concentration of this reaction increases with and have reported on the cycle with molten lead [9, 10].
temperature. The experimental results, however, The cycle was investigated by two sulfurization methods
showed that the optimum temperature for both the H2 in which the circulated H2S was bubbled into molten
concentration and the rate of H2 evolution was 600°C. lead, and soft-blown at the surface of molten lead.
This may be due to the sintered Ag:S covering the Figure 8 shows the conversion of H2S to H2 as a function
surface of A g and hindering further sulfurization at
higher temperatures. Ag2S (m.p. 840°C) was observed
I00 , [
600oC I
100 . 100 80 bubbling into Pb(1)

-- 8 0 - - / -- ,'-~-- - - 80

6 0 - / - 60 ~_

I ,00 m)
i--

20-- 20 ..'5 ~ soft blowing


:3r I at the surface
" ~ ~ 30 60 90 120
°o 30 60 )oo TIME (minute)
TII4E (minute)
Fig. 8. Conversion of H2S to H 2 in the following sulfurization
Fig. 7. Sulfurization of Ag powder to Ag2S at various reaction:
temperatures. Pb(l) + H2S = PbS(s) + H2.
RECOVERY OF HYDROGEN FROM HYDROGEN SULFIDE 481

100 _grit ~ - v "~'9"~ 100 I I


~P" I 6oooc Ag2S+ 02 = 2Ag + SO2
/ 80 ~ 'i
~'--- 600% I
8o P o., I A
60 1 rn%7 lwt-% Cu-Pb
~ 60 ~ 0 20
bubbling ~ ~ 1
...... soft-b]owing
40 ~ 40 --

20 ~.~r -~'~-- u_ 20 ~
i

0 " I 0 - '
0 30 60 90 120 20 40 60 80
TIME (minute) TIME (minute)
Fig. 9. Effect of Ni or Cu addition to molten Pb on conversion Fig. 11. Regeneration of Ag from Ag2S by oxidation.
of HES to H2.

of time. The effects of the addition of metals in molten Fig. 11. As can be seen, regeneration of over 75% was
lead were also investigated (Fig. 9). Ni for the bubbling difficult. From X-ray diffraction identification of the
method, and Cu for the soft-blowing method, were products, the limit was found to be due to the formation
found to act catalytically, of AgESO4. The treatment of AgESO4 by the following
As to the treatment of PbS formed, it was found that mutual reaction was examined:
lead oxide or lead sulfate was not formed and only AgES ÷ Ag2SO4--* 4Ag + 2SO2.
equation (5) took place by the oxidation under low
oxygen partial pressure [9]. The kinetics of this reaction Figure 12 is the reaction behavior of eCluimolar
were investigated by means of the weight loss measure- amounts of AgES and AgESO4 powder under an atmos-
ment technique. Figure 10 shows the Arrhenius plot. phere of argon gas. As the regeneration of Ag from
It was found from X-ray diffraction analysis that only AgESO4 by the above reaction was easy, the cydle whose
equation (5) proceeded at the linear part in the higher overall reaction was expressed by equation (6) was
temperature region, while not only metallic Pb but also possible.
PbO and PbSO4 were formed in the lower temperature The overall reaction in the Shell process [8] is
region, also expressed by equation (6) and metallic ~opper is
In the treatment of HES with metallic Ag, the pos- formed by a mutual reaction between coppebr sulfate
sibility of applying Type 1 has been described pre- formed by oxidation of copper sulfide and remaining
viously, but the regeneration of Ag by equation (5) is copper sulfide. Formation of metallic coppe r by the
possible because silver oxide is thermodynamically mutual reaction between cuprous oxide and i cuprous
unstable at high temperature.The regeneration behav- sulfide is well known in the copper smelting. The overall
ior of Ag by the oxidation of AgES powder is shown in reaction in the combination of the mutual reaction to

5oI'~
"~'~"'"~'~zs°lz'°°cl°~"~gOAo.slzo2 lOO8o~P'~~--'
"~--~
"~:~
-'~ 15-v~..~,~-~ ~°~- ; 60
~
,o - v N
s25

Ag2S + Ag2SO4 =
4Ag + 2S02
0.1 0 '
9 9,5 10 10,5 11 0 20 40 60 80
I04/T (°K) TIME (minute)
Fig. 10. Oxidation rates of PbS by low oxygen partial pressure. Fig. 12. Mutual reaction curves of Ag2S with Ag2SO4.
482 H. KIUCHI, T. NAKAMURA, K. FUNAKI AND T. TANAKA
100 I 600"C I I 400 using Bi(1) were also poor. On the other hand, the
application of a molten alloy can be considered in order to
NI3S2 . . - . . . . . . . . ?'°-Nt~ prevent reaction hindrance through sulfide films formed
-8060 ) f~~ t ~ / INi\ --~ by the sulfurization of solid metal. In the binary alloy, one
300 component is desired to be easily sulfurized and recon-
"," /~ \ ~ Ni ~ - ~ verted to metal, while the other component is desired to
have a large lowering of melting point and be minimally
NI3S2_ ~ sulfurized. Bi-Ag alloy was selected as an example. H2S
40 ~ was bubbled into the melt of a 50-50 wt-% alloy of Bi and
>~ Ag, and the outlet gas showed a constant high H2 concen-
100 ~ tration over a long experimental period. The relation of
20 the steady state H2 concentration and sulfurization tem-
perature is shown in Figure 14. The separation of a Ag2S
phase from the melt was not observed. This is because of
0 20 40 60 so 0 the large solubility of sulfur in Bi(1). Air was bubbled into
TIME (minute) the sulfurized melt. Though Bi was slightly oxidized above
700°C, the melt was desulfurized to - 7 0 % in an hour at a
Fig. 13. Sulfurization of Ni and Cu powders at 600°C. temperature below 650°C. Complete desulfurization is
not required in this cycle. Therefore, application of this
alloy for a cycle of Type 2 may be possible.
the oxidation of copper sulfide is expressed by equation
(5). The production of nickel powder by mutual reaction
of nickel sulfide and nickel oxide is also known [11].
The authors propose the application of the above
metallurgical reactions to the cycle of Type 2. Figure CONCLUSION
13 shows behavior of H2 evolution by sulfurization of
Cu and Ni powders at 600°C. If the final sulfide is Cu2S Cycles using various metals and metal sulfides as an
and Ni3S2 respectively, the maximum H: concentration intermediate have been investigated, as a means of
is obtained when approx, half the metal is sulfurized decomposing H2S to hydrogen and either elemental
in both cases and the completion of the reaction is easy. sulfur (Type 1 reaction) or SO2 (Type 2 reaction). In
Sintering occurred due to the formation of Ni3S;, crush- both types, this research shows that not only the elu-
ing of the sample resulted in the dashed-line in Fig. 13 cidation of the behavior of each reaction of the cycle,
and sulfurization to NiS proceeded easily, but also the effect of hysteresis when the cycle is
The cycle of Type 1 with Bi(s) was proposed by repeated are important. In this case, it must be noted
Soliman et al. [1]. The authors investigated sulfurization that the physical properties or states of the intermediate
of Bi(s), but the gas-solid reaction could barely proceed frequently influence the chemical reaction behavior to
owing to its low melting point (271°C). Furthermore, a great extent.
the calculated values of equilibrium H2 concentration
in the Bi-H2S system are small, e.g. 47.3% at 400°C
and 16.2% at 600°C. Therefore the experimental results
REFERENCES
100 -- 1. M. A. Soliman, R. H. Calty, W. L. Conger and J. E,
L I ! , I _ Funk, Can. J. Chem. Engng53,164-169(1975).
2. R. M. Parsons Co., U.S. Patent 2,979,384 (1961).
~ bubbl ng 3. E. T. Turkdogan, Trans. Am. Inst. Min. metall. Petrol.
80 / 50wt-~ Ag-Bi ollov Engrs. 242, 1665-1672 (1968).
i~ 4. T. Rosenqvist, J. Iron Steel Inst. 176, 37-57 (1954).
60 5. O. Kubaschewski and E. L. Evans, Metallurgical Ther-
mochernistry, Butterworth Springer, London (1951).
6. M. Hansen, Constitution of Binary Alloys, 2rid edn.
McGraw-Hill, New York (1958).
q0 7. F. D. Richardson and J. H. E. Jeffes, J. Iron Steel Inst.
171, 165-175 (1952).
8. Shell International Research, Chemical Abstract, Vol. 12.
20 p. 3685 (1965).
9. H. Kiuchi and T. Tanaka, Trans. Am. Inst, metall. Petrol.
Engrs. 262, 248--254 (1977).
0 J 10. H. Kiuchi, T. Iwasaki and T. Tanaka, J. Min. metall. Inst.
550 600 650 700 750 800 Japan 94, 479--484 (1978).
TEMPERATURE (°C) ll. P. M. Prasad and P. K. Jena, Metallurgical Transactions
Fig. 14. Steady state H2 concentration at various temperatures. 2, 1651-1655 (1971).

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