Beruflich Dokumente
Kultur Dokumente
1986, 2 5 , 429-437
429
m = medium
Literature Cited
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Claus, G. Doctoral Thesis, Universiti! de Nancy, Nancy, France, 1974.
Delvosalle, C.; Vanderschuren, J. " I 1 Jorn6es EuropCennes sur la Fluidization: Societe de Chimle Industrielle: Touiouse, France, 1981; p 13.
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mf = minimum fluidization
h = high
1 = low
Several pure and mixed oxides (ZnO, CuO, ZnO-Fe,O,, CuO-Fe,O,, CuO-AI,O,, and CuO-Fe,O?-Al,O,)
were
investigated as regenerable sorbents for the removal of H,S at high temperatures. A special technique was used
to prepare the sorbents in highly porous form. The sorbents were subjected to successive sulfiation-regeneration
mixtures,
cycles in a packed-bed microreactor. Sulfidation was carried out at 538-650 OC with H,S-H,O-H,-N,
regeneration with 02-N2-H20 mixtures. Fresh, sulfided, and regenerated sorbents were characterized by XRD,
SEM-EDS, and BET surface area analysis. Solid conversion and the prebreakthroughexit concentration of H,S
are discussed in terms of physical structure and thermodynamic properties of the sorbents. The performance of
the sorbents CuO-Fe,O,, Cu0-A1,03, and CuO-Fe,O,-AI2O3 is discussed in terms of changes in the oxidation state
of copper during sulfidation.
430
Ind. Eng. Chem. Process Des. Dev., Vol. 25, No. 2, 1986
sulfidation
regeneration
MS,
0 2
M(S04),
MO,
+ xS02
(3)
Ind. Eng. Chem. Process Des. Dev., Vol. 25, No. 2, 1986 431
20
Lim
(11)
BY-PASS LINE
TCD
AIR
N;
GAS ROTAMETER
THERMOCOUPLE
H2
N - H S
2 2
OR
H -H S
2
2
0PRESSURE GAUGE
@
ON/OFF VALVE
SULFUR
TRAP
METERING VALVE
t
j
wHEATED, tNSULATED LINE
ht
D ILUE NT
CARRIER
N2
N2
432
Ind. Eng. Chem. Process Des. Dev., Vol. 25, No. 2, 1986
mounted vertically inside an electric furnace and instrumented with a K-type thermocouple moving inside a
quartz thermowell (0.3 cm i.d) concentric to the reactor.
The sorbents were loaded in the reactor as -20+40-mesh
particles mixed, with low surface area zirconia or alumina
particles serving as an inert filler. The use of the inert
particles allows us to compress the experimental run time
by decreasing the bed capacity, while maintaining the same
space velocity. Different gases from cylinders passed
through purifiers and then through calibrated flow meters
into a common gas line. The gas mixture then passed
through the reactor in the upward (sulfidation) or downward (regeneration) direction. The lines leading to the
reactor were heated and insulated. Nitrogen bubbling
through water maintained at constant temperature in a
three-neck flask assembly was used to introduce known
amounts of water vapor into the feed gas stream. Temperatures at various locations in the reactor system were
monitored by K-type thermocouples connected to a
multichannel digital readout. The reactor pressure in all
cases was slightly above atmospheric.
The experiments consisted of alternating sulfidation and
regeneration runs. In a sulfidation run, the sulfur-free
sorbent was exposed to a feed gas containing H2 ( 20 mol
%), H,O (7-25 mol %), H2S (0.2-1 mol %), and N,
(balance). In a few tests with Cu0-Fe03-A1,03 sorbents,
the feed gas also contained CO and COS. The temperature
was chosen in the range of 500-700 "C and was held fixed
for the duration of sulfidation. Sulfided sorbents were
regenerated by using nitrogen-air or nitrogen-air-steam
mixtures at temperatures of 600-750 "C.
The product gas was passed through ice traps to condense any elemental sulfur formed and was analyzed for
H2Sand SO2by a HP 5830-A gas chromatograph equiped
with a flame photometric detector. The column was 6 ft
N
ZINC
3mC
TRECEN
v)
OXIDE
C-3
1 atm
I, 5 3 P C 1650OC FOR C-41
INLET H2S * 26W ppm ( I VOL % FOR C-41
H20fH2S 2511
P i
c.2
C-41
725OC
CYCLE NO.
1501
0.2
i'/
0
0.4
0.6
NORWLIZED ABSORPTION TIME Wt.1
0. E
+ H2 = Zn + HzO
in addition to sulfidation
ZnO + H2S = ZnS
+ H20
(4)
(5)
Figure 3 presents successive sulfidation cycles, each followed by regeneration with an air-nitrogen mixture (30:70
molar) a t 725 "C. In the first three cycles, carried out at
Ind. Eng. Chem. Process Des. Dev., Vol. 25, No. 2, 1986 433
zn urn
(b)
400'
350 -
P=
latm
T,
600%
H2S
ulo250 -
1 vel%, H2 = 15 vol46,
CL
5;N 200I
150 -
6oooC
C = CYCLE NO.
T~~~~~
0
3
loo 50 010
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
434
Ind. Eng. Chem. Process Des. Dev., Vol. 25, No. 2, 1986
TF 1 r F l
I
250
Is
J7-L
c-5 c-6
7 PC-1
C_)"O,-
H2S
0.26 VOI %, H
20 VOIYo
73 VOI Yo
Ln
0. 0
Ind. Eng. Chem. Process Des. Dev., Vol. 25, No. 2, 1986
350/
435
ic-2
(WITH NZIAIR
TREGEN
7W'C 70 301
C
CYCLE NO.
~--o-o
D
-,
50
0.4
0.6
0.8
NORMALIZED ABSORPTION TIME llil'l
0.2
1.0
+ A1203+ HzO
~ C+
U H2S = CUZS + H2
(15)
(16)
(9)
436
Ind. Eng. Chem. Process Des. Dev., Vol. 25, No. 2, 1986
280
240
c - 4 7 c-17-
P = latm
200
, i l
i I
TS = 650C
-E.
INLET
v)
H2S
2210 hr-'
S.V.
5c
H 0 = 25 VOI %, N2 = 54 VOI%
TREGEN = 650C
0
3
80
CYCLE NO.
40
0
NORMALIZED ABSORPTION TIME (tit")
(16a)
CU~O
+ H2S = C U ~ +S H20
(16b)
This work was carried out under a contract (DE-AI2183MC20417) from the Department of Energy, Morgantown
Energy Technology Center. The XRD and SEM/EDS
437
James F. Mosby
Research and Development Department, Amoco Oil Company, Naperville, Illinois 60566