Patent US3928000A successfully refreshed from Google Patents.
US3928000A
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Production of a clean methane-rich fuel gas from high-sulfur containing hydrocarbonaceous materials
Assignee: Texaco Inc
•
Filing: 1973-12-28
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Granted: 1975-12-23
•
Expires: 1993-12-28
Abstract
Abstract This is an improved process for converting low-cost high-sulfur containing hydrocarbonaceous materials into a clean methane-rich gas stream which may be burned as a fuel without contaminating the atmosphere. A high-sulfur hydrocarbonaceous fuel is gasified by partial oxidation to produce a process gas stream which is cooled, cleaned and subjected to catalytic methanation over a sulfur-resistant catalyst comprising 0.8 to 10 atoms of an element selected from the group comprising Co, Cr, W or mixtures thereof per atom of an element selected from the group Mo, Ni, or mixtures thereof. The catalyst may be supported on a structure formed from Group III and IV elements e.g. alumina, silica stabilized alumina, zeolite. A distinct advantage of the subject process, is that the sulfur in the process gas stream is not removed prior to the methanation step. Rather, the sulfur is permitted to remain in the process gas stream in order to moderate the highly exothermic methanation reaction. After cooling and purification by removing one or more members of the group H2, CO, H2O, CO2, COS, H2S, Ar, and N2, the resulting methane-rich gas stream comprises about 10 to 95 mole % CH4. Optionally, the CH4 content of said methane-rich gas stream may be increased to about 98 mole % or more by the additional steps of water-gas shift conversion, catalytic methanation, cooling, drying and CO2 removal. The product gas would then have a gross heating value of about 1000 BTU/SCF.
Inventors
- 👤 Edward T Child
- 👤 Allen M Robin
- 👤 William L Slater
- 👤 George N Richter
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 02:44
CPC Classifications
C; C07; C07C; C07C1/00; C07C1/02; C07C1/04; C07C1/0425; C07C1/043; C07C1/0435; C01; C01B; C01B3/00; C01B3/02; C01B3/22; C01B3/32; C01B3/34; C01B3/36; C07C1/0485; C10; C10J; C10J3/00; C10J3/46; C10J3/466; C10K; C10K1/00; C10K1/08; C10K1/10; C10K3/00; C10K3/02; C10K3/04; C10L; C10L3/00; C10L3/06; C10L3/08; C07C2521/00; C07C2521/02; C07C2521/04; C07C2521/06; C07C2521/08; C07C2521/16; C07C2523/00; C07C2523/16; C07C2523/24; C07C2523/26; C07C2523/28; C07C2523/30; C07C2523/70; C07C2523/74; C07C2523/75; C07C2523/755; C07C2523/76; C07C2523/84; C07C2523/85; C07C2523/88; C07C2523/882; C07C2529/00; C07C2529/04; C10J2300/00; C10J2300/16; C10J2300/164; C10J2300/1656; C10J2300/1662; Y; Y02; Y02A; Y02A50/00; Y02A50/20; Y02P; Y02P20/00; Y02P20/50; Y02P20/52
Claims Analysis
Total Claims: 59
Claim 1
Independent Claim
16 words
A PROCESS FOR PRODUCING A METHANE-RICH GAS FROM A SULFURCONTAINING HYDROCARBONACEOUS FUEL COMPRISING THE STEPS OF
Claim 2
Dependent Claim
16 words
A PROCESS FOR PRODUCING A METHANE-RICH GAS FROM A SULFURCONTAINING HYDROCARBONACEOUS FUEL COMPRISING THE STEPS OF
Claim 3
Dependent Claim
130 words
REACTING SAID SULFUR-COTNAINING HYDROCARBONACEOUS FUEL FEED BY PARTIAL OXIDATION WITH SUBSTANTIALLY PURE OXYGEN COMPRISING 95 MOLE % 02 OR MORE AND A TEMPERATURE MODERATOR FROM THE GROUP H2O, CO2, AND MIXTURES THEREOF AT AN AUTOGENOUS TEMPERATURE IN THE RANGE OF ABOUT 170* TO 310*F AND A PRESSURE IN THE RANGE OF ABOUT 1 TO 250 ATMOSPHERES IN THE REACTION ZONE OF A FREE-FLOW UNPACKED NONCATALYTIC SYNTHESIS GAS GENERATOR, WHEREIN THE MOLE RATIO OF OXYGEN IN THE FREE-OXYGEN CONTAINING GAS TO CARBON IN THE HYDROCARBONACEOUS FUEL IS IN THE RANGE OF ABOUT 0.80 TO 1.0, AND THE STREAM OF EFFLUENT GAS LEAVING THE SYNTHESIS GAS GENERATOR COMPRISES MIXTURES OF H2, CO, H2O, CO2, CO2, AND ONE OR MORE MEMBERS OF THE GROUP CH4, H2S, COS, N2, AND AR, AND PARTICULATE CARBON;
Claim 4
Dependent Claim
130 words
REACTING SAID SULFUR-COTNAINING HYDROCARBONACEOUS FUEL FEED BY PARTIAL OXIDATION WITH SUBSTANTIALLY PURE OXYGEN COMPRISING 95 MOLE % 02 OR MORE AND A TEMPERATURE MODERATOR FROM THE GROUP H2O, CO2, AND MIXTURES THEREOF AT AN AUTOGENOUS TEMPERATURE IN THE RANGE OF ABOUT 170* TO 310*F AND A PRESSURE IN THE RANGE OF ABOUT 1 TO 250 ATMOSPHERES IN THE REACTION ZONE OF A FREE-FLOW UNPACKED NONCATALYTIC SYNTHESIS GAS GENERATOR, WHEREIN THE MOLE RATIO OF OXYGEN IN THE FREE-OXYGEN CONTAINING GAS TO CARBON IN THE HYDROCARBONACEOUS FUEL IS IN THE RANGE OF ABOUT 0.80 TO 1.0, AND THE STREAM OF EFFLUENT GAS LEAVING THE SYNTHESIS GAS GENERATOR COMPRISES MIXTURES OF H2, CO, H2O, CO2, CO2, AND ONE OR MORE MEMBERS OF THE GROUP CH4, H2S, COS, N2, AND AR, AND PARTICULATE CARBON;
Claim 5
Dependent Claim
27 words
COOLING THE PROCESS FAS STREAM FROM (1) TO A TEMPERATURE IN THE RANGE OF ABOUT 300* TO 800*F BY INDIRECT HEAT EXHANGE WITH WATER THEREBY PRODUCING STEAM;
Claim 6
Dependent Claim
27 words
COOLING THE PROCESS FAS STREAM FROM (1) TO A TEMPERATURE IN THE RANGE OF ABOUT 300* TO 800*F BY INDIRECT HEAT EXHANGE WITH WATER THEREBY PRODUCING STEAM;
Claim 7
Dependent Claim
27 words
cooling the process gas stream from (1) to a temperature in the range of about 300* to 800*F by indirect heat exchange with water thereby producing steam;
Claim 8
Dependent Claim
27 words
cooling the process gas stream from (1) to a temperature in the range of about 300* to 800*F by indirect heat exchange with water thereby producing steam;
Claim 9
Dependent Claim
27 words
cooling the process gas stream from (1) to a temperature in the range of about 300* to 800*F. by indirect heat exchange with water thereby producing steam;
Claim 10
Dependent Claim
27 words
cooling the process gas stream from (1) to a temperature in the range of about 300* to 800*F. by indirect heat exchange with water thereby producing steam;
Claim 11
Dependent Claim
43 words
The process of claim 1 wherein said sulfur-containing hydrocarbonaceous fuel contains from about 1 to 7 wt. % sulfur and is selected from the group consisting of liquid hydrocarbon fuel, and slurries of coal and petroleum coke in liquid hydrocarbon fuel or water.
Claim 12
Dependent Claim
12 words
separating particulate carbon and H2O from the process gas stream from (2);
Claim 13
Dependent Claim
12 words
separating particulate carbon and H2O from the process gas stream from (2);
Claim 14
Dependent Claim
12 words
separating particulate carbon and H2O from the process gas stream from (2);
Claim 15
Dependent Claim
12 words
separating particulate carbon and H2O from the process gas stream from (2);
Claim 16
Dependent Claim
12 words
SEPARATING PARTICULATE CARBON AND H2O FROM THE PROCESS GAS STREAM FROM (2);
Claim 17
Dependent Claim
12 words
SEPARATING PARTICULATE CARBON AND H2O FROM THE PROCESS GAS STREAM FROM (2);
Claim 18
Dependent Claim
25 words
The process of claim 1 wherein said sulfur-resistant methanation catalyst in step (4) comprises about 1.5 to 4 atoms of Mo per atom of Co.
Claim 19
Dependent Claim
20 words
The process of claim 3 wherein said sulfur-resistant methanation catalyst comprises about 2.5 atoms of Mo per atom of Co.
Claim 20
Dependent Claim
117 words
introducing the process gas stream from (3) without purification of said gas stream directly into a methanation zone containing a sulfur-resistant methanation catalyst comprising about 0.8 to 10 atoms of a first element selected from the group Mo, Cr, W or mixtures thereof per atom of a second element selected from the group CO, Ni or mixtures thereof, and reacting said H2 and CO together at a temperature in the range of about 500 to 1500*F and at a pressure in the range of about 1 to 250 atmospheres to produce an effluent gas stream comprising mixtures of CH4 and one or more members of the group H2, CO, H2O, CO2, COS, H2S, N2 and Ar; and
Claim 21
Dependent Claim
117 words
introducing the process gas stream from (3) without purification of said gas stream directly into a methanation zone containing a sulfur-resistant methanation catalyst comprising about 0.8 to 10 atoms of a first element selected from the group Mo, Cr, W or mixtures thereof per atom of a second element selected from the group CO, Ni or mixtures thereof, and reacting said H2 and CO together at a temperature in the range of about 500 to 1500*F and at a pressure in the range of about 1 to 250 atmospheres to produce an effluent gas stream comprising mixtures of CH4 and one or more members of the group H2, CO, H2O, CO2, COS, H2S, N2 and Ar; and
Claim 22
Dependent Claim
137 words
introducing the process gas stream from (3) without purification of said gas stream directly containing nil to 20, 000 ppm of sulfur and at an inlet temperature in the range of about 500* to 1000*F into a methanation zone comprising at least one fixed bed of sulfur-resistant methanation catalyst comprising in wt. % CoO 3 to 4, MoO3 9.5 to 16 and the remainder alumina, and at a space velocity in the range of about 80 to 10,000 v/v/hr reacting said H2 and CO together at a pressure in the range of about 1 to 250 atmospheres to produce an effluent gas stream at a temperature in the range of about 700 to 1300*F. and comprising CH4, H2, CO and one or more members of the group consisting of H2O, CO2, COS, H2S, Ar, and N2; and
Claim 23
Dependent Claim
137 words
introducing the process gas stream from (3) without purification of said gas stream directly containing nil to 20, 000 ppm of sulfur and at an inlet temperature in the range of about 500* to 1000*F into a methanation zone comprising at least one fixed bed of sulfur-resistant methanation catalyst comprising in wt. % CoO 3 to 4, MoO3 9.5 to 16 and the remainder alumina, and at a space velocity in the range of about 80 to 10,000 v/v/hr reacting said H2 and CO together at a pressure in the range of about 1 to 250 atmospheres to produce an effluent gas stream at a temperature in the range of about 700 to 1300*F. and comprising CH4, H2, CO and one or more members of the group consisting of H2O, CO2, COS, H2S, Ar, and N2; and
Claim 24
Dependent Claim
117 words
INTRODUCING THE PROCESS GAS STREAM FROM (3) WITHOUT PURIFICATION OF SAID GAS STREAM DIRECTLY INTO A METHANATION ZONE CONTAINING A SULFUR-RESISTANT METHANATION CATALYST COMPRISING ABOUT 0.8 TO 10 ATOMS OF A FIRST ELEMENT SELECTED FROM THE GROUP MO, CR, W OR MIXTURES THEREOF PER ATOM OF A SECOND ELEMENT SELECTED FROM THE GROUP CO, NI OR MIXTURES THEREOF, AND REACTING SAID H2 AND CO TOGETHER AT A TEMPERATURE IN THE RANGE OF ABOUT 500 TO 1500*F AND AT A PRESSURE IN THE RANGE OF ABOUT 1 TO 250 ATMOSPHERES TO PRODUCE AN EFFLUENT GAS STREAM COMPRISING MIXTURES OF CH4 AND ONE OR MORE MEMBERS OF THE GROUP H2, CO, H2O, CO2, COS, H2S, N2 AND AR; AND
Claim 25
Dependent Claim
117 words
INTRODUCING THE PROCESS GAS STREAM FROM (3) WITHOUT PURIFICATION OF SAID GAS STREAM DIRECTLY INTO A METHANATION ZONE CONTAINING A SULFUR-RESISTANT METHANATION CATALYST COMPRISING ABOUT 0.8 TO 10 ATOMS OF A FIRST ELEMENT SELECTED FROM THE GROUP MO, CR, W OR MIXTURES THEREOF PER ATOM OF A SECOND ELEMENT SELECTED FROM THE GROUP CO, NI OR MIXTURES THEREOF, AND REACTING SAID H2 AND CO TOGETHER AT A TEMPERATURE IN THE RANGE OF ABOUT 500 TO 1500*F AND AT A PRESSURE IN THE RANGE OF ABOUT 1 TO 250 ATMOSPHERES TO PRODUCE AN EFFLUENT GAS STREAM COMPRISING MIXTURES OF CH4 AND ONE OR MORE MEMBERS OF THE GROUP H2, CO, H2O, CO2, COS, H2S, N2 AND AR; AND
Claim 26
Dependent Claim
22 words
COOLING THE EFFLUENT GAS STREAM FROM (4) AND REMOVING THEREFROM ONE OR MORE MEMBERS OF SAID GROUP IN A GAS PURIFICATION ZONE.
Claim 27
Dependent Claim
22 words
COOLING THE EFFLUENT GAS STREAM FROM (4) AND REMOVING THEREFROM ONE OR MORE MEMBERS OF SAID GROUP IN A GAS PURIFICATION ZONE.
Claim 28
Dependent Claim
38 words
cooling the effluent gas stream from (4) and removing one or more members of said group therefrom in a gas purification zone to produce a methane-rich gas stream comprising 10 to 95 mole % (dry basis) of CH4.
Claim 29
Dependent Claim
38 words
cooling the effluent gas stream from (4) and removing one or more members of said group therefrom in a gas purification zone to produce a methane-rich gas stream comprising 10 to 95 mole % (dry basis) of CH4.
Claim 30
Dependent Claim
15 words
The process of claim 1 wherein the sulfur-resistant methanation catalyst in step (4) comprises cobalt-molybdate-alumina.
Claim 31
Dependent Claim
22 words
cooling the effluent gas stream from (4) and removing therefrom one or more members of said group in a gas purification zone.
Claim 32
Dependent Claim
22 words
cooling the effluent gas stream from (4) and removing therefrom one or more members of said group in a gas purification zone.
Claim 33
Dependent Claim
28 words
The process of claim 5 wherein said sulfur-resistant methanation catalyst comprises in weight percent 1.5 to 15 of CoO, 6 to 60 of MoO3, and 25-92.5 of Al2O3.
Claim 34
Dependent Claim
26 words
introducing supplemental H2O into the process gas stream from step (5) to provide a mole ratio of CO/H2O in the range of about 0.3 to 1.0;
Claim 35
Dependent Claim
26 words
introducing supplemental H2O into the process gas stream from step (5) to provide a mole ratio of CO/H2O in the range of about 0.3 to 1.0;
Claim 36
Dependent Claim
31 words
reacting the gaseous mixture from (6) in a catalytic water-gas shift reactor to provide an effluent gas stream having a mole ratio H2/(CO+CO2) in the range of about 1 to 4;
Claim 37
Dependent Claim
31 words
reacting the gaseous mixture from (6) in a catalytic water-gas shift reactor to provide an effluent gas stream having a mole ratio H2/(CO+CO2) in the range of about 1 to 4;
Claim 38
Dependent Claim
59 words
The process of claim 1 where in said sulfur-resistant methanation catalyst the amount of said first and second elements taken together are in the range of about 5 to 60 weight percent and the remainder is a substrate material selected from the group consisting of alumina, silica, silica stabilized alumina, rare earth metal ions exchanged zeolite, and diatomaceous earth.
Claim 39
Dependent Claim
33 words
The process of claim 5 where in said sulfur-resistant methanation catalyst the amount of Co plus Mo is in the range of about 5 to 60 weight percent and the remainder is alumina.
Claim 40
Dependent Claim
54 words
introducing the process gas stream from (7) into a conventional catalytic methanation zone and reacting substantially all of the H2 and carbon oxides contained therein over a conventional methanation catalyst at a temperature in the range of about 390* to 1000*F. and a pressure in the range of about 1 to 250 atmospheres; and
Claim 41
Dependent Claim
54 words
introducing the process gas stream from (7) into a conventional catalytic methanation zone and reacting substantially all of the H2 and carbon oxides contained therein over a conventional methanation catalyst at a temperature in the range of about 390* to 1000*F. and a pressure in the range of about 1 to 250 atmospheres; and
Claim 42
Dependent Claim
44 words
cooling the effluent gas stream from (8) to condense out H2O, and removing CO2 to produce a product gas comprising about 98 or more mole % CH4 and having a gross heating value in the range of about 800 to 1000 BTU per SCF.
Claim 43
Dependent Claim
44 words
cooling the effluent gas stream from (8) to condense out H2O, and removing CO2 to produce a product gas comprising about 98 or more mole % CH4 and having a gross heating value in the range of about 800 to 1000 BTU per SCF.
Claim 44
Dependent Claim
20 words
The process of claim 5 wherein said alumina is stabilized with up to 5 weight percent (basis alumina) of silica.
Claim 45
Dependent Claim
37 words
The process of claim 1 wherein the sulfur-resistant methanation catalyst in step (4) comprises about 0.9 to 3 atoms of tungsten per atom of an element selected from the group consisting of Co, Ni, or mixtures thereof.
Claim 46
Dependent Claim
51 words
The process of claim 1 wherein the methane-rich gas stream from step (5) has a gross heating value in the range of about 350 to 950 BTU per SCF and comprises in mole % CH4 10 to 95, CO 0 to 50, H2 0 to 50, and Ar+N2 0 to 0.4.
Claim 47
Dependent Claim
11 words
The process of claim 1 provided with the additional steps of
Claim 48
Dependent Claim
60 words
The process of claim 1 wherein the methanation zone in step (4) comprises a fluidized bed methanator, the sulfur resistant catalyst has a particle size in the range of about 20 to 1000 microns, the pressure is in the range of about 1 to 50 atmospheres, and the contact time is in the range of about 0.5 to 10 seconds.
Claim 49
Dependent Claim
29 words
The process of claim 1 wherein said temperature moderating gas is CO2, and said CO2 is obtained at least in part from the gas separation zone in step (5).
Claim 50
Dependent Claim
31 words
The process of claim 1 wherein the pressure in steps (1) through (5) is substantially the same as the pressure in the gas generator in step (1) less ordinary line drop.
Claim 51
Dependent Claim
61 words
The process of claim 1 wherein at least a portion of the sulfur-containing hydrocarbonaceous fuel feed in step (1) comprises a pumpable slurry of a solid hydrocarbonaceous fuel selected from the group consisting of the particulate carbon separated in step (3), coal, and petroleum coke in admixture with a liquid selected from the group consisting of liquid hydrocarbon fuel and water.
Claim 52
Dependent Claim
48 words
The process of claim 1 wherein said sulfur-containing hydrocarbonaceous fuel feed in step (1) is a liquid hydrocarbon selected from the group consisting of petroleum distillate, naphtha, gas oil, residual fuel, asphalt, reduced crude, whole crude, coal tar, coal oil, shale oil, tar sand oil, and mixtures thereof.
Claim 53
Dependent Claim
36 words
The process of claim 1 wherein 0.5-50 volumes of the methane-rich gas stream from step (5) per volume of process gas stream from step (3) are cooled and recycled through the methanation zone in step (4).
Claim 54
Dependent Claim
31 words
The process of claim 1 wherein the process gas stream introduced into the catalytic methanation zone in step (4) contains in ppm H2S nil to 2.0, and COS nil to 0.1.
Claim 55
Dependent Claim
16 words
A process for producing a methane-rich gas from a sulfur-containing hydrocarbonaceous fuel comprising the steps of
Claim 56
Dependent Claim
16 words
A process for producing a methane-rich gas from a sulfur-containing hydrocarbonaceous fuel comprising the steps of
Claim 57
Dependent Claim
170 words
The process of claim 20 provided with the additional steps of a. introducing supplemental H2O into the process gas stream from step (5) to provide a mole ratio of CO/H2O in the range of about 0.3 to 1.0; b. reacting the gaseous mixture from (a) in a catalytic water-gas shift reactor to provide an effluent gas stream having a mole ratio H2/(CO+CO2) in the range of about 1 to 4: c. introducing the process gas stream from (b) into a conventional catalytic methanation zone and Reacting substantially all of the H2 and carbon oxides contained therein over a conventional methanation catalyst at a temperature in the range of about 390* to 1000*F. and a pressure in the range of about 1 to 250 atmospheres; and d. cooling the effluent gas stream from (c) to condense out H2O, and removing CO2 to produce a product gas comprising 70 to 98 or more mole % CH4 and having a gross heating value in the range of 800 to 1000 BTU per SCF.
Claim 58
Dependent Claim
21 words
The process of claim 1 where in step (5) H2O, CO2, COS, and H2S are removed from the effluent gas stream.
Claim 59
Dependent Claim
26 words
The process of claim 1 where in the reaction temperature in the methanation zone in step (4) is in the range of about 500* to 800*F.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1978-12-22 | 1979-06-23 | 1979-12-23 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-12-22 | 1983-06-23 | 1983-12-23 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-12-22 | 1987-06-23 | 1987-12-23 | $7700.00 | Window Closed / Lapsed |