US3890113A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Production of methane
Assignee: Texaco Inc
•
Filing: 1973-06-25
•
Granted: 1975-06-17
•
Expires: 1993-06-25
Abstract
Abstract Continuous process for the production of a gaseous stream comprising about 50 to 97 mole % methane (dry basis) or higher from a sulfur containing hydrocarbonaceous fuel without polluting the environment. A gaseous stream comprising H2 and CO produced by the partial oxidation of a hydrocarbonaceous fuel is subjected to water gas shift reaction to produce a gaseous stream rich in H2 and CO2. Acid gases i.e. CO2 and H2S are separately removed leaving a hydrogen-rich gas stream. At least a portion of the CO2 previously recovered is recombined with the hydrogen-rich stream to produce a gaseous mixture having a mole ratio H2/CO2 of about 4 to 10. This gas mixture is subjected to conventional catalytic methanation to produce a fuel gas comprising in mole % (dry basis) H2 45 to 1, and CH4 50 to 99. By using the reaction of CO2 and H2 rather than the reaction of CO and H2, a reduction of about 25% in the very large heat release encountered with the methanation reaction may be achieved. Optionally, substantially pure methane may be produced by adding a second portion of CO2 to the aforesaid fuel gas to produce a gaseous mixture having a mole ratio H2/CO2 of about 4, subjecting said gas mixture to conventional catalytic methanation to produce CH4 and H2O, and separating H2O from the process gas stream to produce substantially pure methane. Thus, the normally vigorous exothermic methanation reaction may be controlled better by the stepwise addition of CO2 to react with the hydrogen in the process gas stream.
Inventors
- 👤 Edward T Child
- 👤 Allen M Robin
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 15:56
CPC Classifications
C; C10; C10L; C10L3/00; C01; C01B; C01B3/00; C01B3/02; C01B3/22; C01B3/32; C01B3/34; C01B3/36; C01B3/48; C07; C07C; C07C1/00; C07C1/02; C10J; C10J3/00; C10J3/46; C10J3/466; C10J3/48; C10J3/485; C10J3/72; C10J3/74; C10J3/78; C10J3/82; C10J3/84; C10K; C10K1/00; C10K1/002; C10K1/003; C10K1/004; C10K1/005; C10K3/00; C10K3/02; C10K3/04; C01B2203/00; C01B2203/02; C01B2203/025; C01B2203/0255; C01B2203/0283; C01B2203/04; C01B2203/0415; C01B2203/0435; C01B2203/0445; C01B2203/045; C01B2203/0465; C01B2203/0475; C01B2203/0485; C01B2203/049; C01B2203/0495; C01B2203/06; C01B2203/08; C01B2203/0872; C01B2203/0877; C01B2203/0883; C01B2203/10; C01B2203/1041; C01B2203/1047; C01B2203/12; C01B2203/1205; C01B2203/1211; C01B2203/14; C01B2203/146; C01B2203/147; C07C2521/00; C07C2521/02; C07C2521/04; C07C2523/00; C07C2523/70; C07C2523/74; C07C2523/755; C10J2300/00; C10J2300/09; C10J2300/0913; C10J2300/093; C10J2300/0943; C10J2300/0946; C10J2300/0953; C10J2300/0956; C10J2300/0959; C10J2300/16; C10J2300/164; C10J2300/1656; C10J2300/1662; C10J2300/18; C10J2300/1846; C10J2300/1861; C10J2300/1884; C10J2300/1892; Y; Y02; Y02P; Y02P20/00; Y02P20/50; Y02P20/52; Y10; Y10S; Y10S585/00; Y10S585/929; Y10S585/943
Claims Analysis
Total Claims: 46
Claim 1
Independent Claim
82 words
PRODUCING A RAW PROCESS GAS STREAM PRINCIPALLY COMPRISING CO, H2, CO2, AND H2O AND OPTIONALLY CONTAINING PARTICULATE CARBON, CH4, H2S AND COS BY THE PARTIAL OXIDATION OF A HYDROCARBONACEOUS FEEDSTOCK WITH A FREEOXYGEN CONTAINING GAS COMPRISING ABOUT 90 TO 99.9 MOLE % O2 AND OPTIONALLY WITH A TEMPERATURE MODERATOR, IN THE REACTION ZONE OF A GAS GENERATOR AT AN AUTOGENOUS TEMPERATURE IN THE RANGE OF ABOUT 1200* TO 3500*F. AND A PRESSURE IN THE RANGE OF ABOUT 1 TO 350 ATM. ABS.:
Claim 2
Dependent Claim
82 words
PRODUCING A RAW PROCESS GAS STREAM PRINCIPALLY COMPRISING CO, H2, CO2, AND H2O AND OPTIONALLY CONTAINING PARTICULATE CARBON, CH4, H2S AND COS BY THE PARTIAL OXIDATION OF A HYDROCARBONACEOUS FEEDSTOCK WITH A FREEOXYGEN CONTAINING GAS COMPRISING ABOUT 90 TO 99.9 MOLE % O2 AND OPTIONALLY WITH A TEMPERATURE MODERATOR, IN THE REACTION ZONE OF A GAS GENERATOR AT AN AUTOGENOUS TEMPERATURE IN THE RANGE OF ABOUT 1200* TO 3500*F. AND A PRESSURE IN THE RANGE OF ABOUT 1 TO 350 ATM. ABS.:
Claim 3
Dependent Claim
9 words
A PROCESS FOR PRODUCING A METHANE-RICH GAS STREAM COMPRISING
Claim 4
Dependent Claim
9 words
A PROCESS FOR PRODUCING A METHANE-RICH GAS STREAM COMPRISING
Claim 5
Dependent Claim
36 words
cooling, cleaning and adding supplemental H2O to the effluent gas stream from (1) to produce a feed gas stream for water-gas shift conversion having a mole ratio H2O/CO in the range of about 2 to 8;
Claim 6
Dependent Claim
36 words
cooling, cleaning and adding supplemental H2O to the effluent gas stream from (1) to produce a feed gas stream for water-gas shift conversion having a mole ratio H2O/CO in the range of about 2 to 8;
Claim 7
Dependent Claim
35 words
COOLING, CLEANING AND ADDING SUPPLEMENTAL H2O TO THE EFFLUENT GAS STREAM FROM (1) TO PRODUCE A FEED GAS STREAM FOR WATER-GAS SHIFT CONVERSION HAVING A MOLE RATIO H2O/CO IN THE RANGEOF ABOUT 2 TO 8;
Claim 8
Dependent Claim
35 words
COOLING, CLEANING AND ADDING SUPPLEMENTAL H2O TO THE EFFLUENT GAS STREAM FROM (1) TO PRODUCE A FEED GAS STREAM FOR WATER-GAS SHIFT CONVERSION HAVING A MOLE RATIO H2O/CO IN THE RANGEOF ABOUT 2 TO 8;
Claim 9
Dependent Claim
36 words
cooling, cleaning and adding supplemental H2O to the effluent gas stream from (1) to produce a feed gas stream having a mole ratio H2O/CO in the range of about 2 to 8 for water-gas shift conversion;
Claim 10
Dependent Claim
36 words
cooling, cleaning and adding supplemental H2O to the effluent gas stream from (1) to produce a feed gas stream having a mole ratio H2O/CO in the range of about 2 to 8 for water-gas shift conversion;
Claim 11
Dependent Claim
32 words
The process of claim 1 wherein the pressure in steps (2) to (6) is substantially the same as that in the gas generator in step (1) less ordinary drop in the lines.
Claim 12
Dependent Claim
30 words
The process of claim 1 where in step (3) the water-gas shift reaction takes place in contact with a sulfur resistant catalyst comprising 95 mole % Fe2O3 and 4% Cr2O3.
Claim 13
Dependent Claim
55 words
reacting the feed gas stream from (2) in a catalytic water-gas conversion zone at a temperature in the range of about 650 to 950*F. and a pressure in the range of about 1 to 350 atm. abs. until at least 75 mole % of the CO is reacted with H2O to produce H2 and CO2:
Claim 14
Dependent Claim
55 words
reacting the feed gas stream from (2) in a catalytic water-gas conversion zone at a temperature in the range of about 650 to 950*F. and a pressure in the range of about 1 to 350 atm. abs. until at least 75 mole % of the CO is reacted with H2O to produce H2 and CO2:
Claim 15
Dependent Claim
56 words
REACTING THE FEED GAS STREAM FROM (2) IN A CATALYTIC WATERGAS SHIFT CONVERSION ZONE AT A TEMPERATURE IN THE RANGE OF ABOUT 650* TO 950*F. AND A PRESSURE IN THE RANGE OF ABOUT 1 TO 350 ATM. ABS. UNTIL AT LWAST 75 MOLE % OF THE CO IS REACTED WITH H2O TO PRODUCE H2 AND CO2;
Claim 16
Dependent Claim
56 words
REACTING THE FEED GAS STREAM FROM (2) IN A CATALYTIC WATERGAS SHIFT CONVERSION ZONE AT A TEMPERATURE IN THE RANGE OF ABOUT 650* TO 950*F. AND A PRESSURE IN THE RANGE OF ABOUT 1 TO 350 ATM. ABS. UNTIL AT LWAST 75 MOLE % OF THE CO IS REACTED WITH H2O TO PRODUCE H2 AND CO2;
Claim 17
Dependent Claim
56 words
reacting the feed gas stream from (2) in a catalytic water-gas shift conversion zone at a temperature in the range of about 650* to 950*F. and a pressure in the range of about 1 to 350 atm. abs. until at least 75 mole % of the CO is reacted with H2O to produce H2 and CO2;
Claim 18
Dependent Claim
56 words
reacting the feed gas stream from (2) in a catalytic water-gas shift conversion zone at a temperature in the range of about 650* to 950*F. and a pressure in the range of about 1 to 350 atm. abs. until at least 75 mole % of the CO is reacted with H2O to produce H2 and CO2;
Claim 19
Dependent Claim
34 words
cooling, and purifying the effluent gas stream from (3) in an acid-gas purification zone and separating a CO2-rich gas stream and optionally a separate stream of H2S and COS, producing a hydrogen-rich gas stream;
Claim 20
Dependent Claim
34 words
cooling, and purifying the effluent gas stream from (3) in an acid-gas purification zone and separating a CO2-rich gas stream and optionally a separate stream of H2S and COS, producing a hydrogen-rich gas stream;
Claim 21
Dependent Claim
34 words
COOLING, AND PURIFYING THE EFFLUENT GAS STREAM FROM (3) IN AN ACID-GAS PURIFICATION ZONE AND SEPARATING A CO2-RICH GAS STREAM AND OPTIONALLY A SEPARATED STREAM OF HES AND COS, PRODUCING A HYDROGEN-RICH GAS STREAM;
Claim 22
Dependent Claim
34 words
COOLING, AND PURIFYING THE EFFLUENT GAS STREAM FROM (3) IN AN ACID-GAS PURIFICATION ZONE AND SEPARATING A CO2-RICH GAS STREAM AND OPTIONALLY A SEPARATED STREAM OF HES AND COS, PRODUCING A HYDROGEN-RICH GAS STREAM;
Claim 23
Dependent Claim
72 words
cooling, and purifying the effluent gas stream from (3) in an acid-gas purification zone and separating a CO2-rich gas stream comprising at least 95 mole % CO2 and optionally a separate stream of H2S and COS, thereby producing a dry hydrogen-rich gas stream comprising in mole %: H2 52 to 93, CO 0.5 to 12, CH4 44 to 1, CO2 0 to 6, A 0.2 to 0.4, and N2 0 to 7;
Claim 24
Dependent Claim
72 words
cooling, and purifying the effluent gas stream from (3) in an acid-gas purification zone and separating a CO2-rich gas stream comprising at least 95 mole % CO2 and optionally a separate stream of H2S and COS, thereby producing a dry hydrogen-rich gas stream comprising in mole %: H2 52 to 93, CO 0.5 to 12, CH4 44 to 1, CO2 0 to 6, A 0.2 to 0.4, and N2 0 to 7;
Claim 25
Dependent Claim
29 words
The process of claim 1 wherein a portion of the CO2-rich stream separated in step (4) is introduced into the gas generator in step (1) as said temperature moderator.
Claim 26
Dependent Claim
123 words
mixing at least a portion of the CO2-rich gas stream from (4) with the hydrogen-rich gas stream from (4) providing a feed gas mixture having a mole ratio H2/CO2 in the range of 4 to 10, reacting together at a temperature in the range of about 400* to 1500*F. in a catalytic methanation zone hydrogen and substantially all of the carbon oxides in said feed gas mixture, and removing from said methanation zone an effluent gas stream substantially comprising in mole % dry basis CH4 50 to 96, H2 3 to 46, CO 0 to 0.5, CO2 0.3 to 0.7, A+N2 0.2 to 8; and b. cooling the effluent gas stream from (5) and separating H2O therefrom to produce said methane-rich product stream.
Claim 27
Dependent Claim
123 words
mixing at least a portion of the CO2-rich gas stream from (4) with the hydrogen-rich gas stream from (4) providing a feed gas mixture having a mole ratio H2/CO2 in the range of 4 to 10, reacting together at a temperature in the range of about 400* to 1500*F. in a catalytic methanation zone hydrogen and substantially all of the carbon oxides in said feed gas mixture, and removing from said methanation zone an effluent gas stream substantially comprising in mole % dry basis CH4 50 to 96, H2 3 to 46, CO 0 to 0.5, CO2 0.3 to 0.7, A+N2 0.2 to 8; and b. cooling the effluent gas stream from (5) and separating H2O therefrom to produce said methane-rich product stream.
Claim 28
Dependent Claim
67 words
The process of claim 1 wherein said hydrocarbonaceous fuel is a liquid hydrocarbon selected from the group consisting of liquefied petroleum gas; petroleum Distillates and residues, gasoline, naphtha, kerosine, crude petroleum asphalt, gas oil, residual oil, tar-sand oil, shale oil, coal oil; aromatic hydrocarbons such as benzene, toluene, xylene fractions, coal tar, cycle gas oil from fluid-catalytic-cracking operation; furfural extract of coker gas oil; and mixtures thereof.
Claim 29
Dependent Claim
76 words
mixing at least a portion of the CO2-rich gas stream from (4) with the hydrogen-rich gas stream to provide a feed gas mixture having a mole ratio H2/CO2 of greater than 4, and reacting substantially all of the carbon oxides in said feed gas mixture with hydrogen at a temperature in the range of about 400* to 1500*F. in a catalytic methanation zone to produce an effluent gas stream comprising at least 50 mole % CH4;
Claim 30
Dependent Claim
76 words
mixing at least a portion of the CO2-rich gas stream from (4) with the hydrogen-rich gas stream to provide a feed gas mixture having a mole ratio H2/CO2 of greater than 4, and reacting substantially all of the carbon oxides in said feed gas mixture with hydrogen at a temperature in the range of about 400* to 1500*F. in a catalytic methanation zone to produce an effluent gas stream comprising at least 50 mole % CH4;
Claim 31
Dependent Claim
105 words
MIXING AT LEAST A PORTION OF THE CO2-RICH GAS STREAM FORM (4) WITH THE HYDROGEN-RICH GAS STREAM FROM (4) PROVIDING A FEED GAS MIXTURE HAVING A MOLE RATIO HE/CO2 IN THE RANGE OF 4 TO 10 REACTING TOGETHER AT A TEMPERATURE IN THE RANGE OF ABOUT 400* TO 1500*F. IN A CATALYTIC METHANATION ZONE HYDROGEN AND SUBSTANTIALLY ALL OF THE CARBON OXIDES IN SAID FEED GAS MIXTURE, AND REMOVING FROM SAID METHANATION ZONE AN EFFLUENT GAS STREAM SUBSTANTIALLY COMPRISING IN MOLE % DRY BASIS CH4 50 TO 96, H2 3 TO 46, CO 0 TO 0.5, CO2 0.3 TO 0.7, A+N2 0.2 TO 8; AND
Claim 32
Dependent Claim
105 words
MIXING AT LEAST A PORTION OF THE CO2-RICH GAS STREAM FORM (4) WITH THE HYDROGEN-RICH GAS STREAM FROM (4) PROVIDING A FEED GAS MIXTURE HAVING A MOLE RATIO HE/CO2 IN THE RANGE OF 4 TO 10 REACTING TOGETHER AT A TEMPERATURE IN THE RANGE OF ABOUT 400* TO 1500*F. IN A CATALYTIC METHANATION ZONE HYDROGEN AND SUBSTANTIALLY ALL OF THE CARBON OXIDES IN SAID FEED GAS MIXTURE, AND REMOVING FROM SAID METHANATION ZONE AN EFFLUENT GAS STREAM SUBSTANTIALLY COMPRISING IN MOLE % DRY BASIS CH4 50 TO 96, H2 3 TO 46, CO 0 TO 0.5, CO2 0.3 TO 0.7, A+N2 0.2 TO 8; AND
Claim 33
Dependent Claim
17 words
COOLING THE EFFLUENT GAS STREAM FORM (5) AND SEPARATING H2O THEREFROM TO PRODUCE SAID METHANE-RICH PRODUCT STREAM.
Claim 34
Dependent Claim
17 words
COOLING THE EFFLUENT GAS STREAM FORM (5) AND SEPARATING H2O THEREFROM TO PRODUCE SAID METHANE-RICH PRODUCT STREAM.
Claim 35
Dependent Claim
44 words
cooling the effluent gas stream from (5) to below the dew point, separating out condensed water, and mixing same with a second portion of said CO2-rich gas stream from (4) thereby producing a feed gas stream having a mole ration H2/CO2 of about 4;
Claim 36
Dependent Claim
44 words
cooling the effluent gas stream from (5) to below the dew point, separating out condensed water, and mixing same with a second portion of said CO2-rich gas stream from (4) thereby producing a feed gas stream having a mole ration H2/CO2 of about 4;
Claim 37
Dependent Claim
33 words
The process of claim 1 wherein said hydrocarbonaceous fuel is a gaseous hydrocarbon selected from the group consisting of ethane, propane, butane, pentane, refinery gas, acetylene tail gas, ethylene off-gas, and mixtures thereof.
Claim 38
Dependent Claim
16 words
A process for producing a gaseous stream comprising about 97 mole % methane or more comprising
Claim 39
Dependent Claim
16 words
A process for producing a gaseous stream comprising about 97 mole % methane or more comprising
Claim 40
Dependent Claim
37 words
reacting the feed gas stream from (6) in a second separate catalytic methanation zone at a temperature in the range of about 400 to 1500*F., thereby producing an effluent gas stream substantially comprising CH4 and H2O; and
Claim 41
Dependent Claim
37 words
reacting the feed gas stream from (6) in a second separate catalytic methanation zone at a temperature in the range of about 400 to 1500*F., thereby producing an effluent gas stream substantially comprising CH4 and H2O; and
Claim 42
Dependent Claim
27 words
cooling the effluent gas stream from (7) below the dew point, separating water therefrom, and producing said product stream comprising about 97 mole % CH4, or more.
Claim 43
Dependent Claim
27 words
cooling the effluent gas stream from (7) below the dew point, separating water therefrom, and producing said product stream comprising about 97 mole % CH4, or more.
Claim 44
Dependent Claim
24 words
The process of claim 7 where the pressure in all steps is substantially that in the gas generator less ordinary drop in the line.
Claim 45
Dependent Claim
32 words
The process of claim 7 wherein a portion of the CO2-rich gas stream from (4) is introduced into the gas generator in (1) as at least a portion of said temperature moderator.
Claim 46
Dependent Claim
46 words
The prOcess of claim 7 wherein the catalyst in steps (5) and (7) comprises nickel oxide and aluminum oxide and the space velocity in each methanation zone is in the range of about 100 to 10,000 standard volumes of gas per volume of catalyst per hour.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1978-06-16 | 1978-12-16 | 1979-06-17 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-06-16 | 1982-12-16 | 1983-06-17 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-06-16 | 1986-12-16 | 1987-06-17 | $7700.00 | Window Closed / Lapsed |