公开(公告)号：US3927998A

公开(公告)日：1975-12-23

申请号：US42946873

申请日：1973-12-28

Applicant: TEXACO INC

Inventor： CHILD EDWARD T ,  ROBIN ALLEN M ,  SLATER WILLIAM L ,  RICHTER GEORGE N

IPC: C07B61/00 ,  B01J21/00 ,  B01J23/00 ,  C01B3/22 ,  C01B3/36 ,  C07C1/00 ,  C07C1/02 ,  C07C1/04 ,  C07C9/04 ,  C07C67/00 ,  C10G9/38 ,  C10J3/46 ,  C10J3/06

CPC classification number: C01B3/36 ,  C01B3/22 ,  C07C1/0485 ,  C07C2521/04 ,  C07C2523/882 ,  C10G9/00 ,  C10G9/38 ,  C07C9/04

Abstract: Improved process for the production of a methane-rich product gas stream comprising the following steps: partial oxidation of a hydrocarbonaceous fuel feed employing a H2O/fuel weight ratio of 2.2 to 2.9 and an atomic ratio of oxygen in the substantially pure oxygen to carbon in the fuel of 0.80 to 0.84 to produce a process gas stream comprising principally H2, CO and CH4 in which the mole ratio H2/CO is 1 to 2.5, the mole % CH4 is 15 or more, and the particulate carbon is 13 weight % (basis carbon in the fuel) or less; cooling the process gas stream and separating H2O, CO2, carbon, and gaseous impurities; reacting together the H2 and CO in said process gas stream in a catalytic methanation zone to produce a methane-rich gas stream principally comprising CH4 and containing gaseous members selected from the group consisting of H2, CO, H2O, CO2, and mixtures thereof; and removing said H2O and CO2 to produce a methane-rich product gas stream comprising about 93 mole percent of CH4. By means of the subject invention there is produced a high heating value clean fuel gas or a substitute natural gas of about 960 BTU per SCF or more.

Abstract translation: 用于生产富含甲烷的产物气流的改进方法包括以下步骤：使用H 2 O /燃料重量比为2.2至2.9的烃类燃料进料的部分氧化和基本上纯的氧中的氧的原子比与碳的原子比 燃料为0.80至0.84，以产生主要为H 2，CO和CH 4的工艺气流，其中摩尔比H 2 / CO为1至2.5，摩尔％CH 4为15或更大，并且颗粒碳为13重量％ 燃料中的基础碳）或更少; 冷却工艺气流并分离H 2 O，CO 2，碳和气态杂质; 在催化甲烷化区中使所述工艺气流中的H 2和CO一起反应，以产生主要包含CH 4并含有选自H 2，CO，H 2 O，CO 2及其混合物的气态成员的富甲烷气流; 并且除去所述H 2 O和CO 2以产生包含约93％（摩尔）CH 4的富甲烷产物气流。通过本发明，产生高热值清洁燃料气体或约960BTU的替代天然气 SCF或更多。

公开(公告)号：US3598146A

公开(公告)日：1971-08-10

申请号：US3598146D

申请日：1969-09-29

Applicant: TEXACO INC

Inventor： ROBIN ALLEN M ,  JESSE DALE R

IPC: G08B23/00 ,  F16K37/00 ,  H04Q3/02

CPC classification number: G08B23/00 ,  Y10T137/8175 ,  Y10T137/8242

Abstract: An electrical indicator system is connected to a petroleum process where pneumatic controls are employed and where automatic shutdown will take place if any one of a plurality of parameters exceeds predetermined limits. The electrical system uses relays that are actuated by the pneumatic controls which indicate when a parameter goes outside limits. Each such relay has interlocking contacts with the circuits for all the other relays, so that the first actuated relay will lock out the remaining relays. This provides an indication of which condition was first outside limits.

公开(公告)号：US3595619A

公开(公告)日：1971-07-27

申请号：US3595619D

申请日：1968-03-29

Applicant: TEXACO INC

Inventor： SLATER WILLIAM L ,  MUENGER JAMES R ,  SCHLINGER WARREN G ,  ROBIN ALLEN M

IPC: C01B3/16 ,  C01B1/03

CPC classification number: C01B3/16 ,  Y02P20/129

Abstract: IN A STEADY-STATE CONTINUOUS FLOW FIXED-BED WATER-GAS CATALYST SHIFT CONVERSION REACTOR COMPRISING A PLURALITY OF SEPARATE CATALYST BEDS IN SERIES AT A TEMPERATURE IN THE RANGE OF ABOUT 350*F. TO 1050*F. AND A PRESSURE IN THE RANGE OF ABOUT 1 TO 250 ATMOSPHERES, A GASEOUS FEED STREAM COMPRISING H2O AND CO IS CONVERTED INTO H2 AND CO2. A FRACTION OF THE EFFLUENT GAS STREAM FROM THE FIRST CATALYST BED IN THE REACTOR IS RECYCLED AND MIXED WITH A FRESH FEED STREAM OF PROCESS GAS E.G. SYNTHESIS GAS TO COMPRISE SAID GASEOUS FEED STREAM TO THE FIRST CATALYST BED. THE RESIDUAL FRACTION OF SAID EFFLUENT GAS STREAM IS COOLED AND INTRODUCED INTO THE SECOND CATALYST BED IN THE REACTOR. CO CONVERSION IS IMPROVED, PROCESS FEED STEAM REQUIREMENTS ARE REDUCED, LESS CATALYST IS NEEDED, UNDERSIRABLE BACK AND SIDE REACTIONS ARE MINIMIZED, AND THE SYSTEM IS STABILIZED. OPERATING THE SYSTEM AT HIGH PRESSURE ALSO REDUCES OVERALL CATALYST REQUIREMENTS.

公开(公告)号：US3890113A

公开(公告)日：1975-06-17

申请号：US37353373

申请日：1973-06-25

Applicant: TEXACO INC

Inventor： CHILD EDWARD T ,  ROBIN ALLEN M

IPC: C10G9/38 ,  B01J23/00 ,  C01B3/22 ,  C01B3/36 ,  C01B3/48 ,  C07C1/00 ,  C07C1/02 ,  C07C9/04 ,  C07C67/00 ,  C10J3/46 ,  C10L3/00 ,  C10B49/02 ,  C10B57/02

CPC classification number: C10L3/00 ,  C01B3/22 ,  C01B3/36 ,  C01B3/48 ,  C01B2203/0255 ,  C01B2203/0283 ,  C01B2203/0415 ,  C01B2203/0445 ,  C01B2203/045 ,  C01B2203/0475 ,  C01B2203/0485 ,  C01B2203/049 ,  C01B2203/0495 ,  C01B2203/06 ,  C01B2203/0877 ,  C01B2203/0883 ,  C01B2203/1041 ,  C01B2203/1047 ,  C01B2203/1205 ,  C01B2203/1211 ,  C01B2203/147 ,  C07C1/02 ,  C07C2521/04 ,  C07C2523/755 ,  C10J3/466 ,  C10J3/485 ,  C10J3/74 ,  C10J3/78 ,  C10J3/84 ,  C10J2300/093 ,  C10J2300/0943 ,  C10J2300/0946 ,  C10J2300/0956 ,  C10J2300/0959 ,  C10J2300/1662 ,  C10J2300/1846 ,  C10J2300/1884 ,  C10J2300/1892 ,  C10K1/004 ,  C10K1/005 ,  C10K3/04 ,  Y02P20/52 ,  Y10S585/943 ,  C07C9/04

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.

Abstract translation: 用于生产包含约50至97摩尔％甲烷（干基）或更高的含硫烃类燃料而不污染环境的气流的连续方法。

公开(公告)号：US3888043A

公开(公告)日：1975-06-10

申请号：US37335173

申请日：1973-06-25

Applicant: TEXACO INC

Inventor： CHILD EDWARD T ,  ROBIN ALLEN M

IPC: C07C1/00 ,  C07C1/04 ,  C07C1/12 ,  C07C9/04 ,  C07C67/00 ,  C10K3/04 ,  C10L3/08 ,  C10J3/00

CPC classification number: C10L3/08 ,  C07C1/0485 ,  C07C1/12 ,  C10K3/04 ,  Y02P20/129 ,  C07C9/04

Abstract: Continuous process for the production of a gaseous stream comprising at least 90 mole % of methane (dry basis) from a sulfur containing hydrocarbonaceous fuel without polluting the environment including the steps of: partial oxidation of the hydrocarbonaceous fuel with air; cooling, cleaning, and purifying the process gas stream to produce a stream of feed gas comprising CO, H2 and containing N2 in the range of about 30 to 60 mole % (dry basis); two separate catalytic methanation steps with an intervening water-gas shift reaction step; and finally separating CO2 and N2 from the process gas stream to produce said methane stream. The large amount of nitrogen diluent in the reacting gas during the methanation step helps to control the normally vigorous exothermic methanation reaction. The product gas has a heating value in the range of about 900-1000 BTU/SCF. It may be used as a substitute for natural gas or as a feedstock for organic chemical synthesis.

Abstract translation: 用于生产包含至少90摩尔％的来自含硫烃类燃料的甲烷（干基）而不污染环境的气流的连续方法，包括以下步骤：用空气部分氧化烃类燃料; 冷却，清洁和净化工艺气流以产生包含CO，H 2并且含有约30至60摩尔％（干基）范围内的N 2的进料气流; 两个单独的催化甲烷化步骤，其中间的水煤气变换反应步骤; 最后从工艺气流中分离出二氧化碳和氮气以产生所述甲烷物流。 在甲烷化步骤中反应气体中的大量氮稀释剂有助于控制正常剧烈的放热甲烷化反应。 产物气体的热值在约900-1000BTU / SCF的范围内。 它可以用作天然气的替代物或用作有机化学合成的原料。

公开(公告)号：US3928000A

公开(公告)日：1975-12-23

申请号：US42947073

申请日：1973-12-28

Applicant: TEXACO INC

Inventor： CHILD EDWARD T ,  ROBIN ALLEN M ,  SLATER WILLIAM L ,  RICHTER GEORGE N

IPC: C10G9/38 ,  B01J21/00 ,  B01J23/00 ,  B01J29/00 ,  C01B3/22 ,  C01B3/36 ,  C07B61/00 ,  C07C1/00 ,  C07C1/02 ,  C07C1/04 ,  C07C9/04 ,  C07C67/00 ,  C10J3/46 ,  C10J3/06

CPC classification number: C07C1/0435 ,  C01B3/22 ,  C01B3/36 ,  C07C1/0485 ,  C07C2521/04 ,  C07C2521/08 ,  C07C2521/16 ,  C07C2523/26 ,  C07C2523/28 ,  C07C2523/30 ,  C07C2523/75 ,  C07C2523/755 ,  C07C2523/882 ,  C07C2529/04 ,  C10J3/466 ,  C10J2300/1662 ,  C10K1/10 ,  C10K3/04 ,  C10L3/08 ,  Y02A50/2327 ,  Y02P20/52 ,  C07C9/04

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.

Abstract translation: 这是一种将低成本含高含硫烃类材料转化为清洁的富甲烷气流的改进方法，可将其作为燃料燃烧而不污染大气。 高硫含烃燃料通过部分氧化气化，产生一种工艺气体流，其被冷却，清洗并经过包含0.8-10个元素的选自Co，Cr， W或其混合物，每一元素选自Mo，Ni或其混合物。 催化剂可以负载在由III族和IV族元素形成的结构上。 氧化铝，二氧化硅稳定的氧化铝，沸石。 本发明方法的显着优点是，在甲烷化步骤之前，工艺气流中的硫不被除去。 相反，允许硫保留在工艺气流中，以缓和高度放热的甲烷化反应。 在通过除去H 2，CO，H 2 O，CO 2，COS，H 2 S，Ar和N 2组中的一种或多种成分冷却和纯化后，所得富甲烷气流包含约10至95摩尔％的CH 4。 通过水煤气变换转化，催化甲烷化，冷却，干燥和二氧化碳除去的附加步骤，所述富甲烷气流的CH 4含量可增加至约98％（摩尔）或更多。 然后产品气体的总热值为约1000BTU / SCF。

公开(公告)号：US3928001A

公开(公告)日：1975-12-23

申请号：US42947173

申请日：1973-12-28

Applicant: TEXACO INC

Inventor： CHILD EDWARD T ,  ROBIN ALLEN M ,  SLATER WILLIAM L ,  RICHTER GEORGE N

IPC: C07B61/00 ,  B01J21/00 ,  B01J23/00 ,  C01B3/22 ,  C01B3/36 ,  C07C1/00 ,  C07C1/04 ,  C07C4/04 ,  C07C9/04 ,  C07C67/00 ,  C10G9/38 ,  C10J3/46 ,  C10J3/06

CPC classification number: C01B3/36 ,  C01B3/22 ,  C07C1/0485 ,  C07C2521/04 ,  C07C2523/882 ,  C10G9/00 ,  C10G9/38 ,  C07C9/04

Abstract: Improved process for the production of substantially pure methane or clean synthetic natural gas (SNG) including the steps of partial oxidation of a hydrocarbonaceous fuel feed with substantially pure oxygen to produce a process gas stream comprising principally H2, and CO and having a critical mole ratio H2/CO in the range of 1.0 to below 1.5 and preferably 1.0 to 1.3; cooling the process gas stream and separating H2O, CO2 particulate carbon and gaseous impurities therefrom, reacting together the H2 and CO in said process gas stream in a catalytic methanation zone to produce a methane-rich gas stream containing gaseous impurities selected from the group consisting primarily of H2O, and CO2, along with minor amounts of H2, CO, N2, and Ar and mixtures thereof; and removing said H2O and CO2 to produce a product gas stream comprising substantially pure methane i.e. 95 mole % or higher (dry basis). The product gas may be used as a clean substitute natural gas having a gross heating value of about 980 BTU/SCF or higher.

Abstract translation: 用于生产基本上纯的甲烷或清洁合成天然气（SNG）的改进方法，包括以基本上纯的氧气部分氧化烃类燃料进料以产生主要包含H 2和CO并且具有临界摩尔比的工艺气流 在1.0至1.5以下，优选1.0至1.3的范围内的H 2 / CO; 冷却工艺气流并从其中分离H 2 O，CO 2颗粒碳和气态杂质，使催化甲烷化区中所述工艺气流中的H 2和CO一起反应，以产生富含甲烷的气流，其中气态杂质选自主要 的H 2 O和CO 2，以及少量的H 2，CO，N 2和Ar及其混合物; 并除去所述H 2 O和CO 2以产生包含基本上纯的甲烷，即95摩尔％或更高（干基）的产物气流。 产品气体可以用作总热值约980BTU / SCF或更高的洁净的替代天然气。

公开(公告)号：US3927999A

公开(公告)日：1975-12-23

申请号：US42946973

申请日：1973-12-28

Applicant: TEXACO INC

Inventor： CHILD EDWARD T ,  ROBIN ALLEN M

IPC: C07B61/00 ,  B01J21/00 ,  B01J23/00 ,  C07C1/00 ,  C07C1/02 ,  C07C1/04 ,  C07C9/04 ,  C07C67/00 ,  C10G9/38 ,  C10J3/46 ,  C10K3/04 ,  C10J3/06

CPC classification number: C10K3/04 ,  C07C1/0485 ,  C07C2521/04 ,  C07C2523/882 ,  C07C9/04

Abstract: A methane-rich gas stream is produced by catalytic methanation of synthesis gas feed comprising H2 and CO. When the mole ratio H2/CO of the synthesis gas feed is in the range of about 0.5 to 1.15, by adjusting the mole % H2O in the synthesis gas feed to a value in the range of about 0.1 to 15., the gross heating value of the product gas may be increased to a value above that obtained with a dry substantially CO2-free methanator feed gas. This effect of adding H2O becomes more pronounced as the H2/CO ratio drops further below the maximum value of 1.13. Further, in a preferred embodiment the gross heating value of the product gas (with H2O and CO2 removed) was maximized by adjusting the mole % H2O in the synthesis gas feed to the methanator to a critical value in the range of 1.0 to 3.0 and preferably 2.0 while maintaining the H2/CO mole ratio of the synthesis gas feed at a critical value in the range of about 1 to 1.15 and preferably 1.13.

Abstract translation: 通过包含H 2和CO的合成气进料的催化甲烷化产生富甲烷气流。当合成气进料的摩尔比H 2 / CO在约0.5至1.15的范围内时，通过调节 合成气进料量在约0.1至15的范围内，产品气体的总热值可以增加到高于用干燥的基本上不含二氧化碳的甲烷反应器进料气体获得的值。 当H2 / CO比进一步低于1.13的最大值时，加入H 2 O的这种影响变得更加显着。 此外，在优选的实施方案中，通过将合成气进料中的摩尔％H 2 O调节至1.0至3.0的范围内的临界值，将产物气体（通过除去H 2 O和CO 2）的总热值最大化 2.0，同时将合成气进料的H 2 / CO摩尔比保持在约1至1.15，优选1.13的临界值。

公开(公告)号：US3927997A

公开(公告)日：1975-12-23

申请号：US42946773

申请日：1973-12-28

Applicant: TEXACO INC

Inventor： CHILD EDWARD T ,  ROBIN ALLEN M

IPC: C07B61/00 ,  B01J21/00 ,  B01J23/00 ,  C01B3/22 ,  C01B3/36 ,  C07C1/00 ,  C07C1/02 ,  C07C1/04 ,  C07C9/04 ,  C07C67/00 ,  C10G9/38 ,  C10J3/46 ,  C10J3/06

CPC classification number: C07C1/0485 ,  C01B3/22 ,  C01B3/36 ,  C07C1/0435 ,  C07C2521/04 ,  C07C2523/755 ,  C10J3/466 ,  C10J3/84 ,  C10J2300/1662 ,  C10K1/16 ,  Y02P20/52 ,  C07C9/04

Abstract: A methane-rich gas stream is produced by catalytic methanation of synthesis gas feed comprising H2 and CO. When the mole % CO in the synthesis gas feed to the methanator is greater than 10 mole %, and the mole ratio H2/CO is in the range of greater than 1.0 to 3, by adjusting the mole % CO2 in the synthesis gas feed to the methanator to a value in the range of about 0.5 to 20, and the mole ratio H2/CO2 in the range of about 2 to 60 and preferably less than 3.9 it was unexpectedly found that a product gas is produced having a gross heating value which is greater than that which is obtained from a dry CO2-free methanator feed gas.

Abstract translation: 通过包含H 2和CO的合成气进料的催化甲烷化产生富甲烷气流，当进入甲烷转化器的合成气中的摩尔％CO大于10摩尔％时，H2 / CO摩尔比在 范围大于1.0至3，通过将在甲烷器中的合成气进料中的摩尔％CO 2调节至约0.5至20的范围内，并且摩尔比H2 / CO2在约2至60范围内，以及 优选小于3.9，意外地发现产生的总热值大于从干燥的无二氧化碳的甲烷反应器进料气体获得的产品气体。

公开(公告)号：US3652454A

公开(公告)日：1972-03-28

申请号：US3652454D

申请日：1968-05-27

Applicant: TEXACO INC

Inventor： ROBIN ALLEN M ,  TASSONEY JOSEPH P

IPC: C01B3/16 ,  C01B1/08

CPC classification number: C01B3/16

Abstract: HIGH PRESSURE CONTINUOUS CATALYTIC WATER-GAS SHIFT CONVERSION PROCESS IN WHICH CO CONVERSION IS MAXIMIZED AND AN EFFLUENT GAS STREAM COMPRISING ESSENTIALLY H2 AND CO2 IS PRODUCED HAVING A SUBSTANTIALLY CONSTANT COMPOSITION AT ALL TIMES THROUGHOUT THE LIFE OF THE CATALYST. PROCESS DESIGN AND OPERATION ARE OPTIMIZED TO YIELD AN OVERALL CO CONVERSION OF ABOUT FROM 80 TO 98 MOLE PERCENT OVER A PERIOD OF TWO YEARS OR MORE ON STREAM. STEAM AND A CO CONTAINING GASEOUS FEEDSTREAM ARE REACTED IN AN ADIABATIC CATALYTIC REACTION ZONE COMPRISING ONE OR MORE FIXED BEDS OF IRON-CHROMIUM OXIDE CATALYST CONNECTED IN SERIES AND PROVIDED WITH INTERBED COOLING. THE CATALYST IS CHARACTERIZED BY ITS ACTIVITY INCREASING AS A FUNCTION OF PRESSURE OVER THE OPERATING RANGE OF ABOUT 35 TO 250 ATMOSPHERES. THIS IS CONTRARY TO THE PRESENT GENERAL IDEA THAT THE ACTIVITY OF AN IRON OXIDE SHIFT CATALYST LEVELS OUT AT ABOUT 400 P.S.I.G. THE TEMPERATURE OF THE GASES LEAVING EACH BED IS MAINTAINED IN THE RANGE OF ABOUT 30*F. TO 100*F. LESS THAN THE CORRESPONDING EQUILIBRIUM TEMPERATURE AND TO OFFSET CATALYST DEACTIVATION THE INLET AND EXIT TEMPERATURES OF THE GAS STREAM IN EACH BED IS INCREASED AS A LOGARITHMIC FUNCTION OF TIME ON STREAM.