CA1066057A - Process for the production of hydrogen, carbon monoxide and light hydrocarbon-containing gases - Google Patents
Process for the production of hydrogen, carbon monoxide and light hydrocarbon-containing gasesInfo
- Publication number
- CA1066057A CA1066057A CA231,545A CA231545A CA1066057A CA 1066057 A CA1066057 A CA 1066057A CA 231545 A CA231545 A CA 231545A CA 1066057 A CA1066057 A CA 1066057A
- Authority
- CA
- Canada
- Prior art keywords
- residue
- fuel
- stream
- cracking
- zone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
A B S T R A C T
A gas containing hydrogen, carbonmonoxide and light hydrocarbons is produced from a hydrocarbon(s)-containing fuel by introducing at least 50% of the fuel in a cracking zone for contacting the fuel with hot gas from a partial combustion process which process is fed with the residue of the cracking process and remaining fuel, if any.
A gas containing hydrogen, carbonmonoxide and light hydrocarbons is produced from a hydrocarbon(s)-containing fuel by introducing at least 50% of the fuel in a cracking zone for contacting the fuel with hot gas from a partial combustion process which process is fed with the residue of the cracking process and remaining fuel, if any.
Description
~\ ~
1~)66~57 The invention relates to a process for the production of a gas containing hydrogen, carbon monoxlde and liFht hydrocarbons from a hydrocarbon(s)-containin~ fuel by means of partial oxidation and thermal cracking.
In this specification hydrocarbon(s)-containing fuel includes mineral oils or oil fractions, tar sand, tar sand oil or shale oil. Carbon-containin~ particles, such as soot or coal, may be present in the fuel.
Partial oxidation of such fuels is carried out in a hollow reactor with air, with oxygen or with air enriched with oxygen. The pressure may vary within wide limits. Mostly, steam is added to the reaction mlxture.
Such a partial oxidation results in a stream of ~as rich in hydrogen and carbon monoxide at a temperature of at least 1200C. The gas may be used for various purposes, such as combustion, reduction, hydrogenation, synthesis. It is known in the art that the composition of the gas can be adapted to the application concerned by a proper choice of feedstock, oxidant, and process conditions and by means of one or more after-treatments or conversions.
~hermal cracking of organic material is carried out in general by supplying heat to the material in the absence of a catalyst. Partial oxidation of hydrocarbons is an exothermic process and it has already been proposed to utilize the heat content of the hot gases for the '~
1()66057 - 3 - :
endothermic thermal cracking process. In this combination cracking is carried out under hydrogenating conditions because of the direct contact of the hydrocarbons with the heat-carrier which contains free hydrogen. The invention provides a flexible process with various possibilities of optimization.
Accordingly the invention relates to a process for the production of a gas containin~ hydrogen, carbon monoxide and light hydrocarbons from a hydrocarbon(s)-containing ~uel by means of partial oxidation and thermal cracking, in which process a) 50-100% of the fuel is introduced into a cracking zone together with the hot gas as obtained accordin~
to c), resulting in a stream of gaseous products and a residue, b) the residue is separated from the gaseous products, c) the residue as obtained according to b) and the remaining fuel, if any, together with oxygen or an oxygen-containing gas are introduced into a gasification zone, resulting in a stream of hot gas.
According to this process at least 50% of the fresh fuel is introduced into the stream of hot gas.
This implies that most of the heat content of the gas is utilized and ir 100% of the~fresh fuel is introduced into the cracking zone maximum use is made of this heat at the degree of cracking concerned. Furthermore, :
.
the residence time Or the fuel in the cracking zone is of importance with respect to type of products obtained.
The introduction of the major part, up to 100%, o~ the fresh ~uel into the hot gas has the considerable advantage that up to the maximum amount of hydrocarbon material with a high H/C ratio is subjected to crackin~, leading to the maximum yield of light products of the type wanted. It does not matter in principle how much material with the lower H/C ratio is obtained as residue from the cracking zone. The residue is gasified, which process may be carried out properly with any type of fuel, irrespective of the H/C ratio. There are many degrees of freedom in this process, such as temperatures, fuel composition, residence time, fuel/oxygen ratio, fuel/steam ratio, etc., allowing a large flexibility as far as product composition and yield are concerned.
Introduction of up to 100% of the fresh fuel into the hot gas increases this flexibility because of the abundant availability of material with a high H/C ratio for the cracking process.
Introduction of the residue as obtained according to b) into the gasification zone is preferably carried out with a stream of steam. Steam is often introduced in a gasification process as referred to in this specification in order to convert soot into C0 and H2. Gases of an inert type such as N2 may be used as well.
Separation of residue and gaseous products obtained from the cracking zone may be carried out by any suitable mean Mostly the residue will consist of non-sticky particles, which may easily be separated by centrifugal forces such as exist in cyclones or bend separators.
Still more flexibility with regard to products ~ormed is obtained by recirculation to the cracking zone of part of the residue obtained according to b).
This leads to a further degree of cracking. The temperature 10at the exit of the cracking zone is 500-~00C. Without recirculation this temperature is 800-1100C. The heat aontent oP the hot gas is ~urther utilized. The product composition is ~hifted towards more cracking products and less gasification products.
15Recirculation of residue to the cracking zone may be varied within wide limits. A constraint is formed by the heat requirement in the cracking zone, dictating the minimum amount of combustible material to be fed to the gasification zone. The production of heat in the gasification zone is further dependent on the type oP oxidant used.
.
.
- The stream oP gaseous products Prom the cracking zone may be introduced into a fractionation column, ;~resulting in one or more hydrocarbon fractions and ~25~ a stream of gas. At least part of one or several of the hydrocarbon fractions may be recirculated to the .
~ cracking zone. This may be the heavier part of the ~ ~ , ' 10~6~57 products of the column, such as the residue. The final result is formation o~ hydrogen- and carbon monoxide-containing gases and li~hter hydrocarbon fractions, varying from methane and other light ones in the gas to li~uid products, such as tops and naphtha~ The fuel is fully converted.
The process is self-supporting as far as heat reauirements are concerned.
The invention will further be elucidated with the ' aid of some figures.
Figure 1 shows a flow scheme of a process according to the invention.
Fi~ure 2 shows a flow scheme of such a process with recirculation of residue in the cracking zone.
~ igure 3 shows a flow scheme of such a process combined with a fractionation column.
In figure 1 a gasification zone is indicated by 1 and a cracking zone by 2. 50-100% of the fresh fuel 3 is introduced into the cracking zone at 4 and the remaining part, if any, into the gasification zone at 5. Gaseous products and a residue leave the cracking zone 2 and are introduced into a cyclone 6 at 7. The - residue leaves the cyclone at 8 and is taken up in a device 9 into a stream of steam 10, which dispersion is introduced into the gasification zone at 11. Oxygen or an oxygen-containing gas is introduced at 12. Hot gas from the gasification zone 1 is fed to the cracking zone 2 at 13. Gaseous products leave the cyclone S at 14.
10~6C~57 In figure 2 and in fi~ure 3 corresponding elements of the schemes are correspondin~ly numbered. Addition o~ steam and separation of gaseous products and residue are not indicated in fig. 2. Part o~ the residue 15 from the cracking zone 2 is recirculated at 16 to this , zone 2. The remainder is fed to the ~asification zone 1 at 17.
In figure 3 the gasification zone 1 and the crackin~
zone 2 are combined in one vessel 18. In this example 100% of the fresh fuel 3 is introduced into the cracking zone 2 at 20, together with the residue 19 of a column 21. Column 21 is a fractionation column which is fed by the stream 14 of gaseous products from the cyclone 6. Dependin~ upon the operating conditions of the column 21 and upon the composition of' the gaseous products 14, a variety of,.liquid products may be obtai,ned. The gas 22 leavi~ the column 21 contains hydrogen and carbon monoxide and possibly nitrogen and furthermore, light hydrocarbons, like methane, ethane, propane, butane.
Liquid products may be tops 23, light naphtha 24, heavy naphtha 25 and a residue 19. In this example 100%
~ of the residue 19 is recirculated to the cracking zone
1~)66~57 The invention relates to a process for the production of a gas containing hydrogen, carbon monoxlde and liFht hydrocarbons from a hydrocarbon(s)-containin~ fuel by means of partial oxidation and thermal cracking.
In this specification hydrocarbon(s)-containing fuel includes mineral oils or oil fractions, tar sand, tar sand oil or shale oil. Carbon-containin~ particles, such as soot or coal, may be present in the fuel.
Partial oxidation of such fuels is carried out in a hollow reactor with air, with oxygen or with air enriched with oxygen. The pressure may vary within wide limits. Mostly, steam is added to the reaction mlxture.
Such a partial oxidation results in a stream of ~as rich in hydrogen and carbon monoxide at a temperature of at least 1200C. The gas may be used for various purposes, such as combustion, reduction, hydrogenation, synthesis. It is known in the art that the composition of the gas can be adapted to the application concerned by a proper choice of feedstock, oxidant, and process conditions and by means of one or more after-treatments or conversions.
~hermal cracking of organic material is carried out in general by supplying heat to the material in the absence of a catalyst. Partial oxidation of hydrocarbons is an exothermic process and it has already been proposed to utilize the heat content of the hot gases for the '~
1()66057 - 3 - :
endothermic thermal cracking process. In this combination cracking is carried out under hydrogenating conditions because of the direct contact of the hydrocarbons with the heat-carrier which contains free hydrogen. The invention provides a flexible process with various possibilities of optimization.
Accordingly the invention relates to a process for the production of a gas containin~ hydrogen, carbon monoxide and light hydrocarbons from a hydrocarbon(s)-containing ~uel by means of partial oxidation and thermal cracking, in which process a) 50-100% of the fuel is introduced into a cracking zone together with the hot gas as obtained accordin~
to c), resulting in a stream of gaseous products and a residue, b) the residue is separated from the gaseous products, c) the residue as obtained according to b) and the remaining fuel, if any, together with oxygen or an oxygen-containing gas are introduced into a gasification zone, resulting in a stream of hot gas.
According to this process at least 50% of the fresh fuel is introduced into the stream of hot gas.
This implies that most of the heat content of the gas is utilized and ir 100% of the~fresh fuel is introduced into the cracking zone maximum use is made of this heat at the degree of cracking concerned. Furthermore, :
.
the residence time Or the fuel in the cracking zone is of importance with respect to type of products obtained.
The introduction of the major part, up to 100%, o~ the fresh ~uel into the hot gas has the considerable advantage that up to the maximum amount of hydrocarbon material with a high H/C ratio is subjected to crackin~, leading to the maximum yield of light products of the type wanted. It does not matter in principle how much material with the lower H/C ratio is obtained as residue from the cracking zone. The residue is gasified, which process may be carried out properly with any type of fuel, irrespective of the H/C ratio. There are many degrees of freedom in this process, such as temperatures, fuel composition, residence time, fuel/oxygen ratio, fuel/steam ratio, etc., allowing a large flexibility as far as product composition and yield are concerned.
Introduction of up to 100% of the fresh fuel into the hot gas increases this flexibility because of the abundant availability of material with a high H/C ratio for the cracking process.
Introduction of the residue as obtained according to b) into the gasification zone is preferably carried out with a stream of steam. Steam is often introduced in a gasification process as referred to in this specification in order to convert soot into C0 and H2. Gases of an inert type such as N2 may be used as well.
Separation of residue and gaseous products obtained from the cracking zone may be carried out by any suitable mean Mostly the residue will consist of non-sticky particles, which may easily be separated by centrifugal forces such as exist in cyclones or bend separators.
Still more flexibility with regard to products ~ormed is obtained by recirculation to the cracking zone of part of the residue obtained according to b).
This leads to a further degree of cracking. The temperature 10at the exit of the cracking zone is 500-~00C. Without recirculation this temperature is 800-1100C. The heat aontent oP the hot gas is ~urther utilized. The product composition is ~hifted towards more cracking products and less gasification products.
15Recirculation of residue to the cracking zone may be varied within wide limits. A constraint is formed by the heat requirement in the cracking zone, dictating the minimum amount of combustible material to be fed to the gasification zone. The production of heat in the gasification zone is further dependent on the type oP oxidant used.
.
.
- The stream oP gaseous products Prom the cracking zone may be introduced into a fractionation column, ;~resulting in one or more hydrocarbon fractions and ~25~ a stream of gas. At least part of one or several of the hydrocarbon fractions may be recirculated to the .
~ cracking zone. This may be the heavier part of the ~ ~ , ' 10~6~57 products of the column, such as the residue. The final result is formation o~ hydrogen- and carbon monoxide-containing gases and li~hter hydrocarbon fractions, varying from methane and other light ones in the gas to li~uid products, such as tops and naphtha~ The fuel is fully converted.
The process is self-supporting as far as heat reauirements are concerned.
The invention will further be elucidated with the ' aid of some figures.
Figure 1 shows a flow scheme of a process according to the invention.
Fi~ure 2 shows a flow scheme of such a process with recirculation of residue in the cracking zone.
~ igure 3 shows a flow scheme of such a process combined with a fractionation column.
In figure 1 a gasification zone is indicated by 1 and a cracking zone by 2. 50-100% of the fresh fuel 3 is introduced into the cracking zone at 4 and the remaining part, if any, into the gasification zone at 5. Gaseous products and a residue leave the cracking zone 2 and are introduced into a cyclone 6 at 7. The - residue leaves the cyclone at 8 and is taken up in a device 9 into a stream of steam 10, which dispersion is introduced into the gasification zone at 11. Oxygen or an oxygen-containing gas is introduced at 12. Hot gas from the gasification zone 1 is fed to the cracking zone 2 at 13. Gaseous products leave the cyclone S at 14.
10~6C~57 In figure 2 and in fi~ure 3 corresponding elements of the schemes are correspondin~ly numbered. Addition o~ steam and separation of gaseous products and residue are not indicated in fig. 2. Part o~ the residue 15 from the cracking zone 2 is recirculated at 16 to this , zone 2. The remainder is fed to the ~asification zone 1 at 17.
In figure 3 the gasification zone 1 and the crackin~
zone 2 are combined in one vessel 18. In this example 100% of the fresh fuel 3 is introduced into the cracking zone 2 at 20, together with the residue 19 of a column 21. Column 21 is a fractionation column which is fed by the stream 14 of gaseous products from the cyclone 6. Dependin~ upon the operating conditions of the column 21 and upon the composition of' the gaseous products 14, a variety of,.liquid products may be obtai,ned. The gas 22 leavi~ the column 21 contains hydrogen and carbon monoxide and possibly nitrogen and furthermore, light hydrocarbons, like methane, ethane, propane, butane.
Liquid products may be tops 23, light naphtha 24, heavy naphtha 25 and a residue 19. In this example 100%
~ of the residue 19 is recirculated to the cracking zone
2.
At least part of one or more of the other fractions 25, 24 or 23 may be recirculated to the cracking zone.
-.: . . , .. , . . . . : . . . . . :
. :. . ~-- . - ~ . .
,: :: . ; :, ~ . ~. ., : .
At least part of one or more of the other fractions 25, 24 or 23 may be recirculated to the cracking zone.
-.: . . , .. , . . . . : . . . . . :
. :. . ~-- . - ~ . .
,: :: . ; :, ~ . ~. ., : .
Claims (5)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the production of gas containing hydrogen, carbon monoxide and light hydrocarbons from a hydrocarbon(s)-containing fuel by means of partial oxidation and thermal cracking, in which process a) 50-100% of the fuel is introduced into a cracking zone to-gether with the hot gas as obtained according to c), resulting in a stream of gaseous products and a residue, b) the residue is separated from the gaseous products, c) the residue as obtained according to b) and the remaining fuel, if any, together with oxygen or an oxygen-containing gas are introduced into a gasification zone, resulting in a stream of hot gas.
2. A process according to claim 1, in which process the introduction of the residue according to 1-c) is carried out with the aid of a stream of steam.
3. A process according to claim 1 or 2, in which process a part of the residue as obtained according to 1-b) is recirculated to the cracking zone.
4. A process according to claim 1 in which process the stream of gaseous products as obtained according to 1-c) is introduced into a fraction-ation column, resulting in one or more hydrocarbon fractions and a stream of gas.
5, A process according to claim 4, in which process at least part of one of several of the hydrocarbon fractions is recirculated to the cracking zone.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB36367/74A GB1518085A (en) | 1974-08-19 | 1974-08-19 | Process for the production of hydrogen carbon monoxide and light hydrocarbon-containing gases |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1066057A true CA1066057A (en) | 1979-11-13 |
Family
ID=10387507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA231,545A Expired CA1066057A (en) | 1974-08-19 | 1975-07-15 | Process for the production of hydrogen, carbon monoxide and light hydrocarbon-containing gases |
Country Status (15)
| Country | Link |
|---|---|
| JP (1) | JPS5147004A (en) |
| BE (1) | BE832379A (en) |
| BR (1) | BR7505264A (en) |
| CA (1) | CA1066057A (en) |
| CS (1) | CS186225B2 (en) |
| DD (1) | DD119813A5 (en) |
| DE (1) | DE2536724A1 (en) |
| FR (1) | FR2282465A1 (en) |
| GB (1) | GB1518085A (en) |
| IN (1) | IN142507B (en) |
| IT (1) | IT1041914B (en) |
| NL (1) | NL7509793A (en) |
| PL (1) | PL99672B1 (en) |
| SU (1) | SU578851A3 (en) |
| ZA (1) | ZA755268B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8330606D0 (en) * | 1983-11-16 | 1983-12-21 | Shell Int Research | Preparation of hydrocarbons and fuel gas |
| GB8803156D0 (en) * | 1988-02-11 | 1988-03-09 | Shell Int Research | Process for thermal cracking of residual hydrocarbon oils |
| JP4727317B2 (en) * | 2005-06-23 | 2011-07-20 | リンナイ株式会社 | container |
| RU2520482C1 (en) * | 2012-11-13 | 2014-06-27 | Федеральное государственное бюджетное учреждение "Национальный исследовательский центр "Курчатовский институт" | Method of obtaining hydrogen and hydrogen-methane mixture |
| CA2913645C (en) * | 2013-06-17 | 2018-05-01 | Praxair Technology, Inc. | Soot control in oxidation reactions |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE977343C (en) * | 1954-09-29 | 1966-01-13 | Texaco Development Corp | Process for the thermal cracking of liquid hydrocarbons |
| IT610659A (en) * | 1959-05-22 |
-
1974
- 1974-08-19 GB GB36367/74A patent/GB1518085A/en not_active Expired
-
1975
- 1975-07-15 CA CA231,545A patent/CA1066057A/en not_active Expired
- 1975-08-05 SU SU7502163102A patent/SU578851A3/en active
- 1975-08-13 BE BE1006824A patent/BE832379A/en unknown
- 1975-08-15 DD DD187885A patent/DD119813A5/xx unknown
- 1975-08-18 PL PL1975182787A patent/PL99672B1/en unknown
- 1975-08-18 IN IN1600/CAL/1975A patent/IN142507B/en unknown
- 1975-08-18 DE DE19752536724 patent/DE2536724A1/en not_active Withdrawn
- 1975-08-18 JP JP50099564A patent/JPS5147004A/en active Pending
- 1975-08-18 ZA ZA00755268A patent/ZA755268B/en unknown
- 1975-08-18 CS CS7500005650A patent/CS186225B2/en unknown
- 1975-08-18 NL NL7509793A patent/NL7509793A/en not_active Application Discontinuation
- 1975-08-18 IT IT26400/75A patent/IT1041914B/en active
- 1975-08-18 BR BR7505264*A patent/BR7505264A/en unknown
- 1975-08-18 FR FR7525499A patent/FR2282465A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| BE832379A (en) | 1976-02-13 |
| FR2282465B1 (en) | 1977-12-16 |
| BR7505264A (en) | 1976-08-03 |
| GB1518085A (en) | 1978-07-19 |
| DE2536724A1 (en) | 1976-03-04 |
| NL7509793A (en) | 1976-02-23 |
| JPS5147004A (en) | 1976-04-22 |
| FR2282465A1 (en) | 1976-03-19 |
| SU578851A3 (en) | 1977-10-30 |
| ZA755268B (en) | 1976-07-28 |
| CS186225B2 (en) | 1978-11-30 |
| AU8404175A (en) | 1977-02-24 |
| DD119813A5 (en) | 1976-05-12 |
| PL99672B1 (en) | 1978-07-31 |
| IN142507B (en) | 1977-07-23 |
| IT1041914B (en) | 1980-01-10 |
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