GB2077754A - A Process for the Preparation of Hydrocarbons - Google Patents

A Process for the Preparation of Hydrocarbons Download PDF

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GB2077754A
GB2077754A GB8116650A GB8116650A GB2077754A GB 2077754 A GB2077754 A GB 2077754A GB 8116650 A GB8116650 A GB 8116650A GB 8116650 A GB8116650 A GB 8116650A GB 2077754 A GB2077754 A GB 2077754A
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    • 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/74—Iron group metals
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
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    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/0445—Preparation; Activation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0485—Set-up of reactors or accessories; Multi-step processes
    • 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
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    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
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    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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    • C07C2521/10—Magnesium; Oxides or hydroxides thereof
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    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C07C2523/04—Alkali metals
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    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/26—Chromium
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    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
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    • C07C2523/72—Copper
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    • C07C2523/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with alkali- or alkaline earth metals or beryllium
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    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85—Chromium, molybdenum or tungsten
    • C07C2523/86—Chromium

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Syngas with a H2/CO molar ratio less than 1 is contacted in a first stage with a Fe-comprising catalyst having Fischer-Tropsch as well as CO- shift activity; a H2/CO mixture optionally separated from the first stage product and having as such or after adjusting a H2/CO molar ratio of at least 1.5 is contacted in a second stage with a Co- or Ru- comprising Fischer-Tropsch catalyst. In this way the stability of the process is improved.

Description

SPECIFICATION A Process for the Preparation of Hydrocarbons The invention relates to a process for the preparation of a hydrocarbon mixture from a mixture monoxide and hydrogen having an H2/CO molar ratio of less than 1.0, with the use of an Fe-containing bifunctional catalyst or catalyst combination possessing, in addition to activity for the conversion of an H2/CO mixture into substantially hydrocarbons, activity for the conversion of an H2/CO mixture into an H2/CO2 mixture.
In an investigation into said process by the Applicant it has been found that if the process is carried out at a certain high space velocity R, a certain high conversion C can be obtained, but that the stability of the bifunctional catalyst or catalyst combination is not entirely satisfactory. On further investigation into said process by the Applicant it has been found that this drawback can be eliminated by contacting carbon monoxide and hydrogen present in the reaction product, if desired together with other components of the reaction product, in a second stage with a cobalt- or ruthenium-containing monofunctional catalyst having activity for the conversion of an H2/CO mixture into substantially hydrocarbons, with the proviso that if the feed for the second stage has an H2/CO molar ratio of less than 1.5, water is added to said feed and that in the second stage use is made of a cobalt- or ruthenium-containing bifunctional catalyst or catalyst combination having, in addition to activity for the conversion of an H2/CO mixture into substantially hydrocarbons, activity for the conversion of an H2C/CO mixture into an H2/CO2 mixture. This process not only ensures that by the use of the abovementioned high space velocity R (now based on the total catalyst system in the first and second stage) a high conversion can be obtained without stability problems becoming manifest, but that the conversion obtained moreover has a higher value than the above-mentioned conversion C.
The present patent application therefore relates to a process for the preparation of a hydrocarbon mixture, in which a mixture of carbon monoxide and hydrogen having an H2/CO molar ratio of less than 1.0 is contacted in a first stage with an Fe-containing bifunctional catalyst or catalyst combination as defined above and which carbon monoxide and hydrogen present in the reaction product of the first stage, if desired together with other components of said reaction product, are contacted in a second stage with a cobalt- or ruthenium-containing monofunctional catalyst as defined above, with the proviso that if the feed for the second stage has an H2/CO molar ratio of less than 1.5, water is added to said feed and that in the second stage use is made of a cobalt- or ruthenium-containing bifunctional catalyst or catalyst combination as defined above.
In the process according to the invention the starting material is an H2/CO mixture having an H2/CO molar ratio of less than 1.0. Such HCO mixture can very suitably be prepared by steam gasification of a carbon-containing material. Examples of such materials are lignite, anthracite, coke, crude mineral oil and fractions thereof as well as oils produced from tarsand and bituminous shale.
Steam gasification is preferably carried out at a temperature of 900-1 5000C and a pressure of 10100 bar. In the process according to the invention the starting H2/CO mixture preferably has an H2/CO molar ratio of more than 0.25.
The Fe-containing bifunctional catalysts or catalyst combinations that are suitable for use in the first stage of the process according to the invention, should possess, in addiction to activity for the conversion of an H2/CO mixture substantially hydrocarbons, activity for the conversion of an H2/CO mixture into an HJC02 mixture. In the first stage of the process use is preferably made of a bifunctional catalyst prepared by impregnation and containing iron on a carrier.Examples of such catalysts are: (a) catalysts containing 30-75 parts by weight of iron and 5-40 parts by weight of magnesium per 100 parts by weight of alumina and prepared by impregnating an alumina carrier with one or more aqueous solutions of salts of iron and magnesium and subsequently drying the composition, calcining it at a temperature of 700-1 2000C and reducing it.Special preference is given to such catalysts containing, in addition to 40-60 parts by weight of iron and 7.5-30 parts by weight of magnesium, 0.5-5 parts by weight of copper as reduction promoter and 1-5 parts by weight of potassium as selectivity promoter per 100 parts by weight of alumina and calcined at 750-8500C and reduced at 250--350"C.
b) catalysts containing 10-40 parts by weight of iron and 0.25-10 parts by weight of chromium per 100 parts by weight of silica and prepared by impregnating a silica carrier with one or more aqueous solutions of salts of iron and of chromium followed by drying the composition, calcining it and reducing it at a temperature of 350-7500C. Special preference is given to such catalysts containing, in addition to 20-35 parts by weight of iron and 0.5-5 parts by weight of chromium, 15 parts by weight of potassium as selectivity promoter per 100 parts by weight of silica and calcined at 250--7000C and reduced at 350-5000C.
The first stage of the process according to the invention can very suitably be carried out by passing the feed in upward or downward direction through a vertically arranged reactor containing a fixed or moving bed of the Fe-containing bifunctional catalyst combination. The first stage can, for example, be carried out in fixed-bed operation, bunker-flow operation, ebullated-bed operation or fluidized-bed operation. The first stage of the operation is preferably carried out under the following conditions: a temperature of 200-3500C and in particular of 250-3500C, a pressure of 10-70 bar and in particular of 20-50 bar and a space velocity of 500-5000 and in particular of 500-2500 NI of gas/l of catalyst/h.
In the process according to the invention carbon monoxide and hydrogen present in the reaction product of the first stage are used as feed for the second stage. In addition to carbon monoxide and hydrogen, the feed for the second stage may contain other components of the reaction product of the first stage. For example, it is possible to use as feed for the second stage the C2- fraction or C4- fraction of the reaction product of the first stage and even the entire reaction product of the first stage.
In the second stage of the process according to the invention the aim is that the largest possible quantity of the carbon monoxide present in the feed for the second stage is converted into substantially hydrocarbons over a monofunctional cobalt- or ruthenium-containing catalyst having activity for this reaction. To this end the H2/CO molar ratio in the feed for the second stage must be at least 1.5 and preferably 1.75-2.25. If an H2/CO mixture with a high H2/CO molar ratio is used as feed for the first stage, it is possible in the process according to the invention to obtain a reaction product from the first stage having an H2/CO molar ratio of at least 1.5, which is suitable as such to be converted in the second stage over said catalyst.
If in the process according to the invention a reaction product having an H2/CO molar ratio of less than 1.5 is obtained from the first stage, water should be added to the feed for the second stage and a cobalt- or ruthenium-containing bifunctional catalyst or catalyst combination should be used in the second stage that has, in addition to activity for the conversion of an H2/CO mixture into substantially hydrocarbons, activity for the conversion of an H2O/CO mixture into an H2/CO2 mixture.
If in the process according to the invention the feed for the second stage has an H2/CO molar ratio of less than 1.5 a bifunctional catalyst combination consisting of two separate catalysts is preferably used in the second stage, which catalysts will for convenience be indicated as catalysts A and B.
Catalyst A is the cobalt- or ruthenium-containing catalyst having activity for the conversion of an H2/CO mixture into substantially hydrocarbons and catalyst B is the catalyst with activity for the conversion of an H2O/CO mixture into an H2/CO2 mixture. Both in the use of a monofunctional catalyst and in the use of a bifunctional catalyst combination in the second stage of the process according to the invention, as catalyst A preference is given to a cobalt catalyst and in particular to a catalyst prepared by impregnation and containing cobalt on a carrier, Very suitable for the present object are catalysts containing 10-40 parts by weight of cobalt and 0.25-5 parts by weight of zirconium, titanium or chromium and prepared by impregnating a silica carrier with one or more aqueous solutions of salts of cobalt and zirconium, titanium or chromium, followed by drying the composition, calcining it at 350-7000C and reducing it at 200-3500C. Catalysts containing copper and zinc and in which the Cu/Zn atomic ratio lies between 0.25 and 4.0 are especially eligible as catalysts B. In the cobalt or ruthenium-containing bifunctional catalyst combinations the catalyst A and B can be present as a physical mixture. When the second stage of the process is carried out with the use of a fixed catalyst bed, the bed is preferably built up of two or more alternating layers of particle of catalyst B and catalyst A, respectively.In the process according to the invention water can be added to the feed for the second stage and a bifunctional catalyst combination may be used in the second stage both in cases where the reaction product of the first stage has an H2/CO molar ratio of less than 1.5, and in cases where the reaction product of the first stage already has an H2/CO molar ratio of at least 1.5, it being desirable, however, that the feed which is contacted with catalyst A in the second stage has a higher H2/CO molar ratio.If in the process according to the invention an embodiment is chosen in which water is added to the feed for the second stage and a bifunctional catalyst combination is used in the second stage, the quantity of water required is mainly determined by the H2/CO molar ratio of the feed for the second stage, the activity of the catalyst combination for the conversion of an H2O/CO mixture into an H2/CO2 mixture and the desirable H2/CO molar ratio of the product that is contacted with catalyst A.
The second stage of the process according to the invention can very suitably be carried out by passing the feed in upward or downward direction through a vertically arranged reactor containing a fixed bed of the monofunctional catalyst or of the bifunctional catalyst or catalyst combination. The second stage of the process can also be carried out using a suspension of the catalyst or catalyst combination in a hydrocarbon oil.
The second stage of the process is preferably carried out under the following conditions: a temperature of 1 25-3500C, in particular of 1 7 5--275 OC and a pressure of 1-150 bar, in particular of5100bar.
The invention will now be illustrated with reference to the following example.
Example The following catalysts were used during the investigation: Catalyst 1 Co/Zr/SiO2 catalyst containing 25 parts by weight of cobalt and 1.8 parts by weight of zirconium per 100 parts by weight of silica and prepared by impregnating a silica carrier with an aqueous solution containing a cobalt and a zirconium salt, followed by drying the composition, calcining it at 500CC and reducing it at 2800C.
Catalyst 2 Fe/Mg/Cu/KAl2O3 catalyst containing 50 parts by weight of iron, 20 parts by weight of magnesium, 2.5 parts by weight of copper and 4 parts by weight of potassium per 100 parts by weight of alumina and prepared by impregnating an alumina carrier with an aqueous solution containing an iron, magnesium, copper and a potassium salt, followed by drying the composition, calcining it at 8000C and reducing it at 3250C.
Catalyst 3 Cu/Zn/Al203 catalyst with a Cu/Zn atomic ratio of 0.55.
Catalyst Mixture I Catalyst mixture I consisted of a layer of catalyst 3 and a layer of catalyst 1 in a volume ratio of 1 :2. The catalyst 1 and 2 and the catalyst mixture I were tested for the preparation in one or two stages of a hydrocarbon mixture from an H2/CO mixture. The test was carried out in one or two reactors of 50 ml each containing a fixed catalyst bed. Five experiments were carried out. Experiments 1 and 3 were carried out in one stage; the other experiments in two stages. In all experiments a temperature of 2800C was used in the first stage. In all experiments that were carried out in two stages the temperature was 2300C in the second stage.In all experiments the pressure was 30 bar and the space velocity based on the total catalyst system was 1000 Nl.l-1.h-1. In the experiments 2 and 5 the total reaction product from the first stage was used as feed for the second stage. In experiment 4 the C4 fraction of the product from the first stage was used as feed for the second stage. The results of the experiments are stated in the Table.
Table Experiment No. 1 2 3 4 5 Catalyst No. in first stage 2 2 2 2 2 Quantity of catalyst in first stage, ml 10 5 10 5 7 HdCO molar ratio of feed for first stage 0.5 0.5 0.8 0.8 0.8 H2/CO molar ratio of product from first stage after 250 run hours 0.06 0.41 9 1.3 2.2 after 3,000 run hours 0.32 0.44 1.75 1.11 1.73 Number of catalyst or catalyst I I 1 mixture in second stage Quantity of catalyst in second stage, ml - 5 - 5 3 Quantity of water added to feed for second stage, ml (I of catalyst)-'.h-' after 250 run hours - 241 - 66 after 3,000 run hours - 244 - 114 Conversion of the synthesis gas, % after 250 run hours 90 96 85 96 97 after 3,000 run hours 75 93 70 92 95 Of the experiments stated in the table only the two-stage experiments 2, 4 and 5 are in accordance with the invention. The one-stage experiments 1 and 3 fall outside the scope of the invention. For comparison they have been included in the patent application.
The advantages of the two-stage process according to the invention in respect of conversion of the H2/CO mixture and stability of the Fe-containing bifunctional catalyst are evident on comparing the results of: experiment 2 with that of experiment 1, and experiments 4 and 5 with that of experiment 3.

Claims (10)

Claims
1. A process for the preparation of a hydrocarbon mixture, characterized in that a mixture of carbon monoxide and hydrogen having an H2/CO molar ratio of less than 1.0 is contacted in a first stage with an Fe-containing bifunctional catalyst or catalyst combination having, in addition to activity for the conversion of an HCO mixture into substantially hydrocarbons, activity for the conversion of an H20/CO mixture into an H2/CO2 mixture and that carbon monoxide and hydrogen present in the reaction product of first stage, if desired together with other components of said reaction product, are contacted in a second stage with a cobalt or ruthenium-containing monofunctional catalyst having activity for the conversion of an H2/CO mixture into substantially hydrocarbons, with the proviso that if the feed for the second stage has an H2/CO molar ratio of less than 1.5, water is added to said feed and that in the second stage use is made of a cobalt- or ruthenium-containing bifunctional catalyst or catalyst combination having, in addition to activity for the conversion of an H2/CO mixture into substantially hydrocarbons, activity for the conversion of an H20/CO mixture in an H2/CO2 mixture.
2. A process as claimed in claim 1, characterized in that the H2/CO mixture used as feed for the first stage has an H2/CO molar ratio of more than 0.25.
3. A process as claimed in claim 1 or 2, characterized in that a catalyst is used containing 3075 parts by weight of iron and 5-40 parts by weight of magnesium per 100 parts by weight of alumina and prepared by impregnating an alumina carrier with one or more aqueous solutions of salts of iron and magnesium followed by drying the composition, calcining it at a temperature of 700 1200C and reducing it.
4. A process as claimed in claim 3, characterized in that a catalyst is used containing, in addition to 40-60 parts by weight of iron and 7.5-30 parts by weight of magnesium, 0.5-5 parts by weight of copper as reduction promoter and 1-5 parts by weight of potassium as selectivity promoter per 100 parts by weight of alumina and calcined at 750-8500C and reduced at 250--3500C.
5. A process as claimed in claim 1 or 2, characterized in that a catalyst is used containing 1040 parts by weight of iron and 0.25-10 parts by weight of chromium per 100 parts by weight of silica and prepared by impregnating a silica carrier with one or more aqueous solutions of salts of iron and chromium followed by drying the composition, calcining it and reducing it at a temperature of 350 750"C.
6. A process as claimed in claim 5, characterized in that a catalyst is used containing in addition to 20-35 parts by weight of iron and 0.5-5 parts by weight of chromium, 1-5 parts by weight of potassium as selectivity promoter per 100 parts by weight of silica and calcined at 350-7000C and reduced at 350-5000C.
7. A process as claimed in any one of claims 1-6, characterized in that as catalyst with activity for the conversion of an HaCO mixture into substantially hydrocarbons that is used in the second stage of the process, use is made of a catalyst prepared by impregnation and containing cobalt on a carrier.
8. A process as claimed in claim 7, characterized in that a catalyst is used containing 10-40 parts by weight of cobalt and 0.25-5 parts by weight of zirconium, titanium or chromium per 100 parts by weight of silica and prepared by impregnating a silica carrier with one or more aqueous solutions of salts of cobalt and/or zirconium, titanium or chromium, followed by drying the composition, calcining it at 350-7000C and reducing it at 200-3500C.
9. A process as claimed in any one of claims 1-8, characterized in that water is added to the feed for the second stage and that in the second stage of bifunctional catalyst combination is used consisting of two separate catalysts A and B, catalyst A having activity for the conversion of an H2/CO mixture into substantially hydrocarbons and catalyst B having activity for the conversion of an H20/CO mixture into an H2/CO mixture.
10. A process as claimed in claim 9, characterized in that the second stage is carried out with the use of a fixed catalyst bed consisting of two or more alternating layers of particles of catalyst B and catalyst A respectively.
GB8116650A 1980-06-03 1981-06-01 A process for the preparation of hydrocarbons Expired GB2077754B (en)

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NL8003215A NL8003215A (en) 1980-06-03 1980-06-03 PROCESS FOR PREPARING HYDROCARBONS.

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AU (1) AU539212B2 (en)
BE (1) BE888922A (en)
BR (1) BR8103445A (en)
CA (1) CA1152535A (en)
DE (1) DE3121752A1 (en)
ES (1) ES502652A0 (en)
FR (1) FR2483400A1 (en)
GB (1) GB2077754B (en)
IN (1) IN154191B (en)
IT (1) IT1136783B (en)
NL (1) NL8003215A (en)
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ZA (1) ZA813658B (en)

Cited By (14)

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Publication number Priority date Publication date Assignee Title
EP0099715A1 (en) * 1982-07-14 1984-02-01 The British Petroleum Company p.l.c. Catalyst composition, method for its production and its use in the production of hydrocarbons from synthesis gas
GB2130601A (en) * 1982-11-22 1984-06-06 Shell Int Research Preparation of hydrocarbons
EP0142887A2 (en) * 1983-11-15 1985-05-29 Shell Internationale Researchmaatschappij B.V. Process for the preparation of hydrocarbons
EP0142888A2 (en) * 1983-11-15 1985-05-29 Shell Internationale Researchmaatschappij B.V. Process for the preparation of hydrocarbons
GB2154601A (en) * 1984-02-28 1985-09-11 Shell Int Research Process for the preparation of hydrocarbons
US4556645A (en) * 1984-06-27 1985-12-03 Union Carbide Corporation Enhanced catalyst for conversion of syngas to liquid motor fuels
US4579830A (en) * 1984-06-27 1986-04-01 Union Carbide Corporation Enhanced catalyst for converting synthesis gas to liquid motor fuels
US4617320A (en) * 1984-06-27 1986-10-14 Union Carbide Corporation Enhanced conversion of syngas to liquid motor fuels
US4617283A (en) * 1984-06-27 1986-10-14 Union Carbide Corporation Catalyst for converting synthesis gas to liquid motor fuels
US4632941A (en) * 1984-06-27 1986-12-30 Union Carbide Corporation Enhanced catalyst and process for converting synthesis gas to liquid motor fuels
US4663355A (en) * 1984-06-27 1987-05-05 Union Carbide Corporation Catalyst and process for converting synthesis gas to liquid motor fuels
GB2243616A (en) * 1990-05-04 1991-11-06 Shell Int Research Preparation of paraffinic and aromatic hydrocarbons
WO2001064607A2 (en) * 2000-02-29 2001-09-07 Chevron U.S.A. Inc. Increased liquid sensitivity during fischer-tropsch synthesis by olefin incorporation
WO2004052535A1 (en) * 2002-12-06 2004-06-24 Dow Global Technologies Inc. Dehydrogenation catalyst and process for preparing the same

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL8006484A (en) * 1980-11-28 1982-06-16 Shell Int Research PROCESS FOR PREPARING HYDROCARBONS.
NL8006751A (en) * 1980-12-12 1982-07-01 Shell Int Research PROCESS FOR PREPARING OXYGEN-BASED ORGANIC COMPOUNDS AND PARAFFINIC HYDROCARBONS.
GB8330606D0 (en) * 1983-11-16 1983-12-21 Shell Int Research Preparation of hydrocarbons and fuel gas
CA1236454A (en) * 1984-06-27 1988-05-10 John J. Tsai Monomeric cationic glycoside derivatives

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Publication number Priority date Publication date Assignee Title
NL7704658A (en) * 1977-04-28 1978-10-31 Shell Int Research PROCESS FOR THE PREPARATION OF HYDROCARBONS.
NL190603C (en) * 1979-07-13 1994-05-16 Shell Int Research Process for the preparation of iron-chromium catalysts and their use for the preparation of hydrocarbons.
NL184214C (en) * 1979-08-06 1989-05-16 Shell Int Research PROCESS FOR THE PREPARATION OF A HYDROCARBON MIXTURE FROM A MIXTURE CONTAINING CARBON MONOXIDE AND HYDROGEN WITH ONE HŸ2/CO MOL. CONTAINS LESS THAN 1.0 RATIO.

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0099715A1 (en) * 1982-07-14 1984-02-01 The British Petroleum Company p.l.c. Catalyst composition, method for its production and its use in the production of hydrocarbons from synthesis gas
GB2130601A (en) * 1982-11-22 1984-06-06 Shell Int Research Preparation of hydrocarbons
EP0142888A3 (en) * 1983-11-15 1986-04-30 Shell Internationale Research Maatschappij B.V. Process for the preparation of hydrocarbons
EP0142887A2 (en) * 1983-11-15 1985-05-29 Shell Internationale Researchmaatschappij B.V. Process for the preparation of hydrocarbons
EP0142888A2 (en) * 1983-11-15 1985-05-29 Shell Internationale Researchmaatschappij B.V. Process for the preparation of hydrocarbons
EP0142887A3 (en) * 1983-11-15 1986-04-30 Shell Internationale Research Maatschappij B.V. Process for the preparation of hydrocarbons
GB2154601A (en) * 1984-02-28 1985-09-11 Shell Int Research Process for the preparation of hydrocarbons
US4579830A (en) * 1984-06-27 1986-04-01 Union Carbide Corporation Enhanced catalyst for converting synthesis gas to liquid motor fuels
US4556645A (en) * 1984-06-27 1985-12-03 Union Carbide Corporation Enhanced catalyst for conversion of syngas to liquid motor fuels
US4617320A (en) * 1984-06-27 1986-10-14 Union Carbide Corporation Enhanced conversion of syngas to liquid motor fuels
US4617283A (en) * 1984-06-27 1986-10-14 Union Carbide Corporation Catalyst for converting synthesis gas to liquid motor fuels
US4632941A (en) * 1984-06-27 1986-12-30 Union Carbide Corporation Enhanced catalyst and process for converting synthesis gas to liquid motor fuels
US4663355A (en) * 1984-06-27 1987-05-05 Union Carbide Corporation Catalyst and process for converting synthesis gas to liquid motor fuels
GB2243616A (en) * 1990-05-04 1991-11-06 Shell Int Research Preparation of paraffinic and aromatic hydrocarbons
WO2001064607A2 (en) * 2000-02-29 2001-09-07 Chevron U.S.A. Inc. Increased liquid sensitivity during fischer-tropsch synthesis by olefin incorporation
NL1017458C2 (en) * 2000-02-29 2002-02-19 Chevron Usa Inc Increased fluid sensitivity during Fisher-Tropsch synthesis by incorporating olefins.
WO2001064607A3 (en) * 2000-02-29 2002-03-07 Chevron Usa Inc Increased liquid sensitivity during fischer-tropsch synthesis by olefin incorporation
AU780374B2 (en) * 2000-02-29 2005-03-17 Chevron U.S.A. Inc. Increased liquid sensitivity during Fischer-Tropsch synthesis by olefin incorporation
WO2004052535A1 (en) * 2002-12-06 2004-06-24 Dow Global Technologies Inc. Dehydrogenation catalyst and process for preparing the same

Also Published As

Publication number Publication date
IN154191B (en) 1984-09-29
BE888922A (en) 1981-11-23
NL8003215A (en) 1982-01-04
JPS5724314A (en) 1982-02-08
FR2483400B1 (en) 1985-05-03
IT8122074A0 (en) 1981-06-01
ES8303269A1 (en) 1983-02-01
BR8103445A (en) 1982-02-24
AU7121181A (en) 1981-12-10
DE3121752A1 (en) 1982-01-28
AT371793B (en) 1983-07-25
FR2483400A1 (en) 1981-12-04
DE3121752C2 (en) 1989-06-01
NZ197260A (en) 1983-11-18
CA1152535A (en) 1983-08-23
ES502652A0 (en) 1983-02-01
ATA243881A (en) 1982-12-15
SE8103437L (en) 1981-12-04
AU539212B2 (en) 1984-09-13
GB2077754B (en) 1983-06-02
ZA813658B (en) 1982-06-30
SE446971B (en) 1986-10-20
IT1136783B (en) 1986-09-03

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