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WO1993005000A1 - Catalyseur du type fischer-tropsch comprenant du cobalt et du scandium - Google Patents

Catalyseur du type fischer-tropsch comprenant du cobalt et du scandium Download PDF

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Publication number
WO1993005000A1
WO1993005000A1 PCT/AU1992/000457 AU9200457W WO9305000A1 WO 1993005000 A1 WO1993005000 A1 WO 1993005000A1 AU 9200457 W AU9200457 W AU 9200457W WO 9305000 A1 WO9305000 A1 WO 9305000A1
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Prior art keywords
fischer
catalyst
cobalt
tropsch
scandium
Prior art date
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Ceased
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PCT/AU1992/000457
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English (en)
Inventor
Sandra Bessell
Alan Loyd Chaffee
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Broken Hill Proprietary Company Pty Ltd
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Broken Hill Proprietary Company Pty Ltd
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Filing date
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Publication of WO1993005000A1 publication Critical patent/WO1993005000A1/fr
Priority to GB9403713A priority Critical patent/GB2274606A/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • B01J29/072—Iron group metals or copper
    • 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
    • C07C1/0425—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
    • 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
    • C10G2/334—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 molecular sieve catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/10—Magnesium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/12—Silica and alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/16—Clays or other mineral silicates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/12—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of actinides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • 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
    • C07C2523/32—Manganese, technetium or rhenium
    • C07C2523/34—Manganese
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/75—Cobalt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • 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
    • C07C2523/83—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 rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • C07C2529/072—Iron group metals or copper

Definitions

  • the invention relates to catalyst compositions for use in the Fischer-Tropsch process for the conversion of synthesis gas into hydrocarbons, and an improved process using these catalyst compositions. It is particularly aimed at Fischer-Tropsch processes which produce higher hydrocarbons including waxes and hydrocarbons suitable for use as liquid fuels from a natural gas derived synthesis gas.
  • Nickel although one of the most active metals for carbon monoxide hydrogenation, is not preferred for hydrocarbon production because of its high methane (rather than higher hydrocarbon)selectivity. Ruthenium could not be used in any great capacity because of its high cost and limited availability.
  • Activity - Cobalt catalysts are more active than iron catalysts and thus require lower temperatures to reach similar levels of conversion
  • Selectivity - Cobalt catalysts have a greater selectivity to higher hydrocarbons than iron catalysts.
  • hydrocarbon product produced by cobalt catalysts is somewhat dependent on the nature of their support materials, and to a lesser extent operating conditions.
  • zeolite supports such as Zeolite Y and ZSM-5, are used to produce a product which has enhanced levels of aromatics and/or branched hydrocarbons, and thus a high octane rating.
  • US Patent 4086262 (Mobil Oil Corporation) describes the use of zeolites such as ZSM-5 as supports for Fischer-Tropsch metals including iron, cobalt, nickel, ruthenium, thorium and osmium, to produce an aromatic rich product from synthesis gas.
  • Australian Patent Application AU 34883/84 (Union Carbide Corp.) describes the use of catalyst compositions consisting of steam-stabilized Zeolite Y as a catalyst support for conventional Fischer-Tropsch metals such as iron or cobalt. These compositions enhanced branching and aromatisation in the products, as well as the amount of product boiling in the liquid fuel range.
  • Australian Patent Application AU 88929/82 (U.S. Department of Energy) describes a catalyst composition of cobalt, promoted with thoria, on a ZSM-5 type zeolite support to produce high octane liquid hydrocarbon products that are in the gasoline boiling range, but contains branched aliphatic hydrocarbons rather than aromatics to impart high octane numbers.
  • zeolite supported cobalt catalysts When production of both gasoline and distillate is targeted zeolite supported cobalt catalysts can be operated under conditions which produce a naphtha fraction with enhanced branching over that of the corresponding distillate fraction, as described in our Australian Patent Application AU 26671/88.
  • promoter(s) are often used in cobalt catalyst formulations to increase catalyst activity and to reduce methane selectivity (and subsequently increase higher hydrocarbon selectivity) .
  • the use of thoria, magnesia and manganese as such promoters for cobalt Fischer-Tropsch catalysts is well known, and has been described in Storch et al.
  • Shell Internationale have a series of Australian patent Applications including AU 28815/84, 39160/85, 41617/85, 44575/85 and 52402/86, describing improved cobalt Fischer-Tropsch catalysts, supported on silica, alumina, or silica-alumina, promoted by at least one of the group consisting of zirconium, titanium and chromium.
  • Rhenium has also been found to improve the activity of alumina supported cobalt Fischer-Tropsch catalysts by Den Norske Stats Oljeselskap in International Patent Application WO 89/03725. They have also described the use of platinum, iridium and rhodium to have a similar effect on alumina supported cobalt catalysts in International Patent Application WO 90/07377. For any true commercial operation, activity and selectivity must be maximised. A high selectivity to desired products minimises unwanted by-products, whilst increasing catalyst activity will minimise the amount of unconverted gas either wasted in a once through operation, or the amount of gas recycled in a more complex plant.
  • the present invention provides a Fischer-Tropsch catalyst comprising cobalt scandium and a suitable support.
  • the invention provides a process for converting synthesis gas into hydrocarbons which process comprises contacting synthesis gas with a catalyst comprising cobalt, scandium and a suitable support.
  • the synthesis gas for conversion comprises substantial proportions of carbon monoxide and hydrogen, but may also contain carbon dioxide, water, methane and nitrogen. It may be obtained from carbonaceous sources such as natural gas, coal, oil shale and petroleum hydrocarbons by known processes such as partial oxidation, gasification and steam reforming. The relative concentrations of the gaseous components depend on the source of the synthesis gas and the process by which it is obtained. Hydrogen to carbon monoxide molar ratios of these synthesis gases for conversion are in the range of 0.2 to 6.
  • the invention is concerned with increasing the activity and higher hydrocarbon production of supported cobalt Fischer-Tropsch catalysts.
  • cobalt is an essential part of the catalyst composition, and is present in an amount of 1 to 50 weight percent based on the total weight of the catalyst composition.
  • the choice of the support is dependent upon the type of product targeted. When distillate or wax production is targeted, supports such as kieselguhr, silica, alumina, and silica-alumina can be used. When gasoline or gasoline and distillate is to be produced, acidic molecular sieve materials such as zeolites should be used as supports.
  • the support preferably comprises from 10 to 98 weight percent of the total weight of catalyst.
  • thoria and/or other materials such as magnesia and manganese can be used as promoters for cobalt Fischer- Tropsch catalysts in order to improve catalyst activity and selectivity.
  • scandium addition was found to be beneficial to both these promoted and unpromoted catalysts, the presence of these promoter materials is optional, but preferred.
  • Thoria and/or other promoters can be present in an amount of from 0.01 to 25 weight percent, more preferably between 0.05 and 5 weight percent.
  • Scandium is used as an additive to the above described catalyst formulation to achieve the enhanced catalyst activity and higher hydrocarbon production.
  • scandium is preferably present in an amount of from 0.01 to 25 weight percent based on the total weight of the catalyst composition, more preferably between 0.05 and 5 weight percent.
  • the cobalt, promoter and scandium may be loaded onto the support by any of the methods known to those skilled in the art. These methods include:
  • the catalyst of the invention is normally reduced or activated.
  • hydrogen, synthesis gas or another reductant may be used for this reduction step under conditions of elevated temperature and pressures of from atmospheric to the pressures used in the synthesis.
  • Typical reduction temperatures are of the order of 250-300°C, with typical pressures of from atmospheric to 3.5 MPa.
  • the Fischer-Tropsch process can be performed over a wide range of temperatures, pressures and space velocities.
  • the temperature used is dependent upon the required product. Large proportions of waxes are produced at low temperatures (150-230°C), distillates at moderate temperatures (200-260°C) , and gasolines at high temperatures (230-300°C) .
  • Typical pressures used in the synthesis are of the order of from 0 to 5 MPa, usually from 1 to 3.5 MPa, whilst typical space velocities are at GHSV's of the order of from 10 to 10000 hr "1 , usually from 50 to 5000 hr "1 .
  • Example 1 Preparation of Zeolite MA21 (ZSM-5)
  • a solution of 199 g of 40% tetraethylammonium hydroxide and 186 g of Ludox" HS40 (40% silica) in 91 g of water was mixed with a solution of 3.85 g A1(N0 3 ) 3 .9H 2 0 in 99 g of water, and placed in an autoclave maintained at 170°C for 6 days. The resulting product was filtered, washed and dried.
  • the zeolites of Examples 1 to 3 were examined by X-ray diffraction and were found to display the typical X- ray diffraction patterns of ZSM-5, ZSM-11 and ZSM-12, respectively.
  • the ZSM-5 zeolite MA21 was impregnated with appropriate amounts of cobalt carbonyl and scandium and/or thorium nitrates (where appropriate) dissolved in dimethyl ether, so as to make the desired catalyst formulations .
  • the solvent was evaporated from the catalyst in a rotary evaporator, and the catalyst calcined at 500°C for approximately four hours.
  • the resulting catalysts, identified by their "FT" code names, and their desired compositions in parts by weight were as follows: 5. FT672 75 Co:1000 MA21
  • the impregnated zeolites were stirred under vacuum for 30 minutes, dried in a microwave oven, and then calcined at 500°C for approximately 4 hours.
  • the resulting catalysts identified by their "FT" code names, and their desired compositions in parts by weights were as follows:
  • the catalysts Example Nos. 5 to 18 were then pressed, ground and sieved, and size fractions between 1mm- 2mm were charged to a microreactor for testing. Prior to use, the catalysts were reduced in a stream of hydrogen at atmospheric pressure at 250°C with a GHSV of 5000 hr "1 for 16 hours. Each catalyst was used to convert a synthesis gas with a 2:1 hydrogen to carbon monoxide molar ratio. Reaction conditions were a temperature of 240°C, a pressure of 2 MPa and a GHSV of 1000 hr *1 .
  • the catalysts were run under these conditions for five days, and Table 1 summarises the average carbon monoxide conversion levels (averaged after 30 hours on line) , the product selectivities obtained, and the higher hydrocarbon production rates for each.
  • the carbon selectivities quoted represent the weight percentages of carbon from the carbon monoxide feed which have been converted into methane, carbon dioxide, and hydrocarbons containing more than two carbons.
  • the C 2 + production represents the mg of carbon from the carbon monoxide feed which ends up as hydrocarbons with two or more carbon per g of catalyst per hour of running time (averaged over the whole run) . It is assumed that of the carbon converted, that which is not converted to methane or carbon dioxide is converted to higher hydrocarbons, i.e. no carbon is deposited on the catalyst, etc.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La spécification décrit un catalyseur du type Fischer-Tropsch qui comprend du cobalt, du scandium et un support adéquat. La spécification décrit également un procédé de production d'hydrocarbures par contact d'un gaz de synthèse avec le catalyseur Fischer-Tropsch. Les supports adéquats comprennent la silice, l'alumine, l'aluminate de silice et le kieselguhr si le produit requis est une cire ou un produit de distillation. Alternativement le support peut être un matériau tamisé moléculaire acide tel qu'une zéolite si une gazoline ou un produit de distillation et une gazoline est/sont requis.
PCT/AU1992/000457 1991-08-28 1992-08-28 Catalyseur du type fischer-tropsch comprenant du cobalt et du scandium Ceased WO1993005000A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB9403713A GB2274606A (en) 1991-08-28 1994-02-25 Fischer tropsch catalyst comprising cobalt and scandium

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPK7995 1991-08-28
AUPK799591 1991-08-28

Publications (1)

Publication Number Publication Date
WO1993005000A1 true WO1993005000A1 (fr) 1993-03-18

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PCT/AU1992/000457 Ceased WO1993005000A1 (fr) 1991-08-28 1992-08-28 Catalyseur du type fischer-tropsch comprenant du cobalt et du scandium

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CA (1) CA2116558A1 (fr)
GB (1) GB2274606A (fr)
NZ (1) NZ244132A (fr)
WO (1) WO1993005000A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997000231A1 (fr) * 1995-06-16 1997-01-03 Shell Internationale Research Maatschappij B.V. Catalyseur et procede de preparation d'hydrocarbures
WO1999000190A1 (fr) * 1997-06-26 1999-01-07 Agip Petroli S.P.A. Procede pour la preparation d'un catalyseur a base de cobalt et de scandium
RU2484897C1 (ru) * 2011-04-02 2013-06-20 Ваньхуа Индастриал Груп Ко., Лтд Высокоселективный катализатор для производства фракций высококачественного бензина из синтез-газа и способ его изготовления
WO2015080611A1 (fr) 2013-11-26 2015-06-04 Infra XTL Technology Limited Catalyseur pour diriger la production d'huile synthétique riche en isoparaffines et procédé de préparation du catalyseur

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3888792A (en) * 1970-06-26 1975-06-10 African Explosives & Chem Catalyst of cobalt oxide and a rare earth metal oxide and its method of preparation
US4338089A (en) * 1979-08-06 1982-07-06 Shell Oil Company Process for preparation of hydrocarbons
AU4379385A (en) * 1984-07-30 1986-02-06 Shell Internationale Research Maatschappij B.V. Converions of synthesis gas to diesel fuel in controlled particle size fluid system
AU3637784A (en) * 1983-12-07 1986-06-12 Compagnie Francaise De Raffinage Catalyst of iron or cobalt with zeolite
US4880763A (en) * 1987-10-23 1989-11-14 Den Norske Stats Olijeselskap A.S. Catalyst for production of hydrocarbons
WO1990007377A1 (fr) * 1988-12-28 1990-07-12 Den Norske Stats Oljeselskap A.S Catalyseur soutenu servant a la synthese d'hydrocarbures
DE3935112A1 (de) * 1989-10-21 1991-04-25 Basf Ag Verfahren zur herstellung von aminen
AU8965191A (en) * 1990-12-18 1992-06-25 Tosoh Corporation Catalyst for purifying exhaust gas

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3888792A (en) * 1970-06-26 1975-06-10 African Explosives & Chem Catalyst of cobalt oxide and a rare earth metal oxide and its method of preparation
US4338089A (en) * 1979-08-06 1982-07-06 Shell Oil Company Process for preparation of hydrocarbons
AU3637784A (en) * 1983-12-07 1986-06-12 Compagnie Francaise De Raffinage Catalyst of iron or cobalt with zeolite
AU4379385A (en) * 1984-07-30 1986-02-06 Shell Internationale Research Maatschappij B.V. Converions of synthesis gas to diesel fuel in controlled particle size fluid system
US4880763A (en) * 1987-10-23 1989-11-14 Den Norske Stats Olijeselskap A.S. Catalyst for production of hydrocarbons
WO1990007377A1 (fr) * 1988-12-28 1990-07-12 Den Norske Stats Oljeselskap A.S Catalyseur soutenu servant a la synthese d'hydrocarbures
DE3935112A1 (de) * 1989-10-21 1991-04-25 Basf Ag Verfahren zur herstellung von aminen
AU8965191A (en) * 1990-12-18 1992-06-25 Tosoh Corporation Catalyst for purifying exhaust gas

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997000231A1 (fr) * 1995-06-16 1997-01-03 Shell Internationale Research Maatschappij B.V. Catalyseur et procede de preparation d'hydrocarbures
WO1999000190A1 (fr) * 1997-06-26 1999-01-07 Agip Petroli S.P.A. Procede pour la preparation d'un catalyseur a base de cobalt et de scandium
US6096790A (en) * 1997-06-26 2000-08-01 Agip Petroli S.P.A. Process for the preparation of a catalyst based on cobalt and scandium
CN1128012C (zh) * 1997-06-26 2003-11-19 阿吉佩罗里股份公司 以钴和钪为基的催化剂的制备方法
RU2484897C1 (ru) * 2011-04-02 2013-06-20 Ваньхуа Индастриал Груп Ко., Лтд Высокоселективный катализатор для производства фракций высококачественного бензина из синтез-газа и способ его изготовления
WO2015080611A1 (fr) 2013-11-26 2015-06-04 Infra XTL Technology Limited Catalyseur pour diriger la production d'huile synthétique riche en isoparaffines et procédé de préparation du catalyseur

Also Published As

Publication number Publication date
GB2274606A (en) 1994-08-03
CA2116558A1 (fr) 1993-03-18
GB9403713D0 (en) 1994-05-11
NZ244132A (en) 1993-12-23

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