WO1986001499A1 - Catalyseur fischer-tropsch - Google Patents

Catalyseur fischer-tropsch Download PDF

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Publication number
WO1986001499A1
WO1986001499A1 PCT/GB1985/000378 GB8500378W WO8601499A1 WO 1986001499 A1 WO1986001499 A1 WO 1986001499A1 GB 8500378 W GB8500378 W GB 8500378W WO 8601499 A1 WO8601499 A1 WO 8601499A1
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WO
WIPO (PCT)
Prior art keywords
carbon
catalyst
surface area
fischer
bet
Prior art date
Application number
PCT/GB1985/000378
Other languages
English (en)
Inventor
Alan Ivor Foster
Richard William Joyner
John James Mccarroll
Stephen Roy Partington
Ranald Gordon Lyon Spiers
Stephen Robert Tennison
Original Assignee
The British Petroleum Company P.L.C.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by The British Petroleum Company P.L.C. filed Critical The British Petroleum Company P.L.C.
Publication of WO1986001499A1 publication Critical patent/WO1986001499A1/fr

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    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • B01J23/74—Iron group metals
    • 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
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • 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
    • 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
    • C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • C07C2521/18—Carbon
    • 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
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • 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
    • C07C2523/42—Platinum
    • 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
    • C07C2523/745—Iron
    • 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
    • C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals

Definitions

  • the present invention relates to catalysts suitable for use in the Fischer-Tropsch process, and to a Fischer-Tropsch process carried out using the catalysts.
  • GB 1565 074 discloses a catalyst for ammonia synthesis on a graphitised carbon support of defined BET/basal plane and basal plane/edge surface area ratios. There is nothing to suggest that this support would offer any advantages in the different Fischer-Tropsch reaction.
  • a Fischer-Tropsch catalyst comprising cobalt or iron on a support
  • the support is a carbon having a BET surface area of at least 100m 2 /g, a ratio of BET to basal plane surface area not greater than 4:1, and a ratio of basal plane surface area to edge surface area of at least
  • Carbons may be characterised by their BET, basal plane, and edge surface areas.
  • the BET surface area is the surface area determined by nitrogen adsorption using the method of Brunauer
  • the basal plane surface area is the surface area determined from the heat of adsorption on the carbon of n-dotriacontane from n-heptane by the method described In Proc.Roy.Soc. A314 pages 473-498, with particular reference to page 489.
  • the edge surface area is the surface area determined from the heat of adsorption on the carbon of n-butanol from n-heptane as disclosed in the Proc.Roy.Soc. article mentioned above with particular reference to page 495.
  • the carbon supports are known, for example from-GB 1 565 074.
  • the catalysts of the present invention behave in a completely different manner from the catalysts of GB 1565 074.
  • the catalysts of GB 1 565 074 have their activity increased by the presence of alkali metals, and the presence of chloride ion is stated to be undesirable.
  • the catalysts of the present invention have their activity destroyed by the presence of excess alkali metals.
  • the catalyst additionally comprises a platinum or palladium, preferably platinum itself.
  • the platinum group metal is conveniently deposited by
  • Impregnation with an aqueous solution of a compound of a platinum group which Is reducible to give the metal Impregnation with an aqueous solution of a compound of a platinum group which Is reducible to give the metal.
  • the platinum group metal may for example be deposited on the carbon support before the cobalt or iron. It may be preferred to carry out a reduction step to leave the metal before the deposition of the cobalt or iron, particularly if the compound used to deposit the platinum group metal leaves components which interfere with reduction of the iron or cobalt.
  • the quantity of platinum group metal on the catalyst may for example be in the range 0.2 to 10% by weight of total catalyst, preferably 0.5 to 5% by weight.
  • the quantity of iron or cobalt deposited on the catalyst may be In the range 5 to 100% wt based on weight of carbon.
  • the catalyst may be prepared by Impregnation with an aqueous solution of a salt of cobalt or Iron.
  • suitable salts are nitrates.
  • the preferred carbons for use in the present invention have a BET surface area of at least 200 m 2 /g,most preferable at least 300 m 2 /g.
  • the BET surface area is preferably not greater than 1000 m 2 /g, more preferably not greater than 750 m 2 /g.
  • the ratio of BET to basal plane surface area is preferably not greater than 2.5:1. It is particularly preferred to use carbons with ratios of BET to basal plane surface area of not greater than 1.5:1. It is preferred to use carbons with ratios of basal plane surface area to edge surface area of at least 100:1. It is not believed that there is an upper limit on the ratio, although in practice it will not usually exceed 200:1.
  • the preferred carbon support may be prepared by heat treating a carbon-containing starting material.
  • the starting material may be an oleophilic graphite e.g. prepared as disclosed in GB 1 168 785 or may be a carbon black.
  • oleophilic graphites contain carbon in the form of very fine particles in flake form and are therefore not very suitable materials for use as catalyst supports. We prefer to avoid their use. Similar considerations apply to carbon blacks which also have a very fiae particle size.
  • the preferred materials are activated carbons derived from vegetable materials e.g. coconut charcoal, or from peat or coal or from carbonizable polymers.
  • the materials subjected to the heat treatment preferably have particle sizes not less than these indicated above as being preferred for the carbon support.
  • the preferred starting materials have the following characteristics: BET surface area of at least 100, more preferably at least 500m 2 /g.
  • the preferred heat treatment procedure for preparing carbon supports having the defined characteristics comprise successively (1) heating the carbon in an inert atmosphere at a temperature of from 900°C to 3300°C, (2) oxidizing the carbon at a temperature between 300°C and 1200°C, (3) heating in an inert atmosphere at a temperature .of between 900°C and 3000°C.
  • the oxidation step is preferably carried out at temperatures between 300° and 600°C when oxygen (eg as air) is used as the oxidising agent.
  • oxygen eg as air
  • the duration of the heating in inert gas is not critical. The time needed to heat the carbon to the required maximum temperature is sufficient to produce the required changes in the carbon.
  • the oxidation step must clearly not be carried out under conditions such that the carbon combusts completely. It is preferably carried out using a gaseous oxidizing agent fed at a controlled rate to avoid over oxidation.
  • gaseous oxidising agents are steam, carbon dioxide, and gases containing molecular oxygen eg air.
  • the oxidation is preferably carried out to give a carbon weight loss of at least 10% wt based on weight of carbon subjected to the oxidation step, more preferably at least 15% wt.
  • the weight loss is preferably not greater than 40 % wt of the carbon subjected to the oxidation step, more preferably not greater than 25 % wt of the carbon.
  • the rate of supply of oxidizing agent is preferably such that the desired weight loss takes place over at least 2 hours, more preferably at least 4 hours.
  • an inert atmosphere may be supplied by nitrogen or an Inert (Group 0) gas.
  • the catalysts of the present invention may be used for the Fischer-Tropsch conversion of synthesis gas to hydrocarbons which are liquid at normal temperatures and pressures.
  • the temperature may for example be In the range 150 to 300°C, .preferably 200 to 250°C.
  • the pressure may for example be in the range 1 to 50 bar absolute (0.1 to 5 MPa) .
  • the molar ratio of hydrogen to carbon monoxide may for example be in the range 3 : 1 to 1:1, more preferably about 2:1.
  • the gas hourly space velocity may be 100 to 10,000, preferably 500 to 3000.
  • This Example shows the preparation of a cobalt Fischer-Tropsch catalyst-supported on a graphitised carbon.
  • the carbon used as support was prepared from a commercially available extrudate activated carbon sold by Degussa under the designation Katepon BKIV.
  • the carbon was in the form of extrudates of 4mm diameter and had typical BET, basal plane, and edge surface areas of 939,182 and 32rn 2 /g respectively.
  • the activated carbon was heat treated as follows. The carbon was heated from room temperature in a stream of helium to 1700°C over a period of about 1 hour. When the temperature reached 1700°C the carbon was allowed to cool in the stream of helium to 25 °C.
  • the carbon was then heated in air in a muffle furnace at approximately 520°C for a time known from experience to give a weight loss of 20 %wt.
  • the carbon was then heated in helium to between 1800°C and 1850°C as in the helium heating step mentioned above.
  • the carbon was allowed to cool to room temperature in a helium atmosphere.
  • Typical values found for carbon treated in this manner were: BET surface area 710-749 m 2 /g
  • Basal plane surface area 416-666 m 2 /g Edge surface area 3.6-3.8 m 2 /g The support was ground and sieved to 16-30 mesh (0.5-1.0mm) and washed by refluxing in (1) dilute (10% w/w) hydrochloric acid and (2) distilled water to remove sulphur and impurity transition metals before use.
  • the carbon was then impregnated with an aqueous solution of cobalt nitrate (analytical reagent grade).
  • the quantity of cobalt nitrate used was such that 10g of carbon support were treated with 2g of cobalt (giving a nominal metal loading of 16.7% w/w based on weight of catalyst).
  • the quantity of water used was the minimum used necessary to ensure even wetting of the carbon support (a few drops of methanol may be added to assist in wetting of the support).
  • the impregnation of the carbon was conducted in a rotary evaporator at 50-80°C under a vacuum of 200-800 m bar (20 kPa-80 kPa).
  • the impregnated carbon was dried overnight in a vacuum oven at 120°C, 200-300 m bar (20 kPa-80 kPa).
  • the catalyst was tested (using a 2.2ml sample) in a once-through microreactor equipped with an on-line gas chromatography apparatus to analyse for CO, CO 2 , and C 1 -C 10 organic products.
  • the catalyst was reduced before use by treating for 2-8 hours with a stream of hydrogen (25-100ml/min) at 400-450°C and 8 bar (0.8 MPa) gauge.
  • Synthesis gas at a molar ratio of H 2 :CO of 2:1 was then admitted.
  • the conditions used and the results obtained are given in Table 1. Definition of Terms used in the Results
  • the CO conversion is defined as the percentage of the carbon monoxide fed to the reactor that was converted to analysed products. It may be represented as:
  • the selectivity to organic products is defined as the percentage of the total carbon monoxide converted to C 1 -C 10 organic products rather than to CO 2 . It may be represented as:
  • the alpha factor represents the relative quantities of the organic products and is defined by P. Biloen and W.M.H. Sachtler in "Advances in Catalysis", Volume 30, pp 165 et seq, published by the Academic Press Inc 1981. In the present application the factor is calculated for products with carbon numbers from C 3 -G 10 .
  • the gas hourly space velocity is defined as the ml/hour of CO/H 2 feedstock (at NTP) per ml of catalyst.
  • Example 2 A catalyst was prepared as in Example 1 but containing 5g of Co per 10g of support (nominal metal loading 33.3% w/w). This catalyst was tested at two different space velocities and the results obtained are given in Tables 1 and 2.
  • Comparative Test A This is a comparative test not according to the invention.
  • a sample of oxide-supported Fischer-Tropsch catalyst (the conventional' type) was tested using the apparatus used in
  • Example 1 The catalyst contained cobalt, magnesium oxide, and zirconium oxide. It was prepared on a 50-100 mesh silica support according to the general method described by J R Anderson in "Structure of Metallic Catalysts", page 455, published by Academic Press, 1975. It contains 22.7% w/w CO, 1.2% w/w MgO and 2.16% w/w ZrO 2 . It was reduced before use as in Example 1.
  • a sample of graphitised carbon support (as used in Example 1) was impregnated with chloroplatlnic acid from aqueous solution.
  • the technique of impregnation and drying was similar to that described for cobalt Impregnation in Example 1.
  • the quantity of chloroplatinic acid used was such that 10g of carbon support were treated with 0.2g of platinum (giving a nominal metal loading of 1.9% w/w).
  • the dried catalyst was reduced in a stream of flowing hydrogen at atmospheric pressure, 200°C for 5 hours. It was then purged with nitrogen and re-impregnated with cobalt nitrate as described in Example 1.
  • the quantities used were such that 10g of the platinum/carbon catalyst were treated with 2g of cobalt (nominal metal loading of the finished catalyst 16.7% w/w cobalt and 1.7% w/w platinum).
  • the catalyst was then reduced and tested as in Example 1, the results being shown in Table 5.
  • Example 4 A catalyst containing 16.7% w/w iron and 0.8% w/w platinum was prepared from ferric nitrate using the technique described for Example 3. The performance data for this catalyst is presented in Table 7.
  • a catalyst was prepared as in Example 3 containing 16.7% wt/wt cobalt and 1.7% wt/wt platinum.
  • the carbon used as support was not a carbon having the surface area characteristics required for the present invention. It was instead a commercial available activated carbon supplied by BDH Chemicals Ltd, Poole, England, and had the following surface area characteristics.

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

Abstract

Un catalyseur Fischer-Tropsch comprend du cobalt ou du fer sur un support en carbone possédant une surface spécificque BET égale à 100 m2/g au moins, le rapport entre le BET et la surface spécifique du plan de base ne dépassant pas 4:1 et le rapport entre la surface spécifique du plan de base et la surface spécifique de bord étant égal à 10:1 au moins.
PCT/GB1985/000378 1984-08-25 1985-08-23 Catalyseur fischer-tropsch WO1986001499A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB848421646A GB8421646D0 (en) 1984-08-25 1984-08-25 Fischer-tropsch catalysts
GB8421646 1984-08-25

Publications (1)

Publication Number Publication Date
WO1986001499A1 true WO1986001499A1 (fr) 1986-03-13

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EP (1) EP0190307A1 (fr)
AU (1) AU4723985A (fr)
GB (1) GB8421646D0 (fr)
WO (1) WO1986001499A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4904700A (en) * 1988-03-31 1990-02-27 The United States Of America As Represented By The United States Department Of Energy Iron catalyst for preparation of polymethylene from synthesis gas
US4925824A (en) * 1988-03-31 1990-05-15 Sapienza Richard S Iron catalyst for preparation of polymethylene from synthesis gas and method for producing the catalyst
US5817910A (en) * 1996-06-28 1998-10-06 Wellman, Inc. Destroying 1,4-dioxane in byproduct streams formed during polyester synthesis
EP0913193A2 (fr) * 1997-10-21 1999-05-06 Karsten Pedersen Catalysateur, procédé et dispositif pour la destruction de composés nocifs contenus dans l'eau
CN103506145A (zh) * 2012-06-25 2014-01-15 韩国energy技术研究院 用于费-托合成反应以及相关液态烃生产的铁/碳纳米复合催化剂的制备

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB565074A (en) * 1943-04-20 1944-10-25 Edward Arthur Stokes Filters or cleaners for air and other gases
FR947385A (fr) * 1946-11-08 1949-06-30 Standard Oil Dev Co Catalyseur perfectionné de synthèse
US4088671A (en) * 1976-03-19 1978-05-09 Gulf Research & Development Company Conversion of synthesis gas using a cobalt-ruthenium catalyst
EP0016851A1 (fr) * 1978-09-20 1980-10-15 The Dow Chemical Company Procédé de préparation d'oléfines à partir de monoxyde de carbone et d'hydrogène
US4478954A (en) * 1983-05-23 1984-10-23 Standard Oil Company (Indiana) Synthesis gas reaction
EP0128302A1 (fr) * 1983-05-16 1984-12-19 Allied Corporation Catalyseur à base de fer et de silicium ayant une haute sélectivité pour des alcènes en C2-C6 dans des réactions Fischer-Tropsch entre CO et H2

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB565074A (en) * 1943-04-20 1944-10-25 Edward Arthur Stokes Filters or cleaners for air and other gases
FR947385A (fr) * 1946-11-08 1949-06-30 Standard Oil Dev Co Catalyseur perfectionné de synthèse
US4088671A (en) * 1976-03-19 1978-05-09 Gulf Research & Development Company Conversion of synthesis gas using a cobalt-ruthenium catalyst
EP0016851A1 (fr) * 1978-09-20 1980-10-15 The Dow Chemical Company Procédé de préparation d'oléfines à partir de monoxyde de carbone et d'hydrogène
EP0128302A1 (fr) * 1983-05-16 1984-12-19 Allied Corporation Catalyseur à base de fer et de silicium ayant une haute sélectivité pour des alcènes en C2-C6 dans des réactions Fischer-Tropsch entre CO et H2
US4478954A (en) * 1983-05-23 1984-10-23 Standard Oil Company (Indiana) Synthesis gas reaction

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4904700A (en) * 1988-03-31 1990-02-27 The United States Of America As Represented By The United States Department Of Energy Iron catalyst for preparation of polymethylene from synthesis gas
US4925824A (en) * 1988-03-31 1990-05-15 Sapienza Richard S Iron catalyst for preparation of polymethylene from synthesis gas and method for producing the catalyst
US5817910A (en) * 1996-06-28 1998-10-06 Wellman, Inc. Destroying 1,4-dioxane in byproduct streams formed during polyester synthesis
EP0913193A2 (fr) * 1997-10-21 1999-05-06 Karsten Pedersen Catalysateur, procédé et dispositif pour la destruction de composés nocifs contenus dans l'eau
EP0913193A3 (fr) * 1997-10-21 2000-03-22 Karsten Pedersen Catalysateur, procédé et dispositif pour la destruction de composés nocifs contenus dans l'eau
CN103506145A (zh) * 2012-06-25 2014-01-15 韩国energy技术研究院 用于费-托合成反应以及相关液态烃生产的铁/碳纳米复合催化剂的制备
CN103506145B (zh) * 2012-06-25 2015-12-02 韩国energy技术研究院 用于费-托合成反应以及相关液态烃生产的铁/碳纳米复合催化剂的制备

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GB8421646D0 (en) 1984-09-26
AU4723985A (en) 1986-03-24
EP0190307A1 (fr) 1986-08-13

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