ATE299522T1 - COBALT-ALUMINA CATALYSTS WITH IMPROVED ACTIVITY FOR FISCHER-TROPSCH SYNTHESIS - Google Patents

COBALT-ALUMINA CATALYSTS WITH IMPROVED ACTIVITY FOR FISCHER-TROPSCH SYNTHESIS

Info

Publication number
ATE299522T1
ATE299522T1 AT99924511T AT99924511T ATE299522T1 AT E299522 T1 ATE299522 T1 AT E299522T1 AT 99924511 T AT99924511 T AT 99924511T AT 99924511 T AT99924511 T AT 99924511T AT E299522 T1 ATE299522 T1 AT E299522T1
Authority
AT
Austria
Prior art keywords
cobalt catalyst
gamma
alumina support
titanium
amount
Prior art date
Application number
AT99924511T
Other languages
German (de)
Inventor
Alan H Singleton
Rachid Oukaci
James G Goodwin
Original Assignee
Sasol Technology Uk Ltd
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 Sasol Technology Uk Ltd filed Critical Sasol Technology Uk Ltd
Priority claimed from PCT/US1999/011583 external-priority patent/WO1999061550A1/en
Application granted granted Critical
Publication of ATE299522T1 publication Critical patent/ATE299522T1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2/00Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33Production 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
    • C10G2/331Production 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
    • C10G2/332Production 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/75Cobalt
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425Catalysts; their physical properties
    • C07C1/043Catalysts; their physical properties characterised by the composition
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts 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
    • B01J23/78Catalysts 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 alkali- or alkaline earth metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts 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
    • B01J23/83Catalysts 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04Alumina
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74Iron group metals
    • C07C2523/75Cobalt

Landscapes

  • 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)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

1. A cobalt catalyst for hydrocarbon synthesis on Fischer-Tropsch, said cobalt catalyst comprising cobalt supported on a gamma-alumina support, wherein said cobalt catalyst is not promoted with any noble metals, rhenium, technetium or titanium supported on said a gamma-alumina support, said gamma-alumina support includes a dopant in an amount effective for increasing the activity of said cobalt catalyst for said hydrocarbon synthesis. 2. The cobalt catalyst of claim 1, wherein said amount of titanium dopant is an amount effective to render said cobalt catalyst at least 60% as active as a promoted catalyst which is identical to said cobalt catalyst except that said promoted catalyst is promoted with ruthenium in a ruthenium to cobalt weight ratio of 1: 40. 3. The cobalt catalyst of claim 2, wherein said amount of said titanium dopant is an amount effective to render said cobalt catalyst at least 70% as active as said promoted catalyst. 4. The cobalt catalyst of claim 3, wherein said amount of said titanium dopant is an amount effective to render said cobalt catalyst at least 80% as active as said promoted catalyst. 5. The cobalt catalyst of claim 1, wherein said amount of said titanium dopant, expressed as elemental titanium, is at least 500 ppm by weight of the total weight of said gamma-alumina support. 6. The cobalt catalyst of claim 1, wherein said amount of said titanium dopant, expressed as elemental titanium, is in the range of from about 800 to about 2000 ppm by weight of the total weight of said gamma-alumina support. 7. The cobalt catalyst of claim 1, wherein said amount of said titanium dopant, expressed as elemental titanium, is about 1000 ppm by weight of the total weight of said gamma-alumina support. 8. The cobalt catalyst of claim 1, wherein said cobalt catalyst is an activated catalyst which has been reduced in the presence of hydrogen and at a water vapor partial pressure effective to increase said activity of said cobalt catalyst. 9. The cobalt catalyst of claim 1, wherein said cobalt catalyst is promoted with at least one of potassium and lanthana. 10. The cobalt catalyst of claim 1, wherein said gamma-alumina support is produced from synthetic boehmite and said dopant is added to said gamma-alumina support prior to the crystallization of said synthetic boehmite. 11. A process for producing a hydrocarbon comprising the step of reacting a synthesis gas in the presence of a cobalt catalyst wherein said cobalt catalyst comprises cobalt supported on a gamma-alumina support; said cobalt catalyst is not promoted with any noble metals, rhenium, technetium or titanium supported on said gamma-alumina support and said gamma-alumina support includes a dopant in an amount effective for increasing the activity of said cobalt catalyst for said hydrocarbon synthesis on Fischer-Tropsch. 12. The process of claim 11, wherein said amount of said titanium dopant is an amount effective to render said cobalt catalyst at least 60% as active for said hydrocarbon synthesis as a promoted catalyst which is identical to said cobalt catalyst, except that said promoted catalyst is promoted with ruthenium in ruthenium to cobalt weight ratio of 1: 40. 13. The process of claim 12, wherein said amount of said titanium dopant is an amount effective to render said cobalt catalyst at least 70% as active as said promoted catalyst. 14. The process of claim 12, wherein said amount of said titanium dopant is an amount effective to render said cobalt catalyst at least 80% as active as said promoted catalyst. 15. The process of claim 11, wherein said amount of said titanium dopant, expressed as elemental titanium, is at least 500 ppm by weight of the total weight of said gamma-alumina support. 16. The process of claim 11, wherein said amount of said titanium dopant, expressed as elemental titanium, is in the range of from about 800 to about 2000 ppm by weight of the total weight of said gamma-alumina support. 17. The process of claim 11, wherein said amount of said titanium dopant, expressed as elemental titanium, is about 1000 ppm by weight of the total weight of said gamma-alumina support. 18. The process of claim 11 further comprising the step, prior to said step of reacting, of activating said cobalt catalyst by reducing said cobalt catalyst in the presence of hydrogen and at a water vapor partial pressure effective to increase said activity of said cobalt catalyst. 19. The process of claim 18, wherein said water vapor partial pressure is in the range of from 0 to about 0.1 atmospheres. 20. A cobalt catalyst for hydrocarbon synthesis comprising cobalt supported on a gamma-alumina support, wherein said cobalt catalyst is not promoted with any noble metals, rhenium, technetium or titanium supported on said gamma-alumina support, said gamma-alumina support includes an amount of a titanium dopant, and said cobalt catalyst has been reduced in the presence of hydrogen at a water vapor partial pressure effective to increase the activity of said cobalt catalyst for said hydrocarbon synthesis. 21. The cobalt catalyst of claim 20, wherein said gamma-alumina support includes an amount of a titanium dopant of at least 500 ppm by weight, expressed as elemental titanium, of the total weight of said gamma-alumina support. 22. The cobalt catalyst of claim 21, wherein said amount of said titanium dopant, expressed as elemental titanium, is in the range from about 800 to about 2000 ppm by weight of the total weight of said gamma-alumina support. 23. The cobalt catalyst of claim 21, wherein said gamma-alumina support is produced from synthetic boehmite and said dopant is added to said gamma-alumina support prior to the crystallization of said synthetic boehmite. 24. A process for hydrocarbon synthesis comprising the following steps: (a) reducing a cobalt catalyst in the presence of hydrogen and at a water vapor partial pressure effective to increase the activity of said cobalt catalyst for said hydrocarbon synthesis, wherein said cobalt catalyst comprising cobalt supported on a gamma-alumina support, said gamma-alumina support includes an amount of a titanium dopant, and (b) reacting a synthesis gas in the presence of said cobalt catalyst, wherein said cobalt catalyst is not promoted with any noble metals, rhenium, technetium or titanium supported on said gamma-alumina support. 25. The process of claim 24, wherein said gamma-alumina support includes an amount of a titanium dopant of at least 500 ppm by weight, expressed as elemental titanium, of the total weight of said gamma-alumina support. 26. The process of claim 25, wherein said amount of said titanium dopant, expressed as elemental titanium, is in the range of from about 800 to about 2000 ppm by weight of the total weight of said gamma-alumina support. 27. The method of improving the activity of a cobalt catalyst for hydrocarbon synthesis, comprising said cobalt supported on said gamma-alumina support, said method comprising the step of including in said support a titanium dopant in an amount, expressed as elemental titanium, of at least 500 ppm by weight of the total weight of said alumina support.
AT99924511T 1999-05-26 1999-05-26 COBALT-ALUMINA CATALYSTS WITH IMPROVED ACTIVITY FOR FISCHER-TROPSCH SYNTHESIS ATE299522T1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1999/011583 WO1999061550A1 (en) 1998-05-27 1999-05-26 Improved fischer-tropsch activity for 'non-promoted' cobalt-on-alumina catalysts

Publications (1)

Publication Number Publication Date
ATE299522T1 true ATE299522T1 (en) 2005-07-15

Family

ID=22272838

Family Applications (1)

Application Number Title Priority Date Filing Date
AT99924511T ATE299522T1 (en) 1999-05-26 1999-05-26 COBALT-ALUMINA CATALYSTS WITH IMPROVED ACTIVITY FOR FISCHER-TROPSCH SYNTHESIS

Country Status (7)

Country Link
JP (1) JP2003517913A (en)
AT (1) ATE299522T1 (en)
AU (1) AU764183B2 (en)
CA (1) CA2375026A1 (en)
DE (1) DE69926151T2 (en)
EA (1) EA004065B1 (en)
MX (1) MXPA01012035A (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2449002C2 (en) * 2007-02-14 2012-04-27 Ниппон Ойл Корпорейшн Method of producing hydrocarbon by reducing carbon monoxide
US9527782B2 (en) * 2012-08-02 2016-12-27 Sasol Technology (Propietary) Limited Method of preparing a modified support, a catalyst precursor and a catalyst, and a hydrocarbon synthesis process using the catalyst

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4619910A (en) * 1985-06-05 1986-10-28 Air Products And Chemicals, Inc. Catalyst for selective conversion of synthesis gas and method of making the catalyst
US4801573A (en) * 1987-10-23 1989-01-31 501 Den Norske Stats Oljeslenskap A.S. Catalyst for production of hydrocarbons
JP3408811B2 (en) * 1990-10-15 2003-05-19 エクソン リサーチ アンド エンジニアリング カンパニー Activation conditions to maximize HCS activity of supported cobalt catalyst

Also Published As

Publication number Publication date
AU4099399A (en) 1999-12-13
DE69926151D1 (en) 2005-08-18
EA004065B1 (en) 2003-12-25
EA200101245A1 (en) 2002-06-27
AU764183B2 (en) 2003-08-14
DE69926151T2 (en) 2006-04-27
MXPA01012035A (en) 2005-05-12
JP2003517913A (en) 2003-06-03
CA2375026A1 (en) 1999-12-02

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