WO2004041970A1 - Fischer-tropsch process using a fischer-tropsch catalyst and a zeolite-containing catalyst - Google Patents
Fischer-tropsch process using a fischer-tropsch catalyst and a zeolite-containing catalyst Download PDFInfo
- Publication number
- WO2004041970A1 WO2004041970A1 PCT/EP2003/012166 EP0312166W WO2004041970A1 WO 2004041970 A1 WO2004041970 A1 WO 2004041970A1 EP 0312166 W EP0312166 W EP 0312166W WO 2004041970 A1 WO2004041970 A1 WO 2004041970A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fischer
- tropsch
- catalyst
- catalyst particles
- fcc
- Prior art date
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Classifications
-
- 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
Definitions
- the present invention relates to a Fischer-Tropsch process for the conversion of carbon monoxide and hydrogen to Cs + hydrocabon mixtures using a Fischer- Tropsch catalyst and a zeolite-containing catalyst.
- the Fischer-Tropsch process generally comprises the following process steps.
- the first step involves reacting a source of carbon (such as coal or natural gas) with a source of oxygen (such as steam, air or oxygen) to form a mixture of carbon monoxide and hydrogen, usually referred to as synthesis gas.
- the second step involves contacting the carbon monoxide and hydrogen with a Fischer-Tropsch catalyst leading to hydrocarbons and water.
- the main products of the Fischer-Tropsch reaction are linear olefins and paraffins and water, but limited isomerisation and inclusion of heteroatoms such as oxygen may occur.
- Generally applied catalysts for this second step are iron and/or cobalt-containing catalysts. In order to enhance isomerisation during this second step, a co-catalyst can be added.
- the third step involves isomerisation of the hydrocarbons formed in the second step to produce more valuable products.
- the longer chains in the product may be cracked to form products in the diesel or gasoline range, and linear paraffins may be isomerized to improve diesel product properties like cloud point and pour point.
- adapted hydrotreating catalysts are used for this third step.
- US 5,928,980 discloses the use - in the second step of the Fischer-Tropsch process - of a spent fluid catalytic cracking (FCC) catalyst impregnated with a group VIII metal, preferably cobalt and/or iron.
- This catalyst composition is prepared by impregnating the spent FCC catalyst with a metal salt, calcining the impregnated FCC catalyst to obtain a supported metal oxide, and reducing the metal oxide to the metal in a reducing gas atmosphere.
- the impregnated metal serves as the Fischer-Tropsch catalyst.
- a second object is to provide a process using a catalyst system which can be used more flexibly according to need.
- a third object is to provide an inexpensive catalyst system.
- the prior art only discloses the use of spent FCC catalyst in a Fischer-Tropsch process. It is a fourth object of the present invention to enlarge the scope of FCC catalyst to be used in Fischer-Tropsch processes by using also other types of FCC catalysts.
- the process according to the invention uses Fischer-Tropsch catalyst particles and fluid catalytic cracking catalyst particles.
- the catalyst composition according to the present invention can be prepared by simply mixing existing Fischer Tropsch catalyst particles and FCC catalyst particles. Its preparation does not require industrially undesired impregnation steps.
- the Fischer-Tropsch catalyst particles and the FCC catalyst particles may be used in the form of shaped bodies in which both particles are embedded.
- shaped bodies are spray-dried particles (microspheres), extrudates, pellets, spheres, etc.
- Such shaped bodies can be prepared by shaping a physical mixture of Fischer- Tropsch catalyst particles and FCC catalyst particles. Suitable methods to obtain such shaped bodies include spray-drying, pelletising, extrusion (optionally combined with kneading), beading, or any other conventional shaping method used in the catalyst and absorbent fields or combinations thereof.
- the preparation of the Fischer-Tropsch catalyst particles involves a spray-drying step, it is possible to add the FCC catalyst to the Fischer- Tropsch catalyst before spray-drying and subsequently spray-dry the resulting mixture.
- a matrix or binding material can be added to improve the mechanical strength of the shaped bodies.
- suitable matrix or binding materials are alumina, silica, clays, and mixtures thereof. Matrix or binding materials comprising alumina are generally preferred.
- the matrix or binding material, if present, is preferably present in an amount of 10-40 wt%, more preferably 15- 35 wt%, and most preferably 25-35 wt%, based on the total weight of the catalyst composition.
- the term 'FCC catalyst' includes fresh FCC catalysts, spent FCC catalysts and equilibrium catalysts (E-cat).
- a spent FCC catalyst is less expensive than a fresh FCC catalyst. Furthermore, its use results in re-use of waste materials, which is economically and environmentally favourable.
- the Fischer- Tropsch catalyst particles and the FCC catalyst particles are not in the form of shaped bodies in which both particles are embedded, the Fischer- Tropsch catalyst particles and the FCC catalyst particles can be dosed individually - according to need - to the Fischer-Tropsch unit. This creates great flexibility. For instance, if the process conditions change during processing or if one of the catalysts deactivates faster than the other, one of the catalysts might be added with a faster dosing rate than the other. Furthermore, the quality of E-cat or spent FCC catalyst will vary from batch to batch. This difference can be compensated for by adapting the dosing rate of the FCC catalyst particles compared to that of the Fischer-Tropsch catalyst particles. In addition, it is possible to either use both types of catalyst particles in the second step of the Fischer-Tropsch process, or to use the Fischer-Tropsch catalyst particles in the second step and the FCC catalyst particles in the third step.
- the term 'FCC catalyst' refers to any catalyst composition that can suitably be used in FCC processes. Any conventional FCC catalyst can be used in the process according to the invention, although zeolite Y-containing FCC catalysts are preferred. Such FCC catalysts generally contain zeolite Y, clay (e.g. kaolin, metakaolin, bentonite), silica, alumina, rare-earth metal compounds, etc. Examples of suitable metals are rare earth metals, e.g. Ce, La, and transition metals of Groups IV-VIII of the Periodic System, e.g. V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Ru, Re, etc.
- the metal compounds can serve to, e.g., increase the particle strength (e.g. La compounds), enhance the catalyst's stability (e.g. Ni compounds), or enhance CO conversion (e.g. Fe, Co, or Ru compounds).
- This metal compound is preferably present in or on the FCC catalyst particles in amounts of 0.1 to 10 wt%, more preferably 0.3 to 2 wt%, calculated as oxide, and based on the total weight of metal-containing FCC catalyst.
- the metal compound can be deposited on the FCC catalyst particles in any manner known in the art. Examples of such methods are impregnation, ion- exchange, and deposition precipitation of soluble metal salts.
- the metal-deposited FCC catalyst particles is calcined and/or pre- reduced after the metal compound has been deposited.
- An additional advantage of using a spent FCC catalyst compared to a fresh FCC catalyst is that a spent FCC catalyst will generally contain a desired metal compound, due to the fact that the hydrocarbon feed to be cracked in an FCC unit generally contains various metals - e.g. nickel, vanadium. Consequently, no additional deposition step is required to introduce such a metal compound.
- the Fischer-Tropsch catalyst can be any conventional Fischer-Tropsch catalyst, preferably comprising iron and/or cobalt. For the preparation of such catalysts it is referred to, e.g., WO 01/97968, WO 01/89686/ and WO 01/70394.
- the Fischer-Tropsch catalyst can be promoted with various metals, e.g. Al, Ti, Cr, Mn, Ca, Na and/or K.
- the Fischer-Tropsch catalyst particles can contain binder materials, such as silica and/or alumina.
- Both the FCC catalyst particles and the Fischer-Tropsch catalyst particles can be used in the second step of the Fischer-Tropsch process, either in the form of separate particles, or in the form of shaped bodies in which both particles are embedded.
- the FCC catalyst particles are preferably be used in an amount of 5 to 40 wt%, more preferably from 10 to 30 wt%.
- the second step can be carried out in any suitable reactor, such as a (fixed) fluidised bed reactor.
- the temperature ranges preferably from 250° to 400°C, more preferably from 300° to 370°C, and most preferably from 330° to 350°C.
- the pressure preferably ranges from 10 to 60 bar, more preferably 15 to 30 bar, and most preferably about 20 bar.
- the H 2 /CO volume ratio preferably ranges from 0.2 to 6.0, preferably 0.5-6, most preferably 1-3.
- the third step is generally conducted at temperatures of 150 to 600°C, more preferably 200 to 500°C, and most preferably 300 to 400°C
- the pressure preferably ranges from 5 to 60 bar, more preferably from 15 to 40 bar, and most preferably from 20 to 30 bar.
- the resulting hydrocarbon product preferably contains, on a mass basis, at least 35%, more preferably at least 45%, and most preferably at least 50% of C 5 + compounds.
- the process may be used for the production of branched hydrocarbons, olefins, and/or aromatics.
- the process is used for the production of liquid fuel, especially diesel and gasoline, and preferably unleaded gasoline.
- Catalysts which are suitable for this purpose can be used either in the second step (as co-catalyst) or in the third step of the Fischer-Tropsch process in order to enhance the isomerisation of the linear olefinic products.
- FCC catalysts Three different types were tested according to this procedure: a fresh FCC catalyst containing a low amount of rare earth (RE), a fresh FCC catalyst containing a high amount of rare earth metals, and an equilibrium FCC catalyst (E-cat) resulting from the FCC catalyst with a low amount of RE.
- RE rare earth
- E-cat equilibrium FCC catalyst
- n-C ⁇ refers to normal CQ paraffins
- i-C ⁇ refers to branched Ce paraffins
- normal C ⁇ olefins refers to branched C ⁇ olefins
- ⁇ C ⁇ and >C ⁇ refers to compounds with less and more than 6 carbon atoms, respectively.
- the total amounts of isomerized products at 0.5 hr and 17.5 hr runtime were 52.0 wt% and 60.1 wt%, respectively.
- This high isomerization selectivity was accompanied with a low level of cracking; only 3.4 wt% of products smaller than C ⁇ ( ⁇ Ce) were obtained at 17.5 hr runtime.
- the amount of aromatic products was far below 1 wt% during the whole run.
- the total amounts of isomerized products at 0.5 hr and 17.5 hr runtime were 44.8 wt% and 60.5 wt%, respectively.
- the level of cracking was 5.3 wt% at 17.5 hr runtime.
- the amount of aromatic products was far below 1 wt% during the whole run.
- the total amounts of isomerized products at 0.5 hr and 17.5 hr runtime were 38.2 wt% and 39.8 wt%, respectively.
- the level of cracking was only 3.0 wt% at 17.5 hr runtime. Again, the amount of aromatic products was far below 1 wt% during the whole run.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/533,870 US7157501B2 (en) | 2002-11-05 | 2003-10-30 | Fischer-tropsch process using a fischer-tropsch catalyst and a zeolite-containing catalyst |
DK03810426T DK1558701T3 (en) | 2002-11-05 | 2003-10-30 | Fischer-Tropsch process using a Fischer-Tropsch catalyst and a zeolite-containing catalyst |
AU2003276228A AU2003276228A1 (en) | 2002-11-05 | 2003-10-30 | Fischer-tropsch process using a fischer-tropsch catalyst and a zeolite-containing catalyst |
AT03810426T ATE439415T1 (en) | 2002-11-05 | 2003-10-30 | FISCHER-TROPSCH PROCESS, WHICH USES A FISCHER-TROPSCH CATALYST AND A CATALYST CONTAINING ZEOLITE |
EP03810426A EP1558701B1 (en) | 2002-11-05 | 2003-10-30 | Fischer-tropsch process using a fischer-tropsch catalyst and a zeolite-containing catalyst |
DE60328811T DE60328811D1 (en) | 2002-11-05 | 2003-10-30 | FISCHER TROPSCH PROCEDURE USING A FISCHER TROPSCH CATALYST AND A ZEOLITE-CONTAINING CATALYST |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02079646 | 2002-11-05 | ||
EP02079646.2 | 2002-11-05 | ||
US42740802P | 2002-11-19 | 2002-11-19 | |
US60/427,408 | 2002-11-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004041970A1 true WO2004041970A1 (en) | 2004-05-21 |
Family
ID=32313840
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2003/012166 WO2004041970A1 (en) | 2002-11-05 | 2003-10-30 | Fischer-tropsch process using a fischer-tropsch catalyst and a zeolite-containing catalyst |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP1558701B1 (en) |
AT (1) | ATE439415T1 (en) |
AU (1) | AU2003276228A1 (en) |
DE (1) | DE60328811D1 (en) |
DK (1) | DK1558701T3 (en) |
ES (1) | ES2331517T3 (en) |
WO (1) | WO2004041970A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2930733A1 (en) * | 2008-04-30 | 2009-11-06 | Inst Francais Du Petrole | ACTIVE OXYDO-REDUCTION MASS AND CHEMICAL LOOP COMBUSTION METHOD |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9290700B2 (en) | 2014-08-11 | 2016-03-22 | Infra XTL Technology Limited | Method for preparing synthetic liquid hydrocarbons from CO and H2 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3254023A (en) | 1964-06-08 | 1966-05-31 | Socony Mobil Oil Co Inc | Method of heat balancing in organic catalytic reactions |
US4906671A (en) * | 1985-08-29 | 1990-03-06 | Mobil Oil Corporation | Fischer-tropsch process |
US5928980A (en) * | 1997-02-06 | 1999-07-27 | Research Triangle Institute | Attrition resistant catalysts and sorbents based on heavy metal poisoned FCC catalysts |
WO2001070394A2 (en) | 2000-03-17 | 2001-09-27 | Energy International Corporation | Highly active fischer-tropsch catalyst comprising doped, thermally stable catalyst support |
WO2001097968A2 (en) | 2000-06-20 | 2001-12-27 | Sasol Technology (Pty) Ltd | Hydrocarbon synthesis catalyst and process |
-
2003
- 2003-10-30 DK DK03810426T patent/DK1558701T3/en active
- 2003-10-30 AU AU2003276228A patent/AU2003276228A1/en not_active Abandoned
- 2003-10-30 EP EP03810426A patent/EP1558701B1/en not_active Expired - Lifetime
- 2003-10-30 WO PCT/EP2003/012166 patent/WO2004041970A1/en not_active Application Discontinuation
- 2003-10-30 DE DE60328811T patent/DE60328811D1/en not_active Expired - Lifetime
- 2003-10-30 AT AT03810426T patent/ATE439415T1/en not_active IP Right Cessation
- 2003-10-30 ES ES03810426T patent/ES2331517T3/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3254023A (en) | 1964-06-08 | 1966-05-31 | Socony Mobil Oil Co Inc | Method of heat balancing in organic catalytic reactions |
US4906671A (en) * | 1985-08-29 | 1990-03-06 | Mobil Oil Corporation | Fischer-tropsch process |
US5928980A (en) * | 1997-02-06 | 1999-07-27 | Research Triangle Institute | Attrition resistant catalysts and sorbents based on heavy metal poisoned FCC catalysts |
WO2001070394A2 (en) | 2000-03-17 | 2001-09-27 | Energy International Corporation | Highly active fischer-tropsch catalyst comprising doped, thermally stable catalyst support |
WO2001097968A2 (en) | 2000-06-20 | 2001-12-27 | Sasol Technology (Pty) Ltd | Hydrocarbon synthesis catalyst and process |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2930733A1 (en) * | 2008-04-30 | 2009-11-06 | Inst Francais Du Petrole | ACTIVE OXYDO-REDUCTION MASS AND CHEMICAL LOOP COMBUSTION METHOD |
Also Published As
Publication number | Publication date |
---|---|
ATE439415T1 (en) | 2009-08-15 |
EP1558701A1 (en) | 2005-08-03 |
ES2331517T3 (en) | 2010-01-07 |
DK1558701T3 (en) | 2009-12-14 |
EP1558701B1 (en) | 2009-08-12 |
DE60328811D1 (en) | 2009-09-24 |
AU2003276228A1 (en) | 2004-06-07 |
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