EP1436360A1 - Procede de synthese d'hydrocarbures dans un reacteur triphasique en presence d'un catalyseur comprenant un metal du groupe viii supporte sur zircone ou sur oxyde mixte zircone-alumine - Google Patents
Procede de synthese d'hydrocarbures dans un reacteur triphasique en presence d'un catalyseur comprenant un metal du groupe viii supporte sur zircone ou sur oxyde mixte zircone-alumineInfo
- Publication number
- EP1436360A1 EP1436360A1 EP02803430A EP02803430A EP1436360A1 EP 1436360 A1 EP1436360 A1 EP 1436360A1 EP 02803430 A EP02803430 A EP 02803430A EP 02803430 A EP02803430 A EP 02803430A EP 1436360 A1 EP1436360 A1 EP 1436360A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- zirconia
- support
- group viii
- weight
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
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
- 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
-
- 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
Definitions
- the present invention relates to a process for the synthesis of hydrocarbons from a mixture comprising CO- (C0 2 ) -H 2 , that is to say a mixture comprising carbon monoxide, hydrogen and optionally carbon dioxide, called synthesis gas.
- This process comprises the use of a catalyst comprising at least one group VIII metal supported on a zirconia or a particular mixed zirconia-alumina oxide.
- synthesis gas can be converted into hydrocarbons in the presence of a catalyst containing transition metals.
- This conversion carried out at high temperature and under pressure, is known in the literature under the name of Fischer-Tropsch synthesis.
- metals from group VIII of the periodic table of elements such as iron, ruthenium, cobalt and nickel catalyze the transformation of CO- (C0 2 ) -H 2 mixtures, that is to say mixtures comprising carbon monoxide, hydrogen and possibly carbon dioxide, in liquid and / or gaseous hydrocarbons.
- WO-A-99/42214 describes the addition of a stabilizing element to the Al 2 0 3 support used for the preparation of an active catalyst in Fischer-Tropsch synthesis.
- the stabilizing element can be Si, Zr, Cu, Zn, Mn, Ba, Co, Ni and or La. It makes it possible to substantially reduce the solubility of the support in acidic or neutral aqueous solutions. It is added to the preformed alumina support.
- the patents US-A-5, 169,821 and US-A-5,397,806 describe the inclusion of silicon, zirconium or tantalum in a cobalt-based catalyst supported on Ti0 2 in anatase form to stabilize it vis-à-vis high temperature regeneration.
- Patent application EP-A-0 716 883 describes catalysts and catalytic supports essentially formed from monoclinic zirconia prepared from zirconium nitrate or zirconium chloride in aqueous solution. Such catalysts, after addition of metals such as nickel, copper, cobalt or platinum, can be used for the implementation of various reactions and in particular for the Fischer-Tropsch synthesis.
- US-A-5,217,938 describes a process for the preparation of a zirconia-based catalyst optionally containing additional metals from groups IB-VIIB and VIII but preferably from group VIII.
- the catalyst is in the form of extrudates and is used for the Fischer-Tropsch synthesis.
- Patent application EP-A-0 908 232 describes the preparation of an acid catalyst containing a substantial quantity of mass or supported sulphated zirconia in crystallized form (monoclinic or quadratic) and a hydrogenating transition metal.
- This catalyst is used in chemical reactions for the transformation of hydrocarbons requiring the use of an acid type catalyst such as in isomerization reactions of paraffins, olefins, cyclic compounds, aromatics, alkylation reactions, d oligomerization or dehydration of light hydrocarbons.
- the present invention relates to a process for the synthesis of hydrocarbons from a mixture comprising carbon monoxide and hydrogen (CO- H 2 ), optionally carbon dioxide CO 2 , in the presence of a catalyst supported comprising at least one group VIII metal, the support comprising zirconia or a mixed zirconia-alumina oxide and in which the zirconia is in quadratic and / or amorphous form.
- the catalyst is preferably used in suspension in a liquid phase in a three-phase reactor, generally called a slurry reactor. Most often, the three-phase reactor is of the bubble column type, also called slurry bubble column according to English terminology.
- the Applicant has indeed surprisingly discovered that the use of a support comprising zirconia in quadratic and / or amorphous form, optionally containing an alumina phase, after impregnation of at least one group VIII metal, preferably cobalt, to obtain a more active and more selective catalyst than the previous catalysts in the process for the synthesis of hydrocarbons from a mixture comprising carbon monoxide and hydrogen.
- Such catalysts have particularly stable performances and lead to the conversion of synthesis gas into a mixture of linear and saturated hydrocarbons containing at least 50% by weight of C5 + hydrocarbons and less than 20% of methane relative to all of the hydrocarbons formed.
- this catalyst has improved mechanical resistance compared to a catalyst formed from a support for alumina alone or titanium dioxide, the mechanical resistance being determined by measuring the change in particle size for a period of test given in a bubble column type implementation.
- the crystal structure of the quadratic type of zirconia is characterized by X-ray diffraction.
- Amorphous zirconia is characterized by the absence of a significant diffraction line on the diffraction diagram.
- the zirconia included in the catalytic support is entirely devoid of a crystalline structure of monoclinic type. It should also not be sulfated.
- the support used in the process for the synthesis of hydrocarbons according to the present invention contains at least 10% by weight of zirconia in quadratic and / or amorphous form relative to the total mass of the support and contains from 0 to 90% by weight of Al2O3, preferably from 1 to 75%, even more preferably from 5% to 60% by weight of Al 2 0 3 relative to the total mass of the support.
- the support comprising zirconia or a mixed zirconia-alumina oxide and in which the zirconia is in quadratic and / or amorphous form has a specific surface greater than 50 m 2 / g, preferably greater than 80 m 2 / g and more preferably more than 100 m 2 / g.
- any process for the synthesis of zirconia known to a person skilled in the art leading to a quadratic and / or amorphous zirconia advantageously having a specific surface greater than 50 m 2 / g is suitable for preparing the catalyst supports used in the process for the synthesis of hydrocarbons according to the invention.
- the support comprises a mixed zirconia-alumina oxide
- an alumina phase is associated with the zirconia in quadratic and / or amorphous form.
- the catalyst support used in the process for the synthesis of hydrocarbons according to the invention can be prepared by true precipitation or coprecipitation in aqueous solution, under controlled stationary operating conditions (pH, concentration, temperature, time of medium stay) by reaction of an acid solution containing zirconium for example zirconium nitrate or zirconium chloride, optionally aluminum for example aluminum sulphate, aluminum nitrate, with a basic solution such as ammonia or hydrazine.
- a particular method of preparing such supports and resulting from the teaching of patent application EP-A-0 908 232 consists in coprecipitating ZrO (N0 3 ) 2 and AI (N0 3 ) 3 at pH equal to 9.
- Another method inspired by Gao's work (Top. Catal., 6 (1998), 101) consists in coprecipitating ZrOCI 2 and AI (N0 3 ) 3 with ammonia.
- Another preferred method is the precipitation of ZrO (NC> 3) 2 by hydrazine, in the presence or not of AI (NO 3 ) 3, for example, the method cited by Ciuparu (J. Mater. Sci. Lett. 19 (2000) 931).
- the support is then obtained by filtration and washing, drying with shaping and then calcination.
- the unitary drying step with shaping is preferably carried out by atomization, which makes it possible to obtain substantially spherical microbeads of size less than 500 microns.
- the product is preferably calcined in air and in a rotary oven at a temperature between 400 ° C and 1200 ° C, preferably between 400 ° C and 800 ° C and for a sufficient time so that the surface BET specific of the support advantageously has a value greater than 50 m 2 / g, preferably greater than 80 m 2 / g and even more preferably greater than 100 m 2 / g.
- the stabilizing element chosen from the group formed by silicon, niobium, lanthanum, praseodymium and neodymium.
- the stabilizing element is added in a proportion of 0.5 to 5% by weight relative to the preformed zirconia or zirconia-alumina support, in the form of a soluble salt, for example nitrate.
- the support is generally in the form of a fine calibrated powder having a grain size of less than 500 microns, preferably between 10 and 150 microns and even more preferably between 20 and 120 microns, for optimal use in the presence of liquid phase. in a bubble column.
- the support has the following textural properties: a pore volume greater than 0.1 cm 3 / g and an average pore diameter greater than 6 nm, preferably greater than 8 nm.
- the catalyst used in the process for synthesizing hydrocarbons according to the invention comprises at least one metal from group VIII of the periodic table of elements, supported on a quadratic and / or amorphous zirconia, optionally containing an alumina phase and / or optionally at minus one stabilizing.
- the element of group VIII of the periodic table is chosen from the group consisting of iron, cobalt and ruthenium.
- the group VIII metal is cobalt.
- the content by weight relative to the total weight of group VIII metal catalyst is generally between 0.1 and 50%, preferably between 1 and 30%.
- a technique for preparing the catalyst which is particularly suitable is the impregnation on the support comprising zirconia or a mixed zirconia-alumina oxide of an aqueous solution of a precursor of the metal from group VIII of the periodic table, preferably cobalt, for example an aqueous solution of salts such as cobalt nitrates.
- the catalyst can also contain other additional elements, in particular activity promoters, such as for example at least one element chosen from ruthenium, molybdenum and tantalum or reducibility promoters such as for example platinum, palladium or ruthenium.
- activity promoters such as for example at least one element chosen from ruthenium, molybdenum and tantalum or reducibility promoters such as for example platinum, palladium or ruthenium.
- the content, by weight, of an additional element relative to the total weight of catalyst is generally between 0.01 and 5%.
- These additional elements can be introduced at the same time as the group VIII metal or in at least one subsequent step.
- the catalyst contains cobalt and ruthenium.
- the catalyst contains cobalt and tantalum.
- the catalyst comprising at least one group VIII metal impregnated on the support comprising quadratic and / or amorphous zirconia and optionally containing an alumina phase is subjected at drying and calcination stages, then is pre-reduced by at least one reducing compound, for example chosen from the group formed by hydrogen, carbon monoxide and formic acid, optionally brought into contact with a gas inert such as nitrogen, for example in a molar ratio of reductive compound (reducing compound + inert gas) of between 0.001: 1 and 1: 1.
- a gas inert such as nitrogen
- Reduction can be carried out in phase gas at a temperature between 100 ° C and 600 ° C, preferably between 150 ° C and 400 ° C, at a pressure between 0.1 and 10 MPa and at an hourly volumetric speed between 100 and 40,000 volumes of mixture by volume of catalyst and per hour.
- This reduction can also be carried out in the liquid phase, the catalyst being suspended in an inert solvent, for example a paraffinic fraction comprising at least one hydrocarbon having at least 5, preferably at least 10 carbon atoms per molecule if subsequently the hydrocarbon synthesis reaction takes place in the liquid phase comprising at least one hydrocarbon having at least 5, preferably at least 10 carbon atoms per molecule.
- the conversion of synthesis gas to hydrocarbons is then carried out under a total pressure usually between 0.1 and 15 MPa and preferably between 1 and 10 MPa, the temperature being generally between 150 and 350 ° C and preferably between 170 and 300 ° C.
- the hourly volumetric speed is usually between 100 and 20,000 volumes of synthesis gas per volume of catalyst and per hour and preferably between 400 and 5000 volumes of synthesis gas per volume of catalyst and per hour, and the ratio H 2 / CO in the synthesis gas is usually between 1: 2 and 5: 1, preferably between 1.2: 1 and 2.5: 1.
- the catalyst is preferably used in the form of a calibrated fine powder having a grain size of less than 500 microns, preferably between 10 and 150 microns, more preferably between 20 and 120 microns, in the presence of a liquid phase which can be constituted. with at least one hydrocarbon having at least 5, preferably at least 10, carbon atoms per molecule.
- a liquid phase which can be constituted. with at least one hydrocarbon having at least 5, preferably at least 10, carbon atoms per molecule.
- the use of the catalyst in suspension in a liquid phase in a three-phase reactor of the bubble column type is advantageous because this type of implementation allows optimal use of the performances of the catalyst (activity and selectivity), by limiting intra-diffusional phenomena. granular, as well as a very significant limitation of the thermal effects in the grain of catalyst, which is surrounded by a liquid phase.
- This type of implementation requires separation of the catalyst from the reaction products. Under these conditions, the catalyst exhibits improved mechanical properties allowing a optimal separation of the catalyst and products and an increased
- Example 1 (according to the invention): catalyst A
- Catalyst A Co / Zr0 2
- the metal cobalt content is 13%.
- the zirconia is prepared beforehand by precipitation of zirconium nitrate by hydrazine: it is amorphous and has a specific surface of 250 m 2 / g after calcination at 550 ° C.
- the suspension obtained is atomized and the support thus obtained is in the form of a powder with a particle size between 20 and 150 microns.
- the catalyst resulting from the impregnation is dried and calcined at 400 ° C.
- Catalyst B Co / Zr0 2 -AI 2 0 3
- the metal cobalt content is 12.5%.
- the zirconia-alumina is prepared beforehand by coprecipitation of a mixture ZrOCI 2 and AI (NO 3 ) 3 to which NH OH is added. After drying and calcination at 700 ° C, the support is amorphous, its specific surface is 158 m 2 / g. The support contains 15% alumina.
- the catalyst resulting from the impregnation is dried and calcined at 400 ° C.
- Example 3 (according to the invention): catalyst C A catalyst C, Co / Zr0 2 , is prepared by impregnating cobalt nitrate on a zirconia. The metal cobalt content is 13%.
- the zirconia is prepared beforehand by precipitation of ZrOCI 2 with NH 4 OH followed by ripening at constant pH. After drying and calcination at 500 ° C, the zirconia is quadratic and has a specific surface of 135 m / g. The catalyst resulting from the impregnation is dried and calcined at 400 ° C.
- Example 4 (according to the invention): catalyst D Catalyst D is prepared by impregnating cobalt nitrate on a support containing 70% alumina, 25% zirconia and 5% silica. The metal cobalt content is 12%.
- the support is prepared as in Example 2 by coprecipitation of a ZrOCI 2 and AI (NO 3 ) 3 mixture to which NH 4 OH is added. Simultaneously with the addition of NH 4 OH, a small amount of ammonium silicate is added so as to obtain the composition of the catalytic support described above. After drying and calcination at 550 ° C, the support obtained is amorphous and has a surface of 90 m 2 / g. The catalyst resulting from the impregnation is dried and calcined at 400 ° C.
- a catalyst E CO / Al 2 O 3 , is prepared by impregnating cobalt nitrate on a support consisting of a Puralox Seca 5-170 alumina powder with a specific surface area equal to 180 m 2 / g. The final cobalt content is 12.5%.
- the alumina support used is in the form of powder with a particle size between 20 and 150 microns.
- the catalyst resulting from the impregnation is dried and calcined at 400 ° C.
- Example 6 (comparative): catalyst F A catalyst F is prepared by impregnating cobalt nitrate on a support containing 90% alumina, 10% zirconia. The metal cobalt content is 13%.
- the support is prepared by impregnating zirconium isopropoxide on a Puralox Seca 5-170 alumina powder with a specific surface area equal to 180 m 2 / g. After drying and calcination at 550 ° C, the support obtained has zirconia in monoclinic form. The catalyst resulting from the impregnation is dried and calcined at 400 ° C.
- Example 7 (comparative): catalyst G A catalyst G, Co / Zr ⁇ 2 , is prepared by impregnating cobalt nitrate on a zirconia. The metal cobalt content is 13%. The zirconia is prepared by precipitation of ZrOCI 2 with NH OH. The freshly prepared gel is washed with ethanol. After drying and calcination at 500 ° C, the Zirconia is monoclinic and has an area of 112 m 2 / g. The catalyst resulting from the impregnation is dried and calcined at 400 ° C.
- EXAMPLE 8 Catalytic Tests in a Three-Phase Reactor Catalysts A, B, C, D, E, F and G, the preparations of which are described in Examples 1 to 7 above, are tested in a three-phase reactor (slurry type), perfectly stirred, operating continuously and operating with a concentration of 10% (mol) of catalyst in suspension.
- the catalysts are previously reduced at 400 ° C for 8 hours under a mixture of hydrogen and nitrogen containing 30% hydrogen, then for 12 hours under pure hydrogen.
- the conditions for testing the catalysts are as follows:
- Table 2 below gives the percentage of catalyst particles having a size of less than 20 microns formed during the tests of catalysts A to G.
- the catalysts used in the process according to the invention (A to D) have a significantly higher mechanical strength compared to catalysts E, F and G.
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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)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0113138A FR2830858B1 (fr) | 2001-10-11 | 2001-10-11 | Procede de synthese d'hydrocarbures dans un reacteur triphasique en presence d'un catalyseur comprenant un metal du groupe viii supporte sur zircone ou sur oxyde mixte zircone-alumine |
FR0113138 | 2001-10-11 | ||
PCT/FR2002/003415 WO2003044126A1 (fr) | 2001-10-11 | 2002-10-08 | Procede de synthese d'hydrocarbures dans un reacteur triphasique en presence d'un catalyseur comprenant un metal du groupe viii supporte sur zircone ou sur oxyde mixte zircone-alumine |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1436360A1 true EP1436360A1 (fr) | 2004-07-14 |
EP1436360B1 EP1436360B1 (fr) | 2010-04-07 |
Family
ID=8868202
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02803430A Expired - Fee Related EP1436360B1 (fr) | 2001-10-11 | 2002-10-08 | Procede de synthese d'hydrocarbures dans un reacteur triphasique en presence d'un catalyseur comprenant un metal du groupe viii supporte sur zircone ou sur oxyde mixte zircone-alumine |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP1436360B1 (fr) |
CA (1) | CA2462535C (fr) |
DE (1) | DE60235903D1 (fr) |
FR (1) | FR2830858B1 (fr) |
WO (1) | WO2003044126A1 (fr) |
ZA (1) | ZA200402139B (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005079979A1 (fr) * | 2004-02-24 | 2005-09-01 | Japan Oil, Gas And Metals National Corporation | Catalyseur pour la production d'hydrocarbures, procédé de préparation de celui-ci, et procédé de production d'hydrocarbures l'utilisant |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH670250A5 (fr) * | 1986-11-05 | 1989-05-31 | Lonza Ag | |
DE4445142A1 (de) * | 1994-12-17 | 1996-06-20 | Basf Ag | Katalysatoren oder Träger die im wesentlichen aus monoklinem Zirconiumdioxid bestehen |
ZA9711090B (en) * | 1996-12-13 | 1998-06-15 | Shell Int Research | Process for the preparation of hydrocarbons. |
FR2769519B1 (fr) * | 1997-10-13 | 1999-12-31 | Total Raffinage Distribution | Catalyseur acide a base de zircone sulfatee et ses utilisations |
-
2001
- 2001-10-11 FR FR0113138A patent/FR2830858B1/fr not_active Expired - Fee Related
-
2002
- 2002-10-08 DE DE60235903T patent/DE60235903D1/de not_active Expired - Lifetime
- 2002-10-08 CA CA2462535A patent/CA2462535C/fr not_active Expired - Lifetime
- 2002-10-08 EP EP02803430A patent/EP1436360B1/fr not_active Expired - Fee Related
- 2002-10-08 WO PCT/FR2002/003415 patent/WO2003044126A1/fr active Application Filing
-
2004
- 2004-03-17 ZA ZA2004/02139A patent/ZA200402139B/en unknown
Non-Patent Citations (1)
Title |
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See references of WO03044126A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE60235903D1 (de) | 2010-05-20 |
WO2003044126A1 (fr) | 2003-05-30 |
FR2830858B1 (fr) | 2003-12-12 |
ZA200402139B (en) | 2005-09-28 |
CA2462535C (fr) | 2010-06-29 |
CA2462535A1 (fr) | 2003-05-30 |
EP1436360B1 (fr) | 2010-04-07 |
FR2830858A1 (fr) | 2003-04-18 |
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