EP1436360B1 - Method for hydrocarbon synthesis in a three-phase reactor in the presence of a catalyst comprising a group viii metal supported on zirconia or mixed zirconia-alumina oxide - Google Patents
Method for hydrocarbon synthesis in a three-phase reactor in the presence of a catalyst comprising a group viii metal supported on zirconia or mixed zirconia-alumina oxide Download PDFInfo
- Publication number
- EP1436360B1 EP1436360B1 EP02803430A EP02803430A EP1436360B1 EP 1436360 B1 EP1436360 B1 EP 1436360B1 EP 02803430 A EP02803430 A EP 02803430A EP 02803430 A EP02803430 A EP 02803430A EP 1436360 B1 EP1436360 B1 EP 1436360B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- zirconia
- support
- process according
- 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.)
- Expired - Fee Related
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- (CO 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.
- the synthesis gas can be converted to hydrocarbons in the presence of a transition metal-containing catalyst.
- This conversion carried out at high temperature and under pressure is known in the literature as the Fischer-Tropsch synthesis.
- metals of group VIII of the periodic table of elements such as iron, ruthenium, cobalt and nickel catalyze the conversion of mixtures CO- (CO 2 ) -H 2 , that is to say of mixtures comprising carbon monoxide, hydrogen and possibly carbon dioxide, in liquid and / or gaseous hydrocarbons.
- 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 patent application EP-A-0 716 883 describes catalytic catalysts and supports formed essentially of 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 carrying out various reactions and in particular for Fischer-Tropsch synthesis.
- the patent US 5,958,985 discloses a process for preparing hydrocarbons from a synthesis gas in the presence of a catalyst comprising a support selected from alumina, silica, titania, zirconia and mixtures thereof onto which cobalt and manganese in a proportion such that the molar ratio cobalt / manganese is between 13/1 and 9/1 so as to optimize the selectivity to C 5+ .
- the patent US Patent 5,217,938 describes a process for the preparation of a zirconia-based catalyst optionally containing additional metals of groups IB-VIIB and VIII but preferably of group VIII.
- the catalyst is in the form of extrudates and is used for Fischer-Tropsch synthesis.
- EP-A-0 908 232 describes the preparation of an acid catalyst containing a substantial amount of mass or supported sulfated zirconia in crystalline form (monoclinic or quadratic) and a hydrogenating transition metal.
- This catalyst is used in chemical conversion reactions of hydrocarbons requiring the use of an acid catalyst such as in the isomerization reactions of paraffins, olefins, cyclic compounds, aromatics, alkylation reactions, 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 medium comprising at least one Group VIII metal, the support comprising zirconia or a mixed zirconia-alumina oxide and wherein the zirconia is in quadratic and / or amorphous form.
- the catalyst is used in suspension in a liquid phase in a three-phase reactor, generally called slurry reactor. Most often, the triphasic reactor is of the bubble column type, also called slurry bubble column according to English terminology.
- the Applicant has surprisingly discovered that the use of a support comprising zirconia in quadratic and / or amorphous form, optionally containing an alumina phase, allowed after impregnation of at least one metal of group VIII, preferably cobalt, to obtain a more active and 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 the 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 with respect to all hydrocarbons formed.
- this catalyst has an improved mechanical strength compared to a catalyst formed of a support of alumina alone or of titanium dioxide, the mechanical strength being determined by measuring the evolution of the particle size for a duration of test given in a bubble column implementation.
- the quadratic crystalline structure of zirconia is characterized by X-ray diffraction.
- Amorphous zirconia is characterized by the absence of significant diffraction line on the diffraction pattern. It is essential for the implementation of the hydrocarbon synthesis process according to the invention that the zirconia included in the catalytic support is entirely devoid of a monoclinic type crystalline structure. It should not be sulphated.
- 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 Al 2 O 3 , preferably from 1 to 75%, even more preferably from 5% to 60% by weight of Al 2 O 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 area greater than 50 m 2 / g, preferably greater than 80 m 2 / g and still more preferably greater than 100 m 2 / g.
- any zirconia synthesis process known to those skilled in the art leading to a quadratic and / or amorphous zirconia advantageously having a surface area greater than 50 m 2 / g is suitable for preparing the catalyst supports used in the synthesis process of hydrocarbons according to the invention.
- the catalyst support used in the hydrocarbon synthesis process according to the invention can be prepared by true precipitation or coprecipitation in aqueous solution under controlled stationary operating conditions (pH, concentration, temperature, reaction time). average residence time) 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.
- aqueous solution under controlled stationary operating conditions (pH, concentration, temperature, reaction time). average residence time) 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 media and resulting from the teaching of the patent application EP-A-0 908 232 consists in coprecipitating ZrO (NO 3 ) 2 and Al (NO 3 ) 3 at pH equal to 9.
- Another preferred method is the precipitation of ZrO (NO 3 ) 2 by hydrazine, in the presence or absence of Al (NO 3 ) 3, for example, the method mentioned by Ciuparu (J. Mater Sci Lett 19 (2000) 931 ).
- the support is then obtained by filtration and washing, drying with shaping and calcination.
- the unitary step of drying with shaping is preferably carried out by atomization, which makes it possible to obtain substantially spherical microbeads less than 500 microns in size.
- the product is calcined preferably in air and in a rotary oven at a temperature of between 400 ° C. and 1200 ° C., preferably between 400 ° C. and 800 ° C. and for a sufficient time so that the surface
- the specific BET 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 support is generally in the form of a finely graded powder having a grain size of less than 500 microns, preferably of between 10 and 150 microns and even more preferably of between 20 and 120 microns, for optimum use in the presence of a 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 hydrocarbon synthesis process according to the invention comprises at least one metal of group VIII of the periodic table of elements, supported on a quadratic and / or amorphous zirconia, optionally containing an alumina phase and / or optionally minus one stabilizing.
- the element of group VIII of the Periodic Table of Elements is selected 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 between 0.1 and 50%, preferably between 1 and 30%.
- a particularly suitable catalyst preparation technique is the impregnation on the support comprising zirconia or zirconia-alumina mixed oxide of an aqueous solution of a Group VIII metal precursor of the Periodic Table of Elements, preferably cobalt, for example an aqueous solution of salts such as cobalt nitrates.
- the catalyst may also contain other additional elements, in particular promoters of activity, 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.
- additional elements in particular promoters of activity, 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 to at stages of drying and calcination, and then is pre-reduced by at least one reducing compound, for example chosen from the group formed by hydrogen, carbon monoxide and formic acid, possibly brought into contact with a gas inert form such as nitrogen, for example in a reducing compound / reducing compound (reducing compound + inert gas) molar ratio of between 0.001: 1 and 1: 1.
- the reduction can be conducted in phase at a temperature of between 100 ° C.
- the conversion of the synthesis gas into hydrocarbons is then carried out under a total pressure usually of between 0.1 and 15 MPa and preferably between 1 and 10 MPa, the temperature generally being between 150 and 350 ° C. and preferably between 170 and 300 ° C.
- the hourly volumetric rate is usually between 100 and 20 000 volumes of synthesis gas per volume of catalyst per hour and preferably between 400 and 5000 volumes of synthesis gas per volume of catalyst per hour, and the ratio H 2 /
- the 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 fine calibrated powder having a grain size of less than 500 microns, preferably between 10 and 150 microns, more desirably between 20 and 120 microns, in the presence of a liquid phase which may be constituted by at least one hydrocarbon having at least 5, preferably at least 10, carbon atoms per molecule.
- a liquid phase which may be constituted by 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 bubble column type is advantageous because this type of implementation allows optimal use of the catalyst performance (activity and selectivity), by limiting the diffusional phenomena within the granular, as well as a very significant limitation of thermal effects in the catalyst grain, which is surrounded by a liquid phase.
- This type of implementation requires a separation of the catalyst from the reaction products. Under these conditions, the catalyst has improved mechanical properties allowing optimal catalyst and product separation and increased catalyst life.
- Example 1 (according to the invention) : Catalyst A
- a catalyst, Co / ZrO 2 is prepared by impregnating cobalt nitrate on a zirconia powder.
- the cobalt metal content is 13%.
- the zirconia is prepared beforehand by precipitation of zirconium nitrate with hydrazine: it is amorphous and has a specific surface area 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 of between 20 and 150 microns.
- the catalyst resulting from the impregnation is dried and calcined at 400 ° C.
- Example 2 (according to the invention) : Catalyst B
- a catalyst B Co / ZrO 2 -Al 2 O 3 , is prepared by impregnation of cobalt nitrate on a zirconia-alumina.
- the cobalt metal content is equal to 12.5%.
- the zirconia-alumina is prepared beforehand by coprecipitation of a mixture ZrOCl 2 and Al (NO 3 ) 3 to which NH 4 OH is added. After drying and calcining at 700 ° C., the support is amorphous, its specific surface area is 158 m 2 / g. The support contains 15% alumina.
- the catalyst resulting from the impregnation is dried and calcined at 400 ° C.
- a C, Co / ZrO 2 catalyst is prepared by impregnating cobalt nitrate with a zirconia.
- the cobalt metal content is 13%.
- the zirconia is previously prepared by precipitation of ZrOCl 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 area of 135 m 2 / g.
- the catalyst resulting from the impregnation is dried and calcined at 400 ° C.
- a catalyst D is prepared by impregnation of cobalt nitrate on a support containing 70% of alumina, 25% of zirconia and 5% of silica. The content of cobalt metal is equal to 12%.
- the support is prepared as in Example 2 by coprecipitation of a mixture ZrOCl 2 and Al (NO 3 ) 3 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 catalyst support described above. After drying and calcination at 550 ° C., the support obtained is amorphous and has an area of 90 m 2 / g. The catalyst resulting from the impregnation is dried and calcined at 400 ° C.
- An E, Co / Al 2 O 3 catalyst is prepared by impregnating cobalt nitrate on a support consisting of a Puralox Scca 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 employed is in the form of a powder having a particle size of between 20 and 150 microns.
- the catalyst resulting from the impregnation is dried and calcined at 400 ° C.
- Catalyst F is prepared by impregnating cobalt nitrate on a support containing 90% alumina, 10% zirconia. The cobalt metal content is 13%.
- the support is prepared by impregnating zirconium isopropoxide with Puralox Scca 5-170 alumina powder having a specific surface area of 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.
- a catalyst G Co / ZrO 2 , is prepared by impregnation of cobalt nitrate on a zirconia.
- the cobalt metal content is 13%.
- the zirconia is prepared by precipitation of ZrOCl 2 with NH 4 OH.
- the freshly prepared gel is washed with ethanol. After drying and calcining at 500.degree.
- 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.
- 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.
Landscapes
- 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
La présente invention concerne un procédé de synthèse d'hydrocarbures à partir d'un mélange comprenant CO-(CO2)-H2, c'est-à-dire un mélange comprenant du monoxyde de carbone, de l'hydrogène et éventuellement du dioxyde de carbone, appelé gaz de synthèse. Ce procédé comprend la mise en oeuvre d'un catalyseur comprenant au moins un métal du groupe VIII supporté sur une zircone ou un oxyde mixte zircone-alumine particulier.The present invention relates to a process for the synthesis of hydrocarbons from a mixture comprising CO- (CO 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.
Il est connu de l'homme du métier que le gaz de synthèse peut être converti en hydrocarbures en présence d'un catalyseur contenant des métaux de transition. Cette conversion opérée à haute température et sous pression est connue dans la littérature sous le nom de synthèse Fischer-Tropsch. Ainsi des métaux du groupe VIII de la classification périodique des éléments tels que le fer, le ruthénium, le cobalt et le nickel catalysent la transformation de mélanges CO-(CO2)-H2, c'est-à-dire de mélanges comprenant du monoxyde de carbone, de l'hydrogène et éventuellement du dioxyde de carbone, en hydrocarbures liquides et/ou gazeux.It is known to those skilled in the art that the synthesis gas can be converted to hydrocarbons in the presence of a transition metal-containing catalyst. This conversion carried out at high temperature and under pressure is known in the literature as the Fischer-Tropsch synthesis. Thus metals of group VIII of the periodic table of elements such as iron, ruthenium, cobalt and nickel catalyze the conversion of mixtures CO- (CO 2 ) -H 2 , that is to say of mixtures comprising carbon monoxide, hydrogen and possibly carbon dioxide, in liquid and / or gaseous hydrocarbons.
Différentes méthodes ont été décrites et développées dans l'art antérieur et sont destinées à améliorer la préparation de catalyseurs Fischer-Tropsch à base de cobalt supporté sur différents supports. Les supports les plus utilisés sont l'alumine, la silice et le dioxyde de titane, parfois modifiés par des éléments additionnels.Various methods have been described and developed in the prior art and are intended to improve the preparation of Fischer-Tropsch catalysts based on cobalt supported on different supports. The most used supports are alumina, silica and titanium dioxide, sometimes modified by additional elements.
La demande de brevet internationale
Les brevets
La demande de brevet
Le brevet
Le brevet
La demande de brevet
Toutefois, l'ensemble des catalyseurs connus de l'art antérieur et utilisés en synthèse Fischer-Tropsch présentent une sélectivité élevée en faveur des hydrocarbures les plus légers et notamment du méthane, indésirables, au détriment de celle en faveur d'hydrocarbures plus lourds, c'est-à-dire d'hydrocarbures contenant au moins cinq atomes de carbone par chaîne hydrocarbonée. La présente invention se propose de pallier cet inconvénient lié en particulier à la structure et au type de catalyseurs employés pour la conversion du gaz de synthèse et vise à modifier la distribution des produits formés au cours de la synthèse Fischer-Tropsch en améliorant la production d'hydrocarbures contenant au moins cinq atomes de carbone par chaîne hydrocarbonée.However, all the catalysts known from the prior art and used in Fischer-Tropsch synthesis have a high selectivity in favor of the lighter hydrocarbons and in particular methane, undesirable, to the detriment of that in favor of heavier hydrocarbons, that is to say hydrocarbons containing at least five carbon atoms per hydrocarbon chain. The present invention proposes to overcome this drawback related in particular to the structure and type of catalysts used for the conversion of synthesis gas and aims at modifying the distribution of the products formed during Fischer-Tropsch synthesis by improving the production of hydrocarbons containing at least five carbon atoms per hydrocarbon chain.
Ainsi, la présente invention concerne un procédé de synthèse d'hydrocarbures à partir d'un mélange comprenant du monoxyde de carbone et de l'hydrogène (CO-H2), éventuellement du dioxyde de carbone CO2, en présence d'un catalyseur supporté comprenant au moins un métal du groupe VIII, le support comprenant de la zircone ou un oxyde mixte zircone-alumine et dans lequel la zircone est sous forme quadratique et/ou amorphe. Le catalyseur est utilisé en suspension dans une phase liquide dans un réacteur triphasique, généralement appelé réacteur slurry. Le plus souvent, le réacteur triphasique est du type colonne à bulles, également appelé slurry bubble column selon la terminologie anglosaxonne.
La Demanderesse a en effet découvert de manière surprenante que l'utilisation d'un support comprenant de la zircone sous forme quadratique et/ou amorphe, contenant éventuellement une phase alumine, permettait après imprégnation d'au moins un métal du groupe VIII, de préférence le cobalt, d'obtenir un catalyseur plus actif et plus sélectif que les catalyseurs antérieurs dans le procédé de synthèse d'hydrocarbures à partir d'un mélange comprenant du monoxyde de carbone et de l'hydrogène. De tels catalyseurs présentent des performances particulièrement stables et conduisent à la conversion du gaz de synthèse en un mélange d'hydrocarbures linéaires et saturés contenant au moins 50% poids d'hydrocarbures C5+ et moins de 20% de méthane par rapport à l'ensemble des hydrocarbures formés. L'utilisation d'un tel catalyseur en suspension dans une phase liquide dans un réacteur triphasique permet d'obtenir un solide stabilisé vis-à-vis des phénomènes d'attrition. De plus ce catalyseur présente une résistance mécanique améliorée par rapport à un catalyseur formé d'un support d'alumine seule ou de dioxyde de titane, la résistance mécanique étant déterminée par la mesure de l'évolution de la taille des particules pour une durée de test donnée dans une mise en oeuvre de type colonne à bulles.Thus, 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 medium comprising at least one Group VIII metal, the support comprising zirconia or a mixed zirconia-alumina oxide and wherein the zirconia is in quadratic and / or amorphous form. The catalyst is used in suspension in a liquid phase in a three-phase reactor, generally called slurry reactor. Most often, the triphasic reactor is of the bubble column type, also called slurry bubble column according to English terminology.
The Applicant has surprisingly discovered that the use of a support comprising zirconia in quadratic and / or amorphous form, optionally containing an alumina phase, allowed after impregnation of at least one metal of group VIII, preferably cobalt, to obtain a more active and 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 the 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 with respect to all hydrocarbons formed. The use of such a catalyst in suspension in a liquid phase in a three-phase reactor makes it possible to obtain a stabilized solid with respect to the attrition phenomena. In addition, this catalyst has an improved mechanical strength compared to a catalyst formed of a support of alumina alone or of titanium dioxide, the mechanical strength being determined by measuring the evolution of the particle size for a duration of test given in a bubble column implementation.
La structure cristalline de type quadratique de la zircone est caractérisée par diffraction des rayons X. Pour une telle structure, l'affinement du diagramme de diffraction conduit à une structure cristallographique dont les angles α, β et γ sont égaux à 90° et dont les paramètres de maille sont tels que a=b≠c. La zircone amorphe est caractérisée par l'absence de raie de diffraction significative sur le diagramme de diffraction.
Il est essentiel pour la mise en oeuvre du procédé de synthèse d'hydrocarbures selon l'invention que la zircone comprise dans le support catalytique soit entièrement dépourvue de structure cristalline de type monoclinique. Elle ne doit par ailleurs pas être sulfatée.The quadratic crystalline structure of zirconia is characterized by X-ray diffraction. For such a structure, the refinement of the diffraction pattern leads to a crystallographic structure whose angles α, β and γ are equal to 90 ° and whose mesh parameters are such that a = b ≠ c. Amorphous zirconia is characterized by the absence of significant diffraction line on the diffraction pattern.
It is essential for the implementation of the hydrocarbon synthesis process according to the invention that the zirconia included in the catalytic support is entirely devoid of a monoclinic type crystalline structure. It should not be sulphated.
Le support utilisé dans le procédé de synthèse d'hydrocarbures selon la présente invention contient au moins 10% poids de zircone sous forme quadratique et/ou amorphe par rapport à la masse totale du support et contient de 0 à 90% poids de Al2O3, de préférence de 1 à 75%, de manière encore plus préférée de 5% à 60% poids de Al2O3 par rapport à la masse totale du support.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 Al 2 O 3 , preferably from 1 to 75%, even more preferably from 5% to 60% by weight of Al 2 O 3 relative to the total mass of the support.
Avantageusement, le support comprenant de la zircone ou un oxyde mixte zircone-alumine et dans lequel la zircone est sous forme quadratique et/ou amorphe présente une surface spécifique supérieure à 50 m2/g, de manière préférée supérieure à 80 m2/g et de manière encore préférée supérieure à 100 m2/g.
Ainsi tout procédé de synthèse de zircone connu de l'homme du métier conduisant à une zircone quadratique et/ou amorphe présentant avantageusement une surface spécifique supérieure à 50 m2/g convient pour préparer les supports de catalyseurs utilisés dans le procédé de synthèse d'hydrocarbures selon l'invention. Lorsque le support comprend un oxyde mixte zircone-alumine, une phase alumine est associée à la zircone sous forme quadratique et/ou amorphe.
A titre d'exemple, le support de catalyseur utilisé dans le procédé de synthèse d'hydrocarbures selon l'invention peut être préparé par précipitation vraie ou coprécipitation en solution aqueuse, dans des conditions opératoires stationnaires maîtrisées (pH, concentration, température, temps de séjour moyen) par réaction d'une solution acide contenant le zirconium par exemple le nitrate de zirconium ou le chlorure de zirconium, optionnellement de l'aluminium par exemple le sulfate d'aluminium, le nitrate d'aluminium, avec une solution basique telle que l'ammoniaque ou l'hydrazine. Une méthode particulière de préparation de tels supports et issue de l'enseignement de la demande de brevet
Le support est alors obtenu par filtration et lavage, séchage avec mise en forme puis calcination. L'étape unitaire de séchage avec mise en forme est réalisée de manière préférée par atomisation, qui permet d'obtenir des microbilles sensiblement sphériques de taille inférieure à 500 microns. Après séchage, le produit est calciné préférentiellement sous air et dans un four rotatif à une température comprise entre 400°C et 1200°C, de préférence entre 400°C et 800°C et pendant un temps suffisant de manière à ce que la surface spécifique BET du support présente avantageusement une valeur supérieure à 50 m2/g, de préférence supérieure à 80 m2/g et de manière encore plus préférée supérieure à 100 m2/g. Advantageously, 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 area greater than 50 m 2 / g, preferably greater than 80 m 2 / g and still more preferably greater than 100 m 2 / g.
Thus any zirconia synthesis process known to those skilled in the art leading to a quadratic and / or amorphous zirconia advantageously having a surface area greater than 50 m 2 / g is suitable for preparing the catalyst supports used in the synthesis process of hydrocarbons according to the invention. When the support comprises a mixed zirconia-alumina oxide, an alumina phase is associated with zirconia in quadratic and / or amorphous form.
By way of example, the catalyst support used in the hydrocarbon synthesis process according to the invention can be prepared by true precipitation or coprecipitation in aqueous solution under controlled stationary operating conditions (pH, concentration, temperature, reaction time). average residence time) 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 media and resulting from the teaching of the patent application
The support is then obtained by filtration and washing, drying with shaping and calcination. The unitary step of drying with shaping is preferably carried out by atomization, which makes it possible to obtain substantially spherical microbeads less than 500 microns in size. After drying, the product is calcined preferably in air and in a rotary oven at a temperature of between 400 ° C. and 1200 ° C., preferably between 400 ° C. and 800 ° C. and for a sufficient time so that the surface The specific BET 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 .
Dans l'ensemble des méthodes précitées, il peut enfin être souhaité d'ajouter une proportion mineure d'au moins un élément stabilisant choisi dans le groupe formé par le silicium, le niobium, le lanthane, le praséodyme et le néodyme. L'élément stabilisant est ajouté en proportion de 0,5 à 5% en poids par rapport au support zircone ou zircone-alumine préformé, sous forme d'un sel soluble par exemple le nitrate.
Le support est en général sous forme de poudre fine calibrée présentant une taille de grain inférieure à 500 microns, de préférence comprise entre 10 et 150 microns et de manière encore plus préférée entre 20 et 120 microns, pour une utilisation optimale en présence de phase liquide dans une colonne à bulles. Avantageusement, le support présente les propriétés texturales suivantes : un volume poreux supérieur à 0,1 cm3/g et un diamètre de pores moyen supérieur à 6 nm, de préférence supérieur à 8 nm.In all the aforementioned methods, it may finally be desired to add a minor proportion of at least one 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 support zirconia or zirconia-alumina preformed in the form of a soluble salt for example nitrate.
The support is generally in the form of a finely graded powder having a grain size of less than 500 microns, preferably of between 10 and 150 microns and even more preferably of between 20 and 120 microns, for optimum use in the presence of a liquid phase. in a bubble column. Advantageously, 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.
Le catalyseur utilisé dans le procédé de synthèse d'hydrocarbures selon l'invention comprend au moins un métal du groupe VIII de la classification périodique des éléments, supporté sur une zircone quadratique et/ou amorphe, contenant éventuellement une phase alumine et/ou éventuellement au moins un stabilisant. L'élément du groupe VIII de la classification périodique des éléments est choisi dans le groupe constitué par le fer, le cobalt et le ruthénium. De préférence, le métal du groupe VIII est le cobalt. La teneur en poids par rapport au poids total de catalyseur en métal du groupe VIII est comprise entre 0,1 et 50%, préférentiellement entre 1 et 30%. Une technique de préparation du catalyseur qui convient particulièrement est l'imprégnation sur le support comprenant de la zircone ou un oxyde mixte zircone-alumine d'une solution aqueuse d'un précurseur du métal du groupe VIII de la classification périodique des éléments, de préférence le cobalt, par exemple une solution aqueuse de sels tels que les nitrates de cobalt.The catalyst used in the hydrocarbon synthesis process according to the invention comprises at least one metal of group VIII of the periodic table of elements, supported on a quadratic and / or amorphous zirconia, optionally containing an alumina phase and / or optionally minus one stabilizing. The element of group VIII of the Periodic Table of Elements is selected from the group consisting of iron, cobalt and ruthenium. Preferably, the Group VIII metal is cobalt. The content by weight relative to the total weight of Group VIII metal catalyst is between 0.1 and 50%, preferably between 1 and 30%. A particularly suitable catalyst preparation technique is the impregnation on the support comprising zirconia or zirconia-alumina mixed oxide of an aqueous solution of a Group VIII metal precursor of the Periodic Table of Elements, preferably cobalt, for example an aqueous solution of salts such as cobalt nitrates.
Le catalyseur peut aussi contenir d'autres éléments additionnels notamment des promoteurs d'activité, tels que par exemple au moins un élément choisi parmi le ruthénium, le molybdène et le tantale ou des promoteurs de réductibilité tels que par exemple le platine, le palladium ou le ruthénium. La teneur, en poids, d'un élément additionnel par rapport au poids total de catalyseur est généralement comprise entre 0,01 et 5%. Ces éléments additionnels peuvent être introduits en même temps que le métal du groupe VIII ou dans au moins une étape ultérieure.The catalyst may also contain other additional elements, in particular promoters of activity, 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.
Dans un mode particulier de réalisation de l'invention, le catalyseur contient du cobalt et du ruthénium.In a particular embodiment of the invention, the catalyst contains cobalt and ruthenium.
Dans un autre mode particulier de réalisation de l'invention, le catalyseur contient du cobalt et du tantale.In another particular embodiment of the invention, the catalyst contains cobalt and tantalum.
En vue d'être utilisé dans le procédé de synthèse d'hydrocarbures selon l'invention, le catalyseur comprenant au moins un métal du groupe VIII imprégné sur le support comprenant de la zircone quadratique et/ou amorphe et contenant éventuellement une phase alumine est soumis à des étapes de séchage et de calcination, puis est pré-réduit par au moins un composé réducteur, par exemple choisi dans le groupe formé par l'hydrogène, le monoxyde de carbone et l'acide formique, éventuellement mis en contact avec un gaz inerte tel que l'azote, par exemple dans un rapport molaire composé réducteur/(composé réducteur + gaz inerte) compris entre 0,001 :1 et 1 :1. La réduction peut être menée en phase gazeuse à une température comprise entre 100°C et 600°C, de préférence entre 150°C et 400°C, à une pression comprise entre 0,1 et 10 MPa et à une vitesse volumétrique horaire entre 100 et 40 000 volumes de mélange par volume de catalyseur et par heure. Cette réduction peut également être menée en phase liquide, le catalyseur étant mis en suspension dans un solvant inerte, par exemple une coupe paraffinique comprenant au moins un hydrocarbure ayant au moins 5, de préférence au moins 10 atomes de carbone par molécule si par la suite la réaction de synthèse d'hydrocarbures se déroule en phase liquide comprenant au moins un hydrocarbure ayant au moins 5, de préférence au moins 10 atomes de carbone par molécule.For use in the hydrocarbon synthesis process according to the invention, 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 to at stages of drying and calcination, and then is pre-reduced by at least one reducing compound, for example chosen from the group formed by hydrogen, carbon monoxide and formic acid, possibly brought into contact with a gas inert form such as nitrogen, for example in a reducing compound / reducing compound (reducing compound + inert gas) molar ratio of between 0.001: 1 and 1: 1. The reduction can be conducted in phase at a temperature of between 100 ° C. and 600 ° C., preferably between 150 ° C. and 400 ° C., at a pressure of between 0.1 and 10 MPa and at a volumetric hourly velocity of between 100 and 40,000 volumes of mixture per 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 cut comprising at least one hydrocarbon having at least 5, preferably at least 10 carbon atoms per molecule, if thereafter the hydrocarbon synthesis reaction is carried out in the liquid phase comprising at least one hydrocarbon having at least 5, preferably at least 10 carbon atoms per molecule.
La conversion du gaz de synthèse en hydrocarbures est ensuite opérée sous une pression totale habituellement comprise entre 0,1 et 15 MPa et de préférence entre 1 et 10 MPa, la température étant généralement comprise entre 150 et 350°C et de préférence entre 170 et 300°C. La vitesse volumétrique horaire est habituellement comprise entre 100 et 20 000 volumes de gaz de synthèse par volume de catalyseur et par heure et de préférence entre 400 et 5000 volumes de gaz de synthèse par volume de catalyseur et par heure, et le rapport H2/CO dans le gaz de synthèse est habituellement compris entre 1 : 2 et 5 :1, de préférence entre 1,2 :1 et 2,5 :1.The conversion of the synthesis gas into hydrocarbons is then carried out under a total pressure usually of between 0.1 and 15 MPa and preferably between 1 and 10 MPa, the temperature generally being between 150 and 350 ° C. and preferably between 170 and 300 ° C. The hourly volumetric rate is usually between 100 and 20 000 volumes of synthesis gas per volume of catalyst per hour and preferably between 400 and 5000 volumes of synthesis gas per volume of catalyst per hour, and the ratio H 2 / The CO in the synthesis gas is usually between 1: 2 and 5: 1, preferably between 1.2: 1 and 2.5: 1.
Le catalyseur est préférentiellement utilisé sous forme de poudre fine calibrée présentant une taille de grain inférieure à 500 microns, de préférence entre 10 et 150 microns, de manière plus souhaitée entre 20 et 120 microns, en présence d'une phase liquide laquelle peut être constituée par au moins un hydrocarbure ayant au moins 5, de préférence au moins 10, atomes de carbone par molécule. L'utilisation du catalyseur en suspension dans une phase liquide dans un réacteur triphasique de type colonne à bulles est avantageuse car ce type de mise en oeuvre permet une utilisation optimale des performances du catalyseur (activité et sélectivité), par limitation des phénomènes diffusionnels intra-granulaires, ainsi qu'une limitation très importante des effets thermiques dans le grain de catalyseur, qui est entouré d'une phase liquide. Ce type de mise en oeuvre impose une séparation du catalyseur des produits de réaction. Dans ces conditions, le catalyseur présente des propriétés mécaniques améliorées permettant une séparation du catalyseur et des produits optimale et une durée de vie dudit catalyseur augmentée.The catalyst is preferably used in the form of fine calibrated powder having a grain size of less than 500 microns, preferably between 10 and 150 microns, more desirably between 20 and 120 microns, in the presence of a liquid phase which may be constituted by 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 bubble column type is advantageous because this type of implementation allows optimal use of the catalyst performance (activity and selectivity), by limiting the diffusional phenomena within the granular, as well as a very significant limitation of thermal effects in the catalyst grain, which is surrounded by a liquid phase. This type of implementation requires a separation of the catalyst from the reaction products. Under these conditions, the catalyst has improved mechanical properties allowing optimal catalyst and product separation and increased catalyst life.
Les exemples qui suivent illustrent l'invention sans toutefois en limiter la portée. Dans ces exemples les pourcentages sont en poids.The examples which follow illustrate the invention without, however, limiting its scope. In these examples the percentages are by weight.
Un catalyseur A, Co/ZrO2, est préparé par imprégnation de nitrate de cobalt sur une poudre de zircone. La teneur en cobalt métallique est de 13%.
La zircone est préalablement préparée par précipitation de nitrate de zirconium par l'hydrazine : elle est amorphe et présente une surface spécifique de 250 m2/g après calcination à 550°C. La suspension obtenue est atomisée et le support ainsi obtenu se présente sous forme de poudre de granulométrie comprise entre 20 et 150 microns. Le catalyseur issu de l'imprégnation est séché et calciné à 400°C.A catalyst, Co / ZrO 2 , is prepared by impregnating cobalt nitrate on a zirconia powder. The cobalt metal content is 13%.
The zirconia is prepared beforehand by precipitation of zirconium nitrate with hydrazine: it is amorphous and has a specific surface area 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 of between 20 and 150 microns. The catalyst resulting from the impregnation is dried and calcined at 400 ° C.
Un catalyseur B, Co/ZrO2-Al2O3, est préparé par imprégnation de nitrate de cobalt sur une zircone-alumine. La teneur en cobalt métallique est égale à 12,5%.
La zircone-alumine est préalablement préparée par coprécipitation d'un mélange ZrOCl2 et Al(NO3)3 auquel est ajouté NH4OH. Après séchage et calcination à 700°C, le support est amorphe, sa surface spécifique est de 158 m2/g. Le support contient 15% d'alumine. Le catalyseur issu de l'imprégnation est séché et calciné à 400°C.A catalyst B, Co / ZrO 2 -Al 2 O 3 , is prepared by impregnation of cobalt nitrate on a zirconia-alumina. The cobalt metal content is equal to 12.5%.
The zirconia-alumina is prepared beforehand by coprecipitation of a mixture ZrOCl 2 and Al (NO 3 ) 3 to which NH 4 OH is added. After drying and calcining at 700 ° C., the support is amorphous, its specific surface area is 158 m 2 / g. The support contains 15% alumina. The catalyst resulting from the impregnation is dried and calcined at 400 ° C.
Un catalyseur C, Co/ZrO2, est préparé par imprégnation de nitrate de cobalt sur une zircone. La teneur en cobalt métallique est égale à 13%.
La zircone est préalablement préparée par précipitation de ZrOCl2 avec NH4OH suivie d'un mûrissement à pH constant. Après séchage et calcination à 500°C, la zircone est quadratique et présente une surface spécifique de 135 m2/g. Le catalyseur issu de l'imprégnation est séché et calciné à 400°C.A C, Co / ZrO 2 catalyst is prepared by impregnating cobalt nitrate with a zirconia. The cobalt metal content is 13%.
The zirconia is previously prepared by precipitation of ZrOCl 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 area of 135 m 2 / g. The catalyst resulting from the impregnation is dried and calcined at 400 ° C.
Un catalyseur D est préparé par imprégnation de nitrate de cobalt sur un support contenant 70% d'alumine, 25% de zircone et 5% de silice. La teneur en cobalt métallique est égale à 12%.
Le support est préparé comme dans l'exemple 2 par coprécipitation d'un mélange ZrOCl2 et Al(NO3)3 auquel est ajouté NH4OH. Simultanément à l'ajout de NH4OH, une petite quantité de silicate d'ammonium est additionnée de manière à obtenir la composition du support catalytique décrite ci dessus. Après séchage et calcination à 550°C, le support obtenu est amorphe et présente une surface de 90 m2/g. Le catalyseur issu de l'imprégnation est séché et calciné à 400°C.A catalyst D is prepared by impregnation of cobalt nitrate on a support containing 70% of alumina, 25% of zirconia and 5% of silica. The content of cobalt metal is equal to 12%.
The support is prepared as in Example 2 by coprecipitation of a mixture ZrOCl 2 and Al (NO 3 ) 3 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 catalyst support described above. After drying and calcination at 550 ° C., the support obtained is amorphous and has an area of 90 m 2 / g. The catalyst resulting from the impregnation is dried and calcined at 400 ° C.
Un catalyseur E, Co/Al2O3, est préparé par imprégnation de nitrate de cobalt sur un support constitué d'une poudre d'alumine Puralox Scca 5-170 de surface spécifique égale à 180 m2/g. La teneur finale en cobalt est de 12,5%. Le support d'alumine employé se présente sous forme de poudre de granulométrie comprise entre 20 et 150 microns. Le catalyseur issu de l'imprégnation est séché et calciné à 400°C.An E, Co / Al 2 O 3 catalyst is prepared by impregnating cobalt nitrate on a support consisting of a Puralox Scca 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 employed is in the form of a powder having a particle size of between 20 and 150 microns. The catalyst resulting from the impregnation is dried and calcined at 400 ° C.
Un catalyseur F est préparé par imprégnation de nitrate de cobalt sur un support contenant 90% d'alumine, 10% de zircone. La teneur en cobalt métallique est égale à 13%.
Le support est préparé par imprégnation d'isopropoxyde de zirconium sur une poudre d'alumine Puralox Scca 5-170 de surface spécifique égale à 180 m2/g. Après séchage et calcination à 550°C, le support obtenu présente de la zircone sous forme monoclinique. Le catalyseur issu de l'imprégnation est séché et calciné à 400°C.Catalyst F is prepared by impregnating cobalt nitrate on a support containing 90% alumina, 10% zirconia. The cobalt metal content is 13%.
The support is prepared by impregnating zirconium isopropoxide with Puralox Scca 5-170 alumina powder having a specific surface area of 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.
Un catalyseur G, Co/ZrO2, est préparé par imprégnation de nitrate de cobalt sur une zircone. La teneur en cobalt métallique est égale à 13%.
La zircone est préparée par précipitation de ZrOCl2 avec NH4OH. Le gel fraîchement préparé est lavé à l'éthanol. Après séchage et calcination à 500°C, la zircone est monoclinique et présente une surface de 112 m2/g. Le catalyseur issu de l'imprégnation est séché et calciné à 400°C.A catalyst G, Co / ZrO 2 , is prepared by impregnation of cobalt nitrate on a zirconia. The cobalt metal content is 13%.
The zirconia is prepared by precipitation of ZrOCl 2 with NH 4 OH. The freshly prepared gel is washed with ethanol. After drying and calcining at 500.degree. 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.
Les catalyseurs A, B, C, D, E, F et G dont les préparations sont décrites dans les exemples 1 à 7 ci-dessus sont testés dans un réacteur triphasique, (type slurry), parfaitement agité, fonctionnant en continu et opérant avec une concentration de 10% (mol) de catalyseur en suspension.
Les catalyseurs sont préalablement réduits à 400°C pendant 8 heures sous un mélange d'hydrogène et d'azote contenant 30% d'hydrogène, puis pendant 12 heures sous hydrogène pur.
Les conditions de test des catalyseurs sont les suivantes :
- T(°C) = 230°C,
- Pression = 2MPa
- Vitesse volumique horaire (VVH) = 1000 h-1
- Rapport molaire H2/CO = 2/1
The catalysts are reduced beforehand to 400 ° C. for 8 hours under a mixture of hydrogen and nitrogen containing 30% hydrogen, and then for 12 hours under pure hydrogen.
The catalyst test conditions are as follows:
- T (° C) = 230 ° C,
- Pressure = 2MPa
- Hourly volume velocity (VVH) = 1000 h -1
- Molar ratio H 2 / CO = 2/1
Les résultats du tableau 1 montrent que le procédé selon l'invention en présence d'un catalyseur supporté sur zircone amorphe ou quadratique contenant ou non une phase alumine présente une sélectivité en méthane plus faible et un rendement en produits lourds sensiblement amélioré.The results in Table 1 show that the process according to the invention in the presence of a catalyst supported on amorphous or quadratic zirconia containing or not an alumina phase has a lower methane selectivity and a substantially improved yield of heavy products.
Après 500 heures de test, la résistance mécanique des catalyseurs A à G a été évaluée par mesure de la granulométrie des catalyseurs obtenus après séparation des produits de réaction. - Le tableau 2 ci-dessous donne le pourcentage de particules de catalyseur présentant une taille inférieure à 20 microns formées lors des tests des catalyseurs A à G.
Les catalyseurs utilisés dans le procédé selon l'invention (A à D) présentent une résistance mécanique nettement supérieure par rapport aux catalyseurs E, F et 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.
Claims (11)
- A process for synthesising hydrocarbons from a mixture comprising carbon monoxide and hydrogen and possibly carbon dioxide CO2, in the presence of a catalyst comprising at least one group VIII metal in the range 0.1% to 50% by weight with respect to the total catalyst weight and a support containing at least 10% by weight of zirconia in the quadratic and/or amorphous form compared with the total weight of support, said support comprising zirconia or a mixed zirconia-alumina oxide, said catalyst being used in suspension in a liquid phase in a three-phase reactor.
- A process according to claim 1, in which said support containing from 0 to 90% by weight of alumina compared with the total weight of said support.
- A process according to claim 2, in which said support contains at least 10% by weight of zirconia in the quadratic and/or amorphous form compared with the total weight of support and 1% to 75% by weight of alumina compared with the total weight of said support.
- A process according to one of claims 1 to 3, in which said support has a specific surface area of more than 50 m2/g.
- A process according to one of claims 1 to 4, in which said support has a specific surface area of more than 80 m2/g.
- A process according to one of claims 1 to 5, in which said support contains at least one stabilizing element selected from the group formed by silicon, niobium, lanthanum, prascodymium and neodymium.
- A process according to one of claims 1 to 6, in which the group VIII metal is selected from the group formed by iron, cobalt and ruthenium.
- A process according to one of claims 1 to 7, in which the group VIII metal is cobalt.
- A process according to one of claims 1 to 8, in which the catalyst contains at least one activity promoter.
- A process according to one of claims 1 to 9, in which the catalyst contains at least one reducibility promoter.
- A process according to one of claims 1 to 10, in which the catalyst is in the form of a fine powder with a grain size of less than 500 µm.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0113138 | 2001-10-11 | ||
FR0113138A FR2830858B1 (en) | 2001-10-11 | 2001-10-11 | PROCESS FOR THE SYNTHESIS OF HYDROCARBONS IN A THREE-PHASE REACTOR IN THE PRESENCE OF A CATALYST COMPRISING A GROUP VIII METAL SUPPORTED ON ZIRCONIA OR ON MIXED ZIRCONIUM-ALUMINA OXIDE |
PCT/FR2002/003415 WO2003044126A1 (en) | 2001-10-11 | 2002-10-08 | Method for hydrocarbon synthesis in a three-phase reactor in the presence of a catalyst comprising a group viii metal supported on zirconia or mixed zirconia-alumina oxide |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1436360A1 EP1436360A1 (en) | 2004-07-14 |
EP1436360B1 true EP1436360B1 (en) | 2010-04-07 |
Family
ID=8868202
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02803430A Expired - Fee Related EP1436360B1 (en) | 2001-10-11 | 2002-10-08 | Method for hydrocarbon synthesis in a three-phase reactor in the presence of a catalyst comprising a group viii metal supported on zirconia or mixed zirconia-alumina oxide |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP1436360B1 (en) |
CA (1) | CA2462535C (en) |
DE (1) | DE60235903D1 (en) |
FR (1) | FR2830858B1 (en) |
WO (1) | WO2003044126A1 (en) |
ZA (1) | ZA200402139B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1719555A4 (en) * | 2004-02-24 | 2012-04-11 | Japan Oil Gas & Metals Jogmec | Catalyst for producing hydrocarbons, method for preparing the same, and method for producing hydrocarbons using the same |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH670250A5 (en) * | 1986-11-05 | 1989-05-31 | Lonza Ag | |
DE4445142A1 (en) * | 1994-12-17 | 1996-06-20 | Basf Ag | Catalysts or supports consisting essentially of monoclinic zirconia |
DZ2370A1 (en) * | 1996-12-13 | 2002-12-28 | Shell Int Research | Process for the preparation of hydrocarbons |
FR2769519B1 (en) * | 1997-10-13 | 1999-12-31 | Total Raffinage Distribution | ACID CATALYST BASED ON SULFATED ZIRCONE AND USES THEREOF |
-
2001
- 2001-10-11 FR FR0113138A patent/FR2830858B1/en not_active Expired - Fee Related
-
2002
- 2002-10-08 EP EP02803430A patent/EP1436360B1/en not_active Expired - Fee Related
- 2002-10-08 CA CA2462535A patent/CA2462535C/en not_active Expired - Lifetime
- 2002-10-08 WO PCT/FR2002/003415 patent/WO2003044126A1/en active Application Filing
- 2002-10-08 DE DE60235903T patent/DE60235903D1/en not_active Expired - Lifetime
-
2004
- 2004-03-17 ZA ZA2004/02139A patent/ZA200402139B/en unknown
Also Published As
Publication number | Publication date |
---|---|
FR2830858A1 (en) | 2003-04-18 |
WO2003044126A1 (en) | 2003-05-30 |
EP1436360A1 (en) | 2004-07-14 |
ZA200402139B (en) | 2005-09-28 |
CA2462535C (en) | 2010-06-29 |
FR2830858B1 (en) | 2003-12-12 |
CA2462535A1 (en) | 2003-05-30 |
DE60235903D1 (en) | 2010-05-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1666141B1 (en) | Reducing fischer-tropsch catalyst attrition losses in high agitation reaction systems | |
JP4210338B2 (en) | Method for preparing highly active catalyst and catalyst and use thereof | |
EP1827684B1 (en) | Cobalt-based catalyst for fischer-tropsch synthesis | |
EP1053785B1 (en) | Catalytic support based on metal oxide of group IVB, its preparation and uses thereof | |
EP0581619B1 (en) | Process for the conversion of synthesis gas into hydrocarbons with a cobalt based catalyst | |
FR2804689A1 (en) | PROCESS FOR THE SYNTHESIS OF HYDROCARBONS IN THE PRESENCE OF A CATALYST COMPRISING A GROUP VIII METAL SUPPORTED ON SILICA-ALUMINA | |
CA2833079A1 (en) | Catalysts | |
EP3496856B1 (en) | A cobalt-containing catalyst composition | |
US11912943B2 (en) | Fischer-Tropsch process, supported Fischer-Tropsch synthesis catalyst and uses thereof | |
CA2359428C (en) | Process for converting synthesis gas in the presence of a catalyst including one element from group viii dispersed on a support based on alumina modified by aqueous impregnation of quaternary ammonium silicate | |
JP2003024786A (en) | Catalyst for fischer-tropsch synthesis and method for producing hydrocarbon | |
EP0987236B2 (en) | Process for the conversion of synthesis gas in presence of a catalyst comprising a metal of group VIII, its particles being spread as aggregates | |
BE1006539A4 (en) | Synthetic process of hydrocarbons from synthesis gas in the presence of a catalyst of cobalt. | |
EP1436360B1 (en) | Method for hydrocarbon synthesis in a three-phase reactor in the presence of a catalyst comprising a group viii metal supported on zirconia or mixed zirconia-alumina oxide | |
EP3628400A1 (en) | Fischer-tropsch process, supported fischer-tropsch synthesis catalyst and uses thereof | |
EP1702025B1 (en) | Method for converting a synthesis gas into hydrocarbons in the presence of beta-sic and the effluent of said method | |
US7241815B2 (en) | Process for synthesising hydrocarbons in a three-phase reactor in the presence of a catalyst comprising a group VIII metal supported on zirconia or on a zirconia-alumina mixed oxide | |
AU2019350393A1 (en) | Fischer-tropsch process | |
AU2021402423A1 (en) | Fischer-tropsch processes with modified product selectivity | |
CA3201249A1 (en) | Fischer-tropsch processes producing increased amounts of alcohols | |
EA043038B1 (en) | FISCHER-TROPSCH METHOD, SUPPORTED CATALYST FOR FISCHER-TROPSCH SYNTHESIS AND ITS APPLICATION |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20040511 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK RO SI |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: PEDERZANI, GIOVANNI Inventor name: ZENNARO, ROBERTO Inventor name: ENACHE, DAN Inventor name: TISSOT, VIRGINIE Inventor name: REVEL, RENAUD Inventor name: ROY-AUBERGER, MAGALIE |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: PEDERZANI, GIOVANNI Inventor name: ZENNARO, ROBERTO Inventor name: ENACHE, DAN Inventor name: TISSOT, VIRGINIE Inventor name: REVEL, RENAUD Inventor name: ROY-AUBERGER, MAGALIE |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: PEDERZANI, GIOVANNI Inventor name: ZENNARO, ROBERTO Inventor name: ENACHE, DAN Inventor name: TISSOT, VIRGINIE Inventor name: REVEL, RENAUD Inventor name: ROY-AUBERGER, MAGALIE |
|
17Q | First examination report despatched |
Effective date: 20081216 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: PEDERZANI, GIOVANNI Inventor name: ZENNARO, ROBERTO Inventor name: ENACHE, DAN ION Inventor name: TISSOT, VIRGINIE Inventor name: REVEL, RENAUD Inventor name: ROY-AUBERGER, MAGALIE |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE IT NL |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: T3 |
|
REF | Corresponds to: |
Ref document number: 60235903 Country of ref document: DE Date of ref document: 20100520 Kind code of ref document: P |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20101022 Year of fee payment: 9 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20101130 Year of fee payment: 9 |
|
26N | No opposition filed |
Effective date: 20110110 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20101021 Year of fee payment: 9 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R081 Ref document number: 60235903 Country of ref document: DE Owner name: ENI S.P.A., IT Free format text: FORMER OWNERS: INSTITUT FRANCAIS DU PETROLE, RUEIL-MALMAISON, HAUTS-DE-SEINE, FR; ENI S.P.A., ROM/ROMA, IT Effective date: 20110329 Ref country code: DE Ref legal event code: R081 Ref document number: 60235903 Country of ref document: DE Owner name: IFP ENERGIES NOUVELLES, FR Free format text: FORMER OWNERS: INSTITUT FRANCAIS DU PETROLE, RUEIL-MALMAISON, HAUTS-DE-SEINE, FR; ENI S.P.A., ROM/ROMA, IT Effective date: 20110329 Ref country code: DE Ref legal event code: R081 Ref document number: 60235903 Country of ref document: DE Owner name: IFP ENERGIES NOUVELLES, FR Free format text: FORMER OWNER: INSTITUT FRANCAIS DU PETROLE, ENI S.P.A., , IT Effective date: 20110329 Ref country code: DE Ref legal event code: R081 Ref document number: 60235903 Country of ref document: DE Owner name: ENI S.P.A., IT Free format text: FORMER OWNER: INSTITUT FRANCAIS DU PETROLE, ENI S.P.A., , IT Effective date: 20110329 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: V1 Effective date: 20120501 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120501 Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120501 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 60235903 Country of ref document: DE Effective date: 20120501 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20111008 |