WO2017197980A1 - Catalyseur de synthèse de fischer-tropsch bimétallique intégral à base de cobalt/fer et son procédé de préparation - Google Patents

Catalyseur de synthèse de fischer-tropsch bimétallique intégral à base de cobalt/fer et son procédé de préparation Download PDF

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WO2017197980A1
WO2017197980A1 PCT/CN2017/078053 CN2017078053W WO2017197980A1 WO 2017197980 A1 WO2017197980 A1 WO 2017197980A1 CN 2017078053 W CN2017078053 W CN 2017078053W WO 2017197980 A1 WO2017197980 A1 WO 2017197980A1
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cobalt
iron
fischer
monolithic
tropsch synthesis
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PCT/CN2017/078053
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Chinese (zh)
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海国良
李昌元
刘倩倩
饶莎莎
郑申棵
宋德臣
詹晓东
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武汉凯迪工程技术研究总院有限公司
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Publication of WO2017197980A1 publication Critical patent/WO2017197980A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/643—Pore diameter less than 2 nm
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions

Definitions

  • the invention belongs to the technical field of Fischer-Tropsch synthesis catalyst, and specifically relates to a monolithic iron-cobalt bimetal Fischer-Tropsch synthesis catalyst and a preparation method thereof.
  • Fischer-Tropsch synthesis has been closely related to the price of petroleum. With the increasing shortage of petroleum resources and increasingly demanding environmental protection, Fischer-Tropsch synthesis has renewed great interest in the past 20 years.
  • the active metals that can be used in Fischer-Tropsch synthesis are mainly concentrated in the eighth group, such as ruthenium, nickel, cobalt, iron, ruthenium, palladium, platinum, etc., but due to price, activity, selectivity, etc., only the iron and cobalt.
  • Iron catalysts are inexpensive and allow a wide range of operating temperatures and are the first catalysts to be applied to Fischer-Tropsch synthesis.
  • the iron-based catalyst has high water gas shift reaction activity, is easy to deposit carbon and poison, thereby causing catalyst deactivation, and the iron-based catalyst has poor chain growth ability, and easily forms olefins and oxygenates.
  • Cobalt-based catalysts are not sensitive to water gas change reaction, stable in the reaction process, difficult to cause catalyst carbon deposition and poisoning, long life, high Fischer-Tropsch chain growth ability, high single pass conversion, and high molecular weight
  • the formation of hydrocarbons and long-chain hydrocarbon compounds can produce fuels such as lubricating oil and diesel oil through further hydrocracking, and the oxygen-containing compounds in the products are less. It is considered to be the most suitable for Fischer-Tropsch synthesis using syngas as raw material.
  • Catalysts are also hotspots in current research, but cobalt catalysts have lower operating temperatures, lower space-time yields than iron-based catalysts, and less olefin content in the product.
  • active metal cobalt, iron and nickel to prepare a double active component catalyst, the Fischer-Tropsch reaction activity of the catalyst can be improved, and the product distribution can be adjusted, which is a new direction of current research and development.
  • the monolith catalyst is generally composed of a monolithic support, a washcoat, and an active component.
  • the catalyst bed of the monolith catalyst has small lamination loss, high mass transfer and heat transfer efficiency, easy reactor amplification, easy separation of catalyst and product, simple catalyst regeneration, and good heat transfer effect, corrosion resistance and high mechanical strength.
  • the monolithic support has a small surface area, and the catalyst and the reactor wall are liable to cause gaps, resulting in low reaction efficiency.
  • the object of the present invention is to provide a monolithic iron-cobalt bimetallic Fischer-Tropsch synthesis catalyst and a preparation method thereof, in view of the deficiencies of the prior art.
  • the catalyst has the advantages of large surface area of the carrier and strong catalyst adhesion performance, and the preparation method has the advantages of simple process and good product performance stability.
  • the monolithic iron-cobalt bimetallic Fischer-Tropsch synthesis catalyst of the present invention comprises a porous metal iron carrier, a molecular sieve membrane coated on the surface of the porous metal iron carrier, and a metal active component cobalt supported on the molecular sieve membrane.
  • the porous metal iron carrier is a polyurethane foam divided into fragments and is immersed in a binder solution mixed with active powdered alumina, potassium carbonate, calcium carbonate, magnetite and iron powder, and then passed through
  • the monolithic three-dimensional network structure carrier which is dried and sintered, and the weight ratio of the main components in the monolithic three-dimensional network structure carrier satisfies the following mathematical relationship:
  • Fe:Al 2 O 3 :K 2 O:CaO 100: (1.5 ⁇ 6.0): (0.2 ⁇ 2.8): (0.2 ⁇ 3.2);
  • the molecular sieve membrane is a cluster aggregate of ZSM-5 nanoparticles dispersed uniformly;
  • the metal active component cobalt is supported in an amount of 10 to 30% by weight based on the weight of the finished catalyst.
  • the active powder alumina, potassium carbonate, calcium carbonate, magnetite and iron powder have an average particle size of 120 to 240 mesh, and the alumina has a specific surface area of 160 to 290 m 2 /g, the monolithic
  • the three-dimensional network structure carrier has a porosity of 85% or more.
  • the active powder alumina, potassium carbonate, calcium carbonate, magnetite and iron powder have an average particle size of 150 to 200 mesh, and the alumina has a specific surface area of 180 to 270 m 2 /g, the whole
  • the three-dimensional network structure carrier has a porosity of 88% or more.
  • the ZSM-5 nanoparticles have an average particle diameter ranging from 10 to 30 nm, a pore diameter of 2.0 nm or less, and a gap between adjacent ZSM-5 nanoparticles of less than or equal to 100 nm.
  • the ZSM-5 nanoparticles have an average particle diameter ranging from 15 to 25 nm, a micropore diameter of 0.5 to 1.0 nm, and a gap between adjacent ZSM-5 nanoparticles of less than or equal to 80 nm.
  • the metal active component cobalt is supported in an amount of 15 to 25% by weight of the finished catalyst.
  • the preparation method of the monolithic iron-cobalt bimetal Fischer-Tropsch synthesis catalyst is special in that it comprises the following steps:
  • the porous metal iron carrier coated by the molecular sieve self-assembly is washed, and then dried and calcined to obtain a porous metal iron carrier coated by a molecular sieve membrane, which is a cluster uniformly dispersed with ZSM-5 nanoparticles. Aggregates;
  • the metal active component cobalt can be supported on the molecular sieve membrane on the surface of the porous metal iron carrier to obtain a monolithic iron-cobalt bimetallic Fischer-Tropsch synthesis catalyst.
  • the average particle size of alumina, potassium carbonate, calcium carbonate, magnetite and iron powder is 120 to 240 mesh, and the specific surface area of alumina is 160 to 290 m 2 /g.
  • the average particle size of alumina, potassium carbonate, calcium carbonate, magnetite and iron powder is 150 to 200 mesh, and the specific surface area of alumina is 180 to 270 m 2 /g.
  • the grinding time is 4 to 10 hours.
  • the organic binder is sodium carboxymethyl cellulose or glycerin, and the weight percentage of sodium carboxymethyl cellulose or glycerin in the aqueous binder solution is 10 to 30%.
  • the solid solution volume percentage of the active powder and the aqueous binder solution is 20 to 65%.
  • the polishing is continued for 4 to 10 hours.
  • the drying treatment temperature is 90 to 150 °C.
  • the drying treatment temperature is 100 to 110 °C.
  • the temperature of the high-temperature sintering treatment is 1000 to 1500 ° C, and the porosity of the obtained porous metal iron carrier is 85% or more.
  • the temperature of the high-temperature sintering treatment is 1100 to 1400 ° C, and the porosity of the obtained porous metal iron carrier is 88% or more.
  • the stirring time is 0.5 to 1.5 hours.
  • the hydrothermal synthesis reaction is carried out in an blast state, the reaction temperature is 150 to 200 ° C, and the crystallization time is 20 to 30 h.
  • the hydrothermal synthesis reaction is carried out in an blast state, the reaction temperature is 170 to 180 ° C, and the crystallization time is 22 to 26 h.
  • the drying and calcination treatment conditions are as follows: first drying at a temperature of 60 to 120 ° C for 5 to 15 hours, and then baking at a temperature of 300 to 550 ° C for 4 to 8 hours.
  • the cobalt salt is selected from cobalt nitrate and/or cobalt acetate, and is weighed according to the ratio of the loading amount of the metal active component cobalt to the weight of the finished product of 15 to 25%.
  • the cobalt salt is selected from cobalt nitrate and/or cobalt acetate, and is dissolved in anhydrous ethanol to prepare a cobalt salt solution.
  • the evaporation temperature is 40 to 80 °C.
  • the drying and calcination treatment conditions are as follows: first, drying at a temperature of 60 to 120 ° C for 5 to 15 hours, and then baking at a temperature of 300 to 550 ° C for 4 to 8 hours.
  • the monolithic iron-cobalt bimetallic Fischer-Tropsch synthesis catalyst of the invention adopts an organic porous material polyurethane foam as a template to obtain a porous carrier material having a three-dimensional network structure by high-temperature sintering, and the carrier has a larger ratio than a general monolithic carrier.
  • the surface area overcomes the disadvantage of the small specific surface area of the conventional molten iron catalyst.
  • the organic porous material polyurethane foam preparation process is very mature, and as a template, it can have more adjustable space, and is easy to handle and easy to cut, so that the obtained monolithic carrier is better matched with the reactor.
  • the molecular sieve membrane When the molecular sieve membrane is coated, the molecular sieve is coated by hydrothermal method, which greatly increases the specific surface area of the carrier, and is more favorable for the dispersion of the cobalt active component. Then, the active component cobalt is further loaded, and the presence of the molecular sieve also makes the cobalt and the carrier bond more firmly, thereby effectively preventing the activity of the active component from falling off in the reaction.
  • the monolithic iron-cobalt bimetallic Fischer-Tropsch synthesis catalyst of the present invention and a preparation method thereof will be further described in detail below with reference to specific examples.
  • the monolithic iron-cobalt bimetallic Fischer-Tropsch synthesis catalyst A is prepared by the method of the invention, and comprises the following steps:
  • alumina having an average particle size of 180-240 mesh, 3.67 g of potassium carbonate, 0.89 g of calcium carbonate, 110 g of magnetite, and 20 g of iron powder, and ball-milling for 4 hours, and uniformly mixing them to obtain an active powder.
  • the specific surface area of alumina is 190 m 2 /g;
  • the obtained dried molded product is subjected to high-temperature sintering treatment at 1100 ° C to ablate the polyurethane foam, the organic binder, and the impurity component, thereby obtaining a monolithic three-dimensional network structure of the porous metal iron carrier;
  • the porous metal iron carrier self-assembled by molecular sieve is rinsed off, firstly dried at 60 ° C for 15 h, and then calcined at 300 ° C for 8 h to obtain a molecular sieve membrane coated porous metal iron carrier.
  • the molecular sieve membrane is a cluster aggregate of ZSM-5 nanoparticles dispersed uniformly;
  • the impregnated porous metal iron carrier is first dried at 120 ° C for 10 h and then calcined at 550 ° C for 6 h to support the metal active component cobalt on the molecular sieve membrane on the surface of the porous metal iron support.
  • a monolithic iron-cobalt bimetallic Fischer-Tropsch synthesis catalyst was obtained.
  • the monolithic iron-cobalt bimetallic catalyst has been tested to have an average particle size ranging from 10 to 30 nm and a micropore diameter of less than or equal to 2.0 nm between adjacent ZSM-5 nanoparticles.
  • the gap is less than or equal to 100 nm.
  • the monolithic iron-cobalt bimetallic Fischer-Tropsch synthesis catalyst B is prepared by the method of the invention, and comprises the following steps:
  • the obtained dried molded product is sintered at a high temperature of 1400 ° C for 2 h, and the polyurethane foam, the organic binder, and the impurity component are ablated, thereby obtaining a monolithic three-dimensional network structure of the porous metal iron carrier;
  • the porous metal iron carrier self-assembled by molecular sieve is rinsed, firstly dried at 120 ° C for 5 h, and then calcined at 350 ° C for 8 h to obtain a molecular sieve membrane coated porous metal iron carrier.
  • the molecular sieve membrane is a cluster aggregate of ZSM-5 nanoparticles dispersed uniformly;
  • the impregnated porous metal iron carrier is first dried at 60 ° C for 12 h and then calcined at 500 ° C for 4-8 h to support the metal active component cobalt on the surface of the porous metal iron support.
  • a monolithic iron-cobalt bimetallic Fischer-Tropsch synthesis catalyst was obtained.
  • the monolithic iron-cobalt bimetallic catalyst has been tested to have an average particle size ranging from 10 to 30 nm and a micropore diameter of less than or equal to 2.0 nm between adjacent ZSM-5 nanoparticles.
  • the gap is less than or equal to 100 nm.
  • the monolithic iron-cobalt bimetallic Fischer-Tropsch synthesis catalyst C is prepared by the method of the invention, and comprises the following steps:
  • alumina having an average particle size of 140-180 mesh, 3.5 g of potassium carbonate, 5.3 g of calcium carbonate, 110 g of magnetite, and 20 g of iron powder, and ball-milling for 6 hours to uniformly mix them to obtain an active powder.
  • the specific surface area of the alumina is 260 m 2 /g;
  • the obtained dried molded product is sintered at a high temperature of 1200 ° C for 2 h, ablated the polyurethane foam, the organic binder, and the impurity component to obtain a monolithic three-dimensional network structure of the porous metal iron carrier;
  • the porous metal iron carrier self-assembled by molecular sieve is washed with deionized water, firstly dried at 100 ° C for 8 h, and then calcined at 550 ° C for 4 h to obtain a molecular sieve membrane coated porous metal.
  • An iron carrier, the molecular sieve membrane being a cluster aggregate of uniformly dispersed ZSM-5 nanoparticles;
  • the impregnated porous metal iron carrier is first dried at 120 ° C for 8 h and then calcined at 450 ° C for 6 h to support the metal active component cobalt on the molecular sieve membrane on the surface of the porous metal iron support.
  • a monolithic iron-cobalt bimetallic Fischer-Tropsch synthesis catalyst was obtained.
  • the monolithic iron-cobalt bimetallic catalyst has been tested to have an average particle size ranging from 10 to 30 nm and a micropore diameter of less than or equal to 2.0 nm between adjacent ZSM-5 nanoparticles.
  • the gap is less than or equal to 100 nm.
  • the monolithic iron-cobalt bimetallic Fischer-Tropsch synthesis catalyst D is prepared by the method of the invention, and comprises the following steps:
  • alumina having an average particle size of 180-240 mesh, 1.2 g of potassium carbonate, 5.36 g of calcium carbonate, 125 g of magnetite, and 10 g of iron powder, and ball-milling for 4 hours, and uniformly mixing them to obtain an active powder.
  • the specific surface area of the alumina is 240 m 2 /g;
  • the obtained active powder is dispersed into the aqueous binder solution, and further grinding for 8 hours to obtain a mixed slurry;
  • the obtained dried molded product is sintered at a high temperature at 1300 ° C for 3 hours, and the polyurethane foam, the organic binder, and the impurity component are ablated, thereby obtaining a monolithic three-dimensional network structure of the porous metal iron carrier;
  • the porous metal iron carrier self-assembled by molecular sieve is washed with deionized water, firstly dried at 80 ° C for 10 h, and then calcined at 500 ° C for 6 h to obtain a molecular sieve membrane coated porous metal.
  • An iron carrier, the molecular sieve membrane being a cluster aggregate of uniformly dispersed ZSM-5 nanoparticles;
  • the impregnated porous metal iron carrier is first dried at 100 ° C for 5 h and then calcined at 350 ° C for 8 h to support the metal active component cobalt on the molecular sieve membrane on the surface of the porous metal iron support.
  • a monolithic iron-cobalt bimetallic Fischer-Tropsch synthesis catalyst was obtained.
  • the monolithic iron-cobalt bimetallic catalyst has been tested to have an average particle size ranging from 10 to 30 nm and a micropore diameter of less than or equal to 2.0 nm between adjacent ZSM-5 nanoparticles.
  • the gap is less than or equal to 100 nm.
  • the monolithic iron-cobalt bimetallic Fischer-Tropsch synthesis catalyst E is prepared by the method of the invention, and comprises the following steps:
  • the obtained dried molded product is sintered at a high temperature of 1400 ° C for 3 hours, and the polyurethane foam, the organic binder, and the impurity component are ablated, thereby obtaining a monolithic three-dimensional network structure of the porous metal iron carrier;
  • the porous metal iron carrier self-assembled by molecular sieve is washed with deionized water, firstly dried at 120 ° C for 15 h, and then calcined at 450 ° C for 8 h to obtain a molecular sieve membrane coated porous metal.
  • An iron carrier, the molecular sieve membrane being a cluster aggregate of uniformly dispersed ZSM-5 nanoparticles;
  • the impregnated porous metal iron carrier is first dried at 80 ° C for 15 h and then calcined at 300 ° C for 8 h to support the metal active component cobalt on the molecular sieve membrane on the surface of the porous metal iron support.
  • a monolithic iron-cobalt bimetallic Fischer-Tropsch synthesis catalyst was obtained.
  • the monolithic iron-cobalt bimetallic catalyst has been tested to have an average particle size ranging from 10 to 30 nm and a micropore diameter of less than or equal to 2.0 nm between adjacent ZSM-5 nanoparticles.
  • the gap is less than or equal to 100 nm.
  • a comparative catalyst was prepared in the conventional manner of Comparative Examples 1 to 3, and the specific preparation method was as follows:
  • the solid is added to the electric furnace at 1800 ° C for heating and melting, and then the high-temperature melt is rapidly transferred into a cooling tank with a water jacket to be cooled, cooled to room temperature, and then crushed, and 20 to 40 mesh is sieved as a catalyst.
  • the monolith catalyst of each embodiment of the present invention has a CO conversion rate of 73% or more as compared with the conventional catalyst, which is equivalent to the product prepared by the conventional method.
  • the monolith catalyst of the present invention has a selectivity to C 2 -C 4 of less than 12% while maintaining a high conversion rate, largely inhibits the water gas change reaction, and carries out a very high reaction to the Fischer-Tropsch synthesis product.
  • High regulation, selectivity for C 5 -C 20 (such as gasoline and diesel products) is above 70%, and CO 2 is chosen to remain below 6%.

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  • Engineering & Computer Science (AREA)
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Abstract

L'invention concerne un catalyseur de synthèse de Fischer-Tropsch bimétallique intégral à base de cobalt/fer et son procédé de préparation. Le catalyseur comprend un support de fer métallique poreux, une membrane de tamis moléculaire appliquée en revêtement sur la surface du support de fer métallique poreux, et un composant actif métallique chargé sur la membrane de tamis moléculaire. Le support de fer métallique poreux est un support structural de réseau tridimensionnel intégral qui est formé par : division d'une mousse de polyuréthane en morceaux à utiliser comme matrice, immersion de ces derniers dans une solution de liant contenant de l'alumine en poudre active, du carbonate de potassium, du carbonate de calcium, de la magnétite et une poudre de fer, séchage et frittage de façon à former le support. Les poids des composants majeurs dans le support structural de réseau tridimensionnel intégral tenant satisfont la relation mathématique suivante : Fe∶Al2O3:K2O∶CaO＝100∶(1,5-6,0)∶(0,2-2,8)∶(0,2-3,2) ; la membrane de tamis moléculaire est un agrégat de grappes ayant des nanoparticules de ZSM-5 uniformément dispersées ; et la charge du cobalt composant actif métallique représente 10 à 30 % du poids du catalyseur fini comme produit. Le catalyseur a les avantages d'avoir une grande surface spécifique de support et de fortes performances d'adhérence de catalyseur. Le procédé de préparation de catalyseur est simple et la performance du produit est stable.
PCT/CN2017/078053 2016-05-19 2017-03-24 Catalyseur de synthèse de fischer-tropsch bimétallique intégral à base de cobalt/fer et son procédé de préparation WO2017197980A1 (fr)

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CN111659395B (zh) * 2020-05-26 2021-11-26 北京化工大学 具有高全烯烃选择性的泡沫铁基催化剂的制备方法及其应用
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