CN112742381A - Shell-layer distributed catalyst and preparation method and application thereof - Google Patents

Shell-layer distributed catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN112742381A
CN112742381A CN201911037358.0A CN201911037358A CN112742381A CN 112742381 A CN112742381 A CN 112742381A CN 201911037358 A CN201911037358 A CN 201911037358A CN 112742381 A CN112742381 A CN 112742381A
Authority
CN
China
Prior art keywords
catalyst
active component
solvent
shell
solution containing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201911037358.0A
Other languages
Chinese (zh)
Other versions
CN112742381B (en
Inventor
孙霞
夏国富
侯朝鹏
吴玉
张荣俊
阎振楠
徐润
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN201911037358.0A priority Critical patent/CN112742381B/en
Publication of CN112742381A publication Critical patent/CN112742381A/en
Application granted granted Critical
Publication of CN112742381B publication Critical patent/CN112742381B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • B01J35/397—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0242—Coating followed by impregnation
    • 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
    • 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
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

Abstract

The invention relates to the field of catalyst preparation, and discloses a shell-distributed catalyst, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) spraying a porous carrier with a solution containing a film-forming polymer, the amount of said solution sprayed being VL1The pore volume of the porous carrier is VC，VL1/VC0.01-0.6; (2) spraying the product obtained in the step (1) by using a solvent, wherein the spraying amount of the solvent is VL2，VL2/VC0.01-0.6; (3) drying the product obtained in the step (2); (4) dipping the product obtained in the step (3) by using a solution containing a catalytic active component; (5) and (4) roasting the product obtained in the step (4). The preparation method of the shell-distributed catalyst provided by the invention is simple to operate and good in repeatability, and the prepared catalyst has good catalytic performance when being used in catalytic reaction.

Description

Shell-layer distributed catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of catalyst preparation, in particular to a shell-distributed catalyst and a preparation method and application thereof.
Background
If the product molecules generated by the reaction at the deep part of the catalyst pore channel can not be diffused out in time to further react, the selectivity of the catalyst is influenced on one hand, and the service life of the catalyst is influenced on the other hand. Particularly reactions in which internal diffusion is a controlled step, it is desirable that the reaction occur at a site that facilitates diffusion of the reactants and products, and generally at the surface of the catalyst. In addition, in the cost of the catalyst, the proportion of the cost of the active component is larger, and if the component which is not high in utilization rate and distributed in the deep part of the pore channel is moved to the area close to the surface layer of the catalyst, the cost of the catalyst is undoubtedly reduced, and the activity and the selectivity of the catalyst are favorably improved.
US5545674A discloses a process for preparing a shell-type catalyst by spreading the support over a wire mesh, heating the wire mesh in a heating furnace to above 140 ℃ and then removing it from the furnace. Spraying the solution containing the supported component on a heat carrier on a metal wire mesh, evaporating the solution containing the supported component on the surface of the hot carrier, and then putting the metal wire mesh with the catalyst back into the heating furnace for reheating. This was repeated several times until sufficient loading component was loaded.
CN101318133A discloses a shell catalyst for preparing naphtha and diesel oil, which uses active carbon as carrier, sprays the solution onto the rolling carrier by spraying, and then dries or calcines the catalyst in inert gas. However, the catalyst prepared by this method has a low shell fraction.
CN102451722A discloses a preparation method of an eggshell type hydrogenation catalyst. The method comprises the steps of impregnating a carrier with an active metal aqueous solution containing a thickening agent and an active metal dispersing agent, wherein the carrier is impregnated under the condition of introducing air bubbles, and then drying and roasting are carried out to obtain the eggshell type hydrogenation catalyst. The method can effectively adjust the surface activity of the eggshell type hydrogenation catalyst, the thickness of the metal shell layer and the dispersion degree of the active metal, stabilize the active metal component on the hydrogenation catalyst, reduce the loss of the active metal component and reduce the production cost of the catalyst. However, the preparation method has strict requirements on time, is complicated to operate and is not easy to realize large-scale production.
US4599481A discloses a process for the production of hydrocarbons by the catalytic reaction of carbon monoxide with hydrogen, which comprises contacting carbon monoxide and hydrogen with a catalyst comprising a support and cobalt supported on the support, the distribution of the cobalt on the support satisfying (Σ Vp/Σvc) < 0.85, at a temperature of from 125-. The catalyst has high activity and selectivity when the cobalt content in the shell is about 90%. The preparation method of the catalyst comprises the steps of firstly treating the carrier with water, then soaking the carrier in cobalt nitrate solution, and then drying and roasting the carrier. The preparation method has strict requirements on time, is complicated to operate and is not easy to realize large-scale production.
Therefore, the method for preparing the shell-distributed catalyst is complex, and the method for preparing the shell-distributed catalyst still needs to be continuously explored.
Disclosure of Invention
The invention aims to provide a preparation method of a novel shell-distributed catalyst, the shell-distributed catalyst prepared by the method and application of the shell-distributed catalyst. The preparation method of the shell-distributed catalyst provided by the invention is simple to operate and good in repeatability, and the prepared catalyst has good catalytic performance when being used in catalytic reaction.
In order to achieve the above object, the present invention provides, in one aspect, a method for preparing a shell-distributed catalyst, the method comprising:
(1) spraying a porous carrier with a solution containing a film-forming polymer, the amount of said solution sprayed being VL1The pore volume of the porous carrier is VC，VL1/VC＝0.01-0.6；
(2) Spraying the product obtained in the step (1) by using a solvent, wherein the spraying amount of the solvent is VL2，VL2/VC＝0.01-0.6；
(3) Drying the product obtained in the step (2);
(4) dipping the product obtained in the step (3) by using a solution containing a catalytic active component;
(5) and (4) roasting the product obtained in the step (4).
Preferably, the concentration of the solution containing the film-forming polymer is 0.1 to 15 wt%, preferably 0.3 to 10 wt%, more preferably 0.5 to 8 wt%, and still more preferably 1 to 5 wt%.
Preferably, the film-forming polymer is polyvinyl alcohol and/or a vinyl alcohol-olefin copolymer, more preferably a vinyl alcohol-olefin copolymer, most preferably a vinyl alcohol-ethylene copolymer.
In a second aspect, the present invention provides a shell distributed catalyst prepared by the process of the present invention.
In a third aspect, the invention provides the use of the shell distributed catalyst of the invention in a fischer-tropsch synthesis reaction or a hydrofinishing reaction.
The preparation method of the shell-distributed catalyst has the advantages of simple and easily-controlled operation process and good repeatability, and is particularly suitable for large-scale implementation. The shell-distributed catalyst prepared by the method of the invention is used as the catalyst of the Fischer-Tropsch synthesis reaction, and can obtain higher catalytic activity and C5+Hydrocarbon selectivity. The shell-distributed catalyst prepared by the method of the invention is used as a catalyst for hydrofining reaction, and can obtain higher hydrodesulfurization activity and hydrodenitrogenation activity.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The "shell-distributed catalyst" of the present invention is also referred to as an eggshell-type non-uniformly distributed catalyst, which is abbreviated as eggshell-type catalyst, and is defined by those skilled in the art, for example, see the definition in page 199-.
The invention provides a preparation method of a shell-distributed catalyst, which comprises the following steps:
(1) spraying a porous carrier with a solution containing a film-forming polymer, the amount of said solution sprayed being VL1The pore volume of the porous carrier is VC，VL1/VC＝0.01-0.6；
(2) Spraying the product obtained in the step (1) by using a solvent, wherein the spraying amount of the solvent is VL2，VL2/VC＝0.01-0.6；
(3) Drying the product obtained in the step (2);
(4) dipping the product obtained in the step (3) by using a solution containing a catalytic active component;
(5) and (4) roasting the product obtained in the step (4).
According to the method of the present invention, preferably, the film-forming polymer is selected from at least one of polyvinyl alcohol, a vinyl alcohol-olefin copolymer, partially hydrolyzed polyvinyl alcohol, a partially hydrolyzed vinyl alcohol-olefin copolymer, polyvinyl acetate, polyethylene glycol, collagen, polyethylene terephthalate, polyethylene naphthalate, polyamide, polysaccharide, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyacrylate resin, and a copolymer containing an acrylate ester unit.
The degree of hydrolysis of the partially hydrolyzed polyvinyl alcohol and partially hydrolyzed vinyl alcohol-olefin copolymer of the present invention is selected from a wide range and can be selected by conventional techniques in the art, and the present invention is not described herein again.
According to the invention, preferably, the polysaccharide is selected from cellulose and derivatives thereof and/or starch, for example C1-C4 alkylcellulose and/or modified starch.
According to the present invention, the olefin unit in the vinyl alcohol-olefin copolymer is preferably ethylene.
According to a preferred embodiment of the invention, the film-forming polymer is polyvinyl alcohol and/or a vinyl alcohol-olefin copolymer, more preferably a vinyl alcohol-olefin copolymer, most preferably a vinyl alcohol-ethylene copolymer. By adopting the preferred embodiment, the catalytic performance of the prepared catalyst is improved.
The molecular weight of the film-forming polymer is selected from a wide range, and preferably, the weight average molecular weight of the film-forming polymer is 16000-130000.
The concentration of the film-forming polymer in the solution containing the film-forming polymer can be selected from a wide range, and preferably, the concentration of the solution containing the film-forming polymer is 0.1 to 15% by weight, preferably 0.3 to 10% by weight, more preferably 0.5 to 8% by weight, and still more preferably 1 to 5% by weight.
The solvent of the solution of the film-forming polymer is selected from a wide range and can be water and/or an organic solvent.
The solvent used in the step (2) of the invention has a wide selection range, and can be water and/or an organic solvent.
According to a preferred embodiment of the present invention, the solvent of the solution containing the film-forming polymer and the solvent of step (2) are each independently selected from at least one of water, methanol, ethanol, propanol, acetone, ethyl acetate, furfural, benzene, toluene, and cyclohexane, and further preferably water. In the present invention, the solvent of the solution containing the film-forming polymer may be the same as or different from the solvent described in the step (2), and preferably, the solvent of the solution containing the film-forming polymer is the same as the solvent described in the step (2). With this preferred embodiment it is easier to distribute the film-forming polymer uniformly on the support, so that the depth of the solution into the support is comparable when impregnating the solution containing the catalytically active component, and the shell thickness is uniform.
According to a preferred embodiment of the present invention, in step (1), VL1/VC0.05-0.45, preferably, VL1/VC＝0.1-0.3。
According to a preferred embodiment of the present invention, in step (2), VL2/VC0.05 to 0.45, further preferably, VL2/VC＝0.1-0.3。
In the present invention, VCIs equal to the mass of the porous support (in grams) multiplied by the water absorption of the porous support (density of water 1 g/cm)3) The water absorption is the amount of water absorbed (e.g., ml/g) per unit weight of the carrier. Specifically, the water absorption can be measured by the following method: the carrier (by weight) may be treated with water in a ratio of carrier (by weight) to water (by volume) of 1: 3, soaking for 2 hours, filtering, draining the solid, and calculating the water absorption volume of the carrier, wherein the absorption rate is the water absorption volume of the carrier/the weight of the carrier.
According to the method of the present invention, the spraying in step (1) can be carried out by various methods. Specifically, the porous support may be placed in a rotating vessel and then the solution containing the film-forming polymer is sprayed onto the rolling support, and the present invention is not particularly limited to this operation, and a person skilled in the art can know how to operate. The rotating vessel may be a sugarcoating machine.
The spraying in the step (2) can be the same as the spraying way described above, and the invention is not described herein again.
According to the process of the present invention, the porous support may be a conventional porous material suitable as a catalyst support. Specifically, the porous support may be at least one of a heat-resistant inorganic oxide, aluminum silicate, and activated carbon. The heat-resistant inorganic oxide refers to an inorganic oxygen-containing compound with a decomposition temperature of not less than 300 ℃ (for example, the decomposition temperature is 300-1000 ℃) in oxygen or oxygen-containing atmosphere. Specific examples of the porous carrier may include, but are not limited to: at least one of alumina, magnesia, zirconia, calcia, silica, titania, aluminosilicate, molecular sieves, and rare earth oxides. Preferably, the porous support is selected from at least one of alumina, magnesia, zirconia, calcia, silica and titania. More preferably, the porous support is alumina.
The shape of the porous carrier in the present invention is not particularly limited, and may be a conventional shape, for example, a sphere, a tablet, a bar, etc., and preferably a bar. According to the process of the present invention, the average particle diameter of the porous support may be selected according to the specific kind of the catalyst, and is preferably in the range of 0.5 to 6mm, more preferably in the range of 1 to 4 mm.
The invention has wide selection range of the drying conditions in the step (2), and the drying temperature is based on the capability of removing the solvent loaded on the porous carrier. Generally, preferably, the drying conditions include: the temperature is 40-90 ℃ and the time is 1-48 hours; further preferably, the drying is performed under vacuum conditions. The drying temperature is preferably 50 to 90 ℃ and the drying time is preferably 2 to 16 hours.
According to the method of the present invention, the type of the catalytically active component may be selected according to the intended application of the catalyst, so as to obtain a catalyst with predetermined catalytic properties, such as a group VIII metal element and/or a group VIB metal element.
In a preferred embodiment of the invention, the catalytically active component is of a type such that the shell distributed catalyst prepared by the process of the invention is catalytic for the fischer-tropsch synthesis reaction. In this preferred embodiment, the catalytically active component may be a component having a catalytic effect on the fischer-tropsch synthesis reaction, and preferably, the catalytically active component is selected from group VIII metal elements, and specifically, may be one or more of iron, cobalt, and ruthenium.
According to the method of the present invention, the solution containing the catalytically active component may be provided by dissolving a compound containing the catalytically active component in a solvent. The kind of the compound containing the catalytically active component may be selected depending on the kind of the solvent, so as to be soluble in the solvent. For example, when the solvent is water, the compound containing a catalytically active component may be a water-soluble compound. In one embodiment of the present invention, when the catalytically active component is a group VIII metal element, the compound containing the catalytically active component may be a water-soluble non-metal salt of oxygen-containing inorganic acid having a group VIII metal as a cation, a water-soluble salt of organic acid having a group VIII metal as a cation, or two or more thereof. Preferably, the compound containing the catalytic active component is one or more of nitrate taking the VIII group metal as cation, acetate taking the VIII group metal as cation, and chloride taking the VIII group metal as cation of alkali carbonate taking the VIII group metal as cation. Specifically, the compound containing a catalytically active component may be selected from one or more of, but not limited to, iron nitrate, iron acetate, iron citrate, cobalt nitrate, cobalt acetate, cobalt hydroxycarbonate, ruthenium chloride, and ruthenium nitrosyl nitrate.
According to a preferred embodiment of the invention, step (4) comprises the amount of the solution containing the catalytically active component and step (a)2) The spraying amount V of the solventL2Are equal. The preferred embodiment is more favorable for ensuring that the solution enters the carrier with the same depth when the solution containing the catalytic active component is immersed, and the thickness of the shell layer is uniform.
The concentration of the catalytically active component in the solution containing the catalytically active component may be selected according to the desired loading amount of the catalytically active component in the catalyst, and is not particularly limited.
According to the method of the present invention, the loading amount of the solution containing the catalytically active component on the product obtained in step (3) is determined so as to ensure that the finally prepared catalyst is loaded with a sufficient amount of the catalytically active component. Generally, the loading of the catalytically active component on the porous support is such that the content of the catalytically active component, calculated as oxide, is from 0.05 to 30% by weight, preferably from 0.1 to 25% by weight, such as from 1 to 20% by weight, based on the total amount of the finally prepared catalyst.
According to another preferred embodiment of the present invention, the shell-distributed catalyst has a catalytic effect on a hydrorefining reaction. The type of the catalytic active component enables the shell-distributed catalyst prepared by the method to have a catalytic effect on the hydrofining reaction. In this preferred embodiment, the catalytically active component may be a component having a catalytic effect on the hydrorefining reaction, and preferably, the catalytically active component is selected from at least one of group VIII metal elements and at least one of group VIB metal elements, and specifically, the catalytically active component contains cobalt and/or nickel and molybdenum and/or tungsten. The details of the solution containing a catalytically active component in this preferred embodiment may be as described above, and preferably, the compound containing a catalytically active component includes a compound containing a group VIII metal element and a compound containing a group VIB metal element. For example, the group VIII metal element-containing compound is selected from, but not limited to: one or more of nickel nitrate, nickel acetate, nickel sulfate, basic nickel carbonate, cobalt nitrate, cobalt acetate, cobalt sulfate, basic cobalt carbonate, cobalt chloride and nickel chloride; the compound containing the VIB group metal element is one or more than two of nitrate, acetate, sulfate, basic carbonate and chloride of the VIB group metal element, and the types of the compound are not described again. The concentration of the catalytically active component in the solution containing the catalytically active component may be selected according to the desired loading amount of the catalytically active component in the catalyst, and is not particularly limited. According to the method of the present invention, the loading amount of the solution containing the catalytically active component on the product obtained in step (3) is determined so as to ensure that the finally prepared catalyst is loaded with a sufficient amount of the catalytically active component. Generally, the loading of the catalytically active component on the porous support is such that the content of group VIII metal elements, calculated as oxides, is from 1 to 20% by weight, such as from 3 to 10% by weight, and the content of group VIB metal elements, calculated as oxides, is from 5 to 30% by weight, such as from 8 to 20% by weight, based on the total amount of the finally prepared catalyst.
According to the process of the invention, the solution containing the catalytically active component may also contain at least one catalyst promoter component. When the catalyst has a catalytic effect on the Fischer-Tropsch synthesis reaction, the catalyst promoter component can be one or more than two of Li, Na, K, Mg, Ca, Sr, Cu, Mo, Ta, W, Zr, Ti, Hf, Ce, Mn, V and noble metals (such as one or more than two of Pt, Pd, Re, Rh and Ir). When the catalyst has a catalytic effect on a hydrofinishing reaction, the catalyst promoter component may be selected from elemental phosphorus and/or elemental fluorine.
The content of the catalyst promoter component in the solution containing the catalytically active component is based on the content of the catalyst promoter component expected in the finally prepared catalyst. The present invention is not particularly limited to this, and those skilled in the art can appropriately select the catalyst according to the field of application of the catalyst.
According to a specific embodiment of the present invention, the method further comprises drying the product obtained in step (4) before the roasting in step (5). The drying temperature is based on the solvent which can be removed from the solution loaded on the porous carrier. In general, the drying may be carried out at a temperature of 40-250 ℃ for a period of 1-48h, preferably at a temperature of 80-200 ℃ for a period of 2-24 h. The drying may be performed under normal pressure or under reduced pressure.
In the present invention, the conditions for the calcination in the step (5) are not particularly limited and may be selected conventionally. Generally, the calcination may be carried out at a temperature of 250-600 ℃, preferably at a temperature of 300-500 ℃. The duration of the calcination may be 1 to 48 hours, preferably 2 to 12 hours, more preferably 2 to 5 hours.
In a second aspect, the invention provides a shell distributed catalyst prepared by the method.
The third aspect of the invention provides the application of the shell layer distribution type catalyst in Fischer-Tropsch synthesis reaction or hydrofining reaction.
Specifically, the application of the shell-layer distribution type catalyst in the fischer-tropsch synthesis reaction can comprise contacting the synthesis gas with the catalyst under the fischer-tropsch synthesis reaction condition, wherein the catalyst is the shell-layer distribution type catalyst which is prepared by the method and has a catalytic effect on the fischer-tropsch synthesis reaction.
According to the application of the catalyst provided by the invention in Fischer-Tropsch synthesis reaction, before use, the active metal component in an oxidation state is subjected to reduction activation preferably in the presence of hydrogen. The conditions for reductive activation may include: the reduction temperature may be 200 ℃ to 1000 ℃, preferably 200 ℃ to 800 ℃, the reduction time may be 1 to 96 hours, preferably 2 to 24 hours, the reduction activation may be carried out in pure hydrogen, or in a mixed gas of hydrogen and an inert gas, such as a mixed gas of hydrogen and nitrogen, and the hydrogen pressure may be 0.1 to 4MPa, preferably 0.1 to 2MPa, the inert gas refers to a gas that does not participate in the chemical reaction under the conditions of the present invention, such as nitrogen and a group zero element gas.
According to the present invention, the reaction conditions for the Fischer-Tropsch reaction are not particularly limited, and may be carried out under conventional conditions. Specifically, the temperature can be 170-350 ℃, preferably 180-300 ℃; the total pressure can be 1-20MPa, preferably 1.5-15 MPa; the gas hourly space velocity of the synthesis gas can be 1000--1Preferably 2000--1。
Specifically, the application of the shell-distributed catalyst in the hydrorefining reaction may include contacting hydrocarbon oil with the catalyst under the hydrorefining reaction condition, wherein the catalyst is the shell-distributed catalyst which is prepared by the method of the present invention and has a catalytic effect on the hydrorefining reaction.
According to the invention there is provided the use of a catalyst in a hydrofinishing reaction, said catalyst preferably being presulfided prior to use using methods conventional in the art. In general, the conditions of the prevulcanisation may include: presulfiding with one or more of sulfur, hydrogen sulfide, carbon disulfide, dimethyl disulfide or polysulfide in the presence of hydrogen at a temperature of 360-. The pre-vulcanization can be carried out outside the hydrogenation reactor or can be carried out in situ in the hydrogenation reactor.
The catalyst of the invention is suitable for the refining processes of hydrodesulfurization, hydrodenitrogenation and the like of various hydrocarbon oil raw materials. The hydrocarbon oil feedstock may be, for example, one or more of gasoline, diesel oil, lubricating oil, kerosene, and naphtha; and can also be one or more of atmospheric residue, vacuum residue, petroleum wax and Fischer-Tropsch synthetic oil.
According to the present invention, the specific reaction conditions for the hydrorefining reaction are not particularly limited, and may be carried out under conventional conditions. Generally, the hydrofinishing conditions include: the temperature can be 300-400 ℃; the pressure can be 1.0-8.0MPa in gauge pressure; the liquid hourly space velocity of the hydrocarbon oil can be 0.5-3.0 hours-1(ii) a The hydrogen-oil volume ratio can be 100-700.
The present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
In the following examples, the film-forming polymer EVOH (vinyl alcohol-ethylene copolymer) is commercially available from the Nippon Coli group under the designation E151; polyvinyl alcohol (PVA) is commercially available from Shanghai Aladdin reagent, Inc. under the designation PVA 1799.
Example 1
(1) A solution containing a film-forming polymer (the amount and type of which are shown in Table 1) was sprayed onto 200g of a rolling porous support (cylindrical gamma-alumina having a diameter of 2 mm), the rolling of the support during the spraying being carried out in a rotating vessel (model BY300 sugarcoating machine, jin Tai pharmaceutical machinery, Inc., Tanzhou) rotating at 46 revolutions per minute.
(2) The product obtained in step (1) was sprayed with a solvent, the kind and amount of which are shown in table 2.
(3) The product obtained in step (2) was dried at 80 ℃ for 4 hours.
(4) Dissolving ammonium metatungstate and nickel nitrate in water to prepare impregnation liquid (WO)3The concentration of (3) was 402 g/l and the concentration of NiO was 25 g/l). And according to V in Table 2L2/VCThe product obtained in the step (3) is impregnated by the impregnation liquid according to the proportion;
(5) and drying at 120 ℃ for 4 hours after the completion of the impregnation, and roasting the dried sample at 450 ℃ for 2 hours to obtain the shell-distributed catalyst S-1.
Comparative example 1
The procedure is as in example 1, except that step (2) is excluded. Obtaining the catalyst D-1 with a distributed shell layer. It was observed that a white streak appeared on the shell-distributed catalyst D-1, indicating that the impregnation was not uniform.
Examples 2 to 7
The process of example 1 was followed except that the amount and type of the solution containing the film-forming polymer in step (1) were as shown in Table 1 and the type and amount of the solvent in step (2) were as shown in Table 2. Preparing the catalysts S-2 to S-7 with distributed shells.
TABLE 1
Figure BDA0002251893830000121
TABLE 2
Examples Solvent(s) VL2/VC
1 Water (W) 0.24
2 Water (W) 0.20
3 Water (W) 0.13
4 Water (W) 0.16
5 Water (W) 0.13
6 Water (W) 0.14
7 Water (W) 0.18
Example 8
According to the method of example 1, except that the composition of the impregnation solution is different, specifically, the preparation of the impregnation solution in step (4) comprises: dissolving ammonium molybdate, ammonium metatungstate, nickel nitrate and phosphoric acid in water to prepare impregnation liquid (MoO)3In a concentration of 225 g/l, WO3Of 100 g/l, NiOConcentration 50 g/l, P2O5At a concentration of 50 g/l). Obtaining the catalyst S-8 with a distributed shell layer.
Examples 9 to 15
The method of examples 1 to 7 was followed, respectively, except that the composition of the impregnation solution was different, and specifically, the preparation of the impregnation solution in step (4) included: 131 g of cobalt nitrate was weighed and dissolved in water to prepare 100mL of a cobalt nitrate solution as an impregnation solution. Obtaining the catalysts C-1 to C-7 with distributed shells.
Comparative example 2
The procedure is as in example 9, except that step (2) is excluded. Obtaining the catalyst D-2 with distributed shell layers. It was observed that white stripes appeared on the shell-distributed catalyst D-2, indicating that the impregnation was not uniform.
Example 16
The procedure of example 9 was repeated, except that the composition of the impregnation solution was changed, and specifically, the impregnation solution in step (4) was a ruthenium nitrosyl nitrate solution having a concentration of 0.52 mol/l. Obtaining the shell distributed catalyst C-8.
Example 17
The process of example 9 was followed except that the amount of the solvent sprayed in step (2) was varied in accordance with the pore volume V of the porous carrierCThe ratio of (A) to (B) is 0.45: 1. obtaining the shell distributed catalyst C-9.
Test example 1
The catalysts prepared in examples 1-8 and comparative example 1 were evaluated on a 30 ml diesel hydrogenation unit, respectively.
The raw materials used were as follows: middle east straight run diesel; and (2) S content: 9700wppm, N content: 97wppm, density (20 ℃): 0.8321g/cm3Refractive index (20 ℃): 1.4658.
the catalyst is vulcanized before use, and the vulcanization conditions are as follows: the vulcanization pressure is 3.2MPa, and the vulcanized oil contains CS22% by weight of kerosene, the volume space velocity being 2h-1And the hydrogen-oil ratio is 300v/v, the constant temperature is kept for 6h at 230 ℃/h, then the temperature is raised to 360 ℃ for vulcanization for 8h, and the temperature raising rate of each stage is 10 ℃/h. And after vulcanization, switching reaction raw materials to carry out hydrodesulfurization and denitrification activity test. The test conditions were:the pressure is 3.2MPa, and the liquid hourly space velocity is 2.0h-1The hydrogen-oil ratio was 300v/v, and the reaction temperature was 330 ℃. The relative hydrodesulfurization activity and the relative hydrodenitrogenation activity of the catalysts are shown in table 3.
In Table 3, the hydrodesulfurization activity of the catalyst was evaluated by using the relative hydrodesulfurization activity, which was calculated by treating the hydrodesulfurization reaction as a 1.65-stage reaction and calculating the reaction rate constant k (X) of the catalyst X according to the following formulaHDS：
Figure BDA0002251893830000141
Wherein LHSV is the liquid hourly volume space velocity of the hydrocarbon oil during the hydrorefining reaction,
with the hydrodesulfurization activity of catalyst D-1 (denoted as k (D-1)HDS) For reference, the relative hydrodesulfurization activity of catalyst X was calculated as follows:
relative hydrodesulfurization activity (X) ═ k (X)HDS/k(D-1)HDS]×100％。
In Table 3, the hydrodenitrogenation activity of the catalyst was evaluated by using the relative hydrodenitrogenation activity, and the hydrodenitrogenation activity was calculated by treating the hydrodenitrogenation reaction as a 1-stage reaction and calculating the reaction rate constant k (X) of the catalyst X according to the following formulaHDN：
Figure BDA0002251893830000142
Wherein LHSV is the liquid hourly volume space velocity of the hydrocarbon oil during the hydrorefining reaction,
the hydrodenitrogenation activity of the catalyst D-1 (denoted as k (D-1))HDN) For reference, the relative hydrodenitrogenation activity of catalyst X was calculated as follows:
relative hydrodenitrogenation activity (X) ═ k (X)HDN/k(D-1)HDN]×100％。
TABLE 3
Figure BDA0002251893830000151
As can be seen from the data in table 3, the catalyst prepared according to the method of the present invention shows higher catalytic activity in the hydrofinishing of hydrocarbon oil.
Test example 2
The catalysts prepared in examples 9 to 17 and comparative example 2 were tested for their performance in the fischer-tropsch synthesis reaction using the following method.
The test procedure was carried out in a fixed bed fischer-tropsch synthesis reactor using 5 g of catalyst.
The catalyst is reduced prior to use. The reduction is carried out at atmospheric pressure, with the other conditions being: the hydrogen flow was 1000NL/(g-cat h), and the temperature was raised to 400 ℃ at a rate of 4 ℃/min and held for 5 h.
The Fischer-Tropsch synthesis reaction conditions comprise: at a temperature of 223 ℃ H2The ratio of/CO is 2, the pressure is 2.5MPa, and the Gas Hourly Space Velocity (GHSV) is 2000h-1. The results are listed in table 4.
TABLE 4
Figure BDA0002251893830000164
In Table 4, XCOThe conversion rate of CO is shown in the specification,
Figure BDA0002251893830000161
is represented by C5Above (containing C)5) Selectivity of hydrocarbons. The specific definition is shown in the following expression:
Figure BDA0002251893830000162
Figure BDA0002251893830000163
as can be seen from the results in Table 4, catalyst pair C prepared by the process of the present invention5+Hydrocarbons have higher selectivity and can also achieve higher CO conversion.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (11)

1. A method of preparing a shell-distributed catalyst, the method comprising:
(1) spraying a porous carrier with a solution containing a film-forming polymer, the amount of said solution sprayed being VL1The pore volume of the porous carrier is VC，VL1/VC＝0.01-0.6；
(2) Spraying the product obtained in the step (1) by using a solvent, wherein the spraying amount of the solvent is VL2，VL2/VC＝0.01-0.6；
(3) Drying the product obtained in the step (2);
(4) dipping the product obtained in the step (3) by using a solution containing a catalytic active component;
(5) and (4) roasting the product obtained in the step (4).
2. The method of claim 1, wherein the film-forming polymer is selected from at least one of polyvinyl alcohol, vinyl alcohol-olefin copolymers, partially hydrolyzed polyvinyl alcohol, partially hydrolyzed vinyl alcohol-olefin copolymers, polyvinyl acetate, polyethylene glycol, collagen, polyethylene terephthalate, polyethylene naphthalate, polyamide, polysaccharide, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyacrylate resin, and copolymers containing acrylate units;
preferably, the film-forming polymer is polyvinyl alcohol and/or a vinyl alcohol-olefin copolymer, more preferably a vinyl alcohol-olefin copolymer, most preferably a vinyl alcohol-ethylene copolymer.
3. The process according to claim 1 or 2, wherein the concentration of the solution containing the film-forming polymer is 0.1 to 15 wt. -%, preferably 0.3 to 10 wt. -%, further preferably 0.5 to 8 wt. -%, more preferably 1 to 5 wt. -%;
preferably, the solvent of the solution containing the film-forming polymer and the solvent of step (2) are each independently selected from at least one of water, methanol, ethanol, propanol, acetone, ethyl acetate, furfural, benzene, toluene, and cyclohexane;
further preferably, the solvent of the solution containing the film-forming polymer is the same as the solvent in the step (2).
4. The method according to any one of claims 1 to 3, wherein in step (1), VL1/VC0.05-0.45, preferably, VL1/VC＝0.1-0.3；
Preferably, in step (2), VL2/VC0.05 to 0.45, further preferably, VL2/VC＝0.1-0.3。
5. The process of any one of claims 1 to 4, wherein the porous support is selected from at least one of alumina, magnesia, zirconia, calcia, silica, titania, aluminosilicate, molecular sieve and rare earth oxide;
preferably, in the step (2), the drying conditions include: the temperature is 40-90 ℃ and the time is 1-48 hours; preferably under vacuum at a temperature of 50-90 deg.C for 2-16 hr.
6. The method according to any one of claims 1 to 5, wherein the amount of the solution containing the catalytically active component in step (4) and the spraying amount V of the solvent in step (2)L2Are equal.
7. The method of any one of claims 1-6, wherein the shell distributed catalyst catalyzes a Fischer-Tropsch synthesis reaction;
preferably, the catalytic active component is selected from group VIII metal elements, preferably one or more of iron, cobalt and ruthenium;
preferably, the loading of the catalytically active component on the porous support is such that the content of the catalytically active component, calculated as oxide, is from 0.05 to 30% by weight, preferably from 0.1 to 25% by weight, based on the total amount of the finally prepared catalyst.
8. The method of any of claims 1-6, wherein the shell distributed catalyst catalyzes a hydrofinishing reaction;
preferably, the catalytically active component is selected from at least one of group VIII metal elements and at least one of group VIB metal elements;
preferably, the catalytically active component contains cobalt and/or nickel and molybdenum and/or tungsten;
preferably, the loading of the catalytically active component on the porous support is such that the content of group VIII metal elements, calculated as oxides, is from 1 to 20 wt.% and the content of group VIB metal elements, calculated as oxides, is from 5 to 30 wt.%, based on the total amount of the finally prepared catalyst.
9. The method of any one of claims 1-8, wherein the firing conditions of step (5) comprise: the temperature is 250-600 ℃, preferably 300-500 ℃; the time is 1 to 48 hours, preferably 2 to 12 hours.
10. A shell distributed catalyst prepared by the method of any one of claims 1-9.
11. Use of the shell distributed catalyst of claim 10 in a fischer-tropsch synthesis reaction or a hydrofinishing reaction.
CN201911037358.0A 2019-10-29 2019-10-29 Shell-layer distributed catalyst and preparation method and application thereof Active CN112742381B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911037358.0A CN112742381B (en) 2019-10-29 2019-10-29 Shell-layer distributed catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911037358.0A CN112742381B (en) 2019-10-29 2019-10-29 Shell-layer distributed catalyst and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112742381A true CN112742381A (en) 2021-05-04
CN112742381B CN112742381B (en) 2023-03-10

Family

ID=75640922

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911037358.0A Active CN112742381B (en) 2019-10-29 2019-10-29 Shell-layer distributed catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112742381B (en)

Citations (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4599481A (en) * 1984-09-13 1986-07-08 Shell Oil Company Process for the preparation of hydrocarbons
US4977126A (en) * 1987-05-07 1990-12-11 Exxon Research And Engineering Company Process for the preparation of surface impregnated dispersed cobalt metal catalysts
DE4239876C1 (en) * 1992-11-27 1994-07-28 Degussa Process for the uniform and reproducible shell impregnation of fixed bed catalyst supports in bulk and device for carrying out the process
US5545674A (en) * 1987-05-07 1996-08-13 Exxon Research And Engineering Company Surface supported cobalt catalysts, process utilizing these catalysts for the preparation of hydrocarbons from synthesis gas and process for the preparation of said catalysts
CN1419474A (en) * 2000-03-28 2003-05-21 巴斯福股份公司 Shell catalysts, method for producing the same, and the use thereof
WO2006050778A1 (en) * 2004-11-11 2006-05-18 Degussa Gmbh Sodium percarbonate particles having a shell layer comprising thiosulfate
CN101061063A (en) * 2004-12-14 2007-10-24 德古萨有限责任公司 Compressed molded bodies containing coated sodium percarbonate particles
WO2008122636A2 (en) * 2007-04-10 2008-10-16 Shell Internationale Research Maatschappij B.V. Steam or water treatment of a catalyst precursor in order to obtain an egg shell ft catalyst
US20080282882A1 (en) * 2006-11-08 2008-11-20 John Charles Saukaitis gas separation membrane comprising a substrate with a layer of coated inorganic oxide particles and an overlayer of a gas-selective material, and its manufacture and use
CN101318133A (en) * 2007-06-06 2008-12-10 中国科学院大连化学物理研究所 Lamella catalyst for preparing petroleum naphtha and diesel oil, preparation method and application thereof
CN101462079A (en) * 2007-12-20 2009-06-24 中国石油化工股份有限公司 Method for preparing catalyst with lamella distribution
DE102008004485A1 (en) * 2008-01-14 2009-07-16 Bayerisches Zentrum für Angewandte Energieforschung e.V. Covering of organic and inorganic phase change material, comprises introducing the phase change material into a porous, open-cellular carrier structure and providing the filled porous granulates with water vapor-tight layer
US20090297604A1 (en) * 2006-06-12 2009-12-03 Kessler Vadim G Metal oxide hydrogels and hydrosols, their preparation and use
CN102127298A (en) * 2010-12-29 2011-07-20 四川大学 Polymer hollow nano microspheres and preparation method thereof
CN102463090A (en) * 2010-10-29 2012-05-23 财团法人工业技术研究院 Core-shell inorganic polymer composite material and method for producing same
JP2012101950A (en) * 2010-11-05 2012-05-31 Noritake Co Ltd Method for producing porous carbon particle, and porous carbon material including the particle
KR20130094364A (en) * 2012-02-13 2013-08-26 금호석유화학 주식회사 Highly conductive carbon nanotube having bundle moieties with ultra-low bulk density and its manufacturing method
CN103623818A (en) * 2012-08-23 2014-03-12 中国石油天然气股份有限公司 Thin-shell type precious metal catalyst and preparation method thereof
CN105728020A (en) * 2016-03-03 2016-07-06 华侨大学 Preparation method for core-shell type iron carbide catalyst
CN106311358A (en) * 2015-07-08 2017-01-11 中国石油化工股份有限公司 Shell-distributed catalyst and preparation method thereof, and Fischer-Tropsch synthesis method
CN107185509A (en) * 2017-05-31 2017-09-22 北京三聚环保新材料股份有限公司 One kind is with γ Al2O3For the preparation method of the hud typed carrier of shell
JP2018086629A (en) * 2016-11-29 2018-06-07 東洋製罐グループホールディングス株式会社 Forming method of particulate layer
CN109722722A (en) * 2018-11-21 2019-05-07 深圳大学 A kind of equal hole nanofiber and its preparation method and application

Patent Citations (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4599481A (en) * 1984-09-13 1986-07-08 Shell Oil Company Process for the preparation of hydrocarbons
US4977126A (en) * 1987-05-07 1990-12-11 Exxon Research And Engineering Company Process for the preparation of surface impregnated dispersed cobalt metal catalysts
US5545674A (en) * 1987-05-07 1996-08-13 Exxon Research And Engineering Company Surface supported cobalt catalysts, process utilizing these catalysts for the preparation of hydrocarbons from synthesis gas and process for the preparation of said catalysts
DE4239876C1 (en) * 1992-11-27 1994-07-28 Degussa Process for the uniform and reproducible shell impregnation of fixed bed catalyst supports in bulk and device for carrying out the process
CN1419474A (en) * 2000-03-28 2003-05-21 巴斯福股份公司 Shell catalysts, method for producing the same, and the use thereof
WO2006050778A1 (en) * 2004-11-11 2006-05-18 Degussa Gmbh Sodium percarbonate particles having a shell layer comprising thiosulfate
CN101061063A (en) * 2004-12-14 2007-10-24 德古萨有限责任公司 Compressed molded bodies containing coated sodium percarbonate particles
US20090297604A1 (en) * 2006-06-12 2009-12-03 Kessler Vadim G Metal oxide hydrogels and hydrosols, their preparation and use
US20080282882A1 (en) * 2006-11-08 2008-11-20 John Charles Saukaitis gas separation membrane comprising a substrate with a layer of coated inorganic oxide particles and an overlayer of a gas-selective material, and its manufacture and use
WO2008122636A2 (en) * 2007-04-10 2008-10-16 Shell Internationale Research Maatschappij B.V. Steam or water treatment of a catalyst precursor in order to obtain an egg shell ft catalyst
CN101318133A (en) * 2007-06-06 2008-12-10 中国科学院大连化学物理研究所 Lamella catalyst for preparing petroleum naphtha and diesel oil, preparation method and application thereof
CN101462079A (en) * 2007-12-20 2009-06-24 中国石油化工股份有限公司 Method for preparing catalyst with lamella distribution
DE102008004485A1 (en) * 2008-01-14 2009-07-16 Bayerisches Zentrum für Angewandte Energieforschung e.V. Covering of organic and inorganic phase change material, comprises introducing the phase change material into a porous, open-cellular carrier structure and providing the filled porous granulates with water vapor-tight layer
CN102463090A (en) * 2010-10-29 2012-05-23 财团法人工业技术研究院 Core-shell inorganic polymer composite material and method for producing same
JP2012101950A (en) * 2010-11-05 2012-05-31 Noritake Co Ltd Method for producing porous carbon particle, and porous carbon material including the particle
CN102127298A (en) * 2010-12-29 2011-07-20 四川大学 Polymer hollow nano microspheres and preparation method thereof
KR20130094364A (en) * 2012-02-13 2013-08-26 금호석유화학 주식회사 Highly conductive carbon nanotube having bundle moieties with ultra-low bulk density and its manufacturing method
CN103623818A (en) * 2012-08-23 2014-03-12 中国石油天然气股份有限公司 Thin-shell type precious metal catalyst and preparation method thereof
CN106311358A (en) * 2015-07-08 2017-01-11 中国石油化工股份有限公司 Shell-distributed catalyst and preparation method thereof, and Fischer-Tropsch synthesis method
CN105728020A (en) * 2016-03-03 2016-07-06 华侨大学 Preparation method for core-shell type iron carbide catalyst
JP2018086629A (en) * 2016-11-29 2018-06-07 東洋製罐グループホールディングス株式会社 Forming method of particulate layer
CN107185509A (en) * 2017-05-31 2017-09-22 北京三聚环保新材料股份有限公司 One kind is with γ Al2O3For the preparation method of the hud typed carrier of shell
CN109722722A (en) * 2018-11-21 2019-05-07 深圳大学 A kind of equal hole nanofiber and its preparation method and application

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
GANESH SKANDAN: "NANOSTRUCTURED POWDERS: A NEW CLASS OF MATERIALS FOR FORMING", 《MATERIALS RESEARCH SOCIETY》 *
侯玉柏等: "两种钴碳化钨涂层的组织性能研究", 《热喷涂技术》 *
崔珊等: "热喷涂Cr/Al2O3 复合粉末的制备及性能研究", 《表面技术》 *
耿敏等: "自愈性超疏水表面的方法及应用进展＊", 《功能材料》 *

Also Published As

Publication number Publication date
CN112742381B (en) 2023-03-10

Similar Documents

Publication Publication Date Title
JP6506430B2 (en) Improved resid hydroprocessing catalyst containing titania
JP5922372B2 (en) Hydrotreating catalyst and method for producing the same
CA2360121C (en) Hydroprocessing catalyst and use thereof
CN102125878B (en) Modified Al2O3 carrier and preparation method thereof
KR930008440B1 (en) Nickel/silica catalyst and the preparation and use thereof
CN108187709B (en) Preparation method of deep hydrodesulfurization catalyst and application of catalyst
CN1169337A (en) Catalyst treated by distillate added with hydrogen and preparation method thereof
JP5439673B2 (en) Method for hydrotreating heavy hydrocarbon oil
CN112742381B (en) Shell-layer distributed catalyst and preparation method and application thereof
RU2474474C1 (en) Catalyst, method for preparation thereof and method of producing low-sulphur diesel fuel
JP4822705B2 (en) Heavy hydrocarbon oil hydrotreating catalyst composition and method for producing the same
JP5787973B2 (en) Fatty acid hydrogenation process using promoted supported nickel catalyst
CN110860285B (en) Preparation method of catalyst for low-temperature thioetherification and diene selective hydrogenation
CN1508224A (en) Hydrocracking after-treatment catalyst and preparing method thereof
EP2723494B1 (en) Method of making a hydroprocessing catalyst
CN112300834B (en) Heavy oil hydrotreating method
CN112742405A (en) Catalyst impregnation liquid and preparation method of hydrotreating catalyst
CN111195525A (en) Residual oil hydrodesulfurization catalyst and preparation method thereof
CN113019407B (en) Hydrotreating catalyst, preparation method and application thereof
JP3782893B2 (en) Hydrotreating catalyst and hydrotreating method of hydrocarbon oil using the hydrotreating catalyst
CN113019406B (en) Method for preparing hydrotreating catalyst
CN108246324B (en) Preparation method of low-cost residual oil hydrogenation catalyst
JP2010069466A (en) Hydrogenation catalyst
JP3462292B2 (en) Hydrocracking method of petroleum distillate
CN114433053A (en) Hydrotreating catalyst and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant