CN113499763A - Coke-oven gas isothermal methanation catalyst and preparation method thereof - Google Patents
Coke-oven gas isothermal methanation catalyst and preparation method thereof Download PDFInfo
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- CN113499763A CN113499763A CN202110661387.5A CN202110661387A CN113499763A CN 113499763 A CN113499763 A CN 113499763A CN 202110661387 A CN202110661387 A CN 202110661387A CN 113499763 A CN113499763 A CN 113499763A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 37
- 239000000571 coke Substances 0.000 claims abstract description 12
- 238000005470 impregnation Methods 0.000 claims description 57
- 239000007788 liquid Substances 0.000 claims description 56
- 238000002791 soaking Methods 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 43
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 30
- 239000012018 catalyst precursor Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 150000003839 salts Chemical class 0.000 claims description 27
- 230000005484 gravity Effects 0.000 claims description 26
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 26
- 239000011265 semifinished product Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 13
- 238000006386 neutralization reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 6
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 70
- 239000007789 gas Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- -1 magnesium aluminate Chemical class 0.000 description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/005—Spinels
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- 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
- B01J23/83—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 rare earths or actinides
-
- 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
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8871—Rare earth metals or actinides
-
- 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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- 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
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
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- 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
- C07C1/0425—Catalysts; their physical properties
- C07C1/0445—Preparation; Activation
-
- 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
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalysis, and relates to a coke oven gas isothermal methanation catalyst and a preparation method thereof. The catalyst consists of a carrier, an active component and an auxiliary agent, wherein the carrier accounts for 60-80%, the active component accounts for 15-35%, and the auxiliary agent accounts for 1-5% (based on the weight of the catalyst). The catalyst prepared by the invention solves the problems of poor heat and mass transfer performance, poor stability, poor mechanical strength, easy carbon deposition, low conversion rate of carbon monoxide and carbon dioxide and the like of the traditional methane synthesis catalyst under the condition of an isothermal fixed bed reactor.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a coke oven gas isothermal methanation catalyst and a preparation method thereof.
Background
Because of the shortage of natural gas resources in China, the technology of preparing natural gas by using coke oven gas is getting more and more attention. Compared with the process routes of preparing methanol, synthetic ammonia and the like by coke oven gas, the preparation of natural gas by coke oven gas has the advantages of low investment, good economic benefit and the like, and the byproduct hydrogen can also be used for coproducing synthetic ammonia, so that the preparation of natural gas from coke oven gas is the development direction of comprehensive utilization of coke oven gas.
The methanation technology is taken as a core technology for preparing the synthetic natural gas, the circulation multi-section adiabatic fixed bed methanation technology is mainly adopted in the industry at present, the reaction temperature of the technology is high, the heat transfer rate is low, the process flow is complex, the temperature runaway is easily caused by the fault of a circulation compressor, and the requirement on the high temperature resistance of a reactor and a catalyst is strict. Compared with the isothermal fixed bed methanation process, the isothermal fixed bed methanation process has the advantages of high heat exchange efficiency, simple process flow, small number of reactors and the like because water or other liquid is adopted in the reactor as a refrigerant to take away reaction heat. The isothermal bed reactor can effectively avoid the problems of high-temperature sintering or carbon deposition of the catalyst in the fixed bed reactor and the like.
Chinese patent CN105195160A describes an isothermal methanation catalyst and a preparation method thereof, the isothermal methanation catalyst takes a composite oxide formed by magnesium, aluminum and silicon as a shaping catalyst carrier, nickel as an active component, and the space velocity is 4000h-1Pressure 2.0Mpa, temperature 400 ℃, inlet gas CO: 3.63% of CO2: the 1.3 percent isothermal fixed bed shows good low-temperature activity, but the patent adopts a strip extrusion molding mode to obtain a carrier, although the carrier has better external surface area and rich pore channels, the strength of the strip extrusion molded catalyst is lower, the activity and the stability of the catalyst are difficult to ensure after long-term use, and the stability of the catalyst is not mentioned in the patent.
Chinese patent CN 112156786A describes a methanation catalyst with high thermal stability and high strength and a preparation method thereof, firstly, a certain amount of magnesium aluminate spinel and nickel aluminate spinel are synthesized by a high-temperature high-pressure stirring kettle to form the catalyst
A stable framework structure of the carrier is formed, a stable active center is formed on the surface of the carrier structure by a uniform impregnation method, and then a layer of alumina shell is wrapped on the surface of the catalyst phase by spray drying; wherein, the nickel oxide in the nickel aluminate spinel and the nickel oxide generated by uniform impregnation form a dynamic catalytic center with methanation catalytic activity to form a catalyst precursor of a double-yolk type; finally adding a certain amount of carbon removing agent and adhesive for granulation, extruding the mixture into spherical particles by a pair of rollers, and maintaining the spherical particles by steam to prepare the catalyst suitable for the uniform temperature methanation reactor with high activity, high thermal stability, high strength and catalysis
Can stabilize the methanation catalyst. However, the preparation process of the catalyst is complex and has more control points.
At present, the isothermal methanation is more and more emphasized by domestic and foreign scientific research institutes due to short process flow and low energy consumption. However, because the methanation reaction is a strong exothermic reaction, although the isothermal fixed bed reactor can effectively remove the reaction heat, the heat released in the reaction process has higher requirements on the self heat transfer performance of the catalyst, so that the development of the isothermal methanation catalyst which is suitable for the isothermal fixed bed and has good activity, high stability and excellent heat transfer performance is necessary.
Disclosure of Invention
The purpose of the invention is as follows: the preparation method of the coke oven gas isothermal methane synthesis catalyst is provided, and solves the problems that the traditional methane synthesis catalyst is poor in heat and mass transfer performance, poor in stability, easy to deposit carbon, low in conversion rate of carbon monoxide and carbon dioxide and the like under the condition of an isothermal fixed bed reactor.
The main technical scheme of the invention is as follows: the coke-oven gas isothermal methanation catalyst is characterized by comprising a carrier, an active component and an auxiliary agent, wherein the carrier accounts for 60-80% by weight of the catalyst, the active component accounts for 15-35% by weight of the catalyst, and the auxiliary agent accounts for 1-5% by weight of the catalyst.
Generally, the carrier is a composite oxide formed by aluminum and magnesium, and the mass ratio of the aluminum oxide to the magnesium oxide in the carrier is (1.2-2.0): 1.
The auxiliary agent is a mixture of one or more oxides of Ce, Zr, Mo, Mn and La.
The invention provides a preparation method of an isothermal methanation catalyst of coke oven gas, wherein the catalyst is obtained by the following steps:
preparation of the carrier:
dissolving aluminum nitrate and magnesium nitrate in ionized water, and uniformly stirring; performing neutralization reaction on the mixed solution by using a sodium carbonate solution, and controlling the pH value of a terminal to be 8.3-8.5; and washing, drying, tabletting, forming and roasting the neutralized material to obtain the carrier.
Preparation of active ingredients:
dissolving Ni nitrate in water, and adding 0.05-0.1 mol/L nitric acid to adjust the pH value to 5.5-6.0 to obtain the impregnation liquid rich in active components.
Preparation of the catalyst:
dissolving nitrate of the auxiliary agent into the impregnation liquid rich in the active component Ni to obtain the impregnation liquid rich in the active component Ni and the auxiliary agent salt; controlling the temperature to be 60-90 ℃, and soaking the carrier in a soaking solution rich in active component Ni and auxiliary agent salt for 2-5 h; taking out the impregnated catalyst precursor, drying and roasting to obtain a catalyst semi-finished product; controlling the temperature to be 60-90 ℃, and soaking the semi-finished catalyst product obtained in the previous step in a soaking solution rich in active component Ni for 1-3 h; taking out the impregnated catalyst precursor, drying and roasting to obtain a catalyst finished product;
in the step, the temperature of the carrier roasting muffle furnace is 700-1100 ℃, and the roasting time is 2-5 h; the molar concentration of the sodium carbonate solution is 0.5-1.2 mol/L.
The specific gravity of the impregnation liquid rich in the active component Ni and the auxiliary agent salt in the above steps is controlled to be 1.5-1.6, and the specific gravity of the impregnation liquid rich in the active component Ni is controlled to be 1.4-1.5; roasting the semi-finished catalyst at 350-450 ℃ for 2-5 h; the roasting temperature of the finished catalyst product is 350-450 ℃, and the roasting time is 2-4 h.
A typical laboratory preparation procedure of the present invention is as follows:
1) dissolving 100 g-150 g of aluminum nitrate and 100g of magnesium nitrate in 1L of deionized water, and uniformly stirring and mixing;
2) performing neutralization reaction on the mixed solution by using a sodium carbonate solution with the molar concentration of 0.5-1.2 mol/L, and controlling the pH value of the end point to be 8.3-8.5;
3) after the neutralized materials are washed, dried, tabletted and molded, roasting the materials for 2 to 5 hours at the temperature of 700 to 1100 ℃ in a muffle furnace to obtain a carrier;
4) mixing Ni (NO)3)2•6H2Dissolving O in water, and adding 0.05-0.1 mol/L nitric acid to a pH value of 5.5-6.0 to obtain an impregnation liquid rich in an active component Ni;
5) dissolving 5-20 g of nitrate of an auxiliary agent in impregnation liquid rich in an active component Ni to obtain the impregnation liquid rich in the active component Ni and an auxiliary agent salt, wherein the specific gravity of the impregnation liquid is controlled to be 1.5-1.6;
6) controlling the temperature to be 60-90 ℃, and soaking the carrier in a soaking solution rich in active component Ni and auxiliary agent salt for 2-5 h;
7) taking out the impregnated catalyst precursor in the step 6, drying, and roasting at 350-450 ℃ for 2-4 h to obtain a catalyst semi-finished product;
8) controlling the temperature to be 60-90 ℃, and soaking the catalyst semi-finished product obtained in the step a in a soaking solution which is rich in active component Ni and has the specific gravity controlled to be 1.4-1.5 for 1-3 hours;
9) and (4) taking out the impregnated catalyst precursor in the step (8), drying, and roasting at the temperature of 350-450 ℃ for 2-4 h to obtain a catalyst finished product.
The invention has the main characteristics that:
(1) the magnesium aluminate spinel structure formed by the special carrier preparation process has good specific surface area and aperture, and heat and mass transfer performance, and the catalyst has no carbon deposition on the surface and in the pore channel after long-time use, is not sintered and has good stability;
(2) the active components are highly dispersed in the carrier, the auxiliary agent and the active components have synergistic effect, and the conversion rate of carbon dioxide is high.
The catalyst for synthesizing methane by using the coke-oven gas isothermal bed prepared by the invention has simple preparation method, is beneficial to industrial production, and has good activity and stability.
Detailed Description
The process of the present invention is described in detail below with reference to examples, but the examples are only illustrative and are not intended to limit the scope of the present invention.
Example 1
1) Dissolving 130g of aluminum nitrate and 100g of magnesium nitrate in 1L of deionized water, and uniformly stirring and mixing; 2) performing neutralization reaction on the mixed solution by using a sodium carbonate solution with the molar concentration of 0.8mol/L, and controlling the pH value of the end point to be 8.3-8.5; 3) after the neutralized materials are washed, dried, tabletted and molded, roasting the materials for 4 hours at the temperature of 900 ℃ in a muffle furnace to obtain a carrier; 4) 200gNi (NO)3)2•6H2Dissolving O in water, and adding 0.08mol/L nitric acid to a pH value of 5.7-6.0 to obtain an impregnation liquid rich in an active component Ni; 5) controlling the temperature at 80 ℃, and dissolving 10g of lanthanum nitrate in the impregnation liquid rich in the active component Ni to obtain the impregnation liquid rich in the active component Ni and the auxiliary agent salt, wherein the specific gravity of the impregnation liquid is controlled to be 1.5-1.6; 6) soaking the carrier in a soaking solution rich in active component Ni and auxiliary agent salt for 4 hours; 7) taking out the catalyst precursor impregnated in the step 6, drying, and roasting at the temperature of 420 ℃ for 3h to obtain a catalyst semi-finished product; 8) controlling the temperature atB, soaking the semi-finished catalyst obtained in the step a in a soaking solution which is rich in an active component Ni and has a specific gravity controlled to be 1.4-1.5 for 2 hours at 80 ℃; 9) and (4) taking out the catalyst precursor impregnated in the step (8), drying, and roasting at the temperature of 420 ℃ for 3h to obtain a catalyst finished product Y-1.
Example 2
1) Dissolving 120g of aluminum nitrate and 100g of magnesium nitrate in 1L of deionized water, and uniformly stirring and mixing; 2) performing neutralization reaction on the mixed solution by using a sodium carbonate solution with the molar concentration of 0.9mol/L, and controlling the pH value of the end point to be 8.3-8.5; 3) after the neutralized materials are washed, dried, tabletted and molded, roasting the materials for 3 hours at the temperature of 1000 ℃ in a muffle furnace to obtain a carrier; 4) 200gNi (NO)3)2•6H2Dissolving O in water, and adding 0.07mol/L nitric acid to a pH value of 5.5-5.7 to obtain an impregnation liquid rich in an active component Ni; 5) controlling the temperature at 85 ℃, and dissolving 5g of lanthanum nitrate and 5g of zirconium nitrate in an impregnation liquid rich in an active component Ni to obtain the impregnation liquid rich in the active component Ni and an auxiliary agent salt, wherein the specific gravity of the impregnation liquid is controlled to be 1.5-1.6; 6) soaking the carrier in a soaking solution rich in active component Ni and auxiliary agent salt for 2.5 h; 7) taking out the catalyst precursor impregnated in the step 6, drying, and roasting at 400 ℃ for 3.5h to obtain a catalyst semi-finished product; 8) controlling the temperature to be 85 ℃, and soaking the catalyst semi-finished product obtained in the step a in a soaking solution which is rich in an active component Ni and has a specific gravity controlled to be 1.4-1.5 h; 9) and (4) taking out the catalyst precursor impregnated in the step (8), drying, and roasting at 400 ℃ for 3.5h to obtain a catalyst finished product Y-2.
Example 3
1) Dissolving 140g of aluminum nitrate and 100g of magnesium nitrate in 1L of deionized water, and uniformly stirring and mixing; 2) performing neutralization reaction on the mixed solution by using a sodium carbonate solution with the molar concentration of 1.0mol/L, and controlling the pH value of the end point to be 8.3-8.5; 3) after the neutralized materials are washed, dried, tabletted and molded, roasting the materials for 3 hours at the temperature of 950 ℃ in a muffle furnace to obtain a carrier; 4) 200gNi (NO)3)2•6H2Dissolving O in water, and adding 0.1mol/L nitric acid to a pH value of 5.5-5.7 to obtain an impregnation liquid rich in an active component Ni; 5) controlling the temperature at 75 ℃, and dissolving 5g of lanthanum nitrate, 2g of manganese nitrate and 5g of cerium nitrate in impregnation liquid rich in active component NiObtaining an impregnation liquid rich in an active component Ni and an auxiliary salt, wherein the specific gravity of the impregnation liquid is controlled to be 1.5-1.6; 6) soaking the carrier in a soaking solution rich in active component Ni and auxiliary agent salt for 3 hours; 7) taking out the catalyst precursor impregnated in the step 6, drying, and roasting at 450 ℃ for 2.5h to obtain a catalyst semi-finished product; 8) controlling the temperature at 75 ℃, and soaking the catalyst semi-finished product obtained in the step a in a soaking solution which is rich in an active component Ni and has a specific gravity controlled to be 1.4-1.5 h; 9) and (4) taking out the catalyst precursor impregnated in the step (8), drying, and roasting at the temperature of 450 ℃ for 2.5h to obtain a catalyst finished product Y-3.
Example 4
1) Dissolving 100g of aluminum nitrate and 100g of magnesium nitrate in 1L of deionized water, and uniformly stirring and mixing; 2) performing neutralization reaction on the mixed solution by using a sodium carbonate solution with the molar concentration of 0.7mol/L, and controlling the pH value of the end point to be 8.3-8.5; 3) after the neutralized materials are washed, dried, tabletted and molded, roasting the materials for 5 hours at the temperature of 850 ℃ in a muffle furnace to obtain a carrier; 4) 200gNi (NO)3)2•6H2Dissolving O in water, and adding 0.06mol/L nitric acid to a pH value of 5.8-6.0 to obtain an impregnation liquid rich in an active component Ni; 5) controlling the temperature at 65 ℃, dissolving 10g of cerium nitrate and 5g of molybdenum nitrate in an impregnation liquid rich in an active component Ni to obtain the impregnation liquid rich in the active component Ni and an auxiliary salt, wherein the specific gravity of the impregnation liquid is controlled to be 1.5-1.6; 6) soaking the carrier in a soaking solution rich in active component Ni and auxiliary agent salt for 4 hours; 7) taking out the catalyst precursor impregnated in the step 6, drying, and roasting at 380 ℃ for 3.5h to obtain a catalyst semi-finished product; 8) controlling the temperature at 65 ℃, and soaking the catalyst semi-finished product obtained in the step a in a soaking solution which is rich in active component Ni and has the specific gravity of 1.4-1.5 for 2 hours; 9) and (4) taking out the catalyst precursor impregnated in the step (8), drying, and roasting at the temperature of 380 ℃ for 3h to obtain a catalyst finished product Y-4.
Example 5
1) Dissolving 150g of aluminum nitrate and 100g of magnesium nitrate in 1L of deionized water, and uniformly stirring and mixing; 2) performing neutralization reaction on the mixed solution by using a sodium carbonate solution with the molar concentration of 1.2mol/L, and controlling the pH value of the end point to be 8.3-8.5; 3) washing, drying, tabletting and forming the neutralized materials in a horseRoasting the mixture for 2 hours at the temperature of 1100 ℃ in a muffle furnace to obtain a carrier; 4) 200gNi (NO)3)2•6H2Dissolving O in water, and adding 0.05mol/L nitric acid to a pH value of 5.5-5.7 to obtain an impregnation liquid rich in an active component Ni; 5) controlling the temperature at 90 ℃, and dissolving 5g of lanthanum nitrate and 5g of zirconium nitrate in an impregnation liquid rich in an active component Ni to obtain the impregnation liquid rich in the active component Ni and an auxiliary agent salt, wherein the specific gravity of the impregnation liquid is controlled to be 1.5-1.6; 6) soaking the carrier in a soaking solution rich in active component Ni and auxiliary agent salt for 2 h; 7) taking out the catalyst precursor impregnated in the step 6, drying, and roasting at 450 ℃ for 2h to obtain a catalyst semi-finished product; 8) c, controlling the temperature to be 90 ℃, and soaking the catalyst semi-finished product obtained in the step a in a soaking solution which is rich in an active component Ni and has a specific gravity controlled to be 1.4-1.5 h; 9) and (4) taking out the catalyst precursor impregnated in the step (8), drying, and roasting at the temperature of 450 ℃ for 2h to obtain a catalyst finished product Y-5.
Example 6
1) Dissolving 125g of aluminum nitrate and 100g of magnesium nitrate in 1L of deionized water, and uniformly stirring and mixing; 2) performing neutralization reaction on the mixed solution by using a sodium carbonate solution with the molar concentration of 1.2mol/L, and controlling the pH value of the end point to be 8.3-8.5; 3) after the neutralized materials are washed, dried, tabletted and molded, roasting the materials for 3 hours at the temperature of 950 ℃ in a muffle furnace to obtain a carrier; 4) 200gNi (NO)3)2•6H2Dissolving O in water, and adding 0.1mol/L nitric acid to a pH value of 5.8-6.0 to obtain an impregnation liquid rich in an active component Ni; 5) controlling the temperature at 70 ℃, and dissolving 10g of manganese nitrate in the impregnation liquid rich in the active component Ni to obtain the impregnation liquid rich in the active component Ni and the auxiliary agent salt, wherein the specific gravity of the impregnation liquid is controlled to be 1.5-1.6; 6) soaking the carrier in a soaking solution rich in active component Ni and auxiliary agent salt for 2.5 h; 7) taking out the catalyst precursor impregnated in the step 6, drying, and roasting at 400 ℃ for 2h to obtain a catalyst semi-finished product; 8) controlling the temperature at 70 ℃, and soaking the catalyst semi-finished product obtained in the step a in a soaking solution which is rich in an active component Ni and has a specific gravity controlled to be 1.4-1.5 h; 9) and (4) taking out the catalyst precursor impregnated in the step (8), drying, and roasting at 400 ℃ for 2h to obtain a catalyst finished product Y-6.
Example 7
1) Dissolving 110g of aluminum nitrate and 100g of magnesium nitrate in 1L of deionized water, and uniformly stirring and mixing; 2) performing neutralization reaction on the mixed solution by using a sodium carbonate solution with the molar concentration of 0.9mol/L, and controlling the pH value of the end point to be 8.3-8.5; 3) after the neutralized materials are washed, dried, tabletted and molded, roasting the materials for 3 hours at the temperature of 900 ℃ in a muffle furnace to obtain a carrier; 4) 200gNi (NO)3)2•6H2Dissolving O in water, and adding 0.075mol/L nitric acid to a pH value of 5.6-5.8 to obtain impregnation liquid rich in an active component Ni; 5) controlling the temperature at 85 ℃, and dissolving 10g of zirconium nitrate and 5g of lanthanum nitrate in an impregnation liquid rich in an active component Ni to obtain the impregnation liquid rich in the active component Ni and an auxiliary agent salt, wherein the specific gravity of the impregnation liquid is controlled to be 1.5-1.6; 6) soaking the carrier in a soaking solution rich in active component Ni and auxiliary agent salt for 2 h; 7) taking out the catalyst precursor impregnated in the step 6, drying, and roasting at 440 ℃ for 3.5h to obtain a catalyst semi-finished product; 8) controlling the temperature to be 85 ℃, and soaking the catalyst semi-finished product obtained in the step a in a soaking solution which is rich in an active component Ni and has a specific gravity controlled to be 1.4-1.5 for 2 hours; 9) and (4) taking out the catalyst precursor impregnated in the step (8), drying, and roasting at the temperature of 440 ℃ for 2.5h to obtain a catalyst finished product Y-7.
Example 8
1) Dissolving 100g of aluminum nitrate and 100g of magnesium nitrate in 1L of deionized water, and uniformly stirring and mixing; 2) performing neutralization reaction on the mixed solution by using a sodium carbonate solution with the molar concentration of 0.7mol/L, and controlling the pH value of the end point to be 8.3-8.5; 3) after the neutralized materials are washed, dried, tabletted and molded, roasting the materials for 3.5 hours at the temperature of 900 ℃ in a muffle furnace to obtain a carrier; 4) 200gNi (NO)3)2•6H2Dissolving O in water, and adding 0.08mol/L nitric acid to a pH value of 5.5-5.7 to obtain an impregnation liquid rich in an active component Ni; 5) controlling the temperature at 80 ℃, and dissolving 8g of molybdenum nitrate and 5g of lanthanum nitrate in an impregnation liquid rich in an active component Ni to obtain the impregnation liquid rich in the active component Ni and an auxiliary agent salt, wherein the specific gravity of the impregnation liquid is controlled to be 1.5-1.6; 6) soaking the carrier in a soaking solution rich in active component Ni and auxiliary agent salt for 2.5 h; 7) taking out the catalyst precursor impregnated in the step 6, drying, and roasting at 400 ℃ for 3h to obtain a catalyst semi-finished product; 8) controlling the temperature at 80 ℃ and mixingSoaking the catalyst semi-finished product obtained in the step a in a soaking solution which is rich in an active component Ni and has a specific gravity controlled to be 1.4-1.5 for 2 hours; 9) and (4) taking out the catalyst precursor impregnated in the step (8), drying, and roasting at 400 ℃ for 3h to obtain a catalyst finished product Y-8.
Example 9
1) Dissolving 120g of aluminum nitrate and 100g of magnesium nitrate in 1L of deionized water, and uniformly stirring and mixing; 2) performing neutralization reaction on the mixed solution by using a sodium carbonate solution with the molar concentration of 0.6mol/L, and controlling the pH value of the end point to be 8.3-8.5; 3) after the neutralized materials are washed, dried, tabletted and molded, roasting the materials in a muffle furnace at the temperature of 850 ℃ for h to obtain a carrier; 4) 200gNi (NO)3)2•6H2Dissolving O in water, and adding 0.09mol/L nitric acid to a pH value of 5.8-6.0 to obtain an impregnation liquid rich in an active component Ni; 5) controlling the temperature at 75 ℃, dissolving 10g of lanthanum nitrate and 5g of manganese nitrate in the impregnation liquid rich in the active component Ni to obtain the impregnation liquid rich in the active component Ni and the auxiliary agent salt, wherein the specific gravity of the impregnation liquid is controlled to be 1.5-1.6; 6) soaking the carrier in a soaking solution rich in active component Ni and auxiliary agent salt for 3 hours; 7) taking out the catalyst precursor impregnated in the step 6, drying, and roasting at the temperature of 420 ℃ for 3.5 hours to obtain a catalyst semi-finished product; 8) controlling the temperature at 75 ℃, and soaking the catalyst semi-finished product obtained in the step a in a soaking solution which is rich in active component Ni and has the specific gravity of 1.4-1.5 for 2 hours; 9) and (4) taking out the catalyst precursor impregnated in the step (8), drying, and roasting at the temperature of 420 ℃ for 3.5 hours to obtain a catalyst finished product Y-9.
Example 10
1) Dissolving 135g of aluminum nitrate and 100g of magnesium nitrate in 1L of deionized water, and uniformly stirring and mixing; 2) performing neutralization reaction on the mixed solution by using a sodium carbonate solution with the molar concentration of 0.8mol/L, and controlling the pH value of the end point to be 8.3-8.5; 3) after the neutralized materials are washed, dried, tabletted and molded, roasting the materials for 3 hours at the temperature of 950 ℃ in a muffle furnace to obtain a carrier; 4) 200gNi (NO)3)2•6H2Dissolving O in water, and adding 0.07mol/L nitric acid to a pH value of 5.5-5.7 to obtain impregnation liquid 6 rich in an active component Ni; 5) controlling the temperature at 80 ℃, and dissolving 5g of cerium nitrate, 5g of lanthanum nitrate and 5g of manganese nitrate in impregnation liquid rich in active component Ni to obtain the impregnation liquid rich in active component NiThe specific gravity of the impregnation liquid containing the active component Ni and the auxiliary agent salt is controlled to be 1.5-1.6; 6) soaking the carrier in a soaking solution rich in active component Ni and auxiliary agent salt for 1.5 h; 7) taking out the catalyst precursor impregnated in the step 6, drying, and roasting at 450 ℃ for 2.5h to obtain a catalyst semi-finished product; 8) controlling the temperature at 80 ℃, and soaking the catalyst semi-finished product obtained in the step a in a soaking solution which is rich in an active component Ni and has a specific gravity controlled to be 1.4-1.5 h; 9) and (4) taking out the catalyst precursor impregnated in the step (8), drying, and roasting at the temperature of 450 ℃ for 2.5h to obtain a catalyst finished product Y-10.
Comparative example 1
1) Carrying out heat treatment on 100g of pseudo-boehmite at 500 ℃, and tabletting to obtain an alumina carrier; 2) immersing the carrier in Ni (NO) at 75 deg.C3)2And Ce (NO)3)2•6H2O solution for 2 h; 3) and taking out the impregnated catalyst precursor, drying, and roasting at 450 ℃ for 2h to obtain a catalyst finished product D-1 with Ni and Ce loading amounts of 8% and 2% respectively.
Comparative example 2
1) Dissolving 100g of pseudo-boehmite in water to prepare a suspension, and adding 1: 1, preparing aluminum sol from dilute nitric acid; 2) at 80 deg.C, adding a certain amount of Ni (NO)3)2、Ce(NO3)2•6H2Adding O into the sol, and fully mixing; 3) then evaporating the mixed solution to dryness, roasting at 600 ℃ and tabletting to obtain a comparative catalyst D-2 with Ni and Ce loading amounts of 5% and 5% respectively.
Evaluation of catalyst Performance
Filling examples Y-1-Y-10 and comparative examples D-1-D-2 into an isothermal bed reactor, and under the condition of a one-stage isothermal non-circulating reaction process, when the composition of coke oven gas is 6.5 percent of CO, the composition of CO is CO2 4.0%，C2H6 2.5%，H260% and the balance N2 27% and space velocity of 7000h-1And the performance is detected and analyzed under the conditions that the pressure is 3.0MPa and the inlet temperature is 280 ℃.
Specific data are shown in table 1 below.
TABLE 1 comparison of catalyst Performance between examples and comparative examples
As can be seen from the data in table 1: the catalyst prepared by the method shows good CO conversion rate and CO after 72h and 300h2The conversion rate performance, especially the conversion performance of carbon dioxide is better, and the stability is ensured; the comparative example shows good conversion performance in 72h, but the conversion rate is obviously reduced after 300h reaction; meanwhile, after the catalyst prepared by the method is removed after running for 300 hours, the surface and the inside of the catalyst are not blocked or deposited by SEM (scanning electron microscope) detection, the comparative examples have deposited carbon at different degrees, and in addition, the comparative examples have pulverization phenomenon after running for 300 hours, so that the mechanical strength is obviously reduced.
Claims (10)
1. The coke-oven gas isothermal methanation catalyst is characterized by comprising a carrier, an active component and an auxiliary agent, wherein the carrier accounts for 60-80% by weight of the catalyst, the active component accounts for 15-35% by weight of the catalyst, and the auxiliary agent accounts for 1-5% by weight of the catalyst.
2. The coke oven gas isothermal methanation catalyst according to claim 1, characterized in that a carrier is a composite oxide formed by aluminum and magnesium, and the mass ratio of aluminum oxide to magnesium oxide in the carrier is (1.2-2.0): 1.
3. The coke oven gas isothermal methanation catalyst according to claim 1, characterized in that the auxiliary agent is a mixture of one or more oxides of Ce, Zr, Mo, Mn, La.
4. The method for preparing the coke-oven gas isothermal methanation catalyst as claimed in any one of claims 1 to 3
Characterized by comprising the following steps:
(1) preparation of the carrier:
a. dissolving aluminum nitrate and magnesium nitrate in ionized water, and uniformly stirring;
b. b, performing neutralization reaction on the mixed solution in the step a by using a sodium carbonate solution, and controlling the pH value of the end point to be 8.3-8.5;
c. c, washing, drying, tabletting, forming and roasting the material obtained in the step b to obtain a carrier;
(2) preparation of active ingredients:
mixing Ni (NO)3)2•6H2Dissolving O in water, adding 0.05-0.1 mol/L nitric acid to adjust the pH value to 5.5-6.0 to obtain rich
Impregnation liquid containing an active component Ni;
(3) preparation of the catalyst:
a. dissolving nitrate of the auxiliary agent into the impregnation liquid rich in the active component Ni to obtain the impregnation liquid rich in the active component Ni and the auxiliary agent
Impregnation liquid of agent salt;
b. controlling the temperature to be 60-90 ℃, and soaking the carrier in a soaking solution rich in active component Ni and auxiliary agent salt for 2-5 h;
c. taking out the catalyst precursor impregnated in the step b, drying and roasting to obtain a catalyst semi-finished product;
d. c, controlling the temperature to be 60-90 ℃, and soaking the catalyst semi-finished product obtained in the step c in a solution rich in active component Ni
Soaking in the soaking solution for 1-3 h;
e. and d, taking out the catalyst precursor impregnated in the step d, drying and roasting to obtain a catalyst finished product.
5. The preparation method of the coke-oven gas isothermal methanation catalyst according to claim 4, characterized in that the molar concentration of the sodium carbonate solution in the carrier preparation step b is 0.5-1.2 mol/L.
6. The preparation method of the coke-oven gas isothermal methanation catalyst according to claim 4, characterized in that the calcination temperature in the carrier preparation step c is 700-1100 ℃ and the calcination time is 2-5 h.
7. The preparation method of the coke-oven gas isothermal methanation catalyst according to claim 4, characterized in that the specific gravity of the impregnation liquid in the catalyst preparation step a is controlled to be 1.5-1.6.
8. The preparation method of the coke-oven gas isothermal methanation catalyst according to claim 4, characterized in that the calcination temperature in the catalyst preparation step c is 350-450 ℃ and the calcination time is 2-5 h.
9. The preparation method of the coke-oven gas isothermal methanation catalyst according to claim 4, characterized in that the specific gravity of the impregnation liquid in the catalyst preparation step d is controlled to be 1.4-1.5.
10. The preparation method of the coke-oven gas isothermal methanation catalyst according to claim 4, characterized in that in the catalyst preparation step e, the calcination temperature is 350-450 ℃, and the calcination time is 2-4 h.
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Application publication date: 20211015 |