CN110893347A - Low-temperature high-activity nickel-based bimetallic methanation catalyst and preparation method and application thereof - Google Patents
Low-temperature high-activity nickel-based bimetallic methanation catalyst and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 182
- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 81
- 230000000694 effects Effects 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002808 molecular sieve Substances 0.000 claims abstract description 73
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 53
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 53
- 239000011148 porous material Substances 0.000 claims description 49
- 238000002791 soaking Methods 0.000 claims description 39
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 36
- 150000002815 nickel Chemical class 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 20
- 239000012266 salt solution Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 238000005470 impregnation Methods 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000012216 screening Methods 0.000 claims description 13
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229940045032 cobaltous nitrate Drugs 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000007789 gas Substances 0.000 description 17
- 239000012265 solid product Substances 0.000 description 15
- 230000008901 benefit Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000004570 mortar (masonry) Substances 0.000 description 7
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 6
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- DTNVUQFDRPOYFY-UHFFFAOYSA-L nickel(2+);diacetate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O DTNVUQFDRPOYFY-UHFFFAOYSA-L 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910018062 Ni-M Inorganic materials 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229940045029 cobaltous nitrate hexahydrate Drugs 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 2
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000001016 Ostwald ripening Methods 0.000 description 1
- 241001629697 Panicum turgidum Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002383 small-angle X-ray diffraction data Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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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
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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
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- C07C1/0455—Reaction conditions
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
The invention discloses a low-temperature high-activity nickel-based bimetallic methanation catalyst, which takes mesoporous molecular sieve SBA-16-EG as a carrier, metal Ni as a first active component and a second active metal M as a second active component, wherein the second active metal M is at least one of Fe, Co, La and Mo; wherein, based on 100 weight portions of catalyst, calculated by metal elements, the content of nickel is 5-30 weight portions, the content of the second active metal M is 0.1-10 weight portions, and the balance is mesoporous molecular sieve SBA-16-EG. The low-temperature high-activity nickel-based bimetallic methanation catalyst provided by the invention does not contain precious metal components, the preparation method is simple and easy to implement, the precursor is not wasted, the performance is higher, and the cost performance is higher.
Description
Technical Field
The invention belongs to the technical field of industrial catalysis, and relates to a low-temperature high-activity nickel-based bimetallic methanation catalyst, and a preparation method and application thereof.
Background
The methanation technology is the research focus for developing the coal-to-natural gas technology, and the core of the technology is a high-efficiency and stable methanation catalyst. A large amount of heat is evolved due to methanation of the synthesis gasAmount (CO + 3H)2→CH4+H2O,ΔH298KAt-206.1 kJ/mol), the reaction proceeds in the forward direction at both low and high temperatures. However, low temperatures can dramatically reduce the reaction rate and thus the throughput, in terms of reaction kinetics. Therefore, it is necessary to research a catalyst with lower activation energy so that the catalyst can have higher activity at lower temperature, thereby achieving the dual harvest of yield and benefit.
The current industrial application adopts a higher-temperature catalyst, which can utilize a large amount of heat released by the reaction, but the benefit and risk are compatible, and the Ni-based catalyst at high temperature can cause Ni atoms to be thermally migrated through an Ostwald ripening mechanism due to the lower Taman temperature, so that the catalyst particles are agglomerated and even sintered to be inactivated, so that the research of the Ni-based methanation catalyst with high activity at lower temperature is more necessary. Disproportionation of carbon monoxide 2CO (g) → C(s) + CO2(g) At higher temperatures, inactive carbon species are formed and the accumulation of carbon species also leads to deactivation of the Ni-based catalyst, so that the reaction at lower temperatures greatly reduces the formation of carbon and thus prolongs the service life of the catalyst.
Patent CN 104511314A proposes a low-temperature methanation catalyst and a preparation method thereof, and Raney alloy particles are partially embedded and loaded on the surface of an organic polymer material by adopting a Raney method, so that the content of 0.5% of CO in raw material gas can be reduced to be lower than 1ppm at 150 ℃, but the loading amount of active metal nickel is higher (30-60 wt%), and the catalyst cannot be directly used for methanation of synthesis gas. Patent CN 103706373A proposes a low-temperature high-activity methanation catalyst, wherein nickel is an active component, and Al2O3Is used as a carrier, MgO is used as a structural assistant, and rare earth metal lanthanum and metal manganese are used as active assistants, so that CO in the feed gas can be removed2/CH4/H2CO 0.880/94.097/5.0232The content was reduced to 10 ppm. But the content of the supported metal nickel is still high (18-45wt percent), which causes waste of active metal.
Disclosure of Invention
In order to overcome the defects of low utilization rate of metal Ni, easy agglomeration of Ni particles and easy catalyst deactivation caused by carbon deposition of a high-temperature Ni-based methanation catalyst in the prior art, the invention aims to provide a low-temperature high-activity nickel-based bimetallic methanation catalyst with high activity and good stability under a low-temperature condition.
The invention also aims to provide a preparation method of the low-temperature high-activity nickel-based bimetallic methanation catalyst, which has the advantages of simplicity, convenience, low cost and the like.
The invention further aims to provide application of the low-temperature high-activity nickel-based bimetallic methanation catalyst.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a low-temperature high-activity nickel-based bimetallic methanation catalyst, which takes mesoporous molecular sieve SBA-16-EG as a carrier, metal Ni as a first active component and a second active metal M as a second active component, wherein the second active metal M is at least one of Fe, Co, La and Mo; wherein, based on 100 weight portions of catalyst, calculated by metal elements, the content of nickel is 5-30 weight portions, the content of the second active metal M is 0.1-10 weight portions, and the balance is mesoporous molecular sieve SBA-16-EG. The mesoporous molecular sieve SBA-16-EG has stable chemical properties, good heat conduction performance and large specific surface area.
The specific surface area of the low-temperature high-activity nickel-based bimetallic methanation catalyst is 500-1000 m2(ii) a pore diameter of 3 to 12nm and a pore volume of 0.4 to 1.4m3/g。
The mesoporous molecular sieve SBA-16-EG is pretreated by ethylene glycol.
The specific surface area of the mesoporous molecular sieve SBA-16-EG is 500-1000 m2Preferably 600 to 890 m/g2The pore diameter is 2-12 nm, preferably 2-10 nm, the pore wall is 2-6 nm, and the pore volume is 0.4-1.4 cm3Preferably 0.4 to 1 cm/g3/g。
The metal Ni is NiO and Ni2O3In the form of an alloy or in the form of a solid solution.
The invention provides a preparation method of a low-temperature high-activity nickel-based bimetallic methanation catalyst, which comprises the following steps of:
dissolving nickel salt and second active metal M salt in a solvent to prepare an impregnation solution, wherein the concentration range of the nickel salt in the impregnation solution is 0.1-1 g/mL, and the concentration range of the second active metal M salt is 0.005-0.2 g/mL; soaking the dried pretreated mesoporous molecular sieve SBA-16-EG in a soaking solution by adopting an isometric co-soaking method, wherein the mass ratio of the mesoporous molecular sieve SBA-16-EG to the nickel salt and the second active metal M salt is 1 (0.2-2) to 0.008-0.2; stirring, standing, vacuum drying, roasting, grinding and screening to obtain the low-temperature high-activity nickel-based bimetallic methanation catalyst;
or dissolving nickel salt in a solvent to prepare a nickel salt solution with the concentration range of 0.1-1 g/mL, dissolving a second active metal M salt in the solvent to prepare a second active metal M salt solution with the concentration range of 0.004-0.1 g/mL, soaking the dried pretreated mesoporous molecular sieve SBA-16-EG in the nickel salt solution by adopting an isometric impregnation method, stirring, standing, vacuum drying, roasting, and then soaking in the second active metal M salt solution, wherein the mass ratio of the mesoporous molecular sieve SBA-16-EG to the nickel salt and the second active metal M salt is (0.2-2): 0.008-0.2; stirring, standing, vacuum drying, roasting, grinding and screening to obtain the low-temperature high-activity nickel-based bimetallic methanation catalyst;
or dissolving nickel salt in a solvent to prepare a nickel salt solution with the concentration range of 0.1-1 g/mL, dissolving a second active metal M salt in the solvent to prepare a second active metal M salt solution with the concentration range of 0.004-0.1 g/mL, soaking the dried pretreated mesoporous molecular sieve SBA-16-EG in the second active metal M salt solution by adopting an isometric impregnation method, stirring, standing, vacuum drying, roasting, and then soaking in the nickel salt solution, wherein the mass ratio of the mesoporous molecular sieve SBA-16-EG to the nickel salt and the second active metal M salt is (0.2-2): 0.008-0.2; and stirring, standing, vacuum drying, roasting, grinding and screening to obtain the low-temperature high-activity nickel-based bimetallic methanation catalyst.
The pretreatment of the mesoporous molecular sieve SBA-16-EG comprises the following steps: soaking dry mesoporous SiO2 molecular sieve SBA-16-EG in ethylene glycol in equal volume, stirring uniformly, standing at room temperature, and drying to obtain the pretreated mesoporous molecular sieve SBA-16-EG.
The mesoporous molecular sieve SBA-16-EG is dried at the temperature of 80-120 ℃ for 2-24 hours, preferably 8-10 hours.
The nickel salt is at least one of nickel chloride, nickel sulfate, nickel acetate, nickel oxalate and nickel nitrate.
The second active metal M salt is at least one of ferric nitrate, cobalt nitrate, lanthanum nitrate, ammonium molybdate and cobaltous nitrate.
The solvent is at least one of deionized water, methanol, ethanol, acetic acid, ethyl acetate, chloroform and acetone.
The temperature of the isometric impregnation method and the isometric co-impregnation method is room temperature, and the time is 2-12 h, preferably 4-8 h.
The temperature of the vacuum drying is 10-200 ℃, preferably 50-100 ℃, and the time is 1-24 hours, preferably 6-8 hours.
The roasting temperature is 400-900 ℃, preferably 450-600 ℃, and the roasting time is 0.5-10 hours, preferably 3-6 hours.
The screening is performed by a 200-mesh sample separation screen.
In the preparation process of the catalyst, the solvent of the impregnation liquid is changed, so that the aggregation and growth of active component particles can be inhibited, the size of small nickel particles is maintained, and the sintering of the active component particles can be prevented in the reduction process of the catalyst, so that the dispersion degree of the active component nickel in the catalyst is improved, and the low-temperature activity and the stability of the catalyst are influenced finally.
The invention also provides application of the low-temperature high-activity nickel-based bimetallic methanation catalyst in preparation of methane from synthesis gas.
The conditions for preparing methane from the synthesis gas are as follows: the volume airspeed of the synthesis gas treated by the catalyst is 3000-60000 h-1The pressure is from normal pressure to 3.0MPa, the temperature is from 200 ℃ to 500 ℃, and H in the synthesis gas2The ratio of/CO is 2-4.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the low-temperature high-activity nickel-based bimetallic methanation catalyst provided by the invention takes mesoporous molecular sieve SBA-16-EG with stable chemical properties and good thermal conductivity as a carrier, and the prepared catalyst has the advantages of large specific surface area, high catalytic activity (CO can be completely converted at 270 ℃), good stability and the like. The low-temperature high-activity nickel-based bimetallic methanation catalyst provided by the invention has the lowest complete conversion temperature of 265 ℃ and the methane selectivity of over 90% during complete conversion.
The low-temperature high-activity nickel-based bimetallic methanation catalyst provided by the invention does not contain precious metal components, the preparation method is simple and easy to implement, the precursor is not wasted, the performance is higher, and the cost performance is higher.
The low-temperature high-activity nickel-based bimetallic methanation catalyst provided by the invention uses the second active component modified Ni-based catalyst, the second active metal M can form a bimetallic oxide with the active component Ni in the roasting process of catalyst preparation, the two metals can be uniformly dispersed in the pre-reduction process of the catalyst, the obtained nickel-based bimetallic catalyst has the advantages of good catalytic activity, high methane selectivity, long catalyst life and the like under the low-temperature condition, and the catalyst has the air speed of 15000h at the normal pressure, 270 ℃ and the air speed of 15000h-1The conversion rate of CO can reach 100 percent, the selectivity of methane is more than 90 percent, the yield of methane is more than 90 percent, and the method has great industrial prospect.
The low-temperature high-activity nickel-based bimetallic methanation catalyst provided by the invention adopts a mesoporous molecular sieve SBA-16-EG with large specific surface area, stable mechanical strength and good high temperature resistance as a carrier of the Ni-based methanation catalyst, adopts metal Ni as an active component, and adds Fe, Co, La, Mo and the like as a second active component, and prepares a series of Ni-based SBA-16-EG type methanation catalysts by an isometric impregnation method, and has high methanation activity at lower temperature.
The low-temperature high-activity nickel-based bimetallic methanation catalyst provided by the invention adopts the mesoporous molecular sieve SBA-16-EG which is three-dimensional cage-shaped SiO2Molecular sieve materials, three-dimensional structures for mass and heat transferThe effect is better, the problem that active components block the pore channels of the molecular sieve is solved, the molecular sieve has a multi-level pore structure, and larger cage-shaped pores can play a role in limiting the active components. The larger specific surface area and pore volume may provide sufficient space for dispersion of the active component.
The low-temperature high-activity nickel-based bimetallic methanation catalyst provided by the invention shows excellent activity and methane selectivity in the reaction of preparing methane from synthesis gas, has activity in a temperature range of 200-500 ℃, can completely convert CO at 270 ℃, and completely converts CH when CO is completely converted4The selectivity reaches more than 90 percent.
The low-temperature high-activity nickel-based bimetallic methanation catalyst provided by the invention has a very long service life in the reaction of preparing methane from synthesis gas, in a service life test, the activity of the catalyst can not be reduced within 200h, the CO conversion rate can reach 100%, and the methane selectivity can reach more than 90%.
Drawings
FIG. 1 is a small angle XRD pattern of SBA-16-EG of an example vehicle according to the invention.
FIG. 2 is a HRTEM image of a low-temperature high-activity nickel-based bimetallic methanation catalyst of an embodiment of the invention.
Fig. 3 is a wide angle XRD pattern of the low-temperature high-activity nickel-based bimetallic methanation catalyst of the embodiment of the present invention.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers. All percentages, ratios, proportions, or parts are by weight unless otherwise specified.
The weight volume percentage units in the present invention are well known to those skilled in the art and refer to, for example, the weight of solute in a 100 ml solution.
As used herein, "room temperature" means 15-30 deg.C, preferably 20-25 deg.C.
As used herein, "atmospheric pressure" means 0.1 MPa.
As used herein, mesoporous SiO, unless otherwise specified2The synthesis method of the molecular sieve SBA-16-EG comprises the following steps: the hydrothermal synthesis temperature is 100 ℃ and the time is 24h, the drying is carried out at 100 ℃ for 12h, and the calcination is carried out at 550 ℃ for 5 h.
As used herein, the impregnation solvent is typically deionized water unless otherwise specified.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
The reagents and materials used in the present invention are as follows:
nickel nitrate hexahydrate Ni (NO)3)2·6H2O, analytically pure; nickel acetate tetrahydrate Ni (CH)3COO)2·4H2O, analytically pure; iron nitrate nonahydrate Fe (NO)3)3·9H2O, analytically pure; nickel acetate hexahydrate, analytically pure; cobalt (II) nitrate hexahydrate3)2·6H2O, analytically pure; ethanol C2H5OH, analytically pure; ethylene glycol HOCH2CH2OH, analytically pure; the above reagents were purchased from Shanghai national drug group.
Example 1
Drying the mesoporous SiO2Soaking the molecular sieve SBA-16-EG in ethylene glycol in the same volume, uniformly stirring, standing at room temperature, and drying to obtain the pretreated mesoporous molecular sieve SBA-16-EG with the specific surface area of 887m2Per g, pore wall of 4nm, pore volume of 0.75cm3(ii)/g, pore size 4 nm; the pretreated mesoporous molecular sieve dried SBA-16-EG is then used in the next step. The mesoporous molecular sieve SBA-16-EG is dried at the temperature of 80 ℃ for 12 hours.
0.55g of nickel nitrate hexahydrate and 0.08g of ferric nitrate nonahydrate are dissolved in 2.0mL of deionized water to prepare a solutionThe solution is prepared by soaking dried 1.0g of pretreated mesoporous molecular sieve SBA-16-EG in 2.0mL of soaking solution by an equal volume co-soaking method, standing for 8h, and drying for 12h in a vacuum oven at 60 ℃. And roasting the obtained solid product in a muffle furnace at the roasting temperature of 500 ℃ for 5 hours, grinding the solid product by using a mortar, and screening the ground solid product by using a 200-mesh sample sieve to obtain the low-temperature high-activity nickel-based bimetallic methanation catalyst with the nickel load of 10 wt%, wherein the catalyst is marked as 10Ni1Fe/SBA-16-EG, and the content of the second active metal Fe is 1 wt%. The specific surface area of the low-temperature high-activity nickel-based bimetallic methanation catalyst is 685m2Per g, pore volume 0.47cm3(ii)/g, pore diameter of 4 nm.
The small-angle XRD of the SBA-16-EG of the carrier of the invention is shown in figure 1, and figure 1 is the small-angle XRD of the SBA-16-EG of the carrier of the invention; as can be seen from the figure, the carrier SBA-16-EG after the ethylene glycol pretreatment has the characteristic diffraction peaks of SBA-16 at the temperature of about 0.8 degrees and about 2.0 degrees, which indicates that the carrier SBA-16-EG after the ethylene glycol pretreatment still maintains the short-range highly ordered state.
Example 2
Drying the mesoporous SiO2Soaking the molecular sieve SBA-16-EG in ethylene glycol in the same volume, uniformly stirring, standing at room temperature, and drying to obtain the pretreated mesoporous molecular sieve SBA-16-EG with the specific surface area of 887m2Per g, pore wall of 4nm, pore volume of 0.75cm3(ii)/g, pore diameter 3 nm; the pretreated mesoporous molecular sieve dried SBA-16-EG is then used in the next step. The mesoporous molecular sieve SBA-16-EG is dried at the temperature of 120 ℃ for 8 hours.
0.23g of nickel nitrate hexahydrate and 0.04g of ferric nitrate nonahydrate are dissolved in 2.0mL of deionized water to prepare a soaking solution, and 1.0g of dried pretreated mesoporous SiO is prepared by adopting an equal-volume co-soaking method2Molecular sieve SBA-16-EG is soaked in 2.0mL of the soaking solution, stands for 6h, and is dried for 8h in a vacuum oven at the temperature of 60 ℃. Roasting the obtained solid product in a muffle furnace at the roasting temperature of 500 ℃ for 4 hours, grinding the solid product by a mortar, screening the solid product by a 200-mesh sample sieve to obtain the low-temperature high-activity nickel-based bimetallic methanation catalyst with the nickel load of 5 wt%, and recording the nickel load of the low-temperature high-activity nickel-based bimetallic methanation catalyst5Ni0.5Fe/SBA-16-EG, and the content of the second active metal Fe is 0.5 wt%. The specific surface area of the low-temperature high-activity nickel-based bimetallic methanation catalyst is 674m2Per g, pore volume 0.46cm3(ii)/g, pore diameter 3 nm.
The HRTEM image of the low-temperature high-activity nickel-based bimetallic methanation catalyst disclosed by the embodiment of the invention is shown in the attached figure 2, and the HRTEM image of the low-temperature high-activity nickel-based bimetallic methanation catalyst disclosed by the embodiment of the invention is shown in figure 2; as can be seen from the figure, after the carrier SBA-16-EG pretreated by the ethylene glycol is soaked in the nickel salt and iron salt solution, the active components of the catalyst still keep uniform dispersion after being roasted, and are not agglomerated into large particles.
Example 3
Drying the mesoporous SiO2Soaking the molecular sieve SBA-16-EG in ethylene glycol in the same volume, uniformly stirring, standing at room temperature, and drying to obtain the pretreated mesoporous molecular sieve SBA-16-EG with the specific surface area of 887m2Per g, pore wall of 4nm, pore volume of 0.75cm3(ii)/g, pore size 6 nm; the pretreated mesoporous molecular sieve dried SBA-16-EG is then used in the next step. The mesoporous molecular sieve SBA-16-EG is dried at the temperature of 100 ℃ for 12 hours.
0.34g of nickel acetate hexahydrate is dissolved in 2.0mL of deionized water to prepare a nickel salt solution, 0.08g of ferric nitrate nonahydrate is dissolved in 2.0mL of deionized water to prepare a ferric nitrate solution, and 1.0g of dried pretreated mesoporous SiO by adopting an isometric immersion method2Soaking the molecular sieve SBA-16-EG in 2.0mL of ferric nitrate solution, standing for 6h, drying for 10h at the temperature of 50 ℃ in a vacuum oven, and roasting for 6h at the temperature of 500 ℃; subsequently, the sample is immersed in 2.0mL of nickel nitrate solution, kept stand for 12h, dried in a vacuum oven at 50 ℃ for 12h, roasted at 500 ℃ for 5h, ground by a mortar, and sieved by a 200-mesh sample sieve, so that the low-temperature high-activity nickel-based bimetallic methanation catalyst with the nickel loading of 10 wt% is obtained, and is recorded as 1 Fe-10 Ni/SBA-16-EG, and the content of the second active metal Fe is 1 wt%. The specific surface area of the low-temperature high-activity nickel-based bimetallic methanation catalyst is 667m2Per g, pore volume 0.48cm3G, pore diameter of 6 nm.
Example 4
Drying the mesoporous SiO2Soaking the molecular sieve SBA-16-EG in ethylene glycol in the same volume, uniformly stirring, standing at room temperature, and drying to obtain the pretreated mesoporous molecular sieve SBA-16-EG with the specific surface area of 887m2Per g, pore wall of 4nm, pore volume of 0.75cm3(ii)/g, pore diameter 5 nm; the pretreated mesoporous molecular sieve dried SBA-16-EG is then used in the next step. The mesoporous molecular sieve SBA-16-EG is dried at the temperature of 100 ℃ for 12 hours.
0.55g of nickel nitrate hexahydrate is dissolved in 2.0mL of deionized water to prepare a nickel salt solution, 0.08g of ferric nitrate nonahydrate is dissolved in 2.0mL of deionized water to prepare a ferric nitrate solution, and 1.0g of dried pretreated mesoporous SiO is firstly prepared by adopting an isometric impregnation method2Soaking the molecular sieve SBA-16-EG in 2.0mL of nickel nitrate solution, standing for 6h, drying for 12h at the temperature of 50 ℃ in a vacuum oven, and roasting for 6h at the temperature of 450 ℃; subsequently, the sample is immersed in 2.0mL of ferric nitrate solution, kept stand for 6h, dried in a vacuum oven at 50 ℃ for 12h, roasted at 500 ℃ for 5h, ground by a mortar, and sieved by a 200-mesh sample sieve, so that the low-temperature high-activity nickel-based bimetallic methanation catalyst with the nickel loading of 10 wt% is obtained, and is recorded as 10 Ni-1 Fe/SBA-16-EG, and the content of the second active metal Fe is 1 wt%. The specific surface area of the low-temperature high-activity nickel-based bimetallic methanation catalyst is 665m2Per g, pore volume 0.48cm3(ii)/g, pore diameter is 5 nm.
Example 5
Drying the mesoporous SiO2Soaking the molecular sieve SBA-16-EG in ethylene glycol in the same volume, uniformly stirring, standing at room temperature, and drying to obtain the pretreated mesoporous molecular sieve SBA-16-EG with the specific surface area of 887m2Per g, pore wall of 4nm, pore volume of 0.75cm3(ii)/g, pore size 4 nm; the pretreated mesoporous molecular sieve dried SBA-16-EG is then used in the next step. The mesoporous molecular sieve SBA-16-EG is dried at the temperature of 100 ℃ for 12 hours.
0.23g of nickel nitrate hexahydrate and 0.05g of cobaltous nitrate hexahydrate are simultaneously dissolved in 2.0mL of deionized water to prepare a soaking solution, and 1.0g of dried pretreated nickel nitrate hexahydrate is subjected to isovolumetric co-soakingMesoporous SiO2Molecular sieve SBA-16-EG is soaked in 2.0mL of the soaking solution, stands for 6h, and is dried for 12h in a vacuum oven at the temperature of 50 ℃. And roasting the obtained solid product in a muffle furnace at the roasting temperature of 600 ℃ for 4 hours, grinding the solid product by using a mortar, and screening the ground solid product by using a 200-mesh sample sieve to obtain the low-temperature high-activity nickel-based bimetallic methanation catalyst with the nickel loading of 10 wt%, wherein the low-temperature high-activity nickel-based bimetallic methanation catalyst is marked as 5Ni1Co/SBA-16-EG, and the content of the second active metal Co is 1 wt%. The specific surface area of the low-temperature high-activity nickel-based bimetallic methanation catalyst is 634m2Per g, pore volume 0.42cm3(ii)/g, pore diameter of 4 nm.
Example 6
Drying the mesoporous SiO2Soaking the molecular sieve SBA-16-EG in ethylene glycol in the same volume, uniformly stirring, standing at room temperature, and drying to obtain the pretreated mesoporous molecular sieve SBA-16-EG with the specific surface area of 887m2Per g, pore wall of 4nm, pore volume of 0.75cm3(ii)/g, pore diameter 5 nm; the pretreated mesoporous molecular sieve dried SBA-16-EG is then used in the next step. The mesoporous molecular sieve SBA-16-EG is dried at the temperature of 120 ℃ for 8 hours.
0.34g of nickel acetate hexahydrate and 0.08g of ferric nitrate nonahydrate are simultaneously dissolved in 2.0mL of ethanol to prepare a soaking solution, and 1.0g of dried pretreated mesoporous SiO is subjected to isometric co-soaking2Molecular sieve SBA-16-EG is soaked in 2.0mL of the soaking solution, stands for 6h, and is dried for 10h in a vacuum oven at the temperature of 55 ℃. Roasting the obtained solid product in a muffle furnace at the roasting temperature of 550 ℃ for 5 hours, grinding the solid product by using a mortar, and then screening the solid product by using a 200-mesh sample sieve to obtain the low-temperature high-activity nickel-based bimetallic methanation catalyst with the nickel load of 10 wt%, wherein the low-temperature high-activity nickel-based bimetallic methanation catalyst is marked as 10Ni2Fe/SBA-16-EG (E), and the content of the second active metal Fe is 2 wt%. The specific surface area of the low-temperature high-activity nickel-based bimetallic methanation catalyst is 625m2Per g, pore volume 0.45cm3(ii)/g, pore diameter is 5 nm.
Example 7
Drying the mesoporous SiO2Soaking the molecular sieve SBA-16-EG in ethylene glycol in the same volume, uniformly stirring, standing at room temperature, and drying to obtain the pretreated mesoporous moleculesSieve SBA-16-EG with a specific surface area of 887m2Per g, pore wall of 4nm, pore volume of 0.75cm3(ii)/g, pore size 4 nm; the pretreated mesoporous molecular sieve dried SBA-16-EG is then used in the next step. The mesoporous molecular sieve SBA-16-EG is dried at the temperature of 80 ℃ for 12 hours.
0.34g of nickel acetate tetrahydrate and 0.05g of cobaltous nitrate hexahydrate are simultaneously dissolved in 2.0mL of ethanol to prepare a soaking solution, and 1.0g of dried pretreated mesoporous SiO is prepared by adopting an equal-volume co-soaking method2Molecular sieve SBA-16-EG is soaked in 2.0mL of the soaking solution, stands for 6h, and is dried for 10h in a vacuum oven at the temperature of 50 ℃. And roasting the obtained solid product in a muffle furnace at 600 ℃ for 3h, grinding the solid product by using a mortar, and screening the ground solid product by using a 200-mesh sample sieve to obtain the low-temperature high-activity nickel-based bimetallic methanation catalyst with the nickel load of 10 wt%, wherein the low-temperature high-activity nickel-based bimetallic methanation catalyst is marked as 10Ni1Co/SBA-16-EG (E), and the content of the second active metal Co is 1 wt%. The specific surface area of the low-temperature high-activity nickel-based bimetallic methanation catalyst is 633m2Per g, pore volume 0.43cm3(ii)/g, pore diameter of 4 nm.
The wide-angle XRD patterns of the low-temperature high-activity nickel-based bimetallic methanation catalysts of embodiments 1 to 3 and 5 are shown in fig. 3, and fig. 3 is a wide-angle XRD pattern of the low-temperature high-activity nickel-based bimetallic methanation catalyst of the embodiment of the present invention; as can be seen from the figure, the characteristic diffraction peaks of the NiO particles are not obvious, which indicates that the active components still keep well dispersed after the carrier SBA-16-EG pretreated by the glycol is impregnated with the nickel salt and the M salt of the active components and is roasted at high temperature.
The low-temperature high-activity nickel-based bimetallic methanation catalysts prepared in the embodiments 1 to 7 are respectively filled in a fixed bed micro-reactor with the inner diameter of 8mm, and N is used before reaction2Purging air, heating to 500 deg.C at 20 deg.C/min, and introducing high-purity H at the temperature2The catalyst was reduced for 2 hours. And then catalyzing the methanation reaction of the raw material gas by using the catalyst obtained after reduction. The composition of the feed gas and the catalytic reaction conditions were as follows:
the raw material gas composition is as follows: CO: 20% of H2：60％，N2：20％；
Catalyst loading: 200 mg;
reaction temperature: 240-320 ℃;
reaction pressure: 0.1 MPa;
the reaction space velocity: 15000h-1。
The raw material gas composition and the catalytic reaction conditions applicable to the low-temperature high-activity nickel-based bimetallic methanation catalyst provided by the invention can also be as follows: the volume space velocity of the synthesis gas is 3000-60000 h-1The pressure is from normal pressure to 3.0Mpa, the temperature is from 200 ℃ to 500 ℃, and H in the synthesis gas2The ratio of/CO is 2-4.
CO conversion and CH were determined and calculated as follows4The selectivity, results are listed in table 1:
conversion rate of CO: xCO(1-amount of CO contained in product/amount of CO contained in raw material gas). times.100%
CH4And (3) selectivity: sCH4Is converted to CH4CO amount of (2)/amount of CO conversion) × 100%
Light-off temperature T10: temperature when CO conversion reaches 10%
Minimum complete conversion temperature T100: temperature when CO conversion reaches 99.5%
TABLE 1
| Catalyst and process for preparing same | T10/℃ | T100/℃ | At full conversion XCH4/％ | |
| Example 1 | 10Ni1Fe/SBA-16-EG | 260 | 270 | 92.5 |
| Example 2 | 5Ni0.5Fe/SBA-16-EG | 260 | 270 | 93.2 |
| Example 3 | 1Fe-10Ni/SBA-16-EG | 265 | 270 | 93.0 |
| Example 4 | 10Ni-1Fe/SBA-16-EG | 260 | 270 | 92.6 |
| Example 5 | 5Ni1Co/SBA-16-EG | 265 | 270 | 91.4 |
| Example 6 | 10Ni2Fe/SBA-16-EG(E) | 255 | 265 | 95.8 |
| Example 7 | 10Ni1Co/SBA-16-EG(E) | 260 | 270 | 94.2 |
As can be seen from the data in Table 1, all the ethylene glycol pretreatment carriers SBA-16 are impregnated with active metal salts, and are roasted and reduced to form the Ni-M/SBA-16-EG bimetallic catalyst, CO can be completely converted at 270 ℃ in the preparation of methane from synthesis gas, and the temperature required by the reaction is greatly reduced.
The invention uses the mesoporous SiO with stable chemical property, good heat conduction performance and large specific surface area2The molecular sieve SBA-16 is used as a carrier, is pretreated by ethylene glycol, and is prepared into the Ni-M/SBA-16-EG bimetallic catalyst by an isometric step impregnation method and an isometric co-impregnation method, and the catalyst has the advantages of high catalytic activity, good methane selectivity, long service life and the like under a low-temperature condition. The nickel-based double catalyst can achieve the CO conversion rate of 100 percent, the methane selectivity of 95.8 percent and the methane yield of 95.8 percent under the optimal condition, and has great industrial prospect.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A low-temperature high-activity nickel-based bimetallic methanation catalyst is characterized in that: taking mesoporous molecular sieve SBA-16-EG as a carrier, metal Ni as a first active component, and a second active metal M as a second active component, wherein the second active metal M is at least one of Fe, Co, La and Mo; wherein, based on 100 weight portions of catalyst, calculated by metal elements, the content of nickel is 5-30 weight portions, the content of the second active metal M is 0.1-10 weight portions, and the balance is mesoporous molecular sieve SBA-16-EG.
2. The low-temperature high-activity nickel-based bimetallic methanation catalyst as claimed in claim 1, characterized in that: the specific surface area of the low-temperature high-activity nickel-based bimetallic methanation catalyst is 500-1000 m2(ii) a pore diameter of 3 to 12nm and a pore volume of 0.4 to 1.4m3/g。
3. The low-temperature high-activity nickel-based bimetallic methanation catalyst as claimed in claim 1, characterized in that: the mesoporous molecular sieve SBA-16-EG is pretreated by glycol;
the specific surface area of the mesoporous molecular sieve SBA-16-EG is 500-1000 m2Preferably 600 to 890 m/g2The pore diameter is 2-12 nm, preferably 2-10 nm, the pore wall is 2-6 nm, and the pore volume is 0.4-1.4 cm3Preferably 0.4 to 1 cm/g3/g。
4. A preparation method of the low-temperature high-activity nickel-based bimetallic methanation catalyst as claimed in any one of claims 1 to 3, characterized by comprising the following steps: the method comprises the following steps:
dissolving nickel salt and second active metal M salt in a solvent to prepare an impregnation solution, wherein the concentration range of the nickel salt in the impregnation solution is 0.1-1 g/mL, and the concentration range of the second active metal M salt is 0.005-0.2 g/mL; soaking the dried pretreated mesoporous molecular sieve SBA-16-EG in a soaking solution by adopting an isometric co-soaking method, wherein the mass ratio of the mesoporous molecular sieve SBA-16-EG to the nickel salt and the second active metal M salt is 1 (0.2-2) to 0.008-0.2; stirring, standing, vacuum drying, roasting, grinding and screening to obtain the low-temperature high-activity nickel-based bimetallic methanation catalyst;
or dissolving nickel salt in a solvent to prepare a nickel salt solution with the concentration range of 0.1-1 g/mL, dissolving a second active metal M salt in the solvent to prepare a second active metal M salt solution with the concentration range of 0.004-0.1 g/mL, soaking the dried pretreated mesoporous molecular sieve SBA-16-EG in the nickel salt solution by adopting an isometric impregnation method, stirring, standing, vacuum drying, roasting, and then soaking in the second active metal M salt solution, wherein the mass ratio of the mesoporous molecular sieve SBA-16-EG to the nickel salt and the second active metal M salt is (0.2-2): 0.008-0.2; stirring, standing, vacuum drying, roasting, grinding and screening to obtain the low-temperature high-activity nickel-based bimetallic methanation catalyst;
or dissolving nickel salt in a solvent to prepare a nickel salt solution with the concentration range of 0.1-1 g/mL, dissolving a second active metal M salt in the solvent to prepare a second active metal M salt solution with the concentration range of 0.004-0.1 g/mL, soaking the dried pretreated mesoporous molecular sieve SBA-16-EG in the second active metal M salt solution by adopting an isometric impregnation method, stirring, standing, vacuum drying, roasting, and then soaking in the nickel salt solution, wherein the mass ratio of the mesoporous molecular sieve SBA-16-EG to the nickel salt and the second active metal M salt is (0.2-2): 0.008-0.2; and stirring, standing, vacuum drying, roasting, grinding and screening to obtain the low-temperature high-activity nickel-based bimetallic methanation catalyst.
5. The preparation method of the low-temperature high-activity nickel-based bimetallic methanation catalyst as claimed in claim 4, characterized in that: the pretreatment of the mesoporous molecular sieve SBA-16-EG comprises the following steps: soaking dry mesoporous SiO2 molecular sieve SBA-16-EG in ethylene glycol in equal volume, stirring uniformly, standing at room temperature, and drying to obtain pretreated mesoporous molecular sieve SBA-16-EG;
the mesoporous molecular sieve SBA-16-EG is dried at the temperature of 80-120 ℃ for 2-24 hours, preferably 8-10 hours.
6. The preparation method of the low-temperature high-activity nickel-based bimetallic methanation catalyst as claimed in claim 4, characterized in that: the nickel salt is at least one of nickel chloride, nickel sulfate, nickel acetate, nickel oxalate and nickel nitrate;
the second active metal M salt is at least one of ferric nitrate, cobalt nitrate, lanthanum nitrate, ammonium molybdate and cobaltous nitrate.
7. The preparation method of the low-temperature high-activity nickel-based bimetallic methanation catalyst as claimed in claim 4, characterized in that: the solvent is at least one of deionized water, methanol, ethanol, acetic acid, ethyl acetate, chloroform and acetone;
the temperature of the isometric impregnation method and the isometric co-impregnation method is room temperature, and the time is 2-12 h, preferably 4-8 h.
8. The preparation method of the low-temperature high-activity nickel-based bimetallic methanation catalyst as claimed in claim 4, characterized in that: the temperature of the vacuum drying is 10-200 ℃, preferably 50-100 ℃, and the time is 1-24 hours, preferably 6-8 hours;
the roasting temperature is 400-900 ℃, preferably 450-600 ℃, and the roasting time is 0.5-10 hours, preferably 3-6 hours;
the screening is performed by a 200-mesh sample separation screen.
9. Use of a low temperature high activity nickel based bimetallic methanation catalyst as claimed in any one of claims 1 to 3 in the production of methane from synthesis gas.
10. The use of the low-temperature high-activity nickel-based bimetallic methanation catalyst as claimed in claim 9 in the preparation of methane from synthesis gas, characterized in that: the conditions for preparing methane from the synthesis gas are as follows: the volume airspeed of the synthesis gas treated by the catalyst is 3000-60000 h-1The pressure is from normal pressure to 3.0MPa, the temperature is from 200 ℃ to 500 ℃, and H in the synthesis gas2The ratio of/CO is 2-4.
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