CN111229235A - NiO/MgAl2O4Catalyst, preparation method and application thereof - Google Patents
NiO/MgAl2O4Catalyst, preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 138
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 90
- 229910026161 MgAl2O4 Inorganic materials 0.000 claims abstract description 55
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000000498 ball milling Methods 0.000 claims abstract description 40
- 229910020068 MgAl Inorganic materials 0.000 claims abstract description 36
- 239000011029 spinel Substances 0.000 claims abstract description 35
- 239000011777 magnesium Substances 0.000 claims abstract description 34
- -1 magnesium aluminate Chemical class 0.000 claims abstract description 26
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 22
- 238000007084 catalytic combustion reaction Methods 0.000 claims abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000002407 reforming Methods 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 67
- 239000000243 solution Substances 0.000 claims description 51
- 239000000843 powder Substances 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000000227 grinding Methods 0.000 claims description 29
- 239000011324 bead Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 13
- 238000007873 sieving Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 150000002815 nickel Chemical class 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 6
- 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 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 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 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- LDBLRXFNVJQRSI-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate;nickel(3+);hydrate Chemical compound O.[Ni+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O LDBLRXFNVJQRSI-UHFFFAOYSA-K 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- SMAMDWMLHWVJQM-UHFFFAOYSA-L nickel(2+);diformate;dihydrate Chemical compound O.O.[Ni+2].[O-]C=O.[O-]C=O SMAMDWMLHWVJQM-UHFFFAOYSA-L 0.000 claims description 3
- VNYOIRCILMCTHO-UHFFFAOYSA-L nickel(2+);oxalate;dihydrate Chemical compound O.O.[Ni+2].[O-]C(=O)C([O-])=O VNYOIRCILMCTHO-UHFFFAOYSA-L 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000013065 commercial product Substances 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 21
- 230000009467 reduction Effects 0.000 abstract description 10
- 239000002351 wastewater Substances 0.000 abstract description 7
- 239000005416 organic matter Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006057 reforming reaction Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 11
- 239000012495 reaction gas Substances 0.000 description 11
- 229910003303 NiAl2O4 Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910000943 NiAl Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000000508 aqueous-phase reforming Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
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- 230000008021 deposition Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
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- 239000003574 free electron Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—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 alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J23/005—Spinels
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- B01J35/61—
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- B01J35/63—
Abstract
The invention belongs to the technical field of catalyst preparation, and particularly relates to a method for preparing MgAl by a ball milling method2O4The spinel supported NiO or Ni catalyst takes magnesium aluminate spinel as a carrier and NiO or Ni as an active component, wherein the mass of the active component accounts for NiO/MgAl2O45-25% of the total mass of the catalyst. The active component of the catalyst obtained by roasting after ball milling is NiO, and the catalyst can be used for catalytic combustion reaction of low-concentration methane or volatile organic gas. And reducing NiO to obtain the supported Ni metal catalyst which can be used for hydrogenation of organic unsaturated bonds or steam or water phase reforming reaction of the organic matter. The catalyst of the invention can be used for catalytic combustion of low-concentration methane or volatile organic gasBurning, organic matter hydrogenation or reforming hydrogen production. Compared with the prior art, the catalyst has the advantages of high activity, low cost, good thermal stability, simple preparation method, environmental protection, reduction of wastewater discharge and easy industrialization.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to NiO/MgAl2O4A catalyst, a preparation method and application thereof.
Background
The nickel catalyst has the advantages of good catalytic activity, high mechanical strength, insensitivity to poison, good thermal conductivity and the like, so that the nickel catalyst is not only a good catalyst for conversion processes such as oxidative dehydrogenation, dehalogenation, desulfurization and the like, but also widely applied to hydrogenation of various unsaturated hydrocarbons and hydrogen production by reforming organic matters. The nickel catalyst has low preparation cost and is easy to obtain, and has potential in industrial application prospect.
The nickel catalyst is loaded on a proper carrier, and the nickel active species and the carrier form an ordered whole, so that the activity and the stability of the catalyst are effectively improved, and the whole is called a supported nickel catalyst. The carrier increases the active surface of the catalyst, provides a proper pore structure for the active component, and ensures that the active component has a good dispersion state, thereby reducing the using amount of the active component. Meanwhile, the carrier can improve the mechanical strength, the thermal conductivity and the thermal stability of the catalyst and prolong the service life of the catalyst. The support, in addition to providing active sites itself, can also enhance catalyst performance by interacting with the active components. The most common support for supported nickel catalysts is gamma-Al2O3。γ-Al2O3Has good mechanical property and regeneration property and low price, but the strong interaction between the catalyst and the transition metal oxide limits the further improvement of the catalytic activity of the active component. To gamma-Al2O3Other oxides are added for modulation, so that the interaction strength with active components can be reduced, and NiAl difficult to reduce can be reduced2O4The nickel-aluminum spinel structure is formed, and the performance of the catalyst is improved. Such as in the direction of gamma-Al2O3Adding MgO to form stable MgAl2O4The strength of the interaction between the active component nickel and the carrier is reduced in the magnesium aluminate spinel structure. In addition, the magnesium aluminate spinel not only has gamma-Al2O3And MgO, and also has new advantages such as better thermal stability, mechanical strength and hydration resistance. However, the magnesia-alumina spinel needs a high calcination temperature, and a nickel-alumina spinel structure is still formed on the surface of a magnesia-alumina spinel carrier prepared by a common method, and the utilization efficiency of nickel is not high, so that the application of the magnesia-alumina spinel in a supported nickel catalyst is not wide at present.
The preparation method of the catalyst has great influence on the activity and stability of the catalyst, and even if the active components and the loading amount of the catalyst are completely the same, the catalytic performance of the catalyst is different due to different preparation methods and conditions. At present, the preparation method of the supported nickel catalyst is most common in a coprecipitation method, an impregnation method, a sol-gel method, a solution combustion method and the like. The active components of the catalyst prepared by the coprecipitation method and the impregnation method are not distributed uniformly; the sol-gel method has long preparation period and is easy to generate pollution; the solution combustion method has poor controllability. These conventional methods produce waste water or waste gas pollution, which affects the environment.
The supported nickel catalyst is widely applied to various reaction processes of ① organic hydrogenation, and the nickel catalyst is used in COxHigh activity in hydrogenation methanation reaction, CH4The selectivity is good, the catalyst is the most popular methanation catalyst at present, the aniline tar cracking rate can reach 100% under the catalysis of a nickel catalyst in the aniline tar hydrocracking reaction, the pyrolysis gasoline can be used as a raw material for extracting aromatic hydrocarbon after two-stage hydrogenation, the nickel catalyst is a main one-stage hydrogenation catalyst by virtue of excellent arsenic resistance and colloid resistance, ② organic matter catalytic reforming, and the nickel catalyst is used in CH catalytic reforming4-CO2The nickel catalyst has low activity temperature in the reforming reaction of organic steam such as methane, n-butane and the like, can reduce the content of methane and CO in the product, ③ the catalytic oxidation of the organic matter, can obviously improve the yield of ethylene in the oxidative dehydrogenation reaction of ethane, and obviously improves the yield of isobutene in the dehydrogenation reaction of isobutane on the nickel catalyst.
Volatile Organic Compounds (VOC) and low-concentration methane are air pollutants widely existing in factories, coal mines and other places and have environmental protection requirements on purification treatment. The molecular structure of methane is stable, the oxidation difficulty is the greatest in organic gas, the reaction temperature is the highest, and the activity and the stability of the catalyst are required to be higher. The catalytic combustion can realize the high-efficiency conversion of organic matters into CO at a lower temperature2And water and obtain the energy thereof without secondary pollution. Meanwhile, the catalytic combustion is sufficient, the space velocity is high, and no concentration limitation exists. Therefore, the catalyst developed by taking the catalytic combustion of low-concentration methane as a reference can also be applied to the catalyst without containingTypical hydrocarbon organic gases containing heteroatoms such as S, Cl and N. The supported nickel catalyst has wide application in catalytic oxidation of organic matters, catalytic activity for catalytic combustion of low-concentration methane, wide nickel source, low price and application potential. However, the activity of the nickel catalyst for catalytic oxidation of low-concentration methane is not outstanding, the thermal stability is insufficient, and the common preparation methods can generate wastewater, so that the economic efficiency needs to be improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide NiO/MgAl which has excellent catalytic activity and thermal stability and does not generate wastewater2O4A catalyst, a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme: NiO/MgAl2O4The catalyst is characterized in that magnesium aluminate spinel is used as a carrier, NiO or Ni is used as an active component, wherein the mass of the active component accounts for NiO/MgAl2O45-25% of the total mass of the catalyst.
Further, the magnesium aluminate spinel is a commercial product.
Further, the magnesium aluminate spinel is prepared by the following method:
step 1: weighing Mg (NO) according to the ratio of n (Mg) to n (Al) to 1:23)2·6H2O and Al (NO)3)3·9H2O, is dissolved in an ethanol water solution to prepare the total concentration of 0.1-1 mol.L-1The solution of (1);
step 2: weighing a precipitant with the mole number of (1-1.3) sigma niXi, wherein ni is the mole number of metal ions, and Xi is the valence of the metal ions, dissolving the precipitant in an ethanol water solution, and preparing a solution with the same volume as the solution in the step 1;
and step 3: and simultaneously, feeding the solution obtained in the step (1) and the step (2) into a reactor at a constant speed by using a sample injection pump, violently stirring, aging at a constant temperature of 50-70 ℃ for 2-4 h, filtering, drying a filter cake at 100-120 ℃, grinding and sieving by using a sieve with 80-100 meshes, and roasting the sieved powder in a muffle furnace at 800-1000 ℃ for 3-6 h to obtain the magnesia-alumina spinel carrier.
The above MgAl2O4The coprecipitation synthesis method of the magnesium aluminate spinel carrier can also be replaced by other synthesis methods. The other synthesis method is selected from a urea method, a hydrothermal synthesis method and a solution combustion synthesis method.
Further, the ethanol mass fraction of the ethanol water solution is 0-50%
Further, in the step 2, the precipitating agent is selected from Na2CO3、(NH4)2CO3One or a mixture of more of NaOH and KOH.
NiO/MgAl for catalytic combustion of organic matters2O4The preparation method of the catalyst comprises the steps of mixing carrier powder and nickel salt powder, placing the mixture into a ball milling tank, and adding grinding beads, wherein the ball-material ratio is 1: 1-6: 1; a ball milling tank sealing cover is fixed on a rotary table of the planetary ball mill, the rotation speed is set to be 300-800 rpm, the rotation mode is set to be 0-30 min for alternating direction conversion, after ball milling is carried out for 2-8 h, powder in the tank is ground, the powder is sieved by a sieve with 80-100 meshes, the sieved powder is placed in a tube furnace and roasted for 3-6 h at the temperature of 600-800 ℃, and NiO/MgAl is obtained2O4A catalyst.
On the basis of the main catalyst Ni, other components, such as precursors of metals of Fe, Mn, Ce, La, Zr, Cu and the like, can also be added during ball milling to be used as a cocatalyst. The addition of the metal auxiliary agent can improve the dispersion degree of Ni, disperse the electronic distribution of Ni atoms, effectively protect and stabilize Ni nanoparticles, and generate a synergistic effect with Ni to improve the activity of the catalyst. After being added, Fe and Ni form stable Fe-Ni alloy, which is beneficial to the dispersion of Ni on the surface of a carrier, and more active Fe protects Ni from acid corrosion, thus improving the activity and acid-resistant stability of the catalyst; the addition of Mn reduces the acting force between the active component and the carrier, so that the number of active centers with medium strength is increased, and the activity and the stability of the catalyst are improved; ce as CeO2When added, part of Ce4+Reduction to Ce at high temperature3+To generate electron-rich oxygen vacancies, the free electrons released being transferred to Ni0The active sites increase the electron density around the active sites and promote the reduction of Ni species, as well asWhen CeO is present2The redox performance of the catalyst accelerates the transfer of carbon-containing species adsorbed on the surface, and improves the carbon deposition resistance of the catalyst; la promotes the dispersion of NiO on the surface of the carrier, weakens the interaction of the active component and the carrier, and inhibits the formation of nickel aluminate spinel; the addition of the Zr-containing auxiliary agent remarkably improves the adsorption capacity of the catalyst to specific reactants, thereby improving the activity and selectivity of the catalyst; cu can be reduced into copper crystal nuclei at a lower temperature, and then the copper crystal nuclei are used as crystal nuclei of NiO adjacent to the copper crystal nuclei, so that the NiO nucleation rate is increased, the reduction of the NiO is promoted, and the Cu can also promote the dispersion of nickel species on a carrier, so that the stability of the catalyst is improved.
The grinding beads are 95 zirconium beads with the diameter of 2-10 mm.
The nickel salt is one or a mixture of more of nickel nitrate hexahydrate, nickel acetate tetrahydrate, nickel formate dihydrate, nickel oxalate dihydrate and nickel citrate hydrate. Inorganic nickel salts such as nickel nitrate hexahydrate have high hardness, the color of the catalyst prepared by ball milling is uneven, the industrial application is not facilitated, and organic nickel salts are softer and are suitable for preparing the catalyst by a ball milling method, so the organic nickel salts are preferably used as nickel sources. The nickel acetate tetrahydrate is further preferably used as a suitable nickel source because the dispersity of the Ni element in the nickel acetate tetrahydrate crystal is high, NiO crystal grains formed on the surface of the catalyst are small, and the activity of the prepared catalyst is outstanding.
The invention also provides the NiO/MgAl2O4The application of the catalyst in the catalytic combustion of low-concentration methane or volatile organic gas comprises the following steps: in a fixed bed reactor, low-concentration methane or volatile organic gas is used as reaction gas, and NiO/MgAl is added2O4Carrying out catalytic combustion reaction under the action of a catalyst; the flow rate of the reaction gas is 10 to 100 Nml/min-1The content of methane or volatile organic compounds is 1-20 vol%, at 1-2 deg.C/min-1Heating to the reaction temperature of 550-750 ℃, wherein the pressure of the reaction system is 1-2 MPa.
Further, NiO/MgAl prepared by a ball milling method2O4The catalyst is reduced to obtain a load type Ni metal catalyst, namely Ni/MgAl2O4The catalyst can be used for organic mattersUnsaturated bond hydrogenation or organic steam or aqueous phase reforming reaction, comprising the following steps: NiO/MgAl prepared by ball milling method2O4Putting the catalyst into a fixed bed reactor, wherein the flow rate is 30-100 Nml.min-1Under the nitrogen purging, at the temperature of 1-10 ℃ per minute-1Heating to 200-300 ℃, and then switching to a flow of 30-100 Nml/min-1The reducing gas of (2) is 10-100 vol.% H2/N2At 1-10 ℃ per minute-1Heating to 450-700 ℃ to reduce the catalyst; the reduction time is 2-4 h, and the reduction pressure is 1-2 MPa, so that Ni/MgAl is obtained2O4A catalyst.
Further, Ni/MgAl2O4The catalyst is used for hydrogenation reaction of organic unsaturated bonds, and comprises the following steps: Ni/MgAl in fixed bed reactor2O4When the catalyst is reduced and not cooled, the flow rate is switched to 30-100 Nml/min-1The nitrogen is blown, the temperature is adjusted to 300-550 ℃, and the flow is switched to 50-200 Nml/min-1The reaction gas is gas formed by preheating unsaturated organic matters and H2In the mixed gas of Ni/MgAl2O4Carrying out hydrogenation reaction under the action of a catalyst; the pressure of the reaction system is 1-2 MPa.
Further, Ni/MgAl2O4The catalyst is used for organic steam or water phase reforming reaction and comprises the following steps: Ni/MgAl in fixed bed reactor2O4When the catalyst is reduced and not cooled, the flow rate is switched to 30-100 Nml/min-1The nitrogen is blown, the temperature is adjusted to 550-650 ℃, and the flow is switched to 10-100 Nml/min-1The reaction gas is a gas preheated by organic matter aqueous solution or a mixed gas of gas preheated by organic matter and water vapor, and is added into the reaction gas in the form of Ni/MgAl2O4Carrying out reforming reaction under the action of a catalyst; the pressure of the reaction system is 1 MPa.
Compared with the prior art, the invention has the advantages that:
(1) the invention selects magnesium aluminate spinel as a carrier, and prepares the catalyst with the activity and the thermal stability meeting the requirements by a ball milling method. By selecting proper precursors and preparation conditions, proper acting force is generated between the carrier and the active ingredients, and the obtained catalyst has activity and stability far higher than those of catalysts prepared by traditional methods such as a precipitation method or an impregnation method. Meanwhile, the ball milling method does not need a solution environment, can utilize a precursor which is difficult to dissolve, does not produce waste water, and has advantages in the preparation of the catalyst.
(2) MgAl of the catalyst of the invention2O4The magnesia-alumina spinel carrier has larger specific surface area and pore volume and strong heat resistance, so that the catalytic activity and the thermal stability of the catalyst are obviously improved. When the catalyst is used for the catalytic combustion reaction of low-concentration methane, the quasi-first-order reaction rate constant measured at 600 ℃ is 0.2-0.5 L.g-Ni-1·s-1The reaction temperature is 540-570 ℃ when the conversion rate is 50%.
(3) The invention adopts the ball milling method for preparation, does not need solution environment, can utilize insoluble precursor, and does not produce waste water; the prepared powder has small particle size and large specific surface area. The preparation method is simple, easy to industrialize, free of waste water, low in pollution and beneficial to large-scale industrial production.
(4) The cost is greatly reduced, and the raw material is nickel element with low price.
Drawings
FIG. 1 shows MgAl in example 2 of the present invention2O4Magnesium aluminate spinel carrier and NiO/MgAl2O4XRD spectrum of catalyst.
FIG. 2 shows MgAl in example 2 of the present invention2O4Magnesium aluminate spinel carrier and NiO/MgAl2O4H of catalyst2-TPR spectrum.
FIG. 3 shows NiO/MgAl in example 2 of the present invention2O4Methane conversion curve with three catalyst cycles (R1, R2, R3).
Detailed Description
The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The test methods in the following examples are conventional methods unless otherwise specified.
The phase structure of the sample was analyzed by using a D/max-2200/PC X-ray diffractometer from Japan science. The test conditions were: cu target (λ 0.154056nm), scan range 10o to 90o, scan step 0.005o, scan speed 5o · min-1Tube voltage 40kV and tube current 40 mA.
H-chemisorption of samples using PCA-1200 from Peking Piaode electronics Inc2-TPR test.
Common indicators for measuring catalyst performance include T50、k600、Ea。T50I.e. the reaction temperature at which the methane conversion is 50%. At low concentrations, the reaction rate is first order of the methane concentration. From the corresponding methane conversion (x, -) at different reaction temperatures (T,. degree.C.), the pseudo-first order reaction rate constant k, L.g at that temperature can be calculated-1·s-1：
In the formula: l is the flow rate of the reaction gas under standard conditions, L.s-1(ii) a w is the mass of the catalyst active component (NiO), g; r is a molar gas constant, 8.314J (mol. K)-1(ii) a A is a pre-exponential factor, L.g-1·s-1(ii) a Ea is the activation energy of the reaction, kJ. mol-1。k600Is the k value at 600 ℃, k600The higher the specific activity of the catalyst. And (4) correlating the k values at different temperatures by using a least square method, and calculating Ea.
Example 1
NiO/MgAl for catalytic combustion of low-concentration methane2O4Catalyst, said NiO/MgAl2O4Catalyst MgAl2O4Magnesium aluminate spinel is used as a carrier, NiO is used as an active component, wherein the mass of the active component accounts for NiO/MgAl2O45 percent of the total mass of the catalyst.
The NiO/MgAl2O4The preparation method of the catalyst comprises the following steps:
step 1:weighing 7.0g of Mg (NO)3)2·6H2O and 20.3g of Al (NO)3)3·9H2O, dissolved in 200g of deionized water to prepare the product with the total concentration of 0.4 mol.L-1The solution of (1).
Step 2: 12.6g of sodium carbonate was weighed out and dissolved in 200mL of deionized water to prepare a solution having the same volume as the solution in step 1.
And step 3: simultaneously, feeding the solution obtained in the step (1) and the solution obtained in the step (2) into a reactor at a constant speed by using a sample injection pump, violently stirring, aging at a constant temperature of 70 ℃ for 3 hours, filtering, drying a filter cake at 100 ℃, grinding and sieving by using a 80-mesh sieve, and roasting the sieved powder in a muffle furnace at 1000 ℃ for 6 hours to obtain MgAl2O4A magnesium aluminate spinel carrier.
And 4, step 4: mixing 5g of the carrier powder obtained in the step 3 with 1.0g of nickel nitrate hexahydrate solid, placing the mixture into a ball milling tank, and adding grinding beads (95 zirconium beads with the diameter of 4mm) into the ball milling tank, wherein the ball-material ratio (the mass ratio of the grinding beads to the material) is 4: 1. And (3) sealing the ball milling tank, fixing the ball milling tank on a turntable of the planetary ball mill, setting the rotating speed (800rpm) and the rotating mode (the direction is alternately changed every 30 min), grinding the powder in the tank after ball milling for 8 hours, and sieving the powder by using an 80-mesh sieve. The sieved powder is placed in a tube furnace to be roasted for 6 hours at the temperature of 650 ℃ to obtain NiO/MgAl2O4Catalyst, named Cat.1.
MgAl2O4Magnesium aluminate spinel carrier and NiO/MgAl2O4The XRD spectrum of the catalyst is shown in figure 1. MgAl2O4Magnesium aluminate spinel carrier and NiO/MgAl2O4H of catalyst2TPR spectrum is shown in FIG. 2.
Example 2
NiO/MgAl for catalytic combustion of low-concentration methane2O4Catalyst, said NiO/MgAl2O4Catalyst MgAl2O4Magnesium aluminate spinel is used as a carrier, NiO is used as an active component, wherein the mass of the active component accounts for NiO/MgAl2O410% of the total mass of the catalyst.
The NiO/MgAl2O4The preparation method of the catalyst comprises the following steps:
step 1: balance16.5g of Mg (NO) was taken3)2·6H2O and 48.3g of Al (NO)3)3·9H2O, dissolved in 200g of ethanol water solution (the mass fraction of ethanol is 25 percent) to prepare the total concentration of 0.8 mol.L-1The solution of (1).
Step 2: 32.2g of ammonium carbonate was weighed out and dissolved in 240mL of an aqueous ethanol solution (ethanol content: 25% by mass) to prepare a solution having the same volume as that of the solution in step 1.
And step 3: simultaneously, feeding the solution obtained in the step (1) and the solution obtained in the step (2) into a reactor at a constant speed by using a sample injection pump, violently stirring, aging at a constant temperature of 65 ℃ for 4 hours, filtering, drying a filter cake at 110 ℃, grinding and screening by using a 100-mesh sieve, and roasting screened powder in a muffle furnace at 900 ℃ for 4 hours to obtain MgAl2O4A magnesium aluminate spinel carrier.
And 4, step 4: mixing 5g of the carrier powder obtained in the step 3 with 1.9g of nickel acetate tetrahydrate solid, placing the mixture into a ball milling tank, and adding grinding beads (95 zirconium beads with the diameter of 6mm) into the ball milling tank, wherein the ball-material ratio (the mass ratio of the grinding beads to the material) is 2: 1. And (3) sealing the ball milling tank, fixing the ball milling tank on a turntable of the planetary ball mill, setting the rotating speed (400rpm) and the rotating mode (the direction is alternately changed every 15 min), grinding the powder in the tank after ball milling for 4h, and sieving the powder by a 100-mesh sieve. The sieved powder is placed in a tube furnace to be roasted for 4 hours at 700 ℃ to obtain NiO/MgAl2O4Catalyst, named Cat.2.
Example 3
NiO/MgAl for catalytic combustion of low-concentration methane2O4Catalyst, said NiO/MgAl2O4Catalyst MgAl2O4Magnesium aluminate spinel is used as a carrier, NiO is used as an active component, wherein the mass of the active component accounts for NiO/MgAl2O415% of the total mass of the catalyst.
The NiO/MgAl2O4The preparation method of the catalyst comprises the following steps:
step 1: 12.1g of Mg (NO) are weighed out3)2·6H2O and 35.3g of Al (NO)3)3·9H2O, dissolved in 200g of ethanol water solution (ethanol mass fraction is 50 percent) to prepare the total concentration of 0.6 mol.L-1The solution of (1).
Step 2: 15.1g of sodium hydroxide was weighed out and dissolved in 240mL of an aqueous ethanol solution (ethanol content: 50%) to prepare a solution having the same volume as that of the solution in step 1.
And step 3: simultaneously, feeding the solution obtained in the step (1) and the solution obtained in the step (2) into a reactor at a constant speed by using a sample injection pump, violently stirring, aging at a constant temperature of 55 ℃ for 2 hours, filtering, drying a filter cake at 100 ℃, grinding and sieving by using a 90-mesh sieve, and roasting the sieved powder in a muffle furnace at 800 ℃ for 3 hours to obtain MgAl2O4A magnesium aluminate spinel carrier.
And 4, step 4: mixing 5g of the carrier powder obtained in the step 3 with 2.2g of nickel formate dihydrate solid, placing the mixture into a ball milling tank, and adding grinding beads (95 zirconium beads with the diameter of 10mm) in a ball-to-material ratio (the mass ratio of the grinding beads to the material) of 6: 1. And (3) sealing the ball milling tank, fixing the ball milling tank on a turntable of the planetary ball mill, setting the rotating speed (700rpm) and the rotating mode (the direction is alternately changed every 30 min), grinding the powder in the tank after ball milling for 7h, and sieving the powder by a 90-mesh sieve. The sieved powder is placed in a tube furnace to be roasted for 5 hours at 800 ℃ to obtain NiO/MgAl2O4Catalyst, named Cat.3.
Example 4
NiO/MgAl for catalytic combustion of low-concentration methane2O4Catalyst, said NiO/MgAl2O4Catalyst MgAl2O4Magnesium aluminate spinel is used as a carrier, NiO is used as an active component, wherein the mass of the active component accounts for NiO/MgAl2O420 percent of the total mass of the catalyst.
The NiO/MgAl2O4The preparation method of the catalyst comprises the following steps:
step 1: 22.5g of Mg (NO) are weighed out3)2·6H2O and 66.0g of Al (NO)3)3·9H2O, dissolved in 200g of ethanol water solution (the mass fraction of ethanol is 25 percent) to prepare the total concentration of 1.0 mol.L-1The solution of (1).
Step 2: 39.5g of potassium hydroxide was weighed out and dissolved in 260mL of an aqueous ethanol solution (ethanol content: 25% by mass) to prepare a solution having the same volume as that of the solution in step 1.
And step 3: at the same time use a sample injection pumpPutting the solution obtained in the steps 1 and 2 into a reactor at a constant speed, stirring vigorously, aging at a constant temperature of 60 ℃ for 4 hours, filtering, drying a filter cake at 120 ℃, grinding and screening with a 100-mesh sieve, and roasting screened powder in a muffle furnace at 900 ℃ for 4 hours to obtain MgAl2O4A magnesium aluminate spinel carrier.
And 4, step 4: mixing 5g of the carrier powder obtained in the step 3 with 2.5g of nickel oxalate dihydrate solid, placing the mixture into a ball milling tank, and adding grinding beads (95 zirconium beads with the diameter of 2mm) in a ball-to-material ratio (the mass ratio of the grinding beads to the material) of 3: 1. And (3) sealing the ball milling tank, fixing the ball milling tank on a turntable of the planetary ball mill, setting the rotating speed (500rpm) and the rotating mode (the direction is alternately changed every 15 min), grinding the powder in the tank after ball milling for 6 hours, and sieving the powder by a 100-mesh sieve. The sieved powder is placed in a tube furnace to be roasted for 3 hours at the temperature of 750 ℃ to obtain NiO/MgAl2O4Catalyst, named Cat.4.
Example 5
NiO/MgAl for catalytic combustion of low-concentration methane2O4Catalyst, said NiO/MgAl2O4Catalyst MgAl2O4Magnesium aluminate spinel is used as a carrier, NiO is used as an active component, wherein the mass of the active component accounts for NiO/MgAl2O425% of the total mass of the catalyst.
The NiO/MgAl2O4The preparation method of the catalyst comprises the following steps:
step 1: 3.5g of Mg (NO) are weighed out3)2·6H2O and 10.2g of Al (NO)3)3·9H2O, dissolved in 200g of ethanol water solution (ethanol mass fraction is 50 percent) to prepare the total concentration of 0.2 mol.L-1The solution of (1).
Step 2: 7.0g of sodium carbonate was weighed out and dissolved in 200mL of an aqueous ethanol solution (ethanol content: 50%) to prepare a solution having the same volume as that of the solution in step 1.
And step 3: simultaneously, feeding the solution obtained in the step (1) and the solution obtained in the step (2) into a reactor at a constant speed by using a sample injection pump, violently stirring, aging at a constant temperature of 50 ℃ for 2 hours, filtering, drying a filter cake at 120 ℃, grinding and sieving by using a 80-mesh sieve, and roasting the sieved powder in a muffle furnace at 1000 ℃ for 6 hours to obtain MgAl2O4A magnesium aluminate spinel carrier.
And 4, step 4: mixing 5g of the carrier powder obtained in the step 3 with 4.1g of the nickel citrate hydrate solid, placing the mixture into a ball milling tank, and adding grinding beads (95 zirconium beads with the diameter of 8mm) into the ball milling tank, wherein the ball-to-material ratio (the mass ratio of the grinding beads to the material) is 5: 1. And (3) sealing the ball milling tank, fixing the ball milling tank on a turntable of the planetary ball mill, setting the rotating speed (300rpm) and the rotating mode (fixed rotating direction), grinding the powder in the tank after ball milling for 2 hours, and sieving the powder by using an 80-mesh sieve. The sieved powder is placed in a tube furnace to be roasted for 6 hours at the temperature of 600 ℃ to obtain NiO/MgAl2O4Catalyst, named Cat.5.
Table 1 shows activity data of Cat.1-5 catalysts. It can be seen that for the low concentration methane catalytic combustion reaction, k of the catalyst is prepared from the organic nickel source6000.2 to 0.5 L.g-Ni-1·s-1，T 50540 to 570 ℃, Ea 130 to 170kJ & mol-1K of catalyst Cat.2, especially prepared with nickel acetate tetrahydrate as nickel source600Up to 0.489 L.g-Ni-1·s-1，T50Down to 543.5 ℃. It can be seen that the NiO/MgAl prepared by the invention2O4The catalyst has good catalytic activity.
Table 1 activity data for different numbered catalysts
FIG. 3 is a methane conversion curve of the catalyst obtained in example 2, which was cycled three times (R1, R2, R3). It can be seen that the activity of the catalyst is slightly improved in each of three times of use, and k is600Are all kept at 0.4 L.g-Ni-1·s-1Above, T50Are all between 540 and 560 ℃. It can be seen that the NiO/MgAl prepared by the invention2O4The catalyst has good thermal stability.
Example 6
0.15g of NiO/MgAl prepared in example 22O4The catalyst is placed in a constant temperature area of a fixed bed reactor, low-concentration methane is used as reaction gas, and the flow rate of the reaction gas is 50 Nml/min-1The methane content was 1 vol%. The fixed bed reactor is heated by the programmed temperature rise,at 2 ℃ min-1The temperature is raised to 300 ℃ at a constant speed, the temperature is kept for 40min, and then the temperature is increased to 1 ℃ for min-1The temperature is raised to 600 ℃, and the heating is stopped after the constant temperature is kept for 1 min. The reaction gas stream was allowed to cool to room temperature, and then a second and third activity test was carried out.
FIG. 3 is a methane conversion curve of the catalyst obtained in example 2, which was cycled three times (R1, R2, R3). It can be seen that the activity of the catalyst is slightly improved in each of three times of use, and k is600Are all kept at 0.4 L.g-Ni-1·s-1Above, T50Are all between 540 and 560 ℃. It can be seen that the NiO/MgAl prepared by the invention2O4The catalyst has good thermal stability.
Example 7
0.5g of NiO/MgAl prepared in example 22O4The catalyst is placed in a constant temperature area of a fixed bed reactor, and the flow rate is 50 Nml.min-1Under nitrogen purge at 2 ℃ for min-1Heating to 200 deg.C, and switching to 50Nml min-1Reducing gas of 50 vol.% H2/N2At 1 ℃ min-1Heating to 550 ℃ to reduce the catalyst; the reduction time is 4h, and the reduction pressure is 2 MPa. Ni/MgAl2O4When the catalyst is reduced and not cooled, the flow rate is switched to 50 Nml/min-1The nitrogen is used for blowing, when the temperature is reduced to 400 ℃, the flow is switched to be 100Nml min-1The reaction gas of (1) is CO and H2The gas mixture, in a volume ratio of 1:3, has been brought to 200 ℃ by preheating. The pressure of the reaction system is 2 MPa. In the presence of Ni/MgAl2O4Hydrogenation reaction is carried out under the action of the catalyst. The product gas is cooled and dried, and then the content of the product gas is analyzed by a Zhejiang Fuli GC9070 type gas chromatograph. The result shows that the conversion rate of CO reaches 100 percent, and CH in the product4The selectivity of the catalyst reaches 96 percent. After 24h of reaction time, the CO conversion was 96%, CH4The selectivity is 94%; after 100h of reaction time, the CO conversion was 90% and the selectivity was 85%. It can be seen that the Ni/MgAl prepared by the invention2O4The catalyst has good activity and stability.
Example 8
1gNiO/MgAl prepared in example 22O4The catalyst is placed in a constant temperature area of a fixed bed reactor, and the flow rate is 30 Nml.min-1Under nitrogen purge at 5 ℃ C. min-1Heating to 300 deg.C, and switching to flow rate of 30 Nml/min-1The reducing gas of (2) is pure H2At 2 ℃ min-1Heating to 650 ℃ to reduce the catalyst; the reduction time is 2h, and the reduction pressure is 1 MPa. Ni/MgAl2O4When the catalyst is reduced and not cooled, the flow rate is switched to 30 Nml/min-1The nitrogen is used for blowing, when the temperature is reduced to 600 ℃, the flow is switched to be 20Nml min-1The reaction gas is preheated by 50 percent by mass of ethanol water solution at 200 ℃. The pressure of the reaction system is 1 MPa. In the presence of Ni/MgAl2O4Reforming reaction is carried out under the action of the catalyst. The product gas is cooled and dried, and then the components of the product gas are analyzed by a Zhejiang Fuli GC9070 type gas chromatograph. The results show that the conversion rate of ethanol reaches 100 percent at 500 ℃, and H in the product2The selectivity of (A) was 50% at 500 ℃ and 72% at 600 ℃. It can be seen that the Ni/MgAl prepared by the invention2O4The catalyst has good catalytic activity.
The above-mentioned embodiments are merely preferred embodiments of the present invention, which are merely illustrative and not restrictive, and it should be understood that other embodiments may be easily implemented by those skilled in the art by means of replacement or modification according to the technical contents disclosed in the specification, and therefore, all changes and modifications that come within the spirit and technical conditions of the present invention should be included in the claims of the present invention.
Claims (10)
1. NiO/MgAl2O4The catalyst is characterized in that magnesium aluminate spinel is used as a carrier, NiO or Ni is used as an active component, wherein the mass of the active component accounts for NiO/MgAl2O45-25% of the total mass of the catalyst.
2. The method of claim 1NiO/MgAl2O4The catalyst is characterized in that the magnesium aluminate spinel is a commercial product.
3. The NiO/MgAl alloy of claim 12O4The catalyst is characterized in that the magnesium aluminate spinel is prepared by the following method:
step 1: weighing Mg (NO) according to the ratio of n (Mg) to n (Al) to 1:23)2·6H2O and Al (NO)3)3·9H2O, is dissolved in an ethanol water solution to prepare the total concentration of 0.1-1 mol.L-1The solution of (1);
step 2: weighing a precipitant with the mole number of (1-1.3) sigma niXi, wherein ni is the mole number of metal ions, and Xi is the valence of the metal ions, dissolving the precipitant in an ethanol water solution, and preparing a solution with the same volume as the solution in the step 1;
and step 3: and simultaneously, feeding the solution obtained in the step (1) and the step (2) into a reactor at a constant speed by using a sample injection pump, violently stirring, aging at a constant temperature of 50-70 ℃ for 2-4 h, filtering, drying a filter cake at 100-120 ℃, grinding and sieving by using a sieve with 80-100 meshes, and roasting the sieved powder in a muffle furnace at 800-1000 ℃ for 3-6 h to obtain the magnesia-alumina spinel carrier.
4. The NiO/MgAl alloy of claim 32O4The catalyst is characterized in that the ethanol mass fraction of the ethanol aqueous solution is 0-50%.
5. The NiO/MgAl alloy of claim 32O4Catalyst, characterized in that in step 2 the precipitating agent is selected from Na2CO3、(NH4)2CO3One or a mixture of more of NaOH and KOH.
6. The NiO/MgAl alloy of claim 12O4The preparation method of the catalyst is characterized in that carrier powder and nickel salt powder are mixed and placed in a ball milling tank, grinding beads are added, grinding, sieving and roasting are carried out, and NiO/MgA is obtainedl2O4A catalyst.
7. The NiO/MgAl of claim 62O4The preparation method of the catalyst is characterized in that the grinding beads are 95 zirconium beads with the diameter of 2-10 mm, and the ball-material ratio, namely the mass ratio of the grinding beads to the materials, is 1: 1-6: 1;
the grinding process is that the ball milling tank is fixed on a turntable of the planetary ball mill, the rotation speed is set to be 300-800 rpm, the rotation mode is set to be 0-30 min, the directions are alternately switched, and ball milling is carried out for 2-8 h;
sieving is carried out by sieving with a sieve of 80-100 meshes, and roasting is carried out by placing sieved powder in a tubular furnace at 600-800 ℃ for 3-6 h.
8. The NiO/MgAl of claim 62O4The preparation method of the catalyst is characterized in that the nickel salt is one or a mixture of more of nickel nitrate hexahydrate, nickel acetate tetrahydrate, nickel formate dihydrate, nickel oxalate dihydrate and nickel citrate hydrate.
9. The NiO/MgAl of claim 62O4The preparation method of the catalyst is characterized in that on the basis of a main active component Ni, other components can be added during ball milling, and precursors of the other components including Fe, Mn, Ce, La, Zr or Cu are used as promoters.
10. The NiO/MgAl of claim 12O4The application of the catalyst is characterized in that the NiO/MgAl is mixed2O4The catalyst is used for catalytic combustion of low-concentration methane or volatile organic gas, hydrogenation of organic matters or hydrogen production by reforming.
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