CN113522293A - Preparation method and application of catalyst for hydrogen production by dry reforming of methane and carbon dioxide - Google Patents
Preparation method and application of catalyst for hydrogen production by dry reforming of methane and carbon dioxide Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 44
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000001257 hydrogen Substances 0.000 title claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 30
- 238000002407 reforming Methods 0.000 title claims abstract description 21
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 11
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 11
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 11
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 229910003023 Mg-Al Inorganic materials 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000000975 co-precipitation Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 230000008021 deposition Effects 0.000 abstract description 4
- 239000003345 natural gas Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 239000010949 copper Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- -1 sulfur nitride Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ZJKOMXZUJBYOOK-UHFFFAOYSA-M tetraphenylazanium;hydroxide Chemical compound [OH-].C1=CC=CC=C1[N+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 ZJKOMXZUJBYOOK-UHFFFAOYSA-M 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- 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
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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
- 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
- B01J35/613—10-100 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
- B01J35/635—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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- 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
- B01J37/03—Precipitation; Co-precipitation
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- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- C01B2203/1041—Composition of the catalyst
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention discloses a preparation method of a catalyst for hydrogen production by dry reforming of methane and carbon dioxide, wherein the catalyst is a Ni-Cu-Mg-Al hydrotalcite layered catalyst, Ni and Cu are used as active components, a coprecipitation method is used for synthesizing the Ni-Cu-Mg-Al quaternary hydrotalcite catalyst, and the layered structure catalyst obtained by calcination and reduction has larger surface area, pore volume and pore diameter, and can greatly improve CO pairing2Thereby improving the reforming of the catalystThe catalyst has the advantages of reactivity, good stability and anti-carbon deposition capability, low requirement on equipment and no need of CO in natural gas2The separation is carried out, the conversion rate of the methane can reach 89.4%, the hydrogen yield can reach 89.6%, and the demand of the miniaturized hydrogen production reaction of the methane can be met.
Description
The technical field is as follows:
the invention relates to the technical field of catalyst preparation, in particular to a preparation method and application of a catalyst for hydrogen production by dry reforming of methane and carbon dioxide.
Background art:
hydrogen fuels have been developed in great quantities in the aeronautical field. The hydrogen is used as engine fuel, and can preferentially reduce the emission of carbon monoxide and sulfur nitride in the combustion process of gasoline; the chemical energy is converted into electric energy for power supply by utilizing combustion of hydrogen and oxygen, the power generation capacity of a power supply station can be greatly improved, and the hydrogen energy is gradually applied to all corners in life. Therefore, the development of a novel catalyst for promoting the hydrogen preparation efficiency has important research significance.
At present, the methane hydrogen production technology mainly comprises steam reforming, carbon dioxide dry reforming, partial oxidation, catalytic cracking and the like. Wherein, the methane steam reforming hydrogen production technology is mature and widely applied. Patent CN105854885A discloses a method for preparing a catalyst for preparing synthesis gas by reforming methane with carbon dioxide, which takes composite activated carbon as a carrier and utilizes HNO3The solution modifies the carrier, nickel, iron, copper or zinc are used as catalyst auxiliary agent to prepare a series of catalysts with higher specific surface area, but the nitric acid solution used in the preparation process has certain corrosivity to the container, and the reaction process is simpleThe parts are relatively harsh. Patent CN106000444A discloses a preparation method of a high-dispersion nickel-based methane carbon dioxide reforming catalyst, which has a relatively high specific surface area, but since the Ni particles of 3-7 nm are too small, sintering is easy to occur in the high-temperature reforming process, so that the catalytic activity of the catalyst at high temperature is reduced. Therefore, the development of the anti-carbon deposition catalyst with high activity, high stability and difficult sintering is still the key problem for developing large-scale methane carbon dioxide reforming hydrogen production.
The invention content is as follows:
the invention aims to provide a preparation method and application of a catalyst for hydrogen production by methane and carbon dioxide dry reforming.
The invention is realized by the following technical scheme:
a process for preparing the catalyst used for preparing hydrogen by dry reforming of methane and carbon dioxide includes such steps as preparing Ni-Cu-Mg-Al hydrotalcite layered catalyst, and using Ni and Cu as active components3)2·6H2O、Cu(NO3)2·6H2O、Mg(NO3)2·6H2O、Al(NO3)3·6H2A metal salt solution with a total concentration of O metal ions of 1mol/L, NaOH and Na2CO3Preparing an alkaline solution in which n [ Na ]2CO3]＝0.5×n[Al3+]，n[NaOH]＝2×n[Al3++Ni2++Cu2++Mg2+]Slowly dripping two solutions, namely a metal salt solution and an alkali solution, into ultrapure water at the same time, controlling the pH of the solution to be 8-10, uniformly stirring the solutions, crystallizing the solutions in an oil bath kettle at 65 ℃ for 12 hours, and washing, drying, grinding, calcining and reducing the solutions to obtain a Ni-Cu-Mg-Al hydrotalcite catalyst; the calcination is carried out for 3 hours in an air atmosphere at the temperature of 300-600 ℃; the reduction is carried out for 4h under the condition of 400 ℃ at the heating rate of 2 ℃/min in the mixed gas atmosphere with the volume of hydrogen and nitrogen being 7: 3.
Preferably, n [ Ni ]2++Cu2++Mg2+]：n[Al3+]＝3:1，Cu2+And Mg2+Molar ratio of 1:1, Ni2+Molar of Ni2+、Cu2+、Mg2+1/20-1/40 of the total mole of the three.
Preferably, the tetrapropylammonium hydroxide surfactant with the mass fraction of 0.1 percent is added into the water before the metal salt solution is mixed with the alkali solution, so that agglomeration caused by too high dropping speed can be avoided, the dispersibility of metal particles is improved, and the carbon deposition resistance of the catalyst is improved.
Preferably, the pH of the solution is 8.5-10.
Preferably, the drying is vacuum drying at 80 ℃ for 12 h.
The invention also protects the application of the catalyst for preparing hydrogen by dry reforming of methane and carbon dioxide in the preparation of hydrogen by dry reforming of methane and carbon dioxide.
The invention has the following beneficial effects:
1. the invention synthesizes the Ni-Cu-Mg-Al quaternary hydrotalcite catalyst by a coprecipitation method, and makes each metal have good thermal stability by calcining and reducing.
2. The catalyst with the layered structure obtained by the invention has larger surface area, pore volume and pore diameter, and can greatly improve the CO content2Thereby improving the reforming reaction activity of the catalyst.
In a word, the preparation process is simple and convenient, and the obtained catalyst with the layered structure has larger surface area, pore volume and pore diameter, and can greatly improve the CO content2The adsorption capacity of the catalyst is improved, so that the catalyst has better stability and anti-carbon deposition capacity, has lower requirements on equipment and does not need CO in natural gas2The separation is carried out, the conversion rate of the methane can reach 89.4%, the hydrogen yield can reach 89.6%, and the demand of the miniaturized hydrogen production reaction of the methane can be met.
Description of the drawings:
FIG. 1 is a thermogravimetric plot of the calcined Ni-Cu-Mg-Al-1/30 of example 2.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1
Weighing 12g of NaOH and 1.98g of Na2CO3Preparing an alkaline solution, and weighing Ni (NO) according to the molar ratio of Ni to Cu to Mg of 1:9.5:9.53)2·6H2O、Cu(NO3)2·6H2O、Mg(NO3)2·6H2O, then weighing Al (NO)3)3·6H2O，n[Ni2++Cu2++Mg2 +]：n[Al3+]1:1, preparing a metal salt solution with the total molar concentration of 1mol/L of four metal ions of Ni, Cu, Mg and Al, simultaneously dripping the metal salt solution and an alkali solution into 100mL of ultrapure water containing 0.1g of tetraphenyl ammonium hydroxide, uniformly stirring, crystallizing at the speed of 300rpm/min in a 65 ℃ oil bath kettle for 12h, filtering, washing with the ultrapure water to be neutral, drying a filter cake in a 80 ℃ vacuum drying box overnight, grinding and sieving to obtain the Ni-Cu-Mg-Al-1/20. Calcining the precursor in an oxidation state in an air atmosphere at 500 ℃ for 3H, and then calcining the calcined precursor in H2/N2(the volume of hydrogen and nitrogen is 7:3) is reduced for 3h at the temperature rise rate of 2 ℃/min at the temperature of 400 ℃ in the mixed atmosphere, and the sample is ground to obtain the Ni-Cu-Mg-Al-1/20 hydrotalcite catalyst. The resulting catalyst with a layered structure has a large surface area, pore volume and pore diameter, see table 1.
TABLE 1
Comparative example 1:
reference example 1, except that Cu (NO) was not added3)2·6H2O。
Comparative example 2:
reference example 1, except that Mg (NO) was not added3)2·6H2O。
Comparative example 3:
reference example 1, except that Al (NO) was not added3)2·6H2O。
Comparative example 4:
reference example 1, except that Al (NO) was not added3)2·6H2O, addition of Fe (NO)3)2·6H2O。
Example 2:
reference example 1, except that the molar ratio of Ni, Cu, Mg was 1:14.5: 14.5. Obtaining the Ni-Cu-Mg-Al-1/30 hydrotalcite catalyst. The resulting catalyst with a layered structure has a large surface area, pore volume and pore diameter, see table 1. The thermogravimetric graph of the calcined Ni-Cu-Mg-Al-1/30 is shown in FIG. 1, and the catalyst is proved to have better thermal stability.
Example 3:
reference example 1, except that the molar ratio of Ni, Cu, Mg was 1:19.5: 19.5. Obtaining the Ni-Cu-Mg-Al-1/30 hydrotalcite catalyst. The resulting catalyst with a layered structure has a large surface area, pore volume and pore diameter, see table 1.
Example 4:
reference example 1 was repeated except that the molar ratio of Ni, Cu and Mg was 1:14.5:14.5 and the calcination temperature was 300 ℃.
Example 5:
reference example 1 was repeated except that the molar ratio of Ni, Cu and Mg was 1:14.5:14.5 and the calcination temperature was 400 ℃.
Example 6:
reference example 1 was repeated except that the molar ratio of Ni, Cu and Mg was 1:14.5:14.5 and the calcination temperature was 600 ℃.
And (3) testing the activity of the catalyst:
100mg of the catalysts prepared in examples 1 to 6 and comparative examples 1 to 3 were weighed into a quartz tube of a fixed bed reactor, and CO was simultaneously introduced at a flow rate of 20mL/min2And CH4The reaction test temperature was set at 700 ℃ and the gas composition was measured after 30h reaction, with the results shown in Table 2.
TABLE 2
As can be seen by comparing example 1 with comparative examples 1 to 3, the Cu-Mg-Al compositions of the present invention act synergistically.
Claims (6)
1. A preparation method of a catalyst for hydrogen production by dry reforming of methane and carbon dioxide is characterized in that the catalyst is a Ni-Cu-Mg-Al hydrotalcite layered catalyst, Ni and Cu are used as active components, and a Ni-Cu-Mg-Al quaternary hydrotalcite catalyst is synthesized by a coprecipitation method3)2·6H2O、Cu(NO3)2·6H2O、Mg(NO3)2·6H2O、Al(NO3)3·6H2O preparing metal salt solution with total metal ion concentration of 1mol/L, NaOH and Na2CO3Preparing an alkaline solution in which n [ Na ]2CO3]＝0.5×n[Al3+]，n[NaOH]＝2×n[Al3++Ni2++Cu2++Mg2+]Slowly dripping a metal salt solution and an alkali solution into ultrapure water at the same time, controlling the pH of the solution to be 8-10, uniformly stirring the solution, crystallizing the solution in a 65 ℃ oil bath kettle for 12 hours, and washing, drying, grinding, calcining and reducing the solution to obtain a Ni-Cu-Mg-Al hydrotalcite catalyst; the calcination is carried out for 3 hours in an air atmosphere at the temperature of 300-600 ℃; the reduction is carried out for 4h under the condition of 400 ℃ at the heating rate of 2 ℃/min in the mixed gas atmosphere with the volume of hydrogen and nitrogen being 7: 3.
2. The preparation method of the catalyst for preparing hydrogen by dry reforming of methane and carbon dioxide as claimed in claim 1, wherein n [ Ni ]2 ++Cu2++Mg2+]:n[Al3+]＝3:1，Cu2+And Mg2+Molar ratio of 1:1, Ni2+Molar of Ni2+、Cu2+、Mg2+1/20-1/40 of the total mole of the three.
3. The preparation method of the catalyst for dry reforming of methane and carbon dioxide to produce hydrogen according to claim 1 or 2, characterized in that tetrapropylammonium hydroxide surfactant with the mass fraction of 0.1% is added into water before the metal salt solution is mixed with the alkali solution.
4. The preparation method of the catalyst for dry reforming of methane and carbon dioxide to produce hydrogen according to claim 1 or 2, wherein the pH of the solution is 8.5-10.
5. The method for preparing the catalyst for dry reforming of methane and carbon dioxide to produce hydrogen according to claim 1 or 2, wherein the drying is vacuum drying at 80 ℃ for 12 h.
6. The application of the catalyst obtained by the preparation method of the catalyst for hydrogen production by dry reforming of methane and carbon dioxide in the preparation of hydrogen by dry reforming of methane and carbon dioxide.
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