CN111804326A - Preparation method of copper-based composite metal catalyst - Google Patents
Preparation method of copper-based composite metal catalyst Download PDFInfo
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- CN111804326A CN111804326A CN202010626578.3A CN202010626578A CN111804326A CN 111804326 A CN111804326 A CN 111804326A CN 202010626578 A CN202010626578 A CN 202010626578A CN 111804326 A CN111804326 A CN 111804326A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- 239000002184 metal Substances 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 20
- 239000010949 copper Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 13
- 238000002407 reforming Methods 0.000 claims abstract description 12
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 73
- 238000003756 stirring Methods 0.000 claims description 66
- 239000000843 powder Substances 0.000 claims description 31
- 239000007787 solid Substances 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000000725 suspension Substances 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 20
- 238000004108 freeze drying Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 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 13
- 239000000047 product Substances 0.000 claims description 13
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000012265 solid product Substances 0.000 claims description 10
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 150000001879 copper Chemical class 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 229960003280 cupric chloride Drugs 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 abstract description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 4
- 238000001651 catalytic steam reforming of methanol Methods 0.000 abstract description 4
- 150000002431 hydrogen Chemical class 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 230000017525 heat dissipation Effects 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 25
- 239000003921 oil Substances 0.000 description 22
- 239000011787 zinc oxide Substances 0.000 description 22
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 10
- 239000005751 Copper oxide Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910000431 copper oxide Inorganic materials 0.000 description 6
- 239000011148 porous material Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- -1 copper-zinc-aluminum Chemical compound 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- 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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1094—Promotors or activators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
Abstract
The invention discloses a preparation method of a copper-based composite metal catalyst, which is used in the technology of hydrogen production by reforming methanol water, wherein an SBA-15 molecular sieve is used as a carrier, ZnO is used as an auxiliary catalyst, and CuO is used as a main catalyst. The activated SBA-15 has a large number of micropores and mesopores, the surface area is increased, the local heat dissipation of the catalyst is facilitated, the catalyst has good mechanical properties, and the thermal stability of the whole catalyst is improved by a small amount of metal oxide and silicon dioxide in the molecular sieve. In the methanol steam reforming hydrogen production reaction, high hydrogen selectivity and low carbon monoxide selectivity are shown under the condition of higher reaction temperature, and the service life is longer.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a preparation method of a copper-based composite metal catalyst.
Background
The continuous development of social economy, the continuous improvement of the demand of people on primary fossil energy, and the subsequent serious environmental problems of greenhouse gas, acid rain, air pollution, unregulated emission of toxic and harmful wastes, and the like, are brought, so that a green new energy capable of replacing the fossil energy is urgently needed, the new energy is not only nontoxic, but also combustion products are nontoxic and harmless, and hydrogen is one of the most potential ideal energy in recent years.
The hydrogen production process by reforming methanol water is a main means for preparing hydrogen at present, has the advantages of simple raw materials (methanol and water), clean products and the like, is gradually mature in the development of the chemical field in the long term, is regarded as one of important hydrogen production means along with the advocation and continuous popularization of using novel green energy by the country, and can better exert the function and greatly improve the life of human beings by being combined with a fuel cell.
The methanol steam reforming reaction is a strongly endothermic reaction, and the reaction products are hydrogen and carbon monoxide/carbon dioxide. In the existing methanol water reforming hydrogen production technology, the copper-based catalyst has proved to be best in various reforming hydrogen production metal catalysts, wherein the copper-zinc-aluminum catalyst has wider application, but the further popularization is greatly limited due to the defects of no high temperature resistance, easy sintering and the like. Meanwhile, noble metals such as gold, silver, platinum, palladium and the like and transition metals are combined and loaded on one or more carriers to serve as composite metal methanol-water reforming hydrogen production catalysts, and the catalysts are excellent in high temperature resistance and service life, but the high cost hinders the popularization path.
In view of the above, there is an urgent need to develop a catalyst for methanol-water reforming hydrogen production with low carbon monoxide selectivity and better thermal stability.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a copper-based composite metal catalyst with better thermal stability, high activity and high hydrogen selectivity.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of a copper-based composite metal catalyst, which comprises the following stepsThe copper-based composite metal catalyst is used in methanol water reforming hydrogen production technology, wherein the SBA-15 molecular sieve is used as a carrier, and the SBA-15 molecular sieve contains SiO2And a small amount of metal oxide, ZnO as an auxiliary catalyst and CuO as a main catalyst, and the method specifically comprises the following operation steps:
s1: firstly preparing a solution A of zinc salt and copper salt precursor ethanol/water, wherein the concentration of copper ions and the concentration of zinc ions in the solution A are both 0.1-1mol/L, the volume of the solution A is the volume of a mixed solution of ethanol and water, then transferring the mixed solution into a three-neck flask, setting the temperature of an oil bath, carrying out thermal stirring and heating, wherein the temperature of the oil bath is 40-100 ℃, and the time is 20-60 min;
s2: dispersing a quantitatively prepared SBA-15 molecular sieve in 20-100mL of water by ultrasonic, stirring at room temperature for 2-45min, adding 0.1-5mL of 0.05M sodium hydroxide solution, continuously stirring at room temperature for 0-5min, washing with deionized water for three times, and freeze-drying in a freeze-drying box for 12h to obtain activated SBA-15 and solid powder B;
s3: dispersing 0.1-1g of the solid powder B in 20-100mL of water, placing the mixture in an oil bath pan, stirring at a constant temperature of 65 ℃ for 2-15min, adding 0.01-0.1g of hexadecyl trimethyl ammonium bromide, and continuously stirring for 2-15min to obtain a suspension C;
s4: dropwise adding a certain volume of the solution A into the suspension C, continuously stirring at a constant temperature of 65 ℃ for 1-20min after dropwise adding is finished, transferring to a 100mL tetrafluoroethylene removing kettle, placing in a constant temperature oven to react at 100 ℃ for 6-12h, naturally cooling, washing the dark gray product with water and ethanol for three times respectively, and drying to obtain a solid product D;
s5: placing the solid powder D in a muffle furnace, roasting under the air condition, heating up to 200-800 ℃ at the heating rate of 1-10 ℃/min, keeping the temperature for 2-6h, and naturally cooling to obtain CuOx-ZnOyThe catalyst is a composite metal catalyst of SBA-15.
Preferably, the copper salt is one or more of copper dichloride, and/or copper nitrate, and/or copper sulfate pentahydrate, and/or copper acetate, and/or copper nitrate.
Preferably, the zinc salt is one or more of zinc dichloride, zinc acetate and zinc nitrate.
Preferably, the water is deionized water, the ethanol is industrial ethanol with the purity of 98%, and the volume ratio of the water to the ethanol is 1-5.
Preferably, the muffle furnace is in an air condition, the roasting temperature is 300-800 ℃, and the roasting time is 1-5 h;
preferably, in the water bath heating and stirring condition: the oil bath temperature is 40-150 ℃, the magnetons are stirred by magnetic force, and the stirring speed is 300-800 rmp/min.
Preferably, the mixture is subjected to ultrasonic dispersion in a water/ethanol mixed solution, the ultrasonic dispersion time is 1-3 hours, and the ultrasonic frequency is 50-150 kHz, 80-150 kHz and/or 100-150 kHz.
Preferably, the mixture is washed and centrifuged for three times by the deionized water and the ethanol in sequence, the centrifugation speed is 5000 to 10000rmp/min, the mixture is dried in the constant-temperature oven at the constant temperature of 40 to 80 ℃ for 8 to 12 hours, the reaction temperature range of the constant-temperature oven is 50 to 200 ℃, and the reaction time is 4 to 50 hours.
The invention has the advantages and beneficial effects that:
(1) in the composite metal catalyst prepared by the invention, CuO and ZnO metals are uniformly dispersed in the porous SBA-15 pore channel and on the surface of the pore channel, and the uniform distribution of metal particles represents more contact active sites, thereby showing excellent catalytic activity.
(2) The activated and modified SBA-15 has a large number of micropores and mesopores, the surface area is increased, the local heat dissipation of the catalyst is facilitated, the catalyst has good mechanical properties, and the thermal stability of the whole catalyst is improved by a small amount of metal oxide and silicon dioxide in the molecular sieve.
(3) In the methanol steam reforming hydrogen production reaction, high hydrogen selectivity and low carbon monoxide selectivity are shown under the condition of higher reaction temperature, and the service life is longer.
Drawings
FIG. 1 is a flow chart of an embodiment of a method for preparing a copper-based composite metal catalyst according to the present invention.
Detailed Description
The following further describes embodiments of the present invention with reference to the drawings. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
As shown in figure 1, the preparation method of the copper-based composite metal catalyst is used in the technology of hydrogen production by methanol-water reforming, wherein the SBA-15 molecular sieve is used as a carrier, and the SBA-15 molecular sieve contains SiO2And a small amount of metal oxide, ZnO as an auxiliary catalyst and CuO as a main catalyst, and the method specifically comprises the following operation steps:
s1: firstly preparing a solution A of zinc salt and a precursor ethanol/water of copper salt, wherein the concentration of copper ions and the concentration of zinc ions in the solution A are both 0.1-1mol/L, the volume of the solution A is the volume of a mixed solution of ethanol and water, then transferring the mixed solution into a three-neck flask, setting the temperature of an oil bath, heating by stirring, and setting the temperature of the oil bath to be 40-100 ℃ for 20-60 min;
s2: and (2) dispersing a quantitatively prepared SBA-15 molecular sieve in 20-100mL of water by ultrasonic, stirring at room temperature for 2-45min, adding 0.1-5mL of 0.05M sodium hydroxide solution, continuously stirring at room temperature for 0-5min, washing with deionized water for three times, and then placing in a freeze drying box for freeze drying for 12h to obtain the activated SBA-15 and solid powder B.
S3: dispersing 0.1-1g of the solid powder B in 20-100mL of water, placing the mixture in an oil bath pan, stirring at a constant temperature of 65 ℃ for 2-15min, adding 0.01-0.1g of hexadecyl trimethyl ammonium bromide, and continuously stirring for 2-15min to obtain a suspension C;
s4: dropwise adding a certain volume of the solution A into the suspension C, continuously stirring at a constant temperature of 65 ℃ for 1-20min after dropwise adding is finished, transferring to a 100mL tetrafluoroethylene removing kettle, placing in a constant-temperature oven to react at 100 ℃ for 6-12h, naturally cooling, washing the dark gray product with water and ethanol for three times respectively, and drying to obtain a solid product D;
s5: and (3) placing the solid powder D in a muffle furnace, roasting under the air condition, heating to 200-800 ℃ at the heating rate of 1-10 ℃/min, preserving the temperature for 2-6h, and naturally cooling to obtain the CuOx-ZnOy/SBA-15 composite metal catalyst.
Specifically, the invention provides a novel metal composite catalyst aiming at the high-temperature sintering problem generated in the reforming hydrogen production reaction of a copper-based catalyst, the main active components are CuO and ZnO, the carrier is a porous SBA-15 molecular sieve, under the action of a surfactant CTAB, copper ions and zinc ions can be attached to the inner wall and outer wall pore channels of the molecular sieve, CuO-ZnO/SBA-15/SBA-15 with different active component loading amounts obtained after high-temperature roasting and oxidation is used as the carrier, SiO2 in the molecular sieve and a small amount of metal oxide in the molecular sieve also play a role in heat conduction and improve the local sintering problem, and the CuO-ZnO/SBA-15 composite metal catalyst with high activity and high hydrogen selectivity has better thermal stability.
In a preferred embodiment of the invention, the copper salt is one or more of copper dichloride, and/or copper nitrate, and/or copper sulfate pentahydrate, and/or copper acetate, and/or copper nitrate.
In a preferred embodiment of the invention, the zinc salt is one or more of zinc dichloride, zinc acetate and zinc nitrate.
In a preferred embodiment of the present invention, the water is deionized water, the ethanol is industrial ethanol with a purity of 98%, and the volume ratio of the water to the ethanol is 1-5.
5. The preparation method of the copper-based composite metal catalyst as claimed in claim 1, wherein the muffle furnace is in air condition, the calcination temperature is 300-800 ℃, and the calcination time is 1-5 h;
in the preferred embodiment of the present invention, in the water bath heating and stirring condition: the oil bath temperature is 40-150 ℃, the magnetons are stirred by magnetic force, and the stirring speed is 300-800 rmp/min.
In a preferred embodiment of the invention, the mixture is ultrasonically dispersed in the water/ethanol mixed solution, the ultrasonic dispersion time is 1-3 h, and the ultrasonic frequency is 50-150 kHz, 80-150 kHz and/or 100-150 kHz.
In a preferred embodiment of the invention, the mixture is washed and centrifuged for three times by deionized water and ethanol sequentially, the centrifugation speed is 5000 rmp/min-10000 rmp/min, the mixture is dried for 8-12 h at the constant temperature of 40-80 ℃ in a constant temperature oven, the reaction temperature range of the constant temperature oven is 50-200 ℃, and the reaction time is 4-50 h.
Specifically, in this embodiment, the reaction conditions for hydrogen production by methanol-water reforming are as follows: the hourly space velocity of the methanol water solution is 0.02-10kg/h × kgcat, the reaction temperature is 100-. The reaction conditions of the invention are as follows: the liquid hourly space velocity of the methanol/water is 2-5kg/h × kgcat, the reaction temperature is 180-.
Reforming reactor model: the inner diameter is 12mm, the catalyst filling amount is 4g, the raw material gas firstly passes through a thermal evaporator and then passes through a catalyst bed layer from top to bottom, a heating jacket is arranged around the reformer for providing reaction temperature, and the product gas is detected on line by Agilent GC-8860.
The methanol steam reforming hydrogen production reaction of the invention can be carried out in one or more combined devices of a fixed bed reactor, a fluidized bed reactor or a slurry bed reactor which meet the reaction conditions. In this example, a fixed bed reactor was selected.
Other embodiments of the invention are as follows:
the first embodiment:
(1) dissolving 5.6g of copper nitrate and 1.8g of zinc nitrate in a mixed solution of 40mL of water and 60mL of ethanol, placing the mixed solution in an oil bath kettle, keeping the temperature constant at 75 ℃, and stirring for 20min to obtain a mixed solution A;
(2) ultrasonically dissolving 2g of SBA-15 into 100mL of water, stirring for 15min at room temperature, adding 5mL of 0.05M sodium hydroxide solution, continuously stirring for 1min at room temperature, washing with deionized water for three times, and freeze-drying in a freeze-drying oven for 12h to obtain activated SBA-15 and solid powder B;
(3) dispersing the 0.8g of solid powder B in 100mL of water, placing the mixture in an oil bath kettle, stirring at the constant temperature of 65 ℃ for 15min, adding 0.05g of hexadecyl trimethyl ammonium bromide, and continuously stirring for 5min to obtain a suspension C;
(4) dropwise adding 10mL of the solution A into the suspension C, continuously stirring at a constant temperature of 75 ℃ for 20min after dropwise adding is finished, transferring the suspension C into a 100mL tetrafluoroethylene removing kettle, placing the kettle into a constant-temperature oven to react for 8h at a temperature of 100 ℃, naturally cooling, washing the dark gray product with water and ethanol for three times respectively, and drying to obtain a solid product D;
(5) placing the solid powder D in a muffle furnace, roasting under the air condition, heating to 300 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 3h, and naturally cooling to obtain CuO21.37-ZnO6.6the/SBA-15 composite metal catalyst takes the mass sum of metal oxide and SBA-15 as the total mass, the mass fraction of copper oxide is 21.36 wt%, and the mass fraction of zinc oxide is 6.6 wt%.
Example two:
(1) dissolving 5g of copper nitrate and 1.6g of zinc nitrate in a mixed solution of 40mL of water and 60mL of ethanol, placing the mixed solution in an oil bath pan, keeping the temperature constant at 75 ℃, and stirring for 20min to obtain a mixed solution A;
(2) ultrasonically dissolving 2g of SBA-15 into 100mL of water, stirring for 15min at room temperature, adding 5mL of 0.05M sodium hydroxide solution, continuously stirring for 1min at room temperature, washing with deionized water for three times, and freeze-drying in a freeze-drying oven for 12h to obtain activated SBA-15 and solid powder B;
(3) dispersing the 0.8g of solid powder B in 100mL of water, placing the mixture in an oil bath kettle, stirring at the constant temperature of 65 ℃ for 15min, adding 0.05g of hexadecyl trimethyl ammonium bromide, and continuously stirring for 5min to obtain a suspension C;
(4) dropwise adding 10mL of the solution A into the suspension C, continuously stirring at a constant temperature of 75 ℃ for 20min after dropwise adding is finished, transferring the suspension C into a 100mL tetrafluoroethylene removing kettle, placing the kettle into a constant-temperature oven to react for 8h at a temperature of 100 ℃, naturally cooling, washing the dark gray product with water and ethanol for three times respectively, and drying to obtain a solid product D;
(5) placing the solid powder D in a muffle furnace, roasting under the air condition, heating to 300 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 3h, and naturally cooling to obtain CuO19.67-ZnO6.07the/SBA-15 composite metal catalyst takes the mass sum of a metal oxide and the SBA-15 as the total mass and the mass of copper oxideThe weight percentage of the zinc oxide is 19.67 percent, and the mass percentage of the zinc oxide is 6.07 percent.
Example three:
(1) dissolving 6g of copper nitrate and 1.8g of zinc nitrate in a mixed solution of 40mL of water and 60mL of ethanol, placing the mixed solution in an oil bath pan, keeping the temperature constant at 75 ℃, and stirring for 20min to obtain a mixed solution A;
(2) ultrasonically dissolving 2g of SBA-15 into 100mL of water, stirring for 15min at room temperature, adding 5mL of 0.05M sodium hydroxide solution, continuously stirring for 1min at room temperature, washing with deionized water for three times, and freeze-drying in a freeze-drying oven for 12h to obtain activated SBA-15 and solid powder B;
(3) dispersing the 0.8g of solid powder B in 100mL of water, placing the mixture in an oil bath kettle, stirring at the constant temperature of 65 ℃ for 15min, adding 0.05g of hexadecyl trimethyl ammonium bromide, and continuously stirring for 5min to obtain a suspension C;
(4) dropwise adding 10mL of the solution A into the suspension C, continuously stirring at a constant temperature of 75 ℃ for 20min after dropwise adding is finished, transferring the suspension C into a 100mL tetrafluoroethylene removing kettle, placing the kettle into a constant-temperature oven to react for 8h at a temperature of 100 ℃, naturally cooling, washing the dark gray product with water and ethanol for three times respectively, and drying to obtain a solid product D;
(5) placing the solid powder D in a muffle furnace, roasting under the air condition, heating to 300 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 3h, and naturally cooling to obtain CuO22.54-ZnO6.52the/SBA-15 composite metal catalyst takes the mass sum of a metal oxide and a carrier SBA-15 as the total mass, the mass fraction of copper oxide is 22.54 wt%, and the mass fraction of zinc oxide is 6.52 wt%.
Example four:
(1) dissolving 9g of copper nitrate and 1.8g of zinc nitrate in a mixed solution of 40mL of water and 60mL of ethanol, placing the mixed solution in an oil bath pan, keeping the temperature constant at 75 ℃, and stirring for 20min to obtain a mixed solution A;
(2) ultrasonically dissolving 2g of SBA-15 into 100mL of water, stirring for 15min at room temperature, adding 5mL of 0.05M sodium hydroxide solution, continuously stirring for 1min at room temperature, washing with deionized water for three times, and freeze-drying in a freeze-drying oven for 12h to obtain activated SBA-15 and solid powder B;
(3) dispersing the 0.8g of solid powder B in 100mL of water, placing the mixture in an oil bath kettle, stirring at the constant temperature of 65 ℃ for 15min, adding 0.05g of hexadecyl trimethyl ammonium bromide, and continuously stirring for 5min to obtain a suspension C;
(4) dropwise adding 10mL of the solution A into the suspension C, continuously stirring at a constant temperature of 75 ℃ for 20min after dropwise adding is finished, transferring the suspension C into a 100mL tetrafluoroethylene removing kettle, placing the kettle into a constant-temperature oven to react for 8h at a temperature of 100 ℃, naturally cooling, washing the dark gray product with water and ethanol for three times respectively, and drying to obtain a solid product D;
(5) placing the solid powder D in a muffle furnace, roasting under the air condition, heating to 300 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 3h, and naturally cooling to obtain CuO30.39-ZnO5.86the/SBA-15 composite metal catalyst takes the mass sum of metal oxide and SBA-15 as the total mass, the mass fraction of copper oxide is 30.39 wt%, and the mass fraction of zinc oxide is 5.86 wt%.
Example five:
(1) dissolving 4.8g of copper nitrate and 2.5g of zinc nitrate in a mixed solution of 40mL of water and 60mL of ethanol, placing the mixed solution in an oil bath kettle, keeping the temperature constant at 75 ℃, and stirring for 20min to obtain a mixed solution A;
(2) ultrasonically dissolving 2g of SBA-15 into 100mL of water, stirring for 15min at room temperature, adding 5mL of 0.05M sodium hydroxide solution, continuously stirring for 1min at room temperature, washing with deionized water for three times, and freeze-drying in a freeze-drying oven for 12h to obtain activated SBA-15 and solid powder B;
(3) dispersing the 0.8g of solid powder B in 100mL of water, placing the mixture in an oil bath kettle, stirring at the constant temperature of 65 ℃ for 15min, adding 0.05g of hexadecyl trimethyl ammonium bromide, and continuously stirring for 5min to obtain a suspension C;
(4) dropwise adding 10mL of the solution A into the suspension C, continuously stirring at a constant temperature of 75 ℃ for 20min after dropwise adding is finished, transferring the suspension C into a 100mL tetrafluoroethylene removing kettle, placing the kettle into a constant-temperature oven to react for 8h at a temperature of 100 ℃, naturally cooling, washing the dark gray product with water and ethanol for three times respectively, and drying to obtain a solid product D;
(5) taking the solid powder D and placing the solid powder D in a muffle furnace,roasting under the air condition, heating up to 300 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 3h, and naturally cooling to obtain CuO18.4-ZnO9.24the/SBA-15 composite metal catalyst takes the mass sum of metal oxide and SBA-15 as the total mass, the mass fraction of copper oxide is 18.4 wt%, and the mass fraction of zinc oxide is 9.24 wt%.
Example six:
(1) dissolving 4.8g of copper nitrate and 3.2g of zinc nitrate in a mixed solution of 40mL of water and 60mL of ethanol, placing the mixed solution in an oil bath kettle, keeping the temperature constant at 75 ℃, and stirring for 20min to obtain a mixed solution A;
(2) ultrasonically dissolving 2g of SBA-15 into 100mL of water, stirring for 15min at room temperature, adding 5mL of 0.05M sodium hydroxide solution, continuously stirring for 1min at room temperature, washing with deionized water for three times, and freeze-drying in a freeze-drying oven for 12h to obtain activated SBA-15 and solid powder B;
(3) dispersing the 0.8g of solid powder B in 100mL of water, placing the mixture in an oil bath kettle, stirring at the constant temperature of 65 ℃ for 15min, adding 0.05g of hexadecyl trimethyl ammonium bromide, and continuously stirring for 5min to obtain a suspension C;
(4) dropwise adding 10mL of the solution A into the suspension C, continuously stirring at a constant temperature of 75 ℃ for 20min after dropwise adding is finished, transferring the suspension C into a 100mL tetrafluoroethylene removing kettle, placing the kettle into a constant-temperature oven to react for 8h at a temperature of 100 ℃, naturally cooling, washing the dark gray product with water and ethanol for three times respectively, and drying to obtain a solid product D;
(5) placing the solid powder D in a muffle furnace, roasting under the air condition, heating to 300 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 3h, and naturally cooling to obtain CuO17.94-ZnO11.53the/SBA-15 composite metal catalyst takes the mass sum of a metal oxide and a carrier SBA-15 as the total mass, the mass fraction of copper oxide is 17.94 wt%, and the mass fraction of zinc oxide is 11.53 wt%.
Example seven:
(1) dissolving 5g of copper nitrate and 1g of zinc nitrate in 40mL of water and 60mL of ethanol mixed solution, placing the mixture in an oil bath pan, keeping the temperature constant at 75 ℃, and stirring for 20min to obtain a mixed solution A;
(2) ultrasonically dissolving 2g of SBA-15 into 100mL of water, stirring for 15min at room temperature, adding 5mL of 0.05M sodium hydroxide solution, continuously stirring for 1min at room temperature, washing with deionized water for three times, and freeze-drying in a freeze-drying oven for 12h to obtain activated SBA-15 and solid powder B;
(3) dispersing the 0.8g of solid powder B in 100mL of water, placing the mixture in an oil bath kettle, stirring at the constant temperature of 65 ℃ for 15min, adding 0.05g of hexadecyl trimethyl ammonium bromide, and continuously stirring for 5min to obtain a suspension C;
(4) dropwise adding 10mL of the solution A into the suspension C, continuously stirring at a constant temperature of 75 ℃ for 20min after dropwise adding is finished, transferring the suspension C into a 100mL tetrafluoroethylene removing kettle, placing the kettle into a constant-temperature oven to react for 8h at a temperature of 100 ℃, naturally cooling, washing the dark gray product with water and ethanol for three times respectively, and drying to obtain a solid product D;
(5) placing the solid powder D in a muffle furnace, roasting under the air condition, heating to 300 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 3h, and naturally cooling to obtain CuO20.13-ZnO3.88the/SBA-15 composite metal catalyst takes the mass sum of metal oxide and SBA-15 as the total mass, the mass fraction of copper oxide is 20.13 wt%, and the mass fraction of zinc oxide is 3.88 wt%.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (8)
1. A preparation method of a copper-based composite metal catalyst is used in a methanol-water reforming hydrogen production technology, wherein an SBA-15 molecular sieve is used as a carrier, and the SBA-15 molecular sieve contains SiO2And a small amount of metal oxide, ZnO is taken as an auxiliary catalyst, CuO is taken as a main catalyst, and the method is characterized by comprising the following operation steps:
s1: firstly preparing a solution A of zinc salt and copper salt precursor ethanol/water, wherein the concentration of copper ions and the concentration of zinc ions in the solution A are both 0.1-1mol/L, the volume of the solution A is the volume of a mixed solution of ethanol and water, then transferring the mixed solution into a three-neck flask, setting the temperature of an oil bath, carrying out thermal stirring and heating, wherein the temperature of the oil bath is 40-100 ℃, and the time is 20-60 min;
s2: dispersing a quantitatively prepared SBA-15 molecular sieve in 20-100mL of water by ultrasonic, stirring at room temperature for 2-45min, adding 0.1-5mL of 0.05M sodium hydroxide solution, continuously stirring at room temperature for 0-5min, washing with deionized water for three times, and freeze-drying in a freeze-drying box for 12h to obtain activated SBA-15 and solid powder B;
s3: dispersing 0.1-1g of the solid powder B in 20-100mL of water, placing the mixture in an oil bath pan, stirring at a constant temperature of 65 ℃ for 2-15min, adding 0.01-0.1g of hexadecyl trimethyl ammonium bromide, and continuously stirring for 2-15min to obtain a suspension C;
s4: dropwise adding a certain volume of the solution A into the suspension C, continuously stirring at a constant temperature of 65 ℃ for 1-20min after dropwise adding is finished, transferring to a 100mL tetrafluoroethylene removing kettle, placing in a constant temperature oven to react at 100 ℃ for 6-12h, naturally cooling, washing the dark gray product with water and ethanol for three times respectively, and drying to obtain a solid product D;
s5: and (3) placing the solid powder D in a muffle furnace, roasting under the air condition, heating to 200-800 ℃ at the heating rate of 1-10 ℃/min, preserving the temperature for 2-6h, and naturally cooling to obtain the CuOx-ZnOy/SBA-15 composite metal catalyst.
2. The method of claim 1, wherein the copper salt is one or more of copper dichloride, copper nitrate, copper sulfate pentahydrate, copper acetate, and copper nitrate.
3. The method for preparing the copper-based composite metal catalyst according to claim 1, wherein the zinc salt is one or more of zinc dichloride, zinc acetate and zinc nitrate.
4. The preparation method of the copper-based composite metal catalyst according to claim 1, wherein the water is deionized water, the ethanol is industrial ethanol with a purity of 98%, and the volume ratio of the water to the ethanol is 1-5.
5. The method for preparing the copper-based composite metal catalyst as recited in claim 1, wherein the muffle furnace is under air condition, the calcination temperature is 300-800 ℃, and the calcination time is 1-5 h.
6. The method for preparing a copper-based composite metal catalyst according to claim 1, wherein in the water bath heating stirring condition: the oil bath temperature is 40-150 ℃, the magnetons are stirred by magnetic force, and the stirring speed is 300-800 rmp/min.
7. The preparation method of the copper-based composite metal catalyst according to claim 1, wherein the mixture is ultrasonically dispersed in the water/ethanol mixed solution for 1-3 hours at an ultrasonic frequency of 50-150 kHz, 80-150 kHz, and/or 100-150 kHz.
8. The preparation method of the copper-based composite metal catalyst according to claim 1, wherein the mixture is washed and centrifuged three times by the deionized water and the ethanol in sequence, the centrifugation speed is 5000 to 10000rmp/min, the mixture is dried in the constant temperature oven at the constant temperature of 40 to 80 ℃ for 8 to 12 hours, the reaction temperature of the constant temperature oven ranges from 50 to 200 ℃, and the reaction time is 4 to 50 hours.
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