CN112547074A - Catalyst for methanol steam reforming hydrogen production, preparation method and application thereof - Google Patents
Catalyst for methanol steam reforming hydrogen production, preparation method and application thereof Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 81
- 239000001257 hydrogen Substances 0.000 title claims abstract description 81
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 238000001651 catalytic steam reforming of methanol Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 19
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000007598 dipping method Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000005751 Copper oxide Substances 0.000 claims description 6
- 229910000431 copper oxide Inorganic materials 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 238000000629 steam reforming Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- -1 cerium ions Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 230000010718 Oxidation Activity Effects 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003860 storage 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/80—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 zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous 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
- C01B2203/02—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
- C01B2203/12—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst for hydrogen production by methanol steam reforming, and a preparation method and application thereof. The preparation method of the catalyst for hydrogen production by methanol steam reforming comprises the following steps: 1) preparing an aqueous solution of nitrate to saturation, wherein metal ions in the aqueous solution of nitrate comprise copper ions, zinc ions and M ions; 2) dipping alumina balls in the nitrate solution in the step 1); 3) filtering, drying, calcining and cooling the impregnated alumina in the step 2); 4) and (3) repeating the steps 2) and 3) for 2-5 times in sequence to obtain the catalyst for hydrogen production by methanol steam reforming. In addition, the invention also provides a catalyst for hydrogen production by methanol steam reforming, which is prepared by the preparation method, and application thereof. The catalyst has the advantage of large specific surface area, thereby greatly improving the catalytic efficiency and prolonging the service life of the catalyst.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst for hydrogen production by methanol steam reforming, and a preparation method and application thereof.
Background
The development of energy has been the life line of civilization progress in human society, and hydrogen is called "energy currency" and has a calorific value inferior to that of nuclear fuel, three times that of gasoline. Hydrogen is a nontoxic energy carrier, does not generate greenhouse gases and other pollutants after combustion, is very beneficial to energy conservation and emission reduction, and is considered as an ideal clean new energy source in the 21 st century. In recent years, due to the breakthrough and continuous development of proton exchange membrane fuel cell technology, hydrogen energy is one of the important bridges for the transition from fossil energy to renewable energy. Meanwhile, hydrogen is also an important chemical raw material, and is widely used in hydrogenation reactions (such as coal liquefaction and vaporization, heavy oil reforming, pharmacy and the like), metal material processing and manufacturing and the like.
At present, the industrial large-scale hydrogen production technology of fossil fuels (such as natural gas, water gas and the like) is mature, but the reaction conditions are severe, the hydrogen production needs to be carried out at about 800 ℃, the adopted equipment needs special materials, and the problems of heat sources needed by steam for conversion, hydrogen purification and the like are also considered. In addition, the power consumption for hydrogen production by water electrolysis is about 5-8 kW.h/m3·H2The unit hydrogen cost is higher. The hydrogen production method has poor economy in small-scale hydrogen production in large demand in the fine chemical industry and the pharmaceutical industry.
In recent years, a large number of methanol cracking hydrogen production devices developed in China have the characteristics of relatively mild reaction temperature (200-300 ℃), convenience in methanol storage and transportation, no sulfur in hydrogen and the like. The chemical reaction formula of the hydrogen production by methanol steam reforming is as follows: CH (CH)3OH+H2O→CO2+3H2Compared with the hydrogen production device by converting natural gas or light oil with the same scale, the energy consumption of hydrogen production by converting methanol steam is only 50 percent of that of the hydrogen production device by converting natural gas or light oil with the same scale. According to measurement and calculation, a set of scales is 1000m3The unit hydrogen cost of the methanol steam conversion hydrogen production device is not higher than 2 yuan/m3·H2. And the methanol raw material is easy to obtain and low in price, and is the third chemical product discharged after the synthesis of ammonia and ethylene. With the rapid development of economy in China, the methanol steam reforming hydrogen production is rapidly popularized, and the methanol steam reforming hydrogen production catalyst is also rapidly expanded.
At present, the domestic methanol steam reforming hydrogen production catalyst mainly takes Cu, Zn and Al catalysts as main catalysts, but the copper-based catalyst is easy to oxidize in a water atmosphere system, and active components are easy to sinter, deposit carbon, poison and the like. The CO concentration of the byproduct of hydrogen production by methanol steam reforming is high (0.5-2%), and cannot meet the requirements of proton exchange membrane fuel cells (ppm-level CO can poison Pt catalysts of anodes of the fuel cells). In order to meet the requirements of proton exchange membrane fuel cells for hydrogen fuel, the reforming catalyst needs to have higher selectivity.
Disclosure of Invention
The invention aims to provide a preparation method of a catalyst for hydrogen production by methanol steam reforming, which aims to solve the problems of low production efficiency caused by low catalytic efficiency of the existing catalyst.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a catalyst for hydrogen production by methanol steam reforming comprises the following steps:
1) preparing an aqueous solution of nitrate to saturation, wherein metal ions in the aqueous solution of nitrate comprise copper ions, zinc ions and M ions;
2) dipping alumina balls in the nitrate solution in the step 1);
3) filtering, drying, calcining and cooling the impregnated alumina in the step 2);
4) and (3) repeating the steps 2) and 3) for 2-5 times in sequence to obtain the catalyst for hydrogen production by methanol steam reforming.
The preparation method of the catalyst for hydrogen production by methanol steam reforming has the beneficial effects that: the preparation method of the catalyst adopts a method of multiple times of dipping and calcining, can effectively improve the adhesion rate of copper oxide and zinc oxide on the surface of the alumina carrier, and simultaneously adds certain M element oxide (namely oxide auxiliary agent), thereby controlling the grain size of the catalyst and improving the oxidation activity of copper ions and zinc ions.
On the basis of the technical scheme, the invention can further have the following specific selection or optimized selection.
Specifically, the catalyst for hydrogen production by methanol steam reforming comprises, by mass, 10-30 parts of copper oxide, 5-20 parts of zinc oxide, 40-80 parts of aluminum oxide and 1-5 parts of an M element oxide. Wherein the M element oxide is selected from one or a mixture of more than two of magnesium oxide, manganese oxide, cerium oxide and zirconium oxide.
Specifically, in the step 2), the dipping time is 10-30 min.
Specifically, in the step 3), the aperture of the filtration is less than 0.5mm, the drying is carried out under vacuum, the vacuum degree is-0.085, the temperature is 60-100 ℃, and the time is 1-5 hours; the calcining temperature is 300-600 ℃, the time is 4-10 hours, and the cooling is to room temperature.
Specifically, the diameter of the alumina ball is 0.5-2 mm.
Specifically, in the step 4), the catalyst for hydrogen production by methanol steam reforming further comprises an activation step, namely firstly replacing air with nitrogen, then heating the catalyst for hydrogen production by methanol steam reforming to 300 ℃, introducing hydrogen, and finally preserving heat for 1-8 hours. Further, the nitrogen is introduced at the speed of 0.1-3L/min under the pressure of 0.1-0.3 Mpa; the rate of temperature rise is 5 ℃/min; the hydrogen is introduced at a pressure of 0.1-0.3MPa and a flow rate of 0.1-3L/min. The addition of the activation step can greatly improve the catalytic activity of the catalyst.
Note that the nitrate is decomposed into a metal oxide under high-temperature calcination.
The second purpose of the invention is to provide a catalyst for hydrogen production by methanol steam reforming, which is prepared by the preparation method of the catalyst for hydrogen production by methanol steam reforming.
The catalyst for hydrogen production by methanol steam reforming has the beneficial effects that: the alumina used as a carrier has a certain catalytic effect and has the advantage of large specific surface area, so that the catalytic efficiency is greatly improved, and the service life of the catalyst is prolonged.
The third object of the present invention is to provide an application of the catalyst for hydrogen production by methanol steam reforming, which is prepared by the preparation method of the catalyst for hydrogen production by methanol steam reforming, in hydrogen production by methanol steam reforming.
The catalyst for hydrogen production by methanol steam reforming has the beneficial effects that: the catalyst has low manufacturing cost, and the preparation method is simple and convenient and is easy to carry out industrial large-scale production and application.
Detailed Description
For better understanding of the present invention, the following examples are given for further illustration of the present invention, but the present invention is not limited to the following examples.
Example 1:
the invention provides a preparation method of a catalyst for hydrogen production by methanol steam reforming, which is used for preparing the catalyst for hydrogen production by methanol steam reforming, and specifically comprises the following steps:
1) preparing an aqueous solution of nitrate to saturation, wherein the aqueous solution of nitrate consists of copper ions, zinc ions and magnesium ions;
2) dipping alumina balls into the nitrate solution obtained in the step 1) for 20min, wherein the diameter of the alumina balls is 1 mm;
3) filtering the impregnated alumina of step 2), drying under vacuum, calcining at 400 ℃ for 4 hours, and then cooling to room temperature;
4) and (3) repeating the steps 2) and 3) for 5 times in sequence to obtain the catalyst. The obtained catalyst component comprises, in parts by mass, 20 parts of copper oxide, 10 parts of zinc oxide, 60 parts of aluminum oxide and 2 parts of magnesium oxide.
Example 2:
the invention provides a preparation method of a catalyst for hydrogen production by methanol steam reforming, which is used for preparing the catalyst for hydrogen production by methanol steam reforming, and specifically comprises the following steps:
1) preparing an aqueous solution of nitrate to saturation, wherein the aqueous solution of nitrate consists of copper ions, zinc ions, manganese ions and cerium ions;
2) dipping alumina balls into the nitrate solution obtained in the step 1) for 30min, wherein the diameter of the alumina balls is 2 mm;
3) filtering the impregnated alumina in the step 2), drying under vacuum, calcining at 600 ℃ for 6 hours, and then cooling to room temperature;
4) and (3) repeating the steps 2) and 3) for 2 times in sequence to obtain the catalyst. The obtained catalyst component comprises, by mass, 30 parts of copper oxide, 5 parts of zinc oxide and 40 parts of aluminum oxide, as well as 0.1 part of manganese oxide and 0.5 part of cerium oxide.
Further, the catalyst is activated, firstly, nitrogen is used for replacing air, then the temperature of the catalyst is raised to 300 ℃, meanwhile, hydrogen is introduced, and finally, the temperature is kept for 5 hours. Wherein the nitrogen is introduced at a pressure of 0.3MPa and a flow rate of 0.3L/min, the hydrogen is introduced at a pressure of 0.3MPa and a flow rate of 0.3L/min, and the temperature is increased at a rate of 5 ℃/min.
Example 3:
the invention provides a preparation method of a catalyst for hydrogen production by methanol steam reforming, which is used for preparing the catalyst for hydrogen production by methanol steam reforming, and specifically comprises the following steps:
1) preparing an aqueous solution of nitrate to saturation, wherein the aqueous solution of nitrate consists of copper ions, zinc ions, magnesium ions and zirconium ions;
2) dipping alumina balls into the nitrate solution obtained in the step 1) for 10min, wherein the diameter of the alumina balls is 0.5 mm;
3) filtering the impregnated alumina in the step 2), drying under vacuum, calcining at 300 ℃ for 10 hours, and then cooling to room temperature;
4) and (3) repeating the steps 2) and 3) for 4 times in sequence to obtain the catalyst. The obtained catalyst component comprises, in parts by mass, 10 parts of copper oxide, 20 parts of zinc oxide and 40 parts of aluminum oxide, as well as 2 parts of magnesium oxide and 3 parts of zirconium oxide.
Further, the catalyst is activated, firstly, nitrogen is used for replacing air, then the temperature of the catalyst is raised to 300 ℃, meanwhile, hydrogen is introduced, and finally, the temperature is kept for 2 hours. Wherein the nitrogen is introduced at a pressure of 0.1MPa and a flow rate of 0.1L/min, the hydrogen is introduced at a pressure of 0.1MPa and a flow rate of 0.1L/min, and the temperature is increased at a rate of 5 ℃/min.
Examples of the experiments
The catalysts for hydrogen production by methanol steam reforming obtained in examples 1 to 3 and a catalyst (comparative example) commercially available from Jiangsu Nuo Union chemical Co., Ltd were subjected to a methanol cracking catalytic reaction. The reaction results are shown in table 1 below.
TABLE 1 catalytic reaction results for methanol cracking
| Catalyst and process for preparing same | Conversion of methanol (%) | Hydrogen content (%) |
| Example 1 | 83.3 | 76.7 |
| Example 2 | 94.3 | 87.1 |
| Example 3 | 96.7 | 91.5 |
| Comparative example | 56.4 | 62.4 |
As can be seen from Table 1, the catalyst for hydrogen production by methanol steam reforming, which is provided by the application, can be applied to the production of hydrogen production by methanol cracking, and can obviously improve the conversion rate of raw materials and the gas concentration of a target product hydrogen, so that the catalyst has a better catalytic effect. Furthermore, the catalyst is easy to prepare, the steps of the method are simple, and the production time and the labor cost are saved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a catalyst for hydrogen production by methanol steam reforming is characterized by comprising the following steps:
1) preparing an aqueous solution of nitrate to saturation, wherein metal ions in the aqueous solution of nitrate comprise copper ions, zinc ions and M ions;
2) dipping alumina balls in the nitrate solution in the step 1);
3) filtering, drying, calcining and cooling the impregnated alumina in the step 2);
4) and (3) repeating the steps 2) to 3) for 2-5 times to obtain the catalyst for hydrogen production by methanol steam reforming.
2. The method for producing a catalyst for hydrogen production by methanol steam reforming according to claim 1, characterized in that: the catalyst for hydrogen production by methanol steam reforming comprises, by mass, 10-30 parts of copper oxide, 5-20 parts of zinc oxide, 40-80 parts of aluminum oxide and 1-5 parts of M element oxide.
3. The method for producing a catalyst for hydrogen production by methanol steam reforming according to claim 2, characterized in that: the M element oxide is selected from one or a mixture of more than two of magnesium oxide, manganese oxide, cerium oxide and zirconium oxide.
4. The method for producing a catalyst for hydrogen production by methanol steam reforming according to claim 1, characterized in that: in the step 2), the time for soaking is 10-30 min.
5. The method for producing a catalyst for hydrogen production by methanol steam reforming according to claim 1, characterized in that: in the step 3), the pore diameter of the filtration is less than 0.5 mm; the drying is carried out under vacuum, the vacuum degree is-0.085, the temperature is 60-100 ℃, and the time is 1-5 hours; the calcining temperature is 300-600 ℃, and the time is 4-10 hours; the cooling is to room temperature.
6. The method for producing a catalyst for hydrogen production by methanol steam reforming according to claim 1, characterized in that: in step 2), the diameter of the alumina ball is 0.5-2 mm.
7. The method for producing a catalyst for hydrogen production by steam reforming of methanol according to any one of claims 1 to 6, characterized in that: in the step 4), the catalyst for hydrogen production by methanol steam reforming also comprises an activation step, namely firstly replacing air with nitrogen, then heating the catalyst for hydrogen production by methanol steam reforming to 300 ℃, simultaneously introducing hydrogen, and finally preserving heat for 1-8 hours.
8. The method for producing a catalyst for hydrogen production by methanol steam reforming according to claim 7, characterized in that: introducing nitrogen at the pressure of 0.1-0.3Mpa and the flow rate of 0.1-3L/min; the rate of temperature rise is 5 ℃/min; the hydrogen is introduced at a pressure of 0.1-0.3MPa and a flow rate of 0.1-3L/min.
9. A catalyst for hydrogen production by methanol steam reforming, which is produced by the method for producing a catalyst for hydrogen production by methanol steam reforming according to any one of claims 1 to 8.
10. Use of the catalyst for methanol steam reforming hydrogen production prepared by the method for preparing a catalyst for methanol steam reforming hydrogen production according to any one of claims 1 to 8 in methanol steam reforming hydrogen production.
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| CN113336555A (en) * | 2021-06-24 | 2021-09-03 | 浙江大学 | Photocuring type 3D printing manufacturing method of integral SiC-based microreactor |
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| CN116177491A (en) * | 2022-12-30 | 2023-05-30 | 中国矿业大学 | Microwave-driven methanol reforming rapid hydrogen production method |
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