CN115282973A - 3D printing-based monolithic catalyst, preparation method and application - Google Patents
3D printing-based monolithic catalyst, preparation method and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 169
- 238000010146 3D printing Methods 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 61
- 239000002994 raw material Substances 0.000 claims abstract description 49
- 238000001354 calcination Methods 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 238000005516 engineering process Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000000016 photochemical curing Methods 0.000 claims abstract description 12
- 238000007639 printing Methods 0.000 claims abstract description 5
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 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 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 3
- 229940044658 gallium nitrate Drugs 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 23
- 238000012546 transfer Methods 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 84
- 238000006243 chemical reaction Methods 0.000 description 60
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 31
- 239000000243 solution Substances 0.000 description 30
- 239000001257 hydrogen Substances 0.000 description 29
- 229910052739 hydrogen Inorganic materials 0.000 description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 27
- 238000004519 manufacturing process Methods 0.000 description 17
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- 230000000052 comparative effect Effects 0.000 description 10
- 238000004445 quantitative analysis Methods 0.000 description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000011065 in-situ storage Methods 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- SNAFEDKRXGBDJF-UHFFFAOYSA-N butane prop-2-enoic acid Chemical compound CCCC.OC(=O)C=C.OC(=O)C=C SNAFEDKRXGBDJF-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 241001391944 Commicarpus scandens Species 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
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- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- 229930091051 Arenine Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
Images
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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
- 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
- B01J23/002—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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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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
- C01B3/323—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
-
- 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
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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
- 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
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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
- 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
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- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention provides a 3D printing-based monolithic catalyst, a preparation method and application thereof, wherein the preparation method comprises the following steps: s1, preparing slurry by adopting an oxide raw material; s2, printing the slurry into a blank body by a digital photo-curing 3D printing technology; s3, calcining the blank body in an air atmosphere to obtain a carrier; and S4, dripping the active component solution into the carrier to soak for a period of time, drying and calcining to obtain the monolithic catalyst. The preparation method greatly improves the mechanical strength and stability of the monolithic catalyst, strengthens the heat transfer and mass transfer capacity in the catalyst and improves the activity of the catalyst; the catalyst active sites can be not covered under the condition of keeping high mechanical strength, higher catalytic activity is kept in the catalyst forming process, and different working conditions and application occasions are effectively adapted.
Description
Technical Field
The invention belongs to the technical field of chemical catalyst preparation, and particularly relates to a 3D printing-based monolithic catalyst, a preparation method and application thereof.
Background
In the fields of chemical industry and the like, the catalyst plays an extremely important role, and can greatly improve the reaction rate and further increase the yield of chemical products. In the laboratory development stage, catalysts are tested mainly in powder form in order to study deep-layer catalytic properties such as reaction mechanism, intrinsic reaction rate, catalyst surface active sites, etc. In industrial scale-up production, the powder catalyst is often required to be pressed or coated into a block, cylinder, or circular structure with large size for practical industrial production, and the powder catalyst has the effect of reducing bed layer pressure drop. However, active sites are easily covered in the process of amplifying and forming the catalyst, and the mechanical strength after forming is difficult to meet the requirements of some special reaction systems, so that the catalyst is easily broken due to high-speed airflow blowing and the like in the using process, the activity and the service life of the catalyst are greatly influenced, and the economic benefit of the whole production project is further influenced. Researchers and engineers in chemical industry have conducted a lot of research on the amplification of catalysts, but the promotion effect is always limited.
Chemical reaction systems affected by catalyst amplification are numerous, for example: the synthesis of olefin from carbon monoxide and hydrogen and the reaction of the olefin with alcohol, the preparation of methanol by the hydrogenation of carbon dioxide, the reforming of methanol and steam to prepare hydrogen, and the like. As a typical system for generating reaction by contacting a gas-phase raw material with a solid catalyst, methanol and water are mixed to form raw material steam with a certain proportion, and then the raw material steam is subjected to reforming reaction under the conditions of the reaction temperature of 220-350 ℃, the reaction pressure of 1-6 MPa and the like to generate main products of hydrogen and carbon dioxide, and simultaneously generate byproducts of carbon monoxide, methane and the like; the product gas is subjected to pressure swing adsorption separation and other steps, so that high-purity hydrogen can be obtained and used as a gas source for supplying hydrogen to the fuel cell.
With the rapid development of clean energy industries represented by hydrogen energy and the introduction of the "dual carbon" target, methanol steam reforming hydrogen production, which is an ideal hydrogen supply technology, is receiving attention from various parties. The high transportation and storage cost and low energy density of hydrogen are undoubtedly great obstacles to the market popularization and application of hydrogen-powered fuel cell vehicles. Methanol is an ideal hydrogen carrier, is liquid at normal temperature, effectively reduces transportation and storage cost, has volume energy density twice that of liquid hydrogen, can fully utilize the existing fuel storage, transportation and filling system, and has much lower modification and upgrading difficulty than a gaseous hydrogenation system. Meanwhile, based on the resource current situation of 'more coal and less oil' in China, methanol is undoubtedly the optimal solution for further development of hydrogen energy in China as a large number of energy commodities produced by coal conversion, methanol is used as a carrier for storage and transportation, and then hydrogen is prepared on a terminal through a methanol steam reforming technology, such as a vehicle-mounted system, a mobile generator, a distributed signal base station power supply and the like, so that the development of hydrogen energy economy is effectively eliminated, and the method is quite convenient; however, the pain point of the current technical route is that the methanol reforming hydrogen production catalyst is broken and deactivated due to low mechanical strength in high-speed moving environments such as vehicle-mounted environments and the like.
The current methods for forming catalysts mainly comprise a traditional extrusion forming process and a coating process with a later appearance time. The extrusion forming process is simple to operate and low in cost, but the catalyst active sites are covered in the extrusion process and cannot contact with raw material gas to lose the effect, and the extrusion forming process is a pure physical process, so that the produced formed catalyst is limited in mechanical strength and is not suitable for being used as a part of a vehicle-mounted methanol reforming reaction system. Compared with the extrusion forming process, the coating process has the advantages that the problems of insufficient mechanical strength and the like are solved to a certain extent by coating the active components on the wall surface of the reactor or the carrier, but the activity of the catalyst and the convenience in practical use are still not completely satisfactory, and meanwhile, the new problem of difficult catalyst replacement is also existed, the repeated use of the reactor is not facilitated, and the cost in practical production and use is increased.
Therefore, there is a need to provide a solution to the above-mentioned deficiencies in the prior art.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a monolithic catalyst based on 3D printing, a preparation method and applications thereof, which are used to solve the problems of insufficient mechanical strength and easy breakage of the molded catalyst in the prior art, and the problems of insufficient catalyst activity, poor convenience in practical use and high cost.
In order to achieve the above and other related objects, the present invention provides a method for preparing a monolithic catalyst based on 3D printing, the method at least comprising the steps of:
s1, preparing slurry by adopting an oxide raw material;
s2, printing the slurry into a blank body by a digital photo-curing 3D printing technology;
s3, calcining the blank in an air atmosphere to obtain a carrier;
and S4, dripping the active component solution into the carrier to soak for a period of time, drying and calcining to obtain the monolithic catalyst.
Preferably, the oxide raw material in step S1 includes one or a combination of alumina, silica, titania and zirconia.
Preferably, the particle size of the oxide raw material in step S1 is 100nm to 1000nm; wherein, in the oxide raw materials, the mass percentage of the oxide raw materials with the particle size of 100nm is 10wt% -80 wt%.
Preferably, the calcination temperature in step S3 is 1100 ℃ to 1600 ℃, and the calcination time is 4h to 30h.
Preferably, the radial crushing strength of the carrier in the step S3 is 20N/mm-240N/mm; the porosity of the carrier is 25-45%.
Preferably, the active component solution in step S4 includes one or a combination of copper nitrate, zinc nitrate, potassium nitrate, nickel nitrate, gallium nitrate and indium nitrate solution; wherein the molar concentration of the active component solution is 0.1-1.6 mol/L.
Preferably, the soaking time in the step S4 is 30 min-2 h.
Preferably, the drying temperature is 100-120 ℃, and the drying time is 1.5-3 h.
Preferably, the calcining temperature is 300-400 ℃, and the calcining time is 2-6 h.
Preferably, the active component solution is a mixture of copper nitrate and zinc nitrate solutions, wherein the molar concentration of the copper nitrate solution is 0.35mol/L, and the molar concentration of the zinc nitrate solution is 0.175mol/L.
The invention also provides a monolithic catalyst based on 3D printing, which is prepared by the preparation method of the monolithic catalyst based on 3D printing.
The invention also provides application of the monolithic catalyst based on 3D printing in a gas-solid phase reactor, wherein the monolithic catalyst is prepared by the preparation method of the monolithic catalyst based on 3D printing.
As described above, the monolithic catalyst based on 3D printing, the preparation method and the application of the invention have the following beneficial effects:
the novel carrier with high mechanical strength and porosity is prepared on the basis of a digital photocuring 3D printing technology, the 3D printing technology can enable the carrier to be designed into a more complex three-dimensional pore channel structure, the heat and mass transfer capacity of the catalyst is improved more effectively, and the contact between active sites and raw material gas is improved; the surface roughness of the carrier is adjusted by adjusting the composition of the slurry, so that the uniformity and the microscopic surface area of the active component precipitated on the carrier in situ are improved; due to the high mechanical strength of the carrier and the in-situ precipitation of the active component on the carrier, the monolithic catalyst has extremely high stability, can be kept stable under the high-speed airflow purging, and can resist the impact of external force and is not easy to break.
The preparation method greatly improves the mechanical strength and stability of the monolithic catalyst, strengthens the heat transfer and mass transfer capacity in the catalyst and improves the activity of the catalyst; compared with the finished catalyst obtained by traditional compression molding, the monolithic catalyst prepared by the invention can not cover the active site of the catalyst under the condition of keeping high mechanical strength, keeps higher catalytic activity in the catalyst molding process, and effectively adapts to different working conditions and application occasions; the digital photocuring 3D printing technology adopted in the invention can prepare more precise space geometric structures more efficiently, effectively strengthen the flow, mass and heat transfer capacity of the raw material fluid in the integral catalyst and strengthen the reaction process; the invention has wide raw material source, simple preparation process, repeatability, capability of expanding other porous material supported catalysts, suitability for industrial large-scale production and extremely high application potential in the fields of catalysis and energy.
Drawings
FIG. 1 shows a scanning electron micrograph of a monolithic catalyst prepared in example 1 of the present invention.
FIG. 2 is a schematic view showing the channel configuration of the monolithic catalyst in example 1 of the present invention.
FIG. 3 is a schematic view showing the channel configuration of the monolithic catalyst in example 2 of the present invention.
FIG. 4 is a schematic view showing the channel configuration of the monolithic catalyst in example 3 of the present invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1-4. It should be noted that the drawings provided in this embodiment are only for schematically illustrating the basic idea of the present invention, and the components related to the present invention are only shown in the drawings and not drawn according to the number, shape and size of the components in actual implementation, and the form, quantity and proportion of each component in actual implementation may be arbitrarily changed, and the component layout may be more complicated.
The novel carrier with high mechanical strength and porosity is prepared on the basis of a digital photocuring 3D printing technology, the 3D printing technology can enable the carrier to be designed into a more complex three-dimensional pore channel structure, the heat and mass transfer capacity of the catalyst is improved more effectively, and the contact between active sites and raw material gas is improved; the surface roughness of the carrier is adjusted by adjusting the composition of the slurry, so that the uniformity and the microscopic surface area of the active component precipitated on the carrier in situ are improved; due to the high mechanical strength of the carrier and the in-situ precipitation of the active component on the carrier, the monolithic catalyst has extremely high stability, can be kept stable under the high-speed airflow purging, and can resist the impact of external force and is not easy to break; the preparation method greatly improves the mechanical strength and stability of the monolithic catalyst, strengthens the heat transfer and mass transfer capacity in the catalyst and improves the activity of the catalyst; compared with the finished catalyst obtained by traditional compression molding, the monolithic catalyst prepared by the invention can not cover the active site of the catalyst under the condition of keeping high mechanical strength, keeps higher catalytic activity in the catalyst molding process, and effectively adapts to different working conditions and application occasions; the digital photocuring 3D printing technology adopted in the invention can prepare more precise space geometric structures more efficiently, effectively strengthen the flow and mass and heat transfer capacities of raw material fluid in the integral catalyst and strengthen the reaction process; the invention has wide raw material source, simple preparation process, repeatability, capability of expanding other porous material supported catalysts, suitability for industrialized large-scale production and extremely high application potential in the fields of catalysis and energy.
The invention provides a preparation method of a monolithic catalyst based on 3D printing, which at least comprises the following steps:
s1, preparing slurry by adopting an oxide raw material;
s2, printing the slurry into a blank by a digital photo-curing 3D printing technology;
s3, calcining the blank in an air atmosphere to obtain a carrier;
and S4, dripping the active component solution into the carrier to soak for a period of time, drying and calcining to obtain the monolithic catalyst.
Specifically, the preparation of the slurry by adopting the oxide raw material is mainly performed by adopting the oxide raw material, then the binder, the pore-forming agent and the photosensitive resin are added, and the slurry is prepared by mechanical stirring, wherein the binder is polyurethane, the pore-forming agent is calcium carbonate, and the photosensitive resin is 1, 6-hexanediol diacrylate (HDDA), methylpropane diacrylate (TMPDA) or tripropylene glycol diacrylate (TPGDA); in the step S2, a digital photocuring 3D printing technology is adopted to print a blank with a complex three-dimensional pore channel structure, and then a carrier with both mechanical strength and porosity is prepared at a proper calcining temperature, so that the heat and mass transfer capacity of the catalyst is improved more effectively, and the contact between active sites and raw material gas is improved; and S4, fully soaking the whole carrier by slowly dripping the active component solution, and drying the soaked carrier in a closed container to balance the humidity difference inside and outside the whole carrier and the water vapor pressure and promote the active component to be uniformly separated out and grow in the whole carrier.
As an example, the raw oxide material in step S1 includes one or a combination of alumina, silica, titania, and zirconia.
Specifically, the oxide raw material comprises any one of alumina, silica, titania and zirconia, or a mixture of any two or more of them, and the specific requirement is adjusted according to the actual requirement.
As an example, the particle size of the oxide raw material in step S1 is 100nm to 1000nm; wherein, in the oxide raw materials, the mass percentage of the oxide raw materials with the particle size of 100nm is within the range of 10wt% -80 wt%.
Specifically, the particle size of the oxide raw material in step S1 may include any range of values such as 100nm, 200nm, 300nm, 400nm, 500nm, 800nm, 1000nm, and may be specifically adjusted according to the actual conditions; among them, the mass percentage of the oxide raw material having a particle size of 100nm may include values in any range of 79wt%, 75wt%, 70wt%, 60wt%, 50wt%, 40wt%, 30wt%, 20wt%, 10wt%, etc., which are adjusted according to the actual conditions. In this embodiment, the carrier surfaces with different roughness are formed by adjusting the ratio of different particle sizes in the oxide raw material, and the carrier has a suitable roughness surface, so as to improve the uniformity and microscopic surface area of the in-situ precipitation of the active component on the carrier.
In other embodiments, preferably, the oxide raw material is alumina, and the alumina comprises alumina with particle sizes of 100nm and 400nm, wherein the mass ratio between the alumina with particle size of 100nm and the alumina with particle size of 400nm is 1.
As an example, the calcining temperature in the step S3 is 1100-1600 ℃, and the calcining time is 4-30 h.
Specifically, the calcination temperature in step S3 may include values in any range, such as 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃, 1600 ℃ and the like, and may be specifically adjusted according to the actual conditions; the calcination time can include any range of values such as 4h, 10h, 15h, 20h, 25h, 30h and the like, and can be adjusted according to actual conditions.
As an example, the radial crushing strength of the carrier in the step S3 is 20N/mm to 240N/mm; the porosity of the carrier is 25-45%.
Specifically, the radial crushing strength of the carrier can include values in any range of 20N/mm, 50N/mm, 100N/mm, 150N/mm, 200N/mm, 220N/mm, 240N/mm and the like, and can be adjusted according to actual conditions; the porosity of the carrier may include 25%, 30%, 35%, 40%, etc. in any range, which may be adjusted according to the actual application. The crushing strength is the ultimate load when crushing occurs, and when the crushing strength is tested, a target test load is not set any more, and the load is continuously loaded until the load suddenly drops or a drop inflection point appears, and the corresponding value is the crushing strength; radial crush strength refers to the burst strength of an unsintered or sintered annular specimen as measured by application of radial pressure; porosity refers to the percentage of the volume of pores in a bulk material to the total volume of the material in its natural state.
In this embodiment, it is preferable that the calcination temperature in step S3 is 1200 to 1500 ℃ (e.g., 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃, etc.), and the calcination time is 10 to 25 hours (e.g., 10 hours, 15 hours, 20 hours, 25 hours, etc.); the radial crushing strength of the carrier was 150N/mm.
As an example, the active component solution in step S4 includes one or a combination of copper nitrate, zinc nitrate, potassium nitrate, nickel nitrate, gallium nitrate, and indium nitrate solution; wherein the molar concentration of the active component solution is 0.1 mol/L-1.6 mol/L.
Specifically, the molar concentration of the active component solution can include any range of values such as 0.1mol/L, 0.2mol/L, 0.5mol/L, 1.0mol/L, 1.4mol/L, 1.6mol/L and the like, and can be adjusted according to actual conditions; it should be noted that all solutions of the active ingredient mentioned here are aqueous solutions.
As an example, the soaking time in step S4 is 30min to 2h.
Specifically, the soaking time can include any range of values such as 30min, 1h, 1.5h, 2h and the like, and can be adjusted according to the actual conditions.
As an example, the temperature for drying in step S4 is 100 ℃ to 120 ℃, and the time for drying is 1.5h to 3h.
Specifically, the drying temperature may include values in any range such as 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃ and the like, and may be adjusted according to the actual conditions; the drying time can include any range of values such as 1.5h, 2.0h, 2.5h, 3.0h and the like, and can be adjusted according to the actual conditions.
As an example, the calcination temperature in step S4 is 300-400 ℃, and the calcination time is 2-6 h.
Specifically, the calcination temperature may include values in any range, such as 300 ℃, 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃, and the like, and may be adjusted according to the actual conditions; the calcination time can include any range of values such as 2h, 3h, 4h, 5h, 6h and the like, and can be adjusted according to the actual conditions.
By way of example, the active component solution is a mixture of copper nitrate and zinc nitrate solutions, wherein the molar concentration of the copper nitrate solution is 0.35mol/L and the molar concentration of the zinc nitrate solution is 0.175mol/L.
The invention also provides a monolithic catalyst based on 3D printing, which is prepared by the preparation method of the monolithic catalyst based on 3D printing.
Specifically, the monolithic catalyst manufactured by the 3D printing technology with high precision has a special reaction channel shape, the overall thermal efficiency of the catalyst can be obviously improved, the raw material conversion rate and the target product selectivity of catalytic reaction are further improved, the monolithic catalyst comprises a reaction section and a reaction channel which longitudinally penetrates through the reaction section, the reaction channel is provided with a plurality of reaction channels, and each reaction channel is uniformly distributed in the reaction section and is arranged in parallel.
In one embodiment, the number of the reaction channels is 1 to 16 (e.g. 1, 3, 5, 7, 9, 10, 12, 14, 16, etc.), and the cross-sectional shape of the reaction channels is a circular, square or fractal structure to enhance the flow of raw materials and heat transfer inside the catalyst; the fractal structure comprises a primary structure, a secondary structure and a tertiary structure, wherein the primary structure is a square with a first side length, the secondary structure is a square with a second side length, the tertiary structure is a square with a third side length, the secondary structure is positioned in the center of each side of the square of the primary structure, the tertiary structure is positioned in the center of each side of the square of the secondary structure, the first side length is three times the second side length, and the second side length is three times the third side length.
In another embodiment, the reaction channel comprises a central reaction channel and a plurality of auxiliary reaction channels which surround the central reaction channel, and the plurality of auxiliary reaction channels are arranged in pairwise symmetry with respect to the central reaction channel; and each reaction channel has the same shape and size as each other and is uniformly distributed in the reaction section in parallel with each other.
In another embodiment, the ratio of the distance between the geometric center of the cross section of any one of the auxiliary reaction channels and the geometric center of the cross section of the central reaction channel to the radius of the cross section of the reaction section is 1.
In order to better understand the monolithic catalyst based on 3D printing and the preparation method thereof in the invention, the invention also provides the application of the monolithic catalyst based on 3D printing and the application of the monolithic catalyst prepared by the preparation method of the monolithic catalyst based on 3D printing in a gas-solid phase reactor.
Specifically, the reactor comprises a vaporization section, a reaction section and a heat exchange channel, wherein a liquid raw material is vaporized in the vaporization section, then the vaporized raw material is contacted with a solid substance in the reaction section to react and produce a mixed gas flow containing a product, and the mixed gas flow exchanges heat with the reaction section and the vaporization section in sequence in the process of flowing through the heat exchange channel.
Preferably, the monolithic catalyst is applied to a vehicle-mounted methanol reforming hydrogen production reactor, specifically, firstly, nitrogen is introduced to protect the monolithic catalyst, the temperature of the reactor is raised to 250 ℃, and then a mixed solution of methanol and water with the volume ratio of 1 2 The methanol aqueous solution was vaporized by the supply of heat, and then the gaseous raw material was introduced into a tubular reactor to start the reaction, and the temperature of the whole reactor was maintained at 270 ℃ by electric heating during the reaction.
The monolithic catalyst based on 3D printing and the preparation method and application thereof according to the present invention will be described below with reference to specific examples, which are merely illustrative and not intended to limit the present invention in any way.
Example 1
The present embodiment provides a preparation method of a monolithic catalyst based on 3D printing, which includes the following steps:
s1, preparing slurry by adopting an oxide raw material; wherein the oxide raw material is alumina, the alumina comprises 100nm and 400nm particle size alumina, and the mass ratio of the 100nm particle size alumina to the 400nm particle size alumina is 1; the method for preparing the slurry specifically comprises the following steps: mechanically stirring the alumina microspheres, polyurethane, calcium carbonate and methyl propane diacrylate to prepare slurry; one preferred scheme is as follows: in the slurry, the alumina microspheres account for 70wt%, the polyurethane accounts for 1wt%, the calcium carbonate accounts for 2wt%, and the methylpropane diacrylate accounts for 27wt%; if 500g of slurry is formulated, it will contain 350g of alumina microspheres, 5g of polyurethane, 10g of calcium carbonate, 135g of methylpropane diacrylate.
S2, printing the slurry into a blank body by a digital photo-curing 3D printing technology;
s3, calcining the blank body for 15 hours at 1300 ℃ in the air atmosphere to obtain a carrier; wherein the radial crushing strength of the obtained carrier is 150N/mm, and the porosity of the carrier is 39.3%;
s4, dripping the active component solution into the carrier to soak for 2 hours, drying for 2 hours at 110 ℃, and then calcining for 4 hours at 350 ℃ to obtain an integral catalyst; the active component is a mixture of copper nitrate and zinc nitrate solution, the molar concentration of the copper nitrate solution is 0.35mol/L, and the molar concentration of the zinc nitrate solution is 0.175mol/L.
As shown in a scanning electron microscope in figure 1, a copper-zinc sheet layered structure successfully and uniformly grows on the surface of a carrier, the overall size of a microstructure is 2-10 mu m, the surface appearance presents a porous configuration, the contact area of an active component and raw material gas is effectively increased, and the catalytic capability is increased.
This example also provides a monolithic catalyst prepared by the method for preparing monolithic catalyst based on 3D printing in this example, the monolithic catalyst in this example includes a reaction section and a reaction channel penetrating through the reaction section, and the macro-channel configuration of the monolithic catalyst is shown in fig. 2, the total length of the reaction section is 2cm, the outer diameter of the reaction section is 1.3cm, and there are nine cylindrical reaction channels with a diameter of 2 mm.
This example also provides the use OF a monolithic catalyst in a reactor for hydrogen production by methanol reforming, which is packed into a reactor designed according to the structure in "high dry controlled structured catalysts for on-board methanol reforming," Liang, zhuangdian, wang, gan, zeng, gaofeng, et al, high dry controlled structured catalysts for on-board methanol reforming [ J ]. Jrnal OF ENERGY chemical reactor, 2022,68, 19-26 ", as a single-tube structure.
When the test is carried out, firstly nitrogen is introduced to protect the integral catalyst, the temperature of the reactor is raised to 250 ℃, and then a mixed solution of methanol and water with the volume ratio of 1 2 The methanol aqueous solution is vaporized by the heat supply, then the gas raw material is introduced into a reactor with a single-tube structure to start the reaction, and the temperature of the whole reactor is kept at 270 ℃ by electric heating in the reaction process.
After the reaction was smoothly carried out for 30 minutes, the product gas of the reactor was subjected to compositional tests using a gas chromatography model GC-2014 (Shimadzu, japan) equipped with a hydrogen Flame Ionization Detector (FID) and a Thermal Conductivity Detector (TCD) for quantitative analysis of the composition of the product mixture, and the results are shown in Table 1.
Example 2
This example provides a preparation method of monolithic catalyst based on 3D printing, which is the same as that in example 1 and will not be described herein again.
This example also provides a monolithic catalyst prepared by the method for preparing monolithic catalyst based on 3D printing in this example, in which the monolithic catalyst includes a reaction section and a reaction channel penetrating through the reaction section, and the configuration of the macro channel is shown in fig. 3, which is different from that in example 1: the reaction channel in this embodiment is a rectangular channel with a rectangular cross section.
This example also provides an application of the monolithic catalyst in a methanol reforming hydrogen production reactor, the reactor used is the same as that in example 1, and the process conditions and methods tested are also the same as those in example 1, which are not described herein again, and the results of quantitative analysis of the product composition are shown in table 1.
Example 3
This example provides a preparation method of monolithic catalyst based on 3D printing, which is the same as that in example 1 and will not be described herein again.
This example also provides a monolithic catalyst prepared by the method for preparing monolithic catalyst based on 3D printing in this example, in which the monolithic catalyst includes a reaction section and a reaction channel penetrating through the reaction section, and the configuration of the macro channel is shown in fig. 4, which is different from that in example 1: the reaction channel in this example is a typing structure channel.
This example also provides an application of the monolithic catalyst in a methanol reforming hydrogen production reactor, the reactor used is the same as that in example 1, and the process conditions and methods tested are also the same as those in example 1, which are not described herein again, and the results of quantitative analysis of the product composition are shown in table 1.
Example 4
This example provides a preparation method of monolithic catalyst based on 3D printing, which is different from example 1 in that: the raw material of the oxide in the step S1 is alumina with different particle sizes, the alumina comprises particle sizes of 100nm and 800nm, and the mass ratio of the alumina with the particle size of 100nm to the alumina with the particle size of 800nm is 1:1; other steps and methods are the same as those in embodiment 1, and are not described herein again.
This example also provides a monolithic catalyst prepared by the 3D printing-based monolithic catalyst preparation method of this example, wherein the macro-channel configuration of the monolithic catalyst is the same as that of example 1.
This example also provides an application of the monolithic catalyst in a methanol reforming hydrogen production reactor, the reactor used is the same as that in example 1, and the process conditions and methods for testing are also the same as those in example 1, which are not repeated herein, and the results of quantitative analysis of the product composition are shown in table 1.
Example 5
This example provides a preparation method of monolithic catalyst based on 3D printing, which is different from example 1 in that: the raw material of the oxide in the step S1 is alumina with different particle sizes, the alumina comprises 100nm and 400nm particle sizes, and the mass ratio of the alumina with the 100nm particle size to the alumina with the 400nm particle size is 1:3; other steps and methods are the same as those in embodiment 1, and are not described herein again.
This example also provides a monolithic catalyst prepared by the method for preparing monolithic catalyst based on 3D printing of this example, wherein the configuration of macro channels of the monolithic catalyst is the same as that of example 1.
This example also provides an application of the monolithic catalyst in a methanol reforming hydrogen production reactor, the reactor used is the same as that in example 1, and the process conditions and methods tested are also the same as those in example 1, which are not described herein again, and the results of quantitative analysis of the product composition are shown in table 1.
Example 6
This example provides a preparation method of monolithic catalyst based on 3D printing, which is different from example 1 in that: the oxide raw material in the step S1 is a mixture of alumina and silica, and comprises 100nm alumina and 400nm silica particles, and the mass ratio of the 100nm alumina to the 400nm silica particles is 1:1; other steps and methods are the same as those in embodiment 1, and are not described herein again.
This example also provides a monolithic catalyst prepared by the 3D printing-based monolithic catalyst preparation method of this example, wherein the macro-channel configuration of the monolithic catalyst is the same as that of example 1.
This example also provides an application of the monolithic catalyst in a methanol reforming hydrogen production reactor, the reactor used is the same as that in example 1, and the process conditions and methods tested are also the same as those in example 1, which are not described herein again, and the results of quantitative analysis of the product composition are shown in table 1.
Example 7
This example provides a preparation method of monolithic catalyst based on 3D printing, which is different from example 1 in that: in the step S3, the blank is calcined for 15 hours at 1100 ℃, the radial crushing strength of the obtained carrier is 23.3N/mm, and the porosity of the carrier is 46.3%; other steps and methods are the same as those in embodiment 1, and are not described herein again.
This example also provides a monolithic catalyst prepared by the method for preparing monolithic catalyst based on 3D printing of this example, wherein the configuration of macro channels of the monolithic catalyst is the same as that of example 1.
This example also provides an application of the monolithic catalyst in a methanol reforming hydrogen production reactor, the reactor used is the same as that in example 1, and the process conditions and methods for testing are also the same as those in example 1, which are not repeated herein, and the results of quantitative analysis of the product composition are shown in table 1.
Example 8
This example provides a preparation method of monolithic catalyst based on 3D printing, which is different from example 1 in that: the active component solution in the step S4 is nickel nitrate and zinc nitrate, the molar concentration of the nickel nitrate solution is 0.35mol/L, and the molar concentration of the zinc nitrate solution is 0.175mol/L; other steps and methods are the same as those in embodiment 1, and are not described herein again.
This example also provides a monolithic catalyst prepared by the method for preparing monolithic catalyst based on 3D printing of this example, wherein the configuration of macro channels of the monolithic catalyst is the same as that of example 1.
This example also provides an application of the monolithic catalyst in a methanol reforming hydrogen production reactor, the reactor used is the same as that in example 1, and the process conditions and methods for testing are also the same as those in example 1, which are not repeated herein, and the results of quantitative analysis of the product composition are shown in table 1.
Comparative example 1
This comparative example provides a method for preparing a catalyst, which is different from example 1 in that: directly taking alumina powder as a carrier, loading an active component solution on the alumina carrier in an impregnation mode, and drying to obtain the catalyst.
The embodiment also provides a catalyst prepared by the preparation method of the catalyst in the embodiment.
The embodiment also provides an application of the catalyst in a methanol reforming hydrogen production reactor, wherein the catalyst in the embodiment is filled into the reactor, and the structure of the reactor is the same as that in the embodiment 1; the specific process conditions and methods for testing are the same as those in example 1, and are not repeated herein, and the results of quantitative analysis of the product composition are shown in table 1.
Comparative example 2
This comparative example provides a process for the preparation of a monolithic catalyst, which differs from example 1 in that: taking alumina powder as a carrier, loading an active component solution on the alumina carrier in a dipping mode, and drying to obtain catalyst powder; and then pressing and molding the catalyst powder to obtain the monolithic catalyst.
The comparative example also provides a monolithic catalyst prepared by the method of the present embodiment, and the monolithic catalyst in the comparative example has the same shape and structure as those in example 1, and thus is not repeated herein.
The present comparative example also provides an application of the monolithic catalyst in a methanol reforming hydrogen production reactor, the reactor used is the same as that in example 1, and the process conditions and methods tested are also the same as those in example 1, which are not repeated herein, and the results of quantitative analysis of the product composition are shown in table 1.
Table 1 test results of monolithic catalysts prepared in examples 1 to 8 and comparative examples 1 to 2 in a hydrogen production reaction by reforming methanol
From the results, each example shows more excellent catalytic performance than the comparative example, the monolithic catalysts of examples 1 to 3 prepared by the preferred method have good methanol conversion rate, high hydrogen yield and low yield of carbon monoxide as a byproduct, wherein the geometric structure of example 3 adopting similar fractal channels can effectively strengthen the contact between the raw materials and the active sites in the catalyst reaction system and strengthen the heat and mass transfer, and each data reaches the optimal value; the performance of comparative example 1 using the powder catalyst was lower than that of the examples, and the catalyst activity after press molding was further lowered; examples 4 to 8 methanol reforming catalysts having catalytic activity were prepared by adjusting the composition of the support slurry, the calcination temperature, the composition of the active component, etc., but the performance was inferior to examples 1 to 3 using the preferred method.
In conclusion, the novel carrier with high mechanical strength and porosity is prepared on the basis of the digital photocuring 3D printing technology, the 3D printing technology can enable the carrier to be designed into a more complex three-dimensional pore channel structure, the heat and mass transfer capacity of the catalyst is improved more effectively, and the contact between active sites and raw material gas is improved; the surface roughness of the carrier is adjusted by adjusting the composition of the slurry, so that the uniformity and the microscopic surface area of the active component precipitated on the carrier in situ are improved; due to the high mechanical strength of the carrier and the in-situ precipitation of the active component on the carrier, the monolithic catalyst has extremely high stability, can be kept stable under the high-speed airflow purging, and can resist the impact of external force and is not easy to break; the preparation method greatly improves the mechanical strength and stability of the monolithic catalyst, strengthens the heat transfer and mass transfer capacity in the catalyst and improves the activity of the catalyst; compared with the finished catalyst obtained by traditional compression molding, the monolithic catalyst prepared by the invention can not cover the active site of the catalyst under the condition of keeping high mechanical strength, keeps higher catalytic activity in the catalyst molding process, and effectively adapts to different working conditions and application occasions; the digital photocuring 3D printing technology adopted in the invention can prepare more precise space geometric structures more efficiently, effectively strengthen the flow and mass and heat transfer capacities of raw material fluid in the integral catalyst and strengthen the reaction process; the invention has wide raw material source, simple preparation process, repeatability, capability of expanding other porous material supported catalysts, suitability for industrialized large-scale production and extremely high application potential in the fields of catalysis and energy. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which may be made by those skilled in the art without departing from the spirit and scope of the present invention as defined in the appended claims.
Claims (10)
1. A preparation method of a monolithic catalyst based on 3D printing is characterized by comprising the following steps:
s1, preparing slurry by adopting an oxide raw material;
s2, printing the slurry into a blank by a digital photo-curing 3D printing technology;
s3, calcining the blank body in an air atmosphere to obtain a carrier;
and S4, dripping the active component solution into the carrier to soak for a period of time, drying and calcining to obtain the monolithic catalyst.
2. The method for preparing a monolithic catalyst based on 3D printing according to claim 1, wherein: the oxide raw material in the step S1 comprises one or a combination of aluminum oxide, silicon oxide, titanium oxide and zirconium oxide.
3. The method for preparing a monolithic catalyst based on 3D printing according to claim 1, wherein: the particle size of the oxide raw material in the step S1 is 100 nm-1000 nm; wherein, in the oxide raw materials, the mass percentage of the oxide raw materials with the particle size of 100nm is 10wt% -80 wt%.
4. The method for preparing a monolithic catalyst based on 3D printing according to claim 1, wherein: in the step S3, the calcining temperature is 1100-1600 ℃, and the calcining time is 4-30 h.
5. The method for preparing a monolithic catalyst based on 3D printing according to claim 1, wherein: the radial crushing strength of the carrier in the step S3 is 20N/mm-240N/mm; the porosity of the carrier is 25-45%.
6. The method for preparing a monolithic catalyst based on 3D printing according to claim 1, wherein: the active component solution in the step S4 comprises one or a combination of copper nitrate, zinc nitrate, potassium nitrate, nickel nitrate, gallium nitrate and indium nitrate solution; wherein the molar concentration of the active component solution is 0.1-1.6 mol/L.
7. The method for preparing a monolithic catalyst based on 3D printing according to claim 1, wherein: step S4 includes any one or a combination of the following conditions:
the soaking time is 30 min-2 h;
the drying temperature is 100-120 ℃, and the drying time is 1.5-3 h;
the calcination temperature is 300-400 ℃, and the calcination time is 2-6 h.
8. The method for preparing a monolithic catalyst based on 3D printing according to claim 1, wherein: the active component solution is a mixture of copper nitrate and zinc nitrate solution, wherein the molar concentration of the copper nitrate solution is 0.35mol/L, and the molar concentration of the zinc nitrate solution is 0.175mol/L.
9. A monolithic catalyst based on 3D printing, characterized in that the monolithic catalyst is prepared by the method for preparing a monolithic catalyst based on 3D printing according to any one of claims 1 to 8.
10. Use of a monolithic catalyst based on 3D printing in a gas-solid phase reactor, wherein the monolithic catalyst is prepared by the method of any one of claims 1 to 8.
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