CN113058592A - Catalyst for 3D printing of organic hydrogen storage material and preparation method and application thereof - Google Patents
Catalyst for 3D printing of organic hydrogen storage material and preparation method and application thereof Download PDFInfo
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- CN113058592A CN113058592A CN202110320574.7A CN202110320574A CN113058592A CN 113058592 A CN113058592 A CN 113058592A CN 202110320574 A CN202110320574 A CN 202110320574A CN 113058592 A CN113058592 A CN 113058592A
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- hydrogen storage
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 59
- 239000001257 hydrogen Substances 0.000 title claims abstract description 59
- 239000011232 storage material Substances 0.000 title claims abstract description 51
- 238000010146 3D printing Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 38
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000919 ceramic Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 25
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 238000007639 printing Methods 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 238000000016 photochemical curing Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 11
- PKQYSCBUFZOAPE-UHFFFAOYSA-N 1,2-dibenzyl-3-methylbenzene Chemical compound C=1C=CC=CC=1CC=1C(C)=CC=CC=1CC1=CC=CC=C1 PKQYSCBUFZOAPE-UHFFFAOYSA-N 0.000 claims description 10
- 238000005070 sampling Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000013461 design Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 238000003980 solgel method Methods 0.000 claims description 5
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical compound C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 claims description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000001723 curing Methods 0.000 claims description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000004729 solvothermal method Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- HOQAPVYOGBLGOC-UHFFFAOYSA-N 1-ethyl-9h-carbazole Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2CC HOQAPVYOGBLGOC-UHFFFAOYSA-N 0.000 claims description 2
- HIAGSPVAYSSKHL-UHFFFAOYSA-N 1-methyl-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C(C)=CC=C2 HIAGSPVAYSSKHL-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 2
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 238000000593 microemulsion method Methods 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 2
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000004451 qualitative analysis Methods 0.000 description 4
- 238000004445 quantitative analysis Methods 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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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
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0015—Organic compounds; Solutions thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/44—Palladium
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- 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
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Abstract
The invention discloses a catalyst for 3D printing of an organic hydrogen storage material, and a preparation method and application thereof. Pouring the cordierite photosensitive resin slurry into a trough of a DLP photocuring printer for printing to obtain a cordierite honeycomb ceramic blank, and sintering to obtain an integral cordierite honeycomb ceramic carrier; a cordierite honeycomb ceramic carrier is used as a substrate, and a catalyst is carried and synthesized on the surface of the carrier to prepare the monolithic catalyst. The monolithic catalyst is filled in a fixed bed reactor, the organic hydrogen storage material is introduced into the fixed bed reactor, and hydrogenation or dehydrogenation reaction is carried out by controlling the process conditions. The preparation method has the advantages of simple preparation process, high structural precision and high catalyst strength and activity, and has a better application prospect in hydrogenation and dehydrogenation of organic hydrogen storage materials in the future.
Description
Technical Field
The invention discloses a preparation method of a 3D printing monolithic catalyst and application of the catalyst in hydrogenation and dehydrogenation of an organic hydrogen storage material, and belongs to the technical field of catalysts for 3D printing.
Background
The monolithic catalyst is mainly suitable for high-flux rapid reaction occasions, such as tail gas denitration, synthesis gas methanation, macromolecular compound synthesis, oxidative dehydrogenation, hydrodesulfurization and other processes. Taking the novel organic liquid hydrogenation and dehydrogenation reaction as an example, the existing hydrogenation and dehydrogenation reactors widely use fixed bed reactors, and the fixed bed reactors have the advantages of simple design and operation and small catalyst abrasion. However, in practical production processes, conventional particulate catalysts suffer from some significant disadvantages: low porosity, large pressure drop of the catalyst bed layer, large temperature gradient of each point of the catalyst bed layer, serious carbon deposition of the catalyst and the like. In order to overcome the deficiencies of conventional particulate catalysts and to optimize the reaction performance of heterogeneous catalysts, researchers have designed monolithic catalysts. At present, the most used integral carriers are honeycomb ceramics, and the specific surface areas of the honeycomb ceramics are all small (the specific surface area is less than 1 m)2/g), the specific surface area is generally increased by applying a catalyst coating. CN104998645A discloses a preparation method of methanation catalyst using cordierite honeycomb ceramic as carrier, which comprises immersing a catalyst component precursor on the surface of cordierite honeycomb ceramic, and processing by microwave calcination to obtain the required catalyst, but the through holes of the ceramic carrier are straight-hole channels, which further limits the effective reaction area and reaction time.
The 3D printing technology is a rapid prototyping technology based on digital model files, and prepares a material having a certain three-dimensional structure by printing layer by layer. Compared with the traditional forming, the 3D printing is not only beneficial to reducing material loss, but also has lower design cost and operation difficulty. The catalytic material prepared by 3D printing can better control and optimize the structure and the active site distribution of the material, and simultaneously adjust the mass transfer and heat transfer properties of the material and reduce the pressure drop of a bed layer, thereby achieving the purposes of improving the catalytic property and simplifying the operation.
At present, the application of the monolithic catalyst for 3D printing in hydrogenation and dehydrogenation of organic liquid is not reported.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a preparation method of an integral catalyst for hydrogenation and dehydrogenation of a 3D printing organic hydrogen storage material.
In order to solve the technical problem, the invention provides a preparation method of a catalyst for 3D printing of an organic hydrogen storage material, which comprises the following steps:
step 1): mixing the dried cordierite powder with photosensitive resin, and fully ball-milling in a ball mill to obtain cordierite photosensitive resin slurry; using modeling software to design a three-dimensional structure, and pouring cordierite photosensitive resin slurry into a trough of a DLP photocuring printer for printing to obtain a cordierite honeycomb ceramic blank;
step 2): evaporating and pyrolyzing the organic matters in the printed structure by using a cordierite honeycomb ceramic blank, and sintering to obtain an integral cordierite honeycomb ceramic carrier;
step 3): a cordierite honeycomb ceramic carrier is used as a substrate, and the synthesized catalyst component is carried on the surface of the substrate to prepare the monolithic catalyst.
Preferably, the photosensitive resin in step 1) is prepared from 30-70% by mass of a prepolymer, 15-60% by mass of a diluent, 1-5% by mass of a photoinitiator, and 0.1-5.0% by mass of the balance of an additive, wherein the prepolymer and the diluent are both acrylate polymers.
Preferably, the mass ratio of the cordierite powder to the photosensitive resin in the step 1) is 4: 1-1: 4.
preferably, the rotation speed of the ball mill in the step 1) is set to be 300-(ii) a The modeling software is AutoCAD, 3DMAX, SolidWorks or Materialise Magics; the light curing exposure power of the DLP light curing printer is 5-50mW/cm2The exposure time of the first layer is 10-20s, the exposure time of the other layers is 2-15s, and the slice thickness is 25-100 μm.
Preferably, the temperature of evaporation and pyrolysis in the step 2) is 50-450 ℃, and the time is 2-15 h; the sintering temperature is 1200-1400 ℃, and the time is 5-20 h.
Preferably, the catalyst component in step 3) is at least one of platinum nitrate, lead nitrate, rhodium nitrate, ruthenium nitrate, platinum chloride, lead chloride, rhodium chloride, ruthenium chloride and gold chloride, and the catalyst is carried and synthesized by a hydrothermal method, a solvothermal method, a sol-gel method, a direct coating method, a self-assembly method, a chemical vapor deposition method, a microemulsion method, a solvothermal method, a template-assisted solvent method or an immersion method.
The invention also provides the monolithic catalyst for hydrogenation and dehydrogenation of the 3D printing organic hydrogen storage material, which is prepared by the preparation method and has a porous channel three-dimensional structure.
The invention also provides a hydrogenation method of the organic hydrogen storage material, which comprises the steps of filling the monolithic catalyst into a fixed bed reactor, introducing the organic hydrogen storage material into the fixed bed reactor, and regulating and controlling the feeding rate of the organic hydrogen storage material to be 0.5-3.0h-1Then, adjusting the hydrogen pressure to 5-8Mpa, and raising the reaction temperature to 180-250 ℃; and after the device stably operates, sampling and measuring the hydrogenation degree of the organic hydrogen storage material.
Preferably, the organic hydrogen storage material is at least one of 8-methylquinoline, dibenzyltoluene, styrene, toluene, p-xylene, o-xylene, pyridine, ethylene glycol, cyclohexane, methylcyclohexane, decalin, quinoline, isoquinoline, carbazole, methylcarbazole and ethylcarbazole.
The invention also provides a method for dehydrogenating the organic hydrogen storage material, which comprises the steps of filling the monolithic catalyst into a fixed bed reactor, introducing the organic hydrogen storage material into the fixed bed reactor, and regulating and controlling the feeding rate of the organic hydrogen storage material to be 0.3-2.0h-1Then, adjusting the hydrogen pressure to 0-0.1Mpa, and raising the reaction temperature to 200-300 ℃; and after the device stably operates, sampling and measuring the dehydrogenation degree of the organic hydrogen storage material.
Preferably, the organic hydrogen storage material is 100% hydrogenated product of one or more hydrogenation reactions.
The preparation method has the advantages of simple preparation process, high structural precision and high catalyst strength and activity, and has a better application prospect in hydrogenation and dehydrogenation of organic hydrogen storage materials in the future. Compared with the prior art, the invention has the following beneficial effects:
(1) the complex structure suitable for different synthesis conditions and service environments can be customized through three-dimensional software, complex pretreatment and post-treatment are not required to be carried out on the carrier, and the microstructure and the pore structure are simple and controllable.
(2) The obtained 3D printing monolithic catalyst can achieve the effects of simple operation and easy separation and recovery.
(3) The performance test result of the monolithic catalyst prepared by the invention in the hydrogenation and dehydrogenation reactions of the organic hydrogen storage material shows that compared with the traditional powder particle catalyst, the monolithic catalyst has the advantages of reducing the pressure drop of a bed layer, reducing the temperature rise of the bed layer and the like, and has better industrial application prospect in the fields of hydrogenation and dehydrogenation reactions of the organic hydrogen storage material and preparation of 3D printing catalysts with controllable space structures.
Drawings
Fig. 1 is a flow chart of a method for preparing a catalyst for 3D printing of an organic hydrogen storage material provided by the present invention;
FIG. 2 is a GC-MS diagram of dibenzyltoluene;
FIG. 3 is a GC-MS diagram of dibenzyltoluene after hydrogenation.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Example 1
The preparation method of the 3D printing monolithic catalyst comprises the following steps:
A. mixing the dried cordierite powder and photosensitive resin according to a proportion (70 wt%: 30 wt%), and fully ball-milling in a ball mill for 12h to obtain cordierite photosensitive resin slurry.
B. Using modeling software to design a three-dimensional structure, pouring cordierite photosensitive resin slurry into a trough of a DLP photocuring printer for printing, wherein the printing process parameters are as follows: exposure power 30mW/cm2The exposure time is 8s (the exposure time of the first layer is 15s), and the scraper speed is 1.0 cm/s; and after printing, putting the cordierite honeycomb ceramic body into absolute ethyl alcohol for fully cleaning.
C. Drying the formed cordierite honeycomb ceramic blank at constant temperature, and carrying out degreasing sintering under the following degreasing sintering conditions: (1) heating from room temperature to 250 ℃ at the heating rate of 1 ℃/min, and keeping for 1 h; (2) heating from 250 ℃ to 550 ℃ at the heating rate of 0.5 ℃/min, and keeping for 1 h; (3) raising the temperature from 550 ℃ to 1250 ℃ at the temperature raising rate of 5 ℃/min, and keeping the temperature for 6 h. Obtaining the integral cordierite honeycomb ceramic carrier.
D. Preparation of Pd/Al by impregnation2O3Catalyst, using ceramic carrier as substrate and Pd/Al2O3Synthesizing the catalyst on the surface of a carrier by a sol-gel method to prepare a hydrogenation monolithic catalyst taking cordierite honeycomb ceramic as the carrier; preparation of Pt/Al by impregnation2O3Catalyst, taking ceramic carrier as substrate, mixing Pt/Al2O3The catalyst is synthesized on the surface of a carrier by a sol-gel method to prepare the dehydrogenation monolithic catalyst taking cordierite honeycomb ceramic as the carrier.
The method for using the monolithic catalyst for hydrogenating the organic hydrogen storage material comprises the following steps:
the monolithic catalyst for 3D printing is filled in a fixed bed reactor, the reaction temperature is 200 ℃, the hydrogen pressure is 6.0Mpa, and the mass airspeed is 1.0h-1Reacting under the process condition, wherein the organic hydrogen storage material is selected from dibenzyltoluene. After the device stably operates, sampling and analyzing, carrying out qualitative and quantitative analysis through GC-MS and a gas chromatograph, and analyzing the hydrogenation degree of the organic hydrogen storage material. The analysis result shows that the degree of hydrogenation of dibenzyltoluene is 100%.
The method for the dehydrogenation of the organic hydrogen storage material by the monolithic catalyst comprises the following steps:
the monolithic catalyst for 3D printing is filled in a fixed bed reactor, the reaction temperature is 250 ℃, the hydrogen pressure is 0.02Mpa, and the mass space velocity is 1.0h-1Reacting under the process condition, wherein the organic hydrogen storage material is selected from 100 percent hydrogenation products of dibenzyl toluene. After the device stably operates, sampling and analyzing, carrying out qualitative and quantitative analysis through GC-MS and a gas chromatograph, and analyzing the dehydrogenation degree of the organic hydrogen storage material. The degree of dehydrogenation of 18H-dibenzyltoluene was 99.5% as a result of the analysis.
Example 2
The preparation method of the 3D printing monolithic catalyst comprises the following steps:
A. mixing the dried cordierite powder and photosensitive resin according to a proportion (65 wt%: 35 wt%), and fully ball-milling in a ball mill for 12h to obtain cordierite photosensitive resin slurry.
B. Using modeling software to design a three-dimensional structure, pouring cordierite photosensitive resin slurry into a trough of a DLP photocuring printer for printing, wherein the printing process parameters are as follows: exposure power 25mW/cm2The exposure time is 6s (the first layer exposure time is 15s), and the scraper speed is 1.0 cm/s; and after printing, putting the cordierite honeycomb ceramic body into absolute ethyl alcohol for fully cleaning.
C. Drying the formed cordierite honeycomb ceramic blank at constant temperature, and carrying out degreasing sintering under the following degreasing sintering conditions: (1) heating from room temperature to 250 ℃ at the heating rate of 0.5 ℃/min, and keeping for 1 h; (2) heating from 250 ℃ to 550 ℃ at the heating rate of 0.5 ℃/min, and keeping for 1 h; (3) the temperature is increased from 550 ℃ to 1300 ℃ at the temperature increasing rate of 5 ℃/min and is kept for 5 h. Obtaining the integral cordierite honeycomb ceramic carrier.
D. Preparation of Pd/Al by impregnation2O3Catalyst, using ceramic carrier as substrate and Pd/Al2O3Coating the catalyst on the surface of a carrier to prepare an integral catalyst taking cordierite honeycomb ceramic as the carrier; preparation of Pt/Al by impregnation2O3Catalyst, taking ceramic carrier as substrate, mixing Pt/Al2O3The catalyst is synthesized on the surface of the carrier by a sol-gel method to prepare the dehydrogenation whole body taking cordierite honeycomb ceramic as the carrierA catalyst of formula (I).
The method for using the monolithic catalyst for hydrogenating the organic hydrogen storage material comprises the following steps:
the monolithic catalyst for 3D printing is filled in a fixed bed reactor, the reaction temperature is 220 ℃, the hydrogen pressure is 5.8Mpa, and the mass airspeed is 1.5h-1Reacting under the process condition, wherein the organic hydrogen storage material is selected from dibenzyltoluene. After the device stably operates, sampling and analyzing, carrying out qualitative and quantitative analysis through GC-MS and a gas chromatograph, and analyzing the hydrogenation degree of the organic hydrogen storage material. The analysis result shows that the degree of hydrogenation of dibenzyltoluene is 100%.
The method for the dehydrogenation of the organic hydrogen storage material by the monolithic catalyst comprises the following steps:
the monolithic catalyst for 3D printing is filled in a fixed bed reactor, the reaction temperature is 280 ℃, the hydrogen pressure is 0.01Mpa, and the mass space velocity is 1.2h-1Reacting under the process condition, wherein the organic hydrogen storage material is selected from 100 percent hydrogenation products of dibenzyl toluene. After the device stably operates, sampling and analyzing, carrying out qualitative and quantitative analysis through GC-MS and a gas chromatograph, and analyzing the dehydrogenation degree of the organic hydrogen storage material. The degree of dehydrogenation of 18H-dibenzyltoluene was 98.9% as a result of the analysis.
Claims (11)
1. A preparation method of a catalyst for 3D printing of an organic hydrogen storage material is characterized by comprising the following steps:
step 1): mixing the dried cordierite powder with photosensitive resin, and fully ball-milling in a ball mill to obtain cordierite photosensitive resin slurry; using modeling software to design a three-dimensional structure, and pouring cordierite photosensitive resin slurry into a trough of a DLP photocuring printer for printing to obtain a cordierite honeycomb ceramic blank;
step 2): evaporating and pyrolyzing the organic matters in the printed structure by using a cordierite honeycomb ceramic blank, and sintering to obtain an integral cordierite honeycomb ceramic carrier;
step 3): a cordierite honeycomb ceramic carrier is used as a substrate, and the synthesized catalyst component is carried on the surface of the substrate to prepare the monolithic catalyst.
2. The preparation method of claim 1, wherein the photosensitive resin in step 1) comprises 30-70% by mass of a prepolymer, 15-60% by mass of a diluent, 1-5% by mass of a photoinitiator, and 0.1-5.0% by mass of the balance of additives, wherein the prepolymer and the diluent are both acrylate polymers.
3. The preparation method according to claim 1, wherein the mass ratio of the cordierite powder to the photosensitive resin in the step 1) is 4: 1-1: 4.
4. the preparation method as claimed in claim 1, wherein the rotation speed of the ball mill in step 1) is set to be 300-500r/min, and the ball milling time is 2-12 h; the modeling software is AutoCAD, 3DMAX, SolidWorks or Materialise Magics; the light curing exposure power of the DLP light curing printer is 5-50mW/cm2The exposure time of the first layer is 10-20s, the exposure time of the other layers is 2-15s, and the slice thickness is 25-100 μm.
5. The preparation method of claim 1, wherein the temperature of the evaporation and pyrolysis in the step 2) is 50-450 ℃ and the time is 2-15 h; the sintering temperature is 1200-1400 ℃, and the time is 5-20 h.
6. The method according to claim 1, wherein the catalyst component in step 3) is at least one of platinum nitrate, lead nitrate, rhodium nitrate, ruthenium nitrate, platinum chloride, lead chloride, rhodium chloride, ruthenium chloride, and gold chloride, and the method for synthesizing the catalyst by loading is a hydrothermal method, a solvothermal method, a sol-gel method, a direct coating method, a self-assembly method, a chemical vapor deposition method, a microemulsion method, a solvothermal method, a template-assisted solvent method, or an immersion method.
7. The catalyst for 3D printing of organic hydrogen storage material prepared by the preparation method of claim 1, wherein the monolithic catalyst has a multi-channel steric structure.
8. A method for hydrogenating an organic hydrogen storage material, which is characterized in that the catalyst for 3D printing of the organic hydrogen storage material according to claim 7 is filled in a fixed bed reactor, the organic hydrogen storage material is introduced into the fixed bed reactor, and the feeding rate of the organic hydrogen storage material is regulated to be 0.5-3.0h-1Then, adjusting the hydrogen pressure to 5-8Mpa, and raising the reaction temperature to 180-250 ℃; and after the device stably operates, sampling and measuring the hydrogenation degree of the organic hydrogen storage material.
9. The method of hydrogenating an organic hydrogen storage material of claim 8, wherein the organic hydrogen storage material is at least one of 8-methylquinoline, dibenzyltoluene, styrene, toluene, p-xylene, o-xylene, pyridine, ethylene glycol, cyclohexane, methylcyclohexane, decalin, quinoline, isoquinoline, carbazole, methylcarbazole, and ethylcarbazole.
10. A method for dehydrogenating an organic hydrogen storage material, comprising the steps of filling the catalyst for 3D printing of the organic hydrogen storage material according to claim 7 into a fixed bed reactor, introducing the organic hydrogen storage material into the fixed bed reactor, and regulating the feeding rate of the organic hydrogen storage material to be 0.3-2.0h-1Then, adjusting the hydrogen pressure to 0-0.1Mpa, and raising the reaction temperature to 200-300 ℃; and after the device stably operates, sampling and measuring the dehydrogenation degree of the organic hydrogen storage material.
11. The method for hydrogenating an organic hydrogen storage material of claim 10, wherein the organic hydrogen storage material is a 100% hydrogenation product of one or more hydrogenation reactions.
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