CN114436208A - Catalytic hydrogen supply system based on organic liquid and hydrogen supply method thereof - Google Patents
Catalytic hydrogen supply system based on organic liquid and hydrogen supply method thereof Download PDFInfo
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- CN114436208A CN114436208A CN202210115334.8A CN202210115334A CN114436208A CN 114436208 A CN114436208 A CN 114436208A CN 202210115334 A CN202210115334 A CN 202210115334A CN 114436208 A CN114436208 A CN 114436208A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 330
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 330
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 305
- 239000007788 liquid Substances 0.000 title claims abstract description 101
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 140
- 239000002994 raw material Substances 0.000 claims abstract description 94
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 239000000463 material Substances 0.000 claims abstract description 63
- 229910052751 metal Inorganic materials 0.000 claims abstract description 63
- 239000002184 metal Substances 0.000 claims abstract description 62
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 47
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims abstract description 11
- NHCREQREVZBOCH-UHFFFAOYSA-N 1-methyl-1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalene Chemical compound C1CCCC2C(C)CCCC21 NHCREQREVZBOCH-UHFFFAOYSA-N 0.000 claims abstract description 10
- GREARFRXIFVLGB-UHFFFAOYSA-N 2-methyl-1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalene Chemical compound C1CCCC2CC(C)CCC21 GREARFRXIFVLGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract 18
- 239000000852 hydrogen donor Substances 0.000 claims description 76
- 239000010949 copper Substances 0.000 claims description 46
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 42
- 239000002243 precursor Substances 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 29
- 239000000377 silicon dioxide Substances 0.000 claims description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- 150000002431 hydrogen Chemical class 0.000 claims description 26
- 238000005470 impregnation Methods 0.000 claims description 26
- 229910052802 copper Inorganic materials 0.000 claims description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 238000011068 loading method Methods 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 16
- NBPFTXMPUSSROF-UHFFFAOYSA-L [Pt+2].C(C(=O)[O-])(=O)[O-].[K+] Chemical compound [Pt+2].C(C(=O)[O-])(=O)[O-].[K+] NBPFTXMPUSSROF-UHFFFAOYSA-L 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 239000012696 Pd precursors Substances 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- 239000012691 Cu precursor Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- PZKNFJIOIKQCPA-UHFFFAOYSA-N oxalic acid palladium Chemical compound [Pd].OC(=O)C(O)=O PZKNFJIOIKQCPA-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 4
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- 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 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 7
- 239000011344 liquid material Substances 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 description 24
- 229910052906 cristobalite Inorganic materials 0.000 description 24
- 229910052682 stishovite Inorganic materials 0.000 description 24
- 229910052905 tridymite Inorganic materials 0.000 description 24
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 20
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 229910018883 Pt—Cu Inorganic materials 0.000 description 15
- 229910000510 noble metal Inorganic materials 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 230000009467 reduction Effects 0.000 description 14
- 229910052593 corundum Inorganic materials 0.000 description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 description 13
- 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 description 10
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical compound C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- 229940038384 octadecane Drugs 0.000 description 10
- 238000001514 detection method Methods 0.000 description 8
- WBLJAACUUGHPMU-UHFFFAOYSA-N copper platinum Chemical compound [Cu].[Pt] WBLJAACUUGHPMU-UHFFFAOYSA-N 0.000 description 7
- 238000006356 dehydrogenation reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910002668 Pd-Cu Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- SBVSDAFTZIVQEI-UHFFFAOYSA-N 2,3,4,4a,4b,5,6,7,8,8a,9,9a-dodecahydro-1h-carbazole Chemical compound C1CCCC2C3CCCCC3NC21 SBVSDAFTZIVQEI-UHFFFAOYSA-N 0.000 description 2
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical class C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
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- 230000006872 improvement Effects 0.000 description 2
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- 239000007791 liquid phase Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical compound C1CNNNC1 OYWRDHBGMCXGFY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
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- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
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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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- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Combustion & Propulsion (AREA)
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Abstract
The invention discloses a catalytic hydrogen supply system based on organic liquid and a hydrogen supply method thereof, wherein the catalytic hydrogen supply system comprises an organic liquid hydrogen supply material and a hydrogen supply reaction catalyst, the organic liquid hydrogen supply material consists of a hydrogen supply raw material A and a hydrogen supply raw material B, the hydrogen supply raw material A is one or two of dodecahydrobenzyl toluene and octadecahydrodibenzyl toluene, the mass content of the octadecahydrodibenzyl toluene is not more than 80%, and the hydrogen supply raw material B is one or more of decahydronaphthalene, 1-methyldecahydronaphthalene and 2-methyldecahydronaphthalene; the hydrogen-donating reaction catalyst is a supported metal catalyst and comprises a catalyst carrier and a catalyst active metal component. The invention solves the problems that the prior art lacks a hydrogen supply technology based on organic liquid materials, and has the advantages of low raw material cost, large scale, low catalyst cost, large hydrogen supply amount, relatively mild reaction process conditions, high hydrogen supply purity and the like, and the two storage and supply states have low-temperature liquid properties at the same time.
Description
Technical Field
The invention relates to the technical field of hydrogen energy, in particular to a catalytic hydrogen supply system based on organic liquid and a hydrogen supply method thereof.
Background
With the gradual carbon neutralization strategy falling to the ground, hydrogen is more and more widely regarded as a clean energy carrier. Although the heat of mass combustion of hydrogen is the highest among all common fuels, the density of hydrogen at normal temperature and pressure is the lowest among all gases, and therefore, the direct delivery of hydrogen in the conventional method is very inefficient. Meanwhile, hydrogen is a dangerous chemical, has the characteristics of flammability and explosiveness, and particularly needs high caution for industrial personnel due to explosiveness. Therefore, how to safely store and supply hydrogen is an important technical problem in the hydrogen energy industry. The organic liquid hydrogen carrying technology is a technology which takes hydrogen-containing organic matters as hydrogen carriers, can be safely stored and transported when hydrogen is not needed, and can supply hydrogen through catalytic hydrogen discharge when hydrogen is needed. The system has the advantages of high volume and mass hydrogen supply amount and good compatibility of a raw material system and the conventional oil product transportation system, and is widely valued by scientific research personnel and industrial personnel. However, in the current technology for realizing hydrogen supply by using an organic liquid compound system, there are some scientific or technical problems to be overcome in material system selection and catalyst selection.
CN 111056531 a discloses a liquid phase dehydrogenation method based on heterocyclic cycloalkane hydrogen storage and supply material, which uses one or more of perhydro azoethylcarbazole, perhydro triazine, perhydro pyrrole, and perhydro carbazole as hydrogen supply raw material. The invention provides non-noble metal carbide as a catalyst, and is expected to reduce the cost of the catalyst compared with a noble metal catalyst. However, the hydrogen donor raw materials are all nitrogen-containing compounds, so that the raw materials are expensive and have unknown biotoxicity. And thirdly, the hydrogen supply raw material is often in a solid state at normal temperature after hydrogen supply, which is not beneficial to storage and transportation in the whole process. In addition, according to the evaluation of dehydrogenation, the conversion rate of the reaction after 10 hours of the reaction is not high generally, and is less than 80% in most cases.
CN 113501490A discloses a hydrogenated methylindole organic liquid hydrogen donor material, which adopts a mixture of two hydrogenated methylindoles, and the related materials have the advantages of being liquid at normal temperature and high in hydrogen release amount; however, the hydrogenated indole compounds of the substituent groups are high in price, difficult to obtain, difficult to apply on a large scale and unknown in biotoxicity.
CN 109701520 a discloses an organic liquid hydrogen supply method using a catalyst prepared by using graphene as a carrier. The organic liquid raw material adopts methylcyclohexane, decahydronaphthalene, perhydro azoethylcarbazole, perhydro carbazole and other common raw materials in research. The related catalyst system is complex, needs a noble metal combined with another unusual metal such as In, Cs, Ga and the like, and takes graphene as a catalyst carrier. The associated catalyst raw material selection necessarily makes the catalyst more costly. Meanwhile, the graphene carrier has poor mechanical properties, so that the requirement of long-time industrial application is difficult to meet, and the problem of storage safety needs attention.
Disclosure of Invention
In view of the above, the invention provides a catalytic hydrogen supply system based on organic liquid and a hydrogen supply method thereof, and the catalytic hydrogen supply system has the advantages of cheap materials, wide sources, low catalyst cost, mild reaction process conditions, low operation cost and equipment cost, large hydrogen supply amount and high purity of generated hydrogen.
The invention adopts the following technical scheme:
a catalytic hydrogen supply system based on organic liquid comprises an organic liquid hydrogen supply material and a hydrogen supply reaction catalyst, wherein the organic liquid hydrogen supply material consists of a hydrogen supply raw material A and a hydrogen supply raw material B, the hydrogen supply raw material A is one or two of dodecahydrobenzyltoluene and octadecahydrodibenzyltoluene, the mass content of the octadecahydrodibenzyltoluene is not more than 80%, the hydrogen supply raw material B is one or more of decahydronaphthalene, 1-methyldecahydronaphthalene and 2-methyldecahydronaphthalene, and the mass ratio of the hydrogen supply raw material A to the hydrogen supply raw material B is 0.5-10;
the hydrogen-donating reaction catalyst is a supported metal catalyst and comprises a catalyst carrier and a catalyst active metal component.
The hydrogen-donating reaction catalyst is porous particles, and the granularity of the hydrogen-donating reaction catalyst is 10-300 meshes.
The catalyst carrier is one or a mixture of several of porous alumina, porous silica, porous titanium dioxide, molecular sieve and pseudo-boehmite in any proportion, and the active metal component of the catalyst comprises a copper metal component and one or two of palladium or platinum metal components.
Calculated by metal mass, the loading of the active metal component of the catalyst accounts for 5.0-30.0% of the total mass of the hydrogen supply reaction catalyst, and the total loading of palladium and platinum accounts for 0.3-2.0% of the total mass of the hydrogen supply reaction catalyst.
The hydrogen-donating reaction catalyst is prepared by adopting the following method:
preparing a metal precursor of an active metal component into an aqueous solution, impregnating a porous catalyst carrier with the aqueous solution, drying the impregnated catalyst carrier, roasting the catalyst carrier in the air at the temperature of 200-600 ℃, reducing the catalyst carrier in hydrogen at the temperature of 200-500 ℃, and fixing the active metal component on the surface of the catalyst carrier in a reduced state to prepare the hydrogen-donating reaction catalyst.
The metal palladium precursor is one or a mixture of more than one of palladium acetate, palladium oxalate and palladium acetylacetonate;
the metal platinum precursor is one or a mixture of two of platinum acetylacetonate and platinum potassium oxalate;
the metallic copper precursor is one or a mixture of two of copper nitrate and copper sulfate.
The impregnation operation of the metallic copper precursor should precede the impregnation operation of the metallic palladium precursor and the metallic platinum precursor.
The specific surface area of the hydrogen supply reaction catalyst is 10-900 m2/g。
A hydrogen supply method of a catalytic hydrogen supply system based on organic liquid comprises the following steps: and taking the organic liquid hydrogen donor material as a raw material, and carrying out contact reaction on the raw material and the hydrogen donor catalyst through a reactor to generate hydrogen under the conditions of a reaction temperature of 150-290 ℃ and a pressure of 0.01-0.2 MPa. The reactor type may be one selected from a fixed bed or a tank reactor.
When the reactor is a fixed bed reactor, a hydrogen supply reaction catalyst is fixed in a bed layer of the fixed bed reactor, an organic liquid hydrogen supply material flows through the catalyst bed layer from an inlet of a reaction tube of the reactor to react to generate hydrogen, and a gas-liquid separation cooling tank is arranged at an outlet of the reaction tube to separate the hydrogen in a product from the residual organic liquid.
The mass space velocity indicates that the flow velocity of the organic liquid hydrogen supply material is 0.3-30 h-1。
When the reactor is a kettle type reactor, the organic liquid hydrogen supply material and the hydrogen supply reaction catalyst are mixed according to the mass ratio of (1-30): 1 mixing in a kettle type reactor, stirring and reacting through a stirrer to generate hydrogen, wherein a gas outlet is arranged above the kettle type reactor, and a gas-liquid separation cooling pipe is arranged at the outlet to cool and reflux high boiling point substances carried in the product hydrogen.
The stirring speed of the stirrer is 50-1200 rpm, and the reaction time is 1-30 h.
The technical scheme of the invention has the following advantages:
A. the organic liquid hydrogen donor material is prepared by mixing a hydrogen donor raw material A and a hydrogen donor raw material B, wherein the hydrogen donor raw material A has the following main functions: providing a hydrogen donor, and using the hydrogen donor as a main component of a hydrogen supply material system to ensure that the whole hydrogen supply material system is still in a normal-temperature (25 ℃) liquid state before reaction and on any reaction progress after a specified amount of hydrogen supply raw material B is added into the whole hydrogen supply material system, so that the material has good fluidity; the hydrogen donor raw material B has the main functions of: and providing a hydrogen donor, wherein the theoretical hydrogen supply amount of the hydrogen donor is larger than that of the hydrogen supply raw material A, so that the theoretical hydrogen supply amount of the whole hydrogen supply material system is further improved relative to that of the hydrogen supply raw material A. If the hydrogen donor raw material B is not added, the amount of hydrogen donation, i.e., the theoretical upper limit of hydrogen donation of the raw material A, is 6.19% at the maximum depending on the hydrogen donor raw material A alone. The improvement of the hydrogen supply amount has important significance for increasing the energy density of the system and further increasing the unit mass value of potential products.
B. The hydrogen supply reaction catalyst is designed according to the selected organic liquid hydrogen supply material in a matching way, and the selected catalyst has the main function of realizing that the hydrogen supply raw material A and the hydrogen supply raw material B can simultaneously realize catalytic dehydrogenation with high conversion rate, namely hydrogen supply reaction in the same reaction condition interval, thereby realizing high hydrogen supply quantity on the whole. The reaction product of the hydrogen donor raw material B has stronger aromaticity than that of the hydrogen donor raw material A, and is easier to adsorb on the surface of the catalytic metal active component, especially the surface of the noble metal component, so that the catalyst is inactivated. In principle, a relatively high temperature is generally required to achieve a higher catalytic conversion of the hydrogen donor feedstock B compared to the hydrogen donor feedstock a. Therefore, when the type and preparation method of the catalyst are selected, the hydrogen supply reaction temperature of the hydrogen supply raw material B is reduced as much as possible, and the key for realizing the high hydrogen supply of the whole hydrogen supply material system is realized. In principle, compared with noble metals, non-noble metals have weaker adsorption capacity on aromatic rings, but noble metal components have stronger catalytic dehydrogenation activity, and catalytic hydrogen supply activity at lower temperature can be obtained through fine adjustment of the proportion of the two metals and the preparation method, so that hydrogen can be supplied to the hydrogen supply raw material A and the hydrogen supply raw material B simultaneously in the same reaction condition interval, and higher hydrogen supply rate is realized. Meanwhile, the introduction of the non-noble metal component saves the use amount of noble metal and is beneficial to reducing the cost of the catalyst.
C. The invention solves the problems that the prior art lacks a hydrogen supply technology based on organic liquid materials, and has the advantages of low raw material cost, large-scale production, low catalyst cost, large hydrogen supply amount, mild reaction process conditions and high hydrogen supply purity, and the two storage and supply states have low-temperature liquid properties.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings which are needed to be used in the embodiments will be briefly described below, and it is apparent that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained from the drawings without inventive labor to those skilled in the art.
FIG. 1 is a schematic diagram of a fixed bed reactor apparatus used in the present invention;
FIG. 2 is a schematic view of a tank reactor apparatus used in the present invention.
The labels in the figure are as follows:
1-a fixed bed reactor body, 11-a reaction tube; 2-a kettle type reactor body and 21-a stirring paddle.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a catalytic hydrogen supply system based on organic liquid, which comprises an organic liquid hydrogen supply material and a hydrogen supply reaction catalyst, wherein the organic liquid hydrogen supply material consists of a hydrogen supply raw material A and a hydrogen supply raw material B, the hydrogen supply raw material A is one or two of dodecahydrobenzyltoluene and octadecahydrodibenzyltoluene, the mass content of the octadecahydrodibenzyltoluene is not more than 80%, the hydrogen supply raw material B is one or more of decahydronaphthalene, 1-methyldecahydronaphthalene and 2-methyldecahydronaphthalene, and the mass ratio of the hydrogen supply raw material A to the hydrogen supply raw material B is 0.5-10. The hydrogen-donating reaction catalyst is a porous granular supported metal catalyst with the granularity of 10-300 meshes and the specific surface area of 10-900 m2(ii) per gram, comprising a catalyst support and a catalytically active metal component. The catalyst carrier is one or a mixture of several of porous alumina, porous silica, porous titanium dioxide, molecular sieve and pseudo-boehmite in any proportion, and the active metal component of the catalyst comprises a copper metal component and one or two of palladium or platinum metal components. Calculated by metal mass, the loading capacity of the active metal component of the catalyst accounts for 5.0-30.0% of the total mass of the hydrogen supply reaction catalyst, and the total loading capacity of palladium and platinum accounts for 0.3-2.0% of the total mass of the hydrogen supply reaction catalyst.
The hydrogen donor raw material A in the organic liquid hydrogen donor material has the following main functions: and providing a hydrogen donor, and using the hydrogen donor as a main component of a hydrogen supply material system, so that the whole hydrogen supply material system can still be in a normal-temperature (25 ℃) liquid state before reaction and at any reaction progress after a specified amount of hydrogen supply raw material B is added into the whole hydrogen supply material system, the material has good fluidity, and the material viscosity at normal temperature is not more than 50mPa s. The liquid fluidity is always kept at normal temperature, which is of great significance for the convenience of storage, transportation and transportation.
The hydrogen donor raw material B has the main functions of: and providing a hydrogen donor, wherein the theoretical hydrogen supply amount of the hydrogen donor is larger than that of the hydrogen supply raw material A, so that the theoretical hydrogen supply amount of the whole hydrogen supply material system is further improved relative to that of the hydrogen supply raw material A. If the hydrogen donor raw material B is not added, the amount of hydrogen donation, i.e., the theoretical upper limit of hydrogen donation of the raw material A, is 6.19% at the maximum depending on the hydrogen donor raw material A alone. The improvement of the hydrogen supply amount has important significance for increasing the energy density of the system and further increasing the unit mass value of potential products.
Matching the targeted design of organic liquid hydrogen donor materials, catalysts also need to be targeted, i.e., how to provide accurate, reasonable catalysts for feed systems with hydrogen donor feedstocks a and B.
The catalyst selected by the invention has the main function of realizing that the hydrogen supply raw material A and the hydrogen supply raw material B can simultaneously realize catalytic dehydrogenation with high conversion rate, namely hydrogen supply reaction in the same reaction condition interval, thereby realizing high hydrogen supply quantity on the whole. The reaction product of the hydrogen donor raw material B has stronger aromaticity than that of the hydrogen donor raw material A, and is easier to adsorb on the surface of the catalytic metal active component, especially the surface of the noble metal component, so that the catalyst is inactivated. Thus, in principle, a relatively high temperature is generally required to achieve a higher catalytic conversion of the hydrogen donor raw material B than the hydrogen donor raw material a. Therefore, when the type and preparation method of the catalyst are selected, the hydrogen supply reaction temperature of the hydrogen supply raw material B is reduced as much as possible, and the key for realizing the high hydrogen supply of the whole hydrogen supply material system is realized. In principle, compared with noble metals, non-noble metals have weaker adsorption capacity on aromatic rings, but noble metal components have stronger catalytic dehydrogenation activity, and catalytic hydrogen supply activity at lower temperature can be obtained through fine adjustment of the proportion of the two metals and the preparation method, so that hydrogen can be supplied to the hydrogen supply raw material A and the hydrogen supply raw material B simultaneously in the same reaction condition interval, and higher hydrogen supply rate is realized. Meanwhile, the introduction of the non-noble metal component saves the use amount of noble metal and is beneficial to reducing the cost of the catalyst.
The hydrogen-donating reaction catalyst is prepared by the following method:
preparing a metal precursor of an active metal component into an aqueous solution, impregnating a porous catalyst carrier with the aqueous solution, drying the impregnated catalyst carrier, roasting the catalyst carrier in the air at the temperature of 200-600 ℃, reducing the catalyst carrier in hydrogen at the temperature of 200-500 ℃, and fixing the active metal component on the surface of the catalyst carrier in a reduction state to prepare the hydrogen-donating reaction catalyst. The metal palladium precursor is one or a mixture of more than one of palladium acetate, palladium oxalate and palladium acetylacetonate, the metal platinum precursor is one or a mixture of two of platinum acetylacetonate and potassium platinum oxalate, and the metal copper precursor is one or a mixture of copper nitrate and copper sulfate. The impregnation operation of the metallic copper precursor should precede the impregnation operation of the metallic palladium precursor and the metallic platinum precursor.
The invention also provides a hydrogen supply method of the catalytic hydrogen supply system based on the organic liquid, which comprises the following steps:
the organic liquid hydrogen donor material is used as a raw material, and the raw material and the hydrogen donor reaction catalyst are contacted and reacted through a reactor at the reaction temperature of 150-290 ℃ and the pressure of 0.01-0.2 MPa to generate hydrogen.
When the reactor is a fixed bed reactor, the hydrogen-supplying reaction catalyst is fixed in the bed layer of the fixed bed reactor, and the organic liquid hydrogen-supplying material flows through the catalyst bed layer from the inlet of the reaction tube of the reactor to react to generate hydrogen. The mass space velocity indicates that the flow velocity of the organic liquid hydrogen supply material is 0.3-30 h-1. And a gas-liquid separation cooling tank is arranged at the outlet of the reaction tube to separate the hydrogen in the product from the residual organic liquid. The reaction is carried out continuously, and is started and stopped according to actual requirements.
When the reactor is a kettle type reactor, the organic liquid hydrogen supply material and the hydrogen supply reaction catalyst are mixed according to the mass ratio of (1-30): 1 in a kettle type reactor, stirring and reacting through a stirrer to generate hydrogen, wherein the stirring speed of the stirrer is 50-1200 rpm, and the reaction time is 1-30 h. And a gas outlet is arranged above the kettle type reactor, and a gas-liquid separation cooling pipe is arranged at the outlet to cool and reflux the high boiling point substances carried in the product hydrogen.
Supplementary explanations for the above-mentioned catalytic hydrogen donor system and hydrogen donor method are as follows:
the supported metal catalyst is a catalyst door commonly used in laboratory research or industry, and is also a common term in the field of catalysis, and is mainly characterized in that the supported metal catalyst structurally comprises a catalyst carrier and a catalytic active metal component, wherein the catalyst carrier is used as a main mass contribution source of the catalyst, is generally a porous solid material, plays a role of supporting the catalytic active metal component, and can be granular, powdery or blocky in macro; the active metal component is a metal substance which is intentionally introduced in the preparation process and is fixed on the surface of the catalyst carrier and in the pore channel.
Precursors of certain catalytically active metal components, or simply metal precursors, refer to the metal source that needs to be prepared prior to catalyst preparation, in the form of a metal compound. In the preparation of the catalyst, the precursor of one active metal component can be a compound containing the metal element or a mixture of a plurality of compounds. When water is used as the solvent, the hydrate form of the metal compound is equivalent to the anhydrous compound form of the same metal molar amount. Since the nature of the precursor will ultimately affect the catalytic properties of the catalyst product, how to select the metal precursor is also a critical consideration in catalyst preparation. Different catalysts prepared from different types of metal precursors lead to significantly different catalytic reaction effects despite the same type and total content of metal in the final catalyst product.
The hydrogen-donating reaction catalyst in the invention is obtained by an impregnation method. The impregnation method is a catalyst preparation method commonly used in laboratory research or industry, and is mainly characterized in that a metal precursor is prepared into a solution, a porous catalyst carrier is impregnated by the solution, and then the impregnated carrier is subjected to certain post-treatment operation to fix an active metal component on the surface of the catalyst carrier in a reduction state. The concentration of the metal in the solution, as well as the mass ratio of the solution to the catalyst support, will determine the final metal content of the prepared catalyst. The post-treatment operations after impregnation usually comprise drying, roasting, hydrogen reduction and other links, but the following additional and non-unique operations are added, or a certain operation step is repeated more than once, and the preparation method of the used catalyst is not changed, which belongs to the property of the impregnation method of the invention. These additional, non-exclusive operations include, but are not limited to: air drying, oven drying, or electromagnetic radiation, heating, drying in a gas or gas stream, or reduction in other reducing gases, or water washing or solvent washing, or any other manipulation for the purpose of removing inactive metal elements from the precursor compound.
"specific surface area" is a term used in the field of solid catalysts, broadly speaking in the field of solid materials, and refers to the ratio of the surface area of a solid catalyst to its mass, usually in m2The unit is/g; the measurement method commonly used in the art is calculated by BET specific surface area measurement, and is obtained from the adsorption-desorption curve of the catalyst for nitrogen or argon at low temperature. The specific surface area in the present invention is a value obtained by a BET specific surface area test method.
Both the kettle reactor and the fixed bed reactor are reaction devices commonly used in the fields of energy, chemical industry and materials. The kettle reactor is characterized in that raw materials are added into a closed container at one time, and then certain temperature, pressure and stirring speed are controlled to enable substances in the container to generate chemical reaction; different choices of a primary kettle type and an intermittent kettle type can be adopted in actual production, and the two types of technologies belong to the same type; the fixed bed reactor features that solid catalyst is filled in a certain position inside the reaction tube to form a bed layer, and the reactant is pumped by a pump or pressure difference to enter the reaction tube, flow through the bed layer and flow out of the reaction tube.
The "mass space velocity" of a fluid refers to the ratio of the mass flow rate of the fluid to the mass of catalyst packed in the bed, and the invention employs h-1Expressed in units of mass of fluid per hour to mass of catalyst passing through the reaction tube。
Since hydrogen is a permanent gas at normal temperature, and the boiling point of the organic liquid hydrogen donor material is above 200 ℃ even if certain steam is generated before and after the reaction, hydrogen purification and organic matter steam recovery can be easily realized by a gas-liquid separation device such as reflux condensation.
The analysis and calculation method of the hydrogen supply rate in the invention is as follows:
when a fixed bed reactor is used, the hydrogen supply rate is equal to the mass flow rate of hydrogen gas/mass flow rate of fed organic liquid;
when a tank reactor is used, the total mass of hydrogen produced (which can be converted by the total volume flow) over a certain reaction period is collected and calculated according to the following formula: hydrogen supply rate is the mass of generated hydrogen/mass of organic liquid raw material before reaction;
the hydrogen purity is defined as: (1-volume content of all other permanent gases). times.100%.
The flow rate of the hydrogen can be measured by a flow meter corrected by the hydrogen flow with known hydrogen flow rate, the relation between the hydrogen flow rate and time is recorded, the total flow rate of the hydrogen in a given time can be obtained, and the hydrogen supply rate of the reaction system can be further obtained. The purity of hydrogen can be measured by gas chromatography, mass spectrometry, or the like. The measurement methods of hydrogen purity, hydrogen flow rate, liquid quality, liquid mass flow rate and the like are conventional analytical chemistry methods in the field and are well known to those skilled in the art, and the specific method does not belong to the protection scope of the invention.
Example 1
The embodiment provides a hydrogen supply method of a catalytic hydrogen supply system based on organic liquid, which comprises the following steps:
s1, selecting an organic liquid hydrogen donor material: the hydrogen supply raw material A is a mixture of octadecane hydrogen dibenzyl toluene and dodecane hydrogen benzyl toluene, wherein the mass ratio of the octadecane hydrogen dibenzyl toluene to the dodecane hydrogen benzyl toluene is 1:1, the hydrogen supply raw material B is 2-methyl decalin, and the mass ratio of the hydrogen supply raw material A to the hydrogen supply raw material B is 3: 1.
S2, selecting a supported hydrogen supply reaction catalyst:palladium copper catalyst supported on alumina, noted as Pd-Cu/Al2O3Wherein the mass content of Pd is 1.8 wt%, the mass content of Cu is 10.0 wt%, the granularity of the catalyst is 20-60 meshes, and the specific surface area of the catalyst is 182m2/g。
Hydrogen-donating reaction catalyst Pd-Cu/Al2O3The preparation method comprises the following steps:
first, Cu (NO)3)3Loading the copper component to Al for the copper component precursor2O3On a carrier. Drying of Al according to unit mass2O3Water absorption of the Carrier Cu (NO) was formulated at the target concentration3)3The aqueous solution is then impregnated (impregnated for 12h), dried (dried in an oven at 110 ℃ for 4h) and reduced by hydrogen (reduced at 500 ℃ for 4h in hydrogen flow) to obtain the alumina supported copper catalyst which is recorded as Cu/Al2O3；
Then taking palladium oxalate as a palladium precursor, and loading a palladium component to Cu/Al2O3On a carrier. Drying of Al according to unit mass2O3Preparing palladium oxalate aqueous solution with target concentration for water absorption of the carrier, and then obtaining the alumina supported palladium-copper catalyst which is recorded as Pd-Cu/Al by dipping (dipping for 12h), drying (drying for 4h in a 110 ℃ oven), air roasting (roasting for 4h at 250 ℃ in air) and hydrogen reduction (reducing for 4h at 200 ℃ in hydrogen flow)2O3. The elemental content and the physicochemical properties of the catalyst can be obtained by means of characterization conventionally carried out in the field.
S3, using the organic liquid hydrogen supply material and the hydrogen supply reaction catalyst described in S1 and S2, and realizing hydrogen supply reaction through a fixed bed reactor, as shown in FIG. 1, wherein the reaction temperature (namely the catalyst bed temperature) is 285 ℃, the pressure of a reaction system is 0.10MPa, 2.0g of the hydrogen supply reaction catalyst is fixed in the reactor bed, and the organic liquid hydrogen supply material flows through the catalyst bed from the inlet of a reaction tube; wherein the space velocity of the organic liquid is 1.0h-1And (3) setting a gas-liquid separation cooling tank at the outlet of the reaction tube at the flow rate to separate the hydrogen in the product from the residual organic liquid. When all parameters reach the set value or the set range, the reaction is continuously carried out.
Through detection, the hydrogen supply rate obtained by the hydrogen supply method is 6.23%, and the purity of the hydrogen is more than 99.9%.
Example 2
A hydrogen supply method of a catalytic hydrogen supply system based on organic liquid comprises the following steps:
s1, selecting an organic liquid hydrogen supply material: the hydrogen supply raw material A is a mixture of octadecane hydrogen dibenzyl toluene and dodecane hydrogen benzyl toluene, wherein the mass ratio of the octadecane hydrogen dibenzyl toluene to the dodecane hydrogen benzyl toluene is 4:1, the hydrogen supply raw material B is 2-methyl decalin, and the mass ratio of the hydrogen supply raw material A to the hydrogen supply raw material B is 0.5: 1.
S2, selecting a supported hydrogen supply reaction catalyst Pt-Cu/Al2O3-SiO2Wherein the mass content of Pt is 2 wt%, the mass content of Cu is 28 wt%, the granularity of the catalyst is 10-100 meshes, and the specific surface area of the catalyst is 10m2/g。
Catalyst Pt-Cu/Al for hydrogen supply reaction2O3-SiO2The preparation method comprises the following steps:
first, Cu (NO)3)3Loading the copper component to Al as a precursor of the copper component2O3With SiO2On a mixed carrier, wherein Al2O3With SiO2The mass ratio of the carrier is 1: 1. Preparing Cu (NO) with target concentration according to water absorption rate of dry mixed carrier per unit mass3)3The aqueous solution is soaked for 12 hours, dried for 4 hours in a 110 ℃ oven and reduced by hydrogen (reduced for 6 hours at 500 ℃ in hydrogen flow) to obtain Al2O3-SiO2Supported copper catalyst, noted Cu/Al2O3-SiO2；
Then taking potassium platinum oxalate as a platinum precursor, and loading a platinum component to Cu/Al2O3-SiO2On a carrier. Preparing a platinum potassium oxalate aqueous solution with a target concentration according to the water absorption of the dry mixed carrier per unit mass, and then performing impregnation (impregnation for 12 hours), drying (drying for 4 hours in a 110 ℃ oven), air roasting (roasting for 4 hours at 600 ℃ in air), washing with a large amount of deionized water, and drying again (drying for 4 hours in a 110 ℃ oven) to obtain the platinum potassium oxalate aqueous solutionAnd hydrogen reduction (reduction at 200 ℃ for 4h in hydrogen flow) to obtain the mixed carrier loaded platinum-copper catalyst which is marked as Pt-Cu/Al2O3-SiO2. The elemental content and the physicochemical properties of the catalyst can be obtained by means of characterization conventionally carried out in the field.
S3, using the organic liquid hydrogen supply material and the hydrogen supply reaction catalyst described in S1 and S2, realizing hydrogen supply reaction through a fixed bed reactor, wherein the reaction temperature is 150 ℃, the pressure of a reaction system is 0.2MPa, fixing 2.0g of the hydrogen supply reaction catalyst in a reactor bed layer, and allowing the organic liquid hydrogen supply material to flow through the catalyst bed layer from the inlet of a reaction tube; wherein the space velocity of the organic liquid is 30h-1And (3) setting a gas-liquid separation cooling tank from the outlet of the reaction tube at the flow rate to separate the hydrogen in the product from the residual organic liquid. When all parameters reach the set value or the set range, the reaction is continuously carried out.
Through detection, the hydrogen supply rate obtained by the hydrogen supply method is 6.22%, and the purity of the hydrogen is more than 99.9%.
Example 3
The embodiment provides a hydrogen supply method of a catalytic hydrogen supply system based on organic liquid, which comprises the following steps:
s1, selecting an organic liquid hydrogen donor material: the hydrogen supply raw material A is a mixture of octadecane hydrogen dibenzyl toluene and dodecane hydrogen benzyl toluene, wherein the mass ratio of the octadecane hydrogen dibenzyl toluene to the dodecane hydrogen benzyl toluene is 1:2, the hydrogen supply raw material B is 1-methyl decalin, and the mass ratio of the hydrogen supply raw material A to the hydrogen supply raw material B is 1.9: 1.
S2, selecting a supported hydrogen supply reaction catalyst Pt-Cu/Al2O3Wherein the mass content of Pt is 0.9 wt%, the mass content of Cu is 8.0 wt%, the granularity of the catalyst is 200-240 meshes, and the specific surface area of the catalyst is 190m2/g。
Catalyst Pt-Cu/Al for hydrogen supply reaction2O3The preparation method comprises the following steps:
first, Cu (NO)3)3Loading the copper component to Al as a precursor of the copper component2O3On a carrier. Drying of Al according to unit mass2O3Water absorption of the Carrier Cu (NO) was formulated at the target concentration3)3The aqueous solution is then impregnated (impregnated for 12h), dried (dried in an oven at 110 ℃ for 4h) and reduced by hydrogen (reduced at 450 ℃ in hydrogen flow for 6h) to obtain the aluminum oxide supported copper catalyst which is recorded as Cu/Al2O3；
Then taking potassium platinum oxalate as a platinum precursor, and loading a platinum component to Cu/Al2O3On a carrier. Drying of Al according to unit mass2O3Preparing a platinum potassium oxalate aqueous solution with a target concentration according to the water absorption rate of the carrier, and then carrying out impregnation (impregnation for 12h), drying (drying for 4h in a 110 ℃ oven), air roasting (roasting for 4h at 250 ℃ in air), washing with a large amount of deionized water, drying again (drying for 4h in the 110 ℃ oven) and hydrogen reduction (reduction for 4h at 200 ℃ in hydrogen flow) on the obtained product to obtain the alumina-supported platinum copper catalyst which is marked as Pt-Cu/Al2O3. The elemental content and the physicochemical properties of the catalyst can be obtained by means of characterization conventionally carried out in the field.
S3, and using the organic liquid hydrogen donor material and the hydrogen donor reaction catalyst described in S1 and S2, carrying out a hydrogen donor reaction through a tank reactor, as shown in FIG. 2, wherein the reaction temperature is 290 ℃; the pressure of a reaction system is 0.11MPa, the reaction time is 8h, the dosage of a hydrogen supply reaction catalyst is 1.0g, the dosage of an organic liquid hydrogen supply material is 10g, the stirring speed is 400 r/min, a gas-liquid separation cooling pipe is arranged at an outlet, and high boiling point substances carried in the product hydrogen are cooled and refluxed.
The hydrogen flow is measured by a mass flow meter, and the hydrogen purity is analyzed by combining chromatography, so that the hydrogen supply rate obtained by using the hydrogen supply method is 6.31 percent, and the hydrogen purity is more than 99.9 percent.
Example 4
A hydrogen supply method of a catalytic hydrogen supply system based on organic liquid comprises the following steps:
s1, selecting an organic liquid hydrogen donor material: the hydrogen supply raw material A is a mixture of octadecane hydrogen dibenzyl toluene and dodecane hydrogen benzyl toluene, wherein the mass ratio of the octadecane hydrogen dibenzyl toluene to the dodecane hydrogen benzyl toluene is 1:3, the hydrogen supply raw material B is 1-methyl decalin, and the mass ratio of the hydrogen supply raw material A to the hydrogen supply raw material B is 0.8: 1.
S2, selecting a supported hydrogen supply reaction catalyst Pt-Cu/Al2O3-SiO2Wherein the mass content of Pt is 1.0 wt%, the mass content of Cu is 10.0 wt%, the granularity of the catalyst is 200-300 meshes, and the specific surface area of the catalyst is 277m2/g。
Catalyst Pt-Cu/Al for hydrogen supply reaction2O3-SiO2The preparation method comprises the following steps:
first, Cu (NO)3)3Loading the copper component to Al as a precursor of the copper component2O3With SiO2On a mixed carrier, wherein Al2O3With SiO2The mass ratio of the carrier is 1: 1. Preparing Cu (NO) with target concentration according to water absorption rate of dry mixed carrier per unit mass3)3The aqueous solution is soaked for 12 hours, dried for 4 hours in a 110 ℃ oven and reduced by hydrogen (reduced for 6 hours at 450 ℃ in hydrogen flow) to obtain Al2O3-SiO2Supported copper catalyst, noted Cu/Al2O3-SiO2；
Then taking potassium platinum oxalate as a platinum precursor, and loading a platinum component to Cu/Al2O3-SiO2On a carrier. Preparing a platinum potassium oxalate aqueous solution with a target concentration according to the water absorption of a dry mixed carrier with unit mass, and then obtaining a platinum copper catalyst loaded on the mixed carrier through impregnation (impregnation for 12 hours), drying (drying for 4 hours in a 110 ℃ oven), air roasting (roasting for 4 hours at 250 ℃ in air), washing with a large amount of deionized water, drying again (drying for 4 hours in the 110 ℃ oven) and hydrogen reduction (reducing for 4 hours at 200 ℃ in hydrogen flow), wherein the platinum copper catalyst is recorded as Pt-Cu/Al2O3-SiO2. The elemental content and the physicochemical properties of the catalyst can be obtained by means of characterization conventionally carried out in the field.
S3, using the organic liquid hydrogen donor materials and the hydrogen donor reaction catalyst described in S1 and S2 to realize hydrogen donor reaction through a tank reactor, as shown in figure 2, wherein the reaction temperature is 150 ℃; the pressure of a reaction system is 0.2MPa, the reaction time is 8h, the dosage of a hydrogen supply reaction catalyst is 2g, the dosage of an organic liquid hydrogen supply material is 10g, the stirring speed is 1200 r/min, a gas-liquid separation cooling pipe is arranged at an outlet, and high boiling point substances carried in the product hydrogen are cooled and refluxed.
The hydrogen flow is measured by a mass flow meter, and the hydrogen purity is analyzed by combining chromatography, so that the hydrogen supply rate obtained by using the hydrogen supply method is 6.39%, and the hydrogen purity is more than 99.9%.
Example 5
A hydrogen supply method of a catalytic hydrogen supply system based on organic liquid comprises the following steps:
s1, selecting an organic liquid hydrogen donor material: the hydrogen supply raw material A is a mixture of octadecane hydrogen dibenzyl toluene and dodecane hydrogen benzyl toluene, wherein the mass ratio of the octadecane hydrogen dibenzyl toluene to the dodecane hydrogen benzyl toluene is 1:3, the hydrogen supply raw material B is decahydro naphthalene, and the mass ratio of the hydrogen supply raw material A to the hydrogen supply raw material B is 10: 1.
S2, selecting a supported hydrogen supply reaction catalyst Pt-Cu/Al2O3-SiO2Wherein the mass content of Pt is 0.3 wt%, the mass content of Cu is 4.7 wt%, the granularity of the catalyst is 200-300 meshes, and the specific surface area of the catalyst is 900m2/g。
Catalyst Pt-Cu/Al for hydrogen supply reaction2O3-SiO2The preparation method comprises the following steps:
first, Cu (NO)3)3Loading the copper component to Al as a precursor of the copper component2O3With SiO2On a mixed carrier, wherein Al2O3With SiO2The mass ratio of the carrier is 1: 1. Preparing Cu (NO) with target concentration according to water absorption rate of dry mixed carrier per unit mass3)3The aqueous solution is soaked for 12 hours, dried for 4 hours in a 110 ℃ oven and reduced by hydrogen (reduced for 6 hours at 500 ℃ in hydrogen flow) to obtain Al2O3-SiO2Supported copper catalyst, noted Cu/Al2O3-SiO2；
Then taking potassium platinum oxalate as a platinum precursor, and loading a platinum component to Cu/Al2O3-SiO2On a carrier. Water absorption by dry mixing of carriers per unit massPreparing a platinum potassium oxalate aqueous solution with a target concentration, and then obtaining a platinum copper catalyst loaded by a mixed carrier through impregnation (impregnation for 12 hours), drying (drying for 4 hours in a 110 ℃ oven), air roasting (roasting for 4 hours at 600 ℃ in air), washing with a large amount of deionized water, drying again (drying for 4 hours in a 110 ℃ oven) and hydrogen reduction (reduction for 4 hours at 200 ℃ in hydrogen flow), wherein the platinum copper catalyst is marked as Pt-Cu/Al2O3-SiO2. The elemental content and the physicochemical properties of the catalyst can be obtained by means of characterization conventionally carried out in the field.
S3, using the organic liquid hydrogen donor materials and the hydrogen donor reaction catalyst described in S1 and S2 to realize hydrogen donor reaction through a tank reactor, as shown in figure 2, wherein the reaction temperature is 150 ℃; the pressure of a reaction system is 0.01MPa, the reaction time is 30h, the dosage of a hydrogen supply reaction catalyst is 1g, the dosage of an organic liquid hydrogen supply material is 30g, the stirring speed is 50 r/min, a gas-liquid separation cooling pipe is arranged at an outlet, and high boiling point substances carried in the product hydrogen are cooled and refluxed.
The hydrogen flow is measured by a mass flow meter, and the hydrogen purity is analyzed by combining chromatography, so that the hydrogen supply rate obtained by using the hydrogen supply method is 6.25%, and the hydrogen purity is more than 99.9%.
In order to compare the application effects of the invention, the following seven comparative experiments were performed, respectively.
Comparative example 1
To demonstrate the advantages of the organic liquid hydrogen donor material selected in the present invention, this example is a comparative example to example 1, differing from example 1 in that: in step S1, methyl-cyclohexane of the same mass was used instead of 2-methyldecalin. The rest is the same as in example 1. By detection, the hydrogen donor rate was found to be 4.1%, which is much lower than that of example 1. This result indicates the importance of the organic liquid phase feed system selection.
Comparative example 2
This experiment was carried out in order to verify the advantages of the selected catalyst over the ordinary catalyst in the hydrogen donating process. This example is a comparative example to example 1, differing from example 1 in that: in step S2, conventional Ni/Al is used2O3Catalyst for replacing Pd-Cu/Al2O3WhereinThe Ni loading was 11 wt%. By detection, the hydrogen supply rate was found to be 1.72%, which is also much lower than that of example 1. This result indicates the importance of catalyst selection.
Comparative example 3
To further reveal the uniqueness of the catalysts used according to the invention and their importance for the organic liquid hydrogen donor material used, this comparative example was further compared on the basis of example 1.
This example is a comparative example to example 1, differing from example 1 in that:
in step S2, when the supported catalyst is prepared by the impregnation method, palladium chloride is used as a precursor of the palladium component instead of palladium oxalate used in example 1, and other links are unchanged. By detection, the hydrogen supply rate was found to be 4.84%, which is also much lower than that of example 1. The results show that the hydrogen supply performance of the hydrogen supply system can be obviously influenced by the selection of metal precursor components, and the selection of the precursor for preparing the catalyst is very important.
Comparative example 4
To further reveal the uniqueness of the catalysts used according to the invention and their importance for the organic liquid hydrogen donor material used, this comparative example was further compared on the basis of example 1.
This example is a comparative example to example 1, differing from example 1 in that:
in step S2, when the supported catalyst is prepared by the impregnation method, precursors of copper and palladium are simultaneously dissolved in the same solution, and then impregnation (impregnation for 12 hours), drying (drying in an oven at 110 ℃ for 4 hours), air calcination (calcination at 250 ℃ in air for 4 hours), and hydrogen reduction (reduction at 200 ℃ in hydrogen flow for 4 hours) are performed to obtain the alumina supported palladium copper catalyst under the process. By detection, the hydrogen donor rate was found to be 5.30%, which is also much lower than that of example 1. The results indicate that the order of impregnation of the metal components significantly affects the hydrogen donating performance of the hydrogen donating system.
Comparative example 5
This example is a comparative example to example 3, differing from example 3 in that: in step S2, Ni/Al is used2O3Instead of Pt-Cu/Al2O3The Ni loading was 11 wt%. By detecting, obtainThe hydrogen supply rate was 1.46%, which is much lower than that of example 3. The results show that catalyst selection is also of significant importance in the tank reactor route.
Comparative example 6
This example is a comparative example to example 3, differing from example 3 in that: in step S2, Pt-Cu/Al similar to that of example 3 was still used2O3A catalyst, except that chloroplatinic acid was used as a platinum precursor instead of potassium platinate oxalate in the preparation of the catalyst. By detection, the hydrogen supply rate was found to be 3.55%, which is much lower than that of example 3. The results show that the catalyst preparation method, especially the choice of the precursor type, is also of significant importance for the catalytic hydrogen donating performance.
Comparative example 7
This example is a comparative example to example 3, differing from example 3 in that: in step S2, Pt-Cu/Al similar to example 3 was still used2O3The catalyst is distinguished in that, in the preparation of the catalyst, impregnation and aftertreatment of the platinum component are carried out first and then impregnation and aftertreatment of the copper component are carried out, the treatment method being described in example 3. By detection, the hydrogen supply rate was found to be 2.21%, which is much lower than that of example 3. The result shows that the impregnation sequence of the active components of the prepared supported platinum-copper catalyst has obvious influence on the catalytic hydrogen supply performance in the preparation process.
The invention solves the problems that the prior art lacks a hydrogen supply technology based on organic liquid materials, and has the advantages of low raw material cost, large-scale production, low catalyst cost, large hydrogen supply amount, mild reaction process conditions and high hydrogen supply purity, and the two storage and supply states have low-temperature liquid properties.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are intended to be within the scope of the invention.
Claims (13)
1. A catalytic hydrogen supply system based on organic liquid is characterized by comprising an organic liquid hydrogen supply material and a hydrogen supply reaction catalyst; the organic liquid hydrogen donor material consists of a hydrogen donor raw material A and a hydrogen donor raw material B, wherein the hydrogen donor raw material A is one or two of dodecahydrobenzyl toluene and octadecahydrodibenzyl toluene, and the mass content of the octadecahydrodibenzyl toluene is not more than 80%; the hydrogen donor material B is one or more of decahydronaphthalene, 1-methyl decahydronaphthalene and 2-methyl decahydronaphthalene; the mass ratio of the hydrogen donor raw material A to the hydrogen donor raw material B is 0.5-10;
the hydrogen-donating reaction catalyst is a supported metal catalyst and comprises a catalyst carrier and a catalyst active metal component.
2. The catalytic hydrogen donor system based on organic liquid as claimed in claim 1, wherein the hydrogen donor catalyst is porous particles with a particle size of 10-300 mesh.
3. The catalytic hydrogen donor system based on organic liquid as claimed in claim 2, wherein the catalyst carrier is one or a mixture of several of porous alumina, porous silica, porous titania, molecular sieve and pseudo-boehmite in any proportion, and the catalyst active metal component comprises a copper metal component and one or two of palladium or platinum metal components.
4. The catalytic hydrogen donor system based on organic liquid according to claim 3, wherein the loading of the catalyst active metal component is 5.0-30.0% of the total mass of the hydrogen donor catalyst, and the total loading of the two metals of palladium and platinum is 0.3-2.0% of the total mass of the hydrogen donor catalyst.
5. The catalytic hydrogen donor system based on organic liquid according to claim 4, wherein the hydrogen donor reaction catalyst is prepared by the following method:
preparing a metal precursor of an active metal component into an aqueous solution, impregnating a porous catalyst carrier with the aqueous solution, drying the impregnated catalyst carrier, roasting the catalyst carrier in the air at the temperature of 200-600 ℃, reducing the catalyst carrier in hydrogen at the temperature of 200-500 ℃, and fixing the active metal component on the surface of the catalyst carrier in a reduced state to prepare the hydrogen-donating reaction catalyst.
6. A catalytic hydrogen donor system based on organic liquid according to claim 5, characterized in that,
the metal palladium precursor is one or a mixture of more than one of palladium acetate, palladium oxalate and palladium acetylacetonate;
the metal platinum precursor is one or a mixture of two of platinum acetylacetonate and platinum potassium oxalate;
the metallic copper precursor is one or a mixture of two of copper nitrate and copper sulfate.
7. A catalytic hydrogen donor system based on organic liquid according to claim 6, characterized in that the impregnation of the metallic copper precursor is preceded by an impregnation of the metallic palladium precursor and the metallic platinum precursor.
8. The catalytic hydrogen supply system based on organic liquid as claimed in claim 1, wherein the specific surface area of the hydrogen supply reaction catalyst is 10-900 m2/g。
9. A hydrogen supply method of a catalytic hydrogen supply system based on organic liquid is characterized by comprising the following steps: the organic liquid hydrogen donor material of claim 1 is used as a raw material, and the raw material is contacted with the hydrogen donor catalyst of any one of claims 1 to 8 through a reactor to react at a reaction temperature of 150 to 290 ℃ and a pressure of 0.01 to 0.2MPa to generate hydrogen.
10. The method for supplying hydrogen according to claim 9, wherein the reactor is a fixed bed reactor, the hydrogen supply reaction catalyst is fixed in the bed layer of the fixed bed reactor, the organic liquid hydrogen supply material flows through the catalyst bed layer from the inlet of the reaction tube of the reactor to react to generate hydrogen, and a gas-liquid separation cooling tank is arranged at the outlet of the reaction tube to separate the hydrogen in the product from the residual organic liquid.
11. The hydrogen supply method according to claim 10, wherein the flow rate of the organic liquid hydrogen supply material is 0.3 to 30 hours in terms of mass space velocity-1。
12. The hydrogen supply method according to claim 9, wherein the reactor is a kettle-type reactor, and the organic liquid hydrogen supply material and the hydrogen supply reaction catalyst are mixed according to the mass ratio of (1-30): 1 mixing in a kettle type reactor, stirring and reacting through a stirrer to generate hydrogen, wherein a gas outlet is arranged above the kettle type reactor, and a gas-liquid separation cooling pipe is arranged at the outlet to cool and reflux high boiling point substances carried in the product hydrogen.
13. The method for supplying hydrogen according to claim 12, wherein the stirring speed of the stirrer is 50 to 1200 rpm, and the reaction time is 1 to 30 hours.
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