CN114436208B - 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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- 239000001257 hydrogen Substances 0.000 title claims abstract description 364
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 364
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 360
- 239000007788 liquid Substances 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 137
- 239000002994 raw material Substances 0.000 claims abstract description 90
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- 229910052751 metal Inorganic materials 0.000 claims abstract description 68
- 239000002184 metal Substances 0.000 claims abstract description 67
- 239000000463 material Substances 0.000 claims abstract description 64
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 50
- -1 octadecyldibenzyl toluene Chemical compound 0.000 claims abstract description 18
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 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
- 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 6
- 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 abstract description 5
- 239000010949 copper Substances 0.000 claims description 44
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 31
- 239000002243 precursor Substances 0.000 claims description 31
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- 229910052802 copper Inorganic materials 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 238000005470 impregnation Methods 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 12
- 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 11
- 238000001816 cooling Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 9
- 239000012696 Pd precursors Substances 0.000 claims description 8
- 239000012691 Cu precursor Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 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
- 150000002739 metals Chemical class 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 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
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 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
- 239000000377 silicon dioxide 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
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- QKAJDYOYIFCNGL-UHFFFAOYSA-N 1-phenyltetradecan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(CCCCCCCCCCCC)CC1=CC=CC=C1 QKAJDYOYIFCNGL-UHFFFAOYSA-N 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 5
- 239000011344 liquid material Substances 0.000 abstract description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 33
- 229910004298 SiO 2 Inorganic materials 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 21
- 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 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 239000000852 hydrogen donor Substances 0.000 description 9
- WBLJAACUUGHPMU-UHFFFAOYSA-N copper platinum Chemical compound [Cu].[Pt] WBLJAACUUGHPMU-UHFFFAOYSA-N 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 8
- 238000006356 dehydrogenation reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910002668 Pd-Cu Inorganic materials 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 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
- 229910000838 Al alloy Inorganic materials 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007791 liquid phase Substances 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
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical compound C1CNNNC1 OYWRDHBGMCXGFY-UHFFFAOYSA-N 0.000 description 1
- KVSWZGISCXEZGZ-UHFFFAOYSA-N C(C)C1=CC=CC=2C3=CC=CC=C3NC12.[N] Chemical compound C(C)C1=CC=CC=2C3=CC=CC=C3NC12.[N] KVSWZGISCXEZGZ-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
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 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
- 238000007796 conventional method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 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
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
-
- 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 & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
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, wherein the hydrogen supply raw material A is one or two of dodecylbenzyl toluene and octadecyldibenzyl toluene, the mass content of the octadecyldibenzyl toluene is not more than 80 percent, and the hydrogen supply raw material B is one or more of decalin, 1-methyl decalin and 2-methyl decalin; the hydrogen supply 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, has lower raw material cost, can realize large-scale storage and supply, has low-temperature liquid property at the same time, has low catalyst cost, larger hydrogen supply amount, relatively mild reaction process conditions, high hydrogen supply purity and the like.
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 landing of carbon neutralization strategies, hydrogen is gaining more and more attention as a clean energy carrier. While the mass heat of combustion of hydrogen is highest in all common fuels, the density of hydrogen at normal temperature and pressure is lowest in all gases, and therefore, the efficiency of directly transporting hydrogen in conventional methods is very low. Hydrogen is also a dangerous chemical, has the characteristic of inflammability and explosiveness, and particularly has the characteristic that the explosiveness requires high cautions of industry personnel. 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 release when the hydrogen is needed. The hydrogen-rich oil product has the advantages of higher volume and mass hydrogen supply and good compatibility of a raw material system and the existing oil product transportation system, and is widely paid attention to scientific researchers and industrial personnel. However, there are still some scientific or technical problems to be overcome in the selection of material systems and in the selection of catalysts in the current technology for realizing hydrogen supply by using organic liquid compound systems.
CN 111056531A discloses a liquid phase dehydrogenation method based on heterocyclic cycloalkane hydrogen storage and supply materials, which uses one or more of perhydro nitrogen ethyl carbazole, perhydro triazine, perhydro pyrrole and perhydro carbazole as hydrogen supply raw materials. The invention provides non-noble metal carbide as a catalyst, and is expected to reduce the cost of the catalyst relative to noble metal catalysts. However, the above hydrogen-supplying materials are all nitrogen-containing compounds, and the materials are expensive and have unknown biotoxicity. And the hydrogen supply raw material is always in a solid state at normal temperature after hydrogen is supplied, so that the storage and transportation of the whole process are not facilitated. In addition, according to the dehydrogenation evaluation, the reaction conversion rate after 10 hours of reaction is generally not high, and is mostly lower than 80%.
CN 113501490A discloses a hydrogenated methylindole organic liquid hydrogen-supplying material, which adopts a mixture of two types of hydrogenated methylindole, and the related material has the advantages of liquid at normal temperature and higher hydrogen release amount; however, the substituent hydroindoles are expensive, difficult to obtain, difficult to use on a large scale, and have unknown biotoxicity.
CN 109701520A discloses a method for supplying hydrogen from an organic liquid using a catalyst prepared by using graphene as a carrier. The organic liquid raw materials adopt common raw materials in researches such as methylcyclohexane, decalin, perhydroazoethylcarbazole, perhydrocarbazole and the like. The related catalyst system is complex, noble metal is combined with another unusual metal such as In, cs, ga and the like, and graphene is used as a catalyst carrier. The relevant catalyst raw material selection necessarily makes the catalyst costly. Meanwhile, the graphene carrier is poor in mechanical property, the requirement of long-time industrial application is difficult to meet, and the problem of storage safety of the graphene carrier also needs to be concerned.
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, which have the advantages of low material cost, 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:
the catalytic hydrogen supply system based on the 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 dodecylbenzene and octadecyldibenzyl toluene, the mass content of the octadecyldibenzyl toluene is not more than 80%, the hydrogen supply raw material B is one or more of decalin, 1-methyl decalin and 2-methyl decalin, and the mass ratio of the hydrogen supply raw material A to the hydrogen supply raw material B is 0.5-10;
the hydrogen supply reaction catalyst is a supported metal catalyst and comprises a catalyst carrier and a catalyst active metal component.
The hydrogen supply reaction catalyst is porous particles, and the granularity of the porous particles is 10-300 meshes.
The catalyst carrier is one or a mixture of a plurality of porous alumina, porous silica, porous titanium dioxide, molecular sieve and pseudo-boehmite in any proportion, and the catalyst active metal component comprises copper metal component and one or two of palladium or platinum metal components.
Calculated by the mass of metal, the loading of the active metal component of the catalyst accounts for 5.0-30.0% of the mass of the whole hydrogen supply reaction catalyst, and the total loading of two metals of palladium and platinum accounts for 0.3-2.0% of the mass of the whole hydrogen supply reaction catalyst.
The hydrogen supply 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 air at 200-600 ℃ successively, reducing the catalyst carrier in hydrogen at 200-500 ℃, and fixing the active metal component on the surface of the catalyst carrier in a reduced state form to prepare the hydrogen supply reaction catalyst.
The metal palladium precursor is one or more of palladium acetate, palladium oxalate and palladium acetylacetonate;
the metal platinum precursor is one or two of platinum acetylacetonate and potassium platinum oxalate;
the metal copper precursor is one or two of copper nitrate and copper sulfate.
The metallic copper precursor impregnation operation should precede the metallic palladium precursor and metallic platinum precursor impregnation operation.
The specific surface area of the hydrogen supply reaction catalyst is 10-900 m 2 /g。
A catalytic hydrogen supply system hydrogen supply method based on an organic liquid, comprising the steps of: the organic liquid hydrogen supply material is used as a raw material, and the raw material is contacted and reacted with the hydrogen supply reaction catalyst through a reactor to generate hydrogen under the conditions of the reaction temperature of 150-290 ℃ and the pressure of 0.01-0.2 MPa. The reactor type may be selected from one of a fixed bed or a tank reactor.
When the reactor is a fixed bed reactor, a hydrogen supply reaction catalyst is fixed in a fixed bed reactor bed, an organic liquid hydrogen supply material flows through the catalyst bed from the inlet of a 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.
The flow rate of the organic liquid hydrogen supply material is 0.3 to 30h expressed by the mass airspeed -1 。
When the reactor is a kettle reactor, the organic liquid hydrogen supply material and the hydrogen supply reaction catalyst are mixed according to the mass ratio (1-30): and 1, mixing in a kettle-type reactor, stirring and reacting by 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 entrained in the hydrogen product.
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 supply material is formed by mixing a hydrogen supply raw material A and a hydrogen supply raw material B, wherein the hydrogen supply raw material A has the main functions of: the hydrogen donor is provided and is used as a main component of a hydrogen supply material system, so that after a specified amount of hydrogen supply raw material B is added into the whole hydrogen supply material system, the whole hydrogen supply material system can still be in a normal-temperature (25 ℃) liquid state before reaction and on any reaction progress, and the material has good fluidity; the main functions of the hydrogen supply raw material B are as follows: the hydrogen donor is provided with a theoretical hydrogen supply amount which 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-supplying raw material B is not added, the maximum available hydrogen amount is 6.19% of the theoretical upper hydrogen-supplying limit of the raw material A by only the hydrogen-supplying raw material A. 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 in a matching way aiming at the selected organic liquid hydrogen supply material, and the main function of the catalyst is that the hydrogen supply raw material A and the hydrogen supply raw material B are in the same reaction condition interval, and the catalytic dehydrogenation with high conversion rate, namely the hydrogen supply reaction, can be realized at the same time, so that the overall high hydrogen supply quantity is realized. Since the reaction product of the hydrogen supply raw material B has stronger aromaticity than the reaction product of the hydrogen supply raw material a, it is more easily adsorbed on the surface of the catalytic metal active component, especially on the surface of the noble metal component, resulting in deactivation of the catalyst. In principle, a relatively high temperature is generally required to achieve a higher catalytic conversion of hydrogen feed B than hydrogen feed a. Therefore, when the type of the catalyst and the preparation method are selected, the hydrogen supply reaction temperature of the hydrogen supply raw material B is reduced as much as possible, and the key of realizing the high hydrogen supply amount of the whole hydrogen supply material system is realized. In principle, compared with noble metals, the non-noble metals have weaker adsorption capacity on aromatic rings, but at the same time, noble metal components have stronger catalytic dehydrogenation activity, and the 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 the hydrogen supply raw material A and the hydrogen supply raw material B can simultaneously supply hydrogen in the same reaction condition interval, and further 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, has the advantages of lower raw material cost, large scale, low catalyst cost, larger hydrogen supply amount, relatively mild reaction process condition and high hydrogen supply purity, and can simultaneously store and supply two states with low-temperature liquid property.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings that are required for the embodiments will be briefly described, and it will be apparent that the drawings in the following description are some embodiments of the present invention and that other drawings may be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a fixed bed reactor apparatus for use in the present invention;
FIG. 2 is a schematic diagram of a tank reactor apparatus used in the present invention.
The figures are identified as follows:
1-a fixed bed reactor body, 11-a reaction tube; 2-kettle type reactor body, 21-stirring paddle.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a liquid based on organic liquidThe catalytic hydrogen supply system 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 dodecylbenzene and octadecyldibenzyl toluene, the mass content of the octadecyldibenzyl toluene is not more than 80 percent, the hydrogen supply raw material B is one or more of decalin, 1-methyldecalin and 2-methyldecalin, and the mass ratio of the hydrogen supply raw material A to the hydrogen supply raw material B is 0.5-10. The hydrogen-supplying reaction catalyst is porous granular supported metal catalyst with granularity of 10-300 meshes and specific surface area of 10-900 m 2 And/g, comprising a catalyst support and a catalyst active metal component. The catalyst carrier is one or a mixture of a plurality of porous alumina, porous silica, porous titanium dioxide, molecular sieve and pseudo-boehmite in any proportion, and the catalyst active metal component comprises copper metal component and one or two of palladium or platinum metal components. Calculated by the mass of metal, the loading of the active metal component of the catalyst accounts for 5.0-30.0% of the mass of the whole hydrogen supply reaction catalyst, and the total loading of two metals of palladium and platinum accounts for 0.3-2.0% of the mass of the whole hydrogen supply reaction catalyst.
The main functions of the hydrogen supply raw material A in the organic liquid hydrogen supply material are as follows: the hydrogen donor is provided and is used as a main component of the hydrogen supply material system, so that the whole hydrogen supply material system can still be in a normal-temperature (25 ℃) liquid state before the reaction and on any reaction progress after the specified amount of the hydrogen supply raw material B is added, the material has good fluidity, and the viscosity of the material at normal temperature is not more than 50 mPa. The liquid fluidity is always kept at normal temperature, which has important significance for convenience in storage, transportation and transportation.
The main functions of the hydrogen supply raw material B are as follows: the hydrogen donor is provided with a theoretical hydrogen supply amount which 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-supplying raw material B is not added, the maximum available hydrogen amount is 6.19% of the theoretical upper hydrogen-supplying limit of the raw material A by only the hydrogen-supplying raw material A. 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.
In line with the targeted design of organic liquid hydrogen donor materials, catalysts also need to be targeted, i.e., how to provide accurate and rational catalysts for feed systems with hydrogen donor materials a and B.
The catalyst selected by the invention has the main function of realizing the catalytic dehydrogenation with high conversion rate, namely hydrogen supply reaction, of the hydrogen supply raw material A and the hydrogen supply raw material B in the same reaction condition interval, thereby realizing the overall high hydrogen supply amount. Since the reaction product of the hydrogen supply raw material B has stronger aromaticity than the reaction product of the hydrogen supply raw material a, it is more easily adsorbed on the surface of the catalytic metal active component, especially on the surface of the noble metal component, resulting in deactivation of the catalyst. Thus, in principle, a relatively high temperature is generally required to achieve a higher catalytic conversion of hydrogen feed B than hydrogen feed a. Therefore, when the type of the catalyst and the preparation method are selected, the hydrogen supply reaction temperature of the hydrogen supply raw material B is reduced as much as possible, and the key of realizing the high hydrogen supply amount of the whole hydrogen supply material system is realized. In principle, compared with noble metals, the non-noble metals have weaker adsorption capacity on aromatic rings, but at the same time, noble metal components have stronger catalytic dehydrogenation activity, and the 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 the hydrogen supply raw material A and the hydrogen supply raw material B can simultaneously supply hydrogen in the same reaction condition interval, and further 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 supply 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 air at 200-600 ℃ successively, reducing the catalyst carrier in hydrogen at 200-500 ℃, and fixing the active metal component on the surface of the catalyst carrier in a reduced state form to prepare the hydrogen supply reaction catalyst. The metal palladium precursor is one or more than one mixture of palladium acetate, palladium oxalate and palladium acetylacetonate, the metal platinum precursor is one or two mixtures of platinum acetylacetonate and potassium platinum oxalate, and the metal copper precursor is one or two mixtures of copper nitrate and copper sulfate. The metallic copper precursor impregnation operation should precede the metallic palladium precursor and metallic platinum precursor impregnation operation.
The invention also provides a catalytic hydrogen supply system hydrogen supply method based on the organic liquid, which comprises the following steps:
the organic liquid hydrogen-supplying material is used as raw material, and the raw material is contacted and reacted with the hydrogen-supplying reaction catalyst through a reactor under the conditions of the reaction temperature of 150-290 ℃ and the pressure of 0.01-0.2 MPa to generate hydrogen.
When the reactor adopts a fixed bed reactor, the hydrogen supply reaction catalyst is fixed in the bed layer of the fixed bed reactor, and 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. The flow rate of the organic liquid hydrogen supply material is 0.3 to 30h expressed by the mass airspeed -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 continuously carried out, and the reaction is started and stopped according to actual needs.
When the reactor is a kettle reactor, the organic liquid hydrogen supply material and the hydrogen supply reaction catalyst are mixed according to the mass ratio (1-30): 1 are mixed in a kettle reactor, hydrogen is generated by stirring reaction by a stirrer, the stirring speed of the stirrer is 50-1200 r/min, and the reaction time is 1-30 h. The upper part of the kettle-type reactor is provided with a gas outlet, and a gas-liquid separation cooling pipe is arranged at the outlet to cool and reflux high boiling point substances entrained in the product hydrogen.
The supplementary explanation for the catalytic hydrogen supply system and the hydrogen supply method described above is as follows:
the supported metal catalyst is a catalyst category 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 consists of 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 a porous solid material generally and plays a role of supporting the catalytic active metal component, and can be granular, powdery or block in a macroscopic manner; 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 canal.
The precursor of a certain catalytically active metal component, or simply metal precursor, refers to the metal source that needs to be prepared before the catalyst is prepared, 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 hydrated form of the metal compound is equivalent to the anhydrous form of the same molar amount of metal. How to select a metal precursor in the catalyst preparation is also a key consideration, since the nature of the precursor will ultimately affect the catalytic properties of the catalyst product. Different catalysts prepared by different types of metal precursors, although the type of metal, total content on the final catalyst product are the same, can result in distinct catalytic reaction effects.
The hydrogen supply 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, the solution is used for impregnating a porous catalyst carrier, 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 reduced state. The concentration of 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 catalyst produced. Post-treatment operations after impregnation generally comprise links such as drying, roasting, hydrogen reduction, etc., but adding the following additional, non-unique operations, or repeating one or more steps of the operation, does not change the preparation method of the catalyst used, which belongs to the nature of the impregnation method of the present invention. These additional, non-exclusive operations include, but are not limited to: air-drying, oven-drying, or electromagnetic radiation in a gas or gas stream, heating, drying, or reduction in other reducing gases, or water or solvent washing, or any operative treatment aimed at removing inactive metallic elements from the precursor compound.
"specific surface area" is a term in the art of solid catalysts, broadly solid materials, and refers to the ratio of the surface area of a solid catalyst to its mass, typically in m 2 The unit of/g; the measurement method commonly used in the art is calculated by a BET specific surface area measurement method, and is obtained from an adsorption-desorption curve of a catalyst to nitrogen or argon at a low temperature. The specific surface area of the present invention is a value obtained by the BET specific surface area test method.
Both the kettle type reactor and the fixed bed type reactor are one type of reaction device commonly used in the fields of energy, chemical industry and materials. The kettle type reactor is characterized in that raw materials are added into a closed container at one time, and then a certain temperature, a certain pressure and a certain stirring speed are controlled to enable substances in the container to react chemically; in actual production, the one-time kettle type and intermittent kettle type can be adopted, and the two kettle type and intermittent kettle type belong to the same type of technology; the fixed bed reactor features that solid catalyst is packed in certain position inside the reaction pipe to form bed layer, and the reactant enters the reaction pipe and flows through the bed layer and out of the reaction pipe under the driving of pump or pressure difference.
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 h is used in the present invention -1 In units representing the ratio of the mass of fluid passing through the reactor tube to the mass of catalyst per hour.
Because hydrogen is a permanent gas at normal temperature, and the boiling point of the organic liquid hydrogen supply material is above 200 ℃ no matter a certain vapor is generated before and after the reaction, the purification of hydrogen and the recovery of organic vapor can be easily realized through 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, hydrogen feed rate = hydrogen mass flow rate/feed organic liquid mass flow rate;
when using a tank reactor, the total mass produced by collecting hydrogen over a certain reaction period (which can be scaled by the total volume flow) is calculated as follows: hydrogen supply = mass of hydrogen produced/mass of organic liquid feedstock before reaction;
the purity of hydrogen is defined as: (1-the volume content of all other permanent gases). Times.100%.
The flow of hydrogen can be measured by a flow meter corrected by hydrogen flow with known hydrogen flow rate, and the relation between the flow of hydrogen and time is recorded, so that the total flow of hydrogen in a given time can be obtained, and the hydrogen supply amount of the reaction system is further obtained. The purity of hydrogen can be determined by gas chromatography, mass spectrometry, or the like. The measurement methods of the purity of the hydrogen, the flow rate of the hydrogen, the mass of the liquid, the mass flow rate of the liquid and the like are conventional analytical chemistry methods in the field, are well known to those skilled in the art, and the specific methods do not belong to the protection scope of the invention.
Example 1
The embodiment provides a catalytic hydrogen supply system hydrogen supply method based on organic liquid, which comprises the following steps:
s1, selecting an organic liquid hydrogen supply material: the hydrogen supply raw material A is a mixture of octadecyl dibenzyl toluene and dodecyl benzyl toluene, wherein the mass ratio of the octadecyl dibenzyl toluene to the dodecyl 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: alumina supported palladium copper catalyst, noted Pd-Cu/Al 2 O 3 Wherein the mass content of Pd is 1.8wt%, the mass content of Cu is 10.0wt%, the granularity of the catalyst is 20-60 meshes, and the specific surface area of the catalyst is 182m 2 /g。
Catalyst Pd-Cu/Al for hydrogen supply reaction 2 O 3 The preparation method comprises the following steps:
first with Cu (NO) 3 ) 3 For copper component precursor, copper component is loaded to Al 2 O 3 And (3) on a carrier. Drying Al according to unit mass 2 O 3 Water absorption of the Carrier Cu (NO) at the target concentration was formulated 3 ) 3 The aqueous solution is then impregnated (12 h of impregnation), dried (4 h of drying in an oven at 110 ℃) and reduced with hydrogen (4 h of reduction at 500 ℃ in a hydrogen stream) to obtain an alumina-supported copper catalyst, designated Cu/Al 2 O 3 ；
Then palladium oxalate is used as a palladium precursor to load palladium components to Cu/Al 2 O 3 And (3) on a carrier. Drying Al according to unit mass 2 O 3 The water absorption rate of the carrier prepares palladium oxalate aqueous solution with target concentration, and then the palladium-copper catalyst loaded with alumina is obtained by dipping (dipping for 12 hours), drying (drying for 4 hours in a 110 ℃ oven), air roasting (roasting for 4 hours at 250 ℃ in air) and hydrogen reduction (reducing for 4 hours at 200 ℃ in hydrogen flow), and is recorded as Pd-Cu/Al 2 O 3 . The elemental content and physicochemical properties of the catalyst can be obtained by conventional characterization means in the art.
S3, using the organic liquid hydrogen supply materials and the hydrogen supply reaction catalysts described in S1 and S2, and realizing hydrogen supply reaction through a fixed bed reactor, wherein the reaction temperature (namely the catalyst bed temperature) is 285 ℃, the reaction system pressure is 0.10MPa, 2.0g of the hydrogen supply reaction catalyst is fixed in a reactor bed, and the organic liquid hydrogen supply materials flow through the catalyst bed from the inlet of a reaction tube; wherein the space velocity of the organic liquid is 1.0h -1 And a gas-liquid separation cooling tank is arranged at the outlet of the reaction tube at the flow rate, so that hydrogen in the product is separated from the residual organic liquid. When all parameters reach the set values or the set ranges, 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 catalytic hydrogen supply system hydrogen supply method based on an organic liquid, comprising the steps of:
s1, selecting an organic liquid hydrogen supply material: the hydrogen supply raw material A is a mixture of octadecyl dibenzyl toluene and dodecyl benzyl toluene, wherein the mass ratio of the octadecyl dibenzyl toluene to the dodecyl 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/Al 2 O 3 -SiO 2 Wherein the mass content of Pt is 2wt%, the mass content of Cu is 28wt%, the granularity of the catalyst is 10-100 meshes, and the specific surface area of the catalyst is 10m 2 /g。
Catalyst for hydrogen supply reaction Pt-Cu/Al 2 O 3 -SiO 2 The preparation method comprises the following steps:
first with Cu (NO) 3 ) 3 For copper component precursor, copper component is loaded to Al 2 O 3 With SiO 2 On a mixed carrier, wherein Al 2 O 3 With SiO 2 The mass ratio of the carrier is 1:1. Preparation of Cu (NO) at target concentration based on water absorption of dry mix carrier per unit mass 3 ) 3 The aqueous solution is then impregnated (12 h), dried (4 h in an oven at 110 ℃ C.), reduced with hydrogen (6 h in a hydrogen stream at 500 ℃ C.) to obtain Al 2 O 3 -SiO 2 Supported copper catalyst, designated Cu/Al 2 O 3 -SiO 2 ；
Then platinum component is loaded to Cu/Al by taking potassium platinum oxalate as a platinum precursor 2 O 3 -SiO 2 And (3) on a carrier. Preparing a platinum potassium oxalate aqueous solution with a target concentration according to the water absorption rate of a unit mass dry mixed carrier, and then obtaining a platinum copper catalyst loaded by the mixed carrier through dipping (dipping for 12 hours), drying (drying in a baking oven at 110 ℃ for 4 hours), air roasting (baking in air at 600 ℃ for 4 hours), washing with a large amount of deionized water, drying again (drying in the baking oven at 110 ℃ for 4 hours) and hydrogen reduction (reducing in a hydrogen gas stream at 200 ℃ for 4 hours), wherein the platinum copper catalyst is recorded as Pt-Cu/Al 2 O 3 -SiO 2 . The elemental content and physicochemical properties of the catalyst can be obtained by conventional characterization means in the art.
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 reaction system pressure is 0.2MPa, fixing 2.0g of the hydrogen supply reaction catalyst in the reactor bed, and flowing the organic liquid hydrogen supply material from the inlet of the reaction tubePassing through a catalyst bed; wherein the space velocity of the organic liquid is 30h -1 And a gas-liquid separation cooling tank is arranged at the flow rate from the outlet of the reaction tube to separate the hydrogen in the product from the residual organic liquid. When all parameters reach the set values or the set ranges, 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 catalytic hydrogen supply system hydrogen supply method based on organic liquid, which comprises the following steps:
s1, selecting an organic liquid hydrogen supply material: the hydrogen supply raw material A is a mixture of octadecyl dibenzyl toluene and dodecyl benzyl toluene, wherein the mass ratio of the octadecyl dibenzyl toluene to the dodecyl 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/Al 2 O 3 Wherein the mass content of Pt is 0.9wt%, the mass content of Cu is 8.0wt%, the granularity of the catalyst is selected to be 200-240 meshes, and the specific surface area of the catalyst is 190m 2 /g。
Catalyst for hydrogen supply reaction Pt-Cu/Al 2 O 3 The preparation method comprises the following steps:
first with Cu (NO) 3 ) 3 For copper component precursor, copper component is loaded to Al 2 O 3 And (3) on a carrier. Drying Al according to unit mass 2 O 3 Water absorption of the Carrier Cu (NO) at the target concentration was formulated 3 ) 3 The aqueous solution is then impregnated (12 h of impregnation), dried (4 h of drying in an oven at 110 ℃) and reduced with hydrogen (6 h of reduction at 450 ℃ in a hydrogen stream) to obtain the alumina-supported copper catalyst, designated Cu/Al 2 O 3 ；
Then platinum component is loaded to Cu/Al by taking potassium platinum oxalate as a platinum precursor 2 O 3 And (3) on a carrier. Drying Al according to unit mass 2 O 3 The water absorption rate of the carrier was formulated into a platinum potassium oxalate aqueous solution of a target concentration, followed by impregnation (dippingSoaking for 12 h), drying (drying in a 110 ℃ oven for 4 h), air roasting (roasting in air for 4h at 250 ℃), washing with a large amount of deionized water, drying again (drying in a 110 ℃ oven for 4 h), and hydrogen reduction (reducing in a hydrogen stream for 4h at 200 ℃) to obtain an alumina-supported platinum copper catalyst, which is recorded as Pt-Cu/Al 2 O 3 . The elemental content and physicochemical properties of the catalyst can be obtained by conventional characterization means in the art.
S3, using the organic liquid hydrogen supply materials and the hydrogen supply reaction catalyst described in S1 and S2 to realize hydrogen supply reaction through a kettle type reactor, wherein the reaction temperature is 290 ℃ as shown in FIG. 2; the pressure of the reaction system is 0.11MPa, the reaction time is 8h, the dosage of the hydrogen supply reaction catalyst is 1.0g, the dosage of the organic liquid hydrogen supply material is 10g, the stirring speed is 400 rpm, a gas-liquid separation cooling pipe is arranged at the outlet, and the high boiling point substances entrained in the product hydrogen are cooled and refluxed.
The hydrogen flow is measured by a mass flowmeter, and the purity of the hydrogen is analyzed by combining chromatography, so that the hydrogen supply rate is 6.31% and the purity of the hydrogen is more than 99.9% by using the hydrogen supply method.
Example 4
A catalytic hydrogen supply system hydrogen supply method based on an organic liquid, comprising the steps of:
s1, selecting an organic liquid hydrogen supply material: the hydrogen supply raw material A is a mixture of octadecyl dibenzyl toluene and dodecyl benzyl toluene, wherein the mass ratio of the octadecyl dibenzyl toluene to the dodecyl 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/Al 2 O 3 -SiO 2 Wherein the mass content of Pt is 1.0wt%, the mass content of Cu is 10.0wt%, the granularity of the catalyst is selected to be 200-300 meshes, and the specific surface area of the catalyst is 277m 2 /g。
Catalyst for hydrogen supply reaction Pt-Cu/Al 2 O 3 -SiO 2 The preparation method comprises the following steps:
first with Cu (NO) 3 ) 3 Is a copper component precursor, willCopper component loading to Al 2 O 3 With SiO 2 On a mixed carrier, wherein Al 2 O 3 With SiO 2 The mass ratio of the carrier is 1:1. Preparation of Cu (NO) at target concentration based on water absorption of dry mix carrier per unit mass 3 ) 3 The aqueous solution is then impregnated (12 h), dried (4 h in an oven at 110 ℃ C.), and reduced with hydrogen (6 h in a hydrogen stream at 450 ℃ C.) to obtain Al 2 O 3 -SiO 2 Supported copper catalyst, designated Cu/Al 2 O 3 -SiO 2 ；
Then platinum component is loaded to Cu/Al by taking potassium platinum oxalate as a platinum precursor 2 O 3 -SiO 2 And (3) on a carrier. Preparing a platinum potassium oxalate aqueous solution with a target concentration according to the water absorption rate of a unit mass dry mixed carrier, and then obtaining a platinum copper catalyst loaded by the mixed carrier through dipping (dipping for 12 hours), drying (drying in a baking oven at 110 ℃ for 4 hours), air roasting (baking in air at 250 ℃ for 4 hours), washing with a large amount of deionized water, drying again (drying in the baking oven at 110 ℃ for 4 hours) and hydrogen reduction (reducing in a hydrogen gas stream at 200 ℃ for 4 hours), wherein the platinum copper catalyst is recorded as Pt-Cu/Al 2 O 3 -SiO 2 . The elemental content and physicochemical properties of the catalyst can be obtained by conventional characterization means in the art.
S3, using the organic liquid hydrogen supply materials and the hydrogen supply reaction catalyst described in S1 and S2 to realize hydrogen supply reaction through a kettle type reactor, wherein the reaction temperature is 150 ℃ as shown in FIG. 2; the pressure of the reaction system is 0.2MPa, the reaction time is 8h, the dosage of the hydrogen supply reaction catalyst is 2g, the dosage of the organic liquid hydrogen supply material is 10g, the stirring speed is 1200 revolutions per minute, a gas-liquid separation cooling pipe is arranged at the outlet, and the high boiling point substances entrained in the product hydrogen are cooled and refluxed.
The hydrogen flow is measured by a mass flowmeter, and the purity of the hydrogen is analyzed by combining chromatography, so that the hydrogen supply rate is 6.39% and the purity of the hydrogen is more than 99.9% by using the hydrogen supply method.
Example 5
A catalytic hydrogen supply system hydrogen supply method based on an organic liquid, comprising the steps of:
s1, selecting an organic liquid hydrogen supply material: the hydrogen supply raw material A is a mixture of octadecyl dibenzyl toluene and dodecyl benzyl toluene, wherein the mass ratio of the octadecyl dibenzyl toluene to the dodecyl benzyl toluene is 1:3, the hydrogen supply raw material B is decahydronaphthalene, 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/Al 2 O 3 -SiO 2 Wherein the mass content of Pt is 0.3wt%, the mass content of Cu is 4.7wt%, the granularity of the catalyst is selected to be 200-300 meshes, and the specific surface area of the catalyst is 900m 2 /g。
Catalyst for hydrogen supply reaction Pt-Cu/Al 2 O 3 -SiO 2 The preparation method comprises the following steps:
first with Cu (NO) 3 ) 3 For copper component precursor, copper component is loaded to Al 2 O 3 With SiO 2 On a mixed carrier, wherein Al 2 O 3 With SiO 2 The mass ratio of the carrier is 1:1. Preparation of Cu (NO) at target concentration based on water absorption of dry mix carrier per unit mass 3 ) 3 The aqueous solution is then impregnated (12 h), dried (4 h in an oven at 110 ℃ C.), reduced with hydrogen (6 h in a hydrogen stream at 500 ℃ C.) to obtain Al 2 O 3 -SiO 2 Supported copper catalyst, designated Cu/Al 2 O 3 -SiO 2 ；
Then platinum component is loaded to Cu/Al by taking potassium platinum oxalate as a platinum precursor 2 O 3 -SiO 2 And (3) on a carrier. Preparing a platinum potassium oxalate aqueous solution with a target concentration according to the water absorption rate of a unit mass dry mixed carrier, and then obtaining a platinum copper catalyst loaded by the mixed carrier through dipping (dipping for 12 hours), drying (drying in a baking oven at 110 ℃ for 4 hours), air roasting (baking in air at 600 ℃ for 4 hours), washing with a large amount of deionized water, drying again (drying in the baking oven at 110 ℃ for 4 hours) and hydrogen reduction (reducing in a hydrogen gas stream at 200 ℃ for 4 hours), wherein the platinum copper catalyst is recorded as Pt-Cu/Al 2 O 3 -SiO 2 . The elemental content and physicochemical properties of the catalyst can be obtained by conventional characterization means in the art.
S3, using the organic liquid hydrogen supply materials and the hydrogen supply reaction catalyst described in S1 and S2 to realize hydrogen supply reaction through a kettle type reactor, wherein the reaction temperature is 150 ℃ as shown in FIG. 2; the pressure of the reaction system is 0.01MPa, the reaction time is 30h, the dosage of the hydrogen supply reaction catalyst is 1g, the dosage of the organic liquid hydrogen supply material is 30g, the stirring speed is 50 revolutions per minute, a gas-liquid separation cooling pipe is arranged at the outlet, and high boiling point substances entrained in the product hydrogen are cooled and refluxed.
The hydrogen flow is measured by a mass flowmeter, and the purity of the hydrogen is analyzed by combining chromatography, so that the hydrogen supply rate is 6.25% and the purity of the hydrogen is more than 99.9% by using the hydrogen supply method.
To compare the application effects of the present invention, the following seven comparative experiments were performed, respectively.
Comparative example 1
To demonstrate the advantages of the selected organic liquid hydrogen donor material of the present invention, this example is a comparative example to example 1, and differs from example 1 in that: in step S1, the same mass of methyl-cyclohexane was used instead of 2-methyldecalin. The remainder was the same as in example 1. By detection, the hydrogen supply rate was 4.1%, which is far lower than that of example 1. This result indicates the importance of organic liquid phase feed system selection.
Comparative example 2
To verify the superiority of the selected catalyst of the present invention over the conventional catalyst in the hydrogen supply process, this experiment was conducted. This example is a comparative example of example 1, and differs from example 1 in that: in step S2, conventional Ni/Al is used 2 O 3 Catalyst replaces Pd-Cu/Al 2 O 3 Wherein the Ni loading is 11wt%. By detection, the hydrogen supply rate was 1.72%, which was also far lower than that of example 1. This result indicates the importance of catalyst selection.
Comparative example 3
To further reveal the uniqueness of the catalyst used in the present invention and its importance for the organic liquid hydrogen-donor material used, this comparative example is further compared on the basis of example 1.
This example is a comparative example of example 1, and differs from example 1 in that:
in the step S2, palladium chloride is used as a palladium component precursor instead of palladium oxalate in the example 1 when preparing the supported catalyst by the impregnation method, and other links are unchanged. By detection, the hydrogen supply rate was 4.84%, which is also far lower than that of example 1. The results indicate that the selection of metal precursor components can significantly affect the hydrogen supply performance of the hydrogen supply system, and that the selection of the precursor for catalyst preparation is very important.
Comparative example 4
To further reveal the uniqueness of the catalyst used in the present invention and its importance for the organic liquid hydrogen-donor material used, this comparative example is further compared on the basis of example 1.
This example is a comparative example of example 1, and differs from example 1 in that:
in the step S2, when preparing the supported catalyst by an impregnation method, copper and palladium precursors are simultaneously dissolved in the same solution, and then the alumina supported palladium copper catalyst under the process is obtained by impregnation (impregnation for 12 h), drying (drying in a 110 ℃ oven for 4 h), air roasting (roasting in air for 4h at 250 ℃) and hydrogen reduction (reduction in hydrogen stream for 4h at 200 ℃). By detection, the hydrogen supply rate was 5.30%, which is also far lower than that of example 1. The results demonstrate that the order of impregnation of the metal components can significantly affect the hydrogen donating properties of the hydrogen donating system.
Comparative example 5
This example is a comparative example of example 3, and differs from example 3 in that: in step S2, ni/Al is used 2 O 3 Instead of Pt-Cu/Al 2 O 3 The Ni loading was 11wt%. By detection, the hydrogen supply rate was 1.46%, which is far lower than that of example 3. The results indicate that catalyst selection is also of significant importance in the tank reactor route.
Comparative example 6
This example is a comparative example of example 3, and differs from example 3 in that: in step S2, a Pt-Cu/Al alloy similar to that of example 3 was still used 2 O 3 A 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 3.55%, which is far lower than that of example 3. The results show that,the choice of catalyst preparation process, especially of the precursor type, is also of significant importance for the catalytic hydrogen supply performance.
Comparative example 7
This example is a comparative example of example 3, and differs from example 3 in that: in step S2, a Pt-Cu/Al alloy similar to that of example 3 was still used 2 O 3 The catalyst was prepared by the method of example 3, except that the impregnation and the post-treatment of the platinum component were performed first, and then the impregnation and the post-treatment of the copper component were performed. By detection, the hydrogen supply rate was 2.21%, which is far lower than that of example 3. The result shows that the prepared supported platinum copper catalyst has obvious influence on the catalytic hydrogen supply performance due to the fact that the impregnation sequence of active components is regulated in the preparation process.
The invention solves the problems that the prior art lacks a hydrogen supply technology based on organic liquid materials, has the advantages of lower raw material cost, large scale, low catalyst cost, larger hydrogen supply amount, relatively mild reaction process condition and high hydrogen supply purity, and can simultaneously store and supply two states with low-temperature liquid property.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While obvious variations or modifications are contemplated as falling within the scope of the present invention.
Claims (8)
1. A catalytic hydrogen supply system based on an organic liquid, which is characterized by comprising a hydrogen supply material of the organic liquid 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, wherein the hydrogen supply raw material A is one or two of dodecylbenzene and octadecyl dibenzyl toluene, and the mass content of the octadecyl dibenzyl toluene is not more than 80%; the hydrogen supply raw material B is one or more of decalin, 1-methyl decalin and 2-methyl decalin; the mass ratio of the hydrogen supply raw material A to the hydrogen supply raw material B is 0.5-10;
the hydrogen supply reaction catalyst is a supported metal catalyst and comprises a catalyst carrier and a catalyst active metal component;
the catalyst carrier is one or a mixture of a plurality of porous alumina, porous silica, porous titanium dioxide, molecular sieve and pseudo-boehmite in any proportion, and the catalyst active metal component comprises copper metal component and one or two of palladium or platinum metal components;
calculated by the mass of metal, the loading of the active metal component of the catalyst accounts for 5.0-30.0% of the mass of the whole hydrogen supply reaction catalyst, and the total loading of two metals of palladium and platinum accounts for 0.3-2.0% of the mass of the whole hydrogen supply reaction catalyst;
the hydrogen supply 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 air at 200-600 ℃ successively, reducing the catalyst carrier in hydrogen at 200-500 ℃, and fixing the active metal component on the surface of the catalyst carrier in a reduced state form to prepare a hydrogen supply reaction catalyst;
the metal palladium precursor is one or more than two of palladium acetate, palladium oxalate and palladium acetylacetonate;
the metal platinum precursor is one or two of platinum acetylacetonate and potassium platinum oxalate;
the metal copper precursor is one or two of copper nitrate and copper sulfate;
the metallic copper precursor impregnation operation should precede the metallic palladium precursor and metallic platinum precursor impregnation operation.
2. The organic liquid-based catalytic hydrogen supply system according to claim 1, wherein the hydrogen supply reaction catalyst is porous particles having a particle size of 10 to 300 mesh.
3. The catalytic hydrogen-supply system based on organic liquid according to claim 1, wherein the specific surface area of the hydrogen-supply reaction catalyst is 10-900 m 2 /g。
4. A method of supplying hydrogen based on the catalytic hydrogen supply system of the organic liquid of claim 1, comprising the steps of: organic liquid hydrogen-supplying material is used as raw material, and the raw material is contacted and reacted with the hydrogen-supplying reaction catalyst through a reactor to generate hydrogen under the conditions of the reaction temperature of 150-290 ℃ and the pressure of 0.01-0.2 MPa.
5. The hydrogen supplying method according to claim 4, wherein the reactor is a fixed bed reactor, a hydrogen supplying reaction catalyst is fixed in a bed layer of the fixed bed reactor, an organic liquid hydrogen supplying 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 the product from the residual organic liquid.
6. The hydrogen supplying method according to claim 5, wherein the flow rate of the organic liquid hydrogen supplying material is 0.3 to 30h in terms of mass space velocity -1 。
7. The hydrogen supply method according to claim 6, wherein the reactor is a kettle reactor, and the organic liquid hydrogen supply material and the hydrogen supply reaction catalyst are mixed according to the mass ratio (1-30): and 1, mixing in a kettle-type reactor, stirring and reacting by 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 entrained in the hydrogen product.
8. The hydrogen supplying method according to claim 7, 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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