CN114768858A - Non-noble metal catalyst for nitrogen-containing organic liquid hydrogen storage of fixed bed reactor - Google Patents
Non-noble metal catalyst for nitrogen-containing organic liquid hydrogen storage of fixed bed reactor Download PDFInfo
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- CN114768858A CN114768858A CN202210247019.0A CN202210247019A CN114768858A CN 114768858 A CN114768858 A CN 114768858A CN 202210247019 A CN202210247019 A CN 202210247019A CN 114768858 A CN114768858 A CN 114768858A
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- catalyst
- hydrogen storage
- transition metal
- mesoporous
- mcm
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- 239000003054 catalyst Substances 0.000 title claims abstract description 126
- 239000001257 hydrogen Substances 0.000 title claims abstract description 104
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 104
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000003860 storage Methods 0.000 title claims abstract description 77
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 42
- 239000007788 liquid Substances 0.000 title claims abstract description 38
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000002243 precursor Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 27
- 150000003624 transition metals Chemical class 0.000 claims abstract description 23
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 239000012876 carrier material Substances 0.000 claims abstract 2
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 84
- 239000000203 mixture Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- -1 transition metal orA transition metal Chemical class 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 2
- 229910052698 phosphorus Inorganic materials 0.000 claims 2
- 239000011574 phosphorus Substances 0.000 claims 2
- SDFLTYHTFPTIGX-UHFFFAOYSA-N 9-methylcarbazole Chemical compound C1=CC=C2N(C)C3=CC=CC=C3C2=C1 SDFLTYHTFPTIGX-UHFFFAOYSA-N 0.000 claims 1
- QAWLNVOLYNXWPL-UHFFFAOYSA-N 9-propylcarbazole Chemical compound C1=CC=C2N(CCC)C3=CC=CC=C3C2=C1 QAWLNVOLYNXWPL-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 239000012467 final product Substances 0.000 abstract description 2
- 239000013067 intermediate product Substances 0.000 abstract description 2
- 239000012229 microporous material Substances 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 82
- 239000000377 silicon dioxide Substances 0.000 description 17
- 229910052681 coesite Inorganic materials 0.000 description 16
- 229910052906 cristobalite Inorganic materials 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 229910052682 stishovite Inorganic materials 0.000 description 16
- 229910052905 tridymite Inorganic materials 0.000 description 16
- 238000006356 dehydrogenation reaction Methods 0.000 description 14
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 10
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 239000003755 preservative agent Substances 0.000 description 5
- 230000002335 preservative effect Effects 0.000 description 5
- HOQAPVYOGBLGOC-UHFFFAOYSA-N 1-ethyl-9h-carbazole Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2CC HOQAPVYOGBLGOC-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000013335 mesoporous material Substances 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 238000011946 reduction process Methods 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000126 substance 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 compound C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 description 2
- FUUPYXUBNPJSOA-UHFFFAOYSA-N 9-ethyl-1,2,3,4,4a,4b,5,6,7,8,8a,9a-dodecahydrocarbazole Chemical compound C12CCCCC2N(CC)C2C1CCCC2 FUUPYXUBNPJSOA-UHFFFAOYSA-N 0.000 description 2
- 239000005696 Diammonium phosphate Substances 0.000 description 2
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 2
- WBLJAACUUGHPMU-UHFFFAOYSA-N copper platinum Chemical compound [Cu].[Pt] WBLJAACUUGHPMU-UHFFFAOYSA-N 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 235000019838 diammonium phosphate Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000010667 large scale reaction Methods 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical group [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 2
- 229910003445 palladium oxide Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 2
- HIAGSPVAYSSKHL-UHFFFAOYSA-N 1-methyl-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C(C)=CC=C2 HIAGSPVAYSSKHL-UHFFFAOYSA-N 0.000 description 1
- NEKVNWJRLIKKJA-UHFFFAOYSA-N 1-propyl-9h-carbazole Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2CCC NEKVNWJRLIKKJA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910018883 Pt—Cu Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- UYDPQDSKEDUNKV-UHFFFAOYSA-N phosphanylidynetungsten Chemical compound [W]#P UYDPQDSKEDUNKV-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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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
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a non-noble metal catalyst for storing hydrogen in nitrogen-containing organic liquid of a fixed bed reactor, which takes a mesoporous or mesoporous composite material as a carrier and takes transition metal or transition metal phosphide as an active component, wherein the transition metal is at least one of Fe, Co, Ni, Cu and Mo, and the pore size of the carrier material is 2-50 nm. The catalyst is prepared by a method of reducing an oxidation state precursor by temperature programming in a fixed bed. The invention utilizes the nano-pore confinement effect of the mesoporous or mesoporous-microporous material carrier to improve the concentration of the hydrogenation intermediate product in the pore, promote the forward movement of the reaction, further improve the selectivity of the continuous hydrogenation final product, improve the conversion rate and the hydrogen storage capacity of reactants and show higher activity; meanwhile, non-noble metal is used as an active component, so that the cost of the catalyst is obviously reduced; hydrogen storage comparable to noble metals can be achieved by increasing the amount of non-noble metal and/or increasing the residence time.
Description
Technical Field
The invention belongs to the technical field of hydrogen energy, relates to a catalyst for storing hydrogen in a nitrogen-containing organic liquid, and particularly relates to a supported non-noble metal catalyst for storing hydrogen in a nitrogen-containing organic liquid in a fixed bed reactor.
Background
The hydrogen is rich in resources, the combustion heat value is high, the product is only water, and the hydrogen is a recognized clean energy, and is most likely to replace fossil energy in future energy structures, so that the hydrogen is the most potential clean energy carrier.
The application of hydrogen energy does not depart from the storage and transportation of hydrogen gas. The hydrogen has the characteristics of low density, flammability, explosiveness and the like, which brings difficulties for the storage and transportation of hydrogen energy. The current hydrogen storage technology can be mainly divided into two types of physical hydrogen storage and chemical hydrogen storage. Physical hydrogen storage includes pressurized hydrogen storage, liquefied hydrogen storage, adsorption hydrogen storage, etc.; chemical hydrogen storage includes hydride chemisorption hydrogen storage, NH3And organic liquid for hydrogen storage. Wherein, the physical hydrogen storage or the unit mass hydrogen storage density is low, or the energy consumption in the hydrogen storage process is high, or the preparation cost of the adsorption material is high and the industrialization difficulty is large. In chemical hydrogen storage, the problems of low hydrogen storage density, low hydrogen storage speed, high temperature and the like still exist in metal hydride hydrogen storage. The organic liquid is an ideal hydrogen energy storage medium, and has the series advantages of large mass density of hydrogen storage, low temperature of hydrogen storage, high speed, simple transportation equipment, long-term storage, low energy consumption, high purity of released hydrogen, recycling and the like. The organic liquid hydrogen storage medium commonly used at present is aromatic hydrocarbon, nitrogen-containing heterocyclic compounds, alcohols, acids, distillate oil or the mixture of the above organic liquids.
The hydrogen storage principle of the organic liquid is that under the action of a catalyst, the organic liquid undergoes a hydrogenation reaction to store hydrogen; after the hydrogenated organic liquid is transported to a designated place, dehydrogenation reaction is carried out under the action of a catalyst to release hydrogen, and the storage and transportation of the hydrogen are realized. It can be seen that the catalyst is the core of the organic liquid hydrogen storage technology, and determines the efficiency and energy consumption of the organic liquid hydrogen storage process. The catalyst used at present is mainly a supported noble metal or noble metal alloy catalyst, and the reaction temperature is generally below 200 ℃.
The Chinese patent CN111725531A discloses a method for preparing a high-selectivity copper-platinum alloy dehydrogenation catalyst, which uses methylcyclohexane and toluene as hydrogen storage and release media, and uses a high-selectivity copper-platinum alloy as a dehydrogenation catalyst, wherein the loading mass range of noble metal platinum is 0.1-2.0 wt%, the purity of hydrogen generated by dehydrogenation of methylcyclohexane is more than or equal to 99.97%, and the purity requirement of hydrogen source of hydrogen fuel cell can be satisfied without purification.
Chinese patent CN111392691A discloses a method for dehydrogenating a perhydrogenated organic liquid by a palladium-based catalyst, wherein a hydrogen storage and release medium is a mixture of 36 wt% of propylcarbazole, 24 wt% of ethylcarbazole and 40 wt% of 2-methylindole, the catalyst is palladium oxide/carbon or palladium/mesoporous carbon, the content of palladium oxide is 3-10 wt%, and the content of palladium is 1-7 wt%, so that the dehydrogenation temperature of the perhydrogenated organic liquid is effectively reduced, the dehydrogenation conversion rate and yield of the organic liquid at low temperature are improved, the highest dehydrogenation conversion rate is 100%, and the highest yield is 99.9% at 100-160 ℃.
The Chinese invention patent CN111569901A discloses a preparation method and application of a bimetallic catalyst for hydrogenation and dehydrogenation of an organic hydrogen storage medium, wherein the hydrogen storage medium is N-ethyl carbazole, the used non-noble metal is Ni, Cu, Mg or Fe, and the used noble metal is Pt, Pd, Rh, Ru or Au. The highest conversion rate of N-ethyl carbazole is 99% in the hydrogen storage process, and the highest selectivity of dodecahydro N-ethyl carbazole is 98%; the conversion rate of dodecahydro N-ethyl carbazole is 96% at most in the hydrogen discharge process, and the selectivity of N-ethyl carbazole is 98% at most. According to the reports of combined documents, Ru in the noble metal catalyzes N-ethylcarbazole to have the best hydrogen storage performance.
The invention CN110841630A discloses a catalyst which takes one or a combination of more of metal oxide, molecular sieve and porous material as a carrier and has the load of 1-5 wt% of one or more of platinum, lead, rhodium, ruthenium and gold. Wherein the metal oxide carrier comprises one or more of alumina, silica, titanium oxide and cerium oxide, the used molecular sieve is MCM-41 and/or SBA-15, and the used porous material is one or more of graphene, activated carbon and carbon nitride. The hydrogen storage and release medium is one of ethylene glycol, cyclohexane, methylcyclohexane, decahydronaphthalene, quinoline, carbazole, methylcarbazole and ethylcarbazole. The highest conversion rate of ethyl carbazole is 98% in the hydrogen storage process, and the highest selectivity of dodecahydroethyl carbazole is 98%. The highest conversion rate of dodecahydroethylcarbazole in the hydrogen discharge process is 91%, and the highest selectivity of ethylcarbazole is 89%.
The Chinese invention patent CN111054383A discloses a supported catalyst which mainly comprises Pt-Fe and is doped with Fe, alkali metal and lanthanide and a preparation method thereof, and the supported catalyst can effectively improve the dehydrogenation rate for dehydrogenation of at least one of methylcyclohexane, cyclohexane, tetrahydronaphthalene, decahydronaphthalene, perhydroazoethylcarbazole and perhydrocarbazole.
The Chinese invention patent CN111054384A discloses a supported catalyst which is mainly Pt-Cu and is added with at least one of Mg, In or oxides thereof and a preparation method thereof, and the supported catalyst is used for dehydrogenation of at least one of methylcyclohexane, cyclohexane, tetrahydronaphthalene, decahydronaphthalene, perhydroazeethylcarbazole and perhydrocarbazole, so that the stability of the catalyst is improved.
The Chinese patent CN111056531A discloses a method for dehydrogenating naphthene hydrogen storage material liquid phase containing heteroatom, which uses bifunctional catalyst, the main active component is at least one metal or alloy in platinum group metal, the catalyst has higher stability.
It can be seen that the catalysts all use noble metals as main active components, and are expensive, and the development of high-performance non-noble metal catalysts is urgently needed. When distillate oil is used as a hydrogen storage and release medium, transition metal sulfide is reported to be used as a catalyst. Chinese patent CN109704274A and CN109704275A disclose aryl petroleum distillate or coal-based distillate as hydrogen storage medium, and gamma-Al2O3One or more of supported CoMo, NiMo, CoW or NiW sulfide is used as a hydrogen storage and discharge system of the catalyst. However, the hydrogenation temperature is between 200 ℃ and 500 ℃, and the application of the technology is restricted by the excessively high reaction temperature.
Wu et Al disclose a Ni/Al catalyst for the hydrogenation of N-ethylcarbazole2O3The catalyst is characterized in that a rare earth metal hydride YH is added into the catalyst3Remarkably improves Ni/Al2O3Hydrogenation activity, hydrogen storage capability and noble metal Ru/Al2O3Corresponding to (Journal of materials chemistry A,2019,7(28): 16677-16684). But the catalyst is in particular YH3It needs to be prepared under oxygen-free conditions, has difficulty in industrial application, and is difficult to be used in a fixed bed reactor.
It should be noted that the above organic liquid hydrogen storage and discharge reaction is mostly carried out in a batch tank reactor. The batch reactor has high labor intensity and low treatment capacity, is difficult to realize automatic production and is not suitable for large-scale reaction. Compared with a batch kettle type reactor, the fixed bed reactor works in a continuous state, has stable product quality and high labor productivity, is convenient to realize mechanization and automation, and is suitable for large-scale reaction. Therefore, it is necessary to develop a high-efficiency organic liquid dehydrogenation non-noble metal catalyst suitable for a fixed bed reactor, which has catalytic hydrogen storage performance equivalent to that of noble metal and replaces noble metal catalysts.
Disclosure of Invention
The invention aims to develop a non-noble metal heterogeneous solid catalyst which is suitable for a fixed bed reactor and replaces the noble metal catalyst used by the existing nitrogen-containing organic liquid for hydrogen storage, and the catalyst can efficiently realize the hydrogenation of the nitrogen-containing organic liquid at a lower temperature (less than 200 ℃), has the catalytic performance equivalent to that of noble metal and replaces the noble metal catalyst.
Specifically, the invention provides a supported transition metal or transition metal phosphide catalyst taking a mesoporous material as a carrier, wherein the loading amount of the transition metal or transition metal phosphide is 2-50 wt%. The preferable load is 5 wt% -30 wt%, and the further preferable load is 7 wt% -15 wt%, and the mesoporous material refers to a porous material with a pore channel size of 2-50 nm, or a mesoporous and microporous composite material with a pore channel size of 0.1-50 nm. The preferred size of the pore channel is 2-20 nm, and the further preferred size of the pore channel is 3-10 nm, including but not limited to MCM-41, MCM-48, SBA-15, mesoporous Al2O3Mesoporous carbon, mesoporous TiO2And the like and mixtures thereof. Due to the nano-pore confinement effect of the mesoporous or mesoporous-microporous material carrier, the concentration of the hydrogenation intermediate product in the pore is improved, and the forward reaction is promotedThe selectivity of the continuous hydrogenation final product is improved, and the conversion rate and the hydrogen storage capacity of reactants are improved.
The active component of the catalyst is transition metal or transition metal phosphide, and the transition metal comprises at least one or more of Fe, Co, Ni and Cu. The transition metal phosphide includes nickel phosphide (such as Ni)2P、NiP、Ni12P5、Ni5P4Etc.), cobalt phosphide (e.g., Co)2P and CoP, etc.), molybdenum phosphide (MoP), tungsten phosphide (WP), copper phosphide (Cu)3P) and mixtures thereof.
The catalyst is prepared by a method of reducing the oxidation state precursor of the catalyst by temperature programming under hydrogen atmosphere. The catalyst oxidation state precursor can be prepared by adopting an impregnation method. Drying a carrier at 100-150 ℃ for 3-12 h, preferably at 110-120 ℃ for 8-12 h, adding a transition metal salt solution or a transition metal salt and phosphate mixture solution impregnation liquid, standing for 6-12 h, preferably standing for 10-12 h, then drying at 120-220 ℃ for 12-24 h, preferably at 120-150 ℃ for 10-12 h, and then roasting at 500-800 ℃ for 2-8 h, preferably at 500-550 ℃ for 3-5 h in an air or nitrogen atmosphere to obtain a catalyst oxidation state precursor.
Both the catalyst reduction and the organic liquid plus dehydrogenation reactions are carried out in fixed bed reactors. Firstly, the catalyst is filled in a fixed bed reactor H2The pressure is between 0.1 and 10MPa, preferably between 3 and 8MPa, more preferably between 5 and 7MPa, and the pressure is within a certain range of H2Under the flow condition, the temperature is raised to the final reduction temperature of 200-800 ℃, preferably 400-700 ℃, further preferably 500-650 ℃ according to a certain program, the temperature is kept for 0.5-24 h, preferably 2-10 h, further preferably 3-5 h, and the oxidation state precursor of the catalyst is converted into the active transition metal or transition metal phosphide catalyst. Then adjusting the temperature and pressure to the reaction temperature and pressure, and carrying out the dehydrogenation reaction of the nitrogen-containing organic liquid.
The invention has the advantages and beneficial effects that:
the invention uses cheap non-noble metal to replace expensive noble metal catalyst to obtain hydrogen storage activity equivalent to noble metal. The mesoporous or mesoporous-microporous composite material is used as a carrier, so that the hydrogenation activity of the non-noble metal transition metal or transition metal phosphide catalyst can be remarkably improved. The catalyst can be used for storing hydrogen in organic liquid in a continuous flowing fixed bed reactor, and improves the reaction efficiency. The safety is good, and the method is favorable for automatic industrial production. These factors greatly reduce the cost of catalyst and energy consumption in hydrogen storage process, raise production efficiency and raise economic benefit.
Drawings
FIG. 1 is a Ni/MCM-41XRD spectrum prepared by example 1;
FIG. 2 shows Ni/SiO solid prepared in comparative example 12XRD spectrogram;
FIG. 3 shows Ni, Ni/SiO2Ni/MCM-41 catalyst catalyzes NEC hydrogen storage time-conversion rate chart;
FIG. 4 is a NEC hydrogen storage product distribution diagram A) Ni/MCM-41 catalyst, B) Ni/SiO2Catalyst, C) Ni catalyst;
FIG. 5 is a graph of the selectivity of the NEC hydrogen storage product A) Ni/MCM-41 catalyst, B) Ni/SiO2Catalyst, C) Ni catalyst;
FIG. 6 shows Ni prepared in example 212P5a/MCM-41 XRD spectrum;
FIG. 7 is an XRD spectrum of MoP/MCM-41 prepared in comparative example 3;
FIG. 8 shows Ni prepared in comparative example 42P+Ni12P5/SiO2XRD spectrogram;
FIG. 9 shows Ni12P5/MCM-41、MoP/MCM-41、Ni2P+Ni12P5/SiO2Catalyst catalyzed NEC hydrogen storage time-conversion plot;
FIG. 10 is a NEC Hydrogen storage product Profile A) Ni12P5a/MCM-41 catalyst, B) a MoP/MCM-41 catalyst; C) ni2P+Ni12P5/SiO2A catalyst;
FIG. 11 is a NEC Hydrogen storage product selectivity profile A) Ni12P5a/MCM-41 catalyst, B) a MoP/MCM-41 catalyst; C) ni2P+Ni12P5/SiO2A catalyst;
FIG. 12 shows bulk Ni catalysts,14.8 wt% Ni/MCM-41 and Ru/Al2O3The performance of the catalyst catalyzing NEC is compared, wherein A is a conversion rate comparison graph, and B is a hydrogen storage amount comparison graph.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative, not limiting and are not intended to limit the scope of the invention.
Example 1: preparation of 14.8 wt% Ni/MCM-41 catalyst and its hydrogen storage in NEC catalysis
And (5) preparing a precursor. 1.5g of MCM-41 carrier was dried at 120 ℃ for 12h and cooled to room temperature. 1.10g of nickel nitrate (Ni (NO)3)2·6H2O) was dissolved in 1.35mL of deionized water to form a nickel nitrate solution. And dropwise adding the nickel nitrate solution into the MCM-41 carrier by using a dropper, and continuously stirring to ensure that the liquid is not separated out. After the dripping is finished, the preservative film is sealed and placed in the shade for standing for 12 hours. And transferring the mixture into a blast drying oven for drying at 120 ℃ for 12h, grinding the mixture into fine powder after drying, transferring the fine powder into a muffle furnace for roasting at 500 ℃ for 3h in an air atmosphere to obtain a precursor (NiO/MCM-41).
And (4) reducing the precursor. Crushing a Ni/MCM-41 precursor (NiO/MCM-41) into 20-40 meshes in a tabletting manner, filling 0.8g of precursor into a constant-temperature area of a fixed bed reaction tube, filling 20-40 meshes of quartz sand on two sides of the constant-temperature area, connecting the reaction tube and ensuring the air tightness of a fixed bed reaction device; introduction of H2The flow rate is 100mL/min, and the temperature is raised from room temperature to 400 ℃ at a speed of 5 ℃/min and maintained at 400 ℃ for 3 h. And (4) completing the reduction of the precursor to obtain the Ni/MCM-41 catalyst. FIG. 1 shows the XRD spectrum of the prepared Ni/MCM-41 catalyst, and the result shows that the Ni/MCM-41 catalyst is successfully prepared.
Ni/MCM-41 catalyzes NEC to store hydrogen continuously in a fixed bed reactor. After the reduction of the precursor is finished, at H2The temperature is reduced to 180 ℃ under the atmosphere (50 mL/min). To increase H2When the pressure is 5MPa, a mixture containing 8 wt% of N-ethyl carbazole/decalin is taken as an organic liquid hydrogen carrier, and the organic liquid hydrogen carrier is pumped into a reactor through a metering pump at the flow rate of 0.1mL/min, and the hydrogen flow rate is 75 mL/min. After 2h, the performance and the reaction of the catalyst are stable, and all liquid samples in the storage tank are taken out and then treatedAfter 1h, the liquid product was taken and quantitatively analyzed by gas chromatography-mass spectrometer, and the NEC conversion was calculated as shown in FIG. 3, the product distribution as shown by A in FIG. 4 and the selectivity as shown by A in FIG. 5.
Comparative example 1: 14.8 wt% Ni/SiO2Catalyst precursor preparation and its hydrogen storage in catalysis of NEC
The preparation process is the same as that of the 14.8 wt% Ni/MCM-41 catalyst precursor, except that the carrier is replaced by SiO2. The continuous hydrogen storage process of the precursor reduction process and the NEC in the fixed bed reactor is the same as the reduction process of the precursor of the 14.8 wt% Ni/MCM-41 catalyst. The precursors were reduced in a fixed bed reactor and evaluated for NEC continuous hydrogen storage performance. FIG. 2 shows the Ni/SiO prepared2The XRD spectrogram of the catalyst shows that the Ni/SiO is successfully prepared2The catalyst, conversion, is shown in figure 3. Ni/SiO2The product distribution is shown as B in FIG. 4, and the selectivity is shown as B in FIG. 5.
Comparative example 2: preparation of bulk Ni catalyst and its use in catalyzing NEC hydrogen storage
5g of nickel nitrate (Ni (NO))3)2·6H2O) directly placing the crucible into a muffle furnace to be roasted for 3 hours at 500 ℃ in air atmosphere to obtain a precursor NiO; the reduction process of the precursor and the continuous hydrogen storage process of the catalytic NEC in the fixed bed reactor are the same as the reduction process of the precursor of the 14.8 wt% Ni/MCM-41 catalyst. The precursor was reduced in a fixed bed reactor and evaluated for the continuous hydrogen storage performance of NEC. Bulk Ni conversion is shown in figure 3. Bulk Ni product distribution is as C in fig. 4, selectivity is as C in fig. 5.
The comparative analysis result shows that the Ni and the Ni/SiO in bulk phase2Compared with the mesoporous material MCM-41 serving as a carrier, the conversion rate of the catalyst to the NEC is obviously improved, the product is mainly 12H-NEC, and the 12H-NEC is high in selectivity and maintained at about 70%.
Example 2: 30 wt% Ni12P5Preparation of/MCM-41 catalyst and catalysis of NEC for hydrogen storage
And (5) preparing a precursor. 1.5g of MCM-41 were dried at 120 ℃ for 12 h. 1.76g of nickel nitrate was dissolved in 1.35mL of deionized water and added dropwise to MCM-41 with constant stirring. After the dropwise addition is finishedSealing the mixture in the shade with a preservative film and standing for 12 hours. Standing, and drying at 120 deg.C for 12 hr. And after drying, grinding into fine powder, roasting for 3 hours at 500 ℃ in air atmosphere, heating from room temperature to 500 ℃ at a speed of 5 ℃/min, keeping at 500 ℃ for 3 hours, cooling to room temperature, and taking out to obtain NiO/MCM-41. 0.80g of diammonium phosphate is dissolved in 1.35mL of deionized water, and the solution is dropwise added into a NiO/MCM-41 sample and is continuously stirred. After the dripping is finished, sealing the mixture in the shade for standing for 12 hours by using a preservative film. Standing, and drying at 120 deg.C for 12 hr. After drying, grinding into fine powder, roasting at 500 deg.C for 3h in air atmosphere, heating from room temperature to 500 deg.C at 5 deg.C/min, maintaining at 500 deg.C for 3h, cooling to room temperature, and taking out to obtain NiOP2O5/MCM-41, i.e. Ni12P5MCM-41 precursor.
And (4) reducing the precursor. Crushing the precursor tablets to 20-40 meshes, loading 0.8g of the precursor into a constant-temperature area of a fixed bed reaction tube, filling 20-40 meshes of quartz sand on two sides of the constant-temperature area, connecting the reaction tube and ensuring the air tightness of the fixed bed reaction device; introduction of H2The flow rate is 150mL/min, the temperature is raised from room temperature to 400 ℃ at 5 ℃/min, the temperature is raised from 400 ℃ to 550 ℃ at 1 ℃/min, and the temperature is maintained at 550 ℃ for 2 h. The reduction of the precursor is completed to obtain Ni12P5A catalyst/MCM-41 catalyst. FIG. 6 shows Ni prepared12P5XRD spectrogram of/MCM-41 catalyst shows that Ni is successfully prepared12P5A/MCM-41 catalyst.
Ni12P5MCM-41 catalyzed NEC stored hydrogen continuously in a fixed bed reactor. After the reduction of the precursor is finished, at H2The temperature is reduced to 180 ℃ under the atmosphere (50 mL/min). To increase H2When the pressure is 5MPa, a mixture containing 8 wt% of N-ethyl carbazole/decalin is taken as an organic liquid hydrogen carrier, and the organic liquid hydrogen carrier is pumped into a reactor through a metering pump at the flow rate of 0.1mL/min, and the hydrogen flow rate is 75 mL/min. After 2h, the performance and the reaction of the catalyst are stable, all liquid samples in the storage tank are taken out, after 1h, liquid products are taken out and quantitatively analyzed by using a gas chromatograph-mass spectrometer, the NEC conversion rate is calculated and shown in figure 9, the product distribution is shown in A in figure 10, and the selectivity is shown in A in figure 11.
Comparative example 3: preparation of 30 wt% MoP/MCM-41 catalyst and hydrogen storage of NEC catalyzed by catalyst
Preparation of 30 wt% MoP/MCM-41 precursor: 1.5g of MCM-41 were dried at 120 ℃ for 12 h. 0.78g of ammonium molybdate was dissolved in 1.35mL of deionized water and added dropwise to MCM-41 with constant stirring. After the dripping is finished, sealing the mixture in the shade for standing for 12 hours by using a preservative film. Standing, and drying at 120 deg.C for 12 h. After drying, grinding into fine powder, roasting at 500 deg.C for 3h in air atmosphere, heating from room temperature to 500 deg.C at 5 deg.C/min, maintaining at 500 deg.C for 3h, cooling to room temperature, and taking out to obtain MoO3/MCM-41. 0.80g of diammonium phosphate is dissolved in 1.35mL of deionized water and added dropwise to the MoO3In the/MCM-41 sample, stirring is continuously carried out. After the dripping is finished, sealing the mixture in the shade for standing for 12 hours by using a preservative film. Standing, and drying at 120 deg.C for 12 h. After drying, grinding into fine powder, roasting at 500 deg.C for 3h in air atmosphere, heating from room temperature to 500 deg.C at 5 deg.C/min, maintaining at 500 deg.C for 3h, cooling to room temperature, and taking out to obtain MoO3P2O5the/MCM-41, MoP/MCM-41 precursor. Reduction and continuous hydrogen storage process of MoP/MCM-41 precursor and 30 wt% Ni12P5the/MCM-41 catalyst was the same. FIG. 7 shows the XRD pattern of the prepared 30 wt% MoP/MCM-41 catalyst, and the results show that the MoP/MCM-41 catalyst was successfully prepared.
The precursors were reduced in a fixed bed reactor and evaluated for NEC continuous hydrogen storage performance. The conversion is shown in fig. 9, the product distribution is shown as B in fig. 10 and the selectivity is shown as B in fig. 11.
Comparative example 4: 30 wt% Ni2P+Ni12P5/SiO2Preparation of catalyst and its use for catalyzing NEC hydrogen storage
30wt％Ni2P+Ni12P5/SiO2The specific preparation, reduction and continuous hydrogen storage process of the precursor and 30 wt% Ni12P5the/MCM-41 catalyst was identical except that the support was replaced by SiO2. FIG. 8 shows 30 wt% Ni prepared2P+Ni12P5/SiO2XRD spectrogram and result table of catalystObviously successfully prepare Ni2P+Ni12P5A/MCM-41 catalyst.
The precursors were reduced in a fixed bed reactor and evaluated for NEC continuous hydrogen storage performance. The conversion is shown in fig. 9, the product distribution is shown as C in fig. 10 and the selectivity is shown as C in fig. 11.
The comparative analysis result shows that the product is compared with MoP/MCM-41 and Ni2P+Ni12P5/SiO2Compared with the mesoporous material MCM-41 as a carrier, the conversion rate of the catalyst to the NEC is obviously improved, the product mainly comprises 12H-NEC, the selectivity of the 12H-NEC is higher, and the selectivity is maintained at 70%. MoP/MCM-41 and Ni2P+Ni12P5/SiO2The selectivity of the catalyst product 12H-NEC is higher than that of Ni12P5A/MCM-41 catalyst, but with lower conversion to NEC.
The comparison result of the embodiment 1 with the comparison result of the comparison example 1 and the comparison example 2 shows that the catalytic performance is obviously improved when the non-noble metal is loaded on the mesoporous MCM-41 carrier. The comparison results of example 2, comparative example 3 and comparative example 4 also show that when the transition metal phosphide is loaded on the mesoporous support, the catalytic performance is significantly improved, but the activity and stability need to be further improved. In order to obtain a catalytic effect equivalent to the catalytic performance of the noble metal Ru, the method can be realized by increasing the loading of bulk Ni catalyst and Ni/MCM-41 catalyst and prolonging the retention time, and is specifically as follows.
Bulk Ni catalyst was prepared as shown in comparative example 2 with a catalyst loading of 2.8g NiO and the reduction procedure was the same as for the catalyst in example 1. 14.8 wt% Ni/MCM-41 catalyst was prepared as in example 1 with a catalyst loading of 1.2g NiO/MCM-41 and reduced as in example 1. In the hydrogen storage process, the retention time is adjusted by changing the liquid feed flow (0.05mL, 0.1mL, 0.15mL, 0.2mL, 0.25mL and 0.3mL), and the ratio of the liquid feed flow to the volume of hydrogen is ensured to be 1:750, so that the catalytic performance of bulk phase Ni and 14.8 wt% Ni/MCM-41 under different retention times is obtained.
For comparison, commercial 5 wt% Ru/gamma-Al with the highest hydrogen storage activity of NEC was selected2O3As a comparative catalyst, the hydrogen storage conditions were the same as in example 1.Comparative results As shown in FIG. 12, the bulk Ni catalyst having the lowest activity was used, and the high loading of 5 wt% Ru/gamma-Al was achieved by increasing the amount of catalyst and suitably extending the residence time of the reaction mass in the fixed bed2O3Has high catalytic activity. Non-noble metal Ni is loaded on the MCM-41 mesoporous carrier, and the hydrogen storage effect equivalent to that of noble metal can be obtained by increasing the dosage of the catalyst and prolonging the retention time. Although the loading amount of the non-noble metal Ni in this example is different from that of the noble metal Ru, the catalytic effect of the noble metal is achieved. The price of the noble metal Ru is about 120 yuan/g, while the price of the non-noble metal Ni is about 0.15 yuan/g, and the price of Ru is about 800 times that of Ni. Although the loading of the non-noble metal is far higher than that of the noble metal, the price of the non-noble metal catalyst is still significantly lower than that of the noble metal catalyst, which indicates that the non-noble metal catalyst is cheaper and can significantly reduce the cost of the catalyst.
Finally, although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that the present invention may be modified and/or substituted equally without departing from the spirit and scope of the present invention.
Claims (9)
1. A non-noble metal catalyst for hydrogen storage of nitrogen-containing organic liquid of a fixed bed reactor is characterized in that: the catalyst takes a mesoporous or mesoporous-microporous composite material as a carrier, takes a transition metal or transition metal phosphide as an active component, the loading capacity of the active component is 0.1 wt% -50 wt%, the transition metal is at least one of Fe, Co, Ni, Cu and Mo, and the size of a pore channel of the carrier material is 2-50 nm.
2. The catalyst of claim 1, wherein: the carrier is MCM-41, MCM-48, SBA-15 and mesoporous Al2O3Mesoporous carbon, mesoporous TiO2Or a mixture of two or more of them.
3. The catalysis of claim 1An agent characterized by: the transition metal phosphide is Ni2P、NiP、Ni12P5、Ni5P4、Co2P、CoP、MoP、WP、Cu3One or a mixture of two or more of P.
4. The method for preparing a catalyst according to claim 1, characterized in that: the catalyst is prepared by adopting a method of reducing an oxidation state precursor of the catalyst by temperature programming.
5. The method for preparing a catalyst according to claim 4, wherein: the method for preparing the catalyst oxidation state precursor by adopting an impregnation method comprises the following steps:
step 1): drying the carrier at 100-150 ℃ for 3-12 h;
step 2): mixing the transition metal precursor and deionized water according to a certain proportion, and mixing a phosphorus source and the deionized water; or mixing transition metal, phosphorus source and deionized water in a certain proportion;
and step 3): dropwise adding the solution obtained in the step 2) into the sample obtained in the step 1), and continuously stirring uniformly to complete impregnation;
step 4): standing the sample obtained in the step 3) and then drying;
step 5): and 4) putting the sample obtained in the step 4) into a muffle furnace for roasting.
6. The catalyst preparation method according to claim 4, characterized in that: the oxidation state precursor is reduced in a fixed bed reactor by a temperature programming reduction method to prepare the catalyst.
7. The method for preparing a catalyst according to claim 6, wherein: the temperature programmed reduction method is that firstly, a catalyst is filled in a fixed bed reactor, and H2The pressure is between 0.1 and 10MPa and is within a certain range of H2Under the condition of flow rate, the temperature is raised to the final reduction temperature of 200-800 ℃ according to a certain program, the temperature is kept for 0.5-24 h, and the oxidation state precursor of the catalyst is converted into active transition metal orA transition metal phosphide catalyst.
8. The method for applying the catalyst to the hydrogenation reaction of the nitrogen-containing organic liquid according to claim 1, wherein the method comprises the following steps: the reaction is carried out in a fixed bed reactor, the hydrogenation reaction temperature is less than or equal to 200 ℃, and H2The pressure is less than or equal to 10MPa, and the weight hourly space velocity is 0.05-60 h-1The volume ratio of hydrogen to organic liquid is 450-1000.
9. The method of application according to claim 8, characterized in that: the nitrogen-containing organic liquid is one or a mixture of more than two of N-ethyl carbazole, N-propyl carbazole, N-methyl carbazole and carbazole.
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