CN116550348A - Transition metal phosphide, preparation method and application thereof - Google Patents
Transition metal phosphide, preparation method and application thereof Download PDFInfo
- Publication number
- CN116550348A CN116550348A CN202210110916.7A CN202210110916A CN116550348A CN 116550348 A CN116550348 A CN 116550348A CN 202210110916 A CN202210110916 A CN 202210110916A CN 116550348 A CN116550348 A CN 116550348A
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- China
- Prior art keywords
- transition metal
- phosphide
- preparation
- catalyst
- hydrogen
- Prior art date
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- Pending
Links
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 47
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
- 239000011574 phosphorus Substances 0.000 claims abstract description 19
- -1 nitrogen-containing heterocyclic compound Chemical class 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 51
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 239000012298 atmosphere Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 18
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 235000002949 phytic acid Nutrition 0.000 claims description 5
- 239000000467 phytic acid Substances 0.000 claims description 5
- 229940068041 phytic acid Drugs 0.000 claims description 5
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 3
- YDULQTLSFNLWCO-UHFFFAOYSA-N 4,6-dimethyl-1-benzothiophene Chemical compound CC1=CC(C)=C2C=CSC2=C1 YDULQTLSFNLWCO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002028 Biomass Substances 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 claims description 2
- 230000003009 desulfurizing effect Effects 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000003536 tetrazoles Chemical class 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 238000000197 pyrolysis Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 23
- 229910021641 deionized water Inorganic materials 0.000 description 23
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 10
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000005696 Diammonium phosphate Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 6
- 235000019838 diammonium phosphate Nutrition 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- 125000004437 phosphorous atom Chemical group 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000006004 Quartz sand Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 1
- 229910002555 FeNi Inorganic materials 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- 229910039444 MoC Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000013528 artificial neural network Methods 0.000 description 1
- WUPZNKGVDMHMBS-UHFFFAOYSA-N azane;dihydrate Chemical compound [NH4+].[NH4+].[OH-].[OH-] WUPZNKGVDMHMBS-UHFFFAOYSA-N 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- PJDBVVBEOBZFDJ-UHFFFAOYSA-L azanium nickel(2+) phosphate Chemical compound [NH4+].[Ni+2].[O-]P([O-])([O-])=O PJDBVVBEOBZFDJ-UHFFFAOYSA-L 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- VPUSHLJJFFGLIY-UHFFFAOYSA-N decane phenol Chemical compound C1(=CC=CC=C1)O.CCCCCCCCCC VPUSHLJJFFGLIY-UHFFFAOYSA-N 0.000 description 1
- IOOLTBNEXBPMAX-UHFFFAOYSA-N decane thiophene Chemical compound c1ccsc1.CCCCCCCCCC IOOLTBNEXBPMAX-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- HVENHVMWDAPFTH-UHFFFAOYSA-N iron(3+) trinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HVENHVMWDAPFTH-UHFFFAOYSA-N 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 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
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- 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 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of transition metal phosphide, which comprises the following steps: mixing a transition metal salt solution with a nitrogen-containing heterocyclic compound, adding a phosphorus source-containing solution into the mixture, mixing and stirring the mixture for reaction, and drying and roasting the product to obtain the transition metal phosphide. The preparation method is simple and convenient in preparation process, simple in operation, mild in condition, easy in control of technological parameters, applicable to preparation of various transition metal phosphides, wide in application range and relatively low in pyrolysis temperature, the obtained phosphide can be used in various hydrotreating processes such as hydrodesulfurization, hydrodeoxygenation and the like, and has good catalytic effect, and the deoxidization rate and deoxidization rate of the organic matters are both over 95 percent.
Description
Technical Field
The invention relates to a hydrogenation catalyst, in particular to a transition metal phosphide catalytic material, and belongs to the technical field of catalytic materials.
Background
Today, the quality of crude oil is continuously reduced, the environmental protection requirements of the world and China are increasingly strict, and the requirements promote people to continuously improve and perfect the existing oil processing technology so as to obtain target products meeting the requirements. Crude oil contains a large amount of impurities such as N, O, S and metals, and the existence of the impurities ensures that petroleum products are poor in stability and influence secondary processing of the products, and pollution is generated in the application process of the petroleum products, so that the petroleum products are harmful to human bodies and ecological environment.
The hydrotreating is one of modes for effectively reducing impurities in the oil, can remove N, O, S and the like in the oil, can saturate aromatic hydrocarbon, reduces the content of aromatic hydrocarbon and improves the quality of the oil. One of the key points of the hydrotreating technology is the preparation of hydrotreating catalysts, and the development of high-activity low-cost hydrotreating catalysts is a serious issue in the development of the hydrotreating technology. Transition metal phosphides have noble-like properties and find application in a number of hydrogen-related reactions. Transition metal phosphides are compounds formed by the insertion of phosphorus atoms into a metal lattice. Phosphorus forms a covalent bond or a metallic bond with the transition metal element. The phosphorus atoms are larger, so that after the phosphorus is bonded with transition metal, an octahedral coordination structure is more easily formed around the phosphorus atoms, so that the phosphorus atoms are positioned at the central position, and therefore, the phosphorus atoms are different from a sulfide layered structure, the phosphide structure is more similar to a sphere, more active center sites are exposed in a catalytic reaction, macromolecular reactants are more easily accessible to the active sites on the surface of the catalyst, and excellent catalytic performance is shown in a plurality of reactions.
The preparation method of the transition metal phosphide is various. In general, the preparation method of phosphide mainly comprises the following steps: (1) inorganic phosphate and ammonium nickel phosphate reduction; (2) metal organic decomposition method; (3) A low-temperature hydrogen plasma preparation method, wherein the preparation temperature is lower; (3) a metal organic compound decomposition method; (4) solvothermal synthesis; (5) Directly combining metal and red phosphorus simple substance under the action of high temperature and protective atmosphere; (6) synthesizing a nano phosphate precursor; (7) electrolysis of molten salt; (8) a method of reacting a metal halide with phosphine, etc. These methods have problems such as high reduction temperature, expensive raw materials, complex operation, etc., and in summary, the research of the preparation method of the transition metal phosphide is important for the application of the phosphide, the simple and easy preparation method is a precondition for the wide application of the catalyst, and different preparation methods have a certain influence on the performance of the catalyst.
CN113061930a discloses a method for preparing transition metal phosphide, which comprises dissolving transition metal salt and organic ligand in solvent, adding phytic acid solution, then solvothermal treatment to obtain phytic acid doped MOF material, and then thermal pyrolysis carbonization to obtain transition metal phosphide. C111185206A also discloses a preparation method of the chestnut-shaped transition metal phosphide catalyst, which is suitable for preparing various transition metal phosphides (Fe, co, ni, cu, cr, pt, pd, mo, W, etc.), and the preparation method adopts a hydrothermal method, and the roasting temperature is higher (600-800 ℃). CN112108165a discloses a preparation method of a nitrogen and phosphorus double-doped carbon-coated molybdenum phosphide catalyst, which takes phytic acid, ammonium molybdate tetrahydrate and melamine as reaction raw materials, adds water for dissolution, then dries at low temperature to obtain a precursor, and then roasting at high temperature (800-1000 ℃) to obtain the nitrogen and phosphorus double-doped carbon-coated molybdenum phosphide catalyst. The method is simpler, but the roasting temperature is too high, and the obtained molybdenum phosphide catalytic material is coated with carbon on the outer layer, so that the coated carbon is favorable for increasing the conductivity in the electrocatalytic reaction, but the existence of an external carbon layer is easy to cover reaction sites in the hydrogenation reaction, so that the hydrogenation activity of the catalyst is limited. CN107999105a discloses a preparation method of a porous rod-shaped molybdenum phosphide hydrogen evolution catalyst with a morphology structure, absorbent cotton is used as a template agent, a mixed solution of ammonium molybdate and ammonium dihydrogen phosphate is used as a metal source and a molybdenum source, absorbent cotton after absorbing the mixed solution is dried, and the absorbent cotton is kept at a certain temperature for a period of time to obtain a molybdenum phosphide precursor, and then the molybdenum phosphide hydrogen evolution catalyst is obtained at a certain temperature for a period of time under a reducing atmosphere. CN108772089a discloses a preparation method of a nitrogen-doped carbon-linked molybdenum phosphide high-performance hydrogen evolution catalyst with a neural network structure, which comprises the steps of dissolving ammonium molybdate, monoammonium phosphate and urea in deionized water, stirring and aging at 80 ℃, then placing melamine resin foam in the solution for adsorption and drying to obtain a molybdenum phosphide precursor, and finally roasting the precursor at a high temperature (850-900 ℃) in a nitrogen atmosphere to obtain the high-performance molybdenum phosphide hydrogen evolution catalyst. The catalyst metal content prepared by the method depends on the adsorption of melamine resin foam to a metal solution, has uncertainty, cannot ensure uniformity and stability, and has high roasting temperature, so that the application of the catalyst metal content is limited. CN101992109a discloses a hydrofining catalyst of transition metal phosphide and a preparation method thereof, mesoporous carbon is used as a carrier, one or more transition metal phosphate solutions of first transition metals (Fe, co, ni, W, mo, ru, pd and Pt) are loaded by a dipping method, one or more metals or metal oxides of second transition metal elements (Ti, ce, la, Y, zn and Nb) are loaded by a dipping method after drying and roasting, and then the final catalyst is obtained after drying, roasting and reduction. The method adopts secondary metal load to prepare the catalyst, which is easy to cause uneven distribution of active metal on the surface of the catalyst, and the preparation process needs to be dried and roasted for many times, thus increasing the preparation cost of the catalyst.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides the transition metal phosphide, the preparation method and the application thereof, and the preparation method has the advantages of simple process, mild condition, easy implementation and wide application range, is suitable for preparing single-metal and multi-metal phosphide, and meanwhile, the obtained phosphide has high purity, good crystallinity and controllable phase state.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
the first aspect of the invention provides a preparation method of transition metal phosphide, which comprises the following steps: mixing a transition metal salt solution with a nitrogen-containing heterocyclic compound, adding a phosphorus source-containing solution into the mixture, mixing and stirring the mixture for reaction, and drying and roasting the product to obtain the transition metal phosphide.
Further, in one embodiment of the present invention, the nitrogen-containing heterocyclic compound is selected from at least one of imidazole and its derivatives, pyrazole and its derivatives, triazole and its derivatives, tetrazole and its derivatives. Preferably, the compound is selected from one of imidazole and aminotriazole.
Further, in one embodiment of the present invention, the salt solution of the transition metal is selected from at least one of Fe, co, ni, cu, ru, rh, pd, pt and water-soluble salts of Ag. At least one of the water-soluble salts of Fe, co and Ni is preferred.
Further, in one embodiment of the present invention, the phosphorus source is selected from at least one of ammonium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate and phytic acid, and more preferably, is ammonium phosphate and/or phytic acid.
Further, in one embodiment of the present invention, in the reaction system, the molar ratio of the metal to the nitrogen-containing heterocyclic compound is 0.6 to 2:1 in terms of the metal element of the transition metal salt.
Further, in one embodiment of the present invention, in the reaction system, the molar ratio of the metal element of the transition metal salt to the phosphorus element in the phosphorus source is 0.3 to 3:1.
Further, in one embodiment of the invention, the reaction temperature is-20-30 ℃; the reaction time is 0.5 to 6 hours, preferably 1 to 5 hours.
Further, in one embodiment of the present invention, the drying temperature is 60 to 120 ℃ and the drying time is 3 to 8 hours.
Further, in one embodiment of the present invention, the roasting atmosphere is selected from any one of a nitrogen atmosphere, an inert gas atmosphere, a hydrogen/nitrogen atmosphere and a hydrogen/inert gas atmosphere, wherein the hydrogen volume fraction in the hydrogen/nitrogen atmosphere and the hydrogen/inert gas atmosphere is 5-50%. Preferably a nitrogen atmosphere, an argon atmosphere, a hydrogen/nitrogen atmosphere or a hydrogen/helium atmosphere.
Further, in one embodiment of the present invention, the baking temperature is 200 to 600 ℃; and (5) after the temperature is increased to the roasting temperature, the roasting constant temperature time is 1-4 h. As one of more preferable specific embodiments, the roasting adopts a slow heating mode, and the heating rate is 0.5-5 ℃/min.
Further, in one embodiment of the present invention, the stirring is one of magnetic stirring and mechanical stirring.
Further, in one embodiment of the present invention, after the reaction is completed, the solid product is collected by filtration, suction filtration or centrifugation. The collecting step further comprises the step of washing with deionized water and/or ethanol for 3-7 times.
The technical object of the second aspect of the present invention is to provide a transition metal phosphide prepared by the above method. In the preparation method, the nitrogenous heterocyclic compound is added, the transition metal phosphide is obtained through one-step reaction and roasting, the phosphide with different crystal forms can be obtained through controlling the roasting temperature, and the roasting temperature is low.
The technical object of the third aspect of the present invention is to provide a method for deoxidizing an oxygen-containing organic matter, which uses the above-mentioned transition metal phosphide as a catalyst.
Specifically, the transition metal phosphide is used for catalyzing the hydrodeoxygenation process of oxygen-containing organic matters, and the oxygen-containing organic matters are oxygen-containing compounds in furfural, phenol, furan, benzofuran, dibenzofuran, anisole, diphenyl ether, fatty acid ester and other biomass-based diesel oil raw materials. The hydrodeoxygenation reaction temperature is 250-360 ℃ and the pressure is 0.1-4 mpa.
The technical object of the fourth aspect of the present invention is to provide a method for desulfurizing sulfur-containing organic matters, which uses the transition metal phosphide as a catalyst.
Specifically, the transition metal phosphide is used for catalyzing the hydrodesulfurization process of sulfur-containing organic matters, wherein the sulfur-containing organic matters are thiophene, benzothiophene, dibenzothiophene or 4, 6-dimethyl benzothiophene and the like. The temperature of the hydrodesulfurization reaction is 320-400 ℃ and the pressure is 1-6 mpa.
The technical scheme of the invention has the following technical effects:
the preparation process of the transition metal phosphide is simple and convenient, the operation is simple, the condition is mild, the technological parameters are easy to control, the preparation method is suitable for the preparation of various transition metal phosphides, the application range is wide, the pyrolysis temperature is relatively low, the obtained phosphide can be used in various hydrotreating processes such as hydrodesulfurization, hydrodeoxygenation and the like, good catalytic effect is shown, and the deoxidization rate and the desulfurization rate of organic matters are both over 95 percent.
Drawings
FIG. 1 is an XRD pattern of nickel phosphide obtained in example 1;
FIG. 2 is an XRD pattern of nickel phosphide obtained in example 2;
fig. 3 is an XRD pattern of cobalt phosphide obtained in example 3.
Detailed description of the preferred embodiments
The present invention will be described in detail by way of examples, but the present invention is not limited to these examples.
Example 1
0.2908g (1 mmol) of nickel nitrate hexahydrate was dissolved in 10mL of deionized water, and after completion of the dissolution, 0.0841g (1 mmol) of aminotriazole was added to the solution to obtain a clear solution; 0.0551g (0.42 mmol) of diammonium phosphate is dissolved in 10mL deionized water solution; and adding the phosphorus source solution into a nickel source and aminotriazole mixed solution, stirring at room temperature for reaction for 2 hours, filtering a product, washing the product with deionized water, drying the product at 80 ℃ for 4 hours, heating the product to 400 ℃ at a heating rate of 5 ℃/min in an inert atmosphere with an argon flow rate of 40 mL/min, keeping the temperature for 2 hours, closing the gas, and naturally cooling the product to obtain the nickel phosphide catalytic material. The resulting nickel phosphide material was subjected to XRD characterization as shown in fig. 1.
As can be seen from FIG. 1, the nickel phosphide crystalline form obtained is Ni 12 P 5 The nickel phosphide catalytic material has high crystallinity, high purity and Ni 12 P 5 The content is 100%.
Example 2
0.2908g (1 mmol) of nickel nitrate hexahydrate was dissolved in 10mL of deionized water, and after completion of the dissolution, 0.0841g (1 mmol) of aminotriazole was added to the solution to obtain a clear solution; 0.0661g (0.5 mmol) of diammonium phosphate is dissolved in 10mL deionized water solution; and adding the phosphorus source solution into a nickel source and aminotriazole mixed solution, stirring at room temperature for reaction for 2 hours, filtering a product, washing the product with deionized water, drying the product at 80 ℃ for 4 hours, heating the product to 500 ℃ at a heating rate of 5 ℃/min in an inert atmosphere with an argon flow rate of 40 mL/min, keeping the temperature for 2 hours, closing the gas, and naturally cooling the product to obtain the nickel phosphide catalytic material. The resulting nickel phosphide material was subjected to XRD characterization as shown in fig. 2.
As can be seen from FIG. 2, the nickel phosphide crystalline form obtained was Ni 2 P, the obtained nickel phosphide catalytic material has complete crystal structure, high purity and Ni 2 The P phase content was 100%.
Example 3
0.2910g (1 mmol) of cobalt nitrate hexahydrate was dissolved in 10mL of deionized water, and after complete dissolution, 0.0841g (1 mmol) of aminotriazole was added to the cobalt solution to give a clear solution; 0.0661g (0.5 mmol) of diammonium phosphate is dissolved in 10mL deionized water solution; and adding the phosphorus source solution into a cobalt source and aminotriazole mixed solution, stirring at room temperature for reaction for 2 hours, filtering a product, washing the product with deionized water, drying the product at 80 ℃ for 4 hours, heating the product to 500 ℃ at a heating rate of 5 ℃/min in an inert atmosphere with an argon flow rate of 40 mL/min, keeping the temperature for 2 hours, closing the gas, and naturally cooling the product to obtain the cobalt phosphide catalytic material. The resultant cobalt phosphide material was subjected to XRD characterization as shown in fig. 3.
As can be seen from FIG. 3, the cobalt phosphide crystalline form obtained was Co 2 P, the obtained cobalt phosphide catalytic material has complete crystal structure, high purity and Co 2 The P phase content was 100%.
Example 4
0.2908g (1 mmol) of nickel nitrate hexahydrate was dissolved in 10mL of deionized water, after which 0.068g of imidazole (1 mmol) was added to the solution to give a clear solution; 0.0661g (0.5 mmol) phosphoric acidDissolving diammonium hydroxide in 10mL deionized water solution; adding the phosphorus source solution into a nickel source and imidazole mixed solution, stirring at room temperature for reaction for 2 hours, filtering a product, washing the product by deionized water, drying the product at 80 ℃ for 4 hours, heating the product to 500 ℃ at a heating rate of 5 ℃/min in an inert atmosphere with an argon flow rate of 40 mL/min, keeping the temperature for 2 hours, closing gas, and naturally cooling to obtain the nickel phosphide catalytic material. Likewise, the nickel phosphide catalytic material obtained is Ni with high purity 2 And P phase.
Example 5
0.4040g (1 mmol) of ferric nitrate hexahydrate was dissolved in 10mL of deionized water, and after complete dissolution, 0.0841g (1 mmol) of aminotriazole was added to the iron solution to give a clear solution; 0.4624g (0.35 mmol) of diammonium phosphate is dissolved in 10mL deionized water solution; adding the phosphorus source solution into a mixed solution of an iron source and aminotriazole, stirring at room temperature for reaction for 2 hours, filtering a product, washing the product with deionized water, drying the product at 80 ℃ for 4 hours, heating the product to 400 ℃ at a heating rate of 5 ℃/min in an inert atmosphere with an argon flow rate of 40 mL/min, keeping the temperature for 2 hours, closing the gas, and naturally cooling the product to obtain the iron phosphide catalytic material. The obtained iron phosphide catalytic material is high-purity Fe 3 And P phase.
Example 6
0.2020g (0.5 mmol) of ferric nitrate nonahydrate and 0.5816g (2 mmol) of nickel nitrate hexahydrate were dissolved in 30mL of deionized water, and after complete dissolution, 0.4205g (5 mmol) of aminotriazole was added to the above mixed solution to obtain a dark reddish brown clear solution; 0.0793g (0.6 mmol) of diammonium phosphate is dissolved in 20mL deionized water solution; adding the phosphorus source solution into a mixed solution of a metal source and aminotriazole, stirring and reacting for 2 hours at room temperature, filtering a product, washing the product by deionized water, drying the product at 80 ℃ for 4 hours, heating the product to 500 ℃ at a heating rate of 5 ℃/min in an inert atmosphere with an argon flow rate of 40 mL/min, keeping the temperature for 2 hours, closing the gas, and naturally cooling the product to obtain the ferronickel bimetallic phosphide catalytic material. The obtained bimetallic phosphide phase is FeNi with high purity 2 And P phase.
Comparative example 1
Dissolving 0.1766 ammonium heptamolybdate tetrahydrate in 10mL of deionized water, adding 0.0841g of aminotriazole into the solution after the ammonium heptamolybdate tetrahydrate is completely dissolved, and obtaining a clear solution, wherein the clear solution becomes turbid gradually along with the prolonged stirring time; 0.1982g of diammonium phosphate is dissolved in 10mL of deionized water solution; adding the phosphorus source solution into a mixed solution of a molybdenum source and aminotriazole to quickly generate precipitate, continuing stirring for 1h at room temperature, carrying out suction filtration on the product, washing with deionized water, drying at 80 ℃ for 4h, heating to 550 ℃ at a heating rate of 5 ℃/min in a reducing mixed atmosphere with an argon flow rate of 40 mL/min and a hydrogen flow rate of 20 mL/min, keeping the temperature for 4h, closing the gas, and naturally cooling to obtain the molybdenum-based catalytic material. The process is a coprecipitation process, and the obtained precursor is not uniform. The obtained phosphide has complex phase, is not single, is mainly molybdenum carbide phase and is doped with a small amount of molybdenum phosphide phase.
Example 7
The nickel phosphide catalyst in the example 2 is applied to thiophene hydrodesulfurization reaction, 0.1g of the nickel phosphide catalyst is taken, the catalyst is placed in a constant temperature section of a fixed bed reactor, two ends of the catalyst are supported by fine quartz sand (20-40 meshes), the catalyst is pretreated for 2 hours under the hydrogen pressure of 4MPa at 400 ℃, then the temperature is reduced to 330 ℃, the hydrodesulfurization reaction is carried out on the 1.5% thiophene n-decane solution under the hydrogen-oil ratio of 400, after the catalyst is stabilized for 12 hours, the contact time is changed, the sample is sampled, the mass spectrum is used for qualitative, the gas chromatography is used for quantitative analysis, and the product is analyzed, so that the calculated desulfurization rate is 99.3%.
Example 8
The nickel phosphide catalyst in the example 2 is applied to the dibenzothiophene hydrodesulfurization reaction, 0.2g of the nickel phosphide catalyst is taken, the catalyst is placed in a constant temperature section of a fixed bed reactor, two ends of the catalyst are supported by fine quartz sand (20-40 meshes), the catalyst is pretreated for 2 hours under the hydrogen pressure of 4MPa at 400 ℃, then the temperature is reduced to 350 ℃ to carry out the hydrodesulfurization reaction on 3% of the decalin solution of the dibenzothiophene, after the catalyst is stabilized for 12 hours, the contact time is changed to sample, the sample is subjected to qualitative analysis by mass spectrometry, the gas chromatography is subjected to quantitative analysis, and the calculated desulfurization rate is 98.7%.
Example 9
The nickel phosphide catalyst in the example 2 is applied to the hydrogenation reaction of furfural, 0.2g of the nickel phosphide catalyst is taken, the catalyst is placed in a constant temperature section of a fixed bed reactor, both ends of the catalyst are supported by fine quartz sand (20-40 meshes), the catalyst is pretreated for 2 hours under the hydrogen pressure of 1MPa at 400 ℃, then the catalyst is cooled to 240 ℃ to carry out hydrodeoxygenation reaction on 5% of furfural n-decane solution, after the catalyst is stabilized for 12 hours, the sample is sampled by changing the contact time, the sample is qualitatively carried out by mass spectrum, the gas chromatography is used for quantifying, the products are analyzed, and the conversion rate is close to 100% and the deoxidization rate is 98.9% after calculation.
Example 10
The nickel phosphide catalyst in the embodiment 1 is applied to the hydrodeoxygenation reaction of diphenyl ether, 0.2g of the nickel phosphide catalyst is taken, the catalyst is placed in a constant temperature section of a fixed bed reactor, two ends of the catalyst are supported by fine quartz sand (20-40 meshes), the catalyst is pretreated for 2 hours under the hydrogen pressure of 4MPa at 400 ℃, then the temperature is reduced to 320 ℃ to carry out hydrodeoxygenation reaction on a 5% phenol n-decane solution, after the catalyst is stabilized for 12 hours, the contact time is changed to sample, the sample is qualitatively carried out by mass spectrum, the gas chromatography is carried out for quantification, the product is analyzed, the conversion rate is close to 100%, and the deoxidization rate is as high as 99.5% after calculation.
Claims (16)
1. The preparation method of the transition metal phosphide is characterized by comprising the following steps: mixing a transition metal salt solution with a nitrogen-containing heterocyclic compound, adding a phosphorus source-containing solution into the mixture, mixing and stirring the mixture for reaction, and drying and roasting the product to obtain the transition metal phosphide.
2. The method according to claim 1, wherein the nitrogen-containing heterocyclic compound is at least one selected from the group consisting of imidazole and its derivatives, pyrazole and its derivatives, triazole and its derivatives, tetrazole and its derivatives, preferably one selected from the group consisting of imidazole and aminotriazole.
3. The method of claim 1, wherein the salt solution of the transition metal is selected from at least one of Fe, co, ni, cu, ru, rh, pd, pt and a water-soluble salt of Ag.
4. The method according to claim 1, wherein the phosphorus source is at least one selected from the group consisting of ammonium phosphate salts, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate and phytic acid.
5. The method according to claim 1, wherein the molar ratio of the metal to the nitrogen-containing heterocyclic compound in the reaction system is 0.6 to 2:1 in terms of the metal element of the transition metal salt.
6. The method according to claim 1, wherein the molar ratio of the transition metal salt to the phosphorus element in the phosphorus source is 0.3 to 3:1.
7. The preparation method according to claim 1, wherein the reaction temperature is-20 to 30 ℃; the reaction time is 0.5-6 h.
8. The preparation method according to claim 1, wherein the drying temperature is 60-120 ℃ and the drying time is 3-8 hours.
9. The method according to claim 1, wherein the baking atmosphere is selected from any one of a nitrogen atmosphere, an inert gas atmosphere, a hydrogen/nitrogen atmosphere and a hydrogen/inert gas atmosphere, wherein the hydrogen volume fraction in the hydrogen/nitrogen atmosphere and the hydrogen/inert gas atmosphere is 5 to 50%.
10. The method according to claim 1, wherein the baking temperature is 200 to 600 ℃, and the baking constant temperature time is 1 to 4 hours after the baking temperature is raised.
11. The preparation method of claim 10, wherein the roasting adopts a slow heating mode, and the heating rate is 0.5-5 ℃/min.
12. A transition metal phosphide prepared by the method of any one of claims 1-11.
13. A process for deoxidizing an oxygen-containing organic substance, which comprises using the transition metal phosphide as defined in claim 12 as a catalyst.
14. The method of claim 13, wherein the transition metal phosphide is an oxygenate in furfuraldehyde, phenol, furan, benzofuran, dibenzofuran, anisole, diphenyl ether, fatty acid ester and other biomass-based diesel fuel feedstock, which catalyzes a hydrodeoxygenation process of an oxygenate.
15. A method for desulfurizing sulfur-containing organic matter, which comprises using the transition metal phosphide as defined in claim 12 as a catalyst.
16. The method of claim 15, wherein the transition metal phosphide is a catalyst for hydrodesulfurization of sulfur-containing organics, the sulfur-containing organics being thiophene, benzothiophene, dibenzothiophene, or 4, 6-dimethylbenzothiophene.
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