CN114797912B - 一种脱氢催化剂及其制备方法 - Google Patents
一种脱氢催化剂及其制备方法 Download PDFInfo
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- CN114797912B CN114797912B CN202210603741.3A CN202210603741A CN114797912B CN 114797912 B CN114797912 B CN 114797912B CN 202210603741 A CN202210603741 A CN 202210603741A CN 114797912 B CN114797912 B CN 114797912B
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- catalyst
- dehydrogenation
- tio
- catalytic
- noble metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 42
- 239000001257 hydrogen Substances 0.000 claims abstract description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 239000011232 storage material Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- 230000009467 reduction Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 150000004395 organic heterocyclic compounds Chemical class 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 150000003384 small molecules Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 abstract description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 abstract description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 abstract description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 3
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 abstract description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- 238000003860 storage Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 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
- 239000004408 titanium dioxide Substances 0.000 description 5
- 229910018054 Ni-Cu Inorganic materials 0.000 description 4
- 229910018481 Ni—Cu Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 2
- 229910003267 Ni-Co Inorganic materials 0.000 description 2
- 229910003262 Ni‐Co Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000012448 Lithium borohydride Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 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
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 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
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- 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
-
- 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
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
-
- 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
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
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Abstract
本发明具体涉及一种脱氢催化剂及其制备方法，属于催化脱氢技术领域。本发明使用非贵金属作为贵金属主催化剂与非金属改性的二氧化钛催化助剂的“桥梁”，一方面提升了贵金属主催化剂的活性与稳定性，降低了贵金属用量；另一方面增强了金属与载体间的相互作用，使得总体催化性能远高于传统贵金属催化剂，对咔唑、吲哚、喹啉类新型储氢材料实现了在180℃以下可控的完全脱氢。本发明催化剂的原料来源广泛，成本低廉，工艺简单周期短，收率高，可有效降低脱氢催化剂成本，并可实现规模化应用于储氢材料催化脱氢。
Description
技术领域
本发明属于催化脱氢技术领域，具体涉及一种脱氢催化剂及其制备方法。
背景技术
氢能由于其能量密度高、热值大、来源广泛、绿色环保等特点使其成为未来绿色能源中的及其重要组成部分。氢能的利用包括四大部分：氢的制取、存储、运输和氢的利用。其中，氢的安全高效储运是氢能规模化应用的关键环节，也是制约其的瓶颈。因此，当前已发展出多种储氢技术，包括氢气深冷液化储氢、高压气瓶罐储氢、固体氢化物储氢、多孔材料吸附储氢以及有机液体储氢等。
其中，有机液体储氢材料因其储氢密度高、安全性能好，具有与现有石油具有相同的运输架构，使其成为最具发展潜力的储氢技术。然而，有机液体储氢材料释放氢气需要进行催化脱氢，必须使用贵金属催化剂才可在较为温和的条件下进行反应。而目前所使用贵金属如Pt、Pd等资源稀缺，成本高昂，且容易中毒失活，从而造成放氢效率降低达不到使用要求等问题。这些问题的存在是不利于有机液体储氢技术规模化应用的。因此，有必要开发出降低贵金属使用量同时又保持催化性能不降低的新型催化剂。
公开号为CN111569901A的中国专利文献公开了一种贵金属与非贵金属结合的一种脱氢催化剂，但是该催化剂使用氧化铝、分子筛、石墨烯等作为载体，只能起到分散活性金属的作用，对于脱氢本身来说没有作用。值得注意的是，该催化剂对有机液体储氢材料脱氢温度高达280℃，且甚至不能完全释放所储氢的氢气，催化效率远低于当前传统贵金属催化剂Pt/Al2O3和Pd/Al2O3在200℃以内就可以实现的完全脱氢。
有鉴于此，有必要提供一种能够有效降低贵金属用量且催化性能提升的脱氢催化剂及其制备方法。
发明内容
针对现有技术的不足，本发明的目的在于提供一种有效降低贵金属用量且催化性能提升的脱氢催化剂及其制备方法，选择可实现高比表面积制备和表面容易改性掺杂的二氧化钛作为基体进行活性元素引入，利用其与活性组分之间存在的协同效应来实现对催化性能的极大提升。
为实现上述技术目的，达到上述技术效果，本发明是通过以下技术方案实现：
一种脱氢催化剂，该脱氢催化剂其组成为A@B/M-TiO2，其中，
A为主催化剂，包括Pd、Pt、Ru、Au、Ag中的任一种或多种组合；所述主催化剂的摩尔百分含量为0.1％～2％；
B为副催化剂，包括Fe、Co、Ni、Ce、La、Cu、Zn、Mo、W、V、Y、Cr中的任一种或多种组合，所述副催化剂的摩尔百分含量为0.1％～13％；
M-TiO2为催化助剂，其中M包括F、N、H、B、P中的任一种或多种组合，M的摩尔百分比含量为0.001％～5％，余量为TiO2的摩尔百分比含量。
进一步地，所述副催化剂作为主催化剂与催化助剂的“桥梁”存在；其中，所述主催化剂与副催化剂结合形成活性双金属合金，副催化剂与催化助剂结合形成活性金属锚点。
如上所述的脱氢催化剂在储氢材料催化脱氢中的应用。所述材料用催化含有C-H键的饱和芳香烃以及饱和有机杂环化合物等各类储氢材料生成C＝C双键的脱氢反应。
一种脱氢催化剂的制备方法，包括如下步骤：
1)称取1体积份的钛源溶于10～50体积份的有机溶剂中，加入0.2～2体积份的小分子饱和醇类，常温下搅拌均匀，得到含钛混合溶液；
2)向含钛混合溶液中加入一定量的M前驱体溶液，搅拌均匀后转移到高温高压釜中，置于80～200℃温度下进行热反应，反应时间为6～24h；
3)产物通过清洗处理，干燥得到具有高比表面的M-TiO2；
4)称取一定量的B前驱体溶于去离子水中，浸渍负载到M-TiO2上，充分干燥后在300～500℃温度下继续煅烧1～5h，得到B/M-TiO2；
5)称取一定量的A前驱体溶于去离子水中，浸渍负载到B/M-TiO2上，充分干燥；
6)干燥后所得样品，在300～500℃温度下继续煅烧1～6h，在氢气气氛中还原，还原温度为300～500℃，还原时间为0.5～5h；还原得到A@B/M-TiO2型脱氢催化剂。
进一步地，步骤1)中，钛源为钛酸异丙酯、钛酸乙酯中的任一种或组合；所述有机溶剂为丙酮、环己酮中的任一种或组合；小分子饱和醇类为乙二醇、异丙醇中的任一种或组合。
进一步地，步骤2)中，M前驱体溶液为氟化钠、氟化铵、尿素、氨水、三聚氰胺、硝酸铵、硼氢化钠、硼氢化锂、磷酸二氢钠、磷酸中的任一种或多种组合。
进一步地，步骤3)中，产物的清洗处理方式根据所引入的M元素而定，其中清洗剂包括去离子水、有机或无机溶剂。
进一步地，步骤4)中，B前驱体为硝酸铁、氯化铁、硝酸钴、氯化钴、硝酸镍、氯化镍、硝酸铈、硝酸镧、硝酸铜、硝酸锌、钼酸铵、钼酸钠、偏钨酸铵、钨酸钠、偏钒酸铵、硝酸钇、硝酸铬、硫酸铬中的任一种或多种组合。
进一步地，步骤4)中，煅烧温度优选为300～500℃，煅烧时间优选为2～4h。
进一步地，步骤5)中，A前驱体为氯化铂、硝酸铂、氯化钯、氢氧化钯、醋酸钯、硝酸钯、氯化钌、氯化金、氢氧化金、硝酸银、醋酸银中的任一种或多种组合。
进一步地，步骤6)中，煅烧温度优选为400～500℃，煅烧时间优选为2～5h。还原温度优选为400～500℃，优选为1～3h。
与现有技术相比，本发明的有益效果是：
1、本发明使用非贵金属作为贵金属主催化剂与非金属改性的二氧化钛催化助剂的“桥梁”，一方面提升了贵金属主催化剂的活性与稳定性，降低了贵金属用量；另一方面增强了金属与载体间的相互作用，使得总体催化性能远高于传统贵金属催化剂，对咔唑、吲哚、喹啉类新型储氢材料实现了在180℃以下可控的完全脱氢。
2、本发明催化剂的所有原料来源广泛，成本低廉，工艺简单周期短，收率高，可有效降低脱氢催化剂成本，并可实现规模化应用于储氢材料催化脱氢。
当然，实施本发明的任一产品并不一定需要同时达到以上的所有优点。
具体实施方式
下面将结合本发明实施例对技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。
本发明首先以一步溶剂热法合成具有高比表面积的改性二氧化钛催化助剂，其既可为活性组分提供分散和锚定功能的作用，又可改变催化剂的电子结构从而进一步提升其催化活性；其次通过最为简单的浸渍负载还原法把活性金属负载到催化助剂上，最终获得前述具有协同作用的比例可调节的高活性A@B/M-TiO2型催化剂。本发明制备过程简单高效，周期短，成本合理，适合规模化产生与应用。
本发明的具体实施例如下：
实施例1
按体积比1:30，称取1份钛酸异丙酯溶于30份丙酮中，再加入1份异丙醇，常温下搅拌均匀，得到含钛混合溶液；按摩尔比P：TiO2＝2:98向含钛混合溶液中加入一定量的磷酸溶液，搅拌均匀后转移到高温高压釜中，置于120℃下进行12h热反应，自然冷却后产物通过去离子水与乙醇过滤处理，100℃干燥得到具有高比表面的P-TiO2。按摩尔比B:P-TiO2＝5:95将硝酸镍溶液浸渍负载到P-TiO2上，充分干燥后，置于马弗炉中以5℃/min升温至400℃煅烧2h。随后按摩尔比A:Ni/P-TiO2＝1:99将氯铂酸溶液浸渍负载到Ni/P-TiO2上，充分干燥后，置于马弗炉中以5℃/min升温至400℃煅烧3h。随后在氢气气氛下400℃还原2h得到Pt@Ni/P-TiO2型脱氢催化剂。
按活性金属：储氢材料＝1：200，在脱氢反应器中按表中设定温度反应6h，得到结果如表1所示：
表1
实施例2
按体积比1:30，称取1份钛酸异丙酯和钛酸乙酯溶于30份丙酮中，再加入1份乙二醇，常温下搅拌均匀，得到含钛混合溶液；按摩尔比F：TiO2＝5:95向含钛混合溶液中加入一定量的氟化钠，搅拌均匀后转移到高温高压釜中，置于150℃下进行12h热反应，自然冷却后产物通过去离子水与乙醇过滤处理，100℃干燥得到具有高比表面的F-TiO2。按摩尔比B:F-TiO2＝10:90将硝酸镍和硝酸铜溶液浸渍负载到F-TiO2上，充分干燥后，置于马弗炉中以5℃/min升温至400℃煅烧2h。随后按摩尔比A:Ni-Cu/F-TiO2＝1:99将醋酸钯溶液浸渍负载到Ni-Cu/F-TiO2上，充分干燥后，置于马弗炉中以5℃/min升温至450℃煅烧3h。随后在氢气气氛下400℃还原4h得到Pd@Ni-Cu/F-TiO2型脱氢催化剂。
按活性金属：储氢材料＝1：200，在高温高压反应釜中，在脱氢反应器中按表中设定温度反应6h，得到结果如表2所示：
表2
实施例3
按体积比1:30，称取1份钛酸异丙酯和钛酸乙酯溶于30份丙酮中，再加入0.5份异丙醇，常温下搅拌均匀，得到含钛混合溶液；按摩尔比F：TiO2＝5:95向含钛混合溶液中加入一定量的氟化铵，搅拌均匀后转移到高温高压釜中，置于180℃下进行12h热反应，自然冷却后产物通过去离子水与乙醇过滤处理，100℃干燥得到具有高比表面的F-TiO2。按摩尔比B:F-TiO2＝10:90将硝酸镍和硝酸镍溶液浸渍负载到F-TiO2上，充分干燥后，置于马弗炉中以5℃/min升温至400℃煅烧2h。随后按摩尔比A:Ni-Cu/F-TiO2＝0.8:99.2将醋酸钯溶液浸渍负载到Ni-Co/F-TiO2上，充分干燥后，置于马弗炉中以5℃/min升温至450℃煅烧3h。随后在氢气气氛下400℃还原4h得到Pd@Ni-Co/F-TiO2型脱氢催化剂。
按活性金属：储氢材料＝1：200，在高温高压反应釜中，在脱氢反应器中按表中设定温度反应6h，得到结果如表3所示：
表3
以上公开的本发明优选实施例只是用于帮助阐述本发明。优选实施例并没有详尽叙述所有的细节，也不限制该发明仅为具体实施方式。显然，根据本说明书的内容，可作很多的修改和变化。本说明书选取并具体描述这些实施例，是为了更好地解释本发明的原理和实际应用，从而使所属技术领域技术人员能很好地理解和利用本发明。本发明仅受权利要求书及其全部范围和等效物的限制。
Claims (3)
1.一种脱氢催化剂在储氢材料催化脱氢中的应用，其特征在于，该脱氢催化剂其组成为A@B/M-TiO2，其中，
A为主催化剂，为Pd、Pt中的一种或两种；所述主催化剂的摩尔百分含量为0.1%～2%；
B为副催化剂，为Co、Ni、Cu中的一种或多种，所述副催化剂的摩尔百分含量为0.1%～13%；
M-TiO2为催化助剂，其中M为F、P中的一种或两种，M的摩尔百分比含量为0.001%～5%，余量为TiO2的摩尔百分比含量；
所述主催化剂与副催化剂结合形成活性双金属合金，副催化剂与催化助剂结合形成活性金属锚点；
所述脱氢催化剂的制备方法包括如下步骤：
1）称取1体积份的钛源溶于10~50体积份的有机溶剂中，加入0.2~2体积份的小分子饱和醇类，常温下搅拌均匀，得到含钛混合溶液；
2）向含钛混合溶液中加入一定量的M前驱体溶液，搅拌均匀后转移到高温高压釜中，置于80～200℃温度下进行热反应，反应时间为6～24h；
3）产物通过清洗处理，干燥得到具有高比表面的M-TiO2；
4）称取一定量的B前驱体溶于去离子水中，浸渍负载到M-TiO2上，充分干燥后在300～500℃温度下继续煅烧1～5h，得到B/M-TiO2；
5）称取一定量的A前驱体溶于去离子水中，浸渍负载到B/M-TiO2上，充分干燥；
6）干燥后所得样品，在300～500℃温度下继续煅烧1～6h，在氢气气氛中还原，还原温度为300～500℃，还原时间为0.5～5h；还原得到A@B/M-TiO2型脱氢催化剂。
2.根据权利要求1所述的应用，其特征在于，所述材料用于催化含有C-H键的饱和芳香烃以及饱和有机杂环化合物储氢材料生成C=C双键的脱氢反应。
3.根据权利要求1所述的应用，其特征在于，步骤1）中，钛源为钛酸异丙酯、钛酸乙酯中的任一种或组合；所述有机溶剂为丙酮、环己酮中的任一种或组合；小分子饱和醇类为乙二醇、异丙醇中的任一种或组合。
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| CN108654663A (zh) * | 2017-07-28 | 2018-10-16 | 中国地质大学（北京） | 一种混合硝酸盐熔盐法制备硼氮共掺杂单晶介孔TiO2催化材料的方法 |
| CN111892017A (zh) * | 2019-05-06 | 2020-11-06 | 中国石油化工股份有限公司 | 一种有机液体制备高纯度高压氢气的方法 |
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| CN1583263A (zh) * | 2004-06-08 | 2005-02-23 | 南京工业大学 | 用于有机液体氢化物可逆储放氢的催化剂及其制备方法 |
| CN103495429A (zh) * | 2013-07-19 | 2014-01-08 | 西安理工大学 | 一种磷掺杂二氧化钛粉体光催化剂的微波水热合成方法 |
| CN104525169A (zh) * | 2014-12-31 | 2015-04-22 | 哈尔滨师范大学 | F-P-TiO2纳米光催化剂的制备方法 |
| CN108654663A (zh) * | 2017-07-28 | 2018-10-16 | 中国地质大学（北京） | 一种混合硝酸盐熔盐法制备硼氮共掺杂单晶介孔TiO2催化材料的方法 |
| CN111892017A (zh) * | 2019-05-06 | 2020-11-06 | 中国石油化工股份有限公司 | 一种有机液体制备高纯度高压氢气的方法 |
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