CN108579742A - Dehydrogenation and preparation method thereof - Google Patents
Dehydrogenation and preparation method thereof Download PDFInfo
- Publication number
- CN108579742A CN108579742A CN201810400659.4A CN201810400659A CN108579742A CN 108579742 A CN108579742 A CN 108579742A CN 201810400659 A CN201810400659 A CN 201810400659A CN 108579742 A CN108579742 A CN 108579742A
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- Prior art keywords
- added
- zinc
- solution
- carrier
- preparation
- Prior art date
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Links
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 73
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 61
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002131 composite material Substances 0.000 claims abstract description 38
- 239000011701 zinc Substances 0.000 claims abstract description 37
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 37
- -1 Zinc modified zirconium dioxide Chemical class 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000284 extract Substances 0.000 claims abstract description 13
- 238000002803 maceration Methods 0.000 claims abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- 238000007598 dipping method Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 10
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011591 potassium Substances 0.000 claims abstract description 9
- 229910052718 tin Inorganic materials 0.000 claims abstract description 9
- 239000011135 tin Substances 0.000 claims abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 94
- 239000000843 powder Substances 0.000 claims description 74
- 238000003756 stirring Methods 0.000 claims description 72
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 44
- 238000001694 spray drying Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000008367 deionised water Substances 0.000 claims description 35
- 229910021641 deionized water Inorganic materials 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000002002 slurry Substances 0.000 claims description 26
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 26
- 229910052593 corundum Inorganic materials 0.000 claims description 25
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 20
- 239000012279 sodium borohydride Substances 0.000 claims description 19
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 19
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 18
- 239000012018 catalyst precursor Substances 0.000 claims description 18
- 229910052726 zirconium Inorganic materials 0.000 claims description 18
- 238000005352 clarification Methods 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 230000010355 oscillation Effects 0.000 claims description 16
- 239000006228 supernatant Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical group Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 14
- 238000005470 impregnation Methods 0.000 claims description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 11
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 150000003752 zinc compounds Chemical class 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- YTAHJIFKAKIKAV-XNMGPUDCSA-N [(1R)-3-morpholin-4-yl-1-phenylpropyl] N-[(3S)-2-oxo-5-phenyl-1,3-dihydro-1,4-benzodiazepin-3-yl]carbamate Chemical compound O=C1[C@H](N=C(C2=C(N1)C=CC=C2)C1=CC=CC=C1)NC(O[C@H](CCN1CCOCC1)C1=CC=CC=C1)=O YTAHJIFKAKIKAV-XNMGPUDCSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 claims description 3
- CTUFHBVSYAEMLM-UHFFFAOYSA-N acetic acid;platinum Chemical compound [Pt].CC(O)=O.CC(O)=O CTUFHBVSYAEMLM-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 150000003891 oxalate salts Chemical class 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 62
- 239000001294 propane Substances 0.000 abstract description 31
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 20
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 18
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract 1
- 102100030310 5,6-dihydroxyindole-2-carboxylic acid oxidase Human genes 0.000 description 32
- 101000773083 Homo sapiens 5,6-dihydroxyindole-2-carboxylic acid oxidase Proteins 0.000 description 32
- 210000002966 serum Anatomy 0.000 description 23
- 238000000034 method Methods 0.000 description 22
- 239000003643 water by type Substances 0.000 description 22
- 241000219782 Sesbania Species 0.000 description 16
- 239000000969 carrier Substances 0.000 description 14
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 13
- 229910001593 boehmite Inorganic materials 0.000 description 13
- 239000000428 dust Substances 0.000 description 13
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 13
- 239000004411 aluminium Substances 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- 238000004898 kneading Methods 0.000 description 10
- 238000005086 pumping Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000001802 infusion Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910004631 Ce(NO3)3.6H2O Inorganic materials 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910005267 GaCl3 Inorganic materials 0.000 description 1
- 229910003594 H2PtCl6.6H2O Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical class OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical class O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004451 qualitative analysis 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
- 238000011946 reduction process Methods 0.000 description 1
- 239000013558 reference substance Substances 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
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble 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
- 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
-
- 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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- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention belongs to catalyst technical field, a kind of dehydrogenation and preparation method thereof is disclosed：Using the composite oxides formed through Zinc modified zirconium dioxide and activated alumina as carrier,With Pt for main active component,To be selected from potassium,Magnesium,Tin,Lanthanum,Cerium,Iron,Cobalt,One or more of nickel is to help active component,The composite oxide carrier that dipping is formed through Zinc modified zirconium dioxide and activated alumina using Pt nanoparticle sols as maceration extract,The composite oxide carrier drying through Zinc modified zirconium dioxide and activated alumina composition after dipping,Roasting,Reduction obtains the dehydrogenation,Pt can be substantially reduced at high temperature to gather,Pt is evenly distributed in composite oxide carrier,Active component Pt has very big specific surface area,Dehydrogenation of the present invention is applied in preparing propylene by dehydrogenating propane reaction,While maintaining high Propylene Selectivity,Conversion of propane significantly improves,The high-temperature stability of catalyst of the present invention also significantly improves.
Description
Technical field
The present invention relates to chemical technology fields, and the present invention relates to a kind of dehydrogenations and preparation method thereof, further
Say, be related to it is a kind of using Pt nano-particles as active component, it is compound to be formed with activated alumina through Zinc modified zirconium dioxide
Oxide is the dehydrogenation and preparation method thereof of carrier.
Background technology
Propylene is a kind of important basic organic chemical industry raw material being only second to ethylene, can be used for synthesizing polypropylene, acrylic acid, third
The materials such as olefine aldehydr and propylene oxide, it may also be used for the products such as production plastics, organic glass and epoxy resin.The main source of propylene
Divide 3 kinds：Naphtha steam cracking, refinery's FCC by-products and dehydrogenating propane.First two method high energy consumption and the non-renewable stone of palpus consumption
Oily resource.Preparing propylene by dehydrogenating propane can utilize the propane resource compared with horn of plenty, development potentiality huge.
In preparing propylene by dehydrogenating propane technique, the quality of dehydrogenation performance directly affects propene yield and is produced into
This.Catalyst performance is mainly reflected in activity, selectivity, 3 aspect of stability.
CN201510346158.9 discloses a kind of using mesopore molecular sieve as the propane dehydrogenation catalyst of carrier.The catalyst
Active component is group VIII metal, such as Pt, and auxiliary agent includes Group IIB metal and alkaline earth and/or rare earth metal.The catalyst is used for
When dehydrogenating propane, there is good conversion ratio, selectivity and stability.
CN201510696918.9 discloses one kind using multi-walled carbon nanotube as carrier propane dehydrogenation catalyst, active component
Pt, auxiliary agent P.When being reacted applied to dehydrogenating propane, there is higher reaction stability and Propylene Selectivity.
CN201611104718.0 discloses one kind using macroporous aluminium oxide as carrier, and Pt is active component, and Na helps for first
Agent, K, Sn, Ca are the second auxiliary agent.When the catalyst is used for dehydrogenating propane, service life is long, and renewable performance is good.
Nevertheless, because above-mentioned method for preparing catalyst is traditional infusion process, catalyst activity component made from the method
Disperse it is uneven, and be easy to happen under high temperature Pt aggregation.Therefore can have an adverse effect to catalyst performance.
Invention content
It is an object of the invention to solve the deficiencies in the prior art, the purpose of the present invention is use traditional infusion process to overcome
Pt caused by preparing catalyst disperses Pt the shortcomings that easily assembling under bad and high temperature, provides a kind of new activity, selectivity and steady
The qualitative loaded nano Pt catalyst and preparation method thereof improved, and answering in preparing propylene by dehydrogenating propane technique
With.
A kind of dehydrogenation is to carry with the composite oxides formed through Zinc modified zirconium dioxide and activated alumina
Body is to help active component to be selected from one or more of potassium, magnesium, tin, lanthanum, cerium, iron, cobalt, nickel with Pt for main active component,
In the carrier, the mass ratio of zirconium dioxide and activated alumina is ZrO2:Al2O3=1:0.5-40, the zinc exist
Mass content in carrier is 0.1%-20%, and the mass contents of the Pt in the catalyst are 0.01%-10%, described
It is 0%-8% to help the mass content of active component in the catalyst.
The present invention also provides a kind of preparation methods of the dehydrogenation, including：Using Pt nanoparticle sols as
Composite oxide carrier of the maceration extract dipping through Zinc modified zirconium dioxide and activated alumina composition.
Further, further comprising the steps of：After dipping through Zinc modified zirconium dioxide and activated alumina group
At composite oxide carrier drying, roasting, reduction obtain the dehydrogenation.
Further, the preparation of the Pt nanoparticle sols includes：
A, it to the desired amount of surface stabilizer and helps deionized water dissolving is added in active constituent compound, be made containing helping work
The surface stabilizer aqueous solution of property component；
A, it takes the desired amount of compound containing Pt with containing helping the surface stabilizer aqueous solution of active component to mix, stirs at room temperature
Mixed solution is made in 30-60min；
C, deionized water is added into the desired amount of reducing agent and reducing agent solution is made；
D, reducing agent solution is added drop-wise in mixed solution with vigorous stirring, continues to stir 4-6h at room temperature, obtains
Containing the Pt nanoparticle colloidal sols for helping active component.
Further, the preparation of the composite oxide carrier through Zinc modified zirconium dioxide and activated alumina composition
Including：
E, deionized water is added into the desired amount of activated alumina powder, is uniformly mixed, then institute is added thereto
The zirconium-containing compound of requirement and the desired amount of zinc compound solid powder or solution, are uniformly mixed, slurry 1 are made；
F, acid or alkali are added into slurry 1, adjusts the pH=1-10 of slurry, the slurry 2 of solid content 10-50wt% is made；
G, by 2 spray drying forming of slurry, hot wind inlet temperature is 160-560 DEG C, and wind exhausting outlet temperature is 100-240
DEG C, obtain solid particle powder；
H, the solid particle powder obtained after spray drying at 500-700 DEG C is roasted into 4-8h, can obtained through Zinc modified
Composite oxide carrier powder；
I, into step h gained through aequum sesbania powder and concentration are added in Zinc modified composite oxide carrier powder
Mass fraction is the nitric acid of 10-30wt%, and kneader is added after being uniformly mixed and mediates 30min, is then extruded into 2-3mm items
The composite oxides through Zinc modified zirconium dioxide and activated alumina composition are made in shape, dry, 500-700 DEG C of roasting
Carrier.
Further, the preparation method of the dehydrogenation specifically includes following steps：
J, using Pt nanoparticle sols as maceration extract, dipping is formed through Zinc modified zirconium dioxide and activated alumina
Composite oxide carrier, using ultrasonic oscillation impregnation 2-6h, 20-80 DEG C of dipping temperature, until upper solution becomes clarification,
Catalyst precursor is obtained,
K, the supernatant liquor in removing step j steepers, is then filtered by vacuum bottom catalyst precursor, with
Use respectively washing 2 times of deionized water and ethyl alcohol respectively afterwards,
L, the washed product that will be obtained in step k, dry 0.5-12h under conditions of 50-200 DEG C,
M, the desciccate obtained in step l under the conditions of 300-750 DEG C is roasted into 0.5-10h, obtains oxidation catalyst,
N, by the oxidation catalyst obtained in step m at 80-600 DEG C, dehydrogenation is obtained with reducibility gas reduction 0.5-12h
Catalyst.
Further, the surface stabilizer described in step a is cetyl trimethylammonium bromide, polyvinylpyrrolidone
At least one of.
Further, the compound containing Pt described in step b is chloroplatinic acid, platinum nitrate, platinum chloride, platinum acetate, chloroplatinic acid
One or more of in ammonium, it is containing potassium, magnesium, tin, lanthanum, cerium, iron, cobalt, the nitrate of nickel, hydrochloride, grass to help active constituent compound
One or more of hydrochlorate.
Further, the reducing agent described in step c is NaBH4.
Further, the zirconium-containing compound described in step e is zirconium oxychloride or zirconium nitrate, and zinc compound is nitric acid
One or more of zinc, zinc chloride, zinc oxalate.
Advantageous effect：
Compared with prior art, dehydrogenation of the invention is impregnated using Pt nanoparticle sols as maceration extract and is repaiied through zinc
The composite oxide carrier of the zirconium dioxide of decorations and activated alumina composition, can substantially reduce Pt and gather at high temperature, and Pt is multiple
It closes oxide carrier to be evenly distributed, in dehydrogenation, by being supported on through Zinc modified zirconium dioxide and activated alumina group
At composite oxide carrier, active component Pt has greatly opposite specific surface area, significantly increases catalyst activity substance
With the touch opportunity of reaction mass, and this catalyst carrier has a larger specific surface area, obtained catalyst activity with it is steady
Qualitative all to significantly improve, nanometer dehydrogenation of the present invention is applied in preparing propylene by dehydrogenating propane reaction, is maintaining high propylene choosing
While selecting property, conversion of propane significantly improves, and the high-temperature stability of catalyst of the present invention also significantly improves.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be noted that described herein specific
Embodiment is merely to illustrate the present invention, is not intended to restrict the invention.
The present invention provides a kind of dehydrogenations, compound to be formed with activated alumina through Zinc modified zirconium dioxide
Oxide is carrier, is to help to be selected from one or more of potassium, magnesium, tin, lanthanum, cerium, iron, cobalt, nickel with Pt for main active component
Active component, in the carrier, the mass ratio of zirconium dioxide and activated alumina is ZrO2:Al2O3=1:0.5-40, institute
The mass content of the zinc stated in the carrier is 0.1%-20%, and the mass contents of the Pt in the catalyst are 0.01%-
10%, the mass content of active component in the catalyst that helps is 0%-8%.
As the preferred embodiment of the present invention, the group of the dehydrogenation become in carrier zirconium dioxide and
The mass ratio of activated alumina is ZrO2:Al2O3=1:1-30；The mass content of the zinc in the carrier is 1%-15%；It is described
The mass contents of Pt in the catalyst are 0.1%-5.0%；The mass content of active component in the catalyst that helps is
0.1%-7%.
As another preferred embodiment of the present invention, the group of the Pt catalyst becomes zirconium dioxide in carrier
Mass ratio with aluminium oxide is ZrO2:Al2O3=1:1-10；Mass content of the zinc in the carrier is 1%-10%；Institute
The mass contents of the Pt stated in the catalyst are 0.2-1.8%；The mass content of active component in the catalyst that helps is
1%-5%, described helps active component to be selected from one or more of potassium, cobalt, tin, cerium.
The present invention provides a kind of preparation methods of dehydrogenation, including：Using Pt nanoparticle sols as maceration extract
Composite oxide carrier of the dipping through Zinc modified zirconium dioxide and activated alumina composition.
Further, further comprising the steps of：After dipping through Zinc modified zirconium dioxide and activated alumina group
At composite oxide carrier drying, roasting, reduction obtain the dehydrogenation.
As the preferred embodiment of the present invention, the dehydrogenation is obtained through following preparation process steps, the step
Including：
(1) prepared by Pt nanoparticle sols
A, it to the desired amount of surface stabilizer and helps deionized water dissolving is added in active constituent compound, be made containing helping work
The surface stabilizer aqueous solution of property component；
A, it takes the desired amount of compound containing Pt with containing helping the surface stabilizer aqueous solution of active component to mix, stirs at room temperature
Mixed solution is made in 30-60min；
C, deionized water is added into the desired amount of reducing agent and reducing agent solution is made；
D, reducing agent solution being added drop-wise in mixed solution with vigorous stirring, dropwise addition process is emerged with a large amount of bubbles,
Continue to stir 4-6h at room temperature, obtain containing the Pt nanoparticle colloidal sols for helping active component.
(2) prepared by carrier
E, deionized water is added into the desired amount of activated alumina powder, is uniformly mixed, then institute is added thereto
The zirconium-containing compound of requirement and the desired amount of zinc compound solid powder or solution, are uniformly mixed, slurry 1 are made；
F, acid or alkali are added into slurry 1, adjusts the pH=1-10 of slurry, preferred pH=3-7, solid content 10- is made
The slurry 2 of 50wt%；
G, by 2 spray drying forming of slurry, hot wind inlet temperature is 160-560 DEG C, and wind exhausting outlet temperature is 100-240
DEG C, obtain solid particle powder；
H, the solid particle powder obtained after spray drying at 500-700 DEG C is roasted into 4-8h, can obtained through Zinc modified
Composite oxide carrier powder；
I, into step h gained through aequum sesbania powder and concentration are added in Zinc modified composite oxide carrier powder
Mass fraction is the nitric acid of 10-30wt%, and kneader is added after being uniformly mixed and mediates 30min, is then extruded into 2-3mm items
The composite oxides through Zinc modified zirconium dioxide and activated alumina composition are made in shape, dry, 500-700 DEG C of roasting
Carrier.
(3) catalyst preparation
J, the composite oxide carrier through Zinc modified zirconium dioxide and activated alumina composition is quickly adding into step d
It is obtained containing helping in the Pt nanoparticle colloidal sols of active component, using ultrasonic oscillation impregnation 2-6h, dipping temperature 20-
80 DEG C, until upper solution becomes clarification, obtain catalyst precursor；
K, the supernatant liquor in removing step j steepers, is then filtered by vacuum bottom catalyst precursor, with
Use respectively washing 2 times of deionized water and ethyl alcohol respectively afterwards；
L, the washed product that will be obtained in step k, dry 0.5-12h under conditions of 50-200 DEG C；
M, the desciccate obtained in step l under the conditions of 300-750 DEG C is roasted into 0.5-10h, obtains oxidation state catalysis
Agent；
N, it by the oxidized catalyst obtained in step m at 80-600 DEG C, must be taken off with reducibility gas reduction 0.5-12h
Hydrogen catalyst.
As the preferred embodiment of the present invention, the surface stabilizer described in step a is cetyl trimethylammonium bromide
(CATB), polyvinylpyrrolidone (PVP)；
As the preferred embodiment of the present invention, the compound containing Pt described in step b is chloroplatinic acid, platinum nitrate, platinum chloride, vinegar
Sour platinum, ammonium chloroplatinate；Active constituent compound is helped to refer to containing potassium, magnesium, tin, lanthanum, cerium, iron, cobalt, the nitrate of nickel, hydrochloride, oxalic acid
Salt；
As the preferred embodiment of the present invention, the reducing agent described in step c is NaBH4；
As the preferred embodiment of the present invention, the zirconium-containing compound described in step e is zirconium oxychloride or zirconium nitrate；Containing zinc impregnation
Conjunction object is zinc nitrate, zinc chloride, zinc oxalate；
As the preferred embodiment of the present invention, reducibility gas described in step n be hydrogen, carbon monoxide or containing both
One of gaseous mixture.
The present invention still further provides application of above-mentioned catalyst during preparing propylene by dehydrogenating propane；The application be
In fixed bed differential reactor, in 400-600 DEG C of reduction temperature, recovery time 3-6h；The reduction process can be in pure hydrogen
It carries out in atmosphere, can also be carried out with noble gas mixed atmosphere in pure hydrogen.Reaction velocity is 1000-2000h-1, propane/hydrogen charge ratio
1：1-1：5, dehydrogenation reaction temperature is 500-650 DEG C.
The present invention will be described in detail by the following examples, but therefore protection scope of the present invention is not limited
System.
In embodiment, used CATB, H2PtCl6.6H2O、NaBH4、GaCl3、KNO3、Mg(NO3)2、SnCl2、Ce
(NO3)3.6H2O is traditional Chinese medicines reagent, and analysis is pure.Nitric acid manufacturer is Beijing Chemical Plant, and analysis is pure.Ludox manufacturer is Qing Daohai
Foreign Chemical Co., Ltd., 40wt%.Sesbania powder manufacturer is that Chinese and Western is long-range, total sugar content 85.9%.
Boehmite powder is SB powder (import of German Condea companies), and related data is as follows：
SB powder physical properties
| Heap density | g/L | 680-800 |
| Specific surface area | m2/g | 230min |
| Pore volume | mL/g | 0.5min |
SB powder particle diameter distributions
| <25μm | % | 40.0max |
| <45μm | % | 55.0max |
| >90μm | % | 18.0max |
Embodiment 1
(1) prepared by Pt Nano sols
0.75g cetyl trimethylammonium bromides (CATB) are taken then to be moved with liquid-transfering gun with 50.0mL deionized water dissolvings
Take the H of a certain amount of (2.5mL0.10mol/L)2PtCl6Solution is added in above-mentioned CATB solution, stirs 30-40min at room temperature.
Weigh a certain amount of 0.15gNaBH4It is dissolved in 10mL deionized waters and NaBH is made4Solution, with vigorous stirring by NaBH4Solution drips
It is added to H2PtCl6In the mixed solution of CATB, process is added dropwise with a large amount of bubbles in 60 drops of rate of addition/min (about 3ml/min)
It emits, continues to stir 5h at room temperature, Pt Nano sols can be obtained.
(2) prepared by carrier
3kg deionized waters are added in a stirring kettle, 300g boehmite powder is added after opening stirring, stirs evenly
Afterwards, zirconium oxychloride is added, makes zirconium aluminium mass ratio ZrO2:Al2O3=1:4, continue to be uniformly mixed.It will be pre-configured
The zinc nitrate solution 0.3L of 1mol/L, is added in above-mentioned slurries, is uniformly mixed, obtain mixed serum.Mixed serum is used
Spray drying device drying and moulding, spray-drying operation condition are 250 DEG C of hot wind inlet temperature, and wind exhausting outlet temperature is 150 DEG C.
The powder of solid particles obtained after spray drying is roasted into 4h at 600 DEG C, obtains composite oxide carrier powder.
5g sesbania powders, a concentration of 20wt%HNO of 75mL are added into 100g dust carriers3Solution is added into kneader
Middle kneading 30min is then extruded into 2mm strips, and after dry, 600 DEG C of roasting 4h obtain bar shaped carrier.
(3) catalyst preparation
Carrier (bar shaped 2mm) made from 10g steps (2) is quickly adding into Pt Nano sols, using ultrasonic oscillation
Impregnation 5h, until upper solution becomes clarification.Supernatant liquor is removed, vacuum pumping then is carried out to bottom catalyst precursor
Respectively washing 2 times of deionized water and ethyl alcohol are then used in filter respectively.120 DEG C are dried overnight, and 550 DEG C of roasting 2h, roasting rises temperature rate 5
℃/min.Obtain catalyst C1.
Embodiment 2
(1) prepared by Pt Nano sols
0.75g cetyl trimethylammonium bromides (CATB) are taken then to be moved with liquid-transfering gun with 50.0mL deionized water dissolvings
Take the H of a certain amount of (2.5mL0.10mol/L)2PtCl6Solution is added in above-mentioned CATB solution, stirs 30-40min at room temperature.
Weigh a certain amount of 0.15gNaBH4It is dissolved in 10mL deionized waters and NaBH is made4Solution, with vigorous stirring by NaBH4Solution drips
It is added to H2PtCl6In the mixed solution of CATB, process is added dropwise with a large amount of bubbles in 60 drops of rate of addition/min (about 3ml/min)
It emits, continues to stir 5h at room temperature, Pt Nano sols can be obtained.
(2) prepared by carrier
3kg deionized waters are added in a stirring kettle, 300g boehmite powder is added after opening stirring, stirs evenly
Afterwards, zirconium oxychloride is added, makes zirconium aluminium mass ratio ZrO2:Al2O3=1:4, continue to be uniformly mixed.It will be pre-configured
The zinc nitrate solution 0.3L of 2mol/L, is added in above-mentioned slurries, is uniformly mixed, obtain mixed serum.Mixed serum is used
Spray drying device drying and moulding, spray-drying operation condition are 250 DEG C of hot wind inlet temperature, and wind exhausting outlet temperature is 150 DEG C.
The powder of solid particles obtained after spray drying is roasted into 4h at 600 DEG C, obtains composite oxide carrier powder.
5g sesbania powders, a concentration of 20wt%HNO of 75mL are added into 100g dust carriers3Solution is added into kneader
Middle kneading 30min is then extruded into 2mm strips, and after dry, 600 DEG C of roasting 4h obtain bar shaped carrier.
(3) catalyst preparation
Carrier (bar shaped 2mm) made from 10g steps (2) is quickly adding into Pt Nano sols, using ultrasonic oscillation
Impregnation 5h, until upper solution becomes clarification.Supernatant liquor is removed, vacuum pumping then is carried out to bottom catalyst precursor
Respectively washing 2 times of deionized water and ethyl alcohol are then used in filter respectively.120 DEG C are dried overnight, and 550 DEG C of roasting 2h, roasting rises temperature rate 5
℃/min.Obtain catalyst C2.
Embodiment 3
(1) prepared by Pt Nano sols
0.75g cetyl trimethylammonium bromides (CATB) are taken then to be moved with liquid-transfering gun with 50.0mL deionized water dissolvings
Take the H of a certain amount of (2.5mL0.10mol/L)2PtCl6Solution is added in above-mentioned CATB solution, stirs 30-40min at room temperature.
Weigh a certain amount of 0.15gNaBH4It is dissolved in 10mL deionized waters and NaBH is made4Solution, with vigorous stirring by NaBH4Solution drips
It is added to H2PtCl6In the mixed solution of CATB, process is added dropwise with a large amount of bubbles in 60 drops of rate of addition/min (about 3ml/min)
It emits, continues to stir 5h at room temperature, Pt Nano sols can be obtained.
(2) prepared by carrier
3kg deionized waters are added in a stirring kettle, 300g boehmite powder is added after opening stirring, stirs evenly
Afterwards, zirconium oxychloride is added, makes zirconium aluminium mass ratio ZrO2:Al2O3=1:4, continue to be uniformly mixed.It will be pre-configured
The zinc nitrate solution 0.3L of 3mol/L, is added in above-mentioned slurries, is uniformly mixed, obtain mixed serum.Mixed serum is used
Spray drying device drying and moulding, spray-drying operation condition are 250 DEG C of hot wind inlet temperature, and wind exhausting outlet temperature is 150 DEG C.
The powder of solid particles obtained after spray drying is roasted into 4h at 600 DEG C, obtains composite oxide carrier powder.
5g sesbania powders, a concentration of 20wt%HNO of 75mL are added into 100g dust carriers3Solution is added into kneader
Middle kneading 30min is then extruded into 2mm strips, and after dry, 600 DEG C of roasting 4h obtain bar shaped carrier.
(3) catalyst preparation
Carrier (bar shaped 2mm) made from 10g steps (2) is quickly adding into Pt Nano sols, using ultrasonic oscillation
Impregnation 5h, until upper solution becomes clarification.Supernatant liquor is removed, vacuum pumping then is carried out to bottom catalyst precursor
Respectively washing 2 times of deionized water and ethyl alcohol are then used in filter respectively.120 DEG C are dried overnight, and 550 DEG C of roasting 2h, roasting rises temperature rate 5
℃/min.Obtain catalyst C3.
Embodiment 4
(1) prepared by Pt Nano sols
0.75g cetyl trimethylammonium bromides (CATB) are taken then to be moved with liquid-transfering gun with 50.0mL deionized water dissolvings
Take the H of a certain amount of (4.0mL0.10mol/L)2PtCl6Solution is added in above-mentioned CATB solution, stirs 30-40min at room temperature.
Weigh a certain amount of 0.15gNaBH4It is dissolved in 10mL deionized waters and NaBH is made4Solution, with vigorous stirring by NaBH4Solution drips
It is added to H2PtCl6In the mixed solution of CATB, process is added dropwise with a large amount of bubbles in 60 drops of rate of addition/min (about 3ml/min)
It emits, continues to stir 5h at room temperature, Pt Nano sols can be obtained.
(2) prepared by carrier
3kg deionized waters are added in a stirring kettle, 300g boehmite powder is added after opening stirring, stirs evenly
Afterwards, zirconium oxychloride is added, makes zirconium aluminium mass ratio ZrO2:Al2O3=1:4, continue to be uniformly mixed.It will be pre-configured
The zinc nitrate solution 0.3L of 1mol/L, is added in above-mentioned slurries, is uniformly mixed, obtain mixed serum.Mixed serum is used
Spray drying device drying and moulding, spray-drying operation condition are 250 DEG C of hot wind inlet temperature, and wind exhausting outlet temperature is 150 DEG C.
The powder of solid particles obtained after spray drying is roasted into 4h at 600 DEG C, obtains composite oxide carrier powder.
5g sesbania powders, a concentration of 20wt%HNO of 75mL are added into 100g dust carriers3Solution is added into kneader
Middle kneading 30min is then extruded into 2mm strips, and after dry, 600 DEG C of roasting 4h obtain bar shaped carrier.
(3) catalyst preparation
Carrier (bar shaped 2mm) made from 10g steps (2) is quickly adding into Pt Nano sols, using ultrasonic oscillation
Impregnation 5h, until upper solution becomes clarification.Supernatant liquor is removed, vacuum pumping then is carried out to bottom catalyst precursor
Respectively washing 2 times of deionized water and ethyl alcohol are then used in filter respectively.120 DEG C are dried overnight, and 550 DEG C of roasting 2h, roasting rises temperature rate 5
℃/min.Obtain catalyst C4.
Embodiment 5
(1) prepared by Pt Nano sols
0.75g cetyl trimethylammonium bromides (CATB) and 0.259g potassium nitrate are taken, with 50.0mL deionized water dissolvings,
Then the H of a certain amount of (2.5mL0.10mol/L) is pipetted with liquid-transfering gun2PtCl6Solution is added in above-mentioned CATB solution, at room temperature
Stir 30-40min.Weigh a certain amount of 0.15gNaBH4It is dissolved in 10mL deionized waters and NaBH is made4Solution, with vigorous stirring
By NaBH4Solution is added drop-wise to H2PtCl6In the mixed solution of CATB, 60 drops of rate of addition/min (about 3ml/min) were added dropwise
Journey is emitted with a large amount of bubbles, is continued to stir 5h at room temperature, can be obtained Pt Nano sols.
(2) prepared by carrier
3kg deionized waters are added in a stirring kettle, 300g boehmite powder is added after opening stirring, stirs evenly
Afterwards, zirconium oxychloride is added, makes zirconium aluminium mass ratio ZrO2:Al2O3=1:4, continue to be uniformly mixed.It will be pre-configured
The zinc nitrate solution 0.3L of 1mol/L, is added in above-mentioned slurries, is uniformly mixed, obtain mixed serum.Mixed serum is used
Spray drying device drying and moulding, spray-drying operation condition are 250 DEG C of hot wind inlet temperature, and wind exhausting outlet temperature is 150 DEG C.
The powder of solid particles obtained after spray drying is roasted into 4h at 600 DEG C, obtains composite oxide carrier powder.
5g sesbania powders, a concentration of 20wt%HNO of 75mL are added into 100g dust carriers3Solution is added into kneader
Middle kneading 30min is then extruded into 2mm strips, and after dry, 600 DEG C of roasting 4h obtain bar shaped carrier.
(3) catalyst preparation
Carrier (bar shaped 2mm) made from 10g steps (2) is quickly adding into Pt Nano sols, using ultrasonic oscillation
Impregnation 5h, until upper solution becomes clarification.Supernatant liquor is removed, vacuum pumping then is carried out to bottom catalyst precursor
Respectively washing 2 times of deionized water and ethyl alcohol are then used in filter respectively.120 DEG C are dried overnight, and 550 DEG C of roasting 2h, roasting rises temperature rate 5
℃/min.Obtain catalyst C5.
Embodiment 6
(1) prepared by Pt Nano sols
0.75g cetyl trimethylammonium bromides (CATB) and six water colbaltous nitrates of 0.493g are taken, with 50.0mL deionizations
Then water dissolution pipettes the H of a certain amount of (2.5mL0.10mol/L) with liquid-transfering gun2PtCl6Solution is added to above-mentioned CATB solution
In, 30-40min is stirred at room temperature.Weigh a certain amount of 0.15gNaBH4It is dissolved in 10mL deionized waters and NaBH4 solution is made,
It is vigorously stirred lower by NaBH4Solution is added drop-wise to H2PtCl6In the mixed solution of CATB, 60 drops of rate of addition/min (about 3ml/
Min), dropwise addition process is emitted with a large amount of bubbles, is continued to stir 5h at room temperature, can be obtained Pt Nano sols.
(2) prepared by carrier
3kg deionized waters are added in a stirring kettle, 300g boehmite powder is added after opening stirring, stirs evenly
Afterwards, zirconium oxychloride is added, makes zirconium aluminium mass ratio ZrO2:Al2O3=1:4, continue to be uniformly mixed.It will be pre-configured
The zinc nitrate solution 0.3L of 1mol/L, is added in above-mentioned slurries, is uniformly mixed, obtain mixed serum.Mixed serum is used
Spray drying device drying and moulding, spray-drying operation condition are 250 DEG C of hot wind inlet temperature, and wind exhausting outlet temperature is 150 DEG C.
The powder of solid particles obtained after spray drying is roasted into 4h at 600 DEG C, obtains composite oxide carrier powder.
5g sesbania powders, a concentration of 20wt%HNO of 75mL are added into 100g dust carriers3Solution is added into kneader
Middle kneading 30min is then extruded into 2mm strips, and after dry, 600 DEG C of roasting 4h obtain bar shaped carrier.
(3) catalyst preparation
Carrier (bar shaped 2mm) made from 10g steps (2) is quickly adding into Pt Nano sols, using ultrasonic oscillation
Impregnation 5h, until upper solution becomes clarification.Supernatant liquor is removed, vacuum pumping then is carried out to bottom catalyst precursor
Respectively washing 2 times of deionized water and ethyl alcohol are then used in filter respectively.120 DEG C are dried overnight, and 550 DEG C of roasting 2h, roasting rises temperature rate 5
℃/min.Obtain catalyst C6.
Embodiment 7
(1) prepared by Pt Nano sols
0.75g cetyl trimethylammonium bromides (CATB) and 0.160g stannous chlorides are taken, it is water-soluble with 50.0mL deionizations
Solution, then pipettes the H of a certain amount of (2.5mL0.10mol/L) with liquid-transfering gun2PtCl6Solution is added in above-mentioned CATB solution, room
Temperature is lower to stir 30-40min.Weigh a certain amount of 0.15gNaBH4It is dissolved in 10mL deionized waters and NaBH4 solution is made, acutely stirring
It mixes lower by NaBH4Solution is added drop-wise to H2PtCl6In the mixed solution of CATB, 60 drops of rate of addition/min (about 3ml/min), drop
Add process to be emitted with a large amount of bubbles, continues to stir 5h at room temperature, Pt Nano sols can be obtained.
(2) prepared by carrier
3kg deionized waters are added in a stirring kettle, 300g boehmite powder is added after opening stirring, stirs evenly
Afterwards, zirconium oxychloride is added, makes zirconium aluminium mass ratio ZrO2:Al2O3=1:4, continue to be uniformly mixed.It will be pre-configured
The zinc nitrate solution 0.3L of 1mol/L, is added in above-mentioned slurries, is uniformly mixed, obtain mixed serum.Mixed serum is used
Spray drying device drying and moulding, spray-drying operation condition are 250 DEG C of hot wind inlet temperature, and wind exhausting outlet temperature is 150 DEG C.
The powder of solid particles obtained after spray drying is roasted into 4h at 600 DEG C, obtains composite oxide carrier powder.
5g sesbania powders, a concentration of 20wt%HNO of 75mL are added into 100g dust carriers3Solution is added into kneader
Middle kneading 30min is then extruded into 2mm strips, and after dry, 600 DEG C of roasting 4h obtain bar shaped carrier.
(3) catalyst preparation
Carrier (bar shaped 2mm) made from 10g steps (2) is quickly adding into Pt Nano sols, using ultrasonic oscillation
Impregnation 5h, until upper solution becomes clarification.Supernatant liquor is removed, vacuum pumping then is carried out to bottom catalyst precursor
Respectively washing 2 times of deionized water and ethyl alcohol are then used in filter respectively.120 DEG C are dried overnight, and 550 DEG C of roasting 2h, roasting rises temperature rate 5
℃/min.Obtain catalyst C7.
Embodiment 8
(1) prepared by (1) Pt Nano sols
0.75g cetyl trimethylammonium bromides (CATB) and 0.31g cerium nitrate hexahydrates are taken, it is water-soluble with 50.0mL deionizations
Solution, then pipettes the H of a certain amount of (2.5mL0.10mol/L) with liquid-transfering gun2PtCl6Solution is added in above-mentioned CATB solution, room
Temperature is lower to stir 30-40min.Weigh a certain amount of 0.15gNaBH4It is dissolved in 10mL deionized waters and NaBH4 solution is made, acutely stirring
It mixes lower by NaBH4Solution is added drop-wise to H2PtCl6In the mixed solution of CATB, 60 drops of rate of addition/min (about 3ml/min), drop
Add process to be emitted with a large amount of bubbles, continues to stir 5h at room temperature, Pt Nano sols can be obtained.
(2) prepared by carrier
3kg deionized waters are added in a stirring kettle, 300g boehmite powder is added after opening stirring, stirs evenly
Afterwards, zirconium oxychloride is added, makes zirconium aluminium mass ratio ZrO2:Al2O3=1:4, continue to be uniformly mixed.It will be pre-configured
The zinc nitrate solution 0.3L of 1mol/L, is added in above-mentioned slurries, is uniformly mixed, obtain mixed serum.Mixed serum is used
Spray drying device drying and moulding, spray-drying operation condition are 250 DEG C of hot wind inlet temperature, and wind exhausting outlet temperature is 150 DEG C.
The powder of solid particles obtained after spray drying is roasted into 4h at 600 DEG C, obtains composite oxide carrier powder.
5g sesbania powders, a concentration of 20wt%HNO of 75mL are added into 100g dust carriers3Solution is added into kneader
Middle kneading 30min is then extruded into 2mm strips, and after dry, 600 DEG C of roasting 4h obtain bar shaped carrier.
(3) catalyst preparation
Carrier (bar shaped 2mm) made from 10g steps (2) is quickly adding into Pt Nano sols, using ultrasonic oscillation
Impregnation 5h, until upper solution becomes clarification.Supernatant liquor is removed, vacuum pumping then is carried out to bottom catalyst precursor
Respectively washing 2 times of deionized water and ethyl alcohol are then used in filter respectively.120 DEG C are dried overnight, and 550 DEG C of roasting 2h, roasting rises temperature rate 5
℃/min.Obtain catalyst C8.
Embodiment 9
(1) prepared by Pt Nano sols
0.75g cetyl trimethylammonium bromides (CATB), 0.259g potassium nitrate, six water colbaltous nitrates of 0.493g are taken, is used
Then 50.0mL deionized water dissolvings pipette the H of a certain amount of (2.5mL0.10mol/L) with liquid-transfering gun2PtCl6Solution is added to
It states in CATB solution, stirs 30-40min at room temperature.Weigh a certain amount of 0.15gNaBH410mL deionized waters are dissolved in be made
NaBH4Solution, with vigorous stirring by NaBH4Solution is added drop-wise to H2PtCl6In the mixed solution of CATB, the drop of rate of addition 60/
Min (about 3ml/min), dropwise addition process are emitted with a large amount of bubbles, are continued to stir 5h at room temperature, can be obtained Pt Nano sols.
(2) prepared by carrier
3kg deionized waters are added in a stirring kettle, 300g boehmite powder is added after opening stirring, stirs evenly
Afterwards, zirconium oxychloride is added, makes zirconium aluminium mass ratio ZrO2:Al2O3=1:4, continue to be uniformly mixed.It will be pre-configured
The zinc nitrate solution 0.3L of 1mol/L, is added in above-mentioned slurries, is uniformly mixed, obtain mixed serum.Mixed serum is used
Spray drying device drying and moulding, spray-drying operation condition are 250 DEG C of hot wind inlet temperature, and wind exhausting outlet temperature is 150 DEG C.
The powder of solid particles obtained after spray drying is roasted into 4h at 600 DEG C, obtains composite oxide carrier powder.
5g sesbania powders, a concentration of 20wt%HNO of 75mL are added into 100g dust carriers3Solution is added into kneader
Middle kneading 30min is then extruded into 2mm strips, and after dry, 600 DEG C of roasting 4h obtain bar shaped carrier.
(3) catalyst preparation
Carrier (bar shaped 2mm) made from 10g steps (2) is quickly adding into Pt Nano sols, using ultrasonic oscillation
Impregnation 5h, until upper solution becomes clarification.Supernatant liquor is removed, vacuum pumping then is carried out to bottom catalyst precursor
Respectively washing 2 times of deionized water and ethyl alcohol are then used in filter respectively.120 DEG C are dried overnight, and 550 DEG C of roasting 2h, roasting rises temperature rate 5
℃/min.Obtain catalyst C9.
Embodiment 10
(1) prepared by Pt Nano sols
0.75g cetyl trimethylammonium bromides (CATB), six water colbaltous nitrates of 0.493g, 0.160g stannous chlorides are taken,
With 50.0mL deionized water dissolvings, the H of a certain amount of (2.5mL0.10mol/L) is then pipetted with liquid-transfering gun2PtCl6Solution is added to
In above-mentioned CATB solution, 30-40min is stirred at room temperature.Weigh a certain amount of 0.15gNaBH4 be dissolved in 10mL deionized waters be made
NaBH4Solution, with vigorous stirring by NaBH4Solution is added drop-wise to H2PtCl6In the mixed solution of CATB, the drop of rate of addition 60/
Min (about 3ml/min), dropwise addition process are emitted with a large amount of bubbles, are continued to stir 5h at room temperature, can be obtained Pt Nano sols.
(2) prepared by carrier
3kg deionized waters are added in a stirring kettle, 300g boehmite powder is added after opening stirring, stirs evenly
Afterwards, zirconium oxychloride is added, makes zirconium aluminium mass ratio ZrO2:Al2O3=1:4, continue to be uniformly mixed.It will be pre-configured
The zinc nitrate solution 0.3L of 1mol/L, is added in above-mentioned slurries, is uniformly mixed, obtain mixed serum.Mixed serum is used
Spray drying device drying and moulding, spray-drying operation condition are 250 DEG C of hot wind inlet temperature, and wind exhausting outlet temperature is 150 DEG C.
The powder of solid particles obtained after spray drying is roasted into 4h at 600 DEG C, obtains composite oxide carrier powder.
5g sesbania powders, a concentration of 20wt%HNO of 75mL are added into 100g dust carriers3Solution is added into kneader
Middle kneading 30min is then extruded into 2mm strips, and after dry, 600 DEG C of roasting 4h obtain bar shaped carrier.
(3) catalyst preparation
Carrier (bar shaped 2mm) made from 10g steps (2) is quickly adding into Pt Nano sols, using ultrasonic oscillation
Impregnation 5h, until upper solution becomes clarification.Supernatant liquor is removed, vacuum pumping then is carried out to bottom catalyst precursor
Respectively washing 2 times of deionized water and ethyl alcohol are then used in filter respectively.120 DEG C are dried overnight, and 550 DEG C of roasting 2h, roasting rises temperature rate 5
℃/min.Obtain catalyst C10.
Comparative example 1
(1) prepared by maceration extract
The H of a certain amount of (2.5mL0.10mol/L) is pipetted with liquid-transfering gun2PtCl6Solution is diluted to 10ml with deionized water
(2)Al2O3It is prepared by carrier
4h is roasted at 600 DEG C to 200g boehmites powder, obtains Al2O3Carrier.100g dust carriers are taken, are added thereto
Enter 5g sesbania powders (extrusion aid), a concentration of 20wt%HNO of 75mL3Solution is added into kneader and mediates 30min, then squeezes
2mm strips, after dry, 600 DEG C of roasting 4h obtain bar shaped carrier
(3) catalyst preparation
Z1 carriers (bar shaped 2mm) made from 10g are quickly adding into H2PtCl6In maceration extract, impregnated using ultrasonic oscillation
Method impregnates 5h, until upper solution becomes clarification.Supernatant liquor is removed, then bottom catalyst precursor is filtered by vacuum, with
Use respectively washing 2 times of deionized water and ethyl alcohol respectively afterwards.120 DEG C are dried overnight, 550 DEG C of roasting 2h, and 5 DEG C of roasting liter temperature rate/
min.Obtain normal load type Pt/Al2O3Catalyst D1.
Comparative example 2
(1) prepared by maceration extract
The H of a certain amount of (2.5mL0.10mol/L) is pipetted with liquid-transfering gun2PtCl6Solution is diluted to 10ml with deionized water
(2) prepared by carrier
5kg deionized waters are added in a stirring kettle, 300g boehmite powder is added after opening stirring, stirs evenly
Afterwards, zirconium oxychloride is added, makes zirconium aluminium mass ratio ZrO2:Al2O3=1:4, continue to be uniformly mixed.Mixed serum is sprayed
Drying equipment drying and moulding, spray-drying operation condition are 250 DEG C of hot wind inlet temperature, and wind exhausting outlet temperature is 150 DEG C.It will spray
The powder of solid particles that mist obtains after messing up roasts 4h at 600 DEG C, obtains ZrO2:Al2O3Composite oxide carrier.
Into 100g dust carriers be added 5g sesbania powders (extrusion aid), a concentration of 20wt%HNO3 solution of 75mL, by itself plus
Enter and mediate 30min in kneader, be then extruded into 2mm strips, after dry, 600 DEG C of roasting 4h obtain bar shaped carrier.
(3) catalyst preparation
Carrier (bar shaped 2mm) made from 10g is quickly adding into H2PtCl6In maceration extract, using ultrasonic oscillation infusion process
5h is impregnated, until upper solution becomes clarification.Supernatant liquor is removed, then bottom catalyst precursor is filtered by vacuum, then
Respectively washing 2 times of deionized water and ethyl alcohol are used respectively.120 DEG C are dried overnight, and 550 DEG C of roasting 2h, roasting rises 5 DEG C/min of temperature rate.
Obtain normal load type Pt/Al2O3Catalyst D2.
Comparative example 3
(1) prepared by maceration extract
The H of a certain amount of (2.5mL0.10mol/L) is pipetted with liquid-transfering gun2PtCl6Solution is diluted to 10ml with deionized water
(2) prepared by carrier
5kg deionized waters are added in a stirring kettle, 300g boehmite powder is added after opening stirring, stirs evenly
Afterwards, zirconium oxychloride is added, makes zirconium aluminium mass ratio ZrO2:Al2O3=1:4, continue to be uniformly mixed.It will be pre-configured
The zinc nitrate solution 0.3L of 1mol/L, is added in above-mentioned slurries, is uniformly mixed, obtain mixed serum.Mixed serum is used
Spray drying device drying and moulding, spray-drying operation condition are 250 DEG C of hot wind inlet temperature, and wind exhausting outlet temperature is 150 DEG C.
The powder of solid particles obtained after spraying is messed up roasts 4h at 600 DEG C, obtains ZrO2:Al2O3Composite oxide carrier.
5g sesbania powders (extrusion aid), a concentration of 20wt%HNO of 75mL are added into 100g dust carriers3Solution, by itself plus
Enter and mediate 30min in kneader, be then extruded into 2mm strips, after dry, 600 DEG C of roasting 4h obtain bar shaped carrier.
(3) catalyst preparation
Carrier (bar shaped 2mm) made from 10g is quickly adding into H2PtCl6In maceration extract, using ultrasonic oscillation infusion process
5h is impregnated, until upper solution becomes clarification.Supernatant liquor is removed, then bottom catalyst precursor is filtered by vacuum, then
Respectively washing 2 times of deionized water and ethyl alcohol are used respectively.120 DEG C are dried overnight, and 550 DEG C of roasting 2h, roasting rises 5 DEG C/min of temperature rate.
Obtain normal load type Pt/Al2O3Catalyst D2.
The each component quality component parts table 1 of catalyst and comparative catalyst prepared by embodiment 1-10 and comparative example 1-3
Embodiment 11
This example demonstrates that dehydrogenating propane method provided by the invention.
Catalyst C1-C10 prepared by embodiment 1-10 are tested for dehydrogenating propane.Experimental result is shown in Table 2.As right
Than comparative catalyst D1-D3 prepared by comparative example 1-3 also being carried out dehydrogenating propane experimental evaluation, experimental result is same to be listed in table 2
In.
In the present embodiment, propane dehydrogenation catalyst evaluating apparatus is fixed-bed micro-reactor, and raw material and product are
On-line analysis, analytical instrument are SP-2100 gas-chromatographies.Fixed bed reactors internal diameter 10mm, flat-temperature zone 10cm.
In the present embodiment, evaluating catalyst condition is as follows：Catalyst amount 4.0g reaction pressure synthesis under normal pressure temperature 600-
630 DEG C of hydrogen flowing quantity 80ml/min, propane flow 50ml/min, 500 DEG C, recovery time 4h of catalyst reduction temperature, air speed
2300h-1Sample time started 5min；
In the present embodiment, product analysis and computational methods are as follows：
Product mainly has propane, propylene, ethane, ethylene, methane and micro C4 or more components, dehydrogenation after dehydrogenating propane reaction
The chromatographic peak of each product is different according to residence time of the reference substance in chromatography and carry out qualitative analysis in reaction.Reaction product
Content is carried out by gas chromatographicanalyzer in quantitative measurment continuous mode, sample interval 30min.Color used in this method
It composes work station and uses area normalization method.
The amount of each component obtained by chromatography calculates separately conversion of propane X and Propylene Selectivity S.
Table 1
Table 2
As can be seen from Table 2, when inventive samples C1-C10 is applied to dehydrogenating propane reaction, initial propane conversion
Rate is between 35.2-45.3%, and initial Propylene Selectivity is between 91.7%-96.2%.Conversion of propane and selection in 8h
Property respectively stablize 31.8% and 88.4% or more.Especially C8 samples, initial conversion of propane and Propylene Selectivity point for
Conversion of propane is stablized 37.9% and 93.5% or more, significantly respectively with Propylene Selectivity in 41.8% and 96.2%, 8h
Higher than comparative example D1-D3.Illustrate loaded nano Pt catalyst provided by the invention, with Zinc modified ZrO2/Al2O3It is compound
Oxide is carrier, is to help activearm with one or more of potassium, cobalt, magnesium, cerium with nano Pt particles for main active component
Point, when it is applied to preparing propylene by dehydrogenating propane, while maintaining high conversion of propane, Propylene Selectivity significantly improves, and
And the catalyst has good stability.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
Claims (10)
1. a kind of dehydrogenation, which is characterized in that with the composite oxygen formed through Zinc modified zirconium dioxide and activated alumina
Compound is carrier, is to help work to be selected from one or more of potassium, magnesium, tin, lanthanum, cerium, iron, cobalt, nickel with Pt for main active component
Property component, in the carrier, the mass ratio of zirconium dioxide and activated alumina is ZrO2:Al2O3=1:0.5-40, it is described
Zinc mass content in the carrier be 0.1%-20%, the mass contents of the Pt in the catalyst are 0.01%-10%,
The mass content of active component in the catalyst that helps is 0%-8%.
2. a kind of preparation method of dehydrogenation according to claim 1, which is characterized in that including：With Pt nanoparticles
Sub- colloidal sol impregnates the composite oxide carrier through Zinc modified zirconium dioxide and activated alumina composition as maceration extract.
3. the preparation method of dehydrogenation according to claim 2, which is characterized in that further comprising the steps of：By
After dipping through Zinc modified zirconium dioxide and activated alumina composition composite oxide carrier drying, roasting, and also
Original obtains the dehydrogenation.
4. the preparation method of dehydrogenation according to claim 2, which is characterized in that
The preparation of the Pt Nano sols includes：
A, it to the desired amount of surface stabilizer and helps deionized water dissolving is added in active constituent compound, be made containing helping activearm
The surface stabilizer aqueous solution divided；
A, it takes the desired amount of compound containing Pt with containing helping the surface stabilizer aqueous solution of active component to mix, stirs 30- at room temperature
Mixed solution is made in 60min；
C, deionized water is added into the desired amount of reducing agent and reducing agent solution is made；
D, reducing agent solution is added drop-wise in mixed solution with vigorous stirring, continues to stir 4-6h at room temperature, obtained to contain and help
The Pt Nano sols of active component.
5. the preparation method of dehydrogenation according to claim 2, which is characterized in that
The preparation of the composite oxide carrier formed with activated alumina through Zinc modified zirconium dioxide includes：
E, deionized water is added into the desired amount of activated alumina powder, is uniformly mixed, then aequum is added thereto
Zirconium-containing compound and the desired amount of zinc compound solid powder or solution, be uniformly mixed, slurry 1 be made；
F, acid or alkali are added into slurry 1, adjusts the pH=1-10 of slurry, the slurry 2 of solid content 10-50wt% is made；
G, by 2 spray drying forming of slurry, hot wind inlet temperature is 160-560 DEG C, and wind exhausting outlet temperature is 100-240 DEG C, is obtained
To solid particle powder；
H, the solid particle powder obtained after spray drying is roasted into 4-8h at 500-700 DEG C, can through Zinc modified compound
Oxide support powder；
I, into step h gained through aequum sesbania powder and concentration quality are added in Zinc modified composite oxide carrier powder
Score is the nitric acid of 10-30wt%, and kneader is added after being uniformly mixed and mediates 30min, is then extruded into 2-3mm strips, does
Dry, the composite oxide carrier through Zinc modified zirconium dioxide and activated alumina composition is made in 500-700 DEG C of roasting.
6. the preparation method of dehydrogenation according to claim 3, which is characterized in that
Specifically include following steps：
J, using Pt nanoparticle sols as maceration extract dipping formed with activated alumina through Zinc modified zirconium dioxide it is compound
Oxide carrier, using ultrasonic oscillation impregnation 2-6h, 20-80 DEG C of dipping temperature must urge until upper solution becomes clarification
Agent presoma,
K, the supernatant liquor in removing step j steepers, is then filtered by vacuum bottom catalyst precursor, then divides
Not Yong respectively washing 2 times of deionized water and ethyl alcohol,
L, the washed product that will be obtained in step k, dry 0.5-12h under conditions of 50-200 DEG C,
M, the desciccate obtained in step l under the conditions of 300-750 DEG C is roasted into 0.5-10h, obtains oxidation catalyst,
N, by the oxidation catalyst obtained in step m at 80-600 DEG C, catalysis dehydrogenation is obtained with reducibility gas reduction 0.5-12h
Agent.
7. the preparation method of dehydrogenation according to claim 4, which is characterized in that the surface described in step a is steady
It is at least one of cetyl trimethylammonium bromide, polyvinylpyrrolidone to determine agent.
8. the preparation method of dehydrogenation according to claim 4, which is characterized in that contain Ptization described in step b
Conjunction object is chloroplatinic acid, and platinum nitrate, platinum chloride, platinum acetate is one or more of in ammonium chloroplatinate, help active constituent compound be containing
One or more of potassium, magnesium, tin, lanthanum, cerium, iron, cobalt, the nitrate of nickel, hydrochloride, oxalates.
9. the preparation method of dehydrogenation according to claim 4, which is characterized in that the reducing agent described in step c
For NaBH4。
10. the preparation method of dehydrogenation according to claim 5, which is characterized in that contain zirconium described in step e
It is zirconium oxychloride or zirconium nitrate to close object, and zinc compound is one or more of zinc nitrate, zinc chloride, zinc oxalate.
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| CN111686711A (en) * | 2020-06-18 | 2020-09-22 | 浙江师范大学 | Selective oxidation catalyst for non-methane total hydrocarbon and preparation method thereof |
| WO2022018081A1 (en) | 2020-07-21 | 2022-01-27 | Basf Se | A zeolite catalyst and use thereof for the dehydrogenation of alkanes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111054386A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation reaction of light alkane and preparation method thereof |
| CN111054386B (en) * | 2018-10-16 | 2023-04-07 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation reaction of light alkane and preparation method thereof |
| CN111686711A (en) * | 2020-06-18 | 2020-09-22 | 浙江师范大学 | Selective oxidation catalyst for non-methane total hydrocarbon and preparation method thereof |
| CN111686711B (en) * | 2020-06-18 | 2022-12-16 | 浙江师范大学 | Selective oxidation catalyst for non-methane total hydrocarbon and preparation method thereof |
| WO2022018081A1 (en) | 2020-07-21 | 2022-01-27 | Basf Se | A zeolite catalyst and use thereof for the dehydrogenation of alkanes |
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