CN114950401A - 改性铝酸锌载体、低碳烷烃脱氢催化剂及其制备方法和应用 - Google Patents
改性铝酸锌载体、低碳烷烃脱氢催化剂及其制备方法和应用 Download PDFInfo
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- CN114950401A CN114950401A CN202210804223.8A CN202210804223A CN114950401A CN 114950401 A CN114950401 A CN 114950401A CN 202210804223 A CN202210804223 A CN 202210804223A CN 114950401 A CN114950401 A CN 114950401A
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- China
- Prior art keywords
- carrier
- zinc aluminate
- modified zinc
- aluminate carrier
- dehydrogenation catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- -1 Modified zinc aluminate Chemical class 0.000 title claims abstract description 55
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 28
- 239000011701 zinc Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910052738 indium Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 5
- 150000003624 transition metals Chemical class 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 40
- 239000002243 precursor Substances 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004246 zinc acetate Substances 0.000 claims description 9
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000000975 co-precipitation Methods 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 150000004696 coordination complex Chemical class 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 229910001507 metal halide Inorganic materials 0.000 claims description 3
- 150000005309 metal halides Chemical class 0.000 claims description 3
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 229940009827 aluminum acetate Drugs 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 2
- 229910000838 Al alloy Inorganic materials 0.000 claims 1
- 239000003349 gelling agent Substances 0.000 claims 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 26
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 15
- 239000001294 propane Substances 0.000 abstract description 13
- 238000005245 sintering Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 39
- 239000008367 deionised water Substances 0.000 description 38
- 229910021641 deionized water Inorganic materials 0.000 description 38
- 239000011259 mixed solution Substances 0.000 description 36
- 239000000047 product Substances 0.000 description 23
- 238000004090 dissolution Methods 0.000 description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 19
- 239000002253 acid Substances 0.000 description 16
- 238000005303 weighing Methods 0.000 description 15
- 238000001704 evaporation Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- 238000002390 rotary evaporation Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 229910052725 zinc Inorganic materials 0.000 description 11
- 238000009775 high-speed stirring Methods 0.000 description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000000571 coke Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000001282 iso-butane Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910019923 CrOx Inorganic materials 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 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
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 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
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 229910002846 Pt–Sn Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 244000273928 Zingiber officinale Species 0.000 description 1
- 235000006886 Zingiber officinale Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 235000008397 ginger Nutrition 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000011787 zinc oxide Substances 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/62—Platinum group metals with gallium, indium, thallium, 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
- B01J23/38—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
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- 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
- B01J23/63—Platinum group metals with rare earths or actinides
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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
- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- 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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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Abstract
发明公开了一种改性铝酸锌载体、低碳烷烃脱氢催化剂及其制备方法和应用,属于石油化工技术领域。这种改性铝酸锌载体的化学组成为通式ZnxMyAl2O4;M选自碱金属元素、碱土金属元素中的一种或几种;改性铝酸锌载体具有多孔结构。本申请提供的这种催化剂以贵金属Pt、Pd、Ru和Rh中的至少一种为活性组分,以过渡金属Ga、V、In、Sn、Mn、Ce、Fe和Ni中的至少一种为助剂,以上述改性铝酸锌载体为载体。这种改性铝酸锌载体制备的催化剂具有丙烷转化率高、产物丙烯选择性高、抗烧结能力强和稳定性好等特点。
Description
技术领域
本发明属于石油化工技术领域,具体涉及一种改性铝酸锌载体和低碳烷烃脱氢催化剂及其制备方法。
背景技术
丙烯是产量仅次于乙烯的重要有机基础化工原料,广泛地用于生产聚丙烯、丙烯腈、环氧丙烷等化工产品,是三大合成材料(塑料、橡胶、纤维)的基本原料。近年来,随着全球经济的不断发展,丙烯下游产品的需求量不断增加。截至2019年底,我国丙烯产能为4061万吨/年,全年丙烯产量约3288万吨。目前,丙烯供应的来源主要是石脑油蒸汽裂解和催化裂化工艺,这两种工艺被认为是油制丙烯生产路线。然而,传统的油制丙烯生产路线技术难以满足市场对丙烯的需求。因此,开发新型定向高效的丙烯生产技术显得尤为重要。丙烷无氧脱氢(PDH)是工业上定向生产丙烯的工艺之一,该工艺相比于传统的油制丙烯生产路线而言,具有丙烯选择性高、原料来源丰富、产物组成简单且易于分离等优势[ChemicalReviews,2014,114(20):10613-10653.]。尤其是近年来页岩气的成功开发,使得丙烷产量持续上升,PDH工艺引起人们的广泛关注。
PDH反应(C3H8→C3H6+H2,ΔH=124.3kJ·mol-1)是一个正向分子数增加的强吸热反应,往往需要在低压高温下才能实现较高的转化率。目前PDH工艺已经成功地工业化应用,主要有ABB Lummus公司的Catofin工艺、UOP公司的Oleflex工艺、Uhde公司的STAR工艺、Yarsintez公司的FBD工艺以及Linde和BASF公司合作开发的PDH工艺。其中,Catofin和Oleflex工艺应用最为广泛。Catofin工艺以CrOx/Al2O3作为催化剂,采用绝热固定床反应器。反应过程中,一部分反应器进行脱氢反应,另一部分反应器进行催化剂再生反应,交替循环进行(一个完整的循环需要15~30分钟)以保证丙烯的连续生产。Oleflex工艺使用Pt-Sn/Al2O3催化剂,整个装置采用绝热径向流动床反应器,中间串联预热器为反应体系提供热量,最后一个反应器与催化剂再生装置相连。催化剂在整个装置中流动,再生后的催化剂重新进入第一个反应器(一个完整得循环需要5~10天),整个装置是连续运行,不间断地获得反应产物。
相比于CrOx/Al2O3催化剂,Pt基催化剂的反应活性高,丙烯选择性高且毒性低。然而,Pt粒子在高温条件下容易烧结长大,同时也容易积炭失活,稳定性差,大大降低了设备的生产能力。
催化剂载体的表面性质对非均相催化剂的催化性能有着重要影响,特别是催化剂上的强酸位点会促进催化剂上的焦炭沉积。姜发现高温下催化剂失活主要有两个原因,分别是金属烧结和焦炭沉积[Applied Catalysis A:General,2019,572:1-8]。Al2O3表面的Lewis酸(L酸)位点不仅可以引发焦炭沉积,而且可能将脂肪族类焦炭转化为芳香族类焦炭。中国专利(CN105363472A)公开了利用沉淀法合成的铝酸锌复合氧化物为载体的铂系催化剂,该催化剂初始活性较高,但其稳定性较差,十小时后转化率下降
综上,现有发明中报道的铝酸锌载体基脱氢催化剂,由于存在催化活性低、选择活性不高,且抗积碳能力弱,其纵横性能仍需进一步提高,且目前尚无报道使用过渡金属元素为助剂对铝酸锌载体基的脱氢催化剂进行改性。
发明内容
本发明的目的在于解决现有烷烃脱氢技术中催化剂的抗烧结能力低、选择性差的问题,公开了改性铝酸锌载体和低碳烷烃脱氢催化剂及其制备方法,由这种改性铝酸锌载体制备的催化剂具有丙烷转化率高、产物丙烯选择性高、抗烧结能力强和稳定性好等特点。
本发明通过以下技术方案实现:
第一方面,本发明提供一种改性铝酸锌载体,这种改性铝酸锌载体的化学组成为通式ZnxMyAl2O4,其中,x为0.01~0.99,y为0.01~0.99,且满足x+y=1;M选自碱金属元素、碱土金属元素中的一种或几种;改性铝酸锌载体具有多孔结构,比表面积为10-100m2/g,孔径范围为3nm~30nm,孔容范围为0.1~0.7g/mL。
进一步地,在本发明较佳的实施例中,上述通式ZnxMyAl2O4中的Zn元素的前驱体包括氯化锌、硝酸锌、醋酸锌和有机锌盐中的至少一种。
进一步地,在本发明较佳的实施例中,上述通式ZnxMyAl2O4中的Al元素的前驱体包括氯化铝、硝酸铝、醋酸铝、氧化铝、铝石和有机铝盐中的至少一种。
进一步地,在本发明较佳的实施例中,上述改性铝酸锌载体采用凝胶溶胶法、浸渍法、沉淀法、共沉淀法或水热合成法制备得到。
进一步地,在本发明较佳的实施例中,上述改性铝酸锌载体采用沉淀法或共沉淀法制备得到,所用的沉淀剂为氨水、氢氧化钠、氢氧化钾、碳酸钠和尿素中的至少一种;
优选地,所述改性铝酸锌载体采用凝胶溶胶法制备得到,所用凝胶剂为柠檬酸、草酸、聚乙烯醇中的一种或几种;
第二方面,本发明提供一种低碳烷烃脱氢催化剂,这种催化剂以贵金属Pt、Pd、Ru和Rh中的至少一种为活性组分,以过渡金属Ga、V、In、Sn、Mn、Ce、Co、Fe和Ni中的至少一种为助剂,以上述改性铝酸锌载体为载体。
进一步地,在本发明较佳的实施例中,以催化剂干基总质量为基准,活性组分的质量百分含量为1-40wt%,助剂的含量为1~20wt%,余量为改性铝酸锌载体。
优选地,贵金属元素的前驱体选用金属卤化物、金属硝酸盐和金属络合物中的一种或几种;
优选地,过渡元素的前驱体为金属元素的氧化物、无机盐、配合物中的一种或多种。
第三方面,本发明还提供一种低碳烷烃脱氢催化剂的制备方法,包括:
在搅拌的条件下,将含有活性组分和助剂的溶液滴加至含有改性铝酸锌载体的分散液中,搅拌1~3h后,回收溶剂、烘干后焙烧。
进一步地,在本发明较佳的实施例中,焙烧过程中温度为500~700℃,时间为3~5h。
第四方面,本发明还提供一种上述低碳烷烃脱氢催化剂的应用,应用于固定床、移动床或流化床,反应温度为550-620℃,反应压力为10-150kPa,反应空速为0.1-2h-1。
进一步地,在本发明较佳的实施例中,该催化剂用于丙烷脱氢、异丁烷脱氢或丙烷/异丁烷混合气脱氢反应中。
与现有技术相比,本发明至少具有如下技术效果:
相对于现有技术,本发明公开了一种改性铝酸锌载体用于制备低碳烷烃脱氢催化剂,为使用酸性较低的具有特殊结构的多孔铝酸锌材料,作为脱氢催化剂的载体,提高了载体的稳定性并降低载体的表面酸性,降低了传统载体由于B酸过多而导致酸性裂解的问题。
该低碳烷烃脱氢催化剂,选用经过渡金属元素改性的特殊载体负载贵金属作为活性组分,通过过渡金属元素助剂的作用,调变了催化剂中活性中心——贵金属元素的存在状态并保持了其高度分散空间结构。同时,助剂的引入也在一定程度上弥补了载体上的一些高能量缺陷位置,对脱氢催化剂综合性能进行了保障。大幅提升低碳烷烃的转化率,抑制烷烃发生深度脱氢,酸性裂解,以及生成积碳的反应。提高催化剂稳定性,选择性等重要性能,使用本发明所提供的低碳烷烃脱氢催化剂,催化性能和催化剂稳定性优于现有脱氢催化剂,具有潜在的工业应用前景。
具体实施方式
下面将结合实施例对本发明的实施方案进行详细描述,但是本领域技术人员将会理解,下列实施例仅用于说明本发明,而不应视为限制本发明的范围,实施例中未注明的具体条件,按照常规条件或者制造商建议的条件进行,所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
本发明的技术方案为:
本实施方式首先提供一种改性铝酸锌载体,这种改性铝酸锌载体的化学组成为通式ZnxMyAl2O4,其中,x为0.01~0.99,y为0.01~0.99,且满足x+y=1;M选自碱金属元素、碱土金属元素中的一种或几种;改性铝酸锌载体具有多孔结构,比表面积为10-100m2/g,孔径范围为3nm~30nm,孔容范围为0.1~0.7g/mL。
这种改性铝酸锌载体,相比于传统的铝酸锌载体,具有酸性低、比表面积大、机械强度高等特性,有助于后续在制备脱氢催化剂中,提高了载体的稳定性并降低载体的表面酸性,避免传统载体由于B酸过多而导致酸性裂解的缺陷。
这种改性铝酸锌载体采用凝胶溶胶法、浸渍法、沉淀法、共沉淀法或水热合成法制备得到。如下,是我们制备这种改性铝酸锌载体方法之一:
首先,称取铝源、锌源于烧杯中,加入去离子水溶解,搅拌30min后,加入柠檬酸进行溶解,继续搅拌30min,升温至80℃,搅拌至形成凝胶,放入100℃烘箱中烘干,马弗炉中焙烧。通过控制铝源与锌源的比例、柠檬酸的添加量、搅拌时间、焙烧温度、焙烧时间等参数,以控制铝酸锌的比表面积、机械强度、表面酸性等性能。
本实施方式其次提供一种低碳烷烃脱氢催化剂,其采用上述改性铝酸锌载体为载体。这种脱氢催化剂可应用于丙烷脱氢、异丁烷脱氢或丙烷/异丁烷混合气脱氢。
该催化剂以贵金属Pt、Pd、Ru和Rh中的至少一种为活性组分,优选地,以贵金属Pt、Pd、Ru和Rh中的任一种为活性组分,更为优选地,以Pt为活性组分。贵金属元素的前驱体选用金属卤化物、金属硝酸盐和金属络合物中的一种或几种。
其中,以催化剂干基总质量为基准,活性组分的质量百分含量为1-40wt%;优选地活性组分的质量百分含量为5-35wt%,更为优选地,为10~25%。将催化剂中贵金属元素的质量百分含量控制在1%~40%,有助于丙烷脱氢反应;超过这个范围,可能会产生丙烷的深度裂解反应及聚合反应等不利影响。
以过渡金属Ga、V、In、Sn、Mn、Ce、Fe和Ni中的至少一种为助剂,优选地,助剂为过渡金属Ga、V、In、Sn、Mn、Ce、Fe和Ni中的任意一种,更为优选地,助剂为Ce、Fe、Mn、Sn、Ga。过渡元素的前驱体为金属元素的氧化物、无机盐、配合物中的一种或多种。
其中以催化剂干基总质量为基准,助剂的质量百分含量为1~20wt%,优选地,质量百分含量为5~15wt%,更为优选地,质量百分含量为8~12wt%。将催化剂中助剂的质量百分含量控制在1~20%,有助于对活性金属化学状态的调控;超过这个范围,会覆盖活性位点,降低反应转化率。
进一步地,催化剂应用于固定床、移动床或流化床,反应温度为550-620℃,优选为570-610℃,更优选为580-600℃;反应压力为10-150kPa,优选为20-100kPa,更优选为30-70kPa;反应空速为0.1-2h-1,优选为0.3-1.5h-1,更优选为0.5-1.0h-1。
以下对本发明的具体实施方式进行详细说明。应当理解的是,此处所描述的具体实施方式仅用于说明和解释本发明,并不用于限制本发明。
实施例1
本实施例提供一种改性铝酸锌载体,其制备方法包括:
称取754g的硝酸铝、187g的硝酸锌、1.48g硝酸镁溶于1L的去离子水中,进行超声溶解。在高速搅拌下,加入576g柠檬酸,将混合液高速搅拌,使其溶解完全,后进行升温至80℃,得到凝胶。得到的凝胶在80℃烘箱中烘干,1000℃马弗炉中焙烧,即得到Zn0.99Mg0.01Al2O4载体。
经检测,该载体的比表面积为50-100m2/g,孔径范围为20nm~30nm,孔容范围为0.5~0.7g/mL。
本实施例还提供一种低碳烷烃脱氢催化剂,其制备方法包括:
称取上述载体10g分散在50ml去离子水中,高速搅拌30min,得到混合液A。称取含有0.1g的Pt的前驱体溶液氯钯酸和0.1g的Ni的前驱体硝酸镍溶液,加入20ml去离子水进行超声溶解,得到溶液B。在高速搅拌混合液A的条件下,逐滴加入B溶液,混合均匀,室温下搅拌2h后,利用旋蒸将溶剂蒸干。将得到的干品放入80℃烘箱烘干,600℃焙烧4h。
实施例2
本实施例提供一种改性铝酸锌载体,其制备方法包括:
称取754g的硝酸铝、187g的硝酸锌、1.48g硝酸镁溶于1L的去离子水中,进行超声溶解。在高速搅拌下,逐滴加入氨水,调节pH=5~8后,将混合液高速搅拌,使其沉淀完全,后进行静置陈化。将陈化后的产物进行过滤洗涤,得到的滤饼在80℃烘箱中烘干,1000℃马弗炉中焙烧,即得到Zn0.99Mg0.01Al2O4载体。
经检测,该载体的比表面积为50-100m2/g,孔径范围为20nm~30nm,孔容范围为0.5~0.7g/mL。
本实施例还提供一种低碳烷烃脱氢催化剂,其制备方法包括:
称取上述载体10g分散在50ml去离子水中,高速搅拌30min,得到混合液A。称取含有0.01g的Pt的前驱体溶液氯铂酸和0.1g的Ce的前驱体硝酸铈溶液,加入20ml去离子水进行超声溶解,得到溶液B。在高速搅拌混合液A的条件下,逐滴加入B溶液,混合均匀,室温下搅拌2h后,利用旋蒸将溶剂蒸干。将得到的干品放入80℃烘箱烘干,600℃焙烧4h。
实施例3
本实施例提供一种改性铝酸锌载体,其制备方法包括:
称取754g的硝酸铝、183g的醋酸锌、1.01g硝酸钾溶于1L的去离子水中,进行超声溶解。在高速搅拌下,逐滴加入氨水,调节pH=5~8后,将混合液高速搅拌,使其沉淀完全,后进行静置陈化。将陈化后的产物进行过滤洗涤,得到的滤饼在80℃烘箱中烘干,1000℃马弗炉中焙烧,即得到Zn0.99K0.01Al2O4载体。
本实施例还提供一种低碳烷烃脱氢催化剂,其制备方法包括:
称取上述载体10g分散在50ml去离子水中,高速搅拌30min,得到混合液A。称取含有0.01g的Pt的前驱体溶液氯铂酸和0.1g的Co的前驱体硝酸钴溶液,加入20ml去离子水进行超声溶解,得到溶液B。在高速搅拌混合液A的条件下,逐滴加入B溶液,混合均匀,室温下搅拌2h后,利用旋蒸将溶剂蒸干。将得到的干品放入80℃烘箱烘干,600℃焙烧4h。
实施例4
本实施例提供一种改性铝酸锌载体,其制备方法包括:
称取750g硝酸铝、183g的醋酸锌、1.58醋酸钙溶于1L的去离子水中,进行超声溶解。在高速搅拌下,加入292g乙二胺四乙酸,将混合液高速搅拌,使其溶解完全,后进行升温至70℃,得到凝胶。得到的凝胶在80℃烘箱中烘干,1000℃马弗炉中焙烧,即得到Zn0.99Ca0.01Al2O4载体。
本实施例还提供一种低碳烷烃脱氢催化剂,其制备方法包括:
称取上述载体10g分散在50ml去离子水中,高速搅拌30min,得到混合液A。称取含有0.01g的Pt的前驱体溶液氯铂酸和0.1g的Fe的前驱体氯化铁溶液,加入20ml去离子水进行超声溶解,得到溶液B。在高速搅拌混合液A的条件下,逐滴加入B溶液,混合均匀,室温下搅拌2h后,利用旋蒸将溶剂蒸干。将得到的干品放入80℃烘箱烘干,600℃焙烧4h。
实施例5
本实施例提供一种改性铝酸锌载体,其制备方法包括:
称取183g的醋酸锌、0.08g氧化镁溶于1L的去离子水中,并称取固含量为60%的铝石200g、进行超声分散。在高速搅拌下,加入200g聚乙二醇,将混合液高速搅拌,使其溶解完全,后进行升温至70℃,得到凝胶,将凝胶在80℃下静置20h,1000℃马弗炉中焙烧,即得到Zn0.98Mg0.02Al2O4载体。
本实施例还提供一种低碳烷烃脱氢催化剂,其制备方法包括:
称取上述载体10g分散在50ml去离子水中,高速搅拌30min,得到混合液A。称取含有0.01g的Pt的前驱体溶液氯铂酸和0.1g的Mn的前驱体醋酸锰溶液,加入20ml去离子水进行超声溶解,得到溶液B。在高速搅拌混合液A的条件下,逐滴加入B溶液,混合均匀,室温下搅拌2h后,利用旋蒸将溶剂蒸干。将得到的干品放入80℃烘箱烘干,600℃焙烧4h。
实施例6
本实施例提供一种改性铝酸锌载体,其制备方法包括:
称取95g氯化镁、1.83g醋酸锌溶于1L的去离子水中,进行超声溶解,并称取固含量为60%的铝石200g分散其中。称取定量尿素,倒入上述混合液中,并高速搅拌2h,后将水浴锅升温至80℃,使尿素进行分解,使金属沉淀完全,后进行静置陈化。将陈化后的产物进行过滤洗涤,得到的滤饼在80℃烘箱中烘干,1000℃马弗炉中焙烧,即得到Zn0.02Mg0.98Al2O4载体。
本实施例还提供一种低碳烷烃脱氢催化剂,其制备方法包括:
称取上述载体10g分散在50ml去离子水中,高速搅拌30min,得到混合液A。称取含有0.01g的Pt的前驱体溶液氯铂酸和0.01g的Sn的前驱体氯化亚锡溶液,加入20ml去离子水进行超声溶解,得到溶液B。在高速搅拌混合液A的条件下,逐滴加入B溶液,混合均匀,室温下搅拌2h后,利用旋蒸将溶剂蒸干。将得到的干品放入80℃烘箱烘干,600℃焙烧4h。
实施例7
本实施例提供一种改性铝酸锌载体,其制备方法包括:
称取754g的硝酸铝、183g的醋酸锌、0.4g氯化钠溶于1L的去离子水中,进行超声溶解。在高速搅拌下,加入576g柠檬酸,将混合液高速搅拌,使其溶解完全,后进行升温至70℃,得到凝胶100℃烘箱中烘干20h,1000℃马弗炉中焙烧,即得到Zn0.99Na0.01Al2O4载体。
本实施例还提供一种低碳烷烃脱氢催化剂,其制备方法包括:
称取上述载体10g分散在50ml去离子水中,高速搅拌30min,得到混合液A。称取含有0.01g的Pt的前驱体溶液氯铂酸和0.1g的Ga的前驱体硝酸镓溶液,加入20ml去离子水进行超声溶解,得到溶液B。在高速搅拌混合液A的条件下,逐滴加入B溶液,混合均匀,室温下搅拌2h后,利用旋蒸将溶剂蒸干。将得到的干品放入80℃烘箱烘干,600℃焙烧4h。
实施例8
本实施例提供一种改性铝酸锌载体,其制备方法包括:
称取754g的硝酸铝、183g的醋酸锌、0.4g氯化钠溶于1L的去离子水中,进行超声溶解。在高速搅拌下,逐滴加入氨水,调节pH=5~8后,将混合液高速搅拌,使其沉淀完全,后进行静置陈化。将陈化后的产物进行过滤洗涤,得到的滤饼在80℃烘箱中烘干,1000℃马弗炉中焙烧,即得到Zn0.99Na0.01Al2O4载体。
本实施例还提供一种低碳烷烃脱氢催化剂,其制备方法包括:
称取上述载体10g分散在50ml去离子水中,高速搅拌30min,得到混合液A。称取含有0.01g的Pt的前驱体溶液氯铂酸和0.1g的In的前驱体硝酸铟溶液,加入20ml去离子水进行超声溶解,得到溶液B。在高速搅拌混合液A的条件下,逐滴加入B溶液,混合均匀,室温下搅拌2h后,利用旋蒸将溶剂蒸干。将得到的干品放入80℃烘箱烘干,600℃焙烧4h。
实施例9
本实施例提供一种改性铝酸锌载体,其制备方法包括:
称取754g的硝酸铝、183g的醋酸锌、0.4g氯化钠溶于1L的去离子水中,进行超声溶解。在高速搅拌下,逐滴加入氨水,调节pH=5~8后,将混合液高速搅拌,使其沉淀完全,后进行静置陈化。将陈化后的产物进行过滤洗涤,得到的滤饼在80℃烘箱中烘干,1000℃马弗炉中焙烧,即得到Zn0.99Na0.01Al2O4载体。
本实施例还提供一种低碳烷烃脱氢催化剂,其制备方法包括:
称取上述载体10g分散在50ml去离子水中,高速搅拌30min,得到混合液A。称取含有0.01g的Ru的前驱体溶液氯铂酸和0.1g的In的前驱体硝酸铟溶液,加入20ml去离子水进行超声溶解,得到溶液B。在高速搅拌混合液A的条件下,逐滴加入B溶液,混合均匀,室温下搅拌2h后,利用旋蒸将溶剂蒸干。将得到的干品放入80℃烘箱烘干,600℃焙烧4h。
对比例1
本对比例提供一种低碳烷烃脱氢催化剂,其制备方法包括:
称取商业载体α-氧化铝10g分散在50ml去离子水中,高速搅拌30min,得到混合液A。称取含有0.1g的Pt的前驱体溶液氯铂酸加入20ml去离子水进行超声溶解,得到溶液B。在高速搅拌混合液A的条件下,逐滴加入B溶液,混合均匀,室温下搅拌2h后,利用旋蒸将溶剂蒸干。将得到的干品放入80℃烘箱烘干,600℃焙烧4h。
对比例2
本对比例提供一种低碳烷烃脱氢催化剂,其制备方法包括:
称取373g的硝酸铝溶于1L的去离子水中,进行超声溶解。在高速搅拌下,逐滴加入氨水,调节pH=5~8后,将混合液高速搅拌,使其沉淀完全,后进行静置陈化。将陈化后的产物进行过滤洗涤,得到的滤饼在80℃烘箱中烘干,1000℃马弗炉中焙烧,即得到Al2O3载体。
称取上述载体10g分散在50ml去离子水中,高速搅拌30min,得到混合液A。称取含有0.1g的Pt的前驱体溶液硝酸铂于烧杯中,加入20ml去离子水进行超声溶解,得到溶液B。在高速搅拌混合液A的条件下,逐滴加入B溶液,混合均匀,室温下搅拌2h后,利用旋蒸将溶剂蒸干。将得到的干品放入80℃烘箱烘干,600℃焙烧4h。
对比例3
称取102g的氧化铝和81g的氧化锌于烧杯中,加入500g去离子水搅拌分散,高速搅拌30min,得到混合液A。称取含有0.1g的Pt的前驱体溶液硝酸铂于烧杯中,加入20ml去离子水进行超声溶解,得到溶液B。在高速搅拌混合液A的条件下,逐滴加入B溶液,混合均匀,室温下搅拌2h后,利用旋蒸将溶剂蒸干。将得到的干品放入80℃烘箱烘干,600℃焙烧4h。
对比例4
本对比例提供一种低碳烷烃脱氢催化剂,其制备方法包括:
称取实施例1制备的载体10g分散在50ml去离子水中,高速搅拌30min,得到混合液A。称取含有0.1g的Pt的前驱体溶液氯铂酸,加入20ml去离子水进行超声溶解,得到溶液B。在高速搅拌混合液A的条件下,逐滴加入B溶液,混合均匀,室温下搅拌2h后,利用旋蒸将溶剂蒸干。将得到的干品放入80℃烘箱烘干,600℃焙烧4h。
为了进一步说明本发明提供的催化剂的性能,特进行以下实验:
一、丙烷脱氢试验
采用的工艺流程为现有的工艺流程,实施例中不作详细阐述,工艺流程中的控制参数如下:丙烷空速为1h-1,通入适量氢气,保持丙烷分压为50kPa,反应体系总压力为常压;床层温度为550-600℃。其中,各实施例和对比例载体制备及催化剂组成如表1所示,试验结果如表2所示。
表1.各实施例和对比例载体制备及催化剂组成
表2.各催化剂的催化性能评价
由表2可见,本申请实施例1-9提供的催化剂对丙烷脱氢的转化率、选择性、以及丙烯产率均优于对比例1-3,由此说明本申请提供的这种以改性铝酸锌载体,相比于传统的铝酸锌载体、氧化铝载体以及商业α相氧化铝载体,稳定性强且载体的表面酸性低,由此避免了传统载体由于B酸过多而导致酸性裂解的问题,使得催化剂的催化性能和稳定性均有显著提高。本申请实施例1-7提供的催化剂的催化性能也优于对比例4,由此说明,助剂的引入也在一定程度上弥补了载体上的一些高能量缺陷位置,对脱氢催化剂综合性能进行了保障。
最后应说明的是:以上所述仅为本发明的优选实施例而已,并不用于限制本发明的保护范围。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种改性铝酸锌载体,其特征在于,所述改性铝酸锌载体的化学组成为通式ZnxMyAl2O4,其中,x为0.01~0.99,y为0.01~0.99,且满足x+y=1;M选自碱金属元素、碱土金属元素中的一种或几种;所述改性铝酸锌载体具有多孔结构,比表面积为10-100m2/g,孔径范围为3nm~30nm,孔容范围为0.1~0.7g/mL。
2.根据权利要求1所述的改性铝酸锌载体,其特征在于,所述通式ZnxMyAl2O4中的Zn元素的前驱体包括氯化锌、硝酸锌、醋酸锌和有机锌盐中的至少一种。
3.根据权利要求1所述的改性铝酸锌载体,其特征在于,所述通式ZnxMyAl2O4中的Al元素的前驱体包括氯化铝、硝酸铝、醋酸铝、氧化铝、铝石和有机铝盐中的至少一种。
4.根据权利要求1所述的改性铝酸锌载体,其特征在于,所述改性铝酸锌载体采用凝胶溶胶法、浸渍法、沉淀法、共沉淀法或水热合成法制备得到。
5.根据权利要求4所述的改性铝酸锌载体,其特征在于,所述改性铝酸锌载体采用沉淀法或共沉淀法制备得到,所用的沉淀剂为氨水、氢氧化钠、氢氧化钾、碳酸钠和尿素中的至少一种;
优选地,所述改性铝酸锌载体采用凝胶溶胶法制备得到,所用凝胶剂为柠檬酸、草酸、聚乙烯醇中的一种或几种。
6.一种低碳烷烃脱氢催化剂,其特征在于,所述催化剂以贵金属Pt、Pd、Ru和Rh中的至少一种为活性组分,以过渡金属Ga、V、In、Sn、Mn、Ce、Co、Fe和Ni中的至少一种为助剂,以如权利要求1~5任一项所述的改性铝酸锌载体为载体。
7.根据权利要求6的低碳烷烃脱氢催化剂,其特征在于,以所述催化剂干基总质量为基准,所述活性组分的质量百分含量为1-40wt%,所述助剂的质量百分含量为1~20wt%,余量为所述改性铝酸锌载体。
优选地,所述贵金属元素的前驱体选用金属卤化物、金属硝酸盐和金属络合物中的一种或几种;
优选地,所述过渡元素的前驱体为金属元素的氧化物、无机盐、配合物中的一种或多种。
8.一种根据权利要求6或7所述的低碳烷烃脱氢催化剂的制备方法,其特征在于,包括:
在搅拌的条件下,将含有所述活性组分和所述助剂的溶液滴加至含有所述改性铝酸锌载体的分散液中,搅拌1~3h后,回收溶剂、烘干后焙烧。
9.根据权利要求8所述的低碳烷烃脱氢催化剂的制备方法,其特征在于,所述焙烧过程中温度为500~700℃,时间为3~5h。
10.一种根据权利要求6或7所述的低碳烷烃脱氢催化剂的应用,其特征在于,所述催化剂应用于固定床、移动床或流化床,反应温度为550-620℃,反应压力为10-150kPa,反应空速为0.1-2h-1。
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WO2024008164A1 (zh) * | 2022-07-07 | 2024-01-11 | 润和科华催化剂(上海)有限公司 | 改性铝酸锌载体、低碳烷烃脱氢催化剂及其制备方法和应用 |
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