CN115487852A - Spherical non-noble metal catalyst, preparation method thereof and application thereof in preparation of propylene by propane dehydrogenation - Google Patents
Spherical non-noble metal catalyst, preparation method thereof and application thereof in preparation of propylene by propane dehydrogenation Download PDFInfo
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- CN115487852A CN115487852A CN202110678420.5A CN202110678420A CN115487852A CN 115487852 A CN115487852 A CN 115487852A CN 202110678420 A CN202110678420 A CN 202110678420A CN 115487852 A CN115487852 A CN 115487852A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 163
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 133
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000001294 propane Substances 0.000 title claims abstract description 52
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 46
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title abstract description 42
- 239000002131 composite material Substances 0.000 claims abstract description 78
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 26
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims description 55
- 239000011148 porous material Substances 0.000 claims description 39
- 239000002808 molecular sieve Substances 0.000 claims description 37
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 37
- 229910052710 silicon Inorganic materials 0.000 claims description 31
- 239000010703 silicon Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 28
- 239000002994 raw material Substances 0.000 claims description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 24
- 239000012265 solid product Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- 238000007493 shaping process Methods 0.000 claims description 20
- 239000008188 pellet Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000012702 metal oxide precursor Substances 0.000 claims description 14
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 13
- 230000002902 bimodal effect Effects 0.000 claims description 13
- 230000002378 acidificating effect Effects 0.000 claims description 12
- 238000005520 cutting process Methods 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000012216 screening Methods 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000011135 tin Substances 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- 229940024546 aluminum hydroxide gel Drugs 0.000 claims description 2
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229910001679 gibbsite Inorganic materials 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 238000003776 cleavage reaction Methods 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 230000007017 scission Effects 0.000 claims 1
- 238000000527 sonication Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000011805 ball Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 239000011651 chromium Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011806 microball Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 229910000358 iron sulfate Inorganic materials 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005216 hydrothermal crystallization Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002383 small-angle X-ray diffraction data Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000002604 ultrasonography Methods 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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 101100442269 Shewanella piezotolerans (strain WP3 / JCM 13877) dapB gene Proteins 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000012395 formulation development Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- 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
-
- 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 relates to the field of catalysts, and discloses a spherical non-noble metal catalyst, a preparation method thereof and application thereof in preparation of propylene by propane dehydrogenation. The spherical non-noble metal catalyst comprises a spherical composite carrier and a non-noble metal oxide loaded on the spherical composite carrier; wherein the spherical composite carrier is Al 2 O 3 -MCM-48 composite, and the content of the spherical composite support is 70-97 wt% and the content of the non-noble metal oxide is 3-30 wt%, based on the total weight of the spherical non-noble metal catalyst. The spherical non-noble metal catalyst can achieve better propane dehydrogenation activity, propylene selectivity and stability under the condition of not using noble metals and metal oxides with serious pollution.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a spherical non-noble metal catalyst, a preparation method thereof and application thereof in preparation of propylene by propane dehydrogenation.
Background
Propylene is an important organic chemical raw material, and can be used for producing chemical products such as polypropylene, acrolein, acrylic acid, glycerol, isopropanol, polyacrylonitrile, butanol and the like. Currently, propylene is mainly derived from refinery by-products and steam cracking co-production. Recently, with the rapid development of coal chemical industry, the realization of MTP process has effectively increased the source of propylene. Even so, the supply gap of propylene is still not complemented. Under the above circumstances, the dehydrogenation of propane to produce propylene is one of the important ways to increase the yield of propylene. The propane dehydrogenation technology is mainly divided into direct dehydrogenation and oxidative dehydrogenation, wherein the direct dehydrogenation technology has been industrially produced in 90 years in the 20 th century. The propane direct dehydrogenation catalyst for industrial application mainly comprises two types of Cr series catalysts and Pt series catalysts. There are the Catofin process developed by Lummus, linde & BASF, and FBD process developed by Snamprogetti using Cr-series catalysts, the Oleflex process developed by UOP, and the Star process developed by Phillips using Pt-series catalysts. The Cr-based catalyst is low in price but easy to deactivate, and heavy metal chromium causes serious environmental pollution. Relatively speaking, the Pt catalyst has high activity, good selectivity and stability, but the noble metal platinum is expensive and the catalyst cost is high. Therefore, for various processes for preparing propylene by propane dehydrogenation, the development of a catalyst which does not use a non-metallic oxide with serious environmental pollution, has high dehydrogenation catalytic activity and good stability is a main technical problem to be solved at present.
In order to improve various performance indexes of the propane dehydrogenation catalyst, researchers have made many efforts to improve Cr-based catalysts and Pt-based catalysts. Such as: the method is characterized in that the reaction performance of the Pt catalyst is improved by an oxide support modification method (CN 106607100A, CN 106607099A), the catalyst activity is improved by improving a catalyst preparation method (CN 103418376A, CN 106944081A), the catalytic performance of the Cr catalyst is improved by an additive method (CN 104549220A), and the addition of a Cr component is avoided by multi-component catalyst formulation development (CN 102451677B, CN 104607168A). Although the prior art improves the industrial application of Cr catalysts to a certain extent, the problems of complex catalyst components, complex preparation process and catalyst performance to be improved still exist. The Cr catalysts currently used in industry are prepared using alumina as a carrier. Although the alumina carrier is low in price, the pore size distribution is uneven, the specific surface area is small, and the dispersion of active metal oxide on the surface of the carrier is not facilitated, and the diffusion of raw materials and products in the reaction process is also not facilitated.
Therefore, the development of a suitable support with excellent performance is an effective way to improve the performance of the propane dehydrogenation catalyst.
Disclosure of Invention
The invention aims to solve the problems that the cost of a catalyst for preparing propylene by propane dehydrogenation is higher or environmental pollution is easily caused in the prior art, and provides a spherical non-noble metal catalyst, a preparation method thereof and application thereof in preparing propylene by propane dehydrogenation. The spherical non-noble metal catalyst can achieve better propane dehydrogenation activity, propylene selectivity and stability under the condition of not using noble metals and metal oxides with serious pollution.
In order to achieve the above object, a first aspect of the present invention provides a spherical non-noble metal catalyst, wherein the spherical non-noble metal catalyst comprises a spherical composite carrier and a non-noble metal oxide supported on the spherical composite carrier; wherein the spherical composite carrier is Al 2 O 3 -MCM-48 composite and based on total weight of the spherical non-noble metal catalyst,the content of the spherical composite carrier is 70-97 wt%, and the content of the non-noble metal oxide is 3-30 wt%.
The second aspect of the present invention provides a preparation method of the spherical non-noble metal catalyst, wherein the preparation method comprises: under the ultrasonic condition, the spherical composite carrier is contacted with a solution containing a non-noble metal oxide precursor for reaction, a solid product is obtained after the solvent is removed, and the solid product is dried and roasted to obtain the spherical non-noble metal catalyst.
The third aspect of the invention provides an application of the spherical non-noble metal catalyst in the reaction of preparing propylene by propane dehydrogenation.
Through the technical scheme, compared with the prior art, the technical scheme provided by the invention has the following advantages:
(1) The spherical non-noble metal catalyst provided by the invention does not contain noble metals, and can effectively reduce the preparation cost of the propane dehydrogenation catalyst; the spherical non-noble metal catalyst disclosed by the invention does not contain chromium elements and is environment-friendly.
(2) The spherical non-noble metal catalyst provided by the invention is a molded catalyst product, and the mechanical strength can meet the requirements of industrial production.
(3) The spherical non-noble metal catalyst shows good catalytic performance when used for preparing propylene by propane dehydrogenation, and has high propane conversion rate, high propylene selectivity and good catalyst stability;
(4) The preparation method of the spherical non-noble metal catalyst has the advantages of simple process, good product repeatability and easily controlled conditions.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is an XRD spectrum of an MCM-48 all-silicon mesoporous molecular sieve prepared in example 1 of the invention;
FIG. 2 shows Al prepared in example 1 of the present invention 2 O 3 -small angle XRD spectrum of MCM-48 spherical composite carrier a;
FIG. 3 isAl prepared in inventive example 1 2 O 3 -a wide angle XRD spectrum of MCM-48 spherical composite carrier a;
FIG. 4 shows Al prepared in example 1 of the present invention 2 O 3 Pore size distribution of MCM-48 spherical composite Carrier A.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a spherical non-noble metal catalyst in a first aspect, wherein the spherical non-noble metal catalyst comprises a spherical composite carrier and a non-noble metal oxide loaded on the spherical composite carrier; wherein the spherical composite carrier is Al 2 O 3 -MCM-48 composite, and the content of the spherical composite support is 70-97 wt% and the content of the non-noble metal oxide is 3-30 wt%, based on the total weight of the spherical non-noble metal catalyst.
The inventors of the present invention found that: compared with the Pt-based dehydrogenation catalyst, the Cr-based catalyst is lower in cost, but is inferior in stability and serious in pollution. In order to maintain low catalyst cost while considering environmental requirements, non-noble metal elements have been used in the prior art to replace Cr to prepare dehydrogenation catalysts. The research on the alternative catalyst has been continued for nearly two decades, but the performance of the catalyst still can not completely reach the level of the Cr-series catalyst, mainly expressed in the aspects of lower selectivity, poorer stability and the like. In addition, any solid catalyst preparation can not leave the molding process. Under the condition of unchanged raw materials and formula, different forming methods and processes of the catalyst or the catalyst carrier often lead the catalyst to have different use effects. The shape of the catalyst used in the current industrial device mainly includes microsphere type, sphere type, strip type, sheet type, trilobe type, ring type, etc. Under the same composition, the spherical carrier has high bulk density, large loading capacity and handling capacity, low abrasion, small dust during loading, fast mass transfer and high adsorption efficiency or reaction efficiency, can ensure that the industrial reaction is more efficient, and improves the productivity and the product yield. The upgrading of strip products into spherical products in domestic markets is a great trend.
In addition, the inventor of the present invention has found, in the course of research on the preparation of propane dehydrogenation catalysts, that the propane dehydrogenation catalysts prepared by using gamma-alumina or silica as a carrier to support a non-noble metal oxide in the prior art have the disadvantages of poor propylene selectivity and stability. Although the alumina carrier or the silica carrier sold in the market is low in price, the pore size distribution is uneven, the specific surface area is small, and the dispersion of the active metal oxide on the surface of the carrier and the diffusion of raw materials and products in the reaction process are not facilitated. In comparison, the all-silicon mesoporous molecular sieve has the advantages of large specific surface area, large pore volume and uniform pore channel size, and is more favorable for diffusion of reactant molecules and product molecules in the reaction. However, the bulk density of the all-silicon mesoporous molecular sieve material is small, the all-silicon mesoporous molecular sieve material is not easy to form, and the prepared catalyst has poor mechanical strength and abrasion strength, so that the industrial application of the all-silicon mesoporous molecular sieve material is limited.
The inventor of the invention finds that Al is prepared by combining the structural advantages of alumina with stronger viscosity and MCM-48 all-silicon mesoporous molecular sieve 2 O 3 -MCM-48 spherical composite carrier, as the carrier of propane dehydrogenation catalyst, can effectively improve the reaction performance of propane dehydrogenation catalyst.
Furthermore, the inventor of the invention finds that the introduction of an ultrasonic auxiliary method in the preparation process of the spherical non-noble metal catalyst can promote the active component to be better dispersed in Al 2 O 3 -MCM-48 spherical composite carrier surface, and then obtain the propane dehydrogenation catalyst with better catalytic activity.
According to the present invention, preferably, the content of the spherical composite carrier is 80 to 97 wt% and the content of the non-noble metal oxide is 3 to 20 wt%, based on the total weight of the spherical non-noble metal catalyst; more preferably, the content of the spherical composite carrier is 80-95 wt% and the content of the non-noble metal oxide is 5-20 wt% based on the total weight of the spherical non-noble metal catalyst. In the invention, the content of the spherical composite carrier and the content of the non-noble metal oxide are limited to be in the ranges, so that the prepared spherical non-noble metal catalyst can achieve better propane dehydrogenation activity, propylene selectivity and stability under the condition of not using noble metals and metal oxides with serious pollution.
According to the invention, the metal element in the non-noble metal oxide is selected from one or more of iron, zinc, nickel, molybdenum, tin, tungsten, manganese and copper; preferably, the metal element in the non-noble metal oxide is selected from one or more of iron, zinc, nickel and tin.
According to the invention, the specific surface area of the spherical composite carrier is 400-900m 2 The pore volume is 0.5-1.2mL/g, the pore size distribution is bimodal, and the most probable pore sizes corresponding to the bimodal are 2-4nm and 12-18nm respectively; preferably, the specific surface area of the spherical composite carrier is 550-700m 2 The pore volume is 0.6-0.9mL/g, the pore size distribution is bimodal, and the most probable pore sizes corresponding to the bimodal are 2-3nm and 13-16nm respectively; more preferably, the specific surface area of the spherical composite carrier is 603-654m 2 The pore volume is 0.67-0.75mL/g, the pore size distribution is bimodal, and the most probable pore sizes corresponding to the bimodal are 2.3-2.5nm and 13.7-14.8nm respectively. In the invention, the spherical composite carrier is adopted, so that the prepared spherical non-noble metal catalyst has better propane dehydrogenation activity, propylene selectivity and stability.
According to the present invention, the preparation method of the spherical composite carrier comprises:
(1) Contacting and mixing an alumina precursor, an MCM-48 all-silicon mesoporous molecular sieve, an acidic aqueous solution and an extrusion aid, and carrying out pellet ball-making treatment on the obtained mixture to obtain a spherical precursor;
(2) And drying and roasting the spherical precursor to obtain the spherical composite carrier.
According to the inventionThe alumina precursor is selected from one or more of pseudo-boehmite, aluminum hydroxide gel, alumina sol, gibbsite and boehmite; in the present invention, the pseudoboehmite can be obtained commercially or prepared, and in the present invention, specifically, the pseudoboehmite includes: boehmite powder with model number BD-BS03 (purchased from Shandong Zibo Bai chemical Co., ltd., specific surface area of 269 m) 2 Per g, pore volume 0.41cm 3 (g) SB type Germany original package imported pseudoboehmite powder (purchased from Beijing Atotawa chemical auxiliary agent Co., ltd., specific surface area 241 m) 2 Per g, pore volume 0.53cm 3 Perg) and a pseudoboehmite powder having a type P-DF-09-LSi (manufactured by Shandong aluminum Co., ltd., a specific surface area of 286 m) 2 Per g, pore volume 1.08cm 3 One or more of the following components/g).
According to the invention, the MCM-48 all-silicon mesoporous molecular sieve can be a commercial product or a self-made sample. In the invention, preferably, the preparation method of the MCM-48 full-silicon mesoporous molecular sieve comprises the following steps: hydrolyzing a template agent, a silicon source and sodium hydroxide under the condition of hydrolysis gel preparation to obtain a gel mixture; crystallizing the gel mixture under crystallization conditions, filtering, drying and removing the template agent from the solid product to obtain the MCM-48 all-silicon mesoporous molecular sieve.
According to the invention, the silicon source is preferably of the formula (RO) 4 Orthosilicate of Si wherein R is C 1 -C 4 Linear or branched alkyl groups of (a).
According to the invention, the templating agent is a mixture of a quaternary ammonium cationic surfactant and a neutral amine surfactant; and the molar ratio of the quaternary ammonium cationic surfactant to the neutral amine surfactant is 1: (0.03-0.07).
According to the invention, the silicon source: template agent: sodium hydroxide: the molar ratio of water is 1: (0.1-0.2): (0.4-0.6): (50-90), preferably 1: (0.12-0.18): (0.45-0.55): (60-80).
According to the invention, the hydrolysis gel-making conditions comprise: the temperature is 10-60 ℃ and the time is 0.5-10h.
According to the invention, the crystallization conditions include: the temperature is 100-130 ℃, and the time is 12-96h.
According to the invention, the drying conditions comprise: the temperature is 70-150 ℃ and the time is 3-10h.
According to the present invention, the method for removing the template agent is not particularly required, and may be various methods, such as a baking method or an extraction method.
According to the present invention, the acidic aqueous solution may be an aqueous organic acid solution or an aqueous inorganic acid solution, preferably, the acidic aqueous solution is one or more selected from an aqueous formic acid solution, an aqueous acetic acid solution, an aqueous citric acid solution, an aqueous nitric acid solution and an aqueous hydrochloric acid solution, more preferably, the acidic aqueous solution is an aqueous nitric acid solution or an aqueous citric acid solution; in the present invention, the acidic aqueous solution has a mass concentration of 1 to 20%, preferably 2 to 15%.
According to the invention, the extrusion aid is selected from one or more of sesbania powder, polyethylene glycol, polyvinyl alcohol, polyacrylamide and cellulose; preferably, the auxiliary agent is sesbania powder.
According to the invention, the weight ratio of the alumina precursor, the MCM-48 full-silicon mesoporous molecular sieve, the extrusion aid and the acidic aqueous solution is 1: (0.3-0.8): (0.02-0.5): (0.2-5); preferably, the weight ratio of the alumina precursor, the MCM-48 full-silicon mesoporous molecular sieve, the extrusion aid and the acidic aqueous solution is 1: (0.4-0.6): (0.05-0.2): (0.4-2).
According to the invention, in the step (1), an alumina precursor, an MCM-48 all-silicon mesoporous molecular sieve, an acidic aqueous solution and an extrusion assistant are contacted and mixed, wherein the mixing conditions comprise that: stirring at a speed of 50-300r/min and at a temperature of 20-60 deg.C for 0.5-6h; preferably, the stirring speed is 150-200r/min, the temperature is 20-35 ℃, and the time is 0.5-1h.
According to the invention, in step (2), the drying conditions include: the temperature is 70-150 ℃, and the time is 3-24h; preferably, the temperature is 110-120 ℃ and the time is 8-12h.
According to the invention, in the step (2), the roasting conditions include: the temperature is 400-700 ℃, and the time is 2-30h; preferably, the temperature is 550-700 ℃ and the time is 6-15h.
According to the invention, in the step (1), the pellet pelletizing method comprises the following steps:
(1-1) extruding the mixture into strips, and then cutting and extruding the strips into raw material balls;
(1-2) shaping the raw material ball to obtain a standard ball;
(1-3) screening the standard round balls to obtain a spherical precursor.
According to a preferred embodiment of the present invention, the pellet pelletizing method comprises: uniformly mixing an alumina precursor, an MCM-48 all-silicon mesoporous molecular sieve, an acidic aqueous solution and an extrusion aid in a kneader, transferring the mixture into a miniature ball forming machine to extrude a strip with a circular section, and extruding the strip into a raw material ball after cutting; and (3) shaping the raw material balls in a pellet shaping machine to make the raw material balls into standard round spheres, and screening the obtained product in a pellet screening machine to obtain a spherical precursor with a proper size.
According to the invention, in the step (1-1), after uniformly mixing an alumina precursor, an MCM-48 all-silicon mesoporous molecular sieve, an acidic aqueous solution and an extrusion aid, transferring the obtained mixture into a miniature ball making machine to extrude a strip with a circular section, and extruding the strip into a raw material ball after cutting; wherein the conditions for extruding into a bar comprise: the extrusion speed is 0.5-5m/min, and the diameter of the circular section of the strip is 1.5-5.0mm; the cutting conditions include: the cutting speed is 100-3500 granules/min.
According to the invention, in the step (1-2), the raw material ball is put into a pellet shaping machine for shaping, so that the raw material ball becomes a standard round ball shape; wherein the shaping conditions include: the rounding time is 0.5-10 min/time, the rounding times are 1-5 times, and the rotating speed of the sample cavity is 50-1400r/min.
According to the invention, in step (1-3), the standard round balls are placed in a pellet screening machine to screen out spherical precursors of suitable size.
The second aspect of the present invention provides a preparation method of the spherical non-noble metal catalyst, wherein the preparation method comprises: under the ultrasonic condition, the spherical composite carrier is contacted with a solution containing a non-noble metal oxide precursor for reaction, a solid product is obtained after the solvent is removed, and the solid product is dried and roasted to obtain the spherical non-noble metal catalyst.
According to the invention, the conditions of the ultrasound comprise: the temperature is 10-100 ℃, the time is 10-180min, and the power is 100-300W; preferably, the conditions of the ultrasound include: the temperature is 20-80 deg.C, the time is 30-120min, and the power is 150-250W.
According to the invention, the solution containing the non-noble metal oxide precursor is an aqueous solution containing the non-noble metal oxide precursor; preferably, the non-noble metal oxide precursor is selected from one or more of sulfates, sulfites, nitrates and metal chlorides containing non-noble metal elements, preferably sulfates and/or sulfites containing non-noble metal elements; the non-noble metal element is selected from one or more of iron, zinc, nickel, molybdenum, tin, tungsten, manganese and copper.
According to the invention, the concentration of the solution containing non-noble metal oxide precursors is between 0.5 and 10%, preferably between 1 and 7%.
According to the invention, the weight ratio of the spherical composite carrier to the solution containing the non-noble metal oxide precursor is 1: (5-20), preferably 1: (8-15).
According to the invention, the spherical composite carrier is contacted with a solution containing non-noble metal oxide precursors for reaction, wherein the contact conditions comprise: the temperature is 20-100 ℃, preferably 40-80 ℃; the time is 0.5-10h, preferably 2-8h.
According to the present invention, the method for removing the solvent is not particularly limited, and may be a method known in the art, such as: the solvent is removed by evaporation using a rotary evaporator or by heating with stirring.
According to the present invention, the drying conditions are not particularly limited, and may be conditions conventional in the art. Preferably, the drying conditions include: the temperature is 60-150 ℃, preferably 80-130 ℃; the time is 1-20h, preferably 3-15h.
According to the invention, the conditions of the calcination include: the temperature is 400-700 ℃, preferably 500-650 ℃; the time is 2-15h, preferably 3-10h.
The third aspect of the invention provides an application of the spherical non-noble metal catalyst in the reaction of preparing propylene by propane dehydrogenation.
According to the invention, the reaction for preparing propylene by propane dehydrogenation comprises the following steps: the reaction raw material propane contacts with the spherical non-noble metal catalyst.
According to the invention, the conditions of the contacting include: the contact temperature can be 550-650 ℃, the partial pressure of the raw material gas is 0.02-0.5MPa, and the mass space velocity of the propane is 1.0-10.0h -1 。
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
XRD testing of the samples was performed on an X' Pert MPD type X-ray powder diffractometer manufactured by Philips, netherlands, cu ka target, λ =0.154178nm, scan range 2 θ =0.5 ° to 10 °. The pore structure parameter analysis of the samples was performed on an adsorption apparatus model ASAP2020-M + C, available from Micromeritics, USA. The sample was degassed at 350 ℃ for 4 hours under vacuum before measurement, and the specific surface area of the sample was calculated by the BET method and the pore volume was calculated by the BJH model. The elemental analysis experiments of the samples were performed on an Eagle III energy dispersive X-ray fluorescence spectrometer manufactured by EDAX, USA.
The ultrasonic generator is a KQ-300GTDV high-frequency constant-temperature numerical control ultrasonic cleaner produced by ultrasonic instruments Limited in Kunshan, the ultrasonic frequency is 80kHz, and the working voltage is 220V;
the rotary evaporator is produced by German IKA company, and the model is RV10 digital;
the drying box is produced by Shanghai-Hengchang scientific instruments Co., ltd, and is of a type DHG-9030A.
The muffle furnace is manufactured by CARBOLITE corporation, model CWF1100.
The kneader is FN-NH2 type kneader produced by Technology limited company of Tianshuihuan pharmaceutical equipment; the micro ball making machine is a model HWJ-100 micro ball making machine produced by Tianshuihua round pharmaceutical equipment science and technology Limited; the pellet shaper is FN-XZXJ type pellet shaper produced by TIANSHUIHUAYUANYAOWU pharmaceutical equipment science and technology limited; the pellet screening machine is an SWP-1200 type pellet screening machine produced by Tianshuihua round pharmaceutical equipment science and technology limited company.
The reagents used in the examples and comparative examples were purchased from national pharmaceutical group chemical agents, ltd, and the purity of the reagents was analytical grade.
Example 1
This example is presented to illustrate the preparation of a spherical non-noble metal catalyst of the invention.
(1) Preparation of MCM-48 full silicon mesoporous molecular sieve
23.2g of cetyltrimethylammonium bromide, 0.6g of dodecylamine, 8.1g of sodium hydroxide and 500ml of deionized water were mixed and stirred at 45 ℃ for 1 hour; 82.9g of tetraethoxysilane is added into the solution drop by drop and stirred for 1 hour; transferring the mixture to a hydrothermal kettle, and carrying out hydrothermal crystallization at 100 ℃ for 72 hours. After hydrothermal crystallization is finished, separating a solid product from a mother solution, washing the solid product to be neutral by deionized water, and drying the solid product in air at 110 ℃ for 3 hours; then roasting for 20 hours at 550 ℃ to obtain the MCM-48 full-silicon mesoporous molecular sieve.
Fig. 1 is an XRD spectrum of the MCM-48 all-silicon mesoporous molecular sieve prepared in example 1 of the present invention, and as can be seen from fig. 1, the sample shows a sharp strong diffraction peak and a weaker but clearly identifiable diffraction peak between 2 θ =2.5 ° and 3.5 °, which correspond to the (211) and (220) crystal planes, respectively. In addition, there is also a set of diffraction signals at 2 θ =4.0 ° to 6.0 °, including diffraction peaks corresponding to the (420) and (332) crystal planes. The diffraction signal is the characteristic diffraction peak of the MCM-48 mesoporous molecular sieve.
(2)Al 2 O 3 -MCM-48 spherical composite carrier preparation
100g of pseudo-boehmite powder with the model number of P-DF-09-LSi, 50g of MCM-48 full-silicon mesoporous molecular sieve, 78g of dilute nitric acid with the concentration of 5.0 percent and 10g of sesbania powder are mixed and transferred to a kneader to be stirred and mixed uniformly. The kneading temperature is 30 ℃, the rotation speed of the main shaft of the kneader is 200r/min, and the kneading time is 1h. Mixing uniformlyThe raw materials are put into a hopper of a miniature ball making machine, a strip extruding die with the aperture of 1.8mm is selected, the strip extruding speed is regulated to be 1.5m/min, the cutting speed is 900 granules/min, and the raw materials are extruded into strips and extruded and cut into round small granules. Putting the round small particles into a pellet shaping machine for shaping, wherein the shaping conditions are as follows: the rounding time is 2 minutes/time, the rounding times are 4 times, and the rotating speed of the sample cavity is 300r/min. And putting the standard spherical raw material balls obtained after shaping into a pellet screening machine to screen out spherical precursors with the size of 1.8 mm. Drying the spherical precursor at 110 ℃ for 10h, and roasting at 600 ℃ for 12h to obtain Al 2 O 3 -MCM-48 spherical composite support a.
Al 2 O 3 The specific surface area of the-MCM-48 spherical composite carrier A is 631m 2 Pore volume 0.71mL/g, average particle diameter 1.74mm, and average particle crush strength 26.8N.
FIG. 2 shows Al prepared in example 1 of the present invention 2 O 3 -small angle XRD spectrum of MCM-48 spherical composite support a. The figure is similar to figure 1, because alumina has no diffraction signal at a small angle part, which indicates that the crystal phase of the MCM-48 mesoporous molecular sieve is not obviously changed after the spherical composite carrier A is roasted at 600 ℃, and the typical three-dimensional cubic phase mesoporous structure is still maintained.
FIG. 3 shows Al prepared in example 1 of the present invention 2 O 3 The wide-angle XRD pattern of MCM-48 spherical composite carrier A, the XRD wide-angle diffraction pattern of the spherical composite carrier is identical to that of alumina, because the structure of MCM-41 has no diffraction signal in the wide-angle part. The x-ray diffraction angles are mainly: 2 theta is approximately equal to 37.1 degrees, 39.3 degrees, 46.1 degrees, 60.7 degrees and 66.6 degrees, and the five diffraction signals and gamma-Al 2 O 3 Diffraction spectra are identical, which shows that after being roasted at 600 ℃, the spherical composite carrier A presents typical gamma-Al after the pseudoboehmite with the model of P-DF-09-LSi is dehydrated 2 O 3 A crystalline phase. In addition, it should be noted that there is no way for the XRD signal of the spherical composite carrier to be shown in one figure, nor to be detected by the same characterization means. The XRD patterns given here are two, one wide and one small.
FIG. 4 isAl prepared by the invention 2 O 3 The pore size distribution of the MCM-48 spherical composite carrier a, as can be seen from fig. 4, the pore size of this sample is bimodal, the first mode pore size is 2.4nm, mainly contributed by the mesoporous molecular sieve; the second mode pore size is 14.0nm, mainly contributed by alumina.
(3) Preparation of spherical non-noble metal catalyst
3.25g of ferric sulfate was dissolved in 100g of deionized water with 8.7g of Al 2 O 3 -MCM-48 spherical composite carrier A, and stirring and reacting for 60 minutes with the assistance of ultrasonic waves with the power of 200W, wherein the temperature is 50 ℃. After the reaction is finished, water in the system is distilled off by a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 110 ℃ for 6 hours. Then roasting the mixture for 5 hours in a muffle furnace at the temperature of 600 ℃ to obtain the spherical non-noble metal catalyst A.
The specific gravity of each component of the spherical non-noble metal catalyst A is as follows: 13 weight percent of ferric oxide, and the balance of carrier.
(4) Performance evaluation of catalyst in reaction for producing propylene by propane dehydrogenation
The evaluation of the reaction performance of the catalyst was carried out on a fixed bed reactor. 5.0 g of the catalyst A was charged into a fixed bed quartz reactor, the reaction temperature was controlled at 600 ℃, the reaction pressure was 0.1MPa, and the molar ratio of propane: the molar ratio of helium is 1:1, the mass space velocity of propane is 5.0h -1 The reaction time is 6h. By Al 2 O 3 The reaction product separated by the S molecular sieve column directly enters an Agilent 7890A gas chromatograph equipped with a hydrogen flame detector (FID) for on-line analysis. The reaction evaluation results are shown in Table 1.
Example 2
This example is presented to illustrate the preparation of a spherical non-noble metal catalyst of the invention.
An MCM-48 all-silicon mesoporous molecular sieve was prepared in the same manner as in step (1) in example 1.
(2)Al 2 O 3 -MCM-48 spherical composite carrier preparation
100g of boehmite powder with the model number of BD-BS03, 40g of MCM-48 full-silicon mesoporous molecular sieve,62g of a 10% aqueous acetic acid solution and 5g of polyethylene glycol were mixed, and the mixture was transferred to a kneader and stirred to mix uniformly. The kneading temperature is 35 ℃, the rotation speed of the main shaft of the kneader is 150r/min, and the kneading time is 1h. Putting the uniformly mixed raw materials into a hopper of a micro ball making machine, selecting a strip extruding die with the aperture of 2.5mm, adjusting the strip extruding speed to be 5m/min and the cutting speed to be 2000 granules/min, extruding the raw materials into strips, and extruding and cutting the strips into round small granules. The round small particles are put into a pellet shaping machine for shaping, and the shaping conditions are as follows: the rounding time is 0.5 min/time, the rounding times are 2 times, and the rotating speed of the sample cavity is 500r/min. And putting the standard spherical raw material balls obtained after shaping into a pellet screening machine to screen out spherical precursors with the size of 2.5 mm. Drying the spherical precursor at 120 ℃ for 8h, and roasting at 700 ℃ for 6h to obtain Al 2 O 3 -MCM-48 spherical composite carrier B.
Al 2 O 3 Average particle diameter of 2.44mm, average particle crushing strength of 35.4N, specific surface area of 603m for MCM-48 spherical composite Carrier B 2 Pore volume 0.67mL/g, bimodal distribution of pore diameters, first mode pore diameter of 2.5nm, second mode pore diameter of 14.8nm.
(3) Preparation of spherical non-noble metal catalyst
6.95g of ferrous sulfate heptahydrate were dissolved in 100g of deionized water, and 8.0g of Al 2 O 3 -mixing the MCM-48 spherical composite carrier B, and stirring and reacting for 30 minutes with the assistance of ultrasonic waves with the power of 250W, wherein the temperature is 80 ℃. After the reaction is finished, water in the system is distilled off by a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 80 ℃ for 15 hours. Then roasting the mixture for 3 hours in a muffle furnace at the temperature of 650 ℃ to obtain the spherical non-noble metal catalyst B.
The specific gravity of each component of the spherical non-noble metal catalyst B is as follows: 20% by weight of iron sesquioxide, the remainder being the support.
The catalytic performance of the spherical non-noble metal catalyst B in the reaction of propane dehydrogenation to propylene was evaluated in accordance with the method of step (4) in example 1. The reaction evaluation results are shown in Table 1.
Example 3
This example illustrates the preparation of a spherical non-noble metal catalyst according to the invention.
An MCM-48 all-silicon mesoporous molecular sieve was prepared in the same manner as in step (1) in example 1.
(2)Al 2 O 3 -MCM-48 spherical composite carrier preparation
100g of SB type German original package imported pseudo-boehmite powder, 60g of MCM-48 all-silica mesoporous molecular sieve, 80g of 15.0% citric acid aqueous solution and 18g of cellulose are mixed, transferred to a kneader and stirred uniformly. The kneading temperature is 20 ℃, the rotation speed of the main shaft of the kneader is 200r/min, and the kneading time is 0.5h. Putting the uniformly mixed raw materials into a hopper of a micro ball making machine, selecting a strip extruding die with the aperture of 2.0mm, adjusting the strip extruding speed to be 1m/min and the cutting speed to be 500 granules/min, extruding the raw materials into strips, and extruding and cutting the strips into round small granules. Putting the round small particles into a pellet shaping machine for shaping, wherein the shaping conditions are as follows: the rounding time is 2 minutes/time, the rounding times are 4 times, and the rotating speed of the sample cavity is 200r/min. And putting the standard spherical raw material balls obtained after shaping into a pellet screening machine to screen out spherical precursors with the size of 2.0 mm. Drying the spherical precursor at 110 ℃ for 12h, and roasting at 550 ℃ for 15h to obtain Al 2 O 3 -MCM-48 spherical composite carrier C.
Al 2 O 3 -MCM-48 spherical composite Carrier C having an average particle diameter of 1.93mm, an average particle crushing strength of 31.2N, and a specific surface area of 654m 2 Pore volume 0.75mL/g, bimodal pore size distribution, first mode pore size of 2.3nm, second mode pore size of 13.7nm.
(3) Preparation of spherical non-noble metal catalyst
1.0g of anhydrous zinc sulfate was dissolved in 80g of deionized water, and mixed with 9.5g of Al 2 O 3 -MCM-48 spherical composite carrier C, mixing, stirring and reacting for 120 minutes under the assistance of ultrasonic waves with the power of 150W, and the temperature is 30 ℃. After the reaction is finished, water in the system is distilled off by a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 130 ℃ for 3 hours. Then roasting the mixture for 10 hours in a muffle furnace at the temperature of 500 DEG CThen, the spherical non-noble metal catalyst C is obtained.
The specific gravity of each component of the spherical non-noble metal catalyst C is as follows: 5% by weight of zinc oxide, the remainder being the support.
The catalytic performance of the spherical non-noble metal catalyst C in the reaction of propane dehydrogenation to propylene was evaluated in accordance with the method of step (4) in example 1. The reaction evaluation results are shown in table 1.
Example 4
This example is presented to illustrate the preparation of a spherical non-noble metal catalyst of the invention.
A spherical non-noble metal catalyst was prepared in the same manner as in example 1, except that: the preparation conditions of the spherical non-noble metal catalyst of step (3) in example 1 were varied, specifically:
0.8g of iron sulfate was dissolved in 100g of deionized water with 9.7g of Al 2 O 3 -mixing the MCM-48 spherical composite carrier A, and stirring and reacting for 60 minutes under the assistance of ultrasonic waves with the power of 200W, wherein the temperature is 50 ℃. After the reaction is finished, water in the system is distilled off by a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 110 ℃ for 6 hours. And then roasting the mixture for 5 hours in a muffle furnace at the temperature of 600 ℃ to obtain the spherical non-noble metal catalyst D.
Based on the total weight of the spherical non-noble metal catalyst D, the content of the spherical composite carrier is 96.8 wt%, and the content of the non-noble metal oxide is 3.2 wt%.
The catalytic performance of the spherical non-noble metal catalyst D was evaluated in accordance with the performance evaluation of the catalyst of step (4) in example 1 in the reaction of producing propylene by dehydrogenation of propane. The reaction evaluation results are shown in Table 1.
Example 5
This example is presented to illustrate the preparation of a spherical non-noble metal catalyst of the invention.
A spherical non-noble metal catalyst was prepared in the same manner as in example 1, except that: the preparation conditions of the spherical non-noble metal catalyst of step (3) in example 1 were varied, specifically:
5.75g of sulfurIron salt dissolved in 100g deionized water, and 7.7g Al 2 O 3 -MCM-48 spherical composite carrier A, and stirring and reacting for 60 minutes with the assistance of ultrasonic waves with the power of 200W, wherein the temperature is 50 ℃. After the reaction is finished, water in the system is distilled off by a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 110 ℃ for 6 hours. Then roasting the mixture for 5 hours in a muffle furnace at the temperature of 600 ℃ to obtain the spherical non-noble metal catalyst E.
Based on the total weight of the spherical non-noble metal catalyst E, the content of the spherical composite carrier is 77% by weight, and the content of the non-noble metal oxide is 23% by weight.
The catalytic performance of the spherical non-noble metal catalyst E was evaluated according to the performance evaluation of the catalyst of step (4) in example 1 in the reaction of propane dehydrogenation to propylene. The reaction evaluation results are shown in Table 1.
Comparative example 1
A spherical non-noble metal catalyst was prepared in the same manner as in example 1, except that: catalyst D1 was prepared in the same manner as in step (3) in example 1, except that "commercially available silica" was used in place of Al, except that in example 1, step (1) and step (2) were omitted 2 O 3 MCM-48 spherical composite carrier A as catalyst carrier, the silicon dioxide is purchased from Qingdao sea wave silica gel drier factory, the specific surface area is 329m 2 (iv)/g, mean particle diameter 1.5mm; catalyst D1 was obtained.
Based on the total weight of the catalyst D1, the content of iron sesquioxide was 13% by weight, and the remainder was alumina as a carrier.
The performance of the reaction for producing propylene by propane dehydrogenation of the catalyst D1 was measured in the same manner as in the step (4) in example 1, and the results are shown in Table 1.
Comparative example 2
A spherical non-noble metal catalyst was prepared in the same manner as in example 1, except that: al was produced in accordance with the procedures of step (1) and step (2) in example 1 2 O 3 -MCM-48 spherical composite carrier A. Catalyst D2 was prepared by following the procedure of step (3) in example 1, adjusting the catalyst preparation conditions, withBody ground:
0.3g of iron sulfate was dissolved in 100g of deionized water, and mixed with 9.9g of Al 2 O 3 -mixing the MCM-48 spherical composite carrier A, and stirring and reacting for 60 minutes under the assistance of ultrasonic waves with the power of 200W, wherein the temperature is 50 ℃. After the reaction is finished, water in the system is distilled off by a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 110 ℃ for 6 hours. Then, the catalyst was calcined in a muffle furnace at 600 ℃ for 5 hours to obtain a catalyst D2.
So that the content of iron trioxide based on the total weight of the catalyst D2 was 1.2% by weight, the remainder being the carrier.
The performance test of the reaction of producing propylene by propane dehydrogenation of the catalyst D2 was carried out in the same manner as in the step (4) in example 1, and the reaction results are shown in Table 1.
Comparative example 3
A spherical non-noble metal catalyst was prepared in the same manner as in example 1, except that: steps (1) and (2) in example 1 were omitted, and "8.7g of Al in step (3) in example 1 was added 2 O 3 -12.4 g of pseudo-boehmite powder with the model of P-DF-09-LSi is replaced by the MCM-48 spherical composite carrier A to obtain the spherical non-noble metal catalyst D3.
So that the content of alumina was 87 wt% and the content of iron sesquioxide was 13 wt% based on the total weight of the spherical non-noble metal catalyst D3.
The performance of the reaction for producing propylene by propane dehydrogenation of the catalyst D3 was measured in the same manner as in the step (4) in example 1, and the results are shown in Table 1.
Comparative example 4
A spherical non-noble metal catalyst was prepared in the same manner as in example 1, except that: steps (1) and (2) in example 1 were omitted, and "8.7g of Al in step (3) in example 1 was added 2 O 3 -8.7 g MCM-48 full silicon mesoporous molecular sieve is replaced by the MCM-48 spherical composite carrier A to obtain the spherical non-noble metal catalyst D4.
So that the total weight of the spherical non-noble metal catalyst D4 is taken as a reference, the content of the MCM-48 full-silicon mesoporous molecular sieve is 87 weight percent, and the content of the ferric oxide is 13 weight percent.
The performance of the propane dehydrogenation propylene production reaction of catalyst D4 was tested in the same manner as in step (4) in example 1, and the reaction results are shown in Table 1.
Comparative example 5
A spherical non-noble metal catalyst was prepared in the same manner as in example 1, except that: the step (1) in the example 1 was omitted, and "100g of pseudo-boehmite powder having a model number of P-DF-09-LSi and 50g of MCM-48 all-silica mesoporous molecular sieve" in the step (2) in the example 1 was replaced with "50g of pseudo-boehmite powder having a model number of P-DF-09-LSi and 100g of MCM-48 all-silica mesoporous molecular sieve", to obtain a spherical non-noble metal catalyst D5.
So that the content of the spherical composite carrier is 87 wt% and the content of the ferric oxide is 13 wt% based on the total weight of the spherical non-noble metal catalyst D5.
The performance of the propane dehydrogenation propylene production reaction of catalyst D5 was tested in accordance with the procedure in step (4) of example 1, and the reaction results are shown in Table 1.
Comparative example 6
A spherical non-noble metal catalyst was prepared in the same manner as in example 1, except that: steps (1) and (2) in example 1 were omitted, and "iron sulfate" in step (3) in example 1 was replaced with "sodium sulfate", to obtain a spherical non-noble metal catalyst D6.
Based on the total weight of the spherical non-noble metal catalyst D6, the content of the spherical composite carrier is 87 weight percent, and the content of the sodium oxide is 13 weight percent.
The performance of the propane dehydrogenation propylene production reaction of catalyst D6 was tested in accordance with the procedure in step (4) of example 1, and the reaction results are shown in Table 1.
TABLE 1
It can be seen from the results in table 1 that the spherical non-noble metal catalysts provided in examples 1 to 5 of the present invention are excellent in performance when used in the reaction of propane dehydrogenation to produce propylene.
As a result of comparing experimental example 1 and comparative example 1, it can be found that Al is used 2 O 3 The performance of the catalyst A prepared by the MCM-48 spherical composite carrier is obviously superior to that of the catalyst D1 prepared by using commercial silicon dioxide as a carrier, and the conversion rate of propane, the selectivity of propylene and the stability of the catalyst are both greatly improved. The above results show that Al 2 O 3 The MCM-48 spherical composite carrier is more beneficial to the reaction of preparing propylene by propane dehydrogenation.
Comparing the data of example 1 and comparative example 2, it can be seen that the content of non-noble metal oxide ferric oxide is low, and both the propane conversion rate, the propylene selectivity and the catalyst stability are reduced due to the low content of the surface active component of the catalyst.
Comparing the data of example 1 and comparative example 3, it can be seen that the carrier is only alumina, and the alumina has non-uniform pore size distribution and small specific surface area, which is not beneficial to the dispersion of active metal oxide on the surface of the carrier and the diffusion of raw materials and products in the reaction process, resulting in the reduction of both propane conversion, propylene selectivity and catalyst stability.
Comparing the data of example 1 and comparative example 4, it can be seen that the carrier is only MCM-48 all-silicon mesoporous molecular sieve, and because the material bulk density of all-silicon MCM-48 mesoporous molecular sieve is small and not easy to form, the mechanical strength and abrasion strength of the prepared catalyst are poor, the surface of the catalyst is uneven, the dispersion of active components is poor, and the conversion rate of propane, the selectivity of propylene and the stability of the catalyst are reduced.
Comparing the data of example 1 and comparative example 5, it can be seen that the weight ratio of the amounts of pseudo-boehmite powder and MCM-48 all-silica mesoporous molecular sieve is 1:2, and since the proportion of all-silica MCM-48 mesoporous molecular sieve in the carrier is out of the claimed range, the prepared catalyst has poor strength, non-uniform surface, and poor dispersion of active components, resulting in a decrease in both propane conversion, propylene selectivity, and catalyst stability.
Comparing the data of example 1 and comparative example 6, it can be seen that instead of supporting the appropriate non-noble metal oxide, sodium oxide, since sodium oxide is not catalytically active for propane dehydrogenation, results in only a small amount of propane conversion on the D6 catalyst, and propylene selectivity is also poor.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A spherical non-noble metal catalyst is characterized by comprising a spherical composite carrier and a non-noble metal oxide loaded on the spherical composite carrier; wherein the spherical composite carrier is Al 2 O 3 -MCM-48 composite, and the content of the spherical composite support is 70-97 wt% and the content of the non-noble metal oxide is 3-30 wt%, based on the total weight of the spherical non-noble metal catalyst.
2. The spherical non-noble metal catalyst of claim 1, wherein the Al is based on the total weight of the spherical non-noble metal catalyst 2 O 3 -the MCM-48 composite is present in an amount of 80-97 wt%, the non-noble metal oxide is present in an amount of 3-20 wt%;
preferably, the Al is based on the total weight of the spherical non-noble metal catalyst 2 O 3 -the content of MCM-48 composite is 80-95 wt%, the content of non-noble metal oxide is 5-20 wt%.
3. The spherical non-noble metal catalyst of claim 1 or 2, wherein the metal element in the non-noble metal oxide is selected from one or more of iron, zinc, nickel, molybdenum, tin, tungsten, manganese, and copper.
4. The spherical non-noble metal catalyst of claim 1 or 2, wherein the Al 2 O 3 -specific surface area of MCM-48 composite material 400-900m 2 The pore volume is 0.5-1.2mL/g, the pore size distribution is bimodal, and the most probable pore sizes corresponding to the bimodal are 2-4nm and 12-18nm respectively;
preferably, the Al 2 O 3 -specific surface area of MCM-48 composite material 550-700m 2 The pore volume is 0.6-0.9mL/g, the pore size distribution is bimodal, and the most probable pore sizes corresponding to the bimodal are 2-3nm and 13-16nm respectively.
5. The spherical non-noble metal catalyst of any of claims 1-4, wherein the Al 2 O 3 -the method of preparing an MCM-48 composite comprises:
(1) Contacting and mixing an alumina precursor, an MCM-48 all-silicon mesoporous molecular sieve, an acidic aqueous solution and an extrusion aid, and carrying out pellet ball-making treatment on the obtained mixture to obtain a spherical precursor;
(2) And drying and roasting the spherical precursor to obtain the spherical composite carrier.
6. The spherical non-noble metal catalyst of claim 5, wherein the alumina precursor is selected from one or more of pseudo-boehmite, aluminum hydroxide gel, alumina sol, gibbsite, and boehmite;
preferably, the weight ratio of the alumina precursor, the MCM-48 full-silicon mesoporous molecular sieve, the extrusion aid and the acidic aqueous solution is 1: (0.3-0.8): (0.02-0.5): (0.2-5).
7. The spherical non-noble metal catalyst of claim 5, wherein in step (1), the pellet pelletizing process comprises:
(1-1) extruding the mixture into strips, and then cutting and extruding the strips into raw material balls;
(1-2) shaping the raw material ball to obtain a standard ball;
(1-3) screening the standard round balls to obtain a spherical precursor.
8. The spherical non-noble metal catalyst of claim 7, wherein the extrusion into strands conditions comprise: the extrusion speed is 0.5-5m/min, and the diameter of the circular section of the strip is 1.5-5.0mm;
preferably, the conditions for the cleavage include: the cutting speed is 100-3500 grains/min;
preferably, the shaping conditions include: the rounding time is 0.5-10 min/time, the rounding times are 1-5 times, and the rotating speed of the sample cavity is 50-1400r/min.
9. A method of preparing a spherical non-noble metal catalyst according to any of claims 1 to 8, characterized in that it comprises: under the ultrasonic condition, the spherical composite carrier is contacted with a solution containing a non-noble metal oxide precursor for reaction, a solid product is obtained after the solvent is removed, and the solid product is dried and roasted to obtain the spherical non-noble metal catalyst.
10. The production method according to claim 9, wherein the solution containing a non-noble metal oxide precursor is an aqueous solution containing a non-noble metal oxide precursor;
preferably, the non-noble metal oxide precursor is selected from one or more of sulfates, sulfites, nitrates and metal chlorides containing non-noble metal elements; the non-noble metal elements are selected from one or more of iron, zinc, nickel, molybdenum, tin, tungsten, manganese and copper;
preferably, the weight ratio of the spherical composite carrier to the solution containing the non-noble metal oxide precursor is 1: (5-20);
preferably, the concentration of the solution containing the non-noble metal oxide precursor is 0.5 to 10%.
11. The preparation method of claim 9, wherein the conditions of the sonication include: the temperature is 10-100 ℃, the time is 10-180min, and the power is 100-300W;
preferably, the conditions of the reaction include: the temperature is 20-100 ℃, and the time is 0.5-10h;
preferably, the conditions of the calcination include: the temperature is 400-700 ℃, and the roasting time is 2-15h.
12. Use of a spherical non-noble metal catalyst according to any of claims 1 to 8 in the dehydrogenation of propane to propene.
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