CN115487852B - Spherical non-noble metal catalyst, preparation method thereof and application thereof in propylene preparation by propane dehydrogenation - Google Patents
Spherical non-noble metal catalyst, preparation method thereof and application thereof in propylene preparation by propane dehydrogenation Download PDFInfo
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- CN115487852B CN115487852B CN202110678420.5A CN202110678420A CN115487852B CN 115487852 B CN115487852 B CN 115487852B CN 202110678420 A CN202110678420 A CN 202110678420A CN 115487852 B CN115487852 B CN 115487852B
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- noble metal
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- propylene
- propane
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- 239000003054 catalyst Substances 0.000 title claims abstract description 156
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 127
- 239000001294 propane Substances 0.000 title claims abstract description 67
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 58
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 claims abstract description 77
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims description 70
- 239000011148 porous material Substances 0.000 claims description 36
- 239000002808 molecular sieve Substances 0.000 claims description 35
- 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 35
- 229910052710 silicon Inorganic materials 0.000 claims description 28
- 239000010703 silicon Substances 0.000 claims description 28
- 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
- 238000000034 method Methods 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 24
- 239000008188 pellet Substances 0.000 claims description 22
- 239000012265 solid product Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 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
- 238000005520 cutting process Methods 0.000 claims description 13
- 238000009826 distribution Methods 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 238000012216 screening Methods 0.000 claims description 13
- 230000002378 acidificating effect Effects 0.000 claims description 12
- 238000007493 shaping process Methods 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 230000002902 bimodal effect Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 101100442269 Shewanella piezotolerans (strain WP3 / JCM 13877) dapB gene Proteins 0.000 claims description 2
- 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
- 238000003776 cleavage reaction Methods 0.000 claims 1
- 230000007017 scission Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 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
- 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
- 238000011156 evaluation Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 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 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
- 229910001948 sodium oxide Inorganic materials 0.000 description 4
- 239000000126 substance Substances 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
- 239000011865 Pt-based catalyst Substances 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 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
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000969 carrier Substances 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
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 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
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000002383 small-angle X-ray diffraction data Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten 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
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-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
- 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
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007547 defect Effects 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
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000019253 formic acid Nutrition 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
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 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
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 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 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
- 239000010413 mother solution Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction 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
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012545 processing Methods 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
- 238000011160 research Methods 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
- 238000001179 sorption measurement Methods 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
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 preparing propylene by propane dehydrogenation. 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 an Al 2O3 -MCM-48 composite material, the content of the spherical composite carrier is 70-97 wt% based on the total weight of the spherical non-noble metal catalyst, and the content of the non-noble metal oxide is 3-30 wt%. The spherical non-noble metal catalyst can achieve better propane dehydrogenation activity, propylene selectivity and stability under the condition of not using noble metal and metal oxide 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 propylene preparation 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 octanol. At present, propylene is mainly derived from refinery byproducts and steam cracking co-production. Recently, with the great development of coal chemical industry, the realization of MTP process effectively increases the source of propylene. Even so, the supply gap of propylene is still not complemented. Under the above background, the dehydrogenation of propane to propylene is one of the important ways to increase propylene yield. The propane dehydrogenation technology is mainly classified into direct dehydrogenation and oxidative dehydrogenation, wherein the direct dehydrogenation technology has achieved industrial production in the 90 th century of 20 th. The industrial propane direct dehydrogenation catalysts mainly comprise Cr-based catalysts and Pt-based catalysts. The catalyst used for Cr was a Catofin process developed by Lummes, a Linde process developed by Linde & BASF, and an FBD process developed by Snamprogetti, and the catalyst used for Pt was an Oleflex process developed by UOP and a Star process developed by Phillips. Cr-based catalysts are low in price but easy to deactivate, and heavy metal chromium causes serious environmental pollution. Relatively, pt-based catalysts have high activity, good selectivity and stability, but noble metal platinum is expensive and the catalyst cost is high. Therefore, for various processes for preparing propylene by dehydrogenating propane, the development of a catalyst which does not use non-metal oxides with serious environmental pollution, has higher dehydrogenation catalytic activity and better stability is a main technical problem to be solved urgently at present.
In order to improve various performance indexes of propane dehydrogenation catalysts, researchers have made many efforts to improve Cr-based catalysts and Pt-based catalysts. Such as: the reactivity of the Pt catalyst is improved by a method of modifying an oxide carrier (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 a method of adding an auxiliary agent (CN 104549220A), and the addition of Cr components is avoided by developing a multicomponent catalyst formula (CN 102451677B, CN 104607168A). Although the prior art improves the Cr-based catalyst for industrial application to a certain extent, the problems of complex catalyst components, complicated preparation process and catalyst performance to be improved still exist. The Cr catalysts currently used in industry are prepared with alumina as a support. The alumina carrier has low price, but the pore canal size distribution is uneven, and the specific surface area is smaller, 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.
Therefore, developing a suitable support with excellent performance is an effective way to improve the performance of propane dehydrogenation catalysts.
Disclosure of Invention
The invention aims to solve the problems of high cost or easiness in causing environmental pollution of a propylene preparation catalyst by propane dehydrogenation in the prior art, and provides a spherical non-noble metal catalyst, a preparation method thereof and application thereof in propylene preparation 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 metal and metal oxide 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 support and a non-noble metal oxide supported on the spherical composite support; wherein the spherical composite carrier is an Al 2O3 -MCM-48 composite material, the content of the spherical composite carrier is 70-97 wt% based on the total weight of the spherical non-noble metal catalyst, 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 the following steps: 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 a propylene preparation reaction 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 metal, so that the preparation cost of the propane dehydrogenation catalyst can be effectively reduced; the spherical non-noble metal catalyst disclosed by the invention does not contain chromium element 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 provided by the invention has good catalytic performance when being used for the reaction of preparing propylene by propane dehydrogenation, and has the advantages of 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 easy control of 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 present invention;
FIG. 2 is a small angle XRD spectrum of Al 2O3 -MCM-48 spherical composite carrier A prepared in example 1 of the present invention;
FIG. 3 is a wide-angle XRD spectrum of Al 2O3 -MCM-48 spherical composite carrier A prepared in example 1 of the present invention;
FIG. 4 is a graph showing the pore size distribution of the Al 2O3 -MCM-48 spherical composite support A prepared in example 1 of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The 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 an Al 2O3 -MCM-48 composite material, the content of the spherical composite carrier is 70-97 wt% based on the total weight of the spherical non-noble metal catalyst, and the content of the non-noble metal oxide is 3-30 wt%.
The inventors of the present invention found that: compared with Pt-based dehydrogenation catalysts, cr-based catalysts are lower in cost, but are inferior in stability and severe in pollution. In order to maintain low catalyst cost while considering environmental requirements, the dehydrogenation catalyst is prepared by substituting Cr with a non-noble metal element in the prior art. The research of alternative catalysts has been continued for almost twenty years, but the performance of the catalyst still cannot completely reach the level of Cr-based catalysts, and the catalyst is mainly characterized in the aspects of low selectivity, poor stability and the like. In addition, the preparation of any solid catalyst is not separated from the molding process. Under the condition of unchanged raw materials and formulas, different molding methods and processes of the catalyst or the catalyst carrier often lead to different use effects of the catalyst. The shapes of the catalysts used in the current industrial devices mainly comprise microspheres, spheres, strips, flakes, trilobes, rings and the like. Under the same composition, the spherical carrier has high bulk density, high loading and processing capacity, low abrasion, small dust during loading, fast mass transfer, high adsorption efficiency or high reaction efficiency, can make industrial reaction more efficient, and improves productivity and product yield. The upgrading of bar products to spherical products in the domestic market has become a major trend.
In addition, the inventor of the present invention found that, when carrying out a study of preparing a propane dehydrogenation catalyst, the prior art uses gamma-alumina or silica as a carrier to load a non-noble metal oxide for preparing the propane dehydrogenation catalyst, and the prior art has the defects of poor propylene selectivity and poor stability. Commercially available alumina carriers or silica carriers are low in cost, but the pore size distribution is uneven, the specific surface area is small, and the dispersion of active metal oxides on the carrier surface and the diffusion of raw materials and products in the reaction process are not facilitated. In comparison, the all-silicon mesoporous molecular sieve material has large specific surface area, large pore volume and uniform pore channel size, and is more favorable for the 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 molding is difficult, and the mechanical strength and the abrasion strength are poor after the catalyst is prepared, so that the industrial application of the catalyst is limited.
The inventor of the invention discovers that the structural advantages of the alumina with stronger viscosity and the MCM-48 all-silicon mesoporous molecular sieve are combined to prepare the Al 2O3 -MCM-48 spherical composite carrier which is used as the carrier of the propane dehydrogenation catalyst, thus effectively improving the reactivity of the propane dehydrogenation catalyst.
Furthermore, the inventor of the invention discovers that an ultrasonic auxiliary method is introduced in the preparation process of the spherical non-noble metal catalyst, so that active components can be promoted to be better dispersed on the surface of the Al 2O3 -MCM-48 spherical composite carrier, and further, the propane dehydrogenation catalyst with better catalytic activity is obtained.
According to the present invention, preferably, the content of the spherical composite carrier is 80 to 97% by weight and the content of the non-noble metal oxide is 3 to 20% by weight, based on the total weight of the spherical non-noble metal catalyst; more preferably, the content of the spherical composite support is 80 to 95 wt% and the content of the non-noble metal oxide is 5 to 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 within the range, 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 metal and serious pollution metal oxide.
According to the present 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/g, the pore volume is 0.5-1.2mL/g, the pore size distribution is bimodal, and the most probable pore diameters corresponding to the bimodal are respectively 2-4nm and 12-18nm; preferably, the specific surface area of the spherical composite carrier is 550-700m 2/g, the pore volume is 0.6-0.9mL/g, the pore size distribution is bimodal, and the most probable pore diameters corresponding to the two peaks are 2-3nm and 13-16nm respectively; more preferably, the specific surface area of the spherical composite carrier is 603-654m 2/g, the pore volume is 0.67-0.75mL/g, the pore size distribution is bimodal, and the most probable pore diameters corresponding to the two peaks are 2.3-2.5nm and 13.7-14.8nm respectively. In the invention, the spherical composite carrier specified above is adopted, so that the prepared spherical non-noble metal catalyst has better propane dehydrogenation activity, propylene selectivity and stability.
According to the invention, the preparation method of the spherical composite carrier comprises the following steps:
(1) The preparation method comprises the steps of (1) contacting and mixing an alumina precursor, an MCM-48 all-silicon mesoporous molecular sieve, an acidic aqueous solution and an extrusion aid, and performing pellet preparation 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 invention, the alumina precursor is selected from one or more of pseudo-boehmite, aluminum hydroxide gel, alumina sol, gibbsite and boehmite; in the present invention, the pseudo-boehmite may be commercially available or prepared, and in the present invention, specifically, the pseudo-boehmite comprises: one or more of boehmite powder (available from Shandong Zigbee chemical Co., ltd., specific surface area: 269m 2/g, pore volume: 0.41cm 3/g), german original imported pseudo-boehmite powder (available from Beijing Asia Taiwan chemical auxiliary Co., ltd., specific surface area: 241m 2/g, pore volume: 0.53cm 3/g), and pseudo-boehmite powder (available from Shandong Almond Co., ltd., specific surface area: 286m 2/g, pore volume: 1.08cm 3/g) of model number P-DF-09-LSi.
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, the preparation method of the MCM-48 all-silicon mesoporous molecular sieve preferably comprises the following steps: under the condition of preparing an adhesive tape piece by hydrolysis, hydrolyzing a template agent, a silicon source and sodium hydroxide to obtain a gel mixture; crystallizing the gel mixture under crystallization conditions, filtering, drying and removing a template agent from a solid product to obtain the MCM-48 all-silicon mesoporous molecular sieve.
According to the invention, the silicon source is preferably an orthosilicate of the general formula (RO) 4 Si, wherein R is a linear or branched alkyl group of C 1-C4.
According to the invention, the template 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 strip comprises: the temperature is 10-60 ℃ and the time is 0.5-10h.
According to the present invention, the crystallization conditions include: the temperature is 100-130 ℃ and the time is 12-96h.
According to the present invention, the drying conditions include: the temperature is 70-150 ℃ and the time is 3-10h.
According to the invention, the method for removing the template agent is not particularly required, and can be various existing methods, such as a roasting 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 mass concentration of the acidic aqueous solution is 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 all-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 all-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 step (1), an alumina precursor, an MCM-48 all-silica mesoporous molecular sieve, an acidic aqueous solution and an extrusion aid are contacted and mixed, and the mixing conditions comprise: the stirring speed is 50-300r/min, the temperature is 20-60 ℃ and the time is 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 present invention, in step (2), the drying conditions include: the temperature is 70-150 ℃ and the time is 3-24 hours; preferably, the temperature is 110-120 ℃ and the time is 8-12h.
According to the present invention, in step (2), the conditions of the firing 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 present invention, in step (1), the method of pelleting the pellets comprises:
(1-1) extruding the mixture into a strip, and then cutting and extruding into raw material balls;
(1-2) shaping the raw material ball to obtain a standard ball;
(1-3) screening the standard spheres to obtain spherical precursors.
According to a preferred embodiment of the present invention, the method for preparing pellets comprises: uniformly mixing an alumina precursor, an MCM-48 all-silicon mesoporous molecular sieve, an acidic aqueous solution and an extrusion assisting agent in a kneader, transferring the mixture into a miniature ball making machine, extruding a strip with a circular section, and cutting the strip into raw material balls; and (3) putting the raw material balls into a pellet shaper for shaping to form standard spherical shapes, and putting the obtained product into a pellet screening machine for screening spherical precursors with proper sizes.
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 then extruding the strip into raw material balls after cutting; wherein the conditions of extrusion into a strip include: the extrusion speed is 0.5-5m/min, and the diameter of the circular section of the strip is 1.5-5.0mm; the conditions of the cutting include: the cutting speed is 100-3500 grains/min.
According to the invention, in the step (1-2), the raw material balls are put into a pellet shaper for shaping, so that the raw material balls become standard spherical balls; wherein the shaping conditions include: the rounding time is 0.5-10 min/time, the number of times of rounding is 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 spheres 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 the following steps: 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 include: the temperature is 10-100deg.C, the time is 10-180min, and the power is 100-300W; preferably, the conditions of the ultrasound include: the temperature is 20-80 ℃, 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 a sulfate, a sulfite, a nitrate and a metal chloride containing a non-noble metal element, preferably a sulfate and/or a sulfite containing a non-noble metal element; 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 the non-noble metal oxide precursor is 0.5 to 10%, preferably 1 to 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, a spherical composite support is contacted with a solution containing a non-noble metal oxide precursor to effect a reaction, wherein the contacting conditions include: the temperature is 20-100deg.C, preferably 40-80deg.C; the time is 0.5-10h, preferably 2-8h.
The method for removing the solvent according to the present invention 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 and stirring.
According to the present invention, the conditions for drying are not particularly limited, and may be conventional conditions in the art. Preferably, the drying conditions include: the temperature is 60-150deg.C, preferably 80-130deg.C; 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 2-15 hours, preferably 3-10 hours.
The third aspect of the invention provides an application of the spherical non-noble metal catalyst in a propylene preparation reaction by propane dehydrogenation.
According to the present invention, the reaction for producing propylene by dehydrogenating propane comprises: the reaction raw material propane is contacted with a spherical non-noble metal catalyst.
According to the invention, the conditions of the contact include: the contact temperature can be 550-650 ℃, the partial pressure of raw material gas is 0.02-0.5MPa, and the mass airspeed of propane is 1.0-10.0h -1.
The present invention will be described in detail by examples.
In the following examples and comparative examples:
XRD testing of the samples was performed on an X' Pert MPD X-ray powder diffractometer manufactured by Philips corporation of netherlands, cu ka target, λ= 0.154178nm, scan range 2θ=0.5 ° to 10 °. The pore structure parameter analysis of the samples was performed on an ASAP2020-M+C type adsorber available from Micromeritics, inc. The sample was vacuum degassed at 350 ℃ for 4 hours prior to measurement, the specific surface area of the sample was calculated using the BET method, and the pore volume was calculated using the BJH model. Elemental analysis experiments of the samples were performed on an Eagle III energy dispersive X-ray fluorescence spectrometer manufactured by EDAX, inc. of America.
The ultrasonic generator is a KQ-300GTDV high-frequency constant-temperature numerical control ultrasonic cleaner produced by Kunshan ultrasonic instrument Co., ltd, the ultrasonic frequency is 80kHz, and the working voltage is 220V;
the rotary evaporator is manufactured by IKA corporation in Germany, and the model is RV10 digital;
The drying oven is manufactured by Shanghai-Heng scientific instrument Co., ltd, and the model is DHG-9030A.
The muffle furnace is manufactured by CARBOLITE company and is model CWF1100.
The kneader is an FN-NH2 kneader manufactured by Tianshuihua round pharmaceutical equipment science and technology Co., ltd; the miniature ball making machine is HWJ-100 miniature ball making machine produced by Tianshuihua round pharmaceutical equipment science and technology Co., ltd; the pellet shaper is an FN-XZXJ pellet shaper manufactured by Tianshuihua round pharmaceutical equipment science and technology Co., ltd; the micropill screening machine is SWP-1200 micropill screening machine produced by Tianshuihua round pharmaceutical equipment science and technology Co.
The reagents used in examples and comparative examples were purchased from national pharmaceutical chemicals, inc., and the purity of the reagents was analytically pure.
Example 1
This example is intended to illustrate the preparation of the spherical non-noble metal catalyst of the present invention.
(1) Preparation of MCM-48 all-silicon mesoporous molecular sieve
23.2G of cetyltrimethylammonium bromide, 0.6g of dodecylamine were mixed with 8.1g of sodium hydroxide and 500ml of deionized water, and stirred at 45℃for 1 hour; 82.9g of ethyl orthosilicate is added dropwise to the solution and stirred for 1 hour; the mixture was transferred to a hydrothermal kettle and hydrothermally crystallized at 100 ℃ for 72 hours. After the 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; and then roasting for 20 hours at 550 ℃ to obtain the MCM-48 all-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 it can be seen from fig. 1 that the sample exhibits a sharp strong diffraction peak and a weak but clearly discernable diffraction peak between 2θ=2.5° and 3.5 °, which correspond to (211) and (220) crystal planes, respectively. In addition, there is also a set of diffraction signals at 2θ=4.0° to 6.0 °, including diffraction peaks corresponding to (420) and (332) crystal planes. The diffraction signal is a characteristic diffraction peak of the MCM-48 mesoporous molecular sieve.
(2) Preparation of Al 2O3 -MCM-48 spherical composite carrier
100G of pseudo-boehmite powder with the model of P-DF-09-LSi, 50gMCM-48 all-silicon mesoporous molecular sieve, 78g of dilute nitric acid with the concentration of 5.0 percent and 10g of sesbania powder are mixed, transferred into a kneader and stirred and mixed uniformly. The kneading temperature was 30℃and the main shaft rotation speed of the kneader was 200r/min, and the kneading time was 1h. Putting the uniformly mixed raw materials into a hopper of a miniature ball making machine, selecting a strip extruding die with the aperture of 1.8mm, adjusting the strip extruding speed to be 1.5m/min and the cutting speed to be 900 grains/min, extruding the raw materials into strips, and extruding and cutting the strips into round small grains. Putting the round small particles into a pellet shaper for shaping, wherein shaping conditions are as follows: the rounding time is 2 minutes/time, the number of times of rounding is 4, and the rotating speed of the sample cavity is 300r/min. And (5) placing the shaped standard spherical raw material balls into a pellet screening machine to screen out spherical precursors with the size of 1.8 mm. Drying the spherical precursor at 110 ℃ for 10 hours, and roasting at 600 ℃ for 12 hours to obtain the Al 2O3 -MCM-48 spherical composite carrier A.
The specific surface area of the Al 2O3 -MCM-48 spherical composite carrier A is 631m 2/g, the pore volume is 0.71mL/g, the average particle diameter is 1.74mm, and the average particle crushing strength is 26.8N.
FIG. 2 is a small angle XRD spectrum of Al 2O3 -MCM-48 spherical composite carrier A prepared in example 1 of the present invention. The graph is similar to FIG. 1, because alumina has no diffraction signal at small angle, the spherical composite carrier A has no obvious change in the crystal phase of MCM-48 mesoporous molecular sieve after roasting at 600 deg.C, and the typical three-dimensional cubic phase mesoporous structure is maintained.
FIG. 3 is a wide-angle XRD spectrum of the Al 2O3 -MCM-48 spherical composite carrier A prepared in example 1 of the present invention, and 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 at the wide-angle part. The x-ray diffraction angles are mainly: the diffraction signals of 2 theta are approximately equal to 37.1 degrees, 39.3 degrees, 46.1 degrees, 60.7 degrees and 66.6 degrees, and the five diffraction signals are matched with a gamma-Al 2O3 diffraction spectrum, so that the spherical composite carrier A shows typical gamma-Al 2O3 crystalline phase after being dehydrated by pseudo-boehmite with the model of P-DF-09-LSi after being roasted at 600 ℃. In addition, the XRD signal of the spherical composite carrier is not shown in one figure, nor is it detected by the same characterization means. The XRD pattern given here is two, a wide angle and a small angle.
FIG. 4 is a graph showing the pore size distribution of the Al 2O3 -MCM-48 spherical composite carrier A prepared by the invention, and as can be seen from FIG. 4, the pore size of the sample is in bimodal distribution, and the first most probable pore size is 2.4nm and is mainly contributed by a mesoporous molecular sieve; the second most probable pore size is 14.0nm, contributed mainly by alumina.
(3) Preparation of spherical non-noble metal catalyst
3.25G of ferric sulfate was dissolved in 100g of deionized water, mixed with 8.7g of Al 2O3 -MCM-48 spherical composite carrier A, and reacted for 60 minutes under stirring with the aid of ultrasonic waves having a power of 200W at a temperature of 50 ℃. After the reaction is finished, water in the system is distilled off by a rotary evaporator, and a solid product is obtained. The solid product was placed in a drying oven at 110℃and dried for 6 hours. Then roasting in a muffle furnace at 600 ℃ for 5 hours 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% by weight of ferric oxide, the balance being the carrier.
(4) Performance evaluation of catalyst in propylene preparation reaction by propane dehydrogenation
The reactivity of the catalyst was evaluated on a fixed bed reactor. 5.0 g of catalyst A is filled in a fixed bed quartz reactor, the reaction temperature is controlled to be 600 ℃, the reaction pressure is controlled to be 0.1MPa, and propane: the molar ratio of helium is 1:1, the mass space velocity of propane is 5.0h -1, and the reaction time is 6h. The reaction product separated by the Al 2O3 -S molecular sieve column directly enters an Agilent 7890A gas chromatograph equipped with a hydrogen flame detector (FID) for on-line analysis. The results of the reaction evaluation are shown in Table 1.
Example 2
This example is intended to illustrate the preparation of the spherical non-noble metal catalyst of the present invention.
An MCM-48 all-silicon mesoporous molecular sieve was prepared in the same manner as in step (1) of example 1.
(2) Preparation of Al 2O3 -MCM-48 spherical composite carrier
100G of boehmite powder with the model BD-BS03, 40gMCM-48 of all-silicon mesoporous molecular sieve, 62g of 10% acetic acid aqueous solution and 5g of polyethylene glycol are mixed, and the mixture is transferred into a kneader for stirring and mixing uniformly. The kneading temperature was 35℃and the main shaft rotation speed of the kneader was 150r/min, and the kneading time was 1h. Putting the uniformly mixed raw materials into a hopper of a miniature 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 grains/min, extruding the raw materials into strips and extruding and cutting the strips into round small grains. Putting the round small particles into a pellet shaper for shaping, wherein shaping conditions are as follows: the rounding time is 0.5 min/time, the number of times of rounding is 2, and the rotating speed of the sample cavity is 500r/min. And (5) placing the shaped standard spherical raw material balls into a pellet screening machine to screen out spherical precursors with the size of 2.5 mm. Drying the spherical precursor at 120 ℃ for 8 hours, and roasting at 700 ℃ for 6 hours to obtain the Al 2O3 -MCM-48 spherical composite carrier B.
The average particle diameter of the Al 2O3 -MCM-48 spherical composite carrier B is 2.44mm, the average particle crushing strength is 35.4N, the specific surface area is 603m 2/g, the pore volume is 0.67mL/g, the pore diameters are in bimodal distribution, the first most probable pore diameter is 2.5nm, and the second most probable pore diameter is 14.8nm.
(3) Preparation of spherical non-noble metal catalyst
6.95G of ferrous sulfate heptahydrate is dissolved in 100g of deionized water, mixed with 8.0g of Al 2O3 -MCM-48 spherical composite carrier B, and stirred and reacted for 30 minutes at 80 ℃ under the assistance of ultrasonic waves with the power of 250W. After the reaction is finished, water in the system is distilled off by a rotary evaporator, and a solid product is obtained. The solid product was placed in a drying oven at 80℃and dried for 15 hours. Then roasting in a muffle furnace at 650 ℃ for 3 hours 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 ferric oxide, the balance being the carrier.
The catalytic performance of the spherical non-noble metal catalyst B in the propylene-producing reaction by propane dehydrogenation was evaluated in the same manner as in step (4) of example 1. The results of the reaction evaluation are shown in Table 1.
Example 3
This example is intended to illustrate the preparation of the spherical non-noble metal catalyst of the present invention.
An MCM-48 all-silicon mesoporous molecular sieve was prepared in the same manner as in step (1) of example 1.
(2) Preparation of Al 2O3 -MCM-48 spherical composite carrier
100G of German original-package imported pseudo-boehmite powder with the model SB, 60gMCM-48 full-silica mesoporous molecular sieve, 80g of citric acid aqueous solution with the concentration of 15.0 percent and 18g of cellulose are mixed, transferred into a kneader and stirred and mixed uniformly. The kneading temperature was 20℃and the main shaft rotation speed of the kneader was 200r/min, and the kneading time was 0.5h. Putting the uniformly mixed raw materials into a hopper of a miniature 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 grains/min, extruding the raw materials into strips and extruding and cutting the strips into round small grains. Putting the round small particles into a pellet shaper for shaping, wherein shaping conditions are as follows: the rounding time is 2 minutes/time, the number of times of rounding is 4, and the rotating speed of the sample cavity is 200r/min. And (5) placing the shaped standard spherical raw material balls into a pellet screening machine to screen out spherical precursors with the size of 2.0 mm. Drying the spherical precursor at 110 ℃ for 12 hours, and roasting at 550 ℃ for 15 hours to obtain the Al 2O3 -MCM-48 spherical composite carrier C.
The average particle diameter of the Al 2O3 -MCM-48 spherical composite carrier C is 1.93mm, the average particle crushing strength is 31.2N, the specific surface area is 654m 2/g, the pore volume is 0.75mL/g, the pore diameters are in bimodal distribution, the first most probable pore diameter is 2.3nm, and the second most probable pore diameter is 13.7nm.
(3) Preparation of spherical non-noble metal catalyst
1.0G of anhydrous zinc sulfate was dissolved in 80g of deionized water, mixed with 9.5g of Al 2O3 -MCM-48 spherical composite carrier C, and reacted for 120 minutes at 30℃with stirring under the assistance of ultrasonic waves with a power of 150W. After the reaction is finished, water in the system is distilled off by a rotary evaporator, and a solid product is obtained. The solid product was placed in a drying oven at 130 ℃ and dried for 3 hours. Then roasting in a muffle furnace at 500 ℃ for 10 hours to obtain the spherical non-noble metal catalyst C.
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 propylene-producing reaction by propane dehydrogenation was evaluated in the same manner as in step (4) of example 1. The results of the reaction evaluation are shown in Table 1.
Example 4
This example is intended to illustrate the preparation of the spherical non-noble metal catalyst of the present 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 changed, specifically:
0.8g of ferric sulfate is dissolved in 100g of deionized water, mixed with 9.7g of Al 2O3 -MCM-48 spherical composite carrier A, and stirred and reacted for 60 minutes at 50 ℃ under the assistance of ultrasonic waves with the power of 200W. After the reaction is finished, water in the system is distilled off by a rotary evaporator, and a solid product is obtained. The solid product was placed in a drying oven at 110℃and dried for 6 hours. Then roasting in a muffle furnace at 600 ℃ for 5 hours to obtain the spherical non-noble metal catalyst D.
The content of the spherical composite carrier was 96.8 wt% and the content of the non-noble metal oxide was 3.2 wt% based on the total weight of the spherical non-noble metal catalyst D.
The catalytic performance of the spherical non-noble metal catalyst D was evaluated according to the performance evaluation of the catalyst of step (4) in example 1 in the reaction for producing propylene by dehydrogenation of propane. The results of the reaction evaluation are shown in Table 1.
Example 5
This example is intended to illustrate the preparation of the spherical non-noble metal catalyst of the present 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 changed, specifically:
5.75g of ferric sulfate was dissolved in 100g of deionized water, mixed with 7.7g of Al 2O3 -MCM-48 spherical composite carrier A, and reacted for 60 minutes under stirring with the aid of ultrasonic waves having a power of 200W at a temperature of 50 ℃. After the reaction is finished, water in the system is distilled off by a rotary evaporator, and a solid product is obtained. The solid product was placed in a drying oven at 110℃and dried for 6 hours. Then roasting in a muffle furnace at 600 ℃ for 5 hours to obtain the spherical non-noble metal catalyst E.
The content of the spherical composite carrier was 77 wt% and the content of the non-noble metal oxide was 23 wt% based on the total weight of the spherical non-noble metal catalyst E.
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 for producing propylene by dehydrogenation of propane. The results of the reaction evaluation 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 by the method of step (3) in example 1, except that "commercially available silica" was used as the catalyst carrier instead of Al 2O3 -MCM-48 spherical composite carrier A, which was purchased from Qingdao Seawamomum silica gel desiccant plant, specific surface area 329m 2/g, and average particle diameter 1.5mm, and step (1) and step (2) in example 1 were omitted; catalyst D1 was obtained.
The content of ferric oxide is 13% by weight based on the total weight of the catalyst D1, and the balance is alumina as a carrier.
The propylene preparation reaction performance test of catalyst D1 by dehydrogenation of propane was carried out in the same manner as in step (4) of example 1, and the reaction 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 2O3 -MCM-48 spherical composite support A was prepared according to the method of step (1) and step (2) in example 1. Catalyst D2 was prepared according to the procedure of step (3) in example 1, and the catalyst preparation conditions, specifically:
0.3g of ferric sulfate is dissolved in 100g of deionized water, mixed with 9.9g of Al 2O3 -MCM-48 spherical composite carrier A, and stirred and reacted for 60 minutes at 50 ℃ under the assistance of ultrasonic waves with the power of 200W. After the reaction is finished, water in the system is distilled off by a rotary evaporator, and a solid product is obtained. The solid product was placed in a drying oven at 110℃and dried for 6 hours. Then, the mixture was calcined in a muffle furnace at 600℃for 5 hours to obtain catalyst D2.
So that the content of iron sesquioxide is 1.2% by weight, based on the total weight of catalyst D2, the remainder being the support.
The propylene preparation reaction performance test of catalyst D2 by propane dehydrogenation was carried out in the same manner as in step (4) of 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 2O3 -MCM-48 spherical composite carrier A" in step (3) in example 1 was replaced with "12.4g of pseudo-boehmite powder" of model P-DF-09-LSi, to obtain spherical non-noble metal catalyst D3.
So that the content of alumina is 87 wt% and the content of ferric oxide is 13 wt% based on the total weight of the spherical non-noble metal catalyst D3.
The propylene preparation reaction performance test of catalyst D3 by propane dehydrogenation was carried out in the same manner as in step (4) of example 1, and the reaction 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 the "8.7g Al 2O3 -MCM-48 spherical composite carrier A" in step (3) in example 1 was replaced with "8.7g MCM-48 all-silicon mesoporous molecular sieve", to obtain a spherical non-noble metal catalyst D4.
So that the content of the MCM-48 all-silicon mesoporous molecular sieve is 87 weight percent and the content of the ferric oxide is 13 weight percent based on the total weight of the spherical non-noble metal catalyst D4.
The propylene preparation reaction performance test of catalyst D4 by propane dehydrogenation was carried out in the same manner as in step (4) of 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: step (1) in example 1 was omitted, and 100g of pseudo-boehmite powder with the model of P-DF-09-LSi, 50gMCM-48 of all-silicon mesoporous molecular sieve in step (2) in example 1 were replaced with 50g of pseudo-boehmite powder with the model of P-DF-09-LSi, and 100g of MCM-48 of all-silicon mesoporous molecular sieve were replaced with "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 iron sesquioxide is 13 wt% based on the total weight of the spherical non-noble metal catalyst D5.
The propylene preparation reaction performance test of catalyst D5 by propane dehydrogenation was carried out in the same manner as 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 the "iron sulfate" in step (3) in example 1 was replaced with "sodium sulfate" to obtain a spherical non-noble metal catalyst D6.
So that the content of the spherical composite carrier was 87 wt% and the content of sodium oxide was 13 wt% based on the total weight of the spherical non-noble metal catalyst D6.
The propylene preparation reaction performance test of catalyst D6 by propane dehydrogenation was carried out in the same manner as in step (4) of example 1, and the reaction results are shown in Table 1.
TABLE 1
As can be seen from the results of Table 1, the spherical non-noble metal catalysts provided in examples 1 to 5 according to the present invention are excellent in performance when used in the reaction for producing propylene by dehydrogenation of propane.
As can be seen from the experimental results of comparative example 1 and comparative example 1, the performance of the catalyst A prepared by using the Al 2O3 -MCM-48 spherical composite carrier is obviously better than that of the catalyst D1 prepared by using the commercially available silicon dioxide as the carrier, and the conversion rate of propane, the selectivity of propylene and the stability of the catalyst are greatly improved. The above results show that Al 2O3 -MCM-48 spherical composite carrier is more favorable for the propylene preparation reaction by propane dehydrogenation.
The data of comparative examples 1 and 2 show that the lower level of non-noble metal oxide, ferric oxide, results in a decrease in either propane conversion, propylene selectivity, or catalyst stability due to the too low level of the surface active component of the catalyst.
The data of comparative examples 1 and 3 show that the support is alumina only, and the alumina has a small specific surface area due to the non-uniform pore size distribution, which is not beneficial to the dispersion of the active metal oxide on the surface of the support, and the diffusion of the raw materials and products during the reaction, resulting in a decrease in both the propane conversion, the propylene selectivity and the catalyst stability.
As can be seen from the data of comparative examples 1 and 4, the carrier is only MCM-48 all-silica mesoporous molecular sieve, and the bulk density of the all-silica MCM-48 mesoporous molecular sieve material is small and is not easy to form, so that the mechanical strength and the abrasion strength are poor after the catalyst is prepared, the surface of the catalyst is uneven, the dispersion of the active component is poor, and the conversion rate of propane, the selectivity of propylene and the stability of the catalyst are reduced.
As can be seen from the data of comparative examples 1 and 5, the weight ratio of the pseudo-boehmite powder to the amount of the MCM-48 all-silica mesoporous molecular sieve is 1:2, and the proportion of the all-silica MCM-48 mesoporous molecular sieve in the carrier is not in the scope of the claims, so that the prepared catalyst has poor strength, uneven surface and poor dispersion of active components, and the conversion rate of propane, the selectivity of propylene and the stability of the catalyst are reduced.
The data for comparative examples 1 and 6 shows that the sodium oxide is not supported on the appropriate non-noble metal oxide, but rather on the sodium oxide, and that the propylene selectivity is poor due to the fact that sodium oxide is not catalytically active for the dehydrogenation of propane, resulting in only a small amount of propane conversion on the D6 catalyst.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (15)
1. The propylene preparation reaction by propane dehydrogenation catalyzed by a spherical non-noble metal catalyst is characterized by comprising the step of contacting propane with the 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 an Al 2O3 -MCM-48 composite material, the content of the spherical composite carrier is 70-97 wt% based on the total weight of the spherical non-noble metal catalyst, and the content of the non-noble metal oxide is 3-30 wt%; the metal element in the non-noble metal oxide is iron;
The specific surface area of the spherical composite carrier is 603-654m 2/g, the pore volume is 0.67-0.75mL/g, the pore size distribution is in bimodal distribution, and the most probable pore diameters corresponding to the two peaks are 2.3-2.5nm and 13.7-14.8nm respectively;
The preparation method of the Al 2O3 -MCM-48 composite material comprises the following steps:
(1) The preparation method comprises the steps of (1) contacting and mixing an alumina precursor, an MCM-48 all-silicon mesoporous molecular sieve, an acidic aqueous solution and an extrusion aid, and putting the obtained mixture into a pellet shaper for pellet pelleting to obtain a spherical precursor; wherein, the weight ratio of the alumina precursor, the MCM-48 all-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);
(2) And drying and roasting the spherical precursor to obtain the spherical composite carrier.
2. The reaction for producing propylene by dehydrogenation of propane according to claim 1, wherein the Al 2O3 -MCM-48 composite is contained in an amount of 80 to 97% by weight and the non-noble metal oxide is contained in an amount of 3 to 20% by weight, based on the total weight of the spherical non-noble metal catalyst.
3. The propane dehydrogenation propylene production reaction according to claim 2, wherein the Al 2O3 -MCM-48 composite is contained in an amount of 80 to 95 wt% and the non-noble metal oxide is contained in an amount of 5 to 20 wt%, based on the total weight of the spherical non-noble metal catalyst.
4. A propane dehydrogenation propylene production reaction according to any one of claims 1-3 wherein the pellet process comprises:
(1-1) extruding the mixture into strips in a miniature ball making machine, and then cutting and extruding the strips into raw material balls; wherein the miniature ball making machine is HWJ-100 miniature ball making machine produced by Tianshuihua round pharmaceutical equipment technology Co., ltd;
(1-2) shaping the raw material balls in a pellet shaper to obtain standard balls;
Wherein the pellet shaper is an FN-XZXJ pellet shaper manufactured by Tianshuihua round pharmaceutical equipment technology Co., ltd;
the shaping conditions include: the rounding time is 0.5-10 min/time, the rounding times is 1-5 times, and the rotating speed of the sample cavity is 50-1400r/min;
(1-3) screening the standard spheres in a pellet screening machine to obtain spherical precursors; wherein, the micropill screening machine is SWP-1200 micropill screening machine produced by Tianshuihua round pharmaceutical equipment science and technology Co.
5. The reaction for producing propylene by dehydrogenation of propane according to claim 4, wherein the alumina precursor is one or more selected from pseudo-boehmite, aluminum hydroxide gel, alumina sol, gibbsite and boehmite.
6. The propane dehydrogenation to propylene reaction of claim 4, wherein the extrusion conditions include: the extrusion speed is 0.5-5m/min, and the diameter of the circular section of the strip is 1.5-5.0mm.
7. The propane dehydrogenation to propylene reaction of claim 4, wherein the conditions of the cleavage include: the cutting speed is 100-3500 grains/min.
8. The reaction for producing propylene by dehydrogenation of propane according to any one of claims 1 to 3, wherein the preparation method of the spherical non-noble metal catalyst 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.
9. The reaction for producing propylene by dehydrogenation of propane according to claim 8, wherein the solution containing the non-noble metal oxide precursor is an aqueous solution containing the non-noble metal oxide precursor.
10. The propane dehydrogenation to propylene reaction of claim 8, wherein the non-noble metal oxide precursor is selected from one or more of a sulfate, a sulfite, a nitrate, and a metal chloride containing a non-noble metal element; the non-noble metal element is iron.
11. The reaction for producing propylene by dehydrogenation of propane according to claim 8, wherein the weight ratio of the spherical composite support to the solution containing the non-noble metal oxide precursor is 1: (5-20).
12. The reaction for producing propylene by dehydrogenation of propane according to claim 8, wherein the concentration of the solution containing the non-noble metal oxide precursor is 0.5 to 10%.
13. The propane dehydrogenation to propylene reaction of claim 8, wherein the ultrasonic conditions comprise: the temperature is 10-100deg.C, the time is 10-180min, and the power is 100-300W.
14. The reaction for the dehydrogenation of propane to propylene of claim 8, wherein the reaction conditions include: the temperature is 20-100deg.C, and the time is 0.5-10h.
15. The propane dehydrogenation to propylene reaction of claim 8, wherein the calcination conditions comprise: the temperature is 400-700 ℃ and the roasting time is 2-15h.
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| CN103553094A (en) * | 2013-09-27 | 2014-02-05 | 中国海洋石油总公司 | Pelleting forming method for spherical alumina |
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| CN106892648A (en) * | 2015-12-21 | 2017-06-27 | 中国石油天然气股份有限公司 | A kind of preparation method of ball-aluminium oxide |
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| CN103553094A (en) * | 2013-09-27 | 2014-02-05 | 中国海洋石油总公司 | Pelleting forming method for spherical alumina |
| CN106311311A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Catalyst for preparing propylene through propane dehydrogenation, preparation method of catalyst, and method for propylene through propane dehydrogenation |
| CN106892648A (en) * | 2015-12-21 | 2017-06-27 | 中国石油天然气股份有限公司 | A kind of preparation method of ball-aluminium oxide |
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