CN108855054A - The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane - Google Patents
The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane Download PDFInfo
- Publication number
- CN108855054A CN108855054A CN201710325204.6A CN201710325204A CN108855054A CN 108855054 A CN108855054 A CN 108855054A CN 201710325204 A CN201710325204 A CN 201710325204A CN 108855054 A CN108855054 A CN 108855054A
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- China
- Prior art keywords
- filter cake
- propane
- supported catalyst
- conditions
- catalyst
- Prior art date
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000003054 catalyst Substances 0.000 title claims abstract description 122
- 239000001294 propane Substances 0.000 title claims abstract description 70
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 65
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 27
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 26
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 26
- 239000011734 sodium Substances 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000012065 filter cake Substances 0.000 claims description 83
- 239000012528 membrane Substances 0.000 claims description 67
- 239000013335 mesoporous material Substances 0.000 claims description 57
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 51
- 238000002156 mixing Methods 0.000 claims description 45
- 239000000919 ceramic Substances 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 239000011148 porous material Substances 0.000 claims description 34
- 238000000498 ball milling Methods 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000000741 silica gel Substances 0.000 claims description 25
- 229910002027 silica gel Inorganic materials 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 238000001694 spray drying Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 150000007522 mineralic acids Chemical class 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 13
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 13
- 235000019353 potassium silicate Nutrition 0.000 claims description 12
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 11
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 150000003058 platinum compounds Chemical class 0.000 claims description 9
- 159000000000 sodium salts Chemical class 0.000 claims description 9
- 150000003606 tin compounds Chemical class 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000007974 sodium acetate buffer Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- 239000012265 solid product Substances 0.000 description 8
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 7
- 230000005484 gravity Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000009295 crossflow filtration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- 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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical class [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/615—100-500 m2/g
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/638—Pore volume more than 1.0 ml/g
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to catalyst field, the method for a kind of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane is disclosed.The loaded catalyst includes platinum component, tin component and the sodium component of carrier and load on the carrier, wherein the carrier is spherical mesoporous composite material, and the spherical mesoporous composite material uses purpose ceramic-film filter to carry out carrying out washing treatment during the preparation process.Using the reaction of loaded catalyst catalysis preparing propylene by dehydrogenating propane of the invention, conversion of propane is high, and Propylene Selectivity is high.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a supported catalyst, a preparation method of the supported catalyst, application of the supported catalyst in a reaction for preparing propylene by propane dehydrogenation, and a method for preparing propylene by propane dehydrogenation.
Background
Propylene is a basic raw material of petrochemical industry and is mainly used for producing polypropylene, acrylonitrile, acetone, propylene oxide, acrylic acid, butanol and octanol and the like. Half of the propylene supply comes from refinery by-products and about 45% from steam cracking, a few other alternative technologies. In recent years, the demand of propylene is increasing year by year, and the traditional propylene production can not meet the demand of the chemical industry for propylene, so that the propylene yield increase becomes a great hot point for research. The dehydrogenation of propane to propylene is one of the main technologies for increasing the yield of propylene. For more than 10 years, the dehydrogenation of propane to prepare propylene has become an important process for the industrial production of propylene. The main catalysts for propane dehydrogenation are the chromium oxide/alumina catalyst in the Catofin process from ABB Lummus and the platinum tin/alumina catalyst in the Oleflex process from UOP. The chromium catalyst has lower requirements on raw material impurities and lower price compared with noble metals; however, the catalyst is easy to deposit carbon and deactivate, and needs to be regenerated every 15 to 30 minutes, and the chromium in the catalyst is heavy metal, so that the environmental pollution is serious; the platinum-tin catalyst has high activity and good selectivity, the reaction period can reach several days, the catalyst can bear harsher process conditions and is more environment-friendly, but the cost of the catalyst is higher due to the high price of noble metal platinum. The industrial production of the process for preparing propylene by propane dehydrogenation is over twenty years, and the research on dehydrogenation catalysts is more, but the current catalysts still have the defects of low propane conversion rate, easy inactivation and the like, and further improvement and perfection are needed. Therefore, it is of practical significance to develop a propane dehydrogenation catalyst having excellent performance.
Much work has been done by researchers to improve the reaction performance of propane dehydrogenation catalysts. Such as: (1) adopts a molecular sieve carrier to replace the traditional gamma-Al carrier2O3The carrier has good effect and comprises MFI type microporous molecular sieves (CN104307555A, CN101066532A, CN101380587A and CN101513613A), mesoporous MCM-41 molecular sieves (CN102389831A), mesoporous SBA-15 molecular sieves (CN101972664A and CN101972664B) and the like; (2) using calcium silicate salt para-gamma-Al2O3The carrier is modified and is impregnated with various active metal components and metal assistants (CN104368364A) step by step; (3) a composite oxide of alumina and magnesia is taken as a carrier, and various active metal components and metal assistants (CN104888818A) are impregnated step by step. The above-mentioned various methods for improving propane dehydrogenation catalysts lead to more complicated catalyst preparation process, increased preparation cost, prolonged preparation period, and even use of reagents or raw materials which are not favorable for environmental resources.
Disclosure of Invention
The invention aims to overcome the defects of complex preparation process and uneven dispersion of active metal components of the existing dehydrogenation catalyst, and provides a supported catalyst and a preparation method and application thereof. The supported catalyst of the invention is used for catalyzing the reaction of propane dehydrogenation to prepare propylene, the propane conversion rate is high, and the propylene selectivity is high.
Specifically, in a first aspect, the present invention provides a supported catalyst, which includes a carrier, and a platinum component, a tin component, and a sodium component supported on the carrier, wherein the carrier is a spherical mesoporous composite material, and the spherical mesoporous composite material is prepared by a method including the following steps:
(1) carrying out first mixing contact on a template agent, tetramethoxysilane, ethanol, trimethylpentane and an acid agent, and crystallizing and filtering a mixture obtained by the first mixing contact to obtain a first mesoporous material filter cake;
(2) carrying out second mixing contact on ethyl orthosilicate, hexadecyl trimethyl ammonium bromide and ammonia, and filtering a mixture obtained by the second mixing contact to obtain a second mesoporous material filter cake;
(3) carrying out third mixing contact on water glass and inorganic acid, and filtering a mixture obtained after the third mixing contact to obtain a silica gel filter cake;
(4) respectively or after mixing the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake, carrying out ball milling on the ball-milled products, washing the ball-milled products by using a ceramic membrane filter, and then carrying out spray drying to obtain the spherical mesoporous composite material; or,
and (3) washing the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake respectively or after mixing, and then carrying out ball milling and spray drying to obtain the spherical mesoporous composite material.
In a second aspect, the present invention provides a method for preparing the above supported catalyst, the method comprising: the carrier is co-impregnated with a mixed aqueous solution containing a water-soluble platinum compound, a water-soluble tin compound and an inorganic sodium salt, then the solvent water is removed, dried and calcined.
In a third aspect, the invention provides a supported catalyst prepared by the above method.
In a fourth aspect, the invention provides the application of the supported catalyst in the reaction of preparing propylene by propane dehydrogenation.
In a fifth aspect, the present invention provides a process for the dehydrogenation of propane to produce propylene, the process comprising: under the condition of preparing propylene by propane dehydrogenation, contacting propane with a catalyst, wherein the catalyst is the supported catalyst provided by the invention. At present, a plate-and-frame filter press is usually used for removing impurities in the mesoporous material, but the spherical mesoporous composite material obtained by the method has low catalytic activity after being loaded with a catalyst, possibly because the impurities are not completely removed. In addition, the plate and frame filter press still has a lot of shortcomings, for example, plate and frame filter press area is great, simultaneously, because the plate and frame filter press is discontinuous operation, inefficiency, the operation room environment is relatively poor, has secondary pollution, and in addition, because use filter cloth, it is relatively poor to get rid of the impurity effect, and waste water can not recycle, wastes the water source very much in the washing process, simultaneously because the exhaust waste water can't be handled, causes environmental pollution and secondary waste again. The inventor of the present invention has found through intensive research that when the mesoporous material is washed by using a ceramic membrane, the obtained spherical mesoporous composite material has high catalytic activity after loading a polypropylene catalyst, and has high propane conversion rate and high propylene selectivity. The present inventors have completed the present invention based on the above findings.
The supported catalyst and the method have the following advantages: (1) the separation process is simple, the separation efficiency is high, the number of matched devices is small, the energy consumption is low, and the operation is simple and convenient; (2) the cross-flow filtration is adopted, and the higher membrane surface flow rate is used, so that the accumulation of pollutants on the membrane surface is reduced, and the membrane flux is improved; (3) the ceramic membrane has good chemical stability, acid resistance, alkali resistance, organic solvent resistance and strong regeneration capability, and can be suitable for the preparation process of the spherical mesoporous composite material; (4) the production of waste liquid is obviously reduced, and the method is green and environment-friendly. (5) According to the invention, the catalyst is prepared by using the silicon dioxide mesoporous material carrier with macropores, large specific surface area and large pore volume, and the structural characteristics are favorable for good dispersion of metal components on the surface of the carrier, so that the prepared propane dehydrogenation catalyst has excellent performance; (6) the co-impregnation method is adopted to replace the conventional step-by-step impregnation method, the preparation process is simple, the conditions are easy to control, and the product repeatability is good; (7) the catalyst provided by the invention shows good catalytic performance when used for preparing propylene by propane dehydrogenation. High propane conversion rate, high propylene selectivity and good catalyst stability.
Drawings
FIG. 1 is an X-ray diffraction pattern of a spherical mesoporous composite material C1 in example 1;
FIG. 2 is an SEM scanning electron micrograph of a spherical mesoporous composite material C1 in example 1;
fig. 3 is a pore size distribution diagram of the spherical mesoporous composite material C1 in example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those 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 supported catalyst, which comprises a carrier, and a platinum component, a tin component and a sodium component which are loaded on the carrier, wherein the carrier is a spherical mesoporous composite material, and the spherical mesoporous composite material is prepared by adopting a method comprising the following steps:
(1) carrying out first mixing contact on a template agent, tetramethoxysilane, ethanol, trimethylpentane and an acid agent, and crystallizing and filtering a mixture obtained by the first mixing contact to obtain a first mesoporous material filter cake;
(2) carrying out second mixing contact on ethyl orthosilicate, hexadecyl trimethyl ammonium bromide and ammonia, and filtering a mixture obtained by the second mixing contact to obtain a second mesoporous material filter cake;
(3) carrying out third mixing contact on water glass and inorganic acid, and filtering a mixture obtained after the third mixing contact to obtain a silica gel filter cake;
(4) respectively or after mixing the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake, carrying out ball milling on the ball-milled products, washing the ball-milled products by using a ceramic membrane filter, and then carrying out spray drying to obtain the spherical mesoporous composite material; or,
and (3) washing the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake respectively or after mixing, and then carrying out ball milling and spray drying to obtain the spherical mesoporous composite material.
In the invention, the average particle diameter of the spherical mesoporous composite material is 20-60 μm, and the specific surface area is 150-600m2The pore volume is 0.5-1.8mL/g, the pore diameter is in trimodal distribution, and the trimodal corresponds to the first most probable pore diameter of 5-15nm, the second most probable pore diameter of 20-40nm and the third most probable pore diameter of 45-60nm respectively.
Preferably, the average particle diameter of the spherical mesoporous composite material is 40-50 μm, and the specific surface area is 220-300m2The pore volume is 1.1-1.7mL/g, the pore diameter is trimodal distribution, and the trimodal corresponds to the secondA first mode pore size of 6-9nm, a second mode pore size of 25-35nm, and a third mode pore size of 45-54 nm.
In the present invention, the specific surface area, pore volume and pore diameter of the spherical mesoporous composite material may be measured according to a nitrogen adsorption method.
According to the present invention, in the supported catalyst, the contents of the platinum component, the tin component, the sodium component and the carrier may vary within a wide range, for example, the content of the platinum component may be 0.2 to 0.5% by weight, the content of the tin component may be 0.2 to 1.2% by weight, the content of the sodium component may be 0.3 to 0.8% by weight, and the content of the carrier may be 97.5 to 99.3% by weight, in terms of element, based on the total weight of the catalyst. In order to provide a dehydrogenation catalyst with better catalytic performance and reduce the preparation cost of the dehydrogenation catalyst, it is preferable that the content of the platinum component is 0.2 to 0.4 wt%, the content of the tin component is 0.3 to 1 wt%, the content of the sodium component is 0.4 to 0.7 wt%, and the content of the carrier is 97.9 to 99.1 wt%, calculated as elements, based on the total weight of the catalyst.
According to the present invention, in the step (1), the template may be any template that is conventional in the art, as long as the pore structure of the obtained spherical porous mesoporous composite material can meet the requirements. For example, the templating agent may be a triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene. Wherein the templating agent is commercially available (e.g., from Aldrich under the trade name P123, formula EO)20PO70EO20And Mn of 5800) or can be prepared by various conventional methods. When the template is polyoxyethylene-polyoxypropylene-polyoxyethylene, the number of moles of the template is calculated from the number average molecular weight of polyoxyethylene-polyoxypropylene-polyoxyethylene.
In the present invention, the acid agent may be various acidic aqueous solutions conventionally used in the art, and preferably, the acid agent is acetic acid and sodium acetate buffer solution having a pH of 1 to 6. The amount of the acid agent is not particularly limited, and may be varied within a wide range, and it is preferable that the pH value in the first mixing contact is 1 to 7.
According to the present invention, the order of the first mixing and contacting is not particularly limited, and the template, tetramethoxysilane, ethanol, trimethylpentane and acid agent may be mixed at the same time, or any two or three of them may be mixed, and the other components may be added and mixed uniformly. According to a preferred embodiment of the present invention, the template agent, ethanol and acid agent are mixed uniformly, then trimethylpentane is added and mixed uniformly, and then tetramethoxysilane is added and mixed uniformly.
In the present invention, the amount of the template, ethanol, trimethylpentane and tetramethoxysilane may vary over a wide range, for example, the molar ratio of template, ethanol, trimethylpentane and tetramethoxysilane may be 1: 100-500: 200-500: 50-200, more preferably 1: 180-400: 250-400: 70-150.
In the present invention, the conditions of the first mixing contact are not particularly limited, and for example, the conditions of the first mixing contact generally include: the temperature can be 10-60 ℃, preferably 10-20 ℃; the time can be 10 to 72 hours, preferably 10 to 30 hours; the pH may be from 1 to 7, preferably from 3 to 6. In order to further facilitate uniform mixing between the substances, according to a preferred embodiment of the invention, the first mixing contact is carried out under stirring conditions.
In the present invention, the conditions for crystallization of the mixture obtained by the first mixing contact include: the temperature can be 30-150 ℃, preferably 40-80 ℃; the time may be 10 to 72 hours, preferably 20 to 30 hours. According to a preferred embodiment, the crystallization is carried out by hydrothermal crystallization.
According to the invention, the amounts of the individual substances used in the second mixed contact can also be selected and adjusted within wide limits, for example the molar ratio of ethyl orthosilicate, cetyltrimethylammonium bromide and ammonia can be 1: 0.1-1: 0.1 to 5, preferably 1: 0.2-0.5: 1.5-3.5.
In the present invention, the ammonia is preferably added in the form of aqueous ammonia. The aqueous ammonia of the present invention may be present in a concentration of 10 to 25% by weight.
In the present invention, the second mixed contacting process of tetraethyl orthosilicate, cetyltrimethylammonium bromide and ammonia is carried out in the presence of water. Preferably, part of the water is introduced in the form of aqueous ammonia and part of the water is added in the form of deionized water. In the second mixed contact system of tetraethoxysilane, hexadecyl trimethyl ammonium bromide and ammonia, the molar ratio of tetraethoxysilane to water can be 1:100-200, and is preferably 1: 120-180.
In the present invention, the conditions of the second mixing contact are not particularly limited, and may include, for example: the contact temperature is 25-100 ℃, preferably 50-90 ℃; the contact time is 2-8 hours, preferably 3-7 hours, and the pH may be 7.5-11, preferably 8-10. Preferably, the second mixing contact is carried out under agitation to facilitate uniform mixing between the substances.
In the present invention, the conditions of the third mixed contact are not particularly limited and may be appropriately determined according to a conventional process for preparing silica gel. For example, the conditions of the third mixing contact include: the temperature can be 10-60 ℃, preferably 20-40 ℃; the time may be 1 to 5 hours, preferably 1 to 3 hours; the pH value is 2-4. In order to facilitate uniform mixing of the materials, the third mixing contact process is preferably performed under stirring conditions.
In the present invention, the amounts of the water glass and the inorganic acid may vary within a wide range. For example, the weight ratio of the water glass to the inorganic acid may be 3 to 6: 1.
in the present invention, the water glass is an aqueous solution of sodium silicate, and the concentration thereof may be 3 to 20% by weight, preferably 10 to 20% by weight. The inorganic acid may be various inorganic acids conventionally used in the art, and may be, for example, one or more of sulfuric acid, nitric acid, and hydrochloric acid. The inorganic acids can be used in pure form or in the form of their aqueous solutions, preferably in the form of 3 to 20% by weight aqueous solutions. The inorganic acid is preferably used in such an amount that the pH of the contact reaction system of the water glass and the inorganic acid is 2 to 4. The weight of the water glass includes the water content therein. When the inorganic acid is used in the form of a solution, the weight of the inorganic acid includes the amount of water therein.
According to the present invention, in the step (4), the amounts of the first mesoporous material cake, the second mesoporous material cake and the silica gel cake may vary within a wide range, for example, the silica gel cake may be used in an amount of 1 to 200 parts by weight, preferably 20 to 180 parts by weight, and more preferably 50 to 150 parts by weight, relative to 100 parts by weight of the total amount of the first mesoporous material cake and the second mesoporous material cake; the weight ratio of the first mesoporous material filter cake to the second mesoporous material filter cake can be 1:0.1-10, and preferably 1: 0.5-2.
In the invention, the ceramic filter is a gas, liquid and solid separation and purification device which integrates filtration, slag discharge, cleaning and regeneration and takes a ceramic membrane element as a core. The ceramic membrane filter may include a ceramic membrane module and a ceramic membrane element, and the ceramic membrane element may be an inorganic ceramic membrane element (inorganic ceramic membrane for short). The inorganic ceramic membrane is a precise ceramic filter material with a porous structure, which is usually formed by sintering alumina, titanium oxide, zirconium oxide and the like at high temperature, a porous supporting layer, a transition layer and a microporous membrane layer are asymmetrically distributed, and the filtering precision covers micro-filtration, ultra-filtration and nano-filtration. Ceramic membrane filtration is a form of "cross-flow filtration" of fluid separation process: the raw material liquid flows at high speed in the membrane tube, the clarified penetrating fluid containing small molecular components penetrates through the membrane outwards along the direction vertical to the clear penetrating fluid under the drive of pressure, and the turbid concentrated solution containing large molecular components is intercepted by the membrane, so that the purposes of separating, concentrating and purifying the fluid are achieved. The ceramic membrane can be obtained commercially, for example, an inorganic ceramic membrane element obtained from york jiugu high-tech co. The ceramic membrane module may be determined according to the particular circumstances of the ceramic membrane element and the sample to be treated.
According to a specific embodiment, the parameters of the inorganic ceramic membrane elements used in the present invention include: the membrane is made of alumina, and has a shape of multi-channel cylindrical, the number of channels is 19, the diameter of the channel is 4mm, the length is 1016mm, the outer diameter (diameter) is 30mm, and the effective membrane area is 0.24m2。
In the present invention, the conditions for the washing treatment using the ceramic membrane filter include: the operating pressure can be from 2.5 to 3.9bar, preferably from 3 to 3.5 bar; the membrane pressure on the side of the circulation may be from 3 to 5bar, preferably from 3.5 to 4.5 bar; the pressure of the membrane at the circulating side can be 2-2.8bar, preferably 2.2-2.6 bar; the flow rate of the circulating side membrane surface can be 4-5m/s, and is preferably 4-4.5 m/s; the pressure of the permeation side is 0.3-0.5 bar; the temperature may be 10-60 ℃. Wherein the operating pressure is the average of the cycle side membrane inlet pressure and the cycle side membrane outlet pressure.
In the invention, the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake can be washed by using a ceramic membrane filter respectively, or the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake can be mixed and then washed by using a ceramic membrane, and then ball milling and spray drying are carried out, or the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake can be mixed and then ball milling is carried out, and the ball milling product is washed by using the ceramic membrane filter and then spray drying is carried out.
According to a specific embodiment, in the step (4), the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake are respectively washed by using a ceramic membrane filter, and then are mixed, ball-milled and spray-dried to obtain the spherical mesoporous composite material.
According to a specific embodiment, in the step (4), the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake are respectively washed by using a ceramic membrane filter, then are respectively ball-milled, and are mixed and then are spray-dried to obtain the spherical mesoporous composite material.
According to a specific embodiment, in the step (4), the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake are mixed and then washed by using a ceramic membrane filter, and then ball-milled and spray-dried to obtain the spherical mesoporous composite material.
According to a specific embodiment, in the step (4), the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake are respectively ball-milled, then the ball-milled products are respectively washed by using a ceramic membrane filter, and the washed products are mixed and then spray-dried to obtain the spherical mesoporous composite material.
According to a specific embodiment, in the step (4), the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake are respectively ball-milled, and then the ball-milled products are mixed and then are washed and spray-dried by using a ceramic membrane filter, so as to obtain the spherical mesoporous composite material.
According to a specific embodiment, in the step (4), the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake are mixed and then ball-milled, and then the ball-milled product is subjected to washing treatment and spray drying by using a ceramic membrane filter, so as to obtain the spherical mesoporous composite material.
The washing treatment may be performed using water and/or an alcohol (e.g., ethanol). According to a preferred embodiment of the present invention, when the content of sodium ions in the washing liquid of the ceramic membrane filter is detected to be 0.02 wt% or less and the content of the template agent is detected to be less than 1 wt%, the filtration is stopped to obtain a filter cake.
According to the present invention, in the step (4), the conditions and the specific operation method of the ball milling are not particularly limited and may be conventionally selected in the art. For example, the ball milling may be carried out in a ball mill in which the inner walls of the milling bowl are preferably lined with polytetrafluoroethylene and the grinding balls in the ball mill may have a diameter of 2-3 mm; the number of the grinding balls can be reasonably selected according to the size of the ball milling tank, and 1 grinding ball can be generally used for the ball milling tank with the size of 50-150 ml; the material of the grinding ball can be agate, polytetrafluoroethylene and the like, and agate is preferred. The ball milling conditions may include: the rotation speed of the grinding ball can be 300-500r/min, the temperature in the ball milling tank can be 15-100 ℃, and the ball milling time can be 0.1-100 hours.
According to the present invention, in step (4), the spray drying may be carried out according to a conventional method. May be at least one selected from the group consisting of a pressure spray drying method, a centrifugal spray drying method and a pneumatic spray drying method. According to a preferred embodiment of the present invention, the spray drying is a centrifugal spray drying method. The spray drying may be carried out in an atomizer. The conditions of the spray drying may include: the temperature is 100-300 ℃, and the rotating speed is 10000-15000 r/min; preferably, the spray drying conditions include: the temperature is 150-250 ℃, and the rotating speed is 11000-13000 r/min.
The preparation method of the spherical mesoporous composite material in the prior art usually further comprises a step of removing the template agent after spray drying, for example, removing the template agent by a calcination method. Because the method of the invention adopts the ceramic membrane for washing treatment, the method for preparing the spherical mesoporous material of the invention can not comprise the step of calcining to remove the template agent.
In the present invention, the supported catalyst may be prepared according to various conventional methods in the art as long as it can support a platinum component, a tin component and a sodium component on the carrier.
The invention also provides a preparation method of the supported catalyst, which comprises the following steps: the carrier is co-impregnated with a mixed aqueous solution containing a water-soluble platinum compound, a water-soluble tin compound and an inorganic sodium salt, then the solvent water is removed, dried and calcined.
Wherein the carrier is described above, and is not described herein again. In the present invention, there is no particular limitation on the selection of the water-soluble platinum compound, the water-soluble tin compound, and the inorganic sodium salt. For example, the water-soluble platinum compound is at least one of chloroplatinic acid, ammonium chloroplatinate and platinum nitrate, preferably chloroplatinic acid and/or ammonium chloroplatinate, and more preferably chloroplatinic acid; the water-soluble tin compound is tin tetrachloride; the inorganic sodium salt is sodium nitrate and/or sodium chloride.
In the present invention, the amounts of the water-soluble platinum compound, the water-soluble tin compound and the inorganic sodium salt may vary within a wide range, and for example, the amounts of the water-soluble platinum compound, the water-soluble tin compound and the inorganic sodium salt are such that in the prepared supported catalyst, the content of the platinum component is 0.2 to 0.5% by weight, the content of the tin component is 0.2 to 1.2% by weight, the content of the sodium component is 0.3 to 0.8% by weight and the content of the carrier is 97.5 to 99.3% by weight, in terms of elements, based on the total weight of the catalyst. Preferably, the water-soluble platinum compound, the water-soluble tin compound and the inorganic sodium salt are used in such amounts that, in the prepared supported catalyst, the content of the platinum component is 0.2 to 0.4% by weight, the content of the tin component is 0.3 to 1% by weight, the content of the sodium component is 0.4 to 0.7% by weight and the content of the carrier is 97.9 to 99.1% by weight, in terms of elements, based on the total weight of the catalyst.
In the invention, the contents of the platinum component, the tin component and the sodium component in the supported catalyst are calculated according to the charge ratio of raw materials.
In the present invention, the conditions of the co-impregnation are not particularly limited, and for example, the conditions of the co-impregnation include: the temperature can be 15-60 ℃, and the time can be 1-10 hours; preferably, the temperature is 25-40 ℃ and the time is 2-8 hours.
In the present invention, the solvent water removal method is not particularly limited, and may be a method conventionally used in the art, for example, a rotary evaporator may be used.
In the present invention, the drying conditions are not particularly limited, and may be those conventional in the art. For example, the drying conditions include: the temperature can be 90-160 ℃, and preferably 100-130 ℃; the time can be 1 to 20 hours, preferably 2 to 5 hours.
In the present invention, the conditions for the calcination are not particularly limited, and may be those conventionally used in the art. For example, the conditions for the calcination include: the temperature can be 500-700 ℃, preferably 550-650 ℃; the time can be 2 to 15 hours, preferably 3 to 10 hours.
The invention also provides a supported catalyst prepared by the method. The supported catalyst prepared by the method has large specific surface area and pore volume, and the dispersion condition of the metal component on the carrier is good, so that the catalyst shows excellent catalytic performance in catalytic dehydrogenation reaction.
The invention also provides the application of the supported catalyst in the reaction of preparing propylene by propane dehydrogenation.
The invention also provides a method for preparing propylene by propane dehydrogenation, which comprises the following steps: under the condition of preparing propylene by propane dehydrogenation, propane is contacted with a catalyst, and the catalyst is the supported catalyst provided by the invention.
In the present invention, the catalyst provided by the present invention can be used for propane dehydrogenation to prepare propylene by using the conditions conventionally used in the art, and preferably, the method further comprises adding a diluent gas, wherein the diluent gas is usually hydrogen. The contacting of the propane with the catalyst may be carried out in a fixed bed quartz reactor, and the conditions for the dehydrogenation of propane to produce propylene include: the molar ratio of propane to hydrogen may be from 0.5 to 5: 1, the reaction temperature can be 500-650 ℃, the pressure can be 0.05-0.15MPa, and the mass space velocity of the propane can be 1-10h-1. The pressures of the present invention are gage pressures.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examplesThe ceramic membrane filter used was an inorganic ceramic membrane element of JWCM19 x 30, available from Kyosu Jiuwu high-tech Co., Ltd., and a packing membrane area of 0.5m2The ceramic membrane module of (a); the parameters of the inorganic ceramic membrane element include: the shape is a multi-channel cylinder, the number of channels is 19, the diameter of the channel is 4mm, the length is 1016mm, and the outer diameter (diameter) is 30 mm;
the rotary evaporator is produced by German IKA company, and the model is RV10 digital;
the drying box is produced by Shanghai-Hengchun scientific instruments Co., Ltd, and is of a type DHG-9030A;
the muffle furnace is manufactured by CARBOLITE corporation, model CWF 1100.
N of the sample2The adsorption-desorption experiments were carried out on an adsorption apparatus model ASAP2020-M + C manufactured by Micromeritics, USA, and BET method was used for the calculation of the specific surface area and pore volume of the sample.
Scanning Electron Microscope (SEM) analysis was performed on a scanning electron microscope model XL-30 available from FEI, USA;
the content of each component in the prepared dehydrogenation catalyst is determined by calculating the raw material feeding during preparation;
propane conversion and selectivity were analyzed by gas chromatography and calculated as follows:
propane conversion ═ amount of propane consumed by the reaction/initial amount of propane × 100%;
the propylene selectivity was calculated as follows:
propylene selectivity is the amount of propane consumed to form propylene/total propane consumption × 100%;
the propylene yield was calculated as follows:
the propylene yield was determined as the actual yield of propylene/theoretical yield of propylene × 100%.
Example 1
This example illustrates the supported catalyst, the preparation method thereof, and the method for preparing propylene by propane dehydrogenation provided by the present invention
(1) Preparation of spherical mesoporous composite material
1g (0.00017mol) of template P123 and 1.69g (0.037mol) of ethanol are added into 28mL of acetic acid and sodium acetate buffer solution with pH 4.4, the mixture is stirred at 15 ℃ until the template is completely dissolved, 6g (0.05mol) of trimethylpentane is added into the solution, the solution is stirred at 15 ℃ for 8 hours, 2.13g (0.014mol) of tetramethoxysilane is added into the solution, the solution is stirred at 15 ℃ for 20 hours, the solution is transferred into an agate-lined reaction kettle, oven crystallization is carried out at 60 ℃ for 24 hours, and then suction filtration is carried out to obtain a first mesoporous material filter cake A11.
Adding hexadecyl trimethyl ammonium bromide and ethyl orthosilicate into an ammonia water solution with the concentration of 25 weight percent at the temperature of 80 ℃, and then adding deionized water, wherein the adding amount of the ethyl orthosilicate is 1g, and the mol ratio of ammonia to water in the ethyl orthosilicate, the hexadecyl trimethyl ammonium bromide and the ammonia water is 1: 0.37: 2.8: 142 and stirred at the temperature of 80 ℃ for 4 hours, and then the solution is filtered by suction to obtain a second mesoporous material filter cake a 12.
Mixing 15 wt% water glass and 12 wt% sulfuric acid solution in the weight ratio of 5: 1, and then the mixture was subjected to a contact reaction at 20 ℃ for 1.5 hours, followed by adjusting the pH to 3 with sulfuric acid having a concentration of 98% by weight, and then the resulting reaction mass was subjected to suction filtration to obtain a silica gel cake B1.
5g of the filter cake A11 prepared above, 5g of the filter cake A12 prepared above and 10g of the filter cake B1 prepared above are mixed, and the mixture is washed by a ceramic membrane filter until the content of sodium ions is 0.02 wt% and the content of a template agent is less than 1 wt%, so that the spherical mesoporous composite material filter cake is obtained. Wherein the operating pressure of the membrane module is 3.3bar, the pressure of the membrane at the circulating side is 4bar, the pressure of the membrane at the circulating side is 2.5bar, the flow rate of the membrane surface at the circulating side is 4m/s, the pressure of the permeation side is 0.3bar, and the temperature is 20 ℃.3 parts by weight of water is consumed for preparing one part by weight of the spherical mesoporous composite filter cake.
And (3) putting the spherical mesoporous composite filter cake into a 100mL ball milling tank, wherein the ball milling tank is made of agate, the grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, and the rotating speed is 400 r/min. And (3) sealing the ball milling tank, carrying out ball milling for 5h at the temperature of 60 ℃ in the ball milling tank, and carrying out spray drying on the ball-milled slurry at the temperature of 200 ℃ at the rotating speed of 12000r/min to obtain the spherical mesoporous composite material C1.
The spherical mesoporous composite material C1 is characterized by XRD, a scanning electron microscope and a nitrogen adsorption instrument.
Fig. 1 is an X-ray diffraction pattern, wherein a is an XRD pattern of the spherical mesoporous composite material C1, the abscissa is 2 θ, and the ordinate is intensity. As can be seen from a small-angle spectrum peak appearing in an XRD spectrogram, the spherical mesoporous composite material C1 has a 2D hexagonal pore channel structure which is unique to mesoporous materials.
FIG. 2 is an SEM image. As can be seen from the figure, the microscopic morphology of the spherical mesoporous composite material C1 is microspheres with the particle size of 30-60 μm, and the dispersion performance is good.
Fig. 3 is a pore size distribution diagram of the spherical mesoporous composite material C1. As can be seen from the figure, the spherical mesoporous composite material C1 has a porous structure distribution and uniform pore channels.
The pore structure parameters of the spherical mesoporous composite material C1 are shown in table 1 below.
TABLE 1
*: the first most probable aperture, the second most probable aperture, and the third most probable aperture are separated by commas: the first most probable aperture, the second most probable aperture and the third most probable aperture are arranged in the order from left to right.
(2) Preparation of Supported catalysts
0.080g of H2PtCl6·6H2O, 0.207g SnCl4·5H2O and 0.185g NaNO3Dissolved in 100ml of deionized water, mixed with 10g of the spherical mesoporous composite material C1 prepared above, and continuously stirred and reacted for 5 hours at room temperature. And (4) evaporating the solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 120 ℃ for 3 hours. And then placing the product in a muffle furnace, and roasting for 6 hours at the temperature of 600 ℃ to obtain the supported catalyst D1.
The specific gravity of each component of the supported catalyst D1 is as follows: 0.3 wt% of platinum component calculated by platinum element, 0.7 wt% of tin component calculated by tin element, 0.5 wt% of sodium component calculated by sodium element, and the balance of spherical mesoporous composite material C1.
(3) Dehydrogenation of propane to propylene
0.5g of the supported catalyst D1 was charged into a fixed bed quartz reactor, the reaction temperature was controlled at 610 ℃, the reaction pressure was 0.1MPa, the molar ratio of propane: the molar ratio of hydrogen is 1:1, and the mass space velocity of propane is 3.0h-1The reaction time is 50 h. The reaction results are shown in Table 4.
Example 2
This example illustrates the supported catalyst, the preparation method thereof, and the method for preparing propylene by propane dehydrogenation provided by the present invention
(1) Preparation of spherical mesoporous composite material
Adding 1g (0.00017mol) of template P123 and 1.4g (0.03mol) of ethanol into 28mL of acetic acid and sodium acetate buffer solution with the pH value of 4.4, stirring at 10 ℃ until the template is completely dissolved, adding 4.56g (0.04mol) of trimethylpentane into the solution, stirring at 10 ℃ for 8 hours, adding 1.83g (0.012mol) of tetramethoxysilane into the solution, stirring at 10 ℃ for 30 hours, transferring the solution into an agate-lined reaction kettle, oven-crystallizing at 80 ℃ for 20 hours, and filtering to obtain a first mesoporous material filter cake A21.
Adding hexadecyl trimethyl ammonium bromide and ethyl orthosilicate into an ammonia water solution with the concentration of 25 weight percent at 50 ℃, and adding deionized water, wherein the adding amount of the ethyl orthosilicate is 1g, and the mol ratio of ammonia to water in the ethyl orthosilicate, the hexadecyl trimethyl ammonium bromide and the ammonia water is 1: 0.5: 1.5: 180 and stirring at 50 ℃ for 7 hours, and then filtering the solution by suction to obtain a second mesoporous material filter cake A22.
Mixing water glass with the concentration of 20 weight percent and sulfuric acid solution with the concentration of 12 weight percent in a weight ratio of 3: 1, and then the mixture is contacted and reacted at 20 ℃ for 3 hours, then the pH value is adjusted to 4 by using sulfuric acid with the concentration of 98 weight percent, and then the obtained reaction material is filtered by suction to obtain a filter cake B2 of silica gel.
6.7g of the filter cake A11, 3.3g of the filter cake A12 and 15g of the filter cake B1 prepared in the above were mixed, and the mixture was washed with a ceramic membrane filter until the sodium ion content was 0.02% by weight and the content of the template agent was less than 1% by weight, to obtain a spherical mesoporous composite filter cake. Wherein the operating pressure of the membrane module is 3bar, the pressure of the membrane at the circulating side is 3.5bar, the pressure of the membrane at the circulating side is 2.5bar, the flow rate of the membrane surface at the circulating side is 4.5m/s, the pressure of the permeation side is 0.4bar, and the temperature is 60 ℃.
And (3) putting the spherical mesoporous composite filter cake into a 100mL ball milling tank, wherein the ball milling tank is made of agate, the grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, and the rotating speed is 500 r/min. And (3) sealing the ball milling tank, carrying out ball milling for 20h at the temperature of 35 ℃ in the ball milling tank, and carrying out spray drying on the ball-milled slurry at the temperature of 150 ℃ at the rotating speed of 13000r/min to obtain the spherical mesoporous composite material C2.
The pore structure parameters of the spherical mesoporous composite material C2 are shown in table 2 below.
TABLE 2
*: the first most probable aperture, the second most probable aperture, and the third most probable aperture are separated by commas: the first most probable aperture, the second most probable aperture and the third most probable aperture are arranged in the order from left to right.
(2) Preparation of Supported catalysts
0.053g of H2PtCl6·6H2O, 0.09g of SnCl4·5H2O and 0.127g of NaCl are dissolved in 50ml of deionized water, and the mixture is mixed with 10g of the spherical mesoporous composite material C2 prepared in the above manner, and the mixture is continuously stirred and reacted for 2 hours at the temperature of 40 ℃. And (4) evaporating the solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 100 ℃ for 5 hours. Then calcined in a muffle furnace at 650 ℃ for 3 hours to obtain the supported catalyst D2.
The specific gravity of each component of the supported catalyst D2 is as follows: 0.2 wt% of platinum component calculated by platinum element, 0.3 wt% of tin component calculated by tin element, 0.4 wt% of sodium component calculated by sodium element, and the balance of spherical mesoporous composite material C2.
(3) Dehydrogenation of propane to propylene
Propane dehydrogenation was carried out to produce propylene by following the procedure of example 1 except that a supported catalyst D2 was used in place of the supported catalyst D1 in example 1. The reaction results are shown in Table 4.
Example 3
This example illustrates the supported catalyst, the preparation method thereof, and the method for preparing propylene by propane dehydrogenation provided by the present invention
(1) Preparation of spherical mesoporous composite material
Adding 1g (0.00017mol) of template P123 and 3.13g (0.068mol) of ethanol into 28mL of acetic acid and sodium acetate buffer solution with the pH value of 4.4, stirring at 20 ℃ until the template is completely dissolved, adding 7.75g (0.068mol) of trimethylpentane into the solution, stirring at 20 ℃ for 8h, adding 3.8g (0.025mol) of tetramethoxysilane into the solution, stirring at 20 ℃ for 10h, transferring the solution into an agate-lined reaction kettle, carrying out oven crystallization at 40 ℃ for 30h, and carrying out suction filtration to obtain a first mesoporous material filter cake A31.
Adding hexadecyl trimethyl ammonium bromide and ethyl orthosilicate into an ammonia water solution with the concentration of 25 weight percent at 90 ℃, and adding deionized water, wherein the adding amount of the ethyl orthosilicate is 1g, and the mol ratio of ammonia to water in the ethyl orthosilicate, the hexadecyl trimethyl ammonium bromide and the ammonia water is 1: 0.2: 3.5: 120 and stirring for 3 hours at the temperature of 90 ℃, and then filtering the solution by suction to obtain a second mesoporous material filter cake A32.
Mixing water glass with the concentration of 10 weight percent and sulfuric acid solution with the concentration of 12 weight percent in a weight ratio of 4: 1, and then the mixture is contacted and reacted for 1.5h at 30 ℃, then the pH value is adjusted to 2 by using sulfuric acid with the concentration of 98 weight percent, and then the obtained reaction material is filtered by suction to obtain a filter cake B3 of silica gel.
Mixing 7g of the filter cake A31, 14g of the filter cake A32 and 10g of the filter cake B3, and washing the mixture by using a ceramic membrane filter until the content of sodium ions is 0.02 wt% and the content of a template agent is less than 1 wt%, thereby obtaining the spherical mesoporous composite filter cake. Wherein the operating pressure of the membrane module is 3.4bar, the pressure of the membrane at the circulating side is 4.5bar, the pressure of the membrane at the circulating side is 2.3bar, the flow rate of the membrane surface at the circulating side is 4.2m/s, the pressure of the permeate side is 0.5bar, and the temperature is 40 ℃.
And (3) putting the spherical mesoporous composite filter cake into a 100mL ball milling tank, wherein the ball milling tank is made of agate, the grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, and the rotating speed is 500 r/min. And (3) sealing the ball milling tank, carrying out ball milling for 10h at the temperature of 50 ℃ in the ball milling tank, and carrying out spray drying on the ball-milled slurry at the temperature of 250 ℃ at the rotating speed of 11000r/min to obtain the spherical mesoporous composite material C3.
The pore structure parameters of the spherical mesoporous composite material C3 are shown in table 3 below.
TABLE 3
*: the first most probable aperture, the second most probable aperture, and the third most probable aperture are separated by commas: the first most probable aperture, the second most probable aperture and the third most probable aperture are arranged in the order from left to right.
(2) Preparation of Supported catalysts
0.11g of H2PtCl6·6H2O, 0.296g of SnCl4·5H2O and 0.259g NaNO3Dissolved in 200ml of deionized water, mixed with 10g of the spherical mesoporous composite material C3 prepared above, and continuously stirred and reacted for 8 hours at the temperature of 30 ℃. And (4) evaporating the solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 100 ℃ for 5 hours. Then, the catalyst was calcined in a muffle furnace at 550 ℃ for 10 hours to obtain a supported catalyst D3.
The specific gravity of each component of the supported catalyst D3 is as follows: 0.4 wt% of platinum component calculated by platinum element, 1 wt% of tin component calculated by tin element, 0.7 wt% of sodium component calculated by sodium element, and the balance of spherical mesoporous composite material C3.
(3) Dehydrogenation of propane to propylene
Propane dehydrogenation was carried out to produce propylene by following the procedure of example 1 except that a supported catalyst D3 was used in place of the supported catalyst D1 in example 1. The reaction results are shown in Table 4.
Example 4
This example illustrates the supported catalyst, the preparation method thereof, and the method for preparing propylene by propane dehydrogenation provided by the present invention
(1) Preparation of the support
The support was prepared according to the method of example 1.
(2) Preparation of Supported catalysts
The procedure of example 1 was followed except that the contents of the platinum component, the tin component and the sodium component were varied. In particular, H2PtCl6·6H2The dosage of O is 0.133g, SnCl4·5H2The amount of O is 0.355g, NaNO3The same operation was repeated except for using 0.111g of (B), and the same operation as in example 1 was repeated to obtain a supported catalyst D4.
The specific gravity of each component of the supported catalyst D4 is as follows: 0.5 wt% of platinum component calculated by platinum element, 1.2 wt% of tin component calculated by tin element, 0.3 wt% of sodium component calculated by sodium element, and the balance of spherical mesoporous composite material C1.
(3) Dehydrogenation of propane to propylene
Propane dehydrogenation was carried out to produce propylene by following the procedure of example 1 except that a supported catalyst D4 was used in place of the supported catalyst D1 in example 1. The reaction results are shown in Table 4.
Comparative example 1
This comparative example serves to illustrate a reference supported catalyst and a process for the dehydrogenation of propane to propylene
0.080g of H2PtCl6·6H2O, 0.207g SnCl4·5H2O and 0.185g NaNO3Dissolved in 100ml of deionized water, 10g of commercially available gamma-Al were added2O3Carrier (Qingdao Seawa silica gel desiccant company brand is a commercial product of industrial grade low specific surface area activated alumina, and the specific surface area is 162m2Per g, pore volume 0.82cm3And/g) are mixed and the reaction is continued for 5 hours at room temperature with stirring. And (4) evaporating the solvent water in the system by using a rotary evaporator to obtain a solid product. Subjecting the solid product to temperatureDried in a drying oven at 120 ℃ for 3 hours. Then the catalyst is roasted in a muffle furnace for 6 hours at the temperature of 600 ℃ to obtain the supported catalyst DD 1.
The specific gravity of each component of the supported catalyst DD1 is as follows: 0.3 wt% of platinum component calculated by platinum element, 0.7 wt% of tin component calculated by tin element, 0.5 wt% of sodium component calculated by sodium element, and the balance of gamma-Al2O3And (3) a carrier.
(3) Dehydrogenation of propane to propylene
Propane dehydrogenation was carried out to produce propylene according to the procedure of example 1, except that supported catalyst DD1 was used instead of supported catalyst D1 in example 1. The reaction results are shown in Table 4.
Comparative example 2
This comparative example serves to illustrate a reference supported catalyst and a process for the dehydrogenation of propane to propylene
A support and a supported catalyst were prepared by following the procedure of example 1, except that the supported catalyst was prepared by a stepwise impregnation method instead of a co-impregnation method. Specifically, the spherical mesoporous composite material C1 was immersed in an aqueous solution of chloroplatinic acid for 5 hours, the immersed spherical mesoporous composite material C1 was dried and calcined under the conditions of example 1, and then was immersed in an aqueous solution of tin tetrachloride and sodium nitrate for 5 hours, and then was dried and calcined under the conditions of example 1, thereby obtaining the supported catalyst DD 2.
The specific gravity of each component of the supported catalyst DD2 is as follows: 0.3 wt% of platinum component calculated by platinum element, 0.7 wt% of tin component calculated by tin element, 0.5 wt% of sodium component calculated by sodium element, and the balance of spherical mesoporous composite material C1.
(3) Dehydrogenation of propane to propylene
Propane dehydrogenation was carried out to produce propylene according to the procedure of example 1, except that supported catalyst DD2 was used instead of supported catalyst D1 in example 1. The reaction results are shown in Table 4.
TABLE 4
| Average conversion of propane (%) | Average propylene selectivity (%) | Average yield (%) of propylene | |
| Example 1 | 23 | 72 | 99 |
| Example 2 | 19 | 70 | 95 |
| Example 3 | 21 | 73 | 91 |
| Example 4 | 17 | 68 | 87 |
| Comparative example 1 | 9 | 78 | 75 |
| Comparative example 2 | 13 | 61 | 60 |
As can be seen from the results in Table 4, examples 1-4 using the supported catalyst of the present invention for the reaction of propane dehydrogenation to produce propylene have significantly better catalytic performance than the commercially available γ -Al2O3The average conversion of propane and the average yield of propylene were significantly improved in the catalyst prepared from the carrier (comparative example 1). The preparation method of the dehydrogenation catalyst provided by the invention can realize the effect of improving the catalytic performance of the dehydrogenation catalyst. Compared with the catalyst prepared by adopting the step-by-step impregnation method in the comparative example 2, the catalyst disclosed by the invention is simple in preparation process and good in catalytic effect. The effects are clearly most optimal with examples 1-3 in the preferred range.
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 combinations of various technical features 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 supported catalyst comprises a carrier and a platinum component, a tin component and a sodium component which are loaded on the carrier, and is characterized in that the carrier is a spherical mesoporous composite material which is prepared by adopting a method comprising the following steps:
(1) carrying out first mixing contact on a template agent, tetramethoxysilane, ethanol, trimethylpentane and an acid agent, and crystallizing and filtering a mixture obtained by the first mixing contact to obtain a first mesoporous material filter cake;
(2) carrying out second mixing contact on ethyl orthosilicate, hexadecyl trimethyl ammonium bromide and ammonia, and filtering a mixture obtained by the second mixing contact to obtain a second mesoporous material filter cake;
(3) carrying out third mixing contact on water glass and inorganic acid, and filtering a mixture obtained after the third mixing contact to obtain a silica gel filter cake;
(4) respectively or after mixing the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake, carrying out ball milling on the ball-milled products, washing the ball-milled products by using a ceramic membrane filter, and then carrying out spray drying to obtain the spherical mesoporous composite material; or,
and (3) washing the first mesoporous material filter cake, the second mesoporous material filter cake and the silica gel filter cake respectively or after mixing, and then carrying out ball milling and spray drying to obtain the spherical mesoporous composite material.
2. The supported catalyst as claimed in claim 1, wherein the spherical mesoporous composite has an average particle diameter of 20-60 μm and a specific surface area of 150-600m2The pore volume is 0.5-1.8mL/g, the pore diameter is in trimodal distribution, and the trimodal corresponds to the first most probable pore diameter of 5-15nm, the second most probable pore diameter of 20-40nm and the third most probable pore diameter of 45-60nm respectively;
preferably, the average particle diameter of the spherical mesoporous composite material is 40-50 μm, and the specific surface area is 220-300m2The pore volume is 1.1-1.7mL/g, the pore diameter is in trimodal distribution, and the trimodal corresponds to the first most probable pore diameter of 6-9nm, the second most probable pore diameter of 25-35nm and the third most probable pore diameter of 45-54nm respectively.
3. The supported catalyst of claim 1, wherein the platinum component is present in an amount of 0.2 to 0.5 wt.%, the tin component is present in an amount of 0.2 to 1.2 wt.%, the sodium component is present in an amount of 0.3 to 0.8 wt.%, and the carrier is present in an amount of 97.5 to 99.3 wt.%, calculated as elements on the total weight of the catalyst.
4. The supported catalyst of claim 1, wherein the washing treatment conditions using a ceramic membrane filter comprise: the operating pressure is 2.5-3.9bar, the pressure of the circulating side inlet membrane is 3-5bar, the pressure of the circulating side outlet membrane is 2-2.8bar, and the flow rate of the circulating side membrane surface is 4-5 m/s; the pressure of the permeation side is 0.3-0.5 bar; the temperature is 10-60 ℃.
5. The supported catalyst according to claim 1, wherein, in the step (4), the silica gel cake is used in an amount of 1 to 200 parts by weight, preferably 20 to 180 parts by weight, and more preferably 50 to 150 parts by weight, relative to 100 parts by weight of the total amount of the first mesoporous material cake and the second mesoporous material cake; the weight ratio of the first mesoporous material filter cake to the second mesoporous material filter cake is 1:0.1-10, preferably 1: 0.5-2;
preferably, in step (1), the templating agent is a triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene; the acid agent is acetic acid and sodium acetate buffer solution with pH value of 1-6;
preferably, the molar ratio of the template, ethanol, trimethylpentane and tetramethoxysilane is 1: 100-500: 200-500: 50-200, more preferably 1: 180-400: 250-400: 70-150;
preferably, the conditions of the first mixing contact include: the temperature is 10-60 ℃, the time is 10-72 hours, and the pH value is 1-7; the conditions for crystallization of the mixture obtained by the first mixing contact include: the temperature is 30-150 ℃, and the time is 10-72 hours;
preferably, in step (2), the molar ratio of ethyl orthosilicate, cetyltrimethylammonium bromide and ammonia is 1: 0.1-1: 0.1 to 5, preferably 1: 0.2-0.5: 1.5-3.5;
preferably, the conditions of the second mixing contact include: the temperature is 25-100 ℃, and the time is 2-8 hours;
preferably, the weight ratio of the water glass to the inorganic acid is 3-6:1, and the inorganic acid is one or more of sulfuric acid, nitric acid and hydrochloric acid;
preferably, the conditions of the third mixing contact include: the temperature is 10-60 ℃, the time is 1-5 hours, and the pH value is 2-4;
preferably, in step (4), the ball milling conditions include: the rotation speed of the grinding ball is 300-;
preferably, the conditions of the spray drying include: the temperature is 100-300 ℃, and the rotating speed is 10000-15000 r/min.
6. A process for preparing a supported catalyst according to any one of claims 1 to 5, comprising: the carrier is co-impregnated with a mixed aqueous solution containing a water-soluble platinum compound, a water-soluble tin compound and an inorganic sodium salt, then the solvent water is removed, dried and calcined.
7. The method according to claim 6, wherein the water-soluble platinum compound, the water-soluble tin compound and the inorganic sodium salt are used in amounts such that the platinum component is contained in an amount of 0.2 to 0.5 wt%, the tin component is contained in an amount of 0.2 to 1.2 wt%, the sodium component is contained in an amount of 0.3 to 0.8 wt%, and the carrier is contained in an amount of 97.5 to 99.3 wt%, calculated as elements, based on the total weight of the catalyst, in the prepared supported catalyst.
8. The method of claim 6, wherein the co-impregnating conditions comprise: the temperature is 15-60 ℃, and the time is 1-10 hours;
preferably, the conditions of the calcination include: the temperature is 500 ℃ and 700 ℃ and the time is 2-15 hours.
9. A supported catalyst prepared by the process of any one of claims 6 to 8.
10. Use of a supported catalyst according to any one of claims 1 to 5 and 9 in the dehydrogenation of propane to produce propylene.
11. A method for preparing propylene by propane dehydrogenation is characterized by comprising the following steps: contacting propane with a catalyst under conditions for the dehydrogenation of propane to propylene, characterized in that the catalyst is a supported catalyst according to any one of claims 1-5 and 9.
12. The method of claim 11, further comprising adding a diluent gas hydrogen;
preferably, the contacting of the propane with the catalyst is carried out in a fixed bed quartz reactor, and the conditions for the dehydrogenation of propane to produce propylene include: the molar ratio of propane to hydrogen is 0.5-5: 1, the reaction temperature is 500-650 ℃, the pressure is 0.05-0.15MPa, and the mass space velocity of propane is 1-10h-1。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104248986A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical attapulgite mesoporous composite carrier, supported catalyst and preparation method and application thereof and preparation method of ethyl acetate |
| CN104248979A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical mesoporous silica composite carrier and catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method |
| CN104248993A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite and supported catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method |
| CN105330768A (en) * | 2014-06-13 | 2016-02-17 | 中国石油化工股份有限公司 | Supported polyethylene catalyst ingredient and preparation method thereof, and supported polyethylene catalyst and application thereof |
| CN105435852A (en) * | 2014-06-09 | 2016-03-30 | 中国石油化工股份有限公司 | Mesoporous composite material and catalyst and preparation method and application thereof and 2,2-dimethyl-4-methyl-1,3-dioxolane preparation method |
-
2017
- 2017-05-10 CN CN201710325204.6A patent/CN108855054B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104248986A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical attapulgite mesoporous composite carrier, supported catalyst and preparation method and application thereof and preparation method of ethyl acetate |
| CN104248979A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical mesoporous silica composite carrier and catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method |
| CN104248993A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite and supported catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method |
| CN105435852A (en) * | 2014-06-09 | 2016-03-30 | 中国石油化工股份有限公司 | Mesoporous composite material and catalyst and preparation method and application thereof and 2,2-dimethyl-4-methyl-1,3-dioxolane preparation method |
| CN105330768A (en) * | 2014-06-13 | 2016-02-17 | 中国石油化工股份有限公司 | Supported polyethylene catalyst ingredient and preparation method thereof, and supported polyethylene catalyst and application thereof |
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