CN108855054B - 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
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- CN108855054B CN108855054B CN201710325204.6A CN201710325204A CN108855054B CN 108855054 B CN108855054 B CN 108855054B CN 201710325204 A CN201710325204 A CN 201710325204A CN 108855054 B CN108855054 B CN 108855054B
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- filter cake
- weight
- loaded catalyst
- mixed
- mesoporous material
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000003054 catalyst Substances 0.000 title claims abstract description 121
- 238000000034 method Methods 0.000 title claims abstract description 74
- 239000001294 propane Substances 0.000 title claims abstract description 66
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 63
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 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 35
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 35
- 239000011734 sodium Substances 0.000 claims abstract description 35
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 23
- 239000012065 filter cake Substances 0.000 claims description 97
- 239000013335 mesoporous material Substances 0.000 claims description 61
- 239000011148 porous material Substances 0.000 claims description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 238000000498 ball milling Methods 0.000 claims description 35
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000000741 silica gel Substances 0.000 claims description 27
- 229910002027 silica gel Inorganic materials 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000001694 spray drying Methods 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 150000007522 mineralic acids Chemical class 0.000 claims description 14
- 238000005470 impregnation Methods 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 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
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 claims description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 150000003058 platinum compounds Chemical class 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 150000003606 tin compounds Chemical class 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000003125 aqueous solvent Substances 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 8
- -1 polyoxyethylene Polymers 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 230000003204 osmotic effect Effects 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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims 2
- HRHBQGBPZWNGHV-UHFFFAOYSA-N azane;bromomethane Chemical compound N.BrC HRHBQGBPZWNGHV-UHFFFAOYSA-N 0.000 claims 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 159000000000 sodium salts Chemical class 0.000 claims 1
- 229920000428 triblock copolymer Polymers 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 description 30
- 239000000919 ceramic Substances 0.000 description 26
- 229960001866 silicon dioxide Drugs 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000000463 material Substances 0.000 description 20
- 238000006356 dehydrogenation reaction Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- 239000000908 ammonium hydroxide Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000012265 solid product Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000005484 gravity Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 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
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 4
- UXAMZEYKWGPDBI-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)Br(C)(C)C Chemical compound C(CCCCCCCCCCCCCCC)Br(C)(C)C UXAMZEYKWGPDBI-UHFFFAOYSA-N 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 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
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 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
- 230000035484 reaction time Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 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
- 238000001228 spectrum Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 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
- 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
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 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
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 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
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- 230000000149 penetrating effect Effects 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
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical class [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005507 spraying 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
- 239000002023 wood Substances 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
-
- 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
- B01J23/02—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
- 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
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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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
- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
- 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
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
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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
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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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
- 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
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—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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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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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 present invention relates to catalyst fields, and in particular, to a kind of loaded catalyst, a kind of system of loaded catalyst
Preparation Method, application of the loaded catalyst in preparing propylene by dehydrogenating propane reaction, a kind of preparing propylene by dehydrogenating propane
Method.
Background technique
Propylene is the base stock of petrochemical industry, mainly for the production of polypropylene, acrylonitrile, acetone, propylene oxide, propylene
Acid and octyl alconyl etc..The supply half of propylene comes from refinery's by-product, separately has about 45% to come from steam cracking, a small amount of other substitution skills
Art.In recent years, the demand of propylene increases year by year, and traditional production of propylene has been unable to meet demand of the chemical industry to propylene,
Therefore propylene enhancing becomes a big hot spot of research.Wherein, preparing propylene by dehydrogenating propane is a major technique of propylene volume increase.10
For many years, preparing propylene by dehydrogenating propane has become the important process process of industrialization production of propylene.The major catalytic of dehydrogenating propane
Agent has in chromium oxide/aluminum oxide catalyst and Uop Inc.'s Oleflex technique in ABB Lummus company Catofin technique
Platinum tin/aluminium oxide catalyst.Requirement of the chromium-based catalysts to raw material impurity is relatively low, on the low side compared with noble metal；But this
Class catalyst is easy carbon distribution inactivation, will regenerate every 15-30 minutes once, and since the chromium in catalyst is heavy metal,
Environmental pollution is serious；Platinum-tin catalyst activity is high, and selectivity is good, can reach reaction time several days, can bear more harsh
Process conditions, and to more environment-friendly, but since noble metal platinum is expensive, lead to catalyst higher cost.Third
Alkane dehydrogenation producing propylene technique realizes that industrialized production alreadys exceed 20 years, also many to the research of dehydrogenation, but current
Catalyst is not still high there is conversion of propane and is easy to the defects of inactivating, and requires further improvement and perfect.Therefore, it develops
The propane dehydrogenation catalyst of function admirable has realistic meaning.
In order to improve the reactivity worth of propane dehydrogenation catalyst, researcher has done many work.Such as: (1) it uses and divides
Son sieve class carrier substitutes traditional γ-Al2O3Carrier, effect preferably include MFI type micro porous molecular sieve (CN104307555A,
CN101066532A, CN101380587A, CN101513613A), mesoporous MCM-41 molecular sieve (CN102389831A) and mesoporous
SBA-15 molecular sieve (CN101972664A, CN101972664B) etc.；(2) using calsil to γ-Al2O3Carrier is repaired
Decorations, and the various active metal components of step impregnation and metal promoter (CN104368364A)；(3) with aluminium oxide and magnesia
Composite oxides are as carrier, and the various active metal components of step impregnation and metal promoter (CN104888818A).It is above-mentioned
The improved method of various propane dehydrogenation catalysts all can cause catalyst preparation process more cumbersome, and preparation cost increases, preparation
Cycle stretch-out, or even will use the reagent or raw material unfavorable to environmental resource.
Summary of the invention
The purpose of the present invention is overcoming, existing dehydrogenation preparation process is complicated, active metal component dispersion is uneven
Defect, a kind of loaded catalyst and its preparation method and application is provided.Using loaded catalyst catalysis third of the invention
The reaction of alkane preparing propylene by dehydrogenating, conversion of propane is high, and Propylene Selectivity is high.
Specifically, in a first aspect, the catalyst includes carrier and load the present invention provides a kind of loaded catalyst
Platinum component, tin component and sodium component on the carrier, the carrier are spherical mesoporous composite material, and the spherical mesoporous is multiple
Condensation material is prepared using method comprising the following steps:
(1) template, tetramethoxy-silicane, ethyl alcohol, trimethylpentane and sour agent are carried out first to be mixed, and by the
One mixture being mixed carries out crystallization and filtering, obtains the first mesoporous material filter cake；
(2) ethyl orthosilicate, cetyl trimethylammonium bromide and ammonia progress second is mixed, and second is mixed
It contacts obtained mixture to be filtered, obtains the second mesoporous material filter cake；
(3) by waterglass and inorganic acid carry out mixture that third is mixed, and obtains after third is mixed into
Row filtering, obtains silica gel filter cake；
(4) the first mesoporous material filter cake, the second mesoporous material filter cake and silica gel filter cake are subjected to ball milling respectively or after mixing,
Ball milling product is subjected to carrying out washing treatment using purpose ceramic-film filter, is then spray-dried, obtains spherical mesoporous composite material；
Alternatively,
First mesoporous material filter cake, the second mesoporous material filter cake and silica gel filter cake are used into ceramic membrane mistake respectively or after mixing
Filter carries out carrying out washing treatment, then carries out ball milling and spray drying, obtains spherical mesoporous composite material.
Second aspect, the present invention provides the preparation methods of above-mentioned loaded catalyst, this method comprises: by carrier with contain
There is the mixed aqueous solution of water-soluble platinum compound, water-soluble tin compound and inorganic sodium to carry out co-impregnation, then removes solvent
Water, drying simultaneously roast.
The third aspect, the present invention provides the loaded catalysts that the above method is prepared.
Fourth aspect, the present invention provides application of the above-mentioned loaded catalyst in preparing propylene by dehydrogenating propane reaction.
5th aspect, the present invention provides a kind of methods of preparing propylene by dehydrogenating propane, this method comprises: in dehydrogenating propane
Under conditions of preparing propylene, propane is contacted with catalyst, wherein the catalyst is that the support type that aforementioned present invention provides is urged
Agent.Current mesoporous material removes impurity, but the spherical mesoporous obtained using this method usually using plate and frame type filter-press
Catalytic activity of the composite material after supported catalyst is lower, it may be possible to due to impurity removal not enough thoroughly.In addition, plate and frame
There is also shortcomings for filter press, for example, plate and frame type filter-press occupied area is larger, simultaneously as between plate and frame type filter-press is
Disconnected formula operation, low efficiency, operation room environment is poor, there is secondary pollution, further, since removal impurity effect is poor using filter cloth,
Waste water can not regeneration, water source is extremely wasted in washing process, simultaneously because discharge waste water can not be handled, and causes ring
Border pollution and secondary waste.And the present inventor by further investigation after find, when using ceramic membrane to mesoporous material into
When row carrying out washing treatment, obtained spherical mesoporous composite material catalytic activity with higher after loading polypropylene catalyst,
Conversion of propane is high, and the selectivity of propylene is high.The present inventor is based on above-mentioned discovery, completes the present invention.
Have the advantage that (1) separation process is simple using loaded catalyst and method of the invention, separative efficiency
Height, corollary apparatus is few, and low energy consumption, and operation operating is easy；(2) dirt is reduced using higher crossflow velocity using cross-flow filtration
Object is contaminated in the accumulation of film surface, improves membrane flux；(3) chemical stability of ceramic membrane is good, acid-fast alkali-proof organic solvent-resistant, then
Raw ability is strong, can be suitable for the preparation process of spherical mesoporous composite material；(4) waste liquid yield significantly reduces, environmentally protective.
(5) present invention using macropore, specific surface area is larger, the biggish SiO 2 mesoporous materials carrier of pore volume prepares catalyst, on
It states structure feature and is conducive to metal component in carrier surface fine dispersion, and then can guarantee the propane dehydrogenation catalyst of preparation
It can be excellent；(6) present invention step impregnation method conventional using co-impregnation method substitution, preparation process is simple, and condition is easy to control
System, good repetitiveness；(7) it shows when catalyst provided by the invention is reacted for preparing propylene by dehydrogenating propane and urges well
Change performance.Conversion of propane is high, and Propylene Selectivity is high, and catalyst stability is good.
Detailed description of the invention
Fig. 1 is the X-ray diffracting spectrum of the spherical mesoporous composite material C1 in embodiment 1；
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of the spherical mesoporous composite material C1 in embodiment 1；
Fig. 3 is the graph of pore diameter distribution of the spherical mesoporous composite material C1 in embodiment 1.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of loaded catalyst, which includes the platinum group of carrier and load on the carrier
Point, tin component and sodium component, the carrier is spherical mesoporous composite material, the spherical mesoporous composite material be use including with
What the method for lower step was prepared:
(1) template, tetramethoxy-silicane, ethyl alcohol, trimethylpentane and sour agent are carried out first to be mixed, and by the
One mixture being mixed carries out crystallization and filtering, obtains the first mesoporous material filter cake；
(2) ethyl orthosilicate, cetyl trimethylammonium bromide and ammonia progress second is mixed, and second is mixed
It contacts obtained mixture to be filtered, obtains the second mesoporous material filter cake；
(3) by waterglass and inorganic acid carry out mixture that third is mixed, and obtains after third is mixed into
Row filtering, obtains silica gel filter cake；
(4) the first mesoporous material filter cake, the second mesoporous material filter cake and silica gel filter cake are subjected to ball milling respectively or after mixing,
Ball milling product is subjected to carrying out washing treatment using purpose ceramic-film filter, is then spray-dried, obtains spherical mesoporous composite material；
Alternatively,
First mesoporous material filter cake, the second mesoporous material filter cake and silica gel filter cake are used into ceramic membrane mistake respectively or after mixing
Filter carries out carrying out washing treatment, then carries out ball milling and spray drying, obtains spherical mesoporous composite material.
In the present invention, the average grain diameter of the spherical mesoporous composite material is 20-60 μm, specific surface area 150-
600m2/ g, pore volume 0.5-1.8mL/g, aperture is in tri-modal distribution, and three peaks respectively correspond the first most probable pore size 5-
15nm, the second most probable pore size 20-40nm and third most probable pore size 45-60nm.
Under preferable case, the average grain diameter of the spherical mesoporous composite material is 40-50 μm, specific surface area 220-
300m2/ g, pore volume 1.1-1.7mL/g, aperture be in tri-modal distribution, and three peaks respectively correspond the first most probable pore size 6-9nm,
Second most probable pore size 25-35nm and third most probable pore size 45-54nm.
In the present invention, specific surface area, pore volume and the aperture of the spherical mesoporous composite material can be inhaled according to nitrogen
Attached method measures.
According to the present invention, in the loaded catalyst, the platinum component, tin component, the content of sodium component and carrier
It can change in a big way, for example, based on the element, the platinum component contains on the basis of the total weight of the catalyst
Amount can be 0.2-0.5 weight %, and the content of the tin component can be 0.2-1.2 weight %, and the content of the sodium component can
Think 0.3-0.8 weight %, the content of the carrier can be 97.5-99.3 weight %.In order to have dehydrogenation more
Good catalytic performance and the preparation cost for reducing the dehydrogenation, under preferable case, with the total weight of the catalyst
On the basis of, based on the element, the content of the platinum component is 0.2-0.4 weight %, and the content of the tin component is 0.3-1 weight
% is measured, the content of the sodium component is 0.4-0.7 weight %, and the content of the carrier is 97.9-99.1 weight %.
According to the present invention, in step (1), the template can be the various templates of this field routine, as long as energy
The pore structure of the spherical porous mesoporous composite material enough made meets the requirements.For example, the template can be embedding for three
Section copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene.Wherein, which can be commercially available (for example, can purchase
From Aldrich, trade name P123, molecular formula EO20PO70EO20, molecular weight Mn be 5800), can also be by existing
Various methods be prepared.When the template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the template rubs
You are calculated number according to the number-average molecular weight of polyoxyethylene-poly-oxypropylene polyoxyethylene.
In the present invention, the sour agent can be various acidic aqueous solutions commonly used in the art, it is preferable that the acid
Agent is the acetic acid and sodium acetate buffer solution that pH value is 1-6.There is no particular limitation for the dosage of the acid agent, can be in larger model
Enclose interior variation, it is preferable that the first pH value being mixed is 1-7.
According to the present invention, there is no particular limitation for the described first sequence being mixed, can be first by template, four methoxies
Base silane, ethyl alcohol, trimethylpentane and sour agent are mixed simultaneously, any two or three can also be mixed, be added it
He is uniformly mixed component.According to a preferred embodiment of the present invention, first template, ethyl alcohol and sour agent are uniformly mixed,
Then trimethylpentane is added to be uniformly mixed, then adds tetramethoxy-silicane and is uniformly mixed.
In the present invention, the dosage of the template, ethyl alcohol, trimethylpentane and tetramethoxy-silicane can be in larger model
Enclose interior variation, for example, template, ethyl alcohol, trimethylpentane and tetramethoxy-silicane molar ratio can be 1:100-500:
200-500:50-200, more preferably 1:180-400:250-400:70-150.
There is no particular limitation for the condition that the present invention is mixed to described first, for example, described first is mixed
Condition generally includes: temperature can be 10-60 DEG C, preferably 10-20 DEG C；Time can be 10-72 hours, preferably 10-30
Hour；PH value can be 1-7, preferably 3-6.It is a kind of excellent according to the present invention in order to be more advantageous to the uniform mixing between each substance
The embodiment of choosing, described first is mixed and carries out under agitation.
In the present invention, it can be 30- that the condition of the crystallization of the described first mixture being mixed, which includes: temperature,
150 DEG C, preferably 40-80 DEG C；Time can be 10-72 hours, preferably 20-30 hours.According to a kind of preferred embodiment party
Formula, the crystallization are implemented by hydrothermal crystallization method.
According to the present invention, in being mixed described second, the dosage of each substance can also carry out in a wider scope
Selection and adjustment, for example, the molar ratio of the ethyl orthosilicate, cetyl trimethylammonium bromide and ammonia can be 1:0.1-1:
0.1-5, preferably 1:0.2-0.5:1.5-3.5.
In the present invention, the ammonia is added preferably in the form of ammonium hydroxide.The ammonium hydroxide of the invention can be that concentration is 10-
25 weight %.
In the present invention, the second of ethyl orthosilicate, cetyl trimethylammonium bromide and ammonia is mixed process in water
In the presence of carry out.Preferably, part water is introduced in the form of ammonium hydroxide, and part water is added in the form of deionized water.In positive silicon
Acetoacetic ester, cetyl trimethylammonium bromide and ammonia second are mixed in system, and the molar ratio of ethyl orthosilicate and water can
Think 1:100-200, preferably 1:120-180.
There is no particular limitation for the condition that the present invention is mixed to described second, such as may include: the temperature of contact
It is 25-100 DEG C, preferably 50-90 DEG C；The time of contact is 2-8 hours, and preferably 3-7 hours, pH value can be 7.5-11,
Preferable ph is 8-10.Preferably, it second is mixed and carries out under stiring, in favor of the uniform mixing between each substance.
In the present invention, there is no particular limitation for the condition that the third is mixed, can be according to preparing the normal of silica gel
Rule technique suitably determines.For example, the condition that the third is mixed, which includes: temperature, to be 10-60 DEG C, preferably 20-
40℃；Time can be 1-5 hours, preferably 1-3 hours；PH value is 2-4.It is uniform mixed between each substance in order to be more advantageous to
It closes, the process that the third is mixed preferably carries out under agitation.
In the present invention, the dosage of the waterglass and inorganic acid can change in a big way.For example, the water glass
The weight ratio of glass and inorganic acid can be 3-6:1.
In the present invention, the waterglass is the aqueous solution of sodium metasilicate, and concentration can be 3-20 weight %, preferably
10-20 weight %.The inorganic acid can be various inorganic acids commonly used in the art, such as can for sulfuric acid, nitric acid and
One of hydrochloric acid is a variety of.The inorganic acid can use in pure form, can also be used in the form of its aqueous solution,
It is preferred that being used in the form of the aqueous solution of 3-20 weight %.The dosage of the inorganic acid is preferably so that contact of the waterglass with inorganic acid
The pH value of reaction system is 2-4.It should be noted that the weight of above-mentioned waterglass includes the content of wherein water.When described inorganic
Acid is as a solution in use, the weight of above-mentioned inorganic acid includes the content of wherein water.
According to the present invention, in step (4), the first mesoporous material filter cake, the second mesoporous material filter cake and silica gel filter
The dosage of cake can change in a big way, for example, relative to the first mesoporous material filter cake of 100 parts by weight and described
Total dosage of second mesoporous material filter cake, the dosage of the silica gel filter cake can be 1-200 parts by weight, preferably 20-180 weight
Part, more preferably 50-150 parts by weight；The weight ratio of the dosage of the first mesoporous material filter cake and the second mesoporous material filter cake
It can be 1:0.1-10, preferably 1:0.5-2.
In the present invention, ceramic filter is to be by a kind of collection filtering of core, deslagging, cleaning and regeneration of ceramic membrane element
The gas, liquid, solid separation of one and purification device.The purpose ceramic-film filter may include ceramic film component and ceramic membrane element,
The ceramic membrane element can be inorganic ceramic membrane element (referred to as inorganic ceramic membrane).Inorganic ceramic membrane typically refers to aoxidize
Aluminium, titanium oxide, zirconium oxide etc. through made of high temperature sintering with porous structure high technology ceramics filtering material, porous support layer,
Transition zone and microporous film layers are in asymmetric distribution, and filtering accuracy covers micro-filtration, ultrafiltration, nanofiltration.Ceramic membrane filter is a kind of " cross-flow
The fluid separation process of filtering " form: material liquid flow at high speed in membrane tube, driven by pressure containing the clarification of small molecule component
Penetrating fluid penetrates film along direction normal thereto outward, and the muddy concentrate containing macromolecular components is rejected by, so that fluid be made to reach
To the purpose of separation, concentration, purifying.The ceramic membrane can be commercially available, such as can be for purchased from Jiangsu my high-tech long
The inorganic ceramic membrane component of skill limited liability company, concrete specification can be selected according to the actual situation.Ceramic film component can
To be determined according to the concrete condition of ceramic membrane element and sample to be treated.
According to a kind of specific embodiment, the parameter of inorganic ceramic membrane component used herein includes: that membrane material is
Aluminium oxide, shape are that multichannel is cylindrical, channel number 19, channel diameter 4mm, length 1016mm, outer diameter (diameter)
For 30mm, effective membrane area is 0.24m2。
In the present invention, the condition that carrying out washing treatment is carried out using purpose ceramic-film filter includes: that operating pressure can be
2.5-3.9bar preferably 3-3.5bar；Circulation side into film pressure can be 3-5bar, preferably 3.5-4.5bar；Circulation side
Film pressure can be 2-2.8bar, preferably 2.2-2.6bar out；Circulation side crossflow velocity can be 4-5m/s, preferably 4-
4.5m/s；Osmotic lateral pressure is 0.3-0.5bar；Temperature can be 10-60 DEG C.Wherein, operating pressure is circulation side into film pressure
Go out the average value of film pressure with circulation side.
In the present invention, the first mesoporous material filter cake, the second mesoporous material filter cake and silica gel filter cake can be used first respectively
Purpose ceramic-film filter carry out carrying out washing treatment or three mixing after using ceramic membrane carry out carrying out washing treatment, then carry out ball milling and
Spray drying carries out ball milling after can also first mixing the first mesoporous material filter cake, the second mesoporous material filter cake and silica gel filter cake,
Ball milling product is subjected to carrying out washing treatment using purpose ceramic-film filter, is then spray-dried.
According to a kind of specific embodiment, in step (4), by the first mesoporous material filter cake, the second mesoporous material
Material filter cake and silica gel filter cake use purpose ceramic-film filter progress carrying out washing treatment respectively, and ball milling is carried out after then mixing and is done with spraying
It is dry, obtain spherical mesoporous composite material.
According to a kind of specific embodiment, in step (4), by the first mesoporous material filter cake, the second mesoporous material
Material filter cake and silica gel filter cake use purpose ceramic-film filter to carry out carrying out washing treatment respectively, then carry out ball milling respectively, carry out after mixing
Spray drying, obtains spherical mesoporous composite material.
According to a kind of specific embodiment, in step (4), by the first mesoporous material filter cake, the second mesoporous material
It uses purpose ceramic-film filter to carry out carrying out washing treatment after expecting filter cake and the mixing of silica gel filter cake, then carries out ball milling and spray drying, obtain
To spherical mesoporous composite material.
According to a kind of specific embodiment, in step (4), by the first mesoporous material filter cake, the second mesoporous material
Material filter cake and silica gel filter cake carry out ball milling respectively, then carry out carrying out washing treatment to ball milling product respectively using purpose ceramic-film filter,
It is spray-dried after the mixing of carrying out washing treatment product, obtains spherical mesoporous composite material.
According to a kind of specific embodiment, in step (4), by the first mesoporous material filter cake, the second mesoporous material
Material filter cake and silica gel filter cake carry out ball milling respectively, carry out carrying out washing treatment using purpose ceramic-film filter after then mixing ball milling product
And spray drying, obtain spherical mesoporous composite material.
According to a kind of specific embodiment, in step (4), by the first mesoporous material filter cake, the second mesoporous material
Ball milling is carried out after material filter cake and the mixing of silica gel filter cake, ball milling product is then subjected to carrying out washing treatment and spray using purpose ceramic-film filter
Mist is dry, obtains spherical mesoporous composite material.
Water can be used in carrying out washing treatment and/or alcohol (such as ethyl alcohol) carries out.A kind of preferred embodiment party according to the present invention
Formula, when the sodium ions content in the cleaning solution for detecting purpose ceramic-film filter is 0.02 weight % or less, template agent content less than 1
When weight %, it can stop filtering, obtain filter cake.
According to the present invention, in step (4), there is no particular limitation for the condition and concrete operation method of ball milling, Ke Yiwei
The conventional selection of this field.For example, the ball milling can carry out in the ball mill, the inner wall of ball grinder is preferred in the ball mill
For polytetrafluoroethyllining lining, the diameter of the abrading-ball in ball mill can be 2-3mm；The quantity of abrading-ball can be according to the big of ball grinder
Ball grinder that is small reasonably to be selected, being 50-150ml for size, usually can be used 1 abrading-ball；The material of the abrading-ball
Matter can be agate, polytetrafluoroethylene (PTFE) etc., preferably agate.The condition of the ball milling may include: that the revolving speed of abrading-ball can be
300-500r/min, the temperature in ball grinder can be 15-100 DEG C, and the time of ball milling can be 0.1-100 hours.
According to the present invention, in step (4), the spray drying can be implemented according to conventional methods.Pressure can be selected from
At least one of gentle flow type spray seasoning of spray drying process, centrifugal spray drying method.It is a kind of preferred according to the present invention
Embodiment, the spray drying use centrifugal spray drying method.The spray drying can carry out in atomizer.The spray
The dry condition of mist may include: that temperature is 100-300 DEG C, revolving speed 10000-15000r/min；Under preferable case, the spray
The dry condition of mist includes: that temperature is 150-250 DEG C, and the revolving speed of rotation is 11000-13000r/min.
In the preparation method of spherical mesoporous composite material in the prior art, the removing after spray drying is also typically included
The step of template, such as pass through calcination method removed template method.Since method of the invention carries out carrying out washing treatment using ceramic membrane,
So prepared by the present invention can not include the steps that calcining removed template method in the method for spherical mesoporous material.
In the present invention, the loaded catalyst can be prepared according to the various conventional methods in this field, as long as can be
The supported on carriers platinum component, tin component and sodium component.
The present invention also provides a kind of preparation methods of loaded catalyst, this method comprises: by carrier with containing water-soluble
Property platinum compounds, water-soluble tin compound and inorganic sodium mixed aqueous solution carry out co-impregnation, then remove aqueous solvent, it is dry
And it roasts.
Wherein, the carrier hereinbefore has been described, and details are not described herein.To the water-soluble platinum chemical combination in the present invention
There is no particular limitation for the selection of water-soluble platinum compound described in object, the water-soluble tin compound and the inorganic sodium.Example
Such as, the water-soluble platinum compound is at least one of chloroplatinic acid, ammonium chloroplatinate and platinum nitrate, preferably chloroplatinic acid and/or
Ammonium chloroplatinate, more preferably chloroplatinic acid；The water-soluble tin compound is tin tetrachloride；The inorganic sodium be sodium nitrate and/
Or sodium chloride.
In the present invention, the dosage of the water-soluble platinum compound, water-soluble tin compound and inorganic sodium can compared with
It is changed in a wide range of, for example, the dosage of the water-soluble platinum compound, water-soluble tin compound and inorganic sodium preparing
In obtained loaded catalyst, on the basis of the total weight of the catalyst, based on the element, the content of the platinum component is
0.2-0.5 weight %, the content of the tin component are 0.2-1.2 weight %, and the content of the sodium component is 0.3-0.8 weight
% is measured, the content of the carrier is 97.5-99.3 weight %.Under preferable case, the water-soluble platinum compound, water-soluble tin
The dosage for closing object and inorganic sodium makes in the loaded catalyst being prepared, using the total weight of the catalyst as base
Standard, based on the element, the content of the platinum component are 0.2-0.4 weight %, and the content of the tin component is 0.3-1 weight %, institute
The content for stating sodium component is 0.4-0.7 weight %, and the content of the carrier is 97.9-99.1 weight %.
In the present invention, the content of the platinum component in the loaded catalyst, tin component and sodium component is according to raw material
Feed ratio be calculated.
In the present invention, there is no particular limitation for the condition of the co-impregnation, such as the condition of the co-impregnation includes: temperature
Degree can be 15-60 DEG C, and the time can be 1-10 hours；Preferably, temperature is 25-40 DEG C, and the time is 2-8 hours.
In the present invention, to the embodiment for removing aqueous solvent, there is no particular limitation, can be conventional for this field
Embodiment, such as Rotary Evaporators can be used.
In the present invention, it can be condition conventional in the art that the condition of the drying, there is no particular limitation.Example
Such as, the condition of the drying, which includes: temperature, to be 90-160 DEG C, preferably 100-130 DEG C；Time can be 1-20h, preferably
For 2-5h.
In the present invention, it can be condition conventional in the art that the condition of the roasting, there is no particular limitation.Example
Such as, the condition of the roasting, which includes: temperature, to be 500-700 DEG C, preferably 550-650 DEG C；Time can be 2-15h, excellent
It is selected as 3-10h.
The present invention also provides the loaded catalysts prepared by the above method.The supported catalyst prepared by the method
Agent has biggish specific surface area and pore volume, and the dispersion situation of metal component on this carrier is preferable, so that the catalysis
Agent shows excellent catalytic performance in catalytic dehydrogenating reaction.
The present invention also provides application of the above-mentioned loaded catalyst in preparing propylene by dehydrogenating propane reaction.
The present invention also provides a kind of methods of preparing propylene by dehydrogenating propane, this method comprises: preparing third in dehydrogenating propane
Under conditions of alkene, propane is contacted with catalyst, the catalyst is above-mentioned loaded catalyst provided by the invention.
In the present invention, preparing propylene by dehydrogenating propane is carried out using catalyst provided by the invention, this field routine can be used
The condition used, under preferable case, this method further includes that diluent gas is added, and the diluent gas is usually hydrogen.Described third
Alkane is contacted with catalyst can carry out in fixed-bed quartz reactor, and the condition of the preparing propylene by dehydrogenating propane includes: third
The molar ratio of alkane and hydrogen can be 0.5-5:1, and reaction temperature can be 500-650 DEG C, and pressure can be 0.05-0.15MPa,
The mass space velocity of propane can be 1-10h-1.Pressure of the invention is gauge pressure.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples, used purpose ceramic-film filter is that my high-tech share has long purchased from Jiangsu
The inorganic ceramic membrane component and filling membrane area that the number of limit company is JWCM19*30 are 0.5m2Ceramic film component；It is inorganic
The parameter of ceramic membrane element includes: that shape is that multichannel is cylindrical, channel number 19, channel diameter 4mm, and length is
1016mm, outer diameter (diameter) are 30mm；
Rotary Evaporators are the production of IKA company, Germany, model RV10digital；
Drying box is Shanghai Yiheng Scientific Instruments Co., Ltd's production, model DHG-9030A；
Muffle furnace is the production of CARBOLITE company, model C WF1100.
The N of sample2Adsorption-desorption experiment is the ASAP2020-M+C type suction in the production of Micromeritics company, the U.S.
It is carried out on attached instrument, the specific surface area and pore volume of sample, which calculate, uses BET method.
Scanning electron microscope (SEM) analysis is enterprising in the scanning electron microscope of the model XL-30 purchased from FEI Co., the U.S.
Row；
Raw material, which feeds intake, when the content of each component passes through preparation in the dehydrogenation of preparation calculates determination；
Conversion of propane and selectivity are analyzed by gas-chromatography, and calculation method is as follows:
Amount/propane primary quantity × 100% of conversion of propane=reaction consumption propane；
The calculation method of Propylene Selectivity is as follows:
Amount/propane total flow × 100% of Propylene Selectivity=generation propylene consumption propane；
The calculation method of productivity of propylene is as follows:
Productivity of propylene=propylene actual production/propylene theoretical yield × 100%.
Embodiment 1
The present embodiment is for illustrating loaded catalyst provided by the invention and preparation method thereof and preparing propylene by dehydrogenating propane
Method
(1) spherical mesoporous composite material is prepared
1g (0.00017mol) template P123 and 1.69g (0.037mol) ethyl alcohol is added to the pH=4.4's of 28mL
In acetic acid and sodium acetate buffer solution, stirring to template is completely dissolved at 15 DEG C, and 6g (0.05mol) trimethylpentane is added
Into above-mentioned solution, after stirring 8h at 15 DEG C, then 2.13g (0.014mol) tetramethoxy-silicane is added in above-mentioned solution,
At 15 DEG C stir 20h after, transfer the solution into the reaction kettle of agate liner, 60 DEG C of baking oven crystallization for 24 hours after, suction filtration obtain first
Mesoporous material filter cake A11.
At 80 DEG C, cetyl trimethylammonium bromide and ethyl orthosilicate are added to the ammonium hydroxide that concentration is 25 weight %
In solution, deionized water is added, wherein the additional amount of ethyl orthosilicate is 1g, ethyl orthosilicate, cetyl trimethyl bromine
The molar ratio for changing ammonium, the ammonia in ammonium hydroxide and water is 1:0.37:2.8:142, and is stirred 4 hours at a temperature of 80 DEG C, then will be molten
Liquid filters, to the second mesoporous material filter cake A12.
It is the sulfuric acid solution of 12 weight % by waterglass and concentration that concentration is 15 weight % with weight ratio is that 5:1 is mixed
Merge haptoreaction 1.5 hours at 20 DEG C, then adjust pH value to 3 with the sulfuric acid that concentration is 98 weight %, then to obtaining
Reaction mass filtered, obtain silica gel filter cake B1.
5g filter cake A11,5g filter cake A12 and 10g filter cake B1 of above-mentioned preparation is mixed, mixture is used into ceramic membrane
Filter wash to sodium ions content is 0.02 weight %, and template agent content obtains spherical mesoporous composite material less than 1 weight %
Filter cake.Wherein, membrane module operating pressure is 3.3bar, and circulation side is 4bar into film pressure, and it is 2.5bar that circulation side, which goes out film pressure,
Circulation side crossflow velocity is 4m/s, and osmotic lateral pressure 0.3bar, temperature is 20 DEG C.The spherical mesoporous for preparing a parts by weight is compound
Material filter cake consumes 3 parts by weight of water.
Above-mentioned spherical mesoporous composite material filter cake is put into the ball grinder of 100mL, wherein the material of ball grinder is Ma
Nao, Material quality of grinding balls are agate, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 400r/min.Ball grinder is closed, in ball milling
Temperature is ball milling 5h at 60 DEG C in tank, and the slurry after ball milling is spray-dried at 200 DEG C in the case where revolving speed is 12000r/min, is obtained
Spherical mesoporous composite material C1.
Spherical mesoporous composite material C1 is characterized with XRD, scanning electron microscope and nitrogen adsorption instrument.
Fig. 1 is X-ray diffracting spectrum, wherein a is the XRD spectra of spherical mesoporous composite material C1, and abscissa is 2 θ, is indulged
Coordinate is intensity.The low-angle spectral peak occurred by XRD spectra is it is found that spherical mesoporous composite material C1 has mesoporous material institute peculiar
2D hexagonal hole road structure.
Fig. 2 is SEM scanning electron microscope (SEM) photograph.It can be seen from the figure that the microscopic appearance of spherical mesoporous composite material C1 is partial size
For 30-60 μm of microballoon, and its good dispersion property.
Fig. 3 is the graph of pore diameter distribution of spherical mesoporous composite material C1.It can be seen from the figure that it can be seen from the figure that ball
Shape mesoporous composite material C1 is distributed with porous structure, and duct is uniform.
The pore structure parameter of spherical mesoporous composite material C1 is as shown in table 1 below.
Table 1
*: the first most probable pore size, the second most probable pore size and third most probable pore size are separated with comma: according to by it is left extremely
Right sequence is successively the first most probable pore size, the second most probable pore size and third most probable pore size.
(2) preparation of loaded catalyst
By the H of 0.080g2PtCl6·6H2O, the SnCl of 0.207g4·5H2The NaNO of O and 0.185g3Be dissolved in 100ml go from
It in sub- water, is mixed with the above-mentioned 10g spherical mesoporous composite material C1 being prepared, it is small to continuously stir reaction 5 at room temperature
When.The aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product.It is 120 DEG C dry that solid product, which is placed in temperature,
It is 3 hours dry in dry case.Then place the product in Muffle furnace, temperature is 600 DEG C and roasts 6 hours, obtains loaded catalyst
D1。
The specific gravity of each component of loaded catalyst D1 are as follows: platinum component of the 0.3 weight % in terms of platinum element, 0.7 weight %
Tin component in terms of tin element, sodium component of the 0.5 weight % in terms of sodium element, remaining is spherical mesoporous composite material C1.
(3) preparing propylene by dehydrogenating propane
The loaded catalyst D1 of 0.5g is fitted into fixed-bed quartz reactor, control reaction temperature is 610 DEG C, reaction
Pressure is 0.1MPa, and propane: the molar ratio of hydrogen is 1:1, and propane mass space velocity is 3.0h-1, reaction time 50h.Reaction knot
Fruit is shown in Table 4.
Embodiment 2
The present embodiment is for illustrating loaded catalyst provided by the invention and preparation method thereof and preparing propylene by dehydrogenating propane
Method
(1) spherical mesoporous composite material is prepared
1g (0.00017mol) template P123 and 1.4g (0.03mol) ethyl alcohol is added to the second of the pH=4.4 of 28mL
In acid and sodium acetate buffer solution, stirring is completely dissolved to template at 10 DEG C, and 4.56g (0.04mol) trimethylpentane is added
Enter into above-mentioned solution, after stirring 8h at 10 DEG C, then 1.83g (0.012mol) tetramethoxy-silicane is added to above-mentioned solution
In, after stirring 30h at 10 DEG C, transfer the solution into the reaction kettle of agate liner, after 80 DEG C of baking oven crystallization 20h, suction filtration is obtained
First mesoporous material filter cake A21.
At 50 DEG C, cetyl trimethylammonium bromide and ethyl orthosilicate are added to the ammonium hydroxide that concentration is 25 weight %
In solution, deionized water is added, wherein the additional amount of ethyl orthosilicate is 1g, ethyl orthosilicate, cetyl trimethyl bromine
The molar ratio for changing ammonium, the ammonia in ammonium hydroxide and water is 1:0.5:1.5:180, and is stirred 7 hours at 50 °C, then by solution
It filters, to the second mesoporous material filter cake A22.
It is the sulfuric acid solution of 12 weight % by waterglass and concentration that concentration is 20 weight % with weight ratio is that 3:1 is mixed
Merge the haptoreaction 3h at 20 DEG C, then with the sulfuric acid adjustment pH value that concentration is 98 weight % to 4, the then reaction to obtaining
Material is filtered, and the filter cake B2 of silica gel is obtained.
6.7g filter cake A11,3.3g filter cake A12 and 15g filter cake B1 of above-mentioned preparation is mixed, mixture is used into pottery
It is 0.02 weight % that porcelain membrane filter, which is washed to sodium ions content, and it is compound to obtain spherical mesoporous less than 1 weight % for template agent content
Material filter cake.Wherein, membrane module operating pressure is 3bar, and circulation side is 3.5bar into film pressure, and circulation side goes out film pressure and is
2.5bar, circulation side crossflow velocity are 4.5m/s, and osmotic lateral pressure 0.4bar, temperature is 60 DEG C.
Above-mentioned spherical mesoporous composite material filter cake is put into the ball grinder of 100mL, wherein the material of ball grinder is Ma
Nao, Material quality of grinding balls are agate, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 500r/min.Ball grinder is closed, in ball milling
Temperature is ball milling 20h at 35 DEG C in tank, and the slurry after ball milling is spray-dried at 150 DEG C in the case where revolving speed is 13000r/min, is obtained
To spherical mesoporous composite material C2.
The pore structure parameter of spherical mesoporous composite material C2 is as shown in table 2 below.
Table 2
*: the first most probable pore size, the second most probable pore size and third most probable pore size are separated with comma: according to by it is left extremely
Right sequence is successively the first most probable pore size, the second most probable pore size and third most probable pore size.
(2) preparation of loaded catalyst
By the H of 0.053g2PtCl6·6H2O, the SnCl of 0.09g4·5H2The NaCl of O and 0.127g is dissolved in 50ml deionization
It in water, is mixed with the above-mentioned 10g spherical mesoporous composite material C2 being prepared, reaction 2 hours is continuously stirred under the conditions of 40 DEG C.
The aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product.Solid product is placed in the drying box that temperature is 100 DEG C
In, it is 5 hours dry.Then in Muffle furnace, temperature is 650 DEG C and roasts 3 hours, obtains loaded catalyst D2.
The specific gravity of loaded catalyst D2 each component are as follows: platinum component of the 0.2 weight % in terms of platinum element, 0.3 weight % with
The tin component of tin element meter, sodium component of the 0.4 weight % in terms of sodium element, remaining is spherical mesoporous composite material C2.
(3) preparing propylene by dehydrogenating propane
Preparing propylene by dehydrogenating propane is carried out according to the method for embodiment 1, unlike, it is substituted using loaded catalyst D2
Loaded catalyst D1 in embodiment 1.Reaction result is shown in Table 4.
Embodiment 3
The present embodiment is for illustrating loaded catalyst provided by the invention and preparation method thereof and preparing propylene by dehydrogenating propane
Method
(1) spherical mesoporous composite material is prepared
1g (0.00017mol) template P123 and 3.13g (0.068mol) ethyl alcohol is added to the pH=4.4's of 28mL
In acetic acid and sodium acetate buffer solution, stirring to template is completely dissolved at 20 DEG C, by 7.75g (0.068mol) trimethylpentane
It is added in above-mentioned solution, after stirring 8h at 20 DEG C, then 3.8g (0.025mol) tetramethoxy-silicane is added to above-mentioned solution
In, after stirring 10h at 20 DEG C, transfer the solution into the reaction kettle of agate liner, after 40 DEG C of baking oven crystallization 30h, suction filtration is obtained
First mesoporous material filter cake A31.
At 90 DEG C, cetyl trimethylammonium bromide and ethyl orthosilicate are added to the ammonium hydroxide that concentration is 25 weight %
In solution, deionized water is added, wherein the additional amount of ethyl orthosilicate is 1g, ethyl orthosilicate, cetyl trimethyl bromine
The molar ratio for changing ammonium, the ammonia in ammonium hydroxide and water is 1:0.2:3.5:120, and is stirred 3 hours at a temperature of 90 DEG C, then by solution
It filters, to the second mesoporous material filter cake A32.
It is the sulfuric acid solution of 12 weight % by waterglass and concentration that concentration is 10 weight % with weight ratio is that 4:1 is mixed
Merge the haptoreaction 1.5h at 30 DEG C, it is then anti-to what is obtained then with the sulfuric acid adjustment pH value that concentration is 98 weight % to 2
It answers material to be filtered, obtains the filter cake B3 of silica gel.
7g filter cake A31,14g filter cake A32 and 10g filter cake B3 of above-mentioned preparation is mixed, mixture is used into ceramics
It is 0.02 weight % that membrane filter, which is washed to sodium ions content, and template agent content obtains spherical mesoporous composite wood less than 1 weight %
Expect filter cake.Wherein, membrane module operating pressure is 3.4bar, and circulation side is 4.5bar into film pressure, and circulation side goes out film pressure and is
2.3bar, circulation side crossflow velocity are 4.2m/s, and osmotic lateral pressure 0.5bar, temperature is 40 DEG C.
Above-mentioned spherical mesoporous composite material filter cake is put into the ball grinder of 100mL, wherein the material of ball grinder is Ma
Nao, Material quality of grinding balls are agate, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 500r/min.Ball grinder is closed, in ball milling
Temperature is ball milling 10h at 50 DEG C in tank, and the slurry after ball milling is spray-dried at 250 DEG C in the case where revolving speed is 11000r/min, is obtained
To spherical mesoporous composite material C3.
The pore structure parameter of spherical mesoporous composite material C3 is as shown in table 3 below.
Table 3
*: the first most probable pore size, the second most probable pore size and third most probable pore size are separated with comma: according to by it is left extremely
Right sequence is successively the first most probable pore size, the second most probable pore size and third most probable pore size.
(2) preparation of loaded catalyst
By the H of 0.11g2PtCl6·6H2O, the SnCl of 0.296g4·5H2The NaNO of O and 0.259g3Be dissolved in 200ml go from
In sub- water, is mixed with the spherical mesoporous composite material C3 of the above-mentioned 10g being prepared, continuously stir reaction 8 under the conditions of 30 DEG C
Hour.The aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product.It is 100 DEG C that solid product, which is placed in temperature,
It is 5 hours dry in drying box.Then in Muffle furnace, temperature is 550 DEG C and roasts 10 hours, obtains loaded catalyst D3.
The specific gravity of loaded catalyst D3 each component are as follows: platinum component of the 0.4 weight % in terms of platinum element, 1 weight % is with tin
The tin component of element meter, sodium component of the 0.7 weight % in terms of sodium element, remaining is spherical mesoporous composite material C3.
(3) preparing propylene by dehydrogenating propane
Preparing propylene by dehydrogenating propane is carried out according to the method for embodiment 1, unlike, it is substituted using loaded catalyst D3
Loaded catalyst D1 in embodiment 1.Reaction result is shown in Table 4.
Embodiment 4
The present embodiment is for illustrating loaded catalyst provided by the invention and preparation method thereof and preparing propylene by dehydrogenating propane
Method
(1) preparation of carrier
Carrier is prepared according to the method for embodiment 1.
(2) preparation of loaded catalyst
It carries out according to the method for embodiment 1, unlike, platinum component, tin component are different with the content of sodium component.Specifically
Ground, H2PtCl6·6H2The dosage of O is 0.133g, SnCl4·5H2The dosage of O is 0.355g, NaNO3Dosage be 0.111g,
It is remaining same as Example 1, obtain loaded catalyst D4.
The specific gravity of loaded catalyst D4 each component are as follows: platinum component of the 0.5 weight % in terms of platinum element, 1.2 weight % with
The tin component of tin element meter, sodium component of the 0.3 weight % in terms of sodium element, remaining is spherical mesoporous composite material C1.
(3) preparing propylene by dehydrogenating propane
Preparing propylene by dehydrogenating propane is carried out according to the method for embodiment 1, unlike, it is substituted using loaded catalyst D4
Loaded catalyst D1 in embodiment 1.Reaction result is shown in Table 4.
Comparative example 1
The method that this comparative example is used to illustrate the loaded catalyst and preparing propylene by dehydrogenating propane of reference
By the H of 0.080g2PtCl6·6H2O, the SnCl of 0.207g4·5H2The NaNO of O and 0.185g3Be dissolved in 100ml go from
In sub- water, the commercially γ-Al of 10g is added2O3(the Qingdao wave silica-gel desiccant company trade mark is technical grade low specific surface area to carrier
The commercially available product of activated alumina, specific surface area 162m2/ g, pore volume 0.82cm3/ g) mixing, it continuously stirs at room temperature
Mix reaction 5 hours.The aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product.Solid product, which is placed in temperature, is
It is 3 hours dry in 120 DEG C of drying box.Then in Muffle furnace, temperature is 600 DEG C and roasts 6 hours, obtains supported catalyst
Agent DD1.
The specific gravity of each component of loaded catalyst DD1 are as follows: platinum component of the 0.3 weight % in terms of platinum element, 0.7 weight %
Tin component in terms of tin element, sodium component of the 0.5 weight % in terms of sodium element, remaining is γ-Al2O3Carrier.
(3) preparing propylene by dehydrogenating propane
Preparing propylene by dehydrogenating propane is carried out according to the method for embodiment 1, unlike, it is replaced using loaded catalyst DD1
For the loaded catalyst D1 in embodiment 1.Reaction result is shown in Table 4.
Comparative example 2
The method that this comparative example is used to illustrate the loaded catalyst and preparing propylene by dehydrogenating propane of reference
Carrier and loaded catalyst are prepared according to the method for embodiment 1, unlike, the method for not using co-impregnation,
But the method for using step impregnation prepares loaded catalyst.Specifically, by spherical mesoporous composite material C1 first in chloroplatinic acid
5h is impregnated in aqueous solution, after the spherical mesoporous composite material C1 after dipping is dried and is roasted according to the condition of embodiment 1,
5h is impregnated in the aqueous solution of tin tetrachloride and sodium nitrate again, is then dried and roasts according to the condition of embodiment 1, obtain
Loaded catalyst DD2.
The specific gravity of each component of loaded catalyst DD2 are as follows: platinum component of the 0.3 weight % in terms of platinum element, 0.7 weight %
Tin component in terms of tin element, sodium component of the 0.5 weight % in terms of sodium element, remaining is spherical mesoporous composite material C1.
(3) preparing propylene by dehydrogenating propane
Preparing propylene by dehydrogenating propane is carried out according to the method for embodiment 1, unlike, it is replaced using loaded catalyst DD2
For the loaded catalyst D1 in embodiment 1.Reaction result is shown in Table 4.
Table 4
| Propane average conversion (%) | Propylene average selectivity (%) | Propylene average yield (%) | |
| Embodiment 1 | 23 | 72 | 99 |
| Embodiment 2 | 19 | 70 | 95 |
| Embodiment 3 | 21 | 73 | 91 |
| Embodiment 4 | 17 | 68 | 87 |
| Comparative example 1 | 9 | 78 | 75 |
| Comparative example 2 | 13 | 61 | 60 |
From the results shown in Table 4, embodiment 1-4 is prepared using loaded catalyst of the invention for dehydrogenating propane
When the reaction of propylene, catalytic performance is substantially better than commercially available γ-Al2O3The catalyst (comparative example 1) of carrier preparation, propane
Average conversion and propylene average yield are all significantly improved.Illustrate that dehydrogenation preparation method provided by the invention can be real
Now improve the effect of dehydrogenation catalytic performance.Relative to comparative example 2 using the catalyst of step impregnation method preparation, the present invention
The preparation process of catalyst is simple, excellent catalytic effect.And it is obviously optimal using the effect of the embodiment 1-3 in preferred scope.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (24)
1. a kind of loaded catalyst, which includes platinum component, tin component and the sodium of carrier and load on the carrier
Component, which is characterized in that the carrier is spherical mesoporous composite material, and the spherical mesoporous composite material is using including following
What the method for step was prepared:
(1) template, tetramethoxy-silicane, ethyl alcohol, trimethylpentane and sour agent are carried out first to be mixed, and first is mixed
The mixture that splice grafting touches carries out crystallization and filtering, obtains the first mesoporous material filter cake；The template, ethyl alcohol, trimethyl
The molar ratio of pentane and tetramethoxy-silicane is 1:100-500:200-500:50-200；
(2) ethyl orthosilicate, cetyl trimethylammonium bromide and ammonia progress second is mixed, and second is mixed
Obtained mixture is filtered, and obtains the second mesoporous material filter cake；Ethyl orthosilicate, cetyl trimethylammonium bromide and ammonia
Molar ratio be 1:0.1-1:0.1-5；
(3) waterglass the mixture that third is mixed, and obtains after third is mixed is carried out with inorganic acid to carry out
Filter, obtains silica gel filter cake；The weight ratio of the waterglass and inorganic acid is 3-6:1；
(4) the first mesoporous material filter cake, the second mesoporous material filter cake and silica gel filter cake are subjected to ball milling respectively or after mixing, by ball
It grinds product and carries out carrying out washing treatment using purpose ceramic-film filter, be then spray-dried, obtain spherical mesoporous composite material；Or
Person,
First mesoporous material filter cake, the second mesoporous material filter cake and silica gel filter cake are used into purpose ceramic-film filter respectively or after mixing
Carrying out washing treatment is carried out, ball milling and spray drying is then carried out, obtains spherical mesoporous composite material；
Relative to the first mesoporous material filter cake of 100 parts by weight and total dosage of the second mesoporous material filter cake, the silica gel
The dosage of filter cake is 1-200 parts by weight, the weight ratio of the dosage of the first mesoporous material filter cake and the second mesoporous material filter cake
For 1:0.1-10；
The average grain diameter of the spherical mesoporous composite material is 20-60 μm, specific surface area 150-600m2/ g, pore volume 0.5-
1.8mL/g, aperture is in tri-modal distribution, and three peaks respectively correspond the first most probable pore size 5-15nm, the second most probable pore size 20-
40nm and third most probable pore size 45-60nm；
The preparation method of the loaded catalyst includes: by carrier and to contain water-soluble platinum compound, water-soluble tin compound
Co-impregnation is carried out with the mixed aqueous solution of inorganic sodium, then removes aqueous solvent, drying simultaneously roasts.
2. loaded catalyst according to claim 1, wherein the average grain diameter of the spherical mesoporous composite material is
40-50 μm, specific surface area 220-300m2/ g, pore volume 1.1-1.7mL/g, aperture is in tri-modal distribution, and three peaks are right respectively
Answer the first most probable pore size 6-9nm, the second most probable pore size 25-35nm and third most probable pore size 45-54nm.
3. loaded catalyst according to claim 1, wherein on the basis of the total weight of the catalyst, with element
Meter, the content of the platinum component are 0.2-0.5 weight %, and the content of the tin component is 0.2-1.2 weight %, the sodium component
Content be 0.3-0.8 weight %, the content of the carrier is 97.5-99.3 weight %.
4. loaded catalyst according to claim 1, wherein carry out the condition of carrying out washing treatment using purpose ceramic-film filter
It include: operating pressure for 2.5-3.9bar, circulation side is 3-5bar into film pressure, and it is 2-2.8bar that circulation side, which goes out film pressure, is followed
Ring side crossflow velocity is 4-5m/s；Osmotic lateral pressure is 0.3-0.5bar；Temperature is 10-60 DEG C.
5. loaded catalyst according to claim 1, wherein in step (4), relative to described in 100 parts by weight
Total dosage of first mesoporous material filter cake and the second mesoporous material filter cake, the dosage of the silica gel filter cake are 20-180 parts by weight,
The weight ratio of the dosage of the first mesoporous material filter cake and the second mesoporous material filter cake is 1:0.5-2.
6. loaded catalyst according to claim 5, wherein first mesoporous material relative to 100 parts by weight
Total dosage of filter cake and the second mesoporous material filter cake, the dosage of the silica gel filter cake are 50-150 parts by weight.
7. loaded catalyst according to claim 1, wherein in step (1), the template is triblock copolymer
Object polyoxyethylene-poly-oxypropylene polyoxyethylene；The acid agent is the acetic acid and sodium acetate buffer solution that pH value is 1-6.
8. loaded catalyst according to claim 1, wherein the template, ethyl alcohol, trimethylpentane and four methoxies
The molar ratio of base silane is 1:180-400:250-400:70-150.
9. loaded catalyst according to claim 1, wherein the described first condition being mixed includes: that temperature is
10-60 DEG C, the time is 10-72 hours, pH value 1-7；The condition packet of the crystallization of described first mixture being mixed
Include: temperature is 30-150 DEG C, and the time is 10-72 hours.
10. loaded catalyst according to claim 1, wherein in step (2), ethyl orthosilicate, cetyl three
The molar ratio of methyl bromide ammonium and ammonia is 1:0.2-0.5:1.5-3.5.
11. loaded catalyst according to claim 1, wherein the described second condition being mixed includes: that temperature is
25-100 DEG C, the time is 2-8 hours.
12. loaded catalyst according to claim 1, wherein the inorganic acid is one in sulfuric acid, nitric acid and hydrochloric acid
Kind is a variety of.
13. loaded catalyst according to claim 1, wherein the condition that the third is mixed includes: that temperature is
10-60 DEG C, the time is 1-5 hours, pH value 2-4.
14. loaded catalyst according to claim 1, wherein in step (4), the condition of the ball milling includes: mill
The revolving speed of ball is 300-500r/min, and the temperature in ball grinder is 15-100 DEG C, and the time of ball milling is 0.1-100h.
15. loaded catalyst according to claim 1, wherein the condition of the spray drying includes: that temperature is 100-
300 DEG C, revolving speed 10000-15000r/min.
16. a kind of method for preparing loaded catalyst described in any one of claim 1-15, which is characterized in that the party
Method includes: to be total to carrier and the mixed aqueous solution containing water-soluble platinum compound, water-soluble tin compound and inorganic sodium
Dipping, then removes aqueous solvent, and drying simultaneously roasts.
17. according to the method for claim 16, wherein the water-soluble platinum compound, water-soluble tin compound and inorganic
The dosage of sodium salt makes in the loaded catalyst being prepared, on the basis of the total weight of the catalyst, based on the element,
The content of the platinum component is 0.2-0.5 weight %, and the content of the tin component is 0.2-1.2 weight %, the sodium component
Content is 0.3-0.8 weight %, and the content of the carrier is 97.5-99.3 weight %.
18. according to the method for claim 16, wherein the condition of the co-impregnation includes: that temperature is 15-60 DEG C, the time
It is 1-10 hours.
19. according to the method for claim 16, wherein the condition of the roasting includes: that temperature is 500-700 DEG C, the time
It is 2-15 hours.
20. the loaded catalyst of the preparation of the method as described in any one of claim 16-19.
21. loaded catalyst described in any one of claim 1-15 and 20 is in preparing propylene by dehydrogenating propane reaction
Using.
22. a kind of method of preparing propylene by dehydrogenating propane, which is characterized in that this method comprises: in preparing propylene by dehydrogenating propane
Under the conditions of, propane is contacted with catalyst, which is characterized in that the catalyst is any one of claim 1-15 and 20 institute
The loaded catalyst stated.
23. according to the method for claim 22, wherein this method further includes that diluent gas hydrogen is added.
24. according to the method for claim 23, wherein the propane contacts in fixed-bed quartz reactor with catalyst
It carries out, the condition of the preparing propylene by dehydrogenating propane includes: that the molar ratio of propane and hydrogen is 0.5-5:1, and reaction temperature is
500-650 DEG C, pressure 0.05-0.15MPa, the mass space velocity of propane is 1-10h-1。
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