CN108855068A - The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane - Google Patents
The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane Download PDFInfo
- Publication number
- CN108855068A CN108855068A CN201710325437.6A CN201710325437A CN108855068A CN 108855068 A CN108855068 A CN 108855068A CN 201710325437 A CN201710325437 A CN 201710325437A CN 108855068 A CN108855068 A CN 108855068A
- Authority
- CN
- China
- Prior art keywords
- attapulgite
- filter cake
- propane
- supported catalyst
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 239000003054 catalyst Substances 0.000 title claims abstract description 137
- 239000001294 propane Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 73
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title abstract description 34
- 229960000892 attapulgite Drugs 0.000 claims abstract description 95
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 95
- 239000002131 composite material Substances 0.000 claims abstract description 78
- 239000012065 filter cake Substances 0.000 claims abstract description 71
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000002156 mixing Methods 0.000 claims abstract description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000000498 ball milling Methods 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000000047 product Substances 0.000 claims abstract description 37
- 239000000741 silica gel Substances 0.000 claims abstract description 32
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 32
- 239000013335 mesoporous material Substances 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 28
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 27
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 26
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011734 sodium Substances 0.000 claims abstract description 26
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 26
- 239000012528 membrane Substances 0.000 claims description 68
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 58
- 239000000919 ceramic Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000011148 porous material Substances 0.000 claims description 32
- 238000001694 spray drying Methods 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 25
- 238000000227 grinding Methods 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
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 17
- 235000019353 potassium silicate Nutrition 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 15
- 150000007522 mineralic acids Chemical class 0.000 claims description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 9
- 150000003058 platinum compounds Chemical class 0.000 claims description 9
- 159000000000 sodium salts Chemical class 0.000 claims description 9
- 150000003606 tin compounds Chemical class 0.000 claims description 9
- 230000002902 bimodal effect Effects 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000001354 calcination Methods 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
- 238000004519 manufacturing process Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000003085 diluting agent 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
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000243 solution Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- 239000012265 solid product Substances 0.000 description 8
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 230000005484 gravity Effects 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- -1 polypropylene Polymers 0.000 description 7
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000009295 crossflow filtration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 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
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical class [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- 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
- B01J35/60—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
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- 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
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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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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
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, and the carrier is attapulgite mesoporous composite material, and the attapulgite mesoporous composite material is prepared using method comprising the following steps：It prepares mesoporous material filter cake and prepares silica gel filter cake；Mesoporous material filter cake, silica gel filter cake and attapulgite are subjected to ball milling respectively or after mixing, ball milling product is subjected to carrying out washing treatment using purpose ceramic-film filter, the product that optionally washing is obtained mixes, and is then spray-dried, obtains attapulgite mesoporous composite material.Using the reaction of loaded catalyst catalysis preparing propylene by dehydrogenating propane of the invention, conversion of propane is high, and Propylene Selectivity is high.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a supported catalyst, a preparation method of the supported catalyst, application of the supported catalyst in a reaction for preparing propylene by propane dehydrogenation, and a method for preparing propylene by propane dehydrogenation.
Background
Propylene is a basic raw material of petrochemical industry and is mainly used for producing polypropylene, acrylonitrile, acetone, propylene oxide, acrylic acid, butanol and octanol and the like. Half of the propylene supply comes from refinery by-products and about 45% from steam cracking, a few other alternative technologies. In recent years, the demand of propylene is increasing year by year, and the traditional propylene production can not meet the demand of the chemical industry for propylene, so that the propylene yield increase becomes a great hot point for research. The dehydrogenation of propane to propylene is one of the main technologies for increasing the yield of propylene. For more than 10 years, the dehydrogenation of propane to prepare propylene has become an important process for the industrial production of propylene. The main catalysts for propane dehydrogenation are the chromium oxide/alumina catalyst in the Catofin process from ABB Lummus and the platinum tin/alumina catalyst in the Oleflex process from UOP. The chromium catalyst has lower requirements on raw material impurities and lower price compared with noble metals; however, the catalyst is easy to deposit carbon and deactivate, and needs to be regenerated every 15 to 30 minutes, and the chromium in the catalyst is heavy metal, so that the environmental pollution is serious; the platinum-tin catalyst has high activity and good selectivity, the reaction period can reach several days, the catalyst can bear harsher process conditions and is more environment-friendly, but the cost of the catalyst is higher due to the high price of noble metal platinum. The industrial production of the process for preparing propylene by propane dehydrogenation is over twenty years, and the research on dehydrogenation catalysts is more, but the current catalysts still have the defects of low propane conversion rate, easy inactivation and the like, and further improvement and perfection are needed. Therefore, it is of practical significance to develop a propane dehydrogenation catalyst having excellent performance.
Much work has been done by researchers to improve the reaction performance of propane dehydrogenation catalysts. Such as: (1) adopts a molecular sieve carrier to replace the traditional gamma-Al carrier2O3The carrier has good effect and comprises MFI type microporous molecular sieves (CN104307555A, CN101066532A, CN101380587A and CN101513613A), mesoporous MCM-41 molecular sieves (CN102389831A), mesoporous SBA-15 molecular sieves (CN101972664A and CN101972664B) and the like; (2) using calcium silicate salt para-gamma-Al2O3The carrier is modified and is impregnated with various active metal components and metal assistants (CN104368364A) step by step; (3) a composite oxide of alumina and magnesia is taken as a carrier, and various active metal components and metal assistants (CN104888818A) are impregnated step by step. The above-mentioned various methods for improving propane dehydrogenation catalysts lead to more complicated catalyst preparation process, increased preparation cost, prolonged preparation period, and even use of reagents or raw materials which are not favorable for environmental resources.
The attapulgite clay mineral has a clod-like structure and is gray, grey, light yellow or light green. The oil has gloss, light specific gravity, Mohs hardness of 2-3 grade, viscosity and plasticity when being wet, small drying shrinkage, no cracking, strong water absorption of over 150 percent, pH of about 8.5, large specific surface area of 350m due to multiple pore channels in the oil2More than g. Most of cations, water molecules and organic molecules with certain sizes can be directly adsorbed into the pore channels. Its electrochemical performance is stable. The attapulgite crystal with the magnification of 4 ten thousand times is rod-shaped and fibrous, the length of the attapulgite crystal is 0.5 to 5 microns, the width of the attapulgite crystal is 0.05 to 0.15 micron, and the ratio of the attapulgite crystal to the fiber is 2: type 1 clay minerals, two layers of silica tetrahedra sandwiching a layer of aluminoxy octahedra. Attapulgite clay mineral has properties of nanometer material, is natural nanometer structure mineral material with nanometer channel structure, and has great specific surface area and certain ion exchange property, so it is widely used as desiccant, moisture proof bead, adsorbent, catalyst carrier, antibacterial agent carrier, etc。
Disclosure of Invention
The invention aims to overcome the defects of complex preparation process and uneven dispersion of active metal components of the existing dehydrogenation catalyst, and provides a supported catalyst and a preparation method and application thereof. The supported catalyst of the invention is used for catalyzing the reaction of propane dehydrogenation to prepare propylene, the propane conversion rate is high, and the propylene selectivity is high.
Specifically, in a first aspect, the invention provides a supported catalyst, which comprises a carrier, and a platinum component, a tin component and a sodium component which are loaded on the carrier, wherein the carrier is an attapulgite mesoporous composite material, and the attapulgite mesoporous composite material is prepared by a method comprising the following steps:
(1) carrying out first mixing contact on ethyl orthosilicate, cetyl trimethyl ammonium bromide and ammonia, and filtering a mixture obtained by the first mixing contact to obtain a mesoporous material filter cake;
(2) carrying out second mixing contact on water glass and inorganic acid, and filtering a mixture obtained after the second mixing contact to obtain a silica gel filter cake;
(3) respectively or after mixing the mesoporous material filter cake, the silica gel filter cake and the attapulgite, carrying out ball milling on the ball-milled product, washing the ball-milled product by using a ceramic membrane filter, optionally mixing the washed products, and then carrying out spray drying to obtain the attapulgite mesoporous composite material; or,
respectively or after mixing the mesoporous material filter cake and the silica gel filter cake, washing the mixture by using a ceramic membrane filter, then respectively or after mixing the product obtained by washing and attapulgite, carrying out ball milling, optionally mixing the ball-milled product, and then carrying out spray drying to obtain the attapulgite mesoporous composite material.
In a second aspect, the present invention provides a method for preparing the above supported catalyst, the method comprising: the carrier is co-impregnated with a mixed aqueous solution containing a water-soluble platinum compound, a water-soluble tin compound and an inorganic sodium salt, then the solvent water is removed, dried and calcined.
In a third aspect, the invention provides a supported catalyst prepared by the above method.
In a fourth aspect, the invention provides the application of the supported catalyst in the reaction of preparing propylene by propane dehydrogenation.
In a fifth aspect, the present invention provides a process for the dehydrogenation of propane to produce propylene, the process comprising: under the condition of preparing propylene by propane dehydrogenation, contacting propane with a catalyst, wherein the catalyst is the supported catalyst provided by the invention. At present, a plate-and-frame filter press is usually used for removing impurities from a mesoporous material, but the mesoporous material obtained by the method has low catalytic activity after loading a catalyst, possibly because the impurities are not completely removed. In addition, the plate and frame filter press still has a lot of shortcomings, for example, plate and frame filter press area is great, simultaneously, because the plate and frame filter press is discontinuous operation, inefficiency, the operation room environment is relatively poor, has secondary pollution, and in addition, because use filter cloth, it is relatively poor to get rid of the impurity effect, and waste water can not recycle, wastes the water source very much in the washing process, simultaneously because the exhaust waste water can't be handled, causes environmental pollution and secondary waste again. The inventor of the invention finds that when the mesoporous composite material is washed by using the ceramic membrane, the obtained attapulgite mesoporous composite material has higher catalytic activity after loading the polypropylene catalyst, the propane conversion rate is high, and the propylene selectivity is high. The present inventors have completed the present invention based on the above findings.
The attapulgite mesoporous composite material is synthesized by using the attapulgite and the mesoporous composite material, and the advantages of the attapulgite mesoporous composite material and the mesoporous composite material can be organically combined. In addition, the supported catalyst and the method have the following advantages: (1) the separation process is simple, the separation efficiency is high, the number of matched devices is small, the energy consumption is low, and the operation is simple and convenient; (2) the cross-flow filtration is adopted, and the higher membrane surface flow rate is used, so that the accumulation of pollutants on the membrane surface is reduced, and the membrane flux is improved; (3) the ceramic membrane has good chemical stability, acid resistance, alkali resistance, organic solvent resistance and strong regeneration capacity, and can be suitable for the preparation process of the attapulgite mesoporous composite material; (4) the production of waste liquid is obviously reduced, and the method is green and environment-friendly. (5) According to the invention, the catalyst is prepared by using the silicon dioxide mesoporous material carrier with macropores, large specific surface area and large pore volume, and the structural characteristics are favorable for good dispersion of metal components on the surface of the carrier, so that the prepared propane dehydrogenation catalyst has excellent performance; (6) the co-impregnation method is adopted to replace the conventional step-by-step impregnation method, the preparation process is simple, the conditions are easy to control, and the product repeatability is good; (7) the catalyst provided by the invention shows good catalytic performance when used for preparing propylene by propane dehydrogenation. High propane conversion rate, high propylene selectivity and good catalyst stability.
Drawings
FIG. 1 is an X-ray diffraction pattern of attapulgite mesoporous composite C1 in example 1;
FIG. 2 is an SEM scanning electron micrograph of an attapulgite mesoporous composite material C1 in example 1;
fig. 3 is a pore size distribution diagram of the attapulgite mesoporous composite material C1 in example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a supported catalyst, which comprises a carrier, and a platinum component, a tin component and a sodium component which are loaded on the carrier, wherein the carrier is an attapulgite mesoporous composite material, and the attapulgite mesoporous composite material is prepared by a method comprising the following steps:
(1) carrying out first mixing contact on ethyl orthosilicate, cetyl trimethyl ammonium bromide and ammonia, and filtering a mixture obtained by the first mixing contact to obtain a mesoporous material filter cake;
(2) carrying out second mixing contact on water glass and inorganic acid, and filtering a mixture obtained after the second mixing contact to obtain a silica gel filter cake;
(3) respectively or after mixing the mesoporous material filter cake, the silica gel filter cake and the attapulgite, carrying out ball milling on the ball-milled product, washing the ball-milled product by using a ceramic membrane filter, optionally mixing the washed products, and then carrying out spray drying to obtain the attapulgite mesoporous composite material; or,
respectively or after mixing the mesoporous material filter cake and the silica gel filter cake, washing the mixture by using a ceramic membrane filter, then respectively or after mixing the product obtained by washing and attapulgite, carrying out ball milling, optionally mixing the ball-milled product, and then carrying out spray drying to obtain the attapulgite mesoporous composite material.
In the invention, the average grain diameter of the attapulgite mesoporous composite material is 20-60 mu m, and the specific surface area is 150-600m2The pore volume is 0.5-1.5mL/g, the pore diameters are distributed in a bimodal mode, and the bimodal mode corresponds to the first most probable pore diameter of 5-9nm and the second most probable pore diameter of 10-40nm respectively.
Preferably, the average particle diameter of the attapulgite mesoporous composite material is 40-50 μm, and the specific surface area is 150-200m2The pore volume is 0.8-1.2mL/g, the pore diameters are distributed in a bimodal mode, and the bimodal mode corresponds to the first most probable pore diameter of 6-8nm and the second most probable pore diameter of 20-30nm respectively.
In the invention, the specific surface area, the pore volume and the pore diameter of the attapulgite mesoporous composite material can be measured according to a nitrogen adsorption method.
According to the present invention, in the supported catalyst, the contents of the platinum component, the tin component, the sodium component and the carrier may vary within a wide range, for example, the content of the platinum component may be 0.2 to 0.5% by weight, the content of the tin component may be 0.2 to 1.2% by weight, the content of the sodium component may be 0.3 to 0.8% by weight, and the content of the carrier may be 97.5 to 99.3% by weight, in terms of element, based on the total weight of the catalyst. In order to provide a dehydrogenation catalyst with better catalytic performance and reduce the preparation cost of the dehydrogenation catalyst, it is preferable that the content of the platinum component is 0.2 to 0.4 wt%, the content of the tin component is 0.3 to 1 wt%, the content of the sodium component is 0.4 to 0.7 wt%, and the content of the carrier is 97.9 to 99.1 wt%, calculated as elements, based on the total weight of the catalyst.
According to the invention, in step (1), the amounts of the individual substances can be selected and adjusted within wide limits. For example, the molar ratio of ethyl orthosilicate, cetyltrimethylammonium bromide, and ammonia may be 1: 0.1-1: 0.1 to 5, preferably 1: 0.2-0.5: 1.5-3.5.
In the present invention, the ammonia is preferably added in the form of aqueous ammonia. The aqueous ammonia of the present invention may be present in a concentration of 10 to 25% by weight.
In the present invention, the first mixed contacting process of ethyl orthosilicate, cetyltrimethylammonium bromide and ammonia is carried out in the presence of water. Preferably, part of the water is introduced in the form of aqueous ammonia and part of the water is added in the form of deionized water. In the first mixed contact system of tetraethoxysilane, hexadecyl trimethyl ammonium bromide and ammonia, the molar ratio of tetraethoxysilane to water can be 1:100-200, and preferably 1: 120-180.
In the present invention, the conditions of the first mixing contact are not particularly limited, and may include, for example: the contact temperature is 25-100 ℃, preferably 50-90 ℃; the contact time is 2-8 hours, preferably 3-7 hours, and the pH may be 7.5-11, preferably 8-10. Preferably, the first mixing contact is carried out under agitation to facilitate uniform mixing between the substances.
According to the present invention, in the step (2), the weight ratio of the amount of the water glass to the inorganic acid is not particularly limited and may be appropriately determined according to a conventional process for preparing silica gel. Preferably, the weight ratio of the water glass to the inorganic acid may be 3-6: 1. The weight of the water glass includes the water content therein. When the inorganic acid is used in the form of a solution, the weight of the inorganic acid includes the amount of water therein.
In the present invention, the conditions of the second mixing contact are not particularly limited and may be appropriately determined according to the conventional processes for preparing silica gel. Preferably, the conditions of the second mixing contact include: the temperature can be 10-60 ℃, preferably 20-40 ℃; the time may be 1 to 5 hours, preferably 1.5 to 3 hours; the pH value is 2-4. In order to further facilitate uniform mixing between the substances, the second mixing contact is preferably carried out under stirring conditions.
The water glass is an aqueous solution of sodium silicate, and the concentration thereof may be 10 to 50% by weight, preferably 12 to 30% by weight.
According to the present invention, the inorganic acid may be various inorganic acids conventionally used in the art, and for example, may be at least one of sulfuric acid, nitric acid and hydrochloric acid. The inorganic acid may be used in a pure form or in the form of an aqueous solution thereof. The inorganic acid is preferably used in such an amount that the pH of the contact reaction system of the water glass and the inorganic acid is 2 to 4.
In the invention, the ceramic filter is a gas, liquid and solid separation and purification device which integrates filtration, slag discharge, cleaning and regeneration and takes a ceramic membrane element as a core. The ceramic membrane filter may include a ceramic membrane module and a ceramic membrane element, and the ceramic membrane element may be an inorganic ceramic membrane element (inorganic ceramic membrane for short). The inorganic ceramic membrane is a precise ceramic filter material with a porous structure, which is usually formed by sintering alumina, titanium oxide, zirconium oxide and the like at high temperature, a porous supporting layer, a transition layer and a microporous membrane layer are asymmetrically distributed, and the filtering precision covers micro-filtration, ultra-filtration and nano-filtration. Ceramic membrane filtration is a form of "cross-flow filtration" of fluid separation process: the raw material liquid flows at high speed in the membrane tube, the clarified penetrating fluid containing small molecular components penetrates through the membrane outwards along the direction vertical to the clear penetrating fluid under the drive of pressure, and the turbid concentrated solution containing large molecular components is intercepted by the membrane, so that the purposes of separating, concentrating and purifying the fluid are achieved. The ceramic membrane can be obtained commercially, for example, an inorganic ceramic membrane element obtained from york jiugu high-tech co. The ceramic membrane module may be determined according to the particular circumstances of the ceramic membrane element and the sample to be treated.
According to a specific embodiment, the parameters of the inorganic ceramic membrane elements used in the present invention include: the membrane is made of alumina, and has a shape of multi-channel cylindrical, the number of channels is 19, the diameter of the channel is 4mm, the length is 1016mm, the outer diameter (diameter) is 30mm, and the effective membrane area is 0.24m2。
In the present invention, the conditions for the washing treatment using the ceramic membrane filter include: the operating pressure can be from 2.5 to 3.9bar, preferably from 3 to 3.5 bar; the membrane pressure on the side of the circulation may be from 3 to 5bar, preferably from 3.5 to 4.5 bar; the pressure of the membrane at the circulating side can be 2-2.8bar, preferably 2.2-2.6 bar; the flow rate of the circulating side membrane surface can be 4-5m/s, and is preferably 4-4.5 m/s; the pressure of the permeation side is 0.3-0.5 bar; the temperature may be 10-60 ℃. Wherein the operating pressure is the average of the cycle side membrane inlet pressure and the cycle side membrane outlet pressure.
According to the invention, in step (3), "optionally mixing the products obtained by washing" means: when the ball-milled products are separately washed using a ceramic membrane filter, it is necessary to mix the washed products and then spray-dry the mixture. When the mesoporous material filter cake, the silica gel filter cake and the attapulgite are mixed and ball-milled, the material obtained by washing the product after ball milling is the mixture, and the step of mixing the washing materials is not included. Similarly, "optionally mixing the ball milled product" means: when the washed product and attapulgite are respectively subjected to ball milling, the ball-milled product needs to be mixed and then spray-dried. When the washed product is mixed with attapulgite and then ball-milled, the step of mixing the ball-milled product is not included.
According to a specific implementation mode, in the step (3), the mesoporous material filter cake and the silica gel filter cake are respectively washed by using a ceramic membrane filter, and then the product obtained by washing is mixed with attapulgite and then is subjected to ball milling and spray drying to obtain the attapulgite mesoporous composite material.
According to a specific embodiment, in the step (3), the mesoporous material filter cake and the silica gel filter cake are respectively washed by using a ceramic membrane filter, then are respectively subjected to ball milling, and the ball-milled product is mixed with attapulgite and then is subjected to spray drying, so as to obtain the attapulgite mesoporous composite material.
According to a specific implementation mode, in the step (3), the mesoporous material filter cake and the silica gel filter cake are mixed and then washed by using a ceramic membrane filter, and then the product obtained by washing is mixed with attapulgite and then subjected to ball milling and spray drying to obtain the attapulgite mesoporous composite material.
According to a specific implementation mode, in the step (3), the mesoporous material filter cake, the silica gel filter cake and the attapulgite are respectively subjected to ball milling, then the ball-milled products are respectively subjected to washing treatment by using a ceramic membrane filter, and the washing treatment products are mixed and then subjected to spray drying to obtain the attapulgite mesoporous composite material.
According to a specific implementation mode, in the step (3), the mesoporous material filter cake, the silica gel filter cake and the attapulgite are respectively subjected to ball milling, and then the ball-milled products are mixed, washed by using a ceramic membrane filter and subjected to spray drying to obtain the attapulgite mesoporous composite material.
According to a specific implementation mode, in the step (3), the mesoporous material filter cake, the silica gel filter cake and the attapulgite are mixed and then ball-milled, and then the ball-milled product is washed by using a ceramic membrane filter and is spray-dried to obtain the attapulgite mesoporous composite material.
The washing treatment may be performed using water and/or an alcohol (e.g., ethanol). According to a preferred embodiment of the present invention, when the content of sodium ions in the washing liquid of the ceramic membrane filter is detected to be 0.02 wt% or less and the content of the template agent is detected to be less than 1 wt%, the filtration is stopped to obtain a filter cake.
According to the present invention, in the step (3), the amounts of the mesoporous material filter cake, the silica gel filter cake and the attapulgite may vary within a wide range, for example, the silica gel filter cake may be used in an amount of 1 to 200 parts by weight, preferably 20 to 180 parts by weight, more preferably 50 to 150 parts by weight, relative to 100 parts by weight of the mesoporous material filter cake; the attapulgite can be used in an amount of 1-200 parts by weight, preferably 20-180 parts by weight, more preferably 50-150 parts by weight.
According to the present invention, in the step (3), the conditions and the specific operation method of the ball milling are not particularly limited and may be conventionally selected in the art. For example, the ball milling may be carried out in a ball mill in which the inner walls of the milling bowl are preferably lined with polytetrafluoroethylene and the grinding balls in the ball mill may have a diameter of 2-3 mm; the number of the grinding balls can be reasonably selected according to the size of the ball milling tank, and 1 grinding ball can be generally used for the ball milling tank with the size of 50-150 ml; the material of the grinding ball can be agate, polytetrafluoroethylene and the like, and agate is preferred. The ball milling conditions may include: the rotation speed of the grinding ball can be 300-500r/min, the temperature in the ball milling tank can be 15-100 ℃, and the ball milling time can be 0.1-100 hours.
According to the present invention, in step (3), the spray drying may be carried out according to a conventional method. May be at least one selected from the group consisting of a pressure spray drying method, a centrifugal spray drying method and a pneumatic spray drying method. According to a preferred embodiment of the present invention, the spray drying is a centrifugal spray drying method. The spray drying may be carried out in an atomizer. The conditions of the spray drying may include: the temperature is 100-300 ℃, and the rotating speed is 10000-15000 r/min; preferably, the spray drying conditions include: the temperature is 150-250 ℃, and the rotating speed is 11000-13000 r/min.
The preparation method of the mesoporous composite material in the prior art usually further comprises a step of removing the template agent after spray drying, for example, removing the template agent by a calcination method. Because the method adopts the ceramic membrane for washing treatment, the method for preparing the attapulgite mesoporous composite material can not comprise the step of calcining to remove the template agent.
In the present invention, the supported catalyst may be prepared according to various conventional methods in the art as long as it can support a platinum component, a tin component and a sodium component on the carrier.
The invention also provides a preparation method of the supported catalyst, which comprises the following steps: the carrier is co-impregnated with a mixed aqueous solution containing a water-soluble platinum compound, a water-soluble tin compound and an inorganic sodium salt, then the solvent water is removed, dried and calcined.
Wherein the carrier is described above, and is not described herein again. In the present invention, there is no particular limitation on the selection of the water-soluble platinum compound, the water-soluble tin compound, and the inorganic sodium salt. For example, the water-soluble platinum compound is at least one of chloroplatinic acid, ammonium chloroplatinate and platinum nitrate, preferably chloroplatinic acid and/or ammonium chloroplatinate, and more preferably chloroplatinic acid; the water-soluble tin compound is tin tetrachloride; the inorganic sodium salt is sodium nitrate and/or sodium chloride.
In the present invention, the amounts of the water-soluble platinum compound, the water-soluble tin compound and the inorganic sodium salt may vary within a wide range, and for example, the amounts of the water-soluble platinum compound, the water-soluble tin compound and the inorganic sodium salt are such that in the prepared supported catalyst, the content of the platinum component is 0.2 to 0.5% by weight, the content of the tin component is 0.2 to 1.2% by weight, the content of the sodium component is 0.3 to 0.8% by weight and the content of the carrier is 97.5 to 99.3% by weight, in terms of elements, based on the total weight of the catalyst. Preferably, the water-soluble platinum compound, the water-soluble tin compound and the inorganic sodium salt are used in such amounts that, in the prepared supported catalyst, the content of the platinum component is 0.2 to 0.4% by weight, the content of the tin component is 0.3 to 1% by weight, the content of the sodium component is 0.4 to 0.7% by weight and the content of the carrier is 97.9 to 99.1% by weight, in terms of elements, based on the total weight of the catalyst.
In the invention, the contents of the platinum component, the tin component and the sodium component in the supported catalyst are calculated according to the charge ratio of raw materials.
In the present invention, the conditions of the co-impregnation are not particularly limited, and for example, the conditions of the co-impregnation include: the temperature can be 15-60 ℃, and the time can be 1-10 hours; preferably, the temperature is 25-40 ℃ and the time is 2-8 hours.
In the present invention, the solvent water removal method is not particularly limited, and may be a method conventionally used in the art, for example, a rotary evaporator may be used.
In the present invention, the drying conditions are not particularly limited, and may be those conventional in the art. For example, the drying conditions include: the temperature can be 90-160 ℃, and preferably 100-130 ℃; the time can be 1 to 20 hours, preferably 2 to 5 hours.
In the present invention, the conditions for the calcination are not particularly limited, and may be those conventionally used in the art. For example, the conditions for the calcination include: the temperature can be 500-700 ℃, preferably 550-650 ℃; the time can be 2 to 15 hours, preferably 3 to 10 hours.
The invention also provides a supported catalyst prepared by the method. The supported catalyst prepared by the method has large specific surface area and pore volume, and the dispersion condition of the metal component on the carrier is good, so that the catalyst shows excellent catalytic performance in catalytic dehydrogenation reaction.
The invention also provides the application of the supported catalyst in the reaction of preparing propylene by propane dehydrogenation.
The invention also provides a method for preparing propylene by propane dehydrogenation, which comprises the following steps: under the condition of preparing propylene by propane dehydrogenation, propane is contacted with a catalyst, and the catalyst is the supported catalyst provided by the invention.
In the present invention, the catalyst provided by the present invention can be used for propane dehydrogenation to prepare propylene by using the conditions conventionally used in the art, and preferably, the method further comprises adding a diluent gas, wherein the diluent gas is usually hydrogen. The contacting of the propane with the catalyst may be carried out in a fixed bed quartz reactor, and the conditions for the dehydrogenation of propane to produce propylene include: the molar ratio of propane to hydrogen may be from 0.5 to 5: 1, the reaction temperature can be 500-650 ℃, the pressure can be 0.05-0.15MPa, and the mass space velocity of the propane can be 1-10h-1. The pressures of the present invention are gage pressures.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the ceramic membrane filters used were inorganic ceramic membrane elements of JWCM19 x 30, available from Kyoto Jiuwu high-tech Co., Ltd., and the packing membrane area was 0.5m2The ceramic membrane module of (a); the parameters of the inorganic ceramic membrane element include: the shape is a multi-channel cylinder, the number of channels is 19, the diameter of the channel is 4mm, the length is 1016mm, and the outer diameter (diameter) is 30 mm;
the rotary evaporator is produced by German IKA company, and the model is RV10 digital;
the drying box is produced by Shanghai-Hengchun scientific instruments Co., Ltd, and is of a type DHG-9030A;
the muffle furnace is manufactured by CARBOLITE corporation, model CWF 1100.
N of the sample2The adsorption-desorption experiments were carried out on an adsorption apparatus model ASAP2020-M + C manufactured by Micromeritics, USA, and BET method was used for the calculation of the specific surface area and pore volume of the sample.
Scanning Electron Microscope (SEM) analysis was performed on a scanning electron microscope model XL-30 available from FEI, USA;
the content of each component in the prepared dehydrogenation catalyst is determined by calculating the raw material feeding during preparation;
propane conversion and selectivity were analyzed by gas chromatography and calculated as follows:
propane conversion ═ amount of propane consumed by the reaction/initial amount of propane × 100%;
the propylene selectivity was calculated as follows:
propylene selectivity is the amount of propane consumed to form propylene/total propane consumption × 100%;
the propylene yield was calculated as follows:
the propylene yield was determined as the actual yield of propylene/theoretical yield of propylene × 100%.
Example 1
This example illustrates the supported catalyst, the preparation method thereof, and the method for preparing propylene by propane dehydrogenation provided by the present invention
(1) Preparation of attapulgite mesoporous composite material
Adding hexadecyl trimethyl ammonium bromide and ethyl orthosilicate into an ammonia water solution with the concentration of 25 weight percent at the temperature of 80 ℃, and then adding deionized water, wherein the adding amount of the ethyl orthosilicate is 1g, and the mol ratio of ammonia to water in the ethyl orthosilicate, the hexadecyl trimethyl ammonium bromide and the ammonia water is 1: 0.37: 2.8: 142 and stirring for 4 hours at the temperature of 80 ℃, and then carrying out suction filtration on the solution to obtain a mesoporous material filter cake A1.
Mixing 15 wt% water glass and 12 wt% sulfuric acid solution according to the weight ratio of water glass to sulfuric acid of 5: 1, stirring and reacting for 2 hours at 30 ℃, adjusting the pH of the obtained reaction product to 3 by using sulfuric acid with the concentration of 98 weight percent, and then carrying out suction filtration on the reaction material to obtain a silica gel filter cake B1.
Mixing 10g of the filter cake A1 and 10g of the filter cake B1, and washing the mixture by using a ceramic membrane filter until the content of sodium ions is 0.02 wt% and the content of a template agent is less than 1 wt%, thereby obtaining the mesoporous composite material filter cake. Wherein the operating pressure of the membrane module is 3.3bar, the pressure of the membrane at the circulating side is 4bar, the pressure of the membrane at the circulating side is 2.5bar, the flow rate of the membrane surface at the circulating side is 4m/s, the pressure of the permeation side is 0.3bar, and the temperature is 20 ℃.3 parts by weight of water is consumed for preparing one part by weight of the mesoporous composite material filter cake.
And (2) putting 10g of the mesoporous composite filter cake and 10g of attapulgite into a 100ml ball milling tank, wherein the ball milling tank is made of polytetrafluoroethylene, the grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, and the rotating speed is 400 r/min. And (3) sealing the ball milling tank, carrying out ball milling for 5h in the ball milling tank at the temperature of 60 ℃, and carrying out spray drying on the ball-milled slurry at the temperature of 200 ℃ at the rotating speed of 12000r/min to obtain the attapulgite mesoporous composite material C1.
And (3) characterizing the attapulgite mesoporous composite material C1 by using a scanning electron microscope and a nitrogen adsorption instrument.
FIG. 1 is an X-ray diffraction pattern with 2 θ on the abscissa and intensity on the ordinate. The small-angle spectrum peak of the XRD spectrogram shows that the XRD spectrogram of the attapulgite mesoporous composite material C1 has a 2D hexagonal pore structure which is unique to mesoporous materials.
FIG. 2 is an SEM (scanning Electron microscope) image, and it can be seen from FIG. 1 that the micro-morphology of the attapulgite mesoporous composite material C1 is microspheres with the particle size of 30-60 μm, and the dispersion performance is good.
Fig. 3 is a pore size distribution diagram of attapulgite mesoporous composite material C1. As can be seen from the figure, the attapulgite mesoporous composite material C1 has a double-pore distribution structure and uniform pore channels.
The pore structure parameters of the attapulgite mesoporous composite material C1 are shown in the following table 1.
TABLE 1
*: the first most probable aperture and the second most probable aperture are separated by a comma: the first most probable aperture and the second most probable aperture are arranged in the order from left to right.
(2) Preparation of Supported catalysts
0.080g of H2PtCl6·6H2O, 0.207g SnCl4·5H2O and 0.185g NaNO3Dissolving in 100ml deionized water, mixing with the prepared attapulgite mesoporous composite material C1 of 10g, and continuously stirring and reacting for 5 hours at room temperature. And (4) evaporating the solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 120 ℃ for 3 hours. And then placing the product in a muffle furnace, and roasting for 6 hours at the temperature of 600 ℃ to obtain the supported catalyst D1.
The specific gravity of each component of the supported catalyst D1 is as follows: 0.3 percent of platinum component calculated by platinum element, 0.7 percent of tin component calculated by tin element, 0.5 percent of sodium component calculated by sodium element, and the balance of attapulgite mesoporous composite material C1.
(3) Dehydrogenation of propane to propylene
0.5g of the supported catalyst D1 was charged to a fixed bed quartzIn the reactor, the reaction temperature was controlled at 610 ℃, the reaction pressure was 0.1MPa, and the reaction pressure was controlled at propane: the molar ratio of hydrogen is 1:1, and the mass space velocity of propane is 3.0h-1The reaction time is 50 h. The reaction results are shown in Table 4.
Example 2
This example illustrates the supported catalyst, the preparation method thereof, and the method for preparing propylene by propane dehydrogenation provided by the present invention
(1) Preparation of attapulgite mesoporous composite material
Adding hexadecyl trimethyl ammonium bromide and ethyl orthosilicate into an ammonia water solution with the concentration of 25 weight percent at 50 ℃, and adding deionized water, wherein the adding amount of the ethyl orthosilicate is 1g, and the mol ratio of ammonia to water in the ethyl orthosilicate, the hexadecyl trimethyl ammonium bromide and the ammonia water is 1: 0.5: 1.5: 180, stirring for 7 hours at the temperature of 50 ℃, and then carrying out suction filtration on the solution to obtain a mesoporous material filter cake A2.
Mixing 15 wt% water glass and 12 wt% sulfuric acid solution according to the weight ratio of water glass to sulfuric acid of 4: 1, stirring and reacting for 1.5 hours at 40 ℃, adjusting the pH of the obtained reaction product to 2 by using sulfuric acid with the concentration of 98 weight percent, and then carrying out suction filtration on the reaction material to obtain a silica gel filter cake B2.
And respectively washing the 20 g of filter cake A2 and the 30g of filter cake B2 by using a ceramic membrane filter until the content of sodium ions is 0.02 wt% and the content of a template agent is less than 1 wt%, thus obtaining the mesoporous composite material filter cake. Wherein the operating pressure of the membrane module is 3bar, the pressure of the membrane at the circulating side is 3.5bar, the pressure of the membrane at the circulating side is 2.5bar, the flow rate of the membrane surface at the circulating side is 4.5m/s, the pressure of the permeation side is 0.4bar, and the temperature is 60 ℃.
And (3) putting the mesoporous composite filter cake and 10g of attapulgite into a 100mL ball milling tank, wherein the ball milling tank is made of agate, the grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, and the rotating speed is 500 r/min. Sealing the ball milling tank, ball milling for 0.5h in the ball milling tank at the temperature of 80 ℃, and spray drying the ball milled slurry at the temperature of 250 ℃ at the rotating speed of 11000r/min to obtain the attapulgite mesoporous composite material C2.
The pore structure parameters of the attapulgite mesoporous composite material C2 are shown in the following table 2.
TABLE 2
*: the first most probable aperture and the second most probable aperture are separated by a comma: the first most probable aperture and the second most probable aperture are arranged in the order from left to right.
(2) Preparation of Supported catalysts
0.053g of H2PtCl6·6H2O, 0.09g of SnCl4·5H2Dissolving O and 0.127g of NaCl in 50ml of deionized water, mixing with 10g of the attapulgite mesoporous composite material C2 prepared in the above, and continuously stirring and reacting for 2 hours at 40 ℃. And (4) evaporating the solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 100 ℃ for 5 hours. Then calcined in a muffle furnace at 650 ℃ for 3 hours to obtain the supported catalyst D2.
The specific gravity of each component of the supported catalyst D2 is as follows: 0.2 percent of platinum component calculated by platinum element, 0.3 percent of tin component calculated by tin element, 0.4 percent of sodium component calculated by sodium element, and the balance of attapulgite mesoporous composite material C2.
(3) Dehydrogenation of propane to propylene
Propane dehydrogenation was carried out to produce propylene by following the procedure of example 1 except that a supported catalyst D2 was used in place of the supported catalyst D1 in example 1. The reaction results are shown in Table 4.
Example 3
This example illustrates the supported catalyst, the preparation method thereof, and the method for preparing propylene by propane dehydrogenation provided by the present invention
(1) Preparation of attapulgite mesoporous composite material
Adding hexadecyl trimethyl ammonium bromide and ethyl orthosilicate into an ammonia water solution with the concentration of 25 weight percent at 90 ℃, and adding deionized water, wherein the adding amount of the ethyl orthosilicate is 1g, and the mol ratio of ammonia to water in the ethyl orthosilicate, the hexadecyl trimethyl ammonium bromide and the ammonia water is 1: 0.2: 3.5: 120, stirring for 3 hours at the temperature of 90 ℃, and then carrying out suction filtration on the solution to obtain a mesoporous material filter cake A3.
Mixing 15 wt% water glass and 12 wt% sulfuric acid solution according to the weight ratio of water glass to sulfuric acid of 6:1, stirring and reacting at 20 ℃ for 3 hours, adjusting the pH to 4 by using 98 wt% sulfuric acid, and performing suction filtration on the obtained reaction material to obtain a silica gel filter cake B3.
Mixing 20 g of the prepared filter cake A3, 10g of the prepared filter cake B3 and 30g of attapulgite, putting the mixture into a 100mL ball milling tank (wherein the ball milling tank is made of polytetrafluoroethylene, the grinding balls are made of agate, the diameter of the grinding balls is 3mm, the number of the grinding balls is 1, and the rotating speed is 500r/min), sealing the ball milling tank, carrying out ball milling at 40 ℃ in the ball milling tank for 10 hours, and then washing the ball-milled slurry by using a ceramic membrane filter until the content of sodium ions is 0.02 wt% and the content of a template agent is less than 1 wt%, thus obtaining the attapulgite mesoporous composite filter cake. Wherein the operating pressure of the membrane module is 3.4bar, the pressure of the membrane at the circulating side is 4.5bar, the pressure of the membrane at the circulating side is 2.3bar, the flow rate of the membrane surface at the circulating side is 4.2m/s, the pressure of the permeate side is 0.5bar, and the temperature is 40 ℃.
And preparing the attapulgite mesoporous composite filter cake into slurry, and spray-drying at 150 ℃ at the rotating speed of 13000r/min to obtain the attapulgite mesoporous composite C3.
The pore structure parameters of the attapulgite mesoporous composite material C3 are shown in the following table 3.
TABLE 3
*: the first most probable aperture and the second most probable aperture are separated by a comma: the first most probable aperture and the second most probable aperture are arranged in the order from left to right.
(2) Preparation of Supported catalysts
0.11g of H2PtCl6·6H2O, 0.296g of SnCl4·5H2O and 0.259g NaNO3Dissolving in 200ml deionized water, mixing with the prepared attapulgite mesoporous composite material C3 of 10g, and continuously stirring and reacting for 8 hours at the temperature of 30 ℃. And (4) evaporating the solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 100 ℃ for 5 hours. Then, the catalyst was calcined in a muffle furnace at 550 ℃ for 10 hours to obtain a supported catalyst D3.
The specific gravity of each component of the supported catalyst D3 is as follows: 0.4 percent of platinum component calculated by platinum element, 1 percent of tin component calculated by tin element, 0.7 percent of sodium component calculated by sodium element, and the balance of attapulgite mesoporous composite material C3.
(3) Dehydrogenation of propane to propylene
Propane dehydrogenation was carried out to produce propylene by following the procedure of example 1 except that a supported catalyst D3 was used in place of the supported catalyst D1 in example 1. The reaction results are shown in Table 4.
Example 4
This example illustrates the supported catalyst, the preparation method thereof, and the method for preparing propylene by propane dehydrogenation provided by the present invention
(1) Preparation of the support
The support was prepared according to the method of example 1.
(2) Preparation of Supported catalysts
The procedure of example 1 was followed except that the contents of the platinum component, the tin component and the sodium component were varied. In particular, H2PtCl6·6H2The dosage of O is 0.133g, SnCl4·5H2The amount of O is 0.355g, NaNO3The same operation was repeated except for using 0.111g of (B), and the same operation as in example 1 was repeated to obtain a supported catalyst D4.
The specific gravity of each component of the supported catalyst D4 is as follows: 0.5 percent of platinum component calculated by platinum element, 1.2 percent of tin component calculated by tin element, 0.3 percent of sodium component calculated by sodium element, and the balance of attapulgite mesoporous composite material C1.
(3) Dehydrogenation of propane to propylene
Propane dehydrogenation was carried out to produce propylene by following the procedure of example 1 except that a supported catalyst D4 was used in place of the supported catalyst D1 in example 1. The reaction results are shown in Table 4.
Comparative example 1
This comparative example serves to illustrate a reference supported catalyst and a process for the dehydrogenation of propane to propylene
0.080g of H2PtCl6·6H2O, 0.207g SnCl4·5H2O and 0.185g NaNO3Dissolved in 100ml of deionized water, 10g of commercially available gamma-Al were added2O3Carrier (Qingdao Seawa silica gel desiccant company brand is a commercial product of industrial grade low specific surface area activated alumina, and the specific surface area is 162m2Per g, pore volume 0.82cm3And/g) are mixed and the reaction is continued for 5 hours at room temperature with stirring. Evaporating solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 120 ℃ for 3 hours. Then the catalyst is roasted in a muffle furnace for 6 hours at the temperature of 600 ℃ to obtain the supported catalyst DD 1.
The specific gravity of each component of the supported catalyst DD1 is as follows: 0.3 wt% of platinum component calculated by platinum element, 0.7 wt% of tin component calculated by tin element, 0.5 wt% of sodium component calculated by sodium element, and the balance of gamma-Al2O3And (3) a carrier.
(3) Dehydrogenation of propane to propylene
Propane dehydrogenation was carried out to produce propylene according to the procedure of example 1, except that supported catalyst DD1 was used instead of supported catalyst D1 in example 1. The reaction results are shown in Table 4.
Comparative example 2
This comparative example serves to illustrate a reference supported catalyst and a process for the dehydrogenation of propane to propylene
A support and a supported catalyst were prepared by following the procedure of example 1, except that the supported catalyst was prepared by a stepwise impregnation method instead of a co-impregnation method. Specifically, the attapulgite mesoporous composite material C1 was immersed in an aqueous solution of chloroplatinic acid for 5 hours, the immersed attapulgite mesoporous composite material C1 was dried and calcined under the conditions of example 1, and then immersed in an aqueous solution of tin tetrachloride and sodium nitrate for 5 hours, and then dried and calcined under the conditions of example 1, so as to obtain the supported catalyst DD 2.
The specific gravity of each component of the supported catalyst DD2 is as follows: 0.3 percent of platinum component calculated by platinum element, 0.7 percent of tin component calculated by tin element, 0.5 percent of sodium component calculated by sodium element, and the balance of attapulgite mesoporous composite material C1.
(3) Dehydrogenation of propane to propylene
Propane dehydrogenation was carried out to produce propylene according to the procedure of example 1, except that supported catalyst DD2 was used instead of supported catalyst D1 in example 1. The reaction results are shown in Table 4.
Comparative example 3
(1) Preparation of the support
Mixing 15 wt% water glass and 12 wt% sulfuric acid solution in the weight ratio of 5: 1 at 20 c, followed by adjustment of the pH to 3 with 98% by weight sulfuric acid, and then treatment of the resulting reaction mass with a plate and frame filter press, followed by washing with water to a sodium ion content of 0.02% by weight, to give a silica gel filter cake. Eleven parts by weight of water were consumed to prepare one part by weight of the silica gel filter cake.
And (3) putting 10g of the silica gel filter cake into a 100ml ball milling tank, wherein the ball milling tank is made of polytetrafluoroethylene, grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, and the rotating speed is 400 r/min. And (3) sealing the ball milling tank, carrying out ball milling for 5h at the temperature of 60 ℃ in the ball milling tank, carrying out spray drying on the ball-milled slurry at the temperature of 200 ℃ at the rotating speed of 12000r/min, and calcining the spray-dried product in a muffle furnace at the temperature of 400 ℃ for 10h in a nitrogen atmosphere to remove hydroxyl and residual moisture, thereby obtaining the silica gel carrier DA 1.
(2) Preparation of Supported catalysts
The process is carried out according to the method of example 1, except that attapulgite mesoporous composite material C1 is replaced by the silica gel carrier DA1 to obtain supported catalyst DD 3.
(3) Dehydrogenation of propane to propylene
Propane dehydrogenation was carried out to produce propylene according to the procedure of example 1, except that supported catalyst DD3 was used instead of supported catalyst D1 in example 1. The reaction results are shown in Table 4.
Comparative example 4
This comparative example serves to illustrate a reference supported catalyst and a process for the dehydrogenation of propane to propylene
(1) Preparation of attapulgite mesoporous composite material
A mesoporous material filter cake a1 and a silica gel filter cake B1 were prepared according to the method of example 1, and then 10g of the filter cake a1 and 10g of the filter cake B1 were mixed and washed with distilled water using a plate and frame filter press until the sodium ion content was 0.02 wt%, to obtain a mesoporous composite filter cake. Eleven parts by weight of water was consumed to prepare one part by weight of the mesoporous composite.
And then mixing the mesoporous composite filter cake with 10g of attapulgite according to the method in the embodiment 1, performing ball milling and spray drying to obtain the attapulgite mesoporous composite DC 1.
(2) Preparation of Supported catalysts
The process was carried out according to example 1, except that the attapulgite mesoporous composite material C1 was replaced by the attapulgite mesoporous composite material DC1, to obtain the supported catalyst DD 4.
(3) Dehydrogenation of propane to propylene
Propane dehydrogenation was carried out to produce propylene according to the procedure of example 1, except that supported catalyst DD4 was used instead of supported catalyst D1 in example 1. The reaction results are shown in Table 4.
Comparative example 5
Comparative example to illustrate a reference Carrier and Supported catalyst and Process for making the same
The preparation of the support and supported catalyst was carried out according to the method of comparative example 4, except that the following steps were added after spray drying: and calcining the spray-dried product in a muffle furnace at 400 ℃ for 24h in a nitrogen atmosphere, and removing the template agent to obtain the attapulgite mesoporous composite material DC2 and the supported catalyst DD 5.
(3) Dehydrogenation of propane to propylene
Propane dehydrogenation was carried out to produce propylene according to the procedure of example 1, except that supported catalyst DD5 was used instead of supported catalyst D1 in example 1. The reaction results are shown in Table 4.
TABLE 4
| Average conversion of propane (%) | Average propylene selectivity (%) | Average yield (%) of propylene | |
| Example 1 | 14.3 | 54.8 | 99 |
| Example 2 | 15.2 | 52.1 | 91 |
| Example 3 | 14.1 | 55.3 | 95 |
| Example 4 | 12 | 48.5 | 82 |
| Comparative example 1 | 9 | 78 | 75 |
| Comparative example 2 | 8 | 41.3 | 60 |
| Comparative example 3 | 8.2 | 40 | 58 |
| Comparative example 4 | 8.9 | 42 | 61 |
| Comparative example 5 | 9.5 | 45.1 | 66 |
As can be seen from the results in Table 4, examples 1 to 4 used the supported catalyst of the present invention for the reaction of propane dehydrogenation to produce propylene, which was superior in catalytic performance to the commercially available γ -Al2O3The catalyst prepared by the carrier (comparative example 1) shows that the preparation method of the dehydrogenation catalyst provided by the invention can realize the effect of improving the catalytic performance of the dehydrogenation catalyst. Compared with the catalyst prepared by adopting the step-by-step impregnation method in the comparative example 2, the catalyst disclosed by the invention is simple in preparation process and good in catalytic effect. The effects are clearly most optimal with examples 1-3 in the preferred range.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A supported catalyst comprises a carrier and a platinum component, a tin component and a sodium component which are loaded on the carrier, and is characterized in that the carrier is an attapulgite mesoporous composite material which is prepared by adopting a method comprising the following steps:
(1) carrying out first mixing contact on ethyl orthosilicate, cetyl trimethyl ammonium bromide and ammonia, and filtering a mixture obtained by the first mixing contact to obtain a mesoporous material filter cake;
(2) carrying out second mixing contact on water glass and inorganic acid, and filtering a mixture obtained after the second mixing contact to obtain a silica gel filter cake;
(3) respectively or after mixing the mesoporous material filter cake, the silica gel filter cake and the attapulgite, carrying out ball milling on the ball-milled product, washing the ball-milled product by using a ceramic membrane filter, optionally mixing the washed products, and then carrying out spray drying to obtain the attapulgite mesoporous composite material; or,
respectively or after mixing the mesoporous material filter cake and the silica gel filter cake, washing the mixture by using a ceramic membrane filter, then respectively or after mixing the product obtained by washing and attapulgite, carrying out ball milling, optionally mixing the ball-milled product, and then carrying out spray drying to obtain the attapulgite mesoporous composite material.
2. The supported catalyst as claimed in claim 1, wherein the average particle diameter of the attapulgite mesoporous composite material is 20-60 μm, and the specific surface area is 150-600m2The pore volume is 0.5-1.5mL/g, the pore diameters are distributed in a bimodal mode, and the bimodal mode respectively corresponds to a first most probable pore diameter of 5-9nm and a second most probable pore diameter of 10-40 nm;
preferably, the average particle diameter of the attapulgite mesoporous composite material is 40-50 μm, and the specific surface area is 150-200m2The pore volume is 0.8-1.2mL/g, the pore diameters are distributed in a bimodal mode, and the bimodal mode corresponds to the first most probable pore diameter of 6-8nm and the second most probable pore diameter of 20-30nm respectively.
3. The supported catalyst of claim 1, wherein the platinum component is present in an amount of 0.2 to 0.5 wt.%, the tin component is present in an amount of 0.2 to 1.2 wt.%, the sodium component is present in an amount of 0.3 to 0.8 wt.%, and the carrier is present in an amount of 97.5 to 99.3 wt.%, calculated as elements on the total weight of the catalyst.
4. The supported catalyst of claim 1, wherein the washing treatment conditions using a ceramic membrane filter comprise: the operating pressure is 2.5-3.9bar, the pressure of the circulating side inlet membrane is 3-5bar, the pressure of the circulating side outlet membrane is 2-2.8bar, and the flow rate of the circulating side membrane surface is 4-5 m/s; the pressure of the permeation side is 0.3-0.5 bar; the temperature is 10-60 ℃.
5. The supported catalyst of claim 1, wherein in step (1), the molar ratio of ethyl orthosilicate, cetyltrimethylammonium bromide and ammonia is 1: 0.1-1: 0.1 to 5, preferably 1: 0.2-0.5: 1.5-3.5;
preferably, the conditions of the first mixing contact include: the temperature is 25-100 ℃, and the time is 2-8 hours;
preferably, the weight ratio of the water glass to the inorganic acid is 3-6:1, and the inorganic acid is one or more of sulfuric acid, nitric acid and hydrochloric acid;
preferably, the conditions of the second mixing contact include: the temperature is 10-60 ℃, the time is 1-5 hours, and the pH value is 2-4;
preferably, the silica gel filter cake is used in an amount of 1 to 200 parts by weight, preferably 20 to 180 parts by weight, and more preferably 50 to 150 parts by weight, relative to 100 parts by weight of the mesoporous material filter cake; the dosage of the attapulgite is 1 to 200 parts by weight, preferably 20 to 180 parts by weight, more preferably 50 to 150 parts by weight;
preferably, in step (3), the ball milling conditions include: the rotation speed of the grinding ball is 300-;
preferably, the conditions of the spray drying include: the temperature is 100-300 ℃, and the rotating speed is 10000-15000 r/min.
6. A process for preparing a supported catalyst according to any one of claims 1 to 5, comprising: the carrier is co-impregnated with a mixed aqueous solution containing a water-soluble platinum compound, a water-soluble tin compound and an inorganic sodium salt, then the solvent water is removed, dried and calcined.
7. The method according to claim 6, wherein the water-soluble platinum compound, the water-soluble tin compound and the inorganic sodium salt are used in amounts such that the platinum component is contained in an amount of 0.2 to 0.5 wt%, the tin component is contained in an amount of 0.2 to 1.2 wt%, the sodium component is contained in an amount of 0.3 to 0.8 wt%, and the carrier is contained in an amount of 97.5 to 99.3 wt%, calculated as elements, based on the total weight of the catalyst, in the prepared supported catalyst.
8. The method of claim 6, wherein the co-impregnating conditions comprise: the temperature is 15-60 ℃, and the time is 1-10 hours;
preferably, the conditions of the calcination include: the temperature is 500 ℃ and 700 ℃ and the time is 2-15 hours.
9. A supported catalyst prepared by the process of any one of claims 6 to 8.
10. Use of a supported catalyst according to any one of claims 1 to 5 and 9 in the dehydrogenation of propane to produce propylene.
11. A method for preparing propylene by propane dehydrogenation is characterized by comprising the following steps: contacting propane with a catalyst under conditions for the dehydrogenation of propane to propylene, characterized in that the catalyst is a supported catalyst according to any one of claims 1-5 and 9.
12. The method of claim 11, further comprising adding a diluent gas hydrogen;
preferably, the contacting of the propane with the catalyst is carried out in a fixed bed quartz reactor, and the conditions for the dehydrogenation of propane to produce propylene include: the molar ratio of propane to hydrogen is 0.5-5: 1, the reaction temperature is 500-650 ℃, the pressure is 0.05-0.15MPa, and the mass space velocity of propane is 1-10h-1。
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