CN108855201B - The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane - Google Patents
The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane Download PDFInfo
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- CN108855201B CN108855201B CN201710325222.4A CN201710325222A CN108855201B CN 108855201 B CN108855201 B CN 108855201B CN 201710325222 A CN201710325222 A CN 201710325222A CN 108855201 B CN108855201 B CN 108855201B
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- propane
- sepiolite
- carrier
- dehydrogenation catalyst
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 222
- 239000001294 propane Substances 0.000 title claims abstract description 111
- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 238000006356 dehydrogenation reaction Methods 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 39
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 239000004113 Sepiolite Substances 0.000 claims abstract description 107
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 107
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 107
- 239000011148 porous material Substances 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 238000009826 distribution Methods 0.000 claims abstract description 27
- 230000002902 bimodal effect Effects 0.000 claims abstract description 23
- 239000002808 molecular sieve Substances 0.000 claims abstract description 22
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012065 filter cake Substances 0.000 claims description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 150000003839 salts Chemical class 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000013335 mesoporous material Substances 0.000 claims description 18
- 229910002027 silica gel Inorganic materials 0.000 claims description 18
- 239000000741 silica gel Substances 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 12
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 150000007522 mineralic acids Chemical class 0.000 claims description 11
- 235000019353 potassium silicate Nutrition 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000007725 thermal activation Methods 0.000 claims description 6
- 229910001868 water Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229920000428 triblock copolymer Polymers 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 239000007853 buffer solution Substances 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 26
- 239000000126 substance Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 9
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 9
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 9
- -1 polypropylene Polymers 0.000 description 9
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 238000001694 spray drying Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 101150116295 CAT2 gene Proteins 0.000 description 6
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 6
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 6
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 5
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000007974 sodium acetate buffer Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 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
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 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
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 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
- 239000012535 impurity Substances 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- JTXAHXNXKFGXIT-UHFFFAOYSA-N propane;prop-1-ene Chemical group CCC.CC=C JTXAHXNXKFGXIT-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0325—Noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- 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
-
- 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
-
- 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
- B01J35/635—0.5-1.0 ml/g
-
- 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
-
- 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
-
- 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
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
-
- 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)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to catalyst fields, disclose the method for a kind of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane, the propane dehydrogenation catalyst includes the main active component Pt of carrier and load on the carrier, metal promoter Sn and metal promoter Na, wherein, the carrier is spherical mesoporous sepiolite complex carrier, the spherical mesoporous sepiolite complex carrier contains sepiolite and the meso-porous molecular sieve material with one-dimensional hexagonal hole road diplopore distributed architecture, the average grain diameter of the spherical mesoporous sepiolite complex carrier is 10-50 μm, specific surface area is 150-600m2/ g, pore volume 0.5-2mL/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 2-9nm and 10-40nm.The propane dehydrogenation catalyst shows good catalytic performance when reacting for preparing propylene by dehydrogenating propane, conversion of propane is high, and Propylene Selectivity is high, and catalyst stability is good.
Description
Technical field
The present invention relates to catalyst fields, and in particular, to a kind of propane dehydrogenation catalyst and preparation method thereof and third
The method of alkane dehydrogenation producing propylene.
Background technique
Sepiolite category orthorhombic system or single orthorhombic system；Color-variable, generally in light white or canescence；Have silky luster,
It sometimes is in wax-like gloss；Streak is white, opaque, and sense of touch is smooth and viscous tongue；Mohs' hardness is between 2~2.5；Constitution is light,
Density is 1~2.2g/cm3；Shrinking percentage is low, and plasticity is good, can be dissolved in hydrochloric acid.The chemical component of sepiolite is silicon (Si) and magnesium
(Mg)；Its standard crystal chemical formula is Mg8(H2O)4[Si6O16]2(OH)4·8H2O, wherein SiO2Content is generally 54~60%
Between, content of MgO is mostly in 21~25% ranges.Sepiolite has the performances such as extremely strong absorption, decoloration and dispersion, also has high
Thermal stability, for heat-resisting quantity up to 1500~1700 DEG C, formative nature, insulating properties, salt resistance degree are all very good.
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 CYLofin 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, people is studied
Member has done many work.Such as: traditional γ-Al is substituted using molecular sieve carrier2O3Carrier, effect preferably include MFI type
Micro porous molecular sieve (CN104307555A, CN101066532A, CN101380587A, CN101513613A), mesoporous MCM-41 point
Son sieve (CN102389831A) and mesoporous SBA-15 molecular sieve (CN101972664A, CN101972664B) etc..However often at present
Mesoporous material aperture is smaller (6~9nm of average pore size), if carrying out bulky molecular catalysis reaction, macromolecular hole more difficult to get access
Road, so that influencing catalytic effect.Therefore, selecting a kind of excellent carrier is one, dehydrogenating propane field urgent problem to be solved.
Summary of the invention
The purpose of the invention is to overcome existing propane dehydrogenation catalyst preparation process complexity, preparation process to be easy to make
At environmental pollution, conversion of propane and the lower defect of Propylene Selectivity, a kind of propane dehydrogenation catalyst and its preparation side are provided
The method of method and preparing propylene by dehydrogenating propane.
To achieve the goals above, one aspect of the present invention provides a kind of propane dehydrogenation catalyst, the dehydrogenating propane catalysis
Agent includes main active component Pt, metal promoter Sn and the metal promoter Na of carrier and load on the carrier, wherein institute
Stating carrier is spherical mesoporous sepiolite complex carrier, and the spherical mesoporous sepiolite complex carrier contains sepiolite and has one-dimensional
The average grain diameter of the meso-porous molecular sieve material of hexagonal hole road diplopore distributed architecture, the spherical mesoporous sepiolite complex carrier is
10-50 μm, specific surface area 150-600m2/ g, pore volume 0.5-2mL/g, pore-size distribution are bimodal distribution, and described bimodal
Corresponding most probable pore size is respectively 2-9nm and 10-40nm.
Second aspect of the present invention provides a kind of method for preparing above-mentioned propane dehydrogenation catalyst, this method comprises: by carrier
It is impregnated in the mixed solution containing Pt salt, Sn salt and Na salt after thermal activation, the solution after dipping is then removed into solvent
After be dried and roast, wherein the carrier is spherical mesoporous sepiolite complex carrier, and the spherical mesoporous sepiolite is compound
Carrier contains sepiolite and the meso-porous molecular sieve material with one-dimensional hexagonal hole road diplopore distributed architecture, the spherical mesoporous Hai Pao
The average grain diameter of stone complex carrier is 10-50 μm, specific surface area 150-600m2/ g, pore volume 0.5-2mL/g, aperture point
Cloth is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 2-9nm and 10-40nm.
Third aspect present invention provides a kind of propane dehydrogenation catalyst prepared by the above method.
Fourth aspect present invention provides a kind of method of preparing propylene by dehydrogenating propane, which comprises in catalyst and hydrogen
In the presence of gas, propane is subjected to dehydrogenation reaction, wherein the catalyst be propane dehydrogenation catalyst provided by the invention or by
The propane dehydrogenation catalyst that method provided by the invention is prepared.
Spherical mesoporous sepiolite complex carrier according to the present invention, combines with one-dimensional hexagonal hole road distributed architecture
Meso-porous molecular sieve material and sepiolite and the advantages of ball type carrier so that the spherical mesoporous sepiolite complex carrier is suitble to use
Make the carrier of loaded catalyst, is especially suitable as loaded catalyst used in reacting in preparing propylene by dehydrogenating propane
Carrier.
In the loaded catalyst of the invention, the spherical mesoporous sepiolite complex carrier has mesopore molecular sieve
The larger feature of porous structure, large specific surface area, the pore volume of material, in conjunction with natural sepiolite due to biggish specific surface
Long-pending and microcellular structure and the strong adsorption capacity having are conducive to metal component in the fine dispersion of carrier surface, and the load
Body is also loaded active component Pt, metal promoter Sn and metal promoter Na, so that the loaded catalyst was both urged with support type
The advantages of agent such as catalytic activity it is high, side reaction is few, post-processing is simple, and with stronger catalytic activity, so that the load
Type catalyst has better dehydrogenation activity and selectivity in for dehydrogenating propane reaction, significantly improves the conversion of reaction raw materials
Rate, specifically, in the reaction that preparing propylene by dehydrogenating propane is carried out using the loaded catalyst, conversion of propane is up to 36%, third
The selectivity of alkene is close to 100%.
Also, when the method by spray drying prepares the loaded catalyst, the loaded catalyst can be with
It is reused, and still can obtain higher reaction raw materials conversion ratio during recycling.
In addition, the substep leaching that the preparation method of propane dehydrogenation catalyst of the invention is conventional using the method substitution of co-impregnation
Stain method, preparation process is simple, and condition is easily controllable, and preparation cost is low, good economy performance, and good repetitiveness.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the X-ray diffraction spectrogram of the spherical mesoporous sepiolite complex carrier of embodiment 1；
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of the spherical mesoporous sepiolite complex carrier of embodiment 1；
Fig. 3 is the pore size distribution curve of the spherical mesoporous sepiolite complex carrier of embodiment 1.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
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 propane dehydrogenation catalyst, the propane dehydrogenation catalyst includes carrier and is supported on institute
State main active component Pt, metal promoter Sn and the metal promoter Na on carrier, wherein the carrier is spherical mesoporous sepiolite
Complex carrier, the spherical mesoporous sepiolite complex carrier contain sepiolite and with one-dimensional hexagonal hole road diplopore distributed architectures
Meso-porous molecular sieve material, the average grain diameter of the spherical mesoporous sepiolite complex carrier are 10-50 μm, specific surface area 150-
600m2/ g, pore volume 0.5-2mL/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively
2-9nm and 10-40nm.
According to the present invention, there is the spherical mesoporous sepiolite complex carrier special one-dimensional hexagonal hole road diplopore to be distributed knot
The average grain diameter of structure, particle is measured using laser fineness gage, and specific surface area, pore volume and most probable pore size are according to nitrogen
Absorption method measures.In the present invention, granularity refers to the particle size of feed particles, the then granularity ball when feed particles are sphere
The diameter of body indicates that then the side length of granularity cube indicates when feed particles are cube, when feed particles are irregular
Shape when the then granularity sieve that can screen out the feed particles just mesh size indicate.
According to the present invention, the spherical mesoporous sepiolite complex carrier is by by of spherical mesoporous sepiolite complex carrier
Particle size controls within above range, it can be ensured that and the spherical mesoporous sepiolite complex carrier is not susceptible to reunite, and
The reaction raw materials that being used as loaded catalyst made of carrier can be improved in preparing propylene by dehydrogenating propane reaction process convert
Rate.When spherical mesoporous sepiolite complex carrier specific surface area be less than 150m2It, will when/g and/or pore volume are less than 0.5mL/g
Its catalytic activity for being used as loaded catalyst made of carrier can significantly reduce；When the spherical mesoporous sepiolite complex carrier
Specific surface area be greater than 600m2When/g and/or pore volume are greater than 2mL/g, it is used as loaded catalyst made of carrier and exists
Reunion is easy to happen in preparing propylene by dehydrogenating propane reaction process, so that the reaction influenced in preparing propylene by dehydrogenating propane reaction process is former
Expect conversion ratio.
In the preferred case, the average grain diameter of the spherical mesoporous sepiolite complex carrier is 20-50 μm, and specific surface area is
180-600m2/ g, pore volume 0.8-1.5mL/g, pore-size distribution are bimodal distribution, and the bimodal corresponding most probable pore size
Respectively 3-8nm and 20-30nm.
According to the present invention, relative to the propane dehydrogenation catalyst of 100 parts by weight, the content of the carrier is 97.5-
The content of 99.3 weight %, the main active component Pt is 0.2-0.5 weight %, and the content of metal promoter Sn is 0.2-1.2
The content of weight %, metal promoter Na are 0.3-0.8 weight %.
Preferably, the average particle diameter of the propane dehydrogenation catalyst is 10-50 μm, specific surface area 180-400m2/
G, pore volume 0.8-1.5mL/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 3-
8nm and 20-30nm.
According to the present invention, in the spherical mesoporous sepiolite complex carrier, to have one-dimensional six described in 100 parts by weight
On the basis of the weight of the meso-porous molecular sieve material of square duct diplopore distributed architecture, the content of the sepiolite can be 1-50 weight
Part, preferably 20-50 parts by weight.
According to the present invention, the spherical mesoporous sepiolite complex carrier can also contain the titanium dioxide introduced by silica gel
Silicon." silica being introduced by silica gel " refers in the preparation process of the spherical mesoporous sepiolite complex carrier, by silicon
Glue is as the silica component for preparing raw material and bringing into the spherical mesoporous sepiolite complex carrier finally prepared.In the spherical shape
In mesoporous sepiolite complex carrier, to have the mesoporous molecular of one-dimensional hexagonal hole road diplopore distributed architecture described in 100 parts by weight
On the basis of the weight for sieving material, the content of the silica introduced by silica gel can be 1-200 parts by weight, preferably
50-150 parts by weight.
According to the present invention, the meso-porous molecular sieve material with one-dimensional hexagonal hole road diplopore distributed architecture can be ability
The conventional use of meso-porous molecular sieve material in domain, and can be prepared according to the conventional method.
The present invention also provides a kind of methods for preparing propane dehydrogenation catalyst, this method comprises: by after carrier thermal activation
It is impregnated in the mixed solution containing Pt salt, Sn salt and Na salt, is done after the solution after dipping is then removed solvent
Dry and roasting, wherein the carrier is spherical mesoporous sepiolite complex carrier, and the spherical mesoporous sepiolite complex carrier contains
Sepiolite and meso-porous molecular sieve material with one-dimensional hexagonal hole road diplopore distributed architecture, the spherical mesoporous compound load of sepiolite
The average grain diameter of body is 10-50 μm, specific surface area 150-600m2/ g, pore volume 0.5-2mL/g, pore-size distribution are bimodal
Distribution, and the bimodal corresponding most probable pore size is respectively 2-9nm and 10-40nm.
According to the present invention, the dosage of the carrier, Pt salt, Sn salt and Na salt makes the propane dehydrogenation catalyst being prepared
In, on the basis of the total weight of the propane dehydrogenation catalyst, the content of the spherical mesoporous sepiolite complex carrier is 97.5-
Content of 99.3 weight %, the Pt salt in terms of Pt element is that content of 0.2-0.5 weight %, the Sn salt in terms of Sn element is 0.2-1.2
Content of weight %, the Na salt in terms of Na element is 0.3-0.8 weight %.
There is no particular limitation for selection of the present invention to the Pt salt, Sn salt and Na salt, can be with as long as water solubility
For the conventional selection of this field, for example, the Pt salt can be H2PtCl6, the Sn salt can be SnCl4, the Na salt can be with
For NaNO3。
Concentration no spy of the present invention to Pt salt, Sn salt and Na salt in the mixed solution containing Pt salt, Sn salt and Na salt
Other restriction can be the conventional selection of this field, for example, the concentration of the Pt salt is 0.1-0.3mol/L, the Sn salt
Concentration is 0.15-1mol/L, and the concentration of the Na salt is 1-3.5mol/L.
According to the present invention, propane dehydrogenation catalyst is prepared using the conventional step impregnation method of co-impregnation method substitution, made
Standby simple process, condition is easily controllable, good repetitiveness.There is no particular limitation for condition of the present invention to the dipping, can
Think the conventional method of this field.In order to improve the performance of prepared propane dehydrogenation catalyst, under preferable case, the dipping
It is carried out after carrier thermal activation, the condition of the thermal activation includes: that temperature is 300-900 DEG C, and the time is 7-10 hours；The leaching
The condition of stain includes: that temperature is 25-50 DEG C, and the time is 2-6 hours.
According to the present invention, the process of the removal solvent can adopt with the conventional methods in the field, such as can be using rotation
Turn the solvent in evaporimeter removal system.
According to the present invention, the drying can carry out in drying box, and the roasting can carry out in Muffle furnace.This hair
Also there is no particular limitation for the bright condition to the drying and roasting, can be the conventional selection of this field, for example, the drying
Condition may include: temperature be 110-150 DEG C, the time be 3-6 hours；The condition of the roasting may include: that temperature is
600-650 DEG C, the time is 5-8 hours.
According to the present invention, the spherical mesoporous sepiolite complex carrier forming method the following steps are included:
(a) in the presence of template, trimethylpentane and ethyl alcohol, tetramethoxy-silicane is contacted with sour agent, and
It by the product crystallization obtained after contact and filters, obtains mesoporous material filter cake；
(b) waterglass is contacted with inorganic acid, and the product obtained after contact is filtered, obtain silica gel filter cake；
(c) the mesoporous material filter cake, silica gel filter cake and sepiolite are mixed into simultaneously ball milling, and the solid that will be obtained after ball milling
It is spray-dried after powder water slurrying, then by the template removal in obtained product.
In the forming process of above-mentioned spherical mesoporous sepiolite complex carrier, the mesoporous material filter cake is with one-dimensional six
The meso-porous molecular sieve material of square duct diplopore distributed architecture.
It is main to pass through control mesoporous material filter cake, silicon in the forming process of above-mentioned spherical mesoporous sepiolite complex carrier
The composition of glue filter cake and sepiolite controls pore-size distribution for bimodal distribution, and is distributed the sepiolite complex carrier with diplopore
Structure, and by control forming method (that is, mesoporous material filter cake, silica gel filter cake and sepiolite are first mixed simultaneously ball milling, then
To be spray-dried after the water slurrying of obtained solid powder) be by the microscopic appearance control of double mesoporous sepiolite complex carriers
It is spherical.
According to the present invention, during preparing mesoporous material filter cake, the dosage of each substance can be in a wider scope
It is selected and is adjusted.For example, in step (a), the template, ethyl alcohol, trimethylpentane and tetramethoxy-silicane rub
Your ratio can be 1:100-500:200-600:50-200, preferably 1:200-400:250-400:70-150.
According to the present invention, the type of the template is not particularly limited, as long as the spherical mesoporous sea that can make
Afrodite complex carrier has above-mentioned pore structure, it is preferable that the template can be poly- for triblock copolymer polyoxyethylene-
Oxypropylene-polyoxyethylene.Wherein, which can be commercially available (for example, can be purchased from Aldrich, trade name
For P123, molecular formula EO20PO70EO20), it can also be prepared by existing various methods.When the template is poly-
When ethylene oxide-polyoxypropylene polyoxyethylene, the molal quantity of the template is according to polyoxyethylene-poly-oxypropylene polyoxyethylene
Average molecular weight calculates to obtain.
According to the present invention, the type of the sour agent is not particularly limited, and can be the conventional selection of this field, Ke Yiwei
The mixture of existing various acid or acid.Wherein, the mixture of the acid or acid can be used with pure state, can also be water-soluble with its
The form of liquid uses, and preferably uses in form of an aqueous solutions.Preferably, the sour agent is the buffer solution of acetic acid and sodium acetate；
It is highly preferred that the pH value of the acid agent is 1-6；It is further preferred that the pH value of the acid agent is 3-5.
According to the present invention, the condition that the tetramethoxy-silicane is contacted with sour agent is not particularly limited, for example, described four
The condition that methoxy silane is contacted with sour agent may include: that temperature is 10-60 DEG C, and the time is 10-72 hours, pH value 1-7；It is excellent
In the case of choosing, the condition that the tetramethoxy-silicane is contacted with sour agent may include: that temperature is 10-30 DEG C, and the time is that 20-40 is small
When, pH value 3-6.In order to be more advantageous to the uniform mixing between each substance, the tetramethoxy-silicane is contacted with sour agent preferably to exist
It is carried out under stirring condition.The dosage of the acid agent preferably so that the tetramethoxy-silicane and sour agent haptoreaction system pH value
For 1-7, more preferably 3-6.
There is no particular limitation for condition of the present invention to the crystallization, what the condition of the crystallization can be conventional for this field
Selection, for example, it is 30-150 DEG C that the condition of the crystallization, which may include: temperature, the time is 10-72 hours, under preferable case, institute
It is 40-80 DEG C that the condition for stating crystallization, which includes: temperature, and the time is 20-40 hours.The crystallization is implemented by hydrothermal crystallization method.
In addition, the present invention is to the contact between the template, ethyl alcohol, sour agent, trimethylpentane and tetramethoxy-silicane
Mode is not particularly limited, for example, above-mentioned five kinds of substances can be mixed simultaneously, it can also be by several substances therein
It is first mixed, will continue to be mixed in mixture that remaining substance is added again.Under preferable case, the contact side
Formula is first at 10-100 DEG C, after template, ethyl alcohol, acidic aqueous solution and trimethylpentane are stirred, is then added
Tetramethoxy-silicane simultaneously continues to be stirred.
The condition that the present invention contacts the waterglass with inorganic acid is not particularly limited, for example, in step (b),
The condition that the waterglass is contacted with inorganic acid generally includes: temperature can be 10-60 DEG C, preferably 20-40 DEG C；Time can be with
It is 1-5 hours, preferably 1.5-3 hours, pH value 2-4.In order to be more advantageous to the uniform mixing between each substance, the waterglass
It contacts with inorganic acid and preferably carries out under agitation.
According to the present invention, the waterglass is the aqueous solution of the sodium metasilicate of this field routine, and concentration can be 10-50 weight
Measure %, preferably 12-30 weight %.
According to the present invention, the type of the inorganic acid can be the conventional selection of this field, for example, can be sulfuric acid, nitre
One of acid and hydrochloric acid are a variety of.The inorganic acid can use in pure form, can also be in the form of its aqueous solution
It uses.The dosage of the inorganic acid is preferably so that the pH value of the contact conditions reaction system of waterglass and inorganic acid is 2-4.
In addition, it is above-mentioned prepare mesoporous material filter cake and silica gel filter cake during, the mistake of filter cake is obtained by filtering
Journey may include: after filtration, washs (washing times can be 2-10) repeatedly with distilled water, is then filtered.It is preferred that
Ground prepares the washing during silica gel filter cake so that sodium ions content is lower than 0.02 weight %.
According to the present invention, in step (c), the dosage of the mesoporous material filter cake, silica gel filter cake and sepiolite can root
It is anticipated that the component of obtained spherical mesoporous sepiolite complex carrier is selected, under preferable case, described in 100 parts by weight
On the basis of the dosage of mesoporous material filter cake, the dosage of the silica gel filter cake can be 1-200 parts by weight, preferably 50-150 weight
Part；The dosage of the sepiolite can be 1-50 parts by weight, preferably 20-50 parts by weight.
According to the present invention, the concrete operation method of the ball milling and condition are not particularly limited, not destroy or substantially
The structure of mesoporous material is not destroyed and enters silica gel and sepiolite subject to mesoporous material duct.Those skilled in the art can root
Various suitable conditions are selected to implement the present invention according to mentioned above principle.Specifically, the ball milling carries out in the ball mill, wherein
The diameter of abrading-ball can be 2-3mm in ball mill；The quantity of abrading-ball can reasonably be selected according to the size of ball grinder, right
In the ball grinder that size is 50-150mL, 1 abrading-ball usually can be used；The material of the abrading-ball can be agate, polytetrafluoro
Ethylene etc., preferably agate.The condition of the ball milling includes: the revolving speed of abrading-ball can be for 300-500r/min, in ball grinder
Temperature can be 15-100 DEG C, and the time of ball milling can be 0.1-100 hours.
In the present invention, the concrete operation method and condition of the spray drying are the conventional selection of this field.Specifically, will
High speed rotation is added in atomizer by the slurry that the solid powder and water are made into realize spray drying.Wherein, the spray
The dry condition of mist includes: that temperature can be 100-300 DEG C, and the revolving speed of rotation can be 10000-15000r/min；It is preferred that feelings
Under condition, the condition of the spray drying includes: that temperature is 150-250 DEG C, and the revolving speed of rotation is 11000-13000r/min；It is optimal
In the case of choosing, the condition of the spray drying includes: that temperature is 200 DEG C, and the revolving speed of rotation is 12000r/min.
According to the present invention, the method for removed template method is usually calcination method.The condition of the removed template method can be this
Field conventional selection, for example, the condition of the removed template method, which includes: temperature, to be 300-600 DEG C, preferably 350-550
DEG C, most preferably 500 DEG C；Time can be 10-80 hours, preferably 20-30 hours, most preferably 24 hours.
The present invention also provides the propane dehydrogenation catalysts being prepared by the method for the invention.
The present invention also provides a kind of methods of preparing propylene by dehydrogenating propane, which comprises in catalyst and hydrogen
In the presence of, propane is subjected to dehydrogenation reaction, wherein the catalyst is propane dehydrogenation catalyst of the present invention.
According to the present invention, in order to improve conversion of propane and prevent catalyst coking, under preferable case, the dosage of propane with
The molar ratio of the dosage of hydrogen is 0.5-1.5:1.
There is no particular limitation for condition of the present invention to the dehydrogenation reaction, can be the conventional selection of this field, for example,
The condition of the dehydrogenation reaction may include: that reaction temperature is 600-650 DEG C, reaction pressure 0.05-0.2MPa, the reaction time
For 40-60h, propane mass space velocity is 2-5h-1。
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example, polyoxyethylene-poly-oxypropylene polyoxyethylene is purchased from Aldrich, is abbreviated as
P123, molecular formula EO20PO70EO20, the substance for being 9003-11-6 in the registration number of U.S. chemical abstract, average molecular weight is
5800；
In following embodiment and comparative example, X-ray diffraction analysis is in the model for being purchased from Bruker AXS company, Germany
It is carried out on the X-ray diffractometer of D8Advance；Scanning of the scanning electron microscope analysis in the model XL-30 purchased from FEI Co., the U.S.
It is carried out on electron microscope；Pore structure parameter analysis is in the ASAP2020-M+C purchased from the production of U.S. Micromeritics company
It is carried out on type adsorption instrument, the specific surface area and pore volume of sample, which calculate, uses BET method；The particle diameter distribution of sample swashs in Malvern
It is carried out on light particle size analyzer；Rotary Evaporators are the production of IKA company, Germany, model RV10digital；Propane dehydrogenation catalyst
Activity component load quantity is in the Wavelength Dispersive-X-Ray fluorescence spectrum for being Axios-Advanced purchased from Dutch Panaco company model
It is measured on instrument；The analysis of reaction product ingredient carries out on the gas chromatograph purchased from agilent company model 7890A；
In following EXPERIMENTAL EXAMPLE and Experimental comparison's example, the conversion ratio (%) of propane=(in dosage-reaction product of propane
The content of propane) ÷ propane dosage × 100%；
Theoretical yield × 100% of selectivity (%)=propylene actual production ÷ propylene of propylene.
Embodiment 1
The present embodiment is for illustrating propane dehydrogenation catalyst and preparation method thereof.
(1) preparation of spherical mesoporous sepiolite complex carrier
1g (0.0002mol) triblock copolymer surfactant P123 and 1.69g (0.037mol) ethyl alcohol is added to
In 28ml, the acetic acid and sodium acetate buffer that pH value is 4, stirring is completely dissolved to P123 at 15 DEG C, obtain backward it is molten
6g (0.053mol) trimethylpentane is added in liquid, 8h is stirred at 15 DEG C, then 2.13g (0.014mol) tetramethyl is added thereto
Oxysilane stirs 20h under conditions of 15 DEG C, pH value are 4.5, obtained solution is then transferred to polytetrafluoroethyllining lining
Reaction kettle in, at 60 DEG C crystallization for 24 hours, be then filtered and and be washed with deionized 4 times, then filtering is had
The meso-porous molecular sieve material filter cake A1 of one-dimensional hexagonal hole road distributed architecture；
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 the haptoreaction 2h at 30 DEG C, then with the sulfuric acid adjustment pH value that concentration is 98 weight % to 3, the then reaction to obtaining
Material is filtered, and being washed with distilled water to sodium ions content is 0.02 weight %, obtains silica gel filter cake B1.
10g filter cake A1,10g filter cake B1 and 10g sepiolite of above-mentioned preparation is put into togerther in 100ml ball grinder, wherein
The material of ball grinder is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 400r/
min.Ball grinder is closed, temperature is to obtain 35g solid powder ball milling 1 hour at 60 DEG C in ball grinder；The solid powder is molten
Solution is spray-dried at 200 DEG C in the case where revolving speed is 12000r/min in 37.5 grams of deionized waters；By what is obtained after spray drying
Product is calcined 24 hours at 500 DEG C in Muffle furnace, removed template method, is obtained 30g and is distributed with one-dimensional hexagonal hole road diplopore
The spherical mesoporous sepiolite complex carrier C1 of structure.
(2) preparation of propane dehydrogenation catalyst
By 0.08g H2PtCl6·6H2O、0.207g SnCl4·5H2O and 0.185g NaNO3It is dissolved in 100ml deionized water
In, mixture solution is obtained, the spherical mesoporous sepiolite complex carrier C1 that step (1) is obtained is immersed in the mixture solution
In, after being impregnated 5 hours at 25 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product, by solid product
It is placed in the drying box that temperature is 120 DEG C, 3 hours dry, being subsequently placed in temperature is to roast 6 hours, obtain in 600 DEG C of Muffle furnaces
To propane dehydrogenation catalyst Cat-1, (on the basis of the total weight of propane dehydrogenation catalyst Cat-1, the content of Pt is 0.3 weight
% is measured, the content that the content of Sn is 0.7 weight %, Na is 0.5 weight %, remaining is carrier).
With XRD, scanning electron microscope and ASAP2020-M+C type adsorption instrument come to spherical mesoporous sepiolite complex carrier
C1 and propane dehydrogenation catalyst Cat-1 are characterized；
Fig. 1 is X-ray diffracting spectrum, wherein a is the XRD spectra of spherical mesoporous sepiolite complex carrier C1, abscissa
For 2 θ, ordinate is intensity, by the low-angle spectral peak of XRD spectra appearance it is found that the XRD of spherical mesoporous sepiolite complex carrier C1
Spectrogram a has the hexagonal hole road structure of 2D specific to mesoporous material；
Fig. 2 is SEM scanning electron microscope (SEM) photograph, and as seen from the figure, the microscopic appearance of spherical mesoporous sepiolite complex carrier C1 is particle
The Mesoporous Spheres that degree is 10-50 μm；
Fig. 3 is the pore size distribution curve figure of spherical mesoporous sepiolite complex carrier C1；
Table 1 is the pore structure parameter of spherical mesoporous sepiolite complex carrier C1 and propane dehydrogenation catalyst Cat-1.
Table 1
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size*(nm) | Partial size (μm) |
| Complex carrier C1 | 371 | 1.3 | 7.6,30 | 20-50 |
| Catalyst Cat-1 | 265 | 1 | 3,18 | 20-50 |
*: the first most probable pore size and the second most probable pore size are separated with comma: it is the first most probable pore size before comma,
It is the second most probable pore size after comma.
Spherical mesoporous sepiolite complex carrier is in load main active component Pt, metal promoted it can be seen from the data of table 1
After agent Sn and metal promoter Na, specific surface area and pore volume are reduced, this explanation is mainly lived during load-reaction
Property component Pt, metal promoter Sn and metal promoter Na enter the inside of spherical mesoporous sepiolite complex carrier.
Comparative example 1
Spherical mesoporous complex carrier and loaded catalyst are prepared according to the method for embodiment 1, it is different, preparing ball
It is added without sepiolite during the composite mesoporous carrier of shape, so that composite mesoporous carrier D1 and loaded catalyst be made respectively
Cat-D-1。
Comparative example 2
Spherical sepiolite carrier and loaded catalyst are prepared according to the method for embodiment 1, it is different, it is used as in preparation
It is added without mesoporous material during the mesoporous composite material of carrier, so that sepiolite carrier D2 and supported catalyst be made respectively
Agent Cat-D-2.
Comparative example 3
Spherical mesoporous sepiolite complex carrier D3 and loaded catalyst Cat-D-3, institute are prepared according to the method for embodiment 1
Different, during preparing loaded catalyst, (Jilin is purchased from the rodlike mesoporous silicon oxide SBA-15 of identical weight
High-tech limited liability company, university) meso-porous molecular sieve material filter cake A1 is replaced, so that it is multiple that spherical mesoporous sepiolite is made respectively
Close carrier D3 and loaded catalyst Cat-D-3.
Comparative example 4
Spherical mesoporous sepiolite complex carrier and loaded catalyst are prepared according to the method for embodiment 1, it is different,
The step of not being spray-dried during preparing loaded catalyst, and only by the method for dipping by active component Pt, gold
Belong to auxiliary agent Sn and metal promoter Na to be supported on spherical mesoporous sepiolite complex carrier, so that loaded catalyst Cat-D- be made
4。
Embodiment 2
The present embodiment is for illustrating propane dehydrogenation catalyst and preparation method thereof.
(1) preparation of spherical mesoporous sepiolite complex carrier
1g (0.0002mol) triblock copolymer surfactant P123 and 1.84g (0.04mol) ethyl alcohol is added to
In 28ml, the acetic acid and sodium acetate buffer that pH value is 5, stirring is completely dissolved to P123 at 15 DEG C, obtain backward it is molten
9.12g (0.08mol) trimethylpentane is added in liquid, 8h is stirred at 15 DEG C, then 3.04g (0.02mol) four is added thereto
Methoxy silane stirs 15h under conditions of 25 DEG C, pH value are 5.5, then obtained solution is transferred in polytetrafluoroethylene (PTFE)
In the reaction kettle of lining, the crystallization 10h at 100 DEG C, be then filtered and and be washed with deionized 4 times, then filter and obtain
Meso-porous molecular sieve material filter cake A2 with one-dimensional hexagonal hole road distributed architecture；
It is the sulfuric acid solution of 12 weight % by waterglass and concentration that concentration is 15 weight % with weight ratio is that 4:1 is mixed
Merge the haptoreaction 1.5h at 40 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
Material is answered to be filtered, and being washed with distilled water to sodium ions content is 0.02 weight %, obtains silica gel filter cake B2.
20g filter cake A2,10g filter cake B2 and 12g sepiolite of above-mentioned preparation is put into togerther in 100ml ball grinder, wherein
The material of ball grinder is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 300r/
min.Ball grinder is closed, temperature is to obtain 38g solid powder ball milling 0.5 hour at 80 DEG C in ball grinder；By the solid powder
It is dissolved in 12g deionized water, is spray-dried at 250 DEG C in the case where revolving speed is 11000r/min；By what is obtained after spray drying
Product is calcined 15 hours at 500 DEG C in Muffle furnace, removed template method, is obtained 35g and is distributed with one-dimensional hexagonal hole road diplopore
The spherical mesoporous sepiolite complex carrier C2 of structure.
(2) preparation of propane dehydrogenation catalyst
By 0.08g H2PtCl6·6H2O、0.207g SnCl4·5H2O and 0.185g NaNO3It is dissolved in 100ml deionized water
In, mixture solution is obtained, the spherical mesoporous sepiolite complex carrier C2 that step (1) is obtained is immersed in the mixture solution
In, after being impregnated 5 hours at 25 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product, by solid product
It is placed in the drying box that temperature is 120 DEG C, 3 hours dry, being subsequently placed in temperature is to roast 6 hours, obtain in 600 DEG C of Muffle furnaces
To propane dehydrogenation catalyst Cat-2, (on the basis of the total weight of propane dehydrogenation catalyst Cat-2, the content of Pt is 0.3 weight
% is measured, the content that the content of Sn is 0.7 weight %, Na is 0.5 weight %, remaining is carrier).
Table 2 is the pore structure parameter of spherical mesoporous sepiolite complex carrier C2 and propane dehydrogenation catalyst Cat-2.
Table 2
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size*(nm) | Partial size (μm) |
| Complex carrier C2 | 560 | 1.5 | 7.8,28 | 25-45 |
| Catalyst Cat-2 | 330 | 1.3 | 5,23 | 25-45 |
*: the first most probable pore size and the second most probable pore size are separated with comma: it is the first most probable pore size before comma,
It is the second most probable pore size after comma.
Spherical mesoporous sepiolite complex carrier is in load main active component Pt, metal promoted it can be seen from the data of table 2
After agent Sn and metal promoter Na, specific surface area and pore volume are reduced, this explanation is mainly lived during load-reaction
Property component Pt, metal promoter Sn and metal promoter Na enter the inside of spherical mesoporous sepiolite complex carrier.
Embodiment 3
The present embodiment is for illustrating propane dehydrogenation catalyst and preparation method thereof.
(1) preparation of spherical mesoporous sepiolite complex carrier
1g (0.0002mol) triblock copolymer surfactant P123 and 2.76g (0.06mol) ethyl alcohol is added to
In 28ml, the acetic acid and sodium acetate buffer that pH value is 4, stirring is completely dissolved to P123 at 15 DEG C, obtain backward it is molten
6g (0.053mol) trimethylpentane is added in liquid, 8h is stirred at 15 DEG C, then 2.13g (0.014mol) tetramethyl is added thereto
Oxysilane stirs 10h under conditions of 15 DEG C, pH value are 4.5, obtained solution is then transferred to polytetrafluoroethyllining lining
Reaction kettle in, at 60 DEG C crystallization for 24 hours, be then filtered and and be washed with deionized 4 times, then filtering is had
The meso-porous molecular sieve material filter cake A3 of one-dimensional hexagonal hole road distributed architecture；
It is the sulfuric acid solution of 12 weight % by waterglass and concentration that concentration is 15 weight % with weight ratio is that 6:1 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 being washed with distilled water to sodium ions content is 0.02 weight %, obtains silica gel filter cake B3.
20g filter cake A3,30g filter cake B3 and 10g sepiolite of above-mentioned preparation is put into togerther in 100ml ball grinder, wherein
The material of ball grinder is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 550r/
min.Ball grinder is closed, temperature is to obtain 55g solid powder ball milling 10 hours at 40 DEG C in ball grinder；By the solid powder
It is dissolved in 30g deionized water, is spray-dried at 150 DEG C in the case where revolving speed is 13000r/min；By what is obtained after spray drying
Product is calcined 70 hours at 450 DEG C in Muffle furnace, removed template method, is obtained 53g and is distributed with one-dimensional hexagonal hole road diplopore
The spherical mesoporous sepiolite complex carrier C3 of structure.
(2) preparation of propane dehydrogenation catalyst
By 0.08g H2PtCl6·6H2O、0.207g SnCl4·5H2O and 0.185g NaNO3It is dissolved in 100ml deionized water
In, mixture solution is obtained, the spherical mesoporous sepiolite complex carrier C3 that step (1) is obtained is immersed in the mixture solution
In, after being impregnated 5 hours at 30 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product, by solid product
It is placed in the drying box that temperature is 150 DEG C, 3 hours dry, being subsequently placed in temperature is to roast 5h in 650 DEG C of Muffle furnaces, obtain third
(on the basis of the total weight of propane dehydrogenation catalyst Cat-3, the content of Pt is 0.3 weight %, Sn to alkane dehydrogenation Cat-3
Content be 0.7 weight %, Na content be 0.5 weight %, remaining is carrier).
Table 3 is the pore structure parameter of three holes spherical mesoporous composite material C3 and dehydrogenation Cat-3.
Table 3
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size*(nm) | Partial size (μm) |
| Complex carrier C3 | 380 | 1.1 | 6.8,25 | 30-50 |
| Catalyst Cat-3 | 320 | 0.9 | 3.6,20 | 30-50 |
*: the first most probable pore size and the second most probable pore size are separated with comma: it is the first most probable pore size before comma,
It is the second most probable pore size after comma.
Spherical mesoporous sepiolite complex carrier is in load main active component Pt, metal promoted it can be seen from the data of table 3
After agent Sn and metal promoter Na, specific surface area and pore volume are reduced, this explanation is mainly lived during load-reaction
Property component Pt, metal promoter Sn and metal promoter Na enter the inside of spherical mesoporous sepiolite complex carrier.
EXPERIMENTAL EXAMPLE 1
The present embodiment is used for the method for illustrating to prepare propylene using propane dehydrogenation catalyst of the invention
0.5g propane dehydrogenation catalyst Cat-1 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 reaction time 50h, propane mass space velocity is 3h-1.Propane
Conversion ratio and Propylene Selectivity are as shown in table 4.
EXPERIMENTAL EXAMPLE 2-3
Preparing propylene by dehydrogenating propane is carried out according to the method for EXPERIMENTAL EXAMPLE 1, unlike, dehydrogenating propane catalysis is respectively adopted
Agent Cat-2 and propane dehydrogenation catalyst Cat-3 replaces propane dehydrogenation catalyst Cat-1.Conversion of propane and Propylene Selectivity are such as
Shown in table 4.
Experimental comparison's example 1-4
Preparing propylene by dehydrogenating propane is carried out according to the method for EXPERIMENTAL EXAMPLE 1, unlike, dehydrogenating propane catalysis is respectively adopted
Agent Cat-D-1, propane dehydrogenation catalyst Cat-D-2, propane dehydrogenation catalyst Cat-D-3 and propane dehydrogenation catalyst Cat-D-4
Instead of propane dehydrogenation catalyst Cat-1.Conversion of propane and Propylene Selectivity are as shown in table 4.
Table 4
| Dehydrogenation | Conversion of propane | Propylene Selectivity | |
| EXPERIMENTAL EXAMPLE 1 | Cat-1 | 36% | 99% |
| EXPERIMENTAL EXAMPLE 2 | Cat-2 | 31.9% | 99.1% |
| EXPERIMENTAL EXAMPLE 3 | Cat-3 | 34.8% | 99.6% |
| Experimental comparison's example 1 | Cat-D-1 | 10% | 82% |
| Experimental comparison's example 2 | Cat-D-2 | 9% | 67% |
| Experimental comparison's example 3 | Cat-D-3 | 12% | 77% |
| Experimental comparison's example 4 | Cat-D-4 | 18% | 83% |
From table 4, it can be seen that the propane dehydrogenation catalyst prepared using spherical mesoporous sepiolite complex carrier of the invention
When for preparing propylene by dehydrogenating propane reaction, after reaction 50 hours, still available higher conversion of propane and propylene selection
Property, illustrating propane dehydrogenation catalyst of the invention not only has preferable catalytic performance, but also stability is good.
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 (19)
1. a kind of propane dehydrogenation catalyst, which is characterized in that the propane dehydrogenation catalyst includes carrier and is supported on described
Main active component Pt, metal promoter Sn and metal promoter Na on carrier, wherein the carrier is multiple for spherical mesoporous sepiolite
Carrier is closed, the spherical mesoporous sepiolite complex carrier contains sepiolite and Jie with one-dimensional hexagonal hole road diplopore distributed architecture
Porous molecular sieve material, the average grain diameter of the spherical mesoporous sepiolite complex carrier are 10-50 μm, specific surface area 150-
600m2/ g, pore volume 0.5-2mL/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively
2-9nm and 10-40nm,
Wherein, with the weight of the meso-porous molecular sieve material described in 100 parts by weight with one-dimensional hexagonal hole road diplopore distributed architecture
On the basis of, the weight of the sepiolite is 1-50 parts by weight.
2. propane dehydrogenation catalyst according to claim 1, wherein the dehydrogenating propane relative to 100 parts by weight is urged
The content of agent, the spherical mesoporous sepiolite complex carrier is 97.5-99.3 weight %, and the main active component Pt's contains
Amount is 0.2-0.5 weight %, and the content of metal promoter Sn is 0.2-1.2 weight %, and the content of metal promoter Na is 0.3-0.8 weight
Measure %.
3. propane dehydrogenation catalyst according to claim 1, wherein the average particle diameter of the propane dehydrogenation catalyst
It is 10-50 μm, specific surface area 180-400m2/ g, pore volume 0.8-1.5mL/g, pore-size distribution are bimodal distribution, and described
Bimodal corresponding most probable pore size is respectively 3-8nm and 20-30nm.
4. propane dehydrogenation catalyst according to claim 1, wherein to have one-dimensional hexagonal hole described in 100 parts by weight
On the basis of the weight of the meso-porous molecular sieve material of road diplopore distributed architecture, the weight of the sepiolite is 20-50 parts by weight.
5. a kind of method for preparing propane dehydrogenation catalyst, which is characterized in that this method comprises: by containing after carrier thermal activation
It is impregnated in the mixed solution of Pt salt, Sn salt and Na salt, is dried and roasts after the solution after dipping is then removed solvent
It burns, wherein the carrier is spherical mesoporous sepiolite complex carrier, and the spherical mesoporous sepiolite complex carrier contains sepiolite
With the meso-porous molecular sieve material with one-dimensional hexagonal hole road diplopore distributed architecture, the spherical mesoporous sepiolite complex carrier is put down
Equal partial size is 10-50 μm, specific surface area 150-600m2/ g, pore volume 0.5-2mL/g, pore-size distribution are bimodal distribution, and
The bimodal corresponding most probable pore size is respectively 2-9nm and 10-40nm,
Wherein, with the weight of the meso-porous molecular sieve material described in 100 parts by weight with one-dimensional hexagonal hole road diplopore distributed architecture
On the basis of, the weight of the sepiolite is 1-50 parts by weight.
6. according to the method described in claim 5, wherein, the spherical mesoporous sepiolite complex carrier, Pt salt, Sn salt and Na salt
Dosage make in the propane dehydrogenation catalyst being prepared, it is described on the basis of the total weight of the propane dehydrogenation catalyst
The content of spherical mesoporous sepiolite complex carrier is that content of 97.5-99.3 weight %, the Pt salt in terms of Pt element is 0.2-0.5 weight
% is measured, content of the Sn salt in terms of Sn element is that content of 0.2-1.2 weight %, the Na salt in terms of Na element is 0.3-0.8 weight %.
7. the average particle diameter of the propane dehydrogenation catalyst is 10-50 μm according to the method described in claim 5, wherein,
Specific surface area is 180-400m2/ g, pore volume 0.8-1.5mL/g, pore-size distribution are bimodal distribution, and described bimodal corresponding
Most probable pore size is respectively 3-8nm and 20-30nm.
8. the condition of the thermal activation includes: that temperature is 300-900 DEG C according to the method described in claim 5, wherein, the time
It is 7-10 hours；The condition of the dipping includes: that temperature is 25-50 DEG C, and the time is 2-6 hours.
9. the method according to any one of claim 5-8, the formation side of the spherical mesoporous sepiolite complex carrier
Method the following steps are included:
(a) in the presence of template, trimethylpentane and ethyl alcohol, tetramethoxy-silicane is contacted with sour agent, and will connect
The product crystallization that obtains after touch simultaneously filters, and obtains mesoporous material filter cake；
(b) waterglass is contacted with inorganic acid, and the product obtained after contact is filtered, obtain silica gel filter cake；
(c) the mesoporous material filter cake, silica gel filter cake and sepiolite are mixed into simultaneously ball milling, and the solid powder that will be obtained after ball milling
With being spray-dried after water slurrying, then by the template removal in obtained product.
10. according to the method described in claim 9, wherein, in step (a), the template, ethyl alcohol, trimethylpentane with
The molar ratio of tetramethoxy-silicane is 1:100-500:200-600:50-200.
11. according to the method described in claim 9, wherein, the template is triblock copolymer polyoxyethylene-polyoxy third
Alkene-polyoxyethylene, the acid agent are the buffer solution of acetic acid and sodium acetate that pH value is 1-6.
12. according to the method described in claim 9, wherein, the condition that tetramethoxy-silicane is contacted with sour agent includes: that temperature is
10-60 DEG C, the time is 10-72 hours, pH value 1-7；The condition of the crystallization includes: that temperature is 30-150 DEG C, time 10-
72 hours.
13. according to the method described in claim 9, wherein, in step (b), condition that the waterglass is contacted with inorganic acid
Include: temperature be 10-60 DEG C, the time be 1-5 hours, pH value 2-4；The inorganic acid is one in sulfuric acid, nitric acid and hydrochloric acid
Kind is a variety of.
14. according to the method described in claim 9, wherein, in step (c), with the mesoporous material filter cake of 100 parts by weight
Dosage on the basis of, the dosage of the silica gel filter cake is 1-200 parts by weight, and the dosage of the sepiolite is 1-50 parts by weight.
15. according to the method for claim 14, wherein using the dosage of the mesoporous material filter cake of 100 parts by weight as base
Standard, the dosage of the silica gel filter cake are 50-150 parts by weight, and the dosage of the sepiolite is 1-50 parts by weight.
16. the propane dehydrogenation catalyst that method described in any one of claim 5-15 is prepared.
17. a kind of method of preparing propylene by dehydrogenating propane, which comprises in the presence of catalyst and hydrogen, by propane into
Row dehydrogenation reaction, which is characterized in that the catalyst is dehydrogenating propane catalysis described in any one of claim 1-4 and 16
Agent.
18. according to the method for claim 17, wherein the molar ratio of the dosage of the dosage and hydrogen of propane is 0.5-1.5:
1。
19. according to the method for claim 17, wherein the condition of the dehydrogenation reaction includes: that reaction temperature is 600-650
DEG C, reaction pressure 0.05-0.2MPa, reaction time 40-60h, propane mass space velocity are 2-5h-1。
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