CN109382133B - 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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- CN109382133B CN109382133B CN201710666304.5A CN201710666304A CN109382133B CN 109382133 B CN109382133 B CN 109382133B CN 201710666304 A CN201710666304 A CN 201710666304A CN 109382133 B CN109382133 B CN 109382133B
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- propane
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- diatomite
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 220
- 239000001294 propane Substances 0.000 title claims abstract description 110
- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 69
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 154
- 239000000969 carrier Substances 0.000 claims abstract description 61
- 239000011148 porous material Substances 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 31
- 238000009826 distribution Methods 0.000 claims abstract description 29
- 230000002902 bimodal effect Effects 0.000 claims abstract description 23
- 239000002808 molecular sieve Substances 0.000 claims abstract description 21
- 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 21
- 239000012065 filter cake Substances 0.000 claims description 39
- 239000011734 sodium Substances 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 229910002027 silica gel Inorganic materials 0.000 claims description 23
- 239000000741 silica gel Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000013335 mesoporous material 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 14
- 239000007787 solid Substances 0.000 claims description 13
- 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
- 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
- 239000002245 particle Substances 0.000 claims description 11
- 235000019353 potassium silicate Nutrition 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 10
- 239000000843 powder 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
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000007725 thermal activation Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen 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
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229920000428 triblock copolymer Polymers 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 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
- 239000004744 fabric Substances 0.000 claims 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 32
- 239000000243 solution Substances 0.000 description 15
- 239000012752 auxiliary agent Substances 0.000 description 13
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 description 13
- -1 heat-insulated Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 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
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000001694 spray drying Methods 0.000 description 8
- 238000001035 drying Methods 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
- 239000007788 liquid Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000000694 effects Effects 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
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000007974 sodium acetate buffer Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 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
- 238000001354 calcination 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
- 230000007547 defect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 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
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006467 substitution reaction 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
- 241000206761 Bacillariophyta Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012814 acoustic material Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 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
- 238000005272 metallurgy Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000003595 mist Substances 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
- 239000003973 paint Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 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
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 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
- 239000010959 steel Substances 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
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- 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
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- 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
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- 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
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- 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
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- C07C2523/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of germanium, tin or lead
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- C—CHEMISTRY; METALLURGY
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- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/42—Platinum
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- 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
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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 Pt component, Sn component and the Na component of carrier and load on the carrier, wherein, the carrier is spherical double mesoporous diatomite complex carriers, spherical double mesoporous diatomite complex carriers contain diatomite and the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture, the average grain diameter of spherical double mesoporous diatomite complex carriers is 30-60 μm, specific surface area 150-350m2/ g, pore volume 0.5-1.5mL/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 5-15nm and 20-40nm.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
Diatomite is that earth's surface is distributed one of most commonly used clay mineral, it has porosity, lower concentration, biggish
The physical and chemical performances such as specific surface area, opposite Incoercibility and chemical stability, since diatomite has special physicochemical property,
The catalyst carrier being widely used in Chemical Manufacture, paint, rubber, the filler material in papermaking, filtering, bleaching in food industry
Agent, heat-insulated, acoustic material and petroleum refining, ceramics, glass, steel, metallurgy heat treatment etc..
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-Al2O3 carrier is substituted using molecular sieve carrier, effect preferably includes MFI
Type micro porous molecular sieve (CN104307555A, CN101066532A, CN101380587A, CN101513613A), mesoporous MCM-41
Molecular sieve (CN102389831A) and mesoporous SBA-15 molecular sieve (CN101972664A, CN101972664B) etc..However at present
Common mesoporous material aperture is smaller (6~9nm of average pore size), if carrying out bulky molecular catalysis reaction, macromolecular is more difficult to get access
Duct, so that influencing catalytic effect.Therefore, it selects a kind of excellent carrier to be that one, dehydrogenating propane field is urgently to be resolved to ask
Topic.
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 Pt component, Sn component and the Na component of carrier and load on the carrier, wherein the carrier is spherical double Jie
Hole composite diatomite carrier, spherical double mesoporous diatomite complex carriers contain diatomite and have the distribution of one-dimensional hexagonal hole road
The average grain diameter of the meso-porous molecular sieve material of structure, spherical double mesoporous diatomite complex carriers is 30-60 μm, specific surface area
For 150-350m2/ g, pore volume 0.5-1.5mL/g, pore-size distribution are bimodal distribution, and the bimodal corresponding most probable hole
Diameter is respectively 5-15nm and 20-40nm.
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 carried out at dipping in the mixed solution containing Pt component presoma, Sn component presoma and Na component presoma after thermal activation
Then reason is successively removed solvent processing, dry and roasting, wherein the carrier is that spherical double mesoporous composite diatomites carry
Body, spherical double mesoporous diatomite complex carriers contain diatomite and the mesoporous molecular with one-dimensional hexagonal hole road distributed architecture
Material is sieved, the average grain diameter of spherical double mesoporous diatomite complex carriers is 30-60 μm, specific surface area 150-350m2/ g,
Pore volume is 0.5-1.5mL/g, and pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 5-15nm
And 20-40nm.
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 double mesoporous diatomite complex carriers according to the present invention, combine to be distributed with one-dimensional hexagonal hole road and tie
The advantages of meso-porous molecular sieve material of structure, diatomite and ball type carrier, so that the double mesoporous diatomite complex carriers of the spherical shape are suitable
The carrier for making loaded catalyst is shared, the supported catalyst used in preparing propylene by dehydrogenating propane reaction is especially suitable as
The carrier of agent.
In the loaded catalyst of the invention, spherical double mesoporous diatomite complex carriers have mesoporous molecular
The larger feature of porous structure, large specific surface area, the pore volume of material is sieved, in conjunction with natural diatomaceous earth due to comparing table with biggish
Area and microcellular structure and the strong adsorption capacity having are conducive to metal component in the fine dispersion of carrier surface, and described
Carrier is also loaded the Pt component as chief active metal component, the Sn component as auxiliary agent and Na component, so that the load
Type catalyst had not only had the advantages that loaded catalyst such as catalytic activity is high, side reaction is few, post-processing is simple etc., but also had relatively strong
Catalytic activity so that the loaded catalyst for dehydrogenating propane reaction in have better dehydrogenation activity and selectivity,
The conversion ratio of reaction raw materials is significantly improved, specifically, in the reaction that preparing propylene by dehydrogenating propane is carried out using the loaded catalyst,
Conversion of propane is up to 20%, and the selectivity of propylene is up to 73%.
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 preparation cost is low, good economy performance.
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 double mesoporous diatomite complex carriers of spherical shape of embodiment 1；
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of the double mesoporous diatomite complex carriers of spherical shape of embodiment 1.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of propane dehydrogenation catalyst, the propane dehydrogenation catalyst includes carrier and is supported on institute
State Pt component, Sn component and the Na component on carrier, wherein the carrier is spherical double mesoporous diatomite complex carriers, described
Spherical double mesoporous diatomite complex carriers contain diatomite and the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture,
The average grain diameter of spherical double mesoporous diatomite complex carriers is 30-60 μm, specific surface area 150-350m2/ g, pore volume
For 0.5-1.5mL/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 5-15nm and 20-
40nm。
According to the present invention, there is spherical double mesoporous diatomite complex carriers special one-dimensional hexagonal hole road 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, partial size 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, by by the structural parameter control of the spherical double mesoporous diatomite complex carriers in above range
Within, it can be ensured that spherical double mesoporous diatomite complex carriers are not susceptible to reunite, and are used as made of carrier
The reaction raw materials conversion ratio in preparing propylene by dehydrogenating propane reaction process can be improved in loaded catalyst.When described spherical double mesoporous
The specific surface area of composite diatomite carrier is less than 150m2When/g and/or pore volume are less than 0.5mL/g, it is used as carrier and is made
The catalytic activity of loaded catalyst can significantly reduce；When the large specific surface area of spherical double mesoporous diatomite complex carriers
In 350m2When/g and/or pore volume are greater than 1.5mL/g, loaded catalyst made of carrier is used as in dehydrogenating propane system
Reunion is easy to happen in propylene reaction process, to influence the reaction raw materials conversion ratio in preparing propylene by dehydrogenating propane reaction process.
In the preferred case, the average grain diameter of spherical double mesoporous diatomite complex carriers is 35-55 μm, specific surface area
For 250-300m2/ g, pore volume 1-1.5mL/g, pore-size distribution are bimodal distribution, and the bimodal corresponding most probable pore size
Respectively 8-10nm and 25-35nm.
According to the present invention, the propane dehydrogenation catalyst includes carrier and load Pt component on the carrier, Sn
Component and Na component, wherein the Pt group is divided into active metal component, and the Sn component and Na group are divided into metal promoter.
According to the present invention, relative to the propane dehydrogenation catalyst of 100 parts by weight, spherical double mesoporous tripolite compounds
The content for closing carrier is 97.5-99.3 weight %, and content of the Pt component in terms of Pt element is 0.2-0.5 weight %, described
Content of the Sn component in terms of Sn element is 0.2-1.2 weight %, and content of the Na component in terms of Na element is 0.3-0.8 weight
Measure %.
Preferably, the average particle diameter of the propane dehydrogenation catalyst is 30-60 μm, specific surface area 120-300m2/
G, pore volume 0.3-1.3mL/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 7-
12nm and 25-35nm.
According to the present invention, one-dimensional to have described in 100 parts by weight in spherical double mesoporous diatomite complex carriers
On the basis of the weight of the meso-porous molecular sieve material of hexagonal hole road distributed architecture, the weight of the diatomite is 1-50 parts by weight, excellent
It is selected as 20-50 parts by weight.
According to the present invention, spherical double mesoporous diatomite complex carriers can also contain the titanium dioxide introduced by silica gel
Silicon." silica being introduced by silica gel " refers in the preparation process of spherical double mesoporous diatomite complex carriers, by
Silica gel is as the silica component for preparing raw material and bringing into the double mesoporous diatomite complex carriers of spherical shape finally prepared.Described
In spherical double mesoporous diatomite complex carriers, relative to Jie described in 100 parts by weight with one-dimensional hexagonal hole road distributed architecture
The weight of porous molecular sieve 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 distributed architecture can be normal for this field
The meso-porous molecular sieve material used is advised, 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
Carry out impregnation in the mixed solution containing Pt component presoma, Sn component presoma and Na component presoma, then according to
It is secondary to be removed solvent processing, dry and roasting, wherein the carrier is spherical double mesoporous diatomite complex carriers, the ball
The double mesoporous diatomite complex carriers of shape contain diatomite and the meso-porous molecular sieve material with one-dimensional hexagonal hole road distributed architecture, institute
The average grain diameter for stating spherical double mesoporous diatomite complex carriers is 30-60 μm, specific surface area 150-350m2/ g, pore volume are
0.5-1.5mL/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 5-15nm and 20-
40nm。
According to the present invention, in order to remove the hydroxyl and Residual water of the spherical double mesoporous diatomite complex carriers, in institute
It states before spherical double mesoporous diatomite composite carrier load metal components firstly the need of carrying out thermal activation treatment, the thermal activation treatment
Condition may include: in the presence of nitrogen, by carrier temperature be 300-900 DEG C at carry out calcining 7-10h.
According to the present invention, spherical double mesoporous diatomite composite carrier load metal components can be using the side of dipping
Formula, the capillary pressure by the cellular structure of spherical double mesoporous diatomite complex carriers make metal component enter the spherical shape
In the duct of double mesoporous diatomite complex carriers, while metal component can also spherical double mesoporous diatomite complex carriers again
Adsorption, until metal component reaches adsorption equilibrium on the surface of spherical double mesoporous diatomite complex carriers.Preferably,
The impregnation carry out after thermal activation treatment in spherical double mesoporous diatomite complex carriers, the impregnation
It can be handled for co-impregnation, or step impregnation processing.In order to save preparation cost, simplify experimental technique, the dipping
Processing is preferably co-impregnation processing；It is further preferred that the condition of the co-impregnation processing includes: by six Fang Jie after thermal activation
Porous materials are mixed in the solution containing Pt component presoma, Sn component presoma and Na component presoma, the leaching
The temperature of stain can be 25-50 DEG C, and the time of the dipping can be 2-6h.
According to the present invention, the solution of the Pt component presoma, Sn component presoma and Na component presoma is not special
Restriction as long as water-soluble can be the conventional selection of this field.For example, the Pt component presoma can be
H2PtCl6, the Sn component presoma can be SnCl4, the Na component presoma can be NaNO3。
The present invention does not have the concentration of the solution containing Pt component presoma, Sn component presoma and Na component presoma
There is special restriction, can be the conventional selection of this field, for example, the concentration of the Pt component presoma can be 0.1-
The concentration of 0.3mol/L, the Sn component presoma can be 0.15-1mol/L, and the concentration of the Na component presoma can be
1-3.5mol/L。
According to the present invention, spherical double mesoporous diatomite complex carriers, Pt component presoma, Sn component presoma and Na
The dosage of component presoma can be so that preparation propane dehydrogenation catalyst in, with the total weight of the propane dehydrogenation catalyst
On the basis of, it is 0.2-0.5 weight % that the content of the carrier, which is content of 97.5-99.3 weight %, the Pt component in terms of Pt element,
Content of the Sn component in terms of Sn element is that content of 0.2-1.2 weight %, the Na component in terms of Na element is 0.3-0.8 weight %.
According to the present invention, the process of the removal solvent processing can adopt with the conventional methods in the field, such as can adopt
With the solvent in Rotary Evaporators 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, time 3-6h；The condition of the roasting may include: that temperature is 600-
650 DEG C, time 5-8h.
According to the present invention, the spherical double mesoporous diatomite complex carriers 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 diatomite 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 double mesoporous diatomite complex carriers, the mesoporous material filter cake is with one-dimensional
The meso-porous molecular sieve material of hexagonal hole road distributed architecture.
In the forming process of above-mentioned spherical double mesoporous diatomite complex carriers, it is main by control mesoporous material filter cake,
The composition of silica gel filter cake and diatomite controls pore-size distribution for bimodal distribution, makes the double mesoporous diatomite complex carriers tools of the spherical shape
There is diplopore distributed architecture, and by control forming method (that is, first mixing mesoporous material filter cake, silica gel filter cake and diatomite
And ball milling, then will be spray-dried after the water slurrying of obtained solid powder) by the spherical double mesoporous diatomite complex carriers
Microscopic appearance control for spherical shape.
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 shape that can make is double mesoporous
Composite diatomite carrier has above-mentioned pore structure, it is preferable that the template can be triblock copolymer polyoxyethylene-
Polyoxypropylene polyoxyethylene.Wherein, which can be commercially available (for example, can be purchased from Aldrich, commodity
Entitled P123, molecular formula EO20PO70EO20), it can also be prepared by existing various methods.When the template is
When polyoxyethylene-poly-oxypropylene polyoxyethylene, the molal quantity of the template is according to polyoxyethylene-poly-oxypropylene polyoxyethylene
Average molecular weight calculate 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 after being stirred template, ethyl alcohol, sour agent and trimethylpentane, then to add four methoxies first at 10-100 DEG C
Base silane 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 mesoporous material filter cake so that filter cake PH is 7, prepare 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 diatomite can root
It is anticipated that the component of the double mesoporous diatomite complex carriers of obtained spherical shape is selected, under preferable case, with the institute of 100 parts by weight
On the basis of the dosage for giving an account of Porous materials filter cake, the dosage of the silica gel filter cake can be 1-200 parts by weight, preferably 50-150 weight
Measure part；The dosage of the diatomite 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 diatomite 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 double mesoporous diatomite complex carriers
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 4.4, stirring is completely dissolved to P123 at 15 DEG C, obtain backward
6g (0.053mol) trimethylpentane is added in solution, 8h is stirred at 15 DEG C, then 2.13g (0.014mol) four is added thereto
Methoxy silane stirs 20h under conditions of 15 DEG C, pH value are 4.5, then obtained solution is transferred in polytetrafluoroethylene (PTFE)
In the reaction kettle of lining, at 60 DEG C crystallization for 24 hours, be then filtered and and be washed with deionized 4 times, then filter and had
There is the meso-porous molecular sieve material filter cake A1 of one-dimensional hexagonal hole road single hole 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 1.5h at 30 DEG C, it is then anti-to what is obtained then with the sulfuric acid adjustment pH value that concentration is 98 weight % to 3
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 B1.
10g filter cake A1,10g filter cake B1 and 10g diatomite 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 30g 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 30 grams of deionized waters；The production that will be obtained after spray drying
Object is calcined 24 hours at 500 DEG C in Muffle furnace, removed template method, obtains 30g with one-dimensional hexagonal hole road diplopore distribution knot
The double mesoporous diatomite complex carrier C1 of the spherical shape 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, it is molten that the double mesoporous diatomite complex carrier C1 of spherical shape that step (1) obtains are immersed in the mixture
In liquid, after being impregnated 5 hours at 25 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, solid product is obtained, solid is produced
Object is placed in the drying box that temperature is 120 DEG C, 3 hours dry, and being subsequently placed in temperature is to roast 6 hours in 600 DEG C of Muffle furnaces,
Obtaining propane dehydrogenation catalyst Cat-1, (on the basis of the total weight of propane dehydrogenation catalyst Cat-1, Pt component is in terms of Pt element
Content be content of 0.3 weight %, the Sn component in terms of Sn element be that content of 0.7 weight %, the Na component in terms of Na element is
0.5 weight %, remaining is carrier).
Spherical double mesoporous composite diatomites are carried with XRD, scanning electron microscope and ASAP2020-M+C type adsorption instrument
Body C1 and propane dehydrogenation catalyst Cat-1 are characterized；
Fig. 1 is the X-ray diffracting spectrum of spherical double mesoporous diatomite complex carrier C1, wherein abscissa is 2 θ, indulges and sits
It is designated as intensity, the low-angle spectral peak occurred by XRD spectra is it is found that the XRD spectra a of spherical double mesoporous diatomite complex carrier C1 has
There is one-dimensional hexagonal hole road structure specific to mesoporous material；
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of spherical double mesoporous diatomite complex carrier C1, as seen from the figure, spherical double mesoporous silicons
The microscopic appearance of diatomaceous earth complex carrier C1 is the Mesoporous Spheres that granularity is 30-60 μm；
Table 1 is the pore structure parameter of spherical double mesoporous diatomite 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 | 286 | 1 | 9,30 | 30-60 |
| Catalyst Cat-1 | 255 | 0.8 | 7.5,26.7 | 30-60 |
*: the first most probable pore size and the second most probable pore size are separated with comma: being successively according to sequence from left to right
One most probable pore size and the second most probable pore size.
Spherical double mesoporous diatomite complex carriers are in load chief active Pt component, auxiliary agent it can be seen from the data of table 1
After Sn component and auxiliary agent Na component, specific surface area and pore volume are reduced, this explanation is main during load-reaction
Active Pt component, auxiliary agent Sn component and auxiliary agent Na component enter the inside of spherical double mesoporous diatomite complex carriers.
Comparative example 1
Carrier and loaded catalyst are prepared according to the method for embodiment 1, it is different, during preparing carrier not
Diatomite is added, so that carrier D1 and loaded catalyst Cat-D-1 be made respectively.
Comparative example 2
Carrier and loaded catalyst are prepared according to the method for embodiment 1, it is different, during preparing carrier not
Mesoporous material is added, so that carrier D2 and loaded catalyst Cat-D-2 be made respectively.
Comparative example 3
Spherical double mesoporous diatomite complex carrier D3 and loaded catalyst Cat-D-3 are prepared according to the method for embodiment 1,
It is different, during preparing loaded catalyst, with the rodlike mesoporous silicon oxide SBA-15 of identical weight (purchased from Ji
High-tech limited liability company, woods university) meso-porous molecular sieve material filter cake A1 is replaced, so that spherical double mesoporous diatoms be made respectively
Native complex carrier D3 and loaded catalyst Cat-D-3.
Comparative example 4
It is different according to the spherical double mesoporous diatomite complex carriers of the method for embodiment 1 preparation and loaded catalyst,
The step of not being spray-dried during preparing loaded catalyst, and only by the method for dipping by Pt component, Sn group
Divide and Na component is supported on spherical double mesoporous diatomite complex carriers, so that loaded catalyst Cat-D-4 be made.
Embodiment 2
The present embodiment is for illustrating propane dehydrogenation catalyst and preparation method thereof.
(1) preparation of spherical double mesoporous diatomite complex carriers
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 single hole 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 8g diatomite 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 double mesoporous diatomite complex carrier C2 of the spherical shape 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, it is molten that the double mesoporous diatomite complex carrier C2 of spherical shape that step (1) obtains are immersed in the mixture
In liquid, after being impregnated 5 hours at 25 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, solid product is obtained, solid is produced
Object is placed in the drying box that temperature is 120 DEG C, 3 hours dry, and being subsequently placed in temperature is to roast 6 hours in 600 DEG C of Muffle furnaces,
Obtaining propane dehydrogenation catalyst Cat-2, (on the basis of the total weight of propane dehydrogenation catalyst Cat-2, Pt component is in terms of Pt element
Content be content of 0.3 weight %, the Sn component in terms of Sn element be that content of 0.7 weight %, the Na component in terms of Na element is
0.5 weight %, remaining is carrier).
Table 2 is the pore structure parameter of spherical double mesoporous diatomite 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 | 260 | 1.1 | 8.3,27.5 | 35-50 |
| Catalyst Cat-2 | 235 | 0.7 | 7.2,25.7 | 35-50 |
*: the first most probable pore size and the second most probable pore size are separated with comma: being successively according to sequence from left to right
One most probable pore size and the second most probable pore size.
Spherical double mesoporous diatomite complex carriers are in load chief active Pt component, auxiliary agent it can be seen from the data of table 2
After Sn component and auxiliary agent Na component, specific surface area and pore volume are reduced, this explanation is main during load-reaction
Active Pt component, auxiliary agent Sn component and auxiliary agent Na component enter the inside of spherical double mesoporous diatomite complex carriers.
Embodiment 3
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 3, stirring is completely dissolved to P123 at 15 DEG C, obtain backward it is molten
5.7g (0.05mol) trimethylpentane is added in liquid, 8h is stirred at 15 DEG C, then 2.13g (0.014mol) four is added thereto
Methoxy silane stirs 10h under conditions of 40 DEG C, pH value are 3.5, then obtained solution is transferred in polytetrafluoroethylene (PTFE)
In the reaction kettle of lining, the crystallization 40h at 40 DEG C, be then filtered and and be washed with deionized 4 times, then filter and had
There is the meso-porous molecular sieve material filter cake A3 of one-dimensional hexagonal hole road single hole 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 12g diatomite 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 double mesoporous diatomite complex carrier C3 of the spherical shape 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, it is molten that the double mesoporous diatomite complex carrier C3 of spherical shape that step (1) obtains are immersed in the mixture
In liquid, after being impregnated 5 hours at 30 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, solid product is obtained, solid is produced
Object is placed in the drying box that temperature is 150 DEG C, 3 hours dry, and being subsequently placed in temperature is to roast 5h in 650 DEG C of Muffle furnaces, obtain
Propane dehydrogenation catalyst Cat-3 (on the basis of the total weight of propane dehydrogenation catalyst Cat-3, Pt component containing in terms of Pt element
It is content of 0.7 weight %, the Na component in terms of Na element is 0.5 weight that amount, which is content of 0.3 weight %, the Sn component in terms of Sn element,
% is measured, remaining is carrier).
Table 3 is the pore structure parameter of spherical double mesoporous diatomite complex carrier C3 and propane dehydrogenation catalyst 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 | 280 | 1.3 | 8.6,27.3 | 40-55 |
| Catalyst Cat-3 | 263 | 0.9 | 7.1,26.5 | 40-55 |
*: the first most probable pore size and the second most probable pore size are separated with comma: being successively according to sequence from left to right
One most probable pore size and the second most probable pore size.
Spherical double mesoporous diatomite complex carriers are in load chief active Pt component, auxiliary agent it can be seen from the data of table 3
After Sn component and auxiliary agent Na component, specific surface area and pore volume are reduced, this explanation is main during load-reaction
Active Pt component, auxiliary agent Sn component and auxiliary agent Na component enter the inside of spherical double mesoporous diatomite complex carriers.
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 | 20% | 73% |
| EXPERIMENTAL EXAMPLE 2 | Cat-2 | 19.2% | 72.1% |
| EXPERIMENTAL EXAMPLE 3 | Cat-3 | 19.8% | 72.5% |
| Experimental comparison's example 1 | Cat-D-1 | 10.2% | 41.2% |
| Experimental comparison's example 2 | Cat-D-2 | 9.8% | 42.1% |
| Experimental comparison's example 3 | Cat-D-3 | 13.6% | 50.2% |
| Experimental comparison's example 4 | Cat-D-4 | 14.7% | 66.8% |
From table 4, it can be seen that being catalyzed using the dehydrogenating propane of the double mesoporous diatomite complex carrier preparations of spherical shape of the invention
When agent is reacted for preparing propylene by dehydrogenating propane, after reacting 50h, 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 (17)
1. a kind of propane dehydrogenation catalyst, which is characterized in that the propane dehydrogenation catalyst includes carrier and is supported on described
Pt component, Sn component and Na component on carrier, wherein the carrier is spherical double mesoporous diatomite complex carriers, the ball
The double mesoporous diatomite complex carriers of shape contain the silica introduced by silica gel, diatomite and have the distribution of one-dimensional hexagonal hole road
The average grain diameter of the meso-porous molecular sieve material of structure, spherical double mesoporous diatomite complex carriers is 30-60 μm, specific surface area
For 150-350m2/ g, pore volume 0.5-1.5mL/g, pore-size distribution are bimodal distribution, and the bimodal corresponding most probable hole
Diameter is respectively 5-15nm and 20-40nm；
Wherein, in spherical double mesoporous diatomite complex carriers, to have one-dimensional hexagonal hole road point described in 100 parts by weight
On the basis of the weight of the meso-porous molecular sieve material of cloth structure, the weight of the silica introduced by silica gel is 1-200 weight
Part is measured, the weight of the diatomite 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, spherical double mesoporous diatomite complex carriers is 97.5-99.3 weight %, and the Pt component is in terms of Pt element
Content be 0.2-0.5 weight %, content of the Sn component in terms of Sn element be 0.2-1.2 weight %, the Na component is with Na
The content of element meter is 0.3-0.8 weight %.
3. propane dehydrogenation catalyst according to claim 2, wherein the average particle diameter of the propane dehydrogenation catalyst
It is 30-60 μm, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 7-12nm and 25-35nm.
4. a kind of method for preparing propane dehydrogenation catalyst, which is characterized in that this method comprises: by containing after carrier thermal activation
Impregnation is carried out in the mixed solution of Pt component presoma, Sn component presoma and Na component presoma, is then successively carried out
Remove solvent processing, dry and roasting, wherein the carrier is spherical double mesoporous diatomite complex carriers, spherical double Jie
Hole composite diatomite carrier contains the silica introduced by silica gel, diatomite and with one-dimensional hexagonal hole road distributed architecture
The average grain diameter of meso-porous molecular sieve material, spherical double mesoporous diatomite complex carriers is 30-60 μm, specific surface area 150-
350m2/ g, pore volume 0.5-1.5mL/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is distinguished
For 5-15nm and 20-40nm；
Wherein, in spherical double mesoporous diatomite complex carriers, to have one-dimensional hexagonal hole road point described in 100 parts by weight
On the basis of the weight of the meso-porous molecular sieve material of cloth structure, the dosage of the silica introduced by silica gel is 1-200 weight
Part is measured, the dosage of the diatomite is 1-50 parts by weight.
5. according to the method described in claim 4, wherein, spherical double mesoporous diatomite complex carriers, Pt component presoma,
The dosage of Sn component presoma and Na component presoma makes in the propane dehydrogenation catalyst of preparation, with dehydrogenating propane catalysis
On the basis of the total weight of agent, it is 0.2- that the content of the carrier, which is content of 97.5-99.3 weight %, the Pt component in terms of Pt element,
Content of 0.5 weight %, the Sn component in terms of Sn element is that content of 0.2-1.2 weight %, the Na component in terms of Na element is 0.3-0.8
Weight %.
6. according to the method described in claim 5, wherein, the partial size of the propane dehydrogenation catalyst is 30-60 μm, pore-size distribution
For bimodal distribution, and the bimodal corresponding most probable pore size is respectively 7-12nm and 25-35nm.
7. the condition of the thermal activation includes: that temperature is 300-900 DEG C according to the method described in claim 4, wherein, the time
For 7-10h；The condition of the impregnation includes: that temperature is 25-50 DEG C, time 2-6h.
8. the method according to any one of claim 4-7, the formation of spherical double mesoporous diatomite complex carriers
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 diatomite 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.
9. according to the method described in claim 8, wherein, in step (a), the template, ethyl alcohol, trimethylpentane and four
The molar ratio of methoxy silane is 1:100-500:200-600:50-200.
10. 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.
11. according to the method described in claim 8, 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.
12. according to the method described in claim 8, wherein, in step (b), the 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.
13. according to the method described in claim 8, 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 50-150 parts by weight；The dosage of the diatomite is 20-50 parts by weight.
14. the propane dehydrogenation catalyst that method described in any one of claim 4-13 is prepared.
15. 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 1-3 and 14
Agent.
16. according to the method for claim 15, wherein the molar ratio of the dosage of the dosage and hydrogen of propane is 0.5-1.5:
1。
17. according to the method for claim 15, 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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