CN108786800A - The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane - Google Patents
The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane Download PDFInfo
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- CN108786800A CN108786800A CN201710313731.5A CN201710313731A CN108786800A CN 108786800 A CN108786800 A CN 108786800A CN 201710313731 A CN201710313731 A CN 201710313731A CN 108786800 A CN108786800 A CN 108786800A
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- Prior art keywords
- carrier
- loaded catalyst
- catalyst
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- propane
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 67
- 239000001294 propane Substances 0.000 title claims abstract description 65
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000013335 mesoporous material Substances 0.000 claims abstract description 55
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 36
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 36
- 239000011734 sodium Substances 0.000 claims abstract description 36
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 27
- 239000011148 porous material Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 238000005470 impregnation Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 150000003058 platinum compounds Chemical class 0.000 claims description 9
- 239000003125 aqueous solvent Substances 0.000 claims description 8
- 150000003606 tin compounds Chemical class 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 7
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 7
- 235000011151 potassium sulphates Nutrition 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000006356 dehydrogenation reaction Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000007725 thermal activation Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000012265 solid product Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 5
- -1 polypropylene Polymers 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
- 238000003756 stirring Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000000205 computational method Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 210000002659 acromion Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 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
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
- B01J35/617—500-1000 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
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
- C07C2523/04—Alkali metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of germanium, tin or lead
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to catalyst field, discloses a kind of loaded catalyst and preparation method thereof, application and a kind of method of preparing propylene by dehydrogenating propane of the loaded catalyst in preparing propylene by dehydrogenating propane reaction.The loaded catalyst includes platinum component, tin component and the sodium component of carrier and load on the carrier, wherein the carrier is hexagonal mesoporous material, and the specific surface area of the hexagonal mesoporous material is 550-650m2/ g, pore volume 0.3-1.4cm2/ g, aperture 0.3-1.2nm.The reaction of loaded catalyst catalysis preparing propylene by dehydrogenating propane using the present invention, conversion of propane is high, and Propylene Selectivity is high.
Description
Technical field
The present invention relates to catalyst fields, and in particular, to a kind of loaded catalyst, a kind of system of loaded catalyst
Preparation Method, application of the loaded catalyst in preparing propylene by dehydrogenating propane reaction, a kind of preparing propylene by dehydrogenating propane
Method.
Background technology
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 replacement 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 techniques in ABB Lummus companies Catofin techniques
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 be regenerated 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, cause catalyst cost higher.Third
Alkane dehydrogenation producing propylene technique realizes that industrialized production alreadys exceed 20 years, also many to the research of dehydrogenation, but current
Catalyst still there is conversion of propane it is not high and be easy to inactivation the defects of, require further improvement and perfect.Therefore, it develops
The propane dehydrogenation catalyst of function admirable has realistic meaning.
In order to improve the reactivity worth of propane dehydrogenation catalyst, researcher has done many work.Such as：(1) it uses and divides
Son sieve class carrier substitutes traditional γ-Al2O3Carrier, effect preferably include MFI type micro porous molecular sieve (CN104307555A,
CN101066532A, CN101380587A, CN101513613A), mesoporous MCM-41 molecular sieves (CN102389831A) and mesoporous
SBA-15 molecular sieves (CN101972664A, CN101972664B) etc.；(2) use calsil to γ-Al2O3Carrier is repaiied
Decorations, and the various active metal components of step impregnation and metal promoter (CN104368364A)；(3) with aluminium oxide and magnesia
Composite oxides are as carrier, and the various active metal components of step impregnation and metal promoter (CN104888818A).It is above-mentioned
The improved method of various propane dehydrogenation catalysts all can cause catalyst preparation process more cumbersome, and manufacturing cost increases, and prepare
Cycle stretch-out, or even can use and arrive the reagent or raw material unfavorable to environmental resource.
Invention content
The purpose of the present invention is overcoming, existing dehydrogenation preparation process is complicated, active metal component dispersion is uneven
Defect, a kind of loaded catalyst and its preparation method and application is provided.Loaded catalyst catalysis third using the present invention
The reaction of alkane preparing propylene by dehydrogenating, conversion of propane is high, and Propylene Selectivity is high.
Specifically, in a first aspect, the present invention provides a kind of loaded catalyst, which includes carrier and is supported on
Platinum component, tin component on the carrier and sodium component, wherein the carrier is hexagonal mesoporous material, the hexagonal mesoporous material
The specific surface area of material is 550-650m2/ g, pore volume 0.3-1.4cm2/ g, aperture 0.3-1.2nm.
Second aspect, the present invention provides the preparation method of above-mentioned supported catalyst, this method includes：By carrier with contain
The mixed aqueous solution of water-soluble platinum compound, water-soluble tin compound and inorganic sodium carries out co-impregnation, then removes aqueous solvent,
It dries and roasts.
The third aspect, the present invention provides the loaded catalysts that the above method is prepared.
Fourth aspect, the present invention provides application of the above-mentioned loaded catalyst in preparing propylene by dehydrogenating propane reaction.
5th aspect, the present invention provides a kind of method of preparing propylene by dehydrogenating propane, this method includes：In dehydrogenating propane
Under conditions of preparing propylene, propane is contacted with catalyst, wherein the catalyst is that the support type that aforementioned present invention provides is urged
Agent.
Loaded catalyst using the present invention and method have the following advantages：(1) present invention utilizes macropore, specific surface area
The SiO 2 mesoporous materials carrier larger, pore volume is larger prepares catalyst, and above structure feature is conducive to metal component and exists
Carrier surface fine dispersion, and then can ensure the propane dehydrogenation catalyst function admirable prepared；(2) present invention uses co-impregnation
Method substitutes conventional step impregnation method, and preparation process is simple, and condition is easily controllable, good repetitiveness；(3) present invention carries
The catalyst of confession shows good catalytic performance when being reacted for preparing propylene by dehydrogenating propane.Conversion of propane is high, propylene choosing
Selecting property is high, and catalyst stability is good.
Description of the drawings
Fig. 1 is the X-ray diffracting spectrum of the hexagonal mesoporous material FDU6-1 in embodiment 1；
Fig. 2 is nitrogen adsorption-desorption curve figure of the hexagonal mesoporous material FDU6-1 in embodiment 1；
Fig. 3 is the graph of pore diameter distribution of the hexagonal mesoporous material FDU6-1 in embodiment 1；
Fig. 4 is the transmission electron microscope photo of the hexagonal mesoporous material FDU6-1 in embodiment 1；
Fig. 5 is the microscopic appearance figure (SEM) of the hexagonal mesoporous material FDU6-1 in embodiment 1.
Specific implementation mode
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of loaded catalyst, which includes the platinum group of carrier and load on the carrier
Point, tin component and sodium component, wherein the carrier is hexagonal mesoporous material, and the specific surface area of the hexagonal mesoporous material is
550-650m2/ g, pore volume 0.3-1.4cm2/ g, aperture 0.3-1.2nm.
Under preferable case, the specific surface area of the hexagonal mesoporous material is 570-630m2/ g, pore volume 0.5-0.9cm2/
G, aperture 0.4-1nm.
In the present invention, the specific surface area of the hexagonal mesoporous material, pore volume and aperture can be according to nitrogen adsorption methods
It measures.
According to the present invention, in the loaded catalyst, the platinum component, the content of tin component, sodium component and carrier
It can be changed in wide range, for example, on the basis of the total weight of the catalyst, based on the element, the platinum component contains
Amount can be 0.2-0.5 weight %, and the content of the tin component can be 0.2-1.2 weight %, and the content of the sodium component can
Think 0.3-0.8 weight %, the content of the carrier can be 97.5-99.3 weight %.In order to make dehydrogenation have more
Good catalytic performance and the manufacturing cost for reducing the dehydrogenation, under preferable case, with the total weight of the catalyst
On the basis of, based on the element, the content of the platinum component is 0.2-0.4 weight %, and the content of the tin component is 0.3-1 weights
% is measured, the content of the sodium component is 0.4-0.7 weight %, and the content of the carrier is 97.9-99.1 weight %.
In the present invention, the carrier is prepared by method comprising the following steps：By template, potassium sulfate,
Sour agent and silicon source are mixed, and obtained mixture is filtered simultaneously removed template method.
In the present invention, there is no particular limitation for the sequence being mixed in the preparation process of the carrier, can incite somebody to action
Template, potassium sulfate, sour agent and silicon source are carried out at the same time mixing, can also be mixed arbitrary two or three, add other groups
Divide and is uniformly mixed.According to a kind of preferred embodiment, first template, potassium sulfate and sour agent are uniformly mixed, then added
Silicon source is uniformly mixed.
In the present invention, the dosage of the template, potassium sulfate and silicon source can change in wide range, such as template
The molar ratio of agent, potassium sulfate and silicon source can be 1：100-800：50-300, preferably 1：150-700：80-250, more preferably
1：200-400：100-200.
In the present invention, the template can be the various templates of this field routine.For example, the template can be with
For triblock copolymer polyoxyethylene (PEO)-polyoxypropylene (PPO)-polyoxyethylene (PEO), which can be by existing
Method known to a person skilled in the art be prepared, can also be commercially available, for example, it is public to be purchased from Fuka
Department, trade name Synperonic F108, molecular formula PEO132-PPO50-PEO132, average molecular weight Mn=14600.Wherein,
The molal quantity of polyoxyethylene-poly-oxypropylene polyoxyethylene is according to the average molecular weight of polyoxyethylene-poly-oxypropylene polyoxyethylene
It is calculated.
In the present invention, the silicon source can be various silicon sources commonly used in the art, and the preferably described silicon source is positive silicon
At least one of acetoacetic ester, methyl orthosilicate, positive silicic acid propyl ester, sodium metasilicate and Ludox, more preferably ethyl orthosilicate.
In the present invention, the sour agent can be various acidic aqueous solutions commonly used in the art, for example, can be salt
At least one of acid, sulfuric acid, nitric acid and hydrobromic acid aqueous solution, preferably aqueous hydrochloric acid solution.
There is no particular limitation for the dosage of the acid agent, can be changed in wide range, it is preferable that above-mentioned mixing connects
Tactile pH value is 1-7.
There is no particular limitation to the above-mentioned condition being mixed by the present invention, can be the conventional selection of this field.For example,
The condition being mixed includes：Temperature can be 10-60 DEG C, preferably 25-60 DEG C；Time can be 10-72 hours, excellent
It is selected as 10-30 hours；PH value can be 1-7, preferably 3-6.In order to be more advantageous to the uniform mixing between each substance, according to this hair
A kind of bright preferred embodiment, described be mixed carry out under agitation.
In the present invention, in order to remove the impurity in carrier, the preparation method of the carrier preferably further includes the filtering
Washing later and drying process.The washing and drying process can be the conventional selection of this field, can be used for example
Ionized water or distilled water are washed at room temperature, are dried in 80-110 DEG C of drying box.By washing and drying
To mesoporous material raw powder.
In the present invention, the condition of the removed template method can be the conventional selection of this field, such as can be by washing
The mode washed and/or calcined realizes removing.Washing can be that washing and/or alcohol are washed, and washing removed template method condition includes：Temperature
It can be 90-120 DEG C, the time can be 10-40 hours.According to a kind of preferred embodiment, by mesoporous material raw powder second
Alcohol and/or water wash under reflux conditions can removed template method.Calcining removed template method condition include：Temperature can be
300-600 DEG C, preferably 400-600 DEG C；Time can be 8-20 hours, preferably 10-24 hours.According to a kind of preferred reality
Mode is applied, mesoporous material raw powder is calcined in Muffle furnace.
In the present invention, the loaded catalyst can be prepared according to the various conventional use of methods in this field, as long as
It being capable of Supported Pt Nanoparticles component, tin component and sodium component on the carrier.
The present invention also provides a kind of preparation method of loaded catalyst, this method includes：By carrier with containing water-soluble
Property platinum compounds, water-soluble tin compound and inorganic sodium mixed aqueous solution carry out co-impregnation, then remove aqueous solvent, it is dry
And it roasts.
Wherein, the carrier hereinbefore has been described, and details are not described herein.To the water-soluble platinum chemical combination in the present invention
There is no particular limitation for the selection of water-soluble platinum compound described in object, the water-soluble tin compound and the inorganic sodium.Example
Such as, the water-soluble platinum compound is at least one of chloroplatinic acid, ammonium chloroplatinate and platinum nitrate, preferably chloroplatinic acid and/or
Ammonium chloroplatinate, more preferably chloroplatinic acid；The water-soluble tin compound is butter of tin；The inorganic sodium be sodium nitrate and/
Or sodium chloride.
In the present invention, the dosage of the water-soluble platinum compound, water-soluble tin compound and inorganic sodium can compared with
It is changed in a wide range of, for example, the dosage of the water-soluble platinum compound, water-soluble tin compound and inorganic sodium preparing
In obtained loaded catalyst, on the basis of the total weight of the catalyst, based on the element, the content of the platinum component is
The content of 0.2-0.5 weight %, the tin component are 0.2-1.2 weight %, and the content of the sodium component is 0.3-0.8 weights
% is measured, the content of the carrier is 97.5-99.3 weight %.Under preferable case, the water-soluble platinum compound, water-soluble tin
The dosage for closing object and inorganic sodium makes in the loaded catalyst being prepared, using the total weight of the catalyst as base
Standard, based on the element, the content of the platinum component is 0.2-0.4 weight %, and the content of the tin component is 0.3-1 weight %, institute
The content for stating sodium component is 0.4-0.7 weight %, and the content of the carrier is 97.9-99.1 weight %.
In the present invention, the content of the platinum component in the loaded catalyst, tin component and sodium component is according to raw material
Rate of charge be calculated.
In the present invention, there is no particular limitation for the condition of the co-impregnation, such as the condition of the co-impregnation includes：Temperature
Degree can be 15-60 DEG C, and the time can be 1-10 hours；Preferably, temperature is 25-40 DEG C, and the time is 2-8 hours.
In the present invention, to the embodiment for removing aqueous solvent, there is no particular limitation, can be that this field is conventional
Embodiment, such as Rotary Evaporators may be used.
In the present invention, to the condition of the drying, there is no particular limitation, can be condition conventional in the art.Example
Such as, the condition of the drying includes：Temperature can be 90-160 DEG C, preferably 100-130 DEG C；Time can be 1-20h, preferably
For 2-5h.
In the present invention, to the condition of the roasting, there is no particular limitation, can be condition conventional in the art.Example
Such as, the condition of the roasting includes：Temperature can be 500-700 DEG C, preferably 550-650 DEG C；Time can be 2-15h, excellent
It is selected as 3-10h.
It can also be included according to the method for the present invention before the load platinum component, tin component and sodium component, in inertia
In the presence of gas, the carrier is heated 7-10 hours at a temperature of 300-900 DEG C, with remove carrier surface hydroxyl and
Contain in carrier volatile materials (such as：Water).
In the present invention, the inert gas is the gas not reacted with raw material and product, such as can be ability
At least one of group 0 element gas, preferably nitrogen in the nitrogen or the periodic table of elements of domain routine.
The present invention also provides the carried metallocene catalysts prepared by the above method.The load prepared by the method
Type catalyst has larger specific surface area and pore volume, and the dispersion situation of metal component on this carrier is preferable so that
The catalyst shows excellent catalytic performance in catalytic dehydrogenating reaction.
The present invention also provides application of the above-mentioned loaded catalyst in preparing propylene by dehydrogenating propane reaction.
The present invention also provides a kind of method of preparing propylene by dehydrogenating propane, this method includes：Third is prepared in dehydrogenating propane
Under conditions of alkene, propane is contacted with catalyst, the catalyst is above-mentioned loaded catalyst provided by the invention.
In the present invention, preparing propylene by dehydrogenating propane is carried out using catalyst provided by the invention, this field can be used conventional
The condition used, under preferable case, this method further includes that diluent gas is added, and the diluent gas is usually hydrogen.Described third
Alkane is contacted with catalyst to be carried out in fixed-bed quartz reactor, and the condition of the preparing propylene by dehydrogenating propane includes：Third
The molar ratio of alkane and hydrogen can be 0.5-5：1, reaction temperature can be 500-650 DEG C, and pressure can be 0.05-0.15MPa,
The mass space velocity of propane can be 1-10h-1.The pressure of the present invention is gauge pressure.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples, polyoxyethylene-poly-oxypropylene polyoxyethylene is purchased from Fuka companies, trade name
ForF108, molecular formula EO132PO60EO132, it is abbreviated as F108, average molecular mass Mn 14600.
Rotary Evaporators produce for IKA companies of Germany, model RV10digital；
Drying box produces for Shanghai Yiheng Scientific Instruments Co., Ltd, model DHG-9030A；
Muffle furnace produces for CARBOLITE companies, model C WF1100.
X-ray diffraction analysis is on the X-ray diffractometer of the model D8Advance purchased from German Bruker AXS companies
It carries out；The N of sample2Adsorption-desorption experiment is the ASAP2020-M+C type adsorption instruments produced in Micromeritics companies of the U.S.
Upper progress, the specific surface area and pore volume of sample, which calculate, uses BET methods.
Scanning electron microscope (SEM) analysis is enterprising in the scanning electron microscope of the model XL-30 purchased from FEI Co. of the U.S.
Row；The pore structure of sample is observed using 20 type high resolution transmission electron microscopies of FEI Co. Tecnai.
Raw material feeds intake to calculate and determine when the content of each component passes through preparation in the dehydrogenation of preparation；
Conversion of propane and selectivity are analyzed by gas-chromatography, and computational methods are as follows：
Primary quantity × 100% of amount/propane of the propane of conversion of propane=reaction consumption；
The computational methods of Propylene Selectivity are as follows：
Total flow × 100% of amount/propane of the propane of Propylene Selectivity=generation propylene consumption；
The computational methods of productivity of propylene are as follows：
Theoretical yield × 100% of actual production/propylene of productivity of propylene=propylene.
Embodiment 1
The present embodiment is for illustrating loaded catalyst provided by the invention and preparation method thereof and preparing propylene by dehydrogenating propane
Method
(1) preparation of carrier
By the K of 1.46g (0.0001mol) template F108,5.24g (0.03mol)2SO4It is 2 (2N) with 60g equivalent concentration
Hydrochloric acid solution stir to F108 and be completely dissolved at 38 DEG C；
The ethyl orthosilicate of 4.2g (0.02mol) is added in above-mentioned solution, is stirred 15 minutes at 38 DEG C, it is quiet at 38 DEG C
It sets 24 hours；
Then be added the dilution of 100g deionized waters, be filtered, washed it is dry after obtain original powder mesoporous material.Above-mentioned original powder is situated between
Porous materials calcine 10 hours removed template methods at 400 DEG C, obtain hexagonal mesoporous material FDU6-1.
Table is carried out to hexagonal mesoporous material FDU6-1 with X-ray diffraction, transmission electron microscope, scanning electron microscope and nitrogen adsorption instrument
Sign.
Fig. 1 is X-ray diffracting spectrum, and abscissa is 2 θ, and unit is ° that as seen from the figure, sample F DU6-1 goes out in small angular region
The diffraction maximum (2 θ=0.6 °) in existing 1 (110) face being consistent with body-centred cubic Im3m and (200) face diffraction acromion (2 θ=
1.2°).(110) diffraction peak intensity in face is high, peak shape is narrow, illustrates that hexagonal mesoporous material FDU6-1 has good long-range order knot
Structure.In addition to this position of the diffraction acromion (2 θ=1.2 °) in (200) face is different from hexagonal cells or layer structure completely.
Fig. 2 is that (abscissa is relative pressure, and unit is for nitrogen adsorption-desorption curve figure of hexagonal mesoporous material FDU6-1
p/p0), de--attached thermoisopleth of N2 adsorption shows that hexagonal mesoporous material FDU6-1 is that the Section IV class that typical IUPAC is defined is inhaled in Fig. 2
Attached-desorption isotherm, sample have H2Type hysteresis loop, it was demonstrated that hexagonal mesoporous material FDU6-1 has the distinctive of document report
The meso-hole structure of cube cage structure.Desorption branch between relative partial pressure 0.4-0.5 also shows that the material has caged
Opening structure.
Fig. 3 is the graph of pore diameter distribution of hexagonal mesoporous material FDU6-1 (abscissa is aperture, unit 0.1nm).By aperture
Distribution map can be seen that hexagonal mesoporous material FDU6-1 has narrow pore-size distribution, and duct is highly uniform.
It can be gone out by Fig. 2 and Fig. 3：The specific surface area of hexagonal mesoporous material FDU6-1 is 598m2/ g, pore volume 0.7cm3/
G, aperture 0.7nm.
Fig. 4 is the transmission electron microscope photo (TEM) of sample hexagonal mesoporous material FDU6-1.Sample is clearly visible from Fig. 4
The shape in the hole of (100) crystal face of hexagonal mesoporous material FDU6-1, sample all have the Im3m structures of body-centred cubic.
Fig. 5 is the microscopic appearance figure (SEM) of hexagonal mesoporous material FDU6-1.As seen from the figure, hexagonal mesoporous material FDU6-1
Microscopic appearance figure be hexagon, particle size is micron level.
(2) preparation of loaded catalyst
In the presence of nitrogen, hexagonal mesoporous material FDU6-1 is calcined to 10 hours at 400 DEG C to carry out thermal activation, removed
Hydroxyl and Residual water obtain the hexagonal mesoporous material FDU6-1 of thermal activation.
By the H of 0.080g2PtCl6·6H2O, the SnCl of 0.207g4·5H2The NaNO of O and 0.185g3Be dissolved in 100ml go from
In sub- water, mixes with the hexagonal mesoporous material FDU6-1 of the 10g of the above-mentioned thermal activation being prepared, continuously stir at ambient temperature
Mix reaction 5 hours.The aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product.Solid product, which is placed in temperature, is
It is 3 hours dry in 120 DEG C of drying box.Then product is placed in Muffle furnace, temperature is 600 DEG C and roasts 6 hours, is born
Supported catalyst A1.
The proportion of each component of loaded catalyst A1 is：Platinum components of the 0.3 weight % in terms of platinum element, 0.7 weight %
Tin component in terms of tin element, sodium components of the 0.5 weight % in terms of sodium element, remaining is hexagonal mesoporous material carrier.
(3) preparing propylene by dehydrogenating propane
The loaded catalyst A1 of 0.5g is fitted into fixed-bed quartz reactor, controlling reaction temperature is 610 DEG C, reaction
Pressure is 0.1MPa, propane：The molar ratio of hydrogen is 1:1, propane mass space velocity is 3.0h-1, reaction time 50h.Reaction knot
Fruit is shown in Table 1.
Embodiment 2
The present embodiment is for illustrating loaded catalyst provided by the invention and preparation method thereof and preparing propylene by dehydrogenating propane
Method
(1) preparation of carrier
By the K of 1.46g (0.0001mol) template F108,6.96g (0.04mol)2SO4It is 2 (2N) with 60g equivalent concentration
Hydrochloric acid solution stir to F108 and be completely dissolved at 38 DEG C；
The ethyl orthosilicate of 3.1g (0.015mol) is added in above-mentioned solution, 15min is stirred at 45 DEG C, it is quiet at 45 DEG C
It sets 30 hours；
Then be added the dilution of 100g deionized waters, be filtered, washed it is dry after obtain original powder mesoporous material.Above-mentioned original powder is situated between
Porous materials calcine 15 hours removed template methods at 600 DEG C, obtain hexagonal mesoporous material FDU6-2.
The specific surface area 569m of hexagonal mesoporous material FDU6-22/ g, pore volume 0.6cm3/ g, aperture 0.5nm.
(2) preparation of loaded catalyst
In the presence of nitrogen, hexagonal mesoporous material FDU6-2 is calcined to 10 hours at 400 DEG C to carry out thermal activation, removed
Hydroxyl and Residual water obtain the hexagonal mesoporous material FDU6-2 of thermal activation.
By the H of 0.053g2PtCl6·6H2O, the SnCl of 0.09g4·5H2The NaCl of O and 0.127g is dissolved in 50ml deionizations
It in water, mixes, is continuously stirred under the conditions of 40 DEG C anti-with the 10g hexagonal mesoporous materials FDU6-2 of the above-mentioned thermal activation being prepared
It answers 2 hours.The aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product.It is 100 DEG C that solid product, which is placed in temperature,
Drying box in, dry 5 hours.Then in Muffle furnace, temperature is 650 DEG C and roasts 3 hours, obtains loaded catalyst A2.
The proportion of loaded catalyst A2 each components is：Platinum components of the 0.2 weight % in terms of platinum element, 0.3 weight % with
The tin component of tin element meter, sodium components of the 0.4 weight % in terms of sodium element, remaining is hexagonal mesoporous material FDU6-2.
(3) preparing propylene by dehydrogenating propane
Preparing propylene by dehydrogenating propane is carried out according to the method for embodiment 1, unlike, it is substituted using loaded catalyst A2
Loaded catalyst A1 in embodiment 1.Reaction result is shown in Table 1.
Embodiment 3
The present embodiment is for illustrating loaded catalyst provided by the invention and preparation method thereof and preparing propylene by dehydrogenating propane
Method
(1) preparation of carrier
By the K of 1.46g (0.0001mol) template F108,3.48g (0.02mol)2SO4It is 2 (2N) with 60g equivalent concentration
Hydrochloric acid solution stir to F108 and be completely dissolved at 38 DEG C；
The ethyl orthosilicate of 2.1g (0.01mol) is added in above-mentioned solution, 15min is stirred at 35 DEG C, it is quiet at 35 DEG C
It sets 20 hours；
Then be added the dilution of 100g deionized waters, be filtered, washed it is dry after obtain mesoporous material raw powder.By above-mentioned mesoporous material
Expect that original powder ethyl alcohol under 100 DEG C of counterflow conditions washs 24 hours removed template methods, obtains hexagonal mesoporous material FDU6-3.
The specific surface area of hexagonal mesoporous material FDU6-3 is 624m2/ g, pore volume 0.9cm3/ g, aperture 0.8nm.
(2) preparation of loaded catalyst
In the presence of nitrogen, hexagonal mesoporous material FDU6-3 is calcined to 10 hours at 400 DEG C to carry out thermal activation, removed
Hydroxyl and Residual water obtain the hexagonal mesoporous material FDU6-3 of thermal activation.
By the H of 0.11g2PtCl6·6H2O, the SnCl of 0.296g4·5H2The NaNO of O and 0.259g3Be dissolved in 200ml go from
In sub- water, mixes with the hexagonal mesoporous material FDU6-3 of the above-mentioned 10g thermal activations being prepared, continuously stirred under the conditions of 30 DEG C
Reaction 8 hours.The aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product.It is 100 that solid product, which is placed in temperature,
DEG C drying box in, dry 5 hours.Then in Muffle furnace, temperature is 550 DEG C and roasts 10 hours, obtains loaded catalyst
A3。
The proportion of loaded catalyst A3 each components is：Platinum components of the 0.4 weight % in terms of platinum element, 1 weight % is with tin
The tin component of element meter, sodium components of the 0.7 weight % in terms of sodium element, remaining is hexagonal mesoporous material FDU6-3.
(3) preparing propylene by dehydrogenating propane
Preparing propylene by dehydrogenating propane is carried out according to the method for embodiment 1, unlike, it is substituted using loaded catalyst A3
Loaded catalyst A1 in embodiment 1.Reaction result is shown in Table 1.
Embodiment 4
The present embodiment is for illustrating loaded catalyst provided by the invention and preparation method thereof and preparing propylene by dehydrogenating propane
Method
(1) preparation of carrier
Carrier is prepared according to the method for embodiment 1.
(2) preparation of loaded catalyst
It is carried out according to the method for embodiment 1, unlike, platinum component, tin component are different with the content of sodium component.Specifically
Ground, H2PtCl6·6H2The dosage of O is 0.133g, SnCl4·5H2The dosage of O is 0.355g, NaNO3Dosage be 0.111g,
It is remaining same as Example 1, obtain loaded catalyst A4.
The proportion of loaded catalyst A4 each components is：Platinum components of the 0.5 weight % in terms of platinum element, 1.2 weight % with
The tin component of tin element meter, sodium components of the 0.3 weight % in terms of sodium element, remaining is hexagonal mesoporous material FDU6-1.
(3) preparing propylene by dehydrogenating propane
Preparing propylene by dehydrogenating propane is carried out according to the method for embodiment 1, unlike, it is substituted using loaded catalyst A4
Loaded catalyst A1 in embodiment 1.Reaction result is shown in Table 1.
Comparative example 1
The method that this comparative example is used to illustrate the loaded catalyst and preparing propylene by dehydrogenating propane of reference
By the H of 0.080g2PtCl6·6H2O, the SnCl of 0.207g4·5H2The NaNO of O and 0.185g3Be dissolved in 100ml go from
In sub- water, the commercially γ-Al of 10g are added2O3(the Qingdao wave silica-gel desiccant company trade mark is technical grade low specific surface area to carrier
The commercially available product of activated alumina, specific surface area 162m2/ g, pore volume 0.82cm3/ g) mixing, it continuously stirs at ambient temperature
Mix reaction 5 hours.The aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product.Solid product, which is placed in temperature, is
It is 3 hours dry in 120 DEG C of drying box.Then in Muffle furnace, temperature is 600 DEG C and roasts 6 hours, obtains supported catalyst
Agent DA1.
The proportion of each component of loaded catalyst DA1 is：Platinum components of the 0.3 weight % in terms of platinum element, 0.7 weight %
Tin component in terms of tin element, sodium components of the 0.5 weight % in terms of sodium element, remaining is γ-Al2O3Carrier.
(3) preparing propylene by dehydrogenating propane
Preparing propylene by dehydrogenating propane is carried out according to the method for embodiment 1, unlike, it is replaced using loaded catalyst DA1
For the loaded catalyst A1 in embodiment 1.Reaction result is shown in Table 1.
Comparative example 2
The method that this comparative example is used to illustrate the loaded catalyst and preparing propylene by dehydrogenating propane of reference
Carrier and loaded catalyst are prepared according to the method for embodiment 1, unlike, the method for not using co-impregnation,
But the method for using step impregnation prepares loaded catalyst.Specifically, by the carrier FDU6-1 of thermal activation first in chloroplatinic acid
5h is impregnated in aqueous solution, after the carrier FDU6-1 after dipping is dried and is roasted according to the condition of embodiment 1, then in tetrachloro
Change in the aqueous solution of tin and sodium nitrate and impregnate 5h, is then dried and roasts according to the condition of embodiment 1, obtain support type and urge
Agent DA2.
The proportion of each component of loaded catalyst DA2 is：Platinum components of the 0.3 weight % in terms of platinum element, 0.7 weight %
Tin component in terms of tin element, sodium components of the 0.5 weight % in terms of sodium element, remaining is hexagonal mesoporous material carrier FDU6-1.
(3) preparing propylene by dehydrogenating propane
Preparing propylene by dehydrogenating propane is carried out according to the method for embodiment 1, unlike, it is replaced using loaded catalyst DA2
For the loaded catalyst A1 in embodiment 1.Reaction result is shown in Table 1.
Table 1
From the results shown in Table 1, embodiment 1-4 loaded catalysts using the present invention are prepared for dehydrogenating propane
When the reaction of propylene, catalytic performance is substantially better than commercially available γ-Al2O3Catalyst (comparative example 1) prepared by carrier, propane
Average conversion, propylene average selectivity and propylene average yield are all significantly improved.Illustrate catalysis dehydrogenation provided by the invention
Agent preparation method may be implemented to improve the effect of dehydrogenation catalytic performance.Step impregnation legal system is used relative to comparative example 2
The preparation process of standby catalyst, catalyst of the present invention is simple, excellent catalytic effect.And use the embodiment 1- in preferred scope
3 it is with obvious effects optimal.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In the skill of the present invention
In art conception range, technical scheme of the present invention can be carried out a variety of simple variants, 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, belongs to
Protection scope of the present invention.
Claims (11)
1. a kind of loaded catalyst, which includes platinum component, tin component and the sodium of carrier and load on the carrier
Component, which is characterized in that the carrier is hexagonal mesoporous material, and the specific surface area of the hexagonal mesoporous material is 550-650m2/
G, pore volume 0.3-1.4cm2/ g, aperture 0.3-1.2nm.
2. loaded catalyst according to claim 1, wherein the specific surface area of the hexagonal mesoporous material is 570-
630m2/ g, pore volume 0.5-0.9cm2/ g, aperture 0.4-1nm.
3. loaded catalyst according to claim 1, wherein on the basis of the total weight of the catalyst, with element
The content of meter, the platinum component is 0.2-0.5 weight %, and the content of the tin component is 0.2-1.2 weight %, the sodium component
Content be 0.3-0.8 weight %, the content of the carrier is 97.5-99.3 weight %.
4. loaded catalyst according to claim 1, wherein the carrier is prepared by method comprising the following steps
It obtains：Template, potassium sulfate, sour agent and silicon source are mixed, and obtained mixture is filtered and removes template
Agent；
Preferably, the molar ratio of the template, potassium sulfate and silicon source is 1：100-800：50-300；
Preferably, the condition being mixed includes：Temperature is 25-60 DEG C, and the time is 10-72 hours, pH value 1-7；
Preferably, the condition of the removed template method includes：Temperature is 300-600 DEG C, and the time is 8-20 hours.
5. a kind of method preparing the loaded catalyst described in any one of claim 1-4, which is characterized in that this method
Including：Carrier and the mixed aqueous solution containing water-soluble platinum compound, water-soluble tin compound and inorganic sodium are subjected to total immersion
Stain, then removes aqueous solvent, and drying simultaneously roasts.
6. according to the method described in claim 5, wherein, the water-soluble platinum compound, water-soluble tin compound and inorganic sodium
The dosage of salt makes in the loaded catalyst being prepared, on the basis of the total weight of the catalyst, based on the element, institute
The content for stating platinum component is 0.2-0.5 weight %, and the content of the tin component is 0.2-1.2 weight %, and the sodium component contains
Amount is 0.3-0.8 weight %, and the content of the carrier is 97.5-99.3 weight %.
7. according to the method described in claim 5, wherein, the condition of the co-impregnation includes：Temperature is 15-60 DEG C, and the time is
1-10 hours；
Preferably, the condition of the roasting includes：Temperature is 500-700 DEG C, and the time is 2-15 hours；
Preferably, the method further includes before co-impregnation, in the presence of an inert gas, by the carrier at 300-900 DEG C
At a temperature of heat 7-10 hours.
8. the loaded catalyst prepared by the method described in any one of claim 5-7.
9. loaded catalyst the answering in preparing propylene by dehydrogenating propane reaction described in any one of claim 1-4 and 8
With.
10. a kind of method of preparing propylene by dehydrogenating propane, which is characterized in that this method includes：In preparing propylene by dehydrogenating propane
Under the conditions of, propane is contacted with catalyst, which is characterized in that the catalyst is described in any one of claim 1-4 and 8
Loaded catalyst.
11. according to the method described in claim 10, wherein, this method further includes that diluent gas hydrogen is added；
Preferably, the propane is contacted with catalyst carries out in fixed-bed quartz reactor, the preparing propylene by dehydrogenating propane
Condition include：The molar ratio of propane and hydrogen is 0.5-5：1, reaction temperature is 500-650 DEG C, pressure 0.05-
The mass space velocity of 0.15MPa, propane are 1-10h-1。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111250096A (en) * | 2018-11-30 | 2020-06-09 | 中国石油化工股份有限公司 | Non-noble metal isobutane dehydrogenation catalyst with hexagonal mesoporous material as carrier and preparation method and application thereof |
| CN111250085A (en) * | 2018-11-30 | 2020-06-09 | 中国石油化工股份有限公司 | Non-noble metal propane dehydrogenation catalyst with modified hexagonal mesoporous material as carrier and preparation method and application thereof |
| CN112221533A (en) * | 2019-06-30 | 2021-01-15 | 中国石油化工股份有限公司 | Mg and/or Ti component modified hexagonal mesoporous material and propane dehydrogenation catalyst, and preparation methods and applications thereof |
| CN113546670A (en) * | 2020-04-23 | 2021-10-26 | 中国石油化工股份有限公司 | Light gasoline cracking propylene yield-increasing catalyst containing silane modified hexagonal single crystal mesoporous material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103586058A (en) * | 2012-08-14 | 2014-02-19 | 中国石油化工股份有限公司 | Supported phosphotungstic acid catalyst, preparation method and application thereof, and ethyl acetate preparation method |
| CN103816933A (en) * | 2014-02-13 | 2014-05-28 | 中国石油大学(北京) | Dehydrogenation catalyzing material as well as preparation method and application thereof |
| CN104248968A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Catalyst for preparation of propylene by direct dehydrogenation of propane and preparation method thereof |
-
2017
- 2017-05-05 CN CN201710313731.5A patent/CN108786800B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103586058A (en) * | 2012-08-14 | 2014-02-19 | 中国石油化工股份有限公司 | Supported phosphotungstic acid catalyst, preparation method and application thereof, and ethyl acetate preparation method |
| CN104248968A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Catalyst for preparation of propylene by direct dehydrogenation of propane and preparation method thereof |
| CN103816933A (en) * | 2014-02-13 | 2014-05-28 | 中国石油大学(北京) | Dehydrogenation catalyzing material as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 浙江大学等: "《综合化学实验》", 31 July 2001, 高等教育出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111250096A (en) * | 2018-11-30 | 2020-06-09 | 中国石油化工股份有限公司 | Non-noble metal isobutane dehydrogenation catalyst with hexagonal mesoporous material as carrier and preparation method and application thereof |
| CN111250085A (en) * | 2018-11-30 | 2020-06-09 | 中国石油化工股份有限公司 | Non-noble metal propane dehydrogenation catalyst with modified hexagonal mesoporous material as carrier and preparation method and application thereof |
| CN112221533A (en) * | 2019-06-30 | 2021-01-15 | 中国石油化工股份有限公司 | Mg and/or Ti component modified hexagonal mesoporous material and propane dehydrogenation catalyst, and preparation methods and applications thereof |
| CN113546670A (en) * | 2020-04-23 | 2021-10-26 | 中国石油化工股份有限公司 | Light gasoline cracking propylene yield-increasing catalyst containing silane modified hexagonal single crystal mesoporous material and preparation method and application thereof |
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