CN109382144B - Composite material and preparation method thereof, catalyst and preparation method and application thereof, and method for preparing propylene by propane dehydrogenation - Google Patents
Composite material and preparation method thereof, catalyst and preparation method and application thereof, and method for preparing propylene by propane dehydrogenation Download PDFInfo
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- CN109382144B CN109382144B CN201710666301.1A CN201710666301A CN109382144B CN 109382144 B CN109382144 B CN 109382144B CN 201710666301 A CN201710666301 A CN 201710666301A CN 109382144 B CN109382144 B CN 109382144B
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- catalyst
- component
- silica gel
- molecular sieve
- mesoporous molecular
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 239000001294 propane Substances 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 41
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 33
- 239000002808 molecular sieve Substances 0.000 claims abstract description 73
- 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 73
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000741 silica gel Substances 0.000 claims abstract description 60
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 60
- 239000011148 porous material Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 239000013335 mesoporous material Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- 230000003197 catalytic effect Effects 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002736 nonionic surfactant Substances 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000007725 thermal activation Methods 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 39
- 239000011734 sodium Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 19
- 239000002243 precursor Substances 0.000 description 18
- 229910052697 platinum Inorganic materials 0.000 description 13
- 238000005470 impregnation Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 229910052718 tin Inorganic materials 0.000 description 12
- 239000002994 raw material Substances 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 238000001694 spray drying Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- 229920004890 Triton X-100 Polymers 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000011230 binding agent Substances 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
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012229 microporous material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification 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
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 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
- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 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
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- 239000012974 tin catalyst 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/068—Noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 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
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/26—After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure
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- 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)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of catalysts, and discloses a composite material and a preparation method thereof, a catalyst containing the composite material, a preparation method and application of the catalyst, and a method for preparing propylene by propane dehydrogenation. The composite material contains silica gel and spherical mesoporous molecular sieve, wherein the pore volume of the spherical mesoporous molecular sieve is 0.5-1.5mL/g, and the specific surface area is 1000-1500m2Per g, the average pore diameter is 1-2.5nm, and the average particle diameter is 1-20 μm; the specific surface area of the silica gel is 200-300m2Per g, pore volume of 1-2mL/g, average pore diameter of 10-30nm, and average particle diameter of 20-100 μm. The composite material containing the spherical mesoporous molecular sieve and the silica gel has the advantage of stable structure, and when the composite material and the Pt component, the Sn component and the Na component form a catalyst and are used in the reaction of preparing propylene by propane dehydrogenation, the conversion rate of propane and the selectivity of propylene can be obviously improved compared with the prior art.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a composite material and a preparation method thereof, a catalyst containing the composite material, a preparation method and application of the catalyst, and a method for preparing propylene by propane dehydrogenation.
Background
Propylene is a basic raw material of petrochemical industry and is mainly used for producing polypropylene, acrylonitrile, acetone, propylene oxide, acrylic acid, butanol and octanol and the like. Half of the propylene supply comes from refinery by-products and about 45% from steam cracking, a few other alternative technologies. In recent years, the demand of propylene is increasing year by year, and the traditional propylene production can not meet the demand of the chemical industry for propylene, so that the propylene yield increase becomes a great hot point for research. The dehydrogenation of propane to propylene is one of the main technologies for increasing the yield of propylene. For more than 10 years, the dehydrogenation of propane to prepare propylene has become an important process for the industrial production of propylene. The main catalysts for propane dehydrogenation are the chromium oxide/alumina catalyst in the Catofin process from ABB Lummus and the platinum tin/alumina catalyst in the Oleflex process from UOP. The chromium catalyst has lower requirements on raw material impurities and lower price compared with noble metals; however, the catalyst is easy to deposit carbon and deactivate, and is regenerated every 15 to 30 minutes, and the chromium in the catalyst is heavy metal, so that the environmental pollution is serious. The platinum-tin catalyst has high activity and good selectivity, the reaction period can reach several days, and the catalyst can bear harsh process conditions and is more environment-friendly; however, the noble metal platinum is expensive, so that the cost of the catalyst is high. The industrial production of the process for preparing propylene by propane dehydrogenation is over twenty years, and the research on dehydrogenation catalysts is more, but the current catalysts still have the defects of low propane conversion rate, easy inactivation and the like, and further improvement and perfection are needed. Therefore, it is of practical significance to develop a propane dehydrogenation catalyst having excellent performance.
Much work has been done by researchers to improve the reaction performance of propane dehydrogenation catalysts. Such as: the molecular sieve carrier is adopted to replace the traditional gamma-Al 2O3 carrier, and the carrier has good effect and comprises MFI type microporous molecular sieves (CN104307555A, CN101066532A, CN101380587A and CN101513613A), mesoporous MCM-41 molecular sieves (CN102389831A), mesoporous SBA-15 molecular sieves (CN101972664A and CN101972664B) and the like. However, the pore diameter of the commonly used mesoporous material is small (average pore diameter is 3-7 nm), and if macromolecule catalytic reaction is carried out, the macromolecule is difficult to enter the pore channel, so that the catalytic effect is influenced. Therefore, the selection of a good carrier is an urgent problem to be solved in the field of propane dehydrogenation.
Disclosure of Invention
The propane dehydrogenation catalyst in the prior art usually takes Pt as a main metal active component and takes gamma-Al2O3As a carrier, the catalyst has the defects of poor dispersion of active components and poor catalytic activity and stability. The invention aims to overcome the defects of unstable mesoporous structure and low propane conversion rate and propylene selectivity in the prior art.
In order to achieve the above object, the present invention provides a composite material comprising silica gel and a spherical mesoporous molecular sieve, wherein the spherical mesoporous molecular sieve has a pore volume of 0.5-1.5mL/g and a specific surface area of 1000-2Per g, the average pore diameter is 1-2.5nm, and the average particle diameter is 1-20 μm; the specific surface area of the silica gel is 200-300m2Per g, pore volume of 1-2mL/g, average pore diameter of 10-30nm, and average particle diameter of 20-100 μm.
In a second aspect, the present invention provides a method of making the aforementioned composite material, the method comprising:
(1) under the condition of a solution, a template agent, a nonionic surfactant, an acid agent and a silicon source are mixed and contacted to obtain a solution A, wherein the template agent is cetyl trimethyl ammonium bromide, and the nonionic surfactant is polyethylene glycol octyl phenyl ether;
(2) sequentially crystallizing, washing and drying the solution A to obtain mesoporous material raw powder;
(3) carrying out template agent treatment on the mesoporous material raw powder to obtain the spherical mesoporous molecular sieve;
(4) and mixing the spherical mesoporous molecular sieve with silica gel.
In a third aspect, the present invention provides a composite material prepared by the foregoing method.
In a fourth aspect, the present invention provides a catalyst comprising a carrier and a Pt component, a Sn component, and a Na component supported on the carrier, wherein the carrier is the composite material provided by the present invention.
A fifth aspect of the invention provides a process for preparing the aforementioned catalyst, the process comprising; the preparation method comprises the following steps of sequentially carrying out thermal activation treatment, dipping treatment, solvent removal treatment, drying and roasting on a carrier to load a Pt component, a Sn component and a Na component on the carrier, wherein the carrier is the composite material provided by the invention.
In a sixth aspect, the present invention provides a catalyst prepared by the foregoing process.
The seventh aspect of the invention provides the use of the aforementioned catalyst in the catalytic dehydrogenation of propane.
The eighth aspect of the present invention provides a method for producing propylene by propane dehydrogenation, including: and (2) carrying out dehydrogenation reaction on the propane in the presence of a catalyst and hydrogen, wherein the catalyst is the catalyst provided by the invention or the catalyst prepared by the method provided by the invention.
The invention utilizes spherical mesoporous molecular sieve with larger specific surface area and pore volume and silica gel with specific structure to form a composite carrier, which is beneficial to the good dispersion of metal components on the surface of the carrier, and the carrier is also loaded with Pt component, Sn component and Na component, so that the supported catalyst has the advantages of the supported catalyst, such as high catalytic activity, less side reaction, simple post-treatment and the like, and has stronger catalytic activity, the supported catalyst has better dehydrogenation activity and selectivity in the propane dehydrogenation reaction, the conversion rate of reaction raw materials is obviously improved, and particularly, in the reaction of preparing propylene by using the supported catalyst for propane dehydrogenation, the propane conversion rate can reach 17%, and the selectivity of the propylene can reach 70%.
In addition, the co-impregnation method is adopted to replace the conventional step-by-step impregnation method, the preparation process is simple, the conditions are easy to control, and the product repeatability is good.
Further, the carrier of the present invention is obtained by, for example, only mechanical mixing, and does not require the use of a material such as a binder, thereby avoiding the defect that the catalytic activity is affected due to the residue of the binder.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an X-ray diffraction pattern of the spherical mesoporous molecular sieve of example 1;
FIG. 2 is a graph showing the nitrogen adsorption-desorption curves of the spherical mesoporous molecular sieve of example 1;
FIG. 3A is an SEM scanning electron micrograph of the microscopic morphology of the spherical mesoporous molecular sieve of example 1 at 300 times magnification;
FIG. 3B is an SEM scanning electron micrograph of the microstructure of the spherical mesoporous molecular sieve of example 1 at 2000 times magnification;
FIG. 4 is an SEM scanning electron micrograph of the microstructure of ES955 silica gel of example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a composite material comprising silica gel and a spherical mesoporous molecular sieve, wherein the pore volume of the spherical mesoporous molecular sieve is 0.5-1.5mL/g, and the specific surface area is 1000-2Per g, the average pore diameter is 1-2.5nm, and the average particle diameter is 1-20 μm; the specific surface area of the silica gel is 200-300m2Per g, the average pore diameter is 10-30nm, and the average particle diameter is 20-100 μm.
According to the invention, the average particle size of the silica gel and the spherical mesoporous molecular sieve is measured by a laser particle size distribution instrument, and the specific surface area, the pore volume and the average pore diameter are measured by a nitrogen adsorption method. In the present invention, the particle diameter means the particle size of the raw material particles, and when the raw material particles are spherical, the particle size is represented by the diameter of the sphere, when the raw material particles are cubic, the particle size is represented by the side length of the cube, and when the raw material particles are irregularly shaped, the particle size is represented by the mesh size of the screen mesh that is just capable of screening out the raw material particles.
According to the invention, by controlling the structural parameters of silica gel and spherical mesoporous molecular sieve in the composite material within the above range, the composite material is ensured not to be easily agglomerated, and the supported catalyst prepared by using the composite material as a carrier can improve the conversion rate of reaction raw materials in the process of preparing propylene by propane dehydrogenation. When the specific surface area of the spherical mesoporous molecular sieve is less than 1000m2When the volume/g and/or pore volume is less than 0.5mL/g, the catalytic activity of the supported catalyst prepared by using the supported catalyst is remarkably reduced; when the specific surface area of the spherical mesoporous molecular sieve is more than 1500m2When the volume/g and/or the pore volume is more than 1.5mL/g, the supported catalyst prepared by using the supported catalyst as the carrier is easy to agglomerate in the reaction process of preparing propylene by propane dehydrogenation, thereby influencing the conversion rate of the reaction raw materials in the reaction process of preparing propylene by propane dehydrogenation.
Preferably, in the composite material, the pore volume of the spherical mesoporous molecular sieve is 0.6-1mL/g, and the specific surface area is 1100-1300m2Per g, the average pore diameter is 1.5-2nm, and the particle size is 4-15 mu m; the specific surface area of the silica gel is 230-280m2Per g, pore volume of 1.2-1.8mL/g, average pore diameter of 12-18nm, and average particle diameter of 30-70 μm.
More preferably, the content weight ratio of the spherical mesoporous molecular sieve to the silica gel is (1.2-10): 1; more preferably (1.5-5): 1.
preferably, the silica gel is 955 silica gel.
The spherical mesoporous molecular sieve in the composite material containing silica gel and the spherical mesoporous molecular sieve has the advantages of ultrahigh specific surface area, stable structure and larger pore volume, and is applied to the composite with the silica gel to be beneficial to improving the dispersion degree of metal components in the catalyst, so that the catalyst formed by the composite material containing the spherical mesoporous molecular sieve and the silica gel has more excellent catalytic performance in the process of catalyzing propane dehydrogenation to prepare hydrogen, and the beneficial effects of high propane conversion rate and high propylene selectivity are achieved.
As previously mentioned, a second aspect of the invention provides a method of making the aforementioned composite material, the method comprising:
(1) under the condition of a solution, a template agent, a nonionic surfactant, an acid agent and a silicon source are mixed and contacted to obtain a solution A, wherein the template agent is cetyl trimethyl ammonium bromide, and the nonionic surfactant is polyethylene glycol octyl phenyl ether;
(2) sequentially crystallizing, washing and drying the solution A to obtain mesoporous material raw powder;
(3) carrying out template agent treatment on the mesoporous material raw powder to obtain the spherical mesoporous molecular sieve;
(4) and mixing the spherical mesoporous molecular sieve with silica gel.
The solution condition of the present invention may be an aqueous solution condition.
In the present invention, the acid agent may be various acidic aqueous solutions conventionally used in the art, and for example, may be at least one aqueous solution of hydrochloric acid, sulfuric acid, nitric acid and hydrobromic acid, preferably an aqueous hydrochloric acid solution.
The amount of the acid agent is not particularly limited, and may be varied within a wide range, and it is preferable that the pH value of the mixing contact is 1 to 7.
Preferably, in step (1), the conditions of the mixing contact include: the temperature is 25-60 ℃ and the time is 0.1-48 h. In order to further facilitate uniform mixing between the substances, according to a preferred embodiment of the invention, the mixing contact is carried out under stirring conditions.
In the present invention, the amounts of the templating agent, the nonionic surfactant and the silicon source may vary within a wide range, for example, the molar ratio of the templating agent, the nonionic surfactant and the silicon source is (0.1-0.6): (0.1-0.5): 1; more preferably, the molar ratio of the amounts of template, nonionic surfactant and silicon source is (0.1-0.3): (0.1-0.3): 1.
in the present invention, the silicon source may be various silicon sources conventionally used in the art, and preferably the silicon source is at least one of tetraethoxysilane, methyl orthosilicate, propyl orthosilicate, sodium orthosilicate and silica sol, and more preferably tetraethoxysilane.
Preferably, in the step (2), the crystallization conditions include: the temperature is 90-180 ℃ and the time is 4-40 h. According to a preferred embodiment, the crystallization is carried out by hydrothermal crystallization.
Preferably, in the step (2), the washing process may include: after filtration, repeated washing with deionized water (washing times may be 2 to 10) and suction filtration.
Preferably, in the step (3), the drying manner is spray drying, which may be performed according to a conventional manner, and may be selected from at least one of pressure spray drying, centrifugal spray drying, and pneumatic spray drying. According to a preferred embodiment of the present invention, the spray drying is a centrifugal spray drying method. The spray drying may be carried out in an atomizer. The conditions of the spray drying may include: the temperature is 150-; preferably, the spray drying conditions include: the temperature is 150-250 ℃, and the rotating speed is 11000-13000 r/min.
Preferably, in step (3), the method for removing the template agent is a calcining method, and the process of treating the template agent comprises the following steps: calcining the mesoporous material raw powder for 5-40h at the temperature of 300-800 ℃.
Preferably, in the step (4), the manner of mixing the spherical mesoporous molecular sieve and the silica gel is mechanical blending. The spherical mesoporous molecular sieve and the silica gel can be well mixed and dispersed by adopting a mechanical blending mode, so that the spherical mesoporous molecular sieve and the silica gel are mutually dispersed into the space occupied by each other, the initial distribution condition of the space occupied by the spherical mesoporous molecular sieve and the silica gel is changed, the particle sizes of the spherical mesoporous molecular sieve and the silica gel are reduced, and the dispersion of molecular degree is achieved under the extreme condition.
In the present invention, there is no particular limitation on the kind of the silica gel as long as the silica gel has the structural requirements as set forth in the foregoing first aspect of the present invention, and preferably, the silica gel is commercially available ES955 silica Gel (GRACE).
The third aspect of the present invention also provides a composite material prepared by the above method.
As described above, the fourth aspect of the present invention provides a catalyst comprising a support, and a Pt component, a Sn component, and a Na component supported on the support, the support being the aforementioned composite material.
According to the invention, in the catalyst, the Pt component is an active metal component, and the Sn component and the Na component are metal auxiliary agents, so that when the Pt component, the Sn component and the Na component are matched and loaded on the carrier, strong acid centers on the surface of the carrier can be effectively neutralized, and the dispersion degree of the Pt component which is an active metal component is improved, thereby improving the selectivity and the reaction stability of the catalyst.
According to the present invention, the carrier is contained in an amount of 97.5 to 99.3 wt%, the Pt component is contained in an amount of 0.2 to 0.5 wt% in terms of Pt element, the Sn component is contained in an amount of 0.2 to 1.2 wt% in terms of Sn element, and the Na component is contained in an amount of 0.3 to 0.8 wt% in terms of Na element, based on the total weight of the catalyst.
As previously mentioned, a fifth aspect of the present invention provides a method of preparing the foregoing catalyst, the method comprising; the preparation method comprises the following steps of sequentially carrying out thermal activation treatment, dipping treatment, solvent removal treatment, drying and roasting on a carrier to load a Pt component, a Sn component and a Na component on the carrier, wherein the carrier is the composite material provided by the invention.
According to the present invention, in order to remove hydroxyl groups and residual moisture of the composite material, a thermal activation treatment is required before the composite material supports the metal component, and the conditions of the thermal activation treatment may include: in the presence of nitrogen, the carrier is calcined at the temperature of 300-900 ℃ for 7-10 h.
According to the invention, the composite material loaded with the metal component can adopt an impregnation mode, the metal component enters the pore channel of the composite material used as the carrier by virtue of the capillary pressure of the pore channel structure of the composite material, and meanwhile, the metal component is adsorbed on the surface of the composite material until the metal component reaches adsorption balance on the surface of the composite material. Preferably, the impregnation treatment is performed after the composite material is subjected to the thermal activation treatment, and the impregnation treatment can be co-impregnation treatment or step impregnation treatment. In order to save the preparation cost and simplify the experimental process, the dipping treatment is preferably co-dipping treatment; further preferably, the conditions of the co-impregnation treatment include: and mixing and contacting the composite material subjected to thermal activation in a solution containing a Pt component precursor, a Sn component precursor and a Na component precursor, wherein the impregnation temperature can be 25-50 ℃, and the impregnation time can be 2-6 h.
According to the present invention, the solutions of the Pt component precursor, the Sn component precursor, and the Na component precursor are not particularly limited as long as they are water-soluble, and may be conventionally selected in the art. For example, the Pt component precursor can be H2PtCl6The Sn component precursor may be SnCl4The Na component precursor can be NaNO3。
The concentration of the solution containing the Pt component precursor, the Sn component precursor, and the Na component precursor is not particularly limited in the present invention and may be conventionally selected in the art, for example, the concentration of the Pt component precursor may be 0.1 to 0.3mol/L, the concentration of the Sn component precursor may be 0.15 to 1mol/L, and the concentration of the Na component precursor may be 1 to 3.5 mol/L.
According to the present invention, the Pt component precursor, the Sn component precursor, and the Na component precursor are used in amounts such that the composite carrier has a content of 97.5 to 99.3 wt%, the Pt component has a content of 0.2 to 0.5 wt% in terms of Pt element, the Sn component has a content of 0.2 to 1.2 wt% in terms of Sn element, and the Na component has a content of 0.3 to 0.8 wt% in terms of Na element, based on the total weight of the propane dehydrogenation catalyst, in the prepared propane dehydrogenation catalyst.
According to the present invention, the solvent removal treatment can be carried out by a method conventional in the art, for example, a rotary evaporator can be used to remove the solvent in the system.
According to the invention, the drying can be carried out in a drying oven and the baking can be carried out in a muffle furnace. The conditions for the drying and firing are also not particularly limited in the present invention, and may be conventionally selected in the art, for example, the conditions for the drying may include: the temperature is 110-150 ℃ and the time is 3-6 h; the conditions for the firing may include: the temperature is 600 ℃ and 650 ℃, and the time is 5-8 h.
The sixth aspect of the invention also provides a catalyst prepared by the aforementioned method.
As mentioned above, a seventh aspect of the present invention provides the use of a catalyst as described above in the catalytic dehydrogenation of propane.
When the catalyst provided by the invention is used for catalyzing propane dehydrogenation, the conversion rate of propane and the selectivity of propylene can be greatly improved.
As described above, an eighth aspect of the present invention provides a method for producing propylene by dehydrogenation of propane, the method comprising: and (2) carrying out dehydrogenation reaction on the propane in the presence of a catalyst and hydrogen, wherein the catalyst is the catalyst provided by the invention or the catalyst prepared by the method provided by the invention.
According to the present invention, in order to improve the propane conversion and prevent the catalyst from coking, it is preferable that the molar ratio of the amount of propane to the amount of hydrogen is from 0.5 to 1.5: 1.
the conditions for the dehydrogenation reaction in the present invention are not particularly limited and may be conventionally selected in the art, and for example, the conditions for the dehydrogenation reaction may include: the reaction temperature is 600-650 ℃, the reaction pressure is 0.05-0.2MPa, the reaction time is 40-60h, and the propane mass space velocity is 2-5h-1。
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, octyl phenyl ether of polyethylene glycol, commercially available from carbofuran, Beijing, under the trade name Triton X-100, and having the formula C34H62O11；
In the following examples and comparative examples, ES955 silica gel was obtained from GRACE;
in the following examples and comparative examples, X-ray diffraction analysis was carried out on an X-ray diffractometer, model D8Advance, available from Bruker AXS, Germany; scanning electron microscopy analysis was performed on a scanning electron microscope, model XL-30, available from FEI, USA; pore structure parameter analysis was performed on an ASAP2020-M + C type adsorber, available from Micromeritics, USA, and BET method was used for the specific surface area and pore volume calculation of the sample; the particle size distribution of the sample is carried out on a Malvern laser particle sizer; the rotary evaporator is produced by German IKA company, and the model is RV10 digital; the active component loading of the propane dehydrogenation catalyst was measured on a wavelength dispersive X-ray fluorescence spectrometer, model Axios-Advanced, available from parnacco, netherlands; analysis of the reaction product composition was performed on a gas chromatograph available from Agilent under model 7890A;
in the following experimental examples and experimental comparative examples, the conversion (%) of propane is ═ amount of propane-content of propane in the reaction product ÷ amount of propane used × 100%;
selectivity (%) of propylene ÷ actual yield of propylene ÷ theoretical yield of propylene × 100%.
Preparation example 1: preparation of composite material F1 containing spherical mesoporous molecular sieve C1 and ES955 silica gel A
(1) 1.5g (0.004mol) of template CTAB (cetyltrimethylammonium bromide) and 1.5ml (0.002mol) of polyethylene glycol octylphenyl ether (triton-X100) were added to a solution containing 37% by weight of hydrochloric acid (29.6g) and water (75g), and stirred at 40 ℃ until CTAB was completely dissolved; then adding 4.35g (0.02mol) of tetraethoxysilane into the solution, stirring for 15 minutes at 40 ℃, then transferring the obtained solution into a reaction kettle with a polytetrafluoroethylene lining, crystallizing for 24 hours at 120 ℃, filtering, washing for 4 times by using deionized water, and then carrying out suction filtration and drying to obtain mesoporous material raw powder; calcining the mesoporous material raw powder at 600 ℃ for 24h, and removing the template agent to obtain a spherical mesoporous molecular sieve C1;
(2) 20g of a spherical mesoporous molecular sieve C1 was mechanically blended with 10g of ES955 silica gel A (see Table 1 for relevant parameters, available from Grace, USA) at 25 ℃ to give a composite F1 as a carrier.
Respectively characterizing spherical mesoporous molecular sieve C1 and ES955 silica gel A by an XRD, a scanning electron microscope and an ASAP2020-M + C type adsorption instrument;
FIG. 1 is an X-ray diffraction pattern of the spherical mesoporous molecular sieve C1, wherein the abscissa is 2 theta and the ordinate is intensity, and it can be clearly seen from the XRD pattern that the spherical mesoporous molecular sieve C1 has diffraction peaks in the small angle region, which indicates that the spherical mesoporous molecular sieve C1 has a very good mesoporous phase structure, which is consistent with the XRD pattern of mesoporous Materials reported in the literature (XueleiBang, Fangqiong Tang, Micropore and mesopore Materials,2005(85): 1-6);
FIG. 2 is a graph showing the nitrogen adsorption-desorption curves (abscissa relative pressure (p/p)) of the spherical mesoporous molecular sieve C10) Nitrogen adsorption-desorption isotherms show that the spherical mesoporous molecular sieve C1 is a typical IUPAC-defined class IV adsorption-desorption isotherm and has an ultra-high specific surface area, which proves that the spherical mesoporous molecular sieve C1 has a mesoporous structure with a peculiar cubic cage structure reported in the literature (Xuelei Long, Fangqiong Tang, Microporous and mesoporous Materials,2005(85): 1-6; chengzhong Yu, Bozhi Tian, Jie Fan, Galen D.Stucky, Dongyuan Zhao, J.Am.chem.Soc.2002,124, 4556-4557);
FIGS. 3A and 3B are SEM scanning electron micrographs of the microscopic morphology of the spherical mesoporous molecular sieve C1 at 300-fold and 2000-fold magnification, respectively, from which it can be seen that the spherical mesoporous molecular sieve C1 is spherical and has a particle size in the micrometer scale, which is in full agreement with literature reports (Xuelei Pang, Fangqiong Tang, Microporous and mesoporous Materials,2005(85): 1-6);
FIG. 4 is a microscopic morphology (SEM) of ES955 silica gel A, from which it can be seen that the average particle size of the sample is about 50 μm.
The pore structure parameters of the spherical mesoporous molecular sieves C1 and ES955 silica gel a are shown in table 1.
Preparation example 2: preparation of composite material F2 containing spherical mesoporous molecular sieve C2 and ES955 silica gel B
(1) 0.75g (0.002mol) of template CTAB (cetyltrimethylammonium bromide) and 3ml (0.004mol) of polyethylene glycol octylphenyl ether (triton-X100) were added to a solution containing 37% by weight of hydrochloric acid (29.6g) and water (75g), and stirred at 40 ℃ until CTAB was completely dissolved; then adding 4.35g (0.02mol) of tetraethoxysilane into the solution, stirring for 15 minutes at 40 ℃, then transferring the obtained solution into a reaction kettle with a polytetrafluoroethylene lining, crystallizing for 24 hours at 100 ℃, filtering, washing for 4 times by using deionized water, and then carrying out suction filtration and drying to obtain mesoporous material raw powder; calcining the mesoporous material raw powder at 600 ℃ for 24h, and removing the template agent to obtain a spherical mesoporous molecular sieve C2;
(2) 30g of a spherical mesoporous molecular sieve C2 was mechanically blended with 10g of ES955 silica gel B (see Table 1 for relevant parameters, available from Grace, USA) at 25 ℃ to give a composite material F2 as a carrier.
The XRD structure diagram and the SEM micro-morphology diagram of the spherical mesoporous molecular sieve C2 are respectively similar to those of the spherical mesoporous molecular sieve C1, and the SEM micro-morphology diagram of ES955 silica gel B is similar to that of ES955 silica gel A.
The pore structure parameters of the spherical mesoporous molecular sieves C2 and ES955 silica gel B are shown in table 1.
TABLE 1
| Sample (I) | Specific surface area (m)2/g) | Pore volume (ml/g) | Average pore diameter*(nm) | Particle size (. mu.m) |
| C1 | 1200 | 0.7 | 1.9 | 4-15 |
| C2 | 1300 | 1 | 2 | 4-13 |
| ES955 silica gel A | 250 | 1.5 | 15 | 20-50 |
| ES955 silica gel B | 230 | 1.5 | 16 | 30-55 |
Preparation example 3: preparation of composite material F3 containing spherical mesoporous molecular sieve C1 and ES955 silica gel B
First, a spherical mesoporous molecular sieve C1 was prepared in the same manner as in preparation example 1.
Then, 20g of a spherical mesoporous molecular sieve C1 was mechanically blended with 10g of ES955 silica gel B at 25 ℃ to obtain a composite material F3 as a carrier.
Preparation example 4: preparation of composite material F4 containing spherical mesoporous molecular sieve C2 and ES955 silica gel A
First, a spherical mesoporous molecular sieve C2 was prepared in the same manner as in preparation example 2.
Then, 20g of a spherical mesoporous molecular sieve C2 was mechanically blended with 10g of ES955 silica gel A at 25 ℃ to obtain a composite material F4 as a carrier.
Preparation example 5: preparation of composite material F5 containing spherical mesoporous molecular sieve C1 and ES955 silica gel A
First, a spherical mesoporous molecular sieve C1 was prepared in the same manner as in preparation example 1.
Then, 12g of a spherical mesoporous molecular sieve C1 was mechanically blended with 10g of ES955 silica gel A at 25 ℃ to obtain a composite material F5 as a carrier.
Preparation example 6: preparation of composite material F6 containing spherical mesoporous molecular sieve C2 and ES955 silica gel B
First, a spherical mesoporous molecular sieve C2 was prepared in the same manner as in preparation example 2.
Then 80g of spherical mesoporous molecular sieve C1 was mechanically blended with 10g of ES955 silica gel B at 25 ℃ to obtain a composite material F6 as a carrier.
Examples 1 to 6: preparation of propane dehydrogenation catalysts Cat-1-Cat-6
10g of the support obtained in the preparation example are taken in N2Calcining at 400 deg.C for 10 hr under protection, heat activating to remove hydroxyl and residual water to obtain heat activated carrier, and mixing with 0.08g H2PtCl6·6H2O、0.207g SnCl4·5H2O and 0.185g NaNO3Dissolving the carrier in 100mL of deionized water, soaking the carrier in the mixture solution for 5h at 25 ℃, evaporating solvent water in the system by using a rotary evaporator to obtain a solid product, placing the solid product in a drying oven at 120 ℃, drying for 3h, then placing the dried product in a muffle furnace at 600 ℃, and roasting for 6h to respectively obtain the propane dehydrogenation catalysts in the table 2, wherein the names of the propane dehydrogenation catalysts are Cat-1-Cat-6 (in each propane dehydrogenation catalyst, the content of a Pt component in terms of Pt element is 0.3 wt%, the content of a Sn component in terms of Sn element is 0.7 wt%, the content of a Na component in terms of Na element is 0.5 wt%, and the rest is the carrier).
Comparative examples 1 to 4: preparation of propane dehydrogenation catalysts Cat-D-1-Cat-D-4
Propane dehydrogenation catalysts were prepared in the manner of the examples, except that the same weights of the thermally activated spherical molecular sieves C1, C2, ES955 silica gel A and ES955 silica gel B, respectively, were used alone as supports to give the propane dehydrogenation catalysts of Table 2, designated Cat-D-1 to Cat-D-4, respectively.
Comparative examples 5 to 6: preparation of propane dehydrogenation catalysts Cat-D-5-Cat-D-6
A propane dehydrogenation catalyst was prepared in the manner of example 1-2, except that during the impregnation process to prepare the supported catalyst, no NaNO was added3Addition of only 0.133g H2PtCl6·6H2O and 0.295g SnCl4·5H2And O, only loading an active component Pt and a metal auxiliary agent Sn on a heat activated carrier by a co-impregnation method to respectively obtain the propane dehydrogenation catalysts in the table 2, wherein the names of the propane dehydrogenation catalysts are respectively Cat-D-5-Cat-D-6 (in each propane dehydrogenation catalyst, the content of the Pt component calculated by the Pt element is 0.5 wt%, the content of the Sn component calculated by the Sn element is 1 wt%, and the balance is the carrier, based on the total weight of the propane dehydrogenation catalyst).
Test example: carrying out propane dehydrogenation reaction
The propane dehydrogenation catalyst (0.5g) prepared in example was charged into a fixed bed quartz reactor, and the reaction temperature was controlled at 610 ℃, the reaction pressure was 0.1MPa, and the molar ratio of propane: the molar ratio of hydrogen is 1: 1, the mass space velocity of propane is 3h-1The reaction time is 50 h. The reaction results (propane conversion and propylene selectivity) of the gas chromatography are shown in Table 2.
TABLE 2
| Numbering | Carrier | Metal component | Average conversion of propane (%) | Average propylene selectivity (%) |
| Cat-1 | F1 | 0.3％Pt、0.7％Sn、0.5％Na | 17 | 70 |
| Cat-2 | F2 | 0.3％Pt、0.7％Sn、0.5％Na | 16.8 | 70.7 |
| Cat-3 | F3 | 0.3％Pt、0.7％Sn、0.5％Na | 17.1 | 69.9 |
| Cat-4 | F4 | 0.3％Pt、0.7％Sn、0.5％Na | 17 | 71 |
| Cat-5 | F5 | 0.3％Pt、0.7％Sn、0.5％Na | 16.5 | 70.2 |
| Cat-6 | F6 | 0.3％Pt、0.7％Sn、0.5％Na | 16.9 | 70.8 |
| Cat-D-1 | C1 | 0.3％Pt、0.7％Sn、0.5％Na | 13.2 | 45.6 |
| Cat-D-2 | C2 | 0.3％Pt、0.7％Sn、0.5％Na | 13.6 | 40.2 |
| Cat-D-3 | A | 0.3％Pt、0.7％Sn、0.5％Na | 10.2 | 43.1 |
| Cat-D-4 | B | 0.3％Pt、0.7％Sn、0.5％Na | 8.6 | 41.3 |
| Cat-D-5 | F1 | 0.5％Pt、1％Sn | 11.2 | 45.3 |
| Cat-D-6 | F2 | 0.5％Pt、1％Sn | 10.9 | 44.2 |
The results in table 2 show that the catalyst formed by the composite material prepared by the method of the present invention in combination with the Pt component, the Sn component and the Na component has excellent catalytic activity in the preparation of propylene by catalytic propane dehydrogenation, and the average conversion rate of propane and the average selectivity of propylene are both significantly improved, and after 50 hours of reaction, higher conversion rate of propane and propylene selectivity can still be obtained. The composite material product provided by the invention has good catalytic performance and good stability.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (17)
1. The catalyst comprises a carrier and a Pt component, an Sn component and a Na component which are loaded on the carrier, and is characterized in that the carrier is a composite material, the composite material comprises silica gel and a spherical mesoporous molecular sieve, the pore volume of the spherical mesoporous molecular sieve is 0.5-1.5mL/g, and the specific surface area is 1000-2Per g, the average pore diameter is 1-2.5nm, and the average particle diameter is 1-20 μm; the specific surface area of the silica gel is 200-300m2Per g, pore volume of 1-2mL/g, average pore diameter of 10-30nm, and average particle diameter of 20-100 μm.
2. The catalyst as claimed in claim 1, wherein the spherical mesoporous molecular sieve has a pore volume of 0.6-1mL/g and a specific surface area of 1100-1300m2Per g, average pore diameter of 1.5-2nm, particle diameterIs 4-15 μm; the specific surface area of the silica gel is 230-280m2Per g, pore volume of 1.2-1.8mL/g, average pore diameter of 12-18nm, and average particle diameter of 30-70 μm.
3. The catalyst of claim 1, wherein the spherical mesoporous molecular sieve and the silica gel are present in a weight ratio of (1.2-10): 1.
4. the catalyst of claim 1, wherein the silica gel is 955 silica gel.
5. The catalyst of any one of claims 1-4, wherein the composite is prepared by a method comprising:
(1) under the condition of a solution, a template agent, a nonionic surfactant, an acid agent and a silicon source are mixed and contacted to obtain a solution A, wherein the template agent is cetyl trimethyl ammonium bromide, and the nonionic surfactant is polyethylene glycol octyl phenyl ether;
(2) sequentially crystallizing, washing and drying the solution A to obtain mesoporous material raw powder;
(3) carrying out template agent treatment on the mesoporous material raw powder to obtain the spherical mesoporous molecular sieve;
(4) and mixing the spherical mesoporous molecular sieve with silica gel.
6. The catalyst of claim 5, wherein in step (1), the conditions of the mixing contact comprise: the temperature is 25-60 ℃ and the time is 0.1-48 h.
7. The catalyst of claim 6, wherein the templating agent, the non-ionic surfactant, and the silicon source are used in a molar ratio of (0.1-0.6): (0.1-0.5): 1.
8. the catalyst of claim 5, wherein in step (2), the crystallization conditions comprise: the temperature is 90-180 ℃ and the time is 4-40 h.
9. The catalyst of claim 5 wherein in step (3) the stripper plate agent treatment process comprises: calcining the mesoporous material raw powder for 5-40h at the temperature of 300-800 ℃.
10. The catalyst of claim 5, wherein in step (4), the spherical mesoporous molecular sieve is mixed with the silica gel by mechanical blending.
11. The catalyst according to claim 1, wherein the carrier is contained in an amount of 97.5 to 99.3 wt%, the Pt component is contained in an amount of 0.2 to 0.5 wt% in terms of Pt element, the Sn component is contained in an amount of 0.2 to 1.2 wt% in terms of Sn element, and the Na component is contained in an amount of 0.3 to 0.8 wt% in terms of Na element, based on the total weight of the catalyst.
12. A method of preparing the catalyst of any one of claims 1-11, comprising: and sequentially carrying out thermal activation treatment, dipping treatment, solvent removal treatment, drying and roasting on the carrier, so that the carrier is loaded with a Pt component, a Sn component and a Na component.
13. A catalyst prepared by the process of claim 12.
14. Use of a catalyst according to any one of claims 1 to 11 and 13 for the catalytic dehydrogenation of propane.
15. A method for preparing propylene by propane dehydrogenation comprises the following steps: the dehydrogenation of propane in the presence of a catalyst and hydrogen, characterized in that the catalyst is a catalyst according to any one of claims 1 to 11 and 13.
16. The process according to claim 15, wherein the molar ratio of the amount of propane to the amount of hydrogen is between 0.5 and 1.5: 1.
17. the method of claim 15, wherein the dehydrogenation reaction conditions comprise: the reaction temperature is 600-650 ℃, the reaction pressure is 0.05-0.2MPa, the reaction time is 40-60h, and the propane mass space velocity is 2-5h-1。
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| CN102453122A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Loaded metallocene catalyst and preparation method thereof |
| CN105175586A (en) * | 2014-06-13 | 2015-12-23 | 中国石油化工股份有限公司 | Meso-porous composite material, preparation method thereof, catalyst ingredient preparation method, and polyethylene preparation method |
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| CN102453122A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Loaded metallocene catalyst and preparation method thereof |
| CN105175586A (en) * | 2014-06-13 | 2015-12-23 | 中国石油化工股份有限公司 | Meso-porous composite material, preparation method thereof, catalyst ingredient preparation method, and polyethylene preparation method |
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