CN109382144A - The method of composite material and preparation method and catalyst and its preparation method and application and preparing propylene by dehydrogenating propane - Google Patents
The method of composite material and preparation method and catalyst and its preparation method and application and preparing propylene by dehydrogenating propane Download PDFInfo
- Publication number
- CN109382144A CN109382144A CN201710666301.1A CN201710666301A CN109382144A CN 109382144 A CN109382144 A CN 109382144A CN 201710666301 A CN201710666301 A CN 201710666301A CN 109382144 A CN109382144 A CN 109382144A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- component
- molecular sieve
- composite material
- silica gel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 239000001294 propane Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 31
- 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 69
- 239000002808 molecular sieve Substances 0.000 claims abstract description 68
- 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 57
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000011148 porous material Substances 0.000 claims abstract description 35
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 27
- 239000013335 mesoporous material Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000012545 processing Methods 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 238000007725 thermal activation Methods 0.000 claims description 11
- 239000002736 nonionic surfactant Substances 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
- 238000001035 drying Methods 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 38
- 239000011734 sodium Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 13
- 229910052697 platinum Inorganic materials 0.000 description 13
- 229910052718 tin Inorganic materials 0.000 description 13
- 238000005470 impregnation Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001694 spray drying Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 3
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 3
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- 239000013504 Triton X-100 Substances 0.000 description 3
- 229920004890 Triton X-100 Polymers 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012229 microporous material Substances 0.000 description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 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
- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000004115 Sodium Silicate Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002708 enhancing 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
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 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
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 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
- 239000012974 tin catalyst Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to catalyst field, a kind of composite material and preparation method, catalyst containing aforementioned composite material and its preparation method and application and a kind of method of preparing propylene by dehydrogenating propane are disclosed.Contain silica gel and spherical mesoporous molecular sieve in the composite material, the pore volume of the spherical mesoporous molecular sieve is 0.5-1.5mL/g, specific surface area 1000-1500m2/ g, average pore size 1-2.5nm, average grain diameter are 1-20 μm；The specific surface area of the silica gel is 200-300m2/ g, pore volume 1-2mL/g, average pore size 10-30nm, average grain diameter are 20-100 μm.The aforementioned composite material containing spherical mesoporous molecular sieve and silica gel provided by the invention has the advantages that stable structure, when being formed together catalyst with Pt component, Sn component and Na component and in the reacting of preparing propylene by dehydrogenating propane, the selectivity of the conversion ratio and propylene that enable to propane is significantly improved compared with the prior art.
Description
Technical field
The present invention relates to catalyst fields, and in particular, to a kind of composite material and preparation method, containing aforementioned compound
Catalyst of material and its preparation method and application and a kind of method of preparing propylene by dehydrogenating propane.
Background technique
Propylene is the base stock of petrochemical industry, mainly for the production of polypropylene, acrylonitrile, acetone, propylene oxide, propylene
Acid and octyl alconyl etc..The supply half of propylene comes from refinery's by-product, separately has about 45% to come from steam cracking, a small amount of other substitution skills
Art.In recent years, the demand of propylene increases year by year, and traditional production of propylene has been unable to meet demand of the chemical industry to propylene,
Therefore propylene enhancing becomes a big hot spot of research.Wherein, preparing propylene by dehydrogenating propane is a major technique of propylene volume increase.10
For many years, preparing propylene by dehydrogenating propane has become the important process process of industrialization production of propylene.The major catalytic of dehydrogenating propane
Agent has in chromium oxide/aluminum oxide catalyst and Uop Inc.'s Oleflex technique in ABB Lummus company Catofin technique
Platinum tin/aluminium oxide catalyst.Requirement of the chromium-based catalysts to raw material impurity is relatively low, on the low side compared with noble metal；But this
Class catalyst is easy carbon distribution inactivation, will regenerate every 15-30 minutes once, and since the chromium in catalyst is heavy metal,
Environmental pollution is serious.Platinum-tin catalyst activity is high, and selectivity is good, can reach reaction time several days, can bear more harsh
Process conditions, and to more environment-friendly；But since noble metal platinum is expensive, lead to catalyst higher cost.Third
Alkane dehydrogenation producing propylene technique realizes that industrialized production alreadys exceed 20 years, also many to the research of dehydrogenation, but current
Catalyst is not still high there is conversion of propane and is easy to the defects of inactivating, and requires further improvement and perfect.Therefore, it develops
The propane dehydrogenation catalyst of function admirable has realistic meaning.
In order to improve the reactivity worth of propane dehydrogenation catalyst, researcher has done many work.Such as: use molecular sieve
Class carrier substitutes traditional γ-Al2O3 carrier, effect preferably include MFI type micro porous molecular sieve (CN104307555A,
CN101066532A, CN101380587A, CN101513613A), mesoporous MCM-41 molecular sieve (CN102389831A) and mesoporous
SBA-15 molecular sieve (CN101972664A, CN101972664B) etc..However currently used mesoporous material aperture is smaller (flat
Equal 3~7nm of aperture), if carrying out bulky molecular catalysis reaction, macromolecular duct more difficult to get access, so that influencing catalytic effect.Cause
This, selecting a kind of excellent carrier is one, dehydrogenating propane field urgent problem to be solved.
Summary of the invention
Propane dehydrogenation catalyst in the prior art is usually with Pt for main metal active constituent, with γ-Al2O3For carrier,
The active component poor dispersion of the catalyst, catalytic activity and the poor defect of stability.It is existing the purpose of the present invention is overcoming
Technical agency's pore structure is unstable, further results in the not high defect of conversion of propane and Propylene Selectivity.
To achieve the goals above, first aspect present invention provides a kind of composite material, contains silica gel in the composite material
With spherical mesoporous molecular sieve, the pore volume of the spherical mesoporous molecular sieve is 0.5-1.5mL/g, specific surface area 1000-
1500m2/ g, average pore size 1-2.5nm, average grain diameter are 1-20 μm；The specific surface area of the silica gel is 200-300m2/ g, hole
Volume is 1-2mL/g, and average pore size 10-30nm, average grain diameter is 20-100 μm.
Second aspect of the present invention provides a kind of method for preparing aforementioned composite material, this method comprises:
(1) under solution condition, template, nonionic surfactant, sour agent and silicon source are mixed to obtain
To solution A, wherein the template is cetyl trimethylammonium bromide, and the nonionic surfactant is polyethylene glycol
Octyl phenyl ether；
(2) solution A is carried out successively carrying out crystallization, washing and drying, obtains mesoporous material raw powder；
(3) mesoporous material raw powder is subjected to Template removal processing, obtains the spherical mesoporous molecular sieve；
(4) the spherical mesoporous molecular sieve is mixed with silica gel.
Third aspect present invention provides a kind of composite material prepared by preceding method.
Fourth aspect present invention provides a kind of catalyst, the Pt in the catalyst containing carrier and load on the carrier
Component, Sn component and Na component, the carrier are composite material provided by the invention.
Fifth aspect present invention provides a kind of method for preparing aforementioned catalytic agent, and this method includes；Carrier is successively carried out
Thermal activation treatment, impregnation, the processing of removal solvent, dry and roasting, make the supported on carriers Pt component, Sn component and Na
Component, wherein the carrier is composite material provided by the invention.
Sixth aspect present invention provides a kind of catalyst prepared by preceding method.
Seventh aspect present invention provides a kind of application of aforementioned catalytic agent in catalysis dehydrogenating propane.
Eighth aspect present invention provides a kind of method of preparing propylene by dehydrogenating propane, this method comprises: in catalyst and hydrogen
In the presence of, propane is subjected to dehydrogenation reaction, wherein the catalyst provides for catalyst provided by the invention or by the present invention
Method preparation catalyst.
The present invention is using spherical, specific surface area is larger, the biggish mesopore molecular sieve of pore volume and the silicon with specific structure
Glue forms complex carrier, is conducive to metal component in carrier surface fine dispersion, and the carrier has been also loaded Pt component, Sn
Component and Na component so that the loaded catalyst both had the advantages that loaded catalyst such as catalytic activity is high, side reaction is few,
Post-processing is simple etc., and has stronger catalytic activity, so that the loaded catalyst has in for dehydrogenating propane reaction
Better dehydrogenation activity and selectivity, are significantly improved the conversion ratio of reaction raw materials, specifically, are carried out using the loaded catalyst
In the reaction of preparing propylene by dehydrogenating propane, conversion of propane is up to 17%, and the selectivity of propylene is up to 70%.
In addition, the step impregnation method that the present invention is conventional using co-impregnation method substitution, preparation process is simple, and condition is easy to
Control, good repetitiveness.
Also, carrier of the invention is only obtained for example, by mechanical mixture, is not needed using materials such as binders, thus
Avoid the defect that catalytic activity is influenced caused by having residual due to binder.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the X-ray diffracting spectrum of the spherical mesoporous molecular sieve of embodiment 1；
Fig. 2 is nitrogen adsorption-desorption curve figure of the spherical mesoporous molecular sieve of embodiment 1；
Fig. 3 A is the SEM scanning electron microscope for the microscopic appearance that the spherical mesoporous molecular sieve enlargement ratio of embodiment 1 is 300 times
Figure；
Fig. 3 B is the SEM scanning electron microscope for the microscopic appearance that the spherical mesoporous molecular sieve enlargement ratio of embodiment 1 is 2000 times
Figure；
Fig. 4 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of the ES955 silica gel of embodiment 1.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
As previously mentioned, the first aspect of the present invention provides a kind of composite material, silica gel and ball are contained in the composite material
Shape mesopore molecular sieve, the pore volume of the spherical mesoporous molecular sieve are 0.5-1.5mL/g, specific surface area 1000-1500m2/ g,
Average pore size is 1-2.5nm, and average grain diameter is 1-20 μm；The specific surface area of the silica gel is 200-300m2/ g, average pore size are
10-30nm, average grain diameter are 20-100 μm.
According to the present invention, the average grain diameter of the silica gel and spherical mesoporous molecular sieve is measured using laser fineness gage,
Specific surface area, pore volume and average pore size are measured according to nitrogen adsorption methods.In the present invention, partial size refers to the particle of feed particles
Size, when feed particles are sphere, then the diameter of granularity sphere is indicated, when feed particles are cube, then granularity use is vertical
The side length of cube indicates that then granularity uses just the sieve that can screen out the feed particles when feed particles are irregular shape
The mesh size of net indicates.
According to the present invention, by by the structural parameter control of silica gel and spherical mesoporous molecular sieve in the composite material upper
Within the scope of stating, it can be ensured that the composite material is not susceptible to reunite, and is used as supported catalyst made of carrier
The reaction raw materials conversion ratio in preparing propylene by dehydrogenating propane reaction process can be improved in agent.When the ratio table of the spherical mesoporous molecular sieve
Area is less than 1000m2When/g and/or pore volume are less than 0.5mL/g, it is used as urging for loaded catalyst made of carrier
Changing activity can significantly reduce；When the specific surface area of the spherical mesoporous molecular sieve is greater than 1500m2/ g and/or pore volume are greater than
When 1.5mL/g, it is used as the group of being easy to happen in preparing propylene by dehydrogenating propane reaction process of loaded catalyst made of carrier
It is poly-, to influence the reaction raw materials conversion ratio in preparing propylene by dehydrogenating propane reaction process.
Under preferable case, in the composite material, the pore volume of the spherical mesoporous molecular sieve is 0.6-1mL/g, than
Surface area is 1100-1300m2/ g, average pore size 1.5-2nm, partial size are 4-15 μm；The specific surface area of the silica gel is 230-
280m2/ g, pore volume 1.2-1.8mL/g, average pore size 12-18nm, average grain diameter are 30-70 μm.
It is highly preferred that the content weight ratio of the spherical mesoporous molecular sieve and the silica gel is (1.2-10): 1；Further
Preferably (1.5-5): 1.
Under preferable case, the silica gel is 955 silica gel.
Spherical mesoporous molecular sieve in composite material provided by the invention containing silica gel and spherical mesoporous molecular sieve has
The specific surface area of superelevation, while also having the advantages that stable structure, pore volume are larger, itself and silica gel Application of composite facilitate
Improve the degree of scatter of the metal component in catalyst, so that containing the composite wood of the spherical mesoporous molecular sieve and silica gel
Expect that the catalyst formed has more excellent catalytic performance during being catalyzed dehydrogenating propane hydrogen, and thus to obtain third
Alkane high conversion rate and the high beneficial effect of Propylene Selectivity.
As previously mentioned, the second aspect of the present invention provides the method for preparing aforementioned composite material, this method comprises:
(1) under solution condition, template, nonionic surfactant, sour agent and silicon source are mixed to obtain
To solution A, wherein the template is cetyl trimethylammonium bromide, and the nonionic surfactant is polyethylene glycol
Octyl phenyl ether；
(2) solution A is carried out successively carrying out crystallization, washing and drying, obtains mesoporous material raw powder；
(3) mesoporous material raw powder is subjected to Template removal processing, obtains the spherical mesoporous molecular sieve；
(4) the spherical mesoporous molecular sieve is mixed with silica gel.
The solution condition of the invention can be aqueous conditions.
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 change in a big way, it is preferable that the mixing connects
The pH value of touching is 1-7.
Under preferable case, in step (1), the condition being mixed includes: that temperature is 25-60 DEG C, and the time is
0.1-48h.In order to be more advantageous to the uniform mixing between each substance, a kind of preferred embodiment according to the present invention, the mixing
Contact carries out under agitation.
In the present invention, the dosage of the template, nonionic surfactant and silicon source can become in a big way
It is dynamic, such as the molar ratio of the template, the nonionic surfactant and the silicon source dosage is (0.1-0.6): (0.1-
0.5): 1；It is highly preferred that the molar ratio of institute's template, the nonionic surfactant and the silicon source dosage is (0.1-
0.3): (0.1-0.3): 1.
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 silica solution, more preferably ethyl orthosilicate.
Preferably, in step (2), the condition of the crystallization includes: that temperature is 90-180 DEG C, time 4-40h.According to
A kind of preferred embodiment, the crystallization are implemented by hydrothermal crystallization method.
Preferably, in step (2), the process of the washing may include: after filtration, to be washed repeatedly with deionized water
(washing times can be 2-10) is washed, is then filtered.
Preferably, in step (3), the mode of the drying is spray drying, and the spray drying can be according to routine
Mode implement, can be selected from least one in pressure spray dryer method, the gentle flow type spray seasoning of centrifugal spray drying method
Kind.A kind of preferred embodiment according to the present invention, the spray drying use centrifugal spray drying method.The spray drying can
To be carried out in atomizer.The condition of the spray drying may include: that temperature is 150-600 DEG C, revolving speed 10000-
15000r/min；Under preferable case, the condition of the spray drying includes: that temperature is 150-250 DEG C, and the revolving speed of rotation is
11000-13000r/min。
Preferably, in step (3), the method for the removed template method is calcination method, the mistake of the Template removal processing
Journey includes: that the mesoporous material raw powder is calcined 5-40h at 300-800 DEG C.
Preferably, in step (4), the mode that the spherical mesoporous molecular sieve is mixed with silica gel is mechanical blending.Using
The mode of mechanical blending can play good immixture and peptizaiton to the spherical mesoporous molecular sieve and silica gel, make institute
It states spherical mesoporous molecular sieve and silica gel to be mutually distributed in space occupied by other side, the initial distribution feelings for making the two be taken up space
Condition changes, and reduces the particle size of the two, and extreme case reaches the dispersion of molecular level.
In the present invention, to the type of the silica gel, there is no particular limitation, as long as the silica gel has the present invention aforementioned
Structural requirement described in first aspect, it is preferable that the silica gel is commercially available ES955 silica gel (GRACE company).
The third aspect of the present invention additionally provides the composite material of above method preparation.
As previously mentioned, the fourth aspect of the present invention provides a kind of catalyst, carrier is contained in the catalyst and is supported on
Pt component, Sn component and Na component on the carrier, the carrier are composite material above-mentioned.
According to the present invention, in the catalyst, the Pt group is divided into active metal component, the Sn component and Na group
It is divided into metal promoter, when three's cooperation loads on the carrier, can effectively neutralizes the strong acid center of carrier surface, mention
The dispersion degree of high activity metal component Pt, to improve the selectivity and reaction stability of catalyst.
According to the present invention, on the basis of the total weight of the catalyst, the content of the carrier is 97.5-99.3 weight
% is measured, content of the Pt component in terms of Pt element is 0.2-0.5 weight %, and content of the Sn component in terms of Sn element is
0.2-1.2 weight %, content of the Na component in terms of Na element are 0.3-0.8 weight %.
As previously mentioned, the fifth aspect of the present invention provides a kind of method for preparing aforementioned catalytic agent, this method includes；It will
Carrier successively carries out thermal activation treatment, impregnation, the processing of removal solvent, dry and roasting, makes the supported on carriers Pt group
Point, Sn component and Na component, wherein the carrier is composite material provided by the invention.
According to the present invention, in order to remove the hydroxyl and Residual water of the composite material, in the composite material gold-supported
Need to carry out thermal activation treatment before belonging to component, the condition of the thermal activation treatment may include: in the presence of nitrogen, by carrier
Calcining 7-10h is carried out at being 300-900 DEG C in temperature.
According to the present invention, the composite material carried metal component can be by the way of dipping, by the composite wood
The capillary pressure of the cellular structure of material enters metal component in the duct as the composite material of carrier, while metal group
Point can also the composite material again adsorption, until metal component reaches adsorption equilibrium on the surface of the composite material.
Preferably, the impregnation carry out after thermal activation treatment in the composite material, and the impregnation can be total
Impregnation, or step impregnation processing.In order to save preparation cost, simplify experimental technique, the impregnation is preferred
For co-impregnation processing；It is further preferred that the condition of the co-impregnation processing includes: to contain the composite material after thermal activation
The solution of Pt component presoma, Sn component presoma and Na component presoma is mixed, and the temperature of the dipping can be with
It is 25-50 DEG C, the time of the dipping can be 2-6h.
According to the present invention, the solution of the Pt component presoma, Sn component presoma and Na component presoma is not special
Restriction as long as water-soluble can be the conventional selection of this field.For example, the Pt component presoma can be
H2PtCl6, the Sn component presoma can be SnCl4, the Na component presoma can be NaNO3。
The present invention does not have the concentration of the solution containing Pt component presoma, Sn component presoma and Na component presoma
There is special restriction, can be the conventional selection of this field, for example, the concentration of the Pt component presoma can be 0.1-
0.3mol/L, the concentration of the Sn component presoma can be 0.15-1mol/L, and the concentration of the Na component presoma can be with
For 1-3.5mol/L.
According to the present invention, the dosage of the Pt component presoma, Sn component presoma and Na component presoma to prepare
In obtained propane dehydrogenation catalyst, on the basis of the total weight of the propane dehydrogenation catalyst, the composite material carrier
Content is that content of 97.5-99.3 weight %, the Pt component in terms of Pt element is 0.2-0.5 weight %, Sn component in terms of Sn element
Content be content of 0.2-1.2 weight %, the Na component in terms of Na element be 0.3-0.8 weight %.
According to the present invention, the process of the removal solvent processing can adopt with the conventional methods in the field, such as can adopt
With the solvent in Rotary Evaporators removal system.
According to the present invention, the drying can carry out in drying box, and the roasting can carry out in Muffle furnace.This hair
Also there is no particular limitation for the bright condition to the drying and roasting, can be the conventional selection of this field, for example, the drying
Condition may include: temperature be 110-150 DEG C, time 3-6h；The condition of the roasting may include: that temperature is 600-
650 DEG C, time 5-8h.
Sixth aspect present invention additionally provides a kind of catalyst prepared by preceding method.
As previously mentioned, seventh aspect present invention provides a kind of application of aforementioned catalytic agent in catalysis dehydrogenating propane.
When being used for catalyst provided by the invention to be catalyzed dehydrogenating propane, the choosing of the conversion ratio and propylene of propane is enabled to
Selecting property is improved largely.
As previously mentioned, eighth aspect present invention provides a kind of method of preparing propylene by dehydrogenating propane, this method comprises: being catalyzed
In the presence of agent and hydrogen, propane is subjected to dehydrogenation reaction, wherein the catalyst is for catalyst provided by the invention or by this
The catalyst for the method preparation that invention provides.
According to the present invention, in order to improve conversion of propane and prevent catalyst coking, under preferable case, the dosage of propane with
The molar ratio of the dosage of hydrogen is 0.5-1.5:1.
There is no particular limitation for condition of the present invention to the dehydrogenation reaction, can be the conventional selection of this field, for example,
The condition of the dehydrogenation reaction may include: that reaction temperature is 600-650 DEG C, reaction pressure 0.05-0.2MPa, the reaction time
For 40-60h, propane mass space velocity is 2-5h-1。
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples, Triton X-100 is purchased from Beijing Bellingwell company, trade name
Triton x-100, molecular formula C34H62O11；
In the following Examples and Comparative Examples, ES955 silica gel is purchased from GRACE company；
In following embodiment and comparative example, X-ray diffraction analysis is in the model for being purchased from Bruker AXS company, Germany
It is carried out on the X-ray diffractometer of D8Advance；Scanning electron microscope analysis is swept the model XL-30's purchased from U.S. FEI company
It retouches and is carried out on electron microscope；Pore structure parameter analysis is in the ASAP2020-M purchased from the production of U.S. Micromeritics company
It is carried out on+c-type adsorption instrument, the specific surface area and pore volume of sample, which calculate, uses BET method；The particle diameter distribution of sample is in Malvern
It is carried out on laser particle analyzer；Rotary Evaporators are the production of IKA company, Germany, model RV10digital；Propane dehydrogenation catalyst
Activity component load quantity in the Wavelength Dispersive-X-Ray fluorescence light for being Axios-Advanced purchased from Dutch Panaco company model
It is measured on spectrometer；The analysis of reaction product ingredient carries out on the gas chromatograph purchased from agilent company model 7890A；
In following EXPERIMENTAL EXAMPLE and Experimental comparison's example, the conversion ratio (%) of propane=(in dosage-reaction product of propane
The content of propane) ÷ propane dosage × 100%；
Theoretical yield × 100% of selectivity (%)=propylene actual production ÷ propylene of propylene.
Preparation example 1: composite material F1 of the preparation containing spherical mesoporous molecular sieve C1 and ES955 silica gel A
(1) by 1.5g (0.004mol) template CTAB (cetyl trimethylammonium bromide) and 1.5ml (0.002mol)
Triton X-100 (Bio-Rad-Laboratories) be added to the molten of the hydrochloric acid (29.6g) containing 37 weight % and water (75g)
In liquid, it is completely dissolved in 40 DEG C of stirrings to CTAB；4.35g (0.02mol) ethyl orthosilicate is added to above-mentioned solution again later
In, it stirs 15 minutes, then obtained solution is transferred in the reaction kettle of polytetrafluoroethyllining lining, at 120 DEG C at 40 DEG C
Lower crystallization for 24 hours, be then filtered and and be washed with deionized 4 times, then filtered and dried, obtain mesoporous material raw
Powder；The mesoporous material raw powder is calcined for 24 hours at 600 DEG C, removed template method obtains spherical mesoporous molecular sieve C1；
(2) at 25 DEG C, by 20g spherical mesoporous molecular sieve C1 and 10g ES955 silica gel A, (relevant parameter is referring to table 1, purchase
From Grace company, the U.S.) mechanical blending is carried out, obtain the composite material F1 as carrier.
With XRD, scanning electron microscope and ASAP2020-M+C type adsorption instrument respectively to spherical mesoporous molecular sieve C1 and
ES955 silica gel A is characterized；
Fig. 1 is the X-ray diffracting spectrum of the spherical mesoporous molecular sieve C1, wherein abscissa is 2 θ, and ordinate is strong
Degree, it is apparent that spherical mesoporous molecular sieve C1 diffraction maximum occurs in small angular region from XRD spectra, illustrates spherical Jie
Porous molecular sieve C1 has good mesoporous phase structure, this (Xuelei consistent with mesoporous material XRD spectra reported in the literature
Pang, Fangqiong Tang, Microporous and mesoporous Materials, 2005 (85): 1~6)；
Fig. 2 be spherical mesoporous molecular sieve C1 nitrogen adsorption-desorption curve figure (abscissa be relative pressure (p/p0)),
Nitrogen adsorption-desorption isotherm shows that spherical mesoporous molecular sieve C1 is the Section IV class adsorption-desorption isothermal that typical IUPAC is defined
Line, the specific surface area with superelevation, it was demonstrated that spherical mesoporous molecular sieve C1 has distinctive cube of cage structure reported in the literature
Meso-hole structure (Xuelei Pang, 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)；
Fig. 3 A and Fig. 3 B are the microcosmic shape that the spherical mesoporous molecular sieve C1 enlargement ratio is 300 times and 2000 times respectively
The SEM scanning electron microscope (SEM) photograph of looks, as seen from the figure, spherical mesoporous molecular sieve C1 are spherical shape, and particle size is micron level and document report
Road it is completely the same (Xuelei Pang, Fangqiong Tang, Microporous and mesoporous Materials,
2005 (85): 1~6)；
Fig. 4 is the microscopic appearance figure (scanning electron microscope sem) of ES955 silica gel A, as seen from the figure, the average grain diameter of sample
About 50 μm.
The pore structure parameter of spherical mesoporous molecular sieve C1 and ES955 silica gel A is as shown in table 1.
Preparation example 2: composite material F2 of the preparation containing spherical mesoporous molecular sieve C2 and ES955 silica gel B
(1) by 0.75g (0.002mol) template CTAB (cetyl trimethylammonium bromide) and 3ml (0.004mol)
Triton X-100 (Bio-Rad-Laboratories) be added to the molten of the hydrochloric acid (29.6g) containing 37 weight % and water (75g)
In liquid, it is completely dissolved in 40 DEG C of stirrings to CTAB；4.35g (0.02mol) ethyl orthosilicate is added to above-mentioned solution again later
In, it stirs 15 minutes, then obtained solution is transferred in the reaction kettle of polytetrafluoroethyllining lining, at 100 DEG C at 40 DEG C
Lower crystallization for 24 hours, be then filtered and and be washed with deionized 4 times, then filtered and dried, obtain mesoporous material raw
Powder；The mesoporous material raw powder is calcined for 24 hours at 600 DEG C, removed template method obtains spherical mesoporous molecular sieve C2；
(2) at 25 DEG C, by 30g spherical mesoporous molecular sieve C2 and 10g ES955 silica gel B, (relevant parameter is referring to table 1, purchase
From Grace company, the U.S.) mechanical blending is carried out, obtain the composite material F2 as carrier.
The XRD structure chart of spherical mesoporous molecular sieve C2, SEM microscopic appearance figure respectively with spherical mesoporous molecular sieve C1 phase
Seemingly, the SEM microscopic appearance figure of ES955 silica gel B is similar to ES955 silica gel A.
The pore structure parameter of spherical mesoporous molecular sieve C2 and ES955 silica gel B is as shown in table 1.
Table 1
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Average pore size*(nm) | Partial size (μm) |
| 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: composite material F3 of the preparation containing spherical mesoporous molecular sieve C1 and ES955 silica gel B
Firstly, preparing spherical mesoporous molecular sieve C1 using method identical with preparation example 1.
Then at 25 DEG C, 20g spherical mesoporous molecular sieve C1 and 10g ES955 silica gel B is subjected to mechanical blending, is made
For the composite material F3 of carrier.
Preparation example 4: composite material F4 of the preparation containing spherical mesoporous molecular sieve C2 and ES955 silica gel A
Firstly, preparing spherical mesoporous molecular sieve C2 using method identical with preparation example 2.
Then at 25 DEG C, 20g spherical mesoporous molecular sieve C2 and 10g ES955 silica gel A is subjected to mechanical blending, is made
For the composite material F4 of carrier.
Preparation example 5: composite material F5 of the preparation containing spherical mesoporous molecular sieve C1 and ES955 silica gel A
Firstly, preparing spherical mesoporous molecular sieve C1 using method identical with preparation example 1.
Then at 25 DEG C, 12g spherical mesoporous molecular sieve C1 and 10g ES955 silica gel A is subjected to mechanical blending, is made
For the composite material F5 of carrier.
Preparation example 6: composite material F6 of the preparation containing spherical mesoporous molecular sieve C2 and ES955 silica gel B
Firstly, preparing spherical mesoporous molecular sieve C2 using method identical with preparation example 2.
Then at 25 DEG C, 80g spherical mesoporous molecular sieve C1 and 10g ES955 silica gel B is subjected to mechanical blending, is made
For the composite material F6 of carrier.
Embodiment 1-6: propane dehydrogenation catalyst Cat-1~Cat-6 is prepared
The carrier for taking the above-mentioned preparation example of 10g to be prepared is in N2Under protection, 10h is calcined at 400 DEG C, is carried out at thermal activation
Reason, with eliminating hydroxide and Residual water, obtains the carrier of thermal activation, by 0.08g H2PtCl6·6H2O、0.207g SnCl4·
5H2O and 0.185g NaNO3It is dissolved in 100mL deionized water, by the carrier impregnation of above-mentioned thermal activation in the mixture solution
In, after impregnating 5h at 25 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, solid product is obtained, solid product is set
In the drying box that temperature is 120 DEG C, dry 3h, being subsequently placed in temperature is to roast 6h in 600 DEG C of Muffle furnaces, respectively obtain table 2
In propane dehydrogenation catalyst, name be respectively Cat-1~Cat-6 (in each propane dehydrogenation catalyst, be catalyzed with dehydrogenating propane
On the basis of the total weight of agent, content of the Pt component in terms of Pt element is that content of 0.3 weight %, the Sn component in terms of Sn element is
Content of 0.7 weight %, the Na component in terms of Na element is 0.5 weight %, remaining is carrier).
Comparative example 1-4: propane dehydrogenation catalyst Cat-D-1~Cat-D-4 is prepared
Propane dehydrogenation catalyst is prepared by way of example, the difference is that the heat of identical weight is used only respectively
Globular molecule sieve C1, globular molecule sieve C2, ES955 silica gel A and ES955 silica gel B of activation are respectively obtained in table 2 as carrier
Propane dehydrogenation catalyst, name be respectively Cat-D-1~Cat-D-4.
Comparative example 5-6: propane dehydrogenation catalyst Cat-D-5~Cat-D-6 is prepared
Propane dehydrogenation catalyst is prepared in the way of embodiment 1-2, the difference is that preparing loaded catalyst
In dipping process, NaNO is not added3, 0.133g H is only added2PtCl6·6H2O and 0.295g SnCl4·5H2O passes through total immersion
Active component Pt and metal promoter Sn are only supported on the carrier of thermal activation by stain method, and the dehydrogenating propane respectively obtained in table 2 is urged
Agent, name is respectively Cat-D-5~Cat-D-6, (in each propane dehydrogenation catalyst, with the gross weight of propane dehydrogenation catalyst
On the basis of amount, content of the Pt component in terms of Pt element is that content of 0.5 weight %, the Sn component in terms of Sn element is 1 weight %,
Remaining is carrier).
Test case: dehydrogenating propane reaction is carried out
The propane dehydrogenation catalyst (0.5g) that embodiment is prepared is fitted into fixed-bed quartz reactor, control reaction
Temperature is 610 DEG C, reaction pressure 0.1MPa, propane: the molar ratio of hydrogen is 1:1, and propane mass space velocity is 3h-1, when reaction
Between be 50h.The reaction result (conversion of propane and Propylene Selectivity) of gas chromatographic analysis is shown in Table 2.
Table 2
| Number | Carrier | Metal component | Propane average conversion (%) | Propylene average 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 |
By the result of table 2 can be seen that using the method for the present invention preparation composite material cooperate Pt component, Sn component and
The catalyst that Na component is formed when being catalyzed preparing propylene by dehydrogenating propane with excellent catalytic activity, and propane average transformation
Rate, propylene average selectivity are all significantly improved, after reacting 50h, still available higher conversion of propane and propylene choosing
Selecting property.Illustrating composite products provided by the invention not only has preferable catalytic performance, but also stability is good.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (12)
1. a kind of composite material, which is characterized in that contain silica gel and spherical mesoporous molecular sieve, spherical Jie in the composite material
The pore volume of porous molecular sieve is 0.5-1.5mL/g, specific surface area 1000-1500m2/ g, average pore size 1-2.5nm, it is average
Partial size is 1-20 μm；The specific surface area of the silica gel is 200-300m2/ g, pore volume 1-2mL/g, average pore size 10-
30nm, average grain diameter are 20-100 μm.
2. composite material according to claim 1, wherein the pore volume of the spherical mesoporous molecular sieve is 0.6-1mL/g,
Specific surface area is 1100-1300m2/ g, average pore size 1.5-2nm, partial size are 4-15 μm；The specific surface area of the silica gel is
230-280m2/ g, pore volume 1.2-1.8mL/g, average pore size 12-18nm, average grain diameter are 30-70 μm；
Preferably, the content weight ratio of the spherical mesoporous molecular sieve and the silica gel is (1.2-10): 1；
Preferably, the silica gel is 955 silica gel.
3. a kind of method for preparing composite material of any of claims 1 or 2, which is characterized in that this method comprises:
(1) under solution condition, template, nonionic surfactant, sour agent and silicon source are mixed molten to obtain
Liquid A, wherein the template is cetyl trimethylammonium bromide, and the nonionic surfactant is polyethylene glycol octyl
Phenyl ether；
(2) solution A is carried out successively carrying out crystallization, washing and drying, obtains mesoporous material raw powder；
(3) mesoporous material raw powder is subjected to Template removal processing, obtains the spherical mesoporous molecular sieve；
(4) the spherical mesoporous molecular sieve is mixed with silica gel.
4. according to the method described in claim 3, wherein, in step (1), the condition being mixed includes: that temperature is
25-60 DEG C, time 0.1-48h；
Preferably, the molar ratio of the template, the nonionic surfactant and the silicon source dosage is (0.1-0.6):
(0.1-0.5): 1；
Preferably, in step (2), the condition of the crystallization includes: that temperature is 90-180 DEG C, time 4-40h；
Preferably, in step (3), the process of the Template removal processing includes: at 300-800 DEG C, by the mesoporous material
Expect that original powder calcines 5-40h；
Preferably, in step (4), the mode that the spherical mesoporous molecular sieve is mixed with silica gel is mechanical blending.
5. the composite material prepared by method as claimed in claim 4.
6. a kind of catalyst, Pt component, Sn component and Na component in the catalyst containing carrier and load on the carrier,
It is characterized in that, the carrier is composite material described in any one of claim 1,2 and 5.
7. catalyst according to claim 6, wherein on the basis of the total weight of the catalyst, the carrier contains
Amount is 97.5-99.3 weight %, and content of the Pt component in terms of Pt element is 0.2-0.5 weight %, and the Sn component is with Sn
The content of element meter is 0.2-1.2 weight %, and content of the Na component in terms of Na element is 0.3-0.8 weight %.
8. a kind of method for preparing catalyst described in claim 6 or 7, comprising: carrier is successively carried out to thermal activation treatment, leaching
Stain processing, the processing of removal solvent, dry and roasting, make the supported on carriers Pt component, Sn component and Na component, feature exist
In the carrier is composite material described in any one of claim 1,2 and 5.
9. the catalyst prepared by method according to any one of claims 8.
10. application of the catalyst described in any one of claim 6,7 and 9 in catalysis dehydrogenating propane.
11. a kind of method of preparing propylene by dehydrogenating propane, this method comprises: carrying out propane in the presence of catalyst and hydrogen
Dehydrogenation reaction, which is characterized in that the catalyst is catalyst described in any one of claim 6,7 and 9.
12. according to the method for claim 11, wherein the molar ratio of the dosage of the dosage and hydrogen of propane is 0.5-1.5:
1；
Preferably, it is 600-650 DEG C, reaction pressure 0.05-0.2MPa that the condition of the dehydrogenation reaction, which includes: reaction temperature,
Reaction time is 40-60h, and propane mass space velocity is 2-5h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710666301.1A CN109382144B (en) | 2017-08-07 | 2017-08-07 | Composite material and preparation method thereof, catalyst and preparation method and application thereof, and method for preparing propylene by propane dehydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710666301.1A CN109382144B (en) | 2017-08-07 | 2017-08-07 | Composite material and preparation method thereof, catalyst and preparation method and application thereof, and method for preparing propylene by propane dehydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109382144A true CN109382144A (en) | 2019-02-26 |
| CN109382144B CN109382144B (en) | 2019-12-24 |
Family
ID=65413522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710666301.1A Active CN109382144B (en) | 2017-08-07 | 2017-08-07 | Composite material and preparation method thereof, catalyst and preparation method and application thereof, and method for preparing propylene by propane dehydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109382144B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105330767A (en) * | 2014-06-13 | 2016-02-17 | 中国石油化工股份有限公司 | Supported polyethylene catalyst ingredient and preparation method thereof, and supported polyethylene catalyst and application thereof |
-
2017
- 2017-08-07 CN CN201710666301.1A patent/CN109382144B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105330767A (en) * | 2014-06-13 | 2016-02-17 | 中国石油化工股份有限公司 | Supported polyethylene catalyst ingredient and preparation method thereof, and supported polyethylene catalyst and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| XUELEI PANG ET AL.,: "Morphological control of mesoporous materials using inexpensive silica sources", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109382144B (en) | 2019-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109382132A (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN108855197B (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN109745977A (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN109746032B (en) | Propane dehydrogenation catalyst, preparation method thereof and method for preparing propylene by propane dehydrogenation | |
| CN109746033B (en) | Method for preparing propane dehydrogenation catalyst, propane dehydrogenation catalyst and method for preparing propylene by propane dehydrogenation | |
| CN109746029A (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN109746027A (en) | Prepare the method for propane dehydrogenation catalyst and the method for propane dehydrogenation catalyst and preparing propylene by dehydrogenating propane | |
| CN108722402B (en) | A kind of method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN109748294A (en) | The method of spherical mesoporous molecular screen material and preparation method thereof and catalyst and its preparation method and application and preparing propylene by dehydrogenating propane | |
| CN109382129B (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN109382130B (en) | The method of composite material and preparation method and catalyst and its preparation method and application and preparing propylene by dehydrogenating propane | |
| CN109746049B (en) | Composite material and preparation method thereof, catalyst and preparation method and application thereof, and method for preparing propylene by propane dehydrogenation | |
| CN108722403B (en) | A kind of method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN108855201B (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN108786897B (en) | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane | |
| CN108722468B (en) | A kind of method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN108855198B (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN109746028B (en) | Propane dehydrogenation catalyst, preparation method thereof and method for preparing propylene by propane dehydrogenation | |
| CN109382131A (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN109382144A (en) | The method of composite material and preparation method and catalyst and its preparation method and application and preparing propylene by dehydrogenating propane | |
| CN109382133B (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN109382134B (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN109289899B (en) | The method of composite material and preparation method and catalyst and its preparation method and application and preparing propylene by dehydrogenating propane | |
| CN109289935B (en) | The method of complex mesoporous material and preparation method thereof and catalyst and its preparation method and application and preparing propylene by dehydrogenating propane | |
| CN109745978A (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |