CN109513455A - Epoxidation catalyst and preparation method thereof and application method - Google Patents
Epoxidation catalyst and preparation method thereof and application method Download PDFInfo
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- CN109513455A CN109513455A CN201811469861.9A CN201811469861A CN109513455A CN 109513455 A CN109513455 A CN 109513455A CN 201811469861 A CN201811469861 A CN 201811469861A CN 109513455 A CN109513455 A CN 109513455A
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- epoxidation catalyst
- metal hydroxides
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 239000002808 molecular sieve Substances 0.000 claims abstract description 18
- 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 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 238000002803 maceration Methods 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 10
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 10
- 238000001125 extrusion Methods 0.000 claims abstract description 9
- 239000000853 adhesive Substances 0.000 claims abstract description 8
- 230000001070 adhesive effect Effects 0.000 claims abstract description 8
- -1 extrusion aid Substances 0.000 claims abstract description 7
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 53
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 37
- 150000004692 metal hydroxides Chemical class 0.000 claims description 37
- 239000011259 mixed solution Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 150000001451 organic peroxides Chemical class 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 16
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 12
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- HDHOHQHZKXFKOS-UHFFFAOYSA-N ethylbenzene;hydrogen peroxide Chemical compound OO.CCC1=CC=CC=C1 HDHOHQHZKXFKOS-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical group C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 4
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 4
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 4
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 4
- TZBAVQKIEKDGFH-UHFFFAOYSA-N n-[2-(diethylamino)ethyl]-1-benzothiophene-2-carboxamide;hydrochloride Chemical compound [Cl-].C1=CC=C2SC(C(=O)NCC[NH+](CC)CC)=CC2=C1 TZBAVQKIEKDGFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- CSRZQMIRAZTJOY-UHFFFAOYSA-N trimethylsilyl iodide Chemical compound C[Si](C)(C)I CSRZQMIRAZTJOY-UHFFFAOYSA-N 0.000 claims description 4
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 235000014413 iron hydroxide Nutrition 0.000 claims description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229960003511 macrogol Drugs 0.000 claims description 3
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical group CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 238000004448 titration Methods 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 2
- 229910052708 sodium Inorganic materials 0.000 claims 2
- 239000011734 sodium Substances 0.000 claims 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 241000219782 Sesbania Species 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006335 epoxy glue Polymers 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OATWCNSODQAOQC-UHFFFAOYSA-N [SiH4].Br Chemical compound [SiH4].Br OATWCNSODQAOQC-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- GPKFMIVTEHMOBH-UHFFFAOYSA-N cumene;hydrate Chemical compound O.CC(C)C1=CC=CC=C1 GPKFMIVTEHMOBH-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/044—Iron group metals or copper
-
- 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
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a kind of epoxidation catalysts comprising the TiO of 2~15wt%2;The SiO of 84~96wt%2;The M of 0.75~3wt%;TiO2And SiO2Total amount be 97~99.25wt%;9~30nm of aperture of the epoxidation catalyst, 210~700m of specific surface area2/g;Wherein M is CaO, Fe2O3, CuO or Cr2O3At least one of.The preparation method of above-mentioned epoxidation catalyst, step are as follows: (11) template, pH adjusting agent, water are added into reactor, mesoporous silicon rubber powder is made;(12) mesoporous silicon rubber powder, extrusion aid, adhesive are roasted and molded molecular sieve is made;(13) molded molecular sieve roasting is added into reacting furnace, is pumped into titanium source, the first maceration extract is impregnated;(14) it cleans, is dry, modifying agent is added, epoxidation catalyst is made.This application additionally provides the application method of above-mentioned catalyst.The catalyst has the advantage that can be recycled, preparation method cleaning in the case where guaranteeing efficient situation.
Description
Technical field
The present invention relates to a kind of epoxidation catalyst and preparation method thereof and application methods, belong to catalyst synthesis and application
Field.
Background technique
Propylene oxide is important basic organic chemical raw material.Traditional chlorohydrination production propylene oxide process pollution weight,
Corrosion is big.Under the important prerequisite of environmental protection, the epoxidation Green Manufacturing Technology that development technology process is simple, cleaning is economic is especially heavy
It wants.It selects organic peroxide oxyalkylene in related solvents to prepare epoxide to flourish in recent two decades.Such as mistake
Hydrogen oxide cumene oxidation propylene method is due to polluting development that is small and having become Producing Process of Propylene Oxide without joint product generation
One of direction.The hydrogen peroxide ethylbenzene oxidation propylene also heavy industrialization application of Shell Co. Ltd.Therefore, alkene epoxidation is catalyzed
Agent is the core of technological break-through, and catalyst structure form, constituent directly affect the selectivity of the conversion ratio of raw material, product.
And the service life of catalyst directly affects production cost.
Source investigation shows that Titanium Sieve Molecular Sieve has good catalytic activity to the selective oxidation of olefines, is epoxidation
Preferable catalyst in reaction.Mesoporous (2~50nm) molecular sieve is able to satisfy hydrogen peroxide ethylbenzene, cumyl hydroperoxide molecule ruler
Very little requirement.Organic peroxy source, alkene are spread in the duct of Titanium Sieve Molecular Sieve, and contact metallic element is easier to react obtained
Corresponding product.The study found that organic matter can be deposited in molecular sieve pore passage, be blocked with the progress of reaction.Substantially reduce catalysis
Agent service life.Therefore, recyclable effective catalyst is developed as trend.
Summary of the invention
The purpose of the present invention, which first consists in, provides a kind of catalyst, and for the catalyst in the case where guaranteeing efficient situation, having can
The advantage of recycling, specific technical solution are as follows:
A kind of epoxidation catalyst comprising
The TiO of 2~15wt%2;The SiO of 84~96wt%2;The M of 0.75~3wt%;TiO2And SiO2Total amount be 97~
99.25wt%;9~30nm of aperture of the epoxidation catalyst, 210~700m of specific surface area2/g;Wherein M is CaO, Fe2O3、
CuO or Cr2O3At least one of.
The catalyst aperture is big, specific surface area is high, and pole is conducive to reactant disengaging catalyst duct and contacts and leave away with metal,
Improve catalytic efficiency.The catalyst can be the catalyst of epoxidation of propylene, have good economic performance.For organic peroxide
Propylene oxide prepares propylene oxide and provides a kind of efficient metal composite catalyst.
The circulation that the catalyst can be impregnated again by the dipping and cleaning of assistant metal element, both guarantees Titanium Sieve Molecular Sieve
Efficient stable realizes the process in dredging duct, recycling again.On the basis for guaranteeing that catalyst has good catalytic effect
On, realization can be recycled.
Using this catalyst, conversion ratio >=99.9%, selectivity >=99.5% can be made.
Secondly, the application also provides the preparation method of above-mentioned epoxidation catalyst, comprising the following steps:
(11) template, pH adjusting agent, water are added into reactor, is heated to 40~90 DEG C, stirs 0.5~1.5h, adds
Enter silicon source, 40~90 DEG C of 12~48h of heat preservation, then temperature of reactor is risen to 120~150 DEG C the reaction was continued 12~48h, then drop
It is filtered after warming to room temperature, is dry, obtaining mesoporous silicon rubber powder;
(12) mesoporous silicon rubber powder, extrusion aid, adhesive are mixed in proportion, extrusion moulding is mold compound;It will be at
Type product in 100~180 DEG C dry 12~for 24 hours, then in 400~850 DEG C of 3~5h of roasting, obtain molded molecular sieve;
(13) molded molecular sieve is added into reacting furnace, 400~900 DEG C of furnace temperature, by being pumped into titanium source at the top of reacting furnace, keeps
It is cooled to 60~90 DEG C after 6~12h, the first maceration extract is then added and is impregnated, by the first maceration extract after impregnating 4~12h
It releases, drain, which is the first metal hydroxide solutions;
(14) by reacting furnace temperature control at 100~400 DEG C, deionized water cleaning is added, clean heat preservation and dryness 8~for 24 hours afterwards,
Furnace temperature is down to 90~160 DEG C, and modifying agent is added, and keeps the temperature 2~10h, and epoxidation catalyst is made.
The preparation method controls product index by adjusting late phase reaction temperature, simplifies the removal of template extraction or roasting
Process reduces water, gas pollution.
Preferably, in the preparation method of the epoxidation catalyst,
In step (11), template, pH adjusting agent, water and silicon source mass ratio be 1:0.1~0.3:10~25:3~10;
In step (12), the mass ratio of mesoporous silicon rubber powder, extrusion aid and adhesive is 1:0.03~0.1:0.3~1;
In step (13), the mass ratio of molded molecular sieve and titanium source is 1:0.1~0.5;
In step (13), the first metal hydroxide solutions are metal hydroxides aqueous solution, metal hydroxides dissolution
In the first sour solution, metal hydroxides is dissolved in the solution of the first alkali, metal hydroxides is dissolved in the molten of the first solvent
Liquid or metal hydroxides colloidal solution, the mass concentration of the first metal hydroxide solutions are 0.1~2wt%;
It is above-mentioned first acid be hydrochloric acid, nitric acid or perchloric acid, the first alkali be ammonium hydroxide or ammonium salt solution, the first solvent be glycerol or
Sodium cyanide solution;
In step (14), the mass ratio of deionized water, molded molecular sieve and modifying agent is 2~5:1:0.1~0.5.
In above scheme, the first metal hydroxides is introduced with solution or colloid solution form, improves point of metallic element
Property is dissipated, also can remove a large amount of unreacted titanium sources in dipping process, reduces influence of the extra-framework titanium to catalytic performance.Modifying agent
Addition, improve the whole hydrophobic performance of catalyst, reduce the influence that moisture uses catalyst.
Further, in step (11), template is selected from lauryl amine, cetylamine, Macrogol 4000, Tween 80 or dodecane
At least one of base benzene sulfonic acid sodium salt;
In step (11), pH adjusting agent in oxalic acid, ammonium hydroxide, glacial acetic acid, citric acid or tetramethylammonium hydroxide extremely
Few one kind;
In step (11), silicon source is selected from least one of aqueous silica solution, liquid silica solution or sodium metasilicate;
In step (12), extrusion aid in hydroxypropyl methyl cellulose, sesbania gum or Macrogol 6000 at least one
Kind;
In step (12), adhesive is in aqueous silica solution or silica solution, aqueous silica solution or silica solution
The mass concentration of silica is 5~40%;
In step (13), titanium source is selected from titanium tetrachloride, tetramethoxy titanate ester, tetraethyl titanate, metatitanic acid orthocarbonate or metatitanic acid four
At least one of butyl ester;
In step (13), metal hydroxides in the first metal hydroxide solutions be selected from calcium hydroxide, iron hydroxide,
At least one of Kocide SD or chromium hydroxide;
In step (14), modifying agent is selected from hexamethyldisilazane, tetramethyl-disilazane, trim,ethylchlorosilane, front three
At least one of bromide silane or Iodotrimethylsilane.
In above scheme, silicon source avoids the selection of organic silicic acid esters, improves the hydrophilicity of silica white, is metal
More attachment points are provided, while improving the matching with adhesive.
Again, the application also provides the application method of above-mentioned epoxidation catalyst, includes the following steps:
(21) epoxidation catalyst is fitted into tubular reactor, controls the temperature of reactor at 60~125 DEG C, is added third
Alkene and organic peroxide mixed solution, the gas phase composition of sampling analysis reaction product and turning for titrimetry organic peroxide
Rate;
(22) when reaction temperature is lower than 5~10 DEG C of reaction temperature of setting, first stop the addition of organic peroxy mixed solution,
Stop the addition of propylene again, the second maceration extract is then added and is impregnated, releases the second maceration extract after impregnating 4~12h, row
To the greatest extent, circulation is passed through related solvents and cleans to epoxidation catalyst, and after cleaning 4~12h, epoxidation catalyst is repeated again
It utilizes;Second maceration extract is the second metal hydroxide solutions.
In above scheme, combine the detection of conversion ratio that can effectively monitor catalyst catalytic performance by temperature (reaction heat),
Improve technology stability.Catalyst cellular structure can effectively be dredged by impregnating and cleaning again, avoid the loss of active metal, raising is urged
Agent service life.The circulation that the dipping of assistant metal element and cleaning impregnate again, had both guaranteed the efficient stable of Titanium Sieve Molecular Sieve
Property realize again dredging duct, recycling process;
Preferably, in step (21), the molar ratio of propylene and organic peroxide is 1:4~16;It is related in step (22)
The mass ratio of solvent and epoxidation catalyst is 1:2~5.
In above scheme, solvent can effectively remove the residual impurity in maceration extract, meanwhile, solvent can also take away residual water
Point, effectively avoid the reduction of hydrophobic performance after catalyst modification.
In step (22), organic peroxide mixed solution is the mixed solution of cumyl hydroperoxide and isopropylbenzene;Or
Organic peroxide mixed solution is the mixed solution of hydrogen peroxide ethylbenzene and ethylbenzene;The mass percentage of organic peroxide
It is 25~55%;It is related molten when organic peroxide mixed solution is the mixed solution of cumyl hydroperoxide and isopropylbenzene
Agent is isopropylbenzene;When organic peroxide mixed solution is the mixed solution of hydrogen peroxide ethylbenzene and ethylbenzene, related solvents are
Ethylbenzene.
In above scheme, propylene oxide made from organic peroxide mixed solution propylene oxide is since moisture is low, by-product
Few, product quality is high.And cumyl hydroperoxide method pollutes low, Matter Transfer use without coproduction.
Preferably, in step (22), the second metal hydroxide solutions are metal hydroxides aqueous solution, metal hydroxide
It is molten that object is dissolved in the second sour solution, metal hydroxides is dissolved in the solution of the second alkali, metal hydroxides is dissolved in second
The solution or metal hydroxides colloidal solution of agent, the mass concentration of the second metal hydroxide solutions are 0.1~2wt%;
It is above-mentioned second acid be hydrochloric acid, nitric acid or perchloric acid, the second alkali be ammonium hydroxide or ammonium salt solution, the second solvent be glycerol or
Sodium cyanide solution.
Specific embodiment
Embodiment 1
22g Macrogol 4000,500g deionized water are added in the reactor of 1L, is warming up to 60 DEG C of stirring 1h, is added
125 DEG C are warming up to after alkaline silica gel aqueous solution 100g, insulated and stirred 20h that concentration is 40wt% the reaction was continued 20h, filtering, roasting
It burns, obtains mesoporous silicon rubber powder 35g;The quality that 2g is pressed 1:1 by hydroxypropyl methyl cellulose and sesbania gum is added in mesoporous silicon rubber powder
Pass through list after mixing evenly than being formed by epoxy glue, 75g concentration for the aqueous silica solution and 15g deionized water of 40wt%
Screw rod banded extruder is extruded into 2mm shaped molecular sieve of diameter.By it in 550 DEG C of roasting 3.5h after 125 DEG C of dry 20h, finished product is cut
Item is spare.
50g shaped molecular sieve is added in reacting furnace, 610 DEG C of furnace temperature, titanium tetrachloride 12.5g is added, keeps the temperature 8h.Furnace temperature drop
It is added after the calcium hydroxide solution 100g that concentration is 1wt% impregnates 8h and drains to 70 DEG C, reacting furnace is passed through after being warming up to 200 DEG C
The cleaning of 200g deionized water, the heat preservation and dryness 8h after water adds.Reacting furnace is cooled to 150 DEG C, and the hexamethyl two measured is added
Silazane 12.5g keeps the temperature 8h.Gained catalyst is labeled as 1#.
Load a certain amount of epoxidation catalyst prepared by the present invention in fixed bed reactors, control reaction pressure 2~
5MPa, 40~160 DEG C of reaction temperature, cumyl hydroperoxide concentration 35wt%, cumyl hydroperoxide volume space velocity 0.5~
2h-1, propylene and cumyl hydroperoxide molar ratio 10:1.In reaction process, if cumyl hydroperoxide conversion ratio is lower than
95%, stop that cumyl hydroperoxide/isopropylbenzene mixed solution, propylene is added, the iron hydroxide solution that concentration is 1wt% is added
It is drained after dipping 8h, circulation continues to use after being passed through isopropylbenzene cleaning 8h.Service condition is labeled as P1*.
Embodiment 2
The present embodiment is substantially the same manner as Example 1, and difference is: Macrogol 4000 dosage is changed to 16.2g, remaining and reality
It is identical to apply example 1.Gained catalyst is labeled as 2#.Service condition is labeled as P2*.
Embodiment 3
The present embodiment is substantially the same manner as Example 1, and difference is: 22g Macrogol 4000 is replaced by 15g cetylamine,
Remaining is same as Example 1.Gained catalyst is labeled as 3#.Service condition is labeled as P3*.
Embodiment 4
The present embodiment is substantially the same manner as Example 1, and difference is: concentration is that the calcium hydroxide solution 100g of 1wt% is replaced
It is changed to the ferric hydroxide colloid solution 100g that concentration is 1wt%, remaining is same as Example 1.Gained catalyst is labeled as 4#.Make
P4* is labeled as with situation.
Embodiment 5
The present embodiment is substantially the same manner as Example 1, and difference is: 2g is by hydroxypropyl methyl cellulose and sesbania gum by 1:1
Mass ratio be formed by epoxy glue and be replaced by 3g sesbania gum, concentration be the aqueous silica solution of 40wt% dosage by
75g is adjusted to 100g, and it is sweet that the calcium hydroxide solution 100g that concentration is 1wt% is replaced by the Kocide SD that concentration is 1.2wt%
Oil solution 80g, remaining is same as Example 1.Gained catalyst is labeled as 5#.Service condition is labeled as P5*.
Embodiment 6
The present embodiment is substantially the same manner as Example 1, and difference is: propylene and cumyl hydroperoxide molar ratio are adjusted to 6:
1, remaining is same as Example 1.Gained catalyst is labeled as 6#.Service condition is labeled as P6*.
Catalyst prepared by each embodiment is detected, testing result is included in table 1.Catalysis prepared by each embodiment
The using effect of agent is included in table 2.
The testing result of each embodiment catalyst of table 1
The using effect of each embodiment catalyst of table 2
By Tables 1 and 2 as can be seen that the catalyst in the application has good structure and excellent catalysis and makes
Use performance.
Claims (8)
1. a kind of epoxidation catalyst, which is characterized in that including
The TiO of 2~15wt%2;
The SiO of 84~96wt%2;
The M of 0.75~3wt%;
TiO2And SiO2Total amount be 97~99.25wt%;
9~30nm of aperture of the epoxidation catalyst, 210~700m of specific surface area2/g;
Wherein M is CaO, Fe2O3, CuO or Cr2O3At least one of.
2. the preparation method of epoxidation catalyst described in claim 1, comprising the following steps:
(11) template, pH adjusting agent, water are added into reactor, is heated to 40~90 DEG C, stirs 0.5~1.5h, silicon is added
Source, 40~90 DEG C of 12~48h of heat preservation, then temperature of reactor is risen to 120~150 DEG C the reaction was continued 12~48h, then it is cooled to
It is filtered after room temperature, is dry, obtaining mesoporous silicon rubber powder;
(12) mesoporous silicon rubber powder, extrusion aid, adhesive are mixed in proportion, extrusion moulding is mold compound;Molding is produced
Object in 100~180 DEG C dry 12~for 24 hours, then in 400~850 DEG C of 3~5h of roasting, obtain molded molecular sieve;
(13) it is added molded molecular sieve into reacting furnace, 400~900 DEG C of furnace temperature, by being pumped into titanium source at the top of reacting furnace, keep 6~
It is cooled to 60~90 DEG C after 12h, the first maceration extract is then added and is impregnated, puts the first maceration extract after impregnating 4~12h
Out, it drains, which is the first metal hydroxide solutions;
(14) by reacting furnace temperature control at 100~400 DEG C, deionized water cleaning is added, clean heat preservation and dryness 8~for 24 hours afterwards, furnace temperature
90~160 DEG C are down to, modifying agent is added, keeps the temperature 2~10h, epoxidation catalyst is made.
3. preparation method according to claim 2, which is characterized in that
In step (11), template, pH adjusting agent, water and silicon source mass ratio be 1:0.1~0.3:10~25:3~10;
In step (12), the mass ratio of mesoporous silicon rubber powder, extrusion aid and adhesive is 1:0.03~0.1:0.3~1;
In step (13), the mass ratio of molded molecular sieve and titanium source is 1:0.1~0.5;
In step (13), the first metal hydroxide solutions are that metal hydroxides aqueous solution, metal hydroxides are dissolved in
One acid solution, metal hydroxides be dissolved in the solution of the first alkali, metal hydroxides be dissolved in the first solvent solution or
Metal hydroxides colloidal solution, the mass concentration of the first metal hydroxide solutions are 0.1~2wt%;
Above-mentioned first acid is hydrochloric acid, nitric acid or perchloric acid, and the first alkali is ammonium hydroxide or ammonium salt solution, and the first solvent is glycerol or cyaniding
Sodium solution;
In step (14), the mass ratio of deionized water, molded molecular sieve and modifying agent is 2~5:1:0.1~0.5.
4. preparation method according to claim 2, which is characterized in that
In step (11), template is selected from lauryl amine, cetylamine, Macrogol 4000, Tween 80 or neopelex
At least one of;
In step (11), pH adjusting agent in oxalic acid, ammonium hydroxide, glacial acetic acid, citric acid or tetramethylammonium hydroxide at least one
Kind;
In step (11), silicon source is selected from least one of aqueous silica solution, liquid silica solution or sodium metasilicate;
In step (12), extrusion aid is selected from least one of hydroxypropyl methyl cellulose, sesbania gum or Macrogol 6000;
In step (12), adhesive is selected from aqueous silica solution or silica solution, dioxy in aqueous silica solution or silica solution
The mass concentration of SiClx is 5~40%;
In step (13), titanium source is selected from titanium tetrachloride, tetramethoxy titanate ester, tetraethyl titanate, metatitanic acid orthocarbonate or butyl titanate
At least one of;
In step (13), the metal hydroxides in the first metal hydroxide solutions is selected from calcium hydroxide, iron hydroxide, hydrogen-oxygen
Change at least one of copper or chromium hydroxide;
In step (14), modifying agent is selected from hexamethyldisilazane, tetramethyl-disilazane, trim,ethylchlorosilane, front three bromide
At least one of silane or Iodotrimethylsilane.
5. the application method of epoxidation catalyst described in claim 1, comprising the following steps:
(21) epoxidation catalyst is fitted into tubular reactor, controls the temperature of reactor at 60~125 DEG C, be added propylene and
Organic peroxide mixed solution, the gas phase composition of sampling analysis reaction product and the conversion of titrimetry organic peroxide
Rate;
(22) when reaction temperature is lower than 5~10 DEG C of reaction temperature of setting, first stop the addition of organic peroxy mixed solution, then stop
Then the only addition of propylene is added the second maceration extract and is impregnated, release the second maceration extract after impregnating 4~12h, drain,
Circulation is passed through related solvents and cleans to epoxidation catalyst, after cleaning 4~12h, epoxidation catalyst is repeated again sharp
With;Second maceration extract is the second metal hydroxide solutions.
6. application method according to claim 5, which is characterized in that
In step (21), the molar ratio of propylene and organic peroxide is 1:4~16;
In step (22), the mass ratio of related solvents and epoxidation catalyst is 1:2~5.
7. application method according to claim 5, which is characterized in that
In step (22), organic peroxide mixed solution is the mixed solution of cumyl hydroperoxide and isopropylbenzene;Or
Organic peroxide mixed solution is the mixed solution of hydrogen peroxide ethylbenzene and ethylbenzene;
The mass percentage of organic peroxide is 25~55%;
When organic peroxide mixed solution is the mixed solution of cumyl hydroperoxide and isopropylbenzene, related solvents are isopropyl
Benzene;
When organic peroxide mixed solution is the mixed solution of hydrogen peroxide ethylbenzene and ethylbenzene, related solvents are ethylbenzene.
8. application method according to claim 5, which is characterized in that
In step (22), the second metal hydroxide solutions are that metal hydroxides aqueous solution, metal hydroxides are dissolved in
Solution, the metal hydroxides of diacid are dissolved in the solution of the second alkali, metal hydroxides be dissolved in the second solvent solution or
Metal hydroxides colloidal solution, the mass concentration of the second metal hydroxide solutions are 0.1~2wt%;
Above-mentioned second acid is hydrochloric acid, nitric acid or perchloric acid, and the second alkali is ammonium hydroxide or ammonium salt solution, and the second solvent is glycerol or cyaniding
Sodium solution.
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