CN107308982A - The synthetic method of modifying titanium-silicon molecular sieve catalyst and its preparation method and application and epoxychloropropane - Google Patents
The synthetic method of modifying titanium-silicon molecular sieve catalyst and its preparation method and application and epoxychloropropane Download PDFInfo
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- CN107308982A CN107308982A CN201610266533.3A CN201610266533A CN107308982A CN 107308982 A CN107308982 A CN 107308982A CN 201610266533 A CN201610266533 A CN 201610266533A CN 107308982 A CN107308982 A CN 107308982A
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- molecular sieve
- sieve catalyst
- silicon molecular
- titanium
- mass
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- 239000003054 catalyst Substances 0.000 title claims abstract description 154
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 93
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 92
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000010189 synthetic method Methods 0.000 title claims abstract description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 115
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000007493 shaping process Methods 0.000 claims description 36
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 18
- 229910052723 transition metal Inorganic materials 0.000 claims description 16
- 150000003624 transition metals Chemical class 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- -1 olefin epoxide Chemical class 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 5
- 238000009938 salting Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 150000001734 carboxylic acid salts Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 150000003608 titanium Chemical class 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims 2
- 150000004706 metal oxides Chemical class 0.000 claims 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 230000002194 synthesizing effect Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 5
- OWXJKYNZGFSVRC-UHFFFAOYSA-N 1-chloroprop-1-ene Chemical class CC=CCl OWXJKYNZGFSVRC-UHFFFAOYSA-N 0.000 abstract 1
- 238000013537 high throughput screening Methods 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 28
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
- 238000007598 dipping method Methods 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- 238000007605 air drying Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000004088 foaming agent Substances 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910000480 nickel oxide Inorganic materials 0.000 description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical group [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 244000275012 Sesbania cannabina Species 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical class O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 2
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 2
- 229910003445 palladium oxide Inorganic materials 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- YWNYZQTZOONLGU-UHFFFAOYSA-N C(CC)Cl.[O] Chemical compound C(CC)Cl.[O] YWNYZQTZOONLGU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 241001272567 Hominoidea Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- LIABKAQKQSUQJX-UHFFFAOYSA-N [Mn].[Pb] Chemical compound [Mn].[Pb] LIABKAQKQSUQJX-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method 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
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
-
- 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
- B01J2229/60—Synthesis on support
- B01J2229/62—Synthesis on support in or on other molecular sieves
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Epoxy Compounds (AREA)
Abstract
A kind of synthetic method of modifying titanium-silicon molecular sieve catalyst and its preparation method and application and epoxychloropropane, the modifying titanium-silicon molecular sieve catalyst contains the HTS with MFI topological structures, aluminum oxide and transition metal oxide, on the basis of the total amount of the modifying titanium-silicon molecular sieve catalyst, the content of HTS with MFI topological structures is 35 75 mass %, the content of aluminum oxide is 20 60 mass %, the content of transition metal oxide is 0.1 5 mass %, the transition metal oxide is the oxide of zirconium, one or more in the oxide of nickel and the oxide of lanthanum.The modifying titanium-silicon molecular sieve catalyst, in course of reaction of 3 chloropropenes with hydrogen peroxide Direct Epoxidation synthesizing epoxy chloropropane is catalyzed, while showing higher catalytic activity, also with considerably higher activity stability.
Description
Technical field
The present invention relates to a kind of modifying titanium-silicon molecular sieve catalyst and preparation method thereof and in alkene epoxidation
The synthetic method of application and epoxychloropropane in reaction.
Background technology
US4,833,260 is disclosed in HTS (TS-1) catalyst with MFI topological structures
In the presence of solvent methanol, reacted by chlorallylene and hydrogen peroxide Direct Epoxidation come high selectivity
The method of ground synthesizing epoxy chloropropane, to realize the greenization of epoxychloropropane building-up process.It is wherein described
TS-1 catalyst both can be the former powder of TS-1 or the TS-1 catalyst of shaping.Work as use
During former powder catalyst, because its average particulate diameter only has 0.2 μm or so so that by catalyst from liquid
Being separated in reaction product becomes very difficult.
It is to be shaped to solve the former powder catalyst of HTS and difficult method is separated with product liquid
Preformed catalyst with larger particle diameter.US4,701,428 discloses a kind of spray shaping and prepared
Average diameter is the method for 20 μm or so of microballoon TS-1 catalyst, and this method needs are using filtering
Method by microspherical catalyst from chlorallylene with being separated in hydrogen peroxide epoxidizing reaction product, no
It can apply in fixed bed reactors.
US6,603,027 and CN200610013521.6 disclose it is a kind of TS-1 is deposited on it is cellular lazy
The method that property carrier channel surfaces prepare preformed catalyst, the catalyst prepared by this method can be in fixation
It is used for the epoxidation reaction for being catalyzed chlorallylene and hydrogen peroxide in bed reactor.But, such as
US6, disclosed in 603,027, TS-1 content only has 15.7% in catalyst；And
The catalyst prepared in CN200610013521.6 is used for the epoxidation reaction of chlorallylene and hydrogen peroxide,
The selective highest of epoxychloropropane also only has 62.7%, well below the requirement of industrial applications.
US6,699,812 report a kind of method for preparing extruded moulding titanium-silicon molecular sieve catalyst and its
Chlorallylene and the application in hydrogen dioxide epoxidation reaction.Its preparation method is by TS-1 titanium silicon molecules
Sieve, binding agent polymethyl siloxane, plasticizer methylcellulose, pore-foaming agent melamine and paste making agent water
Paste is mixed into, strip formed body is obtained with banded extruder extrusion, dries and roasting strip formed body, obtains
To preformed catalyst, the epoxidation that chlorallylene and hydrogen peroxide are carried out in fixed bed circulatory flow reactor is anti-
Should, the conversion ratio of hydrogen peroxide only has 89%.
CN200710120615.8 discloses a kind of method for preparing extruded moulding titanium-silicon molecular sieve catalyst
And its application in chlorallylene and hydrogen dioxide epoxidation reaction.By TS-1 HTSs, receive
Rice aluminum oxide, Alumina gel, pore-foaming agent, extrusion aid and water are mixed to get plastic thing, are extruded with banded extruder
Plastic thing obtains wet strip formed body, dries and is calcined the strip formed body of extrusion, obtain shaping and urge
Agent, the epoxidation reaction of chlorallylene and hydrogen peroxide is carried out in fixed bed reactors, can be obtained
99.2% hydrogen peroxide conversion and 96.9% epoxychloropropane selectivity, still, the machine of catalyst
Tool intensity only has 20-30N/cm2, it is difficult to meet the requirement of commercial fixed bed reactor.
CN201010184391.9 discloses one kind and prepares high intensity extruded moulding titanium-silicon molecular sieve catalyst
Method and its application in chlorallylene and hydrogen dioxide epoxidation reaction.By TS-1 titanium silicon molecules
Sieve, aluminium hydrate powder, Alumina gel, pore-foaming agent, extrusion aid and water are mixed to get plastic thing, use extrusion
Machine extrudes plastic thing and obtains wet strip formed body, dries and is calcined the strip formed body of extrusion, obtain
Preformed catalyst, the side pressure breaking strength of preformed catalyst is 70-150N/cm, in fixed bed reactors
The middle epoxidation reaction for carrying out chlorallylene and hydrogen peroxide, can obtain 98.9% hydrogen peroxide conversion
Rate and 95.1% epoxychloropropane selectivity, disclosure satisfy that the requirement of commercial fixed bed reactor.But should
Catalyst is after continuous use 118 hours, and the conversion ratio of hydrogen peroxide begins to occur obvious decline,
96.9% has been had descended to by 125 hours.
In order to further improve shaping titanium-silicon molecular sieve catalyst chlorallylene with it is hydrogen peroxide epoxidizing
Catalytic activity and activity stability in the course of reaction of synthesizing epoxy chloropropane, this area has been carried out largely
Research.It is has been common that such as Liu Xuewu (Liu Xuewu, Guo Xinwen, Wang Xiangsheng, Li Gang, it is old
Extra-framework titanium species (TiO in English forever, TS-1 molecular sieves2)xInfluence to propylene ring oxidation reaction, the study of petroleum
Report (PETROLEUM PROCESSING), 2000,16 (5)：41-46) reported, transition metal oxide such as dioxy
Change the presence of titanium, the peroxidating during titanium-silicon molecular sieve catalyst catalysis propylene ring oxidation reaction can be increased
The decomposition of hydrogen, reduces the epoxidation selectivity of hydrogen peroxide.In addition, such as Tian Hanjing (Tian Hanjing,
Zhang Tao, Yang Huanghe, Sun Xiaoying, Liang Dongbai, Lin Liwu, the manganese lead composite oxygen decomposed for hydrogen peroxide
Compound catalyst, is catalyzed journal, 2000,21 (6)：600-602) and Yuan Qiang etc. (Yuan Qiang, Li Hui,
The Co-SiO of hydrogen peroxide is catalytically decomposed in Wu Yingqiu, Yang Le husband efficient cryogenics2Catalyst, Xiamen University
Journal (natural science edition), 2010,49 (4)：589-592) reported, the oxygen of transition metal manganese
The oxide of compound and cobalt is also the decomposition catalyst of known hydrogen peroxide.
To sum up, prior art thinks, the addition of transition metal oxide can accelerate the decomposition of hydrogen peroxide,
In the alkene of titanium molecular sieve catalysis and the epoxidization reaction process of hydrogen peroxide, hydrogen peroxide will be reduced
Epoxidation selectivity, be unfavorable for the epoxidation reaction of titanium molecular sieve catalysis hydrogen peroxide and alkene.Such as
What further improves shaping titanium-silicon molecular sieve catalyst in chlorallylene and hydrogen peroxide epoxidizing synthesis ring
The problem of catalytic activity and/or activity stability in the course of reaction of oxygen chloropropane are still urgent need to resolve.
The content of the invention
The invention aims to improve prior art to be molded titanium-silicon molecular sieve catalyst in chlorallylene
With the catalytic activity in the course of reaction of hydrogen peroxide epoxidizing synthesizing epoxy chloropropane and/or activity stabilized
Property there is provided a kind of modifying titanium-silicon molecular sieve catalyst and its preparation method and application, the modifying titanium-silicon point
Sub- sieve catalyst in the course of reaction of chlorallylene and hydrogen peroxide epoxidizing synthesizing epoxy chloropropane not
Only there is higher catalytic activity, and with considerably higher activity stability.
As described above, prior art is it is believed that the addition of transition metal oxide is unfavorable for titanium silicon molecule
Sieve the epoxidation reaction of catalyzing hydrogen peroxide and alkene.Surprisingly, the present inventor
It was found that, by being loaded on titanium-silicon molecular sieve catalyst at least one in a small amount of transiting metal nickel, zirconium and lanthanum
The oxide planted, in the course of reaction of chlorallylene and hydrogen peroxide epoxidizing synthesizing epoxy chloropropane,
The conversion ratio of hydrogen peroxide not only can be significantly improved, and shaping titanium silicon molecule can be significantly increased
Stability of catalytic activity of the sieve catalyst in fixed bed reactors, makes peroxide within the longer reaction time
The selectivity for changing hydrogen conversion ratio and generation epoxychloropropane maintains higher level always.
The invention provides a kind of modifying titanium-silicon molecular sieve catalyst, the modifying titanium-silicon molecular sieve catalyst contains
There are the HTS with MFI topological structures, aluminum oxide and transition metal oxide, with the Modified Titanium
On the basis of the total amount of silicalite molecular sieve catalyst, the content of the HTS with MFI topological structures is
35-75 mass %, the content of aluminum oxide are 20-60 mass %, and the content of transition metal oxide is 0.1-5
Quality %, the transition metal oxide is one in oxide, the oxide of nickel and the oxide of lanthanum of zirconium
Plant or a variety of.
Present invention also offers a kind of preparation method of modifying titanium-silicon molecular sieve catalyst, the preparation method bag
Include following steps：
A) HTS and oxygen with MFI topological structures are contained with the salt solution impregnation of transition metal
Change the shaping titanium-silicon molecular sieve catalyst that aluminium, side pressure breaking strength are 70-150N/cm；
B) dip compound obtained by drying steps a), obtains dry solid impregnating thing；
C) the solid impregnating thing obtained by calcination stepses b), wherein, the transition metal be zirconium, nickel and
One or more in lanthanum.
It is anti-in alkene epoxidation that the present invention still further provides above-mentioned modifying titanium-silicon molecular sieve catalyst
Application in answering.
The present invention still further provides a kind of synthetic method of epoxychloropropane, and this method is included in titanium silicon point
In the presence of sub- sieve catalyst, under the conditions of epoxidation reaction of olefines, chlorallylene is contacted with hydrogen peroxide,
Characterized in that, the titanium-silicon molecular sieve catalyst is above-mentioned modifying titanium-silicon molecular sieve catalyst.
The modifying titanium-silicon molecular sieve catalyst that the present invention is provided, is closed in chlorallylene with hydrogen peroxide epoxidizing
Into in the reaction of epoxychloropropane, higher hydrogen peroxide conversion can not only be obtained in the early stage, higher
Hydrogen peroxide epoxidation selectivity and the selectivity of generation epoxychloropropane, but also can protect for a long time
The selectivity of higher hydrogen peroxide conversion and generation epoxychloropropane is held, so as to substantially increase catalysis
The service life of agent.In addition, the catalyst can also keep 70-150N/cm side pressure breaking strength,
Meet the application requirement of commercial fixed bed reactor.
The preparation method of the shaping titanium-silicon molecular sieve catalyst for the modification that the present invention is provided is simple, and process is easy
Realize.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that this place is retouched
The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points and any value of disclosed scope are not limited to the accurate scope or value herein, this
A little scopes or value should be understood to comprising the value close to these scopes or value.For number range, respectively
Between the endpoint value of individual scope, between the endpoint value of each scope and single point value, and individually point
Can be combined with each other between value and obtain one or more new number ranges, these number ranges should by regarding
For specific disclosure herein.
The present invention provides a kind of modifying titanium-silicon molecular sieve catalyst, and the modifying titanium-silicon molecular sieve catalyst contains
HTS, aluminum oxide and transition metal oxide with MFI topological structures, with the modifying titanium-silicon
On the basis of the total amount of molecular sieve catalyst, the content of the HTS with MFI topological structures is
35-75 mass %, the content of aluminum oxide are 20-60 mass %, and the content of transition metal oxide is 0.1-5
Quality %, the transition metal oxide is one in oxide, the oxide of nickel and the oxide of lanthanum of zirconium
Plant or a variety of.
Under preferable case, on the basis of the total amount of the modifying titanium-silicon molecular sieve catalyst, with MFI topologys
The content of the HTS of structure is that 50-69.5 mass %, the content of aluminum oxide are 30-49.9 mass %
Content with transition metal oxide is 0.1-0.5 mass %.
In one embodiment, the content sum of each component of the modifying titanium-silicon molecular sieve catalyst is
100 mass %.
In the present invention, the constituent content of catalyst can be obtained using existing various methods, preferably basis
Inventory is calculated and obtained.
According to the present invention, the oxide of the zirconium can be the oxide of the zirconium of various valence states, preferably two
Zirconium oxide.Unless stated otherwise, the present invention in zirconium oxide content with zirconium dioxide ZrO2Meter.
According to the present invention, the oxide of the nickel can be the oxide of the nickel of various valence states, preferably two
The oxide of valency nickel is NiO.Unless stated otherwise, the present invention in nickel oxide content with oxidation
Nickel O is counted.
According to the present invention, the oxide of the lanthanum can be the oxide of the lanthanum of various valence states, preferably three
Aoxidize two lanthanums i.e. La2O3.Unless stated otherwise, the present invention in lanthanum oxide content with La2O3
Meter.
According to the modifying titanium-silicon molecular sieve catalyst of the present invention, the aluminum oxide can be various as shaping
Under the aluminum oxide of catalyst binder, preferable case, the aluminum oxide comes from aluminium hydrate powder and Alumina gel.
The aluminium hydrate powder and the weight ratio of Alumina gel further preferably counted using aluminum oxide is 1-3:1.
According to the modifying titanium-silicon molecular sieve catalyst of the present invention, as long as containing has MFI topological structures simultaneously
HTS, transition metal oxide and aluminum oxide be that the purpose of the present invention can be achieved, three can be with
Intimately mix with one another, under preferable case, the transition metal oxide is supported on MFI topological structures
HTS and aluminum oxide on.
The size and shape of modifying titanium-silicon molecular sieve catalyst is not particularly limited the present invention, can be suitable
Close the size and shape of fluid bed or the size and shape of suitable fixed bed.Under preferable case,
The granular size of the modifying titanium-silicon molecular sieve catalyst is 0.1-10mm, and side pressure breaking strength is
70-150N/cm, preferably 75-120N/cm.In the present invention, the side pressure breaking strength reference
HG/T2782-1996 standards are measured.
The modifying titanium-silicon molecular sieve catalyst that the present invention is provided can be by will be made needed for the catalyst
Composition or its presoma are mediated, shaping and then roasting are obtained, can also by first by HTS and
Aluminum oxide is molded, and shaping titanium-silicon molecular sieve catalyst is made, the transition metal oxide is then loaded.
The preparation method of the modifying titanium-silicon molecular sieve catalyst provided according to the present invention, the preparation method includes
Following steps：
A) HTS and oxygen with MFI topological structures are contained with the salt solution impregnation of transition metal
It is 70-150N/cm, preferably 75-120N/cm shaping HTS to change aluminium, side pressure breaking strength
Catalyst；
B) dip compound obtained by drying steps a), obtains dry solid impregnating thing；
C) the solid impregnating thing obtained by calcination stepses b),
Wherein, the transition metal is the one or more in zirconium, nickel and lanthanum.
The preparation method of the modifying titanium-silicon molecular sieve catalyst provided according to the present invention, the shaping titanium silicon point
The content of HTS and the weight ratio of aluminum oxide with MFI topological structures are in sub- sieve catalyst
35-75：20-60, preferably 50-69.5：30-49.9.
The granular size of the shaping titanium-silicon molecular sieve catalyst is preferably 0.1-10mm.
Above-mentioned shaping titanium-silicon molecular sieve catalyst can be prepared using existing method, for example, can be with
It is made using method disclosed in CN201010184391.9, specifically, for example can be by that there will be MFI
HTS powder, aluminium hydrate powder, Alumina gel and the pore-foaming agent of selectivity addition of topological structure,
Extrusion aid and water mixer kneader, are then molded and are calcined.Wherein aluminium hydrate powder is preferably pure cerium hydroxide aluminium
Powder, i.e., in the case where not considering impurity element, do not include in addition to aluminium, hydrogen and oxygen in aluminium hydrate powder
Other elements, alumina content is preferably 50-80 mass %, and BET specific surface area is preferably
350-700m2/g.Alumina gel is preferably that solid content is more preferably 15-30 mass % for 10-35 mass %
Acidic aluminum sol.The mass ratio of aluminium hydrate powder and Alumina gel is preferably 1-3:1, more preferably 1.2-2:1.
Pore-foaming agent can be APES, and the carbon of wherein alkyl is preferably that 6-12 is more preferably
8-10, the degree of polymerization is preferably 10-30 more preferably 12-24.The extrusion aid can be sesbania powder, starch
With the one or more in citric acid.Pore-foaming agent and the extrusion aid sum preferably accounts for HTS powder
15-75 mass %, more preferably account for 30-70 mass %.
The preparation method of the modifying titanium-silicon molecular sieve catalyst provided according to the present invention, the transition metal
The consumption of salting liquid cause the total amount of modifying titanium-silicon molecular sieve catalyst that is obtained after being calcined using step c) as
Benchmark, the content of transition metal oxide is 0.1-5 mass %, preferably 0.1-0.5 mass %.
The salting liquid of the transition metal is the aqueous solution, alcoholic solution or the alcohol of the soluble-salt of transition metal
The nitrate aqueous solution of water mixed solution, preferably transition metal and/or carboxylic acid salt solution.It is further excellent
It is zirconyl nitrate, nickel nitrate and lanthanum nitrate to select the transition metal salt.
The alcohol can be the one or more in methanol, ethanol, propyl alcohol, the tert-butyl alcohol.
The concentration of the salting liquid of the transition metal is preferably 0.5-5 mass %.
Dipping temperature in the preparation method provided according to the present invention, the step a) is 5-50 DEG C, leaching
The stain time is 1-48 hours, and preferably dipping temperature is 10-40 DEG C, and dip time is 2-24 hours.
Drying temperature in the method provided according to the present invention, the step b) is 60-200 DEG C, is dried
Time is 1-24 hours, and preferably drying temperature is 80-150 DEG C, and drying time is 2-20 hours.
Sintering temperature in the method provided according to the present invention, the step c) is 250-750 DEG C, roasting
Time is 1-48 hours, and preferably sintering temperature is 300-600 DEG C, and roasting time is 2-24 hours.
It is made present invention also offers above-mentioned modifying titanium-silicon molecular sieve catalyst and/or by above-mentioned preparation method
Application of the modifying titanium-silicon molecular sieve catalyst in epoxidation reaction of olefines.
The modifying titanium-silicon molecular sieve catalyst that the present invention is provided, is particularly suitable for use in catalysis chlorallylene and peroxide
Change hydrogen epoxidation synthesizing epoxy chloropropane, catalyst can both be dispersed in the liquid in reactor in the form of granules
Flowed in body with liquid, can also bed form fix use in the reactor, preferably with fixed bed
Form is used in the reactor.
Present invention also offers a kind of synthetic method of epoxychloropropane, this method is included in HTS
In the presence of catalyst, under the conditions of epoxidation reaction of olefines, chlorallylene is contacted with hydrogen peroxide, its
It is characterised by, the above-mentioned modifying titanium-silicon molecular sieve catalysis that the titanium-silicon molecular sieve catalyst provides for the present invention
Modifying titanium-silicon molecular sieve catalyst made from agent and/or above-mentioned preparation method.
According to the present invention, the epoxidation reaction of olefines is preferably carried out in the presence of solvent, and the solvent can
Can be used for the various solvents of epoxidation reaction of olefines, further preferably using methanol as solvent.
The condition of the epoxidation reaction of olefines is referred under prior art progress, preferable case, 3- chlorine
The raw materials components mole ratio of propylene and hydrogen peroxide is 1-10:1st, preferably 1.5-6: 1, methanol and chlorallylene enter
Material mol ratio is 1-20:1st, preferably 2-10: 1, reaction temperature is 20-100 DEG C, preferably 40-80 DEG C, instead
It is 0.1-1MPa (absolute pressure), preferably 0.1-0.6MPa (absolute pressure) to answer pressure.
The titanium-silicon molecular sieve catalyst can be in flow regime in the reactor, now preferred titanium silicon point
The consumption of sub- sieve catalyst is the 0.1-30 mass % of liquid reactants, preferably 0.5-10%, during reaction
Between for 0.1-10 hour, preferably 0.2-5 hours.Or the titanium-silicon molecular sieve catalyst is in reactor
In can also be in stationary state catalyst fix in the reactor, the now charging of preferred hydrogen peroxide
Mass space velocity is 0.01-1h-1, preferably 0.02-0.5h-1, reaction temperature is 20-100 DEG C, preferably 30-80 DEG C,
Reaction pressure is 0.1-1MPa (absolute pressure), preferably 0.3-0.6MPa (absolute pressure).Using methanol as solvent, 3-
The raw materials components mole ratio of chloropropene and hydrogen peroxide is 1-10: 1, preferably 1.5-6: 1, solvent methanol and 3- chlorine third
The raw materials components mole ratio of alkene is 1-20: 1, preferably 2-10: 1.
The present invention is further described below by embodiment and comparative example, but therefore not limited
Present disclosure.
In all embodiments and comparative example, TS-1 HTSs used build long oil by Hunan
Chemical inc is produced, and the trade mark is HTS；Chlorallylene is industrial chlorallylene, chlorallylene
Mass content be more than 98%, by Ba Ling petrochemical industries Co., Ltd produce；Hydrogen peroxide is analysis
Pure reagent, the mass content of hydrogen peroxide is 30%；Methanol is AR, the mass content of methanol
More than 99.5%；Zirconyl nitrate, nickel nitrate, lanthanum nitrate, copper nitrate, chromic nitrate, nickel acetate and nitric acid
Palladium is AR, and water is deionized water.
It is described that there is MFI topology knots containing 40-65 mass % in all embodiments and comparative example
The HTS of structure and 35-60 mass % aluminum oxide, side pressure breaking strength for 70-150N/cm into
Type titanium-silicon molecular sieve catalyst, is prepared according to the method disclosed in CN201010184391.9.
In all embodiments and comparative example, the side pressure breaking strength of catalyst is tested using big connection intelligent
The Intelligent testing machine for particle of ZQJ- II of machine factory production is determined, and is entered with reference to HG/T2782-1996 standards
OK, the side pressure breaking strength measured is the average value of 20 particles.
The content of catalyst components is calculated according to inventory and obtained.
In embodiment and comparative example, when in the liquid that catalyst is dispersed in reactor, chlorallylene
Carried out with the epoxidation reaction of hydrogen peroxide in 350mL agitated autoclave reactor, catalyst quilt
It is broken for the particle of 40-60 mesh.Epoxidation reaction condition is：The charging of chlorallylene and hydrogen peroxide rubs
You are that 5: 1, catalyst amount is liquid reactants than the raw materials components mole ratio of 1.5: 1, methanol and chlorallylene
Quality 1%, 50 DEG C of reaction temperature, 30 minutes reaction time and self-generated pressure.
In embodiment and comparative example, when catalyst is fixed in the reactor, chlorallylene and peroxidating
The epoxidation reaction of hydrogen is carried out in the tubular fixed-bed reactor of jacketed, and catalyst is shaped as being about
5mm billet, its maximum loadings are 100mL.The temperature of reactor is by flowing through reactor jacket
Automatic constant-temperature oil bath be adjusted.The pressure of reactor is adjusted by the counterbalance valve on reactor outlet pipeline
Save as 0.4MPa, maintained by nitrogen.Chlorallylene, aqueous hydrogen peroxide solution and methanol are respectively by 3
Platform measuring pump input reactor.The epoxidation reaction of chlorallylene and hydrogen peroxide is in reaction tube chuck oil bath
Temperature 50 C, reaction pressure 0.4MPa, raw materials components mole ratio 2.5: 1, the first of chlorallylene and hydrogen peroxide
The raw materials components mole ratio of alcohol and chlorallylene is 5：1st, the feedstock quality air speed 0.14h of hydrogen peroxide-1And reaction
Carried out under conditions of the ammonium hydroxide that 0.01% is added in charging.
The content of hydrogen peroxide is determined by indirect iodometric processes in reactor feed and discharging, reactor discharging
The content of middle epoxychloropropane and its ring-opened byproducts is determined by gas chromatography.
Conversion ratio (the X of hydrogen peroxideHPO) calculate according to the formula：
Epoxidation selectivity (the S of hydrogen peroxideEP) the cyclic oxidation reaction product consumption of finger-type hydrogen peroxide
With the mole percent of the hydrogen peroxide converted in reaction, calculated by following formula：
Selectivity (the S of epoxychloropropaneECH) rubbing shared by epoxychloropropane in finger ring oxidation reaction product
That percentage, is calculated by following formula：
Yield (the Y of epoxychloropropaneECH) the hydrogen peroxide generation epoxy chlorine that converts in finger ring oxidation reaction
The mole percent of propane, is calculated by following formula：
YECH=XHPO×SEP×SECH× 100%
Comparative example 1
According to the method for the embodiment 3 disclosed in CN201010184391.9, squeezed using φ 1.2mm orifice plates
Bar is molded, and aluminum oxide, the side pressure for preparing the TS-1 containing 60 mass % and 40 mass % are broken strong
The shaping titanium-silicon molecular sieve catalyst for 84.8N/cm is spent, catalyst has been carried out in stirred tank reactor
Catalytic performance test, evaluation result is shown in Table 1.
Embodiment 1
The water zirconyl nitrates of 0.116g bis- are dissolved in 15.00 grams of deionized waters, zirconyl nitrate solution is obtained,
Then the shaping titanium molecular sieve catalysis that 20.00g is prepared according to comparative example 1 is impregnated at 25-30 DEG C
Agent 12 hours, then dry dipping thing is obtained within 12 hours in 105 DEG C of air drying dip compound,
Then it is calcined 18 hours in 500 DEG C of air, obtains aoxidizing the shaping titanium silicon of modified zirconia after natural cooling
Molecular sieve catalyst, the shaping titanium-silicon molecular sieve catalyst of the oxidation modified zirconia contains 59.84 mass %'s
HTS, 39.89 mass % aluminum oxide and 0.27 mass % zirconium dioxide, its side pressure breaking strength is
98.2N/cm.The catalytic performance test of catalyst is carried out in stirred tank reactor, evaluation result is shown in Table
1。
Embodiment 2
The water nickel nitrates of 0.557g six are dissolved in 46.00 grams of deionized waters, nickel nitrate aqueous solution are obtained, so
The shaping titanium-silicon molecular sieve catalyst that 70.00g is prepared according to comparative example 1 is impregnated at 20-25 DEG C afterwards
24 hours, then dry dipping thing is obtained within 6 hours in 110 DEG C of air drying dip compound, connect
And be calcined 12 hours in 550 DEG C of air, the shaping titanium silicon point of nickel oxide modification is obtained after natural cooling
Sub- sieve catalyst, modified catalyst includes 59.88 mass % HTS, 39.92 mass % aluminum oxide
With 0.20 mass % nickel oxide, its side pressure breaking strength is 91.6N/cm.In stirred tank reactor
The catalytic performance test of catalyst is carried out, evaluation result is shown in Table 1.
Embodiment 3
0.133g lanthanum nitrate hexahydrates are dissolved in 16.00 grams of deionized waters, lanthanum nitrate aqueous solution are obtained, so
The shaping titanium-silicon molecular sieve catalyst that 20.00g is prepared according to comparative example 1 is impregnated at 15-20 DEG C afterwards
18 hours, then dry dipping thing is obtained within 4 hours in 150 DEG C of air drying dip compound, connect
And be calcined 8 hours in 600 DEG C of air, the shaping titanium of lanthanum sesquioxide modification is obtained after natural cooling
Silicalite molecular sieve catalyst, modified catalyst includes 59.85 mass % HTS, 39.90 mass % oxygen
Change aluminium and 0.25 mass % lanthanum sesquioxide, its side pressure breaking strength is 88.4N/cm.In stirred tank
The catalytic performance test of catalyst is carried out in reactor, evaluation result is shown in Table 1.
Embodiment 4
1.333g lanthanum nitrate hexahydrates are dissolved in 26.00 grams of deionized waters, lanthanum nitrate aqueous solution are obtained, so
The shaping titanium-silicon molecular sieve catalyst that 20.00g is prepared according to comparative example 1 is impregnated at 25-35 DEG C afterwards
20 hours, then dry dipping thing is obtained within 10 hours in 115 DEG C of air drying dip compound,
Then it is calcined 12 hours in 600 DEG C of air, the shaping of lanthanum sesquioxide modification is obtained after natural cooling
Titanium-silicon molecular sieve catalyst, the HTS of modified catalyst comprising 58.53 mass %, 39.02 mass %
The lanthanum sesquioxide of aluminum oxide and 2.45 mass %, its side pressure breaking strength is 82.4N/cm.In stirring
The catalytic performance test of catalyst is carried out in kettle reactor, evaluation result is shown in Table 1.
Comparative example 2
0.129g nitrate trihydrate copper is dissolved in 16.00 grams of deionized waters, copper nitrate aqueous solution is obtained, so
The shaping titanium-silicon molecular sieve catalyst that 20.00g is prepared according to comparative example 1 is impregnated at 20-25 DEG C afterwards
24 hours, then dry dipping thing is obtained within 6 hours in 110 DEG C of air drying dip compound, connect
And be calcined 12 hours in 550 DEG C of air, the shaping titanium silicon point of cupric oxide modification is obtained after natural cooling
Sub- sieve catalyst, modified catalyst includes 59.87 mass % HTS, 39.92 mass % aluminum oxide
With 0.21 mass % cupric oxide, its side pressure breaking strength is 78.5N/cm.In stirred tank reactor
The catalytic performance test of catalyst is carried out, evaluation result is shown in Table 1.
Comparative example 3
The water chromic nitrates of 0.168g nine are dissolved in 16.00 grams of deionized waters, chromium nitrate aqueous solution are obtained, so
The shaping titanium-silicon molecular sieve catalyst that 20.00g is prepared according to comparative example 1 is impregnated at 15-20 DEG C afterwards
18 hours, then dry dipping thing is obtained within 4 hours in 150 DEG C of air drying dip compound, connect
And be calcined 8 hours in 600 DEG C of air, the shaping titanium of chrome green modification is obtained after natural cooling
Silicalite molecular sieve catalyst, modified catalyst includes 59.90 mass % HTS, 39.94 mass % oxygen
Change aluminium and 0.16 mass % chrome green, its side pressure breaking strength is 95.3N/cm.In stirred tank
The catalytic performance test of catalyst is carried out in reactor, evaluation result is shown in Table 1.
Comparative example 4
The water palladium nitrates of 0.116g bis- are dissolved in 15.00 grams of deionized waters, palladium nitrate aqueous solution are obtained, so
The shaping titanium-silicon molecular sieve catalyst that 20.00g is prepared according to comparative example 1 is impregnated at 20-25 DEG C afterwards
20 hours, then dry dipping thing is obtained within 6 hours in 120 DEG C of air drying dip compound, connect
And be calcined 16 hours in 550 DEG C of air, the shaping titanium silicon point of palladium oxide modification is obtained after natural cooling
Sub- sieve catalyst, modified catalyst includes 59.84 mass % HTS, 39.89 mass % aluminum oxide
With 0.27 mass % palladium oxide, its side pressure breaking strength is 86.9N/cm.In stirred tank reactor
The catalytic performance test of catalyst is carried out, evaluation result is shown in Table 1.
Table 1
| Title | XHPO/ % | SEP/ % | SECH/ % | YECH/ % |
| Embodiment 1 | 86.9 | 99.1 | 98.4 | 84.7 |
| Embodiment 2 | 86.6 | 99.2 | 98.6 | 84.7 |
| Embodiment 3 | 84.4 | 98.4 | 98.6 | 81.9 |
| Embodiment 4 | 83.8 | 98.3 | 98.8 | 81.5 |
| Comparative example 1 | 79.2 | 98.2 | 98.3 | 76.5 |
| Comparative example 2 | 82.9 | 96.4 | 98.3 | 78.6 |
| Comparative example 3 | 80.4 | 97.9 | 98.2 | 77.3 |
| Comparative example 4 | 69.6 | 98.5 | 98.6 | 67.6 |
Comparative example 5
The 60.00g catalyst prepared according to comparative example 1 is fitted into fixed bed reactors and carries out 3-
The epoxidation reaction synthesizing epoxy chloropropane of chloropropene and hydrogen peroxide, the result such as table 2 of epoxidation reaction
It is shown.
Embodiment 5
The 60.00g catalyst prepared according to embodiment 2 is fitted into fixed bed reactors and carries out 3-
The epoxidation reaction synthesizing epoxy chloropropane of chloropropene and hydrogen peroxide, the result such as table 2 of epoxidation reaction
It is shown.
Embodiment 6
The 60.00g catalyst prepared according to embodiment 4 is fitted into fixed bed reactors and carries out 3-
The epoxidation reaction synthesizing epoxy chloropropane of chloropropene and hydrogen peroxide, the result such as table 2 of epoxidation reaction
It is shown.
Table 2
Comparative example 6
By the former powder of 175.00 grams of HTS, (Shandong Zibo Thailand photoinitiator chemical has 152.13 grams of aluminium hydroxide powders
Limit company produces, the mass % of alumina content 71.9, and BET specific surface area is 358m2/ g), 70.00 grams
Starch and 12.10 grams of sesbania powders (production of Henan Lankao natural plant gum factory) stir mixing 20min in kneading machine；
Then sequentially adding the Alumina gel that 292.88 grams of alumina contents are 22.4 mass %, (long oil is built in Hunan
Chemical inc produce), 14.15 grams of octyl phenol polyoxyethylene (15) ethers (OP-15, Hebei
Xingtai Ke Wang auxiliary chemicals Co., Ltd produces), the kneading of 15.00 grams of deionized waters it is agglomerating, continue to knead
70min obtains extrudable plastic forming body；It is extruded into double screw banded extruder by φ 1.2mm orifice plate
Wet elongated solid cylinder bar, is put into chamber type electric resistance furnace after 24 hours are hung at room temperature, from room
Temperature is heated to 120 DEG C with 5 DEG C/min heating rate and stopped 6 hours, then with 3 DEG C/min heating
Speed is heated to 550 DEG C and stopped 15 hours, and cylindrical bars catalyst is obtained after natural cooling.The catalyst
In the HTS containing 50 mass %, 50 mass % aluminum oxide, its side pressure breaking strength be 95.4N/cm.
The catalytic performance test of catalyst is carried out in stirred tank reactor, evaluation result is shown in Table 3.
Embodiment 7
Shaping titanium-silicon molecular sieve catalyst is prepared using the method for comparative example 6, unlike, by 15.00g
Deionized water changes the nickel acetate aqueous solution of identical weight into, obtains the shaping HTS of nickel oxide modification
Catalyst, the TS-1 of modified catalyst comprising 49.75 mass %, 49.75 mass % aluminum oxide and
0.50 mass % nickel oxide, its side pressure breaking strength is 91.7N/cm.Carried out in stirred tank reactor
The catalytic performance test of catalyst, evaluation result is shown in Table 3.
Table 3
| Title | XHPO/ % | SEP/ % | SECH/ % | YECH/ % |
| Comparative example 6 | 66.2 | 97.7 | 97.8 | 63.3 |
| Embodiment 7 | 72.5 | 99.2 | 98.4 | 70.8 |
The comparative result of embodiment and comparative example shows, transition metal oxide is used using what the present invention was provided
Modified titanium-silicon molecular sieve catalyst carries out the epoxidation reaction synthesizing epoxy of chlorallylene and hydrogen peroxide
Chloropropane, can not only obtain higher hydrogen peroxide conversion, higher epoxidation is selective and generates
The selectivity of epoxychloropropane, and can for longer periods keep in fixed bed reactors higher mistake
The selectivity of hydrogen oxide conversion ratio and generation epoxychloropropane, so as to improve the service life of catalyst.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited to above-mentioned reality
The detail in mode is applied, can be to technical side of the invention in the range of the technology design of the present invention
Case carries out a variety of simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment,
In the case of reconcilable, it can be combined by any suitable means.In order to avoid unnecessary
Repeat, the present invention no longer separately illustrates to various possible combinations.
In addition, various embodiments of the present invention can be combined randomly, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (13)
1. a kind of modifying titanium-silicon molecular sieve catalyst, the modifying titanium-silicon molecular sieve catalyst contains with MFI
HTS, aluminum oxide and the transition metal oxide of topological structure, are urged with the modifying titanium-silicon molecular sieve
On the basis of the total amount of agent, the content of the HTS with MFI topological structures is 35-75 mass %,
The content of aluminum oxide is 20-60 mass %, and the content of transition metal oxide is 0.1-5 mass %, the mistake
The one or more crossed in oxide, the oxide of nickel and the oxide of lanthanum that metal oxide is zirconium.
2. modifying titanium-silicon molecular sieve catalyst according to claim 1, wherein, with the Modified Titanium
On the basis of the total amount of silicalite molecular sieve catalyst, the content of the HTS with MFI topological structures is
50-69.5 mass %, the content of aluminum oxide are 30-49.9 mass % and the content of transition metal oxide is
0.1-0.5 mass %.
3. modifying titanium-silicon molecular sieve catalyst according to claim 1 or 2, wherein, the oxygen
Change aluminium and come from aluminium hydrate powder and Alumina gel.
4. the modifying titanium-silicon molecular sieve catalyst according to any one in claim 1-3, wherein,
The transition metal oxide is supported on the HTS and aluminum oxide with MFI topological structures.
5. the modifying titanium-silicon molecular sieve catalyst according to any one in claim 1-4, wherein,
The granular size of the modifying titanium-silicon molecular sieve catalyst is 0.1-10mm, and side pressure breaking strength is
70-150N/cm, preferably 75-120N/cm.
6. a kind of preparation method of modifying titanium-silicon molecular sieve catalyst, the preparation method comprises the following steps：
A) HTS and oxygen with MFI topological structures are contained with the salt solution impregnation of transition metal
Change the shaping titanium-silicon molecular sieve catalyst that aluminium, side pressure breaking strength are 70-150N/cm；
B) dip compound obtained by drying steps a), obtains dry solid impregnating thing；
C) the solid impregnating thing obtained by calcination stepses b), wherein, the transition metal be zirconium, nickel and
One or more in lanthanum.
7. preparation method according to claim 6, wherein, the salting liquid of the transition metal
Consumption cause by step c) be calcined after on the basis of the obtained total amount of modifying titanium-silicon molecular sieve catalyst, mistake
The content for crossing metal oxide is 0.1-5 mass %, preferably 0.1-0.5 mass %；The shaping titanium silicon
The content and the weight ratio of aluminum oxide of HTS with MFI topological structures in molecular sieve catalyst
For 35-75：20-60, preferably 50-69.5：30-49.9.
8. the preparation method according to claim 6 or 7, wherein, the salt of the transition metal is molten
Liquid is the aqueous solution, alcoholic solution or the alcohol water mixed solution of the soluble-salt of transition metal, preferably transition
The nitrate aqueous solution of metal and/or carboxylic acid salt solution.
9. the preparation method according to any one in claim 6-8, wherein, the shaping titanium
The granular size of silicalite molecular sieve catalyst is 0.1-10mm；The temperature of the roasting is 250-750 DEG C, roasting
The burning time is 1-48 hours.
10. the modifying titanium-silicon molecular sieve catalyst and/or right in claim 1-5 described in any one will
Modifying titanium-silicon molecular sieve catalyst made from the preparation method in 6-9 described in any one is sought in olefin epoxide
Change the application in reaction.
11. a kind of synthetic method of epoxychloropropane, this method is included in titanium-silicon molecular sieve catalyst presence
Under, under the conditions of epoxidation reaction of olefines, chlorallylene is contacted with hydrogen peroxide, it is characterised in that
The titanium-silicon molecular sieve catalyst is urged for the modifying titanium-silicon molecular sieve described in any one in claim 1-5
Modifying titanium-silicon molecular sieve made from preparation method in agent and/or claim 6-9 described in any one
Catalyst.
12. method according to claim 11, wherein, the epoxidation reaction of olefines is with methanol
For solvent, the raw materials components mole ratio of chlorallylene and hydrogen peroxide is 1-10:1, methanol and chlorallylene enter
Material mol ratio is 1-20:1, reaction temperature is 20-100 DEG C, and reaction pressure is 0.1-1MPa.
13. the method according to claim 11 or 12, wherein, the titanium-silicon molecular sieve catalyst
Flow regime is in the reactor, and the consumption of titanium-silicon molecular sieve catalyst is the 0.1-30 of liquid reactants
Quality %；Or the titanium-silicon molecular sieve catalyst is in stationary state in the reactor, hydrogen peroxide
Feedstock quality air speed is 0.01-1h-1。
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