CN101979137B - Catalyst for styrene epoxidation and preparation method thereof - Google Patents
Catalyst for styrene epoxidation and preparation method thereof Download PDFInfo
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- CN101979137B CN101979137B CN2010102855307A CN201010285530A CN101979137B CN 101979137 B CN101979137 B CN 101979137B CN 2010102855307 A CN2010102855307 A CN 2010102855307A CN 201010285530 A CN201010285530 A CN 201010285530A CN 101979137 B CN101979137 B CN 101979137B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000004048 modification Effects 0.000 claims abstract description 21
- 238000012986 modification Methods 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 81
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 9
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 9
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 9
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000012453 solvate Substances 0.000 claims description 9
- 238000012546 transfer Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 4
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- 239000010936 titanium Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000010941 cobalt Substances 0.000 abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- 229910052719 titanium Inorganic materials 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 2
- 239000004480 active ingredient Substances 0.000 abstract 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract 1
- 235000013980 iron oxide Nutrition 0.000 abstract 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 238000003980 solgel method Methods 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- XPRLBVADEUEGBY-UHFFFAOYSA-N bromobenzene ethanol Chemical compound C(C)O.BrC1=CC=CC=C1 XPRLBVADEUEGBY-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- HLFSDGLLUJUHTE-SNVBAGLBSA-N Levamisole Chemical compound C1([C@H]2CN3CCSC3=N2)=CC=CC=C1 HLFSDGLLUJUHTE-SNVBAGLBSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 and wherein Co Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229960001614 levamisole Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention discloses a catalyst for styrene epoxidation and a preparation method thereof. The catalyst consists of Ti, Co, Fe and Si, wherein the Co and the Fe are used as main active ingredients of the catalyst, and the mass percentages of the Co and the Fe are 0.9 to 4.6 percent and 1.0 to 4.9 percent respectively; the Si is used as a carrier of the catalyst, and the mass percentage of the Si is 88.9 to 97.3 percent; and the Ti is used as an auxiliary active ingredient of the catalyst, and the percentage of the Ti is 0.8 to 1.6 percent. The catalyst is prepared by adopting a precipitation method and a surface sol-gel method. Cobalt and iron oxides are loaded on silicon oxide at the same time, and a titanium oxide coating is used for modification, so the catalytic activity and the stability of the catalyst are improved.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method that is used for epoxidation of styrene.
Background technology
Styryl oxide is called styrene oxide again, is a kind of fine chemicals, can be used as epoxy resin diluent, UV-absorbent, fumet, also is the important intermediate of organic synthesis, pharmaceuticals industry, perfume industry.Styryl oxide is produced bata-phenethyl alcohol through catalytic hydrogenation and is adopted because of its technology maturation, simple being gone up by industry of technology; Bata-phenethyl alcohol is the main component of attar of rose, caryophyllus oil, clear caul-fat, and is widely used in synthetic food, tobacco, soap and cosmetic essence.Domestic main manufacturer has the logical spices Co., Ltd of Wuxi China, Shanghai skyization chemical industry Co., Ltd, Jiaxing Perfume Factory, perfumery, Tianjin, and its device capability is more than 2500t/a.In recent years, to bata-phenethyl alcohol and the sharp increase of medical levamisol demand, supply falls short of demand for Styryl oxide on the domestic and international market both at home and abroad, and market prospects are wide.
Styryl oxide is industrial main synthetic with bromohydrin method, chlorohydrination or hydrogen peroxide catalyzed epoxidation vinyl benzene.The bromohydrin method is the method that present domestic production producer mainly adopts; Be that primary raw material adds sodium bromide, sodium chlorate, sulfuric acid and carries out halogenation and generate bromobenzene ethanol with styrene, bromobenzene ethanol carries out saponification with NaOH again and generates thick Styryl oxide.Chlorohydrination is early to be applied to industry to go up the method for producing expoxy propane, still continues to use so far in the production of expoxy propane and epoxychloropropane and the preparation of small lot epoxide, and Styryl oxide just can prepare with the method.Though bromohydrin method and chlorohydrination are very succinct production technologies, material consumption and energy consumption are higher, and not easy to operate, and environmental pollution is serious.Producing Styryl oxide with the hydrogen peroxide solution for the oxygen source styrene oxide is an environmentally friendly technology, non-environmental-pollution, and this explained hereafter cost is low, technological process is simple, reaction condition is gentle, has favorable industrial and is worth.The dioxygen water law mainly adopts the titanium molecular sieve catalysis epoxidation; Its prospects for commercial application is optimistic; But the subject matter that present HTS epoxidation faces is how to reduce the production cost of HTS and the technology, particularly regeneration techniques and the corresponding reactor of exploitation of exploitation and reacting phase coupling significantly.In the catalytic oxidation, using oxygen or air is inexpensive method as oxygen source, so when producing Styryl oxide, with oxygen or air oxidant, then can reduce production costs greatly, in this respect research in recent years has certain progress.
Chinese patent CN101463020 with Ag-γ-ZrP as catalyst; With the TBHP is the direct epoxidation vinyl benzene synthesizing epoxy of oxygen source vinylbenzene; Though obtain very high conversion ratio and selectivity, this technology is not environmental friendliness, and TBHP has certain danger.Patent CN1754866 discloses the method for synthetic phenylacetaldehyde, benzaldehyde and Styryl oxide of a kind of titanium molecular sieve catalysis styrene oxide; Though this method has the high and high advantage of hydrogen peroxide utilization rate of styrene conversion rate; But the titanium-silicon molecular sieve catalyst preparation with MFI structure is complicated, and cost is higher.Patent CN1557553 is employed on the mesoporous silicon oxide load cobalt or iron as catalyst, and selectivity reaches 60%, and relevant bibliographical information is that the cobalt of carrier is better to the alkene epoxidation effect with silica.In view of the supported cobalt catalysts on HTS and the silica has reasonable activity to epoxidation of styrene.The present invention intends the cobalt of load simultaneously, ferriferous oxide on silica, and uses the titania coating modification, to improve catalytic activity and stability.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of Catalysts and its preparation method that is used for epoxidation of styrene is provided.
The catalyst that is used for epoxidation of styrene is made up of Ti, Co, Fe and Si, and wherein Co, Fe are as the main active component of catalyst, and its quality percentage composition is respectively 0.9～4.6%, 1.0～4.9%; Si is as the carrier of catalyst, its quality percentage composition 88.9～97.3%; Ti is as catalyst auxiliary activity component, and its percentage composition is 0.8～1.6%.
The carrier S i of said catalyst is a silica.Described Co is a cobaltosic oxide.Described Fe is a di-iron trioxide.Described Ti is a titanium dioxide.
The Preparation of catalysts method that is used for epoxidation of styrene comprises the steps:
1) with 4.0g SiO
2Carrier, 0.14～0.75g cobalt nitrate hexahydrate, 0.10～0.55g ferric sulfate, 100mL deionized water mix, and place water-bath, are warming up to 50～60 ℃; Transfer pH to 10～11 with the 0.1M sodium hydroxide solution, stirring reaction 1～2h filters; Wash 2～3 times with deionized water; 80～110 ℃ of drying 2～4h, 500～600 ℃ of roasting 3～5h obtain Co
3O
4And Fe
2O
3SiO after the modification
2Carrier;
2) 5.4～10.8mL butyl titanate, 10～20mL absolute methanol and 10～20mL toluene are mixed, add 2.0g Co
3O
4And Fe
2O
3SiO after the modification
2Carrier evenly mixes, and leaves standstill 30～60min; Vacuum is removed mixed solution, and with absolute methanol washing 2～3 times, vacuum is removed methanol solvate; After adding 10～20mL deionized water dipping, 1～2h; Vacuumize to remove and anhydrate, 100～120 ℃ are descended dry 2～4h, obtain being used for the catalyst of epoxidation of styrene.
The present invention intends the cobalt of load simultaneously, ferriferous oxide on silica, and uses the titania coating modification, to improve catalytic activity and stability.
The specific embodiment
Below be embodiments of the invention.
Embodiment 1: the preparation of catalyst A.
1) with 4.0g SiO
2Carrier, 0.14g cobalt nitrate hexahydrate, 0.10g ferric sulfate, 100mL deionized water mix, and place water-bath, are warming up to 50 ℃, transfer pH to 10 with the 0.1M sodium hydroxide solution; Stirring reaction 1h filters, and washes 2 times with deionized water; 80 ℃ of dry 2h, 500 ℃ of roasting 3h obtain Co
3O
4And Fe
2O
3SiO after the modification
2Carrier;
2) 5.4mL butyl titanate, 10mL absolute methanol and 10mL toluene are mixed, add 2.0g Co
3O
4And Fe
2O
3SiO after the modification
2Carrier evenly mixes, and leaves standstill 30min, and vacuum is removed mixed solution, and with absolute methanol washing 2 times, vacuum is removed methanol solvate, add 10mL deionized water dipping 1h after, vacuumize to remove and anhydrate, 100 ℃ of dry 2h down, catalyst A, its composition is seen table 1.
Embodiment 2: the preparation of catalyst B.
1) with 4.0g SiO
2Carrier, 0.16g cobalt nitrate hexahydrate, 0.5g ferric sulfate, 100mL deionized water mix, and place water-bath, are warming up to 50 ℃, transfer pH to 10 with the 0.1M sodium hydroxide solution; Stirring reaction 1h filters, and washes 2 times with deionized water; 80 ℃ of dry 4h, 500 ℃ of roasting 3h obtain Co
3O
4And Fe
2O
3SiO after the modification
2Carrier;
2) 5.4mL butyl titanate, 10mL absolute methanol and 10mL toluene are mixed, add 2.0g Co
3O
4And Fe
2O
3SiO after the modification
2Carrier evenly mixes, and leaves standstill 30min, and vacuum is removed mixed solution, and with absolute methanol washing 3 times, vacuum is removed methanol solvate, add 10mL deionized water dipping 1h after, vacuumize to remove and anhydrate, 100 ℃ of dry 2h down, catalyst B, its composition is seen table 1.
Embodiment 3: the preparation of catalyst C.
1) with 4.0g SiO
2Carrier, 0.70g cobalt nitrate hexahydrate, 0.12g ferric sulfate, 100mL deionized water mix, and place water-bath, are warming up to 50 ℃, transfer pH to 10 with the 0.1M sodium hydroxide solution; Stirring reaction 1h filters, and washes 2 times with deionized water; 80 ℃ of dry 2h, 500 ℃ of roasting 4h obtain Co
3O
4And Fe
2O
3SiO after the modification
2Carrier;
2) 5.4mL butyl titanate, 10mL absolute methanol and 10mL toluene are mixed, add 2.0g Co
3O
4And Fe
2O
3SiO after the modification
2Carrier evenly mixes, and leaves standstill 30min, and vacuum is removed mixed solution, and with absolute methanol washing 3 times, vacuum is removed methanol solvate, add 10mL deionized water dipping 1h after, vacuumize to remove and anhydrate, 110 ℃ of dry 3h down, catalyst C, its composition is seen table 1.
Embodiment 4: the preparation of catalyst D.
1) with 4.0g SiO
2Carrier, 0.44g cobalt nitrate hexahydrate, 0.30g ferric sulfate, 100mL deionized water mix, and place water-bath, are warming up to 60 ℃, transfer pH to 11 with the 0.1M sodium hydroxide solution; Stirring reaction 2h filters, and washes 3 times with deionized water; 110 ℃ of dry 4h, 600 ℃ of roasting 4h obtain Co
3O
4And Fe
2O
3SiO after the modification
2Carrier;
2) 8.1mL butyl titanate, 15mL absolute methanol and 15mL toluene are mixed, add 2.0g Co
3O
4And Fe
2O
3SiO after the modification
2Carrier evenly mixes, and leaves standstill 60min, and vacuum is removed mixed solution, and with absolute methanol washing 3 times, vacuum is removed methanol solvate, add 20mL deionized water dipping 2h after, vacuumize to remove and anhydrate, 100 ℃ of dry 3h down, catalyst D, its composition is seen table 1.
Embodiment 5: the preparation of catalyst E.
1) with 4.0g SiO
2Carrier, 0.16g cobalt nitrate hexahydrate, 0.30g ferric sulfate, 100mL deionized water mix, and place water-bath, are warming up to 60 ℃, transfer pH to 11 with the 0.1M sodium hydroxide solution; Stirring reaction 2h filters, and washes 3 times with deionized water; 110 ℃ of dry 2h, 600 ℃ of roasting 5h obtain Co
3O
4And Fe
2O
3SiO after the modification
2Carrier;
2) 8.1mL butyl titanate, 15mL absolute methanol and 15mL toluene are mixed, add 2.0g Co
3O
4And Fe
2O
3SiO after the modification
2Carrier evenly mixes, and leaves standstill 60min, and vacuum is removed mixed solution, and with absolute methanol washing 2 times, vacuum is removed methanol solvate, add 20mL deionized water dipping 2h after, vacuumize to remove and anhydrate, 120 ℃ of dry 4h down, catalyst E, its composition is seen table 1.
Embodiment 6: the preparation of catalyst F.
1) with 4.0g SiO
2Carrier, 0.75g cobalt nitrate hexahydrate, 0.55g ferric sulfate, 100mL deionized water mix, and place water-bath, are warming up to 60 ℃, transfer pH to 11 with the 0.1M sodium hydroxide solution; Stirring reaction 2h filters, and washes 3 times with deionized water; 110 ℃ of dry 4h, 600 ℃ of roasting 5h obtain Co
3O
4And Fe
2O
3SiO after the modification
2Carrier;
2) 10.8mL butyl titanate, 20mL absolute methanol and 20mL toluene are mixed, add 2.0g Co
3O
4And Fe
2O
3SiO after the modification
2Carrier evenly mixes, and leaves standstill 60min, and vacuum is removed mixed solution, and with absolute methanol washing 3 times, vacuum is removed methanol solvate, add 20mL deionized water dipping 2h after, vacuumize to remove and anhydrate, 120 ℃ of dry 4h down, catalyst F, its composition is seen table 1.
Embodiment 7: the preparation of catalyst G.
1) with 4.0g SiO
2Carrier, 0.72g cobalt nitrate hexahydrate, 0.30g ferric sulfate, 100mL deionized water mix, and place water-bath, are warming up to 60 ℃, transfer pH to 11 with the 0.1M sodium hydroxide solution; Stirring reaction 2h filters, and washes 2 times with deionized water; 110 ℃ of dry 4h, 600 ℃ of roasting 5h obtain Co
3O
4And Fe
2O
3SiO after the modification
2Carrier;
2) 10.8mL butyl titanate, 20mL absolute methanol and 20mL toluene are mixed, add 2.0g Co
3O
4And Fe
2O
3SiO after the modification
2Carrier evenly mixes, and leaves standstill 60min, and vacuum is removed mixed solution, and with absolute methanol washing 2 times, vacuum is removed methanol solvate, add 20mL deionized water dipping 2h after, vacuumize to remove and anhydrate, 120 ℃ of dry 4h down, catalyst G, its composition is seen table 1.
Embodiment 8: the catalytic performance test of catalyst A～G.
0.11g catalyst, 1mmol styrene, 20mL dimethyl formamide are joined in the 50mL there-necked flask, after oil bath is warming up to 100 ℃, opens and stir aerating oxygen simultaneously; Oxygen flow is 30mL/min; Behind the back flow reaction 6h, be cooled to room temperature, the centrifugation of sucking-off reactant liquor.Reactant liquor carries out quantitative analysis with GC-1690 gas chromatograph (SE-54 capillary chromatographic column, specification: 30m * 0.32mm * 0.5 μ m, fid detector), and normal heptane is as internal standard compound, and analysis result is seen table 2.
The composition of table 1 catalyst A～G
The catalytic performance test of table 2 catalyst A～G
Reaction condition: 1mmol styrene, 20mL dimethyl formamide, 0.11g catalyst, oxygen 30mL/min, 100 ℃ of reaction temperatures, reaction time 6h.
Claims (1)
1. Preparation of catalysts method that is used for epoxidation of styrene; This catalyst is made up of titanium dioxide, cobaltosic oxide, di-iron trioxide and silica; Wherein cobaltosic oxide, di-iron trioxide are as the main active component of catalyst, and its quality percentage composition is respectively 0.9～4.6%, 1.0～4.9%; Silica is as the carrier of catalyst, its quality percentage composition 88.9～97.3%; Titanium dioxide is as catalyst auxiliary activity component, and its percentage composition is 0.8～1.6%, and each constituent mass percentage composition sum is 100%; Preparation process is following:
1) with 4.0g SiO
2Carrier, 0.14～0.75g cobalt nitrate hexahydrate, 0.10～0.55g ferric sulfate, 100mL deionized water mix, and place water-bath, are warming up to 50～60 ℃; Transfer pH to 10～11 with the 0.1M sodium hydroxide solution, stirring reaction 1～2h filters; Wash 2～3 times with deionized water; 80～110 ℃ of drying 2～4h, 500～600 ℃ of roasting 3～5h obtain Co
3O
4And Fe
2O
3SiO after the modification
2Carrier;
2) 5.4～10.8mL butyl titanate, 10～20mL absolute methanol and 10～20mL toluene are mixed, add 2.0g Co
3O
4And Fe
2O
3SiO after the modification
2Carrier evenly mixes, and leaves standstill 30～60min; Vacuum is removed mixed solution, and with absolute methanol washing 2～3 times, vacuum is removed methanol solvate; After adding 10～20mL deionized water dipping, 1～2h; Vacuumize to remove and anhydrate, 100～120 ℃ are descended dry 2～4h, obtain being used for the catalyst of epoxidation of styrene.
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| CN104557785B (en) * | 2014-12-31 | 2017-06-06 | 浙江工业大学 | A kind of heterogeneous catalysis epoxidation vinyl benzene combines the method for preparing Styryl oxide and benzaldehyde |
| CN105628855A (en) * | 2015-12-31 | 2016-06-01 | 浙江理工大学 | Method for efficiently predicting service life of catalyst for alkene epoxidation |
| CN108395417A (en) * | 2017-02-08 | 2018-08-14 | 中国石化扬子石油化工有限公司 | A kind of method of epoxidation of styrene synthesizing epoxy vinylbenzene |
| CN109939693B (en) * | 2019-03-29 | 2021-09-28 | 扬州大学 | CoMn2O4Bimetallic oxide catalyst, preparation method and application |
| CN110026196B (en) * | 2019-05-06 | 2020-07-28 | 中国科学院山西煤炭化学研究所 | Supported heterogeneous catalyst and preparation method and application thereof |
| CN113387908B (en) * | 2021-05-31 | 2023-02-03 | 扬州大学 | Application of magnesium cobaltate catalyst in selective oxidation reaction of styrene |
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| CN1268427C (en) * | 2004-01-13 | 2006-08-09 | 厦门大学 | Solid catalyst for preparing epoxy phenylethane by epoxidation of styrene and preparation method |
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