CN106608860A - 苯乙烯氧化制环氧苯乙烷的方法 - Google Patents
苯乙烯氧化制环氧苯乙烷的方法 Download PDFInfo
- Publication number
- CN106608860A CN106608860A CN201510689830.4A CN201510689830A CN106608860A CN 106608860 A CN106608860 A CN 106608860A CN 201510689830 A CN201510689830 A CN 201510689830A CN 106608860 A CN106608860 A CN 106608860A
- Authority
- CN
- China
- Prior art keywords
- styrene
- sio
- amorphous
- oxidation
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 66
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 144
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 74
- 239000000463 material Substances 0.000 claims abstract description 43
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 40
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 40
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 40
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 40
- 239000011148 porous material Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 10
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 229920000428 triblock copolymer Polymers 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 241001597008 Nomeidae Species 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000026030 halogenation Effects 0.000 claims description 5
- 238000005658 halogenation reaction Methods 0.000 claims description 5
- 238000005191 phase separation Methods 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- -1 polyoxyethylene Polymers 0.000 claims description 3
- 239000011698 potassium fluoride Substances 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- WENLKAKVZDPNQX-UHFFFAOYSA-N methanetetrol silicic acid Chemical compound C(O)(O)(O)O.[Si](O)(O)(O)O WENLKAKVZDPNQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 244000248349 Citrus limon Species 0.000 claims 2
- 235000005979 Citrus limon Nutrition 0.000 claims 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims 2
- 239000004593 Epoxy Substances 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 230000006698 induction Effects 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract 1
- HEHINIICWNIGNO-UHFFFAOYSA-N oxosilicon;titanium Chemical group [Ti].[Si]=O HEHINIICWNIGNO-UHFFFAOYSA-N 0.000 abstract 1
- 241000894007 species Species 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 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
- 239000000376 reactant Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/657—Pore diameter larger than 1000 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种苯乙烯氧化制环氧苯乙烷的方法,主要解决现有苯乙烯氧化制环氧苯乙烷的催化剂存在对环氧苯乙烷选择性低,收率低的问题。本发明通过采用一种苯乙烯氧化制环氧苯乙烷的方法,以苯乙烯为原料,在反应温度为20~100℃,反应压力为0.0.1MPa~1MPa,反应重量空速为0.2~5h‑1,异丙苯过氧化氢/苯乙烯摩尔比为0.1~15的条件下反应生成环氧苯乙烷,所用的催化剂为复合孔结构钛硅氧化物材料,其中TiO2/SiO2的重量比为0.002~0.4;介孔孔径分布为2~40纳米;大孔孔径分布为0.5~40微米;比表面积为100~1300m2·g‑1;孔容为0.05~1.5cm3·g–1的技术方案较好地解决了该问题,可用于苯乙烯氧化制环氧苯乙烷的工业生产中。
Description
技术领域
本发明涉及一种苯乙烯氧化制环氧苯乙烷的方法。
背景技术
氧化硅整体材料(monolith)是80年代后期液相色谱领域发展起来的一种新型多孔材料,它具有高的比表面积和发达的孔隙结构,在扩散、传质等方面具有优于其它材料的特性;另外,整体材料具有一体成型的宏观形貌,避免了繁杂的成型步骤,这样可避免成型中对孔道的堵塞和对活性位点的包埋。基于以上优点,复合孔结构的氧化硅整体材料逐渐受到催化材料研究者的关注,成为人们研究的热点。但是氧化硅基本属于惰性材料,本身不具有丰富的活性中心,而且也没有适宜的酸性位点,这极大地限制了整体材料在石油化工领域的进一步应用。
为解决以上问题,研究人员试图将杂原子引入氧化硅整体材料,制备出具有丰富活性位的复合孔结构整体材料。近些年来,含钛材料在光催化、烯烃环氧化等方面的应用引起广泛的关注。为了获得具有高催化活性和可调催化性能的钛硅氧化物材料,研究人员开发出众多的合成方法,但主要集中在微孔材料(M.F.Borin,T.da Silva,R.F.Felisbino,D.Cardoso,J.Phys.Chem.B 110(2006):15080-15084)和介孔材料(W.Tanglumlert,T.Imae,T J.White,S.Wongkasemjit,Materials Letters 62(2008):4545–4548)上,对于同时含有大孔和介孔的钛硅氧化物整体材料的制备至今未见报道。这主要归结于钛物种和硅物种的水解速度的差异。整体材料需要在较强酸性条件下合成,而钛物种在该条件下的水解速度要比硅源快很多,导致钛物种和硅物种的聚合速度不匹配,从而使得制备同时具有可调控的复合孔结构以及钛分散均匀的钛硅氧化物独石具有相当大的难度。
尽管各国研究人员开发出众多的合成方法,但目前复合孔结构钛硅氧化物整体材料的制备仍是合成领域中的难点之一。由此可见,开发一种制备过程简单,对环境友好并且具有较好传质性能的复合孔结构钛硅氧化物整体材料的制备方法是实现和扩大其实际应用的关键所在。
发明内容
本发明所要解决的技术问题是现有苯乙烯氧化制环氧苯乙烷的催化剂存在对环氧苯乙烷选择性低,收率低的问题。本发明提供了一种新的苯乙烯氧化制环氧苯乙烷的方法,该方法用于苯乙烯氧化制环氧苯乙烷反应时,具有环氧苯乙烷选择性高,收率高的特点。
为解决上述技术问题,本发明采用的技术方案如下:一种苯乙烯氧化制环氧苯乙烷的方法,以苯乙烯为原料,在反应温度为20~100℃,反应表压力为0.01MPa~1MPa,反应重量空速为0.2~5h-1,异丙苯过氧化氢/苯乙烯摩尔比为0.1~15的条件下,原料与介孔/大孔复合孔结构钛硅氧化物材料反应生成环氧苯乙烷。
上述技术方案中,优选的,反应温度为20~100℃,反应压力为0.1MPa~1MPa,反应重量空速为0.2~5h-1,异丙苯过氧化氢/苯乙烯摩尔比为0.1~15。
上述技术方案中,优选的,介孔/大孔复合孔结构钛硅氧化物材料中TiO2/SiO2的重量比为0.002~0.4;介孔孔径分布为2~40纳米;大孔孔径分布为0.5~40微米;比表面积为100~1300m2·g-1;孔容为0.05~1.5cm3·g– 1,其中大孔孔容占3~80%,介孔孔容5~90%。
上述技术方案中,更优选的,介孔/大孔复合孔结构钛硅氧化物材料中TiO2/SiO2的重量比为0.002~0.4;介孔孔径分布为2.5~30纳米;大孔孔径分布为1~15微米;比表面积为200~1000m2·g-1;孔容为0.1~1.3cm3·g– 1,其中大孔孔容占5%~70%,介孔孔容10%~80%。
上述技术方案中,优选的,介孔/大孔复合孔结构钛硅氧化物材料的制备方法,包括以下步骤:a)将相分离诱导剂R1、结构导向剂R2、催化剂R3、醇R4、酸、水、硅源和铝源的混合物发生水解反应得到钛硅氧化物材料前驱体Ⅰ,混合物重量比组成为:R1/SiO2=0.01~1.0,R2/SiO2=0.3~2.5,R3/SiO2=0~0.1,R4/SiO2=0~10,H2O/SiO2=3.0~20,H+/SiO2=0.01~0.45,TiO2/SiO2=0.002~0.4;
b)将上述钛硅氧化物材料前驱体Ⅰ在30~100℃温度下凝胶老化,老化2~96小时,得到钛硅氧化物材料前驱体Ⅱ;
c)钛硅氧化物材料前驱体Ⅱ经干燥、焙烧后制得介孔/大孔复合孔结构钛硅氧化物材料;
其中相分离诱导剂R1选自聚乙二醇、聚氧乙烯或聚环氧乙烷的中的至少一种,其平均分子量为3000~100000;
结构导向剂R2选自三嵌段共聚物、长链烷基三甲基卤化氨((CH3)nN+(CH3)3X-)、 柠檬酸、酒石酸、苹果酸或乳酸中的至少一种;其中三嵌段共聚物是聚氧乙烯-聚氧丙烯-聚氧乙烯,其平均分子量为1500~12000;长链烷基三甲基卤化氨的碳链长度为8~18,X为Cl或者Br;
催化剂R3选自氟化铵、氟化钾、氯化铵、磷酸铵、碳酸铵中的至少一种;
酸选自硝酸、磷酸、盐酸或醋酸中的至少一种。
上述技术方案中,硅源优选方案为选自正硅酸四甲酯、正硅酸四乙酯、正硅酸四丙酯、正硅酸四丁酯中的至少一种。钛源优选方案为选自三氯化钛、异丙醇钛或异丁醇钛中至少一种。步骤a)中混合物重量比组成优选范围为:R1/SiO2=0.02~0.9,R2/SiO2=0.25~2.4,R3/SiO2=0.001~0.9,R4/SiO2=0~10,H2O/SiO2=2.9~19,H+/SiO2=0.02~0.40,TiO2/SiO2=0.003~0.35。步骤b)中凝胶老化温度优选范围为40~80℃,老化时间优选范围为12~72小时。步骤c)中,干燥温度优选范围为25~80℃,干燥时间优选范围为1~7天;焙烧温度优选范围为550~800℃,焙烧时间优选范围为2~10小时。相分离诱导剂R1的平均分子量优选范围为5000~50000。三嵌段共聚物的平均分子量优选范围为2600~10000。长链烷基三甲基卤化氨的碳链长度优选范围为10~16。催化剂R3优选方案为选自氟化铵、氟化钾、氯化铵、碳酸铵中的至少一种。
本发明方法中,将钛硅氧化物材料前驱体Ⅰ放入任意形状的模具里,就可以得到相应形状的复合孔钛硅氧化物整体材料。
目前,苯乙烯氧化制环氧苯乙烷的反应中普遍存在催化剂失活速度快;环氧苯乙烷的选择性低,收率低的问题。这主要是由于催化剂扩散性能差,导致易积碳引起的。积碳主要从两方面影响催化剂的活性:一方面是积碳覆盖催化剂的活性位导致失活;另一方面是积碳堵塞催化剂的孔道,使得反应物无法扩散到达活性位或者产物无法扩散出催化剂孔道。本发明采用同时含有介孔和大孔的钛硅氧化物整体材料作为苯乙烯氧化制环氧苯乙烷(SO)的催化剂,由于其贯通的大孔有利于反应物分子与催化剂的活性中心接触,同时也有利于反应产物快速扩散出催化剂的孔道,从而减少积炭的生成,使其催化性能比以往催化剂有了明显改善,同时通过调节反应条件,使异丙苯过氧化氢(CHP)的转化率和选择性明显提高,应用该方法制得的钛硅氧化物整体材料作为催化剂使得异丙苯过氧化氢(CHP)的转化率和选择性分别达到68.22%和84.9%,取得了较好的技术效果。
下面通过实施例对本发明作进一步的阐述。
附图说明
图1为【实施例1】得到的介孔/大孔复合孔结构钛硅氧化物材料的扫描电镜(SEM)照片。
具体实施方式
【实施例1】
向0.1mol/L的硝酸溶液中加入1g三嵌段共聚物P123,室温下搅拌1h后加入0.4g分子量为10000的聚乙二醇(PEG)和少量的氟化氨,搅拌均匀后将其冷却到0℃。然后向混合溶液中加入5ml的正硅酸甲酯(TMOS)和含计算量异丙醇钛的异丙醇溶液,剧烈搅拌10min后,将混合液倒入密封的模具中,在60℃静置老化48h。然后经过脱模、洗涤、干燥等处理后,在450℃焙烧5h,得到介孔/大孔钛硅氧化物整体材料。对实施例1制备的催化剂(A)和传统的Ti/SBA-15分子筛(B)进行苯乙烯氧化制环氧苯乙烷反应活性评价,考察所用的工艺条件为:反应液总体积106mL,丙酮为溶剂,CHP 0.08mol,苯乙烯0.44mol,催化剂用量0.5g,反应温度60℃,反应时间2h。反应产物经Agilent 6820色谱分析组成。考评结果如表1所示。各组分的重量比为:R1/SiO2=0.2,R2/SiO2=0.5,R3/SiO2=0.005,R4/SiO2=2,H2O/SiO2=5,H+/SiO2=0.05,TiO2/SiO2=0.01。
表1
【实施例2~27】
按照【实施例1】的各个步骤及条件,制得复合孔结构钛硅氧化物材料,只是改变原料组成(表2)等参数,合成的产物经表征说明其结果具有与【实施例1】产物相似的孔结构,其具体的反应条件和反应结果分别见表2。
表2
Claims (10)
1.一种苯乙烯氧化制环氧苯乙烷的方法,以苯乙烯为原料,在反应温度为20~100℃,反应表压力为0.01MPa~1MPa,反应重量空速为0.2~5h-1,异丙苯过氧化氢/苯乙烯摩尔比为0.1~15的条件下,原料与介孔/大孔复合孔结构钛硅氧化物材料反应生成环氧苯乙烷。
2.根据权利要求1所述苯乙烯氧化制环氧苯乙烷的方法,其特征在于反应温度为20~100℃,反应压力为0.1MPa~1MPa,反应重量空速为0.2~5h-1,异丙苯过氧化氢/苯乙烯摩尔比为0.1~15。
3.根据权利要求1所述的苯乙烯氧化制环氧苯乙烷的方法,其特征在于所述介孔/大孔复合孔结构钛硅氧化物材料中TiO2/SiO2的重量比为0.002~0.4;介孔孔径分布为2~40纳米;大孔孔径分布为0.5~40微米;比表面积为100~1300m2·g-1;孔容为0.05~1.5cm3·g–1,其中大孔孔容占3~80%,介孔孔容5~90%。
4.根据权利要求3所述的苯乙烯氧化制环氧苯乙烷的方法,其特征在于所述介孔/大孔复合孔结构钛硅氧化物材料中TiO2/SiO2的重量比为0.002~0.4;介孔孔径分布为2.5~30纳米;大孔孔径分布为1~15微米;比表面积为200~1000m2·g-1;孔容为0.1~1.3cm3·g–1,其中大孔孔容占5%~70%,介孔孔容10%~80%。
5.根据权利要求1所述的苯乙烯氧化制环氧苯乙烷的方法,其特征在于介孔/大孔复合孔结构钛硅氧化物材料的制备方法,包括以下步骤:
a)将相分离诱导剂R1、结构导向剂R2、催化剂R3、醇R4、酸、水、硅源和钛源的混合物在0~40℃条件下水解反应5~60分钟得钛硅氧化物材料前驱体Ⅰ,混合物重量比组成为:R1/SiO2=0.01~1.0,R2/SiO2=0.3~2.5,R3/SiO2=0~0.1,R4/SiO2=0~10,H2O/SiO2=3.0~20,H+/SiO2=0.01~0.45,TiO2/SiO2=0.002~0.4;
b)将上述钛硅氧化物材料前驱体Ⅰ在30~100℃温度下凝胶老化,老化2~96小时,得到钛硅氧化物材料前驱体Ⅱ;
c)钛硅氧化物材料前驱体Ⅱ经干燥、焙烧后制得介孔/大孔复合孔结构钛硅氧化物材料;
其中相分离诱导剂R1选自聚乙二醇、聚氧乙烯或聚环氧乙烷的中的至少一种,其平均分子量为3000~100000;
结构导向剂R2选自三嵌段共聚物、长链烷基三甲基卤化氨((CH3)nN+(CH3)3X-)、柠檬酸、酒石酸、苹果酸或乳酸中的至少一种;其中三嵌段共聚物是聚氧乙烯-聚氧丙烯-聚氧乙烯,其平均分子量为1500~12000;长链烷基三甲基卤化氨的碳链长度为8~18,X为Cl或者Br;
催化剂R3选自氟化铵、氟化钾、氯化铵、磷酸铵、碳酸铵中的至少一种;
醇R4选自异丙醇、异丁醇中的至少一种;
酸选自硝酸、磷酸、盐酸或醋酸中的至少一种。
6.根据权利要求5所述的苯乙烯氧化制环氧苯乙烷的方法,其特征在于硅源选自正硅酸四甲酯、正硅酸四乙酯、正硅酸四丙酯或正硅酸四丁酯中的至少一种。
7.根据权利要求5所述的苯乙烯氧化制环氧苯乙烷的方法,其特征在于钛源为四氯化钛、三氯化钛、异丙醇钛或异丁醇钛中的至少一种。
8.根据权利要求5所述的苯乙烯氧化制环氧苯乙烷的方法,其特征在于步骤a)中混合物重量比组成为:R1/SiO2=0.01~1.0,R2/SiO2=0.3~2.5,R3/SiO2=0~0.1,R4/SiO2=0~10,H2O/SiO2=3.0~20,H+/SiO2=0.01~0.45,TiO2/SiO2=0.002~0.4。
9.根据权利要求5所述的苯乙烯氧化制环氧苯乙烷的方法,其特征在于相分离诱导剂R1的平均分子量为5000~50000。
10.根据权利要求5所述的苯乙烯氧化制环氧苯乙烷的方法,其特征在于三嵌段共聚物的平均分子量为2600~10000。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510689830.4A CN106608860A (zh) | 2015-10-22 | 2015-10-22 | 苯乙烯氧化制环氧苯乙烷的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510689830.4A CN106608860A (zh) | 2015-10-22 | 2015-10-22 | 苯乙烯氧化制环氧苯乙烷的方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN106608860A true CN106608860A (zh) | 2017-05-03 |
Family
ID=58611226
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510689830.4A Pending CN106608860A (zh) | 2015-10-22 | 2015-10-22 | 苯乙烯氧化制环氧苯乙烷的方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106608860A (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113956216A (zh) * | 2021-11-09 | 2022-01-21 | 万华化学集团股份有限公司 | 一种环氧苯乙烷及其制备方法 |
CN114436902A (zh) * | 2022-02-28 | 2022-05-06 | 苏州大学张家港工业技术研究院 | 一种用于流动相系统的异相光催化方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102745705A (zh) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | 介孔/大孔复合孔结构钛硅氧化物材料的制备方法 |
CN102746256B (zh) * | 2011-04-20 | 2014-10-15 | 中国石油化工股份有限公司 | 环己烯氧化制环氧环己烷的方法 |
-
2015
- 2015-10-22 CN CN201510689830.4A patent/CN106608860A/zh active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102745705A (zh) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | 介孔/大孔复合孔结构钛硅氧化物材料的制备方法 |
CN102746256B (zh) * | 2011-04-20 | 2014-10-15 | 中国石油化工股份有限公司 | 环己烯氧化制环氧环己烷的方法 |
Non-Patent Citations (2)
Title |
---|
XUE FENG LI ET AL.: "Characterization of silylated Ti-grafted HMS catalyst and its excellent epoxidation performance", 《CHINESE CHEMICAL LETTERS》 * |
杨贺勤: "复合孔结构整体材料的制备、表征及应用", 《中国博士学位论文全文数据库,工程科技1辑,华东理工大学博士学位论文》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113956216A (zh) * | 2021-11-09 | 2022-01-21 | 万华化学集团股份有限公司 | 一种环氧苯乙烷及其制备方法 |
CN113956216B (zh) * | 2021-11-09 | 2024-01-23 | 万华化学集团股份有限公司 | 一种环氧苯乙烷及其制备方法 |
CN114436902A (zh) * | 2022-02-28 | 2022-05-06 | 苏州大学张家港工业技术研究院 | 一种用于流动相系统的异相光催化方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101525137B (zh) | 介孔/大孔复合孔结构硅胶独石的制备方法 | |
CN101274766A (zh) | 一种有序介孔氧化钛硅分子筛的合成方法 | |
CN104556092A (zh) | 多级孔结构sapo分子筛材料及其制备方法 | |
CN101723393A (zh) | 介孔/大孔复合孔结构硅铝氧化物材料的制备方法 | |
CN104211078A (zh) | 一种金属掺杂的介孔硅基分子筛纳米球及其制备方法 | |
CN106362791A (zh) | 一种用于丙烷脱氢转化制丙烯介孔‑微孔复合孔道分子筛催化剂及其制备方法 | |
CN107500312A (zh) | 一种氟改性分子筛h‑zsm‑35及其制备方法 | |
CN102745710B (zh) | 多级孔结构钛硅分子筛材料的制备方法 | |
CN105031664A (zh) | 三重杂化的蛋黄-蛋壳结构的介孔有机氧化硅及制备方法 | |
CN106608860A (zh) | 苯乙烯氧化制环氧苯乙烷的方法 | |
CN102746256B (zh) | 环己烯氧化制环氧环己烷的方法 | |
CN108821304A (zh) | 高活性多级孔钛硅分子筛及其制备方法和应用 | |
CN102145300A (zh) | 一种微球ts-1催化剂及其制备方法 | |
CN107500308B (zh) | 一种稀土改性的多级孔道钛硅分子筛的制备方法 | |
CN106517227B (zh) | 一种微波法快速制备短棒状的sba-15的方法 | |
CN112774663A (zh) | 用于甲烷直接制乙烯的多级孔催化剂及其制备方法与应用 | |
CN108273547A (zh) | 一种采用真空浸渍法制备负载型分子筛催化剂的方法 | |
CN101905891B (zh) | 一种有序介孔氧化钛硅分子筛的合成方法 | |
CN104150506B (zh) | 制备介孔zsm-5沸石的方法 | |
CN103418425B (zh) | 甲醇转化制丙烯的催化剂及其制备方法 | |
CN102745705A (zh) | 介孔/大孔复合孔结构钛硅氧化物材料的制备方法 | |
CN105460944A (zh) | 层状结构sapo分子筛材料及其制备方法 | |
CN103030610B (zh) | 氯丙烯氧化制环氧氯丙烷的方法 | |
CN114436325A (zh) | 一种二元低共熔溶剂中制备无机多孔材料的方法 | |
CN106466619B (zh) | 甲醇转化制丙烯催化剂及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170503 |
|
RJ01 | Rejection of invention patent application after publication |