CN100369907C - 环氧丙烷的制造方法 - Google Patents
环氧丙烷的制造方法 Download PDFInfo
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- CN100369907C CN100369907C CNB991210905A CN99121090A CN100369907C CN 100369907 C CN100369907 C CN 100369907C CN B991210905 A CNB991210905 A CN B991210905A CN 99121090 A CN99121090 A CN 99121090A CN 100369907 C CN100369907 C CN 100369907C
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- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 20
- GQNOPVSQPBUJKQ-UHFFFAOYSA-N 1-hydroperoxyethylbenzene Chemical compound OOC(C)C1=CC=CC=C1 GQNOPVSQPBUJKQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 11
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 6
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- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 16
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- DCSOPUDOZMRWRP-UHFFFAOYSA-N Cc1cc(C)cc([SiH2]Cl)c1 Chemical compound Cc1cc(C)cc([SiH2]Cl)c1 DCSOPUDOZMRWRP-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
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- ITKVLPYNJQOCPW-UHFFFAOYSA-N chloro-(chloromethyl)-dimethylsilane Chemical compound C[Si](C)(Cl)CCl ITKVLPYNJQOCPW-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- ATYRWKGHNCIOGX-UHFFFAOYSA-N 1-chlorohexane silane Chemical compound [SiH4].C(CCCCC)Cl ATYRWKGHNCIOGX-UHFFFAOYSA-N 0.000 description 1
- NRKYWOKHZRQRJR-UHFFFAOYSA-N 2,2,2-trifluoroacetamide Chemical compound NC(=O)C(F)(F)F NRKYWOKHZRQRJR-UHFFFAOYSA-N 0.000 description 1
- BWZNUKUXXWKJRI-UHFFFAOYSA-N 2-[diethylamino(dimethyl)silyl]propanenitrile Chemical compound CCN(CC)[Si](C)(C)C(C)C#N BWZNUKUXXWKJRI-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
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- 241000212978 Amorpha <angiosperm> Species 0.000 description 1
- PHERXFRBCOIFIX-UHFFFAOYSA-N C(CCC)(=O)N.[F] Chemical class C(CCC)(=O)N.[F] PHERXFRBCOIFIX-UHFFFAOYSA-N 0.000 description 1
- PUBKITDKWJFTDL-UHFFFAOYSA-N CN(C)C.[O-][N+]([SiH3])=O Chemical compound CN(C)C.[O-][N+]([SiH3])=O PUBKITDKWJFTDL-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- JQKNLVKYLHDVCQ-UHFFFAOYSA-N Cl[SiH3].C1(=CC=CC=C1)C#CC1=CC=CC=C1 Chemical compound Cl[SiH3].C1(=CC=CC=C1)C#CC1=CC=CC=C1 JQKNLVKYLHDVCQ-UHFFFAOYSA-N 0.000 description 1
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- XJOVUXIJZZFRIH-UHFFFAOYSA-N N-(chloromethylsilyl)-N-trimethylsilylmethanamine Chemical compound ClC[SiH2]N([Si](C)(C)C)C XJOVUXIJZZFRIH-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- MSPCIZMDDUQPGJ-UHFFFAOYSA-N N-methyl-N-(trimethylsilyl)trifluoroacetamide Chemical compound C[Si](C)(C)N(C)C(=O)C(F)(F)F MSPCIZMDDUQPGJ-UHFFFAOYSA-N 0.000 description 1
- YKFRUJSEPGHZFJ-UHFFFAOYSA-N N-trimethylsilylimidazole Chemical compound C[Si](C)(C)N1C=CN=C1 YKFRUJSEPGHZFJ-UHFFFAOYSA-N 0.000 description 1
- VJOJBPHQBSIICD-UHFFFAOYSA-N NC[SiH](Cl)C1=CC=CC=C1 Chemical compound NC[SiH](Cl)C1=CC=CC=C1 VJOJBPHQBSIICD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
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- RQEJIBJBKAUWJU-UHFFFAOYSA-N [SiH4].CI(CCCC)C Chemical compound [SiH4].CI(CCCC)C RQEJIBJBKAUWJU-UHFFFAOYSA-N 0.000 description 1
- WYUIWUCVZCRTRH-UHFFFAOYSA-N [[[ethenyl(dimethyl)silyl]amino]-dimethylsilyl]ethene Chemical compound C=C[Si](C)(C)N[Si](C)(C)C=C WYUIWUCVZCRTRH-UHFFFAOYSA-N 0.000 description 1
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- 235000019445 benzyl alcohol Nutrition 0.000 description 1
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- ABHNFDUSOVXXOA-UHFFFAOYSA-N benzyl-chloro-dimethylsilane Chemical compound C[Si](C)(Cl)CC1=CC=CC=C1 ABHNFDUSOVXXOA-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
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- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- KAHVZNKZQFSBFW-UHFFFAOYSA-N n-methyl-n-trimethylsilylmethanamine Chemical compound CN(C)[Si](C)(C)C KAHVZNKZQFSBFW-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- VUENSYJCBOSTCS-UHFFFAOYSA-N tert-butyl-imidazol-1-yl-dimethylsilane Chemical class CC(C)(C)[Si](C)(C)N1C=CN=C1 VUENSYJCBOSTCS-UHFFFAOYSA-N 0.000 description 1
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- UTXPCJHKADAFBB-UHFFFAOYSA-N tribenzyl(chloro)silane Chemical compound C=1C=CC=CC=1C[Si](CC=1C=CC=CC=1)(Cl)CC1=CC=CC=C1 UTXPCJHKADAFBB-UHFFFAOYSA-N 0.000 description 1
- JSQJUDVTRRCSRU-UHFFFAOYSA-N tributyl(chloro)silane Chemical compound CCCC[Si](Cl)(CCCC)CCCC JSQJUDVTRRCSRU-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Abstract
通过丙烯与乙苯过氧化氢反应制造环氧丙烷的方法，其中所述反应在包括了含钛二氧化硅并满足所有的如下(1)至(5)的条件的催化剂存在下进行：(1)在X射线衍射中有至少一个峰显示出大于18的晶面间距(d)，(2)平均孔径等于或大于10，(3)在总孔体积中有90%或更多的孔的孔径为5-200，(4)比孔容等于或大于0.2cm3/g，(5)使用下式(Ⅰ)表示的季铵离子作为“模板”，然后通过煅烧操作除去该“模板”；[NR1R2R3R4]+(Ⅰ)这里，R1表示一个具有2-36个碳原子的直链或分支的烃链，R2至R4表示具有1-6个碳原子的烷基。
Description
本发明涉及环氧丙烷的制造方法。更具体说，本发明涉及通过丙烯与乙苯过氧化氢反应制造环氧丙烷，以高产率和高选择性得到环氧丙烷的方法。
众所周知，可以通过丙烯与乙苯过氧化氢反应制造环氧丙烷。比如，UPP 4,367,342公开了使用载钛二氧化硅催化剂的方法。然而，在传统的方法中不一定会以高产率和高选择性得到环氧丙烷。
在这些情况下，本发明的目标是提供经丙烯与乙苯过氧化氢反应制造环氧丙烷，以高产率和高选择性得到环氧丙烷的方法。
这就是说，本发明涉及通过丙烯与乙苯过氧化氢反应制造环氧丙烷的方法，其中所述反应在催化剂存在下进行，该催化剂包括含钛二氧化硅并满足所有的如下(1)至(5)的条件：
(1)：在X射线衍射中有至少一个峰显示出大于18的晶面间距
(d)。
(2)：平均孔径等于或大于10。
(3)：在总孔体积中有90％或更多的孔的孔径为5-200。
(4)：比孔容等于或大于0.2cm3/g。
(5)：使用下式(I)表示的季铵离子作为“模板”(template)，然后通过煅烧除去该“模板”。
[NR1R2R3R4]+ (I)
这里，R1表示一个具有2-36个碳原子的直链或分支的烃链，R2至R4表示具有1-6个碳原子的烷基。
图1是在实施例1中的催化剂的X射线衍射图。
在本发明中使用的催化剂是包括了含钛二氧化硅和满足如下(1)至(5)的全部条件的催化剂。使用所述的催化剂可以完全实现本发明的效果。
条件(1)表明该催化剂在X衍射(XRD)中具有至少一个峰显示出大于18的晶面间距(d)。在这里所指的显示晶面间距(d)的峰意味着该峰来源于固体的结晶度和规整度，也可以有来源于无定形部分的宽峰存在。当在X射线中有显示出大于18的晶面间距(d)的峰存在时，此峰优选是显示六方晶系结构的峰组的一部分。
条件(2)表明该催化剂的平均孔径等于或大于10。
条件(3)表明该催化剂的总孔体积中有90％或更多的孔的孔径为5-200。
条件(4)表明该催化剂的比孔容等于或大于0.2cm3/g。比孔容意味着每1g该催化剂的孔体积。
在上述的条件(2)至(4)中所叙述的该催化剂的性能可以通过通常的方法，使用如氮、氩等气体的物理吸附来测定。
条件(5)表明使用如下式(I)表示的季铵离子作为“模板”，然后通过煅烧操作除去所述“模板”来得到该催化剂；
[NR1R2R3R4]+ (I)
这里，R1表示一个具有2-36个碳原子的直链或分支的烃链，R2至R4表示具有1-6个碳原子的烷基。
R1表示一个具有2-36个碳原子，优选10-18个碳原子的直链或分支的烃链，R2至R4表示具有1-6个碳原子的烷基，优选R2至R4均表示甲基。
通式(I)所表示的季铵离子的特定的例子包括如十六烷基三甲基铵、十二烷基三甲基铵、苄基三甲基铵、二甲基二(十二烷基)铵、十六烷基吡啶阳离子、十六烷基三甲基等的阳离子。
得到本发明催化剂的具体的优选实施方案如下。
在液体条件中混合和搅拌二氧化硅源、钛源和作为“模板”的季铵离子。当要使用的试剂是固体时，可以将其溶解于溶剂中，作为溶液来使用。
二氧化硅源的例子包括无定形的二氧化硅和烷氧基硅烷，比如原硅酸四甲酯、原硅酸四乙酯、原硅酸四丙酯等。
钛源的例子包括烷氧基钛，比如钛酸四甲酯、钛酸四乙酯、钛酸四丙酯、钛酸四异丙酯、钛酸四丁酯、钛酸四异丁酯、钛酸四-2-乙基己酯、钛酸四(十八烷基)酯以及氧乙酰基丙酮酸钛(IV)、二异丙氧基二乙酰基丙酮酸钛(IV)等，以及卤化钛如四氯化钛、四溴化钛、四碘化钛等。
溶剂的例子包括水和醇类，比如甲醇、乙醇、正丙醇、2-丙醇、正丁醇、仲丁醇、叔丁醇、乙烯基醇、烯丙基醇、环己醇、苄醇等，以及二元醇，或者它们的混合物等。
基于二氧化硅源的钛源的使用量按照摩尔比为10-5-1，优选从0.00008至0.4。基于此二氧化硅源和钛源总量的季铵离子使用量按照摩尔比优选为10-2-2。
为了促进二氧化硅源和钛源的反应，优选使混合的溶液具有碱性或酸性。作为碱源，优选季铵氢氧化物，其例子包括氢氧化四甲基铵、氢氧化四乙基铵、氢氧化四丙基铵等。酸的例子包括如盐酸、硫酸、硝酸等的无机酸，以及如甲酸、乙酸、丙酸等的有机酸。
混合和搅拌的温度一般为-30-100℃。通过混合和搅拌形成了固体，可以将该固体陈化以使其进一步生长。陈化时间一般是180小时或更短，陈化温度一般为0-200℃。当陈化须要加热时，优选将该混合物转移到一个压力釜中进行加热以避免溶剂汽化。过滤并收集得到的固体。可以用水和溶剂洗涤收集到的固体。将得到的固体干燥。干燥过的固体被煅烧，除去“模板”。煅烧温度一般是400-800℃，需要的时间一般为1-100小时。
按照上述的操作，就得到了本发明中使用的催化剂，优选随后进行甲硅烷基化处理。甲硅烷基化一般通过将煅烧后的催化剂和甲硅烷基化试剂接触来进行，将在催化剂表面上存在的羟基转化为甲硅烷基。甲硅烷基化试剂的例子包括有机硅烷、有机甲硅烷基胺、有机甲硅烷基酰胺及其衍生物，以及有机硅氮烷和其它的甲硅烷基试剂。
有机硅烷的例子包括三甲基氯硅烷、二甲基二氯硅烷、二甲基氯溴硅烷、三甲基硝基硅烷、三乙基氯硅烷、二甲基丁基碘硅烷、二甲基苯基氯硅烷、二甲基一氯硅烷、二甲基正丙基氯硅烷、二甲基异丙基氯硅烷、叔丁基二甲基氯硅烷、三丙基氯硅烷、二甲基辛基氯硅烷、三丁基氯硅烷、三己基氯硅烷、二甲基乙基氯硅烷、二甲基十八烷基氯硅烷、正丁基二甲基氯硅烷、溴甲基二甲基氯硅烷、氯甲基二甲基氯硅烷、3-氯丙基二甲基氯硅烷、二甲氧基甲基氯硅烷、甲基苯基氯硅烷、三乙氧基氯硅烷、二甲基苯基氯硅烷、甲基苯基乙烯基氯硅烷、苄基二甲基氯硅烷、二苯基氯硅烷、二苯基甲基氯硅烷、二苯基乙烯基氯硅烷、三苄基氯硅烷、3-氰丙基二甲基氯硅烷。
有机甲硅烷基胺的例子包括N-三甲基甲硅烷基咪唑、N-叔丁基二甲基甲硅烷基咪唑、N-二甲基乙基甲硅烷基咪唑、N-二甲基正丙基甲硅烷基咪唑、N-二甲基异丙基甲硅烷基咪唑、N-三甲基甲硅烷基二甲基胺、N-三甲基甲硅烷基二乙基胺、N-三甲基甲硅烷基吡咯、N-三甲基甲硅烷基吡咯烷、N-三甲基甲硅烷基哌啶、1-氰乙基(二乙基氨基)二甲基硅烷、五氟苯基二甲基甲硅烷基胺。
有机甲硅烷基酰胺和衍生物的例子包括N，O-二(三甲基甲硅烷基)乙酰胺、N，O-二(三甲基甲硅烷基)三氟乙酰胺、N-三甲基甲硅烷基乙酰胺、N-甲基-N-三甲基甲硅烷基乙酰胺、N-甲基-N-三甲基甲硅烷基三氟乙酰胺、N-甲基-N-三甲基甲硅烷基七氟丁酰胺、N-(叔丁基二甲基甲硅烷基)-N-三氟乙酰胺、N，O-二(二乙基氢化甲硅烷基)三氟乙酰胺。
有机硅氮烷的例子包括六甲基二硅氮烷、七甲基二硅氮烷、1，1，3，3-四甲基二硅氮烷、1，3-二(氯甲基)四甲基二硅氮烷、1，3-二乙烯基-1，1，3，3-四甲基二硅氮烷、1，3-二苯基四甲基二硅氮烷。
其它甲硅烷基化试剂包括N-甲氧基-N，O-二(三甲基甲硅烷基)三氟乙酰胺、N-甲氧基-N，O-二(三甲基甲硅烷基)氨基甲酸酯、N，O-二(三甲基甲硅烷基)氨基磺酸酯、三甲基甲硅烷基三氟甲烷磺酸酯、N’N’-二(三甲基甲硅烷基)脲。
优选的甲硅烷基化试剂是六甲基二硅氮烷。
本发明的催化剂优选是在红外吸收光谱的960±5cm-1范围具有吸收峰的催化剂。此峰被看作是相当于引入二氧化硅骨架中的钛。
本发明是通过在上述的催化剂存在下使丙烯与乙苯过氧化氢反应制造环氧丙烷的方法。
用作原料的乙苯过氧化氢可以是稀释的或浓缩的纯产品，或者是不纯的产品。
可以在液相中，使用溶剂和/或稀释剂来进行环氧化反应。在反应的温度和压力下该溶剂和稀释剂必须是液体，而且对反应物和产品基本上呈惰性。该溶剂可以包括在使用的过氧化氢溶液中存在的物质。当乙苯过氧化氢(EBHP)是包括了EBHP和作为EBHP原料的乙苯的混合物时，就不特别须要加入溶剂，它也可以被作为溶剂使用。再有，可以使用过量的丙烯作为溶剂。
要使用的丙烯/乙苯过氧化氢的比例一般为0.1-20。反应温度一般为0-200℃，反应压力一般为1-100kg/cm2。
可以方便地使用固定床形式的催化剂来实施本发明的方法。在大规模工业操作的情况下，优选使用固定床。可以通过间歇的、半连续的或连续的方法实施本发明的方法。当含有反应物的溶液被引入通过固定床时，从反应溶液得到的液体混合物完全不含有催化剂，或者基本不含有催化剂。
实施例
实施例1
制备含钛的MCM41催化剂(本发明的催化剂)
在室温下，将26g十六烷基三甲基溴化铵和24g25wt％的四甲基氢氧化铵水溶液与87g水混合，在此混合物中加入38g原硅酸四甲酯、2.5g二异丙氧基二乙酰基丙酮酸钛(IV)和30g异丙醇的混合物。将混合物搅拌3小时，然后过滤得到的沉淀，用水洗涤。水洗一直进行到洗涤溶液成为中性。在70℃下将过滤出的白色固体减压干燥5小时。将该固体转移到管式炉中，以2℃/min的速度升温至530℃，并在氮气流中保持1小时。然后用空气取代氮气，再煅烧5小时。将此物质(5g)与六甲基二硅氮烷(3.4g)和甲苯(50g)混合，在搅拌回流下加热此混合物1小时。过滤混合物蒸出液体。用100g甲苯洗涤并减压干燥(120℃，10mmHg，3hr)得到催化剂。如此得到的催化剂的比表面积为1390m2/g，平均孔径为41，孔体积为1.4cm3/g。
合成环氧丙烷(PO)
在装有电磁搅拌的高压釜中加入上述的催化剂(2g)和35％(重量)的乙苯过氧化氢(16g)及丙烯(12g)，让它们在90℃下反应0.5小时。反应的结果显示在表1中。
对照实施例1
制备载钛催化剂(非本发明的催化剂)
在搅拌和氮气流下，向钛酸四异丙酯(2.2g)在异丙醇(20mL)的溶液中缓慢加入乙酰丙酮(1.6g)，然后在室温下搅拌该混合物30分钟。在商品硅胶(10-20目，表面积326m2/g，平均孔径10nm)(50g)和异丙醇(230mL)的混合物中滴加上述溶液，然后在室温下搅拌该混合物1小时，再过滤该混合物。用异丙醇(总量250mL)洗涤固体部分三次。在空气气氛下，在150℃下干燥该固体部分2小时。再在空气气氛下，在600℃下进一步煅烧该固体部分4小时。将此物质(10g)、六甲基二硅氮烷(4g)和甲苯(50g)进行混合和搅拌，回流加热1小时。通过过滤从混合物中蒸出液体。用甲苯(100g)洗涤和减压干燥(120℃，10mmHg，3小时)，得到一种催化剂。
使用上述的催化剂进行环氧化反应1小时。结果显示在表1中。
对照实施例2
以与对照实施例1相同的方式进行环氧化反应，不同之处是使用NEChemcat Corp.制造的TS-1催化剂(非本发明的催化剂)(表面积468m2/g，Si/Ti＝50)。结果显示在表1中。
表1
| 实施例1 | 对照实施例1 | 对照实施例2 | |
| 催化剂性能X-射线衍射显示晶面间距d＞18的峰显示晶面间距不满足d＞18的峰平均孔径孔隙分布范围比孔容cm<sup>3</sup>/g“模板” | 被鉴别出被鉴别出415-801.43T-1 | 无无1385-2000.95未用 | 无被鉴别出155-100.17T-2 |
| 反应结果反应时间hEBHP转化率％PO的选择性％ | 0.599.289.2 | 1.094.989.2 | 1.032.275.6 |
*1T-1：十六烷基三甲基溴化铵
*2T-2：四丙基氢氧化铵
如上所述，按照本发明可以提供通过丙烯和乙苯过氧化氢反应制造环氧丙烷的方法，以高产率和高选择性得到环氧丙烷。
Claims (4)
1.通过丙烯与乙苯过氧化氢反应制造环氧丙烷的方法，其中所述反应在包括了含钛二氧化硅并满足所有的如下(1)至(5)的条件的催化剂存在下进行：
(1)：在X射线衍射中有至少一个峰显示出大于18的晶面间距(d)，
(2)：平均孔径等于或大于10，
(3)：在总孔体积中有90％或更多的孔的孔径为5-200，
(4)：比孔容等于或大于0.2cm3/g，
(5)：使用下式(I)表示的季铵离子作为“模板”，然后通过煅烧操作除去该“模板”，
[NR1R2R3R4]+ (I)
这里，R1表示一个具有2-36个碳原子的直链或分支的烃链，R2至R4表示具有1-6个碳原子的烷基。
2.按照权利要求1的方法，其中的X-射线衍射峰是显示六方晶系的峰组的一部分。
3.按照权利要求1的方法，其中的催化剂在红外吸收光谱中的960±5cm-1的范围内具有吸收峰。
4.按照权利要求1的方法，其中的催化剂是进一步进行了甲硅烷基化处理的催化剂。
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| ES009802135A ES2156506B1 (es) | 1998-10-14 | 1998-10-14 | Metodo para la produccion de oxido de propileno. |
| ES9802135 | 1998-10-14 |
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| US (1) | US6211388B1 (zh) |
| JP (2) | JP3848027B2 (zh) |
| KR (1) | KR100596348B1 (zh) |
| CN (1) | CN100369907C (zh) |
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| SG82626A1 (en) | 1998-08-04 | 2001-08-21 | Sumitomo Chemical Co | Titanium-containing silicon oxide catalyst |
| JP2001031662A (ja) * | 1999-07-14 | 2001-02-06 | Sumitomo Chem Co Ltd | プロピレンオキサイドの製造方法 |
| ES2165771B1 (es) * | 1999-07-20 | 2003-05-01 | Sumitomo Chemical Co | Catalizador de oxido de silicio que contiene titanio. |
| ATE334744T1 (de) * | 2000-02-02 | 2006-08-15 | Sumitomo Chemical Co | Geformter katalysator, verfahren zu dessen herstellung sowie verfahren zur herstellung einer oxirankomponente |
| JP4889865B2 (ja) * | 2001-01-31 | 2012-03-07 | 住友化学株式会社 | チタン含有珪素酸化物触媒の製造方法 |
| JP2002239381A (ja) * | 2001-02-22 | 2002-08-27 | Sumitomo Chem Co Ltd | チタン含有珪素酸化物触媒の製造方法及び触媒 |
| FR2824565B1 (fr) * | 2001-05-09 | 2003-07-04 | Solvay | Procede de desulfuration d'un melange d'hydrocarbures |
| US9186322B2 (en) * | 2002-08-02 | 2015-11-17 | Insmed Incorporated | Platinum aggregates and process for producing the same |
| BRPI0413615A (pt) * | 2003-08-19 | 2006-10-17 | Shell Int Research | processos para a preparação de óxido de alquileno, e de óxido de propileno |
| MX2007004955A (es) * | 2004-11-08 | 2007-06-14 | Transave Inc | Metodo de tratar cancer con formulaciones de compeusto de platino a base de lipido administradas intraperitonealmente. |
| JP2006289341A (ja) * | 2005-03-17 | 2006-10-26 | Sumitomo Chemical Co Ltd | チタン含有珪素酸化物触媒の保存方法 |
| WO2007056264A2 (en) * | 2005-11-08 | 2007-05-18 | Transave, Inc. | Methods of treating cancer with high potency lipid-based platinum compound formulations administered intraperitoneally |
| US9107824B2 (en) | 2005-11-08 | 2015-08-18 | Insmed Incorporated | Methods of treating cancer with high potency lipid-based platinum compound formulations administered intraperitoneally |
| US8993714B2 (en) * | 2007-10-26 | 2015-03-31 | Imiplex Llc | Streptavidin macromolecular adaptor and complexes thereof |
| US9102526B2 (en) | 2008-08-12 | 2015-08-11 | Imiplex Llc | Node polypeptides for nanostructure assembly |
| US9285363B2 (en) | 2009-05-11 | 2016-03-15 | Imiplex Llc | Method of protein nanostructure fabrication |
| JP2015530387A (ja) | 2012-09-04 | 2015-10-15 | エライゾン ファーマシューティカルズ， エルエルシー | 脂質複合体化シスプラチンによる肺癌の再発防止 |
| TWI628146B (zh) * | 2016-11-28 | 2018-07-01 | 東聯化學股份有限公司 | Preparation method and application of titanium-containing cerium oxide material with high thermal stability |
| CN107715868B (zh) | 2017-10-27 | 2019-07-23 | 万华化学集团股份有限公司 | 一种丙烯环氧化催化剂的制备方法及其用途 |
| CN107930610B (zh) | 2017-11-29 | 2019-09-20 | 万华化学集团股份有限公司 | 一种烯烃环氧化催化剂的制备方法及由此制备的催化剂 |
| US11918987B2 (en) | 2020-01-14 | 2024-03-05 | Wanhua Chemical Group Co., Ltd. | Preparation method for propylene epoxidation catalyst and use thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4367342A (en) * | 1969-04-02 | 1983-01-04 | Shell Oil Company | Olefin epoxidation |
| US5783167A (en) * | 1993-06-15 | 1998-07-21 | Consejo Superior Investigaciones Cientificas | Structure material of the zeolite type with ultralarge pores and a lattice comprised of silicone and titanium oxides: its synthesis and utilization for the selective oxidation of organic products |
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| JPH07300312A (ja) | 1994-03-09 | 1995-11-14 | Nippon Shokubai Co Ltd | メソポアチタノシリケートおよびその合成方法 |
| US5795555A (en) * | 1994-11-24 | 1998-08-18 | Alive; Keshavaraja | Micro-meso porous amorphous titanium silicates and a process for preparing the same |
| US5723637A (en) * | 1995-12-06 | 1998-03-03 | Sumitomo Chemical Company, Limited | Process for producing propylene oxide |
| US5663384A (en) * | 1996-03-06 | 1997-09-02 | Arco Chemical Technology, L.P. | Asymetric epoxidation using a titanium-containing zeolite and a chiral hydroperoxide |
| US6011162A (en) * | 1997-05-05 | 2000-01-04 | Arco Chemical Technology, L.P. | Epoxidation process using improved heterogeneous catalyst composition |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4367342A (en) * | 1969-04-02 | 1983-01-04 | Shell Oil Company | Olefin epoxidation |
| US5783167A (en) * | 1993-06-15 | 1998-07-21 | Consejo Superior Investigaciones Cientificas | Structure material of the zeolite type with ultralarge pores and a lattice comprised of silicone and titanium oxides: its synthesis and utilization for the selective oxidation of organic products |
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| US6211388B1 (en) | 2001-04-03 |
| JP3848027B2 (ja) | 2006-11-22 |
| KR20000028973A (ko) | 2000-05-25 |
| JP2000119266A (ja) | 2000-04-25 |
| JP4355404B2 (ja) | 2009-11-04 |
| ES2156506A1 (es) | 2001-06-16 |
| JP2000117101A (ja) | 2000-04-25 |
| SG74753A1 (en) | 2000-08-22 |
| NL1013256A1 (nl) | 2000-04-17 |
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