CN101501012A - 使用混合催化剂体系的直接环氧化方法 - Google Patents
使用混合催化剂体系的直接环氧化方法 Download PDFInfo
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- CN101501012A CN101501012A CNA2007800259368A CN200780025936A CN101501012A CN 101501012 A CN101501012 A CN 101501012A CN A2007800259368 A CNA2007800259368 A CN A2007800259368A CN 200780025936 A CN200780025936 A CN 200780025936A CN 101501012 A CN101501012 A CN 101501012A
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- Prior art keywords
- oxide
- zeolite
- titanium
- loaded catalyst
- alkene
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000006735 epoxidation reaction Methods 0.000 title description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 66
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000010457 zeolite Substances 0.000 claims abstract description 38
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 37
- 239000010936 titanium Substances 0.000 claims abstract description 33
- 150000001336 alkenes Chemical class 0.000 claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000001301 oxygen Substances 0.000 claims abstract description 32
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 32
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 18
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 17
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- 229910004339 Ti-Si Inorganic materials 0.000 claims description 6
- 229910010978 Ti—Si Inorganic materials 0.000 claims description 6
- 150000002924 oxiranes Chemical class 0.000 claims description 6
- 239000003610 charcoal Substances 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 4
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 3
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims 2
- 239000010955 niobium Substances 0.000 claims 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- UVFOVMDPEHMBBZ-UHFFFAOYSA-N zinc oxosilicon(2+) oxygen(2-) Chemical compound [Si+2]=O.[O-2].[Zn+2].[O-2] UVFOVMDPEHMBBZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 16
- -1 alkyl hydroperoxide Chemical compound 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000001294 propane Substances 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 239000012159 carrier gas Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
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- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
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- 238000003756 stirring Methods 0.000 description 4
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- 229920000620 organic polymer Polymers 0.000 description 3
- 150000002941 palladium compounds Chemical class 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
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- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
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- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
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Abstract
本发明是在催化剂混合物的存在下用氢气和氧气环氧化烯烃的方法,所述催化剂混合物含有钛或钒沸石和负载型催化剂,所述负载型催化剂包含钯、铼和载体。所述方法导致显著降低的由烯烃加氢而生成的烷烃副产物。
Description
发明领域
本发明涉及使用混合催化剂体系以由氢气、氧气和烯烃生产环氧化物的环氧化方法。所述混合催化剂含有钛或钒沸石和包含钯、铼和载体的负载型催化剂。令人惊讶地,与相似的催化剂体系相比,该方法导致对由烯烃加氢而生成的不想要的烷烃副产物的更低的选择性。
发明背景
已经开发了许多用于环氧化物制备的不同的方法。环氧化物通常通过在催化剂的存在下烯烃与氧化剂的反应而生成。从丙烯和有机氢过氧化物氧化剂(例如乙苯氢过氧化物或叔丁基氢过氧化物)生产环氧丙烷是商业上实践的技术。该方法在溶解的钼催化剂(见美国专利号3,351,635)或非均相的位于氧化硅上的氧化钛催化剂(见美国专利号4,367,342)的存在下进行。另一个商业上实践的技术是在银催化剂上通过与氧气反应使乙烯直接环氧化生成环氧乙烷。不幸的是,所述银催化剂没有被证实用于更高级烯烃的商业环氧化。
除氧气和烷基氢过氧化物外,另一种用于环氧化物制备的氧化剂是过氧化氢。例如美国专利号4,833,260、4,859,785和4,937,216公开了在硅酸钛催化剂存在下用过氧化氢对烯烃进行的环氧化。
大量当前的研究实施在用氧气和氢气对烯烃进行直接环氧化。在该方法中,据信氧气和氢气原位反应以生成氧化剂。已经提出很多不同的催化剂用于高级烯烃的直接环氧化。这些催化剂一般包含负载于钛硅酸盐上的贵金属。例如JP 4-352771公开了使用含有第VIII族金属(例如位于晶体钛硅酸盐上的钯)的催化剂由丙烯、氧气和氢气生成环氧丙烷。认为所述第VIII族金属促进氧气和氢气的反应,以生成过氧化氢原位氧化剂。美国专利号5,859,265公开了一种催化剂,其中选自Ru、Rh、Pd、Os、Ir和Pt中的铂金属被负载于钛或钒硅沸石上。其他的直接环氧化催化剂的实例包括负载于钛硅酸盐上的金,参见例如PCT国际申请WO98/00413。
所描述的直接环氧化催化剂的一个缺点是,它们易于产生非选择性的副产物,例如由所述环氧化物产物的开环而生成的二醇或二醇醚;或由烯烃的加氢而生成的烷烃副产物。美国专利号6,008,388描述了直接烯烃环氧化方法,其中通过向反应混合物中加入氮化合物,例如氢氧化铵,增强了在贵金属改性的钛沸石存在下的烯烃、氧气和氢气的反应的选择性。美国专利号6,399,794教导了碳酸氢铵改性剂的使用,以降低开环副产物的产生。美国专利号6,005,123教导了磷、硫、硒或砷改性剂(例如苯并噻吩)的使用以降低丙烷的产生。
就任何化学方法而言,期望仍在环氧化方法和催化剂方面获得进一步改进。我们已经发现一个有效的、方便的方法,用以生成环氧化催化剂及它在烯烃环氧化中的用途。
发明概述
本发明是烯烃的环氧化方法,其包括在钛或钒沸石和负载型催化剂的存在下使烯烃、氢气和氧气反应。所述负载型催化剂包含钯、铼和载体。该方法令人惊讶地给出显著降低了的由烯烃加氢而生成的烷烃副产物。
发明详述
本发明的方法使用了包含钛或钒沸石和负载型催化剂的催化剂混合物,所述负载型催化剂包含钯、铼和载体。钛或钒沸石包括其中钛或钒原子取代了分子筛晶格骨架中的一部分硅原子的一类沸石物质。这样的物质和它们的生产,在本领域中是公知的。参见例如,美国专利号4,410,501和4,666,692。
合适的钛或钒沸石是具有在骨架中取代的钛或钒原子的那些具有多孔分子筛结构的晶体材料。所使用的钛或钒沸石的选择将取决于包括待环氧化的烯烃的尺寸和形状在内的许多因素。例如,如果所述烯烃是低级脂族烯烃,例如乙烯、丙烯或1-丁烯,优选使用相对小孔的钛或钒沸石,例如钛硅沸石。当所述烯烃是丙烯时,使用TS-1钛硅沸石是尤其有利的。对于大的烯烃,例如环己烯,可优选更大孔的钛或钒沸石,例如具有与β沸石同晶型的结构的沸石。
特别优选的钛沸石包括通常称之为钛硅沸石的一类分子筛,特别是“TS-1”(具有与ZSM-5硅铝酸盐沸石相似的MFI拓扑结构)、“TS-2”(具有与ZSM-11硅铝酸盐沸石相似的MEL拓扑结构)和“TS-3”(如比利时专利号1,001,038中描述的)。具有与β沸石、丝光沸石、ZSM-48、ZSM-12和MCM-41同晶型的骨架结构的含钛分子筛也适合于使用。所述钛沸石优选在晶格骨架上不含除了钛、硅和氧外的其他元素,尽管可以存在微量的硼、铁、铝、钠、钾、铜等。
优选的钛沸石一般具有对应如下经验化学式的组成,xTiO2(1-x)SiO2,其中x在0.0001和0.5000之间。更优选,x的值是0.01-0.125。所述沸石晶格骨架中的Si:Ti的摩尔比有利地是9.5:1-99:1(最优选9.5:1-60:1)。相对富含钛的沸石的使用也是理想的。
本发明的方法中所采用的催化剂混合物也包含负载型催化剂,该负载型催化剂包含钯、铼和载体。所述载体优选为多孔材料。载体是本领域公知的。例如,所述载体可以是无机氧化物、粘土、炭和有机聚合物树脂。优选的无机氧化物包括2、3、4、5、6、13或14族元素的氧化物。特别优选的无机氧化物载体包括氧化硅、氧化铝、氧化硅-氧化铝、氧化钛、氧化锆、铌氧化物、钽氧化物、钼氧化物、钨氧化物、无定形氧化钛-氧化硅、无定形氧化锆-氧化硅、无定形氧化铌-氧化硅等。所述载体可以是沸石,但不是钛或钒沸石。优选的有机聚合物树脂包括聚苯乙烯、苯乙烯-二乙烯基苯共聚物、交联的聚乙烯亚胺和聚苯并咪唑(polybenzimidizole)。合适的载体也包括接枝到无机氧化物载体上的有机聚合物树脂,例如聚乙烯亚胺-氧化硅。优选的载体也包括炭。特别优选的载体包括炭、氧化硅、氧化硅-氧化铝、氧化钛、氧化锆和氧化铌。
优选所述载体具有约1-约700m2/g的表面积,最优选约10-约500m2/g。优选所述载体孔容积是约0.1-约4.0mL/g,更优选约0.5-约3.5mL/g,和最优选约0.8-约3.0mL/g。优选地,所述载体的平均颗粒尺寸是约0.1微米-约0.5英寸,更优选约1微米-约0.25英寸,和最优选约10微米-约1/16英寸。优选的颗粒尺寸取决于所使用的反应器的类型,例如,对于固定床反应,较大的颗粒尺寸是优选的。平均孔直径一般是约10-约1000,优选约20-约500,和最优选约50-约350。
所述负载型催化剂也含有钯和铼。一般地,存在于所述负载型催化剂中的钯的量是0.01-20wt%,优选0.1-10wt%。将钯加入到所述负载型催化剂中的方式不认为是特别关键的。例如,钯化合物(例如溴化四胺合钯)可以通过浸渍、吸附、离子交换、沉淀等负载到所述载体上。
对于在所述负载型催化剂中用作钯源的钯化合物或络合物的选择没有特别的限制。例如合适的化合物包括硝酸盐、硫酸盐、卤化物(例如,氯化物、溴化物)、羧酸盐(例如乙酸盐)和钯的胺络合物。
类似地,不认为钯的氧化态是关键的。在例如钯的情况下,钯可以是从0到+4的任何氧化态或这些氧化态的任何组合。为了获得想要的氧化态或氧化态的组合,在被引入到所述负载型催化剂中之后,所述钯化合物可以被全部或部分预还原。然而,不经任何预还原也能获得满意的催化性能。
用于本发明的方法中的所述负载型催化剂也含有铼。存在于所述负载型催化剂中的铼的一般量是大约0.01-10wt%,优选0.01-2wt%。尽管在所述负载型催化剂中用作铼源的铼化合物的选择不是关键的,合适的化合物包括卤化铼(例如,氯化物、溴化物、碘化物)、高铼酸(HReO4)和高铼酸铵(NH4ReO4)。铼可以在加入钯之前、之时或之后,被加入到所述载体中。任何合适的方法能用于将铼加入到所述负载型催化剂中。就像钯的加入一样,铼可以通过浸渍等负载到所述载体上。初始润湿和沉积-沉淀技术也可以用来加入铼。
在加入钯和铼后,回收所述负载型催化剂。合适的催化剂回收方法包括过滤和洗涤、旋转蒸发等。所述负载型催化剂在用于环氧化之前,一般在高于约50℃的温度下干燥。所述干燥温度优选约50-约200℃。所述负载型催化剂可额外地包含粘结剂等,并可以在用于环氧化前被成型、喷雾干燥、定型或挤出成任何想要的形状。
在负载型催化剂生成后,可以任选地在例如氮气、氦气、真空、氢气、氧气、空气等的气体中热处理所述负载型催化剂。所述热处理温度一般是约50-约500℃,优选约100-约400℃。优选在含氧气体的存在下在约100-400℃下热处理所述负载型催化剂,和任选地在含氢气体的存在下在约100-400℃下还原所述负载型催化剂。
所述钛或钒沸石和所述负载型催化剂可以作为粉末的混合物或作为小球的混合物用在所述环氧化方法中。此外,所述钛或钒沸石和负载型催化剂也可以在用于环氧化之前被共同成丸或挤出。如果共同成丸或挤出,所述催化剂混合物可额外地包含粘结剂等并可以在用于环氧化之前被成型、喷雾干燥、定型或挤出成任何想要的形状。钛或钒沸石:负载型催化剂的重量比不是特别关键的。然而,钛或钒沸石:负载型催化剂的比例优选为0.01-100(钛或钒沸石的克数/负载型催化剂的克数),更优选1-20的比例,最优选5-15的比例。
本发明的方法包括在所述催化剂混合物的存在下使烯烃、氧气和氢气在溶剂中接触。合适的烯烃包括任何具有至少一个C-C双键并且通常为2-60个碳原子的烯烃。优选所述烯烃是2-30个碳原子的无环烯烃;本发明的方法特别适合于环氧化C2-C6烯烃。可以存在多于一个双键,例如在二烯或三烯中。所述烯烃可以是烃(即,仅含有碳和氢原子),或可以含有官能团,例如卤素、羧基、羟基、醚、羰基、氰基或硝基等。本发明的方法尤其用于将丙烯转化为环氧丙烷。
所述环氧化方法也需要氧气和氢气。虽然任何氧源和氢源是合适的,但分子氧和分子氢是优选的。
根据本发明的环氧化在有效获得想要的烯烃环氧化的温度下进行,优选在0-250℃下,更优选20-100℃。氢气与氧气的摩尔比通常在H2:O2 -=1:10-5:1范围内变化,并且特别有利的是在1:5-2:1。氧气与烯烃的摩尔比通常是2:1-1:20,并优选1:1-1:10。在所述环氧化方法中也可使用载气。任何想要的惰性气体可以用作所述载气。那么,烯烃与载气的摩尔比通常为100:1-1:10,并尤其是20:1-1:10。
除了氮气和二氧化碳外,稀有气体例如氦气、氖气和氩气也适合作为所述惰性载气。具有1-8、尤其是1-6以及优选具有1-4个碳原子的饱和烃,例如甲烷、乙烷、丙烷和正丁烷,也是合适的。氮气和饱和的C1-C4烃是优选的惰性载气。也能使用所列的惰性载气的混合物。
特别在丙烯的环氧化中,能以这样的方式提供丙烷,在适当过量的载气的存在下,丙烯、丙烷、氢气和氧气的混合物的爆炸极限被安全避免,并且因此在反应器内或在进料和排放管路中没有爆炸性的混合物能够生成。
所使用的催化剂的量,可以根据含在所述钛沸石中的钛与每单位时间供应的烯烃的摩尔比来确定。一般存在足够的催化剂,以提供0.0001-0.1的钛/烯烃每小时摩尔进料比。
取决于待反应的烯烃,根据本发明的环氧化能够在液相、气相或在超临界相中进行。当使用液体反应介质时,所述催化剂优选是悬浮物或固定床的形式。该方法可以使用连续流、半间歇或间歇的操作模式来进行。
如果环氧化在液(或超临界或亚临界)相中进行,在1-100巴的压力下和在一种或多种溶剂的存在下运行是有利的。合适的溶剂包括在反应条件下是液体的任何化学品,包括但不限于含氧的烃,例如醇、醚、酯和酮、芳烃和脂族烃(例如甲苯和己烷)、液体CO2(在超临界或亚临界状态下)和水。优选的溶剂包括水、液体CO2和含氧的烃,例如醇、醚、酯、酮等。优选的含氧的溶剂包括低级脂族C1-C4醇,例如甲醇、乙醇、异丙醇和叔丁醇或它们的混合物,和水。氟代的醇能使用。特别优选使用所列举的醇与水的混合物。
如果环氧化在液(或超临界)相中进行,使用缓冲剂是有利的。所述缓冲剂一般加入到所述溶剂中以生成缓冲剂溶液。所述缓冲剂溶液被应用于反应,以抑制环氧化过程中二醇或二醇醚的生成。缓冲剂是本领域公知的。
用于本发明的缓冲剂包括任何合适的含氧酸的盐,它在混合物中的性质和比例使得其溶液的pH值可以为3-10,优选4-9,和更优选5-8。合适的含氧酸的盐含有阴离子和阳离子。所述盐的阴离子部分可以包括阴离子,例如磷酸根、硫酸根、碳酸根、碳酸氢根、羧酸根(例如乙酸根、邻苯二甲酸根等)、柠檬酸根、硼酸根、氢氧根、硅酸根、硅铝酸根等。所述盐的阳离子部分可以包括阳离子,例如铵、烷基铵(例如四烷基铵、吡啶鎓等)、碱金属、碱土金属等。阳离子实例包括NH4、NBu4、NMe4、Li、Na、K、Cs、Mg和Ca阳离子。更优选的缓冲剂包括碱金属磷酸盐和磷酸铵缓冲剂。缓冲剂可以优选含有多于一种的合适盐的组合。缓冲剂在溶剂中的浓度通常是约0.0001M-约1M,优选约0.001M-约0.3M。用于本发明的缓冲剂也可以包括加入反应体系的氨气。
下面的实施例仅仅举例说明本发明。本领域技术人员将认识到在本发明的主旨和权利要求的范围内的多种变化。
对比实施例1:Pd/TS-1催化剂的制备
将喷雾干燥的TS-1(15.778磅;20wt%氧化硅粘结剂,2.1wt%Ti,在550℃下煅烧过)加入到50L混合槽中的去离子水(17.89L)中,并在500rpm下用搅拌桨搅拌。使用3%氢氧化铵水溶液将浆料的pH值调节至7.0,然后在搅拌下通过在液面以下注射经1min时间加入硝酸四氨合钯水溶液(0.166磅Pd,稀释成1L)。在加入钯的过程中,浆料的pH值通过加入3%氢氧化铵溶液而维持在7.0。加入钯后,使用氢氧化铵调节pH值至7.5,并且将浆料在30℃下搅拌60min,同时维持pH值在7.4。浆料被过滤和洗涤(使用17L去离子水洗涤三次)。然后固体在真空中在50℃下干燥,直到获得恒重,在300℃下在空气中煅烧1h,然后用氮气中的4%的氢气处理1h。然后该固体在马弗炉中在空气中在400℃下再煅烧8小时(20-110℃,以5℃/min的速度;保持4小时;以2℃/min的速度升至400℃;保持8小时),冷却至室温,然后在400℃下在垂直安装在电子管马弗炉中的石英管中用氮气中的5%的氢气(300sccm)还原8小时(20-110℃,以5℃/min的速度;保持4小时;以2℃/min的速度从110℃升至400℃;保持8小时),并在H2/N2流下冷却。将充满油的鼓泡器安置在出口处以防止空气回流到炉内。生成了对比催化剂1。对比催化剂1含0.1wt%的钯、2.1wt%的钛和44wt%的硅。
对比实施例2:Pd-Re/TS-1的制备
经25分钟将高铼酸溶液(4.8975g溶液,由9.739g去离子水与0.0335g来自Strem的Re=53wt%的高铼酸溶液(99.99%Re-Puratrem)混合而生成)逐滴加入到Pd/TS-1(15.07g,350℃煅烧/还原过,0.1wt%的Pd在喷雾干燥的TS-1上;平均30微米的直径)中,同时搅拌。一旦达到初始润湿点,该催化剂在N2吹扫的烘箱中在60℃下干燥22小时,在60℃下真空干燥4小时,然后在马弗炉中在400℃下空气煅烧8小时(20-110℃,以5℃/min的速度;保持4小时;以2℃/min的速度升至400℃;保持8小时)。然后根据对比实施例1的步骤将该Pd-Re/TS-1在400℃下在垂直安装在电子管马弗炉中的石英管中用氮气中的5%的氢气(300sccm)还原8小时以产生对比催化剂2。元素分析显示有0.1wt%的Pd和0.04wt%的Re。
实施例3:Pd/TiO2和Pd-Re/TiO2催化剂的制备
对比催化剂3A:将(NH3)4Pd(NO3)2水溶液(2.3747g的5.37wt%的Pd溶液)加入到100ml烧杯中并与去离子水(7.41ml)混合。然后经20-30分钟将该Pd溶液逐滴加入到二氧化钛(15.1g喷雾干燥的TiO2,此前煅烧至700℃)中。一旦达到初始润湿点,该湿TiO2在N2吹扫的烘箱中在60℃下干燥22-23小时,在60℃下真空干燥4小时,然后在马弗炉中在400℃下空气煅烧8小时(20-110℃,以5℃/min的速度;保持4小时;以2℃/min的速度升至400℃;保持8小时)。然后根据对比实施例1的步骤将该Pd/TiO2在400℃下在垂直安装在电子管马弗炉中的石英管中用氮气中的5%的氢气还原8小时。对比催化剂3A显示0.85wt%的Pd。
催化剂3B:将高铼酸铵溶液(0.0918g NH4ReO4,在4.904g去离子水中)逐滴加入到在100ml烧杯中的对比催化剂3A(Pd/TiO2;7.5g)中,直到达到润湿点。该Pd-Re/TiO2在N2吹扫的烘箱中在60℃下干燥22小时,在60℃下真空干燥4小时,在110-120℃下空气煅烧4小时,然后根据对比例1中的步骤在400℃下在垂直安装在电子管马弗炉中的石英管中用氮气中的5%的氢气还原8小时。然后该材料再次在马弗炉中在400℃下煅烧8小时(20-110℃,以5℃/min升温;保持4小时;以2℃/min的速度升至400℃;保持8小时),并再次根据对比实施例1中的步骤在400℃下在垂直安装在电子管马弗炉中的石英管中用氮气中的5%的氢气还原8小时以产生催化剂3B。元素分析显示有0.85wt%的Pd和0.5wt%的Re。BET表面积为44m2/g。
实施例4:环氧化反应
将催化剂(催化剂的量示于表1)、甲醇(约100g)和13g缓冲剂(0.1M磷酸铵水溶液,pH=6)充入300ml不锈钢反应器中。该反应器然后用由2%氢气、4%氧气、5%丙烯、0.5%甲烷及其余为氮气(体积%)组成的进料增压至300psig。通过背压调节器,用以1600ml/min(在23℃和一个大气压下测量)的速率连续通过该反应器的进料气体,将反应器内的压力维持在300psig。为了维持实验过程中反应器内恒定的溶剂液位,氧气、氮气和丙烯进料经过在反应器前的含有1.5L甲醇的2L不锈钢容器(饱和器)。反应器在1500rpm下搅拌。反应混合物被加热到60℃,并且每小时通过在线GC分析气体流出物,并在18h的实验结束时通过离线GC分析液体。除了由丙烯加氢而生成的丙烷以外,在反应过程中还产生环氧丙烷和等价物(“POE”),它包括环氧丙烷(“PO”)、丙二醇(“PG”)和丙二醇甲基醚(PM)。
环氧化结果(见表2)显示,与Pd/TS-1、Pd-Re/TS-1或TS-1和Pd/TiO2混合催化剂相比,TS-1和Pd-Re/TiO2混合催化剂在催化剂活性和由减少的丙烷生成而产生的丙烯选择性方面显示了显著的增加。
表1:用于环氧化实验的催化剂量
实验 | 催化剂 | 加入的催化剂量(g) | 加入的TS-1(g) |
4A* | 1 | 0.7 | - |
4B* | 2 | 0.7 | - |
4C* | 3A | 0.07 | 0.63 |
4D | 3B | 0.07 | 0.63 |
表2:环氧化结果
实验 | 催化剂生产能力1 | PO/POE选择性(%)2 | 丙烯选择性(%)3 |
4A* | 0.38 | 91 | 73 |
4B* | 0.33 | 92 | 78 |
4C* | 0.34 | 91 | 84 |
4D | 0.4 | 90 | 88 |
1生产能力=产生的POE的克数/催化剂的克数每小时
2PO/POE选择性=PO的摩尔数/(PO的摩尔数+丙二醇的摩尔数)*100
3丙烯选择性=100-(丙烷的摩尔数/POE的摩尔数+丙烷的摩尔数)*100
*对比实施例
Claims (17)
1.用于生产环氧化物的方法,包括在钛或钒沸石和负载型催化剂存在下使烯烃、氢气和氧气反应,所述负载型催化剂包含钯、铼和载体。
2.权利要求1的方法,其中所述钛沸石是钛硅沸石。
3.权利要求2的方法,其中所述钛沸石是TS-1。
4.权利要求1的方法,其中所述负载型催化剂包含0.01-10wt%的钯。
5.权利要求1的方法,其中所述载体选自由炭、氧化钛、氧化锆、氧化铌、氧化硅、氧化铝、氧化硅-氧化铝、钽氧化物、钼氧化物、钨氧化物、氧化钛-氧化硅、氧化锆-氧化硅、氧化铌-氧化硅及它们的混合物组成的组。
6.权利要求1的方法,其中所述反应在溶剂的存在下进行。
7.权利要求6的方法,其中所述溶剂是含氧的溶剂。
8.权利要求7的方法,其中所述含氧的溶剂选自由醇、醚、酯、酮、水及它们的混合物组成的组。
9.权利要求1的方法,其中所述烯烃是C2-C6烯烃。
10.权利要求9的方法,其中所述烯烃是丙烯。
11.权利要求6的方法,其中所述反应在缓冲剂的存在下进行。
12.用于生产环氧丙烷的方法,包括在钛硅沸石和负载型催化剂的存在下在含氧的溶剂中使丙烯、氢气和氧气反应,所述负载型催化剂包含钯、铼和载体。
13.权利要求12的方法,其中所述钛硅沸石是TS-1。
14.权利要求12的方法,其中所述负载型催化剂包含0.01-10wt%的钯。
15.权利要求12的方法,其中所述载体选自由炭、氧化钛、氧化锆、氧化铌、氧化硅、氧化铝、氧化硅-氧化铝、钽氧化物、钼氧化物、钨氧化物、氧化钛-氧化硅、氧化锌-氧化硅、氧化铌-氧化硅及它们的混合物组成的组。
16.权利要求12的方法,其中所述含氧的溶剂选自由醇、醚、酯、酮、水及它们的混合物组成的组。
17.权利要求12的方法,其中所述反应在缓冲剂的存在下进行。
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DE3780476T2 (de) * | 1986-01-28 | 1992-12-17 | Enichem Sintesi | Verfahren zur epoxydation von olefinischen verbindungen. |
IT1216500B (it) | 1988-03-23 | 1990-03-08 | Eniricerche S P A Milano Enich | Procedimento per la preparazione di materiali sintetici cristallini porosi costituiti da ossidi di silicio e titanio. |
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ES2156391T3 (es) | 1996-07-01 | 2001-06-16 | Dow Chemical Co | Proceso para la oxidacion directa de olefinas a oxidos de olefinas. |
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US6008388A (en) * | 1998-04-16 | 1999-12-28 | Arco Chemical Technology, L.P. | Epoxidation process |
US6399794B1 (en) * | 2001-11-15 | 2002-06-04 | Arco Chemical Technology, L.P. | Direct epoxidation process using carbonate modifiers |
JP4352771B2 (ja) | 2003-06-11 | 2009-10-28 | 株式会社ジェイ・エム・エス | カプラー連結具と該カプラー連結具を装着したカプラー |
US20050171365A1 (en) | 2004-02-03 | 2005-08-04 | Grey Roger A. | Epoxidation process using a mixed catalyst system |
-
2006
- 2006-07-12 US US11/484,906 patent/US7671222B2/en not_active Expired - Fee Related
-
2007
- 2007-06-28 WO PCT/US2007/015057 patent/WO2008008195A2/en active Application Filing
- 2007-06-28 CN CNA2007800259368A patent/CN101501012A/zh active Pending
- 2007-06-28 KR KR1020087031157A patent/KR20090028719A/ko not_active Application Discontinuation
- 2007-06-28 JP JP2009519449A patent/JP2009542808A/ja not_active Withdrawn
- 2007-06-28 EP EP07796558A patent/EP2038270A2/en not_active Withdrawn
- 2007-06-28 CA CA002655848A patent/CA2655848A1/en not_active Abandoned
- 2007-06-28 BR BRPI0714180-7A patent/BRPI0714180A2/pt not_active IP Right Cessation
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102558100A (zh) * | 2012-01-20 | 2012-07-11 | 中国天辰工程有限公司 | 以钛硅分子筛为催化剂催化丙烯环氧化反应的方法 |
Also Published As
Publication number | Publication date |
---|---|
US7671222B2 (en) | 2010-03-02 |
KR20090028719A (ko) | 2009-03-19 |
CA2655848A1 (en) | 2008-01-17 |
WO2008008195A2 (en) | 2008-01-17 |
WO2008008195A3 (en) | 2008-05-15 |
BRPI0714180A2 (pt) | 2012-12-25 |
EP2038270A2 (en) | 2009-03-25 |
US20080015372A1 (en) | 2008-01-17 |
JP2009542808A (ja) | 2009-12-03 |
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