CN102239154B - 使用改进的催化剂的直接环氧化方法 - Google Patents
使用改进的催化剂的直接环氧化方法 Download PDFInfo
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- CN102239154B CN102239154B CN200980148075.1A CN200980148075A CN102239154B CN 102239154 B CN102239154 B CN 102239154B CN 200980148075 A CN200980148075 A CN 200980148075A CN 102239154 B CN102239154 B CN 102239154B
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- Prior art keywords
- catalyst
- zeolite
- carrier
- mixture
- titanium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000006735 epoxidation reaction Methods 0.000 title abstract description 24
- 239000010457 zeolite Substances 0.000 claims abstract description 41
- 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
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 239000010936 titanium Substances 0.000 claims abstract description 29
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 16
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002118 epoxides Chemical class 0.000 claims abstract 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 30
- 229910052763 palladium Inorganic materials 0.000 claims description 25
- 239000010970 precious metal Substances 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- 239000004408 titanium dioxide Substances 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229960001866 silicon dioxide Drugs 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 6
- 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 6
- 150000002825 nitriles Chemical class 0.000 claims description 5
- 229910004339 Ti-Si Inorganic materials 0.000 claims description 4
- 229910010978 Ti—Si Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 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 4
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 abstract description 23
- 239000006227 byproduct Substances 0.000 abstract description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 22
- 239000011133 lead Substances 0.000 description 20
- -1 alkyl hydroperoxide Chemical compound 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 11
- 239000001294 propane Substances 0.000 description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000012159 carrier gas Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 150000002611 lead compounds Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 150000002924 oxiranes Chemical class 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 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
- 238000007865 diluting Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 239000002808 molecular sieve Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
- GQNOPVSQPBUJKQ-UHFFFAOYSA-N 1-hydroperoxyethylbenzene Chemical compound OOC(C)C1=CC=CC=C1 GQNOPVSQPBUJKQ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
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- 239000007791 liquid phase Substances 0.000 description 1
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Abstract
公开了用于烯烃直接环氧化的负载型催化剂和催化剂混合物。所述负载型催化剂包含贵金属、铅和载体,所述载体通过与硝酸接触已进行处理。所述催化剂混合物包含钛沸石或钒沸石与所述负载型催化剂。本发明还包括用于生产环氧化物的方法,该方法包括在所述催化剂混合物存在下使烯烃、氢气和氧气反应。该方法产生显著降低的由烯烃氢化形成的烷烃副产物。
Description
发明领域
本发明涉及负载型催化剂、催化剂混合物及其在由氢气、氧气和烯烃生产环氧化物中的用途。
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。通常,在催化剂存在下通过烯烃与氧化剂的反应形成环氧化物。商业上通过乙烯与氧气在银催化剂上的反应生产环氧乙烷。商业上通过丙烯与有机氢过氧化物氧化剂例如乙苯过氧化氢或叔丁基过氧化氢反应来生产环氧丙烷。该方法在溶解的钼催化剂存在下(参见美国专利No.3,351,635)或在于二氧化硅上的非均相二氧化钛催化剂存在下(参见美国专利No.4,367,342)进行。
除了氧气和烷基氢过氧化物之外,对于环氧化物的形成,过氧化氢也是有用的氧化剂。例如美国专利No.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的烯烃环氧化。
大量当前研究在烯烃与氧气和氢气的直接环氧化中进行。在该方法中,据信氧气和氢气原位反应以形成氧化剂。已经提出许多不同的催化剂用于该直接环氧化方法中。典型地,催化剂包含贵金属和钛硅酸盐。例如JP 4-352771公开了使用含有VIII族金属(例如在晶体钛硅酸盐上的钯)的催化剂由丙烯、氧气和氢气形成环氧丙烷。认为所述VIII族金属促进氧气和氢气的反应以原位形成过氧化氢氧化剂。美国专利No.6,498,259描述了钛沸石和负载的钯络合物的催化剂混合物,其中将钯负载在碳、二氧化硅、二氧化硅-氧化铝、二氧化钛、氧化锆和氧化铌上。其它直接环氧化催化剂的实例包括在钛硅酸盐上负载的金,参见例如PCT国际申请WO 98/00413。
所描述的直接环氧化催化剂的一个缺点是,它们倾向于产生非选择性的副产物,例如通过环氧化物产物的开环形成的二醇或二醇醚或通过烯烃氢化形成的烷烃副产物。美国专利No.6,008,388教导了通过向反应混合物中加入氮化合物,例如氢氧化铵来提高直接烯烃环氧化方法的选择性。美国专利No.6,399,794教导了使用碳酸氢铵改性剂以降低开环副产物的产生。
美国专利No.6,005,123教导了使用磷、硫、硒或砷改性剂例如三苯基膦或苯并噻吩以降低丙烷的产生。美国专利No.7,026,492公开了一氧化碳、甲基乙炔和/或丙二烯改性剂的存在显著减少了烷烃副产物。美国申请公开No.2008/0021230公开了使用铅改性的含钯的钛沸石或钒沸石降低烷烃副产物形成。另外,共同待决的美国专利申请序列No.11/977,360教导了使用包含钛沸石或钒沸石、贵金属、铅和铋的催化剂也降低烷烃副产物形成。
与任何化学方法一样,期望仍在环氧化方法和催化剂方面获得进一步改进。我们已经发现了一种新的催化剂及其在烯烃环氧化中的用途。
发明概述
本发明为包含贵金属、铅和载体的负载型催化剂,所述载体通过与硝酸接触进行了处理。本发明还包括含有钛沸石或钒沸石与所述负载型催化剂的催化剂混合物。该催化剂混合物可用于烯烃环氧化中。因此,本发明还包括烯烃环氧化方法,该方法包括在所述催化剂混合物存在下使烯烃、氧气和氢气进行反应。该方法出人意料地显著降低由烯烃氢化形成的烷烃副产物。
发明详述
本发明的负载型催化剂包含贵金属、铅和载体。所述载体优选是无机多孔材料,特别是无机氧化物和粘土。所述载体最优选是无机氧化物。优选的无机氧化物包括2、3、4、5或14族元素的氧化物。特别优选的无机氧化物载体包括二氧化硅、二氧化钛、氧化锆、氧化铌、氧化钽、无定形二氧化钛-二氧化硅、无定形氧化锆-二氧化硅、无定形氧化铌-二氧化硅等。该载体可以是沸石,但不是钛沸石或钒沸石。特别优选的无机氧化物包括二氧化硅、二氧化钛、氧化锆和氧化铌。最优选二氧化钛。
优选地,所述载体具有约1-约1000m2/g,最优选约10-约500m2/g的表面积。优选地,所述载体的孔体积为约0.1-约4.0mL/g,更优选约0.5-约3.5mL/g,最优选约0.8-约3.0mL/g。优选地,所述载体的平均粒径为约0.1微米-约1.4cm,更优选约1微米-约0.7cm,最优选约10微米-约0.2cm。优选的粒径取决于所用反应器的类型,例如较大的粒径优选用于固定床反应。平均孔径典型地为约10-约优选约20-约最优选约50-约
负载型催化剂还含有贵金属和铅。虽然可以单独或组合使用任意贵金属(即金、银、铂、钯、铱、钌、锇),但特别期望使用钯、铂、金、钯/铂或钯/金组合。最优选钯。
典型地,存在于负载催化剂中的贵金属的量可为0.01-20重量%,优选0.1-10重量%。其中将贵金属引入到负载型催化剂中的方式并不认为特别关键。例如,可以通过浸渍、吸附、离子交换或沉淀等将贵金属化合物(例如二硝酸钯)负载到载体上。
关于对用于负载催化剂中贵金属来源的贵金属化合物或络合物的选择没有特别的限制。例如,合适的化合物包括贵金属的硝酸盐、硫酸盐、卤化物(例如氯化物、溴化物)、羧酸盐(例如乙酸盐)和胺络合物。
类似地,贵金属的氧化态认为并非关键。在例如钯的情形中,钯可以处于0至+4的任意氧化态或者这些氧化态的任意组合。为了获得期望的氧化态或氧化态组合,可以在将贵金属化合物在引入到负载型催化剂中之后进行全部或部分预还原。然而,在不进行任何预还原的情况下能够获得令人满意的催化性能。
本发明的负载型催化剂还含有铅。存在于负载型催化剂中的铅的典型的量可为约0.01-10重量%,优选0.01-2重量%。用作负载型催化剂中铅源的合适的铅化合物包括铅的硝酸盐、羧酸盐(例如乙酸盐)、卤化物(例如氯化物、溴化物、碘化物)、氰化物和硫化物。特别优选铅的硝酸盐和羧酸盐。最优选硝酸铅。可以将铅在贵金属加入之前、期间或之后加入到载体中。可使用任何适合的方法将铅引入到负载型催化剂中。与贵金属加入一样,可以通过浸渍(例如通过初湿法等)、吸附、离子交换、沉积-沉淀或其它引入方法将铅负载在载体上。
将载体通过与硝酸接触进行处理。硝酸优选是含有1-70重量%的硝酸水溶液。可按间歇或连续方式,优选按间歇方式进行接触。接触温度并非关键,但优选15-60℃的温度。接触所需的时间量并非关键,但可典型地为约0.1-24小时。
可以按各种方法使载体与硝酸接触,这些方法包括但不限于以下手段。硝酸处理可以在以下时机进行:(1)在加入贵金属化合物和铅化合物之前;(2)在加入铅化合物之前或之后,与贵金属化合物的加入同时;(3)在加入贵金属化合物之前或之后,与铅化合物的加入同时;(4)与贵金属化合物和铅化合物的加入同时;以及(5)在加入贵金属化合物和铅化合物之后。
在硝酸处理、贵金属和铅引入之后,回收负载型催化剂。合适的催化剂回收方法包括过滤并洗涤、旋转蒸发等。该负载型催化剂在用于环氧化之前优选在大于约50℃的温度下干燥。干燥温度优选为约50℃-约700℃,更优选约250℃-约450℃。该负载型催化剂可以任选在气体例如氮气、氦气、真空、氢气、氧气或空气等中进行热处理。热处理温度典型地为约50℃-约700℃。优选在含氧气体存在下于约400℃-约650℃的温度下将该负载型催化剂进行热处理,并任选在含氢气体存在下于约50℃-约300℃的温度下将该负载型催化剂进行还原。
该负载型催化剂可以另外包含粘合剂等并且可以在用于环氧化之前进行模制、喷雾干燥、成型或挤出而成为任意所需的形式。
本发明的催化剂混合物包含负载型催化剂与钛沸石或钒沸石。钛沸石或钒沸石包含其中钛或钒原子取代分子筛晶格骨架中的部分硅原子的沸石类物质。这类物质及它们的制备在本领域中是公知的。参见例如美国专利No.4,410,501和4,666,692。
合适的钛沸石或钒沸石是具有骨架中用钛或钒原子取代的多孔分子筛结构的那些结晶材料。所使用的钛沸石或钒沸石的选择将取决于许多因素,包括待环氧化的烯烃的大小和形状。
特别优选的钛或钒沸石包括一般称作钛硅沸石的分子筛,特别是“TS-1”(具有类似于ZSM-5铝硅酸盐沸石的MFI拓扑结构),“TS-2”(具有类似于ZSM-11铝硅酸盐沸石的MEL拓扑结构),“TS-3”(如比利时专利No.1,001,038中所述),和Ti-MWW(具有类似于MWW铝硅酸盐沸石的拓扑结构)。骨架结构与沸石β、丝光沸石、ZSM-48、ZSM-12、SBA-15、TUD、HMS和MCM-41同晶型的含钛分子筛也适合使用。特别优选TS-1和Ti-MWW。钛沸石优选在晶格骨架中不含除钛、硅和氧外的元素,尽管可以存在较少量的硼、铁、铝、钠,钾和铜等。
优选的钛沸石可通常具有相应于以下经验式xTiO2(1-x)SiO2的组合物,其中x为0.0001-0.5000。更优选地,x值为0.01-0.125。该沸石晶格骨架中的Si∶Ti摩尔比有利地为9.5∶1-99∶1(最优选9.5∶1-60∶1)。还可以期望使用相对富含钛的沸石。
本发明的环氧化方法包括在包含钛沸石或钒沸石与负载型催化剂的催化剂混合物存在下使烯烃、氧气和氢气接触,所述负载型催化剂包含贵金属、铅和通过与硝酸接触已进行处理的载体。合适的烯烃包括具有至少一个碳-碳双键且通常为2-60个碳原子的任意烯烃。优选地,烯烃为2-30个碳原子的无环烯烃;本发明的方法特别适合于使C2-C6烯烃环氧化。可以存在多于一个的双键,例如在二烯或三烯中。所述烯烃可以为烃(即仅含有碳原子和氢原子)或者可以含有官能团例如卤素(halide)、羧基、羟基、醚、羰基、氰基或硝基等。本发明的方法特别适用于使丙烯转化为环氧丙烷。
环氧化方法还需要氧气和氢气。尽管氧气和氢气的任何来源都合适,但是优选分子氧和分子氢。
根据本发明的环氧化在有效实现期望的烯烃环氧化的温度下,优选在0-250℃,更优选在20-100℃的温度下进行。氢气与氧气的摩尔比优选为H2∶O2=1∶10-5∶1,特别有利地是在1∶5-2∶1。氧气与烯烃的摩尔比优选为2∶1-1∶20,更优选1∶1-1∶10。在环氧化方法中还可以使用载气。可使用任何期望的惰性气体作为载气。烯烃与载气的摩尔比则优选为100∶1-1∶10,特别地为20∶1~1∶10。
作为载气,除了氮气和二氧化碳外,惰性气体例如氦气、氖气和氩气也是适合的。具有1-8、特别是1-6、优选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。还可使用所列出的载气的混合物。
具体地,在丙烯环氧化中,以在适当过量的载气存在下可安全避免丙烯、丙烷(甲烷)、氢气和氧气的混合物的爆炸极限并因此在反应器或者在进料和出料管线中不会形成爆炸混合物的方式供应丙烯、丙烷或甲烷。
取决于待反应的烯烃,可在液相、气相或超临界相中进行根据本发明的环氧化。当使用液体反应介质时,催化剂混合物优选为悬浮物或固定床的形式。可以使用连续流、半间歇或间歇操作模式实施本方法。
如果在液(或超临界或亚临界)相中进行环氧化,则有利地是在1-100巴的压力下并且在一种或多种溶剂存在下进行操作。合适的溶剂包括在反应条件下为液体的任何化学品,包括但不限于含氧烃例如醇、醚、酯和酮,芳族烃和脂族烃例如甲苯和己烷,腈例如乙腈,液体CO2(处于超临界或亚临界状态),以及水。优选的溶剂包括液体CO2、腈、醇、酮和它们的混合物,以及这些溶剂与水的混合物。优选的腈包括乙腈和其它具有适当水溶性的腈。优选的醇包括低级脂族C1-C4醇例如甲醇、乙醇、异丙醇和叔丁醇、或它们的混合物。可使用氟化的醇。特别优选使用所列举的醇与水的混合物。
如果在液(或超临界或亚临界)相中进行环氧化,则使用缓冲剂是有利的。可典型地将缓冲剂加入到溶剂中以形成缓冲溶液。在反应中使用缓冲溶液以在环氧化期间抑制二醇或二醇醚的形成。缓冲剂是本领域中公知的。
用于本发明的缓冲剂包括任何合适的含氧酸的盐,其性质和在混合物中的比例使得它们的溶液的pH可以为3-10,优选4-9,更优选5-7。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例如磷酸根、磷酸一氢根、磷酸二氢根、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、硅酸根或铝硅酸根等的阴离子。所述盐的阳离子部分可以包括例如铵、烷基铵(例如四烷基铵、吡啶鎓等)、碱金属或碱土金属等的阳离子。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的盐的组合。典型地,缓冲剂在溶剂中的浓度为约0.0001M-约1M,优选约0.001M-约0.3M。用于本发明的缓冲剂还可以包括向反应体系中加入氨气。
以下实施例仅说明本发明。本领域技术人员将认识到在本发明的精神和权利要求范围内的许多变化。
实施例1:Pd-Pb/TiO2催化剂的制备
催化剂1A:硝酸与Pd和Pb一起加入到TiO2
将硝酸铅(0.35g)加入到硝酸溶液(5mL的2.56M HNO3(16.6体积%的HNO3),进一步用10g蒸馏水稀释;总的酸溶液=15g)中。在搅拌下向该溶液中加入二硝酸钯的水溶液(1.07g,20.64wt.%Pd)。然后通过初湿法将Pd-Pb硝酸溶液加入到经喷雾干燥的二氧化钛(20g,30微米大小,40m2/g,在空气中于700℃下煅烧过)中。将该固体在马弗炉内于空气中通过在110℃下加热4小时(以10℃/min的速度升温之后)并然后在300℃下加热4小时(以2℃/min的速度升温之后)进行煅烧。再次将该固体在马弗炉中通过在110℃下加热4小时(以10℃/min的速度升温之后)并然后在600℃下加热4小时(以2℃/min的速度升温之后)进行煅烧。然后将该固体转移到石英管中并在100℃下用氮气流中4体积%的氢气处理1小时(100cc/h),接着用氮气处理30分钟并同时从100℃冷却至30℃以产生催化剂1A。催化剂1A含有0.93wt.%Pd、0.9wt.%Pb和57wt.%Ti。
催化剂1B:在Pd和Pb加入之前将硝酸加入到TiO2
通过初湿法将硝酸水溶液(60mL的2.56M HNO3水溶液,16.6体积%HNO3)加入到经喷雾干燥的二氧化钛(75g,30微米大小,40m2/g,在空气中于700℃下煅烧过)中。将硝酸处理的二氧化钛通过在马弗炉内于110℃下加热4小时(以10℃/min的速度升温之后)并然后于300℃下加热4小时(以2℃/min的速度升温之后)进行煅烧。将硝酸铅(0.17g)加入到去离子水(8g)中以形成硝酸铅溶液,并在搅拌下将二硝酸钯的水溶液(0.53g,20.64wt.%Pd)加入到该硝酸铅溶液中。然后通过初湿法将Pd-Pb溶液加入到硝酸处理的经喷雾干燥的二氧化钛(10g)。然后按照催化剂1A的程序煅烧和还原所述固体以产生催化剂1B。催化剂1B含有0.95wt.%的Pd、0.9wt.%的Pb和57wt.%的Ti。
对比催化剂1C:无硝酸
将硝酸铅(0.35g)加入到14.5mL的去离子水(14.5mL)中以形成硝酸铅溶液,并在搅拌下加入二硝酸钯水溶液(1.07g,20.64wt.%Pd)。然后通过初湿法将Pd-Pb溶液加入到经喷雾干燥的二氧化钛(20g,30微米大小,40m2/g,在空气中于700℃下煅烧过)中。然后按照催化剂1A的程序煅烧和还原所述固体以产生对比催化剂1C。对比催化剂1C含有0.9wt.%Pd、0.9wt.%Pb和58wt.%Ti。
实施例2:Pd/TiO2催化剂的制备
对比催化剂2:硝酸与Pd一起加入到TiO2
在搅拌下将二硝酸钯的水溶液(2.13g,20.64wt.%Pd)加入到硝酸的水溶液(10mL的2.5M HNO3,进一步用19mL蒸馏水稀释)中。然后通过初湿法将Pd、硝酸溶液加入到经喷雾干燥的二氧化钛(40g,30微米大小,40m2/g,在空气中于700℃下煅烧过)中。然后按照催化剂1A的程序煅烧和还原所述固体以产生对比催化剂2。对比催化剂2含有0.9wt.%的Pd和57wt.%的Ti。
实施例3:环氧化反应
向300cc的不锈钢反应器中装入负载型贵金属催化剂(0.07g的1A、1B、1C或2)、TS-1粉末(0.63g)、甲醇(约100g)和缓冲溶液(13g的0.1M磷酸铵水溶液,pH=6)。然后,用4%氢气、4%氧气、5%丙烯、0.5%甲烷和余量氮气(体积%)所构成的进料将反应器充压至300psig。通过背压调节器使该反应器内的压力维持在300psig,并同时进料气体以1600cc/分钟(在23℃和一个大气压下测得)连续通过反应器。为了在运行期间使反应器内的溶剂水平维持恒定,将氧气、氮气和丙烯进料通过在反应器之前的含有1.5L甲醇的两升不锈钢容器(饱和器)。以1500rpm的速度搅拌该反应器。将反应混合物加热至60℃,并通过在线GC对气体流出物每小时进行分析并且在运行18小时结束时通过离线GC对液体进行分析。除了由丙烯氢化产生的丙烷外,在反应期间还产生环氧丙烷和等价物(“POE”),所述等价物包括环氧丙烷(“PO”)、丙二醇(“PG”)和丙二醇甲基醚(PMs)。
环氧化的结果(参见表1)显示,与TS-1和没有HNO3用处理的Pd-Pb/TiO2的混合物相比,TS-1和Pd-Pb/TiO2混合催化剂当TiO2用HNO3处理时显示出显著降低的丙烷生成率(make)。此外,HNO3处理的Pd/TiO2(没有铅)产生非常高的丙烷量。
表1:环氧化结果
催化剂 | 催化剂生产率1 | 丙烷生成率(%)2 |
1A | 0.65 | 6 |
1B | 0.59 | 4 |
1C* | 0.7 | 12 |
2* | 0.7 | 26 |
1生产率=产生的POE的克数/催化剂的克数/小时。
2丙烷生成率=丙烷的摩尔数/(POE的摩尔数+丙烷的摩尔数)×100。
*对比例
Claims (12)
1.一种用于生产环氧化物的方法,该方法包括在钛沸石或钒沸石与包含钯、铅和载体的负载型催化剂存在下使C2-C6烯烃、氢气和氧气反应,所述载体通过与硝酸接触已进行处理。
2.权利要求1的方法,其中所述钛沸石或钒沸石是钛硅沸石。
3.权利要求1的方法,其中所述反应在选自醇、酮、腈、水、液体CO2和它们的混合物的溶剂存在下进行。
4.权利要求1的方法,其中所述载体选自二氧化钛、氧化锆、氧化铌、二氧化硅、氧化钽、二氧化钛-二氧化硅、氧化锆-二氧化硅、氧化铌-二氧化硅和它们的混合物。
5.一种负载型催化剂,该负载型催化剂包含钯、铅和载体,所述载体通过与硝酸接触已进行处理。
6.权利要求5的负载型催化剂,其中所述载体选自二氧化钛、氧化锆、氧化铌、二氧化硅、氧化钽、二氧化钛-二氧化硅、氧化锆-二氧化硅、氧化铌-二氧化硅和它们的混合物。
7.权利要求6的负载型催化剂,其中所述载体是二氧化钛。
8.权利要求7的负载型催化剂,其中在引入贵金属和铅之前使所述二氧化钛与硝酸接触。
9.一种催化剂混合物,该催化剂混合物包含钛沸石或钒沸石和负载型催化剂,所述负载型催化剂包含钯、铅和载体,所述载体通过与硝酸接触已进行处理。
10.权利要求9的催化剂混合物,其中所述钛沸石是钛硅沸石。
11.权利要求10的催化剂混合物,其中所述钛硅沸石是TS-1或Ti-MWW。
12.权利要求9的催化剂混合物,其中所述载体选自二氧化钛、氧化锆、氧化铌、二氧化硅、氧化钽、二氧化钛-二氧化硅、氧化锆-二氧化硅、氧化铌-二氧化硅和它们的混合物。
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2009
- 2009-11-13 KR KR1020117013975A patent/KR101663333B1/ko active IP Right Grant
- 2009-11-13 EP EP09756868.7A patent/EP2376466B1/en active Active
- 2009-11-13 ES ES09756868.7T patent/ES2483142T3/es active Active
- 2009-11-13 WO PCT/US2009/006104 patent/WO2010080090A1/en active Application Filing
- 2009-11-13 CN CN200980148075.1A patent/CN102239154B/zh active Active
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Also Published As
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WO2010080090A1 (en) | 2010-07-15 |
US7767835B2 (en) | 2010-08-03 |
US20100160654A1 (en) | 2010-06-24 |
BRPI0922343A2 (pt) | 2015-08-11 |
ES2483142T3 (es) | 2014-08-05 |
EP2376466B1 (en) | 2014-05-21 |
CN102239154A (zh) | 2011-11-09 |
KR20110101160A (ko) | 2011-09-15 |
KR101663333B1 (ko) | 2016-10-06 |
EP2376466A1 (en) | 2011-10-19 |
BRPI0922343B1 (pt) | 2017-12-05 |
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