CN102281947A - 具有高可及性指数的层状球形催化剂 - Google Patents
具有高可及性指数的层状球形催化剂 Download PDFInfo
- Publication number
- CN102281947A CN102281947A CN2009801544912A CN200980154491A CN102281947A CN 102281947 A CN102281947 A CN 102281947A CN 2009801544912 A CN2009801544912 A CN 2009801544912A CN 200980154491 A CN200980154491 A CN 200980154491A CN 102281947 A CN102281947 A CN 102281947A
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- CN
- China
- Prior art keywords
- catalyst
- metal
- skin
- aluminium oxide
- alumina
- 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.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 229910052751 metal Inorganic materials 0.000 claims abstract description 53
- 239000002184 metal Substances 0.000 claims abstract description 53
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 32
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 70
- 239000000463 material Substances 0.000 claims description 40
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 17
- 230000000694 effects Effects 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- -1 spinelle Chemical compound 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- INJRKJPEYSAMPD-UHFFFAOYSA-N aluminum;silicic acid;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O INJRKJPEYSAMPD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052878 cordierite Inorganic materials 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052839 forsterite Inorganic materials 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- 229910052850 kyanite Inorganic materials 0.000 claims description 2
- 239000010443 kyanite Substances 0.000 claims description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229910052863 mullite Inorganic materials 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 229910052609 olivine Inorganic materials 0.000 claims description 2
- 239000010450 olivine Substances 0.000 claims description 2
- 229910000275 saponite Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 26
- 239000005977 Ethylene Substances 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 10
- 239000011149 active material Substances 0.000 abstract 1
- 239000011162 core material Substances 0.000 description 20
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000011800 void material Substances 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
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- 238000005336 cracking Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 235000013847 iso-butane Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000013528 metallic particle Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- VWWMOACCGFHMEV-UHFFFAOYSA-N dicarbide(2-) Chemical compound [C-]#[C-] VWWMOACCGFHMEV-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
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Abstract
提供一种用于将乙炔选择性加氢成乙烯的方法和催化剂。催化剂包含层状结构,其中催化剂具有内芯和具有活性材料的外层。催化剂还包括沉积在外层上的金属,且形成催化剂使得催化剂具有3-500的可及性指数。
Description
发明领域
本发明涉及层状催化剂组合物,制备该组合物的方法和使用该组合物的烃转化方法。层状组合物包含内芯和结合在内芯上且包含无机氧化物的外层。
发明背景
钯基催化剂用于大量烃转化方法中。在许多应用中,还使用促进剂和改性剂。一种这种烃转化方法为烃,特别是烷烃如异丁烷的脱氢,将异丁烷转化成异丁烯。例如US 3,878,131(和相关的US 3,632,503和US 3,755,481)公开了一种包含铂金属、氧化锡组分和氧化锗组分的催化剂。所有组分均匀地分散在整个氧化铝载体上。US 3,761,531(和相关的US 3,682,838)公开了包含都分散在氧化铝载体材料上的铂族组分,族IVA金属组分如锗,族VA金属组分如砷、锑和碱或碱土组分的催化复合材料。所有组分也均匀地分布在载体上。
US 3,558,477、US 3,562,147、US 3,584,060和US 3,649,566都公开了包含在耐熔氧化物载体上的铂族组分和铼组分的催化复合材料。然而,如前,这些参考文献公开了当铂族组分和铼组分均匀分布在整个催化剂上时实现的最好结果。
已知对所需产物的某些方法选择性受到进料或产物在催化剂活性部位的过多停留时间抑制。因此,US 4,716,143描述了一种催化剂,其中铂族金属沉积在载体外层(400μm)中。没有参考文献给出改性剂金属在整个载体上应如何分布。类似地,US 4,786,625公开了一种催化剂,其中铂沉积在载体的表面上,而改性剂金属均匀地分布在整个载体上。
US 3,897,368描述了一种生产贵金属催化剂的方法,其中贵金属为铂,铂选择性地沉积在催化剂的外表面上。然而,该公开内容描述了仅将铂浸渍在外层上的优点和使用具体类型的表面活性剂实现贵金属的表面浸渍。
本领域还公开了几个参考文献,其中催化剂含有内芯和外层或壳。例如US 3,145,183公开了具有不透性中心和多孔壳的球。尽管它公开了不透性中心可以为小的,但总直径为1/8″或更大。据说对于更小直径的球(小于1/8″),均匀性难以控制。US 5,516,740公开了结合在催化惰性材料内芯上的薄催化材料外壳。外壳可具有沉积在它上面的催化金属如铂。′740专利还公开了该催化剂用于异构方法中。最后,在将它涂覆在内芯上以前,外层材料含有催化金属。
US 4,077,912和US 4,255,253公开了具有基础载体的催化剂,其具有沉积在其上的催化金属氧化物或催化金属氧化物和氧化物载体组合的层。WO98/14274公开了一种催化剂,其包含催化惰性芯材料,含活性部位的薄材料壳沉积和结合在其上。
本发明提供关于乙炔化合物选择性加氢的改善的活性和选择性。
发明概述
本发明提供用于将乙炔选择性加氢成乙烯的新催化剂。该方法是提高用于聚合物原料的乙烯料流的纯度。催化剂包含具有由惰性材料构成的内芯的层状催化剂。外层结合在内芯上,其中外层包含金属氧化物。第一催化金属和第二催化金属沉积在外层上,其中第一金属选自IUPAC族8-10金属,且第二金属选自IUPAC族11或族14金属。选择用于层状催化剂的材料并配置在催化剂上,其中催化剂的可及性指数为3-500。
在另一实施方案中,新催化剂还可具有低空隙空间指数。催化剂包含具有由惰性材料构成的内芯的层状催化剂。外层结合在内芯上,其中外层包含金属氧化物。第一催化金属和第二催化金属沉积在外层上,其中第一金属选自IUPAC族8-10金属,且第二金属选自IUPAC族11或族14金属。选择用于层状催化剂的材料并配置在催化剂上,其中催化剂的空隙空间指数为0-1。
本发明的其他目的、优点和应用将由以下详述和图变得为本领域技术人员所了解。
附图简述
图1为催化剂在乙炔加氢中的前端使用的图;和
图2为催化剂在乙炔加氢中的尾端使用的图。
发明详述
乙烯和丙烯、每分子具有2或3个碳原子的轻质烯烃分别为用于生产其它有用材料如聚乙烯和聚丙烯中的重要化学品。聚乙烯和聚丙烯是目前发现的两种最常用塑料,具有作为材料制造和包装材料的宽范围用途。乙烯和丙烯的其它用途包括生产氯乙烯、氧化乙烯、乙苯和醇。烃的蒸汽裂化或热解产生大多数乙烯和一些丙烯。乙烯通过几种方式如烃蒸汽裂化、烃催化裂化,或较大烯烃原料的烯烃裂化生产。然而,用于聚乙烯生产中的乙烯需要为基本纯的。生产乙烯的方法产生具有基本量乙炔的产物料流,所述量可高达乙烯/乙烷料流的2-3体积%。
乙炔选择性加氢改善乙烯产物料流的质量,同时通过使用更具选择性的催化剂实现乙烯量的提高。本发明中的催化剂包含具有使它区别于现有商业催化剂的性能。这些性能可由活性指数确定以选择在该方法中具有良好选择性的催化剂。催化剂将乙炔选择性加氢至小于乙烯产物料流的5ppm的量,优选将乙炔降低至小于1ppm。
催化剂为具有包含惰性材料的内芯的层状催化剂。外层结合在内芯上,其中外层包含金属氧化物。催化剂包括沉积在外层上的选自IUPAC族8-10金属的第一金属和沉积在外层上的选自IUPAC族11或族14金属的第二金属。催化剂还具有3-500的可及性指数(AI),优选可及性指数为3-20,更优选可及性指数为4-20。可及性指数等于外层表面积乘粒径乘100除以以微米表示的层的有效厚度,或cm2/(g),但其中表面积仅来自外层,考虑整个颗粒重量。
沉积在外层上的第一金属优选为铂或钯或其混合物,并以催化剂的100-50,000重量ppm的浓度沉积。优选第一金属以催化剂的200-20,000重量ppm的浓度沉积。
沉积在外层上的第二金属优选为包括铜、银、金、锡、锗和铅在内的一种或多种金属。第二金属以一定量沉积在外层上使得第一金属与第二金属的原子比为0.1-10。
催化剂内芯包含由一种或多种如下材料构成的惰性材料:堇青石、莫来石、橄榄石、氧化锆、尖晶石、蓝晶石、氧化铝、硅石、铝酸盐、硅酸盐、二氧化钛、氮化物、碳化物、硼硅酸盐、氧化硼、硅酸铝、氧化镁、镁橄榄石、高岭土、高岭石、蒙脱石、皂石、膨润土、具有小或低酸活性的粘土、γ-氧化铝、δ-氧化铝、η-氧化铝和θ-氧化铝。内芯的有效直径为0.05-10mm,优选0.8-5mm,更优选0.8-3mm。对于非球形形状,有效直径意指如果将它模制成球,成型颗粒的直径。在优选实施方案中,干燥的成型颗粒在形状上是基本球形的。
外层沉积并结合在内芯上至1-200μm的有效厚度。优选的外层厚度为20-100μm,更优选的外层厚度为20-70μm。实际厚度将在颗粒周围稍微变化。术语有效厚度意欲意指如果材料均匀地分布在内芯的表面上,基于层的厚度。内芯具有不规则表面,这可导致外层材料分布的不规则性。外层材料选自以下一种或多种:γ-氧化铝、δ-氧化铝、η-氧化铝、θ-氧化铝、硅石-氧化铝、沸石、非沸石分子筛、二氧化钛和氧化锆。
在可选择的实施方案中,催化剂为具有包含惰性材料的内芯的层状催化剂。外层结合在内芯上,其中外层包含金属氧化物。催化剂包括沉积在外层上的选自IUPAC族8-10金属的第一金属和沉积在外层上的选自IUPAC族11或族14金属的第二金属。催化剂还具有0-1的空隙空间指数(VSI),优选的空隙空间指数为0.0001-0.5,更优选的空隙空间指数为0.001-0.3。空隙空间指数等于孔体积乘外层平均孔半径乘粒径并除以外层的有效厚度,或以cm3*μm/g单位表示。孔体积为外层的孔体积,而考虑整个催化剂的重量,而不是仅外层的重量。
惰性内芯选自如上所述材料,外层包含来自上列的材料。沉积在外层上的第一和第二金属选自以上关于第一和第二金属所列的金属。
控制选择性加氢方法对使乙烯加氢,由此损失一些产物最小化而言是重要的,该控制可通过选择AI大于3或VSI小于1的催化剂而改善。
该催化剂用于将乙炔选择性加氢成乙烯,同时具有最小的副反应,例如乙烯加氢成乙烷。该方法显示于图1,或前端方法中。首先使包含乙烯、乙烷和乙炔的工艺进料流12通过脱乙烷塔10,并使富含乙烯的塔顶料流14进入选择性加氢反应器20中。通常在进入选择性加氢反应器20中以前将富含乙烯的料流14压缩,并因此调整温度。通常,温度调整会冷却已被压缩的富含乙烯的料流14。该使用催化剂的方法包括使具有乙烯和乙炔的塔顶进料流14与AI为3-500或VSI为0-1,或AI为3-500且VSI为0-1的催化剂在反应条件下接触,由此产生乙烯输出料流,其中催化剂如上所述。选择性加氢反应条件包括100kPa-14.0MPa的压力,优选500kPa-10.0MPa的压力,更优选800kPa-7.0MPa的压力。选择性加氢的温度为10-300℃,优选的温度为30-200℃。
选择性加氢条件包括0.1-10,000的氢气/乙炔摩尔比,优选0.1-10的摩尔比。摩尔比更优选为0.5-5,最优选的比为0.5-3。工艺进料流12的来源可以来自催化石脑油裂化器,在生产富含乙烯的进料流的过程中,产生明显量的一氧化碳。一氧化碳的量可以为1-8000体积ppm。当存在大量一氧化碳时,一氧化物用作活性催化剂部位的可逆阻断剂。选择性加氢反应器的操作条件可包括1,000-15,000hr-1的气时空速(GHSV),优选2,000-12,000hr-1的气时空速。在最优选的操作中,GHSV为8,000-12,000hr-1。
选择性加氢反应器20传递具有降低乙炔含量的输出料流22。输出料流22被冷却并产生一些冷凝物。输出料流22分成冷凝物料流26和蒸气料流24,其中所述冷凝物料流作为回流返回脱乙烷塔10中。蒸气料流24进入脱甲烷塔30中,在那里使蒸气料流24分成包含氢气和残余一氧化碳的富含甲烷的料流32和乙烷/乙烯料流34。乙烷/乙烯料流34进入乙烷/乙烯分离器40中以将乙烷与乙烯分离。产生用作聚合物原料的质量水平的含乙烯的塔顶料流42。将包含乙烷的塔底料流44送入其它加工单元,或作为最终产物。
在另一实施方案中,将乙炔选择性加氢成乙烯的方法显示于图2,或尾端方法中。首先使工艺进料流12通过脱甲烷塔30,产生包含甲烷和一氧化碳的塔顶料流32和包含乙烷、乙烯、乙炔和C3+烃的脱甲烷塔塔底料流34。脱甲烷塔塔底料流34进入脱乙烷塔10中,其中脱乙烷塔将脱甲烷塔塔底料流分成包含乙烷、乙烯和乙炔的脱乙烷塔塔顶料流,或乙烯料流14,和包含C3+烃的塔底料流。脱乙烷塔塔顶料流14进入选择性加氢反应器20中,在其中将乙炔选择性转化成乙烯。可在进入选择性加氢反应器20中以前将塔顶料流14压缩并因此调整温度。通常温度调整将由于压缩而被加热的塔顶料流14冷却。根据需要,选择性加氢进料可包括另外的氢气进料流。使乙烯料流14与AI为3-500,或VSI为0-1,或AI为3-500且VSI为0-1的选择性加氢催化剂在反应器内在反应条件下接触,其中催化剂如上所述。
选择性加氢条件包括100kPa-14.0MPa的压力,优选500kPa-10.0MPa的压力,更优选800kPa-7.0MPa的压力。选择性加氢的温度为10-300℃,优选的温度为30-200℃。氢气/乙炔摩尔比为0.1-20,但优选的摩尔比0.1-10。摩尔比更优选为0.5-5,最优选的比为0.5-3。工艺进料流12的来源可以来自催化石脑油裂化器、蒸汽裂化器或烯烃裂化单元,在生产富含乙烯的进料流的方法中,产生明显量的一氧化碳。然而,在进入选择性加氢反应器20中以前随着进料流通过脱甲烷塔30,一氧化碳的量可以为0.1-10体积ppm。选择性加氢反应器的操作条件可包括1,000-5,000hr-1的气时空速(GHSV),优选的GHSV为4,000hr-1以下。
选择性加氢反应器20产生具有降低乙炔含量的产物料流22并进入乙烷/乙烯分离器40中。产物料流22被冷却并产生一些冷凝物。产物料流22进入蒸气-液体分离器中,在其中回收冷凝物26并作为回流返回脱乙烷塔10中。蒸气料流24进入分离器中,其中分离器40产生用作聚合物原料的质量水平的含乙烯的塔顶料流42,将包含乙烷的塔底料流44送入其它加工单元中,或作为最终产物。
可将具有在选择性加氢以前除去的甲烷和一部分一氧化碳的尾端方法中所用的催化剂用碱金属处理以降低催化剂的酸度。将催化剂以量为小于外层的0.5重量%,优选外层的0.1-0.5重量%的碱金属处理。有用的碱金属包括锂(Li)、钠(Na)、钾(K)、铷(Rb)和铯(Cs)。当用碱金属处理时,它为赋予可比活性的摩尔量,即Li原子赋予与K原子同样的响应。因此,较轻的锂的重量根据原子量比降低。例如用仅Pd和Pd/Ag催化剂,3300重量ppm K和500重量ppm Li具有类似的活性和选择性。
然而,对于前端催化剂,碱金属的加入显示出提高的活性,但降低的选择性。对于在外层上仅具有Pd的测试催化剂,较低的钾得到较高的活性和选择性,或较低的乙烷形成。这显示乙炔加氢优先于乙烯加氢,锂得到较高的活性,但较低的选择性。对于在外层上具有Pd/Ag的测试催化剂,较低的钾也得到较高的活性和较低的选择性。
表1比较了γ-或θ-氧化铝的层厚度为5-200μm的本发明层状催化剂和在α-氧化铝上制备的常规催化剂,其中常规催化剂具有浸渍到25-300μm的各种深度的表面。取所有催化剂为3mm球用于一般呈现基础。参数显示对于常规催化剂,为什么非常薄的活性区是没有实效的。活性区定义为其中出现至少90%活性金属/活性部位的区域。通常负载变得非常高百分单层覆盖率,这得到差的金属利用且通常具有非常大的金属颗粒聚结体。特别特异的参数为表面积*粒径*100/活性区厚度(cm2/g),或AI,和孔体积*平均孔半径*粒径/厚度(cm3*μm/g),或VSI。
表1-活性指数
活性区材料 | 活性层厚度(μm) | 空隙空间指数(VSI) | 可及性指数(AI) |
γ-氧化铝 | 5 | 0.0562 | 11.94 |
γ-氧化铝 | 12.5 | 0.0282 | 11.85 |
γ-氧化铝 | 25 | 0.0154 | 11.71 |
γ-氧化铝 | 50 | 0.00815 | 11.43 |
γ-氧化铝 | 100 | 0.00424 | 10.91 |
γ-氧化铝 | 200 | 0.00222 | 10.02 |
θ-氧化铝 | 5 | 0.135 | 5.37 |
θ-氧化铝 | 12.5 | 0.0791 | 5.33 |
θ-氧化铝 | 25 | 0.0469 | 5.27 |
θ-氧化铝 | 50 | 0.0260 | 5.14 |
θ-氧化铝 | 100 | 0.0139 | 4.91 |
θ-氧化铝 | 200 | 0.00738 | 4.51 |
α-氧化铝 | 25 | 21.22 | 0.293 |
α-氧化铝 | 50 | 20.72 | 0.286 |
α-氧化铝 | 100 | 19.78 | 0.273 |
α-氧化铝 | 200 | 18.16 | 0.250 |
α-氧化铝 | 300 | 16.80 | 0.232 |
本发明使用γ-和θ-氧化铝用于催化剂的外层,且具有各种有效厚度。相对于使用α-氧化铝作为外涂层的标准商业催化剂,本发明催化剂具有大于3的高可及性指数,和小于1的低空隙空间指数。使用α-氧化铝的常规催化剂具有非常大的平均孔径。指数显示对于常规催化剂为什么薄活性区是没有实效的。活性区为其中出现>90%活性金属部位的区域。由于在薄活性区内它们具有非常高的百分数单层覆盖率和大的金属颗粒聚结体,常规催化剂获得差的金属利用。改变催化剂的孔径大小改善了前端方法的选择性加氢性能。
从试验来看,对于外层有效厚度为5-50μm的催化剂而言,催化剂活性倾向于提高。这表明较薄的层将得到较好的性能。本发明催化剂容许具有较低金属沉积的较薄的层。这可能降低重质副产物聚集的倾向,由此降低催化剂减活化。
催化剂制备程序:
催化剂通过将合适的金属盐的溶液加入所需量的载体中而制备。合适的金属盐通常为硝酸盐。特别地,将相对于载体重量1%HNO3溶液用去离子水稀释以提供大约相当于载体体积的溶液体积,或1∶1溶液/载体体积比。使溶液与载体在室温下接触1小时,同时持续搅拌,或滚动以确保良好的载体和溶液接触。然后将溶液加热至100℃,液体经大于3小时的时间蒸发,由此产生浸渍的载体。最终载体应为在容器中“自由滚动”或自由移动的。最终含水量随具体载体变化,但通常为20-30重量%。
然后将浸渍的载体转移至适于煅烧和还原的容器中。将载体在120℃下在流动的干燥空气中干燥3小时,然后在流动的干燥空气中以5℃/分钟的速率上升至450℃,并保持在450℃下1小时。将试样冷却至室温。
为还原,将试样在流动的干N2中以5℃/分钟的速率下降至200℃,并保持在200℃下1小时。然后切断流动的干N2,然后使氢气流过催化剂并保持3小时。然后将氢气转换成氮气,将催化剂试样冷却至室温。
对于两步骤程序,来自第一步骤的煅烧并还原的催化剂用作第二步骤和通常浸渍、干燥、煅烧和还原步骤的载体,其后是第二套在溶液中的金属盐。
尽管已用目前认为优选的实施方案描述本发明,应当理解本发明不限于所公开的实施方案,而是意欲涵盖包括在附属权利要求范围内的各种改进和等效配置。
Claims (10)
1.一种用于将乙炔选择性加氢成乙烯的催化剂,其包含:
层状催化剂,其具有包含惰性材料的内芯;
结合在内芯上的外层,其中所述外层包含金属氧化物;
沉积在外层上的第一金属,其中所述第一金属为IUPAC族8-10金属;和
沉积在外层上的第二金属,其中所述第二金属为IUPAC族11或族14金属;
其中所述催化剂具有3-500的可及性指数(AI)。
2.根据权利要求1的催化剂,其中所述可及性指数为3-20。
3.根据权利要求1的催化剂,其中所述第一金属的浓度为催化剂的100-50,000重量ppm。
4.根据权利要求3的催化剂,其中所述第一金属的浓度为催化剂的200-20,000重量ppm。
5.根据权利要求1的催化剂,其中所述第一金属选自铂、钯及其混合物。
6.根据权利要求1的催化剂,其中所述第二金属选自铜、银、金、锡、锗、铅及其混合物。
7.根据权利要求1的催化剂,其中所述内芯具有0.05-10mm的有效直径。
8.根据权利要求1的催化剂,其中所述外层具有20-100μm的有效厚度。
9.根据权利要求1的催化剂,其中所述外层选自γ-氧化铝、δ-氧化铝、η-氧化铝、θ-氧化铝、硅石-氧化铝、沸石、非沸石分子筛、二氧化钛、氧化锆及其混合物。
10.根据权利要求1的催化剂,其中所述内芯包含选自如下的固体材料:堇青石、莫来石、橄榄石、氧化锆、尖晶石、蓝晶石、氧化铝、硅石、铝酸盐、硅酸盐、二氧化钛、氮化物、碳化物、硼硅酸盐、氧化硼、硅酸铝、氧化镁、镁橄榄石、高岭土、高岭石、蒙脱石、皂石、膨润土、具有小或低酸活性的粘土、γ-氧化铝、δ-氧化铝、η-氧化铝、θ-氧化铝及其混合物。
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