CN1108187C - 可使用于有机化合物转化反应的催化剂的制备方法 - Google Patents
可使用于有机化合物转化反应的催化剂的制备方法 Download PDFInfo
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- CN1108187C CN1108187C CN98125889A CN98125889A CN1108187C CN 1108187 C CN1108187 C CN 1108187C CN 98125889 A CN98125889 A CN 98125889A CN 98125889 A CN98125889 A CN 98125889A CN 1108187 C CN1108187 C CN 1108187C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 title claims description 7
- 150000002894 organic compounds Chemical class 0.000 title claims description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 5
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 5
- 229910052738 indium Inorganic materials 0.000 claims abstract description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052716 thallium Inorganic materials 0.000 claims abstract description 5
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000000737 periodic effect Effects 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 37
- 239000007864 aqueous solution Substances 0.000 claims description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 11
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- 238000001035 drying Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- -1 hydroxy, carboxyl Chemical group 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
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- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 5
- 238000006424 Flood reaction Methods 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 229910052755 nonmetal Inorganic materials 0.000 claims description 4
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
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- 238000001914 filtration Methods 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- PWBHRVGYSMBMIO-UHFFFAOYSA-M tributylstannanylium;acetate Chemical compound CCCC[Sn](CCCC)(CCCC)OC(C)=O PWBHRVGYSMBMIO-UHFFFAOYSA-M 0.000 claims description 3
- 239000013598 vector Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
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- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims 2
- 150000001336 alkenes Chemical class 0.000 claims 2
- 229920006395 saturated elastomer Polymers 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 239000002152 aqueous-organic solution Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000007787 solid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
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- 229910052799 carbon Inorganic materials 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 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
- 208000035126 Facies Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- NFOHLBHARAZXFQ-UHFFFAOYSA-L platinum(2+);dihydroxide Chemical compound O[Pt]O NFOHLBHARAZXFQ-UHFFFAOYSA-L 0.000 description 1
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- 238000003672 processing method Methods 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- B01J37/082—Decomposition and pyrolysis
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Abstract
含有至少一种载体、至少一种元素周期分类表第VIII族金属和至少一种选自锗、锡、铅、铼、镓、铟和铊的附加元素M催化剂的制备方法,该方法中所述金属M被加入到一种含有至少一种碳-M键的有机金属化合物的含水溶剂中。
Description
本发明涉及一种新的催化剂制备方法,该催化剂含有至少一种载体、至少一种元素周期分类表第VIII族金属和至少一种附加元素M,M选自锗、锡、铅、镓、铟和铊。这种催化剂还可以含有选自碱金属的其他金属和/或如硫之类的非金属和/或如卤素或含卤素化合物的其他化学元素。
有大量的专利与出版物证明了在基础金属中添加助催化剂以改善催化剂的质量。这些元素是以有机金属盐或化合物的不同形式添加的。通常得到的催化剂比相应的单金属催化剂活性更强,选择性更好,有时稳定性也更好。添加这些改性剂不是无关紧要的,因为它对催化剂的性质有很强的调节作用。
这样,在烃转化方法中使用的催化剂配方就成为人们大量研究的课题。具体在US-A-3 998 900和FR-A-2 495 605专利中描述过载带的金属催化剂。这些催化剂含有以铂为主要成分的金属相,这些催化剂采用如锡之类附加金属改性,用如氧化铝之类的难熔无机氧化物载带。有利地,通过加入金属M有机金属化合物,有利地实施上述金属M的加入。这种金属M加入方法已经在本申请人的US3 531 543和US 4 548 98专利中描述过。
已引证的方法描述了使用至少一种金属M有机金属化合物生产催化剂。该金属M是以至少一种有机金属化合物形式加入的,该化合物选自配合物,具体金属M的羰基配合物,多酮配合物和金属M的羟基金属配合物,如烷基、环烷基、芳基、烷基芳基和芳基烷基金属配合物。
加入以有机金属化合物形式的附加元素M得到性能更优良的催化剂,但是必需使用有机溶剂。根据US4 548 918专利的技术所描述的浸渍溶剂选自每个分子有2-8个碳原子的含氧有机溶剂,和基本上每个分子有6-15个碳原子的链烷烃、环烷烃或芳族烃,以及每个分子有1-15个碳原子的含氧的含卤素的有机化合物。这些溶剂可以单独使用或彼此混合使用。
现在本发明发现,有可能的是加入在含水溶剂中可溶的呈有机金属配合物形式的金属M,制备出这些性能特别优良的催化剂。这表明在易于实施制备催化剂方面获得很大的进步。事实上,使用工业量的有机溶剂从安全(易燃性、毒性)和成本角度考虑是有严重缺陷的。
本发明催化剂载体包括至少一种难熔氧化物,一般地,这种氧化物选自元素周期分类表第IIA、IIIA、IIIB、IVA或IVB族金属氧化物,例如像镁、铝、硅、钛、锆、钍氧化物,它们单独或彼此混合使用,或与元素周期分类表的其他元素氧化物混合使用。还可以使用炭。也可以使用X、Y型沸石或分子筛,丝光沸石、八面沸石、ZSM-5、ZSM-4、ZSM-8,以及第IIA、IIIA、IIIB、IVA或IVB族金属氧化物与沸石物质的混合物。
对于烃的转化反应,优选的载体是氧化铝,其比表面有利地是5-400米2/克,优选地50-350米2/克。在有机官能转化领域中所使用的优选载体是二氧化硅、炭和氧化铝。
本发明的催化剂还含有一种载体:
a)至少一种选自铱、镍、钯、铂、铑和钌的VIII族金属。铂和钯是烃转化反应的优选金属。铑和钌是官能分子转化的优选金属,其重量百分数是0.1-10%,优选地是0.1-5%。
b)至少一种附加元素M,M选自锗、锡、铅、铼、镓、铟和铊的附加元素M。锡和锗是优选元素。其重量百分数例如是0.01-10%,优选地是0.02-5%。在某些情况下有利地可以同时使用这组中的至少两种金属。
根据应用范围,该催化剂任选地还含有例如0.1-3%(重量)卤素或含卤素的化合物。还可以含有0.1-3%(重量)碱金属或碱上金属。任选地,可以含有0.01-2%(重量)如硫之类的元素。
该催化剂可以采用不同的浸渍载体方法制备,本发明不限于已确定的浸渍方法。使用多种溶液时,可以进行中间的干燥和/或煅烧。
附加元素M可以在制备载体时加入。一种方法例如是将湿的载体粉末与催化剂前体混合,然后成形并干燥。
可以同时或相继地加入第VIII族金属、附加金属M,任选地卤素或含卤素化合物,任选地碱金属或碱土金属,任选地非金属,不论其顺序如何。根据本发明,有机金属元素M进行接触的特征在于将这种元素加入含水溶剂中。
在其他方法中,当根据Sol-Gel类技术合成载体时可以加入附加元素M。例如,对于含有氧化铝的载体,可以通过用金属M的有机金属化合物含水溶液在如ROH或R′OH之类的溶剂中水解Al(OR′)3有机溶液,可以得到金属M-氧化铝混合凝胶,R和R′可以代表烷基,如甲基、乙基、异丙基、n-丙基、丁基,甚至更重的基团,如n-己基。该醇溶剂在加入醇化铝之前应该强化脱水。在水解之后,所得到凝胶进行热处理的温度是200-800℃,优选地300-700℃,更优选地是400-500℃,这样能够保证金属M水溶性有机金属化合物与该凝胶完全反应,导致生成Al2O3-MOx混合氧化物。
在另一种方法中,金属M可以加入氧化铝溶胶中。US3 929 683描述了将例如SnCl2之类的凝胶形式的锡加入氧化铝溶胶中。根据本发明,有可能将金属M水溶性有机金属化合物加入到氧化铝水溶胶中,而水溶胶例如通过在pH4-5沉淀AlCl3酸性溶液得到,然后例如在热或碱的作用下,促进金属M化合物与氧化铝水溶胶的反应。
元素M前体可以非限制性地选自元素M有机金属化合物的含卤素化合物、氢氧化物、氧化物、碳酸盐和羧酸盐,但不要受到这个清单的限制。这些化合物含有至少一种碳-M键。元素M前体也可以选自通式(R1)XM(R2)Y化合物,其中x+y=金属M价态,R1选自烷基、环烷基、芳基、烷基芳基和芳基烷基官能团,而R2是CaHbR′c,式中R′代表氢氧化物、羧酸酯、PO3H或SO3H官能。
在本发明优选制备技术中,该催化剂是用至少一种VIII族金属化合物的含水溶液或有机溶液经浸渍载体得到的,该溶液的体积优选地是与载体吸留相等体积相比过量或等于这个体积。然后过滤已浸渍的载体,任选地用蒸馏水洗涤并在110-500℃空气下煅烧,再在温度一般约200-600℃,优选地300-500℃氢气下还原。这时所得到的产物用至少一种锡、锗、铅、铼、镓、铟和铊的化合物的含水溶液浸渍。特别有利地使用羧酸锡化合物的含水溶液。该水溶液的体积优选地等于至少载体吸留的体积,并最好前者超过后者。在该水溶液中至少一种金属M的浓度值有利地选择为0.01-25毫摩尔/升,优选地为0.5-20毫摩尔/升,更优选地为0.5-15毫摩尔/升。该水溶液的pH值有利地选择为10-14,优选地10-12。
在第VIII族金属浸渍的载体与含有至少一种元素M化合物的含水溶液接触几小时后,过滤产物,任选地用水洗涤,再干燥。根据这种方法,在300-600℃,优选地用氢气吹除并还原几小时后结束该过程。还可能的是在干燥步骤之后,在空气吹除下在300-600℃煅烧结束该过程。
在本发明另外一种技术中,该催化剂是通过浸渍至少一种所述金属M化合物的含水溶液得到的,该溶液的体积优选地等于载体吸留体积,更优选地相对于该体积是过量的。特别有利地,使用羧酸锡化合物含水溶液。有利地,选择该含水溶液中至少一种金属M浓度值是0.01-25毫摩尔/升,优选地是0.01-20毫摩尔/升,优选地是0.01-15毫摩尔/升。该水溶液的pH值有利地选择为10-14,优选地10-12。在固体与浸渍溶液接触几小时后,干燥所得到的产物。其中在300-600℃用空气吹除与煅烧几小时后结束该过程。所得到的固体用至少一种第VIII族金属化合物的含水溶液或有机溶液浸渍,该溶液的体积优选地相对于载体吸留体积是过量的,或等于这个体积。在接触几小时后,所得到的产物再进行干燥,然后在300-600℃空气下煅烧,优选地在空气吹除下煅烧几小时。
在使用前,例如在20-600℃用氢气还原催化剂,以得到活性金属相。这种处理方法例如是在氢气流下缓慢升温,直到最高的还原温度,例如20-600℃,优选地90-500℃,接着在这个温度下保持例如1-6小时。
使用者可以在煅烧后立刻或稍迟些进行这种还原。使用者也可能直接还原已干燥的产物。
还可能用如甲酸之类的具有还原剂特性的有机分子在溶液中预先还原第VIII族金属化合物。这时可以同时或相继地加入附加元素M化合物。当催化反应必需是含水溶剂时,这时可以直接使用该固体。这特别应用于在有机官能转化领域中。另外一种可能性是过滤,然后干燥所得到的催化剂,这时可以煅烧,再在上述条件下还原。还可能由这种干燥产物直接进行还原。
根据本发明制备的催化剂可以用于涉及精炼和石油化学领域中的烃转化方法中。还可以用于化学领域的方法。
下述实施例说明本发明而不限制其保护范围。
实施例1
制备2种催化剂A和B,它们分别含有0.7%(重量)铂和0.15%(重量)锡。载体是比表面为每克200米2的Degussa二氧化硅。
催化剂A(对比)
该载体在500℃在干燥空气下煅烧5小时,然后在氮鼓泡下与氨溶液(1N)接触15小时。这时加入四胺铂氢氧化物溶液使铂沉积。然后过滤该悬浮液,用蒸馏水洗涤,再在110℃氮气流下干燥。然后在450℃氢气下还原3克含有0.7%(重量)铂的固体达4小时。再在氢气下将该催化剂装入装有庚烷的反应器中。在20℃注入四丁基锡。在室温氢气氛下反应24小时后,过滤固体,用庚烷洗涤,然后在80℃干燥。再在550℃氢气流下还原4小时。
催化剂B(本发明)
由3克含有0.7%(重量)铂的固体,在450℃在氢气流下还原4小时制备催化剂B。然后在氢气下将该催化剂装入反应器中,该反应器装有50厘米3氨的水溶液(pH11),而该氨溶液含有呈乙酸三丁基锡(Bu3SnOC(O)CH3)形式的锡。在氢气氛下接触24小时后,过滤反应混合物,洗涤,再在80℃干燥。然后在550℃氢气流下还原4小时。
催化剂C(本发明)
在异丙醇中,用乙酸三丁基锡(Bu3SnOC(O)CH3)水溶液水解异丙醇铝Al(OiPr)3溶液,接着在450℃热处理制备出载体。然后,通过浸渍六氯铂酸至干达到铂沉积,铂以干燥载体计为0.7%(重量)。在450℃煅烧12小时后,该催化剂在500℃氢气流下还原4小时。
实施例2
在等温管式反应器中对催化剂A、B和C进行异丁烷脱氢作用的试验。1克催化剂在每小时2升氢的流量下在550℃还原2小时。注入物料后,将温度稳定在550℃。采用气相色谱法在线分析气体流出物。
操作条件如下:
-物料 iC4液体空气N35
-温度 550℃
-压力 0.1MPa
-H3/iC4(摩尔) 1
-每小时液体iC4质量流量/催化剂质量 725小时-1
在这些条件下所得到的结果汇集表1。
表1
催化剂 | 时间,小时 | 活性(a) | 异丁烯选择性(b) |
A | 1 | 20.0 | 99.1 |
3 | 18.4 | 99.1 | |
5 | 17.6 | 99.3 | |
B | 1 | 25.0 | 99.2 |
3 | 23.5 | 99.2 | |
5 | 23.0 | 99.3 | |
C | 1 | 22.1 | 99.1 |
3 | 18.8 | 99.1 | |
5 | 17.8 | 99.3 |
(a)(摩尔.g Pt-1.s-1.103)
(b)(%摩尔)
这些结果清楚地表明,根据本发明由含水相中元素M的有机金属前体制备的催化剂B和C具有的催化性能,与根据现有技术由有机相中四丁基锡制备的催化剂A的催化性能至少相同,甚至超过。
Claims (26)
1.含有至少一种载体、至少一种元素周期表第VIII族金属和到少一种选自锗、锡、铅、铼、镓、铟和铊的附加元素M的催化剂的制备方法,其特征在于将所述金属M以至少一种含有至少一个碳-M键的有机金属化合物形式加入含水溶剂中,其中元素M前体选自元素M的有机化合物的氢氧化物、含卤素化合物、碳酸盐、羧酸盐和通式(R1)XM(R2)Y化合物,其中x+y=金属M价态,R1选自烷基、环烷基、芳基、烷芳基和芳烷基官能团,而R2是CaHbRc′,式中R′代表羟基、羧基、PO3H或SO3H官能团。
2.根据权利要求1的方法,其中元素M的前体选自元素M的有机化合物的羧酸盐。
3.根据权利要求1的方法,其中元素M的前体是乙酸三丁基锡。
4.根据权利要求1-3任一项的方法,其中该催化剂还包括至少一种碱金属或碱土金属。
5.根据权利要求1-3任一项的方法,其中该催化剂还包括至少一种非金属。
6.根据权利要求1-3任一项的方法,其中该催化剂还包括至少一种卤素或含卤素化合物。
7.根据权利要求1-3任一项的方法,其中第VIII族金属选自铱、镍、钯、铂、铑和钌。
8.根据权利要求7的方法,其中第VIII族金属选自铂和钯。
9.根据权利要求4的方法,其中同时或相继地加入第VIII族金属、附加元素M和碱金属或碱土金属。
10.根据权利要求5的方法,其中同时或相继地加入第VIII族金属、附加元素M和非金属。
11.根据权利要求6的方法,其中同时或相继地加入第VIII族金属、附加元素M和卤素或含卤素化合物。
12.根据权利要求1-3任一项的方法,其中以任意顺序操作如下步骤:
·用至少一种第VIII族金属的含水溶液或有机溶液浸渍载体、过滤、干燥、煅烧与还原,
·用至少一种附加元素M化合物的含水溶液浸渍所得到的产物、过滤、干燥,任选地还原、煅烧。
13.根据权利要求1-3任一项的方法,其中用至少一种金属M化合物的含水溶液浸渍载体,该溶液的体积至少等于载体吸留体积。
14.根据权利要求13的方法,其中溶液的体积大于载体吸留体积。
15.根据权利要求1-3任一项的方法,其中在该含水溶液中至少一种金属M的浓度是0.01-25毫摩尔/升。
16.根据权利要求15的方法,其中在该含水溶液中至少一种金属M的浓度是0.5-20毫摩尔/升。
17.根据权利要求16的方法,其中在该含水溶液中至少一种金属M的浓度是0.5-15毫摩尔/升。
18.根据权利要求1-3任一项的方法,其中至少一种金属M含水溶液的pH是10-14。
19.根据权利要求18的方法,其中至少一种金属M的含水溶液的pH是10-12。
20.根据权利要求1-3任一项的方法,其中在生产载体时加入附加元素M。
21.根据权利要求20的方法,其中根据SOL-GEL类技术,在合成载体时加入附加元素M。
22.根据权利要求2 1的方法,其中在醇溶利中,用金属M的有机金属化合物的含水溶液水解载体金属烷氧基化合物的有机溶液,然后加热到200-800℃的温度。
23.根据权利要求1-22任一项的方法所制备的催化剂。
24.权利要求23的催化剂用于有机化合物的转化反应。
25.权利要求23的催化剂用于饱和脂族烃脱氢反应生成相应烯烃。
26.权利要求23的催化剂用于饱和C3-C4脂族烃脱氢反应生成相应烯烃。
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FR97/13684 | 1997-10-31 | ||
FR9713684A FR2770421B1 (fr) | 1997-10-31 | 1997-10-31 | Procede de preparation de catalyseurs utilisables dans les reactions de transformation de composes organiques |
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CN1222406A CN1222406A (zh) | 1999-07-14 |
CN1108187C true CN1108187C (zh) | 2003-05-14 |
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CN98125889A Expired - Fee Related CN1108187C (zh) | 1997-10-31 | 1998-10-31 | 可使用于有机化合物转化反应的催化剂的制备方法 |
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US (1) | US6281160B1 (zh) |
EP (1) | EP0913198B1 (zh) |
JP (1) | JP4374557B2 (zh) |
KR (1) | KR100552314B1 (zh) |
CN (1) | CN1108187C (zh) |
CA (1) | CA2250374C (zh) |
DE (1) | DE69829722T2 (zh) |
ES (1) | ES2242266T3 (zh) |
FR (1) | FR2770421B1 (zh) |
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ITMI20112403A1 (it) | 2011-12-28 | 2013-06-29 | Polimeri Europa Spa | Composizione catalitica e procedimento per la deidrogenazione di buteni o miscele di butani e buteni a dare 1-3 butadiene |
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BR112014015584A8 (pt) | 2012-01-06 | 2017-07-04 | Celanese Int Corp | catalisadores de hidrogenação com suportes modificados com cobalto |
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- 1998-10-27 ES ES98402678T patent/ES2242266T3/es not_active Expired - Lifetime
- 1998-10-27 CA CA002250374A patent/CA2250374C/fr not_active Expired - Fee Related
- 1998-10-27 EP EP98402678A patent/EP0913198B1/fr not_active Expired - Lifetime
- 1998-10-27 DE DE69829722T patent/DE69829722T2/de not_active Expired - Lifetime
- 1998-10-30 US US09/182,658 patent/US6281160B1/en not_active Expired - Lifetime
- 1998-10-30 KR KR1019980046058A patent/KR100552314B1/ko not_active IP Right Cessation
- 1998-10-30 JP JP30994798A patent/JP4374557B2/ja not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
---|---|
DE69829722T2 (de) | 2005-09-01 |
CA2250374C (fr) | 2008-05-13 |
EP0913198A1 (fr) | 1999-05-06 |
EP0913198B1 (fr) | 2005-04-13 |
FR2770421B1 (fr) | 1999-12-10 |
CN1222406A (zh) | 1999-07-14 |
KR19990037511A (ko) | 1999-05-25 |
DE69829722D1 (de) | 2005-05-19 |
US6281160B1 (en) | 2001-08-28 |
KR100552314B1 (ko) | 2006-06-20 |
JPH11221464A (ja) | 1999-08-17 |
JP4374557B2 (ja) | 2009-12-02 |
CA2250374A1 (fr) | 1999-04-30 |
ES2242266T3 (es) | 2005-11-01 |
FR2770421A1 (fr) | 1999-05-07 |
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