CN1221402A - 6-氨基己腈的制备方法 - Google Patents
6-氨基己腈的制备方法 Download PDFInfo
- Publication number
- CN1221402A CN1221402A CN97195209A CN97195209A CN1221402A CN 1221402 A CN1221402 A CN 1221402A CN 97195209 A CN97195209 A CN 97195209A CN 97195209 A CN97195209 A CN 97195209A CN 1221402 A CN1221402 A CN 1221402A
- Authority
- CN
- China
- Prior art keywords
- aminocapronitrile
- hydrogen
- hydrogenation
- catalyzer
- effluent
- 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.)
- Granted
Links
- KBMSFJFLSXLIDJ-UHFFFAOYSA-N 6-aminohexanenitrile Chemical compound NCCCCCC#N KBMSFJFLSXLIDJ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 239000001257 hydrogen Substances 0.000 claims abstract description 45
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 40
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 39
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 19
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 19
- ISBHMJZRKAFTGE-UHFFFAOYSA-N pent-2-enenitrile Chemical compound CCC=CC#N ISBHMJZRKAFTGE-UHFFFAOYSA-N 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 239000010949 copper Substances 0.000 claims abstract description 10
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 7
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 37
- 238000007037 hydroformylation reaction Methods 0.000 claims description 31
- 239000010948 rhodium Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 17
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 16
- 229910017052 cobalt Inorganic materials 0.000 claims description 14
- 239000010941 cobalt Substances 0.000 claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 14
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- 125000001118 alkylidene group Chemical group 0.000 claims description 8
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- 125000000217 alkyl group Chemical group 0.000 claims description 3
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
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- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 claims 7
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- 150000003839 salts Chemical class 0.000 description 5
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- SWRNIYAQKATHDJ-UHFFFAOYSA-N dichloro(dichlorophosphanyl)phosphane Chemical compound ClP(Cl)P(Cl)Cl SWRNIYAQKATHDJ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- WUOIAOOSKMHJOV-UHFFFAOYSA-N ethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CC)C1=CC=CC=C1 WUOIAOOSKMHJOV-UHFFFAOYSA-N 0.000 description 1
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- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- BCTWNMTZAXVEJL-UHFFFAOYSA-N phosphane;tungsten;tetracontahydrate Chemical group O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.P.[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W] BCTWNMTZAXVEJL-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- BDDWSAASCFBVBK-UHFFFAOYSA-N rhodium;triphenylphosphane Chemical compound [Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BDDWSAASCFBVBK-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
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- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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Abstract
本发明提供了一种制备6-氨基己腈或6-氨基己腈/六亚甲基二胺混合物的方法,该方法包括:a)在催化剂存在下,使至少一种选自2-戊烯腈、3-戊烯腈和4-戊烯腈的戊烯腈与一氧化碳及氢气反应得到一种加氢甲酰化流出物Ⅰ,其中所述催化剂包含至少一种第八族元素作为活性成分,b)任选地从加氢甲酰化流出物Ⅰ中除去一氧化碳、氢气和催化剂以得到加氢甲酰化流出物Ⅱ,c)从所述加氢甲酰化流出物Ⅰ或Ⅱ中除去5-甲酰基戊腈,d)在加氢催化剂存在下,使排出的5-甲酰基戊腈与氨气和氢气反应以得到一种加氢流出物,其中所述催化剂选自铼、铜和其化合物,以及第八族的金属和金属化合物,和e)将6-氨基己腈或6-氨基己腈与六亚甲基二胺一起从加氢流出物中分离出来。
Description
本发明涉及一种制备6-氨基己腈或6-氨基己腈-六亚甲基二胺混合物的方法。
EP-A11401描述了在钴催化剂存在下,在超计大气压下使3-戊烯腈与一氧化碳和氢气反应得到异构的甲酰基戊腈及从醛得到相应的醇的混合物。该文献还描述了将δ-氰基戊醛还原胺化成六亚甲基二胺。按照该文献的实施例4所述,60%的δ-氰基戊醛混合物与氨和氢气在100℃及氢压140巴及雷内镍存在下反应2小时,但转化率(基于δ化合物)仅有25%。低转化率表明,在一个分子和相同的分子中醛基团还原胺化及腈基团加氢成二胺造成了难以进行加氢的问题。此外,该文献也未描述6-氨基己腈的形成。进而,所采用的催化剂的运转系数对于工业化应用而言还不能令人满意。
US-A 2,777,873公开了在镍、钴、铁、铂或钯催化剂存在下,在100-160℃及1-1000大气压下使5-甲酰基戊酸酯与氨和氢气进行还原胺化,得到6-氨基己酸酯。EP-A 376 121也描述了采用钌催化剂的该反应,反应温度为80-140℃,压力为40-1000巴。
按照US-A 3,461,167(第3栏,66-74行),钴、铜和铼催化剂适用于在氨存在下使己二腈加氢成六亚甲基二胺。优选的条件是70-170℃和300-7000psi。按照US-A 3,471,563,该反应也可采用钌催化剂。
EP-A 214 622提到在铑/亚磷酸盐鳌合物催化剂存在下,对3-丁烯腈进行加氢甲酰化。
WO 94/26688描述了一种方法,该方法包括
(a)将内取代的烯烃异构化为端烯烃,
(b)在内烯烃存在下,优先加氢甲酰化端烯烃,
(c)除去加氢甲酰化产物,和
(d)将内烯烃循环至异构化反应中。
WO 94/26688的权利要求3涉及含腈基的烯烃。所采用的加氢甲酰化催化剂为铑-三苯膦体系,其中三苯膦通过适宜的官能基团可溶解于水中。
WO 95/18783描述了用水溶性铂催化剂对内腈基烯烃进行的加氢甲酰化反应。
本发明的目的是提供一种制备6-氨基己腈或6-氨基己腈与六亚甲基二胺的混合物的方法,该方法由2-和/或3-和/或4-戊烯腈起始,转化率非常高。更具体地说,本发明的方法也会保证催化剂具有较长的操作期限。
业已发现,上述目的可以通过下述6-氨基己腈或6-氨基己腈/六亚甲基二胺混合物的制备方法实现,该方法包括:
a)在催化剂存在下,使至少一种选自2-戊烯腈、3-戊烯腈和4-戊烯腈的戊烯腈与一氧化碳及氢气反应得到一种加氢甲酰化流出物Ⅰ,其中所述催化剂包含至少一种第八族元素作为活性成分,
b)任选地从加氢甲酰化流出物Ⅰ中除去一氧化碳、氢气和催化剂以得到加氢甲酰化流出物Ⅱ,
c)从所述加氢甲酰化流出物Ⅰ或Ⅱ中除去5-甲酰基戊腈,
d)在加氢催化剂存在下,使排出的5-甲酰基戊腈与氨气和氢气反应以得到一种加氢流出物,其中所述催化剂选自铼、铜和其化合物,以及第八族的其它金属和金属化合物,和
e)使6-氨基己腈或6-氨基己腈与六亚甲基二胺一起从加氢流出物中分离出来。
按照本发明,采用至少一种选自2-戊烯腈、3-戊烯腈和4-戊烯腈的戊烯腈,优选3-或4-戊烯腈。
3-戊烯腈是该方法中最重要的一种原料,它可例如在镍(O)/亚磷酸配合物作为催化剂存在下,通过氢氰酸与丁二烯的加成反应而制得(K.Weissermel,H.-J.Arpe,Industrielle organische Chemie,第4版,VCH Verlag Weinheim,1994,P268)。
2-戊烯腈和4-戊烯腈可通过例如3-戊烯腈的异构化反应获得(例如,在镍(0)/磷酸配合物和Lewis酸存在下,可参见:Tolman等,Adv.in Catal.,33卷(1985),第23页;或者在加氢甲酰催化剂存在下在反应条件下)。
按照本发明,戊烯腈或戊烯腈混合物与一氧化碳与氢气的反应(“加氢甲酰化”)在催化剂存在下进行,得到一种加氢甲酰化流出物Ⅰ,所述催化剂包含至少一种第八族元素作为活性成分。
加氢甲酰化反应通常是在温度为30-180℃,特别是50-130℃,压力为0.01-100巴,特别是5-20巴下进行的。用于一氧化碳与氢气混合物的摩尔比通常为1∶100-10∶1,特别是1∶20-1∶2。
在优选的实施方案中,加氢甲酰化反应是在对反应惰性的溶剂存在下进行的,所述溶剂为例如芳族或脂环族化合物,如甲苯或环己烷。同样适宜的溶剂为高沸点酯,如双(2-乙基己基)邻苯二甲酸酯或TEXANOL(来自EASTMAN的2,2,4-三甲基戊烷-1,3-二醇单异丁酸酯)。特别优选甲酰基戊腈类,其是在所用的戊烯腈的加氢甲酰化反应中生产的,还优选在通过缩合如前所述的甲酰基戊腈而进行的加氢甲酰化反应过程中形成的那些高沸点化合物(相对于形成的甲酰基戊腈类而言)。
用于本发明的催化剂包含至少一种第八族元素作为活性成分,如铁、钴、镍、钌、铑、钯、锇、铱或铂。特别优选的元素是钴、铑和铂。
在特别优选的实施方案中,可添加助催化剂如亲脂和亲水性配位体,特别是膦、二膦、亚磷酸或二及多亚磷酸的磺酸盐、铵盐或羧酸盐。
目前,特别优选的加氢甲酰化催化剂为铑羰基配合物如铑双(羰基)乙酰丙酮化物(Rh(CO)2acac)及助催化剂,助催化剂选自三芳基膦如三苯膦、双(二芳基膦基)烷烃如2,2′-双二苯基膦基甲基联苯或二苯基膦基乙烷、三芳基亚磷酸酯如三苯基亚磷酸酯或三-2-叔丁基苯基亚磷酸酯和式Ⅰ和Ⅱ的多亚磷酸酯,其是公知的,例如可参见EP-A 472 071、US-A 4,769,498、EP-A 149 894、EP-A 96 988和EP-A96 986。
式Ⅰ的多亚磷酸酯为Ⅰ其中,X为二价双亚芳基或R1,W为二价的取代或未取代的亚芳基、双亚芳基或亚烷基,和
R1和R2可相同或不同,分别为取代或未取代的亚烷基或邻亚芳基。
R2为邻亚苯基、2,2-二甲基-1,3-亚丙基或1,1,2,2-四甲基亚乙基。更为优选的式Ⅰ的化合物为其中W、R1和R2彼此独立地为邻亚苯基、2,2-二甲基-1,3-亚丙基或1,1,2,2-四甲基亚乙基的式Ⅰ化合物。
式Ⅰ的多亚磷酸酯可按照常规方法通过适当选择的卤化磷/醇缩合反应次序制备,例如,按照:
a)使三氯化磷与二醇反应形成单氯亚磷酸酯;
b)使这种中间体再与二醇反应形成相应的羟基取代的二有机亚磷酸酯中间体;
c)使这种二有机亚磷酸酯中间体与三氯化磷反应形成相应的二氯化磷中间体;
d)最后,使这种二氯化物与适宜的二醇反应形成所需的双亚磷酸酯。
虽然这种合成路线对于制备不对称取代的亚磷酸酯为必要的,但对称取代的化合物可通过步骤a)的产物与适宜的二醇以摩尔比2∶1反应。
已提及的缩合反应通常是在一种辅助碱如三乙胺作为HCl受体存在下,在适宜的溶剂如甲苯中进行的。
Ar和Ar′可相同或不同,为具有6-18个碳原子的取代或未取代的亚芳基;
X为具有2-30个碳原子的间位结合的基团,其选自亚烷基、亚烷基-氧-亚烷基、亚芳基和下式的基团:
亚芳基-(CH2)y-(Q)n-(CH2)y-亚芳基
其中各亚芳基如上所定义,以及
y为0或1;
Q为二价桥基团,选自氧、硫、-CO-、-CR3R4-,其中,R3和R4分别为氢、具有1-12个碳原子的烷基或苯基、甲苯基或茴香基,
及-NR5-,其中R5为氢或甲基;
n为0或1,和
m为2、3、4、5或6。
在式Ⅱ的优选化合物中,Ar和Ar′分别为亚苯基,y和n分别为0,m为2,其中,在邻位的两个亚苯基相互连接,并且可在相对于氧桥与磷原子间键的邻位和对位,被1-4个碳原子的烷基或C1-C4-烷氧基,特别是甲氧基和叔丁基取代。
戊烯腈与催化剂的摩尔比通常为100∶1至100,000∶1,优选500∶1至10,000∶1。
催化剂与助催化剂与戊烯腈的摩尔比通常为1∶1∶100至1∶200∶100,000,特别优选1∶2∶500至1∶100∶10,000。
从加氢甲酰化流出物中任选地排出来自加氢甲酰化的氢气、一氧化碳、催化剂和溶剂,得到加氢甲酰化流出物Ⅱ。
在特别优选的实施方案中,将排出的物质即氢气、一氧化碳、催化剂和加氢甲酰化溶剂(如果使用的话)循环回加氢甲酰化步骤a)中。
按照本发明,从加氢甲酰化流出物Ⅰ或Ⅱ中排出5-甲酰基戊腈。该排出过程优选通过蒸馏来完成。
在特别优选的实施方案中,高沸点物质和催化剂首先从加氢甲酰化流出物Ⅰ或Ⅱ中排出。该过程特别优选采用温热处理过程,具体例如常规方法中采用的闪蒸器、降膜蒸发器或刮桨式(wiping-blade)蒸发器。如果需要的话,排出的高沸点物质和催化剂,特别是含铼催化剂,可再循环回加氢甲酰化步骤(步骤a)中。
如果使用含钴催化剂,优选的实施方案包括用氧气,优选用空气,将加氢甲酰化流出物Ⅰ或Ⅱ氧化,将钴转化成为不挥发形式,特别是钴(Ⅱ)盐。
除去了高沸点物质如羟醛缩合产物和催化剂的混合物优选进行进一步的蒸馏以排出低沸点物质(与甲酰基戊腈相比)如未转化的戊烯腈。所回收的戊烯腈部分或全部循环回加氢甲酰化步骤中。
为了得到所需的具有价值的产物即5-甲酰基戊腈,优选将经除去戊烯腈后得到的反应混合物(其主要包含5-、4-和3-甲酰基戊烯腈)进行分馏,其中5-甲酰基戊腈(bp95℃/3毫巴)与4-和3-甲酰基戊腈(bp77-81℃/3毫巴)分离。通常,将支化的甲酰基戊腈的混合物从系统中排出。
令人惊奇的是,5-甲酰基戊腈与支化异构体4-和3-甲酰基戊腈间的沸点差即使在低真空下也足够大。例如,在3mbar下沸点差为14℃。这意味着,即使在工业化意义的真空范围内,即压力不小于10毫巴下,仍可实现从经济上说也是可接受的分离过程。
当然,5-甲酰基戊腈也可以以别的方式进行分离,例如在仅一步或两步中进行蒸馏。
根据反应条件不同,此时也会形成一定量的6-羟基戊腈。6-羟基戊腈也是一种有价值的产品,它可与5-甲酰基戊腈一起或单独地转化成为6-氨基己腈。
如果甲酰基戊腈被用作溶剂,则所需比例的甲酰基戊腈产品可有利地从系统中排出,其余的进行循环。
按照本发明,在第一步(步骤a),在加氢催化剂存在下,在40-150℃,优选50-140℃,特别优选60-130℃下,在压力为2-350巴,优选20-300巴,特别优选40-250巴下,使5-甲酰基戊腈与氨气和氢气反应,得到一种加氢流出物。
反应优选在液氨作为溶剂存在下进行,此时,氨也用作反应物。氨的用量通常为1-80摩尔/1摩尔5-甲酰基戊腈,特别是10-50摩尔/1摩尔5-甲酰基戊腈。除了氨外,也可有利地使用反应惰性的溶剂,例如醇、酯、醚、烃,此时,溶剂通常的用量为:溶剂与5-甲酰基戊腈的重量比为0.1∶1至5∶1,优选0.5∶1至3∶1。特别优选醇如甲醇和乙醇。
通常,应选择氢气的用量为:氢气与5-甲酰基戊腈的摩尔比为1∶1至100∶1,优选5∶1至50∶1。
本发明采用的催化剂为加氢催化剂,选自铑、铜和第八族元素(以下称为“加氢金属”),特别是铁、钴、镍、钌、铑、钯、锇、铱和铂,特别优选钌、钴、钯和镍的金属或金属化合物,条件是,加氢催化剂不包含铜、镍或铜和镍作为单独使用的成分。
可用于本发明的催化剂可为负载型或非负载型催化剂。适宜的载体材料包括,例如多孔氧化物如氧化铝、二氧化硅、硅铝酸盐、氧化镧、二氧化钛、二氧化锆、氧化镁、氧化锌和沸石及活性炭或其混合物。
催化剂可在上流或下流操作中用作固定床催化剂或用作悬浮床催化剂。催化剂上方的空间速度优选为0.1-2.0,优选0.3-1千克的5-甲酰基戊腈/1催化剂·小时。
同样,可以使用上述金属的化合物作为均匀溶解的加氢催化剂。
在优选的实施方案中,以加氢金属(以元素计)的总量计,上述催化剂可进一步包含0.01-25wt%,优选0.1-5wt%的至少一种助催化剂,助催化剂基于选自铜、银、金、锰、锌、镉、铅、锡、锶、钇、镧和镧系元素、钛、锆、铪、铬、钼、钨、钒、钽、锑、铋、铝的金属,以加氢金属(以元素计)计,也可掺入0.01-5wt%,优选0.1-3wt%的化合物,所述化合物基于碱金属或碱土金属,优选碱金属和碱土金属的氢氧化物如氢氧化锂、氢氧化钠、氢氧化钾、氢氧化铷、氢氧化铯,特别优选氢氧化锂。
用于本发明的催化剂可为例如沉淀型催化剂。这种催化剂可这样制备:将这些催化活性成分从其盐溶液中沉淀出来,特别是从其硝酸盐和/或乙酸盐溶液中沉淀出来,例如通过加入碱金属和/或碱土金属氢氧化物和/或碳酸盐溶液,例如难溶的氢氧化物、氧化物水合物、碱性盐或碳酸盐溶液,然后,将形成的沉淀干燥,随后通过锻烧将它们转化成相应的氧化物、混合氧化物和/或混合价态氧化物,锻烧温度通常为300-700℃,优选400-600℃,通常,再将所述氧化物用氢气或含氢气体在50-700℃,优选100-400℃下处理,还原为相应的金属和/或低氧化态的氧化化合物,从而转化成实际催化活性的形式。此时,还原过程通常进行至不再形成水时。
在含载体材料的沉淀型催化剂的制备过程中,使催化活性成分在所述载体材料存在下沉淀。但是,催化活性成分也可有利地从各自的盐溶液中同时作为载体材料沉淀出来。本发明的方法优选采用包含催化加氢的金属或金属化合物沉淀于载体材料上的加氢催化剂进行。除了上述的沉淀型催化剂(其除包含催化活性成分外,还包含一种载体材料),适宜的用于本发明方法的载体材料通常也是那些通过例如浸渍法将催化加氢的成分负载于载体材料上的催化剂材料。
催化活性金属负载于载体上的方式通常并不重要,可以采用各种方式完成。例如,催化活性金属可通过用各元素的盐或氧化物的溶液或悬浮液进行饱和而负载于这些载体材料上,干燥,再通过还原剂,优选氢气或配合氢化物,将金属化合物还原成相应的金属或低氧化态化合物。
另一类负载催化活性金属至其载体上的方法包括用催化活性金属的加热易分解的盐,例如硝酸盐,或加热易分解的配合物,如羰基配合物或氢化配合物的溶液浸渍这些载体,将形成的浸渍过的载体通常加热至300-600℃以对吸附的金属化合物进行热分解。该热分解过程优选在保护性气氛下进行。适宜的保护性气体可为,例如,氮气、二氧化碳、氢气或希有气体。
进而,催化活性金属可通过气相沉积或火焰喷涂负载至催化剂载体上。原则上,对本发明方法的成功而言,这些负载型催化剂的催化活性金属含量并不重要。本领域的技术人员将会理解,这些负载型催化剂的催化活性金属的含量高通常会比所述含量低时导致更高的时空转化率。通常,以催化剂总重量计,负载型催化剂包含0.1-90wt%,优选0.5-40wt%的催化活性金属。由于这些活性含量是基于包括载体材料的总催化剂重量,但是,各种载体材料会具有差异很大的比重和比表面积,所以这些数字在可能对本发明方法的结果没有有害影响时可以偏大或偏小。当然,也可以负载多种催化活性金属于具体的载体材料上。进而,催化活性金属也可按例如下述文献所述方法负载于载体上:DE-A 2 519 817,EP-A 1 477 219和EP-A 285 420。在上述文献的催化剂中,催化活性金属以合金的形式存在,其可用热处理和/或还原来生产,例如通过用上述金属的盐或配合物进行浸渍。
沉淀型催化剂和负载型催化剂均可通过氢气在反应开始时就地活化,但优选将这些催化剂在使用前分开活化。
将本发明方法步骤a)得到的加氢流出物进行常规处理过程如蒸馏,以回收6-氨基己腈和六亚甲基二胺或仅6-氨基己腈(步骤b)。
在优选的实施方案中,过量的氨、氢气和任选地加氢催化剂在步骤e)分离6-氨基己腈和六亚甲基二胺或仅6-氨基己腈之前排出。
另一个优选的实施方案包括:首先,在40-150℃下用氨处理5-甲酰基戊腈(步骤d′),得到含氨的流出物。例如,这可在预反应器中进行。该反应可在酸性、均相或非均相的催化剂不存在或优选在这些催化剂存在下进行。催化剂的空间速度(对于非均相催化剂而言)通常为0.1-2.0千克5-甲酰基戊腈/1催化剂·小时。
然后,如果需要的话,可将含氨的流出物与酸性催化剂分离(步骤e′)。
另一步骤(步骤f)包括使d′的含氨的流出物或e′的溶液与氨和氢气反应,反应是在加氢催化剂存在下进行的,所述催化剂选自铜、铼和其化合物及第八族金属和金属化合物,得到一种加氢流出物,该过程通常以与上述方法相同的方式进行。
之后,(步骤g)是,按照常规方法,从加氢流出物中回收6-氨基己腈或6-氨基己腈和六亚甲基二胺。
使用的酸性催化剂例如可为H型沸石、酸性离子交换剂、杂多酸、任选地用硫酸盐或磷酸盐掺杂的酸性和超酸性金属氧化物,和无机或有机酸。
适宜的代表性沸石例如为丝光沸石、毛沸石或菱沸石型的窄孔径沸石或八面沸石型沸石,例如Y-沸石、X-沸石或L-沸石。这些沸石也包括八面沸石型的“超稳定”沸石,即,脱铝沸石。
特别优选的沸石为具有pentasil结构的沸石,如ZSM-5、ZSM-11和ZSM-10。它们具有通常由二氧化硅四面体组成的五元环作为基本结构单元。它们的特点是,高SiO2/Al2O3比,其孔径介于A型沸石与X或Y型沸石之间。
用于本发明的杂多酸为无机多酸,其与异多酸不同,具有至少两个不同的中心原子。其实例为十二钨磷酸H3PW12O40·xH2O,十二钼磷酸H3PMo12O40·xH2O。原则上,可以使用那些在EP-A 158 229中提到的催化剂和催化剂组合。
优选的杂多酸为钼或钨与磷酸、碲酸、硒酸、砷酸、硅酸的杂多酸,特别是与磷酸的杂多酸。
杂多酸的质子可部分由金属原子代替,此时,优选采用碱金属和碱土金属离子。
优选的酸性离子交换剂例如可为具有磺酸基团的交联聚苯乙烯。
酸性金属氧化物的实例为:SiO2、Al2O3、ZrO2、Ga2O3、PbO2、Sc2O3、La2O3、TiO2、SnO2等,或各氧化物的组合。这些氧化物也可用无机酸进行处理以提高酸强度,如用硫酸处理。
适宜的酸的实例为无机酸如硫酸和磷酸,以及有机酸如磺酸。
过酸性金属氧化物的实例为硫酸盐掺杂的ZrO2或含钼或钨的ZrO2。
在另一个优选实施方案中,加氢反应是经负载于提到的氧化性载体之一上的加氢金属而进行的。在过量的氢气与催化剂一起或仅是过量的氢气被排出后,加氢流出物优选通过分馏对6-氨基己腈与六亚甲基二胺或仅是6-氨基己腈进行后处理。
本发明的方法得到6-氨基己腈,具有非常好的转化率,良好的收率和选择性。通过改变温度和催化剂空间速度,也可得到6-氨基己腈与六亚甲基二胺的混合物。高温和低催化剂空间速度有助于形成六亚甲基二胺,而低温和高催化剂空间速度有助于形成6-氨基己腈。
6-氨基己腈和六亚甲基二胺均是重要的纤维中间体。6-氨基己腈可被环化形成己内酰胺,它是形成尼龙6的单体。
六亚甲基二胺主要与己二酸反应形成6,6-盐,其是尼龙6,6的前体。
实施例
实施例1
在1升的搅拌中的提升式(lift)高压釜中,将100克的3-戊烯腈、作为溶剂的350克的间二甲苯和作为催化剂的0.08wt%的钴(八羰基合二钴形式)加热至105℃。在达到最后温度时,将反应混合物在140下与各50体积%的一氧化碳和氢气的混合物混合。在反应期间,通过进一步注入各50体积%的CO和H2的气体混合物保持反应器中的压力恒定。在反应3小时后,通过冷却和释压,使反应中止。反应混合物的GC分析显示出下述反应混合物组成(摩尔%):
转化率 7.5(3-戊烯腈的转化率)
选择性
戊腈 9.0
5-甲酰基戊腈 39.0
3-和4-甲酰基戊腈 52.0
甲酰基戊腈(3-、4-和5-FVN的总和)的收率为6.8%,5-甲酰基戊腈与3-和4-甲酰基戊腈的摩尔比为43∶57。
实施例2
在1升的搅拌中的提升式高压釜中,将100克的3-戊烯腈、作为溶剂的350克的间二甲苯和作为催化剂的0.04wt%的钴(八羰基合二钴形式)加热至170℃。在达到最后温度时,将反应混合物在280巴下与各50体积%的一氧化碳和氢气的混合物混合。在反应期间,通过进一步注入各50体积%的CO和H2的气体混合物保持反应器中的压力恒定。在反应2小时后,通过冷却和释压,使反应中止。反应混合物的GC分析显示出下述反应混合物组成(摩尔%):
转化率 >99.9
选择性
戊腈 41.0
5-甲酰基戊腈 16.0
3-和4-甲酰基戊腈 6.4
6-羟基己腈 23.0
4-和5-羟基甲基戊腈 3.6
5-甲酰基戊腈和6-羟基己腈的总收率为39%,5-甲酰基戊腈与3-和4-甲酰基戊腈的摩尔比为60∶40。
实施例3
在磁力搅拌器搅拌下的300毫升HC高压釜中,将以下物质加热至100℃:20克的3-戊烯腈、100克的甲苯(作为溶剂)、100ppm的铑(配合物Rh(CO)2acac(acac=乙酰丙酮化物,25毫克))和式Ⅲ的二亚磷酸酯(557毫克)(基于铑计,6倍摩尔过量)Ⅲ
在达到最后温度时,将反应混合物在5巴下与各50体积%的一氧化碳和氢气的混合物混合。反应期间,反应器的压力经压力调节器,通入再注入各50体积%的一氧化碳和氢气的混合物保持稳定在5巴。在反应5小时后,通过降温至室温和释压,使反应中止。反应混合物的GC分析显示出下述反应混合物组成(摩尔%):
转化率 >99.9
选择性
2-和4-戊烯腈 19.5
戊腈 21.3
5-甲酰基戊腈 29.7
3-和4-甲酰基戊腈 29.5
有价值的5-甲酰基戊腈的收率为29.7%,5-甲酰基戊腈与3-和4-甲酰基戊腈的摩尔比为50.2∶49.8。
实施例4
在磁力搅拌器搅拌下的300毫升HC高压釜中,将以下物质加热至100℃:20克的3-戊烯腈、100克的PalatinolC(邻苯二甲酸二正丁酯,作为溶剂)、100ppm的铑(配合物Rh(CO)2acac(acac=乙酰丙酮化物,25毫克))和亚磷酸三苯酯(基于铑计,25倍摩尔过量)。在达到最后温度时,将反应混合物在5巴下与各50体积%的一氧化碳和氢气的混合物混合。反应期间,反应器的压力经压力调节器通入再注入各50体积%的一氧化碳和氢气的混合物保持稳定在5巴。在反应5小时后,通过降温至室温和释压,使反应中止。反应混合物的GC分析显示出下述反应混合物组成(摩尔%):
转化率 98.6
选择性
2-和4-戊烯腈 0
戊腈 10.3
5-甲酰基戊腈 18.2
3-和4-甲酰基戊腈 71.5
有价值的5-甲酰基戊腈的收率为17.9%,5-甲酰基戊腈与3-和4-甲酰基戊腈的摩尔比为20∶80。
实施例5
在磁力搅拌器搅拌下的300毫升HC高压釜中,将以下物质加热至100℃:20克的4-戊烯腈、100克的甲苯(作为溶剂)、100ppm的铑(配合物Rh(CO)2acac(acac=乙酰丙酮化物,25毫克))和式Ⅲ的二亚磷酸酯(557毫克)(基于铑计,6倍摩尔过量)。在达到最后温度时,将反应混合物在5巴下与各50体积%的一氧化碳和氢气的混合物混合。反应期间,反应器的压力经压力调节器通入再注入各50体积%的一氧化碳和氢气的混合物保持稳定在5巴。在反应5小时后,通过降温至室温和释压,使反应中止。反应混合物的GC分析显示出下述反应混合物组成(摩尔%):
转化率 >99.9
选择性
2-和4-戊烯腈 34.0
戊腈 6.0
5-甲酰基戊腈 49.2
3-和4-甲酰基戊腈 10.8
有价值的5-甲酰基戊腈的收率为49.2%,5-甲酰基戊腈与3-和4-甲酰基戊腈的摩尔比为82∶18。
实施例6
将按照实施例3得到的多个加氢甲酰化流出物合并。蒸馏排出2-和4-戊烯腈和戊腈,留下130克的反应混合物,按照GC色谱分析,其包含48wt%的5-甲酰基戊腈和46wt%的4-和3-甲酰基戊腈。在旋带精馏柱上进行分馏得到59克的5-甲酰基戊腈(其沸点为93-95℃/3毫巴)(纯度为99%),56克的4-和3-甲酰基戊腈(其沸点为77-81℃/3毫巴)(4-和3-异构体的纯度为96%)。
实施例7
在保护性氩气氛下,向带有样品入口的300毫升(HC4作为结构材料)高压釜中加入11克的5-甲酰基戊腈和3克的Ru(3%)/Al2O3(4毫米挤出物)。将高压釜密封,注150毫升的氨气。将内容物在磁力搅拌器搅拌下混合。加热于80℃后(高压釜压力约39巴),将混合物在80℃下保温2小时,然后,用氢气使总压力升高至70。通过连续注入氢气,使压力保持在70巴。25小时后,将高压釜释压,通过气相色谱分析加氢流出物。形成的产物为73%的6-氨基己腈和12%的六亚甲基二胺。转化率为100%。
Claims (7)
1.一种制备6-氨基己腈或6-氨基己腈/六亚甲基二胺混合物的方法,该方法包括:
a)在催化剂存在下,使至少一种选自2-戊烯腈、3-戊烯腈和4-戊烯腈的戊烯腈与一氧化碳及氢气反应得到一种加氢甲酰化流出物Ⅰ,其中所述催化剂包含至少一种第八族元素作为活性成分,
b)任选地从加氢甲酰化流出物Ⅰ中除去一氧化碳、氢气和催化剂以得到加氢甲酰化流出物Ⅱ,
c)从所述加氢甲酰化流出物Ⅰ或Ⅱ中除去5-甲酰基戊腈,
d)在加氢催化剂存在下,使排出的5-甲酰基戊腈与氨气和氢气反应以得到一种加氢流出物,其中所述催化剂选自铼、铜和其化合物,以及第八族的金属和金属化合物,和
e)使6-氨基己腈或6-氨基己腈与六亚甲基二胺一起从加氢流出物中分离出来。
2.根据权利要求1的方法,其中,在步骤e)分离6-氨基己腈或6-氨基己腈/六亚甲基二胺之前,将过量的氨气、氢气和任选地加氢催化剂排出。
3.根据权利要求1或2的方法,其中,步骤a)采用一种包含钴或铑或铂作为活性成分的催化剂。
4.根据权利要求1或2的方法,其中,步骤a)的反应是在铑羰基配合物催化剂存在下,通过加入助催化剂进行的,助催化剂选自三芳基膦、二(二芳基膦基)烷烃、三芳基亚磷酸酯和式Ⅰ和Ⅱ的多亚磷酸酯,并任选地包含磺酸基团或羧酸基团,Ⅰ
其中,
X为二价双亚芳基或R1,
W为二价的取代或未取代的亚芳基、双亚芳基或亚烷基,和R1和R2可相同或不同,分别为取代或未取代的亚烷基或邻亚芳基,Ⅱ其中
Ar和Ar′可相同或不同,为具有6-18个碳原子的取代或未取代的亚芳基;
X为具有2-30个碳原子的间位结合的基团,其选自亚烷基、亚烷基-氧-亚烷基、亚芳基和下式的基团
亚芳基-(CH2)y-(Q)n-(CH2)y-亚芳基其中各亚芳基如上所定义,
y为0或1;
Q为二价桥基团,选自氧、硫、-CO-、-CR3R4-,其中,R3和R4分别为氢、1-12个碳原子的烷基或苯基、甲苯基或茴香基,及-NF5-,其中R5为氢或甲基;
n为0或1,和
m为2-6的整数。
5.根据权利要求4的方法,其中助催化剂的加入量为助催化剂(以磷当量计算)与铑的摩尔比为1∶1至300∶1。
6.根据权利要求1-5任一项的方法,其中步骤a)或d)的反应是在溶剂存在下进行的。
7.根据权利要求1的方法,其中步骤d)和e)可用下述步骤替换:
d′)任选地在酸性催化剂存在下,首先用氨气处理5-甲酰基戊腈得到一种含氨的流出物,
e′)然后,任选地排出酸性催化剂以得到一种氨的溶液,
f)在加氢催化剂存在下,使d′)的含氨流出物或e′)的氨溶液与氨气和氢气反应,得到一种加氢流出物,其中所述的加氢催化剂选自铜、铼和其化合物和第八族的金属和金属化合物,和
g)从加氢流出物中分离出6-氨基己腈或6-氨基己腈与六亚甲基二胺。
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DE19631521A DE19631521A1 (de) | 1996-08-03 | 1996-08-03 | Verfahren zur Herstellung von 6-Aminocapronitril |
DE19631521.2 | 1996-08-03 |
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EP (1) | EP0915839B1 (zh) |
JP (1) | JP2000516919A (zh) |
KR (1) | KR100502605B1 (zh) |
CN (1) | CN1100752C (zh) |
AU (1) | AU4377697A (zh) |
BR (1) | BR9710890A (zh) |
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DE (2) | DE19631521A1 (zh) |
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DE19923894A1 (de) | 1999-05-25 | 2000-11-30 | Basf Ag | Verfahren zur Herstellung von Polyamiden |
DE19933611A1 (de) | 1999-07-17 | 2001-01-18 | Aventis Res & Tech Gmbh & Co | Verfahren zur Herstellung von Aminen durch homogen katalysierte reduktive Aminierung von Carbonylverbindungen |
US6372939B1 (en) * | 2000-11-16 | 2002-04-16 | E.I. Du Pont De Nemours And Company | Production of 6-aminocaproic acid |
US6365770B1 (en) | 2000-11-16 | 2002-04-02 | E. I. Du Pont De Nemours And Company | Production of alkyl 6-aminocaproate |
DE102013217166A1 (de) * | 2013-08-28 | 2015-03-05 | Evonik Industries Ag | Verfahren zur Hydroformylierung von ungesättigten Verbindungen durch SILP-Katalyse |
JP7306649B2 (ja) * | 2019-04-26 | 2023-07-11 | 国立大学法人九州大学 | シアノアルデヒド化合物の製造方法 |
CN113698300B (zh) * | 2021-08-26 | 2023-07-14 | 万华化学集团股份有限公司 | 一种戊二胺的制备方法 |
CN116603567B (zh) * | 2023-03-27 | 2024-05-17 | 湖北兴发化工集团股份有限公司 | 一种用于合成6-氨基己腈的催化剂及其制备方法和应用 |
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US1477219A (en) * | 1919-12-08 | 1923-12-11 | Oliver E Becker | Clamp |
US2777873A (en) * | 1954-07-01 | 1957-01-15 | Eastman Kodak Co | Preparation of esters of omega-amino acids |
US3461167A (en) * | 1967-09-19 | 1969-08-12 | Du Pont | Process for making hexamethylene-diamine from adiponitrile |
US3471563A (en) * | 1968-05-17 | 1969-10-07 | Du Pont | Hydrogenation of adiponitrile over alkali moderated ruthenium |
DE2519817A1 (de) * | 1975-05-03 | 1976-11-11 | Hoechst Ag | Verfahren zur herstellung von butandiol-(1.4) |
DE2965583D1 (en) * | 1978-11-08 | 1983-07-07 | Ici Plc | Process for the production of hexamethylenediamine |
ATE26696T1 (de) * | 1982-06-11 | 1987-05-15 | Davy Mckee London | Hydroformylierungsverfahren. |
DE3372361D1 (en) * | 1982-06-11 | 1987-08-13 | Davy Mckee London | Hydroformylation process |
GB8334359D0 (en) * | 1983-12-23 | 1984-02-01 | Davy Mckee Ltd | Process |
US4668651A (en) * | 1985-09-05 | 1987-05-26 | Union Carbide Corporation | Transition metal complex catalyzed processes |
GB8707595D0 (en) * | 1987-03-31 | 1987-05-07 | British Petroleum Co Plc | Chemical process |
DE3843792A1 (de) * | 1988-12-24 | 1990-07-05 | Basf Ag | Verfahren zur herstellung von 6-aminocapronsaeureestern |
DE4026406A1 (de) * | 1990-08-21 | 1992-02-27 | Basf Ag | Rhodiumhydroformylierungskatalysatoren mit bis-phosphit-liganden |
US5296628A (en) * | 1992-02-13 | 1994-03-22 | E. I. Du Pont De Nemours And Company | Preparation of 6-aminocapronitrile |
SG49213A1 (en) * | 1993-05-06 | 1998-05-18 | Dsm Nv | Process for the preparation of a linear aldehyde organic |
DE69508744T2 (de) * | 1994-01-07 | 1999-12-02 | Dsm Nv | Verfahren zur herstellung von einer linearen formylverbindung |
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- 1997-07-23 JP JP10507544A patent/JP2000516919A/ja not_active Withdrawn
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- 1997-07-23 ES ES97941891T patent/ES2165087T3/es not_active Expired - Lifetime
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EP0915839B1 (de) | 2001-09-19 |
TR199900222T2 (en) | 2000-09-21 |
WO1998005632A1 (de) | 1998-02-12 |
US6048997A (en) | 2000-04-11 |
JP2000516919A (ja) | 2000-12-19 |
CZ23899A3 (cs) | 1999-04-14 |
BR9710890A (pt) | 1999-08-17 |
DE59704683D1 (de) | 2001-10-25 |
DE19631521A1 (de) | 1998-02-05 |
ES2165087T3 (es) | 2002-03-01 |
KR20000029788A (ko) | 2000-05-25 |
ID17978A (id) | 1998-02-12 |
MY119330A (en) | 2005-05-31 |
CN1100752C (zh) | 2003-02-05 |
EP0915839A1 (de) | 1999-05-19 |
TW432033B (en) | 2001-05-01 |
AU4377697A (en) | 1998-02-25 |
KR100502605B1 (ko) | 2005-07-22 |
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