CN1171778A - 制备脂族α,ω－氨基腈的方法 - Google Patents
制备脂族α,ω－氨基腈的方法 Download PDFInfo
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- CN1171778A CN1171778A CN95197139A CN95197139A CN1171778A CN 1171778 A CN1171778 A CN 1171778A CN 95197139 A CN95197139 A CN 95197139A CN 95197139 A CN95197139 A CN 95197139A CN 1171778 A CN1171778 A CN 1171778A
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- 125000001931 aliphatic group Chemical group 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title 1
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 11
- 239000010941 cobalt Substances 0.000 claims abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 11
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- 239000011575 calcium Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
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- 239000011777 magnesium Substances 0.000 claims description 3
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- 150000002736 metal compounds Chemical class 0.000 abstract 1
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- 238000002360 preparation method Methods 0.000 description 10
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- 238000009835 boiling Methods 0.000 description 9
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 4
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- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
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- -1 carboxylate salt Chemical class 0.000 description 3
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- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
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- 150000001721 carbon Chemical group 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
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- 239000011261 inert gas Substances 0.000 description 2
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- RPMBPYXLPIWSFJ-UHFFFAOYSA-N 2-aminopentanenitrile Chemical compound CCCC(N)C#N RPMBPYXLPIWSFJ-UHFFFAOYSA-N 0.000 description 1
- 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
- XGYKKVTZDQDYJQ-UHFFFAOYSA-N 4-aminobutanenitrile Chemical compound NCCCC#N XGYKKVTZDQDYJQ-UHFFFAOYSA-N 0.000 description 1
- GACPJEGITQYOGZ-UHFFFAOYSA-N 6-aminohexanenitrile Chemical compound NCCCCCC#N.NCCCCCC#N GACPJEGITQYOGZ-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052804 chromium Inorganic materials 0.000 description 1
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- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 description 1
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- 230000002939 deleterious effect Effects 0.000 description 1
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- RILTWTZTURZUEO-UHFFFAOYSA-N formic acid;nickel Chemical compound [Ni].OC=O RILTWTZTURZUEO-UHFFFAOYSA-N 0.000 description 1
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LLEVMYXEJUDBTA-UHFFFAOYSA-N heptanedinitrile Chemical compound N#CCCCCCC#N LLEVMYXEJUDBTA-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 description 1
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- BTNXBLUGMAMSSH-UHFFFAOYSA-N octanedinitrile Chemical compound N#CCCCCCCC#N BTNXBLUGMAMSSH-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
通过在高温和超大气压下在溶剂和催化剂存在下部分氢化脂族α,ω－二腈制备脂族α,ω－氨基腈,采用的方法包括使用通过热分解选自金属羰基化物、C1－C6羧酸和C2－C6二羧酸的金属盐及具有二酮的金属配合物的金属化合物得到相应金属和/或其金属氧化物的方式制备的催化剂,条件是所用的金属为镍或钴。
Description
本发明涉及一种通过在高温和超大气压下在溶剂和催化剂存在下部分氢化脂族α，ω-二腈制备脂族α，ω-氨基腈的改进方法。
WO 92/21650公开了在阮内镍催化剂和氨作为溶剂存在下将己二腈部分氢化为6-氨基己腈，在转化率为70％时收率为60％。形成9％的己二胺副产品。当将甲醇用作溶剂并加入除氨外的碱时，在转化率为70％时可使选择性提高至89.5％。这种方法的缺点是催化剂的寿命短。
US 2,257,814和2,208,598还公开了由己二腈起始制备6-氨基己腈的方法，所用的催化剂为阮内钴和铁，载在各种载体上的镍和钴催化剂。选择性为50至60％，这对于工业应用太低，为这些方法的一个缺点。
在WO93/16034的方法中，可通过在阮内镍，碱如氢氧化钠、氢氧化钾、氢氧化锂或氢氧化铵，过渡金属(如铁、钴、铬或钨)配合物和溶剂存在下氢化己二腈，提高氨基己腈的收率。在该方法中，描述了在转化率45至60％下氨基己腈的定量收率。这种方法的一个缺点是要从所得反应混合物中精制除去通常有毒的过渡金属配合物。
EP-A 161,419描述了在氨存在下用载在氧化镁载体上的含铑的催化剂部分氢化己二腈的方法。在转化率70％时，选择性达到94％。其缺点是Rh/MgO催化剂的制备方法昂贵(参见，催化剂期刊(J.of Cat.)，112(1988)，145-156)。
本发明目的在于提供一种通过部分氢化己二腈制备脂族α，ω-氨基腈的方法，该方法无上述缺点；本发明特别试图找到一种其中所用的催化剂与现有的催化剂相比具有较长寿命的方法。
我们已发现本发明目的可通过在高温和超大气压下在溶剂和催化剂存在下部分氢化脂族α，ω-二腈制备脂族α，ω-氨基腈的方法实现，所述方法包括使用通过热分解选自金属羰基化物、C1-C6羧酸和C2-C6二羧酸的金属盐及具有二酮的金属配合物的金属化合物得到金属和/或其金属氧化物的方式制备的催化剂，条件是所用的金属为镍或钴。
我们还发现由热分解制得的催化剂用于部分氢化α，ω-二腈的用途。
在适合本发明的金属化合物，即金属羰基化物、C1-C6羧酸和C2-C6二羧酸的金属盐及具有二酮(优选1，2-和1，3-二酮，如乙酰丙酮化物或二甲基乙二肟)的金属配合物中，优选使用C1-C6羧酸和C2-C6二羧酸的金属盐，这些羧酸拟包括不饱和羧酸和二羧酸以及含羟基的羧酸和二羧酸，如马来酸、乳酸和酒石酸。甲酸、乙酸、丙酸、丁酸、戊酸、己酸、草酸、丙二酸、丁二酸、戊二酸、己二酸和马来酸的镍和钴盐是特别优选的，更特别优选甲酸镍、甲酸钴、乙酸镍、乙酸钴、草酸镍和草酸钴。
羧酸和二羧酸的金属盐可市购或可(例如)根据物理化学期刊(J.ofPhys.Chem.)68.4(1964)，731-732或美国化学会志81(1959)，2930-2933制备。
由羧酸和二羧酸的金属盐制备的相应催化剂描述于“催化剂制备”V，1991，Elsevier Science Publishers B.V.，Amsterdam，p165-174 Coll.Czech.Chem.Comm.46(1981)1011-1022中或可通过与其中类似的方法制备，因此这方面的进一步信息是不必要的。
金属羰基化物的热分解可(例如)通过DRP 511 564或FP 1,317,934中的方法进行。
具有二酮的金属配合物的热分解通常类似于羧酸盐的热分解，但在氢气气氛中进行。
通常热分解在温度150至500℃，优选180至400℃，特别优选190至350℃下进行。选取的温度具体取决于所用的起始化合物。同时，热分解可在惰性气体气氛(氮气、氩气或氦气)和在还原性气氛(氢气)中，在压力1Pa至10MPa，优选100Pa至1MPa，特别优选在大气压下，在常规反应器中进行。为制备载体催化剂，该热分解在所需的载体或载体前体存在下进行。
在热分解中，所用的金属化合物通常被转化为相应的金属或金属与各金属氧化物的混合物，这取决于所用的金属化合物、热分解的时间、选取的温度和气相组成。
镍或钴在催化剂中的含量取决于是否制备无载体或有载体的催化剂。对于有载体的催化剂，金属含量通常为1至70，优选10至40wt％。
除了镍或钴外，催化剂还可含有另一些金属，特别是过渡金属和元素周期表第二至第4主族的金属，其中银、铜、锌、镁、钙和铁是特别优选的。该制备通常通过同时或先后热分解相应金属化合物(使用金属化合物混合物，尤其其中所含非金属残余物部分相同的金属化合物的混合物是有利的)进行。例如，可将共沉淀氧化镍和氧化镁在惰性气体气氛如氮气、氩气或氦气，或含氢气的还原性气氛下转化为于氧化镁上细分散的镍(参见催化剂制备(Pre.of Cat.)V，1991，Elsevier，Amsterdam，p165-174和Coll.Czech.Chem.Comm.46(1981)，1011-1022)。
在优选的实施方案中，镍催化剂通过按照Ind.Eng.Chem.32，No.9(1940)1193-1199的方法，在高沸点液体中加热甲酸镍获得。
其它镍和钴催化剂优选可在液相中按类似于Ind.Eng.Chem.Vol.32，No.9(1940)1193-1199的方法进行，在该方法中使用在大气压下具有高沸点的惰性物质，特别是高沸点C9-C30-饱和烃，如白油和石蜡，高沸点CnH2n+3N-胺(其中n为7至2 5)，高沸点CmH2m+4N-二胺(其中m为5至35)如己二胺，聚胺如聚乙烯-亚胺，和组成为(OH)pC7H2n+2-p高沸点醇如辛醇、丙二醇和甘油。这种方法的优点在于可将镍或钴和(若需要)另一些金属用高沸点物质(当然其在室温下也可为固体)包裹。迄今的观察证明这种包裹可防止氧气进入，这样不会发生催化剂的惰化，并可按简单方式使用催化剂。
新方法中使用的起始物质是通式I脂族α，ω-二腈
NC-(CH2)n-CN I其中n为1至10的整数，特别是2、3、4、5或6，特别优选的化合物I是丁二腈、戊二腈、己二腈、庚二腈和辛二腈，己二腈是更特别优选的。
在该新方法中，将上述二腈I在溶剂和(若需要)碱如碱金属的氢氧化物，特别是氢氧化锂、氢氧化钠或氢氧化钾，优选氢氧化锂和上述一种催化剂存在下部分氢化，得到通式II的α，ω-氨基腈
NC-(CH2)n-CH2-NH2 II其中n具有前述含义。特别优选的氨基腈II是其中n为2、3、4、5或6，特别是4的那些氨基腈，即4-氨基丁腈、5-氨基戊腈、6-氨基己腈(6-氨基己腈)，7-氨基庚腈和8-氨基辛腈，特别优选6-氨基己腈。
若反应在悬浮液中进行，则选取的温度为30至150℃，优选50至100℃，特别优选60至90℃；选取的压力通常为2至20，优选3至10，特别优选4至8MPa。停留时间基本上取决于所需的收率和选择性并取决于所需的转化率；选取的停留时间通常应获得最大收率，例如当使用己二腈时，停留时间为30分钟至10小时，优选1至5小时。
在悬浮液方法中，使用的溶剂优选为氨，胺，二胺和1至6个碳原子的三胺，如三甲胺、三乙胺、三丙胺和三丁胺，或醇类，优选甲醇和乙醇，特别优选氨。选取的二腈浓度有利地为10至90，优选30至80，特别优选40至70wt％(按二腈和溶剂的总重量计)。
在悬浮液中的氢化通常可在液相中间歇或优选连续进行。
部分氢化还可通过喷淋床或液相方式在固定床反应器中间歇或连续进行，选取的温度为20至150℃，优选30至90℃，压力通常为2至30，优选3至20MPa。根据本发明，部分氢化在溶剂，优选氨，胺，二胺或1至6个碳原子的三胺，如三甲胺、三乙胺、三丙胺或三丁胺，或醇类，优选甲醇和乙醇，特别优选氨存在下进行。在优选的实施方案中，所选的氨含量为1至10，优选2至6g/g己二腈。优选选取的催化剂空间速度为0.1至1.0kg己二腈/1*h。这里转化率和相应的选择性也可通过改变停留时间控制。
在该新方法中，可以良好选择性获得α，ω-氨基腈，与现有技术相比，催化剂具有更长的寿命。α，ω-氨基腈是用于制备环内酰胺的重要起始化合物，特别是6-氨基己腈是制备己内酰胺的重要起始化合物。
实施例1-制备催化剂
将0.5mol硝酸镍、0.5mol硝酸锌、1升水、1mol乙酸和1mol乙酸铵加热至70℃。向该搅拌溶液中在1小时内滴加在2升水中的1.5mol草酸。将如此制得的悬浮液在温度70℃下搅拌24小时然后过滤。将洗涤过的沉淀物在80℃下干燥16小时。然后将已干燥的沉淀物在350℃下在氢气气氛中分解16小时，制得Ni/Zn摩尔比为1∶1的产品。实施例2-氢化己二腈(ADN)
将60g己二腈(ADN)、6g实施例1中制得的催化剂和100ml液氨在高压釜中在氢气氛中(100巴)加热至100℃。3小时后停止反应。ADN的转化率为59％。获得如下收率：6-氨基己腈(ACN)：50％，己二胺(HMD)：7％，Azepane(氢化氮杂)：0.36％，氮杂：0.07％，高沸点物：0.65％(所有百分数都为按反应混合物总重量计的重量百分数)。实施例3-比较例
用阮内镍催化剂(购自Degussa，K 111 W)重复实施例2。在转化率为58％时，获得如下收率：6-氨基己腈(ACN)：50％，HMD：6.7％，Azepane：0.23％，氮杂：0.15％，高沸点物：1.29％(所有百分数都为按反应混合物总重量计的重量百分数)。
Claims (6)
1.一种通过在高温和超大气压下在溶剂和催化剂存在下部分氢化脂族α，ω-二腈制备脂族α，ω-氨基腈的方法，包括使用通过热分解选自金属羰基化物、C1-C6羧酸和C2-C6二羧酸的金属盐及具有二酮的金属配合物的金属化合物得到相应金属和/或其金属氧化物的方式制备的催化剂，条件是所用的金属为镍或钴。
2.如权利要求1的方法，其中催化剂还含有选自银、铜、锌、镁、钙和铁的金属作为进一步的组分。
3.用通过热分解选自金属羰基化物、C1-C6羧酸和C2-C6二羧酸的金属盐及具有二酮的金属配合物的金属化合物得到相应金属和/或其金属氧化物的方式制备的催化剂在高温和超大气压下在溶剂存在下部分氢化脂族α，ω-二腈的用途，条件是所用的金属为镍或钴。
4.如权利要求1或2的方法，其中使用的α，ω-二腈为己二腈，并制得6-氨基己腈。
5.如权利要求3的催化剂用途，用于制备6-氨基己腈。
6.如权利要求3的方法，其中催化剂还含有选自银、铜、锌、镁、钙和铁的金属作为进一步的组分。
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| DE4446895A DE4446895A1 (de) | 1994-12-27 | 1994-12-27 | Verfahren zur Herstellung von aliphatischen a,w-Aminonitrilen |
| DEP4446895.4 | 1994-12-27 |
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| DE19614154C1 (de) * | 1996-04-10 | 1997-09-25 | Basf Ag | Verfahren zur gleichzeitigen Herstellung von 6-Aminocapronitril und Hexamethylendiamin |
| DE19614283A1 (de) * | 1996-04-11 | 1997-10-16 | Basf Ag | Verfahren zur Herstellung von Aminen und Aminonitrilen |
| DE19636768A1 (de) * | 1996-09-10 | 1998-03-12 | Basf Ag | Für die Herstellung von aliphatischen alpha, omega-Aminonitrilen durch partielle Hydrierung von aliphatischen Dinitrilen geeignete Katalysatoren |
| CN103084180B (zh) * | 2013-02-28 | 2014-08-20 | 中国矿业大学 | 催化芳环全加氢负载型超细非晶金属镍催化剂的制备方法 |
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| US2208598A (en) * | 1938-09-24 | 1940-07-23 | Du Pont | Aliphatic amino-nitriles and process of producing them |
| US2257814A (en) * | 1940-05-02 | 1941-10-07 | Du Pont | Preparation of omega-amino nitriles |
| US2762835A (en) * | 1953-03-12 | 1956-09-11 | Celanese Corp | Preparation of amino nitriles |
| US4601859A (en) * | 1984-05-04 | 1986-07-22 | Allied Corporation | Selective hydrogenation of aliphatic dinitriles to omega-aminonitriles in ammonia with supported, finely dispersed rhodium-containing catalyst |
| US5151543A (en) * | 1991-05-31 | 1992-09-29 | E. I. Du Pont De Nemours And Company | Selective low pressure hydrogenation of a dinitrile to an aminonitrile |
| NL9102112A (nl) * | 1991-12-18 | 1993-07-16 | Dsm Nv | Werkwijze voor het bereiden van een aminonitril door het partieel hydrogeneren van een nitrilverbinding met twee of meer nitrilgroepen. |
| US5296628A (en) * | 1992-02-13 | 1994-03-22 | E. I. Du Pont De Nemours And Company | Preparation of 6-aminocapronitrile |
| DE4235466A1 (de) * | 1992-10-21 | 1994-04-28 | Bayer Ag | Verfahren zur Herstellung von (cyclo)aliphatischen Aminonitrilen |
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| US5557004A (en) | 1996-09-17 |
| EP0800509A1 (de) | 1997-10-15 |
| RU2158254C2 (ru) | 2000-10-27 |
| AU4386796A (en) | 1996-07-19 |
| CA2208774A1 (en) | 1996-07-04 |
| EP0800509B1 (de) | 1999-09-22 |
| TW408100B (en) | 2000-10-11 |
| BR9510111A (pt) | 1997-11-11 |
| DE59506919D1 (de) | 1999-10-28 |
| JPH10511373A (ja) | 1998-11-04 |
| MX9704754A (es) | 1997-10-31 |
| KR980700959A (ko) | 1998-04-30 |
| DE4446895A1 (de) | 1996-07-04 |
| CN1089752C (zh) | 2002-08-28 |
| MY114116A (en) | 2002-08-30 |
| WO1996020167A1 (de) | 1996-07-04 |
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