CN1077883C - 非共轭2-烷基-3-单烯腈的催化气相异构化 - Google Patents
非共轭2-烷基-3-单烯腈的催化气相异构化 Download PDFInfo
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- 239000003446 ligand Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 29
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
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- C07—ORGANIC CHEMISTRY
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- 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
- C07F9/6571—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 having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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- 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
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
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Abstract
2-烷基-3-单烯腈催化异构化为3和/或4-单烯腈的气相方法,其中使用零价镍和二配位基亚磷酸酯配位体的载体组合物作为催化剂。
Description
发明领域
本发明一般涉及2-烷基-3-单烯腈异构化以产生3-和/或4-单烯直链腈的气相方法。更具体地,本发明涉及使用零价镍和二配位基亚磷酸酯配位体将2-烷基-3-单烯腈异构化以产生3-和/或4-单烯直链腈的气相方法。
发明背景
在现有技术中,例如US 3,766,237已知通过丁二烯的氢氧化以形成戊烯腈(PN)。如此形成占优势的戊烯腈,例如3-戊烯腈,4-戊烯腈和2-甲基-3-丁烯腈,可进一步氢氰化和/或异构化,以形成已二腈(ADN),这在合成尼龙中是一种重要的工业材料。
在液相中,在零价镍催化剂存在下,2-甲基-3-丁烯腈能够有效地异构化而成3和/或4-戊烯腈,戊烯腈产物易于进一步氢氰化而形成己二腈。但是在气相中进行这种异构化的技术还不知晓。Kurokawa等人进行的有关研究(Journal of Catalysis(催化剂杂志)141,94-101(1993))叙述了3-戊烯腈气相通过异构化可成为支链和直链戊烯腈混合物。催化剂包括在350℃和370℃温度下使用的SiO2,MgO或CaO。据报道,支链产物与直链产物的比在19/35,24/18和10/49的范围内。在所有情况下,只得到共轭的支链化合物;也就是说,未形成2-甲基-3-丁烯腈。
发明概述
本发明提供一种无环的,脂族的,非共轭的2-烷基-3-单烯腈的气相异构化方法,优选为2-甲基-3-丁烯腈,该方法包括:使原料腈在约135°-170℃,优选140℃-160℃的温度范围内与含有零价镍和至少一种二配位基亚磷酸酯配位体的载体催化剂组合物接触,以产生非共轭的,直链的,无环的3-和4-单烯腈,优选为3-和4-戊烯腈,所述二配位基亚磷酸酯配位体选自式I和式II所示配位体:式I其中每个R1分别为3-12个碳原子的二级或三级烃基,每个R2分别为H,C1-C12烷基,或者OR3,其中R3是C1-C12烷基;式II其中每个R4分别为最多12个碳原子的三级烃,或者OR5,其中R5是C1-C12烷基;和每个R6分别为最多12个碳原子的三级烃。
在上述的式I和式II的定义中,“二级”和“三级”是指与芳香环相连的碳原子。此外,对于本发明的公开和权利要求来说,术语“烯腈”,“戊烯腈”和“丁烯腈”分别意指氰基的碳原子是第一碳原子的氰基烯烃;氰基丁烯,和氰基丙烯。
本发明提供一种催化气相方法,此方法在非共轭2-烷基-3-单烯腈的异构化中,是快速的,有选择性的,有效和稳定的。本发明气相方法的优点是排除了绝大多数液相方法中所使用的溶剂,例如反应稀释剂或产物萃取剂。此外,在此气相方法中,使用催化剂作为不动的固相,这可以减少催化剂合成,回收,再循环和副产物废物处置的费用。这样的优点也能消除对与液相方法有关的设备的需求,并能进一步节省费用。
优选的实施方案详细描述
当原料腈是2-甲基-3-丁烯腈(2M3BN)时,本发明的气相异构化方法生产了主要由3-戊烯腈(3PN)和4-戊烯腈(4PN)组成的戊烯腈混合物。
零价镍在本领域是已知的,零价镍能以许多方法来制造。最普通的用于构成本发明催化组合物的零价镍是从含有邻-亚磷酸三甲酚酯,对-亚磷酸三甲酚酯,环辛二烯和乙烯的Ni(0)配合物得到的。在适宜的配位体(例如参见下文的例2,其中Ni(NO3)2用H2还原,以得到载带在硅胶上的Ni(0)存在时,Ni(0)也可以用分子氢或其它的还原剂还原Ni(II)的化合物来制备。此外,含有二配位基的配位体的Ni(0)配合物可以由还原Ni(II)的化合物(例如参见下文的例1,在例1中制备了Ni(配位体A)(乙烯)),以及通过金属镍和二配位基的配位体来制备。也能成功地使用本领域技术人员所熟知的其它的零价镍。
实际的催化剂是零价镍与二配位基的亚磷酸酯的配位体的配合物,当这两种物质化合时就形成了此配合物。有效的催化剂对于一克原子的零价镍至少需要一摩尔的二配位基的亚磷酸酯配位体。
上述催化剂组合物通常载带在二氧化硅,氧化铝,碳或其它合适的载体上。在某些场合下可以使用未载带的催化剂,但是它们的催化效率可能很低。在B,C,Gates所著非均相催化,Vol 2,第1-29页,Ed.B.L Shapiro,德克萨斯A和M大学出版社,大学区,德克萨斯,1984年的文章中可以找到金属催化剂载体处理的通用技术。另外,给定的载体也可以用均匀分散涂复零价镍金属来制备,然后可以用所需要的二配位基的亚磷酸酯配位体进行处理。
典型情况下,根据本发明,零价镍催化剂分配在二氧化硅、氧化铝或碳载体上的浓度要足够产生含有0.3%重量-1.0%重量镍的载体催化剂组合物。然后催化剂组合物装入管式反应器中,气体2-烷基-3-单烯腈,例如2-甲基-3-丁烯腈,在温度足够高以维持原料腈和异构化的产物处于气相的条件下在固体催化剂上方连续地通过。
优选的温度范围是约140°-150℃,最优选的范围是145°-150℃。温度必须高,到足以使所有的有机物挥发掉,同时又要低至足以防止催化剂变质。优选的温度在某种程度上取决于所应用的特定的催化剂,所使用的特定的2-烷基-3-单烯腈和所需要的反应速度。操作压力并非特别紧要,约1-10个大气压(101.3-1013KPa)可能是较适合的。高于上述范围,预期将无经济利益。
2-烷基-3-单烯腈原料既可以以纯蒸汽的形式,也可以以一种挥发性溶剂例如乙腈或甲苯中的蒸发溶液的形式导入使用。在大气的压力下,使用附加的氮气或其它的惰性气体源作为载体,典型地在140-150℃的温度下使用。氮气是优选的,因为它的价格低。氧气,水蒸汽或其它能够与催化剂或者原料2-烷基-3单烯腈发生反应的气态物质应该避免。在室温下异构化产物是液体,因而可利用冷却作用方便地加以回收。
在本发明方法中用作原料的2-烷基-3-单烯腈的烯烃双键不能与氰基的三键共轭。合适的原料2-烷基-3-单烯烃腈也能够带有与催化剂不起化学反应的基团,例如另外的氰基。原料2-烷基-3-单烯腈优选地含有5-8个碳原子,不包括任何额外的取代。在生产己二腈时,2-甲基-3-丁烯腈特别重要。其它的具有代表性的腈包括2-乙基-3-丁烯腈和2-丙基-3-丁烯腈。
下列的式III和式IV例示了合适的代表性的原料2-烷基-3-单烯腈。当原料腈是2-甲基-3-丁烯腈时,异构化产物是式V和式VI所表示的那些产物。式III式IV其中R7是H或C1-C3烷基
CH2=CH-CH2-CH2CN
式V和 CH3-CH2=CH-CH2CN
式VI可以看到式III是式IV的特例,其中R7是氢。
本发明的异构化方法可以这样实施,例如首先将特定的载体催化剂组合物装入管式反应器内,优选地在惰性气氛下进行,然后将管式反应器与连续进料和回收的装置相连,同时利用惰性气流,例如氮气,氩气或氦气流合适地清扫所有给料管线,以使与空气的接触最少。装有热电偶的反应器在连续的惰性气流通过或者进出口关闭而让惰性气体流过旁路的情况下,加热到所需要的反应温度。原料2-烷基-3-单烯腈既可以以纯净的方式进料,也可以以溶解在合适的溶剂例如乙腈或甲苯中的方式进料。原料腈和任何的溶剂都通过加热到反应温度的进料管线部分,以保证完全的蒸发。从反应器出口引出的气体产物混合物,如果需要的话可以穿过气相色谱的加热气体取样回路,以检测反应进展的情况。另外,为了以液体的形式回收产物,气体流出物也可以冷却到0℃-25℃。每小时连续进料的不饱和化合物与催化剂的摩尔比通常可以在约5∶1/小时-100∶1/小时的范围内变化。
异构化反应优选地是在没有溶剂的情况下进行的。如果使用任何的溶剂的话,那末该溶剂在反应温度和压力的条件下应该是气体,并对原料腈,反应产物和催化剂是惰性的。典型的溶剂包括烃类例如己烷,苯,甲苯和二甲苯,或者腈例如乙腈。
优选的是,溶剂选自饱和的和芳香的烃以及脂族腈,而这些饱和烃,芳香烃和脂族腈在异构化的反应温度下是气态。
实例
下列非限定性的,具有代表性的实例举例说明了本发明的情况。如果不另作说明,所有的比例和百分数都是以重量计。在这些实例中,配位体“A”是式II所示的配位体,其中每个R4是OCH3,每个R6是叔-丁基。
实例1
碳载体Ni(0)(配位体“A”)CH2=CH2的合成,
其中配位体“A”是式II所示的配位体,式II中
每个R4是OCH3,每个R6是叔丁基。
所有的操作步骤都是在充氮的手套箱中进行的。0.385克(1.5毫摩)的镍(乙酰丙酮酸根)2,1.18克(1.5毫摩)配位体“A”,和20毫升甲苯放入玻璃瓶中。接着乙烯鼓泡通过溶液。此后,2.3毫升的1.9M(C2H5)3Al的甲苯溶液逐滴加入,而乙烯继续鼓泡通过溶液。在几分钟后,中断乙烯流,用隔膜密封玻璃瓶。反应内含物彻夜搅拌。第二天,在减压的条件下,除去约1/2的溶剂。一部分固体反应产物利用过滤回收。将甲醇加到滤液中,使另外的固体反应产物沉淀下来。回收的产物进行真空干燥,得到0.78克的金色粉末。成品的31P核磁共振谱在169.9ppm处显示出主单峰(Ni(配位体“A”)CH2=CH2),和在162.8ppm处显示出次单峰(Ni(配位体“A”)2)。
5克酸洗的碳放在石英管中,在管式炉中在氮气流中加热到100℃达1小时。石英管冷却到室温,密封,和转移到充氮手套箱中。干燥的碳然后用0.5克(0.57毫摩)〔Ni(配位体“A”)CH2=CH2〕的10毫升无水甲苯溶液搅拌30分钟。甲苯溶剂在真空下进行蒸发,以提供干燥的{Ni(配位体“A”)CH2=CH2}/C催化剂。
实例2
SiO2载体镍(0)(配位体“A”)2的合成,
其中配位体“A”是式II所示的配位体,式II中
每个R4是OCH3,每个R6是叔丁基
在玻璃反应器中,放入0.25克(0.86毫摩)的Ni(NO3)2·6H2O和25ml的水。向所得到的溶液中加入10克的二氧化硅颗粒。搅拌混合物,然后在真空下干燥。在石英管中,在氮气流下加热进一步干燥得到的涂有Ni(NO3)2的二氧化硅。温度以30℃/分的速度由室温逐渐增加到300℃,并在300℃的温度下维持1小时。中断氮气流,打开氢气流。在1小时内温度上升到500℃,保持2小时。石英管内含物冷却到室温,然后转移到充氮手套箱内。在20毫升的玻璃瓶中,用0.17克(0.22毫摩)溶解在5毫升无水甲苯中的配位体“A”处理1.28克所得到的SiO2-载体零价镍。该混合物搅拌10分钟;然后在真空下除去甲苯,以形成{Ni(0)+(配位体“A”)2/SiO2}催化剂。
实例3-11
2-甲基-3-丁烯腈的气相异构化
在充氮手套箱内,在中空的直径0.25英寸(0.64厘米)×长度15英寸(38.1厘米)的不锈钢管反应器的底部放入玻璃棉塞。将表1所示的数量和类型的零价Ni(0)催化剂引入反应器中。在使用包含二配位基的亚磷酸酯配位体的催化剂组合物的所有实例中,配位体都是配位体“A”。然后反应器与用氮气冲洗过的进料和产物回收装置相连。原料腈以8.2-10.6%2M3BN的乙腈溶液送入或以纯净的2M3BN送入。用冷却到0℃的乙二醇循环的夹套接受器与反应器出口侧相连。液体产物定期的移出,用气相色谱(GC)进行分析。气相色谱分析是在由J&WScientific,Folsom,加利福尼亚提供的内径0.32毫米的30m DB-23毛细血管柱中进行的。0.5%1-氰基辛烷的甲苯溶液也送入接受器中,该溶液用作气相色谱的内标。为保证完全蒸发,氮气,2M3BN和乙腈料液流预热到165℃。反应器在剖分管式炉中加热到表1所示的温度。大致每隔1小时收集一次产物样品。
作为进料使用的原料2M3BN含有少量的3PN和4PN,对应于约1.5%的转化率,下文报道的数据中包含了此转化率。实例5,6,7使用了相同的催化剂,表明二氧化硅是比碳或氧化铝更为优选的载体。在没有二配位基亚磷酸酯配位体存在时,例8和例11的实验仅给出了很低的转化率,例8和例11都使用零价镍作催化剂。在表中,“A”代表配位体“A”;“PTTP”代表亚磷酸对-三甲苯基酯;“OTPP”代表亚磷酸邻-三甲苯基酯。
表1
2M3BN气相异构化为3PN和4PN
催化剂 催化剂 2M3BN给料 N2给料 2M3BN/Ni (3PN) (4PN)实例 (载体) g,%Ni 毫摩/小时 毫升/分 摩/克原子 温度℃ 经过时间小时 气相色谱面积% 转化率%3 Ni["A"]CH2=CH2 0.61,0.61 1.0 5 15.7 150 1 0.98 0.01 76
150 2 1.64 0.03 69
(碳) 150 3 1.48 0.02 53
150 4 1.10 0 38
150 5 0.87 0 304 Ni["A"]CH2=CH2 1.12,0.47 0.95 10 10.6 145 1 2.18 0.14 89.6
145 2 2.89 0.13 92.1
(SiO2) 145 3 3.05 0.11 91.9
145 4 3.14 0.10 91.8
145 5 3.08 0.09 91.6
145 6 3.09 0.08 91.45 Ni["A"]2 1.0,0.35 1 10 16.7 145 1 0.08 0 1.5用2当量的(C2H5)3Al/当量Ni预处理的催化剂 145 2 0.10 0 1.9
(Al2O3) 145 3 0.10 0 2.0
Ni["A]2 1.0,0.33 1 10 17.8 145 1 2.84 0.26 88.8
145 2 3.37 0.30 91.8
(SiO2) 145 3 3.47 0.28 92.4
145 4 3.56 0.24 91.8
145 5 3.57 0.20 90.8
145 5.5 3.54 0.18 90.3
催化剂 催化剂 2M3BN给料 N2给料 2M3BN/Ni (3PN) (4PN)实例 (载体) g,%Ni 毫摩/小时 毫升/分 摩/克原子 温度℃ 经过时间小时 气相色谱面积% 转化率%7 Ni["A"]2 1.05,0.35 5.1 10 81.3 150 1 0.01 0 0.9
150 2 0.26 0 5.0
(碳) 150 3 0.34 0 6.1
150 4 0.31 0 5.58 Ni[PTTP]4 1.00,1.14 1 10 5.1 145 1 0.05 0 10.6
145 2 0.07 0 7.1
(碳) 145 3 0.07 0 4.1
145 4 0.08 0 3.09 Ni+2["A"] 1.63,0.47 0.95 10 7.3 145 1 0.42 0 10.1
145 2 0.55 0 13.8
(SiO2) 145 3 0.55 0 13.8
145 4 0.51 0 12.9
145 5 0.47 0 11.710 Ni[OTTP]2CH2=CH2 1.00,0.42
(+"A") 0.95 10 13.3 145 1 0.19 0 25.3
145 2 0.70 0.03 23.8
(碳) 145 3 0.72 0 19.5
145 4 0.63 0 16.4
145 5 0.57 0 14.611 Ni[OTTP]2CH2=CH21.04,0.37 5.1 10 77.7 150 1 0.07 0 1.3
150 2 0.08 0 1.5
(碳) 150 3 0.10 0 1.5
150 4 0.09 0 1.6
150 5 0.08 0 1.5
实例12-13
利用在线的气相色谱分析检测得到的
2-甲基-3-丁烯腈的气相异构化
使用与实例3-11所叙述的相同的反应器和步骤,且此反应器与步骤与连续的气相色谱检测过程相适应。进料和出料管线用反应气体吹洗。出料管线与气相色谱相连,管线和取样阀都加热到165℃。反应温度145℃;实例12的催化剂是Ni(配位体“A”)2/SiO2,实例13的催化剂是(Ni(OTPP)2CH2=CH2+配位体“A”)/SiO2。原料2M3BN的进料含有3PN和4PN,一同相应于约10.9%的转化率,下文报道的结果包括了此转化率。PN的总百分数值按下式测定有用的PN的百分值是按下式测定
下文表2中的实例12和表3中的实例1 3给出了实验条件也给出了实验结果。
表2
在145℃时2M3BN气相异构化为3PN和4PN催化剂 催化剂 2M3BN给料 N2给料 2M3BN/Ni (3PN) (4PN)实例 (载体) 克,重量%Ni 毫摩/时 毫升/分 毫摩/克原子 经过时间小时 %转化率 %PN/总量 气相色谱面积% %有用的PN12 Ni["A″]2 0.99,0.33 2.06 10 26.9
(SiO2) 1 92.3 89.7 32.62 2.77 45.5
2 92.8 97.7 62.66 5.51 78.4
3 92.6 98.1 62.49 4.76 77.2
4 92.5 98.6 65.28 3.72 77.8
5 92.4 99.0 67.00 3.10 78.5
6 92.1 98.5 67.04 2.81 78.3
7 92.4 98.6 67.58 2.60 78.3
8 92.0 98.9 67.99 2.23 78.2
9 92.5 99.0 69.31 2.08 79.0
10 91.7 98.9 68.29 1.94 78.2
11 92.7 98.8 69.83 1.99 79.1
12 91.3 99.0 67.41 1.73 77.2
13 91.8 99.1 68.38 1.80 77.9
14 92.0 99.1 69.03 1.70 78.1
15 91.8 99.4 69.39 1.68 78.6
16 92.0 99.2 69.11 1.67 78.3
17 91.9 99.3 69.54 1.60 78.5
18 92.1 99.3 69.79 1.66 78.7
19 92.0 99.3 69.99 1.63 78.9
20 91.6 99.3 69.33 1.50 78.3
21 92.0 99.3 69.40 1.60 78.2
进料 10.9 78.5 0.12 -- 81.5
表3
在145℃时2M3BN气相异构化为3PN和4PN
催化剂 催化剂 2M3BN给料 N2给料 2M3BN/Ni 经过时间 % (3PN) (4PN)实例 (载体) (克,%Ni) 毫摩/小时 毫升/分 毫摩/克原子 小时 转化率 %PN/总量 气相色谱面积% %有用的PN13 Ni[OTTP]2CH2=CH2+"A" 1.01,0.31 2.06 10 28.6
(SiO2) 0.75 92.7 89.3 58.92 4.89 77.7
1.75 93.0 98.4 67.89 4.63 79.5
2.75 92.0 98.9 69.00 4.13 79.9
3.75 91.5 98.2 67.24 3.38 78.3
4.75 92.3 99.1 69.96 3.38 80.1
5.75 92.5 99.3 68.65 3.72 79.0
6.75 93.1 99.2 70.37 3.46 80.0
7.75 93.1 98.9 70.58 3.28 80.1
8.75 90.4 99.2 60.66 2.91 72.7
9.75 93.3 99.4 70.96 3.34 80.3
10.75 90.2 99.3 66.34 2.68 76.4
11.75 91.7 99.2 62.88 2.81 73.5
12.75 91.1 99.3 68.14 2.68 78.9
13.75 93.7 98.8 73.29 2.82 80.5
14.75 93.0 98.9 65.63 2.59 75.8
16.75 90.8 99.6 66.18 2.53 76.7
17.75 92.8 97.9 68.85 2.86 79.2
18.75 93.0 98.3 70.76 2.89 78.8
19.75 93.2 99.0 71.84 2.61 79.6
20.75 92.6 98.5 70.76 2.45 80.4
进料 10.9 99.5 1.37 -- 87.9
虽然前面的说明已描述了本发明的具体实施方案,但是本领域的技术人员应当懂得,在不背离本发明的精神和实质的情况下,本发明可以作出多种更改,替换和重新安排。应当参照所附权利要求书,而不是前述的说明书来表示本发明的范围。
Claims (12)
2.权利要求1的方法,其中反应温度是140°-160℃。
3.权利要求2的方法,其中反应温度是145°-150℃。
5.权利要求4的方法,其中原料腈是2-甲基-3-丁烯腈。
6.权利要求1的方法,其中原料2-烷基-3-单烯腈进一步被至少一个其它基团所取代,该基团对催化剂没有不利的影响。
7.权利要求1的方法,其中异构化是在101.3kPa到1013kPa的压力下进行的。
8.权利要求1的方法,其中异构化是以连续的方式进行的,给料速要使原料2-烷基-3-烯腈与催化剂的摩尔比在5∶1/小时-100∶1/小时之间。
9.权利要求1的方法,其中催化剂载带在载体上,载体选自二氧化硅,氧化铝和碳。
10.权利要求1的方法,其中原料2-烷基-3-烯腈以纯蒸汽的形式引入异构化反应。
11.权利要求1的方法,其中原料2-烷基-3-烯腈是以挥发性溶剂的蒸发溶液形式引入异构化反应。
12.权利要求11的方法,其中溶剂选自饱和的和芳香的烃以及脂族腈,而这些饱和烃,芳香烃和脂族腈在异构化的反应温度下是气态。
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CN1168664A CN1168664A (zh) | 1997-12-24 |
CN1077883C true CN1077883C (zh) | 2002-01-16 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN95196268A Expired - Lifetime CN1077883C (zh) | 1994-11-18 | 1995-11-01 | 非共轭2-烷基-3-单烯腈的催化气相异构化 |
Country Status (13)
Country | Link |
---|---|
US (1) | US5440067A (zh) |
EP (1) | EP0792260B1 (zh) |
JP (1) | JP3478400B2 (zh) |
KR (1) | KR100267821B1 (zh) |
CN (1) | CN1077883C (zh) |
AT (1) | ATE182136T1 (zh) |
BR (1) | BR9510346A (zh) |
CA (1) | CA2200302C (zh) |
DE (1) | DE69510816T2 (zh) |
ES (1) | ES2136320T3 (zh) |
IN (1) | IN186365B (zh) |
MY (1) | MY112489A (zh) |
WO (1) | WO1996016025A1 (zh) |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BR9408151A (pt) * | 1993-11-23 | 1997-08-05 | Du Pont | Processos de hidrocianação de precursor de catalisador |
ES2151958T3 (es) | 1994-04-14 | 2001-01-16 | Du Pont | Composiciones de catalizador de niquel y fosfito bidentado para hidrocianacion de monoolefinas. |
US5512696A (en) * | 1995-07-21 | 1996-04-30 | E. I. Du Pont De Nemours And Company | Hydrocyanation process and multidentate phosphite and nickel catalyst composition therefor |
TW315370B (zh) * | 1994-10-07 | 1997-09-11 | Du Pont | |
US5821378A (en) * | 1995-01-27 | 1998-10-13 | E. I. Du Pont De Nemours And Company | Hydrocyanation of diolefins and isomerization of nonconjugated 2-alkyl-3-monoalkenenitriles |
IN187044B (zh) * | 1995-01-27 | 2002-01-05 | Du Pont | |
US5693843A (en) * | 1995-12-22 | 1997-12-02 | E. I. Du Pont De Nemours And Company | Process for hydrocyanation of diolefins and isomerization of nonconjugated 2 alkyl-3-monoalkenenitriles |
IN191158B (zh) * | 1996-04-02 | 2003-10-11 | Du Pont | |
DE19825212A1 (de) | 1998-06-05 | 1999-12-09 | Basf Ag | Katalysator, umfassend einen Komplex eines Metalls der VIII. Nebengruppe auf Basis eines zweizähnigen Phosphonitliganden und Verfahren zur Herstellung von Nitrilen |
FR2823746B1 (fr) * | 2001-04-20 | 2003-05-23 | Rhodia Polyamide Intermediates | Procede d'isomerisation de mononitriles insatures ramifies en mononitriles insatures lineaires |
FR2849027B1 (fr) * | 2002-12-23 | 2005-01-21 | Rhodia Polyamide Intermediates | Procede de synthese de composes comprenant des fonctions nitriles a partir de composes a insaturations ethyleniques |
FR2850966B1 (fr) | 2003-02-10 | 2005-03-18 | Rhodia Polyamide Intermediates | Procede de fabrication de composes dinitriles |
DE10311119A1 (de) * | 2003-03-12 | 2004-09-23 | Basf Ag | Verfahren zur Isomerisierung von 2-Methyl-3-butennitril zu linearem Pentennitril |
DE10323803A1 (de) * | 2003-04-22 | 2004-11-11 | Basf Ag | Verfahren zur Isomerisierung von cis-2-Pentennitril zu trans-3-Pentennitril |
FR2854891B1 (fr) | 2003-05-12 | 2006-07-07 | Rhodia Polyamide Intermediates | Procede de preparation de dinitriles |
FR2854892B1 (fr) * | 2003-05-12 | 2005-06-24 | Rhodia Polyamide Intermediates | Procede de fabrication de dinitriles |
US7709674B2 (en) | 2006-07-14 | 2010-05-04 | Invista North America S.A R.L | Hydrocyanation process with reduced yield losses |
DE102008043584A1 (de) | 2008-11-07 | 2010-05-12 | Evonik Oxeno Gmbh | Verfahren zur Herstellung von 6-Chlorodibenzo(d,f) (1,3,2)-dioxaphosphepin |
DE102008043582A1 (de) | 2008-11-07 | 2010-05-12 | Evonik Oxeno Gmbh | Verfahren zur Herstellung von 6-Chlorodibenzo(d,f) (1,3,2)-dioxaphosphepin |
DE102011002639A1 (de) | 2011-01-13 | 2012-07-19 | Evonik Oxeno Gmbh | Verfahren zur Herstellung von Biphephos |
DE102011002640B4 (de) | 2011-01-13 | 2021-10-07 | Evonik Operations Gmbh | Verfahren zur Aufreinigung von Biphephos |
PL3145940T4 (pl) | 2014-05-20 | 2019-05-31 | Evonik Degussa Gmbh | Sposób redukcji zawartości chloru w organomonofosfitach przy zastosowaniu dwóch roztworów |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3676481A (en) * | 1970-06-29 | 1972-07-11 | Du Pont | Catalytic isomerization of 2-methyl-3-butenenitrile to linear pentenenitriles in the presence of certain metal salt and/or tri(hydrocarbyl)boron promoters |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3853948A (en) * | 1965-11-23 | 1974-12-10 | Du Pont | Catalytic isomerization of 2-methyl-3-butenenitrile to linear pentene-nitriles |
US3526654A (en) * | 1968-05-17 | 1970-09-01 | Du Pont | Isomerization of 2-pentenenitrile to 3-pentenenitrile |
US3739011A (en) * | 1971-04-30 | 1973-06-12 | Du Pont | Catalytic isomerization of 2-methyl-3-butenenitrile to linear pentenenitriles |
US3766237A (en) * | 1972-01-25 | 1973-10-16 | Du Pont | Hydrocyanation of olefins |
US3852325A (en) * | 1973-08-29 | 1974-12-03 | Du Pont | Selective isomerization of pentenenitriles |
US3852328A (en) * | 1973-09-26 | 1974-12-03 | Du Pont | Catalytic isomerization of 2-methyl-3-butenenitrile to a linear pentenenitrile |
US3852329A (en) * | 1973-10-02 | 1974-12-03 | Du Pont | Process for isomerization of 2-methyl-3-butene-nitrile to a linear pentenenitrile |
US4298546A (en) * | 1980-08-05 | 1981-11-03 | E. I. Du Pont De Nemours And Company | Isomerization of 2-methyl-3-butenenitrile |
US4783546A (en) * | 1987-06-02 | 1988-11-08 | E. I. Du Pont De Nemours And Company | Preparation of 4-pentenenitrile by isomerization |
-
1994
- 1994-11-18 US US08/341,726 patent/US5440067A/en not_active Expired - Lifetime
-
1995
- 1995-10-26 IN IN1321CA1995 patent/IN186365B/en unknown
- 1995-11-01 WO PCT/US1995/014790 patent/WO1996016025A1/en active IP Right Grant
- 1995-11-01 CN CN95196268A patent/CN1077883C/zh not_active Expired - Lifetime
- 1995-11-01 BR BR9510346A patent/BR9510346A/pt not_active IP Right Cessation
- 1995-11-01 KR KR1019970703330A patent/KR100267821B1/ko not_active IP Right Cessation
- 1995-11-01 AT AT95941392T patent/ATE182136T1/de not_active IP Right Cessation
- 1995-11-01 JP JP51695496A patent/JP3478400B2/ja not_active Expired - Fee Related
- 1995-11-01 CA CA002200302A patent/CA2200302C/en not_active Expired - Fee Related
- 1995-11-01 EP EP95941392A patent/EP0792260B1/en not_active Expired - Lifetime
- 1995-11-01 ES ES95941392T patent/ES2136320T3/es not_active Expired - Lifetime
- 1995-11-01 DE DE69510816T patent/DE69510816T2/de not_active Expired - Lifetime
- 1995-11-18 MY MYPI95003526A patent/MY112489A/en unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3676481A (en) * | 1970-06-29 | 1972-07-11 | Du Pont | Catalytic isomerization of 2-methyl-3-butenenitrile to linear pentenenitriles in the presence of certain metal salt and/or tri(hydrocarbyl)boron promoters |
Also Published As
Publication number | Publication date |
---|---|
DE69510816D1 (de) | 1999-08-19 |
CN1168664A (zh) | 1997-12-24 |
US5440067A (en) | 1995-08-08 |
EP0792260B1 (en) | 1999-07-14 |
MY112489A (en) | 2001-06-30 |
DE69510816T2 (de) | 2000-02-17 |
ATE182136T1 (de) | 1999-07-15 |
IN186365B (zh) | 2001-08-18 |
CA2200302C (en) | 2007-01-09 |
WO1996016025A1 (en) | 1996-05-30 |
CA2200302A1 (en) | 1996-05-30 |
BR9510346A (pt) | 1998-06-02 |
ES2136320T3 (es) | 1999-11-16 |
KR970707079A (ko) | 1997-12-01 |
JP3478400B2 (ja) | 2003-12-15 |
JPH10509175A (ja) | 1998-09-08 |
EP0792260A1 (en) | 1997-09-03 |
KR100267821B1 (ko) | 2000-10-16 |
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