CN100386128C - 从氢氰化反应产品混合物中回收催化剂的方法 - Google Patents
从氢氰化反应产品混合物中回收催化剂的方法 Download PDFInfo
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 8
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- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical group [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 4
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Abstract
本文公开了使用液-液萃取法从包含有机单腈和有机二腈的混合物中回收含二亚磷酸酯的化合物的方法。还公开了用于提高含二亚磷酸酯的化合物的可萃取性的预处理。
Description
技术领域
本发明涉及使用液-液萃取法从包含有机二腈的氢氰化反应产物混合物中回收催化剂和配体。
背景技术
在现有技术中,众所周知,镍与含磷配体的配合物可用作氢氰化反应中的催化剂。已知,这类使用单齿亚磷酸酯的镍配合物能够催化丁二烯的氢氰化反应,产生戊烯腈的混合物。这些催化剂还可用于随后的戊烯腈的氢氰化反应,产生己二腈,这是生产尼龙的重要中间体。还已知,二齿亚磷酸酯和phosphinite配体可用于形成用于进行这种氢氰化反应的镍-基催化剂。
美国专利3,773,809描述了用于从包含有机腈的产品流体中回收有机亚磷酸酯的镍配合物的方法,所述包含有机腈的产品流体通过烯属不饱和有机单腈例如3-戊烯腈的氢氰化产生,该方法包括用链烷烃或者环烷烃熔剂萃取所述产品流体。其中描述到,单腈与二腈的比值必须为0.65或者以下,以获得有效的回收,当该比值降低时,效率提高。因此,当氢氰化反应条件产生高于0.65的单腈与二腈比值时,在进行萃取之前必须将单腈从产品混合物中除去。
与回收包含单齿亚磷酸酯和镍的催化剂不同,本申请人已经注意到,在氢氰化反应中用作促进剂的Lewis酸类会抑制二亚磷酸酯-镍催化剂的有效回收。因此希望寻找能够减少或者消除这种抑制作用的条件。
希望提供较好的回收镍二亚磷酸酯配合物的方法,其需要最少的设备和附加萃取溶剂。
本发明的另一个目的是以这样一种方式进行配合物的回收和萃取操作,即能够从具有宽组成范围的反应器产品中回收催化剂。本发明的另一个目的是限定操作条件,借此使催化剂的经济回收成为可能。
根据以下详细说明,本发明的其他目的、特征和优点将更加明确。
发明内容
本文公开了使用液-液萃取法,从包含含二亚磷酸酯的化合物与有机单腈和有机二腈的混合物回收含二亚磷酸酯的化合物的方法,其中存在的有机单腈与有机二腈的摩尔比为大约0.65到大约2.5,并且其中萃取溶剂是饱和或者不饱和烷烃或者饱和或者不饱和环烷烃。
还公开了使用液-液萃取法,从包含含二亚磷酸酯的化合物、有机单腈、有机二腈和路易斯酸的混合物回收含二亚磷酸酯的化合物的方法,其中存在的有机单腈与有机二腈的摩尔比为大约0.01到大约2.5,并且其中在液体萃取之前该混合物用路易斯碱化合物处理,该路易斯碱化合物选自单齿亚磷酸酯配体、醇、水、有机基胺、氨和碱性树脂,并且其中萃取溶剂是饱和或者不饱和烷烃或者饱和或者不饱和环烷烃。
具体实施方式
本发明的方法涉及使用液-液萃取法,从包含含二亚磷酸酯的化合物和有机二腈的混合物回收含二亚磷酸酯的化合物的方法。本申请人已经发现,包含镍的二亚磷酸酯配合物的催化剂能够通过液-液萃取法,在与美国专利3,773,809中描述的相比较高的有机单腈与有机二腈的比值下进行回收。虽然当单腈与二腈比值降低时萃取效率仍然能被最大化,但是本申请人已经成功地证明可以在高达2.3的单腈与二腈比值下进行催化剂回收,该比值显著地高于US 3,773,809中报导的比值。因此,在产生的单腈与二腈的比值高于0.65的氢氰化反应条件下,不必为了回收催化剂而在萃取之前将未反应的单腈除去,从而获得工艺优点。优选的单腈与二腈比值范围是0.01到2.5。最优选的范围是0.01到1.5。
本申请人还已经发现,路易斯酸对通过液-液萃取法回收二亚磷酸酯-镍催化剂的抑制作用通过在萃取期间提高温度而得到降低。虽然最高温度由使用的烃熔剂的挥发性限制,但是本申请人已经发现当温度被提高时回收得到改善。优选的工作范围为40℃到100℃。最优选的范围为50℃到80℃。
本申请人还已经发现,通过将路易斯碱化合物引入含催化剂的混合物,该路易斯碱化合物显然既结合到镍催化剂也结合到路易斯酸,并且使路易斯酸与催化剂的缔合破裂,因此能够降低路易斯酸对通过液-液萃取法回收二亚磷酸酯-镍催化剂的抑制作用。本申请人已经发现,将单齿亚磷酸酯引入催化剂混合物能够改善萃取回收效率。如果这些单齿亚磷酸酯的尺寸变大,则该效果被降低。可以作为萃取增强处理剂的单亚磷酸酯配体中的某些是公开于Drinkard等的US3,496,215、US3,496,217、US3,496,218、US5,543,536和BASF的WO01/36429中的那些。
本申请人已经发现,加入弱的路易斯碱化合物,例如水或者醇,或更强的路易斯碱化合物,例如氨,芳基-或者烷基胺,例如吡啶或者三乙胺,或者碱性树脂例如Amberlyst 21(一种由Rohm and Haas生产的市售可得的碱性树脂),能够降低或者消除路易斯酸对催化剂回收的抑制作用。
该方法可以用于回收各种二齿含磷配体和其镍配位催化剂。
用于本发明的适合的配体是二齿含磷配体,其选自二齿亚磷酸酯和二齿phosphinite。优选的配体是二齿亚磷酸酯配体。
优选的二齿亚磷酸酯配体具有以下结构式:
其中,在I、II和III中,R1是未取代的或者被一个或多个C1到C12烷基或者C1到C12烷氧基取代的苯基;或者未取代的或者被一个或多个C1到C12烷基或者C1到C12烷氧基取代的萘基;并且Z和Z1独立地选自结构式IV、V、VI、VII和VIII:
其中
R2、R3、R4、R5、R6、R7、R8和R9独立地选自H、C1到C12烷基和C1到C12烷氧基;X是O、S或者CH(R10);
R10是H或者C1到C12烷基;
其中
R11和R12独立地选自H、C1到C12烷基和C1到C12烷氧基;和CO2R13,
R11是C1到C12烷基或者未取代的或者被C1到C4烷基取代的C6到C10芳基;
Y是O、S或者CH(R14);
R14是H或者C1到C12烷基;
其中
R15选自H、C1到C12烷基和C1到C12烷氧基和CO2R16;
R16是C1到C12烷基或者未取代的或者被C1到C4烷基取代的C6到C10芳基。
在结构式I到VIII中,C1到C12烷基和C1到C12烷氧基可以是直链或者支链的。
可用于本发明方法的二齿亚磷酸酯配体的实例包括具有以下通式IX到XXXII的那些,其中对于每个通式,R17选自甲基、乙基或者异丙基,并且R18和R19独立地选自H或者甲基:
其他适合的二齿亚磷酸酯是公开于以下专利中的类型:美国专利5,512,695;5,512,696;5,663,369;5,688,986;5,723,641;5,847,191;5,95 9,135;6,120,700;6,171,996;6,171,997;6,399,534;其中公开的内容引入本文作为参考。适合的二齿phosphinite是公开于以下专利的类型:美国专利5,523,453和5,693,843,其中公开的内容引入本文作为参考。
利用这些处理的一种或者结合,可以使用较少的萃取级更有效地回收催化剂。其重要的益处在于增加了工艺的适应性并且降低了工艺成本。使用这些处理剂,能够在较小的萃取塔中或者在简单的混合沉降器中进行萃取,和/或能够使用与以前报导的相比少得多的溶剂进行萃取。萃取能够在宽范围的组成下进行。为了获得最有效的结果,这些处理应该在萃取之前进行。
本发明与现有技术中用于回收用作催化剂的亚磷酸酯和二亚磷酸酯Ni配合物的方法相比具有优点。这些优点包括:能够获得很高的分级回收率;能够在简单的设备中实现经济回收,例如代替更复杂的萃取塔的混合沉降槽;能够在较宽的氢氰化反应组成范围上进行萃取;并且能够在各种形式的适合萃取的容器中加强萃取而显著地提高催化剂的可回收性。
本发明还涉及使用液-液萃取法,从由有机二腈组成的氢氰化反应产品混合物中回收亚磷酸酯和镍二亚磷酸酯配合物的经济方法。
实施例
在下面的实施例中,萃取系数的值是萃取液(烃相)中催化剂的重量分数与萃取残液(有机腈相)中催化剂重量分数的比值。萃取系数的提高导致较高的催化剂回收效率。
实施例1-5:
这些实施例举例说明了在单腈与二腈比值高于0.65时,能够有效地进行催化剂回收。
将五种不同的混合物分别用等重量的cyane进行液-液间歇萃取,所述混合物由以下物质组成:镍二亚磷酸酯配合物,该配合物具有示于结构IX(其中R17是异丙基,R18是H,和R19是甲基)中的二亚磷酸酯配体,ZnCl2(与镍等摩尔),并且单腈与二腈的比值不同。有机单腈与有机二腈的摩尔比和得到的萃取系数示于以下表1中。在使用逆流多级萃取器时,在溶剂与进料比高于1下,如果化合物具有1或者更大的萃取系数,则该化合物可以被有效地回收。
表1
单腈与二腈的各种比值下催化剂和配体的萃取系数
实施例 | 单腈/二腈 | 催化剂萃取系数 | 配体萃取系数 |
1 | 2.33 | 1.28 | 4.09 |
2 | 1.85 | 1.33 | 8.08 |
3 | 1.19 | 2.02 | 16.97 |
4 | 0.91 | 2.63 | 35.99 |
5 | 0.57 | 4.82 | 49.59 |
实施例6和7表明,在有限的滞留时间下,提高温度能够更有效地进行催化剂回收。
实施例6:
温度对二亚磷酸酯配体催化剂的可萃取性的影响
将主要包含以下物质的混合物分成两个部分:有机二腈和镍二亚磷酸酯配合物,该二亚磷酸酯配体的结构示于结构IX(其中R17是异丙基,R18是H,和R19是甲基),和ZnCl2(与镍等摩尔)。使用等重量的环己烷,将一部分在40℃下进行间歇液-液萃取,并且另一部分在50℃下进行间歇液-液萃取。随时间的延长对两个部分进行取样,催化剂回收进入萃取相的进展示于表2中,由在给定的时间下达到最终稳态值%表示。
表2:在萃取溶剂相中二亚磷酸酯配体的浓度随时间的变化
时间,分钟 | 在40℃下稳态浓度的% | 在50℃下稳态浓度的% |
2 | 12 | 11 |
4 | 19 | 38 |
8 | 34 | 53 |
14 | 52 | 95 |
30 | 78 | 104 |
60 | 100 | 102 |
91 | 100 | 100 |
实施例7:温度对催化剂的可萃取性的影响
将主要包含以下物质的混合物分成三个部分:有机二腈和镍二亚磷酸酯配合物,该二亚磷酸酯配体的结构示于结构XIII(其中R17是甲基,R18是甲基,和R19是H),和ZnCl2(与镍等摩尔)。将所述部分用等重量的正辛烷分别在50℃、65℃和80℃下间歇地液-液萃取,并且随时间进行监测。结果示于表3。
表3
时间 | 在50℃下稳态的% | 在65℃下稳态的% | 在80℃下稳态的% |
2 | 0.0 | 0.0 | 1.8 |
4 | 0.0 | 0.0 | 1.6 |
8 | 0.0 | 0.0 | 3.8 |
14 | 0.0 | 0.0 | 4.3 |
20 | 0.0 | 0.0 | 3.6 |
30 | 0.0 | 0.0 | 7.6 |
60 | 0.0 | 1.6 | 16.3 |
90 | 0.7 | 4.0 | 48.6 |
实施例8:加入水的影响
将15克主要包含以下物质的混合物,在50℃的温度下,用等重量的环己烷间歇液-液萃取一个小时:有机二腈和镍二亚磷酸酯配合物,所述二亚磷酸酯配体的结构示于结构XIII(其中R17是甲基、R18是甲基和R19是H)和ZnCl2(与镍等摩尔),导致4.3的催化剂萃取系数。在这种混合物中加入100微升水。在继续加热和搅动另外一小时之后,测量的二亚磷酸酯镍萃取系数为13.4-提高到三倍。
实施例9-20:加入有机单亚磷酸酯化合物的影响
实施例9-20举例说明了在催化剂混合物中加入单亚磷酸酯对催化剂回收的有益影响。它们使用了共同的如下实验过程:将包含以下物质的混合物分成三个部分:戊烯腈和己二腈(比值为0.3)和镍二亚磷酸酯配合物(2-5重量%)和ZnCl2(与镍等摩尔)和很少量的(<0.3重量%)的单亚磷酸酯(作为配体合成的副产品存在)。在各个实施例中,在第二和第三个部分中加入不同的单亚磷酸酯,如表4所示,产生最高5wt%的单亚磷酸酯浓度。每个部分用等重量的环己烷在50℃下间歇萃取30分钟,然后冷却到25℃,保持一个小时,并且在室温下取样。测量的催化剂萃取系数示于表4。
表4-单亚磷酸酯添加剂的影响
实施例 | 配体 | R<sup>17</sup> | R<sup>18</sup> | R<sup>19</sup> | 添加剂 | 萃取系数 |
9 | XXV | 甲基 | H | H | 无 | 0.9 |
10 | XXV | 甲基 | H | H | XXXIII | 9.2 |
11 | XXV | 甲基 | H | H | XXXIV | 12.8 |
12 | XX | 甲基 | H | H | 无 | 0.3 |
13 | XX | 甲基 | H | H | XXXV | 2.4 |
14 | XX | 甲基 | H | H | XXXIV | 3.9 |
15 | XXV | 乙基 | H | H | 无 | 4.7 |
16 | XXV | 乙基 | H | H | XXXVI | >10 |
17 | XXV | 乙基 | H | H | XXXVII | >10 |
18 | XX | 乙基 | H | H | 无 | 1.6 |
19 | XX | 乙基 | H | H | XXXVII | 2.9 |
20 | XX | 乙基 | H | H | XXXVIII | 7 |
实施例21-32显示用无水氨、氨基树脂或者可溶的有机胺处理包含催化剂的溶液,提高了萃取效率。
实施例21:
将主要包含以下物质的混合物分成两个部分:有机二腈和镍二亚磷酸酯配合物,该二亚磷酸酯配体的结构示于结构IX(其中R17是异丙基,R18是H,和R19是甲基)和ZnCl2(与镍等摩尔)。通过混合物用无水氨鼓泡,将一个部分用过量氨处理,并且另一个部分未进行处理,以进行对比。使用环己烷在Karr型柱中分别地对氨-处理和未处理的部分两者进行液-液萃取。对于氨-处理的混合物,催化剂回收是完全的,而对于未处理的混合物,仅仅回收76%。
实施例22:
将主要包含以下物质的混合物分成两个部分:有机二腈和镍二亚磷酸酯配合物,该二亚磷酸酯配体的结构示于结构IX(其中R17是异丙基,R18是H,和R19是甲基)和ZnCl2(与镍等摩尔)。一个部分通过与等重量的Amberlyst 21树脂接触进行处理,而另一个部分未进行处理,以便对比。树脂-处理的和未处理的部分两者分别地用等重量的环己烷进行液-液间歇萃取。对于树脂-处理的混合物,催化剂回收是基本上完全的,而对于未处理的混合物,仅仅回收77%。
实施例23:
将主要包含以下物质的混合物分成两个部分:有机二腈和镍二亚磷酸酯配合物,该二亚磷酸酯配体的结构示于结构XXII(其中R17是甲基,R18是甲基,和R19是H),和ZnCl2(与镍等摩尔)。一个部分通过与等重量的Amberlyst 21树脂接触进行处理,而另一个部分未进行处理,以便对比。树脂-处理的和未处理的部分两者分别地用等重量的环己烷进行液-液间歇萃取。对于树脂-处理的混合物,催化剂回收是91%,而对于未处理的混合物,仅仅回收45%。
实施例24-35使用以下共同流程:
将衍生自戊烯腈氢氰化反应的催化剂混合物分成三个部分,该催化剂混合物由戊烯腈和比例为大约0.3的二腈(主要地己二腈)、镍二亚磷酸酯催化剂(1.5重量%)和ZnCl2(大约0.25重量%)组成,并且第二和第三部分用AmberlystA-21树脂(1体积的Amberlyst A-21树脂比2体积的二腈溶液)或者吡啶进行处理,并且在50℃下加热。在每个部分中加入等重量的环己烷,加热到50℃,并且剧烈地搅拌,然后在50℃下沉淀大约30分钟。将样品小心地从顶部和底部液相排出。顶部相是溶剂或者萃取相,底部是萃取残液相。对所有样品进行分析。结果示于表5。
实施例36-43使用相同的共同流程,用无水NH3处理。
将衍生自戊烯腈氢氰化反应的催化剂混合物分成两个部分,该催化剂混合物由戊烯腈和比例为大约0.3的二腈(主要地己二腈)、镍二亚磷酸酯催化剂(1-1.5重量%)和ZnCl2(大约0.2重量%)组成。一个部分不进行处理。第二个部分通过经过溶液用NH3鼓泡10分钟进行处理,然后用氮气鼓泡以除去任何未反应的NH3。在每个部分中加入等重量的环己烷,并且在室温下剧烈地搅拌,然后沉淀。将样品小心地从顶部和底部液相排出。顶部相是溶剂或者萃取相,底部是萃取残液相。对所有样品进行分析。结果示于表6。
表6:用氨处理
实施例 | 配体 | R17 | R18 | R19 | 未处理的萃取系数 | NH3处理的萃取系数 |
36 | XIII | 甲基 | H | H | 0.6 | 9 |
37 | XVI | 甲基 | H | H | 1.3 | 133 |
38 | XV | 甲基 | H | H | 0.4 | 55 |
39 | XI | 甲基 | H | H | 2 | 7.8 |
40 | XIX | 甲基 | H | H | <~0.1 | 9.7 |
41 | XVIII | 甲基 | H | H | 1 | 21 |
42 | XIII | 乙基 | H | H | 1.2 | 21 |
43 | XIII | ** | ** | ** | 0.9 | 35 |
**R17、R18和R19的1/3是甲基,另外的2/3是H。其方式是对于给定的芳香环,R17、R18或者R19的仅仅一个是甲基。
Claims (13)
1.使用液-液萃取法,从包含含二亚磷酸酯的化合物与有机单腈和有机二腈的混合物回收含二亚磷酸酯的化合物的方法,其中存在的有机单腈与有机二腈的摩尔比为0.65到2.5,并且其中萃取溶剂是饱和或者不饱和烷烃或者饱和或者不饱和环烷烃。
2.权利要求1的方法,其中有机单腈与有机二腈的摩尔比为1.0到1.5。
3.使用液-液萃取法,从包含含二亚磷酸酯的化合物、有机单腈、有机二腈和路易斯酸的混合物回收含二亚磷酸酯的化合物的方法,其中存在的有机单腈与有机二腈的摩尔比为0.01到2.5,并且其中在液体萃取之前该混合物用路易斯碱化合物处理,该路易斯碱化合物选自单齿亚磷酸酯配体、醇、水、有机基胺、氨和碱性树脂,并且其中萃取溶剂是饱和或者不饱和烷烃或者饱和或者不饱和环烷烃。
5.权利要求1、2或者3的方法,其中萃取在40℃以上进行。
6.权利要求3的方法,其中路易斯碱化合物选自水、甲醇、乙醇、异丙醇或乙二醇。
7.权利要求3的方法,其中路易斯碱化合物是单齿三芳基亚磷酸酯,其中芳基基团是未取代的或者被具有1到12个碳原子的烷基基团取代的,并 且其中芳基基团相互连接或不相互连接.
8.权利要求3的方法,其中路易斯碱化合物选自无水氨、吡啶、烷基胺、二烷基胺和三烷基胺,其中烷基基团具有1到12个碳原子.
10.权利要求1、2或者3的方法,其中萃取溶剂是环己烷。
11.权利要求1,2或者3的方法,其中所述方法在萃取塔或者混合沉降槽中进行。
12.权利要求1,2或者3的方法,其中所述方法被用于氢氰化反应方法。
13.权利要求3的方法,其中所述混合物用选自苯酚、甲酚或二甲苯酚的化合物处理。
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TW (1) | TW200417412A (zh) |
WO (1) | WO2004062765A1 (zh) |
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FR2850966B1 (fr) | 2003-02-10 | 2005-03-18 | Rhodia Polyamide Intermediates | Procede de fabrication de composes dinitriles |
FR2854891B1 (fr) | 2003-05-12 | 2006-07-07 | Rhodia Polyamide Intermediates | Procede de preparation de dinitriles |
DE102004050935A1 (de) * | 2004-10-18 | 2006-04-20 | Basf Ag | Extraktion von Nickel(0)-Komplexen aus Nitrilgemischen mit verminderter Mulmbildung |
CN101460229A (zh) * | 2006-04-07 | 2009-06-17 | 巴斯夫欧洲公司 | 从腈混合物分离镍(0)配合物和含磷配体的方法 |
US7709673B2 (en) * | 2006-07-14 | 2010-05-04 | Invista North America S.A R.L. | Process for making 3-pentenenitrile by hydrocyanation of butadiene |
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US7919646B2 (en) | 2006-07-14 | 2011-04-05 | Invista North America S.A R.L. | Hydrocyanation of 2-pentenenitrile |
US7880028B2 (en) | 2006-07-14 | 2011-02-01 | Invista North America S.A R.L. | Process for making 3-pentenenitrile by hydrocyanation of butadiene |
WO2009091771A2 (en) | 2008-01-15 | 2009-07-23 | Invista Technologies S.A R.L | Process for making and refining 3-pentenenitrile, and for refining 2-methyl-3-butenenitrile |
CN101918356B (zh) | 2008-01-15 | 2013-09-25 | 因温斯特技术公司 | 戊烯腈的氢氰化 |
CN103080075B (zh) | 2010-07-07 | 2014-10-29 | 因温斯特技术公司 | 用于制备腈的方法 |
CN103402595B (zh) | 2011-12-21 | 2016-02-03 | 因温斯特技术公司 | 用于减少稳定乳液的萃取溶剂控制 |
EP2794048B1 (en) * | 2011-12-21 | 2022-01-05 | INVISTA Textiles (U.K.) Limited | Extraction solvent control for reducing stable emulsions |
EP2794046B1 (en) | 2011-12-21 | 2016-02-03 | Invista Technologies S.A R.L. | Extraction solvent control for reducing stable emulsions |
CN104039412B (zh) * | 2011-12-21 | 2016-08-24 | 因温斯特技术公司 | 用于减少稳定乳液的萃取溶剂控制 |
WO2014205183A1 (en) | 2013-06-20 | 2014-12-24 | Invista Technologies S.A.R.L. | Extraction solvent control for reducing stable emulsions |
CN105307742B (zh) * | 2013-06-20 | 2018-10-02 | 英威达纺织(英国)有限公司 | 用于减少稳定乳液的萃取溶剂控制 |
WO2014205195A1 (en) * | 2013-06-20 | 2014-12-24 | Invista Technologies S.A.R.L. | Extraction solvent control for reducing stable emulsions |
US9676800B2 (en) | 2013-06-20 | 2017-06-13 | Invista North America S.A.R.L. | Extraction solvent control for reducing stable emulsions |
EP3010616B1 (en) | 2013-06-20 | 2022-09-28 | INVISTA Textiles (U.K.) Limited | Extraction solvent control for reducing stable emulsions |
CN105531257B (zh) | 2013-07-17 | 2019-12-17 | 英威达纺织(英国)有限公司 | 通过蒸馏将溶剂与镍催化剂分离 |
CN103408178B (zh) * | 2013-08-22 | 2015-07-22 | 太原理工大学 | 从hpf焦化脱硫废液中回收脱硫催化剂的工艺 |
WO2015200630A1 (en) | 2014-06-27 | 2015-12-30 | Invista North America S.A R.L. | Integrated process for nitrile manufacture with enhanced liquid-liquid extraction |
EP3160907B1 (en) | 2014-06-27 | 2019-11-20 | INVISTA Textiles (U.K.) Limited | Enhanced extraction of impurities from mixture comprising nitriles |
CN113044904B (zh) * | 2021-05-10 | 2022-06-03 | 中国科学院过程工程研究所 | 协同萃取煤化工废水中难降解污染物和酚的萃取剂及方法 |
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- 2003-11-19 TW TW092132428A patent/TW200417412A/zh unknown
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2004
- 2004-01-07 AT AT04700629T patent/ATE475467T1/de not_active IP Right Cessation
- 2004-01-07 EP EP04700629A patent/EP1581323B1/en not_active Expired - Lifetime
- 2004-01-07 DE DE602004028336T patent/DE602004028336D1/de not_active Expired - Lifetime
- 2004-01-07 MY MYPI20040029A patent/MY135238A/en unknown
- 2004-01-07 CN CNB2004800019873A patent/CN100386128C/zh not_active Expired - Fee Related
- 2004-01-07 WO PCT/US2004/000375 patent/WO2004062765A1/en active Application Filing
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Also Published As
Publication number | Publication date |
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EP1581323A4 (en) | 2008-07-02 |
US20040140263A1 (en) | 2004-07-22 |
EP1581323B1 (en) | 2010-07-28 |
ATE475467T1 (de) | 2010-08-15 |
EP1581323A1 (en) | 2005-10-05 |
DE602004028336D1 (de) | 2010-09-09 |
TW200417412A (en) | 2004-09-16 |
US6936171B2 (en) | 2005-08-30 |
WO2004062765A1 (en) | 2004-07-29 |
CN1723067A (zh) | 2006-01-18 |
MY135238A (en) | 2008-03-31 |
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