CN1049801A - 新催化剂组合物及其在低聚单烯烃中的应用 - Google Patents
新催化剂组合物及其在低聚单烯烃中的应用 Download PDFInfo
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Abstract
本发明涉及由使至少一种二价镍化合物与至少
一种卤化烃基铝和至少一种环氧化合物按任何顺序
进行接触而得到的催化剂组合物。
本发明也涉及该催化剂组合物在低聚单烯烃的
工艺中的应用。
Description
本发明的主题是一种新催化剂组合物及其在低聚单烯烃中,特别是在二聚和三聚单烯烃中的应用。更准确地说,它涉及使至少一种二价镍化合物与至少一种卤化烃基铝和至少一种环氧化合物按任何顺序进行接触而得到的组合物。
制备用于二聚单烯烃或共二聚单烯烃,例如乙烯、丙烯或正丁烯的催化剂是熟知的。例如这类催化剂可由下述方法得到:兀烯丙基镍化膦的卤化物和路易斯酸之间相互作用(FR-B-1410430),镍化膦的卤化物和路易斯酸之间相互作用(US-A-3485881),或某些羧酸镍和卤化烃基铝之间相互作用(US-A-3321546)。其他催化剂使用零价镍化合物。然而,因为这些催化剂的不稳定性和高的费用,它们是不实用的。通常,最好使用在烃类物质中可溶的镍化合物。
上述催化剂组合物在工业上应用到烯烃馏分(例如由石油化学加工分离的那些烯烃馏分,如催化裂化或蒸汽裂化)上遇到困难,特别是由于在其馏分中含有杂质。
这些困难通过使用改进的催化剂配方已部分地得到克服,上述催化剂配方中含有二价镍化合物、卤化烃基铝和天然的布朗期台德酸化合物(US-A-4283305),或镍与烷基铝相结合的化合物(US-A-4316851、4366087和4398049)。这些改进的催化剂配方,通常包括卤代羧酸或相应的阴离子。
意想不到的是,已经发现,如果使至少一种二价镍化合物与至少一种卤化烃基铝和至少一种环氧化合物接触,这将产生比现有技术的配方具有更高活性的催化剂组合物,并且该组合物将具有与在低聚进料中存在的杂质有关的同样的性质。
在本发明中可使用的镍化合物包括所有的二价镍化合物,优选的化合物是可溶于烃类介质(例如,于+20℃下,在庚烷中)中达0.1g/L以上,并且更特别优选的是溶于反应物或反应介质中。例如,它们可包括其通式为(RCOO)2Ni的乙酰丙酮镍/或羧酸镍,在上述通式中,其中R是烃基,例如,含有达20个碳原子的烷基、环烷基、链烯基、芳基、芳烷基或烷芳基,最好是具有5至20个碳原子的烃基,两个R基可一起形成具有6至18个碳原子的亚烷基。某些不受限制的镍化合物的实施例是下述的二价镍盐:二价镍的辛酸盐、2-乙基己酸盐、硬脂酸盐、油酸盐、环烷酸盐和己二酸盐。
卤化烃基铝最好是具有通式AlR′xXy,其中R′代表一价烃基,例如含达12个碳原子的一价烃基,如烷基、芳基、芳烷基、烷芳基或环烷基;X代表卤素,例如选自氯、溴和碘,且X最好为氯原子;X为1至2,Y为1至2,同时X+Y=3,且最好X=1和Y=2。式AlR′xXy这类化合物的某些实例是三氯化二乙基铝、二氯乙基铝、二氯异丁基铝和氯二乙基铝。
环氧化合物最好具有下述通式:
其中,R1、R2、R3和R4可相同或不同,且通常选自由氢原子和含有,如达12个碳原子的烃基,例如烷基、芳基或环烷基组成的一类基。这类化合物的某些实例是环氧乙烷、1,2-环氧丙烷、1,2-环氧丁烷和环氧苯乙烯。R1和R4可一起形成具有4至10个碳原子的亚烷基,R2和R3定义如上,例如,1,2-环氧环己烷可作为代表。
在本发明的催化剂组合物中包含的三种化合物可以以任何顺序相混合。然而,最好是二价镍化合物首先与环氧化合物混合,其温度通常为-10至+200℃,最好为+20至+100℃,可能的是在脂族或芳族烃类溶剂存在下进行混合。然后,将如此得到的混合物或组合物与卤化烃基铝同时或在其之前加入到低聚反应介质中。
环氧化合物与二价镍化合物的摩尔比通常为0.1∶1至10∶1,最好为0.5∶1至3∶1。卤化烃基铝与二价镍化合物的摩尔比通常为1∶1至50∶1,且最好为2∶1至20∶1。
本发明也涉及,在上述定义的催化剂组合物存在下,最好于温度-20至+100℃下,在反应物至少基本上保持在液相中的压力条件下,用于低聚单烯烃的工艺中。
能够二聚或低聚的某些单烯烃的实例是乙烯、丙烯、正丁烯和正戊烯,其单烯烃,既可以以纯物质的形式,也可以以混合物,例如由合成加工,如催化裂化或蒸汽裂化分离出来的那些混合物的形式进行二聚化或低聚化作用。它们可以相互之间或异丁烯进行共低聚化作用,例如,乙烯与丙烯和正丁烯,丙烯与正丁烯或正丁烯与异丁烯。
在低聚反应的液相中,用镍表示的催化剂组合物的浓度通常为5至500PPm(重量)。
低聚工艺尤其可用于串联的具有一个或多个反应步骤的反应器 中,而烯烃进料和/或催化系统的组分或者在第一步骤或者在第一步和至少任何一个其他步骤中连续引入。当催化剂离开反应器时,可用,例如氨和/或氢氧化钠水溶液减活。然后,通过蒸馏可将存在的未转化的烯烃和烷烃从低聚物中分离出来。
另一种方法是,低聚工艺可以简单地以间歇法进行。
由本发明低聚工艺得到的产物特别可用于作为汽车的燃料组分,或作为用于合成醛和醇的羰基化工艺中的进料。
下述的实施例可说明本发明,但它的范围不受此限制。
实施例1
将含有13%(重量)镍的石油溶剂中的100g2-乙基己酸镍的商业溶液放入具有有效容积为300ml的不锈钢高压釜中。关闭高压釜,并在真空下驱气,然后与放在天平上的环氧乙烷瓶相连。高压釜被加热至70℃,并开始搅拌。35分钟后,9.7克环氧乙烷被吸收,每克原子镍相当于吸收一当量环氧乙烷。断开高压釜,并将其放置,以便冷却,然后,在搅拌的同时,加入100ml庚烷,排出所得溶液,然后进行真空蒸发,得到具有镍含量为13.45%(重量)的粘性液体。
实施例2
5ml庚烷溶液中的46mg实施例1制备的混合物(即1.05×10-4克原子镍)放入预先已干燥并用氩气净化的具有有效容积为250ml的不锈钢高压釜中。下一个放入的物质是以来自用于二聚丙烯的预先处 理而分离出的异己烯混合物形式的100g11.5%(重量)的丙烯溶液。以在己烷中的50%(重量)商业溶液的形式加入上述的0.2g二氯乙基铝后,通过高压釜双夹套中的循环水将温度调至40℃。反应进行后,每隔一定时间从高压釜中取样。反应10分钟后,66.1%的丙烯被转化成低聚物。
实施例3(比较例)
该实施例说明用现有技术的催化剂得到的结果。
除了首先放入高压釜中的物料不是实施例1制备的混合物,而是含有13%(重量)镍(即1.05×10-4克原子镍)的石油溶剂的47.6mg(2-乙基己酸镍商业溶液之外,设备和操作方式与实施例2所述的相同。在与实施例2相同的条件(特别是加入二氯乙基铝)下,反应10分钟后,24.1%的丙烯转化成低聚物。
实施例4(比较例)
该实施例说明用改进的现有技术的催化剂组合物得到的结果。
除了首先放入高压釜中的物料不是实施例1制备的混合物,而是每克原子镍含有一当量三氟乙酸和具有镍含量为10%(重量)(即1.05×10-4克原子镍)的石油溶剂中的62mg2-乙基己酸镍的溶液之外,设备和操作方式与实施例2所述的相同。在与实施例2相同的条件(特别是加入二氯乙基铝)下,反应10分钟后,58.9%的丙烯转化成低聚物。
实施例5
将50ml庚烷溶液中的272mg实施例1制备的混合物加入到与实施例2所述的相同的设备中。然后加入含有14.7%(重量)的饱和烃和85.3%(重量)的正丁烯的118gC4馏分。温度再次调至40℃,然后,以在己烷中的50%(重量)的商业溶液的形式,加入1.18g二氯乙基铝。反应1小时后,62.8%正丁烯转化成低聚物。
实施例6
除了含有13%(重量)镍的每100g镍盐吸收29.1g环氧乙烷之外,用实施例1所述的方法配制2-乙基己酸镍和环氧乙烷的混合物。当按照实施例1所述的方法处理时,所得混合物具有镍含量为11.47%(重量)。
实施例7
除了首先放入在高压釜中的物料不是实施例1制备的混合物,而是以5ml庚烷溶液形式的实施例6制备的319mg混合物之外,设备和操作方式与实施例5所述的相同。在与实施例5相同的条件(特别是加入二氯乙基铝)下,反应1小时后,60.1%正丁烯转化成低聚物。
实施例8
将含有13%(重量)镍的石油溶剂中的100g2-乙基己酸镍的商业溶液加入到具有有效容积为250ml的不锈钢高压釜中,然后加入100ml庚烷。10g环氧乙烷放入与高压釜相连的分子筛中,然后将2巴余压氮气施加于高压釜中,在70℃下,该混合物加热9小时。当庚烷已被冷却并在真空下蒸发时,便得到具有镍含量为13%(重量)的粘性液体。
实施例9
在反应器上配有为控制温度而安装的换热器的外循环回路,且总容积为7.6升。以1000g/h的流量向反应器中连续加入组成为75%正丁烯、6%异丁烯和19%丁烷的进料。也连续加入2种单独的物流:(a)20g/h实施例8制备的庚烷混合物溶液(每1000g溶液含有21.45g混合物),和(b)30g/h含6%(重量)二氯乙基铝的庚烷溶液。温度保持在42℃。
当流出物离开反应器时,通过连续加入氨气和15%(重量)的氢氧化钠水溶液,使其连续减活。
流出物的分析表明,正丁烯转化76.4%,和异丁烯转化72.2%。流出物的组成(重量)是,85.2%辛烯,10.8%十二碳烯,2%十六碳烯和2%高于C16的烯烃。就转化的单体进行计算的二聚物的选择性是,对于正丁烯为86.9%,和对于异丁烯为58.1%。
实施例10(比较例)
该实施例说明用现有技术的催化剂组合物得到的结果。
除了用每克原子镍含有1当量三氟乙酸并含有0.28%(重量)镍的2-乙基己酸镍的庚烷中的20g/h物流溶液代替实施例8制备的混合物的物流溶液之外,继续使用实施例9中所述的相同的设备,并使用其相同的操作条件。这表示与实施例9中的每小时镍的数量相同。
流出物的分析表明,正丁烯转化72.6%,和异丁烯转化90.9%。该流出物的组成(重量)是,78.6%辛烯,13.1%十二碳烯,4.3%十六碳烯和4%高于C16的烯烃。就转化的单体进行计算的二聚物的选择性是,对于正丁烯为83.7%,和对于异丁烯为22.8%。
Claims (9)
1、一种催化剂组合物,其特征在于,它是由使至少一种二价镍化合物与至少一种卤化烃基铝和至少一种环氧化合物以任何顺序接触所得到的产物。
3、权利要求2的催化剂组合物,其特征在于环氧化合物选自由环氧乙烷、1,2-环氧丙烷、1,2-环氧丁烷、环氧苯乙烯和1,2-环氧环己烷组成的一类物质。
4、权利要求1至3的任一催化剂组合物,其特征在于卤化烃基铝具有通式AlRx′Xy,其中R′代表一价烃基,X代表选自氯、溴和碘的卤素,X为1至2,且Y为1至2,同时X+Y=3。
5、权利要求4的催化剂组合物,其特征在于在卤化烃基铝的通式中,X=1,Y=2和X代表氯。
6、权利要求1至5的任一催化剂组合物,其特征在于二价镍化合物选自式为(RCOO)2Ni的乙酰丙酮镍和羧酸镍,式中R是具有5至20个碳原子的烃基,或两个R一起形成具有6至18个碳原子的亚烷基。
7、权利要求1至6的任一催化剂组合物,其中卤化烃基铝与二价镍化合物的摩尔比为1∶1至50∶1,和环氧化合物与二价镍化合物的摩尔比为0.1∶1至10∶1。
8、权利要求1至6的任一催化剂组合物,其中卤化烃基铝与二价镍化合物的摩尔比为2∶1至20∶1,且环氧化合物与二价镍化合物的摩尔比为0.5∶1至3∶1。
9、权利要求1至8的任一催化剂组合物用于低聚单烯烃的工艺中。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR89/10758 | 1989-08-08 | ||
FR8910758A FR2650760B1 (fr) | 1989-08-08 | 1989-08-08 | Nouvelle composition catalytique et sa mise en oeuvre pour l'oligomerisation des monoolefines |
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Publication Number | Publication Date |
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CN1049801A true CN1049801A (zh) | 1991-03-13 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN90107356A Pending CN1049801A (zh) | 1989-08-08 | 1990-08-08 | 新催化剂组合物及其在低聚单烯烃中的应用 |
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Country | Link |
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US (2) | US5059571A (zh) |
EP (1) | EP0412872B1 (zh) |
JP (1) | JP3154060B2 (zh) |
KR (1) | KR0145416B1 (zh) |
CN (1) | CN1049801A (zh) |
AR (1) | AR247118A1 (zh) |
AT (1) | ATE83395T1 (zh) |
AU (1) | AU6006590A (zh) |
BR (1) | BR9003861A (zh) |
CA (1) | CA2022862A1 (zh) |
DE (1) | DE69000596T2 (zh) |
FR (1) | FR2650760B1 (zh) |
NO (1) | NO301315B1 (zh) |
NZ (1) | NZ234782A (zh) |
ZA (1) | ZA906207B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103649022A (zh) * | 2011-06-22 | 2014-03-19 | 开放型股份公司"希布尔控股" | 用于分离烯烃低聚产物以及分解低聚催化剂残余物的方法 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2794038B1 (fr) * | 1999-05-27 | 2001-06-29 | Inst Francais Du Petrole | Composition catalytique amelioree et son application a l'oligomerisation des olefines |
KR100729433B1 (ko) | 2006-07-11 | 2007-06-15 | 금호석유화학 주식회사 | 높은 용해도를 갖는 단분자 니켈 카르복실레이트 및 이를이용한 디엔 중합용 촉매 |
FR3045414B1 (fr) * | 2015-12-18 | 2019-12-27 | IFP Energies Nouvelles | Nouvelle composition catalytique a base de nickel et de ligand de type phosphine et d'une base de lewis et son utilisation dans un procede d'oligomerisation des olefines |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
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DE1770844C2 (de) * | 1968-07-10 | 1981-11-19 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von trans-Polypentenamer |
DE1961865C3 (de) * | 1969-12-10 | 1980-06-12 | Bayer Ag, 5090 Leverkusen | Copolymerisation von cyclischen Monoolefinen mit cyclischen Polyolefinen |
SU517318A1 (ru) * | 1974-07-25 | 1976-06-15 | Предприятие П/Я А-7629 | Способ приготовлени катализатора дл полимеризации циклических ненасыщенных углеводородов |
US3937745A (en) * | 1974-08-29 | 1976-02-10 | The Goodyear Tire & Rubber Company | Selective hydrogenation of cyclopentadiene |
US4028429A (en) * | 1976-01-09 | 1977-06-07 | E. I. Du Pont De Nemours And Company | Preparation of high trans-isomer content 1,4-dienes |
US4025570A (en) * | 1976-01-09 | 1977-05-24 | E. I. Du Pont De Nemours And Company | Preparation of 1,4-dienes of high trans-isomer content |
SU649458A1 (ru) * | 1976-03-09 | 1979-02-28 | Предприятие П/Я А-7629 | Способ приготовлени катализатора дл регулировани молекул рной массы полимеров сопр женных диенов |
US4188348A (en) * | 1978-08-11 | 1980-02-12 | The Goodyear Tire & Rubber Company | Hydrogenation of cyclopentadiene to form cyclopentene |
FR2443877A1 (fr) * | 1978-12-11 | 1980-07-11 | Inst Francais Du Petrole | Nouvelle composition catalytique et sa mise en oeuvre pour l'oligomerisation des olefines |
FR2464243A1 (fr) * | 1979-09-03 | 1981-03-06 | Inst Francais Du Petrole | Nouveaux composes du nickel, leur preparation et leur utilisation en tant que catalyseurs pour l'oligomerisation des olefines |
FR2481950A1 (fr) * | 1980-05-08 | 1981-11-13 | Inst Francais Du Petrole | Composition catalytique amelioree et son utilisation comme catalyseur d'oligomerisation des olefines |
DE3360376D1 (en) * | 1982-04-06 | 1985-08-14 | Exxon Research Engineering Co | Butene dimerization method |
FR2555570B1 (fr) * | 1983-11-29 | 1986-10-03 | Inst Francais Du Petrole | Nouvelle composition du nickel bivalent soluble dans les hydrocarbures |
US4709112A (en) * | 1986-01-06 | 1987-11-24 | Sumitomo Chemical Company, Limited | Process for dimerizing lower α-olefins |
-
1989
- 1989-08-08 FR FR8910758A patent/FR2650760B1/fr not_active Expired - Fee Related
-
1990
- 1990-07-27 AT AT90402168T patent/ATE83395T1/de active
- 1990-07-27 EP EP90402168A patent/EP0412872B1/fr not_active Expired - Lifetime
- 1990-07-27 DE DE9090402168T patent/DE69000596T2/de not_active Expired - Fee Related
- 1990-08-01 US US07/560,960 patent/US5059571A/en not_active Expired - Lifetime
- 1990-08-01 AU AU60065/90A patent/AU6006590A/en not_active Abandoned
- 1990-08-06 NZ NZ234782A patent/NZ234782A/en unknown
- 1990-08-06 NO NO903439A patent/NO301315B1/no unknown
- 1990-08-07 ZA ZA906207A patent/ZA906207B/xx unknown
- 1990-08-07 BR BR909003861A patent/BR9003861A/pt unknown
- 1990-08-07 KR KR1019900012045A patent/KR0145416B1/ko not_active IP Right Cessation
- 1990-08-08 JP JP21142690A patent/JP3154060B2/ja not_active Expired - Fee Related
- 1990-08-08 AR AR90317559A patent/AR247118A1/es active
- 1990-08-08 CN CN90107356A patent/CN1049801A/zh active Pending
- 1990-08-08 CA CA002022862A patent/CA2022862A1/fr not_active Abandoned
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1991
- 1991-07-18 US US07/732,001 patent/US5095162A/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103649022A (zh) * | 2011-06-22 | 2014-03-19 | 开放型股份公司"希布尔控股" | 用于分离烯烃低聚产物以及分解低聚催化剂残余物的方法 |
CN103649022B (zh) * | 2011-06-22 | 2015-11-25 | 公共型股份公司"希布尔控股" | 用于分离烯烃低聚产物以及分解低聚催化剂残余物的方法 |
Also Published As
Publication number | Publication date |
---|---|
EP0412872B1 (fr) | 1992-12-16 |
JPH0377645A (ja) | 1991-04-03 |
KR910004251A (ko) | 1991-03-28 |
JP3154060B2 (ja) | 2001-04-09 |
US5095162A (en) | 1992-03-10 |
KR0145416B1 (ko) | 1998-07-15 |
EP0412872A1 (fr) | 1991-02-13 |
AU6006590A (en) | 1991-02-14 |
NO301315B1 (no) | 1997-10-13 |
BR9003861A (pt) | 1991-09-03 |
FR2650760B1 (fr) | 1991-10-31 |
ATE83395T1 (de) | 1993-01-15 |
NO903439L (no) | 1991-02-11 |
CA2022862A1 (fr) | 1991-02-09 |
NZ234782A (en) | 1992-03-26 |
US5059571A (en) | 1991-10-22 |
ZA906207B (en) | 1992-03-25 |
DE69000596D1 (de) | 1993-01-28 |
FR2650760A1 (fr) | 1991-02-15 |
NO903439D0 (no) | 1990-08-06 |
DE69000596T2 (de) | 1993-04-22 |
AR247118A1 (es) | 1994-11-30 |
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