CN1087305C - 烯烃的聚合方法 - Google Patents
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Abstract
循环的烯烃流经含有沉积在载体上的镍的物质，所述镍的形式为金属镍和氧化镍。改进了催化剂的产率并更好的控制了聚合物的性能。
Description
本发明涉及一种改进了的烯烃聚合方法。更具体地说，本发明涉及使用高产率Ziegler-Natta型催化剂的烯烃聚合方法，从而可更好地控制产品的性能和/或得到更高的产率。
含烃烯烃特别是液化丙烯的工业应用越来越多的被研究。最近开发的技术使用了高效率的催化剂将这些轻烯烃转化成最终产品如聚合物，多余的则被循环使用。在最新丙烯聚合技术中用丙烯本身作溶剂，大量过量的丙烯则循环使用。由于这些高效率的催化剂相当敏感，在循环烯烃中的杂质可使它们减活至少部分导致生产能力的降低。而且，一些杂质逐渐在循环液中累积，也已经发现聚合物的一些性能特别是熔体流动指数对时间不是一个稳定的函数。
因此确有必要改进烯烃聚合技术，尤其是使用高产率催化剂的时候。
本发明目标之一即提供改进了的烯烃聚合方法。
本发明另一个目标即提供包含有单体循环的方法，从而提高了聚合物/催化剂比率。
本发明还有一个目标即提供包含有单体循环的方法，从而可更好地控制聚合物的性能。
根据本发明，本发明的方法包括至少如下步骤：
(i)用Ziegler-Natta型催化剂将烃原料中的部分轻烯烃转化为聚合物；
(ii)从未反应的原料中分离出聚合物；
(iii)使所述未反应原料流经含有积沉在载体上的镍的物质，其中镍是以金属镍和氧化镍的形式存在；
(iv)将原料循环至步骤(i)
此处用的轻烯烃为C2-C6烯烃。特别是乙烯和丙烯，有时使用用于与乙烯一起制备共聚物的1-己烯。
烃原料可含大量纯烯烃、其混合物、或烯烃与饱和烃的混合物，如己烯或环己烯。在聚丙烯生产中，烃原料常含有75％(重量)以上的丙烯，更具体地为85-90％(重量)的丙烯。在聚乙烯生产中，烃原料常会有80％(重量)以上的乙烯，更具体地为90-99％(重量)的乙烯。
本发明提供的改进方法可用于任何使用Ziegler-Natta型催化剂的聚合过程。这些方法和催化剂在本领域是众所周知的，无需进一步叙述。
聚合反应后，所形成的聚合物常用闪蒸法从烯烃和任何饱和烃的残液中分离出来。
下一步，原料中的残留部分在循环前流经一物质。该物质含有沉积于载体上的镍，此镍以金属镍和氧化镍的形式出现。二氧化硅、二氧化硅-氧化铝、氧化铝、硅藻土、沸石和其它类似物质(无定型或是晶质的)都可以用作载体，只要可获得足够的金属分散就行。
镍和氧化镍的总重量可为所述物质的10％(重量)到约80％(重量)。因此，所述物质可包括20-90％(重量)的载体。优选金属镍与氧化镍的重量比为0.4-2.0，并满足下述条件：金属镍含量不低于所述物质的6％(重量)又不高于50％(重量)，且所述物质含40-70％(重量)的镍(总重量，Ni+NiO)，以及30-60％(重量)的载体。当使用这个范围之外的物质来进行本发明的方法时，所得结果就没那么理想。由于本发明不为任何理论所限，如果Ni/NiO比率大于2.0，相信会形成较大的微晶体而导致较低效率。类似地，总镍含量过高时会导致比表面的降低最终导致效率的降低而太低的总镍含量又导致生产能力的不足。
镍可通过合适的技术沉积在载体上，本领域技术人员已熟知其中一些方法。如用下述方法将镍沉积于载体上：将硝酸镍溶于水，将溶液与载体混合，然后沉淀其中的镍，如以碳酸镍的形式沉淀下来，最后洗涤，干燥和煅烧沉淀物。然后用这种方法沉积的镍通过氢气部分还原以形成金属镍，残留部分为氧化镍的形式。
一般说来，还原后镍微晶体的尺寸为约1-20毫微米(nm)。更具体的尺寸范围为约1-2nm。镍微晶体体的尺寸取决于所进行的还原程度。实际上，如果提高还原的程度，镍微晶体的尺寸将增加到大于前述的范围，而所获得的物质则没有所优选的性能。另一方面，如果还原程度太低，镍微晶体依然有着较合适的尺寸，但这种情况下所得的镍的数量太少以致无法保证原料的成功净化。
还原后所得物质的比表面积一般大于100m2/g。
所述物质的颗粒尺寸尤其取决于反应器允许的压力降。所用的物质一般为粉末状、颗粒状、挤出物状或球状。当为球状时这种物质的颗粒直径优选不超过约3.5mm，最优选为1-2.5mm；当所用颗粒为圆筒状时，它们的直径优选为1-4mm，长度优选为3-8mm。当使用挤出物状时，优选三裂片的形式以增加颗粒的外表面积以利于吸附。
在本发明的一个实施方案中，丙烯原料在温度为-10℃-90℃，优选10-40℃下通过所述物质，并有足够的压力以使介质保持在液相。所采用的重时空速(WHSV)为0.1-25，优选1-10。
令人惊讶的是，本发明方法所用物质在聚合反应后没有一点效用，事实上我们知道该物质已用于下述方面：比利时专利902942从烯烃原料液中去除COS以及欧洲专利308469从同样的原料液中去除胂。我们知道，即使是痕量的COS和胂都可与聚合反应催化剂发生反应，因此聚合后回收的原料液便不会含有COS或胂，那么本领域的技术人员都知道它无需任何处理就可以循环。
现参照附图更详尽的说明本发明，其中：
图1示意了将被循环的烯烃原料在与新鲜的原料混合之前流经所述物质的实施方案；
图2-4示意了将被循环的原料在与新鲜原料共同流经同一物质前与新鲜原料相混合的实施方案。
现在参阅图1，新鲜烯烃进料通过管线11进入蒸馏柱12。较重馏分(主要包含相应链烷烃)通过管13得到回收，而较轻馏分从管14流出。烯烃馏分经管15流入干燥器16，然后经管17进入净化单元18，其中含有或者相同或者不同或者是与本发明所要求的同类型的COS和胂的吸收物质。经过净化的原料经管19送至聚合单元20，其它成分(催化剂、助催化剂、立体调整剂、氢和其它聚合过程所要求的物质)通过管21送进。然后聚合物、未反应的单体以及可能存在的链烷烃的混合物经管22送入闪蒸单元23以从烃中分离出聚合物(24)，然后经管25将所述烃原料送入装有本发明载体Ni/NiO物质的反应器26中，然后经管27循环进管19。
图2和3叙述了实施例，其中从闪蒸单元23回收的烃原料经管25循环进入管11(图2)、管17(图3)或管15(图4)，单元18内的吸附物质为本发明所要求的类型。
虽然在以上具体描述中已叙述了本发明的特定的实施例，但这些叙述并不想将本发明局限于上文公开的特定的形式或实施例，因为它们只是用来作为说明，而非限制，而且对一个本领域的技术人员来说很显然本发明并不这么受局限。
例如，被回收的烃原料，无论分别处理与否，都可以在聚合单元的其它合适部分中循环。而且，根据新鲜原料的纯度，聚合单元可以包含或多或少的净化单元。也可以设想聚合单元的其它排布或构件。
以下例子目的在于提供本发明方法的一个更好的说明，但并不限制其范畴：
实施例：
液体丙烯被送进如图3排布的中间聚合单元中。
在单元18中的吸附物质为作为载体的二氧化硅-氧化铝[为该物质的43.3％(重量)]，镍沉积于其上，为NiO和金属镍的形式，Ni/NiO重量比为0.668。吸附物质为圆筒状挤出物，直径约为1mm，3mm长。该物质的比表面积为142m/g，镍微晶体的尺寸为约2mm。
在管11中，液体丙烯原料组成和杂质如下：丙烯 96.5％(重量)丙烷 3.1％(重量)C4烃 0.4％(重量)水 30ppmCOS 10ppb胂 75ppb
流过单元18后[温度为20℃，压力1.5MPa(15巴)，WHSV为6kg/kg.h)，原料中的COS含量低于5ppb(检测极限)，胂的含量低于3ppb(检测极限)。
将Ziegler-Natta型催化剂以及其它常规聚合过程所要求的其它成分通过管21送入，在单元20进行连续聚合反应。平均产率为每克催化剂13200克聚丙烯(标准误差为100g/g)。熔体流动指数稳定在1％以下。
对比例：
重复实施例1，不同之处在于管25与管19连接，从而循环原料不再流经单元18。平均产率为11800g/g(标准误差为150g/g)。熔体流动指数不稳定，在恒定实验条件下一天之中有很大变化，约为8％。
Claims (3)
1.烯烃的聚合方法，它至少包括以下步骤：
(i)用Ziegler-Natta型催化剂将烃原料中的部分轻烯烃转化为聚合物；
(ii)从未反应的原料中分离出聚合物；
(iii)使所述未反应原料流经含有积沉在载体上的镍的物质，其中镍以金属镍和氧化镍的形式存在；
(iv)将原料循环至步骤(i)
2.在将未反应烯烃循环并使用Ziegler-Natta型催化剂的烯烃聚合法中，改进的方面包括将循环烯烃流经含有沉积在载体上的镍的物质上，所述镍的形式为金属镍和氧化镍。
3.根据权利要求1或2的方法，其中金属镍和氧化镍的重量比在满足下述条件下为0.4-2.0：金属镍的含量不低于所述物质的6％重量又不高于50％重量，且所述物质含40-70％重量的以Ni+NiO总重量表示的镍以及30-60％重量的载体。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP93870188A EP0643028B1 (en) | 1993-09-15 | 1993-09-15 | Process for the polymerization of olefins |
| EP93870188.5 | 1993-09-15 |
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| CN1100430A CN1100430A (zh) | 1995-03-22 |
| CN1087305C true CN1087305C (zh) | 2002-07-10 |
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| CN94116301A Expired - Fee Related CN1087305C (zh) | 1993-09-15 | 1994-09-15 | 烯烃的聚合方法 |
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| Country | Link |
|---|---|
| US (1) | US5432243A (zh) |
| EP (1) | EP0643028B1 (zh) |
| JP (1) | JP3574684B2 (zh) |
| KR (1) | KR100331718B1 (zh) |
| CN (1) | CN1087305C (zh) |
| AT (1) | ATE165803T1 (zh) |
| AU (1) | AU678501B2 (zh) |
| CA (1) | CA2132115C (zh) |
| CZ (1) | CZ289049B6 (zh) |
| DE (1) | DE69318403T2 (zh) |
| DK (1) | DK0643028T3 (zh) |
| ES (1) | ES2117120T3 (zh) |
| FI (1) | FI109205B (zh) |
| TW (1) | TW316910B (zh) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6160060A (en) * | 1998-08-04 | 2000-12-12 | Eastman Chemical Company | Process for the synthesis of high molecular weight predominantly amorphous polymers with improved color and adhesive properties |
| US6593506B1 (en) | 2000-10-12 | 2003-07-15 | Exxonmobil Chemical Patents Inc. | Olefin recovery in a polyolefin production process |
| US6495609B1 (en) | 2000-11-03 | 2002-12-17 | Exxonmobil Chemical Patents Inc. | Carbon dioxide recovery in an ethylene to ethylene oxide production process |
| US20020103406A1 (en) | 2001-02-01 | 2002-08-01 | Georges Mathys | Production of olefin dimers and oligomers |
| US6875899B2 (en) * | 2001-02-01 | 2005-04-05 | Exxonmobil Chemical Patents Inc. | Production of higher olefins |
| US20030147604A1 (en) * | 2002-02-01 | 2003-08-07 | Tapia Alejandro L. | Housing assembly for providing combined electrical grounding and fiber distribution of a fiber optic cable |
| EP2006011A1 (en) * | 2007-06-22 | 2008-12-24 | Total Petrochemicals Research Feluy | Process for reducing carbon monoxide in olefin-containing hydrocarbon feedstocks |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0308569A1 (en) * | 1987-09-24 | 1989-03-29 | Fina Research S.A. | Process for removing arsine from light olefin-containing hydrocarbon feedstocks |
| US5134208A (en) * | 1991-09-27 | 1992-07-28 | Shell Oil Company | Polymerization process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LU85487A1 (fr) * | 1984-07-27 | 1986-02-12 | Labofina Sa | Procede de purification de charges d'hydrocarbures liquides |
-
1993
- 1993-09-15 AT AT93870188T patent/ATE165803T1/de not_active IP Right Cessation
- 1993-09-15 DE DE69318403T patent/DE69318403T2/de not_active Expired - Lifetime
- 1993-09-15 DK DK93870188T patent/DK0643028T3/da active
- 1993-09-15 ES ES93870188T patent/ES2117120T3/es not_active Expired - Lifetime
- 1993-09-15 EP EP93870188A patent/EP0643028B1/en not_active Expired - Lifetime
-
1994
- 1994-09-12 TW TW083108393A patent/TW316910B/zh active
- 1994-09-13 JP JP24347394A patent/JP3574684B2/ja not_active Expired - Fee Related
- 1994-09-13 KR KR1019940022987A patent/KR100331718B1/ko not_active IP Right Cessation
- 1994-09-14 CZ CZ19942245A patent/CZ289049B6/cs not_active IP Right Cessation
- 1994-09-14 FI FI944251A patent/FI109205B/fi active
- 1994-09-15 CA CA002132115A patent/CA2132115C/en not_active Expired - Fee Related
- 1994-09-15 US US08/305,318 patent/US5432243A/en not_active Expired - Lifetime
- 1994-09-15 CN CN94116301A patent/CN1087305C/zh not_active Expired - Fee Related
- 1994-09-15 AU AU72997/94A patent/AU678501B2/en not_active Ceased
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0308569A1 (en) * | 1987-09-24 | 1989-03-29 | Fina Research S.A. | Process for removing arsine from light olefin-containing hydrocarbon feedstocks |
| US5134208A (en) * | 1991-09-27 | 1992-07-28 | Shell Oil Company | Polymerization process |
Also Published As
| Publication number | Publication date |
|---|---|
| AU7299794A (en) | 1995-03-30 |
| EP0643028A1 (en) | 1995-03-15 |
| EP0643028B1 (en) | 1998-05-06 |
| CZ289049B6 (cs) | 2001-10-17 |
| TW316910B (zh) | 1997-10-01 |
| DE69318403D1 (de) | 1998-06-10 |
| JP3574684B2 (ja) | 2004-10-06 |
| DE69318403T2 (de) | 1998-10-01 |
| AU678501B2 (en) | 1997-05-29 |
| CZ224594A3 (en) | 1995-04-12 |
| FI944251A0 (fi) | 1994-09-14 |
| DK0643028T3 (da) | 1999-03-15 |
| JPH07149827A (ja) | 1995-06-13 |
| ATE165803T1 (de) | 1998-05-15 |
| FI944251A (fi) | 1995-03-16 |
| FI109205B (fi) | 2002-06-14 |
| CN1100430A (zh) | 1995-03-22 |
| KR950008539A (ko) | 1995-04-19 |
| CA2132115C (en) | 2006-08-29 |
| US5432243A (en) | 1995-07-11 |
| CA2132115A1 (en) | 1995-03-16 |
| ES2117120T3 (es) | 1998-08-01 |
| KR100331718B1 (ko) | 2002-08-22 |
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