CN115555048A - 一种乙烯三聚催化剂及其应用 - Google Patents
一种乙烯三聚催化剂及其应用 Download PDFInfo
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- 239000005977 Ethylene Substances 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 238000005829 trimerization reaction Methods 0.000 title claims abstract description 32
- 239000003446 ligand Substances 0.000 claims abstract description 24
- -1 4-phenylimidazole compound Chemical class 0.000 claims abstract description 16
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- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical group ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 4
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- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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Abstract
本发明公开了一种乙烯三聚催化剂及其应用，其在金属铬盐、烷基铝、卤代烃组分保持不变的基础上，首次使用4‑苯基咪唑化合物作为配体，本发明由铬金属盐、咪唑化合物、烷基铝和有机氯化物共同组成乙烯三聚组合物。该配体成本低廉，制备的催化剂活性高，1‑己烯选择性高，且生成的聚合物极少，有利于长周期运行。
Description
技术领域
本发明属于催化剂技术领域，具体涉及一种乙烯三聚催化剂及其应用。
背景技术
线性α-烯烃是重要的有机化工原料，其中以1-己烯的应用最为广泛。1-己烯作为重要的有机原料和化学中间体，主要用于生产高端聚乙烯（PE）。与1-丁烯共聚树脂相比，由1-己烯与乙烯共聚生产的线性低密度聚乙烯（LLDPE）及高密度聚乙烯(HDPE)在聚乙烯的机械加工、耐热性、柔韧性和透明性等方面具有明显优势。特别适合于生产包装膜和农用覆盖膜。用1-己烯代替1-丁烯生产高性能的LLDPE和HDPE已经成为今后发展的必然趋势。1-己烯也是被列为入到国家石油和化工发展指南的鼓励重点发展化工产品。乙烯齐聚是目前工业上制备α-烯烃的主要方法之一，其产品质量更高。乙烯选择性齐聚制备1-己烯可以更好的适应市场需求，也是近年研究的热点。
乙烯选择性三聚生产1-己烯反应机理普遍认同单金属环三聚机理，最先由Manyik等提出，后经Briggs修正。该机理可描述为两分子的乙烯配位到铬中心，通过氧化加成生成铬金属环戊烷，然后第三个乙烯分子配位到铬中心上，并插入到铬环戊烷中生成铬环庚烷，该七元环通过β-氢转移和还原消除释放一分子的1-己烯。
对于乙烯选择性齐聚催化剂体系的活性和目的产物的选择性是评价该技术先进性的关键，现有的乙烯三聚催化剂体系大多是含有配体的铬系配合物，在铬源相对固定的条件下，调节配体的结构成了改变主催化剂结构及调节催化剂性能的必然手段。且催化剂体系中配体的结构对乙烯齐聚产物碳数的调控具有重要的作用，对催化性能有很大的影响，因此新型配体的研究和开发是乙烯三聚领域研究的热点。目前已报道的高选择性齐聚催化剂能得到将近90%的共选择性，但这还不能满足工业化的需求，因此，仍需进一步开发设计新型配体催化剂。
在乙烯选择性三聚方面，已有大量的专利。
1999年，Phillips申请专利US5856257采用铬系催化剂催化乙烯发生选择性三聚反应生成选择性高达95%的1-己烯，该装置工艺是目前世界上最先进的1-己烯工艺技术。
中国石油化工股份有限公司在专利CN102558107A中通过微波辐射快速高效的制备CrCl3THF3，以此为基础制备的铬系催化剂生产1-己烯选择性高于92%，纯度高达99.2%，并且该工艺于2007年在北京燕山石化公司建成5万吨/年的1-己烯生产工艺。
CN107233919B保护了一种催化剂组合物，包含专利中提到的配体化合物、过渡金属化合物和含铝助催化剂，该组合物对乙烯三聚的催化活性高，产物分布优，C6选择性高，1-己烯的选择性有95.5%。
CN105566026A公开了一种包含双膦配体、过渡金属化合物、含铝主催化剂和作为有机溶剂的脂肪烃的催化体系，独特的溶剂效应使1-己烯收率非常高，达98.4%。现有技术中，普遍认为水对乙烯齐聚反应工艺非常不利，因此齐聚反应一般都严格控制无水无氧环境。
专利CN105566044B在对双膦配体进行研究中发现，链烷烃溶剂中含有一定量水分的乙烯在该专利中提到的金属主催化剂和含铝助催化剂作用下，反而具有更高的三聚活性，C6选择性70.1%，1-己烯的纯度高达98.4%。总体而言，目前已产业化的或者在研的乙烯三聚技术，绝大部分采用吡咯或吡咯衍生物作为金属铬的配体。
根据大量披露的专利或报道，现有技术仍然存在催化剂活性低、原料成本高、1-己烯的选择性低、聚合过程中会生成少量聚合物，影响装置连续运行的问题。
发明内容
为了解决上述技术问题，本发明公开了一种乙烯三聚催化剂及其应用，其采用铬化物、咪唑化合物、烷基铝助剂和给电子体组成的乙烯三聚催化剂体系催化乙烯三聚反应时，具有催化剂活性高、1-己烯选择性高、产物中聚乙烯副产物少，且在产业化中能降低成本等优点。
为实现上述目的，本发明的技术方案为：
一种乙烯三聚催化剂，包括以下组分：铬化物、配体、烷基铝助剂和给电子体，其中配体为4-苯基咪唑化合物，结构式如下：
，其中R1、R2、R3、R4、R5、R6、R7和R8相同或不同，选自氢、烷基、烷氧基、环烷基或卤素。
进一步地，所述铬化物、配体、烷基铝助剂和给电子体的摩尔比为：1:0.1~100:1~1000:1~1000；优选为1:0.1~10:1~500:1~50；更优选为1: 1~8：1~100:1~10。
进一步地，所述铬化物为异辛酸铬、乙酰丙酮铬、四氢呋喃氯化铬中的一种或多种。
进一步地，所述烷基铝助剂为三乙基铝、甲基铝氧烷、三甲基铝或异丁基铝。
进一步地，所述给电子体为四氯乙烷或六氯乙烷。
上述以4-苯基咪唑化合物为配体的乙烯三聚催化剂组合物在乙烯齐聚中的应用：将以4-苯基咪唑化合物为配体的乙烯三聚催化剂组合物中各成分分别溶于惰性溶剂中，以均相催化剂形式依次注入或提前混合均匀注入乙烯三聚反应体系中，随后提高乙烯压力，与催化剂充分接触，进行乙烯三聚反应，得到1-己烯。
进一步地，乙烯三聚反应的条件为：温度为30~250℃，压力为0.5~20MPa，时间为0.1~2h；所述惰性溶剂包括苯、甲苯、环己烷、甲基环己烷、正庚烷或正己烷。
进一步地，本发明的乙烯三聚催化剂的应用具体包括以下步骤：
（1）乙烯三聚催化剂制备：将乙烯三聚催化剂中各成分分别溶于经除水处理的惰性溶剂中制备成铬化物溶液、配体溶液、烷基铝助剂溶液和给电子体溶液备用；
（2）反应前先将反应釜釜体和内衬置于烘箱中120 ℃烘干过夜，安装到反应釜上后密封，抽真空条件下加热至105℃恒温1 h，除去残留的水、氧和含氧杂质，然后温度设置为反应温度，使其自然降温，同时氮气填充，随后抽真空，重复三次，确保空气被置换干净，然后用真空泵抽走氮气，用乙烯填充，重复三次，保证釜体充满乙烯；
（3）在搅拌条件下使用注射器注入步骤（1）制得的烷基铝助剂溶液，待温度稳定至反应温度后，用注射器依次注入铬化物溶液、配体溶液和给电子体溶液，关闭尾气阀，调节减压阀，待压力升至预定压力值后开始计时，并记录质量流量计数据，反应结束后关闭乙烯气体，反应停止，关闭进气口阀门，卸下反应釜体，浸泡至冰水浴中使反应釜冷却至10℃以下。
开启尾气阀泄压后在搅拌条件下注入一定量5 ml 10%HCl/乙醇溶液，使烷基铝助剂淬灭，随后称取重量记录。取少量液相产物使用GC-MS分析产物。将剩余样品过滤，滤纸提前称量记录质量，随后搅拌桨上的聚合物用勺子刮下来，用溶剂清洗至烧杯里，将所得的聚合物置于真空烘箱中60℃干燥过夜，分别称重，计算获得聚合物的质量。根据MS可标定组分种类，根据GC结果结合液相产物质量和聚合物质量，可计算获得各产物的选择性以及催化剂活性。
本发明与现有技术相比：本发明在金属铬盐、烷基铝、卤代烃组分保持不变的基础上，首次使用4-苯基咪唑化合物作为配体，本发明由铬金属盐、4-苯基咪唑化合物、烷基铝和有机氯化物共同组成乙烯三聚组合物。该配体成本低廉，制备的催化剂活性高，1-己烯选择性高，且生成的聚合物极少，有利于长周期运行。即反应产物中1-己烯选择性高，与已公开的催化剂相比（吡咯为配体），副产物聚乙烯含量极少，且具有更高的活性；在产业化中可通过原位聚合进行乙烯三聚反应，不需要预聚。本发明中4-苯基咪唑化合物中咪唑环和旁边的苯环为双环结构，且咪唑环上的杂原子有较强的给电子性能，整体构成了一个给电子能力适中的体系，且给电子能力可由两个共轭环协调，与金属铬、烷基铝以及含卤素给电子体共同作用，可以更加灵活地调节给单子性能，高效的催化乙烯分子与金属形成七元环，经β脱氢后释放一个1-己烯分子，且与吡咯相比，4-苯基咪唑化合物具有较大的空间位阻，可以有效降低聚合物的生成，有利于长周期运行。
具体实施方式
下面结合具体实施例对本发明进一步说明，但本发明不限于此。
实施例1
乙烯齐聚反应在高压不锈钢反应釜中进行。反应前高压反应釜在抽真空条件下加热至100℃恒温1 h，然后将温度设置为80℃，使其自然降温，同时氮气置换数次，然后用乙烯置换数次，保证釜体充满乙烯。随后依次向其中加入溶剂环己烷和催化剂，催化剂中乙酰丙酮铬：4-苯基咪唑：三乙基铝：六氯乙烷=1: 1:100: 10。控制反应压力为3MPa，反应1h后后停止反应，关闭进气口阀门，卸下反应釜体，浸泡至冰水浴中使反应釜冷却至10℃以下。开启尾气阀泄压后在搅拌条件下注入5 mL 10% HCl/乙醇溶液，使烷基铝淬灭，随后称取重量记录。取少量液相产物使用GC-MS分析产物。将剩余样品过滤，滤纸提前称量记录质量，随后搅拌桨上的聚合物用勺子刮下来，用溶剂清洗至烧杯里，将所得的聚合物置于真空烘箱中6℃干燥过夜，分别称重，计算获得聚合物的质量。根据MS可标定组分种类，根据GC结果结合液相产物质量和聚合物质量，可计算获得各产物的选择性以及催化剂活性。数据结果见表1。
实施例2
同实施例1，不同之处在于反应温度为130℃，数据结果见表1。
实施例3
同实施例1，不同之处在于反应压力为6MPa，数据结果见表1。
实施例4
同实施例1，不同之处在于将三乙基铝改为甲基铝氧烷，数据结果见表1。
实施例5
同实施例1，不同之处在于将乙酰丙酮铬和三氯化磷的比例改为1:5，数据结果见表1。
对比例1
同实施例1，不同之处在于将4-苯基咪唑改为吡咯，数据结果见表1。
表1 本发明的实施例和对比例反应条件及反应性能汇总表
以上实施例仅为了清楚的说明本发明内容，本发明的实施方式并不限制于此。凡在本发明的精神与原则之内，所做的任何修改、替换、改进等均应包含在本发明的保护范围之内。
Claims (5)
1.一种乙烯三聚催化剂，其特征在于：包括以下组分：铬化物、配体、烷基铝助剂和给电子体，其中配体为4-苯基咪唑化合物，结构式如下：
，其中R1、R2、R3、R4、R5、R6、R7和R8相同或不同，选自氢、烷基、烷氧基、环烷基或卤素。
2.根据权利要求1所述的乙烯三聚催化剂，其特征在于：所述铬化物、配体、烷基铝助剂和给电子体的摩尔比为：1:0.1~100:1~1000:1~1000。
3.根据权利要求1所述的乙烯三聚催化剂，其特征在于：所述铬化物为异辛酸铬、乙酰丙酮铬、四氢呋喃氯化铬中的一种或多种。
4.根据权利要求1所述的乙烯三聚催化剂，其特征在于：所述烷基铝助剂为三乙基铝、甲基铝氧烷、三甲基铝或异丁基铝。
5.根据权利要求1所述的乙烯三聚催化剂，其特征在于：所述给电子体为四氯乙烷或六氯乙烷。
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