CN115501914A - 一种含解聚剂的乙烯三聚催化剂及其应用 - Google Patents
一种含解聚剂的乙烯三聚催化剂及其应用 Download PDFInfo
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- B01J31/1805—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 nitrogen
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Abstract
本发明公开了一种含解聚剂的乙烯三聚催化剂及其应用，所述乙烯三聚催化剂由铬化物、吡咯及其衍生物、烷基铝助剂和无机含磷卤化物解聚剂组成，本发明首次采用了无机含磷卤化物作为解聚剂，不仅能将聚合的烷基铝拆解为单分子结构，保持有机卤化物的高选择性和活性，还能减少环境污染以及对操作人员的身体伤害，此外无机含磷卤化物作为路易斯酸与有机卤化物相比价格低廉，有利于工业化推广。本发明中含解聚剂的乙烯三聚催化剂具有优异的乙烯三聚催化性能，成本低，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，具体涉及一种含解聚剂的乙烯三聚催化剂及其应用。
背景技术
乙烯选择性三聚生产1-己烯多采用铬系催化剂，催化体系主要包含配体、主催化剂和助催化剂。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。乙烯齐聚制备1-己烯的选择性主要取决于铬金属环上中间体乙烯插入的速率和分解速率。当铬环戊烷的乙烯插入速率明显大于分解速率时，其金属环状结构能够进一步插入乙烯，扩张新城铬环庚烷；反之，则表现出选择性三聚，生成1-己烯。
在乙烯选择性三聚方面，已有大量的专利。专利JP 08134131中探讨了以末端相邻两个碳原子上含有三个以上卤素原子为特征的饱和卤代烃作为异辛酸铬、2,5-二甲基吡咯和三乙基铝催化剂的促进剂，该四元催化体系在乙烯选择性三聚制备1-己烯时，催化活性明显提高。中国石油天然气股份有限公司申请的专利CN1490291中催化剂体系包含异辛酸铬、2,4-二甲基吡咯、三乙基铝、1,2,3,4,5,6-六氯环己烷γ体等，1-己烯的选择性高达99.3%，利用该三聚技术中石油分别于2007年和2014年在大庆石化公司和独山子石化公司实现1-己烯的产业化。三菱化学公司申请了专利US08790479保护了一种含有铬基催化剂的反应溶液存在下使α-烯烃在反应区中进行齐聚来制备α-烯烃齐聚物的方法，催化剂组合物为铬源、吡咯衍生物、烷基铝和有机卤化物（六氯乙烷或四氯乙烷）。
中石化在专利CN 1108193C中披露了一种能够促进乙烯选择性三聚反应的含卤促进剂，该促进剂是一种芳环上至少含有一个被至少二个卤素原子在α-位取代的C1-2-烷基的卤代烷基取代的芳烃或卤代芳烃化合物，促进剂的加入，能显著提高催化剂的活性和1-己烯的选择性。
由上述可见，在乙烯选择性三聚催化剂中，除铬源、烷基铝和配体外，第四组份是影响催化剂活性和选择性的关键因素，开发出优良的第四组份，不但能提高催化活性和目标产物的选择性，还能有效降低聚合物的生成，从而简化工艺流程。
发明内容
为了解决上述技术问题，本发明提供了一种含解聚剂的乙烯三聚催化剂及其应用，其中催化剂由铬化物a、吡咯及其衍生物b、烷基铝助剂c和无机含磷卤化物解聚剂d组成，其用于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：
一种含解聚剂的乙烯三聚催化剂包括以下组分：
（1）铬化物a：异辛酸铬、乙酰丙酮铬、四氢呋喃氯化铬中的一种或多种；
（2）吡咯及其衍生物b：吡咯，2,4-二甲基吡咯或2,5-二甲基吡咯；
（3）烷基铝助剂c：三乙基铝、甲基铝氧烷、三甲基铝或异丁基铝；
（4）无机含磷卤化物解聚剂d：PCl3、PCl5、PBr5或PBr3；
进一步地，所述a、b、c、d的摩尔比为：1:0.1~100:1~1000:1~1000，优选地，a、b、c和d的摩尔比为1:0.1~10:1~500:1~50；更优选地，a、b、c和d的摩尔比为1: 1~8：1~100:1~10。
进一步地，本发明的含解聚剂的乙烯三聚催化剂在催化乙烯三聚反应中的应用：将催化剂中各成分分别溶于惰性溶剂，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；其中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。具体应用包括以下步骤：
（1）催化剂制备：将催化剂中各成分分别溶于经除水处理的惰性溶剂制备成铬化物溶液、吡咯及其衍生物溶液、烷基铝助剂溶液、解聚剂溶液备用；
（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、吡咯及其衍生物溶液和解聚剂溶液，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，使烷基铝助催化剂淬灭，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60oC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：
金属Cr在烷基铝的作用下还原成一价，随后与配体配位后形成一定空间构型的配合物，但是在该过程中烷基铝为缺电子结构，极容易聚集，另一方面，卤代烃作为乙烯三聚催化剂的第四组份也起了非常重要的作用，其能显著提高催化剂的选择性，主要有两个作用，其一为卤素原子能与烷基铝中的Al原子形成配位键，从而将二聚体的烷基铝拆解为单分子结构，增加烷基铝单体的浓度，提高其利用率；其二为由于卤素原子比氮原子具有更大的电负性，能打开含氮配体中的N-H键，使含氮配体能以单分子形式存在于催化体系中，利于其与中心原子Cr配位；基于此，本发明在铬系催化剂前三种主要成分保持不变的情况下，首次采用了无机含磷卤化物作为解聚剂，不仅能将聚合的烷基铝拆解为单分子结构，保持有机卤化物的高选择性和活性，还能减少环境污染以及对操作人员的身体伤害，此外无机含磷卤化物作为路易斯酸与有机卤化物相比价格低廉，有利于工业化推广。本发明在铬金属盐、吡咯化合物、烷基铝基础上加入无机含磷卤化物解聚剂，其具有适当的给电子能力，可与烷基铝试剂结合，阻止其聚集，但又不影响其还原能力，最终该催化剂组合物具有优异的乙烯三聚催化性能。包含该解聚剂的催化剂成本低，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。
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，催化剂中中乙酰丙酮铬：吡咯：三乙基铝：三氯化磷=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60oC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，不同之处在于将乙酰丙酮铬改为四氢呋喃氯化铬，数据结果见表1。
实施例3：
同实施例1，不同之处在于将三氯化磷改为五氯化磷，数据结果见表1。
实施例4：
同实施例1，不同之处在于将三氯化磷改为三溴化磷，数据结果见表1。
实施例5：
同实施例1，不同之处在于将三氯化磷改为五溴化磷，数据结果见表1。
实施例6：
同实施例1，不同之处在于将吡咯改为2,5-二甲基吡咯。
对比例1：
同实施例1，不同之处在于将三氯化磷改为六氯乙烷，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 (10)
1.一种含解聚剂的乙烯三聚催化剂，其特征在于：包括以下组分：铬化物、吡咯及其衍生物、烷基铝助剂、解聚剂；所述解聚剂为无机含磷卤化物。
2.根据权利要求1所述的催化剂，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。
3.根据权利要求1所述的催化剂，其特征在于：所述吡咯及其衍生物为吡咯，2,4-二甲基吡咯或2,5-二甲基吡咯。
4.根据权利要求1所述的催化剂，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所述的催化剂，其特征在于：所述解聚剂为无机含磷卤化物，具体为PCl3、PCl5、PBr5或PBr3。
6.根据权利要求1所述的催化剂，其特征在于：所述铬化物、吡咯及其衍生物、烷基铝助剂、解聚剂摩尔比为：1:0.1~100:1~1000:1~1000。
7.根据权利要求1所述的催化剂，其特征在于：所述铬化物、吡咯及其衍生物、烷基铝助剂、解聚剂的摩尔比为1:0.1~10:1~500:1~50。
8.一种如权利要求1-7任一项所述含解聚剂的乙烯三聚催化剂在乙烯三聚反应中的应用，其特征在于：将催化剂中各成分分别溶于惰性溶剂，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；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。
9.根据权利要求8所述的应用，其特征在于：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。
10.根据权利要求8所述的应用，其特征在于：具体应用包括以下步骤：
（1）催化剂制备：将催化剂中各成分分别溶于经除水处理的惰性溶剂制备成铬化物溶液、吡咯及其衍生物溶液、烷基铝助剂溶液、解聚剂溶液备用；
（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、吡咯及其衍生物溶液和解聚剂溶液，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。
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