CN102464545A - 一种乙烯齐聚制备1-辛烯的方法 - Google Patents
一种乙烯齐聚制备1-辛烯的方法 Download PDFInfo
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- 239000005977 Ethylene Substances 0.000 title claims abstract description 29
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 24
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- 239000011651 chromium Substances 0.000 claims description 7
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- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
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Abstract
本发明涉及一种在乙烯齐聚催化剂体系存在下制备1-辛烯的方法，该方法包括部分原料乙烯气与溶剂预混后，再与催化体系a+b组分、c组分、d组分混合之后进入反应器，另一部分原料乙烯气直接进入反应器；上述反应器的反应液由中上部流出至溢流槽，在溢流槽内加入催化剂终止剂，而后反应液进入分离装置；该方法用于乙烯齐聚制1-辛烯，具有较高的催化活性和1-辛烯选择性。
Description
技术领域
本发明涉及一种在乙烯齐聚催化剂体系存在下制备1-辛烯的方法。
背景技术
EP 0608447A1中报道了一种铬系催化剂组合物，作为乙烯齐聚和/或共聚的催化剂，其中使用一种含铬的化合物作为催化剂组合物的组分之一；使用吡咯化合物作为铬系催化剂组合物的组分之二；采用了一种以路易士酸和/或金属烷基化合物为活化剂作为该催化剂组合物的组分之三；同时还指出，催化剂体系中还可任选一种卤素源作为该催化剂组合物中的组分之四，该卤素源既可为无机卤化物，也可为众多类型的有机卤化物。
JP 0832519中使用了Sn(OSO2F3)2化合物代替EP 0608447A1中第四组分的卤素源，形成了一种新的四元铬系催化剂组合物，该四元铬系催化剂的活性和选择性未得到明显的改进。
USP 5,910,619中报道了采用1，2，3，4，5，6-六氯环己烷作为改进剂，组成四元催化剂组合物，该催化剂的活性虽有所提高，但仍不能满足要求，人们希望进一步改进催化剂的性能，以提高催化活性。
以上的乙烯齐聚方法都侧重于对催化剂的研究，尽管WO 99/19380对乙烯齐聚方法进行了研究，但与其他专利相似，反应基本上是在普通高压反应釜中进行的，而由此产生了传质和传热不均等问题。由于该反应是强放热反应，而且反应初期放热速率更快，因此往往由于传热速率慢而导致局部温度过高，造成部分催化剂失活，影响了催化剂的效率；而且由于在这种反应釜中的传质速率慢，使得络合催化剂的催化效果受到影响，催化活性降低，往往反应时间较长，造成能耗增加。
发明内容
本发明的目的是提供一种在乙烯齐聚催化剂体系存在下制备1-辛烯的方法，使在较短的反应时间内制得1-辛烯产品，催化剂活性高，1-辛烯选择性高，整个方法能耗低。
本发明所述的一种在乙烯齐聚催化剂体系存在下制备1-辛烯的方法是原料乙烯在进入反应器前，使部分原料乙烯的溶剂进行预混，预混在预混器和/或管道内进行，预混的作用是使乙烯与溶剂进行充分的传质，增加乙烯在溶剂中的溶解度，可以达到20％，由此提高产物生成量，提高乙烯单程转化率。乙烯预混的溶液再分别与催化剂的a+b、c、d组分溶液混合后与另一部分原料乙烯进入反应器反应；反应液进入分离装置进行产物分离，其中的1-辛烯直接作为LLDPE的共聚单体，溶剂回收利用，剩余的催化剂回收处理。在进入分离装置前，进行采样分析。
气体分布器
气体分布器是中间开有许多小孔的不锈钢管，小孔直径为不锈钢管直径的0.2～90％，通常为5～70％，优选为20～50％。
催化剂和溶剂
乙烯齐聚制1-辛烯催化剂和溶剂见中国专利《一种乙烯低聚的催化剂组合物及其应用》(申请号：200610057254.2)。
它包括：铬化物a、含P和N的配体b、活化剂c和促进剂d，
其中a为乙酰丙酮铬、四氢呋喃氯化铬和/或异辛酸铬；
b的通式为，
R1、R2、R3、R4为苯基、苯甲基、芴基或萘基；R5为异丙基、丁基、环丙基、环戊基、环己基或芴基；
c为甲基铝氧烷、乙基铝氧烷、丙基铝氧烷和/或丁基铝氧烷；
d的通式为X1R6X2，中X1、X2为F、Cl、Br、I或烷氧基；R6为烷基或芳香基；
a、b、c和d的摩尔比为1∶0.5～10∶50～3000∶0.5～10。
反应条件
在反应器内，反应压力、反应温度见中国专利《一种乙烯低聚的催化剂组合物及其应用》(申请号：200610057254.2)。
反应温度为30～200℃；反应压力为0.5～20.0MPa；时间为0.1～2小时。
催化剂及溶剂的进料量以满足反应器内催化剂a组分的浓度在1～10ppm为宜，较理想的是1～3ppm。
进入预混器的乙烯流量(wt)占进入反应器的乙烯总流量(wt)的比例可以为任何满足反应条件的比例，一般为0～100％，较理想的为20～90％，较优的为60～80％。
有益效果
a.采用该方法后，反应物混合均匀，传质、传热效果好。
b.1-辛烯的选择性高，大于70％。
c.催化剂的催化活性高，大于1×106g产物/gCr·h。
附图说明
图1乙烯齐聚制备1-辛烯的工艺简图。
具体实施方式
本发明所述的一种乙烯齐聚制备1-辛烯的方法是原料乙烯在进入反应器前，将原料乙烯的一部分与溶剂进行预混，预混在预混器和/或管道内进行，乙烯预混溶液分别与催化剂的a+b、c、d组分溶液混合后，通过位于反应器底部的气体分布器管上的小孔进入反应器；原料乙烯的另一部分直接通过反应器顶部进入反应器反应；将反应器用环己烷洗净后，在100℃下真空干燥1小时，冷却至室温，用乙烯置换，打开乙烯进气阀，保持反应器内压力维持在5.0Mpa，按一定流量通入溶剂，a+b、c和d组分，保持反应器内温度维持在50℃，打开溢流槽出口阀，使反应液进入分离装置，反应液进入分离装置进行产物分离，其中的1-辛烯直接作为LLDPE的共聚单体，溶剂回收利用，剩余的催化剂回收处理。在进入分离装置前，进行采样分析。
所述的预混器可以是一个或多个长径比大于20的不锈钢管或不锈钢压力容器，内部可以添加填料。
所述的气体分布器是中间开有许多小孔的不锈钢管，小孔直径为不锈钢管直径的0.2～90％，通常为5～70％，优选为20～50％。
催化剂和溶剂
乙烯齐聚制1-辛烯催化剂和溶剂见中国专利《一种乙烯低聚的催化剂组合物及其应用》(申请号：200610057254.2)。
反应条件
在反应器内，反应压力、反应温度见中国专利《一种乙烯低聚的催化剂组合物及其应用》(申请号：200610057254.2)。
催化剂及溶剂的进料量以满足反应器内催化剂a组分的浓度在1～10ppm为宜，较理想的是1～3ppm。
进入预混器的乙烯流量(wt)占进入反应器的乙烯总流量(wt)的比例可以为任何满足反应条件的比例，一般为0～100％，较理想的为20～90％，较优的为60～80％。
表1工艺条件及结果
其他反应条件：
反应温度50℃，反应压力5.0Mpa，催化剂配比a∶b∶c∶d＝1∶1.05∶300∶5，改进剂1，1，2，2，-四氯乙烷，溶剂：环己烷，乙烯进料总量20kg/h，溶剂进料总量13kg/h。
Claims (6)
1.一种乙烯齐聚制备1-辛烯的方法，其特征在于：
(1)部分原料乙烯气与溶剂在预混器预混后，再与催化体系a+b组分、c组分、d组分混合之后经气体分布器进入反应器，另一部分原料乙烯气直接进入反应器；
催化剂包括：铬化物a、含P和N的配体b、活化剂c和促进剂d，
其中a为乙酰丙酮铬、四氢呋喃氯化铬和/或异辛酸铬；
b的通式为，
R1、R2、R3、R4为苯基、苯甲基、芴基或萘基；R5为异丙基、丁基、环丙基、环戊基、环己基或芴基；
c为甲基铝氧烷、乙基铝氧烷、丙基铝氧烷和/或丁基铝氧烷；
d的通式为X1R6X2，中X1、X2为F、Cl、Br、I或烷氧基；R6为烷基或芳香基；
a、b、c和d的摩尔比为1∶0.5～10∶50～3000∶0.5～10。
(2)反应器的反应液由中上部流出至溢流槽，在溢流槽内加入催化剂终止剂，而后反应产物进入分离装置。
2.按照权利要求1所述的一种乙烯齐聚制备1-辛烯的方法，其特征在于：所述的预混器可以是一个或多个长径比大于20的不锈钢管或不锈钢压力容器，内部可以添加填料。
3.按照权利要求1所述的一种乙烯齐聚制备1-辛烯的方法，其特征在于：所述的气体分布器是中间开有许多小孔的不锈钢管，小孔直径为不锈钢管直径的0.2％～90％。
4.按照权利要求3所述的一种乙烯齐聚制备1-辛烯的方法，其特征在于：气体分布器所述的小孔直径为不锈钢管直径的5％～70％。
5.按照权利要求1所述的一种乙烯齐聚制备1-辛烯的方法，其特征在于：进入预混器的乙烯流量重量占进入反应器的乙烯总流量重量的比例为20～90％。
6.按照权利要求1所述的一种乙烯齐聚制备1-辛烯的方法，其特征在于：催化剂及溶剂的进料量以满足反应器内催化剂a组分的浓度在1～10ppm。
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| EP11839905.4A EP2639213A4 (en) | 2010-11-11 | 2011-06-03 | PROCESS FOR THE PREPARATION OF 1-OCTES BY OLIGOMERIZATION OF ETHYLENE |
| US13/704,961 US20130090508A1 (en) | 2010-11-11 | 2011-06-03 | Method for Preparing 1-Octene by Oligomerization of Ethylene |
| PCT/CN2011/000945 WO2012062028A1 (zh) | 2010-11-11 | 2011-06-03 | 一种乙烯齐聚制备1-辛烯的方法 |
| JP2013538032A JP2014500251A (ja) | 2010-11-11 | 2011-06-03 | エチレンのオリゴマー化による１−オクテンを製造する方法 |
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| CN104086349A (zh) * | 2013-04-01 | 2014-10-08 | 中国石油化工股份有限公司 | 乙烯齐聚生产alpha烯烃的方法 |
| CN104086350A (zh) * | 2013-04-01 | 2014-10-08 | 中国石油化工股份有限公司 | 乙烯齐聚生产alpha烯烃的方法 |
| CN112915930A (zh) * | 2016-05-27 | 2021-06-08 | 切弗朗菲利浦化学公司 | 选择性乙烯低聚的工艺改进 |
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Also Published As
| Publication number | Publication date |
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| EP2639213A1 (en) | 2013-09-18 |
| WO2012062028A1 (zh) | 2012-05-18 |
| EP2639213A4 (en) | 2016-05-18 |
| JP2014500251A (ja) | 2014-01-09 |
| US20130090508A1 (en) | 2013-04-11 |
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