Ti-Mg催化剂的活性及载体研究
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摘要
Ziegler-Natta催化剂具有制备简单、对杂质敏感性低的优点，是目前聚乙烯工业中应用最多的催化剂。然而，催化活性不高、产品堆密度低等问题困扰着Ziegler-Natta催化剂的工业应用。因此，对Ziegler-Natta催化剂进行相应改进，以提高催化剂活性、增加产品堆密度，具有非常重要的现实意义。
目前对Ziegler-Natta催化剂的研究主要集中在氯化镁载体结构的改进和电子给体的优选。以此为指导，本论文首先研究了影响催化剂活性的各个要素，确定催化剂达到最佳活性的生产条件；其次，考察了影响聚乙烯产品堆密度的各种因素；最后，在乙醇溶解氯化镁重结晶法制备催化剂载体的基础上，考察了一元醇、二元醇与电子给体对催化剂载体的影响，获得了催化剂载体粒径及比表面积随处理条件(溶剂的种类、电子给体的种类)和电子给体变化的变化规律，对于改进催化剂载体的制备方式，提高催化剂的活性具有重要的指导意义。论文主要开展的三方面研究工作如下：
1．研究了影响催化剂活性的各个要素。实验发现，在催化剂取得最佳活性时的温度在80-85℃，铝钛摩尔比在120-140之间；在加入电子给体时，苯甲酸乙酯(EB)对催化剂活性的影响最大，能提高催化剂活性50％-70％；乙酸乙酯可提高催化剂活性30％左右；而邻苯二甲酸二正丁酯(DNBP)和1,4-二氧六环的使用则使催化剂活性降低。
2．研究了影响聚乙烯产品堆密度的各个要素。论文考察了聚合时间、铝钛比、电子给体加入量、聚合温度和助催化剂对聚乙烯产品堆密度的影响，实验发现，影响聚乙烯产品堆密度的主要因素是催化剂活性，当活性提高时，聚乙烯堆密度降低，当活性降低时，聚乙烯堆密度提高。
3．基于以乙醇为溶剂的氯化镁载体制备方式，系统研究了多种一元醇、二元醇对催化剂载体特性的影响。
(1)研究了乙醇、1-丙醇、1-丁醇、1-戊醇和1-己醇等一元醇对氯化镁载体的影响。并通过激光粒度分析仪、BET比表面分析仪等考察了所得载体的粒径分布、比表面积等。结果发现，对于乙醇、1-丙醇、1-丁醇，随着一元醇碳链的加长，所得载体的粒径减小，比表面积增大，其中，乙醇处理过的氯化镁载体的粒径和比表面积分别为19．816μm和101．5m~2／g，而1-丁醇处理过的氯化镁载体的粒径和比表面积分别为11．014μm和160．8m~2／g；当一元醇碳链进一步加长，所得载体的粒径和比表面积不再发生显著变化。
(2)研究了一元醇与四氢呋喃(THF)的混合溶剂对氯化镁载体的影响。实验发现，所得载体的粒径和比表面积由混合溶剂中对氯化镁溶解度最大的溶剂决定。在所用的几种溶剂中，溶解度的顺序为：正己醇>正戊醇>正丁醇>正丙醇≈THF>乙醇。
(3)研究了以乙醇为溶剂时，EB、DNBP和1,4-二氧六环等电子给体对氯化镁载体比表面积及粒径的影响。其中，EB和DNBP的使用都使得氯化镁载体的粒径减小，比表面积增大。EB的加入获得的载体的粒径及比表面积为13．991μm、137．2m~2／g，而加入DNBP获得的载体的粒径及比表面积为13．855μm、180．6m~2／g；1，4-二氧六环的使用则使载体流动性变差，且所得载体粒径变大，约为69．179μm。
(4)研究了二元醇的引入对所制备氯化镁载体的影响。实验发现，氯化镁经二元醇处理后，体积明显增大。激光粒度分析仪、BET比表面分析仪等表征结果表明，乙二醇处理后获得的载体的粒径及比表面积为10．986μm、187．4m~2／g，而1，4-丁二醇的加入获得的载体的粒径及比表面积为9．454μm、197．9m~2／g。1，4-丁二醇处理过的氯化镁载体再经TiCl_4处理后，比表面积可增至251．4m~2／g。在8atm条件下聚合时，以1-己醇为处理过的氯化镁为载体的活性可达3029gPE／gcat／2h，而以1，4-丁二醇处理过的氯化镁为载体的催化剂活性可达3374gPE／gcat／2h，相对于同等条件下的硅胶／氯化镁复合载体，活性可分别提高39％、54％。
Ziegler-Natta catalysts for polyethylene is the most widely-used catalyst for itsmerits in easy preparation and low sensitivity on O_2 and H_2O, but the existingquestions about low catalytic activity and low bulk density still puzzle the operatorsand managers. Therefore, the impovement on the catalytic activity and bulk densityis indispensable and significative.
The study on Ziegler-Natta catalyst focuses on the MgCl_2 support and electrondonor. In this paper, the factors that affect the catalytic activity were studied, and theoptimal polymerization condition were determined. Second, the factors that affectthe bulk density were investigated. Thirdly, based on the recrystallization techniques,several ethanols, diols and electron donors were studied and the methods about howto get supports with smaller particle size and greater surface area were obtained. Themain results in this theis can be summarized as follows:
1. The factors that affect of the activity of the catalyst were studied. Theexperimental results showed that the catalyst got its best activity at 80-85℃andAl/Ti molar ratio 120-140. The electron donor ethyl benzoate(EB) can improvethe activity by 50% to 70%, and ethyl acetate can improve the activity by 30%. ButDibutyl o-phthalate(DNBP) and 1,4-dioxane reduce the activity.
2. The factors that affect of the bulk density of the polyethylene were studied. Theexperimental results showed that the bulk density increase as the polymerizationtime decrease, as the catalytic activity decrease. the reason is that as the catalyticincreases and the polymerization time increases, the polymer chain get longer, andthe polymer particles get bigger, so the void fraction between different particlesincrease. As a result, the bulk density decrease.
3. Based on the recrystallization techniques, several ethanols, diols and electrondonors were studied and the methods about how to get supports with smaller particlesize and greater surface area were obtained.
(1) The effects of ethanol, n-propanol, n-butanol, n-pentanol and n-hexanol onMgCl_2 supports were studied. The result showed that as the C-chain of the ethanolincrease, the surface area of the obtained supports increase and the particle sizedecrease. The surface area and particle size of the support obtained from ethanolsolvent was 101.5m~2/g and 19.816μm, and the surface area and particle size of thesupport obtained from ethanol solvent was 160.8m~2/g and 11.014μm.
(2) The effects of THF/ethanol hybrid solvents on MgCl_2 supports were studied.The result showed that the surface area and particle size of the support weredetermined by the part of the hybrid solvent which have bigger solubility on MgCl_2.The solubility on MgCl_2 varies in this order: n-hexanol≈n-pentanol≈n-butanol≈n-propanol>THF>ethanol.
(3) The effects of electron donors on MgCl_2 supports were studied. EB and DNBPcan improve the support well. The addtion of EB makes a support with surface area137.2m~2/g and particle size 13.991μm, while the addtion of DNBP makes a supportwith surface area 180.6m~2/g and particle size 13.855μm. But 1,4-dioxane makes thesupport agglomerate, the particle size grows to 69.179μm.
(4) The effects of diols on MgCl_2 supports were studied. The analytical resultsshow that after treated by diols, the surave area and the particle size improve a lot.The surface area and particle size of the support obtained from ethanediol was187.4m~2/g and 10.986μm, and the surface area and particle size of the supportobtained from 1,4-butanediol was 197.9m~2/g and 9.454μm. After TiCl_4 treatment, thesurface area of the support obtained from 1,4-butanediol increase to 251.4m~2/g. Theactivity of the catalysts based on the MgCl_2 treated by n-hexanol and1,4-butanediol can reach 3029gPE/gcat/2h and 3374gPE/gcat/2h, improved by 39% and 54%compared with the catalyst with MgCl_2/silical support.
目前对Ziegler-Natta催化剂的研究主要集中在氯化镁载体结构的改进和电子给体的优选。以此为指导，本论文首先研究了影响催化剂活性的各个要素，确定催化剂达到最佳活性的生产条件；其次，考察了影响聚乙烯产品堆密度的各种因素；最后，在乙醇溶解氯化镁重结晶法制备催化剂载体的基础上，考察了一元醇、二元醇与电子给体对催化剂载体的影响，获得了催化剂载体粒径及比表面积随处理条件(溶剂的种类、电子给体的种类)和电子给体变化的变化规律，对于改进催化剂载体的制备方式，提高催化剂的活性具有重要的指导意义。论文主要开展的三方面研究工作如下：
1．研究了影响催化剂活性的各个要素。实验发现，在催化剂取得最佳活性时的温度在80-85℃，铝钛摩尔比在120-140之间；在加入电子给体时，苯甲酸乙酯(EB)对催化剂活性的影响最大，能提高催化剂活性50％-70％；乙酸乙酯可提高催化剂活性30％左右；而邻苯二甲酸二正丁酯(DNBP)和1,4-二氧六环的使用则使催化剂活性降低。
2．研究了影响聚乙烯产品堆密度的各个要素。论文考察了聚合时间、铝钛比、电子给体加入量、聚合温度和助催化剂对聚乙烯产品堆密度的影响，实验发现，影响聚乙烯产品堆密度的主要因素是催化剂活性，当活性提高时，聚乙烯堆密度降低，当活性降低时，聚乙烯堆密度提高。
3．基于以乙醇为溶剂的氯化镁载体制备方式，系统研究了多种一元醇、二元醇对催化剂载体特性的影响。
(1)研究了乙醇、1-丙醇、1-丁醇、1-戊醇和1-己醇等一元醇对氯化镁载体的影响。并通过激光粒度分析仪、BET比表面分析仪等考察了所得载体的粒径分布、比表面积等。结果发现，对于乙醇、1-丙醇、1-丁醇，随着一元醇碳链的加长，所得载体的粒径减小，比表面积增大，其中，乙醇处理过的氯化镁载体的粒径和比表面积分别为19．816μm和101．5m~2／g，而1-丁醇处理过的氯化镁载体的粒径和比表面积分别为11．014μm和160．8m~2／g；当一元醇碳链进一步加长，所得载体的粒径和比表面积不再发生显著变化。
(2)研究了一元醇与四氢呋喃(THF)的混合溶剂对氯化镁载体的影响。实验发现，所得载体的粒径和比表面积由混合溶剂中对氯化镁溶解度最大的溶剂决定。在所用的几种溶剂中，溶解度的顺序为：正己醇>正戊醇>正丁醇>正丙醇≈THF>乙醇。
(3)研究了以乙醇为溶剂时，EB、DNBP和1,4-二氧六环等电子给体对氯化镁载体比表面积及粒径的影响。其中，EB和DNBP的使用都使得氯化镁载体的粒径减小，比表面积增大。EB的加入获得的载体的粒径及比表面积为13．991μm、137．2m~2／g，而加入DNBP获得的载体的粒径及比表面积为13．855μm、180．6m~2／g；1，4-二氧六环的使用则使载体流动性变差，且所得载体粒径变大，约为69．179μm。
(4)研究了二元醇的引入对所制备氯化镁载体的影响。实验发现，氯化镁经二元醇处理后，体积明显增大。激光粒度分析仪、BET比表面分析仪等表征结果表明，乙二醇处理后获得的载体的粒径及比表面积为10．986μm、187．4m~2／g，而1，4-丁二醇的加入获得的载体的粒径及比表面积为9．454μm、197．9m~2／g。1，4-丁二醇处理过的氯化镁载体再经TiCl_4处理后，比表面积可增至251．4m~2／g。在8atm条件下聚合时，以1-己醇为处理过的氯化镁为载体的活性可达3029gPE／gcat／2h，而以1，4-丁二醇处理过的氯化镁为载体的催化剂活性可达3374gPE／gcat／2h，相对于同等条件下的硅胶／氯化镁复合载体，活性可分别提高39％、54％。
Ziegler-Natta catalysts for polyethylene is the most widely-used catalyst for itsmerits in easy preparation and low sensitivity on O_2 and H_2O, but the existingquestions about low catalytic activity and low bulk density still puzzle the operatorsand managers. Therefore, the impovement on the catalytic activity and bulk densityis indispensable and significative.
The study on Ziegler-Natta catalyst focuses on the MgCl_2 support and electrondonor. In this paper, the factors that affect the catalytic activity were studied, and theoptimal polymerization condition were determined. Second, the factors that affectthe bulk density were investigated. Thirdly, based on the recrystallization techniques,several ethanols, diols and electron donors were studied and the methods about howto get supports with smaller particle size and greater surface area were obtained. Themain results in this theis can be summarized as follows:
1. The factors that affect of the activity of the catalyst were studied. Theexperimental results showed that the catalyst got its best activity at 80-85℃andAl/Ti molar ratio 120-140. The electron donor ethyl benzoate(EB) can improvethe activity by 50% to 70%, and ethyl acetate can improve the activity by 30%. ButDibutyl o-phthalate(DNBP) and 1,4-dioxane reduce the activity.
2. The factors that affect of the bulk density of the polyethylene were studied. Theexperimental results showed that the bulk density increase as the polymerizationtime decrease, as the catalytic activity decrease. the reason is that as the catalyticincreases and the polymerization time increases, the polymer chain get longer, andthe polymer particles get bigger, so the void fraction between different particlesincrease. As a result, the bulk density decrease.
3. Based on the recrystallization techniques, several ethanols, diols and electrondonors were studied and the methods about how to get supports with smaller particlesize and greater surface area were obtained.
(1) The effects of ethanol, n-propanol, n-butanol, n-pentanol and n-hexanol onMgCl_2 supports were studied. The result showed that as the C-chain of the ethanolincrease, the surface area of the obtained supports increase and the particle sizedecrease. The surface area and particle size of the support obtained from ethanolsolvent was 101.5m~2/g and 19.816μm, and the surface area and particle size of thesupport obtained from ethanol solvent was 160.8m~2/g and 11.014μm.
(2) The effects of THF/ethanol hybrid solvents on MgCl_2 supports were studied.The result showed that the surface area and particle size of the support weredetermined by the part of the hybrid solvent which have bigger solubility on MgCl_2.The solubility on MgCl_2 varies in this order: n-hexanol≈n-pentanol≈n-butanol≈n-propanol>THF>ethanol.
(3) The effects of electron donors on MgCl_2 supports were studied. EB and DNBPcan improve the support well. The addtion of EB makes a support with surface area137.2m~2/g and particle size 13.991μm, while the addtion of DNBP makes a supportwith surface area 180.6m~2/g and particle size 13.855μm. But 1,4-dioxane makes thesupport agglomerate, the particle size grows to 69.179μm.
(4) The effects of diols on MgCl_2 supports were studied. The analytical resultsshow that after treated by diols, the surave area and the particle size improve a lot.The surface area and particle size of the support obtained from ethanediol was187.4m~2/g and 10.986μm, and the surface area and particle size of the supportobtained from 1,4-butanediol was 197.9m~2/g and 9.454μm. After TiCl_4 treatment, thesurface area of the support obtained from 1,4-butanediol increase to 251.4m~2/g. Theactivity of the catalysts based on the MgCl_2 treated by n-hexanol and1,4-butanediol can reach 3029gPE/gcat/2h and 3374gPE/gcat/2h, improved by 39% and 54%compared with the catalyst with MgCl_2/silical support.
引文
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