Advances in the preparation processes of spherical MgCl2 support

doi:10.16085/j.issn.1000-6613.2016.s1.026

Abstract

Abstract: Spherical MgCl₂ is an efficient support for Ziegler-Natta catalyst and suitable for the preparation of catalysts for propylene polymerization.The MgCl₂ support has significant influence on the morphologies and properties of the catalysts and polymers.The preparation process of the spherical MgCl₂ support is one of the core technologies in such catalyst development.This paper presents the advantages of the MgCl₂ support, analyzes the effect of milling activation and chemical activation on the properties of MgCl₂.The characteristics of the preparation processes of the spherical MgCl₂ support including high-speed stirring, tubule extrusion, spray shaping, shearing emulsification and high gravity are discussed in detail.It is pointed out that the intensification of the emulsion mixing is the controlling factor in the preparation of MgCl₂ support, and good emulsion mixing is the prerequisite for the preparation of spherical MgCl₂ support with regular morphology and narrow size distribution.

Key words: catalyst support, preparation, size distribution, spherical MgCl₂

摘要： 球形氯化镁载体是氯化镁基齐格勒-纳塔催化剂的一种高效载体,尤其适用于丙烯聚合催化剂的制备,对于催化剂及聚合物的形态和性能有重要影响。球形氯化镁载体制备技术是此类催化剂开发过程中的核心技术之一。本文论述了氯化镁作为催化剂载体的优势,分析了研磨活化和化学活化对氯化镁性能的影响,并详细介绍了高速搅拌法、细管挤出法、喷雾成型法、剪切乳化法和超重力法等球形氯化镁载体制备技术的特点,指出在氯化镁载体制备过程中的关键控制因素是对乳液混合过程的强化,良好的乳液混合是制备形貌规整、粒径分布窄的氯化镁球形载体的先决条件。

关键词: 催化剂载体, 制备, 粒度分布, 球形氯化镁

CLC Number:

TQ32

CUI Weisong, LI Yingwen, YI Jianjun, LI Zhenhao, CHEN Jianfeng, SHAO Lei. Advances in the preparation processes of spherical MgCl₂ support[J]. Chemical Industry and Engineering Progree, 2016, 35(S1): 152-158.

崔伟松, 李应文, 义建军, 李振昊, 陈建峰, 邵磊. 球形氯化镁载体制备技术进展[J]. 化工进展, 2016, 35(S1): 152-158.

References

[1] ZIEGLER K,HOLZKAMP E,BREIL H.The Mülheim low pressure polyethylene process[J].Angew.Chem.Int.Ed.,1955,67(19/20):541-547.
[2] NATTA G.Isotactic polymers[J].Makromol.Chem.,1955,16(3):213-217.
[3] NATTA G.Kinetic studies of α-olefin polymerization[J].J.Polm.Sci.,1959,34(127):21-48.
[4] JIANG T,ZHAO L N,LUO M J,et al.High activity and good hydrogen response silica-supported Ziegler-Natta catalyst for ethylene polymerization[J].Chinese J.Polym.Sci.,2012,30(4):561-567.
[5] GRAY S D,COFFY T J,SHAMSHOUM E S,et al. Pretreated and prepolymerized polyolefin catalyst,production thereof and method of use:US7365138[P].2008-04-29.
[6] SOGA K,KOIDE R,UOZUMI T.Syndiotactic polymerization of styrene with Al₂O₃-supported Cp^*TiCl₃ catalyst activated by trialkylaluminiums[J].Macromol.Rapid Comm.,1993,14(8):511-514.
[7] LUFT N W,YUSUF W D.Process for polymerizing olefins:US2981725[P].1961-04-25.
[8] 刘强,王霞,宋赛楠,等.球形氯化镁载体[J].化工进展,2012,31(s2):130-133.
[9] BARBÉ P C,CECCHIN G,NORISTI L.The catalytic system Ti-complex MgCl₂[J].Adv.Polym.Sci.,1987,81:1-81.
[10] GALLI P,BARB? P,GUIDETTI G,et al.The activation of MgCl₂-supported Ziegler-Natta catalysts:a structural investigation[J].Eur.Polym.J.,1983,19(1):19-24.
[11] HUTCHINSON R A,RAY W H.Polymerization of olefins through heterogeneous catalysis.VIII.Monomer sorption effects[J].J.Appl.Polym.Sci.,1990,41(1/2):51-81.
[12] KASHIWA N,TOKUZUMI T,FUJIMURA H.Process for the polymerization and/or copolymerization of olefins with the use of Ziegler-type catalysts supported on carrier:US 3642746A[P].1972-02-15.
[13] 肖士镜,余赋生.烯烃配位聚合催化剂及聚烯烃[M].北京:北京工业大学出版社,2002:18-26.
[14] GIANNINI U,CASSATA A,LONGI P,et al.Process for the stereoregular polymerization of alpha olefins:US 4156063[P].1979-05-22.
[15] LONGI P,CAMELI N,VALVASSORI A,et al.Process for preparing saturated and unsaturated elastomeric copolymers of ethylene and/or higher alpha-olefins:US 3789036[P].1974-01-29.
[16] GIANNINI U,ALBIZZATI E,PARODI S.Components of catalysts useful for the polymerization of.alpha.-olefins,and catalysts prepared therefrom:US4149990[P].1979-04-17.
[17] GRECO C C,TRIPLETT K B.Method for preparing a magnesium halide support for catalysts:US4350612[P].1982-09-21.
[18] NOTO V D,BRESADOLA S.New synthesis of a highly active δ-MgCl₂ for MgCl₂/TiCl₄/AlEt₃ catalytic systems[J].Macromol.Chem.Phys.,1996,197(11):3827-3835.
[19] FORTE M C,COUTINHO F M B.Highly active magnesium chloride supported Ziegler-Natta catalysts with controlled morphology[J].Eur.Polym.J.,1996,32(2):223-231.
[20] 毛炳权,杨菊秀,李珠兰,等.烯烃聚合用的球形催化剂:1091748[P].1994-09-07.
[21] WAGNER K P.Solid catalyst component for olefin polymeriza-tion:US4186107[P].1980-01-29.
[22] NORISTI L,MONTE A.Components and catalysts for the polymerization of olefins:US5244854[P].1993-09-14.
[23] MONTE A,NORISTI L.Components and catalysts for the polymerization of olefins:US5064799[P].1991-11-12.
[24] HOCK C W.How TiCl₃ catalysts control the texture of as-polymerized polypropylene[J].J.Polym.Sci.A,1966,4(12):3055-3064.
[25] MACKIE P,BERGER M N,GRIEVESON B M,et al. Replication in Ziegler polymerization[J].J.Polym.Sci.B,1967,5(6):493-494.
[26] USHIDA O Y,AMINOTO I Y,TOYOTA I A,et al. Process for the production of spherical carrier particles for olefin polymerization catalysts:US4315874[P].1982-02-16.
[27] KO Y S,RO K S,LEE Y J,et al.Catalysts for olefin polymerization and method of olefin polymerization using the same:US6884746[P].2005-04-26.
[28] SACCHETTI M,GOVONI G,FAIT A.Magnesium dischloride-alcohol adducts and catalyst components obtained therefrom:US 6127304[P].2000-10-03.
[29] SACCHETTI M,GOVONI G.Magnesium dichloride alcohol adducts process for their preparation and catalyst components obtained therefrom:US6323152[P].2001-11-27.
[30] INCERNIZZI R,MOALLI A,MASI F.A catalyst component for polymerizing ethylene or copolymerizing ethylene with an alpha-olefin:EP0281524A2[P].1988-09-07.
[31] FERRARIS M,ROSATI F.Process for preparing spheroidally shaped products,solid at room temperature:US4469648[P].1984-09-04.
[32] ARLETTI A,FAIT A.Process for the preparation of a spherical support comprising a Mg dihalide:US6861385[P].2005-03-01.
[33] MASI F,INVERNIZZI R,CARBONARO A,et al. Supported catalyst for the polymerization and copolymerization of olefinically unsarurated compounds,and a(co)polymerization process which uses it:EP0449355B1[P].1996-05-29.
[34] BØYUM Ø,ERIKSEN K E,SOLBERG P,et al. Spraying,cooling,dehydrating magnesium chloride:CA947923A1[P].1974-05-28.
[35] BITTORF K J,KATSTRA J,GASPAR F.Fluidized spray drying:US20100011610A1[P].2010-01-21.
[36] INVERNIZZI R,LIGORATI F,FONTANESI M,et al. Supported catalysts for the polymerization of ethylene:US4421674[P].1983-12-20.
[37] UWAI T,TACHIBANA M,SAITO J.Process for producing a solid catalyst component for olefin polymerization and a process for producing an olefin polymer:US6020279[P].2000-02-01.
[38] 马丽,杨克勇,洪晓宇,等.一种丙烯聚合催化剂载体的制备方法:1136243C[P].2004-01-28.
[39] ARLETTI A,VINCENZI P.Process for the continuous production of emulsions:US7942572[P].2011-05-17.
[40] 杨元一,李振虎,杜宏斌,等.一种卤化镁/醇加合物及其制备方法和应用:1267508C[P].2006-08-02.
[41] 杨元一,杜宏斌,李振虎,等.用于烯烃聚合反应的球形催化剂组分及其催化剂:1289542C[P].2006-12-13.
[42] YANG Y Y,LI Z H,DU H B,et al.Magnesium halide/alcohol adduct,its preparation and use:US7361621[P].2008-04-22.

Advances in the preparation processes of spherical MgCl₂ support

球形氯化镁载体制备技术进展

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	GAO Yanjing. Analysis of international research trend of single-atom catalysis technology [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4667-4676.
[2]	WANG Lanjiang, LIANG Yu, TANG Qiong, TANG Mingxing, LI Xuekuan, LIU Lei, DONG Jinxiang. Synthesis of highly dispersed Pt/HY catalyst by rapid pyrolysis of platinum precursors and its performance for deep naphthalene hydrogenation [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4159-4166.
[3]	LI Runlei, WANG Ziyan, WANG Zhimiao, LI Fang, XUE Wei, ZHAO Xinqiang, WANG Yanji. Efficient catalytic performance of CuO-CeO₂/TiO₂ for CO oxidation at low-temperature [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4264-4274.
[4]	WU Haibo, WANG Xilun, FANG Yanxiong, JI Hongbing. Progress of the development and application of 3D printing catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 3956-3964.
[5]	YU Junnan, YU Jianfeng, CHENG Yang, QI Yibo, HUA Chunjian, JIANG Yi. Performance prediction of variable-width microfluidic concentration gradient chips by deep learning [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3383-3393.
[6]	YU Zhiqing, HUANG Wenbin, WANG Xiaohan, DENG Kaixin, WEI Qiang, ZHOU Yasong, JIANG Peng. B-doped Al₂O₃@C support for CoMo hydrodesulfurization catalyst and their hydrodesulfurization performance [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3550-3560.
[7]	GONG Pengcheng, YAN Qun, CHEN Jinfu, WEN Junyu, SU Xiaojie. Properties and mechanism of eriochrome black T degradation by carbon nanotube-cobalt ferrite composites activated persulfate [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3572-3581.
[8]	CHU Tiantian, LIU Runzhu, DU Gaohua, MA Jiahao, ZHANG Xiao’a, WANG Chengzhong, ZHANG Junying. Preparation and chemical degradability of organoguanidine-catalyzed dehydrogenation type RTV silicone rubbers [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3664-3673.
[9]	CHEN Yixin, ZHEN Yaoyao, CHEN Ruihao, WU Jiwei, PAN Limei, YAO Chong, LUO Jie, LU Chunshan, FENG Feng, WANG Qingtao, ZHANG Qunfeng, LI Xiaonian. Preparation of platinum based nanocatalysts and their recent progress in hydrogenation [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 2904-2915.
[10]	ZHANG Wei, QIN Chuan, XIE Kang, ZHOU Yunhe, DONG Mengyao, LI Jie, TANG Yunhao, MA Ying, SONG Jian. Application and performance enhancement challenges of H₂-SCR modified platinum-based catalysts for low-temperature denitrification [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 2954-2962.
[11]	YANG Jiatian, TANG Jinming, LIANG Zirong, LI Yinhong, HU Huayu, CHEN Yuan. Preparation and application of novel starch-based super absorbent polymer dust suppressant [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3187-3196.
[12]	MA Yuan, XIAO Qingyue, YUE Junrong, CUI Yanbin, LIU Jiao, XU Guangwen. CO _xco-methanation over a Ni-based catalyst supported on CeO₂-Al₂O₃ composite [J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2421-2428.
[13]	CHEN Mingxing, WANG Xinya, ZHANG Wei, XIAO Changfa. Development of thermally stable fiber-based air filter materials [J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2439-2453.
[14]	ZHANG Ning, WU Haibin, LI Yu, LI Jianfeng, CHENG Fangqin. Recent advances in preparation and application of floating photocatalysts in water treatment [J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2475-2485.
[15]	YU Jie, ZHANG Wenlong. Development status and progress of lithium ion battery separator [J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1760-1768.