气液法流化床乙烯云聚合工艺开发及产品高性能化

doi:10.11949/0438-1157.20220467

化工学报 ›› 2022, Vol. 73 ›› Issue (6): 2742-2747.DOI: 10.11949/0438-1157.20220467

• 材料化学工程与纳米技术 • 上一篇下一篇

气液法流化床乙烯云聚合工艺开发及产品高性能化

范小强¹(),黄正梁^1,²,孙婧元^1,²(),王靖岱^1,³,王晓飞⁴,胡晓波⁵,韩国栋⁴,阳永荣^1,³,吴文清⁴

^1.浙江大学化学工程与生物工程学院，浙江杭州 310027
^2.浙江省化工高效制造技术重点实验室，浙江杭州 310027
^3.化学工程联合国家重点实验室（浙江大学），浙江杭州 310027
^4.中国石化天津石化分公司，天津 300271
^5.杭州福斯特应用材料股份有限公司，浙江杭州 311300

收稿日期:2022-03-31 修回日期:2022-05-31 出版日期:2022-06-05 发布日期:2022-06-30
通讯作者: 孙婧元
作者简介:范小强（1991—），男，博士，助理研究员，orionfxq@126.com
基金资助:
国家自然科学基金项目(22178304);国家自然科学基金创新研究群体科学基金项目(61621002)

Development of cloudy gas-liquid fluidized bed ethylene polymerization process and high performance products

Xiaoqiang FAN¹(),Zhengliang HUANG^1,²,Jingyuan SUN^1,²(),Jingdai WANG^1,³,Xiaofei WANG⁴,Xiaobo HU⁵,Guodong HAN⁴,Yongrong YANG^1,³,Wenqing WU⁴

^1.College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
^2.Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, Hangzhou 310027, Zhejiang, China
^3.State Key Laboratory of Chemical Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
^4.SINOPEC Tianjin Company, Tianjin 300271, China
^5.Hangzhou First Applied Material Co. , Ltd. , Hangzhou 311300, Zhejiang, China

Received:2022-03-31 Revised:2022-05-31 Online:2022-06-05 Published:2022-06-30
Contact: Jingyuan SUN

摘要/Abstract

摘要：

随着国内聚烯烃产量的不断增加，聚烯烃通用料市场竞争加剧，开发新型高性能聚烯烃产品至关重要。针对气液法流化床乙烯云聚合工艺的构建以及聚乙烯产品高性能化，在气液法流化床所包含的典型介尺度结构实验和理论研究基础上，明确聚合反应条件，优化气液法流化床进料系统，最终应用于气液法流化床乙烯云聚合工艺的开发。通过对工业试验产品的分子链结构的表征分析，证明云聚合工艺是生产高性能聚乙烯产品的全新成功途径。

关键词: 流化床, 多相流, 聚合, 竞争协调机制, 聚乙烯微观结构, 工业试验

Abstract:

With the continuous increase of domestic polyolefin production, the competition in the polyolefin general material market has intensified, and it is very important to develop new high-performance polyolefin products. Aiming at the construction of the cloudy gas-liquid fluidized bed ethylene polymerization process and the development of high-performance polyethylene, the polymerization conditions were determined and the liquid feeding system was optimized on the basis of experiments and theoretical analysis of mesoscale structures in the gas-liquid fluidized bed. Furthermore, the cloudy gas-liquid fluidized bed polymerization process is developed and industrial tests were carried out. The molecular chain structure of the industrial products proved that the cloudy gas-liquid fluidized bed polymerization process is a novel and successful way to produce high-performance polyethylene products.

Key words: fluidized-bed, multiphase flow, polymerization, competition and coordination relationship, polyethylene microstructure, industrial tests

中图分类号:

TQ 320.2

范小强, 黄正梁, 孙婧元, 王靖岱, 王晓飞, 胡晓波, 韩国栋, 阳永荣, 吴文清. 气液法流化床乙烯云聚合工艺开发及产品高性能化[J]. 化工学报, 2022, 73(6): 2742-2747.

Xiaoqiang FAN, Zhengliang HUANG, Jingyuan SUN, Jingdai WANG, Xiaofei WANG, Xiaobo HU, Guodong HAN, Yongrong YANG, Wenqing WU. Development of cloudy gas-liquid fluidized bed ethylene polymerization process and high performance products[J]. CIESC Journal, 2022, 73(6): 2742-2747.

图/表 7

图1 云聚合工艺流程示意图

Fig.1 Schematic diagram of cloudy polymerization

表1 气相主体和液相中的H2/C2H4和C6H12/C2H4

Table 1 H2/C2H4 and C6H12/C2H4 in gas phase and liquid phase

Item

PE1

Tianjin Petrochemical

PE2

Tianjin Petrochemical

H₂/C₂H₄

C₆H₁₂/C₂H₄

图2 工业试验结果

Fig.2 Commercial scale experiment results

表2 气相聚合工艺和云聚合工艺产品分析

Table 2 Product analysis of gas-phase polymerization and cloudy polymerization

Product	Process	Comonomer	Density/(g/cm³)	Crystallinity/%
PE-A	gas-phase polymerization	1-butene (4.10%)	0.918	25.4
PE-B	cloudy polymerization	1-butene+1-hexene (6.23%)	0.912	22.5

图3 PE-A和PE-B各级分的质量分数

Fig.3 Distribution of relative mass fraction contents of PE-A and PE-B

图4 PE-A和PE-B各级分的分子量

Fig.4 Weight average molecular weight of PE-A and PE-B

图5 PE-A和PE-B的支链分布

Fig.5 Distribution of branches of PE-A and PE-B

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气液法流化床乙烯云聚合工艺开发及产品高性能化

Development of cloudy gas-liquid fluidized bed ethylene polymerization process and high performance products

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