聚合物高效脱挥技术进展

doi:10.16085/j.issn.1000-6613.2018-1281

摘要/Abstract

摘要：

聚合物中挥发分含量的不同导致聚合物脱挥过程遵循不同的热质传递机理，基于脱挥过程关键机制开发高能效的聚合物脱挥技术与装备具有重要工程意义。本文分别简述了闪蒸脱挥、起泡脱挥以及扩散脱挥3种脱挥方式的传递机理、过程特征以及过程模型，在此基础上从脱挥工艺和装备两个方面综述了近年来聚合物脱挥过程强化的手段与方法，并系统介绍了栅缝降膜脱挥、超重力旋转强化脱挥、超临界流体辅助脱挥、超声空化强化脱挥等过程强化新技术及其应用现状，提出了未来聚合物脱挥理论与工程实践的研究方向：一方面仍需深入研究扩散脱挥与起泡脱挥的耦合作用机制，建立精准、普适的脱挥过程模型；另一方面指出立式降膜脱挥技术因其能效优势，有望成为未来大规模工业脱挥器的重要选择。

关键词: 聚合物脱挥, 传递过程, 挥发分, 比表面积, 表面更新, 降膜脱挥器

Abstract:

The devolatilization process follows different heat and mass transfer mechanisms due to different volatile contents in polymers. It is of great significance to develop efficient devolatilization technology and equipment based on its determining mechanism. In this paper, different theories, models and characteristics of three consecutive stages of polymer devolatilization process, namely, flash-devolatilization, foam-devolatilization and diffusion-controlled-devolatilization, have been systematically introduced. The intensification methods of devolatilization process have also been reviewed in both engineering and technology perspectives. Correspondingly, new technologies, such as grid falling film reactor, higee, supercritical fluid assistance and ultrasonic enhancement, and their applications were described in detail. Future research directions of polymer devolatilization theory and engineering practice were proposed as following: the coupling mechanism between diffusion-controlled-devolatilization and foam-devolatilization needs to be studied further to establish more precise and universal devolatilization mechanisms; and the grid falling film devolatilization technology is prospective in mass-scale industrial devolatilization process due to its energy efficiency advantages.

Key words: polymer devolatilization, transport processes, volatile compounds, specific surface area, surface renewal, falling film devolatilization device

中图分类号:

TQ31

奚桢浩, 仇枭逸, 赵玲. 聚合物高效脱挥技术进展[J]. 化工进展, 2019, 38(01): 80-90.

Zhenhao XI, Xiaoyi QIU, Ling ZHAO. Advances in high-efficiency polymer devolatilization[J]. Chemical Industry and Engineering Progress, 2019, 38(01): 80-90.

图/表 10

图1 聚合物生产加工流程[4]

图2 闪蒸流程示意图[4]

图3 FSD示意图[4]

图4 SMX型静态混合器及其CFD模拟图[32]

图5 刮板式薄膜蒸发器成膜原理示意图[34]

图6 螺杆挤出机脱挥示意图

图7 新型高黏降膜脱挥设备

图8 超重力旋转填充床结构示意图

图9 两级超重力装置并联脱挥[47]

图10 利用超临界二氧化碳在固定床和搅拌釜中脱挥装置示意图

参考文献 60

1	BIESENBERGER J A , SEBASTIAN D H ．Principles of polymerization engineering[M]. New York: John Wiley＆Sons, 1983.
2	MARK H F . Encyclopedia of polymer science and engineering[M]. New York: Wiley, 1985.
3	谢建军, 潘勤敏, 潘祖仁 . 聚合物系脱挥研究进展[J]. 合成橡胶工业, 1998, 21（3）: 135-141.
	XIE J J , PAN Q M , PAN Z R . Progress on polymer devolatilization[J]. China Synthetic Rubber Industry, 1998, 21（3）: 135-141.
4	SULZER . Polymer production technology[EB/OL]. [2017-04-07]. https: // production_technology/brochures/polymer_production . ashx.
5	BAI Z H , LIU Y , SU T T , et al . Effect of hydroxyl monomers on the enzymatic degradation of poly(ethylene succinate), poly(butylene succinate), and poly(hexylene succinate)[J]. Polymers, 2018, 10（1）: 90.
6	中华人民共和国国家卫生和计划生育委员会 . 食品安全国家标准食品接触用塑料树脂: GB4806. 6—2016[S]. 北京: 中国标准出版社, 2017.
	People’s Republic of China state health and Family Planning Commission . Chinese Standards for Food Additives, Plastic resins for food contact: GB4806. 6-2016[S]. Beijing: Standard Press of China, 2017.
7	The Commission of The European Communities . Amending Directive 2002/72/EC relating to plastic materials and articles intended to come into contact with food and council Directive 85/572/EEC laying down the list of simulants to be used for testing migration of constituents of plastic materials and articles intended to come into contact with foodstuffs: 2007/19/EC[S].
8	The Commission of The European Communities . Relating to plastic materials and articles intended to come into contact with foodstuffs: 2002/72/EC[S].
9	STEPHEN M , ALLEN C . Thermal degradation kinetic study of polystyrene/organophosphate composite[J]. Thermochimica Acta, 2018, 662: 8-15.
10	SHIBAEY L A , GINZBURG B M , ANTONOVA T A , et al . Thermal and thermooxidative degradation of poly(methyl methacrylate) in the presence of fullerene[J]. Polymer Science: Series A, 2017, 33（7）: 1027-1029.
11	MEISTER B J , PLATT A E . Evaluation of the performance of a commercial polystyrene devolatilizer[J]. Industrial & Engineering Chemistry Research, 1989, 28: 1659-1664.
12	于志家 . 泡点露点与闪蒸计算[J]. 化工高等教育, 2013(2): 84-87.
	YU Z J . About bubble point, dew point and flash calculations[J]. Higher Education in Chemical Engineering, 2013(2): 84-87.
13	CHANG D H , HEE J Y . Studies on structural foam processing. Ⅳ. Bubble growth during mold filling[J]. Polymer Engineering and Science, 1981, 21（9）: 518-533.
14	FOSTER R W , LINT J T . Bubble growth controlled devolatilization in twin-screw extruders[J]. Polymer Engineering and Science, 1989, 29（3）: 178-185.
15	FOSTER R W , LINT J T . Twin screw extrusion devolatilization: from foam to bubble free mass transfer[J]. Polymer Engineering and Science, 1990, 30（11）: 621-634.
16	HOBBS S Y . Bubble growth in thermoplastic structural foams[J]. Polymer Engineering and Science, 1976, 16（4）: 270-275.
17	DEBDARSAN N , RAJINDER K , KANDUKURI S G , et al . Modeling of bubble-size distribution in water and freon co-blown free rise polyurethane foams[J]. Journal of Applied Polymer Science, 2014, 131（18）: 9098-9110.
18	CHANG D H , VILLAMIZAR C A . Studies on structural foam processing Ⅰ. The rheology of foam extrusion[J]. Polymer Engineering and Science, 1978, 18（9）: 687-698.
19	VILLAMIZAR C A , CHANG D H . Studies on structural foam processing Ⅱ. Bubble dynamics in foam injection molding[J]. Polymer Engineering and Science, 1978, 18（9）: 699-710.
20	陈敏恒, 齐明斋, 周明华, 等 . 化工原理(下册) [M]. 3版. 北京: 化学工业出版社, 2006.
	CHEN M H , QI M Z , ZHOU M H , et al . Principles of Chemical Engineering(vol2). [M]. 3rd ed. Beijing: Chemical Industry Press, 2006.
21	YANGXU H , ZHIPING L . Molecular mechanism for liquid-liquid extraction: two-film theory revisited [J]. AIChE Journal, 2017, 63（6）: 2464-2470.
22	WOYUAN W , WEI W . A mass transfer model for devolatilization of highly viscous media in rotating packed bed [J]. Chinese Journal of Chemical Engineering, 2010, 18（2）: 194-201.
23	WOYUAN W , WEI W . Process intensification of VOC removal from high viscous media by rotating packed bed [J]. Chinese Journal of Chemical Engineering, 2009, 17（3）: 389-393.
24	RAMON J A . Polymer devolatilization[M]. New York: Academic Press, 1996.
25	康鹏, 金滟, 蔡涛 . 聚丙烯中挥发性有机物释放行为的研究[J]. 合成树脂及塑料, 2010, 27（1）: 60 - 63.
	KANG P , JIN Y , CHAI T . Study on release behavior of VOC from polypropylene[J]. China Synthetic Resin and Plastics, 2010, 27（1）: 60 - 63.
26	康鹏, 武鹏, 金滟 . 车用聚丙烯材料螺杆脱挥技术的研究[J]. 石油化工, 2018, 47（3）: 286 - 290.
	KANG P , WU P , JIN Y , et al . Study on screw devolatilizing technology of polypropylene for automobile [J]. Petrochemical Technology, 2018, 47（3）: 286 - 290.
27	奥尔布莱克 . 聚合物脱挥[M]. 赵旭涛, 龚光碧, 谷育生, 等译. 北京: 化学工业出版社, 2005.
	ALBALAK R J . Polymer devolatilization[M]. ZHAO X T, GONG G B, GU Y S, et al, trans. Beijing: Chemical Industry Press, 2005.
28	WERNER H . Devolatilization of polymers in multi-screw devolatilizers[J]. Kunststoffe-German Plastics, 1981, 71（1）: 18-26.
29	王凯, 孙建中 . 工业聚合反应装置[M]. 北京: 中国石化出版社, 1997.
	WANG K , SUN J Z . Industrial polymerization unit [M]. Beijing: China Petrochemical Press, 1997.
30	GRAIG T O . Application of an enhanced flash-tank devolatilization system to a degassing extruder[J]. Advances in Polymer Technology, 1990, 10（4）: 323-325.
31	夏燕敏, 陈德铨 . 落条式脱挥器在本体聚合中的应用[J]. 石油化工, 2000, 29（11）: 879-884.
	XIA Y M , CHEN D S . Falling strip devolatilization in bulk polymerization[J]. Petrochemical Technology, 2000, 29（11）: 879-884.
32	SULZER . SMX™ plus static mixer: perfect homogenization of viscous liquids nearly without pressure drop[EB/OL]. [2017-03-22]. https: //www. sulzer. com/-/media/files/products/static-mixers/flyer_smx_plus_d. ashx?la=en.
33	李沃源, 毋伟, 邹海魁, 等 . 超重力旋转填充床用于高黏聚合物脱挥的研究进展[J]. 化工进展, 2010, 29（2）: 211-216.
	LI W Y , WU W , ZOU H K , et al . Devolatilization of high viscous polymer via high gravity rotating packed bed[J]. Chemical Industry and Engineering Progress, 2010, 29（2）: 211-216.
34	周增龙 . 底部传动立式降膜薄膜蒸发器: CN02110628. 2[P]. 2003-08-06.
	ZHOU Z L . Bottom driven vertical falling film evaporator: CN02110628. 2[P]. 2003-08-06.
35	MATARRESE S , ROSSI G A , CONSOLO M L , et al . Process for the continuous production in solution of styrene thermoplastic resins: EP88105485[P]. 1988-04-04.
36	FERES V . Thin-film evaporators: US4707220[P]. 1987-11-17.
37	PARRILLO D , SINGH P . Method for isolating polyphenylene ether polymer resins from solution: JP20080223146 [P]. 2008-09-01.
38	STEFAN H , LUTZ H , OLAF W . Polymer devolatilization in a rotating apparatus[J]. PAMM, 2015, 15（1）: 511-512.
39	ALEXANDER T , YESHAYAHYU T , ZEHEV T , et al . Foam-enhanced devolatilization of polystyrene melt in a vented extruder [J]. American Institute of Chemical Engineers, 1994, 40（4）: 670-675.
40	SILVI N . Method of separating a polymer from a solvent: US11755415 [P]. 2007-05-30.
41	WANG H . Method for removing volatile components from solid polymeric materials: US20010942065 [P]. 2001-08-29.
42	陈庆, 郭林, 陈兵, 等 . 聚乳酸制备方法: US6365710[P]. 2002-04-02.
	CHEN Q , GUO L , CHEN B , et al . A way to prepare polylactic acid: US6365710[P]. 2002-04-02.
43	刘睿 . 螺杆挤出机优化设计的现状[J]. 塑料科技, 2016, 44（3）: 85-88.
	LIU R . Present situation of optimal design of screw extruder[J]. Plastics Science and Technology, 2016, 44（3）: 85-88.
44	奚桢浩 . 流场结构化的新型高粘缩聚反应器[D]. 上海: 华东理工大学, 2010.
XI	Z H . A new high viscosity polycondensation reactor with flow field structure[D]. Shanghai: East China University of Science and Technology, 2010.
45	赵玲, 奚桢浩, 孙伟振, 等 . 一种新型的多层落条式缩聚反应器及其应用: CN101524632A[P]. 2009-09-09.
	ZHAO L , XI Z H , SUN W Z , et al . A new multi-layer falling strip polycondensation reactor and its application: CN 101524632 A[P]. 2009-09-09.
46	刘兆彦, 奚桢浩, 孙伟振, 等 . 流场结构化的新型降膜缩聚反应器及其应用: CN 101837276 A[P]. 2010-09-22.
	LIU Z Y , XI Z H , SUN W Z , et al . A new falling film polycondensation reactor with flow field structure and its application: CN101837276 A[P]. 2010-09-22.
47	陈建峰, 李沃源 . 一种脱除聚合物挥发分的方法及装置: CN200710120712.7 [P]. 2007-10-12.
	CHEN J F , LI W Y . Method and device for removing volatile matter of polymer: CN200710120712.7 [P]. 2007-10-12.
48	JIMKUO H . Mass transfer of centrifugally enhanced polymer devolatilization by using foam metal packed bed[D]. Cleveland: Case Western Reserve University, 1995.
49	杨胜, 林佳璋 . 利用旋转填充床从高粘度液体中移除其中所含的挥发成分的方法: CN 02118837.8 [P]. 2002-04-30.
	YANG S , LIN J Z . Method for removing volatile components from high viscosity liquid by rotating packed bed: CN 02118837.8[P]. 2002-04-30.
50	ISKENDER Y , JAMES E . Novel supercritical fluid techniques for polymer fractionation and purification[J]. Polymer Bulletin, 1984, 12（6）: 491-497.
51	ALSOY S , DUDA J L . Supercritical devolatilization of polymers[J]. AIChE Journal, 1998, 44（3）: 582-590.
52	CRISTANCHO D E , GUZMEN J D , TAYLOR C , et al . Supercritical extraction of volatile organic components from polyethylene pellets[J]. Journal of Supercritical Fluids, 2012（69）: 124-130.
53	DANESHVAR M , KAMALI H . Supercritical carbon dioxide grafting of glycidyl methacrylate onto medium density polyethylene and purification of residual monomer and initiator[J]. Journal of Supercritical Fluids, 2012（70）: 119-125.
54	蒋春跃, 高建荣 . 一种聚苯乙烯的超临界流体脱挥方法: CN200810059443.2 [P]. 2008-10-05.
	JIANG C Y , GAO J R . A method using supercritical CO₂ to devolatilization for polystyrene: CN200810059443.2[P]. 2008-10-05.
55	弗里德斯多夫 . 用于超临界聚合方法的相分离器和单体再循环: CN10563374A[P]. 2009-09-13.
	FRIEDERSDORF, et al . Phase separators and monomer recirculation for supercritical polymerization: CN101563374A[P]. 2009-09-13.
56	冯若, 李化茂 . 声化学及其应用[M]. 合肥: 安徽科学技术出版社, 1992.
	FENG R , LI H M . Sonochemistry and its applications[M]. Hefei: Anhui Science and Technology Press, 1992.
57	CHEN Guangshun , GUO Shaoyun , LI Huilin , et al . Ultrasonic improvement of the compatibility and rheological behavior of high-density polyethylene/polystyrene blends[J]. Journal of Applied Polymer Science, 2002, 86: 23-32.
58	XIE Tingting , WU Hong , BAO Wenting , et al . Enhanced compatibility of PA6/POE blends by POE-g-MAH prepared through ultrasound-assisted extrusion[J]. Journal of Applied Polymer Science, 2010, 118（3）: 1846-1852.
59	TANG Siye , WANG Ye , LIU Dazhuang , et al . Novel approach to the ultrasonic degradation of polymers: development of a general kinetic equation[J]. Progress in Reaction Kinetics and Mechanism, 2013, 38（4）: 397-407.
60	ASHISH V M , PARAG R G . Ultrasonic degradation of polymers: effect of operating parameters and intensification using additives for carboxymethyl cellulose (CMC) and polyvinyl alcohol (PVA)[J]. Ultrasonics Sonochemistry, 2011, 18（3）: 727-734.

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