Progress in simulation of the multiscale flow field in free radical polymerization reactors

doi:10.16085/j.issn.1000-6613.2018-1050

Abstract

Abstract:

During the free radical polymerization process, due to the interactions of mixing, transfer and polymerization, the complex multiscale flow fields, such as the macroscopic velocity, concentration and temperature distributions, the mesoscopic droplet size distribution, the microscopic polymerization rate, polymer molecular weight and polydispersity index distributions, exist within the reactor，thus making the modeling of polymerization reactors be a difficult issue. In this paper, the multiscale phenomena existing in the free radical polymerization reactors were systematically introduced. Modeling and simulation methods of flow field distributions of microscopic polymer properties were briefly described. The simulation research progress of mesoscopic droplet size distributions were introduced from two aspects of suspension polymerization and emulsion polymerization. At macroscopic scale, the research progress of multiphase flow field distributions were expounded from the perspective of non-ideal mixing. Finally, the coupled solution methods of multiscale models were analyzed. This review is our preliminary views, which can be used as a reference for the design, optimization and scale-up of polymerization reactors.

Key words: polymerization, reactor, multiscale, computational fluid dynamics(CFD), numerical simulation

摘要：

自由基聚合过程中，由于混合、传递及聚合反应的相互作用使得反应器内部存在复杂的多尺度流场，例如宏观尺度的速度、浓度、温度分布，介观尺度的液滴粒径分布，微观尺度的聚合反应速率、聚合物分子量和多分散性指数分布。这些复杂的多尺度流场分布使得聚合反应器的模型化研究成为难题。本文较为系统地介绍了自由基聚合反应器中存在的多尺度现象；简述了微观尺度聚合物性质流场分布的模型化与模拟研究方法；从悬浮聚合和乳液聚合两个方面介绍了介观尺度液滴粒径分布的模拟研究进展；从非理想混合的角度阐述了宏观尺度多相流流场分布的研究进展。最后，本文分析了多尺度模型的耦合求解方法。本综述也有本文作者对这个领域的初步观点，可为聚合反应器的设计、优化和放大提供参考。

关键词: 聚合, 反应器, 多尺度, 计算流体力学, 数值模拟

CLC Number:

TQ315

Le XIE, Zhenghong LUO. Progress in simulation of the multiscale flow field in free radical polymerization reactors[J]. Chemical Industry and Engineering Progress, 2019, 38(01): 72-79.

谢乐, 罗正鸿. 自由基聚合反应器中多尺度流场的模拟进展[J]. 化工进展, 2019, 38(01): 72-79.

Figures/Tables 3

反应类型	反应机理
链引发	$I → f k d 2 R ?$
链增长	$R ? + M → k i n P 1 ?$
链增长	$P n ? + M → k p P n + 1 ?$
链转移	$P n ? + M → k t r P n + P 1 ?$
链终止	$P m ? + P n ? → k t c P n + m$ $P m ? + P n ? → k t d P m + P n$ $R ? + R ? → k t R R R$

反应类型	反应机理
链引发	$I → f k d 2 R ?$
链增长	$R ? + M → k i n P 1 ?$
链增长	$P n ? + M → k p P n + 1 ?$
链转移	$P n ? + M → k t r P n + P 1 ?$
链终止	$P m ? + P n ? → k t c P n + m$ $P m ? + P n ? → k t d P m + P n$ $R ? + R ? → k t R R R$

References 52

1	BALDYGA J , BOURNE J R . Interactions between mixing on various scales in stirred tank reactors[J]. Chem. Eng. Sci., 1992, 47(8): 1839-1848.
2	FOX R O . Computational methods for turbulent reacting flows in the chemical process industry[J]. Rev. Inst. Fr. Pet., 1996, 51: 215-243.
3	KOLHAPURE N H , FOX R O . CFD analysis of micromixing effects on polymerization in tubular low-density polyethylene reactors[J]. Chem. Eng. Sci., 1999, 54(15): 3233-3242.
4	ASUA J . Polymer reaction engineering[M]. New York: John Wiley & Sons, 2008.
5	ZHANG S X , RAY W H . Modeling of imperfect mixing and its effects on polymer properties[J]. AIChE J., 1997, 43(5): 1265-1277.
6	TOPALIS E , PLADIS P , KIPARISSIDES C , et al . Dynamic modelling and steady-state multiplicity in high pressure multizone LDPE autoclaves[J]. Chem. Eng. Sci., 1996, 51(10): 2461-2470.
7	ZHU S P . Modeling of molecular weight development in atom transfer radical polymerization[J]. Macromol. Theor. Simul., 1999, 8(1): 29-37.
8	ZHU S P . Modeling stable free-radical polymerization[J]. J. Polym. Sci. Pol. Phys., 1999, 37(18): 2692-2704.
9	WANG R , LUO Y W , LI B G , et al . Design and control of copolymer composition distribution in living radical polymerization using semi-batch feeding policies: a model simulation[J]. Macromol. Theor. Simul., 2006, 15(4): 356-368.
10	KALFAS G , RAY W H . Modeling and experimental studies of aqueous suspension polymerization processes. 1. Modeling and simulations[J]. Ind. Eng. Chem. Res., 1993, 32(9): 1822-1830.
11	KALFAS G , YUAN H , RAY W H . Modeling and experimental studies of aqueous suspension polymerization processes. 2. Experiments in batch reactors[J]. Ind. Eng. Chem. Res., 1993, 32(9): 1831-1838.
12	ZHANG S X , RAY W H . Modeling and experimental studies of aqueous suspension polymerization processes. 3. Mass-transfer and monomer solubility effects[J]. Ind. Eng. Chem. Res., 1997, 36(4): 1310-1321.
13	WANG W , ZHOU Y N , LUO Z H . Modeling of the atom transfer radical copolymerization processes of methyl methacrylate and 2-(trimethylsilyl) ethyl methacrylate under batch, semibatch, and continuous feeding: a chemical reactor engineering viewpoint[J]. Ind. Eng. Chem. Res., 2014, 53(30): 11873-11883.
14	WANG W , ZHOU Y N , SHI L , et al . Kinetic modeling of atom transfer radical copolymerization of methyl methacrylate and 2-(trimethylsilyl) ethyl methacrylate in a train of continuous stirred‐tank reactors[J]. Polym. Eng. Sci., 2015, 55(5): 1030-1038.
15	XIE L , LUO Z H . Modeling of the methyl methacrylate atom transfer radical suspension polymerization process: polymerization and particle kinetics[J]. Macromol. React. Eng., 2016, 10 (5): 479-489.
16	XIE L , ZHU L T , LUO Z H , et al . Multiscale modeling of mixing behavior in a 3D atom transfer radical copolymerization stirred-tank reactor[J]. Macromol. React. Eng., 2016, 11(2): 1600022.
17	XIE L , LUO Z H . Multiscale computational fluid dynamics–population balance model coupled system of atom transfer radical suspension polymerization in stirred tank reactors[J]. Ind. Eng. Chem. Res., 2017, 56(16): 4690-4702.
18	XIE L , LIU Q , LUO Z H . A multiscale CFD-PBM coupled model for the kinetics and liquid-liquid dispersion behavior in a suspension polymerization stirred tank[J]. Chem. Eng. Res. Des., 2018, 130: 1-17.
19	D’HOOGE D R , REYNIERS M F , STADLER F J , et al . Atom transfer radical polymerization of isobornyl acrylate: a kinetic modeling study[J]. Macromolecules, 2010, 43(21): 8766-8781.
20	LUTZ J F , MATYJASZEWSKI K . Nuclear magnetic resonance monitoring of chain‐end functionality in the atom transfer radical polymerization of styrene[J].J.Polym Sci.Part A:Polym. Chem., 2005, 43(4): 897-910.
21	ROO T D , HEYNDERICKX G J , MARIN G B . Diffusion-controlled reactions in vinyl chloride suspension polymerization[J]. Macromol. Symp., 2004, 206(1): 215-228.
22	SCHMIDT A D , RAY W H . The dynamic behavior of continuous polymerization reactors—Ⅰ: Isothermal solution polymerization in a CSTR[J]. Chem. Eng. Sci., 1981, 36(8): 1401-1410.
23	CHENG J , XIN F , CHENG D , et al . Retrospect and perspective of micro-mixing studies in stirred tanks[J]. Chin J. Chem.Eng., 2012, 20(1): 178-190.
24	CABALLERO S , DE LA CAL J C , ASUA J M . Radical entry mechanisms in alkali-soluble-resin-stabilized latexes[J]. Macromolecules, 2009, 42(6): 1913-1919.
25	VAN STEENBERGE P H M , D’HOOGE D R , REYNIERS M F , et al . 4-Dimensional modeling strategy for an improved understanding of miniemulsion NMP of acrylates initiated by SG1-macroinitiator[J]. Macromolecules, 2014, 47(22): 7732-7741.
26	CHESTERS A K . The modeling of coalescence processes in fluid-liquid dispersions: a review of current understanding[J]. Chem. Eng. Res. Des., 1991, 69(4): 259-270.
27	LIAO Y , LUCAS D . A literature review of theoretical models for drop and bubble breakup in turbulent dispersions[J]. Chem. Eng. Sci., 2009, 64(15): 3389-3406.
28	LIAO Y , LUCAS D . A literature review on mechanisms and models for the coalescence process of fluid particles[J]. Chem. Eng. Sci., 2010, 65(10): 2851-2864.
29	ALEXOPOULOS A H , MAGGIORIS D , KIPARISSIDES C . CFD analysis of turbulence non-homogeneity in mixing vessels : a two-compartment model[J]. Chem. Eng. Sci., 2002, 57(10): 1735-1752.
30	ALEXOPOULOS A H , KIPARISSIDES C . On the prediction of internal particle morphology in suspension polymerization of vinyl chloride. Part I: The effect of primary particle size distribution[J]. Chem. Eng. Sci., 2007, 62(15): 3970-3983.
31	CHATZI E G , BOUTRIS C J , KIPARISSIDES C . On-line monitoring of drop size distributions in agitated vessels: 2. Effect of stabilizer concentration[J]. Ind. Eng. Chem. Res. 1991, 30(6): 1307-1313.
32	KOTOULAS C , KIPARISSIDES C . A generalized population balance model for the prediction of particle size distribution in suspension polymerization reactors[J]. Chem. Eng. Sci., 2006, 61(2): 332-346.
33	MAGGIORIS D , GOULAS A , ALEXOPOULOS A H , et al . Use of CFD in prediction of particle size distribution in suspension polymer reactors[J]. Comput. Chem. Eng., 1998, 22(12): S315-S322.
34	MAGGIORIS D , GOULAS A , ALEXOPOULOS A H , et al . Prediction of particle size distribution in suspension polymerization reactors: effect of turbulence nonhomogeneity[J]. Chem. Eng. Sci., 2000, 55(20): 4611-4627.
35	SALIAKAS V , KOTOULAS C , MEIMAROGLOU D , et al . Dynamic evolution of the particle size distribution in suspension polymerization reactors: a comparative study on monte carlo and sectional grid methods[J]. Can.J. Chem Eng., 2008, 86(5): 924-936.
36	JAHANZAD F . Evolution of particle size distribution in suspension polymerisation reactions[D]. Loughborough: Loughborough University, 2004.
37	JAHANZAD F , SAJJADI S , BROOKS B W . Characteristic intervals in suspension polymerisation reactors: an experimental and modelling study[J]. Chem. Eng. Sci., 2005, 60(20): 5574-5589.
38	JAHANZAD F , SAJJADI S , YIANNESKIS M , et al . In situ mass-suspension polymerisation[J]. Chem. Eng. Sci., 2008, 63(17): 4412-4417.
39	JAHANZAD F , SAJJADI S , BROOKS B W . On the evolution of particle size average and size distribution in suspension polymerization processes[J]. Macromol. Symp., 2004, 206(1): 255-262.
40	JAHANZAD F , SAJJADI S , BROOKS B W . Comparative study of particle size in suspension polymerization and corresponding monomer−water dispersion[J]. Ind. Eng. Chem. Res., 2005, 44(11): 4112-4119.
41	VONKA M , SOOS M . Characterization of liquid-liquid dispersions with variable viscosity by coupled computational fluid dynamics and population balances[J]. AIChE J., 2015, 61(8): 2403-2414.
42	VAFA E , SHAHROKHI M , ABEDINI H . Inferential closed-loop control of particle size and molecular weight distribution in emulsion polymerization of styrene[J]. Polym. Eng. Sci., 2010, 50(12): 2306-2320.
43	ALEXOPOULOS A H , PLADIS P , KIPARISSIDES C . Nonhomogeneous mixing population balance model for the prediction of particle size distribution in large scale emulsion polymerization reactors[J]. Ind. Eng. Chem. Res., 2013, 52(35): 12285-12296.
44	BITSCH B , BARNER-KOWOLLIK C , ZHU S . Modeling the effects of reactor backmixing on RAFT polymerization[J]. Macromol. React. Eng., 2011, 5(1): 55-68.
45	CORDOVI C M , DE LUCAS A , DURAN A , et al . Development of a suspension copolymerization process for bone cement production[J].
	Appl J. . Polym. Sci., 2000, 76(6): 814-823.
46	TOSUN G . A mathematical model of mixing and polymerization in a semibatch stirred-tank reactor[J]. AIChE J., 1992, 38(3): 425-437.
47	KIM J Y , LAURENCE R L . The mixing effect on the free radical MMA solution polymerization[J]. Korean J. Chem. Eng., 1998, 15(3): 273-286.
48	PATEL H , DHIB R , EIN-MOZAFFARI F . Computational fluid dynamics study of a styrene polymerization reactor[J]. Chem. Eng. Technol., 2010, 33(2): 258-266.
49	ROUDSARI S F , EIN-MOZAFFARI F , DHIB R . Use of CFD in modeling MMA solution polymerization in a CSTR[J]. Chem. Eng. J., 2013, 219(3): 429-442.
50	CHERBANSKI R , ALEKSANDRA M A , MOLGA E . Safety aspects in batch reactors for styrene suspension polymerization[J]. Ind. Eng. Chem. Res., 2007, 46(46): 5898-5906.
51	POHN J , CUNNINGHAM M , MCKENNA T F L . Scale-up of emulsion polymerization reactors. Part Ⅰ: Development of a model framework[J]. Macromol. React. Eng., 2013, 7(8): 380-392.
52	POHN J , CUNNINGHAM M , MCKENNA T F L . Scale-up of emulsion polymerization reactors Part Ⅱ: simulations and interpretations[J]. Macromol. React. Eng., 2013, 7(8): 393-408.

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