本研究利用Aspen Plus模擬軟體，設計一苯乙烯丙烯腈樹脂之整廠製程。由於在過去的高分子模擬製程文獻中，大多皆以一種單體聚合的聚苯乙烯製程為例，極少文獻針對兩種單體以上共聚反應模擬及整廠製程設計進行相關的探討。故本研究以苯乙烯丙烯腈樹脂製程作為研究主題，分別探討兩種單體共聚反應之熱力學、動力學及整廠製程的設計。
此高分子整廠製程可分為六個區域: 反應區、脫烴區、真空回收區、製程廢水區、寡聚物去除區及DMF回收區。本研究將針對每個區域進行穩態設計並探討其製程改善的方法。最後，針對關鍵的反應器建立自動冷凝反應器的動態模型，並藉由進料改變測試了解其控制響應，以及探討緊急停車時，反應器內的溫壓變化。
在穩態模擬結果顯示，反應區利用自動冷凝技術移除聚合反應熱，能減少冷卻設備的應用；脫烴區則驗證樹脂之物性與真實數據相符；真空回收區能將多餘的單體及溶劑利用水封進行回收；廢水區利用苯乙烯將單體及溶劑從水中萃取出，並得到純度99.8 wt.%的水；寡聚物去除區可回收90 wt.%的寡聚物；製程清洗所使用的DMF溶劑需回收利用，使純度到達99.6 wt.%。最後，為了降低製程的複雜性，若將回收後單體改做為液封於真空回收區，則此設計不需廢水區。在反應區之動態模擬結果顯示，反應器在進料流量擾動下，其所放出的熱量幾乎能由上方冷凝器帶走，並藉由調整反應溫度維持轉化率及品質。而緊急停車結果顯示，反應器上升至最高溫度為178 ℃，最高壓力為4.09 kg/cm2g，由此結果可做為反應器設備設計時的參考。

This study designs plant-wide process for styrene-acrylonitrile (SAN) copolymers. In the literature of polymer simulation, most of the processes were focused on single monomer polymerization. Few studies discussed the simulation of two monomers copolymerization. This study also researches thermodynamics and kinetics for SAN copolymers.
This plant-wide process can divide into six zones: reaction zone, devolatilizer zone, vacuum recovery zone, wastewater zone, oligomers removal zone and DMF removal zone. This study designs steady-state model and improves each zone. Finally, the dynamics scheme is developed for autorefrigerated reactor. It can use the throughput disturbance to realize control response. During shutdowns, it can explore the maximum pressure and temperature in the reactor.
The result of steady-state simulation shows that the reaction zone uses autorefrigerated reactor can eliminate the internal coil equipment; Devolatilizer zone demonstrates the properties of SAN copolymers in the simulation are close to the realistic; The excess monomers and solvent are recovered by water in the vacuum recovery zone; Wastewater zone can extract 99.8 wt% water; Oligomers removal zone recovers 90 wt.% oligomers; The purity of DMF achieves 99.6 wt.% in the DMF removal zone. To reduce the complexity of the process proposes the design that the excess monomers and solvent are recovered by recovery monomers in the vacuum recovery zone. Meanwhile, this proposal design can remove wastewater zone. The result of dynamics simulation shows that the reaction heat can be taken away by autorefrigeration when the ±20% throughput disturbance. During shutdowns, the maximum temperature achieves 178 ℃ and the maximum pressure achieves 4.09 kg/cm2g. This result can be a reference when design the reactor equipment.

[中文]
1. 王文清，聚苯乙烯工业装置的建模与优化，博士論文，浙江大學，2004年。
2. 吴福生， SAN 树脂工艺条件关系式的建立及应用，兰化科技， 15(2)，73-76，1997年。
3. 索延輝，ABS树脂生产实践及应用，中国石化出版社，2015年。
4. 葉竣凱，苯乙烯高分子製程模擬與品別轉換之研究，碩士論文，國立台灣科技大學，2017年。
5. 楊宗樺，類神經網路之動態估測器於高壓共聚合反應之應用，碩士論文，國立台灣大學，2007年。
6. 张辉、王毅、王亮、陆书来、刘姜、李中宇，打火机专用 SAN 树脂生产技术开发，弹性体，49-52，2016年。
7. 赵牡丹、李洪涛，本体法 SAN 树脂生产工艺研究，辽宁化工，38(6)，401-403，2009年。

[英文]
8. Almeida, A.; Wada, K.; Secchi, A., Simulation of styrene polymerization reactors: kinetic and thermodynamic modeling. Brazilian Journal of Chemical Engineering, 25(2), 337-349, 2008.
9. de Toledo, E. C. V.; Martini, R. F.; Maciel, M. R. W.; Maciel Filho, R., Process intensification for high operational performance target: Autorefrigerated CSTR polymerization reactor. Computers & chemical engineering, 29(6), 1447-1455, 2005.
10. Gharaghani, M.; Abedini, H.; Parvazinia, M., Dynamic simulation and control of auto-refrigerated CSTR and tubular reactor for bulk styrene polymerization. Chemical Engineering Research and Design, 90(10), 1540-1552, 2012.
11. Global Market Insights, 2017. [online] Available at: https://gminsights.wordpress.com/tag/acrylonitrile-butadiene-styrene-abs-market-analysis/
12. Green, D. W.; Perry, R. H., Perry's Chemical Engineers' Handbook, 2008.
13. Henderson III, L. S.; Cornejo, R. A., Temperature control of continuous, bulk styrene polymerization reactors and the influence of viscosity: An analytical study. Industrial & Engineering Chemistry Research, 28(11), 1644-1653, 1989.
14. Hui, A. W.; Hamielec, A. E., Thermal polymerization of styrene at high conversions and temperatures. An experimental study. Journal of Applied Polymer Science, 16(3), 749-769, 1972.
15. IHS Markit, 2018. [online] Available at: https://ihsmarkit.com/products/styrene-acrylonitrile-chemical-economics-handbook.html
16. Lin, C. C.; Chiu, W. Y.; Wang, C. T., Simulation model for the solution copolymerization of acrylonitrile and styrene in azeotropic composition. Journal of Applied Polymer Science, 23(4), 1203-1222, 1979.
17. Louli, V.; Tassios, D., Vapor–liquid equilibrium in polymer–solvent systems with a cubic equation of state. Fluid Phase Equilibria, 168(2), 165-182, 2000.
18. Luyben, W. L., Temperature control of autorefrigerated reactors. Journal of Process Control, 9(4), 301-312, 1999.
19. McAuley, K.; MacGregor, J.; Hamielec, A. E., A kinetic model for industrial gas‐phase ethylene copolymerization. AIChE Journal, 36(6), 837-850, 1990.
20. Van Dootingh, M.; Viel, F.; Rakotopara, D.; Gauthier, J.; Hobbes, P., Nonlinear deterministic observer for state estimation: Application to a continuous free radical polymerization reactor. Computers & chemical engineering, 16(8), 777-791, 1992.
21. Van Krevelen, D. W.; Te Nijenhuis, K., Chapter 20 - Thermochemical Properties Properties of Polymers (Fourth Edition), 749-762, 2009.