聚對苯二甲酸丁二酯（PBT）為一種半結晶型熱塑性樹脂，可應用於諸多領域，尤以在射出成型領域市場中最受青睞。製備上，PBT可藉由1,4-丁二醇（BDO）與對苯二甲酸（TPA）經酯化反應後行熔融聚合得到，經反應後的氣相生成物主要包含原料BDO及副產物四氫呋喃（THF）和水，THF和水必須自反應器移除，透過一蒸餾塔將BDO與副產物進行分離予以回收。
本研究將根據中國PBT廠生產實際例子利用化工製程軟體CHEMCAD進行PBT酯化段製程模擬，首先參照Hu et al.和Wang et al.的PBT動力學模型，考慮三條主要酯化反應、一條不可逆熔融聚合反應、二條副反應建立起PBT酯化反應機構；THF分離的蒸餾模擬採用NRTL熱力學模型描述物質氣液平衡之關係，缺少NRTL熱力學參數的物質則以Modified UNIFAC 和 VLE UNIFAC估計之；再者進行動態控制，探討兩種控制策略與不同操作壓力和溫度下，對於TPA酯化轉化率、副產物THF生成量及酯化物BDO/TPA莫耳比例的影響。
在反應總進料改變的情況下，固定反應物在反應器的滯留時間可以有效地控制整個製程之TPA轉化率及酯化物BDO/TPA莫耳比例，使酯化物在後續預縮聚與終縮聚反應後的PBT成品性質穩定；然而在BDO/TPA進料莫耳比改變時，兩種控制策略並無法有效固定住酯化物BDO/TPA莫耳比，使多餘的BDO在後續反應中產生THF，影響PBT產品的穩定性；在反應壓力與反應溫度改變的情況下，建議將反應壓力下降、反應溫度提高，使酯化物BDO/TPA莫耳比維持低比值，減少BDO在後續反應中降解為THF。

Poly(butylene terephthalate) (PBT) resins are semi-crystalline thermoplastics used in a wide variety of applications, most commonly in durable goods that are formed by injection moulding. PBT can be manufactured by the esterification of 1,4-Butanediol (BDO) and Terephthalic Acid (TPA) followed by poly-condensation. The by-product Tetrahydrofuran (THF) and water has to be removed from the reactor as vapour. The BDO in the removed vapour has to be separated and recycled.
Based on a real PBT manufacturing process in China, we establish the PBT esterification simulation via process simulator CHEMCAD. First, according to the kinetic models proposed by Hu et al. and Wang et al., three main esterifications as well as one irreversible poly-condensation reaction and two THF-forming side reactions were considered in the reactor. NRTL model was used for modelling vapour liquid equilibrium in the distillation column, with missing parameters estimated by Modified UNIFAC and VLE UNIFAC. Second, two dynamic control strategies as well as reaction pressure and temperature were investigated for the TPA conversion, THF production and product’s BDO/TPA molar ratio.
In the case of total feed change condition, Control Strategy 1 can effectively control TPA conversion and product’s BDO/TPA molar ratio; while under BDO/TPA molar feed ratio change condition, both control strategies could not play a big role to control THF production in the following reaction. In the case of reaction pressure and temperature change condition, it is suggested that the reaction pressure should be lower as reaction temperature should be higher in order to remaining product’s BDO/TPA molar ratio at low value, reducing THF formation form BDO degradation.

摘要 I
Abstract II
誌謝 III
目錄 IV
圖目錄 VI
表目錄 XI
第一章 緒論 1
1-1 PBT簡介 1
1-2 PBT國際發展情況 3
1-3 PBT應用 6
1-4 PBT原料製備法 10
1-5 PBT製備法 12
1-6 研究動機 15
第二章 文獻回顧 16
2-1 PBT直接酯化法反應機構 16
2-2 中國PBT廠操作例子 21
2-3 PBT生產因素 26
第三章 研究方法 28
3-1 成分建立 28
3-2 動力學模型 28
3-3 熱力學模型 30
3-4 反應器操作 38
3-5 蒸餾塔操作 39
3-6 整廠模擬 41
3-7 PBT生產控制策略 42
第四章 結果與討論 45
4-1 穩態模擬結果 45
4-2 兩種控制策略下反應總進料量改變的影響 47
4-3 兩種控制策略下BDO/TPA進料莫耳比改變的影響 54
4-4 反應壓力改變的影響 69
4-5 反應溫度改變的影響 74
4-6 結果與討論 79
第五章 總結與未來工作 80
第六章 參考文獻 81

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