批式反應器自主管理技術研究-以水性壓克力樹脂製程為例

Abstract

中文摘要 一般的化學工業中，有許多生產製程是以放熱反應來進行，在國內採取批式製程的化學工廠中，其生產製程之反應情形更絕大部分是屬於放熱反應，而放熱反應的製程若操作不慎，使得反應所產生的熱量無法迅速移除，而導致反應物溫度上升，則容易造成「失控反應」，反應製程中若造成失控反應往往將釀成火災、爆炸等重大危害，而造成事業單位很大的損失。民國85年桃園縣永興樹脂公司發生爆炸、民國90年新竹縣福國化工公司之爆炸案，都是因為在生產過程中產生失控反應而造成的重大工安事件。 本次研究針對壓克力樹脂製程所用反應原物料以及混合單體反應，進行個別化學品失控溫度評估，以及混合單體反應槽失控後所需之冷卻水量以及冷卻槽體體積設計，經過熱分析DSC昇溫掃描實驗以及C80恆溫卡計實驗後，獲得苯乙烯、丙烯酸及丙烯酸丁酯單體與觸媒過硫酸鉀個別的反應起始溫度為134.7℃、180.19℃、169.42℃與205.59℃，而混合單體槽反應物起始反應溫度為80.88℃（82℃恆溫約10小時），發生失控後反應溫度可達235.6℃。本研究亦同時經由VSP2絕熱實驗進行混合單體反應槽失控反應測試，結果發現：絕熱失控反應的起始溫度在150℃，一但發生失控反應，最高溫度可達329℃，最高壓力可達82psig。若採取緊急排放冷卻槽的安全設計，由反應放熱量結果可以計算混合單體槽失控後，計需742.9 kg冷卻水於體積3.65m3冷卻槽內，進行緊急排放冷卻處理。 本次除研究批式反應器於失控反應發生後的緊急排放冷卻技術，另針對批式反應製程進行自主管理研究，藉由瞭解自主管理系統內涵，建構批式製程自主管理的政策擬定方法、組織、人員、規劃及執行系統，並利用績效評量、稽核及管理階層審查等措施，確認批式反應器操作程序之自主管理制度與效果。最終研究成果，結合技術及設備面的本質反應危害預防，以及建構完善的自主管理制度，將此資訊推廣至批式反應製程業界，宣導設計製程本質較安全之緊急排放冷卻系統，並提昇國內批式製程安全管理的水平及標準，達到產業降災目的。

Abstract

In chemical industry, many production processes are carried out by exothermic reactions. In Taiwan, exothermic reactions are mostly employed in the production processes for the chemical factories using batch processes. During the exothermic reaction processes, if any careless operation is taken that may cause the difficulty in the immediate removal of reaction heat and bring about an increase of the temperature, then, runaway reaction is prone to occur. Hazards, such as the fire and explosion resulted from the runaway reaction during the reaction processes, are likely to bring substantial damage to the organizations. Accidents like the explosions occurring at Yun Hsin Resin Corp., Taoyuan, 1996, and at Fu Kuo Chemical Industrial Corp., Hsinchu, 2001, were attributed to the runaway reactions that occur during the production processes. This study assesses the runaway onset temperature of individual reactant and the quantity of required quench water and corresponding vessel volume for the mixed monomer reaction in acrylic resin process. The dynamic scanning thermal analysis by DSC and the isothermal experiments by C80 are utilized. To summarize, the onset reaction temperatures of monomers of styrene, acrylic acid, butyl acrylate and catalyst potassium persulfate are obtained as 134.7℃、180.19℃、169.42℃ and 205.59℃, respectively. In addition, the onset reaction temperature of mixed monomers is 80.88℃（isothermal at 82℃ for 10hrs） and can be reached to the maximum one up to 235.6℃.This study conducts the adiabatic experiments by using VSP2 as well to investigate the runaway scenario internal the mixed monomer reactor. Development from the experimental results the adiabatic runaway onset temperature at 150℃ and the maximum temperature and pressure are respectively 329℃ and 82psig. Therefore, it needs 742.9 kg of quench water within a 3.65 m3 of quench vessel to conduct the emergency disposal quench. It is expected that such the strategy information of this study can directly be used by the industry and applied to design an inherently safer emergency disposal system. Besides the emergency venting quench technology, this work also studies the voluntary protection program for the batch process. Based on the understanding of voluntary protection program, this work establishes the planning methods for the strategy, organization, operator, scheme and implement system. In addition, the measures of achieved assessment can be used to inspect, audit and examine the management to confirm the efficiency of voluntary protection program. Eventually, the conclusion of this thesis integrates the inherently hazard prevention technology and equipment and establishes the voluntary protection program that can be applied to reaction process industry popularly. It is wished to preach the inherently safer design of emergency venting quench system and enhance the level and regulation of process safety management in the domestic industry to achieve the goal of lowering the accident rate.