臺灣博碩士論文加值系統

論文目的在研究三成份有機混合物以及雙成份有機水溶液的獨特閃火點（FP）‎行為。‎
在研究的第一部分中，專注於三成份混合物的特殊和獨特的FP行為，研究了四種三成份混合物的FP行為，分別是1-丁醇+醋酸+乙苯、2-戊醇+醋酸+乙苯、丙酸丁酯+醋酸+2-戊醇和丙酸丁酯+醋酸+1-丁醇，由最低FP行為（MinFPB）和最高FP行為（MaxFPB）的雙成份構成。研究得出結論，醋酸與醇的混合物表現出MaxFPB行為，而所有包含乙苯的雙成份混合物和2-戊醇/1-丁醇+丙酸丁酯的兩種雙成份混合物表現出MinFPB行為。研究還發現，原始UNIFAC和UNIFAC-Dortmund模型對於預測某些雙成份混合物（1-丁醇+醋酸，2-戊醇+醋酸，丙酸丁酯+醋酸）的FP和趨勢線是不可靠的，使用這些模型時應謹慎。這些發現可用於制定降低處理、儲存、運輸和處理此類混合物的成本和安全風險的方法。‎
在研究的第二部分中，研究了雙成份有機水溶液的獨特FP行為，以找出維持有機水溶液易燃性的最大水量（MaxWF）和這些混合物的最大FP（Tfp,max）。論文中引入了一個新模型來預測MaxWF和Tfp,max。該模式準確地預測了MaxWF和Tfp,max。該模式背後的基本概念是，當氣相中的蒸汽濃度超過惰化點時，FP將測不到。研究發現，‎少量水足以使低揮發性易燃液體不易燃，而高揮發性易燃液體需要更多的水才能達到惰化點。這些發現有助於制定防止燃燒過程中火焰擴散的最佳水分限制，並制定防火安全法規。‎
在論文的第三部分中，對二苯醚和二苯的雙成份混合物進行了研究。這種混合物在各個行業中都有廣泛的應用，特別是在可再生能源系統中，如集中太陽能發電（CSP）設施中被廣泛使用。這項研究的重點是該混合物的FP行為，這是一個關鍵問題，因為相關製程中的操作溫度較高，特別是在其作為傳熱流體的角色中。該研究目的在通過實驗測量和基於SLE數據的獨特數學方法來分析整個組成範圍，這與依賴VLE數據的一般方法不同。閃火點預測結果與實驗數據相比表現出令人滿意的一致性。該研究的發現可用於減少使用二苯醚+二苯雙成份混合物的製程中與火災和爆炸有關的風險。‎
總而言之，該研究的結果可用於評估有機和有機水溶液的火災與爆炸風險，‎以減少相關的危害。‎

The thesis aimed to investigate the unique flash point (FP) behavior of ternary ‎organic mixtures, as well as binary aqueous-organic solutions. ‎
In the first part of the study that focus on the special and unique FP behavior of ‎ternary mixtures, the FP behavior of four ternary mixtures was examined, namely 1-‎butanol + acetic ‎acid + ethylbenzene, 2-pentanol + acetic acid + ethylbenzene, propyl ‎butyrate + acetic ‎acid + 2-pentanol, and propyl butyrate + acetic acid + 1-butanol, ‎consisting of binary constituents with minimum FP behavior (MinFPB) and maximum FP ‎behavior (MaxFPB). The study concluded that mixtures of acetic acid with the alcohols ‎exhibit MaxFPB behavior, while ‎all binary mixtures containing ethylbenzene and two ‎binary blends of 2-pentanol/1-butanol + ‎propyl butyrate exhibit MinFPB behavior. ‎The ‎study also found that the original UNIFAC and UNIFAC-Dortmund models are unreliable ‎for predicting FPs and trend lines for certain binary mixtures (1-butanol + acetic ‎acid, 2-‎pentanol + acetic acid, propyl butyrate + acetic ‎acid), and caution should be used when ‎using these models. The findings can be used in developing approaches to reduce costs ‎and safety risks associated with handling, storing, transporting, and processing such ‎mixtures. ‎
In the second part of the research, the unique FP behavior of binary aqueous-‎organic mixture was studied to find out the maximum amount of water that maintains an ‎aqueous-organic mixture flammable (MaxWF) and the maximum FP (Tfp,max) of those ‎mixtures. A new model was introduced to forecast the MaxWF and Tfp,max. The model ‎accurately predicted MaxWF and Tfp,max. The fundamental concept behind the model is that ‎the FP will come to an end when the steam concentration in the gas phase exceeds the ‎point of inertization. It was found that a small quantity of water is sufficient to make low-‎volatile combustible liquids nonflammable, while highly volatile flammable liquids need a ‎considerably larger amount of water to reach the inertization point. The findings can aid in ‎formulating fire safety regulations and establishing optimal restrictions on the water ‎content of liquid fuels to prevent inhibiting flame propagation during combustion. ‎
In the third section of the thesis, an examination was conducted on the binary ‎combination of diphenyl ether and biphenyl. This particular blend is extensively applied ‎across various industries, notably playing a significant role in renewable energy systems ‎such as concentrated solar power (CSP) facilities. The primary focus of this investigation ‎is the FP behavior of the blend, a crucial aspect given the elevated operating temperatures ‎in related processes, particularly in its role as a heat transfer fluid (HTF). The research ‎aims to address the dearth of studies on this subject by comprehensively analyzing the ‎entire composition range through experimental measurements and a distinctive ‎mathematical approach grounded in solid-liquid equilibrium (SLE) data, in contrast to the ‎conventional method relying on vapor-liquid equilibrium (VLE) data. The predicted FP ‎results exhibited satisfactory agreement when compared to the experimental data. The ‎insights derived from this study can be applied to minimize the potential risks of fire and ‎explosions associated with processes utilizing the binary mixture of diphenyl ether + ‎biphenyl.‎
Overall, the study's results can be used to evaluate the F&E hazards of organic and ‎aqueous-organic mixtures in order to decrease the corresponding risks. ‎

Table of content
ABSTRACT iii
ACKNOWLEDGEMENTS v
Table of content viii
List of Tables xi
List of Figures xiii
List of Symbols and Abbreviations xv
Chapter 1: Introduction ‎1‎
‎1.1.‎ Flash point explanation ‎1‎
‎1.1.1.‎ Importance of Flash Point Investigation of Ignitable Liquids ‎1‎
‎1.1.2.‎ Flammability of Aqueous-Organic Mixtures ‎2‎
‎1.1.3.‎ Flash Point and Safety Evaluation of Flammable Heat Transfer Fluids ‎3‎
‎1.2.‎ Main Objectives of the Study ‎4‎
‎1.3.‎ Structure of the Dissertation ‎6‎
Chapter 2: Literature Review ‎7‎
‎2.1.‎ FP of Ternary Mixtures ‎9‎
‎2.2.‎ Non-flammability in aqueous-organic mixtures ‎14‎
‎2.3.‎ Flammability hazard investigation of diphenyl ether + biphenyl mixture ‎15‎
‎2.4.‎ Essential questions that shape the research investigation ‎16‎
Chapter 3: Equipment and apparatuses utilized in the research ‎17‎
‎3.1.‎ FP apparatuses ‎17‎
‎3.1.1.‎ HFP 362-Tag tester ‎17‎
‎3.1.2.‎ HFP 360-Pensky Martens tester ‎19‎
‎3.2.‎ Mass balance ‎20‎
‎3.3.‎ Harmony Hotplate Stirrer ‎21‎
Chapter 4: FP Investigation of Ternary Ignitable Mixtures‎ ‎23‎
‎4.1.‎ Ternary mixtures ‎23‎
‎4.1.1.‎ Significance of the research ‎23‎
‎4.1.2.‎ Experimental investigation ‎25‎
‎4.2.‎ Mathematical modeling and simulation ‎26‎
‎4.2.1.‎ Activity coefficient models ‎26‎
‎4.2.2.‎ FP prediction of ternary mixtures ‎27‎
‎4.2.3.‎ Acquisition of the parameters ‎30‎
‎4.3.‎ FP investigation ‎33‎
‎4.3.1.‎ FP of pure ignitable chemicals ‎33‎
‎4.3.2.‎ FP of 1-butanol + acetic acid + ethylbenzene mixture ‎33‎
‎4.3.3.‎ FP of 2-pentanol + acetic acid + ethylbenzene mixture ‎49‎
‎4.3.4.‎ ‎FP of propyl butyrate + acetic acid + 1-butanol mixture ‎56‎
‎4.3.5.‎ FP of propyl butyrate + acetic acid + 2-pentanol mixture ‎63‎
‎4.4.‎ Discussion on the findings of the research ‎69‎
Chapter 5: The Maximum Required Water to Maintain a Binary‎ Aqueous-‎Organic ‎Mixture to be Flammable ‎73‎
‎5.1.‎ Aqueous-organic ignitable solutions ‎73‎
‎5.1.1.‎ Significance of the research ‎73‎
‎5.1.2.‎ Experimental investigation ‎76‎
‎5.2.‎ Mathematical modeling and simulation ‎77‎
‎5.2.1.‎ Activity coefficient models and FP prediction model ‎77‎
‎5.2.2.‎ Prediction of last ignitable point and its FP ‎78‎
‎5.2.3.‎ Acquisition of the parameters ‎83‎
‎5.3.‎ FP and nonflammable composition investigation ‎89‎
‎5.3.1.‎ FP of pure chemicals ‎89‎
‎5.3.2.‎ Aqueous mixtures of DMSO and 1,2-propanediol ‎89‎
‎5.3.3.‎ Aqueousorganic mixtures of 1-heptanol, 2-butoxyethanol, 1,2-ethanediol, and 1-‎octanol ‎94‎
‎5.3.4.‎ Aqueousorganic mixtures of ε-caprolactam, 1,4-butanediol, and NMP ‎98‎
‎5.3.5.‎ Verifying the proposed model's precision through aqueous solutions containing highly ‎volatile components ‎102‎
‎5.3.6.‎ Amount of water required to prevent ignition of a low-volatile combustible substance ‎104‎
Chapter 6: Flash Point and Safety Evaluation of Binary Mixture of Diphenyl Ether + ‎Biphenyl: A Commonly Utilized Heat Transfer Fluid ‎106‎
‎6.1.‎ Binary mixture of diphenyl ether + biphenyl ‎106‎
‎6.1.1.‎ Significance of the research ‎106‎
‎6.1.2.‎ Experimental investigation ‎107‎
‎6.2.‎ Mathematical modeling and simulation ‎108‎
‎6.3.‎ Flash point behavior of binary mixture of diphenyl ether + biphenyl ‎111‎
Chapter 7: Summary and Conclusions ‎116‎
References ‎119‎
Appendix I: The information of used chemicals ‎132‎
Appendix II: The parameters used in the FP apparatuses‎ ‎134‎
Appendix III: The Author’s publications at the NKUST ‎135‎

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