【摘要】：過氧化氫是世界主要的基礎化學產品之一。目前國內過氧化氫生產工藝主要采用蒽醌法,經氫化、氧化、萃取、純化及濃縮制得不同濃度的過氧化氫水溶液。在萃取過程中,當萃取塔中過氧化氫超過一定濃度后,會與工作液形成多元非均相體系,有爆炸風險,大大制約了直接萃取得到高濃度過氧化氫工藝的發(fā)展。進行萃取塔中過氧化氫-工作液體系爆炸反應研究對蒽醌法工藝安全及萃取工藝優(yōu)化具有重要意義。本文以中石化河北某煉化雙氧水中試裝置為研究對象,研究萃取塔中工作液雙氧水體系爆炸規(guī)律。為簡化多元體系,研究了過氧化氫-磷酸三辛酯-三甲苯三元體系的爆炸規(guī)律,并確定工作液中單一組分對體系爆炸規(guī)律的影響。研究發(fā)現三甲苯雙氧水體系在雙氧水濃度大于59%之后進入爆炸區(qū)間。加入表面活性劑之后,濃度高于46.3%后進入爆炸區(qū)間。磷酸三辛酯雙氧水體系中,雙氧水濃度大于42.9%進入爆炸區(qū)間。工作液雙氧水體系未加表面活性劑時雙氧水濃度高于46.7%已經進入了爆炸范圍,并且隨著過氧化氫濃度升高,體系的爆炸范圍在擴大。加入表面活性劑后,雙氧水濃度高于42.3%時,進入爆炸區(qū)間。在上述爆炸實驗基礎上,對過氧化氫-三甲苯體系爆炸產物進行收集、分析,推測體系爆炸反應機理。采用密度泛函理論方法,運用量子化學軟件,首先對過氧化氫自分解反應機理中每一步基元反應的過渡態(tài)進行計算,通過頻率分析及IRC驗證了過渡態(tài)存在的真實性,并且計算了分解反應焓變。然后采用同樣方法對過氧化氫-三甲苯初步反應機理進行模擬研究,通過分子模擬以及電子云分布和電荷分布分析,得到了三甲苯-過氧化氫爆炸反應初期的反應過程。通過在分子尺度上對過氧化氫分解及過氧化氫-三甲苯體系反應機理進行分析研究,為高濃度過氧化氫安全生產和使用提供依據和指導。
[Abstract]:Hydrogen peroxide is one of the main basic chemical products in the world. At present, hydrogen peroxide aqueous solution with different concentration is prepared by hydrogen peroxide production process by hydrogenation, oxidation, extraction, purification and concentration. In the process of extraction, when the concentration of hydrogen peroxide in the extraction column exceeds a certain concentration, a multicomponent heterogeneous system will be formed with the working liquid, which has the risk of explosion, which greatly restricts the development of the process of direct extraction to obtain high concentration hydrogen peroxide. It is of great significance to study the explosion reaction of hydrogen peroxide-working liquid system in extraction column for the safety of anthraquinone process and the optimization of extraction process. In this paper, a pilot plant in Hebei Province of Sinopec was used to study the explosion law of hydrogen peroxide system in the working liquid of extraction tower. In order to simplify the multicomponent system, the explosion law of the ternary system of hydrogen peroxide, trioctyl phosphate and trimethylbenzene was studied, and the effect of a single component in the working liquid on the explosion law of the system was determined. It is found that the system of tritoluene and hydrogen peroxide enters the explosion zone after the concentration of hydrogen peroxide is greater than 59%. After the addition of surfactant, the concentration was higher than 46.3% and then entered the explosion zone. In the system of trioctyl phosphate hydrogen peroxide, the concentration of hydrogen peroxide is more than 42.9%. When the concentration of hydrogen peroxide is higher than 46.7%, the concentration of hydrogen peroxide in the system without surfactant has entered the range of explosion, and with the increase of hydrogen peroxide concentration, the explosion range of the system is expanding. After the addition of surfactant, the concentration of hydrogen peroxide was higher than 42.3 and entered the explosion zone. On the basis of the above explosion experiments, the explosive products of hydrogen peroxide-trimethylbenzene system were collected and analyzed, and the mechanism of the system explosion reaction was inferred. By using density functional theory and quantum chemical software, the transition states of each step of the radical reaction in the mechanism of hydrogen peroxide self-decomposition are calculated. The existence of the transition state is verified by frequency analysis and IRC. The enthalpy change of decomposition reaction was calculated. Then the initial reaction mechanism of hydrogen peroxide and trimethylbenzene was simulated by the same method. The initial reaction process of trimethylbenzene hydrogen peroxide explosion reaction was obtained by molecular simulation and electron cloud distribution and charge distribution analysis. The decomposition of hydrogen peroxide and the reaction mechanism of hydrogen peroxide with trimethylbenzene were studied on the molecular scale, which provided the basis and guidance for the safe production and use of high concentration hydrogen peroxide.
【學位授予單位】：青島科技大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TQ123.6

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