本文關(guān)鍵詞：氣液反應(yīng)本征動力學(xué)研究策略及其在氧化反應(yīng)中的應(yīng)用　出處：《浙江大學(xué)》2017年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 液相空氣氧化 傳質(zhì) 本征動力學(xué) 4-甲基愈創(chuàng)木酚 香蘭素 生物素 位阻效應(yīng) 氧化機(jī)理

【摘要】：液相空氣氧化是以氧氣或空氣為氧化劑,反應(yīng)發(fā)生在液相區(qū)域的多相反應(yīng)。多相反應(yīng)的特點(diǎn)決定液相空氣氧化是傳質(zhì)因素與本征反應(yīng)耦合的過程。但是,很多研究者在開展氧化反應(yīng)過程分析、動力學(xué)探究、機(jī)理分析以及催化劑設(shè)計(jì)等工作時(shí),忽略傳質(zhì)因素,容易給同行研究者帶來誤導(dǎo)。而反應(yīng)本征動力學(xué)是不受傳質(zhì)參數(shù)影響下的反應(yīng)動力學(xué)信息,是多相反應(yīng)中反應(yīng)信息的最本征體現(xiàn)。氣液本征動力學(xué)研究策略可描述為:當(dāng)本征反應(yīng)為慢反應(yīng)或極慢反應(yīng)時(shí),可通過強(qiáng)化傳質(zhì)過程消除傳質(zhì)阻力,本征動力學(xué)研究類同均相反應(yīng);對于中速反應(yīng)或快速反應(yīng),傳質(zhì)阻力很難完全排除,可通過解耦宏觀動力學(xué)策略獲得本征動力學(xué)信息;對于瞬間反應(yīng)本征動力學(xué)無法求解,需改變反應(yīng)參數(shù),調(diào)整動力學(xué)區(qū)域、改變反應(yīng)類型,再進(jìn)一步進(jìn)行本征動力學(xué)分析。本文在對氣液反應(yīng)本征動力學(xué)探究規(guī)律進(jìn)行梳理的基礎(chǔ)上,以4-甲基愈創(chuàng)木酚液相氧化合成香蘭素以及(3 S,7R,7aR)-6-芐基-7-(1-羥基-2-氧環(huán)己基)-3-苯基四氫化-5H-咪唑[1,5-c][1,3]噻唑-5-酮液相氧化合成6-[(3S,7R,7aR)-芐基-5-氧-3-苯基四氫化-1H-咪唑[1,5-c][1,3]噻唑-7-基]-6-氧己酸為研究對象,探究香蘭素以及生物素中間體兩個(gè)重要氧化體系的本征動力學(xué),并將本征動力學(xué)相關(guān)信息用于反應(yīng)機(jī)理等問題的探究中去。邏輯實(shí)驗(yàn)、柱分析以及液相色譜質(zhì)譜聯(lián)用等手段證明4-甲基愈創(chuàng)木酚液相氧化可描述為4-甲基愈創(chuàng)木酚氧化生成芳醚中間體,中間體進(jìn)一步氧化生成香蘭素的連串反應(yīng)。傳質(zhì)分析實(shí)驗(yàn)表明4-甲基愈創(chuàng)木酚氧化連串反應(yīng)兩步均可視為擬一級快速反應(yīng),反應(yīng)發(fā)生區(qū)域主要集中在液膜內(nèi),由此確定本征動力學(xué)探究策略。在滿足碳平衡要求并計(jì)算物性參數(shù)與傳質(zhì)參數(shù)的前提下,探究了反應(yīng)本征動力學(xué)。動力學(xué)結(jié)果表明4-甲基愈創(chuàng)木酚氧化生成芳醚中間體反應(yīng)活化能為31.95 kJ/mol,中間體氧化生成香蘭素反應(yīng)活化能為29.77 kJ/mol。不同氧氣壓力、催化劑濃度實(shí)驗(yàn)表明,連串反應(yīng)的兩步對氧氣以及催化劑均為一級反應(yīng)。同時(shí),溶劑探究實(shí)驗(yàn)證明連串反應(yīng)的兩步對乙二醇甲醚均為零級反應(yīng)。反應(yīng)副產(chǎn)物網(wǎng)絡(luò)分析表明,自由基聚合產(chǎn)生的低聚物為反應(yīng)主要副產(chǎn)物。本征動力學(xué)指導(dǎo)機(jī)理探究結(jié)果表明:4-甲基愈創(chuàng)木酚液相氧化反應(yīng)速率控制步驟是酚氧負(fù)離子的催化氧化,亞甲基醌主要通過催化氧化獲得,反應(yīng)過程中醇類溶劑與亞甲基醌1,6-加成反應(yīng)形成芳醚化合物,提高氧自由基向亞甲基梖的轉(zhuǎn)變速率是提高反應(yīng)選擇性的關(guān)鍵所在,反應(yīng)產(chǎn)物中的少量香蘭酸是通過Cannizzaro歧化生成的。堿作為對甲酚類化合物氧化反應(yīng)中的關(guān)鍵組分,其作用機(jī)理可描述為:堿與底物酚進(jìn)行酸堿反應(yīng)形成酚氧負(fù)離子活化反應(yīng)底物;堿通過與催化劑作用或單獨(dú)作用,加快酚氧自由基催化氧化生成亞甲基醌,抑制了偶合終止反應(yīng),降低低聚物的生成;堿參與了醛的歧化反應(yīng),但反應(yīng)速率很慢,堿并不是醛深度氧化的抑制劑;堿的最優(yōu)使用量和溶劑的種類、水含量是相關(guān)的,無水條件或pKa值比較低的溶劑對反應(yīng)體系有利。為進(jìn)一步驗(yàn)證堿作用機(jī)理,設(shè)計(jì)了無鈷催化劑下香蘭醇及系列化合物的堿催化氧化,實(shí)驗(yàn)現(xiàn)象與堿作用機(jī)理吻合。實(shí)驗(yàn)還首次提出了無過渡金屬條件下的堿催化氧化合成對羥基苯甲醛類化合物新路線。(3S,7R,7aR)-6-芐基-7-(1-羥基-2-氧環(huán)己基)-3-苯基四氫化-5H-咪唑[1,5-c][1,3]噻唑-5-酮液相氧化主反應(yīng)可描述為簡單反應(yīng),反應(yīng)過程沒有檢測出明顯中間體。不同攪拌轉(zhuǎn)速以及通氣速率下的傳質(zhì)實(shí)驗(yàn)表明,該氧化反應(yīng)為動力學(xué)控制,反應(yīng)主要發(fā)生在液相主體區(qū)。(3S,7R,7aR)-6-芐基-7-(1-羥基-2-氧環(huán)己基)-3-苯基四氫化-5H-咪唑[1,5-c][1,3]噻唑-5-酮液相氧化可描述為生成目標(biāo)產(chǎn)物酮酸為主反應(yīng),鹵代反應(yīng)與羰基另一側(cè)的C-C鍵斷裂為副反應(yīng)的平行反應(yīng)。鹵代副反應(yīng)對氧氣反應(yīng)級數(shù)為零級,C-C鍵斷裂氧化反應(yīng)對氧氣為一級反應(yīng)。催化劑濃度升高,主反應(yīng)與副反應(yīng)速率均增加,對催化劑反應(yīng)級數(shù)均為1級。其中,主反應(yīng)活化能為54.67 kJ/mol,鹵代副反應(yīng)活化能為105.44 kJ/mol,另一側(cè)的C-C鍵斷裂反應(yīng)活化能為88.67 kJ/mol,該結(jié)論與八田數(shù)等證據(jù)證明了慢反應(yīng)動力學(xué)結(jié)論。紅外與紫外相關(guān)數(shù)據(jù)表明催化劑的主要結(jié)構(gòu)為[Fe(DMSO)4C12]Cl,溶劑起著溶解與配體的雙攻能作用,氧配體對催化劑活性起積極作用。該體系與傳統(tǒng)甲基環(huán)己酮類似體系差異主要在于位阻效應(yīng),位阻效應(yīng)可通過增加催化劑的量進(jìn)行克服,可利用位阻效應(yīng)調(diào)控反應(yīng)進(jìn)行的方向。自由基猝滅實(shí)驗(yàn)與自由基捕獲實(shí)驗(yàn)證明該氧化反應(yīng)是自由基機(jī)理和離子型機(jī)理共同作用的結(jié)果,二者比例為52:48,這也與本征動力學(xué)結(jié)論一致。
[Abstract]:Liquid air oxidation is a multiphase reaction that takes oxygen or air as an oxidant, and the reaction occurs in the liquid phase. The characteristics of the multiphase reaction determine that the liquid air oxidation is the process of coupling the mass transfer factor with the intrinsic reaction. However, many researchers ignore the factors of mass transfer during the process of oxidation reaction analysis, dynamic exploration, mechanism analysis and catalyst design. The reaction intrinsic kinetics is the dynamic information of the reaction under the influence of the mass transfer parameters, and is the most important manifestation of the reaction information in the multiphase reaction. Research on the intrinsic kinetics gas-liquid strategy can be described as: when the intrinsic reaction is slow or very slow reaction, mass transfer resistance can be eliminated by strengthening the mass transfer process, the intrinsic kinetic study of similar homogeneous reaction; for medium reaction or rapid reaction, mass transfer resistance is difficult to completely eliminate, can obtain the intrinsic kinetic information through macro decoupling dynamic strategy; for the moment the intrinsic reaction kinetics can not be solved, the need to change the reaction parameters, adjust the dynamic area, change the type of reaction, further analyzes the intrinsic kinetics. Based on the gas-liquid reaction the intrinsic kinetics of exploring the law on carding, by 4- methyl guaiacol oxidation in liquid phase synthesis of vanillin and (3 S, 7R, 7aR) -6- benzyl -7- (1- hydroxy -2- oxocyclohexyl) synthesis of 6-[-3- four phase oxidation of phenyl imidazole thiazole ketone hydrogenation of -5H- [1,5-c][1,3] -5- (3S fluid 7R, 7aR, -5-) - benzyl oxygen -3- phenyl four hydrogenated -1H- imidazo [1,5-c][1,3] thiazole -7- base]-6- oxygen acid as the research object, to explore the intrinsic kinetics of two important oxidation system of vanillin and biotin intermediates, and the intrinsic kinetic information for exploring the reaction mechanism in the. Logical experiments, column analysis and liquid chromatography-mass spectrometry proved that 4- methyl guaiacol liquid phase oxidation can be described as 4- methyl guaiacol oxidation to produce aromatic ether intermediates, and intermediates are further oxidized to produce vanillin. The mass transfer analysis experiments showed that the two steps of 4- methyl guaiacol oxidation and consecutive reaction were regarded as pseudo first order rapid reaction. The reaction area was mainly concentrated in the liquid membrane, so the intrinsic kinetics inquiry strategy was determined. In order to meet the requirements of carbon balance and to calculate the physical and mass transfer parameters, the reaction intrinsic kinetics is explored. The kinetic results showed that 4- methyl guaiacol was oxidized to produce aromatic ether intermediate, the reaction activation energy was 31.95 kJ/mol, and the activation energy of intermediate oxidation to vanillin was 29.77 kJ/mol. The experiment of different oxygen pressure and catalyst concentration showed that the two steps of the series reaction were first order reaction to oxygen and catalyst. At the same time, the solvent inquiry experiment proved that the two step of the series reaction was zero order reaction to ethylene glycol methyl ether. The reaction byproduct network analysis showed that the oligomer produced by the free radical polymerization was the main reaction product. The kinetic mechanism of guiding the results show that: 4- methyl guaiacol oxidation in liquid phase reaction rate controlling step is the catalytic oxidation of phenol oxygen negative ion, Ya Jiaji quinones mainly obtained through catalytic oxidation reaction process in alcohol solvent and Ya Jiaji addition reaction to form quinone 1,6- aryl ether compounds, improve the oxygen free radical to the change rate of the Ya Jiaji Bei is the key to improve the selectivity of reaction, a small amount of vanillic acid in the reaction product is generated by Cannizzaro disproportionation. As a key group of compounds of alkali oxidation reaction of cresol, its mechanism can be described as: alkali phenol and substrate of acid-base reaction formation of phenolic oxygen negative ion activation by alkali catalyst and substrate; or individually, accelerate the phenoxy radical generation of catalytic oxidation of methylene quinone, inhibited the coupling termination reaction. Reduction of oligomer formation; alkali in the disproportionation reaction of aldehydes, but the reaction rate is very slow, and not the aldehyde oxidation inhibitor alkali; alkali amount and optimal use of solvent, water content is related to the anhydrous conditions or pKa value relatively low solvent is favorable to the reaction system. In order to further verify the base mechanism, designed and vanillyl alcohol series compound alkali catalytic oxidation of cobalt free catalyst. The experimental results agree well with the mechanism of alkali. It is also the first time that a new route for the synthesis of hydroxy benzaldehyde under the condition of non transition metal is also proposed. (3S, 7R, 7aR) -6- benzyl -7- (1- hydroxyl -2- oxygen cyclohexyl) -3- phenyl four hydrogenation, -5H-, imidazole, [1,5-c][1,3] thiazolone, the main reaction of liquid phase oxidation can be described as simple reaction, and no obvious intermediate has been detected in the reaction process. The mass transfer experiments under different stirring speed and aeration rate show that the reaction is controlled by kinetics, and the reaction occurs mainly in the main liquid phase. (3S, 7R, 7aR) -6- benzyl -7- (1- hydroxyl -2- oxygen cyclohexyl) -3- phenyl four hydrogenation, -5H-, imidazole, [1,5-c][1,3] thiazolone, liquid phase oxidation can be described as the target product, keto acid as the main reaction, halogenation reaction with the side bond of the carbonyl on the other side as a parallel reaction of side reactions. The reaction order of the halogenated side reaction to oxygen is zero, and the C-C bond oxidation reaction is a first-order reaction to oxygen. As the concentration of catalyst increases, both the main reaction and the secondary reaction rate increase, and the reaction order of the catalyst is 1. The activation energy of the main reaction is 54.67 kJ/mol, the activation energy of halogenation reaction is 105.44 kJ/mol, and the activation energy of C-C bond breaking reaction on the other side is 88.67 kJ/mol, which is proved by the eight field number and other evidences. The IR and UV correlation data indicate that the main structure of the catalyst is [Fe (DMSO) 4C12]Cl. The solvent plays a dual role in the dissolution and ligand interaction, and the oxygen ligand plays a positive role in the activity of the catalyst. The difference between the system and traditional methyl cyclohexanone is mainly the steric hindrance effect. The steric hindrance effect can be overcome by increasing the amount of catalyst, and the direction of reaction can be controlled by steric effect. Free radical quenching experiment and free radical
【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O643.1

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