本文選題：成對電合成 + 苯甲醇��； 參考：《太原理工大學(xué)》2017年碩士論文

【摘要】：化學(xué)工業(yè)產(chǎn)品在改善人們的生活質(zhì)量中起著關(guān)鍵性作用,影響著人們的方方面面。然而由于它在生產(chǎn)過程中會不可避免的對環(huán)境造成破壞,對各國的經(jīng)濟(jì)、社會和環(huán)境帶來了巨大的壓力,因此為了避免事態(tài)進(jìn)一步惡化,綠色化學(xué)得到了各國廣泛的重視,即在生產(chǎn)過程達(dá)到污染零排放。由于電化學(xué)是以電為能源,在生產(chǎn)過程中主要產(chǎn)生氫氣和氧氣,對環(huán)境的破壞程度小,已經(jīng)成為綠色化學(xué)重要的分支。電化學(xué)主要應(yīng)用在對工業(yè)廢水的降解處理,土壤的降解和大氣顆粒的吸附等方面。而現(xiàn)在越來越多的研究者將電化學(xué)技術(shù)應(yīng)用到有機(jī)合成。該技術(shù)與傳統(tǒng)的化學(xué)合成方法相比,具有操作過程容易控制,產(chǎn)品純度高,副產(chǎn)物少,經(jīng)濟(jì)優(yōu)勢更高的特點(diǎn)。苯甲醛和鄰氨基苯酚都是重要的有機(jī)化工產(chǎn)品中間體。其中苯甲醛是杏仁和許多水果中最簡單的芳香成分。其廣泛的應(yīng)用于醫(yī)藥、香料、農(nóng)業(yè)和工業(yè)等領(lǐng)域。而鄰氨基苯酚則廣泛應(yīng)用于染料、醫(yī)藥、印刷業(yè)以及生物領(lǐng)域。近年來人們發(fā)現(xiàn)鄰氨基苯酚也可用于脂肪酸的分析,制備Schiff堿。然而,無論是苯甲醛還是鄰氨基苯酚其傳統(tǒng)生產(chǎn)工藝都會對環(huán)境造成比較大破壞。本實(shí)驗(yàn)通過文獻(xiàn)調(diào)研以及本課題組以往的研究工作,發(fā)現(xiàn)苯甲醛和鄰氨基苯酚電解制備的反應(yīng)條件比較接近,都在堿性介質(zhì)中進(jìn)行電解,且槽電壓也差別不大,故采用綠色、清潔的成對電合成技術(shù),通過陽極電氧化苯甲醇得到苯甲醛,陰極電還原鄰硝基苯酚制備鄰氨基苯酚,在一個電解過程中同時制備得到了兩種具有較高附加值的精細(xì)化學(xué)品。具體研究內(nèi)容如下:首先,對陽極工作電極進(jìn)行了研制。通過查閱相關(guān)文獻(xiàn)發(fā)現(xiàn):苯甲醇在泡沫鎳電極電極表面能夠發(fā)生氧化反應(yīng)生成苯甲醛。在對該電極進(jìn)行循環(huán)伏安分析時,此電極對苯甲醇的催化氧化效率不高,為提高電極的催化氧化效率,制備得到更多的目標(biāo)產(chǎn)品,本實(shí)驗(yàn)采用多電流階躍法以泡沫鎳電極為基體,制得了Ni OOH電極,通過對比相同條件下苯甲醇的循環(huán)伏安圖得出:新制的Ni OOH電極對苯甲醇具有更高的催化氧化活性。其次,通過查閱文獻(xiàn)發(fā)現(xiàn)沒有對陰極電解產(chǎn)物分析的方法,對電解后產(chǎn)物的分析帶來不便,因此,本實(shí)驗(yàn)在已閱文獻(xiàn)的基礎(chǔ)上,根據(jù)鄰硝基苯酚和鄰氨基苯酚的性質(zhì)差異建立了同時測定鄰氨基苯酚和鄰硝基苯酚的高效液相色譜法,探討了檢測波長,柱溫,流動相的配比和流速對檢測結(jié)果的影響,并最終確定液相色譜分析的最優(yōu)條件,即流動相為純甲醇,流速為0.8 min/L,檢測波長為285nm,柱溫為35℃,將其應(yīng)用于電還原鄰硝基苯酚合成鄰氨基苯酚電解液的分析,其加標(biāo)回收率分別在93.0%~105.6%和90.6%~106.2%之間,相對標(biāo)準(zhǔn)偏差分別≤3.75%和≤1.44%。第三,以Pb片為陽極,Cu片為陰極,NaOH溶液為電解液,研究了鄰硝基苯酚在Cu電極表面的電化學(xué)行為,實(shí)驗(yàn)結(jié)果顯示,鄰硝基苯酚在Cu電極表面有中間產(chǎn)物生成,氧氣的存在會發(fā)生與鄰硝基苯酚爭奪電子現(xiàn)象。因此,在電還原鄰硝基苯酚制備鄰氨基苯酚過程中,需通入氮?dú)膺M(jìn)行保護(hù),通過正交試驗(yàn)獲得的最佳電解條件為:鄰硝基苯酚加入量與理論量的物質(zhì)的量之比為2:1,NaOH加入量3.0g,反應(yīng)溫度為35℃,電流強(qiáng)度為0.3A,電流效率為在98%以上。第四,在滿足陰極制備鄰氨基苯酚最大電流效率條件下,將陽極制備苯甲醛的過程與陰極進(jìn)行配對。在H型電解槽中,以Ni OOH為陽極,Cu為陰極,Na2SO4為電解質(zhì),保持陰極電解條件基本不變的基礎(chǔ)上,通過正交試驗(yàn)考察了陽極電解過程中苯甲醇加入量與理論量的物質(zhì)的量之比,反應(yīng)溫度和NaOH加入量對陰陽極電流效率和總電解電流效率的影響情況。實(shí)驗(yàn)結(jié)果顯示:反應(yīng)溫度35℃,電解電流0.3A,鄰硝基苯酚加入量為理論量的2倍,陰極堿用量為3.0g,苯甲醇的加入量為理論量的5倍,陽極堿用量2.0g,電解反應(yīng)的總電流效率最高可達(dá)156.95%。為今后工業(yè)化生產(chǎn)奠定了良好的理論基礎(chǔ)。
[Abstract]:Chemical industry products play a key role in improving people's quality of life, affecting all aspects of the people. However, because it will inevitably cause damage to the environment in the process of production, it has brought great pressure on the economy, society and environment of each country. Therefore, the green chemistry has been obtained to avoid the further deterioration of the situation. All countries attach great importance to the zero emission of pollution in the process of production. Because electrochemistry is the energy source of electricity, hydrogen and oxygen are produced mainly in the production process, and the damage to the environment is small, and it has become an important branch of green chemistry. Electrochemistry is mainly used in the degradation treatment of industrial waste water, soil degradation and atmospheric particles. More and more researchers have applied electrochemical technology to organic synthesis. Compared with traditional chemical synthesis, the technology has the characteristics of easy operation, high purity, less byproducts and higher economic advantages. Both benzaldehyde and O aminophenol are important intermediates of organic chemical products. Benzaldehyde is the simplest aroma component in almond and many fruits. It is widely used in the fields of medicine, spice, agriculture and industry, while o aminophenol is widely used in dyes, medicine, printing and biological fields. In recent years, it has been found that o aminophenol can also be used for the analysis of fatty acids and the preparation of Schiff bases. However, no matter what it is, The traditional production process of benzaldehyde or o aminophenol will cause a lot of damage to the environment. Through literature investigation and previous research work, we found that the reaction conditions of electrolysis of benzaldehyde and O aminophenol are relatively close, both are electrolyzed in alkaline medium and the voltage of the groove is not very different, so it is adopted. Green, clean pair electric synthesis technology, by the anode electrooxidation of benzyl alcohol to obtain benzaldehyde, the cathode electroreduction of O nitrophenol for the preparation of O aminophenol, two kinds of fine chemicals with high added value have been prepared at the same time in an electrolysis process. The specific contents are as follows: first, the anode working electrode was developed. After consulting related literature, it is found that benzyl alcohol can produce benzaldehyde on the surface of foam nickel electrode. When the electrode is analyzed by cyclic voltammetry, the catalytic oxidation efficiency of the electrode to benzyl alcohol is not high. In order to improve the catalytic oxidation efficiency of the electrode, more target products are prepared. This experiment uses a multi current order. The Ni OOH electrode was prepared on the base of nickel foam electrode in the jump method. By comparing the cyclic voltammetry of benzyl alcohol under the same condition, the new Ni OOH electrode has higher catalytic oxidation activity to benzyl alcohol. Secondly, the method of separating the cathode electrolysis products from the cathode electrolysis product is found by consulting the literature, and it is inconvenient for the analysis of the products after electrolysis. On the basis of the literature, the high performance liquid chromatography (HPLC) for simultaneous determination of O aminophenol and O nitrophenol was established on the basis of the properties of O nitrophenol and O aminophenol. The influence of detection wavelength, column temperature, flow phase ratio and flow rate on the determination of the fruit was discussed. The optimum conditions are that the flow phase is pure methanol, the flow rate is 0.8 min/L, the detection wavelength is 285nm, the column temperature is 35 C, and it is applied to the electroreduction of O aminophenol electrolyte by electric reduction of O nitrophenol. The recovery rate is between 93.0%~105.6% and 90.6%~106.2%, respectively, the relative standard deviation is less than 3.75% and less than 1.44%. third, and Pb films are used as anode, Cu as cathode and NaOH solution as electrolyte, the electrochemical behavior of O nitrophenol on the surface of Cu electrode has been studied. The experimental results show that o nitrophenol has intermediate products on the surface of Cu electrode, and the presence of oxygen will compete for the electron phenomenon of O nitrophenol. Therefore, in the process of the preparation of O aminophenol by the electroreduction of O nitrophenol, the process of O aminophenol is prepared by electric reduction of O nitrophenol. The optimum electrolysis conditions obtained through orthogonal test are: the ratio of the quantity of the adjacent nitrophenol to the quantity of the material is 2:1, the NaOH is 3.0g, the reaction temperature is 35, the current is 0.3A, the current efficiency is above 98%. Fourth, under the condition of the maximum current efficiency of the full cathode preparation of the o aminophenol, The process of preparing benzaldehyde with the anode is paired with the cathode. In the H cell, the Ni OOH as the anode, the Cu as the cathode and the Na2SO4 as the electrolyte, on the basis of the basic condition of the cathode electrolysis, the ratio of the amount of benzyl alcohol to the theoretical quantity, the reaction temperature and the NaOH addition in the anode electrolysis process are investigated by orthogonal test. The experimental results show that the reaction temperature is 35, the electrolysis current is 0.3A, the addition of O nitrophenol is 2 times the theoretical amount, the amount of the cathode base is 3.0g, the amount of benzyl alcohol is 5 times the theoretical amount, and the anodic alkali amount is 2.0g, the total current efficiency of the electrolysis reaction can reach 156.95%. It lays a good theoretical foundation for industrial production in the future.
【學(xué)位授予單位】：太原理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TQ24

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