CN107915618A - A kind of synthetic method of benzoic acid using illumination as 9 thiophene ketone compound for catalysis of condition - Google Patents
A kind of synthetic method of benzoic acid using illumination as 9 thiophene ketone compound for catalysis of condition Download PDFInfo
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Abstract
Description
技术领域technical field
本发明属于化工技术领域，具体涉及苯甲酸的合成方法。The invention belongs to the technical field of chemical industry, in particular to a synthesis method of benzoic acid.
背景技术Background technique
苯甲酸为具有苯或甲醛的气味的鳞片状或针状结晶，熔点122.13℃，沸点249℃，相对密度1.2659（15/4℃），结构式为：。在100℃时迅速升华，它的蒸气有很强的刺激性，吸入后易引起咳嗽。微溶于水，易溶于乙醇、乙醚等有机溶剂。Benzoic acid is a scaly or needle-like crystal with the smell of benzene or formaldehyde, with a melting point of 122.13°C, a boiling point of 249°C, and a relative density of 1.2659 (15/4°C). The structural formula is: . It sublimates rapidly at 100°C, and its vapor is highly irritating, which can easily cause coughing after inhalation. Slightly soluble in water, easily soluble in organic solvents such as ethanol and ether.
苯甲酸可以作为生产苯甲酸酯和苯二甲酸酯的中间体，苯甲酸酯和苯二甲酸酯是重要的增塑剂。也可以用作制药和染料的中间体，用于制取增塑剂和香料等。Benzoic acid can be used as an intermediate in the production of benzoate and phthalate, which are important plasticizers. It can also be used as an intermediate for pharmaceuticals and dyes, and for the preparation of plasticizers and spices.
目前，全球普遍采用的是甲苯热氧化法制备苯甲酸的工艺。该方法利用重金属盐钴或锰作为催化剂，在高温高压的条件下实现甲苯的氧化，并最终合成苯甲酸。然而这种方法一直存在着能耗高，污染严重等问题。At present, the process of preparing benzoic acid by thermal oxidation of toluene is widely used in the world. The method uses heavy metal salt cobalt or manganese as a catalyst to realize the oxidation of toluene under high temperature and high pressure conditions, and finally synthesize benzoic acid. However, this method has always had problems such as high energy consumption and serious pollution.
随着节能环保概念的提出，传统的甲苯氧化生成苯甲酸的方法所暴露出来的具有不可持续发展性的弊端已经越来越不被人们所接受。With the introduction of the concept of energy saving and environmental protection, the disadvantages of unsustainable development exposed by the traditional method of oxidizing toluene to benzoic acid have been increasingly unaccepted by people.
光化学，作为一门新兴的科学，已经得到了高速的发展。与传统的热化学相比，光化学更为清洁节能。因此，一种新型的光照条件下的苯甲酸的合成方法亟待解决。Photochemistry, as an emerging science, has been developed at a high speed. Compared with traditional thermochemistry, photochemistry is cleaner and more energy-efficient. Therefore, the synthetic method of the benzoic acid under a kind of novel light condition needs to be solved urgently.
发明内容Contents of the invention
本发明的目的在于提供一种能够减少环境污染、大幅降低能耗的以光照为条件9-噻吩酮类化合物催化的苯甲酸的合成方法。The object of the present invention is to provide a kind of synthetic method of the benzoic acid catalyzed by 9-thienone compound under the condition of light that can reduce environmental pollution and greatly reduce energy consumption.
本发明所提供的以光照为条件9-噻吩酮类化合物催化的苯甲酸的合成方法，采用有机光化学的方法，具体以甲苯为原料，9-噻吩酮类化合物为催化剂，无需溶剂，室温（如10-40℃）、空气条件下反应40-48h，在可见光照射下即可高效的实现甲苯氧化生成苯甲酸。The synthesis method of the benzoic acid catalyzed by the 9-thiophenone compound under the condition of illumination provided by the present invention adopts the method of organic photochemistry, specifically takes toluene as a raw material, and the 9-thiophenone compound is a catalyst without solvent, at room temperature (such as 10-40°C), react in air for 40-48h, and oxidize toluene to produce benzoic acid efficiently under visible light irradiation.
本发明所提供的一种以光照为条件9-噻吩酮类化合物催化下的苯甲酸的合成方法，其特征在于，该合成方法可实现5-10公斤级的规模放大反应。The present invention provides a method for synthesizing benzoic acid catalyzed by 9-thienone compounds under the condition of light, which is characterized in that the synthesis method can realize scale-up reactions of 5-10 kg level.
优选的，本发明中，所述的9-噻吩酮类化合物催化剂为2-甲氧基-9-噻吩酮，其结构式为：。Preferably, in the present invention, the 9-thienone compound catalyst is 2-methoxy-9-thienone, and its structural formula is: .
优选的，本发明中，所述的9-噻吩酮类化合物的用量为甲苯质量分数的1-5%。Preferably, in the present invention, the amount of the 9-thienone compound is 1-5% of the mass fraction of toluene.
优选的，本发明中，所述的可见光照为4台800 W投光灯。Preferably, in the present invention, the visible light is four 800 W floodlights.
本发明提供的以光照为条件9-噻吩酮类化合物催化下的苯甲酸的合成方法可实现5-10公斤级的规模放大反应。The method for synthesizing benzoic acid under the catalysis of 9-thienone compounds under the condition of light provided by the invention can realize the scale-up reaction of 5-10 kg level.
本发明的原理在于：2-甲氧基-9-噻吩酮在可见光的照射下由基态变为激发态，之后，与反应底物甲苯分子发生碰撞将能连传递给反应底物分子，使底物分子达到高能量的激发态，从而活化催化底物分子甲苯使其脱除一个氢原子，生成相应的苄基自由基中间体，随后苄基自由基在空气的氧化作用下氧化成苯甲醛，苯甲醛进一步被空气氧化生成苯甲酸。The principle of the present invention is: 2-methoxy-9-thienone changes from the ground state to the excited state under the irradiation of visible light, and then, after colliding with the reaction substrate toluene molecule, the energy will be continuously transferred to the reaction substrate molecule, making the substrate The molecule reaches a high-energy excited state, thereby activating the catalytic substrate molecule toluene to remove a hydrogen atom to generate the corresponding benzyl radical intermediate, and then the benzyl radical is oxidized to benzaldehyde under the oxidation of air, Benzaldehyde is further oxidized by air to produce benzoic acid.
本发明所提供的以光照为条件9-噻吩酮类化合物催化下的苯甲酸的合成方法，与传统的热化学工艺相比有着显著的优点：The synthesis method of benzoic acid under the catalysis of 9-thienone compound under the condition of light irradiation provided by the present invention has significant advantages compared with traditional thermochemical process:
第一，反应在室温条件下进行，与传统的加热生产工艺相比，能耗大为降低。First, the reaction is carried out at room temperature, which greatly reduces the energy consumption compared with the traditional heating production process.
第二，反应在无溶剂条件下进行，从而解决了传统工艺中由于采用醋酸做溶剂而带来的所有问题。大大降低了能耗，解决了废酸排放对环境的严重污染，大大降低了对设备的腐蚀性，从而可以采用不锈钢代替钛合金材料来制造反应釜，大大降低了设备制造成本。Second, the reaction is carried out under solvent-free conditions, thereby solving all the problems caused by using acetic acid as a solvent in the traditional process. It greatly reduces energy consumption, solves the serious pollution of waste acid discharge to the environment, and greatly reduces the corrosion of equipment, so that stainless steel can be used instead of titanium alloy materials to manufacture reactors, which greatly reduces equipment manufacturing costs.
第三，采用可见光催化剂而非重金属催化剂，从而彻底解决了传统工艺中由于采用过渡金属催化剂而造成的环境污染问题，以及产品中的重金属残留问题。这意味着，此法有可能直接用来生产食品甚至药品级的苯甲酸产品。这将大大降低食品药品级苯甲酸的生产成本。而且，催化剂成本较传统的甲苯热氧化法有所降低。Third, the use of visible light catalysts instead of heavy metal catalysts completely solves the problem of environmental pollution caused by the use of transition metal catalysts in traditional processes, as well as the problem of heavy metal residues in products. This means that this method may be directly used to produce food or even pharmaceutical grade benzoic acid products. This will greatly reduce the production cost of food and pharmaceutical grade benzoic acid. Moreover, the catalyst cost is lower than that of the traditional toluene thermal oxidation method.
第四，本发明采用空气作为氧化剂来源，进一步节约了成本。Fourth, the present invention uses air as the source of oxidant, further saving costs.
第五，本发明后处理简单易操作，不再涉及醋酸和水的分离以及重金属对环境的污染。所产生的废水中不含醋酸和重金属，可以方便地进行综合处理，而且光敏剂可以回收利用。Fifth, the post-treatment of the present invention is simple and easy to operate, and no longer involves the separation of acetic acid and water and the pollution of the environment by heavy metals. The generated waste water does not contain acetic acid and heavy metals, can be conveniently processed comprehensively, and the photosensitizer can be recycled.
第六，本发明所提供的苯甲酸的生产方法使用的原料单一，提高了工艺的经济性，并且甲苯的转化率超过99%，苯甲酸的收率超过97%。Sixth, the raw material used in the production method of benzoic acid provided by the present invention is single, which improves the economical efficiency of the process, and the conversion rate of toluene exceeds 99%, and the yield of benzoic acid exceeds 97%.
第七，本发明所提供的苯甲酸的生产方法采用可见光作为能源，无需热氧化，后处理设备简单，整体耗电量较现有氧化生产工艺降低50%以上。Seventh, the production method of benzoic acid provided by the present invention uses visible light as an energy source, does not require thermal oxidation, has simple post-processing equipment, and reduces overall power consumption by more than 50% compared with the existing oxidation production process.
第八，本发明所提供的苯甲酸的生产方法无需氧化反应塔，气提塔，精馏塔，可以采用不锈钢代替钛合金材料来制造反应釜，设备投资较传统的生产工艺降低30%以上。The 8th, the production method of benzoic acid provided by the present invention does not need oxidation reaction tower, stripping tower, rectifying tower, can adopt stainless steel to replace titanium alloy material to manufacture reactor, and equipment investment reduces more than 30% compared with traditional production technology.
第九，本发明所提供的苯甲酸的生产方法无需重金属催化剂，无需溶剂，无需氧化反应塔，无需气提塔，无需精馏塔，常温光照下即可进行，整体运营成本较传统生产工艺降低50%以上。Ninth, the production method of benzoic acid provided by the present invention does not need a heavy metal catalyst, does not need a solvent, does not need an oxidation reaction tower, does not need a stripping tower, does not need a rectifying tower, can be carried out under normal temperature and light, and the overall operating cost is lower than the traditional production process above 50.
总之，本项目将要发展的节能环保新技术，在环保上面将彻底解决重金属污染问题以及废酸污染问题；在产品品质上将有望应用此技术直接生产食品药品级的苯甲酸产品，从而大大提高产品的附加值。In short, the new technology of energy saving and environmental protection to be developed in this project will completely solve the problem of heavy metal pollution and waste acid pollution in terms of environmental protection; in terms of product quality, it is expected to apply this technology to directly produce food and pharmaceutical grade benzoic acid products, thereby greatly improving the product quality. added value.
附图说明Description of drawings
图1为苯甲酸核磁谱图。Fig. 1 is the NMR spectrum of benzoic acid.
具体实施方式Detailed ways
实施例1Example 1
在50 L的反应釜中加入9kg的甲苯，2%质量分数的光催化剂2-甲氧基-9-噻吩酮，在空气氛围中搅拌，25 ℃温度下，在4台800 W投光灯的照射下反应48 h。反应时间到达后，经高效液相色谱分析，只有单一的产物苯甲酸生成，甲苯转化率超过99%。反应混合物中加入氢氧化钠水溶液至PH为中性，乙酸乙酯萃取回收光敏剂，水层加入稀盐酸调至PH = 1-2，重结晶，真空干燥，核磁鉴定，产品质量为11.8kg，产率为99%。Add 9kg of toluene and 2% mass fraction of photocatalyst 2-methoxy-9-thienone into a 50 L reactor, stir in the air atmosphere, and at a temperature of 25 °C, under the conditions of four 800 W floodlights Reacted for 48 h under irradiation. After the reaction time was up, through high-performance liquid chromatography analysis, only a single product benzoic acid was generated, and the conversion rate of toluene exceeded 99%. Add aqueous sodium hydroxide solution to the reaction mixture until the pH is neutral, extract and recover the photosensitizer with ethyl acetate, add dilute hydrochloric acid to the aqueous layer to adjust to pH = 1-2, recrystallize, vacuum dry, NMR identification, the product quality is 11.8kg, The yield was 99%.
实施例2Example 2
在50 L的反应釜中加入9kg的甲苯，3%质量分数的光催化剂2-甲氧基-9-噻吩酮，在空气氛围中搅拌，25 ℃温度下，在4台800 W投光灯的照射下反应46h。反应时间到达后，经高效液相色谱分析，只有单一的产物苯甲酸生成，甲苯转化率超过99%。反应混合物中加入氢氧化钠水溶液至PH为中性，乙酸乙酯萃取回收光敏剂，水层加入稀盐酸调至PH = 1-2，重结晶，真空干燥，核磁鉴定，产品质量为11.8kg，产率为99%。Add 9kg of toluene and 3% mass fraction of photocatalyst 2-methoxy-9-thienone into a 50 L reactor, stir in the air atmosphere, and at a temperature of 25 °C, under the conditions of four 800 W floodlights Reaction under irradiation for 46h. After the reaction time was up, through high-performance liquid chromatography analysis, only a single product benzoic acid was generated, and the conversion rate of toluene exceeded 99%. Add aqueous sodium hydroxide solution to the reaction mixture until the pH is neutral, extract and recover the photosensitizer with ethyl acetate, add dilute hydrochloric acid to the aqueous layer to adjust to pH = 1-2, recrystallize, vacuum dry, NMR identification, the product quality is 11.8kg, The yield was 99%.
实施例3Example 3
在50 L的反应釜中加入9kg的甲苯，4%质量分数的光催化剂2-甲氧基-9-噻吩酮，在空气氛围中搅拌，25 ℃温度下，在4台800 W投光灯的照射下反应45h。反应时间到达后，经高效液相色谱分析，只有单一的产物苯甲酸生成，甲苯转化率超过99%。反应混合物中加入氢氧化钠水溶液至PH为中性，乙酸乙酯萃取回收光敏剂，水层加入稀盐酸调至PH = 1-2，重结晶，真空干燥，核磁鉴定，产品质量为11.8 kg，产率为99%。Add 9kg of toluene and 4% mass fraction of photocatalyst 2-methoxy-9-thienone into a 50 L reactor, stir in the air atmosphere, and at 25 °C, under four sets of 800 W floodlights Reaction under irradiation for 45h. After the reaction time was up, through high-performance liquid chromatography analysis, only a single product benzoic acid was generated, and the conversion rate of toluene exceeded 99%. Add aqueous sodium hydroxide solution to the reaction mixture until the pH is neutral, extract and recover the photosensitizer with ethyl acetate, add dilute hydrochloric acid to the aqueous layer to adjust to PH = 1-2, recrystallize, vacuum dry, NMR identification, the product quality is 11.8 kg, The yield was 99%.
实施例4Example 4
在50 L的反应釜中加入9kg的甲苯，5%质量分数的光催化剂2-甲氧基-9-噻吩酮，在空气氛围中搅拌，25 ℃温度下，在4台800 W投光灯的照射下反应40h。反应时间到达后，经高效液相色谱分析，只有单一的产物苯甲酸生成，甲苯转化率超过99%。反应混合物中加入氢氧化钠水溶液至PH为中性，乙酸乙酯萃取回收光敏剂，水层加入稀盐酸调至PH = 1-2，重结晶，真空干燥，核磁鉴定，产品质量为11.8kg，产率为99%。Add 9kg of toluene and 5% mass fraction of photocatalyst 2-methoxy-9-thienone into a 50 L reactor, stir in the air atmosphere, and at a temperature of 25 °C, under the conditions of four 800 W floodlights Reaction under irradiation for 40h. After the reaction time was up, through high-performance liquid chromatography analysis, only a single product benzoic acid was generated, and the conversion rate of toluene exceeded 99%. Add aqueous sodium hydroxide solution to the reaction mixture until the pH is neutral, extract and recover the photosensitizer with ethyl acetate, add dilute hydrochloric acid to the aqueous layer to adjust to pH = 1-2, recrystallize, vacuum dry, NMR identification, the product quality is 11.8kg, The yield was 99%.
实施例5Example 5
在50 L的反应釜中加入10kg的甲苯，3%质量分数的光催化剂2-甲氧基-9-噻吩酮，在空气氛围中搅拌，25 ℃温度下，在4台800 W投光灯的照射下反应48 h。反应时间到达后，经高效液相色谱分析，只有单一的产物苯甲酸生成，甲苯转化率超过99%。反应混合物中加入氢氧化钠水溶液至PH为中性，乙酸乙酯萃取回收光敏剂，水层加入稀盐酸调至PH = 1-2，重结晶，真空干燥，核磁鉴定，产品质量为13.1 kg，产率为99%。10kg of toluene and 3% mass fraction of photocatalyst 2-methoxy-9-thiophene were added to a 50 L reactor, stirred in the air atmosphere, and at a temperature of 25 °C, under four sets of 800 W floodlights Reacted for 48 h under irradiation. After the reaction time was up, through high-performance liquid chromatography analysis, only a single product benzoic acid was generated, and the conversion rate of toluene exceeded 99%. Add aqueous sodium hydroxide solution to the reaction mixture until the pH is neutral, extract and recover the photosensitizer with ethyl acetate, add dilute hydrochloric acid to the aqueous layer to adjust to pH = 1-2, recrystallize, vacuum dry, NMR identification, the product quality is 13.1 kg, The yield was 99%.
实施例6Example 6
在50 L的反应釜中加入10kg的甲苯，4%质量分数的光催化剂2-甲氧基-9-噻吩酮，在空气氛围中搅拌，25 ℃温度下，在4台800 W投光灯的照射下反应47h。反应时间到达后，经高效液相色谱分析，只有单一的产物苯甲酸生成，甲苯转化率超过99%。反应混合物中加入氢氧化钠水溶液至PH为中性，乙酸乙酯萃取回收光敏剂，水层加入稀盐酸调至PH = 1-2，重结晶，真空干燥，核磁鉴定，产品质量为13.1 kg，产率为99%。Add 10kg of toluene and 4% mass fraction of photocatalyst 2-methoxy-9-thienone into a 50 L reactor, stir in the air atmosphere, and at a temperature of 25 °C, under the conditions of four 800 W floodlights Reaction under irradiation for 47h. After the reaction time was up, through high-performance liquid chromatography analysis, only a single product benzoic acid was generated, and the conversion rate of toluene exceeded 99%. Add aqueous sodium hydroxide solution to the reaction mixture until the pH is neutral, extract and recover the photosensitizer with ethyl acetate, add dilute hydrochloric acid to the aqueous layer to adjust to pH = 1-2, recrystallize, vacuum dry, NMR identification, the product quality is 13.1 kg, The yield was 99%.
实施例7Example 7
在50 L的反应釜中加入10 kg的甲苯，5%质量分数的光催化剂2-甲氧基-9-噻吩酮，在空气氛围中搅拌，25 ℃温度下，在4台800 W投光灯的照射下反应45h。反应时间到达后，经高效液相色谱分析，只有单一的产物苯甲酸生成，甲苯转化率超过99%。反应混合物中加入氢氧化钠水溶液至PH为中性，乙酸乙酯萃取回收光敏剂，水层加入稀盐酸调至PH = 1-2，重结晶，真空干燥，核磁鉴定，产品质量为13.1kg，产率为99%。Add 10 kg of toluene and 5% mass fraction of photocatalyst 2-methoxy-9-thienone into a 50 L reactor, stir in the air atmosphere, and at 25 °C, under four 800 W floodlights Under the irradiation of the reaction for 45h. After the reaction time was up, through high-performance liquid chromatography analysis, only a single product benzoic acid was generated, and the conversion rate of toluene exceeded 99%. Add aqueous sodium hydroxide solution to the reaction mixture until the pH is neutral, extract and recover the photosensitizer with ethyl acetate, add dilute hydrochloric acid to the aqueous layer to adjust to PH = 1-2, recrystallize, vacuum dry, NMR identification, the product quality is 13.1kg, The yield was 99%.
实施例8Example 8
在50 L的反应釜中加入8kg的甲苯，3%质量分数的光催化剂2-甲氧基-9-噻吩酮，在空气氛围中搅拌，25 ℃温度下，在4台800 W投光灯的照射下反应45h。反应时间到达后，经高效液相色谱分析，只有单一的产物苯甲酸生成，甲苯转化率超过99%。反应混合物中加入氢氧化钠水溶液至PH为中性，乙酸乙酯萃取回收光敏剂，水层加入稀盐酸调至PH = 1-2，重结晶，真空干燥，核磁鉴定，产品质量为10.5 kg，产率为99%。Add 8 kg of toluene and 3% mass fraction of photocatalyst 2-methoxy-9-thienone into a 50 L reactor, stir in the air atmosphere, and at a temperature of 25 ° C, under four sets of 800 W floodlights Reaction under irradiation for 45h. After the reaction time was up, through high-performance liquid chromatography analysis, only a single product benzoic acid was generated, and the conversion rate of toluene exceeded 99%. Add aqueous sodium hydroxide solution to the reaction mixture until the pH is neutral, extract and recover the photosensitizer with ethyl acetate, add dilute hydrochloric acid to the aqueous layer to adjust to pH = 1-2, recrystallize, vacuum dry, NMR identification, the product quality is 10.5 kg, The yield was 99%.
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