CN107805196A - A kind of synthetic method of benzoic acid of the visible ray according under - Google Patents
A kind of synthetic method of benzoic acid of the visible ray according under Download PDFInfo
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- CN107805196A CN107805196A CN201711023215.5A CN201711023215A CN107805196A CN 107805196 A CN107805196 A CN 107805196A CN 201711023215 A CN201711023215 A CN 201711023215A CN 107805196 A CN107805196 A CN 107805196A
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000005711 Benzoic acid Substances 0.000 title claims abstract description 42
- 235000010233 benzoic acid Nutrition 0.000 title claims abstract description 42
- 238000010189 synthetic method Methods 0.000 title claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 150000008366 benzophenones Chemical class 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- CKGKXGQVRVAKEA-UHFFFAOYSA-N (2-methylphenyl)-phenylmethanone Chemical group CC1=CC=CC=C1C(=O)C1=CC=CC=C1 CKGKXGQVRVAKEA-UHFFFAOYSA-N 0.000 claims description 11
- 229910052724 xenon Inorganic materials 0.000 claims description 10
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 10
- -1 benzophenone compound Chemical class 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 12
- 239000003504 photosensitizing agent Substances 0.000 abstract description 10
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 235000019249 food preservative Nutrition 0.000 description 1
- 239000005452 food preservative Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于化工技术领域，具体为一种可见光照下的苯甲酸的合成方法。本发明方法包括：以甲苯为原料，二苯甲酮类化合物为催化剂，无需溶剂，室温、空气条件下，在可见光照射下40‑48h，即可高效的实现甲苯氧化生成苯甲酸。本发明方法在室温和无溶剂的条件下进行甲苯的光氧化法制备苯甲酸，从而实现了对甲苯氧化法制备苯甲酸的现行生产工艺进行优化及改造。本发明采用可见光光敏剂作为催化剂，降低了成本。本发明能够大幅降低能耗，并彻底解决由重金属和醋酸溶剂带来的废弃物排放污染环境的问题和产品中重金属残留的问题，节能环保。本发明方法与传统的生产工艺相比较，整体耗电量，设备投资以及整体运营成本大大降低。
The invention belongs to the technical field of chemical industry, in particular to a method for synthesizing benzoic acid under visible light. The method of the invention comprises: using toluene as a raw material, benzophenone compounds as catalysts, and without solvent, under room temperature and air conditions, and under visible light irradiation for 40-48 hours, toluene can be efficiently oxidized to generate benzoic acid. The method of the invention prepares benzoic acid by photooxidizing toluene under room temperature and solvent-free conditions, thereby realizing the optimization and transformation of the current production process for preparing benzoic acid by toluene oxidation. The invention adopts the visible light photosensitizer as the catalyst, which reduces the cost. The invention can greatly reduce energy consumption, and thoroughly solve the problems of waste discharge and environmental pollution caused by heavy metals and acetic acid solvents and the problems of heavy metal residues in products, and is energy-saving and environment-friendly. Compared with the traditional production process, the method of the invention can greatly reduce the overall power consumption, equipment investment and overall operation cost.
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：。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: . Slightly soluble in water, easily soluble in organic solvents such as ethanol and ether.
苯甲酸主要用于抗真菌及消毒防腐，用于医药、染料载体、增塑剂、香料和食品防腐剂等的生产，也用于醇酸树脂涂料的性能改进，也作为钢铁设备的防锈剂、农业化学品。Benzoic acid is mainly used for antifungal, disinfection and anticorrosion, in the production of medicines, dye carriers, plasticizers, spices and food preservatives, as well as in the performance improvement of alkyd resin coatings, and as an antirust agent for steel equipment , Agricultural chemicals.
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 traditional method of oxidizing toluene to generate benzoic acid has become increasingly unacceptable.
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、大幅降低能耗的可见光照下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 under the visible light that can reduce environmental pollution, greatly reduce energy consumption.
本发明所提供的可见光照下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，二苯甲酮类化合物为催化剂，无需溶剂，室温（10-40℃）、空气条件下，在可见光照射下反应40-48h，即可高效的实现甲苯氧化生成苯甲酸。The synthesis method of benzoic acid under visible light provided by the present invention adopts the method of organic photochemistry, specifically, toluene is used as a raw material, benzophenone compounds are used as catalysts, no solvent is needed, at room temperature (10-40° C.) and under air conditions , reacting for 40-48h under visible light irradiation, can efficiently realize the oxidation of toluene to generate benzoic acid.
本发明所提供的一种可见光照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。A synthetic method of benzoic acid under visible light provided by the present invention is characterized in that the synthetic method can realize a scale-up reaction of 5-10 kg level.
优选的，本发明中，所述的二苯甲酮类化合物催化剂为2-甲基二苯甲酮，结构式为：。Preferably, in the present invention, the described benzophenone compound catalyst is 2-methylbenzophenone, and its structural formula is: .
优选的，本发明中，所述的二苯甲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 benzophenone compounds is 1-5% of the mass fraction of toluene.
优选的，本发明中，所所述的可见光照为2台1500 W氙灯光源。Preferably, in the present invention, the visible light is two 1500 W xenon light sources.
本发明提供的可见光照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 synthesis method of benzoic acid under visible light provided by the invention can realize scale-up reaction of 5-10 kg level.
本发明d原理在于：2-甲基二苯甲酮在可见光的照射下由基态变为激发态，从而活化催化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 that 2-methylbenzophenone changes from a ground state to an excited state under the irradiation of visible light, thereby activating and catalyzing toluene to remove a hydrogen atom, generating a corresponding benzyl radical intermediate, and then benzyl radical intermediate Radical radicals are oxidized to benzaldehyde under the oxidation of air, and benzaldehyde is further oxidized by air to generate benzoic acid.
本发明提供的可见光照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 synthetic method of benzoic acid under the visible light provided by the 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-甲基二苯甲酮，在空气氛围中搅拌，25 ℃温度下，在2台1500 W氙灯光源的照射下反应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11.7 kg，产率为98%。Add 9kg of toluene and 2% mass fraction of photocatalyst 2-methylbenzophenone into a 50 L reactor, stir in the air atmosphere, and react under the irradiation of two 1500 W xenon light sources at a temperature of 25 °C 48 h. 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 11.7 kg, The yield was 98%.
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-甲基二苯甲酮，在空气氛围中搅拌，25 ℃温度下，在2台1500 W氙灯光源的照射下反应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-methylbenzophenone into a 50 L reactor, stir in the air atmosphere, and react under the irradiation of two 1500 W xenon light sources at a temperature of 25 °C 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-甲基二苯甲酮，在空气氛围中搅拌，25 ℃温度下，在2台1500 W氙灯光源的照射下反应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11.7 kg，产率为98%。Add 9kg of toluene and 4% mass fraction of photocatalyst 2-methylbenzophenone into a 50 L reactor, stir in the air atmosphere, and react under the irradiation of two 1500 W xenon light sources at a temperature of 25 °C 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 11.7 kg, The yield was 98%.
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-甲基二苯甲酮，在空气氛围中搅拌，25 ℃温度下，在2台1500 W氙灯光源的照射下反应42h。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11.7 kg，产率为98%。Add 9kg of toluene and 5% mass fraction of photocatalyst 2-methylbenzophenone into a 50 L reactor, stir in the air atmosphere, and react under the irradiation of two 1500 W xenon light sources at a temperature of 25 °C 42h. 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 11.7 kg, The yield was 98%.
实施例5Example 5
在50 L的反应釜中加入10kg的甲苯，2%质量分数的光催化剂2-甲基二苯甲酮，在空气氛围中搅拌，25 ℃温度下，在2台1500 W氙灯光源的照射下反应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%。Add 10kg of toluene and 2% mass fraction of photocatalyst 2-methylbenzophenone into a 50 L reactor, stir in the air atmosphere, and react under the irradiation of two 1500 W xenon light sources at a temperature of 25 °C 48 h. 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-甲基二苯甲酮，在空气氛围中搅拌，25 ℃温度下，在2台1500 W氙灯光源的照射下反应43h。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13.0 kg，产率为98%。Add 10kg of toluene and 4% mass fraction of photocatalyst 2-methylbenzophenone into a 50 L reactor, stir in the air atmosphere, and react under the irradiation of two 1500 W xenon light sources at a temperature of 25 °C 43h. 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 13.0 kg, The yield was 98%.
实施例7Example 7
在50 L的反应釜中加入8 kg的甲苯，3%质量分数的光催化剂2-甲基二苯甲酮，在空气氛围中搅拌，25 ℃温度下，在2台1500 W氙灯光源的照射下反应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10.5 kg，产率为99%。Add 8 kg of toluene and 3% mass fraction of photocatalyst 2-methylbenzophenone into a 50 L reactor, stir in the air atmosphere, and at a temperature of 25 °C, under the irradiation of two 1500 W xenon light sources Reaction 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 10.5 kg, The yield was 99%.
实施例8Example 8
在50 L的反应釜中加入8kg的甲苯，2%质量分数的光催化剂2-甲基二苯甲酮，在空气氛围中搅拌，25 ℃温度下，在2台1500 W氙灯光源的照射下反应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10.4 kg，产率为98%。Add 8kg of toluene and 2% mass fraction of photocatalyst 2-methylbenzophenone into a 50 L reactor, stir in the air atmosphere, and react under the irradiation of two 1500 W xenon light sources at a temperature of 25 °C 48 h. 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 10.4 kg, The yield was 98%.
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