CN106431885B - Method for synthesizing glyoxylic acid by ozonation of maleic anhydride mixed solvent - Google Patents
Method for synthesizing glyoxylic acid by ozonation of maleic anhydride mixed solvent Download PDFInfo
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Abstract
本发明涉及顺丁烯二酸酐混合溶剂臭氧化合成乙醛酸的方法，属于乙醛酸的制备技术领域。本发明解决的技术问题是提供低成本的顺丁烯二酸酐混合溶剂臭氧化合成乙醛酸的方法。该方法以廉价的顺丁烯二酸酐为原料，在混合溶剂中，通过水解、臭氧氧化、还原、减压蒸馏和结晶等步骤，最终得到乙醛酸固体。通过本发明方法，可以直接获得纯度较高的乙醛酸固体，产品品质用途广泛，且操作简单，乙醛酸收率高，实现了顺丁烯二酸酐向乙醛酸的廉价转化，可用于工业化大生产，为顺丁烯二酸酐过剩局面做出了一定的贡献。同时也刺激了传统乙醛酸生产工艺的优化和落后工艺的淘汰，采用绿色氧化剂，为环保做出巨大的贡献。The invention relates to a method for synthesizing glyoxylic acid by ozonation of a maleic anhydride mixed solvent, and belongs to the technical field of preparation of glyoxylic acid. The technical problem solved by the present invention is to provide a low-cost method for synthesizing glyoxylic acid by ozonation of a maleic anhydride mixed solvent. In the method, cheap maleic anhydride is used as a raw material, and the glyoxylic acid solid is finally obtained through the steps of hydrolysis, ozone oxidation, reduction, vacuum distillation and crystallization in a mixed solvent. The method of the invention can directly obtain the glyoxylic acid solid with higher purity, the product quality is widely used, the operation is simple, the glyoxylic acid yield is high, the cheap conversion of maleic anhydride to glyoxylic acid is realized, and the product can be used for Large-scale industrial production has made a certain contribution to the surplus situation of maleic anhydride. At the same time, it also stimulated the optimization of the traditional glyoxylic acid production process and the elimination of outdated processes, and the use of green oxidants has made a huge contribution to environmental protection.
Description
Technical Field
The invention relates to a method for synthesizing glyoxylic acid by ozonation of a maleic anhydride mixed solvent, belonging to the technical field of glyoxylic acid preparation.
Background
Glyoxylic acid is used as an important organic chemical intermediate raw material, and downstream products of glyoxylic acid are continuously developed in recent years, so that glyoxylic acid has a good market prospect. Glyoxylic acid can synthesize vanillin, 2-hydroxyquinoline, 2-hydroxyphosphonoacetic acid, D-p-hydroxyphenylglycine, allantoin and the like, and in recent years, with the rapid development and development of downstream products of glyoxylic acid, the market demand is continuously expanded. In particular, the demand for high-purity solid glyoxylic acid is getting larger and wider, and the application range is wider.
At present, the production method of glyoxylic acid mainly comprises an oxalic acid electrolytic reduction method, a glyoxal oxidation method, a glycolic acid selective oxidation method, a dibromoacetic acid hydrolysis method, a maleic anhydride ozonization method and the like. The oxalic acid electrolytic reduction method and the glyoxal oxidation method both realize industrial production, but the oxalic acid electrolytic reduction method mainly has the defects of low space-time yield of equipment and large amount of oxalic acid which is difficult to separate in the product. The glyoxal oxidation method is widely applied, and has the defects of large solvent loss, easy corrosion of equipment, low raw material yield, poor product quality and serious environmental pollution. The disadvantage of the glycolic acid selective oxidation method is that the synthesis cost is high, and the key is to obtain a high-selectivity catalyst. The reaction condition of the dibromo-acetic acid hydrolysis method is mild, but the separation of reaction products is difficult, the price of the used raw materials is high, and the yield and the quality of the product are not ideal. Therefore, a new process route with high production efficiency and small environmental pollution is found to have strong practical value for preparing the glyoxylic acid.
The maleic anhydride (short for maleic anhydride) yield in China and even in the whole world is in an excessive state, the national maleic anhydride production capacity in 2012 is about 130 ten thousand tons, the actual yield is 70.63 ten thousand tons, and the national maleic anhydride device annual production capacity in 2015 exceeds 170 ten thousand tons. With the continuous development of modern science and technology, the rapid development of the petrochemical industry will further promote the excess of the yield of maleic anhydride, and the maleic anhydride ozonization method can adopt cheaper maleic anhydride as the raw material, and simultaneously solves the problem of excess of the yield of maleic anhydride, so that the method is favored by domestic and foreign scholars and becomes a research hotspot in the field.
The maleic anhydride ozone oxidation process is most and earliest studied abroad, and in 1964, Thompson et al ozonize butyl maleate at-40 ℃ and then rapidly reduce the butyl maleate with hypophosphorous acid ester at low temperature to obtain butyl glyoxylate with the yield of 78.9%. In 1972, Arashiba et al dissolved maleic anhydride and maleic anhydride derivatives in methanol or formic acid, introduced ozone diluted with oxygen, ozonized at a temperature below 10 ℃, purged excess ozone with nitrogen after completion of the reaction, then added antioxidant and platinum catalyst for hydrogenation reduction to produce glyoxylic acid hemiacetal, separated and hydrolyzed, and distilled under reduced pressure to remove excess solvent, and finally the product was obtained with the highest yield of glyoxylic acid up to 93%. In the same year Callighan et al dissolved maleic anhydride in ethyl acetate, reacted at 5 ℃ and then passed over with SO2Reducing, adding calcium oxide or calcium carbonate to precipitate sulfate ion, and distilling under reduced pressureRemoving excessive solvent, crystallizing at 10 deg.C to obtain crystalline glyoxylic acid with the highest yield up to 99.5%.
The domestic research on preparing glyoxylic acid by an ozonization method mainly comprises the following steps: the Xinjiang physicochemical technology research institute of the Chinese academy uses maleic acid ozone to continuously oxidize glyoxal, avoids expensive hydrogenation catalysts, has mild reaction conditions, saves raw materials, has no pollution to the environment, and is beneficial to large-scale industrial production; by taking maleic anhydride as a raw material and water as a solvent, the peletima, Wangqingjun and the like at Qingdao university of science and technology prepare the crystalline glyoxylic acid by using an ozone oxidation method in a laboratory, and cooperate with the Qingdao national forest industry, namely, the Limited liability company, a set of pilot-scale test device for preparing the crystalline glyoxylic acid by using the ozone oxidation method is built, and pilot-scale test research is carried out. The result shows that the whole process is simple, does not need other catalysts and reducing agents, has high product purity and few byproducts, and has wide application prospect in producing the glyoxylic acid by the maleic anhydride ozonization method. By taking solid acid as a catalyst, the shangxi coal chemical research institute of Chinese academy of sciences Gaojie et al firstly synthesize maleic acid ester from maleic anhydride and methanol, then ozonize the maleic acid ester, perform catalytic hydrogenation reduction and hydrolyze to obtain high-purity glyoxylic acid, and provide an optimization process adopting a plurality of reactors to perform reaction in series by combining the characteristic of an ozone oxidation process.
The above researches are laboratory researches, and industrial large-scale production is not formed yet. At present, two main methods for industrial production are established:
firstly, maleic anhydride is dissolved in water, ozone is introduced into a bubble reactor for ozonization reaction, the reaction temperature is adjusted to be proper, after the reaction end point is reached, the reaction liquid is subjected to reduced pressure suction filtration under 16kPa to remove formic acid, water and other impurities, and finally crystallization is carried out at 2 ℃ to obtain the crystal glyoxylic acid. The method has higher requirements on the ozone generator, difficult control of reaction engineering and higher energy consumption. At present, only the Linz company of Austria worldwide adopts the production method for production, and no enterprise adopts the production method at home.
Secondly, dissolving maleic anhydride in methanol or formic acid, introducing ozone diluted by oxygen, and reacting at the temperature below 10 ℃. Then the ozonide is decomposed by adopting a catalytic hydrogenation or zinc powder reduction mode, a hydrogenation catalyst or zinc slag is separated, hydrolysis is carried out, and an excessive solvent is evaporated to obtain a finished product. The method has the advantages of high requirements on an ozone generating device, high equipment investment, high energy consumption, strong dependence of yield on a hydrogenation catalyst, need of an expensive hydrogenation catalyst and high production cost.
Disclosure of Invention
Aiming at the defects, the technical problem solved by the invention is to provide a low-cost method for synthesizing glyoxylic acid by ozonizing a maleic anhydride mixed solvent, wherein the method is simple and easy to control, and the glyoxylic acid with higher price and large market demand is produced by using maleic anhydride with wide raw material sources and low price.
The invention relates to a method for synthesizing glyoxylic acid by ozonation of a maleic anhydride mixed solvent, which comprises the following steps:
a. hydrolysis: mixing maleic anhydride, water and a mixed solvent for hydrolysis, wherein the hydrolysis temperature is 55-70 ℃, the hydrolysis time is 30-70 min, and a hydrolysis product is obtained, wherein each mole of maleic anhydride is mixed with 20-30 mL of water and 50-150 mL of the mixed solvent;
b. ozone oxidation: adding a mixed solvent into the hydrolysate, and then introducing ozone to carry out oxidation reaction at the reaction temperature of 0-5 ℃ for 2-3.5 h; obtaining an ozonide, wherein the adding amount of the mixed solvent is 0.5-1.5 times of the using amount of the mixed solvent in the step a;
c. reduction: dropwise adding ozonide into a sulfurous acid solution, continuously reacting for 30-50 min after dropwise adding, cooling, adding CaO, then adding distilled water, controlling the temperature below 10 ℃, standing, and filtering to obtain filtrate;
d. and (3) reduced pressure distillation: carrying out reduced pressure distillation on the filtrate, controlling the final temperature to be 45-75 ℃ and the pressure to be 3.5-10 kPa;
e. and (3) crystallization: crystallizing the solution after reduced pressure distillation at 0-5 ℃ for 2-3 days to obtain glyoxylic acid solid;
the mixed solvent is a mixture of methanol and an organic solvent I, wherein the volume ratio of the methanol to the organic solvent I is 1: 1-3; the organic solvent I is ethyl acetate, butyl acetate, n-hexane, cyclohexane or trichloromethane.
Further, it is preferable that the organic solvent i is ethyl acetate.
Among them, methanol and ethyl acetate are preferred in a volume ratio of 1: 2.
Preferably, in the step a, the hydrolysis temperature is 65 ℃ and the hydrolysis time is 50 min.
Preferably, in step a, 25mL of water and 75mL of mixed solvent are mixed for each mole of maleic anhydride.
Preferably, in the step b, the reaction temperature is 5 ℃, the reaction time is 3 hours, and the adding amount of the mixed solvent is the using amount of the mixed solvent in the step a.
In the step c, the concentration of the sulfurous acid solution is preferably 5-12 wt%; more preferably, the concentration of the sulfurous acid solution is 8 wt%.
Further, the ratio of sulfurous acid in step c: the ratio of maleic anhydride in the step a is 0.8-1.2: 1; preferably, the ratio of sulfurous acid in step c: and (b) maleic anhydride in the step a is 1: 1.
Preferably, in the step d, the final temperature is controlled to be 50-60 ℃ and the pressure is 4.7 kPa.
Further, it is preferable that the solvent distilled under reduced pressure in the step d is used as the mixed solvent in the step a.
Compared with the prior art, the invention has the following beneficial effects:
1) the method adopts maleic acid as a raw material, has simple process, realizes the cheap conversion of maleic anhydride to glyoxylic acid, can be used for industrial mass production, and makes a certain contribution to the situation of maleic anhydride excess. Meanwhile, the optimization of the traditional glyoxylic acid production process and the elimination of the laggard process are stimulated, and a green oxidant is also adopted, so that the method makes a great contribution to environmental protection.
2) The method adopts the mixed solvent during the hydrolysis of the maleic anhydride, can realize low-temperature hydrolysis, and has short hydrolysis time.
3) The method of the invention can directly obtain the crystal glyoxylic acid instead of the glyoxylic acid solution, and the product quality and the application are wide.
4) The maleic anhydride has high mass fraction in the mixed solvent, greatly improves the yield and reduces the cost of single preparation.
5) In the invention, a part of mixed solvent is added in the hydrolysis stage, and a certain amount of solvent is supplemented in the ozonization stage, so that a good mass transfer effect is always kept. Meanwhile, the yield of the solid glyoxylic acid obtained by production is high, and the purity is high.
Detailed Description
The invention relates to a method for synthesizing glyoxylic acid by ozonation of a maleic anhydride mixed solvent, which comprises the following steps:
a. hydrolysis: mixing maleic anhydride, water and a mixed solvent for hydrolysis, wherein the hydrolysis temperature is 55-70 ℃, the hydrolysis time is 30-70 min, and a hydrolysis product is obtained, wherein each mole of maleic anhydride is mixed with 20-30 mL of water and 50-150 mL of the mixed solvent; the adding sequence is not required during mixing, and the method of mixing water and the mixed solvent firstly and then adding maleic anhydride, or adding maleic anhydride into water firstly and then adding the mixed solvent is feasible;
b. ozone oxidation: adding a mixed solvent into the hydrolysate, and then introducing ozone to carry out oxidation reaction at the reaction temperature of 0-5 ℃ for 2-3.5 h; obtaining an ozonide, wherein the adding amount of the mixed solvent is 0.5-1.5 times of the using amount of the mixed solvent in the step a;
c. reduction: dropwise adding ozonide into a sulfurous acid solution, continuously reacting for 30-50 min after dropwise adding, cooling, slowly adding CaO, then adding distilled water, controlling the temperature below 10 ℃, standing, adding calcium oxide, and filtering to obtain filtrate;
d. and (3) reduced pressure distillation: carrying out reduced pressure distillation on the filtrate, controlling the final temperature to be 45-75 ℃ and the pressure to be 3.5-10 kPa;
e. and (3) crystallization: crystallizing the solution after reduced pressure distillation at 0-5 ℃ for 2-3 days to obtain glyoxylic acid solid;
the mixed solvent is a mixture of methanol and an organic solvent I, wherein the volume ratio of the methanol to the organic solvent I is 1: 1-3; the organic solvent I is ethyl acetate, butyl acetate, n-hexane, cyclohexane or trichloromethane.
In order to improve the reaction yield, the organic solvent I is preferably ethyl acetate.
The volume ratio of methanol to ethyl acetate is preferably 1: 2. experimental research shows that the volume ratio of methanol to ethyl acetate is 1:2 as the reaction solvent, the yield of glyoxylic acid after the reaction is the highest.
The invention adopts a methanol, ethyl acetate and distilled water three-solvent system, which is beneficial to the dispersion of gas and the absorption of ozone, and when a mixed solvent of polar solvent methanol and non-polar solvent ethyl acetate is adopted, the reaction liquid always keeps homogeneous phase during the reaction, so that the mass transfer effect is good, the reaction yield is high, and the by-product is less. The glyoxylic acid monohydrate is readily formed when the water addition is primarily an ozone intermediate reduction.
Each step is described in detail below.
Step a is a hydrolysis stage of maleic anhydride.
In the step a, the maleic anhydride is hydrolyzed by adopting a mixed solvent, so that low-temperature hydrolysis can be realized, and the hydrolysis time can be shortened. The optimal hydrolysis temperature is 55-70 ℃, and the hydrolysis time is 30-70 min; more preferably, the hydrolysis temperature is 65 ℃ and the hydrolysis time is 50 min.
Preferably, 25mL of water and 75mL of mixed solvent are mixed with each mole of maleic anhydride; at this time, the mass fraction of maleic anhydride exceeds 50%, which can improve the yield and reduce the dosage of organic solvent.
a certain amount of water is added in the step a, so that maleic anhydride can be hydrolyzed, and glyoxylic acid monohydrate can be easily formed during the subsequent reduction of an ozone intermediate.
Step b is an ozone oxidation stage.
The ozone oxidation in the step b is the core stage of the reaction of the invention, a bubble reactor can be adopted for ozonization, and ozone is blown from the bottom of the maleic acid solution (namely the hydrolysate in the step a), so that the ozone and the solution can be fully contacted, and the sufficient contact time is provided, thereby being beneficial to the reaction. After a period of reaction, a small amount of reaction liquid can be taken from the reactor into a small test tube, 5% bromine carbon tetrachloride solution is dripped, the color change of the liquid in the test tube is observed, and the reaction is finished when the bromine water begins to fade.
The amount of the mixed solvent added in the step b has an influence on the reaction yield. The larger the amount of the solvent, the lower the concentration of the maleic acid, the lower the viscosity of the reaction liquid, the better the mass transfer effect, and the possibility of self-polymerization reaction is reduced when the ozonide is oxidized and decomposed, and the amount of the ozonide taken away due to the loss of the solvent is also reduced. However, the amount of the solvent used is too large, the amount of the product is reduced, the utilization rate of equipment is reduced, and the load and the cost of solvent recovery are increased, so that the amount of the mixed solvent added in the step b is preferably the same as that in the step a.
In a preferred embodiment of the present invention, 1mol of maleic acid is preferably hydrolyzed by adding 25mL of water +25mL of methanol +50mL of ethyl acetate, and after the hydrolysis is completed, 25mL of methanol +50mL of ethyl acetate are supplemented for ozone oxidation.
And (c) regarding the reaction temperature in the step b, the diffusion effect of ozone is poor in a lower range, the reaction is mainly controlled by diffusion, and in a higher range of the reaction temperature, the ozone activity is stronger, so that the product is easily oxidized to generate oxalic acid, and the product yield is low. At too high a temperature, the product crystals are slightly yellowish and may be contaminated with small amounts of decomposition products. Therefore, the reaction temperature is preferably controlled to 0 to 5 ℃. The preferred reaction temperature is 5 deg.C, at which time the crystalline color of the product obtained is better.
The reaction time of the step b is related to the reaction progress degree, the reaction degree is nearly complete along with the increase of the reaction time, the overoxidation of the product can be caused by the overlong reaction time, the theoretically calculated reaction time is 2.5h, but the actual utilization of ozone cannot reach 100%, so the theoretical reaction time is properly prolonged, the reaction time is too short, the raw materials cannot be completely reacted, and the reaction yield is reduced and the raw materials are wasted. Therefore, the reaction time is preferably 2 to 3.5 hours, and more preferably 3 hours.
The step c is mainly a reduction stage.
At the end of the ozone oxidation stage, some glyoxylic acid is produced and some primary ozonides are produced, which ozonides are reduced using sulfurous acid as reducing agent in order to increase the yield. Introducing air to discharge residual ozone in a reaction system, adding the ozone into a certain amount of sulfurous acid with a certain concentration (the adding amount of the sulfurous acid is just negative in a potassium iodide starch test), wherein the reduction process is a strong heat release process, the temperature of the system is controlled to be 55-65 ℃, after the sulfurous acid is completely added, a certain amount of CaO is slowly added, then 5mL of water is added, the temperature is controlled to be below 10 ℃, standing the solution to precipitate the solution, and filtering to remove the CaSO4Precipitation gave a pale yellow solution. CaO is added mainly for removing sulfate radicals, and the adding amount of CaO can be obtained by theoretical calculation according to the using amount of sulfurous acid.
In the step c, the yield of the dropwise adding method of the ozonide into the sulfurous acid solution is obviously higher than that of the dropwise adding method of the sulfurous acid solution into the ozonide. This is because the reaction is performed by a dropwise addition method in which a sulfurous acid solution is added dropwise to an ozonide, and at the beginning of the reaction, the amount of the reducing agent is small, the polar solvent is not diluted, the concentration is high, and acetal is easily formed. And the reaction of dripping ozonide into the sulfurous acid solution is adopted, so that the defect is avoided. The reductive decomposition reaction is always carried out in the condition that the polar solvent is maximally diluted and the reducing agent is excessive, so that the formation of acetal is greatly inhibited, and the reaction yield is improved. Therefore, the present invention adopts a dropping manner of dropping the ozonide into the sulfurous acid solution.
Preferably, in the step c, the concentration of the sulfurous acid solution is 5-12 wt%; the concentration of the sulfurous acid solution is preferably 8 wt%.
In the method of the present invention, sulfurous acid in step c: and (a) maleic anhydride in the step (a) is 0.8-1.2: 1. The reaction yield is also influenced by the dosage of the reducing agent, and the reaction yield is increased along with the dosage of the reducing agent, when the molar ratio of the dosage of the reducing agent to the dosage of the maleic acid reaches 1: when 1 hour, the yield can reach 96.8 percent; and then, the dosage of the reducing agent is increased, so that the yield is not changed greatly. This is probably because when the amount of the reducing agent used is small, the amount of the reducing agent is insufficient and the reaction is incomplete; when the dosage reaches the molar ratio of 1:1, the reaction proceeds sufficiently, and the yield increases. But the dosage is more than 1:1, the reaction proceeds sufficiently, so that the yield is hardly affected. Therefore, the ratio of sulfurous acid in the step c: and (b) maleic anhydride in the step a is 1: 1.
In the reduction reaction, the reaction yield does not change greatly with the temperature within the range of 55-65 ℃. The reaction yield increases with the time of the reduction reaction, and when the reaction time is 20min, the reaction yield is 73.2%, and when the reaction time reaches 40min, the reaction yield is almost unchanged after the time is prolonged. Therefore, the preferred reaction temperature in step c is 60 ℃ and the reaction time is 40 min.
And d, a reduced pressure distillation stage.
The conventional vacuum distillation equipment is suitable for the invention.
Preferably, the final temperature of the step d is controlled to be 50-60 ℃ and the pressure is 4.7 kPa.
As an embodiment, the following specific operations may be employed: and c, transferring the filtrate obtained by filtering in the step c to a three-neck flask, adding a plurality of grains of zeolite, carrying out reduced pressure distillation under the water bath heating condition of 55 ℃, controlling the pressure to be 4.7kPa, constantly observing the temperature of the solution, controlling the temperature to be not more than 55 ℃, stopping heating and stopping a vacuum device when the temperature of the solution is constant, and recording the final temperature of the reduced pressure distillation.
In order to save cost, the solvent distilled under reduced pressure in the step d can be used as the mixed solvent in the step a. The method for synthesizing glyoxylic acid by ozonation of the maleic anhydride mixed solvent can realize solvent recovery and reuse, the yield of the generated formic acid is not influenced, the formic acid can be continuously used, and the formic acid can be further concentrated to be used as a byproduct after the concentration of the formic acid exceeds a certain value.
Step e is a crystallization stage.
And when the reduced pressure distillation is finished, cooling and crystallizing the residual solution, wherein the temperature is controlled to be 0-5 ℃, and the time is 2-3 days. The preferred time is 3 days.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
a. Firstly, 19.6120g of maleic anhydride is melted in a hydrolysis reactor, water bath heating is adopted, 5mL of distilled water, 5mL of methanol and 10mL of ethyl acetate are added for hydrolysis reaction, the hydrolysis temperature is 65 ℃, and the hydrolysis time is 50 min.
b. And after the hydrolysis is finished, moving the hydrolysate into a self-made bubble reactor, supplementing a mixed solvent of 5mL of methanol and 10mL of ethyl acetate, carrying out ozonization, blowing ozone from the bottom of the maleic acid solution to ensure that the ozone and the solution can be fully contacted, and controlling the reaction temperature to be 5 ℃ and the reaction time to be 3 hours.
c. And when the ozone oxidation stage is finished, stopping introducing the ozone, and continuously introducing air for 10min to purge residual ozone in the system.
d. And slowly adding the reacted solution into 8% sulfurous acid solution, and controlling the temperature of the system at 55-65 ℃.
e. After all the CaO was added, an amount of CaO was slowly added, followed by 5mL of water, and the temperature was controlled to 10 ℃ or lower, and then the solution was allowed to stand to precipitate, and CaSO was removed by filtration4Precipitation gave a pale yellow solution.
f. Transferring the filtered solution to a three-neck flask, adding several grains of zeolite, distilling under reduced pressure under the water bath heating condition of 55 ℃, controlling the pressure at 4.7kPa, constantly observing the temperature of the solution, controlling the temperature not to exceed 55 ℃, and stopping heating when the temperature of the solution is constant. And (d) returning the distilled formic acid and the mixed solvent to the step (a) for reuse.
g. At the end of the reduced pressure distillation, the remaining solution was crystallized by cooling at 5 ℃ for 3 days.
h. The glyoxylic acid product is detected, the melting point of the product is 52.5 ℃, the yield is 98.3 percent, and the purity of the product is 98 percent by liquid chromatography analysis.
Example 2
a. Firstly, 19.6120g of maleic anhydride is melted in a hydrolysis reactor, water bath heating is adopted, 5mL of distilled water, 5mL of methanol and 10mL of n-hexane three-solvent are added for hydrolysis reaction, the hydrolysis temperature is 60 ℃, and the hydrolysis time is 60 min.
b. And after the hydrolysis is finished, moving the hydrolysate into a self-made bubble reactor, supplementing a mixed solvent of 7.5mL of methanol and 15mL of n-hexane, carrying out ozonization, blowing ozone from the bottom of the maleic acid solution to ensure that the ozone and the solution can be fully contacted, and controlling the reaction temperature to be 0 ℃ and the reaction time to be 2.5 hours.
c. And when the ozone oxidation stage is finished, stopping introducing the ozone, and continuously introducing air for 10min to purge residual ozone in the system.
d. Slowly adding the reacted solution into 8% sulfurous acid solution, and controlling the temperature of the system at 55-65 ℃.
e. After all the CaO was added, an amount of CaO was slowly added, followed by 5mL of water, and the temperature was controlled to 20 ℃ or lower, and then the solution was allowed to stand to precipitate, and CaSO was removed by filtration4Precipitation gave a pale yellow solution.
f. Transferring the filtered solution to a three-neck flask, adding several grains of zeolite, carrying out reduced pressure distillation under the water bath heating condition of 50 ℃, controlling the pressure at 5kPa, constantly observing the temperature of the solution, controlling the temperature not to exceed 50 ℃, and stopping heating when the temperature of the solution is constant. And (d) returning the distilled formic acid and the mixed solvent to the step (a) for reuse.
g. And (3) cooling and crystallizing the residual solution at 0-5 ℃ for 3 days after the reduced pressure distillation is finished.
h. The glyoxylic acid product is detected, the melting point of the product is 51.8 ℃, the yield is 94.3 percent, and the purity of the product is 94.6 percent by liquid chromatography analysis.
Example 3
a. Firstly, 19.6120g of maleic anhydride is melted in a hydrolysis reactor, water bath heating is adopted, 5mL of distilled water, 5mL of methanol and 10mL of ethyl acetate are added for hydrolysis reaction, the hydrolysis temperature is 65 ℃, and the hydrolysis time is 30 min.
b. And after the hydrolysis is finished, moving the hydrolysate into a self-made bubble reactor, supplementing a mixed solvent of 5mL of methanol and 10mL of ethyl acetate, carrying out ozonization, blowing ozone from the bottom of the maleic acid solution to ensure that the ozone and the solution can be fully contacted, and controlling the reaction temperature to be 5 ℃ and the reaction time to be 2.5 h.
c. And when the ozone oxidation stage is finished, stopping introducing the ozone, and continuously introducing air for 10min to purge residual ozone in the system.
d. And slowly adding the reacted solution into a 10% sulfurous acid solution, and controlling the temperature of the system to be 55-65 ℃.
e. After all the CaO was added, an amount of CaO was slowly added, followed by 5mL of water, and the temperature was controlled to 20 ℃ or lower, and then the solution was allowed to stand to precipitate, and CaSO was removed by filtration4Precipitation gave a pale yellow solution.
f. Transferring the filtered solution to a three-neck flask, adding several grains of zeolite, carrying out reduced pressure distillation under the water bath heating condition of 50 ℃, controlling the pressure at 5kPa, constantly observing the temperature of the solution, controlling the temperature not to exceed 50 ℃, and stopping heating when the temperature of the solution is constant. And (d) returning the distilled formic acid and the mixed solvent to the step (a) for reuse.
g. And when the reduced pressure distillation is finished, cooling and crystallizing the residual solution, wherein the temperature is controlled to be 0-5 ℃, and the time is 3 days.
h. The glyoxylic acid product is detected, the melting point of the product is 51.2 ℃, the yield is 95.3 percent, and the purity of the product is 96.8 percent through liquid chromatography analysis.
Example 4
a. Firstly, 19.6120g of maleic anhydride is melted in a hydrolysis reactor, water bath heating is adopted, 6mL of distilled water, 5mL of methanol and 10mL of ethyl acetate are added for hydrolysis reaction, the hydrolysis temperature is 55 ℃, and the hydrolysis time is 60 min.
b. And after the hydrolysis is finished, moving the hydrolysate into a self-made bubble reactor, supplementing a mixed solvent of 5mL of methanol and 10mL of ethyl acetate, carrying out ozonization, blowing ozone from the bottom of the maleic acid solution to ensure that the ozone and the solution can be fully contacted, and controlling the reaction temperature to be 3 ℃ and the reaction time to be 3.5 h.
c. And when the ozone oxidation stage is finished, stopping introducing the ozone, and continuously introducing air for 10min to purge residual ozone in the system.
d. And slowly adding the reacted solution into 8% sulfurous acid solution, and controlling the temperature of the system at 55-65 ℃.
e. After all the CaO was added, a certain amount of CaO was slowly added, 4mL of water was then added, the temperature was controlled to 20 ℃ or lower, and then the solution was allowed to stand to precipitate, and CaSO was removed by filtration4Precipitation gave a pale yellow solution.
f. Transferring the filtered solution to a three-neck flask, adding several grains of zeolite, carrying out reduced pressure distillation under the water bath heating condition of 75 ℃, controlling the pressure at 10kPa, constantly observing the temperature of the solution, controlling the temperature not to exceed 75 ℃, and stopping heating when the temperature of the solution is constant. And (d) returning the distilled formic acid and the mixed solvent to the step (a) for reuse.
g. And when the reduced pressure distillation is finished, cooling and crystallizing the residual solution, wherein the temperature is controlled to be 0-5 ℃, and the time is 2 days.
h. The glyoxylic acid product is detected, the melting point of the product is 52.2 ℃, the yield is 94.3 percent, and the purity of the product is 94.8 percent through liquid chromatography analysis.
Comparative example 1
a. Firstly, 19.6120g of maleic anhydride is melted in a hydrolysis reactor, water bath heating is adopted, 5mL of distilled water and 15mL of methanol are added for hydrolysis reaction, the hydrolysis temperature is 65 ℃, and the hydrolysis time is 60 min.
b. And after the hydrolysis is finished, moving the hydrolysate into a self-made bubble reactor, supplementing 15mL of methanol, carrying out ozonization, blowing ozone from the bottom of the maleic acid solution to ensure that the ozone can be fully contacted with the solution, and controlling the reaction temperature to be 5 ℃ and the reaction time to be 3 hours.
c. And when the ozone oxidation stage is finished, stopping introducing the ozone, and continuously introducing air for 10min to purge residual ozone in the system.
d. And slowly adding the reacted solution into 8% sulfurous acid solution, and controlling the temperature of the system at 55-65 ℃.
e、After all the CaO was added, an amount of CaO was slowly added, followed by 5mL of water, and the temperature was controlled to 10 ℃ or lower, and then the solution was allowed to stand to precipitate, and CaSO was removed by filtration4Precipitation gave a pale yellow solution.
f. Transferring the filtered solution to a three-neck flask, adding several grains of zeolite, distilling under reduced pressure under the water bath heating condition of 55 ℃, controlling the pressure at 4.7kPa, constantly observing the temperature of the solution, controlling the temperature not to exceed 55 ℃, and stopping heating when the temperature of the solution is constant. And (d) returning the distilled formic acid and the mixed solvent to the step (a) for reuse.
g. At the end of the reduced pressure distillation, the remaining solution was crystallized by cooling at 5 ℃ for 3 days.
h. The glyoxylic acid product is detected, the melting point of the product is 52.6 ℃, the yield is 92.3 percent, and the purity of the product is 93 percent by liquid chromatography analysis.
Comparative example 2
a. Firstly, 19.6120g of maleic anhydride is melted in a hydrolysis reactor, water bath heating is adopted, 5mL of distilled water and 15mL of ethyl acetate are added for hydrolysis reaction, the hydrolysis temperature is 65 ℃, and the hydrolysis time is 60 min.
b. And after the hydrolysis is finished, moving the hydrolysate into a self-made bubble reactor, supplementing 15mL of ethyl acetate, carrying out ozonization, blowing ozone from the bottom of the maleic acid solution to ensure that the ozone can be fully contacted with the solution, and controlling the reaction temperature to be 5 ℃ and the reaction time to be 3 hours.
c. And when the ozone oxidation stage is finished, stopping introducing the ozone, and continuously introducing air for 10min to purge residual ozone in the system.
d. And slowly adding the reacted solution into 8% sulfurous acid solution, and controlling the temperature of the system at 55-65 ℃.
e. After all the CaO was added, an amount of CaO was slowly added, followed by 5mL of water, and the temperature was controlled to 10 ℃ or lower, and then the solution was allowed to stand to precipitate, and CaSO was removed by filtration4Precipitation gave a pale yellow solution.
f. Transferring the filtered solution to a three-neck flask, adding several grains of zeolite, distilling under reduced pressure under the water bath heating condition of 55 ℃, controlling the pressure at 4.7kPa, constantly observing the temperature of the solution, controlling the temperature not to exceed 55 ℃, and stopping heating when the temperature of the solution is constant. And (d) returning the distilled formic acid and the mixed solvent to the step (a) for reuse.
g. At the end of the reduced pressure distillation, the remaining solution was crystallized by cooling at 5 ℃ for 3 days.
h. The glyoxylic acid product is detected, the melting point of the product is 52.4 ℃, the yield is 92.8 percent, and the purity of the product is 93.8 percent through liquid chromatography analysis.
Claims (10)
1. The method for synthesizing the glyoxylic acid by ozonation of the maleic anhydride mixed solvent is characterized by comprising the following steps of:
a. hydrolysis: mixing maleic anhydride, water and a mixed solvent for hydrolysis, wherein the hydrolysis temperature is 55-70 ℃, the hydrolysis time is 30-70 min, and a hydrolysis product is obtained, wherein each mole of maleic anhydride is mixed with 20-30 mL of water and 50-150 mL of the mixed solvent;
b. ozone oxidation: adding a mixed solvent into the hydrolysate, and then introducing ozone to carry out oxidation reaction at the reaction temperature of 0-5 ℃ for 2-3.5 h; obtaining an ozonide, wherein the adding amount of the mixed solvent is 0.5-1.5 times of the using amount of the mixed solvent in the step a;
c. reduction: dropwise adding ozonide into a sulfurous acid solution, continuously reacting for 30-50 min after dropwise adding, cooling, adding CaO, then adding distilled water, controlling the temperature below 10 ℃, standing, and filtering to obtain filtrate;
d. and (3) reduced pressure distillation: carrying out reduced pressure distillation on the filtrate, controlling the final temperature to be 45-75 ℃ and the pressure to be 3.5-10 kPa;
e. and (3) crystallization: crystallizing the solution after reduced pressure distillation at 0-5 ℃ for 2-3 days to obtain glyoxylic acid solid;
the mixed solvent is a mixture of methanol and ethyl acetate, and the volume ratio of the methanol to the ethyl acetate is 1: 2.
2. The method for synthesizing glyoxylic acid by ozonation of a mixed maleic anhydride solvent according to claim 1, wherein the reaction is carried out by the following steps: in the step a, the hydrolysis temperature is 65 ℃, and the hydrolysis time is 50 min.
3. The method for synthesizing glyoxylic acid by ozonation of a mixed maleic anhydride solvent according to claim 1, wherein the reaction is carried out by the following steps: in the step a, 25mL of water and 75mL of mixed solvent are mixed with each mole of maleic anhydride.
4. The method for synthesizing glyoxylic acid by ozonation of a mixed maleic anhydride solvent according to claim 1, wherein the reaction is carried out by the following steps: in the step b, the reaction temperature is 5 ℃, the reaction time is 3 hours, and the adding amount of the mixed solvent is the using amount of the mixed solvent in the step a.
5. The method for synthesizing glyoxylic acid by ozonation of a mixed maleic anhydride solvent according to claim 1, wherein the reaction is carried out by the following steps: in the step c, the concentration of the sulfurous acid solution is 5-12 wt%.
6. The method for synthesizing glyoxylic acid by ozonation of a mixed maleic anhydride solvent according to claim 5, wherein the reaction conditions are as follows: the concentration of the sulfurous acid solution is 8 wt%.
7. The method for synthesizing glyoxylic acid by ozonation of a mixed maleic anhydride solvent according to claim 5 or 6, wherein the reaction conditions are as follows: molar ratio, sulfurous acid in step c: and (a) maleic anhydride in the step (a) is 0.8-1.2: 1.
8. The method for synthesizing glyoxylic acid by ozonation of a mixed maleic anhydride solvent according to claim 7, wherein the reaction conditions are as follows: molar ratio, sulfurous acid in step c: and (b) maleic anhydride in the step a is 1: 1.
9. The method for synthesizing glyoxylic acid by ozonation of a mixed maleic anhydride solvent according to claim 1, wherein the reaction is carried out by the following steps: and d, controlling the final temperature to be 50-60 ℃ and the pressure to be 4.7 kPa.
10. The method for synthesizing glyoxylic acid by ozonation of a mixed maleic anhydride solvent according to claim 1, wherein the reaction is carried out by the following steps: the solvent distilled off under reduced pressure in the step d is used as the mixed solvent in the step a.
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