CN110577467A - Synthetic method of 3-hydroxypropionic acid - Google Patents
Synthetic method of 3-hydroxypropionic acid Download PDFInfo
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- CN110577467A CN110577467A CN201910881585.5A CN201910881585A CN110577467A CN 110577467 A CN110577467 A CN 110577467A CN 201910881585 A CN201910881585 A CN 201910881585A CN 110577467 A CN110577467 A CN 110577467A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/16—Preparation of carboxylic acid nitriles by reaction of cyanides with lactones or compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/08—Preparation of carboxylic acids or their salts, halides or anhydrides from nitriles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
Abstract
The invention relates to the technical field of chemical industry, and particularly provides a synthetic method of 3-hydroxypropionic acid, which comprises the following steps: (1) under the action of a catalyst, hydrogen cyanide and ethylene oxide react to generate 3-hydroxypropionitrile; (2) adding acid into the 3-hydroxypropionitrile obtained in the step (1) for hydrolysis, and reacting to generate 3-hydroxypropionic acid and inorganic salt; (3) and (3) separating the reaction liquid obtained in the step (2) by electrodialysis to obtain 3-hydroxypropionic acid and an inorganic salt solution, and concentrating the obtained inorganic salt solution to obtain a byproduct. The method adopts electrodialysis to treat the 3-hydroxypropionitrile acid hydrolysis reaction liquid, can effectively reduce waste water, waste gas and waste residue, obtains a high-content target product with high yield, and reduces the production cost.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a synthetic method of 3-hydroxypropionic acid.
Background
3-hydroxypropionic acid (3-hydroxypropionic acid, abbreviated as 3-HP), has a molecular formula of C3H6O3, a molecular weight of 90.08, is an achiral organic acid having three carbon atoms, has an acid dissociation constant (pKa) of 4.5, is liquid, viscous, colorless and odorless, is soluble in water, ethanol and ether, and can be used for synthesizing various chemicals such as acrylic acid. 3-HP and lactic acid are isomers, but the molecule of 3-HP has two functional groups of hydroxyl and carboxyl, so the chemical property of 3-HP is more active. In industry, 3-HP has been widely used both as a monomer and as a raw material for synthesizing the corresponding derivatives, and for example, 3-HP can be converted into a variety of important chemical substances such as acrylic acid, 1, 3-propanediol, malonic acid, poly-3-HP, etc. through oxidation, hydrogenation, dehydration, esterification, etc.; 3-HP can be used as additive and antiseptic for food or feed; 3-HP is a precursor of many optically active substances and can be used as a monomer for polymers of biological origin. These excellent properties of 3-HP have made it commercially valuable for development and have received considerable attention from scientists in various countries. In 8 months 2004, the U.S. department of energy reported that 3-HP is listed as one of the 12 most potential chemical products currently in the world.
At present, chemical methods and microbial fermentation methods are used for preparing 3-HP. The microbial fermentation method has low yield and high separation cost, and is not beneficial to large-scale production. The chemical methods mainly comprise the following steps:
1. method for hydrating acrylic acid
The method is reported in the preparation and characterization of a high-temperature hydration method of 3-hydroxypropionic acid (Liuhuamei and the like, the chemical world, 2015, 2, 80-83), the reaction temperature is 215 ℃, the reaction is a reversible reaction, so the conversion rate is only 40.2%, and the product yield is very low. Reported in the research on resin catalysis acrylic acid hydration reaction kinetics (Wenlyu, etc., chemical and biological engineering, 2014, 31(10), 36-38), the product yield can be improved by adding acidic resin to catalyze acrylic acid hydration reaction, the reaction temperature is about 120 ℃, and the conversion rate can reach 60%; preparation of 3-hydroxypropionic acid by protonic acid-catalyzed hydration of acrylic acid (Wenlyu et al, chemical and biological engineering, 2013,30(1), 51-53) mention the use of phosphoric acid as catalyst in the preparation of V (acrylic acid): under the optimal conditions of 1: 5V (water), 120 ℃ reaction temperature, 0.6 pH value and 3h reaction time, the conversion rate of acrylic acid is 78.81 percent, and the selectivity of 3-hydroxypropionic acid is 92.38 percent. The processes of the two above-mentioned articles, although increasing the yield of 3-hydroxypropionic acid prepared by the acrylic acid hydration process, are not very high.
2. 3-hydroxypropanal (3-HPA) oxidation process
Thomas Haas et al, Germany, have studied the preparation of 3-hydroxypropionic acid by catalytic oxidation of 3-hydroxypropanal in O2Or is O2In the presence of platinum group metal such as Pd, Pt, pH is controlled at 7.5-9, temperature is controlled at 40-60 ℃, m (catalyst): m (3-HPA) ═ 1: 10-1: 5, the final 3-HPA conversion is between 80.5% and 92.7%, the 3-HP selectivity is between 89.5% and 93.7%, and the 3-pH yield increases with increasing catalyst usage. Although the method has high yield, the production process is complicated and the production cost is high.
3. 1, 3-propanediol oxidation process
The method takes 1, 3-propylene glycol as a raw material to obtain the 3-hydroxypropionic acid through catalytic oxidation. In the 90 s of the 20 th century, Arno Behr Duesseldorf et Al, in patent US5321156, described a specific synthesis method, in an aqueous solution of an alkali metal, with supported Pd as a catalyst (the carrier being activated carbon or Al)2O3) The temperature is 40-55 ℃, the pH is 8-12, and the yield of the obtained 3-hydroxypropionic acid is 70.5-81.8%. The product yield of the method is also not high.
4. Hydrolysis method of 3-hydroxypropionitrile
Adding 3-hydroxypropionitrile into a sodium hydroxide solution, reacting at 30 ℃, evaporating the reaction mixture to dryness under reduced pressure, and continuously raising the temperature until the product becomes pasty; cooling, adding sulfuric acid, stirring, extracting the generated 3-hydroxypropionic acid by using ether, and evaporating to remove the ether to obtain syrup-like 3-hydroxypropionic acid with the content of 75-80 percent, wherein the yield is 28-31 percent. The reaction has low yield and poor product quality, consumes a large amount of acid and alkali, and produces low-price inorganic salt as a by-product.
The chemical methods for preparing 3-hydroxypropionic acid all have the defects of complicated production process, low product yield, high energy consumption and the like, so that a more economical and effective method for preparing 3-hydroxypropionic acid is urgently needed.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention aims to provide a method for synthesizing 3-hydroxypropionic acid, which is used to solve the problems of complicated production process, low product yield, high energy consumption, etc. of the method for synthesizing 3-hydroxypropionic acid in the prior art.
In order to achieve the above objects and other related objects, the present invention provides a method for synthesizing 3-hydroxypropionic acid, comprising the steps of:
(1) Under the action of a catalyst, hydrogen cyanide and ethylene oxide react to generate 3-hydroxypropionitrile;
(2) Adding acid into the 3-hydroxypropionitrile obtained in the step (1) for hydrolysis, and reacting to generate 3-hydroxypropionic acid and inorganic salt;
(3) And (3) separating the reaction liquid obtained in the step (2) by electrodialysis to obtain inorganic salt and 3-hydroxypropionic acid, and concentrating the obtained inorganic salt solution to obtain a byproduct.
alternatively, in step (1), the molar ratio of hydrogen cyanide to ethylene oxide is (1.0-1.1):1, preferably (1.0-1.05): 1. A slight excess of hydrogen cyanide can complete the reaction of ethylene oxide.
Optionally, in the step (1), the hydrogen cyanide is selected from at least one of gaseous hydrocyanic acid, liquid hydrocyanic acid, and an aqueous hydrocyanic acid solution; liquid hydrocyanic acid or an aqueous hydrocyanic acid solution is preferred.
Optionally, in step (1), the catalyst is selected from at least one of organic base, cyanide, inorganic base or polybasic organic acid salt.
optionally, the organic base is selected from at least one of triethylamine and N, N-lutidine.
Optionally, the cyanide is selected from at least one of sodium cyanide and potassium cyanide.
Optionally, the inorganic base is at least one selected from strong inorganic bases and weak inorganic bases.
Optionally, the inorganic strong base is selected from at least one of sodium hydroxide and potassium hydroxide.
Optionally, the weak inorganic base is at least one selected from sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
Optionally, the polybasic organic acid salt is selected from at least one of tartaric acid, sodium or potassium citrate salt.
Alternatively, step (1) is carried out in the absence of a solvent, or in a solvent, preferably in the presence of a solvent. The solvent-free condition has the advantages of high reaction concentration and high yield, and the solvent condition has the advantages of mild and easily controlled reaction.
optionally, when step (1) is carried out in a solvent, the solvent is selected from water. As the hydrolysis reaction in step (2) requires addition of an aqueous solution of sodium hydroxide or potassium hydroxide, the solvent in step (1) is preferably water.
Alternatively, in step (2), the molar ratio of the acid to 3-hydroxypropionitrile is (1.0-1.5):1, preferably (1.0-1.1): 1. The molar ratio of the acid should theoretically be the same as that of 3-hydroxypropionitrile, but an excess of acid ensures complete reaction and an insufficient amount of acid results in incomplete hydrolysis reaction.
Optionally, in step (2), the acid is at least one of hydrochloric acid or sulfuric acid.
The reaction equation of the chemical reaction involved in the present invention is as follows:
As described above, the method for synthesizing 3-hydroxypropionic acid of the present invention has the following advantageous effects: the invention adopts electrodialysis to treat 3-hydroxypropionitrile acid hydrolysis reaction liquid to obtain electrodialysis treatment liquid, and the principle is as follows: when dialysis is performed under the action of an electric field, charged solute particles (such as ammonium sulfate and ammonium chloride) in the solution migrate through the membrane, while 3-hydroxypropionic acid which is difficult to ionize does not migrate, so that the separation of the 3-hydroxypropionic acid from inorganic salts generated by the hydrolysis reaction is realized.
The method effectively reduces waste water, waste gas and waste residue, obtains a high-content target product with high yield, and reduces the production cost.
Drawings
FIG. 1 shows a process flow diagram for the production of 3-hydroxypropionic acid in an example of the present invention.
FIG. 2 is a process flow diagram showing the separation of 3-hydroxypropionic acid and by-produced ammonium salt by electrodialysis in an example of the present invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The reagents used in the following examples are as follows:
Aqueous hydrocyanic acid solution: chongqing purple light International chemical industry Co., Ltd is ready for production and use; triethylamine: chengdu Kelong chemical and chemical reagent plant, AR; ethylene oxide: chengdu pure science and technology limited, AR; sodium citrate: chengdu Kelong chemical and chemical reagent plant, AR; hydrochloric acid: chengdu Kelong chemical and chemical reagent plant, AR; sulfuric acid: chengdu Kelong chemical and chemical reagent plant, AR.
FIG. 1 shows a process flow diagram for 3-hydroxypropionic acid in examples 1-3.
FIG. 2 is a process flow diagram showing the separation of 3-hydroxypropionic acid and by-produced ammonium salt by electrodialysis in examples 1 to 3.
Example 1
Adding 275g (2.04mol) of 20% hydrocyanic acid aqueous solution and 0.5g (catalyst) of triethylamine into a closed pressure-resistant cyanidation reaction kettle, keeping the temperature at 15-20 ℃, adding 88.9g (2.0mol) of ethylene oxide (99%), and reacting for 2 h; sampling and GC analysis shows that the content of ethylene oxide is less than 1 percent, stopping the reaction, adding 268.0g (2.2mol) of hydrochloric acid with the concentration of 30 percent into the reaction solution, heating to a boiling state for reaction for 4 hours after the addition is finished, sampling and HPLC analysis shows that the content of 3-hydroxypropionitrile (calculated by an area normalization method) is less than 1 percent, cooling, adding ammonia for neutralization until the pH value is 4.0-4.5, obtaining a mixed solution containing 3-hydroxypropionic acid and ammonium chloride, and then separating by electrodialysis to obtain an ammonium chloride solution and a 3-hydroxypropionic acid solution, wherein the specific process of electrodialysis separation is as follows: keeping the temperature of the obtained mixed solution containing the 3-hydroxypropionic acid and the ammonium chloride at 25 ℃, and enabling the mixed solution to enter a homogeneous membrane electrodialysis treatment system for desalination treatment, wherein the homogeneous membrane electrodialysis treatment system comprises three chambers, namely an electrode chamber, a feed chamber (dilute chamber) and a receiving chamber (concentrated chamber), and the ammonium chloride is transferred to the concentrated chamber in the desalination process, as shown in figure 2; when the ammonium chloride in the feed liquid chamber is reduced to 5%, the material in the feed liquid chamber is transferred to an out-phase membrane electrodialysis treatment system for deep desalination, and the ammonium chloride content in the feed liquid is lower than 1% after two times of electrodialysis desalination.
The 3-hydroxypropionic acid solution was concentrated by distillation under reduced pressure and crystallized to give 164.4g of a solid product having a content of 98.0% (measured by HPLC external standard method) and a yield of 89.5% (based on ethylene oxide) calculated by the following calculation method. Ammonium chloride solution is concentrated, cooled, crystallized and separated by a solid-liquid separator to obtain ammonium chloride solid and mother liquor, the mother liquor contains a small amount of products, and part of products can be recycled after the mother liquor is recycled to an electrodialysis procedure, so that the product yield is improved.
The yield of 3-hydroxypropionic acid was calculated as follows:
Example 2
Adding 275g (2.04mol) of hydrocyanic acid aqueous solution with the content of 20 percent and 0.5g (catalyst) of sodium cyanide into a closed pressure-resistant cyaniding reaction kettle, keeping the temperature at 15-20 ℃, adding 88.9g (2.0mol) of ethylene oxide (99 percent) into the reaction kettle, and reacting for 2 hours; when the content of ethylene oxide was less than 1% by sampling and GC analysis, the reaction was stopped, 274.4g (2.1mol) of 75% sulfuric acid was added to the reaction mixture, and after the addition was completed, the mixture was warmed to boiling for 4 hours, and the content of 3-hydroxypropionitrile (calculated by area normalization) was analyzed by sampling and HPLC to be less than 1%, and then the mixture was cooled, neutralized with ammonia until the pH became 4.0 to 4.5, and separated by electrodialysis (the process was similar to example 1), to obtain an ammonium sulfate solution and a 3-hydroxypropionic acid solution.
The 3-hydroxypropionic acid solution was concentrated by distillation under reduced pressure and crystallized to give 158.6g of a solid product having a content of 98.5% (measured by HPLC external standard method) and a yield of 86.8% (based on ethylene oxide) calculated by the calculation in example 1. The ammonium sulfate solution is concentrated, cooled, crystallized and separated by a solid-liquid separator to obtain ammonium sulfate solid and mother liquor, the mother liquor contains a small amount of products, and part of products can be recycled in the electrodialysis process, so that the product yield is improved.
Example 3
Adding 57.3g (2.1mol) of 99% liquid hydrocyanic acid and 1.0g (catalyst) of sodium citrate into a closed pressure-resistant cyanidation reaction kettle, keeping the temperature at 10-15 ℃, adding 88.9g (2.1mol) of ethylene oxide (99%) at constant speed, wherein the adding time is 1.0h, and continuing to react for 2h after the adding is finished; when the content of ethylene oxide was less than 1% by sampling GC analysis, the reaction was stopped, the reaction mixture was added to 30% hydrochloric acid (268g, 2.2mol), after the addition, the reaction mixture was heated to boiling for 4 hours, and the content of 3-hydroxypropionitrile (calculated by area normalization) was less than 1% by sampling HPLC analysis, and the mixture was separated by electrodialysis (similar to example 1) to obtain an ammonium chloride solution and a 3-hydroxypropionic acid solution.
The 3-hydroxypropionic acid solution was concentrated by distillation under reduced pressure and crystallized to give 156.1g of a solid product having a content of 98.8% (measured by HPLC external standard method) and a yield of 85.7% (based on ethylene oxide) calculated by the calculation in example 1. Ammonium chloride solution is concentrated, cooled, crystallized and separated by a solid-liquid separator to obtain ammonium chloride solid and mother liquor, the mother liquor contains a small amount of products, and part of products can be recycled after the mother liquor is recycled to an electrodialysis procedure, so that the product yield is improved.
In conclusion, the electrodialysis treatment liquid is obtained by treating the 3-hydroxypropionitrile acid hydrolysis reaction liquid through electrodialysis, so that the wastewater, waste gas and waste residues can be effectively reduced, the target product with high content can be obtained in high yield, and the production cost is reduced.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A method for synthesizing 3-hydroxypropionic acid is characterized by comprising the following steps: the method comprises the following steps:
(1) Under the action of a catalyst, hydrogen cyanide and ethylene oxide react to generate 3-hydroxypropionitrile;
(2) Adding acid into the 3-hydroxypropionitrile obtained in the step (1) for hydrolysis, and reacting to generate 3-hydroxypropionic acid and inorganic salt;
(3) And (3) separating the reaction liquid obtained in the step (2) by electrodialysis to obtain 3-hydroxypropionic acid and an inorganic salt solution, and concentrating the obtained inorganic salt solution to obtain a byproduct.
2. The method of synthesizing 3-hydroxypropionic acid as claimed in claim 1, wherein: in step (1), the molar ratio of hydrogen cyanide to ethylene oxide is (1.0-1.1):1, preferably (1.0-1.05): 1.
3. the method of synthesizing 3-hydroxypropionic acid as claimed in claim 1, wherein: in the step (1), the hydrogen cyanide is at least one selected from gaseous hydrocyanic acid, liquid hydrocyanic acid and aqueous hydrocyanic acid solution; liquid hydrocyanic acid or an aqueous hydrocyanic acid solution is preferred.
4. The method of synthesizing 3-hydroxypropionic acid as claimed in claim 1, wherein: in the step (1), the catalyst is at least one selected from organic base, cyanide, inorganic base or polybasic organic acid salt.
5. The method of synthesizing 3-hydroxypropionic acid according to claim 4, wherein: the organic base is at least one of triethylamine and N, N-dimethylpyridine;
And/or, the cyanide is selected from at least one of sodium cyanide and potassium cyanide;
And/or, the inorganic base is selected from at least one of inorganic strong base and inorganic weak base;
And/or the polybasic organic acid salt is selected from at least one of tartaric acid, sodium salt or potassium salt of citric acid.
6. The method of synthesizing 3-hydroxypropionic acid as claimed in claim 5, wherein: the inorganic strong base is at least one of sodium hydroxide and potassium hydroxide;
and/or the inorganic weak base is selected from at least one of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
7. the method of synthesizing 3-hydroxypropionic acid as claimed in claim 1, wherein: step (1) is carried out in the absence of a solvent or in a solvent, preferably in the absence of a solvent.
8. The method of synthesizing 3-hydroxypropionic acid as claimed in claim 7, wherein: when step (1) is carried out in a solvent, the solvent is water.
9. the method of synthesizing 3-hydroxypropionic acid as claimed in claim 1, wherein: in the step (2), the molar ratio of the acid to the 3-hydroxypropionitrile is (1.0-1.5):1, preferably (1.0-1.1): 1.
10. the method of synthesizing 3-hydroxypropionic acid as claimed in claim 1, wherein: in the step (2), the acid is at least one of hydrochloric acid or sulfuric acid.
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| CN111423321A (en) * | 2020-04-28 | 2020-07-17 | 南昌大学 | Green and efficient synthesis method of 3-hydroxypropionic acid |
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Application publication date: 20191217 |