CN110498740A - A method of producing 3- hydracrylic acid - Google Patents
A method of producing 3- hydracrylic acid Download PDFInfo
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- CN110498740A CN110498740A CN201910881013.7A CN201910881013A CN110498740A CN 110498740 A CN110498740 A CN 110498740A CN 201910881013 A CN201910881013 A CN 201910881013A CN 110498740 A CN110498740 A CN 110498740A
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- acid
- hydracrylic
- hydracrylic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid 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
- C07C51/08—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
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
Abstract
The present invention relates to chemical technology fields, specifically provide a kind of method for producing 3- hydracrylic acid, include the following steps: (1) under the action of catalyst, and hydrogen cyanide and reacting ethylene oxide generate 3- hydroxypropionitrile；(2) acid hydrolysis into 3- hydroxypropionitrile obtained by step (1), reaction generate 3- hydracrylic acid and inorganic salts；(3) the isolated 3- hydracrylic acid of reaction solution continuous chromatography obtained by step (2) and inorganic salt solution, resulting inorganic salt solution are concentrated to get by-product.The present invention handles 3- hydroxypropionitrile acid hydrolytic reaction liquid using continuous chromatography, can effectively reduce waste water and gas and waste residue, obtains the target product of high-content in high yield, reduces production cost.
Description
Technical field
The present invention relates to chemical fields, more particularly to a kind of method for producing 3- hydracrylic acid.
Background technique
3- hydracrylic acid (3-hydroxypropionic acid, write a Chinese character in simplified form 3-HP), molecular formula C3H6O3, molecular weight are
90.08, it is a kind of tool there are three the achirality organic acid of carbon atom, acid ionization constant (pKa) is 4.5, is in a liquid state, and is had glutinous
Property, colorless and odorless, water-soluble, ethyl alcohol, ether can be used for the synthesis of the multi-chemicals such as acrylic acid.3-HP and lactic acid are
Isomer, but there are two functional group's hydroxyl and carboxyls for the molecular band of 3-HP, therefore the chemical property of 3-HP is more active.In
Industrially, no matter as monomer, or as the raw material of synthesis corresponding derivative, the application of 3-HP is all very extensive, for example, 3-
HP can be converted into a variety of important chemical substances through oxidation, hydrogenation, dehydration, esterification etc., such as acrylic acid, 1,3- the third two
Alcohol, malonic acid, poly- 3-HP etc.；3-HP can be used as the additive and preservative of food or feed；3-HP is many optical active matters
The precursor of matter, can be as the monomer of biological source polymer.These good characteristics of 3-HP make it commercially and have great
Development volue, thus the extensive concern by scientists from all over the world.3-HP is classified as currently by August, 2004, U.S. Department of Energy report
One of the chemical products of 12 kinds of most potentialities to be exploited in the world.
Currently, the preparation method of 3-HP has chemical method and microbial fermentation processes.Microbe fermentation method low output, separation
It is at high cost, it is unfavorable for being mass produced.Chemical method mainly include the following types:
1, acrylic acid hydration method
This method " preparation and characterization of 3- hydracrylic acid hydration at high temperature " (Liu Huanmei etc., chemistry world, 2015,2,
It is had been reported that in 80-83), reaction temperature is 215 DEG C, because reaction is reversible reaction, conversion ratio only has 40.2%, product
Yield is very low." researchs of resin catalysis acrylic acid hydration kinetics " (Wen Liyuan etc., chemistry and bioengineering, 2014,
31 (10), 36-38) in report, acrylic acid hydration reaction can be catalyzed by Plus acidic resin to improve product yield, reaction temperature
Degree is at 120 DEG C or so, and conversion ratio is up to 60%；" Protic Acid Catalyzed acrylic acid hydration preparation 3- hydracrylic acid " (Wen Liyuan etc. changes
Learn and bioengineering, 2013,30 (1), 51-53) in mention, using phosphoric acid as catalyst, at V (acrylic acid): V (water)=1:5, anti-
Under the optimum condition that answer temperature be 120 DEG C, pH value 0.6, reaction time are 3h, the conversion ratio of acrylic acid is 78.81%, 3- hydroxyl
The selectivity of base propionic acid is 92.38%.Although method in above-mentioned two articles improves acrylic acid hydration method preparation 3- hydroxyl
The yield of propionic acid, but yield is not still very high.
2,3-HPA (3-HPA) oxidizing process
The Thomas Haas et al. of Germany, which has studied 3-HPA catalysis oxidation, can prepare 3- hydracrylic acid, this is anti-
It should be in O2Either O2In gaseous mixture, in platinum group metal in the presence of such as Pd, Pt, pH is controlled in 7.5-9, and temperature is at 40-60 DEG C
Under, carried out in m (catalyst): m (3-HPA)=1:10-1:5, the conversion ratio of final 3-HPA in 80.5%-92.7%, 3-HP's
Selective 89.5%-93.7%, and increase with catalyst amount, 3-PH yield will increase.Although this method high income,
Complex production process, high production cost.
3,1,3-PD oxidizing process
This method is to aoxidize to obtain 3- hydracrylic acid as catalytic material using 1,3-PD.In the 1990s, Arno
Behr Duesseldorf etc. describes specific synthetic method in patent US5321156, in the aqueous solution of alkali metal, with negative
The Pd of load type is that (carrier is active carbon or Al to catalyst2O3), temperature is 40-55 DEG C, and pH is in 8~12 ranges, obtained 3- hydroxyl
Base propionic acid yield is 70.5%~81.8%.The product yield of this method is not also high.
4,3- hydroxypropionitrile Hydrolyze method
This method is that 3- hydroxypropionitrile is added in sodium hydroxide solution, is reacted at 30 DEG C, and reaction mixture is evaporated under reduced pressure
To doing, continue to increase temperature until product becomes paste；It is cooling, add sulfuric acid to stir, the 3- hydracrylic acid generated with extracted by ether,
Ether is evaporated off, obtains the syrupy shape 3- hydracrylic acid of content 75%~80%, yield 28%~31%.The reaction yield is low, product
It is of poor quality, but also a large amount of bronsted lowry acids and bases bronsted lowry can be consumed, and the inorganic salts of by-product low price.
The above-mentioned chemical method for being used to prepare 3- hydracrylic acid has that complex production process, product yield are low and energy consumption is high
The defects of, therefore, need to propose a kind of more economical and effective method for preparing 3- hydracrylic acid.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of sides for producing 3- hydracrylic acid
Method, for solving to produce the method complex production process of 3- hydracrylic acid, product yield are low and energy consumption is high etc. in the prior art
Problem.
In order to achieve the above objects and other related objects, the present invention provides a kind of method for producing 3- hydracrylic acid, including
Following steps:
(1) under the action of catalyst, hydrogen cyanide and reacting ethylene oxide generate 3- hydroxypropionitrile；
(2) acid hydrolysis into 3- hydroxypropionitrile obtained by step (1), reaction generate 3- hydracrylic acid and inorganic salts；
(3) resulting inorganic by the isolated inorganic salts of reaction solution continuous chromatography obtained by step (2) and 3- hydracrylic acid
Salting liquid is concentrated to get by-product.
Optionally, in step (1), the molar ratio of the hydrogen cyanide and ethylene oxide is (1.0-1.1): 1, preferably
(1.0-1.05):1.Micro- excessive hydrogen cyanide can make reacting ethylene oxide complete.
Optionally, in step (2), the molar ratio of the acid and 3- hydroxypropionitrile is (1.0-1.5): 1, preferably (1.0-
1.1):1.Theoretically acid should be identical with the molar ratio of 3- hydroxypropionitrile, but excessive acid can guarantee fully reacting, and acid amount is insufficient
It is incomplete to will lead to hydrolysis.Optionally, in step (1), the hydrogen cyanide is selected from gas hydrogen cyanide, liquid hydrogen cyanide, hydrogen
At least one of cyanic acid aqueous solution；Preferably liquid hydrogen cyanide or hydrocyanic acid aqueous solution.
Optionally, in step (1), the catalyst is in organic base, cyanide, inorganic base or multicomponent organic acid salt
It is at least one.
Optionally, the organic base is selected from triethylamine, N, at least one of N- lutidines.
Optionally, the cyanide is selected from least one of Cymag, potassium cyanide.
Optionally, the inorganic base is selected from least one of inorganic strong alkali, inorganic weak bases.
Optionally, the inorganic strong alkali is selected from least one of sodium hydroxide, potassium hydroxide.
Optionally, the inorganic weak bases are selected from least one of sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus.
Optionally, the multicomponent organic acid salt is selected from at least one of tartaric acid, sodium citrate salt or sylvite.
Optionally, step (1) carries out under solvent-free conditions, or carries out in a solvent, preferably in the case where there is solvent condition into
Row.Condition of no solvent is advantageous in that reaction density height, and production capacity is big, has solvent condition to be advantageous in that reaction is mild easy to control.
Optionally, when step (1) carries out in a solvent, the solvent is water.Since the hydrolysis of step (2) will be added
Sodium hydroxide or potassium hydroxide aqueous solution, therefore the solvent in step (1) preferably selects water.
Optionally, in step (2), the acid is at least one of hydrochloric acid or sulfuric acid.
Optionally, in step (3), the chromatograph packing material that continuous chromatography separation uses is selected from sodium form, potassium type, ammonium type or calcium type
One of chromatographic isolation resin is a variety of.
Optionally, in step (3), the temperature of continuous chromatography separation is 20~80 DEG C, preferably 20~50 DEG C.
The reaction equation of chemical reaction according to the present invention is as follows:
As described above, the method for production 3- hydracrylic acid of the invention, has the advantages that the present invention using continuous
Chromatography 3- hydroxypropionitrile acid hydrolytic reaction liquid, obtains continuous chromatography treatment fluid, principle is: based on 3- hydracrylic acid with
By-product inorganic salts (ammonium sulfate, ammonium chloride) are different with the distribution coefficient of mobile phase in stationary phase and separated.
The present invention effectively reduces waste water and gas and waste residue, obtains the target product of high-content in high yield, reduces and be produced into
This.
Detailed description of the invention
Fig. 1 is shown as synthesizing the process flow chart of 3- hydracrylic acid in the embodiment of the present invention.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
The reagent used in following embodiment is as follows:
Hydrocyanic acid aqueous solution: Chongqing purple light world chemical inc produces and uses；Triethylamine: Chengdu section Long Huagong
Chemical reagent factory, AR；Ethylene oxide: Chengdu Dian Chun Science and Technology Ltd., AR；Sodium citrate: Chengdu section dragon chemical industry chemical reagent
Factory, AR；Hydrochloric acid: dragon chemical industry chemical reagent factory, Chengdu section, AR；Sulfuric acid: dragon chemical industry chemical reagent factory, Chengdu section, AR.
Fig. 1 is shown as the synthetic schemes of the 3- hydracrylic acid in embodiment 1-3.
Embodiment 1
20% hydrocyanic acid aqueous solution 275g (2.04mol) and triethylamine are added into the cyanogenation kettle of closed pressure resistant
0.5g (catalyst) maintains the temperature at 15-20 DEG C of addition ethylene oxide (99%) 88.9g (2.0mol), reacts 2h；Sample GC points
Analysis display ethylene oxide content stops reaction, 30% hydrochloric acid 268.0g (2.2mol) is added to reaction solution, adds less than 1%
After be warming up to boiling reaction 4h, sampling HPLC analysis 3- hydroxypropionitrile content (being calculated using area normalization method) is cold less than 1%
But, ammonification is neutralized to pH=4.0-4.5, separates (stationary phase: ammonium type ion exchange resin with continuous chromatography；Mobile phase:
0.008mol/LHCl solution；Flow velocity: 16mL/min；Column temperature: 25 DEG C) obtain ammonium chloride solution and 3- hydracrylic acid solution.
The vacuum distillation of 3- hydracrylic acid solution is concentrated, is crystallized, obtains solid product 163.4g, content 98.1% (uses
HPLC external standard method), yield is calculated using calculation set forth below, is 89.0% (in terms of ethylene oxide).Ammonium chloride
Solution is concentrated, crystallisation by cooling, chloride solid and mother liquor is obtained after solid-liquid separator separates, and contains a small amount of production in mother liquor
Portioned product can be recycled in product, reuse to continuous chromatography process, improves product yield.
The yield calculation of 3- hydracrylic acid:
Embodiment 2
Hydrocyanic acid aqueous solution 275g (2.04mol) and the cyaniding of content 20% are added into the cyanogenation kettle of closed pressure resistant
Sodium 0.5g (catalyst) maintains the temperature at 15-20 DEG C of addition ethylene oxide (99%) 88.9g (2.0mol), reacts 2h；Sample GC
Analysis shows that stopping reaction when ethylene oxide content is less than 1%, 75% sulfuric acid 274.4g (2.1mol) is added to reaction solution,
Be warming up to boiling reaction 4h after adding, sampling HPLC analysis 3- hydroxypropionitrile content (being calculated using area normalization method) less than 1%,
Cooling, ammonification is neutralized to pH=4.0-4.5, separates (stationary phase: ammonium type ion exchange resin with continuous chromatography；Mobile phase: water；
Flow velocity: 15mL/min；Column temperature: 25 DEG C), obtain ammonium sulfate and 3- hydracrylic acid solution.
The vacuum distillation of 3- hydracrylic acid solution is concentrated, is crystallized, obtains solid product 157.5g, content 98.3% (uses
HPLC external standard method), yield is calculated using the calculation in embodiment 1, is 86.0% (in terms of ethylene oxide).Ammonium sulfate
Solution is concentrated, crystallisation by cooling, ammonium sulfate solids and mother liquor is obtained after solid-liquid separator separates, and contains a small amount of production in mother liquor
Portioned product can be recycled in product, reuse to continuous chromatography process, improves product yield.
Embodiment 3
99% liquid hydrogen cyanide 57.3g (2.1mol) and sodium citrate are added into the cyanogenation kettle of closed pressure resistant
1.0g (catalyst) maintains the temperature at 10-15 DEG C and ethylene oxide (99%) 88.9g (2.1mol), feed time is at the uniform velocity added
1.0h, the reaction was continued 2h after adding；GC is sampled analysis shows that when ethylene oxide content is less than 1%, stops reaction, by reaction solution plus
Enter in 30% hydrochloric acid (268g, 2.2mol), boiling reaction 4h is warming up to after adding, sampling HPLC analyzes 3- hydroxypropionitrile content
(being calculated using area normalization method) separates (stationary phase: ammonium type ion exchange resin less than 1%, with continuous chromatography；Mobile phase:
0.008mol/LHCl solution；Flow velocity: 16mL/min；Column temperature: 25 DEG C), obtain ammonium chloride solution and 3- hydracrylic acid solution.
The vacuum distillation of 3- hydracrylic acid solution is concentrated, is crystallized, obtains solid product 153.7g, content 98.6% (uses
HPLC external standard method), yield is calculated using the calculation in embodiment 1, is 84.2% (in terms of ethylene oxide).Ammonium chloride
Solution is concentrated, crystallisation by cooling, chloride solid and mother liquor is obtained after solid-liquid separator separates, and contains a small amount of production in mother liquor
Portioned product can be recycled in product, reuse to continuous chromatography process, improves product yield.
In conclusion the present invention handles 3- hydroxypropionitrile acid hydrolytic reaction liquid using continuous chromatography, obtain at continuous chromatography
Liquid is managed, waste water and gas and waste residue can be effectively reduced, obtains the target product of high-content in high yield, reduces production cost.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
1. a kind of method for producing 3- hydracrylic acid characterized by comprising include the following steps:
(1) under the action of catalyst, hydrogen cyanide and reacting ethylene oxide generate 3- hydroxypropionitrile；
(2) acid hydrolysis into 3- hydroxypropionitrile obtained by step (1), reaction generate 3- hydracrylic acid and inorganic salts；
(3) resulting inorganic by the isolated 3- hydracrylic acid of reaction solution continuous chromatography obtained by step (2) and inorganic salt solution
Salting liquid is concentrated to get by-product.
2. the method for production 3- hydracrylic acid according to claim 1, it is characterised in that: in step (1), the hydrogen cyanide
Molar ratio with ethylene oxide is (1.0-1.1): 1, preferably (1.0-1.05): 1；
And/or in step (2), the molar ratio of the acid and 3- hydroxypropionitrile is (1.0-1.5): 1, preferably (1.0-1.1):
1。
3. the method for production 3- hydracrylic acid according to claim 1, it is characterised in that: in step (1), the hydrogen cyanide
Selected from least one of gas hydrogen cyanide, liquid hydrogen cyanide, hydrocyanic acid aqueous solution；Preferably liquid hydrogen cyanide or hydrogen cyanide water
Solution.
4. the method for production 3- hydracrylic acid according to claim 1, it is characterised in that: in step (1), the catalyst
Selected from least one of organic base, cyanide, inorganic base or multicomponent organic acid salt.
5. the method for production 3- hydracrylic acid according to claim 4, it is characterised in that: the organic base is selected from three second
Amine, N, at least one of N- lutidines；
And/or the cyanide is selected from least one of Cymag, potassium cyanide；
And/or the inorganic base is selected from least one of inorganic strong alkali, inorganic weak bases；
And/or the multicomponent organic acid salt is selected from at least one of tartaric acid, sodium citrate salt or sylvite.
6. the method for production 3- hydracrylic acid according to claim 5, it is characterised in that: the inorganic strong alkali is selected from hydrogen-oxygen
Change at least one of sodium, potassium hydroxide；
And/or the inorganic weak bases are selected from least one of sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus.
7. the method for production 3- hydracrylic acid according to claim 1, it is characterised in that: step (1) is in condition of no solvent
Lower progress, or carry out in a solvent, preferably carried out in the case where there is solvent condition.
8. the method for production 3- hydracrylic acid according to claim 7, it is characterised in that: step (1) carries out in a solvent
When, the solvent is water.
9. the method for production 3- hydracrylic acid according to claim 1, it is characterised in that: in step (2), the acid is salt
At least one of acid or sulfuric acid.
10. the method for production 3- hydracrylic acid according to claim 1, it is characterised in that: in step (3), continuous chromatography
It separates the chromatograph packing material used and is selected from one of sodium form, potassium type, ammonium type or calcium type chromatographic isolation resin or a variety of；
And/or in step (3), the temperature of continuous chromatography separation is 20~80 DEG C, preferably 20~50 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111592460A (en) * | 2020-06-18 | 2020-08-28 | 南通华康医药科技有限公司 | Preparation method of 3-hydroxy propionate |
| CN111635302A (en) * | 2020-07-08 | 2020-09-08 | 江南大学 | Method for purifying glycolic acid by multi-column continuous chromatographic desalination |
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| CN111635302A (en) * | 2020-07-08 | 2020-09-08 | 江南大学 | Method for purifying glycolic acid by multi-column continuous chromatographic desalination |
| CN111635302B (en) * | 2020-07-08 | 2021-06-15 | 江南大学 | Method for purifying glycolic acid by multi-column continuous chromatographic desalination |
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Application publication date: 20191126 |