CN1031638C - Process for synthesizing hydroxyacetic acid - Google Patents
Process for synthesizing hydroxyacetic acid Download PDFInfo
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- CN1031638C CN1031638C CN 92104616 CN92104616A CN1031638C CN 1031638 C CN1031638 C CN 1031638C CN 92104616 CN92104616 CN 92104616 CN 92104616 A CN92104616 A CN 92104616A CN 1031638 C CN1031638 C CN 1031638C
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Abstract
The present invention provides a new process for synthesizing hydroxyacetic acid by using glycolonitrile and passing through the steps of hydrolyzation, extraction and concentration, etc., which comprises the following steps: hydrolyzing the glycolonitrile in an acid medium to prepare a mixing water solution of the glycolic acid; taking purified glycolic acid prepared by the mixing water solution by an extraction agent. Compared with the existing process, the present invention has the advantages of wide raw material source, mild reaction condition, simple process line, no harm and no pollution; large industrial continuous production can be carried out; both economical and social benefits are obvious.
Description
The present invention relates to the novel process of industrialization synthesis of hydroxy acetate, particularly by hydroxyacetonitrile through hydrolysis, extraction, the novel process that step is come synthesis of hydroxy acetate such as concentrate.
In known references, U.S.Patent 3,867,440 disclosedly are: hydroxyacetonitrile hydrolysis under the effect of catalyzer phosphorous acid or sulfurous acid (its Pka is 1.5-2.5) prepares oxyacetic acid, hydrolysis temperature is 75-175 ℃, the best is 140-150 ℃, and hydroxyacetonitrile is 1-2: 1 with the mol ratio of acid.
US4,054,601 have disclosed the method that reclaims pure oxyacetic acid from the aqueous solution that contains impurity, this method is the hydrolysis 3 hours under 135-140 ℃ temperature of sulfuric acid with 88% hydroxyacetonitrile and 55%, use trialkyl phosphates (employing be the Tributyl phosphate ester) and dialkyl ether (employing be Di Iso Propyl Ether) to separate then with 1: 1 blended extraction agent, water is stripped again, obtains pure oxyacetic acid, and the concentration of oxyacetic acid is 18-20%.
The present invention seeks in order to provide a kind of technology simple, and can carry out big industrialization continuous production, by hydroxyacetonitrile through hydrolysis, extraction, the novel process that step is come synthesis of hydroxy acetate such as concentrate.
The present invention mainly comprises two big contents, and the first adopts new raw material synthesis of hydroxy acetate, promptly with concentration be 40-50% hydroxyacetonitrile be raw material through acidic hydrolysis synthesis of hydroxy acetate, its principles of chemistry are as follows:
It two is to adopt appropriate organic solvent to make extraction agent, and oxyacetic acid is separated from the mixture that contains other water-soluble salts, acid, alkali, obtains purified oxyacetic acid, and detailed process is performed such:
(1) synthesis of hydroxy acetate
By 37% formaldehyde (domestic market is the specification of supply extensively and in a large number) and pure prussic acid (liquid state, it can be the by product of petrochemical industry vinyl cyanide, it also can be the preparation of Sweet natural gas iS-One method, and light oil cracking preparation and sodium cyanide and sulfuric acid are anti-upright makes etc.) synthesis of hydroxy acetonitrile solution under acidity or base catalysis condition, the concentration of this solution is 40-50%, the hydrolysis hydroxyacetonitrile gets the mixed aqueous solution of oxyacetic acid in acidic medium, used acidic medium is a sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, and their mixing acid, particularly concentration are 60-98% sulfuric acid.Hydrolysis reaction carries out under normal pressure, and its temperature is 100-160 ℃, and the best is 115-130 ℃, and the reaction times is 1-10 hours, and the best is 4-7 hours, and wherein hydroxyacetonitrile and vitriolic mol ratio are 1.8-2.0: 1.
(2) extracting and separating oxyacetic acid
Contact with above-mentioned oxyacetic acid mixed aqueous solution with a kind of extraction agent of forming according to a certain ratio by multiple organic solvent, oxyacetic acid is extracted, extraction temperature is 5-45 ℃, extraction agent is 1-4: 1 (volume ratio) with the ratio (according to the concentration of oxyacetic acid and the progression of extraction requirement) of the consumption of oxyacetic acid mixed solution, and extraction progression: (according to the concentration of different extraction agent and oxyacetic acid) is 6-10 grades.
Extraction agent is by (1) organic phosphorus compound, as dialkyl alkylphosphonate, and trialkyl phosphine, wherein the carbonatoms of alkyl is 1-10, is preferably 6-8; (2) organic compounds containing nitrogen: as trialkylamine, wherein the carbonatoms of alkyl is 1-10, is preferably 6-8; (3) organic compounds containing sulfur: as dialkyl sulphoxide, wherein the alkyl carbon atoms number is 1-10, in one or more and organic thinner, as sulfonated kerosene, dialkyl ketones etc. are formed, and wherein the proportioning of organic compound and organic thinner is 0.1-1: 1 (volume ratio).(3) reextraction and concentrated
With purified water the extraction agent that contains oxyacetic acid is stripped, obtain purified oxyacetic acid solution, the temperature of reextraction is 5-45 ℃, and extraction agent is 1-6: 1 with the ratio of the consumption of water, and reextraction progression is 2-6 grades.
Obtain purified hydroxy acid solution after stripping, the content of oxyacetic acid is 5-20%, and this aqueous solution is carried out evaporation concentration under reduced pressure, and temperature is controlled at 50-75 ℃, obtains 30-70% oxyacetic acid after concentrating.
(4) reaction mixture after the extraction can be through evaporation concentration, crystallisation by cooling, and steps such as separation obtain purified solid ammonium salt.As ammonium sulfate etc., can make industrial raw material and agricultural fertilizer.
The present invention compares with existent method, has obvious superiority, is that 40-50% hydroxyacetonitrile is that raw material is extensive through acidic hydrolysis synthesis of hydroxy acetate (1) raw material sources with concentration, and price is low; (2) reaction conditions gentleness, (3) can carry out suitability for industrialized production, have to produce and feasibility economically.It is simple to adopt suitable extraction agent extraction to obtain purified oxyacetic acid solution (1) technology, and can carry out big industrialization continuous production; (2) not to be only applicable to the hydroxyacetonitrile be that raw material is through acidic hydrolysis synthetic oxyacetic acid to this method, and be applicable to the Mono Chloro Acetic Acid to be raw material, the oxyacetic acid that alkaline hydrolysis obtains, and the oxyacetic acid that obtains of other raw materials or processing method, obtain hydroxy acid sodium as sodium cyanide and formaldehyde reaction, acidifying obtains oxyacetic acid then; Obtain oxyacetic acid or the like after the industry by product hydroxy acid sodium acidifyings such as agricultural chemicals; (3) to be particularly useful for the hydroxyacetonitrile be the oxyacetic acid of raw material production to this method, because behind this route reaction be the mixture of ammonium salt and oxyacetic acid, after oxyacetic acid extracts, remaining ammonium salt also is industrial raw material and agricultural fertilizer, can make whole operational path realize harmless, CR production like this, economic benefit and social benefit are all remarkable.
Enumerate the several specific embodiments of the present invention below
Embodiment 1 is furnished with agitator at one, in the four-hole boiling flask of thermometer and condenser, add the sulfuric acid of 360ml97% and the solution that 195ml water is blended into, start stirring, flask external application glycerol bath heat temperature raising, when solution in the bottle reaches 120 ℃, add 45% hydroxyacetonitrile 1500ml, producing has hydrolysis reaction strongly, the control hydrolysis temperature is at 120 ℃, behind the boiling reflux 6 hours, stop heating, make the material cooling.99% hydroxyacetonitrile changes into oxyacetic acid after measured, does not have other organic by-products and produces.
The solution 300ml that reaction obtains is separated in water intaking, the extraction agent of forming with 650ml trioctylphosphine amine, dimethyl sulfoxide (DMSO) and metacetone carries out extracting operation, wherein the volume ratio of three kinds of components is 20: 30: 50, extraction back extraction liquid is stripped with 500ml water, it is 41.67% oxyacetic acid that the hydroxy acid solution that obtains obtains 280ml content after the inspissation through decompression, and yield counts 97.5% with hydroxyacetonitrile.
Get the raffinate behind the above-mentioned extracting operation, regulate pH value to neutral with the saturated ammonia aqueous solution earlier, the inspissation that reduces pressure then, through cooling, crystallization is filtered, and obtains 98 white crystalline solid that restrain ammonium sulfate, and filtrate can be used repeatedly, and total yield counts 95% with sulfuric acid.
Embodiment 2 is in the mini-reactor of the stirring of a band, condenser, thermometer, hydrochloric acid and each 200ml of phosphoric acid of adding 37%, when being heated to 60 ℃ with glycerol bath, begin to add 45% hydroxyacetonitrile 1000ml, hydrolysis reaction takes place, and control reaction temperature is (± 2.0 ℃) about 115 ℃, boiling reflux 5.5 hours, stop heating, material is cooled off fast, have 96.6% hydroxyacetonitrile to change into oxyacetic acid after measured.
Solution 200ml that obtains and 600ml tricresyl phosphate butyl ester, the extraction agent that dialkyl methyl phosphonate (alkyl is 6-8 carbon atoms) and Di Iso Propyl Ether are formed carries out extracting operation, wherein the volume ratio of three kinds of components is 20: 10: 70, strip with 400ml water then, it is 53.4% oxyacetic acid that the oxyacetic acid that obtains obtains 135ml content after the inspissation through decompression, and yield counts 95.4% with hydroxyacetonitrile.
Embodiment 3 is in the experimental installation of embodiment 2, the mixed acid (volume ratio is 2: 2: 1) that adds phosphorous acid and sulfurous acid and nitric acid is total to 200ml, with glycerol bath heat temperature raising to 70 ℃, begin to add 45% hydroxyacetonitrile 600ml, hydrolysis reaction takes place, and the control hydrolysis temperature is at 125 ℃, 6 hours boiling reflux time, stop heating, material cooling back is measured has 98.7% hydroxyacetonitrile to change into oxyacetic acid.
The extraction agent that the solution 200ml that obtains of reaction and 800ml trioctyl phosphine oxide (TOPU) and sulfonated kerosene composition are separated in water intaking carries out extracting operation, wherein the volume ratio of trioctyl phosphine oxide and sulfonated kerosene is 40: 60, extraction back extraction liquid is stripped with 400ml water, and the hydroxy acid solution that obtains obtains 180ml content after decompression inspissation be 42.5% oxyacetic acid.Yield counts 97% with hydroxyacetonitrile.
What narrate above only is the relevant condition that adopts according to qualifications usually in this invention of enforcement, and it is intended that all flexible and adjustment that comprise this invention actual conditions in order to separate.The purpose of selecting these conditions to show here can not depart from the marrow and the scope of claim.
Claims (5)
1. the novel process of an industrialization synthesis of hydroxy acetate, comprise with the hydroxyl acetonitrile aqueous solution being raw material, reaction is hydrolyzed in acidic medium, generate the mixed aqueous solution of oxyacetic acid and ammonium salt, it is characterized in that, and then use the extraction agent of forming according to a certain ratio by multiple organic solvent to extract oxyacetic acid in the mixed aqueous solution, organic phase after the extraction is stripped through water and is obtained pure hydroxy acid solution, organic extractant can be recycled, water after the extraction is an ammonium salt aqueous solution, obtain the solid ammonium salt through evaporation concentration, the concentration of raw material hydroxyl acetonitrile aqueous solution is 40-50%, used acidic medium is that concentration is 60-98% sulfuric acid, and hydrolysising reacting temperature is 100-160 ℃.
2. the novel process of industrialization synthesis of hydroxy acetate as claimed in claim 1 is characterized in that wherein used extraction agent is by organic phosphorus compound, as, dialkyl alkylphosphonate, trialkyl phosphine etc., wherein the carbonatoms of alkyl is 4-8; Organic compounds containing nitrogen, as, trialkylamine, wherein the carbonatoms of alkyl is 4-8; Organic compounds containing sulfur, as, dialkyl sulphoxide, wherein the carbonatoms of alkyl is 1-3, in one or more, form with organic thinner, used thinner is a non-ionic type, as sulfonated kerosene, dialkyl ketone etc., wherein the carbonatoms of alkyl is 1-4 in the dialkyl ketone, and the proportioning of organic extraction compound and organic thinner is 0.1-1: 1 (volume ratio) in the extraction agent, and extraction and reextraction service temperature are 5-45 ℃.
3. the novel process of industrialization synthesis of hydroxy acetate as claimed in claim 1 is characterized in that the concentration of the pure hydroxy acid solution of gained behind extracting operation is 5-20%, under reduced pressure, and evaporation concentration to 30-70%.
4. the novel process of industrialization synthesis of hydroxy acetate as claimed in claim 1 is characterized in that used acidic medium can also be phosphoric acid, nitric acid, hydrochloric acid and their mixing acid.
5. the novel process of industrialization synthesis of hydroxy acetate as claimed in claim 1 is characterized in that the raw material hydroxyl acetonitrile aqueous solution is obtained by 37% industrial formol and prussic acid reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92104616 CN1031638C (en) | 1992-06-10 | 1992-06-10 | Process for synthesizing hydroxyacetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92104616 CN1031638C (en) | 1992-06-10 | 1992-06-10 | Process for synthesizing hydroxyacetic acid |
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| Publication Number | Publication Date |
|---|---|
| CN1066650A CN1066650A (en) | 1992-12-02 |
| CN1031638C true CN1031638C (en) | 1996-04-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 92104616 Expired - Fee Related CN1031638C (en) | 1992-06-10 | 1992-06-10 | Process for synthesizing hydroxyacetic acid |
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| CN (1) | CN1031638C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343220C (en) * | 2005-07-21 | 2007-10-17 | 太仓市新月化工有限公司 | Technology of preparing hdyroxy acetic acid |
| CN102153460B (en) * | 2011-02-12 | 2013-05-01 | 上海多纶化工有限公司 | Method for preparing glycollic acid by glycol |
| CN102153461B (en) * | 2011-02-12 | 2013-05-01 | 上海多纶化工有限公司 | Method for preparing glycollic acid with ethylene glycol |
| CN104744239B (en) * | 2015-02-15 | 2016-09-07 | 太仓市新毛涤纶化工有限公司 | The preparation method of hydroxyacetic acid |
| CN112125775B (en) * | 2020-10-15 | 2023-03-24 | 江苏蓝色星球环保科技股份有限公司 | Method and device for producing 1, 2-tetrafluoroethane and co-producing glycolic acid |
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- 1992-06-10 CN CN 92104616 patent/CN1031638C/en not_active Expired - Fee Related
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