CN104177250A - Process for producing glycollic acid from methyl glycolate - Google Patents
Process for producing glycollic acid from methyl glycolate Download PDFInfo
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- CN104177250A CN104177250A CN201410471402.XA CN201410471402A CN104177250A CN 104177250 A CN104177250 A CN 104177250A CN 201410471402 A CN201410471402 A CN 201410471402A CN 104177250 A CN104177250 A CN 104177250A
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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
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
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- 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
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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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
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to a process for producing glycollic acid from methyl glycolate. The process comprises the following steps: (1) adding methyl glycolate and water into a rectifying tower, performing reactive rectification in the presence of a catalyst, recycling methanol from the top of the tower, collecting an glycollic acid solution from the bottom of the tower, keeping the temperature of the bottom of the rectifying tower in the reaction process, condensing on the top of the tower, and recycling methanol steam; (2) performing evaporation and concentration on the glycollic acid solution obtained in the step (1); (3) decoloring till being colorless; (4) crystallizing a product obtained in the step (3), separating out glycollic acid in a crystal manner, performing filtering separation to obtain glycollic acid crystals, washing the glycollic acid crystals with a solvent, and drying in vacuum so as to obtain glycollic acid crystals; and (5) directly concentrating the filtrate in the step (4), or mixing the filtrate with the glycollic acid solution obtained in the step (1) according to a certain ratio, concentrating, and recycling for further use. The process is beneficial for completely converting the reactant methyl glycolate, the process procedures are simple, the reaction time is short, the glycollic acid is low in impurity, the purity of the glycollic acid can be greater than 99%, and the total yield is greater than 50%.
Description
Technical field
The invention belongs to chemical production technical field, relate to a kind of production technique of oxyacetic acid, especially, relate to a kind of technique of being produced oxyacetic acid by methyl glycolate.
Background technology
Oxyacetic acid is in the past mainly for the manufacture of boiler descaling agent, clean-out system etc.Be widely used as in recent years makeup and pharmaceuticals, its raw material as polyglycolic acid also receives publicity.Along with the purposes of oxyacetic acid is more and more extensive, to the purity of product and impurity, require also more and more higher.
At present, the production technique of industrial oxyacetic acid mainly adopts Mono Chloro Acetic Acid hydrolysis method and formaldehyde carbonyl process.
(1) Mono Chloro Acetic Acid hydrolysis method: Mono Chloro Acetic Acid sodium hydroxide catalytic hydrolysis is prepared oxyacetic acid, yield can reach more than 95%, and quality product mark can reach more than 98%.This method is less demanding to reaction raw materials, and the impurity dichloro acetic acid in raw material is also hydrolyzed to oxyacetic acid, and Mono Chloro Acetic Acid toxicity is large, and corrodibility is strong, is unfavorable for environmental protection, and contains chlorion in product.
Patent CN103450006A discloses and has adopted Monochloro Acetic Acid to produce the technique of oxyacetic acid, and the method adopts the mode of secondary crystal to remove the chlorion in product.
(2) formaldehyde carbonyl process: this method is current external topmost industrial method.Formaldehyde, CO and water is synthesizing of glycolate under the effect of catalyzer.Under 90MPa, the yield of oxyacetic acid approaches 90%, and the method raw materials cost is low, but high to equipment requirements, product separation, refining complicated.
In addition, also have some other synthetic methods:
Patent CN100343220C discloses after hydroxyacetonitrile hydrolysis, adds methanol esterification, steams water, methyl alcohol, methyl glycolate, then adds water hydrolysis to make oxyacetic acid, the method long reaction time, and yield is low.
This patent adopts methyl glycolate hydrolysis to prepare oxyacetic acid, and wherein methyl glycolate is to be obtained by prepared by dimethyl oxalate plus hydrogen.Dimethyl oxalate can be synthetic by C1 chemical route, and the method raw material sources are extensive, can not cause environmental pollution, operational safety.
Patent CN101265174B discloses use synergic reagent extraction and back-extraction and has obtained glycollic acid solution, and product that the method obtains contains micro-extraction agent, affects the purity of product.
Japanese Patent JP03802950.2 discloses the method for decrease temperature crystalline and has prepared oxyacetic acid crystal, and the method can obtain the oxyacetic acid crystal that purity is higher, but crystal yield is lower, is 20～30%.
Commercially available oxyacetic acid product comprises 70% glycollic acid solution and oxyacetic acid crystal now.The methoxyacetic acid and the diglycollic acid that in technical grade 70% glycollic acid solution, contain certain content, the product that part manufacturer production goes out contains a certain amount of sodium-chlor.The oxyacetic acid crystal obtaining thus also contains a small amount of diglycollic acid or chloride ion impurities.Thereby quality and the range of application of product have been affected.
Summary of the invention
The object of the present invention is to provide a kind of technique of being produced oxyacetic acid by methyl glycolate, this technique, for the production of oxyacetic acid, is conducive to reactant methyl glycolate and transforms completely, technical process is simple, reaction times is short, and oxyacetic acid impurity is few, and purity and yield are higher.
For achieving the above object, technological design design of the present invention is as follows:
This patent technical problem to be solved be existing oxyacetic acid product contain more impurity and product yield low, the problem of complex process, provides a kind of new Method and process of preparing oxyacetic acid.
Reactive distillation is a kind of technique that reaction and rectifying are coupled, and is suitable for reactant relative volatility similar, and the product reaction system different from reactant volatility.Reversible reaction is subject to equilibrium-limited, adopts reactive distillation, removes product balance is moved to positive dirction, can improve the transformation efficiency of reactant.Methyl glycolate hydrolysis belongs to reversible reaction, in reaction process, constantly methyl alcohol is removed from separation system, balance is moved to positive dirction, thereby methyl glycolate is transformed completely, meets the conditional request of reactive distillation.This patent adopts the mode of reactive distillation to carry out this reaction.
Based on above-mentioned design concept, the present invention mainly adopts following technical scheme:
A technique of being produced oxyacetic acid by methyl glycolate, comprises the steps:
1) methyl glycolate and water being take to the ratio that mol ratio is 1:5～30 adds rectifying tower, under the effect of resene solid acid catalyst, be evacuated to 10～101kPaA, be heated to the boiling of tower reactor still liquid, boiling temperature is 80～85 ℃, carry out reactive distillation, keep tower reactor still liquid temperature boiling temperature constant in reaction process, tower top continues to reclaim methanol condensed liquid, after total reflux 10～30min, regulating reflux ratio is 0.5～3, reaction times 2～6h, tower reactor extraction glycolic acid aqueous solution;
2) evaporation-concentration step 1) in the glycolic acid aqueous solution that obtains, by mass content concentrate to the 70～90wt% of oxyacetic acid in glycolic acid aqueous solution;
3) decolouring is to colourless;
4) by step 3) in the product crystallization that obtains, separate out crystalline oxyacetic acid, filter to isolate oxyacetic acid crystal, drip washing, vacuum-drying obtains finished product oxyacetic acid crystal;
5) by step 4) in filtrate directly concentrated or with step 1) in the glycolic acid aqueous solution that obtains concentrate after mixing, repeating step 2)～4), recycle.
Further, described tower bottom of rectifying tower thermal load is 23.6～70.9W/kg methyl glycolate.
Separately, described resene solid acid catalyst is 001*7 type resin solid acid catalyst, D072 type resin solid acid catalyst, NKC-9 type resin solid acid catalyst, Amberlyst 15 type resin solid acid catalysts or Amberlyst 35 type resin solid acid catalysts.
Again, the consumption of described resene solid acid catalyst is 2～15wt%, described step 1) reaction finish after from resene solid acid catalyst described in described tower bottom of rectifying tower filtered and recycled.
Wherein, step 1) described reactive distillation reaction formula is as follows:
A technique of being produced oxyacetic acid by methyl glycolate, comprises the steps:
A) to rectifying tower, add pre-configured 70～80wt% glycolic acid aqueous solution, ebuillition of heated is to total reflux, stablize after 10～20min, add methyl glycolate and water, the mol ratio of described methyl glycolate and water is 1:5～30, the described pre-configured glycolic acid aqueous solution of take is catalyzer, 80～85 ℃ of temperature of reaction, under the condition of pressure 30～5kpa, carry out self-catalyzed reaction rectifying, reflux ratio is 0.5～3, reaction 8～9h hour, overhead condensation reclaims methanol steam, tower reactor extraction glycolic acid aqueous solution;
B) glycolic acid aqueous solution that evaporation-concentration step obtains in a), by mass content concentrate to the 70～90wt% of oxyacetic acid in glycolic acid aqueous solution;
C) decolouring is to colourless;
D) by step c) in the product crystallization that obtains, separate out crystalline oxyacetic acid, filter to isolate oxyacetic acid crystal, drip washing, vacuum-drying obtains finished product oxyacetic acid crystal;
E) by steps d) in filtrate directly concentrated or with step 1) in the glycolic acid aqueous solution that obtains concentrate after mixing, repeating step b)～d), recycle.
Wherein, step a) described in self-catalyzed reaction rectification process formula as follows:
Further, described step a) in, when described rectifying tower tower top temperature is down to 60～70 ℃, the simultaneously discharging of tower reactor tower top.
Separately, in described concentration process, working pressure is 0.1～5kpaA, and Heating temperature is 20～70 ℃.
Separately have, adopt gac to decolour, activated carbon consumption is 0.5～5wt%.
Again, the product after decolouring is cooled to-10～10 ℃, 0.1～2 ℃/min of cooling rate, adds crystal seed in temperature-fall period, and described crystal seed adds temperature-10～20 ℃, stirs 1～5h, stirring velocity 50～400rpm.
Have, described drip washing solvent is 70～85wt% glycolic acid aqueous solution again.
Compared with prior art, beneficial effect of the present invention is:
1. technique of the present invention comprises methyl glycolate reactive distillation hydrolysis, concentrated, decolouring, crystallization, obtains the process of oxyacetic acid crystal.Wherein, adopt the method for reactive distillation by hydrolysis reaction and rectification process coupling, thereby by-product carbinol is removed from tower top, methyl glycolate is transformed completely, technical process is simple, and the reaction times is short, and oxyacetic acid impurity is few.
2. the present invention adopts resin solid acid catalyst catalytic reaction rectification, can be by hydrolysis reaction and rectifying coupling, and Reaction time shorten, improves hydrolysis reaction transformation efficiency and selectivity.
3. the present invention adopts the glycolic acid aqueous solution of first configuration to carry out reactive distillation as autocatalysis agent, can, under the prerequisite of assurance oxyacetic acid yield and purity, effectively reduce production costs.
4. the present invention makes in oxyacetic acid and does not contain methoxyacetic acid and formic acid, and purity and yield are higher.Wherein hydrolysis, concentration process, oxyacetic acid yield reaches 80-99%; In crystallisation process, adopt optimal conditions of the present invention, can make oxyacetic acid crystal yield reach 40-60%, purity is more than 99%; Technique total recovery of the present invention is greater than 50%.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the method for the invention.
In figure, 1 is methyl glycolate feeding line; 2 is tower top discharging pipeline; 3 is rectifying tower; 4 is tower reactor discharging pump; 5 is strainer; 6 is concentrated decolouring still; 7 is activated charcoal filter; 8 is crystallization kettle; 9 is crystal filtration unit; 10 is Minton dryer.
Embodiment
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment 1
As shown in Figure 1, the technique that the present invention produces oxyacetic acid by methyl glycolate comprises the steps:
1) by methyl glycolate feeding line 1, in rectifying tower 3 tower reactors, add methyl glycolate, water, resene solid acid catalyst, the molar ratio of methyl glycolate and water is 1:10, the consumption of described catalyzer (selecting 001*7 type resin solid acid catalyst) is 10wt%, open heating, tower reactor thermal load is 31.2W/kg, under the effect of 001*7 type resin solid acid catalyst, carry out reactive distillation, be evacuated to reaction pressure 50kPaA, heating tower reactor still liquid is to boiling, 85 ℃ of boiling temperatures, total reflux 20min, regulating reflux ratio is 1, in reaction process, tower top discharging pipeline 2 continues extraction recovery methanol condensed liquid, regulate vacuum tightness, maintain reaction tower reactor still liquid boiling temperature constant, reaction times is 4.5h, transform completely to methyl glycolate in tower reactor, stop heating.By 001*7 type resin solid acid catalyst filtered and recycled in tower reactor, by tower reactor discharging pump 4, obtain glycolic acid aqueous solution, the transformation efficiency of methyl glycolate is more than 99%, oxyacetic acid yield is 85%, to make glycollic acid solution and carry out NMR composition analysis, main component is oxyacetic acid and oxyacetic acid dimer.
2) reaction product obtaining (glycolic acid aqueous solution) is sent into concentrated decolouring still 6 through filter 5, at 0.5kPa, rotary evaporation at 60 ℃ of bath temperatures, by the mass content concentrate of oxyacetic acid in glycolic acid aqueous solution to 80wt%;
3) send into activated charcoal filter 7, add 2wt% activated carbon decolorizing, filter;
4) glycollic acid solution obtaining is added in crystallization kettle 8, stirring velocity is 100rpm, and cooling rate is 0.3 ℃/min, when temperature is down to 5 ℃, add crystal seed, crystallization terminal temperature is 2 ℃, filters, with 75% glycolic acid aqueous solution washing after stirring 3h in crystal filtration unit 9, after again filtering, in crystal drying installation 10, carry out vacuum-drying, obtain oxyacetic acid crystal, purity is more than 99%, and total recovery is 54.2%.
5) filtrate is directly concentrated, recycling.
Embodiment 2
The molar ratio of methyl glycolate and water is 1:20, reaction times is 3h, catalyzer adopts D072 type resin solid acid catalyst, filtrate is mixed with glycolic acid aqueous solution concentrated after, recycling, remaining same embodiment 1, step 1) gained oxyacetic acid yield is 94.1%, oxyacetic acid crystal purity is more than 99%, and total recovery is 60.0%.
Embodiment 3
Still liquid boiling is 80 ℃, and the reaction times is 5h, and catalyzer adopts NKC-9 type resin solid acid catalyst, and all the other are with embodiment 1, step 1) gained oxyacetic acid yield is 80.55%, and oxyacetic acid crystal purity is more than 99%, and total recovery is 51.4%.
Embodiment 4
Tower reactor thermal load is 43.06W/kg methyl glycolate, and the reaction times is 3.3h, and catalyzer adopts Amberlyst 35 solid acid catalysts, all the other are with embodiment 1, step 1) gained oxyacetic acid yield is 84.8%, and oxyacetic acid crystal purity is more than 99%, and total recovery is 54.1%.
Embodiment 5
The molar ratio of methyl glycolate and water is 1:30, reaction times is 5h, catalyzer adopts D072 type resin solid acid catalyst, tower reactor thermal load is 69.01W/kg methyl glycolate, filtrate is mixed with glycolic acid aqueous solution concentrated after, recycling, all the other are with embodiment 1, step 1) gained oxyacetic acid yield is 92.4%, and oxyacetic acid crystal purity is more than 99%, and total recovery is 58.9%.
Embodiment 6
The molar ratio of methyl glycolate and water is 1:5, reaction times is 2h, catalyzer adopts Amberlyst 35 type resin solid acid catalysts, tower reactor thermal load is 23.8W/kg methyl glycolate, after filtrate is directly concentrated, and recycling, all the other are with embodiment 1, step 1) gained oxyacetic acid yield is 91.3%, and oxyacetic acid crystal purity is more than 99%, and total recovery is 58.2%.
Embodiment 7
It is 2 ℃ that crystal seed adds temperature, stirs 2h, and with 85% glycolic acid aqueous solution washing, all the other are with embodiment 1, and the purity that obtains oxyacetic acid crystal is more than 99%, and total recovery is 64.8%.
Embodiment 8
Stirring velocity is 400rpm, 0.1 ℃/min of cooling rate, and temperature is down to-10 ℃, adds crystal seed, and it is 10 ℃ that crystal seed adds temperature, stirs 5h, and all the other are with embodiment 1, and the purity that obtains oxyacetic acid crystal is more than 99%, total recovery is 67.2%.
Embodiment 9
Cooling rate is 1 ℃/min, and it is 20 ℃ that crystal seed adds temperature, stirs 1h, and with 70% glycolic acid aqueous solution washing, all the other are with embodiment 1, and the purity that obtains oxyacetic acid crystal is more than 99%, and total recovery is 56.8%.
Embodiment 10
Embodiment 1 step 4) in, when temperature is down to-8 ℃, add crystal seed, after stirring 3h, filter, with 80% glycolic acid aqueous solution washing, all the other are with embodiment 1, and it is more than 99% obtaining oxyacetic acid crystal purity, and total recovery is 65.9%.
Embodiment 11
As shown in Figure 1, the present invention also provides another kind of technique of being produced oxyacetic acid by methyl glycolate, comprises the steps:
In tower bottom of rectifying tower, add 80% pre-configured glycolic acid aqueous solution, ebuillition of heated is to total reflux, stablize after 20min, from described rectifier, add methyl glycolate and water, the mol ratio of described methyl glycolate and water is 1:5, the described pre-configured glycolic acid aqueous solution of take is catalyzer, at 85 ℃, under the condition of pressure 30kpa, carry out self-catalyzed reaction rectifying, reaction reflux ratio is 1, in reaction process, tower top discharging pipeline 2 continues extraction recovery methanol condensed liquid, reaction 9h, tower reactor starts discharging, keep tower bottoms invariant position, when tower top temperature is down to 70 ℃, regulating reflux ratio is 2.5, tower reactor extraction glycolic acid aqueous solution, the transformation efficiency of methyl glycolate is more than 99%, and oxyacetic acid yield is 84%.
All the other steps, with embodiment 1, obtain oxyacetic acid crystal, and purity is more than 99%, and total recovery is 53.6%.
Embodiment 12
Add 70% pre-configured glycolic acid aqueous solution, stablize 10min after total reflux, the mol ratio of methyl glycolate and water is 1:20, reaction 8h, and all the other are with embodiment 11, and the purity that obtains oxyacetic acid crystal is more than 99%, and total recovery is 51.5%.
Embodiment 13
Add 75% pre-configured glycolic acid aqueous solution, stablize 15min after total reflux, the mol ratio of methyl glycolate and water is 1:10,80 ℃ of temperature of reaction, pressure 50kpa, all the other are with embodiment 11, the purity that obtains oxyacetic acid crystal is more than 99%, and total recovery is 58.8%.
Embodiment 14
The mol ratio of methyl glycolate and water is 1:30, and reaction reflux ratio is 0.5, reaction 8.5h, and when tower top temperature is down to 60 ℃, regulating reflux ratio is 2, and all the other are with embodiment 11, and the purity that obtains oxyacetic acid crystal is more than 99%, and total recovery is 55.7%.
Embodiment 15
The mol ratio of methyl glycolate and water is 1:15, and reaction reflux ratio is 1, reaction 8.5h, and when tower top temperature is down to 65 ℃, regulating reflux ratio is 3, and all the other are with embodiment 11, and the purity that obtains oxyacetic acid crystal is more than 99%, and total recovery is 51.5%.
It should be noted that, above embodiment is only unrestricted in order to technical scheme of the present invention to be described.Although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement the technical scheme of invention, and not depart from the scope of technical solution of the present invention, it all should be encompassed in claim scope of the present invention.
Claims (10)
1. by methyl glycolate, produced a technique for oxyacetic acid, comprise the steps:
1) methyl glycolate and water being take to the ratio that mol ratio is 1:5～30 adds rectifying tower, under the effect of resene solid acid catalyst, be evacuated to 10～101kPaA, be heated to the boiling of tower reactor still liquid, boiling temperature is 80～85 ℃, carry out reactive distillation, keep tower reactor still liquid temperature boiling temperature constant in reaction process, tower top continues to reclaim methanol condensed liquid, after total reflux 10～30min, regulating reflux ratio is 0.5～3, reaction times 2～6h, tower reactor extraction glycolic acid aqueous solution;
2) evaporation-concentration step 1) in the glycolic acid aqueous solution that obtains, by mass content concentrate to the 70～90wt% of oxyacetic acid in glycolic acid aqueous solution;
3) decolouring is to colourless;
4) by step 3) in the product crystallization that obtains, separate out crystalline oxyacetic acid, filter to isolate oxyacetic acid crystal, drip washing, vacuum-drying obtains finished product oxyacetic acid crystal;
5) by step 4) in filtrate directly concentrated or with step 1) in the glycolic acid aqueous solution that obtains concentrate after mixing, repeating step 2)～4), recycle.
2. technique according to claim 1, is characterized in that, described tower bottom of rectifying tower thermal load is 23.6～70.9W/kg methyl glycolate.
3. technique according to claim 1, it is characterized in that, described resene solid acid catalyst is 001*7 type resin solid acid catalyst, D072 type resin solid acid catalyst, NKC-9 type resin solid acid catalyst, Amberlyst 15 type resin solid acid catalysts or Amberlyst 35 type resin solid acid catalysts.
4. technique according to claim 1, is characterized in that, the consumption of described resene solid acid catalyst is 2～15wt%, described step 1) reaction finish after from resene solid acid catalyst described in described tower bottom of rectifying tower filtered and recycled.
5. by methyl glycolate, produced a technique for oxyacetic acid, comprise the steps:
A) to rectifying tower, add pre-configured 70～80wt% glycolic acid aqueous solution, ebuillition of heated is to total reflux, stablize after 10～20min, add methyl glycolate and water, the mol ratio of described methyl glycolate and water is 1:5～30, the described pre-configured glycolic acid aqueous solution of take is catalyzer, 80～85 ℃ of temperature of reaction, under the condition of pressure 30～50kpa, carry out self-catalyzed reaction rectifying, reaction reflux ratio is 0.5～3, reaction 8～9h hour, overhead condensation reclaims methanol steam, tower reactor extraction glycolic acid aqueous solution;
B) glycolic acid aqueous solution that evaporation-concentration step obtains in a), by mass content concentrate to the 70～90wt% of oxyacetic acid in glycolic acid aqueous solution;
C) decolouring is to colourless;
D) by step c) in the product crystallization that obtains, separate out crystalline oxyacetic acid, filter to isolate oxyacetic acid crystal, drip washing, vacuum-drying obtains finished product oxyacetic acid crystal;
E) by steps d) in filtrate directly concentrated or with step 1) in the glycolic acid aqueous solution that obtains concentrate after mixing, repeating step b)～d), recycle.
6. technique according to claim 5, is characterized in that, described step a) in, when described rectifying tower tower top temperature is down to 60～70 ℃, the simultaneously discharging of tower reactor tower top.
7. technique according to claim 1 or 5, is characterized in that, in described concentration process, working pressure is 0.1～5kpaA, and Heating temperature is 20～70 ℃.
8. technique according to claim 1 or 5, is characterized in that, adopts gac to decolour, and activated carbon consumption is 0.5～5wt%.
9. technique according to claim 1 or 5, it is characterized in that, described crystallization method is: the product after decolouring is cooled to-10～10 ℃, 0.1～2 ℃/min of cooling rate, in temperature-fall period, add crystal seed, described crystal seed adds temperature-10～20 ℃, stirs 1～5h, stirring velocity 50～400rpm.
10. technique according to claim 1 or 5, is characterized in that, described drip washing solvent is 70～85wt% glycolic acid aqueous solution.
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Cited By (13)
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| CN104829445A (en) * | 2015-05-04 | 2015-08-12 | 上海华谊（集团）公司 | Method for producing aqueous solution of glycolic acid |
| CN105085227A (en) * | 2015-09-08 | 2015-11-25 | 上海华谊（集团）公司 | Method for producing glycolic acid solution |
| CN106478401A (en) * | 2015-08-28 | 2017-03-08 | 中国石油化工股份有限公司 | The method that methyl glycollate prepares ethanol acid crystal |
| CN106478414A (en) * | 2015-08-28 | 2017-03-08 | 中国石油化工股份有限公司 | The method that methyl glycollate prepares glycolic-aqueous mixtures |
| CN106478403A (en) * | 2015-08-28 | 2017-03-08 | 中国石油化工股份有限公司 | The method that glycolic-aqueous mixtures are prepared by methyl glycollate |
| CN106478402A (en) * | 2015-08-28 | 2017-03-08 | 中国石油化工股份有限公司 | The method that ethanol acid crystal is prepared by methyl glycollate |
| CN107814709A (en) * | 2017-10-30 | 2018-03-20 | 江苏金聚合金材料有限公司 | A kind of high-quality glycolic purifying technique |
| CN109603907A (en) * | 2019-01-04 | 2019-04-12 | 丹东明珠特种树脂有限公司 | Cation resin catalyzing agent, preparation method and its catalytic applications that glycolic is prepared in methyl glycollate Hydrolyze method |
| CN113845415A (en) * | 2021-10-21 | 2021-12-28 | 中国石油大学(华东) | Method and device for separating and purifying glycolic acid rectification crystallization coupling technology and application |
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| CN106478402A (en) * | 2015-08-28 | 2017-03-08 | 中国石油化工股份有限公司 | The method that ethanol acid crystal is prepared by methyl glycollate |
| CN105085227A (en) * | 2015-09-08 | 2015-11-25 | 上海华谊（集团）公司 | Method for producing glycolic acid solution |
| CN107814709A (en) * | 2017-10-30 | 2018-03-20 | 江苏金聚合金材料有限公司 | A kind of high-quality glycolic purifying technique |
| CN109603907A (en) * | 2019-01-04 | 2019-04-12 | 丹东明珠特种树脂有限公司 | Cation resin catalyzing agent, preparation method and its catalytic applications that glycolic is prepared in methyl glycollate Hydrolyze method |
| CN109603907B (en) * | 2019-01-04 | 2024-03-26 | 丹东明珠特种树脂有限公司 | Preparation method of glycollic acid by catalytic hydrolysis of methyl glycolate |
| CN114057563A (en) * | 2020-08-06 | 2022-02-18 | 天津华信化工技术有限公司 | Method for rectifying and hydrolyzing organic acid ester by slurry catalytic reaction |
| WO2022052223A1 (en) * | 2020-09-08 | 2022-03-17 | 南京延长反应技术研究院有限公司 | Intensified microinterface preparation system and method for polyglycolic acid |
| CN113845415A (en) * | 2021-10-21 | 2021-12-28 | 中国石油大学(华东) | Method and device for separating and purifying glycolic acid rectification crystallization coupling technology and application |
| CN114452924A (en) * | 2022-01-19 | 2022-05-10 | 长乐力恒锦纶科技有限公司 | System and method for improving quality of recovered caprolactam and improving recovery process |
| CN114452924B (en) * | 2022-01-19 | 2024-06-04 | 福建省力恒锦纶实业有限公司 | System and method for improving quality of recovered caprolactam and recovery process |
| CN115160122A (en) * | 2022-08-26 | 2022-10-11 | 东华工程科技股份有限公司 | Novel process for preparing glycollic acid by hydrolyzing methyl glycolate |
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