CN104355982B - A kind of method being prepared oxyacetic acid by glycerine - Google Patents

A kind of method being prepared oxyacetic acid by glycerine Download PDF

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Publication number
CN104355982B
CN104355982B CN201410479145.4A CN201410479145A CN104355982B CN 104355982 B CN104355982 B CN 104355982B CN 201410479145 A CN201410479145 A CN 201410479145A CN 104355982 B CN104355982 B CN 104355982B
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oxyacetic acid
glycerine
stablizer
prepared
oxygenant
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CN104355982A (en
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佘振
朱锦
那海宁
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Huzhou Guanchen Biotechnology Co.,Ltd.
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Ningbo Institute of Material Technology and Engineering of CAS
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/285Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds

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Abstract

The invention discloses a kind of method being prepared oxyacetic acid by glycerine, take glycerine as raw material, water is solvent, under oxygenant and stablizer exist, the oxidative degradation under ultraviolet irradiation condition, obtains described oxyacetic acid; Described stablizer is zinc compounds.The present invention produces free radical by UV-light decompose hydroperoxide, coordinates simultaneously, realize the selective regulation of product with stablizer.The step that present method prepares oxyacetic acid is simple, does not need heating and pressurizing, is easy to control; Oxygenant used and stablizer cheap, degradation process is without the need to organic solvent; Namely the preparation achieving product in a mild condition transforms, and the small-molecule starting material conversion method comparing existing petroleum-based sources has clear superiority, be a kind ofly to have a high potential, environmental protection, efficient economy oxyacetic acid production method.

Description

A kind of method being prepared oxyacetic acid by glycerine
Technical field
The present invention relates to the preparation method of oxyacetic acid, particularly relate to a kind of method being prepared oxyacetic acid by glycerine of environment-friendly high-efficiency.
Background technology
Oxyacetic acid another name oxyacetic acid or glycolic acid, be the acid of the simplest aliphatic hydroxyl, be mainly present in sugarcane beet and immature grape, but content be lower at occurring in nature.Oxyacetic acid is a kind of important organic synthesis intermediate and Chemicals, and it is of wide application: can be used as clean-out system, sterilant, fiber dyeing agent, purification agent, the batching of welding compound, varnish batching, copper erosion agent, tackiness agent, petroleum demulsifier and metal chelator etc.; Sodium salt, the sylvite of oxyacetic acid can be used as electroplate liquid additive, for the production of organic synthesis platform chemicals such as ethylene glycol; Oxyacetic acid is still for the preparation of the important source material of biological degradation novel material simultaneously.Country is one of basic chemical industry product oxyacetic acid being classified as main exploitation in 10th Five-Year Plan, is enough to illustrate its importance in chemical industry.Domestic oxyacetic acid market potential demand is about 100,000 tons, market value aspect domestic at about 20000 yuan/ton, import at about 30000 yuan/ton.
At present, the technology of preparing of domestic oxyacetic acid mainly contains two kinds of methods.First method is, take Mono Chloro Acetic Acid as raw material, under sodium hydroxide and methyl alcohol exist, be obtained by reacting hydroxy methyl acetate, and then hydrolysis obtains oxyacetic acid.This technical process is long, and yield is low, and has the defects such as the serious and environmental pollution of small scale, equipment corrosion, makes the cost of production oxyacetic acid high.The cyanide process that another kind method is is raw material with formaldehyde and prussic acid (or sodium-chlor), owing to using the prussiate of severe toxicity, in production operation, security requirement is higher.Due to above two kinds of methods be all based on small molecules between conversion prepare oxyacetic acid, technique falls behind, yield poorly, environmental pollution is serious, the second-rate demand that far can not meet market, therefore inhibits widely using of oxyacetic acid to a certain extent.
As can be seen here, based on small-molecule chemical product transform prepare oxyacetic acid also exist at present very large can room for improvement, particularly need the preparation method realizing nontoxic raw material cheap again and environmental protection.Glycerine is the raw material that a kind of wide material sources are cheap again, and it both can be raw material production with natural fats and oils also can be that raw material carrys out chemosynthesis with propylene.Industrialized glycerine price, at 3000-5000 yuan/ton, therefore has larger profit margin with the oxyacetic acid that glycerol production economic worth is at a low price high.
Although be at present that the technology that material oxidation prepares oxyacetic acid has report with glycerine, also depend on expensive precious metal as catalyzer.
Summary of the invention
The invention provides the novel method that oxyacetic acid is prepared in a kind of degraded based on glycerine, raw material sources are extensive, cheap, method environmental protection, and mild condition is simple to operate, be easy to regulating and controlling, and the productive rate of product is very high, has wide industrial prospect.
Prepared a method for oxyacetic acid by glycerine, take glycerine as raw material, water is solvent, under oxygenant and stablizer exist, the oxidative degradation under ultraviolet irradiation condition, obtains described oxyacetic acid; Described stablizer is zinc compounds.
The photochemical reaction of being decomposed with hydrogen peroxide the superoxide being representative by UV-light is the effective ways of the hydroxyl free radical generating strong oxidizing property, in preparation method of the present invention, be produce free radical to glycerine of degrading by ultraviolet catalytic peroxide breakdown, and employ zinc compounds and make stablizer to regulate and control reaction and carry out to generating the direction of oxyacetic acid.
As preferably, described zinc compounds be can in and the zinc oxide of acidic substance, zinc hydroxide, zinc carbonate or zinc subcarbonate.Zinc compounds as stablizer has the effect that selective regulation product generates, preferred several zinc compounds, all can suppress the generation of byproduct formic acid, simultaneously and acidic substance oxyacetic acid thus impel DeR to carry out to the direction generating oxyacetic acid.
As preferably, described oxygenant and the mass ratio of glycerine are 0.5 ~ 10:1; Described stablizer and the mass ratio of glycerine are 0.2 ~ 2:1.Oxygenant is crossed and is decomposed not exclusively at least, and crossing by-products content at most increases; It is poor that selectivity of product at least crossed by zinc class stablizer, and too high then speed of reaction is on the low side.Only under above-mentioned optimum condition, rate of decomposition can reach best with selectivity of product.
As preferably, the superoxide of described oxygenant to be general formula be R-O-O-R', wherein, R and R' is independently selected from H, C 1~ C 5alkyl or metal ion.Carbon number is selected to be less than the alkyl of 5 to guarantee the solubleness of oxygenant in water.
Carry out in ultraviolet lighting degradation process, illumination condition is: the power of light source is 100 ~ 1000W, and light application time is 1 ~ 10h.
According to above-mentioned reason, more preferably:
Described oxygenant is hydrogen peroxide or sodium peroxide;
Described oxygenant and the mass ratio of glycerine are 1 ~ 5:1; Described stablizer and the mass ratio of glycerine are 0.5 ~ 1:1;
Described ultraviolet lamp wavelength is 365nm, and power is 500W, and light application time is 3 ~ 5h.
The productive rate of the oxyacetic acid prepared under above-mentioned optimum condition can up to 77%.
The product that oxidative degradation under ultraviolet irradiation condition obtains also needs to carry out separation and purification.After testing, degraded product of the present invention mainly oxyacetic acid and byproduct formic acid.Because oxyacetic acid fusing point is 75 ~ 80 DEG C and difficult volatilization, and formic acid boiling point is lower and volatile.Therefore formic acid can be separated by the method for distillation or underpressure distillation at about 80 DEG C.And metal salt catalyst remaining in solution can be removed by adding the method precipitation of basic cpd as soda ash; Also according to metal-salt and oxyacetic acid solvability difference in organic solvent, repeatedly can extract by adding ethyl acetate and purify.
Compared with prior art, tool of the present invention has the following advantages:
The present invention is with wide material sources, and cheap glycerine is raw material, and using water as solvent, reaction belongs to homogeneous reaction, is therefore swift in response and thoroughly.
The present invention select can in and the zinc compounds of acidic substance be stablizer, on the one hand and acidic substance oxyacetic acid thus impel DeR to carry out to the direction generating oxyacetic acid, suppress the generation of byproduct formic acid simultaneously, therefore can obtain the oxyacetic acid of high yield.
The step of present method is simple, is easy to control, and not with an organic solvent, and without the need to heating and pressurizing, achieve the condition gentleer than the precious metal catalyst method of existing production technique and bibliographical information, be a kind of oxyacetic acid production method of efficient economy to degradation process.
Embodiment
For a better understanding of the present invention, set forth technical scheme of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
The present embodiment glycerine used is business-like product and not purified direct use.
The photodegradation reaction of glycerine is carry out in the disc open glass container of 10cm at a diameter.The underlying magnetic agitation of container, whole reactor is placed in immediately below ultraviolet lamp source, and ultraviolet lamp wavelength is 365nm, and power is 500W, and the distance bottom Glass Containers and between ultraviolet lamp source is 15cm.
Embodiment 1
First 3g glycerine is placed in the disc Glass Containers filling 30ml water, then container is placed in water-bath.Adding 15mL mass concentration is again the hydrogen peroxide of 30% and the zinc oxide of 1.5g, starts magnetic agitation, and rotating speed is 200rpm, after container is placed in irradiation under UV-light, the irradiation-induced degradation time is 3 hours.
Removed by undissolved solid filtering after having reacted, filtrate oxyacetic acid productive rate is by analysis 77%.
Embodiment 2
First 3g glycerine is placed in the disc Glass Containers filling 30ml water, then container is placed in water-bath.Adding 20mL mass concentration is again the hydrogen peroxide of 30% and the zinc hydroxide of 2g, starts magnetic agitation, and rotating speed is 200rpm, after container is placed in irradiation under UV-light, the irradiation-induced degradation time is 5 hours.
Removed by undissolved solid filtering after having reacted, filtrate oxyacetic acid productive rate is by analysis 71%.
Embodiment 3
First 3g glycerine is placed in the disc Glass Containers filling 30ml water, then container is placed in water-bath.Adding 15mL mass concentration is again the hydrogen peroxide of 30% and the zinc subcarbonate of 3g, starts magnetic agitation, and rotating speed is 200rpm, after container is placed in irradiation under UV-light, the irradiation-induced degradation time is 5 hours.
Removed by undissolved solid filtering after having reacted, filtrate oxyacetic acid productive rate is by analysis 68%.

Claims (7)

1. prepared a method for oxyacetic acid by glycerine, it is characterized in that, take glycerine as raw material, water is solvent, under oxygenant and stablizer exist, the oxidative degradation under ultraviolet irradiation condition, obtains described oxyacetic acid; Described stablizer is zinc compounds;
Described zinc compounds is zinc oxide, zinc hydroxide, zinc carbonate or zinc subcarbonate.
2. the method being prepared oxyacetic acid by glycerine according to claim 1, is characterized in that, described oxygenant and the mass ratio of glycerine are 0.5 ~ 10:1;
Described stablizer and the mass ratio of glycerine are 0.2 ~ 2:1.
3. the method being prepared oxyacetic acid by glycerine according to claim 2, is characterized in that, the superoxide of described oxygenant to be general formula be R-O-O-R', wherein, R and R' is independently selected from H, C 1~ C 5alkyl or metal ion.
4. the method being prepared oxyacetic acid by glycerine according to claim 3, is characterized in that, described oxygenant is hydrogen peroxide or sodium peroxide.
5. the method being prepared oxyacetic acid by glycerine according to claim 4, is characterized in that, the mass ratio of described oxygenant and glycerine is 1 ~ 5:1.
6. the method being prepared oxyacetic acid by glycerine according to claim 5, is characterized in that, described stablizer and the mass ratio of glycerine are 0.5 ~ 1:1.
7. the method being prepared oxyacetic acid by glycerine according to claim 1, is characterized in that, described illumination condition is: the power of light source is 100 ~ 1000W, and light application time is 1 ~ 10h.
CN201410479145.4A 2014-09-18 2014-09-18 A kind of method being prepared oxyacetic acid by glycerine Active CN104355982B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2610257C1 (en) * 2015-11-19 2017-02-08 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский государственный университет" (ТГУ, НИ ТГУ) Method for separating glycolic acid from mixed glyoxal disproportionation products
CN106977391B (en) * 2017-04-25 2019-12-24 中国科学院宁波材料技术与工程研究所 Method for preparing glycolic acid from glycerol
CN115246770B (en) * 2021-04-26 2023-11-17 四川大学 Method for preparing glycolic acid by catalytic conversion of glycerol

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101184717A (en) * 2005-05-27 2008-05-21 旭化成化学株式会社 Method for producing glycolic acid
JP2009137891A (en) * 2007-12-06 2009-06-25 Lion Corp Method for producing dihydroxyacetone or glycolic acid
JP2011016782A (en) * 2009-07-10 2011-01-27 Lion Corp Method for producing glycolic acid, and glycolic acid-containing composition
CN103025698A (en) * 2010-06-25 2013-04-03 卡迪夫大学学院顾问有限公司 Selective oxidation of hydrocarbons using heterogeneous catalysts

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101184717A (en) * 2005-05-27 2008-05-21 旭化成化学株式会社 Method for producing glycolic acid
JP2009137891A (en) * 2007-12-06 2009-06-25 Lion Corp Method for producing dihydroxyacetone or glycolic acid
JP2011016782A (en) * 2009-07-10 2011-01-27 Lion Corp Method for producing glycolic acid, and glycolic acid-containing composition
CN103025698A (en) * 2010-06-25 2013-04-03 卡迪夫大学学院顾问有限公司 Selective oxidation of hydrocarbons using heterogeneous catalysts

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