CN106831429A - A kind of method that maleic anhydride waste residue prepares diethyl phthalate - Google Patents
A kind of method that maleic anhydride waste residue prepares diethyl phthalate Download PDFInfo
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- CN106831429A CN106831429A CN201710066042.9A CN201710066042A CN106831429A CN 106831429 A CN106831429 A CN 106831429A CN 201710066042 A CN201710066042 A CN 201710066042A CN 106831429 A CN106831429 A CN 106831429A
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- maleic anhydride
- waste residue
- diethyl phthalate
- acid
- anhydride waste
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P13/00—Preparation of nitrogen-containing organic compounds
- C12P13/04—Alpha- or beta- amino acids
- C12P13/20—Aspartic acid; Asparagine
Abstract
The present invention relates to a kind of method that diethyl phthalate is prepared with maleic anhydride waste residue, belong to the disposal of three wastes and chemical production technical field in environmental protection.The method is first using the treatment for carrying out imurity-removal to maleic anhydride waste residue than more conventional method, obtain purer phthalic acid and suitable fumaric acid mixture, then with Escherichia coli under given conditions, in maleic anhydride waste residue aspartic acid will be converted into along fumaric acid, under specific acid condition, by aspartic acid in maleic anhydride waste residue and phthalic acid, crystallization out and is subject to drying simultaneously.Simultaneously be esterified for aspartic acid and O-phthalic acid blend using special method again by the present invention, finally using the physicochemical property of diethyl phthalate, is separated diethyl phthalate with water, and whole technical process is simple to operate.
Description
Technical field
The present invention relates to a kind of method that diethyl phthalate is prepared with maleic anhydride waste residue, belong to the three wastes in environmental protection
Administer and chemical production technical technical field.
Background technology
The chemical name of cis-butenedioic anhydride is maleic anhydride.Normal butane legal system maleic anhydride process, because the later stage is to improve yield of maleic anhydride,
Solvent absorption is used, so the content of organic acid is more in waste water, to be studied and be recycled.
Substantial amounts of phthalic acid can be produced in the production process of maleic anhydride and along fumaric acid, manufacturer
Also various means have been taken therefrom to separate part phthalic acid, rich horse has partly also been produced along fumaric acid
Acid, even so, still having not a small amount of phthalic acid and method deals never again along fumaric acid, this part does not have
There is the phthalic acid that deals and will be sent in incinerator along fumaric acid and burn, so not only cause resource
Waste, return environment and bring harm.
The content of the invention
Present invention solves the technical problem that being：A kind of comprehensive utilization of Industrial Solid Waste maleic anhydride waste residue is proposed, and in cis-butenedioic anhydride
During the comprehensive utilization of waste residue, maleic anhydride waste residue is processed using special technique, then adjacent benzene is prepared with special method
The method of dicarboxylic acid ethyl ester.
In order to solve the above-mentioned technical problem, technical scheme proposed by the present invention is：A kind of maleic anhydride waste residue prepares adjacent benzene two
The method of formic acid diethylester, comprises the following steps：
(1) maleic anhydride waste residue is filtered with water-soluble, crystallization obtains brown along fumaric acid and O-phthalic acid blend, will
The mixture is dissolved in water, plus activated carbon decolorizing, adds Escherichia coli conversion, and PH to 2~4 is adjusted with hydrochloric acid, is separated out after concentration
Phthalic acid and aspartic acid white hybrid solid, leach white solid and dry；
(2) by the mixture addition ethanol of step (1) gained phthalic acid and aspartic acid white hybrid solid, delay
It is slow to add thionyl chloride, it is heated to reflux 5-12 hours, net unreacted ethanol and thionyl chloride are steamed, it is subsequently adding leftover materials body
The water stirring that 1-3 times of product is measured, stands, and separates oil reservoir；
(3) dehydration of step (2) gained oil reservoir, vacuum distillation can be obtained into aspartic acid carbethoxy hydrochloride.
Preferably, along fumaric acid and O-phthalic acid blend and Escherichia coli charged material weight in the step (1)
Than being 1:0.002-0.02, the PH of reaction system is 8.5-10.0.
Preferably, phthalic acid and aspartic acid mixture and ethanol charged material weight ratio are 1 in the step (2):4-
10。
Preferably, phthalic acid and aspartic acid mixture are with thionyl chloride charged material weight ratio in the step (2)
1：1-3.
Preferably, in the step (2) phthalic acid and aspartic acid mixture esterification at reflux, instead
Answer 5-12 hours.
Preferably, after steaming ethanol and thionyl chloride in the step (2), the volume for adding water should be the 1- of residue
3 times, after stirring, stand, separate water layer, oil reservoir is washed with water 1-3 times.
Preferably, oil reservoir uses the dense dehydration of low vacuum in the step (3), and vacuum is 200-300mmHg.
Preferably, oil reservoir, through vacuum distillation, obtains phthalic acid diethyl of the purity more than 96wt% in the step (3)
Ester.
Preferably, it is 2~4 to adjust PH with hydrochloric acid in the step (1).
Beneficial effects of the present invention：
The present invention is obtained purer first using the treatment for carrying out imurity-removal to maleic anhydride waste residue than more conventional method
Phthalic acid and along fumaric acid mixture, then with Escherichia coli under given conditions, will be suitable in maleic anhydride waste residue
Fumaric acid is converted into aspartic acid, under specific acid condition, by aspartic acid in maleic anhydride waste residue and phthalic acid
Crystallization out and is subject to drying simultaneously.The present invention again using special method by aspartic acid and O-phthalic acid blend simultaneously
Esterification, finally, using the physicochemical property of diethyl phthalate, is separated diethyl phthalate with water, entirely
Technical process is simple to operate.
The present invention is exactly using special technique, first by the suitable fumaric acid in maleic anhydride waste residue in alkalescence condition and large intestine
Under the catalytic action of bacillus, aspartic acid is converted into, then under specific acid condition, phthalic acid is common with aspartic acid
Separate out, common esterification, finally using property insoluble in diethyl phthalate water, is separated with aspartic acid carbethoxy hydrochloride
Come.So can very easily obtain diethyl phthalate so that phthalic acid is obtained and made profits again to greatest extent
With.
The present invention is not high to equipment requirement, and simple to operate, diethyl phthalate added value is higher, and it is rubber plastic
The most frequently used plasticizer of industry, it can bring bigger economic benefit to manufacturer.
Specific embodiment
It is exactly below that the present invention is described further with specific example
Embodiment 1
Maleic anhydride waste residue 1000g is weighed, is put into the glass beaker of 5000ml, add water 2000g, and be heated to 80 degree, stirring 1
Hour, to filter while hot, filtrate is cooled to room temperature, separates out a large amount of solids.Leach in the glass beaker that solid adds 5000ml, add water
1500g, adds granular activated carbon 20g, is heated to 90 degree, stirs 1 hour, filters while hot, and filtrate is cooled to room temperature.Filtrate ammoniacal liquor
PH to 9 is adjusted, Escherichia coli 5g is added, is stirred at room temperature 18 hours, adjust PH to 2.5 with hydrochloric acid, steam 1000ml moisture content, be cooled to room
Temperature, separates out a large amount of solids, and solid is leached, and is dried 3 hours at 100 degree, obtains solid 512g, and mother liquor can be applied mechanically.
During above-mentioned drying solid 512g pulverized into addition 3000ml there-necked flasks, 600ml absolute ethyl alcohols are added, side stirring
Side is added dropwise thionyl chloride 438g, is flowed back 8 hours after adding, and steams ethanol and thionyl chloride.Then add water 700ml, stirs,
Stand, separate oil reservoir, oil reservoir adds water 400ml, stirs, stand, separate oil reservoir, oil reservoir adds water 400ml, and stirring is equal
It is even, stand, separate oil reservoir.Organic phase (oil reservoir) low vacuum is dehydrated, and then vacuum distillation, vacuum is 200-300mmHg, obtains shallow
Yellow liquid 365g (contains diethyl phthalate 97.1wt%)
Embodiment 2
Maleic anhydride waste residue 1200g is weighed, is put into the glass beaker of 5000ml, add water 2500g, and be heated to 80 degree, stirring 1
Hour, to filter while hot, filtrate is cooled to room temperature, separates out a large amount of solids.Leach in the glass beaker that solid adds 5000ml, add water
1500g, adds granular activated carbon 25g, is heated to 92 degree, stirs 1 hour, filters while hot, and filtrate is cooled to room temperature.Filtrate ammoniacal liquor
PH to 9.5 is adjusted, Escherichia coli 8g is added.It is stirred at room temperature 20 hours, adjusts PH to 2.8 with hydrochloric acid, steam 1200ml moisture content, is cooled to room
Temperature, separates out a large amount of solids, and solid is leached, and is dried 3 hours at 100 degree, obtains solid 594g, and mother liquor can be applied mechanically.
During above-mentioned drying solid 594g pulverized into addition 3000ml there-necked flasks, 800ml absolute ethyl alcohols are added, side stirring
Side is added dropwise thionyl chloride 560g, is flowed back 10 hours after adding, and steams ethanol and thionyl chloride.Then add water 800ml, and stirring is equal
It is even, stand, oil reservoir is separated, oil reservoir adds water 400ml, stirs, and stands, and separates oil reservoir, and oil reservoir adds water 400ml, stirring
Uniformly, stand, separate oil reservoir.Organic phase (oil reservoir) low vacuum is dehydrated, and then vacuum distillation, vacuum is 200-300mmHg, is obtained
Light yellow liquid 427g (contains diethyl phthalate 96.4wt%)
Embodiment 3
Maleic anhydride waste residue 1400g is weighed, is put into the glass beaker of 5000ml, add water 2800g, and be heated to 80 degree, stirring 1
Hour, to filter while hot, filtrate is cooled to room temperature, separates out a large amount of solids.Leach in the glass beaker that solid adds 5000ml, add water
2000g, adds granular activated carbon 30g, is heated to 90 degree, stirs 1 hour, filters while hot, and filtrate is cooled to room temperature.Filtrate ammoniacal liquor
PH to 10 is adjusted, Escherichia coli 10g is added.It is stirred at room temperature 18 hours, adjusts PH to 3 with hydrochloric acid, steam 1400ml moisture content, is cooled to room
Temperature, separates out a large amount of solids, and solid is leached, and is dried 3 hours at 100 degree, obtains solid 671g, and mother liquor can be applied mechanically.
During above-mentioned drying solid 671g pulverized into addition 3000ml there-necked flasks, 850ml absolute ethyl alcohols are added, side stirring
Side is added dropwise thionyl chloride 690g, is flowed back 9 hours after adding, and steams ethanol and thionyl chloride.Then add water 900ml, stirs,
Stand, separate oil reservoir, oil reservoir adds water 450ml, stirs, stand, separate oil reservoir, oil reservoir adds water 450ml, and stirring is equal
It is even, stand, separate oil reservoir.Organic phase (oil reservoir) low vacuum is dehydrated, and then vacuum distillation, vacuum is 200-300mmHg, obtains shallow
Yellow liquid 498g (contains diethyl phthalate 96.7wt%)
The concrete technical scheme being not limited to described in above-described embodiment of the invention, the technology that all use equivalents are formed
Scheme is the protection domain of application claims.
Claims (9)
1. a kind of method that maleic anhydride waste residue prepares diethyl phthalate, it is characterised in that:Comprise the following steps：
(1) maleic anhydride waste residue is filtered with water-soluble, crystallization obtains brown along fumaric acid and O-phthalic acid blend, this is mixed
Compound is dissolved in water, plus activated carbon decolorizing, adds Escherichia coli conversion, and PH to 2~5 is adjusted with hydrochloric acid, and adjacent benzene is separated out after concentration
Dioctyl phthalate and aspartic acid white hybrid solid, leach white solid and dry；
(2) by the mixture addition ethanol of step (1) gained phthalic acid and aspartic acid white hybrid solid, slowly add
Enter thionyl chloride, be heated to reflux 5-12 hours, steam net unreacted ethanol and thionyl chloride, be subsequently adding leftover materials volume 1-
3 times of water stirrings of amount, stand, and separate oil reservoir；
(3) dehydration of step (2) gained oil reservoir, vacuum distillation can be obtained into aspartic acid carbethoxy hydrochloride.
2. the method that maleic anhydride waste residue according to claim 1 prepares diethyl phthalate, it is characterised in that：It is described
Suitable fumaric acid and O-phthalic acid blend and Escherichia coli charged material weight ratio are 1 in step (1):0.002-0.02, instead
The PH for answering system is 8.5-10.0.
3. the method that maleic anhydride waste residue according to claim 1 prepares diethyl phthalate, it is characterised in that：It is described
Phthalic acid and aspartic acid mixture and ethanol charged material weight ratio are 1 in step (2):4-10.
4. the method that maleic anhydride waste residue according to claim 1 prepares diethyl phthalate, it is characterised in that：It is described
Phthalic acid and aspartic acid mixture and thionyl chloride charged material weight ratio are 1 in step (2)：1-3.
5. the method that maleic anhydride waste residue according to claim 1 prepares diethyl phthalate, it is characterised in that：It is described
Phthalic acid and aspartic acid mixture esterification at reflux, are reacted 5-12 hours in step (2).
6. the method that maleic anhydride waste residue according to claim 1 prepares diethyl phthalate, it is characterised in that：It is described
After steaming ethanol and thionyl chloride in step (2), the volume for adding water should be 1-3 times of residue, quiet after stirring
Put, separate water layer, oil reservoir is washed with water 1-3 times.
7. the method that maleic anhydride waste residue according to claim 1 prepares diethyl phthalate, it is characterised in that：It is described
Oil reservoir uses the dense dehydration of low vacuum in step (3), and vacuum is 200-300mmHg.
8. the method that maleic anhydride waste residue according to claim 1 prepares diethyl phthalate, it is characterised in that：It is described
Oil reservoir obtains diethyl phthalate of the purity more than 96wt% through vacuum distillation in step (3).
9. the method that maleic anhydride waste residue according to claim 1 prepares diethyl phthalate, it is characterised in that：It is described
It is 2~4 to adjust PH with hydrochloric acid in step (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710066042.9A CN106831429A (en) | 2017-02-06 | 2017-02-06 | A kind of method that maleic anhydride waste residue prepares diethyl phthalate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710066042.9A CN106831429A (en) | 2017-02-06 | 2017-02-06 | A kind of method that maleic anhydride waste residue prepares diethyl phthalate |
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| CN106831429A true CN106831429A (en) | 2017-06-13 |
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| CN201710066042.9A Pending CN106831429A (en) | 2017-02-06 | 2017-02-06 | A kind of method that maleic anhydride waste residue prepares diethyl phthalate |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050260258A1 (en) * | 2003-12-18 | 2005-11-24 | The Texas A&M University System | Use of vitelline protein B as a microencapsulating additive |
| CN101343210A (en) * | 2008-08-21 | 2009-01-14 | 四川德莱投资有限公司 | Method for preparing BDO/succinic acid diester and phthalandione diester with by-product from benzoic anhydride preparation |
| CN102153559A (en) * | 2011-02-28 | 2011-08-17 | 南京工业大学 | Novel method for synthesizing sitagliptin phosphate and derivative thereof |
| CN103508892A (en) * | 2013-10-10 | 2014-01-15 | 上海市计量测试技术研究院 | Synthetic method for phthalate compound |
| CN103525880A (en) * | 2013-10-17 | 2014-01-22 | 张家港市华昌药业有限公司 | Application of maleic anhydride waste residue in preparation of aspartic acid and method for preparing aspartic acid by using maleic anhydride waste residue |
| CN106588682A (en) * | 2016-10-28 | 2017-04-26 | 张家港市华昌药业有限公司 | New preparation method of ethyl aspartate hydrochloride |
-
2017
- 2017-02-06 CN CN201710066042.9A patent/CN106831429A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050260258A1 (en) * | 2003-12-18 | 2005-11-24 | The Texas A&M University System | Use of vitelline protein B as a microencapsulating additive |
| CN101343210A (en) * | 2008-08-21 | 2009-01-14 | 四川德莱投资有限公司 | Method for preparing BDO/succinic acid diester and phthalandione diester with by-product from benzoic anhydride preparation |
| CN102153559A (en) * | 2011-02-28 | 2011-08-17 | 南京工业大学 | Novel method for synthesizing sitagliptin phosphate and derivative thereof |
| CN103508892A (en) * | 2013-10-10 | 2014-01-15 | 上海市计量测试技术研究院 | Synthetic method for phthalate compound |
| CN103525880A (en) * | 2013-10-17 | 2014-01-22 | 张家港市华昌药业有限公司 | Application of maleic anhydride waste residue in preparation of aspartic acid and method for preparing aspartic acid by using maleic anhydride waste residue |
| CN106588682A (en) * | 2016-10-28 | 2017-04-26 | 张家港市华昌药业有限公司 | New preparation method of ethyl aspartate hydrochloride |
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Application publication date: 20170613 |