CN112592272A - Environment-friendly production method for greatly reducing sewage discharge of dimethyl succinyl succinate - Google Patents
Environment-friendly production method for greatly reducing sewage discharge of dimethyl succinyl succinate Download PDFInfo
- Publication number
- CN112592272A CN112592272A CN202011537127.9A CN202011537127A CN112592272A CN 112592272 A CN112592272 A CN 112592272A CN 202011537127 A CN202011537127 A CN 202011537127A CN 112592272 A CN112592272 A CN 112592272A
- Authority
- CN
- China
- Prior art keywords
- dimethyl
- succinate
- sewage discharge
- production method
- methanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
-
- 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
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Abstract
The invention provides an environment-friendly production method for greatly reducing the sewage discharge of dimethyl succinyl succinate. According to the technical scheme, firstly, succinic acid and methanol are reacted under the protection of nitrogen to generate dimethyl succinate, the dimethyl succinate is taken as a reaction solvent, sodium methoxide is dropwise added into the reaction solvent under the condition of ultrasonic oscillation, after the dropwise addition is finished, the reflux reaction is continued for a period of time, and the microscopic vibration of fluid is helpful for improving the sufficiency of the reaction; after the reaction is finished, stirring and slurrying, then carrying out suction filtration, washing with anhydrous methanol, and then fractionating to recover methanol and dimethyl succinate; and neutralizing the filter cake with dilute sulfuric acid, and then carrying out reduced pressure distillation to obtain the final product. On the basis, the invention utilizes the residual liquid of reduced pressure distillation to prepare pickling solution, and adds calcium chloride into the excessive pickling solution, thereby obtaining calcium sulfate by-product; meanwhile, the high-temperature residual liquid after fractionation is used as dimethyl succinate in the next stage for heating, so that the waste heat is effectively utilized, and the sewage discharge is reduced.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to an environment-friendly production method for greatly reducing the sewage discharge of dimethyl succinyl succinate.
Background
Dimethyl succinylsuccinate is an important organic synthesis intermediate. The synthesis process of the compound has a plurality of processes, and generally adopts a process route that dimethyl succinate is subjected to self condensation in an inert solvent under the action of sodium alkoxide to generate dimethyl succinylsuccinate. The solvents commonly used are high boiling compounds such as xylene, toluene, dowels and the like, and a small amount of a polar cosolvent is often added to promote the reaction. Common polar cosolvents are dimethyl sulfoxide, N-dimethylformamide, sulfolane, and the like. No matter what mixed solvent composed of inert solvent and cosolvent is adopted, the defects of complex product separation and purification process, low product yield, overlong reaction time and the like exist.
Aiming at the problem, the applicant firstly utilizes succinic acid and methanol to react under the protection of nitrogen to generate dimethyl succinate, takes the dimethyl succinate as a reaction solvent, dropwise adds sodium methoxide into the reaction solvent under the ultrasonic oscillation condition, and continuously performs reflux reaction for a period of time after the dropwise addition is finished, so that the reaction sufficiency is improved by virtue of microscopic vibration of fluid; after the reaction is finished, stirring and slurrying, then carrying out suction filtration, washing with anhydrous methanol, and then fractionating to recover methanol and dimethyl succinate; and neutralizing the filter cake with dilute sulfuric acid, and then carrying out reduced pressure distillation to obtain the final product. The process method effectively ensures the product yield, simplifies the process steps to a certain extent, and has relatively large sewage discharge amount.
Disclosure of Invention
The invention aims to provide an environment-friendly production method for greatly reducing the sewage discharge of dimethyl succinyl succinate aiming at the technical defects of the prior art so as to solve the technical problem of larger sewage discharge amount of the conventional production method.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
an environment-friendly production method for greatly reducing the sewage discharge of dimethyl succinyl succinate comprises the following steps:
1) adding succinic acid into a container, stirring, heating to 56 ℃, then heating to 95 ℃ under the protection of nitrogen, dropwise adding excessive methanol into the system for 5 hours, then evaporating excessive methanol under normal pressure, then carrying out reduced pressure distillation to collect a product to obtain dimethyl succinate, and meanwhile collecting a residual liquid for later use;
2) continuously stirring the reacted dimethyl succinate solution under the protection of nitrogen, heating the reacted dimethyl succinate solution to 120 ℃ under the condition of heat exchange of an electric heating combined jacket, maintaining the temperature for 30min, then dropwise adding a sodium methoxide solution into the reacted dimethyl succinate solution under the condition of ultrasonic oscillation, performing reflux reaction for 25min after dropwise adding is finished, cooling the reactant, adding anhydrous methanol, stirring, slurrying, performing suction filtration, washing a filter cake with the anhydrous methanol, combining mother liquor and washing liquid for fractionation, recovering methanol and dimethyl succinate, and filling residual liquid obtained by fractionation into the jacket as a heat exchange working medium;
3) diluting sulfuric acid with the concentration of 98% to 20% by using the residual liquid obtained in the step 1), after the cake is dried by pumping, neutralizing by using the diluent, separating out a product, performing suction filtration to respectively collect a solid phase and a liquid phase, performing reduced pressure drying on the solid phase at the temperature of 45 ℃ and the pressure of 0.5 atmospheric pressure for 6 hours to obtain a finished product of dimethyl succinyl succinate, adding excessive calcium chloride into the liquid phase, and collecting a precipitate.
Preferably, the molar amount of the total dropwise addition amount of methanol in the step 1) is 4 times that of succinic acid.
Preferably, the product collected in step 1) is a 120 ℃/650mmHg cut.
Preferably, the ultrasonic oscillation condition in the step 2) is 1.7 MHz; the dropping speed of sodium methoxide in the step 2) is 10 mL/min.
Preferably, the dosage ratio of the dimethyl succinate solution to the sodium methoxide in the step 2) is 5mL to 2.3 g.
Preferably, the method further comprises the following step 4): and crushing the finished product of the dimethyl succinyl succinate after decompression drying, grinding the crushed product in a grinder, and packaging the ground product.
The invention provides an environment-friendly production method for greatly reducing the sewage discharge of dimethyl succinyl succinate. According to the technical scheme, firstly, succinic acid and methanol are reacted under the protection of nitrogen to generate dimethyl succinate, the dimethyl succinate is taken as a reaction solvent, sodium methoxide is dropwise added into the reaction solvent under the condition of ultrasonic oscillation, after the dropwise addition is finished, the reflux reaction is continued for a period of time, and the microscopic vibration of fluid is helpful for improving the sufficiency of the reaction; after the reaction is finished, stirring and slurrying, then carrying out suction filtration, washing with anhydrous methanol, and then fractionating to recover methanol and dimethyl succinate; and neutralizing the filter cake with dilute sulfuric acid, and then carrying out reduced pressure distillation to obtain the final product. On the basis, the invention utilizes the residual liquid of reduced pressure distillation to prepare pickling solution, and adds calcium chloride into the excessive pickling solution, thereby obtaining calcium sulfate by-product; meanwhile, the high-temperature residual liquid after fractionation is used as dimethyl succinate in the next stage for heating, so that the waste heat is effectively utilized, and the sewage discharge is reduced. The invention has the advantages of high yield, remarkably reduced pollutant discharge amount and outstanding technical advantages.
Drawings
FIG. 1 is a molecular structure diagram of dimethyl succinylsuccinate in the present invention.
Detailed Description
Hereinafter, specific embodiments of the present invention will be described in detail. Well-known structures or functions may not be described in detail in the following embodiments in order to avoid unnecessarily obscuring the details. Approximating language, as used herein in the following examples, may be applied to identify quantitative representations that could permissibly vary in number without resulting in a change in the basic function. Unless defined otherwise, technical and scientific terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Example 1
An environment-friendly production method for greatly reducing the sewage discharge of dimethyl succinyl succinate comprises the following steps:
1) adding succinic acid into a container, stirring, heating to 56 ℃, then heating to 95 ℃ under the protection of nitrogen, dropwise adding excessive methanol into the system for 5 hours, then evaporating excessive methanol under normal pressure, then carrying out reduced pressure distillation to collect a product to obtain dimethyl succinate, and meanwhile collecting a residual liquid for later use;
2) continuously stirring the reacted dimethyl succinate solution under the protection of nitrogen, heating the reacted dimethyl succinate solution to 120 ℃ under the condition of heat exchange of an electric heating combined jacket, maintaining the temperature for 30min, then dropwise adding a sodium methoxide solution into the reacted dimethyl succinate solution under the condition of ultrasonic oscillation, performing reflux reaction for 25min after dropwise adding is finished, cooling the reactant, adding anhydrous methanol, stirring, slurrying, performing suction filtration, washing a filter cake with the anhydrous methanol, combining mother liquor and washing liquid for fractionation, recovering methanol and dimethyl succinate, and filling residual liquid obtained by fractionation into the jacket as a heat exchange working medium;
3) diluting sulfuric acid with the concentration of 98% to 20% by using the residual liquid obtained in the step 1), after the cake is dried by pumping, neutralizing by using the diluent, separating out a product, performing suction filtration to respectively collect a solid phase and a liquid phase, performing reduced pressure drying on the solid phase at the temperature of 45 ℃ and the pressure of 0.5 atmospheric pressure for 6 hours to obtain a finished product of dimethyl succinyl succinate, adding excessive calcium chloride into the liquid phase, and collecting a precipitate.
Example 2
An environment-friendly production method for greatly reducing the sewage discharge of dimethyl succinyl succinate comprises the following steps:
1) adding succinic acid into a container, stirring, heating to 56 ℃, then heating to 95 ℃ under the protection of nitrogen, dropwise adding excessive methanol into the system for 5 hours, then evaporating excessive methanol under normal pressure, then carrying out reduced pressure distillation to collect a product to obtain dimethyl succinate, and meanwhile collecting a residual liquid for later use;
2) continuously stirring the reacted dimethyl succinate solution under the protection of nitrogen, heating the reacted dimethyl succinate solution to 120 ℃ under the condition of heat exchange of an electric heating combined jacket, maintaining the temperature for 30min, then dropwise adding a sodium methoxide solution into the reacted dimethyl succinate solution under the condition of ultrasonic oscillation, performing reflux reaction for 25min after dropwise adding is finished, cooling the reactant, adding anhydrous methanol, stirring, slurrying, performing suction filtration, washing a filter cake with the anhydrous methanol, combining mother liquor and washing liquid for fractionation, recovering methanol and dimethyl succinate, and filling residual liquid obtained by fractionation into the jacket as a heat exchange working medium;
3) diluting sulfuric acid with the concentration of 98% to 20% by using the residual liquid obtained in the step 1), after the cake is dried by pumping, neutralizing by using the diluent, separating out a product, performing suction filtration to respectively collect a solid phase and a liquid phase, performing reduced pressure drying on the solid phase at the temperature of 45 ℃ and the pressure of 0.5 atmospheric pressure for 6 hours to obtain a finished product of dimethyl succinyl succinate, adding excessive calcium chloride into the liquid phase, and collecting a precipitate.
Wherein the molar weight of the total dropwise adding amount of the methanol in the step 1) is 4 times of that of the succinic acid. The product collected in step 1) is a 120 ℃/650mmHg cut. The ultrasonic oscillation condition in the step 2) is 1.7 MHz; the dropping speed of sodium methoxide in the step 2) is 10 mL/min. In the step 2), the dosage ratio of the dimethyl succinate solution to the sodium methoxide is 5mL to 2.3 g. Further comprising the following step 4): and crushing the finished product of the dimethyl succinyl succinate after decompression drying, grinding the crushed product in a grinder, and packaging the ground product.
The embodiments of the present invention have been described in detail, but the description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention. Any modification, equivalent replacement, and improvement made within the scope of the application of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. An environment-friendly production method for greatly reducing the sewage discharge of dimethyl succinyl succinate is characterized by comprising the following steps:
1) adding succinic acid into a container, stirring, heating to 56 ℃, then heating to 95 ℃ under the protection of nitrogen, dropwise adding excessive methanol into the system for 5 hours, then evaporating excessive methanol under normal pressure, then carrying out reduced pressure distillation to collect a product to obtain dimethyl succinate, and meanwhile collecting a residual liquid for later use;
2) continuously stirring the reacted dimethyl succinate solution under the protection of nitrogen, heating the reacted dimethyl succinate solution to 120 ℃ under the condition of heat exchange of an electric heating combined jacket, maintaining the temperature for 30min, then dropwise adding a sodium methoxide solution into the reacted dimethyl succinate solution under the condition of ultrasonic oscillation, performing reflux reaction for 25min after dropwise adding is finished, cooling the reactant, adding anhydrous methanol, stirring, slurrying, performing suction filtration, washing a filter cake with the anhydrous methanol, combining mother liquor and washing liquid for fractionation, recovering methanol and dimethyl succinate, and filling residual liquid obtained by fractionation into the jacket as a heat exchange working medium;
3) diluting sulfuric acid with the concentration of 98% to 20% by using the residual liquid obtained in the step 1), after the cake is dried by pumping, neutralizing by using the diluent, separating out a product, performing suction filtration to respectively collect a solid phase and a liquid phase, performing reduced pressure drying on the solid phase at the temperature of 45 ℃ and the pressure of 0.5 atmospheric pressure for 6 hours to obtain a finished product of dimethyl succinyl succinate, adding excessive calcium chloride into the liquid phase, and collecting a precipitate.
2. The environment-friendly production method for greatly reducing the sewage discharge of dimethyl succinylsuccinate according to claim 1, wherein the molar amount of the total dropwise added amount of methanol in the step 1) is 4 times of that of succinic acid.
3. The environmental-friendly production method for greatly reducing the sewage discharge of dimethyl succinyl succinate according to claim 1, wherein the product collected in the step 1) is a fraction of 120 ℃/650 mmHg.
4. The environment-friendly production method for greatly reducing the sewage discharge of dimethyl succinylsuccinate according to claim 1, wherein the ultrasonic oscillation condition in the step 2) is 1.7 MHz; the dropping speed of sodium methoxide in the step 2) is 10 mL/min.
5. The environment-friendly production method for greatly reducing the sewage discharge of dimethyl succinyl succinate according to claim 1, wherein the dosage ratio of the dimethyl succinate solution to sodium methoxide in the step 2) is 5mL:2.3 g.
6. The environment-friendly production method for greatly reducing the sewage discharge of dimethyl succinylsuccinate according to claim 1, further comprising the following step 4): and crushing the finished product of the dimethyl succinyl succinate after decompression drying, grinding the crushed product in a grinder, and packaging the ground product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011537127.9A CN112592272A (en) | 2020-12-23 | 2020-12-23 | Environment-friendly production method for greatly reducing sewage discharge of dimethyl succinyl succinate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011537127.9A CN112592272A (en) | 2020-12-23 | 2020-12-23 | Environment-friendly production method for greatly reducing sewage discharge of dimethyl succinyl succinate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112592272A true CN112592272A (en) | 2021-04-02 |
Family
ID=75200668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011537127.9A Withdrawn CN112592272A (en) | 2020-12-23 | 2020-12-23 | Environment-friendly production method for greatly reducing sewage discharge of dimethyl succinyl succinate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112592272A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003147121A (en) * | 2001-11-16 | 2003-05-21 | Teijin Ltd | Method for chemically recycling all aromatic polyester |
| CN102050738A (en) * | 2009-10-28 | 2011-05-11 | 襄樊高隆磷化工有限责任公司 | Synthesis technology of dimethyl succinylsuccinate |
| CN102093219A (en) * | 2010-11-22 | 2011-06-15 | 天津市职业大学 | Method for synthesizing succinyl succinic dialkyl ester |
| CN102584593A (en) * | 2012-01-09 | 2012-07-18 | 浙江永泉化学有限公司 | Preparation method for dimethyl succinylo succinate (DMSS) |
| CN106986771A (en) * | 2017-06-02 | 2017-07-28 | 淄博鸿润新材料有限公司 | A kind of method of continuous production DMSS |
| CN109824511A (en) * | 2019-04-09 | 2019-05-31 | 淄博鸿润新材料有限公司 | The preparation method of high-purity dimethyl succinyl succinate |
| CN112094189A (en) * | 2020-09-28 | 2020-12-18 | 彩客化学(沧州)有限公司 | Synthesis method of dimethyl succinylsuccinate |
-
2020
- 2020-12-23 CN CN202011537127.9A patent/CN112592272A/en not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003147121A (en) * | 2001-11-16 | 2003-05-21 | Teijin Ltd | Method for chemically recycling all aromatic polyester |
| CN102050738A (en) * | 2009-10-28 | 2011-05-11 | 襄樊高隆磷化工有限责任公司 | Synthesis technology of dimethyl succinylsuccinate |
| CN102093219A (en) * | 2010-11-22 | 2011-06-15 | 天津市职业大学 | Method for synthesizing succinyl succinic dialkyl ester |
| CN102584593A (en) * | 2012-01-09 | 2012-07-18 | 浙江永泉化学有限公司 | Preparation method for dimethyl succinylo succinate (DMSS) |
| CN106986771A (en) * | 2017-06-02 | 2017-07-28 | 淄博鸿润新材料有限公司 | A kind of method of continuous production DMSS |
| CN109824511A (en) * | 2019-04-09 | 2019-05-31 | 淄博鸿润新材料有限公司 | The preparation method of high-purity dimethyl succinyl succinate |
| CN112094189A (en) * | 2020-09-28 | 2020-12-18 | 彩客化学(沧州)有限公司 | Synthesis method of dimethyl succinylsuccinate |
Non-Patent Citations (2)
| Title |
|---|
| 王立久 编著: "《建筑材料工艺原理》", 31 March 2006, 中国建材工业出版社 * |
| 高红武 主编: "《水污染治理技术 工学结合教材 第2版》", 31 January 2015, 中国环境工业出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101489970B (en) | Method for producing succinic acid | |
| CN1445266A (en) | Method for recycling colvent utilized in producting polyphenylene sulfide | |
| CN111138347B (en) | Industrial method and device for water diversion of vinyl pyridine compounds | |
| RU2036900C1 (en) | Method of industrial synthesis of urea | |
| CN114349663A (en) | Preparation method of 2-methoxyethyl-2- (4-tert-butylphenyl) cyanate | |
| CN112592272A (en) | Environment-friendly production method for greatly reducing sewage discharge of dimethyl succinyl succinate | |
| CN112390748A (en) | Preparation method of 2-cyano-3-fluoro-5-trifluoromethylpyridine | |
| RU2404952C1 (en) | Methyl chloride synthesis method | |
| CN115353458B (en) | Method for preparing aclonifen | |
| CN112694409B (en) | Method and device for recycling triethylamine in wastewater | |
| CN110563669A (en) | Method and device for improving morpholine purity | |
| JP3899834B2 (en) | Method for producing 2- (4-pyridyl) ethanethiol | |
| CN111518861B (en) | Novel process for preparing D-calcium pantothenate | |
| CN211752616U (en) | Caprolactam device is refined in crystallization | |
| KR102062143B1 (en) | Method for producing high purity Ethyl 3-Ethoxypropionate | |
| CN115181060B (en) | Clean production process for producing 2-amino-3-chloro-5-trifluoromethyl pyridine | |
| US2776972A (en) | Recovery of morpholine from aqueous solutions thereof | |
| CN110330470A (en) | A method of realizing that biomass-based furfuran compound purifies using Schiff reaction | |
| CN114085132B (en) | Preparation method of 2, 6-dihydroxytoluene | |
| CN115845421B (en) | System and method for continuously separating perfluorinated hexanone | |
| CN113582932A (en) | Purification method of 4,6-dichloropyrimidine | |
| CN108623474A (en) | It is a kind of to purify N, N, N, the method for N- tetramethyl-1,3-propane diamines using azeotropic distillation | |
| CN115028555A (en) | Diethyl sulfate continuous synthesis process | |
| CN107188783B (en) | Method for recovering formaldehyde in system for synthesizing isopentenol by supercritical method | |
| CN117430270A (en) | Method for recycling glycine production wastewater by chloroacetic acid method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210402 |
|
| WW01 | Invention patent application withdrawn after publication |