CN103819336A - Preparation method of diester succinate - Google Patents
Preparation method of diester succinate Download PDFInfo
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- CN103819336A CN103819336A CN201410100605.8A CN201410100605A CN103819336A CN 103819336 A CN103819336 A CN 103819336A CN 201410100605 A CN201410100605 A CN 201410100605A CN 103819336 A CN103819336 A CN 103819336A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- -1 diester succinate Chemical class 0.000 title abstract 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 175
- 239000001384 succinic acid Substances 0.000 claims abstract description 88
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- 239000007864 aqueous solution Substances 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000002148 esters Chemical class 0.000 claims abstract description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 3
- 239000002608 ionic liquid Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 75
- 238000000605 extraction Methods 0.000 claims description 42
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 19
- 230000032050 esterification Effects 0.000 claims description 19
- 238000005886 esterification reaction Methods 0.000 claims description 19
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 8
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000013517 stratification Methods 0.000 claims description 4
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 26
- 239000003054 catalyst Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000007795 chemical reaction product Substances 0.000 description 19
- 239000002253 acid Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 12
- 230000009466 transformation Effects 0.000 description 7
- 238000000855 fermentation Methods 0.000 description 4
- 230000004151 fermentation Effects 0.000 description 4
- 238000004064 recycling Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000001577 simple distillation Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 0 C[N+](**1C=*(*)C=C1)(C#*)[O-] Chemical compound C[N+](**1C=*(*)C=C1)(C#*)[O-] 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012262 fermentative production Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of diester succinate. The method comprises the following steps: mixing a low-concentration succinic acid aqueous solution, alcohol, an extracting agent and a catalyst for reaction to obtain succinic acid diester. The reaction adopts an immobilized sulfonic acid heteropoly acid ionic liquid as a catalyst, has good catalytic effect and can be recycled; during the reaction process, polychlorinated alkane is adopted to continuously extract the product ester, so that the reaction is continuously promoted to be carried out in the positive direction, and the conversion rate of succinic acid is greatly improved. The experimental result shows that the yield of the succinic acid diester obtained by the method is more than 97%. The preparation method is simple, the related catalyst, alcohol and extractant can be recycled, so that the cost is greatly reduced, and the preparation method is simple, reasonable in process flow, low in energy consumption and good in product quality.
Description
Technical field
The present invention relates to the direct esterification of a kind of succinic acid aqueous solution and prepare the preparation method of succinate.
Background technology
In fermentative Production succinic acid process, fermentation later succinic acid is present in the fermented liquid that has large water gaging, and the concentration that increases succinic acid by concentrated mode can increase power consumption.There is successively domestic and international correlative study mechanism to report out about extract succinic acid from fermented liquid, the main calcium salt of its extracting method and ammonium salt process, solvent extration, ion exchange adsorption, membrane separation process, electroosmose process and direct esterification hydrolysis method etc., wherein direct esterification hydrolysis method is a kind of good succinic acid extraction method.Due to the characteristic of esterification, from system, removing in time product is the important means that improves reaction conversion ratio.
From fermented liquid, directly succinic acid esterification is obtained to the more succinate of high value, directly obtain target product, it has shortened technological process, has reduced energy consumption, has greatly reduced cost.Due to the existence of large water gaging, the concentration of reactant is very low, and it is slow that esterification is carried out, and the esterification yield of succinic acid also can be very low.By the characteristic of esterification, from system, removing in time product is the important means that improves reaction conversion ratio.Can take good solid acid catalyst to accelerate speed of reaction, and can constantly ester be extracted from water by the mode of extraction, will increase to a great extent like this transformation efficiency of succinic acid.The extraction agent adopting easily separates with product ester, can recycle, more economically.
Dimethyl succinate has another name called succsinic acid (English name: Dimethyl succinate, CAS No:106-65-0), colourless to weak yellow liquid (under room temperature), cooling rear curable, be grape wine and ether perfume (or spice) and fruital and burnt odor, 195～196 ℃ of boiling points, or 80 ℃ (1466Pa), 18～19 ℃ of fusing points, be slightly soluble in water (1%), be dissolved in ethanol (3%), miscible in oils, natural product are present in to be fried in fibert.It is widely used in the industries such as spices, food, daily-use chemical industry, medicine, coating.
The method of industrial synthesis of dimethyl succinate is, take succinic acid and methyl alcohol as raw material, makes catalyzer through esterification and obtains with the vitriol oil.Such synthetic method side reaction is many, and equipment is easily corroded, and final treatment techniques is complicated and easily cause environmental pollution.
In the existing bibliographical information about succinic acid esterification, majority is under various catalyzer, to react and obtain corresponding succinate from different esterifying agents with sterling succinic acid.In various reports, the transformation efficiency of succinic acid and product yield have also obtained good effect.But seldom about the succinic acid direct esterification in fermented liquid being obtained to the report of target product.By succinic acid direct esterification add extraction agent that product ester is extracted to such an extent that the method for succinate has shortened technological process in the aqueous solution, reduce energy consumption, greatly reduce cost.
Summary of the invention
The invention provides a kind of preparation method who prepares succinate, solved utilizing biological fermentation process to produce in the process of succinic acid, the succinic acid solution direct esterification after fermentation is obtained to the dimethyl succinate being possessed of higher values.
The technical solution used in the present invention is:
A preparation method for succinate, its step is as follows:
(1) by the succinic acid aqueous solution, the esterifying agent of lower concentration, add in reactor, add catalyzer, extraction agent simultaneously, the mass concentration of the succinic acid aqueous solution of described lower concentration is 3%～7%, described esterifying agent is the one in methyl alcohol, ethanol, n-propyl alcohol, Virahol, described catalyzer is silica gel load sulfonic acid type heteropolyacid double-core ionic liquid as shown in the formula (I)
Described extraction agent is the many chloroparaffins containing reactive hydrogen;
(2) at temperature 50 C～100 ℃, the succinic acid aqueous solution and esterifying agent carry out esterification;
(3) separate: by reacted mixture, carry out solid-liquid separation, stratification, again the extraction liquid containing ester layer distilled, get final product to obtain dimethyl succinate.
The mass concentration of the described succinic acid aqueous solution of step (1) is 6%～8%.
Described in step (1), the mol ratio of succinic acid and esterifying agent is 1:3～1:10.
The mol ratio of described succinic acid and esterifying agent is 1:6～1:8.
Extraction agent described in step (1) is methylene dichloride, chloroform, 1,2-ethylene dichloride, vinyl trichloride, the one in 1,1,2,2-trichloroethane, propylene dichloride etc.
The volume that adds extraction agent is 1/2～3/2 of succinic acid aqueous solution volume.
Temperature of reaction described in step (2) is 50 ℃～90 ℃.
Reaction times described in step (2) is 4～8 hours.
Described in step (3), filter, solid catalyst and mixed solution can be separated to catalyzer reusable edible; Described stratification, can separate in ester and the aqueous solution, then goes out recycle by reacting last separating methanol in the aqueous solution; Described simple distillation, because the boiling point of selected extraction agent and ester differs greatly, so under normal pressure, can steam extraction agent with general distillation technique, extraction agent can recycling.
Innovation of the present invention and advantage
(1) the present invention can obtain the dimethyl succinate being possessed of higher values by the succinic acid solution direct esterification after fermentation.The method has been saved succinic acid and has been strengthened process concentrated, that extract, directly obtains target product by the esterification recycling abstraction technique in fermented liquid.
(2) the present invention adopts solid acid as catalyst, has overcome liquid acid as catalyst and has existed catalyzer and reaction system to be difficult to separate, can not to reuse and the deficiency such as discharge contaminate environment.Making reaction, to finish rear gained mixture more easily separated, and its flow process is simplified more, and catalyzer can recycle, thereby greatly reduce costs.
(3) the present invention, in the esterification stage, adopts extraction agent constantly gained ester to be extracted, and is that reaction is carried out to positive dirction, has greatly increased the transformation efficiency of succinic acid.
(4) the present invention is at separation phase, only reacted mixture simply need be filtered, stratification, simple distillation can separate each material one by one, related catalyzer, esterifying agent, all reusable edibles of extraction agent.Products obtained therefrom quality is good.
The method has been saved the process that succinic acid is concentrated, extract, and directly obtains target product by the esterification recycling abstraction technique in fermented liquid.The method has greatly reduced energy consumption, has simplified technical process, and its preparation method is simple, and the product that its quality product of preparing is high, process cost is low, obtain is worth larger.
Concrete embodiment
Embodiment 1
3g succinic acid and 47g water are added in there-necked flask, obtain the succinic acid aqueous solution of 6wt%; Add again 2.44g methyl alcohol, add 1.5g(3wt% simultaneously) catalyzer, finally add 75ml extraction agent (methylene dichloride).Temperature of reaction is 70 ℃, and 4h is carried out in reaction, obtains reaction product.Experimental results is as following table 1.
Embodiment 2
3g succinic acid and 47g water are added in there-necked flask, obtain the succinic acid aqueous solution of 6wt%; Add again 7.03g ethanol, add 3.0g catalyzer simultaneously, finally add 75ml extraction agent (1,2-ethylene dichloride).Temperature of reaction is 70 ℃, and 5h is carried out in reaction, obtains reaction product.Experimental results is as following table 1.
Embodiment 3
3g succinic acid and 47g water are added in there-necked flask, obtain the succinic acid aqueous solution of 6wt%; Add again 9.17g n-propyl alcohol, add 3.0g catalyzer simultaneously, finally add 75ml extraction agent (1,2-ethylene dichloride).Temperature of reaction is 70 ℃, and 6h is carried out in reaction, obtains reaction product.Experimental results is as following table 1.
Embodiment 4
3g succinic acid and 47g water are added in there-necked flask, obtain the succinic acid aqueous solution of 6wt%; Add again 4.88g methyl alcohol, add 3.5g(7wt% simultaneously) catalyzer, finally add 75ml extraction agent (1,2-ethylene dichloride).Temperature of reaction is 70 ℃, and 7h is carried out in reaction, obtains reaction product.Experimental results is as following table 1.
Embodiment 5
3g succinic acid and 47g water are added in there-necked flask, obtain the succinic acid aqueous solution of 6wt%; Add again 8.13g methyl alcohol, add 3.0g catalyzer simultaneously, finally add 75ml extraction agent (chloroform).Temperature of reaction is 70 ℃, and 8h is carried out in reaction, obtains reaction product.Experimental results is as following table 1.
The result of table 1 example 1-example 5
| Project | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Succinic acid concentration of aqueous solution/% | 6 | 6 | 6 | 6 | 6 |
| Succinic acid/methyl alcohol (mol ratio) | 1:3 | 1:6 | 1:6 | 1:6 | 1:10 |
| Reaction times/h | 4 | 5 | 6 | 7 | 8 |
| Temperature of reaction/℃ | 70 | 70 | 70 | 70 | 70 |
| Catalytic amount/g | 1.5（3%） | 3.0 | 3.0 | 3.5(7%) | 3.0 |
| Extraction dosage/ml | 75 | 75 | 75 | 75 | 75 |
| The transformation efficiency of succinic acid | 86.12 | 93.32 | 95.57 | 99.98 | 98.47 |
| The productive rate of dimethyl succinate | 80.23 | 91.67 | 93.36 | 98.89 | 96.23 |
Embodiment 6
3g succinic acid and 72g water are added in there-necked flask, obtain the succinic acid aqueous solution of 4wt%; Add again 4.88g methyl alcohol (acid alcohol ratio is about 1:6), add 3.0g catalyzer simultaneously, finally add 75ml extraction agent (1,2-ethylene dichloride).Temperature of reaction is 70 ℃, and 7h is carried out in reaction, obtains reaction product.Experimental results is as following table 2.
Embodiment 7
3g succinic acid and 47g water are added in there-necked flask, obtain the succinic acid aqueous solution of 6wt%; Add again 4.88g methyl alcohol (acid alcohol ratio is about 1:6), add 3.0g catalyzer simultaneously, finally add 75ml extraction agent (1,2-ethylene dichloride).Temperature of reaction is 70 ℃, and 7h is carried out in reaction, obtains reaction product.Experimental results is as following table 2.
Embodiment 8
3g succinic acid and 34.5g water are added in there-necked flask, obtain the succinic acid aqueous solution of 8wt%; Add again 4.88g methyl alcohol (acid alcohol ratio is about 1:6), add 3.0g catalyzer simultaneously, finally add 75ml extraction agent (1,2-ethylene dichloride).Temperature of reaction is 70 ℃, and 7h is carried out in reaction, obtains reaction product.Experimental results is as following table 2.
Embodiment 9
3g succinic acid and 27g water are added in there-necked flask, obtain the succinic acid aqueous solution of 10wt%; Add again 4.88g methyl alcohol (acid alcohol ratio is about 1:6), add 3.0g catalyzer simultaneously, finally add 75ml extraction agent (1,2-ethylene dichloride).Temperature of reaction is 70 ℃, and 7h is carried out in reaction, obtains reaction product.Experimental results is as following table 2.
The result of table 2 example 6-example 9
| Project | Example 6 | Example 7 | Example 8 | Example 9 |
| Succinic acid concentration of aqueous solution/% | 4 | 6 | 8 | 10 |
| Succinic acid/methyl alcohol (mol ratio) | 1:6 | 1:6 | 1:6 | 1:6 |
| Reaction times/h | 7 | 7 | 7 | 7 |
| Temperature of reaction/℃ | 70 | 70 | 70 | 70 |
| Catalytic amount/g | 3.0 | 3.0 | 3.0 | 3.0 |
| Extraction dosage/ml | 75 | 75 | 75 | 75 |
| The transformation efficiency of succinic acid | 90.33 | 99.56 | 99.77 | 99.98 |
| The yield of dimethyl succinate | 83.23 | 97.89 | 98.03 | 98.31 |
Embodiment 10
3g succinic acid and 47g water are added in there-necked flask, obtain the succinic acid aqueous solution of 6wt%; Add again 4.88g methyl alcohol (acid alcohol ratio is about 1:6), add 3.0g catalyzer simultaneously, finally add 30ml extraction agent (1,2-ethylene dichloride).Temperature of reaction is 70 ℃, and 7h is carried out in reaction, obtains reaction product.Experimental results is as following table 3.
Embodiment 11
3g succinic acid and 47g water are added in there-necked flask, obtain the succinic acid aqueous solution of 6wt%; Add again 4.88g methyl alcohol (acid alcohol ratio is about 1:6), add 3.0g catalyzer simultaneously, finally add 45ml extraction agent (1,2-ethylene dichloride).Temperature of reaction is 70 ℃, and 7h is carried out in reaction, obtains reaction product.Experimental results is as following table 3.
Embodiment 12
3g succinic acid and 47g water are added in there-necked flask, obtain the succinic acid aqueous solution of 6wt%; Add again 4.88g methyl alcohol (acid alcohol ratio is about 1:6), add 3.0g catalyzer simultaneously, finally add 60ml extraction agent (1,2-ethylene dichloride).Temperature of reaction is 70 ℃, and 7h is carried out in reaction, obtains reaction product.Experimental results is as following table 3.
Embodiment 13
3g succinic acid and 47g water are added in there-necked flask, obtain the succinic acid aqueous solution of 6wt%; Add again 4.88g methyl alcohol (acid alcohol ratio is about 1:6), add 3.0g catalyzer simultaneously, finally add 75ml extraction agent (1,2-ethylene dichloride).Temperature of reaction is 70 ℃, and 7h is carried out in reaction, obtains reaction product.Experimental results is as following table 3.
Embodiment 14
3g succinic acid and 47g water are added in there-necked flask, obtain the succinic acid aqueous solution of 6wt%; Add again 4.88g methyl alcohol (acid alcohol ratio is about 1:6), add 3.0g catalyzer simultaneously, finally add 90ml extraction agent (1,2-ethylene dichloride).Temperature of reaction is 70 ℃, and 7h is carried out in reaction, obtains reaction product.Experimental results is as following table 3.
The result of table 3 example 10-example 14
| Project | Example 10 | Example 11 | Example 12 | Example 13 | Example 14 |
| Succinic acid concentration of aqueous solution/% | 6 | 6 | 6 | 6 | 6 |
| Succinic acid/methyl alcohol (mol ratio) | 1:6 | 1:6 | 1:6 | 1:6 | 1:6 |
| Reaction times/h | 7 | 7 | 7 | 7 | 7 |
| Temperature of reaction/℃ | 70 | 70 | 70 | 70 | 70 |
| Catalytic amount/g | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 |
| Extraction dosage/ml | 30（1/2） | 45 | 60 | 75 | 90（3/2） |
| The transformation efficiency of succinic acid | 95.60 | 97.34 | 98.65 | 99.56 | 98.31 |
| The yield of dimethyl succinate | 81.23 | 93.67 | 95.21 | 97.89 | 96.33 |
Embodiment 15
3g succinic acid and 47g water are added in there-necked flask, obtain the succinic acid aqueous solution of 6wt%; Add again 4.88g methyl alcohol (acid alcohol ratio is about 1:6), add 3.0g catalyzer simultaneously, finally add 75ml extraction agent (1,2-ethylene dichloride).Temperature of reaction is 50 ℃, and 7h is carried out in reaction, obtains reaction product.Experimental results is as following table 4.
Embodiment 16
3g succinic acid and 47g water are added in there-necked flask, obtain the succinic acid aqueous solution of 6wt%; Add again 4.88g methyl alcohol (acid alcohol ratio is about 1:6), add 3.0g catalyzer simultaneously, finally add 75ml extraction agent (1,2-ethylene dichloride).Temperature of reaction is 60 ℃, and 7h is carried out in reaction, obtains reaction product.Experimental results is as following table 4.
Embodiment 17
3g succinic acid and 47g water are added in there-necked flask, obtain the succinic acid aqueous solution of 6wt%; Add again 4.88g methyl alcohol (acid alcohol ratio is about 1:6), add 3.0g catalyzer simultaneously, finally add 75ml extraction agent (1,2-ethylene dichloride).Temperature of reaction is 70 ℃, and 7h is carried out in reaction, obtains reaction product.Experimental results is as following table 4.
Embodiment 18
3g succinic acid and 47g water are added in there-necked flask, obtain the succinic acid aqueous solution of 6wt%; Add again 4.88g methyl alcohol (acid alcohol ratio is about 1:6), add 3.0g catalyzer simultaneously, finally add 75ml extraction agent (1,2-ethylene dichloride).Temperature of reaction is 80 ℃, and 7h is carried out in reaction, obtains reaction product.Experimental results is as following table 4.
Embodiment 19
3g succinic acid and 47g water are added in there-necked flask, obtain the succinic acid aqueous solution of 6wt%; Add again 4.88g methyl alcohol (acid alcohol ratio is about 1:6), add 3.0g catalyzer simultaneously, finally add 75ml extraction agent (1,2-ethylene dichloride).Temperature of reaction is 100 ℃, and 7h is carried out in reaction, obtains reaction product.Experimental results is as following table 4.
The result of table 4 example 15-example 19
| Project | Example 15 | Example 16 | Example 17 | Example 18 | Example 19 |
| Succinic acid concentration of aqueous solution/% | 6 | 6 | 6 | 6 | 6 |
| Succinic acid/methyl alcohol (mol ratio) | 1:6 | 1:6 | 1:6 | 1:6 | 1:6 |
| Reaction times/h | 7 | 7 | 7 | 7 | 7 |
| Temperature of reaction/℃ | 50 | 60 | 70 | 80 | 100 |
| Catalytic amount/g | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 |
| Extraction dosage/ml | 75 | 75 | 75 | 75 | 75 |
| The transformation efficiency of succinic acid | 93.33 | 97.20 | 99.56 | 98.04 | 97.87 |
| The yield of dimethyl succinate | 81.23 | 93.67 | 97.89 | 97.21 | 96.90 |
Claims (8)
1. a preparation method for succinate, its step is as follows:
(1) by the succinic acid aqueous solution, the esterifying agent of lower concentration, add in reactor, add catalyzer, extraction agent simultaneously, the mass concentration of the succinic acid aqueous solution of described lower concentration is 3%～7%, described esterifying agent is the one in methyl alcohol, ethanol, n-propyl alcohol, Virahol, described catalyzer is silica gel load sulfonic acid type heteropolyacid double-core ionic liquid as shown in the formula (I)
Described extraction agent is the many chloroparaffins containing reactive hydrogen;
(2) at temperature 50 C～100 ℃, the succinic acid aqueous solution and esterifying agent carry out esterification;
(3) separate: by reacted mixture, carry out solid-liquid separation, stratification, again the extraction liquid containing ester layer distilled, get final product to obtain dimethyl succinate.
2. preparation method according to claim 1, is characterized in that: the mass concentration of the described succinic acid aqueous solution of step (1) is 6%～8%.
3. preparation method according to claim 1, is characterized in that: described in step (1), the mol ratio of succinic acid and esterifying agent is 1:3～1:10.
4. preparation method according to claim 3, is characterized in that: the mol ratio of described succinic acid and esterifying agent is 1:6～1:8.
5. preparation method according to claim 1, is characterized in that: extraction agent described in step (1) is methylene dichloride, chloroform, 1,2-ethylene dichloride, vinyl trichloride, the one in 1,1,2,2-trichloroethane, propylene dichloride etc.
6. preparation method according to claim 1 or 5, is characterized in that: the volume that adds extraction agent is 1/2～3/2 of succinic acid aqueous solution volume.
7. preparation method according to claim 1, is characterized in that: temperature of reaction described in step (2) is 50 ℃～90 ℃.
8. preparation method according to claim 1, is characterized in that: the reaction times described in step (2) is 4～8 hours.
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