CN104926655A - Technology and device for diethyl oxalate synthesis through vapor permeation dehydration process - Google Patents
Technology and device for diethyl oxalate synthesis through vapor permeation dehydration process Download PDFInfo
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- CN104926655A CN104926655A CN201510320561.4A CN201510320561A CN104926655A CN 104926655 A CN104926655 A CN 104926655A CN 201510320561 A CN201510320561 A CN 201510320561A CN 104926655 A CN104926655 A CN 104926655A
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- diethyl oxalate
- permeable membrane
- vapor permeable
- water vapour
- oxalate synthesis
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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
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
Abstract
The invention relates to a technology and device for diethyl oxalate synthesis through a vapor permeation dehydration process, and belongs to the technical field of pervaporation membrane separation application and organic compound synthesis technologies. The technology comprises the following steps: under the action of a catalyst, oxalic acid and ethyl alcohol are subjected to esterification reaction in a reaction kettle provided with a rectification column, and after steam generated during the reaction passes through the rectification column, heavy components return into the reaction kettle; light components are condensed, then, one part of the light components are sent to the top of the rectification column for refluxing, the other part of the light components enter a pervaporation membrane raw material solution side to be subjected to vapor permeation dehydration, and the obtained products are condensed to return into the reaction kettle. According to the invention, water in the esterification reaction process is continuously removed in the situation that an azeotropic dehydration agent causing pollution to the environment is not introduced, so that the reaction is facilitated, the conversion rate of the reaction is increased, the problem about the post-processing of the azeotropic dehydration agent and the problem of environment pollution of the azeotropic dehydration agent are avoided, and the production cost is reduced.
Description
Technical field
The present invention relates to a kind of water vapour penetration dehydration for the technique of diethyl oxalate synthesis and device, belong to the application of infiltration evaporation membrane sepn and organic synthesis technology technical field.
Background technology
Oxalic acid diethyl ester is the intermediate of the products such as medicine, plastics, dyestuff, also can make the solvent of Mierocrystalline cellulose, spices etc.The direct oxalic acid esterification process of domestic main employing produces oxalic acid diethyl ester.This method makes azeotropic aqua with benzene or toluene, then phase-splitting reflux dewatering, takes out of from reactive material to anhydrous, and distillation removing benzene (toluene) and ethanol, can obtain oxalic acid diethyl ester crude product.But the method use benzene or toluene, must remove, cause pollution to environment in the treating process of oxalic acid diethyl ester, benzene or toluene need reclaim, and bring extra production cost simultaneously.
Summary of the invention
The technical problem to be solved in the present invention overcomes diethyl oxalate synthesis technique to use in three components and reaction process except water problem, proposes a kind of water vapour penetration dehydration for the technique of diethyl oxalate synthesis and device.Light constituent in reactor is sent into vapor permeation membrane component dewatered by rectifying column, condenser, feed pump vaporizer, this method can in time except the water that dereaction generates when not introducing three components.
A kind of water vapour penetration dehydration is used for the technique of diethyl oxalate synthesis, comprise the steps: under the effect of catalyzer, esterification is carried out by oxalic acid and ethanol, the gaseous mixture that reaction produces carries out rectifying, the tower top light constituent that at least part of rectifying obtains enters vapor permeable membrane and dewaters, and the material after dehydration is back to the reaction system of oxalic acid and ethanol.
The material of vapor permeable membrane elects molecular screen membrane, soft silica film, chitosan film, PVA film or sodium alginate film as, preferred molecular sieve film.
Catalyzer is selected from the vitriol oil, to toluene yellow acid, Ammonium ferric sulfate dodecahyrate, Zeo-karb.
Rectifying column tower top pressure operating method is decompression, normal pressure or pressurization.
Light constituent enters vapor permeable membrane, preferably 100 ~ 110 DEG C after vaporizer vaporization is to 100 ~ 130 DEG C.
The absolute pressure of infiltrating and vaporizing membrane per-meate side is 10 ~ 3000Pa.
A kind of water vapour penetration dehydration is used for the device of diethyl oxalate synthesis, include reactor, rectifying column, vapor permeable membrane, rectifying column is arranged at the top of reactor, the top of rectifying column is connected to the entrance of the feed liquid side of vapor permeable membrane successively by overhead condenser, tundish, transferpump, tundish are also provided with outlet and are connected to rectifying column top; The outlet of the feed liquid side of vapor permeable membrane is connected to reactor.
Transferpump is the entrance of the feed liquid side being connected to vapor permeable membrane by vaporizer again.
The per-meate side of vapor permeable membrane is connected with penetrating fluid condenser, vacuum pump and penetrating fluid storage tank.
The outlet of feed liquid side of vapor permeable membrane with the mode of connection of reactor is: the outlet of the feed liquid side of vapor permeable membrane is connected with reactor by stock liquid condenser, raw material flow container, raw material liquid pump successively.
beneficial effect
Water permeable membrane has the advantages such as high water selective, excellent permeability, and it can be used in the osmotic, evaporating and dewatering process of organic solvent.Infiltrating and vaporizing membrane dehydration technique mainly utilizes the dissolving of water in film and rate of diffusion to be greater than the dissolving of organism in film and rate of diffusion, thus by the moisture removal in organism.Infiltrating and vaporizing membrane dehydration technique being used for diethyl oxalate synthesis technique, the online dehydration of esterification can be realized when not using benzene (toluene), improve the transformation efficiency of reaction.
Compared with conventional art, the present invention is not when introducing three components, the water that esterification reaction process generates can constantly be removed, and film dewatering efficiency is higher, can ensure that the high conversion of reaction within the shorter reaction times, wherein reacting the ethanol steamed can utilize by direct circulation, avoids later stage ester crude product except the recovery problem of benzene or toluene in benzene (toluene) and waste liquid, eliminate the pollution of three components to environment, reduce production cost simultaneously; Light constituent in reactor is sent into vapor permeation membrane component dewatered by rectifying column, condenser, feed pump vaporizer by the present invention, which makes reactor and vapor permeation membrane component separate in operational condition, and the selectivity of reactor operating method is many; Organic substance in water content through film in film dewatering system of the present invention is less, can not increase the weight of the burden of Sewage treatment systems.
Accompanying drawing explanation
Fig. 1 is the schema of water vapour penetration dehydration provided by the invention for diethyl oxalate synthesis technique: 1 is reactor, and 2 is rectifying column, and 3 is overhead condenser, 4 is tundish, 5 is transferpump, and 6 is vaporizer, and 7 is vapor permeable membrane, 8 is stock liquid condenser, 9 is raw material flow container, and 10 is raw material liquid pump, and 11 is penetrating fluid condenser, 12 is penetrating fluid storage tank, and 13 is vacuum pump.
Embodiment
Embodiment 1
In a kettle., under the catalyst action of the 0.01kg vitriol oil, esterification is carried out with 1 kg oxalic acid and 3.5 L dehydrated alcohols, temperature in reactor is 90 DEG C, rectifying column height 0.8 m, tower diameter is about 40 mm, the glass spring filler of 3 mm × 0.5 mm specifications is filled with in rectifying column, rectifying column tower top controls at about 78 DEG C at ambient pressure, after rectifying column, in reactant, the heavy component of steam is back in reactor, the tower top that light constituent delivers to rectifying column by a transferpump part after overhead condenser condensation makes phegma, reflux ratio is 5, another part enters vaporizer, enter vapor permeable membrane to 110 DEG C and dewater through vaporizer is heat vaporized, membrane module is 2 membrane areas is 0.03 m
2single tube NaA molecular sieve membrane assembly be in series, osmotic lateral pressure is 250 Pa, stores under the effect of vacuum pump through the penetrant of film through penetrating fluid condenser condenses to penetrating fluid storage tank, returning in reactor after light constituent condensation after dehydration continues see reaction, and after reacting 17.2 h, in reactor, water-content is 0.34 wt.%, and stopped reaction steam ethanol in reactant, then underpressure distillation obtains product, and calculated yield is 89.6%.
Embodiment 2
In a kettle., at 0.03kg under the catalyst action of toluene yellow acid, esterification is carried out with 2 kg oxalic acid and 7 L dehydrated alcohols, temperature in reactor is 110 DEG C, rectifying column height 0.8 m, tower diameter is about 40 mm, the glass spring filler of 3 mm × 0.5 mm specifications is filled with in rectifying column, under about 0.1 MPa working pressure, rectifying column tower top controls at about 100 DEG C, after rectifying column, in reactant, the heavy component of steam is back in reactor, the tower top that light constituent delivers to rectifying column by a transferpump part after overhead condenser condensation makes phegma, reflux ratio is 4, another part enters vaporizer, enter vapor permeable membrane to 120 DEG C and dewater through vaporizer is heat vaporized, membrane module is 4 membrane areas is 0.03 m
2single tube type T molecular sieve membrane module be in series, osmotic lateral pressure is 470 Pa, stores under the effect of vacuum pump through the penetrant of film through penetrating fluid condenser condenses to penetrating fluid storage tank, returning in reactor after light constituent condensation after dehydration continues see reaction, and after reacting 15.8 h, in reactor, water-content is 0.22 wt.%, and stopped reaction steam ethanol in reactant, then underpressure distillation obtains product, and calculated yield is 91.4%.
Claims (10)
1. a water vapour penetration dehydration is used for the technique of diethyl oxalate synthesis, it is characterized in that, comprise the steps: under the effect of catalyzer, esterification is carried out by oxalic acid and ethanol, the gaseous mixture that reaction produces carries out rectifying, the tower top light constituent that at least part of rectifying obtains enters vapor permeable membrane and dewaters, and the material after dehydration is back to the reaction system of oxalic acid and ethanol.
2. water vapour penetration dehydration according to claim 1 is used for the technique of diethyl oxalate synthesis, it is characterized in that: the material of vapor permeable membrane elects molecular screen membrane, soft silica film, chitosan film, PVA film or sodium alginate film as.
3. water vapour penetration dehydration according to claim 1 is used for the technique of diethyl oxalate synthesis, it is characterized in that: catalyzer is selected from the vitriol oil, to toluene yellow acid, Ammonium ferric sulfate dodecahyrate, Zeo-karb.
4. water vapour penetration dehydration according to claim 1 is used for the technique of diethyl oxalate synthesis, it is characterized in that: rectifying column tower top pressure operating method is decompression, normal pressure or pressurization.
5. water vapour penetration dehydration according to claim 1 is used for the technique of diethyl oxalate synthesis, it is characterized in that: light constituent enters vapor permeable membrane, preferably 100 ~ 110 DEG C after vaporizer vaporization is to 100 ~ 130 DEG C.
6. water vapour penetration dehydration according to claim 1 is used for the technique of diethyl oxalate synthesis, it is characterized in that: the absolute pressure of infiltrating and vaporizing membrane per-meate side is 10 ~ 3000Pa.
7. a water vapour penetration dehydration is used for the device of diethyl oxalate synthesis, include reactor (1), rectifying column (2), vapor permeable membrane (7), it is characterized in that: rectifying column (2) is arranged at the top of reactor (1), the top of rectifying column (2) is connected to the entrance of the feed liquid side of vapor permeable membrane (7) successively by overhead condenser (3), tundish (4), transferpump (5), tundish (4) are also provided with outlet and are connected to rectifying column (2) top; The outlet of the feed liquid side of vapor permeable membrane (7) is connected to reactor (1).
8. water vapour penetration dehydration according to claim 7 is used for the device of diethyl oxalate synthesis, it is characterized in that: transferpump (5) is the entrance of the feed liquid side being connected to vapor permeable membrane (7) by vaporizer (6) again.
9. water vapour penetration dehydration according to claim 7 is used for the device of diethyl oxalate synthesis, it is characterized in that: the per-meate side of vapor permeable membrane (7) is connected with penetrating fluid condenser (11), vacuum pump (13) and penetrating fluid storage tank (12).
10. water vapour penetration dehydration according to claim 7 is used for the device of diethyl oxalate synthesis, it is characterized in that: the outlet of the feed liquid side of vapor permeable membrane (7) with the mode of connection of reactor (1) is: the outlet of the feed liquid side of vapor permeable membrane (7) is connected with reactor (1) by stock liquid condenser (8), raw material flow container (9), raw material liquid pump (10) successively.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106045872A (en) * | 2016-06-06 | 2016-10-26 | 南京工业大学 | System for recovering DMF (dimethylformamid) waste liquor with pervaporation method and method |
| CN106220501A (en) * | 2016-08-25 | 2016-12-14 | 江苏九天高科技股份有限公司 | A kind of water vapour penetration dehydration technique is for the method and apparatus of Synthesis of ethyl lactate |
| CN106518683A (en) * | 2016-11-14 | 2017-03-22 | 江苏九天高科技股份有限公司 | Method and device for synthesizing triethyl citrate by applying vapor permeation dehydration technique |
| CN114292191A (en) * | 2021-12-17 | 2022-04-08 | 重庆新氟科技有限公司 | Preparation method of fluorine-containing methacrylic acid monomer |
| CN116099455A (en) * | 2023-04-12 | 2023-05-12 | 西南化工研究设计院有限公司 | Carbonylation reaction system and method based on multi-kettle serial connection |
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| CN104262140A (en) * | 2014-09-22 | 2015-01-07 | 江苏九天高科技股份有限公司 | Method and device for producing diethyl maleate by virtue of rectification and steam osmosis coupling |
| CN204752568U (en) * | 2015-06-11 | 2015-11-11 | 江苏九天高科技股份有限公司 | Vapor permeation dehydration is used for synthetic device of diethyl oxalate |
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2015
- 2015-06-11 CN CN201510320561.4A patent/CN104926655A/en active Pending
Patent Citations (2)
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| CN104262140A (en) * | 2014-09-22 | 2015-01-07 | 江苏九天高科技股份有限公司 | Method and device for producing diethyl maleate by virtue of rectification and steam osmosis coupling |
| CN204752568U (en) * | 2015-06-11 | 2015-11-11 | 江苏九天高科技股份有限公司 | Vapor permeation dehydration is used for synthetic device of diethyl oxalate |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106045872A (en) * | 2016-06-06 | 2016-10-26 | 南京工业大学 | System for recovering DMF (dimethylformamid) waste liquor with pervaporation method and method |
| CN106045872B (en) * | 2016-06-06 | 2018-04-27 | 南京工业大学 | The pervaporation method recovery system and method for a kind of Dimethylformamide Residue |
| CN106220501A (en) * | 2016-08-25 | 2016-12-14 | 江苏九天高科技股份有限公司 | A kind of water vapour penetration dehydration technique is for the method and apparatus of Synthesis of ethyl lactate |
| CN106518683A (en) * | 2016-11-14 | 2017-03-22 | 江苏九天高科技股份有限公司 | Method and device for synthesizing triethyl citrate by applying vapor permeation dehydration technique |
| CN114292191A (en) * | 2021-12-17 | 2022-04-08 | 重庆新氟科技有限公司 | Preparation method of fluorine-containing methacrylic acid monomer |
| CN116099455A (en) * | 2023-04-12 | 2023-05-12 | 西南化工研究设计院有限公司 | Carbonylation reaction system and method based on multi-kettle serial connection |
| CN116099455B (en) * | 2023-04-12 | 2023-07-07 | 西南化工研究设计院有限公司 | Carbonylation reaction system and method based on multi-kettle serial connection |
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Application publication date: 20150923 |
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