CN205188172U - Sour production system of time based on membrane processing technique - Google Patents
Sour production system of time based on membrane processing technique Download PDFInfo
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- CN205188172U CN205188172U CN201520971951.3U CN201520971951U CN205188172U CN 205188172 U CN205188172 U CN 205188172U CN 201520971951 U CN201520971951 U CN 201520971951U CN 205188172 U CN205188172 U CN 205188172U
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/584—Recycling of catalysts
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Abstract
The utility model discloses a sour production system of time based on membrane processing technique, the production system includes: reaction system and reaction after treatment system, the reaction system includes addition reaction cauldron, ring closure reation kettle and saponification reation kettle, reaction after treatment system includes addition reaction after treatment system, ring -closure reaction after treatment system and saponification reaction after treatment system, and addition reaction after treatment system arranges between addition reaction cauldron and ring closure reation kettle that ring -closure reaction after treatment system arranges between ring closure reation kettle and saponification reation kettle that saponification reaction after treatment system arranges after saponification reation kettle that saponification reaction after treatment system includes bipolar membrane device. The utility model discloses a ceramic membrane filter equipment retrieves the catalyst, and the rate of recovery that makes the catalyst is showing and improves, through membrane distillation plant recovery trifluoro 1, 1, 1 -trichloroethane, need not high temperature and negative pressure, reduce energy loss, it is energy -concerving and environment -protective, adopt bipolar membrane device not only environmental protection but also economy, the high danger of no acid -base transportation.
Description
Technical field
The utility model belongs to pesticide chemical field, relates to acid of a kind of time based on membrane technology production system.
Background technology
Time acid is the important intermediate of the pyrethroids such as synthesizing efficient cyhalothrin, is widely used in the synthesis of the former medicines such as cyhalothrin, bifenthrin, Flumethrin.Domestic market year, demand was at about 2000t, world market demand more than 4000t, good market prospects.The market lambda-cyhalothrin sales volumes such as India, Japan and Korea S, America and Europe and South East Asia increase significantly, and the corresponding demand to the acid of intermediate time is also in increase.Therefore, the acid of pesticide intermediate time has the larger market requirement and economic benefit.
Although the time acid synthesis technique that document is delivered has 3 kinds of methods, what select both at home and abroad at present is all the industrialized route that is starting raw material with Ben Ting acid esters.Namely Ben Ting acid esters (methyl esters and ethyl ester) first carries out addition reaction with Freon 113, then through cyclization, saponification, acidifying, recrystallization five step, finally obtains the conforming articls acid of cis isomerism body burden more than 98%.Find after deliberation: 1) in above-mentioned operational path, between addition reaction and ring-closure reaction, need the recovery carrying out catalyzer and Freon 113, tradition recovery process is by staticly settling recovery catalyzer, time of repose is long, serious reduction production capacity, Freon 113 is reclaimed by underpressure distillation, energy consumption is higher, and production cost increases; 2) in saponification reaction and acidification reaction process alkali and sour consumption large, produce the strong brine water yield after reaction large, cost for wastewater treatment increases, and indirectly adds production cost.Therefore, comprehensively analyze from environmental protection and economic angle, all should adjust traditional technology, enhance productivity, reduce wastewater displacement.
Ceramic membrane is with the high technology ceramics filtering material with vesicular structure through 1600 DEG C of high temperature sinterings such as aluminum oxide, titanium oxide, zirconium white.It is by the ceramic monolith of porosity 30% ~ 50%, 50nm ~ 15, aperture μm, adopts the asymmetric compound film that sol-gel method or other technique are made.Its structure is generally " sandwich " formula: supporting layer (also known as carrier layer), transition layer (also known as middle layer), rete (also known as function separating layer).Wherein the aperture of supporting layer is generally 1 ~ 20 μm, and porosity is 30% ~ 65%, and its effect is the physical strength increasing film; The aperture of the aperture ratio supporting layer in middle layer is little, and its effect prevents in Film preparation process that particle is to the infiltration of porous support layer, and thickness is about 20 ~ 60 μm, and porosity is 30% ~ 40%; Rete has separation function, and from 0.8nm ~ 1 μm not etc., thickness is about 3 ~ 10 μm, and porosity is 40% ~ 55% in aperture.The pore size distribution of whole film is reduced to rete gradually by supporting layer, forms asymmetric structure distribution.Ceramic membrane can be divided into the kinds such as micro-filtration (aperture is greater than 50nm), ultrafiltration (aperture 2 ~ 50nm), nanofiltration (aperture is less than 2nm) according to aperture.Ceramic membrane filter is a kind of fluid sepn process of " cross flow filter " form: stock liquid is flow at high speed in film pipe, clarified permeation liquid edge containing small molecule component under pressure-driven is outside through film with face vertical direction (radial direction), muddy concentrated solution tunicle containing macromolecular components retains, thus makes fluid reach the object of separation, concentrated, purifying.
Membrane distillation is the new membrane isolation technique that membrane technique combines with evaporative process, is the sepn process that is impellent with film both sides differing temps solution vapor pressure difference.Membrane distillation as a new membrane separation technique, be mainly used at present sea water desaltination, the preparation of ultrapure water and solution special type concentrated and be separated.The hydrophobic high-performance tubular membrane material application multi tension technique that it adopts, its aperture is less than 0.2 μm, be have that fiber height is strong, super-hydrophobic, anti-pollution, anti-oxidant and porosity is high, unit surface large and can adapt to all kinds of strong acid, concentrated, the separation of highly basic material, the novel hitech materials of recovery.Distillation film component adopts unique interior switch type, tubular membrane is immersed in be intended in 60 DEG C of processed hydrothermal solution grooves, by exchanged form in special construction composition, without the need to vacuum, high top pressure operation, the temperature difference motivating force that cold and hot liquid indirect contact is formed makes the micropore of gas permeation tubular membrane be cooled to phlegma, and cold liquid is warmed heat energy and obtains and reclaim completely, the revolutionary character really achieving energy-saving membrane distillation breaks through.Can plural serial stage be done according to this principle, all can form effective temperature head, good utilization be carried out to heat and reclaims, reach and save efficiency greatly.
Electrodialytic technique refers to that ion is by the membrane separating process of selective ion exchange membrane under electrical forces effect, its core is anion and cation exchange membrane, namely utilize cationic exchange membrane only to allow positively charged ion to pass through, the characteristic that anion-exchange membrane only allows negatively charged ion to pass through carries out the technology of selective separation to effects of ion.Under electrical forces effect, the zwitterion generation directional migration in solution, moves to another part water body from a part of water body, thus reaches solution separating, purification and concentrated object.The appearance of Bipolar Membrane, makes electrodialytic purposes be expanded.Bipolar Membrane is composited by anion-exchange membrane and cationic exchange membrane, is commonly referred to intermediate catalyst layer in two-layer centre.Its principle is: when Bipolar Membrane both sides add voltage, can directional migration be there is in the ion in solution, meanwhile water molecules can enter into intermediate catalyst layer through anion and cation exchange membrane, under the active group effect of both sides, there is electrolysis generate hydrogen ion and hydroxide ion, serve as charge carrier with this, the water of consumption is supplemented to the infiltration of film middle layer by the water in surrounding medium again.Compared with conventional electrodialysis, under Bipolar Membrane effect, water decomposition speed is enhanced more than 5 thousands of times, and therefore energy consumption reduces greatly, and electrodialytic range of application also extends greatly.Bipolar membrane electrodialysis also belongs to electrodialysis range of application, is by Bipolar Membrane being combined with ion-exchange membrane, forms different compartments (sour room, alkali room and feed liquid room), makes it have unique advantage in soda acid preparation field.Under certain voltage effect, zwitterion respectively by anion and cation exchange membrane, can combine with the hydrogen ion that Bipolar Membrane produces and hydroxide ion and produces corresponding bronsted lowry acids and bases bronsted lowry.
Summary of the invention
For the above deficiency existed, the purpose of this utility model is to provide acid of a kind of time based on membrane technology production system.
For this reason, the utility model adopts following technical scheme:
Based on a time acid production system for membrane technology, described production system comprises: reactive system and post-reaction treatment system, described reactive system comprises addition reaction still, ring-closure reaction still and saponification reaction still, described addition reaction still, ring-closure reaction still and saponification reaction still are arranged successively, described addition reaction still for hold Ben Ting acid esters in the presence of a catalyst with Freon 113 generation addition reaction, described ring-closure reaction still is for holding the product after addition reaction and sodium alkoxide generation ring-closure reaction, and described saponification reaction still is for holding the product generation saponification reaction after ring-closure reaction, described post-reaction treatment system comprises addition reaction after-treatment system, ring-closure reaction after-treatment system and saponification reaction after-treatment system, described addition reaction after-treatment system is arranged between addition reaction still and ring-closure reaction still, described ring-closure reaction after-treatment system is arranged between ring-closure reaction still and saponification reaction still, after described saponification reaction after-treatment system is arranged in saponification reaction still, described saponification reaction after-treatment system comprises bipolar membrane device, described bipolar membrane device is used for the Ficus caricaL after saponification reaction to become alkali lye and acid solution, alkali lye reuse is in saponification reaction still.Addition reaction is there is and generates chloro-7,7, the 7-trifluoro heptanoates of 3,3-dimethyl-4,6,6-tri-in Ben Ting acid esters, Freon 113 and catalyzer in addition reaction still.
Further, described addition reaction after-treatment system comprises ceramic membrane filter device and distillation device, described ceramic membrane filter device for retain and the catalyst residue reclaimed in addition reaction product in addition reaction still, all the other materials form dialyzate with solvent permeation ceramic membrane filtration unit, and described distillation device is for reclaiming Freon 113 in addition reaction product in addition reaction still.
Further, described ring-closure reaction after-treatment system comprises the first vacuum distillation apparatus, and described first vacuum distillation apparatus is for reclaiming solvent in ring-closure reaction product in ring-closure reaction still.
Further, arrange the second vacuum distillation apparatus between described saponification reaction still and bipolar membrane device, described second vacuum distillation apparatus is for removing methanol solvate residual in saponification reaction product.
Further, after the process of post-reaction treatment system, obtain time acid crude, time acid crude is through methanol wash and obtain time acid product after drying.
Further, the catalyzer in described addition reaction still is cuprous chloride.
Further, the sodium alkoxide in described ring-closure reaction still is sodium tert-butoxide.
The utility model provides acid of a kind of time based on membrane technology production system, and described production system tool has the following advantages:
1) time acid production system provided by the utility model reclaims catalyzer by ceramic membrane filter device, the rate of recovery of catalyzer is significantly improved, what the time simultaneously recycled was more traditional staticly settles process obviously shortening, it is less that floor space staticly settles device than use, level of automation improves, and cost of labor reduces;
2) time acid production system provided by the utility model reclaims Freon 113 by distillation device, without the need to high temperature and negative pressure, directly utilizes the waste heat of addition reaction namely can run, thus reduces energy waste, energy-conserving and environment-protective;
3) time acid production system provided by the utility model replaces the acidification reaction process in traditional technology by bipolar membrane device, bipolar membrane device is directly utilized to prepare organic acid and alkali lye, namely the organic acid of preparation carries out refining and drying can obtain time acid product, the alkali lye of preparation can reuse in saponification reaction still; Time of the present utility model acid production system adopts bipolar membrane device not only environmental protection but also economic, without the high risk of soda acid transportation, has promotional value.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of a kind of acid of the time based on membrane technology production system provided by the utility model;
In figure: R101-addition reaction still; R201-ring-closure reaction still; R301-saponification reaction still; P102-ceramic membrane filter device; P103-distillation device; P202-first vacuum distillation apparatus; P302-second vacuum distillation apparatus; P303-bipolar membrane device.
Embodiment
With specific embodiment, the utility model is described in further detail with reference to the accompanying drawings.
Based on a time acid production system for membrane technology, described production system comprises: reactive system and post-reaction treatment system; Described reactive system comprises addition reaction still, ring-closure reaction still and saponification reaction still, described addition reaction still R101, ring-closure reaction still R201 and saponification reaction still R301 arrange successively, addition reaction is there is with Freon 113 (F113A) in the presence of a catalyst in described addition reaction still R101 for holding Ben Ting acid esters, described ring-closure reaction still R201 is for holding the product after addition reaction and sodium alkoxide generation ring-closure reaction, and described saponification reaction still R301 is for holding the product generation saponification reaction after ring-closure reaction; Described post-reaction treatment system is used for carrying out aftertreatment to the product of saponification reaction in the product of ring-closure reaction in the product of addition reaction in addition reaction still R101, ring-closure reaction still R201 and saponification reaction still R301 respectively.Addition reaction is there is and generates chloro-7,7, the 7-trifluoro heptanoates of 3,3-dimethyl-4,6,6-tri-in Ben Ting acid esters, Freon 113 and catalyzer in addition reaction still R101.
Described post-reaction treatment system comprises addition reaction after-treatment system, ring-closure reaction after-treatment system and saponification reaction after-treatment system; Described addition reaction after-treatment system is used for for the product of addition reaction in addition reaction still R101 carries out aftertreatment, described ring-closure reaction after-treatment system is used for in ring-closure reaction still R201, the product of ring-closure reaction carries out aftertreatment, and described saponification reaction after-treatment system is used for in saponification reaction still R301, the product of saponification reaction carries out aftertreatment.
Described addition reaction after-treatment system comprises ceramic membrane filter device P102 and distillation device P103, described ceramic membrane filter device P102 for retain and the catalyst residue reclaimed in addition reaction product in addition reaction still R101, all the other materials form dialyzate with solvent permeation ceramic membrane filtration unit P102, and described distillation device P103 is for reclaiming Freon 113 in addition reaction product in addition reaction still R101.
Described ring-closure reaction after-treatment system comprises the first vacuum distillation apparatus P202, and described first vacuum distillation apparatus P202 is for reclaiming solvent in ring-closure reaction product in ring-closure reaction still R201.
Described saponification reaction after-treatment system comprises bipolar membrane device P303, and described bipolar membrane device P303 is used for the Ficus caricaL after saponification reaction to become alkali lye and acid solution, and alkali lye reuse is in saponification reaction still R301.
Arrange the second vacuum distillation apparatus P302 between described saponification reaction still and bipolar membrane device, described second vacuum distillation apparatus P302 is for removing methanol solvate residual in saponification reaction product.
After the process of post-reaction treatment system, obtain time acid crude, time acid crude is through methanol wash and obtain time acid product after drying.
Catalyzer in described addition reaction still R101 is cuprous chloride.
In described ring-closure reaction still, the sodium alkoxide of R201 is sodium tert-butoxide.
Above-mentioned embodiment is used for explaining and the utility model is described; be only preferred embodiment of the present utility model; instead of the utility model is limited; in the protection domain of spirit of the present utility model and claim; the any amendment made the utility model, equivalent replacement, improvement etc., all fall into protection domain of the present utility model.
Claims (6)
1., based on a time acid production system for membrane technology, it is characterized in that, described production system comprises: reactive system and post-reaction treatment system, described reactive system comprises addition reaction still, ring-closure reaction still and saponification reaction still, described addition reaction still, ring-closure reaction still and saponification reaction still are arranged successively, described addition reaction still for hold Ben Ting acid esters in the presence of a catalyst with Freon 113 generation addition reaction, described ring-closure reaction still is for holding the product after addition reaction and sodium alkoxide generation ring-closure reaction, and described saponification reaction still is for holding the product generation saponification reaction after ring-closure reaction, described post-reaction treatment system comprises addition reaction after-treatment system, ring-closure reaction after-treatment system and saponification reaction after-treatment system, described addition reaction after-treatment system is arranged between addition reaction still and ring-closure reaction still, described ring-closure reaction after-treatment system is arranged between ring-closure reaction still and saponification reaction still, after described saponification reaction after-treatment system is arranged in saponification reaction still, described saponification reaction after-treatment system comprises bipolar membrane device, described bipolar membrane device is used for the Ficus caricaL after saponification reaction to become alkali lye and acid solution, alkali lye reuse is in saponification reaction still.
2. a kind of acid of the time based on membrane technology production system according to claim 1, it is characterized in that, described addition reaction after-treatment system comprises ceramic membrane filter device and distillation device, described ceramic membrane filter device for retain and the catalyst residue reclaimed in addition reaction product in addition reaction still, described distillation device is for reclaiming Freon 113 in addition reaction product in addition reaction still.
3. a kind of acid of the time based on membrane technology production system according to claim 1, it is characterized in that, described ring-closure reaction after-treatment system comprises the first vacuum distillation apparatus, and described first vacuum distillation apparatus is for reclaiming solvent in ring-closure reaction product in ring-closure reaction still.
4. a kind of acid of the time based on membrane technology production system according to claim 1, it is characterized in that, arrange the second vacuum distillation apparatus between described saponification reaction still and bipolar membrane device, described second vacuum distillation apparatus is for removing methanol solvate residual in saponification reaction product.
5. a kind of acid of the time based on membrane technology production system according to claim 1, it is characterized in that, the catalyzer in described addition reaction still is cuprous chloride.
6. a kind of acid of the time based on membrane technology production system according to claim 1, it is characterized in that, the sodium alkoxide in described ring-closure reaction still is sodium tert-butoxide.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111620495A (en) * | 2019-02-27 | 2020-09-04 | 江苏优士化学有限公司 | Recycling method of wastewater containing cuprous chloride |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111620495A (en) * | 2019-02-27 | 2020-09-04 | 江苏优士化学有限公司 | Recycling method of wastewater containing cuprous chloride |
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Address after: Hangzhou City, Zhejiang province 311121 District of Yuhang future science and Technology City Sea Park No. 11 Haishu Road, building 2, Room 201 Patentee after: SUNUP ENVIRONMENTAL TECHNOLOGY CO.,LTD. Address before: Hangzhou City, Zhejiang province 311121 District of Yuhang future science and Technology City Sea Park No. 11 Haishu Road, building 2, Room 201 Patentee before: HANGZHOU SUNUP ENVIRONMENTAL TECHNOLOGY CO.,LTD. |
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Effective date of registration: 20171208 Address after: 313100 Zhejiang city of Huzhou province Changxing County Lijiaxiang Town Industrial Zone in the East Jin Lu Hua Patentee after: CHANGXING SHANGTUO ENVIRONMENTAL TECHNOLOGY CO.,LTD. Address before: Hangzhou City, Zhejiang province 311121 District of Yuhang future science and Technology City Sea Park No. 11 Haishu Road, building 2, Room 201 Patentee before: SUNUP ENVIRONMENTAL TECHNOLOGY CO.,LTD. |
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Address after: 313100 East Huajin Road, industrial concentration area, Lijiaxiang Town, Changxing County, Huzhou City, Zhejiang Province Patentee after: Shangtuo Environmental Technology (Changxing) Co.,Ltd. Address before: 313100 East Huajin Road, industrial concentration area, Lijiaxiang Town, Changxing County, Huzhou City, Zhejiang Province Patentee before: CHANGXING SHANGTUO ENVIRONMENTAL TECHNOLOGY Co.,Ltd. |
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