CN107376650A - A kind of method of bipolar membrane electrodialysis method production thio-2 acid - Google Patents
A kind of method of bipolar membrane electrodialysis method production thio-2 acid Download PDFInfo
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- CN107376650A CN107376650A CN201710859579.0A CN201710859579A CN107376650A CN 107376650 A CN107376650 A CN 107376650A CN 201710859579 A CN201710859579 A CN 201710859579A CN 107376650 A CN107376650 A CN 107376650A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/445—Ion-selective electrodialysis with bipolar membranes; Water splitting
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- Urology & Nephrology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
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Abstract
A kind of method of bipolar membrane electrodialysis method production thio-2 acid, it is characterised in that：Condensation reaction is carried out as raw material using vulcanized sodium and acrylic acid, the feed liquid (main component is thio dipropionic acid) after the completion of condensation reaction removes Sodium Polyacrylate and solid particle using high speed centrifugation sedimentation techniques；The condensation feed liquid after visible foreign will be removed again by filter element, then pass to the salt room for the bipolar membrane electrodialysis device being made up of Bipolar Membrane and anode membrane；Low-concentration sodium hydroxide solution is passed through into bipolar membrane electrodialysis device alkali room, to ensure that DC current passes through, keep temperature≤35 DEG C in salt room and alkali room, anode and negative electrode are respectively connected to "+" "-" pole direct current and carry out electrodialysis, with electrodialytic progress, the pH value for being condensed feed liquid is gradually transitions 2~3, removes the thio-2 acid in salt room, thio-2 acid turns into product after refined, dry, and alkali room obtains 6% or so caustic-soda aqueous solution.
Description
Technical field
The present invention relates to industrial chemicals synthesis technique field, and in particular to the synthetic method of thio-2 acid, especially one
The method of kind bipolar membrane electrodialysis method production thio-2 acid.
Background technology
Thio-2 acid is the primary raw material for synthesizing thio esters antioxidant, at present, the production technology of thio-2 acid
Route using：Acrylic acid and vulcanized sodium react to obtain thio dipropionic acid, and thio dipropionic acid is acidified to obtain sulphur through sulfuric acid
For dipropyl acid crude, finally the chemical engineering unit operation such as crystallized, elution, dry again, obtains thio-2 acid.In this process,
Substantial amounts of high salt, high-COD waste water are produced during the chemical engineering unit operations such as many crystallization, elution.The waste water is through multiple-effect evaporation
Or MVR processing, it is high energy consumption, expensive, it is impossible to realize cleaning procedure.Therefore, thio-2 acid new cleanproduction process is developed,
The generation of waste water is completely eliminated from source, becomes passive administer and is administered into active, it is very necessary, it is very urgent.
Solve the problems, such as that thio-2 acid high salt, high-COD waste water there are two kinds of technical schemes：One kind is methyl acrylate technique,
Another kind is bipolar membrane electrodialysis technique.Methyl acrylate technique carries out condensation reaction using methyl acrylate and hydrogen sulfide, raw
Into thio-2 acid dimethyl ester, monothioester kind antioxidant is obtained with fatty alcohol progress ester exchange reaction again after rectification and purification.Should
The characteristics of technique maximum is the generation that waste water is completely eliminated from technique, becomes passive administer and is administered into active.Shortcoming is in life
Peculiar smell ratio is more serious as caused by methyl acrylate and hydrogen sulfide during production, the buying of hydrogen sulfide, transport, is asked using all existing
Topic.Bipolar membrane electrodialysis technique is to substitute sulfuric acid using bipolar membrane electrodialysis to be acidified, and condensation material thio dipropionic acid is converted into
The production Technology of thio-2 acid.Raw material sulphuric acid has been eliminated, has avoided sulfuric acid caused peculiar smell in use, simultaneously
Also sodium sulphate is not produced.Using bipolar membrane electrodialysis technique productions thio-2 acid, a small amount of salt-free thio two are only produced
Propionic acid waste water, it can be discharged by biochemical treatment after up to standard.The technique obtains by-product caustic soda while thio-2 acid.
The content of the invention
In view of the above-mentioned problems, it is an object of the invention to provide a kind of bipolar membrane electrodialysis method production thio-2 acid method,
Unidirectional using light electrolysis and film passes through characteristic, and thio dipropionic acid is made into thio-2 acid, is the characteristics of the technique maximum
It is acidified without using sulfuric acid, no acid mist produces, and no high slat-containing wastewater produces, and operating environment is greatly improved.
Technical scheme is used by the present invention solves above-mentioned technical problem：A kind of bipolar membrane electrodialysis method production thio two
The method of propionic acid, it is characterised in that：Condensation reaction, the condensation after the completion of condensation reaction are carried out as raw material using vulcanized sodium and acrylic acid
Feed liquid removes Sodium Polyacrylate and solid particle using high speed centrifugation sedimentation techniques；By the condensation feed liquid after removal visible foreign again
It is secondary by filter element, then pass to the salt room for the bipolar membrane electrodialysis device being made up of Bipolar Membrane and anode membrane；To Bipolar Membrane electricity
Low-concentration sodium hydroxide solution is passed through in electrodialysis apparatus alkali room, to ensure DC current by keeping the temperature in salt room and alkali room
≤ 35 DEG C of degree, anode and negative electrode are respectively connected to "+" "-" pole direct current and carry out electrodialysis, with electrodialytic progress, condensation
The pH value of feed liquid is gradually transitions 2~3, removes the thio-2 acid in salt room, and thio-2 acid turns into production after refined, dry
Product, alkali room obtain 6% or so caustic-soda aqueous solution.
Further, the filtering includes secondary filter, ultrafiltration and chelating resin filter, and wherein secondary filter, ultrafiltration filters out
Solid particle, chelating resin processing unit is set to remove high volence metal ion, to prevent high volence metal ion fouling on diaphragm plate,
Hinder the progress of Ion transfer.
Further, water unnecessary in the salt room enters Bipolar Membrane deep treatment system.Waste water is handed over by small-sized cation
Change resin and sodium salt is converted into thio-2 acid, after reclaiming thio-2 acid by polymeric adsorbent, waste water reaches biochemical treatment requirement,
The qualified discharge after biochemical treatment.
Further, from salt room separate out thio-2 acid refined into crystallizer, wash, centrifuge after obtain sulphur
For dipropyl acid product, caused water carries out next round circulation as process water reuse in subtractive process.
Further, the alkali room obtains 6% or so caustic-soda aqueous solution, after further electrodialysis concentration, obtains 12%
Caustic-soda aqueous solution.
Bipolar Membrane is that a kind of novel ion exchanges composite membrane, and it is generally compound by cation exchange layer and anion exchange layer
Form, with the membrane material for having different charge densities, thickness and performance under different compound conditions, can be made into different performance and use
The Bipolar Membrane on way, the most basic principle of these purposes are that dissociation of the hydrone of Bipolar Membrane boundary layer in reverse pressurization (is also known as
Bipolar Membrane water decomposition), that is, split water into hydrogen ion and hydroxide ion.Bipolar membrane electrodialysis is namely based on above-mentioned water decomposition
With grow up on the basis of common electrodialysis principle, it is to replace common electrodialytic part yin, yang film with Bipolar Membrane,
Or formed between common electrodialytic yin, yang film plus Bipolar Membrane.The most basic application of bipolar membrane electrodialysis is from salt
Solution prepares corresponding bronsted lowry acids and bases bronsted lowry.Feed liquid enters bipolar membrane electrodialysis membrane stack, and in the presence of DC electric field, salt anionic passes through
Anion-exchange membrane enters sour room, and generates acid with the hydrogen ion of Bipolar Membrane dissociation.And salt cation passes through cation-exchange membrane
Into alkali room, the hydroxide ion dissociated there with Bipolar Membrane forms alkali.
Using bipolar membrane electrodialysis device thio-2 acid, according to the property of material, it is not necessary to be separately provided cavity block.Only
Combined using the membrane stack being made up of Bipolar Membrane BPM and anode membrane CM.
Its course of work：After thio-2 acid condensation reaction is completed, condensation material first has to settle skill by high speed centrifugation
Art removes acrylate copolymer.Then mechanical admixture is further filtered out by secondary filter, ultrafiltration again.Chelating resin is set to handle
Unit removes high volence metal ion, to prevent high volence metal ion fouling on diaphragm plate, hinders the progress of Ion transfer.
After thio dipropionic acid and water enter the passage being made up of Bipolar Membrane and anode membrane, in the presence of DC electric field,
Thio dipropionic acid is dissociated into thio-2 acid acid radical anion and sodium ion.Thio-2 acid acid radical anion and Bipolar Membrane from
The hydrogen ion generation thio-2 acid of solution, is circulated, with system thio two in the channel together with thio dipropionic acid and water
The concentration of propionic acid is gradually risen, and thio-2 acid crystallization is begun with crystallizer and is separated out.Because thio dipropionic acid is molten in water
Xie Du is much larger compared with thio-2 acid, therefore is separated out on this condition without thio dipropionic acid crystallization.At any time by the thio of crystallization
Dipropionic acid removes, until thio dipropionic acid changes into thio-2 acid substantially.Unnecessary water passes through Bipolar Membrane deep treatment, will
Thio dipropionic acid is further converted to thio-2 acid.Sodium salt is converted into thio-2 acid using small-sized cation.Through inhaling
After attached resin recovery thio-2 acid, because of not saliferous in waste water, qualified discharge after biochemical treatment can be removed.
In opposite side, the alkali room that sodium ion enters anode membrane by cation-exchange membrane and Bipolar Membrane forms, with Bipolar Membrane
The hydroxide ion of dissociation forms sodium hydroxide.Sodium hydrate aqueous solution concentration can reach 6~8%, by special film process,
Sodium hydrate aqueous solution concentration highest can reach 15%, be sold as byproduct.
The characteristics of technique maximum, is acidified without using sulfuric acid, and no acid mist produces, and operating environment is greatly improved.Simultaneously
Because of the raising of thio-2 acid quality, without adhesive propylene acid polymer, produce the esterification of monothioester, can be smooth
Filter out the operation of catalyst, reduce the COD of monothioester kind antioxidant production waste water.
The advantage of the invention is that：
1st, substitute sulfuric acid with bipolar membrane electrodialysis to be acidified, produced without high slat-containing wastewater.
Bipolar membrane electrodialysis is to pass through characteristic using light electrolysis and the unidirectional of film, and thio dipropionic acid is made into thio dipropyl
Acid.The characteristics of technique maximum, is acidified without using sulfuric acid, and no acid mist produces, and no high slat-containing wastewater produces, and operating environment obtains
Larger improvement.
2nd, acrylate copolymer is removed using high speed centrifugation sedimentation techniques, is bipolar membrane electrodialysis production thio-2 acid
Basic assurance.
Main side reaction is the polymerisation of acrylic acid in condensation reaction, after the completion of condensation reaction, can be contained in system
Substantial amounts of Sodium Polyacrylate, Sodium Polyacrylate are in aqueous gel state, easily block Bipolar Membrane, cause Bipolar Membrane to be lost
Effect.Acrylate copolymer is removed using high speed centrifugation sedimentation techniques, can ensure that bipolar membrane electrodialysis method produces thio dipropyl
Acid operation is smoothed out.
3rd, it is successful key to be removed caused thio-2 acid in time from system using crystallization technique.
Using bipolar membrane electrodialysis technical finesse thio dipropionic acid, substantial amounts of thio dipropyl can be quickly generated in system
Acid, thio-2 acid will separate out from solution, cause stifled film to cause systemic breakdown.It is guarantee system to remove thio-2 acid in time
The key of normal operation.
Brief description of the drawings
In order to illustrate more clearly of the specific embodiment of the invention, will use below required in embodiment
Accompanying drawing is briefly described, it should be apparent that, drawings in the following description are some embodiments of the present invention, for this area
For those of ordinary skill, on the premise of not paying creative work, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is the experiment flow figure of the present invention.
Embodiment
The present invention is further illustrated with embodiment below, but the present invention is not intended to be limited thereto.Do not noted in the following example
The experimental method of bright actual conditions, generally according to normal condition, or according to the condition proposed by manufacturer.
Embodiment one
Sodium sulfide solution is added in reactor, by vulcanized sodium：Acrylic acid mol ratio is 1:Propylene is added dropwise in 2.1 ratio
Acid, reaction temperature are 70~80 DEG C, are reacted 2 hours, and the crude yield of thio-2 acid is 90%, obtain thio-2 acid condensation
Feed liquid, condensation feed liquid is pumped into high speed centrifugation sedimentation unit by conveying and removes polymer and mechanical admixture, is then passed through again
Secondary filter, ultrafiltration further remove Sodium Polyacrylate, and chelating resin processing unit removes high volence metal ion, will go the removal of impurity
Condensation feed liquid afterwards is passed through the salt room of bipolar membrane electrodialysis device；Low concentration hydrogen-oxygen is passed through into bipolar membrane electrodialysis device alkali room
Change sodium solution (naoh concentration is 0.1~0.5%), to ensure DC current by keeping the temperature in salt room and alkali room
≤35℃.Anode and negative electrode are respectively connected to "+" "-" pole direct current and carry out electrodialysis, with electrodialytic progress, condensation material
The pH value of liquid is gradually transitions 2~3, when there is solid precipitation in salt room, constantly removes the thio-2 acid in salt room, works as salt
In room there is no solid separate out after, stop be powered, by the thio-2 acid separated out from salt room addition crystallizer, refined,
Washing, thio-2 acid product is obtained after centrifuging, the purity of thio-2 acid is more than 99%.Will be remaining residual in salt room
Water enters Bipolar Membrane deep treatment system, and waste water removes sodium salt by small-sized cation, thio-2 acid is reclaimed by polymeric adsorbent
Afterwards, waste water meets biochemical treatment requirement, the qualified discharge after biochemical treatment.
Caused water is again introduced into the salt room of bipolar membrane electrodialysis device in subtractive process, carries out next round circulation.
Alkali room obtains 6% or so caustic-soda aqueous solution, through further electrodialysis concentration after, obtain 12% caustic soda it is water-soluble
Liquid.
After production technology using the present invention, one ton of thio-2 acid product is often produced, reduces the height of 14 tons or so of discharge
Salt, high-COD waste water.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
Cross above preferred embodiment the present invention is described in detail, it is to be understood by those skilled in the art that can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (5)
- A kind of 1. method of bipolar membrane electrodialysis method production thio-2 acid, it is characterised in that：Using vulcanized sodium and acrylic acid as original Material carries out condensation reaction, and the feed liquid (main component is thio dipropionic acid) after the completion of condensation reaction is using high speed centrifugation sedimentation skill Art removes Sodium Polyacrylate and solid particle；By the condensation feed liquid after removal visible foreign again by filter element, Ran Houtong Enter the salt room for the bipolar membrane electrodialysis device being made up of Bipolar Membrane and anode membrane；It is passed through into bipolar membrane electrodialysis device alkali room low dense Sodium hydroxide solution is spent, to ensure DC current by temperature≤35 DEG C in salt room and alkali room being kept, by anode and negative electrode point Not Jie Ru "+" "-" pole direct current carry out electrodialysis, with electrodialytic progress, the pH value that is condensed feed liquid is gradually transitions 2~ 3, the thio-2 acid in salt room is removed, thio-2 acid turns into product after refined, dry, and alkali room obtains 6% or so burning Aqueous alkali.
- A kind of 2. method of bipolar membrane electrodialysis method production thio-2 acid according to claim 1, it is characterised in that：Institute State that filtering includes secondary filter, ultrafiltration and chelating resin filter, wherein secondary filter and ultrafiltration further filters out solid particle, if Put chelating resin processing unit and remove high volence metal ion, to prevent high volence metal ion fouling on diaphragm plate, hinder ion to move The progress of shifting.
- A kind of 3. method of bipolar membrane electrodialysis method production thio-2 acid according to claim 1, it is characterised in that：Institute State water unnecessary in salt room and enter Bipolar Membrane deep treatment system, be converted into sodium salt by small-sized cationic ion-exchange resin thio Dipropionic acid, after reclaiming thio-2 acid by polymeric adsorbent, waste water reaches biochemical treatment requirement, the qualified discharge after biochemical treatment.
- A kind of 4. method of bipolar membrane electrodialysis method production thio-2 acid according to claim 1, it is characterised in that：From The thio-2 acid that salt room separates out is refined into crystallizer, wash, centrifuge after obtain thio-2 acid product, it is refined During caused water as process water reuse, carry out next round circulation.
- A kind of 5. method of bipolar membrane electrodialysis method production thio-2 acid according to claim 1, it is characterised in that：Institute State alkali room and obtain 6% or so caustic-soda aqueous solution, after further electrodialysis concentration, obtain 12% caustic-soda aqueous solution.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114368864A (en) * | 2021-12-30 | 2022-04-19 | 嘉兴诚毅环保科技有限责任公司 | Industrial sewage treatment device |
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| CN101798278A (en) * | 2010-04-07 | 2010-08-11 | 天津力生化工有限公司 | Method for preparing thiodipropionic acid |
| WO2012114837A1 (en) * | 2011-02-23 | 2012-08-30 | 住友化学株式会社 | Method for producing aminoalkyl thiosulfate compound |
| CN103341322A (en) * | 2013-07-24 | 2013-10-09 | 宜宾海翔化工有限责任公司 | Pretreatment method for preparing acid/base from viscose fiber sodium sulfate waste liquid by using bipolar membrane electrodialysis method |
| CN106008296A (en) * | 2016-06-13 | 2016-10-12 | 重庆紫光化工股份有限公司 | Thiodipropionic acid clean synthesizing technology |
| CN206103721U (en) * | 2016-10-08 | 2017-04-19 | 安徽师范大学 | Electrodialysis pretreatment device |
-
2017
- 2017-09-21 CN CN201710859579.0A patent/CN107376650A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798278A (en) * | 2010-04-07 | 2010-08-11 | 天津力生化工有限公司 | Method for preparing thiodipropionic acid |
| WO2012114837A1 (en) * | 2011-02-23 | 2012-08-30 | 住友化学株式会社 | Method for producing aminoalkyl thiosulfate compound |
| CN103341322A (en) * | 2013-07-24 | 2013-10-09 | 宜宾海翔化工有限责任公司 | Pretreatment method for preparing acid/base from viscose fiber sodium sulfate waste liquid by using bipolar membrane electrodialysis method |
| CN106008296A (en) * | 2016-06-13 | 2016-10-12 | 重庆紫光化工股份有限公司 | Thiodipropionic acid clean synthesizing technology |
| CN206103721U (en) * | 2016-10-08 | 2017-04-19 | 安徽师范大学 | Electrodialysis pretreatment device |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114368864A (en) * | 2021-12-30 | 2022-04-19 | 嘉兴诚毅环保科技有限责任公司 | Industrial sewage treatment device |
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Application publication date: 20171124 |