CN105833729A - Bipolar membrane electrodialysis system and method for preparing high-purity tetramethylammonium hydroxide through system - Google Patents
Bipolar membrane electrodialysis system and method for preparing high-purity tetramethylammonium hydroxide through system Download PDFInfo
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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
- B01D61/46—Apparatus therefor
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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
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
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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
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/366—Apparatus therefor
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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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Abstract
The invention discloses a bipolar membrane electrodialysis system and a method for preparing high-purity tetramethylammonium hydroxide through the system. A tetramethylammonium hydroxide halogenated brine solution serves as the raw material and is introduced into a liquid chamber of the four-partition bipolar membrane electrodialysis system, pure water is introduced into an acid chamber and an alkali chamber, and sulfuric acid solutions are introduced into a polar liquid chamber and a buffering liquid chamber respectively; the yield of a tetramethylammonium hydroxide solution obtained through bipolar membrane electrodialysis treatment can reach 95% or above, and the impurity halide ion concentration is lower than 70 ppm. In the process, low-concentration haloid acid is generated and concentrated and reused through the membrane distillation technology, and the mass fraction of the low-concentration haloid acid can reach 15-20%. The situation that a lot of waste brine is generated is avoided, and the prepared tetramethylammonium hydroxide is high in purity and yield. Besides, production cost is reduced due to concentration and reuse of the by-product haloid acid, and no waste is discharged in the whole technological process.
Description
Technical field
The present invention relates to Integrated Membrane Technology application on chemical industry, be specifically related to a kind of bipolar membrane electrodialysis system and use its method preparing high-purity Tetramethylammonium hydroxide.
Background technology
Tetramethylammonium hydroxide (TMAH) is a kind of organic alkali, has extensive use at chemical industry and quasiconductor field.Such as fields such as the catalyst in the synthesis of organosilicon series of products, polyesters polymerization, weaving, plastic and leathers.At present, Tetramethylammonium hydroxide is widely used in electronic applications, be mainly used as the photoetching development agent of printed circuit board (PCB) and microelectronic chip manufacture in abluent etc..Along with the development of integrated circuit, the purity of Tetramethylammonium hydroxide is had higher requirement.
The method of preparation Tetramethylammonium hydroxide is broadly divided at present: (1) silver oxide method；(2) ion-exchange-resin process；(3) alkali displacement method；(4) membrane electrolysis；(5) bipolar membrane electrodialysis method；Wherein there is cost height in silver oxide method, and product is easily by shortcomings such as silver ion pollutions.Ion-exchange-resin process products obtained therefrom purity is the highest, resin regeneration difficulty.Alkali displacement method is also easily mixed into foreign ion in process of production.Although it is higher that membrane electrolysis obtains product purity, but compare bipolar membrane electrodialysis method and still suffer from the shortcomings such as energy consumption is higher.
Bipolar Membrane is a kind of Novel ion exchange membrane being composited by anions and canons switching layer.When reversely applying voltage, the water decomposition in Bipolar Membrane intermediate layer becomes hydrion and hydroxide ion, and migrates to cathode and anode through two film layers respectively.This special ion film is combined by bipolar membrane electrodialysis technology exactly with anion and cation exchange membrane, thus realizes being converted into by the salt in aqueous solution the technology of the bronsted lowry acids and bases bronsted lowry of correspondence in the case of not introducing new component.The presently disclosed patent utilizing bipolar membrane electrodialysis technology to be applied to Tetramethylammonium hydroxide production is CN201410848595.6.But its microbial cultivation process existed easily makes technique be affected by external condition, and owing to being limited by negative and positive film, the acid solution mass fraction produced during bipolar membrane electrodialysis general about 10%, it is unfavorable for recycling.
Thus, Bipolar membrane water splitting produces Tetramethylammonium hydroxide and there is complex process, and relatively low being unfavorable for of halogen acids concentration produced is reclaimed, and easily causes the shortcomings such as environmental pollution.
Film distillation technology is a kind of non-isothermal Physical Separation Technology, with the steam pressure difference of hydrophobic porous film both sides as motive force, make hot side steam molecule through after fenestra in the condensation enrichment of cold side, be considered as the set of membrane process and still-process.As a kind of novel high efficient separation technology, compared with traditional distillation and reverse osmosis process, have many advantages, such as: equipment is volume required little；Relatively low operation temperature and pressure；Theoretical rejection to fixedness component 100%；Good chemical stability；Can integrate mutually with other separation processes；Separation heat-sensitive substance and high-concentration waste water etc. can be processed.Therefore, since within 1963, being proposed first, it has been constantly subjected to the concern of many scholars.
Summary of the invention
Shortcoming for prior art, the invention provides a kind of bipolar membrane electrodialysis system and use its method preparing high-purity Tetramethylammonium hydroxide, the method can use Membrane Materials to process its by-product halogen acids further, from but receive cleaning preparation Tetramethylammonium hydroxide.
For achieving the above object, the present invention adopts the technical scheme that bipolar membrane electrodialysis system, including several bipolar membrane electrodialysis devices, several bipolar membrane electrodialysis devices described are in series or in parallel, and described bipolar membrane electrodialysis device includes the pole liquid chamber being arranged on both sides and is positioned at the electrodialysis compartment in the middle of two side pole liquid chambers；If described electrodialysis compartment includes organizing film unit, several film units described are in series, described film unit includes the first Bipolar Membrane BM1 being sequentially arranged at intervals, first cation exchange membrane CM1, anion exchange membrane AM1, second cation exchange membrane CM2, second Bipolar Membrane BM2, compartment is formed between adjacent each film, buffer chamber is constituted between described first Bipolar Membrane BM1 and the first cation exchange membrane CM1, acid solution room is constituted between described first cation exchange membrane CM1 and described anion exchange membrane AM1, raw material liquid chamber is constituted between described anion exchange membrane AM1 and described second cation exchange membrane CM2, alkali liquor room is constituted between described second cation exchange membrane CM2 and described second Bipolar Membrane BM2.
In one embodiment of the invention, described pole liquid chamber includes that anode chamber and cathode chamber, described anode chamber are located close to the side of described first Bipolar Membrane BM1, and described cathode chamber is located close to the side of described second Bipolar Membrane BM2.
In one embodiment of the invention, described the first Bipolar Membrane BM1, the first cation exchange membrane CM1, anion exchange membrane AM1, the second cation exchange membrane CM2, the material of the second Bipolar Membrane BM2 are all homogeneous membrane.
A kind of method using bipolar membrane electrodialysis system to prepare high-purity Tetramethylammonium hydroxide, comprises the following steps:
Step 1: Tetramethylammonium hydroxide halogeno salt aqueous solution is passed through raw material liquid chamber, is respectively passed through pure water in acid solution room and alkali liquor room, each leads into sulfuric acid solution in pole liquid chamber and buffer chamber；
Step 2: the first Bipolar Membrane BM1 and the second Bipolar Membrane BM2 are applied DC electric field, first Bipolar Membrane BM1 and the second Bipolar Membrane BM2 water that can dissociate under DC electric field effect produces hydrion and hydroxide ion, the hydrion that first Bipolar Membrane BM1 produces enters buffer chamber under electric field action, and then enter into acid solution room through the first cation exchange membrane CM1, and move to the halide ion of acid solution room be combined with passing anion exchange membrane AM1 from raw material liquid chamber against direction of an electric field, generate halogen acids；
Step 3: the hydroxide ion that the second Bipolar Membrane BM2 produces enters alkali liquor room under electric field action, and is combined with the tetramethylammonium cation entering into alkali room through the second cation exchange membrane CM2 from raw material liquid chamber, generates Tetramethylammonium hydroxide.
In one embodiment of the invention, the mass fraction of described sulfuric acid solution is 0.5% ~ 3%.
In one embodiment of the invention, the electric current density of described DC electric field is 100 ~ 600A/m2, the temperature that system is run is 25 ~ 35 DEG C, and in each compartment, flow rate of liquid controls is 100 ~ 2000L/h.
In one embodiment of the invention, the described halogen acids generated is heated to 30 ~ 80 DEG C, after solution temperature is stable, halogen acid solution is carried out Membrane Materials through the membrane component of hydrophobic property, making solution is 15%-20% through continuous concentration cycles to mass fraction, collect concentrated solution, be back to Tetramethylammonium hydroxide halogeno salt and produce.
In one embodiment of the invention, described membrane component structure is plate type membrane assembly or hollow fiber form membrane module.
In one embodiment of the invention, the material of described membrane component is hydrophobic microporous membrane, polyvinylidene fluoride dewatering film, polypropylene hydrophobic film or the hydrophobic film after hydrophobic modified.
In one embodiment of the invention, described Membrane Materials is direct contact membrane distillation or vacuum type Membrane Materials or gap field orientation.
Described direct contact membrane distillation process is: halogen acid solution is heated to 40 ~ 80 DEG C by (1)；(2) after solution temperature is stable, halogen acid solution is passed through the feed side of membrane component and carries out Membrane Materials, in the range of the cold side at direct contact membrane distillation assembly is coolant, and temperature is maintained at 0 ~ 30 DEG C.Through concentration cycles repeatedly, feed liquid is concentrated into mass fraction when being 15 ~ 20%, i.e. completes Membrane Materials process, collects concentrated solution, is back to Tetramethylammonium hydroxide halogeno salt and produces.Wherein said coolant is water.
Described vacuum type Membrane Materials process is: halogen acid solution is heated to 30 ~ 80 DEG C by (1)；(2) after solution temperature is stable, the feed side of the membrane component that halogen acid solution is passed through carries out Membrane Materials.It is 0.1 ~ 3kPa that cold side at membrane module is evacuated to vacuum,.Through concentration cycles repeatedly, feed liquid is concentrated into mass fraction when being 15 ~ 20%, i.e. completes Membrane Materials process, collects concentrated solution, is back to Tetramethylammonium hydroxide halogeno salt and produces.
Described gap field orientation process is: halogen acid solution is heated to 40 ~ 80 DEG C by (1)；(2) after solution temperature is stable, halogen acid solution is passed through the feed side of membrane component and carries out Membrane Materials, the coolant of membrane component condenser in assembly is cooled to-5 ~ 5 DEG C simultaneously, through concentration cycles repeatedly, feed liquid is concentrated into mass fraction when being 15 ~ 20%, i.e. complete Membrane Materials process, collect concentrated solution, be back to Tetramethylammonium hydroxide halogeno salt and produce.Wherein said coolant be volumn concentration be 30 ~ 70% glycol waters.
The method have the advantages that
The bipolar membrane electrodialysis technology that the present invention uses, water decomposition occurs for it and to produce the voltage of soda acid relatively low, and by the way of bipolar membrane device is provided with buffer chamber in membrane structure, avoid the foreign ion pollution to product, therefore its running not only energy consumption is low, and highly purified Tetramethylammonium hydroxide can be obtained, its mass fraction is 5% ~ 30%.During the Tetramethylammonium hydroxide response rate be more than 95%, the impurity halogen ion concentration in product solution be less than 70ppm.
Simultaneously, by-product halogen acid solution in production process of the present invention carries out concentrating reuse by film distillation technology, feed liquid is 15% ~ 20% through continuous concentration cycles to mass fraction, solve the problem that halogen acid solution is not easily recycled, achieve the resource reclaim of garbage, there is energy consumption low, efficiency advantages of higher.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention；
Fig. 2 is bipolar membrane electrodialysis apparatus structure schematic diagram；
Fig. 3 is distillation device structural representation.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the invention will be further described.
Embodiment 1
The bipolar membrane electrodialysis system that this example uses is 1 bipolar membrane electrodialysis device, this device is made up of the pole liquid chamber of both sides and the electrodialysis compartment being clipped in two side pole liquid chambers middle, pole liquid chamber is respectively cathode chamber and anode chamber, electrodialysis compartment is made up of 10 groups of film unit arranged in series, described film unit is four cell structure: first Bipolar Membrane BM1, one the first cation exchange membrane CM1, one anion exchange membrane AM1, one the second cation exchange membrane CM2, one the second Bipolar Membrane BM2 is spaced composition buffer chamber, acid solution room, raw material liquid chamber, alkali liquor room.The first Bipolar Membrane BM1 of wherein using, the first cation exchange membrane CM1, anion exchange membrane AM1, the second cation exchange membrane CM2, the material of the second Bipolar Membrane BM2 are all homogeneous membrane, and negative electrode, anode etc. all use Ti-Ru electrode.
Additionally, the Membrane Materials equipment that this example uses is the doughnut hydrophobic film assembly after hydrophobic modified, use direct contact membrane distillation mode.
Be passed through the feed liquid room of four compartment bipolar membrane electrodialysis system using 4 bromide aqueous solution 1L that mass fraction is 18.1% as raw material, acid solution room and alkali liquor room are respectively passed through pure water, and pole liquid chamber and buffer chamber each lead into the sulfuric acid solution that mass fraction is 3%.On minus plate, the positive plate in bipolar membrane device being applied DC electric field, controls electric current density and stablize at 300A/m2, running temperature is 25 DEG C, and each compartment flow rate of liquid controls as 100L/h.
Through bipolar membrane electrodialysis circular treatment, obtaining the tetramethyl ammonium hydroxide solution that mass fraction is 14.3%, wherein foreign ion bromide ion concentration is 50ppm, and product yield is 97.2%.
Simultaneously, the hydrobromic acid that the mass fraction generated during bipolar membrane electrodialysis is 5.3% is heated to 50 DEG C, after solution temperature is stable, the feed side that hydrobromic acid solution is passed through membrane component carries out Membrane Materials, cold side at direct contact membrane distillation assembly is coolant, described coolant is water, and temperature is maintained at 5 DEG C.Through concentration cycles repeatedly, feed liquid is concentrated into mass fraction when being 19.31%, i.e. completes Membrane Materials process, collects concentrated solution, is back to 4 bromide and produces.
Embodiment 2
The bipolar membrane electrodialysis system that this example uses is 1 bipolar membrane electrodialysis device, this device is made up of the pole liquid chamber of both sides and the electrodialysis compartment being clipped in two side pole liquid chambers middle, pole liquid chamber is respectively cathode chamber and anode chamber, electrodialysis compartment is made up of 30 groups of film unit arranged in series, described film unit is four cell structure, including first Bipolar Membrane BM1, one the first cation exchange membrane CM1, one anion exchange membrane AM1, one the second cation exchange membrane CM2, one the second Bipolar Membrane BM2 is spaced composition buffer chamber, acid solution room, raw material liquid chamber, alkali liquor room.The Bipolar Membrane that wherein uses, cation exchange membrane, anion exchange membrane AM1 are homogeneous membrane, and negative electrode, anode etc. all use Ti-Ru electrode.
Additionally, the Membrane Materials equipment that this example uses is the doughnut hydrophobic film assembly after hydrophobic modified, use vacuum type Membrane Materials mode.
Be passed through the feed liquid room of four compartment bipolar membrane electrodialysis system using 4 bromide aqueous solution 50L that mass fraction is 20% as raw material, acid room and alkali room are respectively passed through pure water, and pole liquid chamber and buffer chamber each lead into the sulfuric acid solution that mass fraction is 3%.On minus plate, the positive plate in bipolar membrane device being applied DC electric field, controls electric current density and stablize at 570A/m2, running temperature is 25 DEG C, and each compartment flow rate of liquid controls as 1500L/h.
Through bipolar membrane electrodialysis circular treatment, obtaining the tetramethyl ammonium hydroxide solution that mass fraction is 17%, wherein foreign ion bromide ion concentration is 30ppm, and product yield is 95.2%.
Meanwhile, the hydrobromic acid that the mass fraction generated during bipolar membrane electrodialysis is 7.1% being heated to 40 DEG C, after solution temperature is stable, the feed side of the membrane component that hydrobromic acid solution is passed through carries out Membrane Materials.It is 0.13kPa that cold side at film distillation film component is evacuated to vacuum.Through concentration cycles repeatedly, feed liquid is concentrated into mass fraction when being 17.3%, i.e. completes Membrane Materials process, collects concentrated solution, is back to 4 bromide and produces.
Embodiment 3
The bipolar membrane electrodialysis system that this example uses is that 2 bipolar membrane electrodialysis devices are connected in parallel, liquid is entered each bipolar membrane electrodialysis device by the fluid reservoir one-to-two road of each compartment and finally collaborates to be recycled to corresponding fluid reservoir, wherein this bipolar membrane electrodialysis device is made up of the pole liquid chamber of both sides and the electrodialysis compartment being clipped in two side pole liquid chambers middle, pole liquid chamber is respectively cathode chamber and anode chamber, electrodialysis compartment is made up of 25 groups of film unit arranged in series, described film unit is four cell structure: first Bipolar Membrane BM1, one the first cation exchange membrane CM1, one anion exchange membrane AM1, one the second cation exchange membrane CM2, one the second Bipolar Membrane BM2 is spaced composition buffer chamber, acid solution room, raw material liquid chamber, alkali liquor room.The Bipolar Membrane that wherein uses, cation exchange membrane, anion exchange membrane AM1 are the homogeneous membrane that market is buied, and negative electrode, anode etc. all use Ti-Ru electrode.
Additionally, the Membrane Materials equipment that this example uses is the doughnut hydrophobic film assembly after hydrophobic modified, use gap field orientation mode.
Be passed through the feed liquid room of four compartment bipolar membrane electrodialysis system using 4 bromide aqueous solution 10L that mass fraction is 25% as raw material, acid room and alkali room are respectively passed through pure water, and pole liquid chamber and buffer chamber each lead into the sulfuric acid solution that mass fraction is 3%.On minus plate, the positive plate in bipolar membrane device being applied DC electric field, controls electric current density and stablize at 400A/m2, running temperature is 25 DEG C, and each compartment flow rate of liquid controls as 200L/h.
Through bipolar membrane electrodialysis circular treatment, obtaining the tetramethyl ammonium hydroxide solution that mass fraction is 19.3%, wherein foreign ion bromide ion concentration is 21ppm, and product yield is 93.4%.
Simultaneously, the hydrobromic acid that the mass fraction generated during bipolar membrane electrodialysis is 5.2% is heated to 40 DEG C, after solution temperature is stable, halogen acid solution is passed through the feed side of membrane component and carries out Membrane Materials, and the coolant of membrane component condenser in assembly is cooled to 0 DEG C simultaneously, through concentration cycles repeatedly, feed liquid is concentrated into mass fraction when being 16.2%, i.e. complete Membrane Materials process, collect concentrated solution, be back to Tetramethylammonium hydroxide halogeno salt and produce.Wherein said coolant be volumn concentration be 30% glycol water.
Above-mentioned specific embodiment is used only to illustrate the present invention; rather than be to limit the invention; in spirit of the invention and scope of the claims, any replacement not paying creative work that the present invention is made and change, fall within the protection domain of patent of the present invention.
Claims (10)
1. a bipolar membrane electrodialysis system, it is characterized in that, including several bipolar membrane electrodialysis devices, several bipolar membrane electrodialysis devices described are in series or in parallel, and described bipolar membrane electrodialysis device includes the pole liquid chamber being arranged on both sides and is positioned at the electrodialysis compartment in the middle of two side pole liquid chambers；If described electrodialysis compartment includes organizing film unit, several film units described are in series, described film unit includes the first Bipolar Membrane BM1 being sequentially arranged at intervals, first cation exchange membrane CM1, anion exchange membrane AM1, second cation exchange membrane CM2, second Bipolar Membrane BM2, buffer chamber is constituted between described first Bipolar Membrane BM1 and the first cation exchange membrane CM1, acid solution room is constituted between described first cation exchange membrane CM1 and described anion exchange membrane AM1, raw material liquid chamber is constituted between described anion exchange membrane AM1 and described second cation exchange membrane CM2, alkali liquor room is constituted between described second cation exchange membrane CM2 and described second Bipolar Membrane BM2.
2. bipolar membrane electrodialysis system as claimed in claim 1, it is characterised in that described pole liquid chamber includes that anode chamber and cathode chamber, described anode chamber are located close to the side of described first Bipolar Membrane BM1, and described cathode chamber is located close to the side of described second Bipolar Membrane BM2.
3. bipolar membrane electrodialysis system as claimed in claim 1, it is characterised in that described the first Bipolar Membrane BM1, the first cation exchange membrane CM1, anion exchange membrane AM1, the second cation exchange membrane CM2, the material of the second Bipolar Membrane BM2 are all homogeneous membrane.
4. one kind uses the method that the arbitrary described bipolar membrane electrodialysis system of claims 1 to 3 prepares high-purity Tetramethylammonium hydroxide, it is characterised in that comprise the following steps:
Step 1: Tetramethylammonium hydroxide halogeno salt aqueous solution is passed through raw material liquid chamber, is respectively passed through pure water in acid solution room and alkali liquor room, each leads into sulfuric acid solution in pole liquid chamber and buffer chamber；
Step 2: the first Bipolar Membrane BM1 and the second Bipolar Membrane BM2 are applied DC electric field, first Bipolar Membrane BM1 and the second Bipolar Membrane BM2 water that can dissociate under DC electric field effect produces hydrion and hydroxide ion, the hydrion that first Bipolar Membrane BM1 produces enters buffer chamber under DC electric field effect, and then enter into acid solution room through the first cation exchange membrane CM1, and move to the halide ion of acid solution room be combined with passing anion exchange membrane AM1 from raw material liquid chamber against direction of an electric field, generate halogen acids；
Step 3: the hydroxide ion that the second Bipolar Membrane BM2 produces enters alkali liquor room under DC electric field effect, and is combined with the tetramethylammonium cation entering into alkali room through the second cation exchange membrane CM2 from raw material liquid chamber, generates Tetramethylammonium hydroxide.
5. the method preparing high-purity Tetramethylammonium hydroxide as claimed in claim 4, it is characterised in that the mass fraction of described sulfuric acid solution is 0.5% ~ 3%.
6. the method preparing high-purity Tetramethylammonium hydroxide as claimed in claim 4, it is characterised in that described Tetramethylammonium hydroxide halogeno salt tetramethyl quaternary ammonium salt including tetramethyl ammonium chloride, 4 bromide.
7. the method preparing high-purity Tetramethylammonium hydroxide as claimed in claim 4, it is characterised in that the electric current density of described DC electric field is 100 ~ 600A/m2, the temperature that system is run is 25 ~ 35 DEG C, and in each compartment, flow rate of liquid controls is 100 ~ 2000L/h.
8. the method preparing high-purity Tetramethylammonium hydroxide as claimed in claim 4, it is characterized in that, the described halogen acids generated is heated to 30 ~ 80 DEG C, after solution temperature is stable, halogen acid solution is carried out Membrane Materials through the membrane component of hydrophobic property, making the continuous concentration cycles of halogen acid solution to mass fraction is 15% ~ 20%, collects concentrated solution, is back to Tetramethylammonium hydroxide halogeno salt and produces.
9. the method preparing high-purity Tetramethylammonium hydroxide as claimed in claim 8, it is characterised in that described membrane component structure is plate type membrane assembly or hollow fiber form membrane module.
10. the method preparing high-purity Tetramethylammonium hydroxide as claimed in claim 8, it is characterized in that, the material of described membrane component is hydrophobic microporous membrane, polyvinylidene fluoride dewatering film, polypropylene hydrophobic film or the hydrophobic film after hydrophobic modified.
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| CN107118105A (en) * | 2017-07-03 | 2017-09-01 | 杭州龙智科技有限公司 | The method that coupling bipolar membrane electrodialysis and membrane distillation prepare methyl triethylammonium hydroxide |
| CN107298644A (en) * | 2017-07-03 | 2017-10-27 | 杭州龙智科技有限公司 | The method that bipolar membrane electrodialysis device prepares TMAH |
| CN107365258A (en) * | 2017-07-03 | 2017-11-21 | 杭州龙智科技有限公司 | The preparation facilities and preparation method of tetraethyl ammonium hydroxide solution |
| CN107382737A (en) * | 2017-07-03 | 2017-11-24 | 杭州龙智科技有限公司 | The application method of the preparation methods of double quaternary ammonium bases, preparation facilities and preparation facilities |
| CN107602394A (en) * | 2017-09-18 | 2018-01-19 | 浙江工业大学 | Method for preparing N, N, N-trimethyl-1-adamantyl ammonium hydroxide by bipolar membrane electrodialysis |
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| CN110644014A (en) * | 2019-10-30 | 2020-01-03 | 盐城泛安化学有限公司 | Preparation method of tetraethyl ammonium hydroxide |
| CN111848409A (en) * | 2020-06-30 | 2020-10-30 | 浙江工业大学 | Method for preparing tetraethyl ammonium tetrafluoroborate by bipolar membrane electrodialysis assistance |
| CN113981476A (en) * | 2021-09-17 | 2022-01-28 | 镇江润晶高纯化工科技股份有限公司 | Preparation method of energy-saving tetraethylammonium hydroxide with high production efficiency |
| US11673818B2 (en) | 2020-12-30 | 2023-06-13 | Industrial Technology Research Institute | System and method of treating waste water |
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| CN107118105A (en) * | 2017-07-03 | 2017-09-01 | 杭州龙智科技有限公司 | The method that coupling bipolar membrane electrodialysis and membrane distillation prepare methyl triethylammonium hydroxide |
| CN107298644A (en) * | 2017-07-03 | 2017-10-27 | 杭州龙智科技有限公司 | The method that bipolar membrane electrodialysis device prepares TMAH |
| CN107365258A (en) * | 2017-07-03 | 2017-11-21 | 杭州龙智科技有限公司 | The preparation facilities and preparation method of tetraethyl ammonium hydroxide solution |
| CN107382737A (en) * | 2017-07-03 | 2017-11-24 | 杭州龙智科技有限公司 | The application method of the preparation methods of double quaternary ammonium bases, preparation facilities and preparation facilities |
| CN107652185A (en) * | 2017-07-03 | 2018-02-02 | 杭州龙智科技有限公司 | The preparation facilities and preparation method of benzyltrimethylammonium hydroxide |
| CN107602394A (en) * | 2017-09-18 | 2018-01-19 | 浙江工业大学 | Method for preparing N, N, N-trimethyl-1-adamantyl ammonium hydroxide by bipolar membrane electrodialysis |
| CN108017121A (en) * | 2017-12-12 | 2018-05-11 | 浙江迪萧环保科技有限公司 | A kind of clean preparation method of diethylamine |
| CN108467347A (en) * | 2018-03-22 | 2018-08-31 | 新乡化纤股份有限公司 | A method of electrolysis tetrabutyl ammonium sulfate recycles tetrabutylammonium hydroxide |
| CN109331663A (en) * | 2018-11-13 | 2019-02-15 | 北京廷润膜技术开发股份有限公司 | Bipolar membrane displacement electrodialysis plant and the method that lithium hydroxide is prepared using bipolar membrane displacement electrodialysis plant |
| CN110644014A (en) * | 2019-10-30 | 2020-01-03 | 盐城泛安化学有限公司 | Preparation method of tetraethyl ammonium hydroxide |
| CN111848409A (en) * | 2020-06-30 | 2020-10-30 | 浙江工业大学 | Method for preparing tetraethyl ammonium tetrafluoroborate by bipolar membrane electrodialysis assistance |
| US11673818B2 (en) | 2020-12-30 | 2023-06-13 | Industrial Technology Research Institute | System and method of treating waste water |
| CN113981476A (en) * | 2021-09-17 | 2022-01-28 | 镇江润晶高纯化工科技股份有限公司 | Preparation method of energy-saving tetraethylammonium hydroxide with high production efficiency |
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Application publication date: 20160810 |