CN102234813A - Bipolar membrane acid-base liquid generating device for chromatographic technology - Google Patents
Bipolar membrane acid-base liquid generating device for chromatographic technology Download PDFInfo
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- CN102234813A CN102234813A CN2010101567069A CN201010156706A CN102234813A CN 102234813 A CN102234813 A CN 102234813A CN 2010101567069 A CN2010101567069 A CN 2010101567069A CN 201010156706 A CN201010156706 A CN 201010156706A CN 102234813 A CN102234813 A CN 102234813A
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a bipolar membrane acid-base liquid generating device for a chromatographic technology. In the invention, a principle of disassociating water with bipolar membranes is adopted, H<+> and OH<-> are generated by disassociating water on the bipolar membranes, the reaction equation is that: H2O=H<+>+OH<->, an ion exchange membrane is used through cooperating with an electric field to make ions to move to a specific part through directional migration and to be subjected to a chemical reaction to prepare the acid-base liquid with a preset concentration. Pure H<+> and OH<-> ions are generated by a system cooperating with the cation exchange membrane and the anion exchange membrane, the concentration of the acid and the base can be changed according to the change of the extraneous electric field, and the device is especially suitable for the ion chromatography field.
Description
Technical field:
The present invention relates to a kind of Bipolar Membrane soda acid liquid generating unit that is used for chromatographic technique, especially for the automatic leacheate generating unit of chromatography of ions, and the ion restraining device.
Background technology:
Chromatography of ions is as a kind of effective separation and analytical technology, its separating mechanism is: leacheate and testing sample flow into the separation that is filled with ion exchange resin and lean on, treat that measured ion forms different chromatographic zone band outflow separation and leans on, if use the chromatography of ions of inhibition method, the chromatographic column effluent liquid also will carry out background suppression through suppressor.But in chromatography of ions is used, guarantee at any time that the ionic concn of leacheate conforms to requirement, so actually operating complex steps.During this external liquid chromatography is used, the pH value of leacheate is also very big to the influence of analytical results, the operation of regulating the moving phase pH value is also very loaded down with trivial details, U.S. Dai An company has developed a kind of leacheate automatic generating apparatus at chromatography of ions (US Patent No.:US 6316270B1), and trade name is RFIC-EG.But this device adopts the monofilm electrolysis principle, utilizes the electrolysis principle of water on electrode to produce hydrogen ion and hydroxide ion, also produces hydrogen and oxygen when producing hydrogen ion and hydroxide ion, and the reflection mode becomes as follows, and anodic reaction is:
Cathodic reaction is: H
2O+2e=2OH
-+ H
2↑, because its use is the monofilm electrolysis principle, need the oxygen or the hydrogen discharge system that take place in the stream could be used the employing degasifying device.And in order to prepare as Na
2CO
3, NaHCO
3Such composite components also need add an electrolyzer and regulate proportioning.Domestic in addition also have similar patent to apply for, (number of patent application: 200810223916), the still principle of male or female brine electrolysis of use, it produces hydrogen ion, and the principle of hydroxide ion is identical with the principle of wearing peace, and anodic reaction is:
Cathodic reaction is: H
2O+2e=2OH
-+ H
2↑, because the restriction of reaction principle, it does not solve the problem that reactive system produces gas at all.But it makes the gas of generation not enter in the chromatographic system by flow path designs cleverly, but above have the common problem to be exactly by electrolysis water, 1) the theoretical current potential (2.075V) of electrolysis water theoretical decomposition voltage (0.828V) relative and water differs bigger, and the result consumes more energy.The brine electrolysis energy consumption is 198.5kJ/mol, and the energy consumption of Bipolar Membrane dissociate water is 79.9kJ/mol.2) only on electrode electrolysis produce hydrogen ion and hydroxide ion, repeat the more complicated of arranging.
People utilize the electrolysis of water on negative electrode and anode to generate H traditionally
+And OH
-, the electrolytic while has also generated O
2And H
2, the superpotential of following in this process has consumed about general energy, and Bipolar Membrane is different from ion-exchange membrane in the past, water directly can be dissociated into H
+And OH
-Simultaneously can not generate gas, by suitable combination, salt can be transformed into corresponding bronsted lowry acids and bases bronsted lowry, this process has been utilized Bipolar Membrane (BPM) and traditional cationic exchange membrane (CEM) simultaneously, anion-exchange membrane (AEM), wherein ionic separates and in conjunction with the influence that seen through by DC electric field motivating force and ion-exchange membrane ion selectivity, therefore, utilizes the characteristics of Bipolar Membrane, can be applied to chromatographic field, especially the leacheate in chromatography of ions field produces.As Fig. 1 is Bipolar Membrane water dissociating synoptic diagram.
Explanation of nouns: CEL (Cation Exchange Level) anionresin layer, AEL (AnionExchange Level) cationic exchange layer, J water decomposition interface, X
-Represent negatively charged ion, M
+Represent positively charged ion.
Summary of the invention:
The technical problem to be solved in the present invention provides a kind of simple in structure, and no gas produces in the generation chamber, cheap, the easy to use soda acid liquid generating unit that is used for chromatographic technique.The present invention is suitable as the automatic leacheate generating unit of chromatography of ions very much, and the method that solves this technical problem is to adopt the principle of Bipolar Membrane (Bipolar Membranes) water dissociating, and water dissociating produces H on Bipolar Membrane
+Ion and OH
-Ion, reaction equation are H
2O=H
++ OH
-, whole process does not produce gas, cooperates ion-exchange membrane and electric field to use, and makes the ion directional migration make the soda acid liquid of setting concentration to appointed part generation chemical reaction.And can produce purified H simultaneously
+And OH
-Radical ion, and the concentration of soda acid can change according to the variation of external electrical field.
A kind of soda acid liquid generating unit that is used for chromatographic technique, its schematic diagram is referring to Fig. 2, and total system is by negative electrode (1), cathode compartment (2), cationic exchange membrane (3) (9), salt chamber (4) (10), anion-exchange membrane (5) (11), acid chamber (6), Bipolar Membrane (7), alkali chamber (8), anolyte compartment (12), anode (13)
Abbreviation implication: CEM:Cation Exchange Membranes, AEM:Anion Exchange Membranes, BPM:Bipolar Membranes, X
-Represent negatively charged ion, M
+Represent positively charged ion, MX represents salt, H
2O represents water, and HX represents acid, and MOH represents alkali, H
+Represent hydrogen ion, OH
-Represent hydroxide ion.
Reaction in the total system working process is as follows, to produce KOH and H
2SO
4Be example, in the working process, sour chamber (6) and alkali chamber (8) feed deionized water, and salt chamber (4) (10) feeds the K of high density
2SO
4Solution, and the electrolytic solution that electrode vessel feed to be fit to as electrode solution (as K
2SO
4Solution), in the energising of negative electrode (1) and anode (2), set up electric field like this in total system, because the effect of electrical forces, Bipolar Membrane is because the principle of its special brine electrolysis, and water molecules dissociates at the interface place of anode membrane and cavity block in Bipolar Membrane, resolves into H
+And OH
-Ion, and H
+Move to sour chamber (6), OH
-Move to alkali chamber (8).Simultaneously because the effect of electrical forces, K in salt chamber (4)
+Moved to cathode compartment (1) by cationic exchange membrane (3), and SO
4 2-Moved to sour chamber (6) by anion-exchange membrane (5), with Bipolar Membrane electrolysis H
2The H that O obtains
+In conjunction with, obtained purified H
2SO
4Solution, the while is owing to the ion selectivity of anion-exchange membrane (5) and Bipolar Membrane (7), the H in sour chamber (6)
+Can not be moved to salt chamber (4) in the electrical forces effect, and the SO in sour chamber (6)
4 2-Can not under the electrical forces effect, move to alkali chamber (8) by Bipolar Membrane.In like manner, since the effect of electrical forces, K in salt chamber (10)
+Alkali chamber (8) and Bipolar Membrane electrolysis H have been moved to by cationic exchange membrane (9)
2The OH that O obtains
-The knot combination has obtained purified KOH solution, and SO
4 2-Moved to anolyte compartment (12) by anion-exchange membrane (11), the while is owing to the ion selectivity of anion-exchange membrane (9) and Bipolar Membrane (7), the OH in alkali chamber (6)
-Can not be moved to salt chamber (10) and K in alkali chamber (8) in the electrical forces effect
+Can not under the electrical forces effect, move to sour chamber (6), thereby in sour chamber (6) and alkali chamber (8), obtain purified bronsted lowry acids and bases bronsted lowry liquid respectively by Bipolar Membrane.
By the distinctive water decomposition reaction of Bipolar Membrane, and the ion directional migration under electric field and the ion-exchange membrane acting in conjunction, can generate purified bronsted lowry acids and bases bronsted lowry by pure water and salt acting in conjunction, its reaction equation is H2O+MX=HX+MOH.Sour chamber (6) and alkali chamber (7) can also be not limited only to feed pure water in this external application process, satisfy the demand and two salt chambers (4) (10) can feed different salt as required.
In at the chromatography of ions use, can use the acid of generation or alkali to carry sample and enter chromatographic column and separate, and can change the concentration of leacheate easily by regulating extra electric field as the leacheate of chromatography of ions.
Especially be directed to the applicable cases under the chromatography of ions suppression mode, a kind of valuable using method is, acid chamber (4) effusive acid solution body is carried secretly as the leacheate of chromatography of ions and can be refluxed into alkali chamber (8) after sample separates by chromatographic column, and with the OH of its generation
-Ionic bond generates water, has finished the effect that ion suppresses, and same like this device both can use as leacheate producer and leacheate suppressor simultaneously, and traditional chromatography of ions also is that above device separated into two parts is finished.
Above situation is suitable for too for the chromatography of ions that uses alkali lye as leacheate, and the thing of being done is just changed the order of corresponding stream.Simplify the complicacy of whole chromatography of ions device like this, saved cost
So this device can be finished following being used in combination at chromatography of ions.
1. positively charged ion leacheate producer
2. negatively charged ion leacheate producer
3. positively charged ion suppressor
4. negatively charged ion suppressor
5. positively charged ion leacheate producer+positively charged ion suppressor
6. negatively charged ion leacheate producer+negatively charged ion suppressor
The core of this device is the water decomposition characteristic of Bipolar Membrane uniqueness, in the use of reality, can also increase or reduce the quantity of Bipolar Membrane according to concrete arts demand, increases or reduce the quantity of ion-exchange membrane.Do the output that can obtain increasing acid or alkali like this, improve results such as ion selectivity, come the application power of lifting gear in some field but also can increase ion exchange resin between film, when using as suppressor ion, it is higher that the device that contains ion-exchange packing suppresses ability.
So the present invention need not to adopt degasifying device, can automatic on-line be chromatography of ions preparation leacheate.Make chromatography of ions in operational process, need not manually to prepare leacheate." only add water " with regard to continuously-running several weeks, even the longer time.This device can make simple to operate, easy of chromatography of ions, and data are more accurately reliable.Make the experimental data of different personnel, different location, different time have the circulation ratio and the comparability of height, the present invention is applicable to the automatic preparation of various ion chromatography leacheates, and its principle is with above-mentioned similar.
Description of drawings:
Fig. 1: Bipolar Membrane water dissociating synoptic diagram.
Fig. 2: the Bipolar Membrane soda acid liquid generating unit schematic diagram that is used for chromatographic technique.
Fig. 3: soda acid liquid generating unit.
Fig. 4: filling type soda acid liquid generating unit
Fig. 5: utmost point acid alkali lye body generating unit in pairs
Fig. 6: Bipolar Membrane acid solution generating unit
Fig. 7: Bipolar Membrane alkali lye generating unit
Embodiment:
1. soda acid liquid generating unit, as shown in Figure 3, total system by, negative electrode (1), cathode compartment (2), cationic exchange membrane (3) (9), salt chamber (4) (10), anion-exchange membrane (5) (11), sour chamber (6), Bipolar Membrane (7), alkali chamber (8), anolyte compartment (12), anode compositions such as (13), cathode compartment (2) wherein, salt chamber (4) (10), acid chamber (6), alkali chamber (8), anolyte compartment (12) are rectangle, thickness is 1mm, and volume is not more than 1ml, and material is a tetrafluoroethylene, anode and cathode material all are titanium plates, and the titanium plate thickness is 0.8mm, anion-exchange membrane, cationic exchange membrane, Bipolar Membrane, electrode, cathode compartment, the anolyte compartment, salt chamber, sour chamber, alkali chamber etc. is pressed the order of Fig. 3 and is placed, periphery makes it keep stopping property by mechanical grip power, and fluid exchange can be carried out by default entrance and exit and the external world in each chamber, in device between each chamber owing to the existence of film UNICOM not mutually, electrode is drawn by platinum filament, can external source.
2. filling type soda acid liquid generating unit, by shown in Figure 4, total system by, negative electrode (1), cathode compartment (2), cationic exchange membrane (3) (9), salt chamber (4) (10), anion-exchange membrane (5) (11), sour chamber (6), Bipolar Membrane (7), alkali chamber (8), anolyte compartment (12), anode compositions such as (13), cathode compartment (2) wherein, salt chamber (4) (10), acid chamber (6), alkali chamber (8), anolyte compartment (12) are rectangle, thickness is 1mm, and volume is not more than 1ml, and material is a tetrafluoroethylene, anode and cathode material all are titanium plates, and the titanium plate thickness is 0.8mm, anion-exchange membrane, cationic exchange membrane, Bipolar Membrane, electrode, cathode compartment, the anolyte compartment, salt chamber, sour chamber, alkali chamber etc. is pressed the order of Fig. 3 and is placed, periphery makes it keep stopping property by mechanical grip power, and fluid exchange can be carried out by default entrance and exit and the external world in each chamber, in device between each chamber owing to the existence of film UNICOM not mutually, electrode is drawn by platinum filament, can external source.
In addition, in each chamber, can optionally fill ion-exchange material, as ion exchange resin, ion-exchange fiber etc.In this example, sour chamber (6) filler is the Zeo-karb of the sulfonic acid group of 50um, and alkali chamber (8) filler is the anionite-exchange resin of the quaternary ammonium group of 50um.
3. utmost point acid alkali lye body generating unit in pairs, as shown in Figure 5, total system by, negative electrode (1), cathode compartment (2), Bipolar Membrane (3) (9), alkali chamber (4), cationic exchange membrane (5), salt chamber (6), anion-exchange membrane (7), sour chamber (8), anolyte compartment (10), anode compositions such as (11), cathode compartment (2) wherein, alkali chamber (4), salt chamber (6), sour chamber (8), anolyte compartment (10) are rectangle, thickness is 1mm, and volume is not more than 1ml, and material is a tetrafluoroethylene, anode and cathode material all are titanium plates, and the titanium plate thickness is 0.8mm, anion-exchange membrane, cationic exchange membrane, Bipolar Membrane, electrode, cathode compartment, the anolyte compartment, salt chamber, sour chamber, alkali chamber etc. is pressed the order of Fig. 5 and is placed, periphery makes it keep stopping property by mechanical grip power, and fluid exchange can be carried out by default entrance and exit and the external world in each chamber, in device between each chamber owing to the existence of film UNICOM not mutually, electrode is drawn by platinum filament, can external source.
4. Bipolar Membrane acid solution generating unit as shown in Figure 6, in use, only needs simple generation acid solution sometimes, and perhaps the acid of Sheng Chenging is weak acid, and specific conductivity is lower, can adopt following pattern.
Total system by, negative electrode (1), cathode compartment (2), Bipolar Membrane (3) (7), salt chamber (4), anion-exchange membrane (5), acid chamber (6), anolyte compartment (8), anode compositions such as (9), cathode compartment (2) wherein, salt chamber (4), sour chamber (6), anolyte compartment (8) is rectangle, and thickness is 1mm, and volume is not more than 1mL, material is a tetrafluoroethylene, and anode and cathode material all are titanium plates, and the titanium plate thickness is 0.8mm, anion-exchange membrane, Bipolar Membrane, electrode, cathode compartment, the anolyte compartment, salt chamber, sour chamber etc. are pressed the order of Fig. 6 and are placed, and periphery makes it keep stopping property by mechanical grip power, fluid exchange can be carried out by the default entrance and exit and the external world in each chamber, in device between each chamber owing to the existence of film UNICOM not mutually, electrode is drawn by platinum filament, can external source.
5. Bipolar Membrane alkali lye generating unit as shown in Figure 7, in use, only needs simple generation alkali lye sometimes, and perhaps the alkali of Sheng Chenging is weak base, and specific conductivity is lower, can adopt following pattern.
Total system by, negative electrode (1), cathode compartment (2), Bipolar Membrane (3) (7), alkali chamber (4), cationic exchange membrane (5), salt chamber (6), anolyte compartment (8), anode compositions such as (9), cathode compartment (2) wherein, alkali chamber (4), salt chamber (6), anolyte compartment (8) is rectangle, and thickness is 1mm, and volume is not more than 1mL, material is a tetrafluoroethylene, and anode and cathode material all are titanium plates, and the titanium plate thickness is 0.8mm, cationic exchange membrane, Bipolar Membrane, electrode, cathode compartment, the anolyte compartment, salt chamber, alkali chamber etc. are pressed the order of Fig. 7 and are placed, and periphery makes it keep stopping property by mechanical grip power, fluid exchange can be carried out by the default entrance and exit and the external world in each chamber, in device between each chamber owing to the existence of film UNICOM not mutually, electrode is drawn by platinum filament, can external source.
Claims (7)
1. its characteristics of Bipolar Membrane soda acid liquid generating unit that are used for chromatographic technique have been to introduce the H that the Bipolar Membrane brine electrolysis produces
+And OH
-Ion changes the H in the solution
+And OH
-Ionic concn, its reaction equation are H
2O=H
++ OH
-, rather than the electrolysis water that in the past adopted, its anodic reaction is:
Cathodic reaction is: H
2O+2e=2OH
-+ H
2↑.
2. device according to claim 1 can be by forming as the lower section, negative electrode (1), cathode compartment (2), cationic exchange membrane (3) (9), salt chamber (4) (10), anion-exchange membrane (5) (11), sour chamber (6), Bipolar Membrane (7), alkali chamber (8), anolyte compartment (12), anode (13), and can constitute special application apparatus by above each several part increase and decrease.
3. device according to claim 1 wherein can be filled ion-exchange material in each chamber according to actual needs, the perhaps chromatograph packing material of other type, and resemblance is for long, and wide, there is a dimension in senior middle school less than 1mm.
4. device according to claim 1 can increase the quantity of Bipolar Membrane and ion-exchange membrane as required and puts in order, to reach generation efficient that increases acid-base solution and the purity purpose that improves acid-base solution.
5. device according to claim 1, native system can use a plurality of repetition Bipolar Membrane sequence of unit to be arranged between the two arrays of electrodes, reaching the purpose that improves acid-base solution output, and do not need to increase extra electrode.
6. device according to claim 1, native system can be applied to the chromatographic separation field, in order to the pH value of regulator solution, is particularly useful for the separation and the analysis field of chromatography of ions, particularly as automatic leacheate producer, perhaps ion restraining device.
7. a Bipolar Membrane soda acid liquid generating unit that is used for chromatographic technique can use by the following method, can flow into the alkali chamber then through chromatographic column by effusive liquid from sour chamber, carrying out ion suppresses, perhaps effusive liquid flows into the alkali chamber then through chromatographic column from the alkali chamber, carry out ion and suppress, a device serves as leacheate producer and suppressor ion use simultaneously.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012129735A1 (en) * | 2011-04-01 | 2012-10-04 | General Electric Company (A New York Corporation) | Electrolysis device and related detergentless washing machine |
| CN106290698A (en) * | 2016-07-29 | 2017-01-04 | 青岛鲁海光电科技有限公司 | A kind of generation in chromatography of ions detects stablizes method and the generating means of leacheate |
| CN109136975A (en) * | 2018-07-05 | 2019-01-04 | 华东理工大学 | Double membranous type acid or the online generator of aqueous slkali |
| CN109704444A (en) * | 2019-03-06 | 2019-05-03 | 苏州明昊色谱技术有限公司 | A kind of Bipolar Membrane cation suppressor |
| CN110508139A (en) * | 2019-08-28 | 2019-11-29 | 华东理工大学 | A kind of electrodialysis Micropump |
| CN111549354A (en) * | 2020-02-14 | 2020-08-18 | 北京历元仪器有限公司 | Acid-base generating device without degassing |
| CN112782334A (en) * | 2020-12-24 | 2021-05-11 | 苏州明昊色谱技术有限公司 | Ion chromatography carbonate leacheate concentration ratio adjusting device and method |
| CN115432778A (en) * | 2021-06-03 | 2022-12-06 | 广东栗子科技有限公司 | Bipolar membrane electric auxiliary deionization device, acid making method and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012129735A1 (en) * | 2011-04-01 | 2012-10-04 | General Electric Company (A New York Corporation) | Electrolysis device and related detergentless washing machine |
| CN106290698A (en) * | 2016-07-29 | 2017-01-04 | 青岛鲁海光电科技有限公司 | A kind of generation in chromatography of ions detects stablizes method and the generating means of leacheate |
| CN109136975A (en) * | 2018-07-05 | 2019-01-04 | 华东理工大学 | Double membranous type acid or the online generator of aqueous slkali |
| WO2020007180A1 (en) * | 2018-07-05 | 2020-01-09 | 华东理工大学 | Dual-membrane on-line generator for acid or alkali solution |
| US11827990B2 (en) | 2018-07-05 | 2023-11-28 | East China University Of Science And Technology | Dual-membrane on-line generator for acid or alkali solution |
| CN109704444A (en) * | 2019-03-06 | 2019-05-03 | 苏州明昊色谱技术有限公司 | A kind of Bipolar Membrane cation suppressor |
| CN109704444B (en) * | 2019-03-06 | 2022-01-18 | 苏州明昊色谱技术有限公司 | Bipolar membrane cation suppressor |
| CN110508139A (en) * | 2019-08-28 | 2019-11-29 | 华东理工大学 | A kind of electrodialysis Micropump |
| CN110508139B (en) * | 2019-08-28 | 2021-08-03 | 华东理工大学 | Electrodialysis micropump |
| CN111549354A (en) * | 2020-02-14 | 2020-08-18 | 北京历元仪器有限公司 | Acid-base generating device without degassing |
| CN112782334A (en) * | 2020-12-24 | 2021-05-11 | 苏州明昊色谱技术有限公司 | Ion chromatography carbonate leacheate concentration ratio adjusting device and method |
| CN115432778A (en) * | 2021-06-03 | 2022-12-06 | 广东栗子科技有限公司 | Bipolar membrane electric auxiliary deionization device, acid making method and application thereof |
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