CN109704444B - Bipolar membrane cation suppressor - Google Patents
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Abstract
The invention discloses a bipolar membrane cation suppressor in the technical field of design and manufacture of key components of analytical instruments, which sequentially comprises an upper layer electrolytic cell cover plate, a cathode electrode, an upper layer regenerated liquid channel supporting surface, an intermediate isolating layer, a lower layer regenerated liquid channel supporting surface, an anode electrode and a lower layer electrolytic cell cover plate from top to bottom; an anion membrane is arranged between the middle eluent channel and the lower regenerated liquid channel, a bipolar membrane is arranged between the upper regenerated liquid channel and the middle eluent channel, the cathode membrane surface of the bipolar membrane faces the middle eluent channel, and through holes for liquid to pass in and out are respectively arranged on the bipolar membrane and the anion membrane. This patent utilizes bipolar membrane-ion exchange membrane combination to replace the anion membrane-anion membrane combination in the traditional design, avoids using the anion membrane of unstability in negative pole district alkaline solution, can improve the life of positive inhibitor, and design simple structure, and the equipment is convenient.
Description
Technical Field
The invention relates to the technical field of design and manufacture of key parts of an analytical instrument, in particular to a bipolar membrane cation suppressor which realizes the directional migration of ions under the combined action of electrodialysis and an ion exchange membrane and converts pickling solution in ion chromatography into pure water.
Background
Ion chromatography is one of the most common analytical techniques currently used for analyzing ionic samples. Conductivity detectors are the detection mode of ion chromatographs, whose response principle is based on the product of ion concentration and its ion mobility. The hydrogen ions have the highest ion mobility among all the cations, so the acid rinse has a high response value in the conductivity detector, and is therefore prone to generate large background noise, ultimately resulting in a low system signal-to-noise ratio. On one hand, the suppressor can convert acid leacheate into pure water to reduce background noise, and meanwhile, anions accompanied by cations can be converted into hydroxide ions to remarkably improve detection signals of a target sample, so that the signal to noise ratio of sample analysis is greatly improved.
The electric film suppressor is used for generating suppressor ions required by the suppressor based on the principle of electrolyzing water, and is the latest generation suppressor technology of the current ion chromatographic system. The electric membrane suppressor is usually of a sandwich structure, and two layers of ion exchange membranes respectively separate a middle eluent channel from two regeneration liquid channels on two sides. Two electrodes (anode and cathode) are respectively arranged in the regeneration liquid channels at two sides.
For the cation electro-membrane suppressor for analyzing cations, two identical anion membranes are adopted to separate a middle leacheate channel from regeneration liquid channels on two sides respectively. Under the action of an electric field, hydroxide ions generated by water electrolysis in the cathode region in a regeneration liquid channel on one side of the cathode region are electro-migrated into an eluent liquid channel through an anion membrane (the electrolysis process is accompanied with the generation of hydrogen), and are subjected to neutralization reaction with hydrogen ions in an acidic eluent liquid (such as methanesulfonic acid) to produce pure water; at the same time, anions (such as methylsulfonate) which are paired with hydrogen ions are electro-migrated through the anodic side anion membrane into the regenerant channel of the anodic region. The process can realize the inhibition of the acid leacheate. Because pure water is not conductive on the conductivity detector, the background signal output by the conductivity detector is very low, and the background noise is correspondingly very low; when a sample (such as sodium chloride) enters the suppressor, chloride ions in the sample can enter the regeneration liquid channel of the anode region through the anion membrane on the anode side by electromigration under the action of an electric field, and sodium ions in the sample are repelled by the anion membrane of the cathode region, cannot enter the regeneration liquid channel on one side of the cathode region and only stay in the eluent channel, and are combined with hydroxide ions which are electrolyzed in the cathode region to become sodium hydroxide. So that equimolar sodium chloride is converted to equimolar sodium hydroxide. The hydroxide ion is much more mobile than the chloride ion, so the sample sodium chloride is converted to a more responsive sodium hydroxide due to the suppressor. The suppressor can achieve a significant improvement in the signal-to-noise ratio of the system.
The above-mentioned currently reported or commercialized electromembrane positive suppressors are constructed by using two anionic membranes. However, the currently commercialized anion membranes have the obvious defect that the anion membranes are easily degraded in alkaline solution (namely, the widely known Hofmann rearrangement reaction) in the cathode region, so that the service life and the operation stability of the suppressor are directly influenced. Therefore, the service life of the cation suppressor is obviously shorter than that of the anion suppressor with the same structure at present, and further research is still needed.
A special type of ion exchange membrane-bipolar membrane commonly used in the existing seawater desalination industry is formed by pressing a piece of anion membrane and a piece of cation membrane through a special process. The characteristics of which are significantly different from those of a simple anion membrane and a simple cation membrane, and are considered as a third ion exchange membrane which is distinguished from the anion membrane and the cation membrane. Numerous studies have shown that the transition layer between the anionic and cationic membrane surfaces of a bipolar membrane can undergo enhanced dissociation of water, i.e. one water molecule can dissociate into one hydroxide ion and one hydrogen ion. This dissociation process is different from the water electrolysis process, the former involving no gas generation and a low dissociation voltage ratio, and the latter involving gas generation and a high electrolysis voltage ratio. The gas generation and the operating voltage drop directly reduce the final energy consumption. The combination of bipolar membranes and anionic membranes applied to cation suppressors has not been reported in the literature.
SUMMARY OF THE PATENT FOR INVENTION
Solves the technical problem
In response to the problems of the prior background, the present patent provides a bipolar membrane cation suppressor.
Technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme:
a bipolar membrane cation suppressor comprises an upper layer electrolytic cell cover plate, an upper layer regenerated liquid channel supporting surface, a middle isolating layer, a lower layer regenerated liquid channel supporting surface and a lower layer electrolytic cell cover plate which are fixedly connected through fastening screws from top to bottom in sequence; the surfaces of the upper-layer regeneration liquid channel supporting surface, the middle isolating layer and the lower-layer regeneration liquid channel supporting surface are respectively and correspondingly provided with an upper-layer regeneration liquid channel, a middle leacheate channel, a lower-layer regeneration liquid channel and through holes for mutual circulation of leacheate and regeneration liquid; and a cathode electrode with one end connected with the upper layer electrolytic cell cover plate is arranged in the upper layer regenerated liquid channel, and an anode electrode with one end connected with the lower layer electrolytic cell cover plate is arranged in the lower layer regenerated liquid channel.
An anion membrane is arranged between the middle leacheate channel and the lower regenerated liquid channel, a bipolar membrane is arranged between the upper regenerated liquid channel and the middle leacheate channel (namely the bipolar membrane is adopted to replace a cathode membrane used by a traditional cation suppressor), and the anode membrane surface of the bipolar membrane and the cathode membrane surface of the bipolar membrane have directionality: the cathode surface of the bipolar membrane faces the middle leacheate channel, and the anode surface of the bipolar membrane faces the cathode; the bipolar membrane and the anion membrane are respectively provided with the through holes.
The bipolar membrane cation suppressor suppression mode is different from the way conventional cation suppressors generate the suppression ions. Conventional cation suppressors are based on water electrolysis, i.e. the reduction of water molecules produces the hydroxide ions needed to suppress the acid, while hydrogen gas is produced. In the patent of the invention, one piece of anionic membrane and one piece of bipolar membrane are adopted, and the generation of the hydroxide ions is inhibited based on the enhanced dissociation of water molecules in the bipolar membrane, but not water electrolysis. The dissociation process does not involve any hydrogen generation. In addition, the cathode membrane surface of the bipolar membrane faces the leacheate channel and is not in direct contact with the cathode electrode, so that the possible degradation reaction is avoided, and the service life of the suppressor is prolonged.
Furthermore, the through holes at the upper layer regeneration liquid channel and the middle leacheate channel are respectively an inlet of the leacheate channel, an outlet of the leacheate channel, an inlet of the regeneration liquid channel and an outlet of the regeneration liquid channel; the through holes at the lower layer regeneration liquid channel are respectively a regeneration liquid channel inlet and a regeneration liquid channel outlet; the effluent of the cation chromatographic column flows through the middle eluent channel from the eluent channel inlet and flows out of the eluent channel outlet to enter the detection pool; and the regeneration liquid flows through the upper layer regeneration liquid channel and the lower layer regeneration liquid channel from the inlet of the regeneration liquid channel respectively, and then flows out from the outlet of the regeneration liquid channel to enter the waste liquid.
Further, the cathode electrode and the anode electrode adopt a porous platinum electrode structure.
Furthermore, the cathode electrode and the anode electrode are respectively tightly attached to the outer sides of the upper layer regeneration liquid channel supporting surface and the lower layer regeneration liquid channel supporting surface.
Further, the bipolar membrane and the anionic membrane are ion exchange flat sheet membranes in shape.
Further, the solution entering the intermediate eluent channel is an acid solution, or an acid solution doped with a salt solution, wherein the molar ratio of the acid solution to the salt solution is more than 5 ten thousand times.
Further, the acid solution entering the intermediate rinse solution passage is an inert acid, such as methanesulfonic acid, sulfuric acid.
Further, the cathode electrode and the anode electrode are externally connected with a constant current source or a constant voltage source.
Further, when the anion membrane is replaced by a cation membrane, the position of the cation membrane is changed over with that of the bipolar membrane, and the positions of the cathode electrode and the anode electrode are simultaneously changed over, so that the cation battery membrane suppressor can be used as an anion electro-membrane suppressor.
Advantageous effects
Compared with the known public technology, the technical scheme provided by the invention has the following beneficial effects:
the invention utilizes the bipolar membrane capable of dissociating water to replace the anionic membrane at one side of the cathode area in the common cation suppressor, and because one side of the anode membrane surface of the bipolar membrane is positioned at the cathode area, and one side of the cathode membrane surface of the bipolar membrane is not directly contacted with the cathode area, the probability of Hofmann degradation of the anionic membrane in the traditional design is avoided, the structure is simple, the assembly is convenient, the working efficiency is effectively improved, and the online inhibition of acid leacheate in the field of ion chromatography is enhanced.
Drawings
In order to more clearly illustrate the patented embodiments or prior art solutions of the present invention, the drawings that are needed in the description of the embodiments or prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention patent, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
Fig. 1 is a schematic diagram of the working principle of the invention.
Fig. 2 is a schematic structural diagram of the present invention.
Fig. 3 is an assembly view of the present invention.
Fig. 4 is a voltage-current curve of the present invention.
FIG. 5 shows the suppression efficiency of the bipolar membrane cation suppressor of the present invention.
FIG. 6 shows the operation repeatability of the bipolar membrane cation suppressor of the present invention in the day.
FIG. 7 is a table showing the variation of retention time of ions on the same bipolar membrane cation suppressor on different days according to the present invention.
FIG. 8 is a table showing the peak-to-peak response variation of the present invention on the same bipolar membrane cation suppressor for different days.
Reference numbers in the figures:
a-an upper layer regeneration liquid channel; b-intermediate leacheate channel; c-lower layer regeneration liquid channel; 1-upper layer electrolytic cell cover plate; 2-a cathode electrode; 3-upper layer regeneration liquid channel supporting surface; 4-bipolar membrane, 401-anode face; 402-anion face; 5-an intermediate isolation layer; 6-anionic membrane; 7-lower layer regeneration liquid channel supporting surface; 8-an anode electrode; 9-lower layer electrolytic cell cover plate; 10-eluent channel inlet; 11-eluent passage outlet; 12-regeneration fluid channel inlet; 13-regeneration liquid channel outlet; 14-fastening screws.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It is understood that the embodiments described are some, but not all embodiments of the inventions of the present patent application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given in the present patent application without inventive step, shall fall within the scope of protection of the present patent application.
The present invention will be further described with reference to the following examples.
Example 1, with reference to fig. 1, the bipolar membrane cation suppressor described in the present patent operates on the following principle: under the action of an electric field, hydroxide ions generated by the enhanced dissociation of water molecules in the bipolar membrane are electro-migrated to the middle leacheate channel (B) and H in the channel through the cathode surface (402) of the bipolar membrane+Y-Solution (H)+Y-Is an acid solution and is an electrically inert acid. The most common inert acid is methanesulfonic acid) the hydrogen ion is neutralized to form water, and H+Y-Y in solution-Ions are electro-migrated into the lower regeneration liquid channel (C) through the anion membrane (6), so that H is generated in the process+Y-The final product of the solution is water, and the cation suppressor is used for H+Y-On-line inhibition of the solution.
With reference to fig. 2, a bipolar membrane cation suppressor comprises, from top to bottom, an upper-layer electrolytic cell cover plate 1, an upper-layer regenerated liquid channel supporting surface 3, a middle isolation layer 5, a lower-layer regenerated liquid channel supporting surface 7 and a lower-layer electrolytic cell cover plate 9 which are fixedly connected by fastening screws 14; the surfaces of the upper-layer regeneration liquid channel supporting surface 3, the middle isolating layer 5 and the lower-layer regeneration liquid channel supporting surface 7 are respectively and correspondingly provided with an upper-layer regeneration liquid channel A, a middle leacheate channel B, a lower-layer regeneration liquid channel C and through holes for mutual circulation of leacheate and regeneration liquid; a cathode electrode 2 with one end connected with the upper layer electrolytic cell cover plate 1 is arranged in the upper layer regenerated liquid channel A, and an anode electrode 8 with one end connected with the lower layer electrolytic cell cover plate 9 is arranged in the lower layer regenerated liquid channel C; an anion membrane 6 is arranged between the middle eluent channel B and the lower regenerated liquid channel C, a bipolar membrane 4 is arranged between the upper regenerated liquid channel A and the middle eluent channel B, wherein the anode membrane surface 401 of the bipolar membrane 4 faces the upper regenerated liquid channel A, and the cathode membrane surface 402 of the bipolar membrane 4 faces the middle eluent channel B; through holes for the solution to enter and exit are respectively arranged on the bipolar membrane 4 and the anion membrane 6.
With reference to fig. 3, after the present invention is assembled in sequence, the middle eluent channel B is independent from the upper regenerated liquid channel a and the lower regenerated liquid channel C. The structure ensures that the cathode membrane surface 402 of the bipolar membrane 4 used in the bipolar membrane cation suppressor of the invention is not in direct contact with the regeneration liquid channel A on the upper layer of the cathode electrode 2, thereby avoiding the degradation mentioned above and being beneficial to improving the operation stability and repeatability of the suppressor.
Furthermore, through holes at the upper layer regeneration liquid channel A and the middle leacheate channel B are respectively an leacheate channel inlet 10, an leacheate channel outlet 11, a regeneration liquid channel inlet 12 and a regeneration liquid channel outlet 13; the through holes at the lower layer regeneration liquid channel C are respectively a regeneration liquid channel inlet 12 and a regeneration liquid channel outlet 13; the effluent of the cation chromatographic column flows through the middle eluent channel B from an eluent channel inlet 10 and flows out from an eluent channel outlet 11 to enter a detection pool; the regeneration liquid flows through the upper layer regeneration liquid channel A and the lower layer regeneration liquid channel C from the regeneration liquid channel inlet 12 respectively, and then flows out from the regeneration liquid channel outlet 13 to enter waste liquid.
The working modes of the bipolar membrane cation suppressor are as follows: the effluent of the cation chromatographic column flows through the middle eluent channel B from an eluent channel inlet 10 and flows out from an eluent channel outlet 11 to enter a detection pool; the regeneration liquid flows through the upper layer regeneration liquid channel A and the lower layer regeneration liquid channel C from the regeneration liquid channel inlet 12 respectively, and then flows out from the regeneration liquid channel outlet 13 to enter waste liquid.
Further, the cathode electrode 2 and the anode electrode 8 adopt a porous platinum electrode structure.
Furthermore, the cathode electrode 2 and the anode electrode 8 are respectively closely attached to the outer sides of the upper layer regeneration liquid channel supporting surface 3 and the lower layer regeneration liquid channel supporting surface 7.
Further, the bipolar membrane 4 and the anionic membrane 6 are ion exchange flat sheet membranes in shape.
Further, the cathode electrode 2 and the anode electrode 8 are externally connected with a constant current source or a constant voltage source.
Example 2, as shown in figure 4, is a bipolar membrane cation suppressor voltage-current curve. Conditions are as follows: leacheate: 25mM methanesulfonic acid; flow rate: 0.8 mL/min; sample introduction amount: 20 mu L of the solution; and (3) analyzing the column: dionex IonPacTM CS 12A; column temperature: 35 ℃; sample concentration: 5 mg/L. It can be seen that when the applied voltage across the application suppressor is less than 3V, the current generated in the path is almost zero, and when the applied voltage across the application suppressor is greater than 3V, the current generated in the path rapidly increases. This is in good agreement with the water electrolysis characteristics of the bipolar membrane 4, i.e. the water can only be effectively dissociated between the cathode side 402 and the anode side 401 of the bipolar membrane 4 when the voltage exceeds a certain threshold (the threshold of the bipolar membrane is different from that of different manufacturers).
Example 3 was examined for inhibition efficiency using the present bipolar membrane cation inhibitor, as shown in fig. 5. Conditions are as follows: conditions are as follows: leacheate, methanesulfonic acid, 20 mM; flow rate, 1.0 mL/min;
sample size, 20 μ L; a chromatographic column: CS 12A; column temperature, 35C; sample concentration, 5 ppm. The methane sulfonic acid solution will have a very high response signal (conductivity) on the conductivity detector downstream of the suppressor if not suppressed. To avoid irreversible damage to the downstream conductivity detector, the study did not choose to have uninhibited methanesulfonic acid solution directly enter the conductivity detector, but rather chose to start with a current of 32mA applied to the bipolar membrane electrofusion suppressor (note: under this experimental condition, the desired suppression current is about 32 mA). It can be seen that at 32mA suppression current, the response of the conductivity detector is still quite high, about 42 mus/cm. The conductance detector response decreased significantly when a higher suppression current was applied, e.g., the suppression background of the conductance detector decreased to about 0.3 μ S/cm when 40mA of suppression current was applied, the response signal was close to that of pure water, and the level of suppression of conventional electromembrane cations was completely achieved, which is considered to be complete suppression of a given concentration of methanesulfonic acid solution. The current efficiency of the electro-film suppressor at this time was calculated to be 80% (32 x 100/40). Under the same conditions, the recommended rejection current using a commercial electrofilm cation suppressor of conventional design is 59mA, with a current efficiency of about 54.2%. It can be seen that the bipolar membrane cation suppressor described in the present invention has a higher current efficiency than the conventional electrocatalytic suppressor.
Example 4, as shown in fig. 6, is the operation repeatability within the day of the bipolar membrane cation suppressor of the present invention. The conditions were the same as in example 3. The operation is continuously carried out for 9 times in the same day, and as can be seen from figure 6, the spectrograms obtained by 9 times of 6 model cations are almost completely overlapped after being superposed, the retention time and the peak height repeatability are both ideal, and the RSD of the retention time and the peak height are respectively less than 0.119% and 1.0%; in addition, the operation repeatability of the bipolar membrane cation inhibitor in different times is also considered, and the specific data are shown in figure 7 (repeatability of retention time) and figure 8 (repeatability of peak height). It can be seen that retention times and peak height reproducibility of the 6 model ions remained ideal over a period of more than 5 months, as evidenced by retention times RSD < 1.7% and peak heights RSD < 4.4%. Although it is contemplated that for such a long time, there may be some variation in other components of the ion chromatograph, such as the flow rate of the pump and the column. Nevertheless, the repeatability is still relatively ideal. This indicates that the bipolar membrane cation suppressor has good operation stability.
In the description herein, reference to the description of "one embodiment," "an example," "a specific example" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the patent. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Claims (8)
1. A bipolar membrane cation suppressor comprises an upper layer electrolytic cell cover plate (1), an upper layer regenerated liquid channel supporting surface (3), a middle isolating layer (5), a lower layer regenerated liquid channel supporting surface (7) and a lower layer electrolytic cell cover plate (9) which are fixedly connected through fastening screws (14) from top to bottom in sequence; the surfaces of the upper-layer regeneration liquid channel supporting surface (3), the middle isolating layer (5) and the lower-layer regeneration liquid channel supporting surface (7) are respectively and correspondingly provided with an upper-layer regeneration liquid channel (A), a middle leacheate channel (B), a lower-layer regeneration liquid channel (C) and through holes for mutual circulation of leacheate and regeneration liquid; a cathode electrode (2) with one end connected with the upper layer electrolytic cell cover plate (1) is arranged in the upper layer regenerated liquid channel (A), and an anode electrode (8) with one end connected with the lower layer electrolytic cell cover plate (9) is arranged in the lower layer regenerated liquid channel (C); an anion membrane (6) is arranged between the middle leacheate channel (B) and the lower regenerated liquid channel (C), and is characterized in that,
a bipolar membrane is arranged between the upper-layer regeneration liquid channel (A) and the middle leacheate channel (B), an anode membrane surface (401) of the bipolar membrane (4) faces the upper-layer regeneration liquid channel (A), a cathode membrane surface (402) of the bipolar membrane faces the middle leacheate channel (B), and the bipolar membrane (4) and the cathode membrane (6) are respectively provided with the through holes.
2. The bipolar membrane cation suppressor of claim 1, wherein: the through holes of the upper layer regeneration liquid channel (A) and the middle leacheate channel (B) are respectively an leacheate channel inlet (10), an leacheate channel outlet (11), a regeneration liquid channel inlet (12) and a regeneration liquid channel outlet (13); the through holes at the lower layer regeneration liquid channel (C) are respectively a regeneration liquid channel inlet (12) and a regeneration liquid channel outlet (13); effluent of the cation chromatographic column flows through the middle eluent channel (B) from an eluent channel inlet (10) and flows out from an eluent channel outlet (11) to enter a detection pool; the regeneration liquid flows through the upper layer regeneration liquid channel (A) and the lower layer regeneration liquid channel (C) from the regeneration liquid channel inlet (12) respectively, and then flows out from the regeneration liquid channel outlet (13) to enter waste liquid.
3. The bipolar membrane cation suppressor of claim 1, wherein: the cathode electrode (2) and the anode electrode (8) are respectively tightly attached to the outer sides of the upper layer regeneration liquid channel supporting surface (3) and the lower layer regeneration liquid channel supporting surface (7).
4. The bipolar membrane cation suppressor of claim 1, wherein: the anode membrane surface (401) of the bipolar membrane (4), the cathode membrane surface (402) of the bipolar membrane and the anion membrane (6) are ion exchange flat membranes in shape.
5. The bipolar membrane cation suppressor of claim 1, wherein: the solution entering the intermediate eluent channel (B) is an acid solution, or an acid solution doped with a salt solution, wherein the molar ratio of the acid solution to the salt solution exceeds 5 ten thousand times.
6. The bipolar membrane cation suppressor of claim 1 or 5, wherein: the acid solution entering the intermediate eluent channel (B) is an electrically inert acid.
7. The bipolar membrane cation suppressor of claim 1, wherein: the cathode electrode (2) and the anode electrode (8) are externally connected with a constant current source or a constant voltage source.
8. The bipolar membrane cation suppressor of claim 1, wherein: when the anion membrane (6) is replaced by a cation membrane, the position of the cation membrane is changed over with that of the bipolar membrane (4), and the positions of the cathode electrode (2) and the anode electrode (8) are simultaneously changed over, so that the cation battery membrane suppressor can be used as an anion electro-membrane suppressor.
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| CN109136975B (en) | 2018-07-05 | 2020-10-09 | 华东理工大学 | Double-film type acid or alkali solution on-line generator |
| CN110038440B (en) * | 2019-05-30 | 2021-07-27 | 河北工业大学 | Bipolar membrane electrodialysis device and method for seawater decalcification |
| CN110508139B (en) * | 2019-08-28 | 2021-08-03 | 华东理工大学 | Electrodialysis micropump |
| CN112569793B (en) * | 2020-12-25 | 2021-11-23 | 苏州明昊色谱技术有限公司 | Degassing-free trace anion impurity online remover and removing method in strong alkali solution |
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| CN1081120A (en) * | 1992-07-09 | 1994-01-26 | 清华大学 | The equipment and technology of preparing organic acid with bipolar film electrodialysis method |
| CN102234813A (en) * | 2010-04-27 | 2011-11-09 | 张晨光 | Bipolar membrane acid-base liquid generating device for chromatographic technology |
| CN205263043U (en) * | 2015-11-25 | 2016-05-25 | 华东理工大学 | Electrolysis of ion chromatogram is from regenerating dull and stereotyped membrane inhibitor |
| 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 |
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| JP6365292B2 (en) * | 2014-12-19 | 2018-08-01 | 株式会社島津製作所 | Ion chromatograph apparatus, ion chromatograph, ion component analysis method and electrolyte solution generation method |
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| CN1081120A (en) * | 1992-07-09 | 1994-01-26 | 清华大学 | The equipment and technology of preparing organic acid with bipolar film electrodialysis method |
| CN102234813A (en) * | 2010-04-27 | 2011-11-09 | 张晨光 | Bipolar membrane acid-base liquid generating device for chromatographic technology |
| CN205263043U (en) * | 2015-11-25 | 2016-05-25 | 华东理工大学 | Electrolysis of ion chromatogram is from regenerating dull and stereotyped membrane inhibitor |
| 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 |
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