WO2012039312A1 - Dispositif d'élimination d'ions d'impureté - Google Patents

Dispositif d'élimination d'ions d'impureté Download PDF

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Publication number
WO2012039312A1
WO2012039312A1 PCT/JP2011/070775 JP2011070775W WO2012039312A1 WO 2012039312 A1 WO2012039312 A1 WO 2012039312A1 JP 2011070775 W JP2011070775 W JP 2011070775W WO 2012039312 A1 WO2012039312 A1 WO 2012039312A1
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WIPO (PCT)
Prior art keywords
ion
exchange membrane
electrode
impurity
impurity ions
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PCT/JP2011/070775
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English (en)
Japanese (ja)
Inventor
洋登 増長
昇 丸山
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日理工業株式会社
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Priority to CN201180003777.8A priority Critical patent/CN102576005B/zh
Priority to JP2012513379A priority patent/JP5019663B2/ja
Publication of WO2012039312A1 publication Critical patent/WO2012039312A1/fr

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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
    • B01D61/463—Apparatus therefor comprising the membrane sequence AC or CA, where C is a cation exchange membrane
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/26—Cation exchangers for chromatographic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/20—Anion exchangers for chromatographic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/014—Ion-exchange processes in general; Apparatus therefor in which the adsorbent properties of the ion-exchanger are involved, e.g. recovery of proteins or other high-molecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/02—Column or bed processes
    • B01J47/022—Column or bed processes characterised by the construction of the column or container
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/02—Column or bed processes
    • B01J47/06—Column or bed processes during which the ion-exchange material is subjected to a physical treatment, e.g. heat, electric current, irradiation or vibration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis

Definitions

  • the present invention relates to an apparatus for removing impurity ions contained in a solution.
  • the present invention relates generally to a device for removing impurity ions contained in a solution suitable for general use in chemical analysis, synthesis and processing, and in particular, a suppressor (ion removing device) suitably used for an ion chromatograph (device), An eluent purification apparatus is provided. It has been a long time since a suppressor was proposed in ion chromatography (separation method), and it is not necessary to explain it again.
  • ions adsorbed on the separation column are separated and eluted, and this is applied to a detector. In this case, electrolyte ions serving as a background other than the detection target ions are removed to obtain a highly sensitive analysis value.
  • the former is a detection method in which the column is filled with H-type cation exchange resin or OH-type anion exchange resin and becomes a background. Ions other than the target are removed by ion exchange, and the latter is a method of removing ions other than the detection target that are the background through the ion exchange membrane. Furthermore, an electric field is applied to enable continuous operation in combination with electrolysis.
  • the present invention is a column type that applies an electric field
  • some typical suppressors close to the present invention include a suppressor described in JP-T-2002-509238, which combines a column type electric field.
  • the column is filled with cation exchange resin, and electrodes (upper: cathode, lower: anode) are attached to the upper and lower sides of the column via cation exchange membranes.
  • electrodes upper: cathode, lower: anode
  • cation exchange membranes When an eluent containing an anion) is introduced, the cation that becomes the background is adsorbed and removed by the cation exchange resin in the column.
  • water is introduced into both electrode chambers partitioned by a cation exchange membrane and attached with electrodes, and hydronium ions and hydroxide ions are produced in the same chamber by electrolysis of water.
  • the cations adsorbed in the column through the cation exchange membrane are electromoved into the cathode chamber and reacted with the generated hydroxide ions to generate a base, which is discharged out of the system together with water.
  • the generated hydronium ions permeate through the cation exchange membrane and electrotransfer into the column system, and the cation exchange resin adsorbing sodium ions is regenerated with hydronium ions.
  • suppressor As another typical suppressor, there is a suppressor described in Japanese Patent Application Laid-Open No. 2001-188063 which is also a column type combined with an electric field.
  • a column placed horizontally is filled with cation exchange resin, electrodes are attached to both ends via filters, and a solution inlet is provided near the electrode at the top of the column and a solution outlet is provided near the opposite electrode at the bottom.
  • an eluent containing ions to be inspected anions in this case
  • the cation that becomes the background is adsorbed and removed by the cation exchange resin in the column.
  • the conductivity detector shows only a small peak. That is, it becomes a factor of sensitivity reduction.
  • the latter ions pass through the solution along with the solution from two lateral outlets of the column. Therefore, a partition membrane is provided with an ion exchange membrane between the electrode and the ion exchange resin so that the sample ions are not electrolyzed by the electrode, and further, the electrode reaction is performed while preventing the solution from being discharged out of the system. Prevent the resulting gas from entering the system.
  • the present invention it is possible to provide an apparatus with excellent detection sensitivity, continuous and stable impurity ion removal operation, and long operating life.
  • the present invention relates to a device in which a plurality of impurity ion removal devices and a plurality of impurity ion removal devices are connected.
  • FIG. 1 illustrates a configuration for removing cations.
  • the apparatus has a horizontally long container (21) sandwiched with a layer filled with a cation exchanger (23), fixed on both ends of the container with ion exchange membranes (27a, 27b), and an electrode (31a) on the outside of the cation exchange membrane.
  • the main body container (21) is made of PEEK (polyetheretherketone), PP (polypropylene), etc., because it has a strong acid / base resistance and needs to be made of an electrically insulating material.
  • the column shape is preferably a horizontally long shape. This is because, as described above, it is easy to balance the formation of the liquid flow path.
  • the ion exchanger (23) refers to a substance having an ion exchange function, and in particular, an ion exchange resin having an ion exchange group in an insoluble polymer compound can be suitably used.
  • the beads, flakes, fibers, and nonwoven fabrics can be used. Shaped in the form of film or film.
  • cation exchange resin Amberlite IR120B (manufactured by Dow Chemical Company, registered trademark), DOWEX 50WX2, 50WX4, 50WX8 (manufactured by Dow Chemical Company, registered trademark) can be suitably used.
  • DOWEX50WX8 registered trademark
  • a cation exchange resin is used in FIG. 1, an anion exchange resin is used in an apparatus for removing anions.
  • DOWEX1X8, 2X8 registered trademark having an ion exchange group having a charge opposite to that of the cation exchange resin and having a strong base resistance and a high exchange capacity can be suitably used.
  • a cation exchange membrane (27a) is used on the cathode side, and an anion exchange membrane (27b) is used on the anode side.
  • Each of the cation exchange membranes has a function of permeating cations but not liquid.
  • the anion exchange membrane has a function of allowing anions to pass but not allowing liquids to pass.
  • the cation exchange membrane (27a) has a function of transmitting the cation of the impurity through the cooperation with a voltage-applied cathode and discharging it from the outlet (22b). I try not to get inside.
  • the anion exchange membrane (27b) has a similar function.
  • the restriction on the quality of water flowing to the outlets (22b, 22c) can be relaxed. Furthermore, it plays the role of a partition membrane that prevents the solution containing ions to be inspected from leaking out of the system. Moreover, it plays a role of pressing and fixing the resin filled in the container from the left and right. Further, it has a role of preventing the electrode from coming into direct contact with the ion exchanger, and a tough material that can withstand a strong acid and a strong base generated around the electrode is required.
  • Such cation exchange membranes include Neocepta (registered trademark) C66 (manufactured by Tokuyama), Teflon (registered trademark) -based Nafion (registered trademark) NRE-212, 115, 117, 324, 424, 551 (manufactured by DuPont). ) Is preferably used. Further, Neoceptor (registered trademark) AHA (trade name: manufactured by Atoms), AMX, ACM, ACS, AFN, and AFX are preferably used as the anion exchange membrane.
  • various conductors such as metals, alloys, graphite, semiconductors, and metal oxides are used.
  • those having corrosion resistance such as platinum, titanium, gold and rhodium are preferable, and can be a mesh, a line, a rod, a plate or the like.
  • a mesh or the like is preferable.
  • the type of voltage to be applied may be either a DC voltage or an AC voltage to which a positive bias voltage is added.
  • a solution containing the anion to be analyzed separated and eluted in the column (7) is introduced into the inlet (21a) of this apparatus, enters the zone (51) filled with the cation exchange resin, and the solution enters the outlet (22a). It flows toward.
  • the cations contained in the solution are adsorbed on the cation exchange resin, but since an electric field is applied from both electrodes, the cation in the solution and the cation adsorbed on the cation exchange resin are electrophoresed toward the cathode ( Ion movement).
  • Ion movement the cathode
  • the hydronium ions and hydroxide ions that move in the system described above are produced from the dissociation equilibrium of water that occurs at the interface between the anion exchange membrane and the cation exchange membrane resin (hereinafter referred to as “ion interface”). It is a nium ion and a hydroxide ion, and is generated by supplying water.
  • hydroxide ions generated from the dissociation equilibrium of water are taken into the anion exchange membrane, and the hydronium ions are supplied into the system by being taken into the cation exchange resin.
  • Hydronium ions supplied through the ion interface move toward the cathode, hydroxide ions move toward the anode, and both ions move in directions opposite to each other.
  • Impurity cations adsorbed in the cation exchange resin packed bed in the system are interfacial conductive phenomena such as electrophoresis (ion movement) and electroosmotic flow (the surrounding solvent surrounding the ions as the ions move). It is thought that it moves toward the cathode as the counter electrode and is discharged to the outside.
  • the hydronium ions move toward the cathode as the counter electrode while ion exchange with the impurity cations adsorbed on the cation exchange resin filled in the system.
  • the hydronium ions generated at the anode and the hydroxide ions generated at the cathode are anion-exchanged in the system. Due to the electrostatic repulsion between the membrane and the cation exchange membrane, it is discharged out of the system with the flow of introduced water as soon as it is generated. Therefore, ions derived from electrolysis of water generated at the external electrode are not supplied into the system.
  • the present invention is the invention described in claim 2, and will be described with reference to FIG. Since the present invention is an impurity ion removing apparatus in which a bubble discharge promoting part by pure water is incorporated in the basic structure described in (1) above, the configuration of the additional part will be described mainly.
  • the apparatus shown in FIG. 2 is also an apparatus for removing cations, and a pure water injection zone is provided between the electrode (31a) and the cation exchange membrane (27a) in the cathode portion.
  • the cross section is composed of a cation exchange membrane (27a), a cation exchanger (25B) layer, a cation exchange membrane (28a) imparted with liquid permeability, and an electrode (31a), and the cation exchanger (25B).
  • a pure water inlet is provided at the top of the bed.
  • the cation exchange membrane imparted with liquid permeability is obtained by imparting liquid permeability by subjecting a normal cation exchange membrane to slit processing or the like. This slit processing, on the contrary, cannot avoid the ingress of liquid or gas containing impurities from the outside into the system. For this reason, pure water is always supplied from the pure water supply device 41a, and impurities from the outside into the system are contained.
  • the cation exchange membrane (28a) is placed between the electrode (31a) and the cation exchanger (25B) so that the electrode (31a) and the cation exchanger (25B) are not in direct contact with each other. This is because the exchanger (25B) is not exposed to electrolysis.
  • such a structure is rather more effective in the anion removing device (FIG. 6), and the anion exchanger (25B) and the electrode (31a) are slightly less durable than the cation exchanger.
  • Such a cation exchange membrane is a Teflon (registered trademark) -based cation exchange membrane having excellent durability, and Nafion (registered trademark) NRE-212, 115, 117, 324, 424, 551 (manufactured by DuPont).
  • a cation exchanger such as a non-woven fabric ion exchange resin, a mesh-shaped ion exchange resin, or the like exhibiting an equivalent function may be used.
  • the description of other structures is omitted because the description is the same as in (1). Next, the operation of this apparatus will be described.
  • the pure water injection zone provided in the cathode portion can be said to be injected from the inside of the main body and discharged outside.
  • discharge of hydrogen gas generated by electrolysis can be further promoted.
  • the strong base produced near the cathode and the reduced active substance can be diluted and discharged to the outside.
  • the life of an electrode for example, a platinum electrode can be extended, and the deionization efficiency can be improved as shown in Example 8.
  • electroosmotic flow is a flow of solvent accompanying electrophoresis (ion movement) of cations and hydronium ions. Inferred. However, since this flow is very small, the discharge flow is increased by injecting pure water by pump lift.
  • Impurity ion removal device incorporating a bubble discharge promoting part with pure water at both ends in the basic structure
  • the present invention is the invention described in claim 3, and will be described with reference to FIG.
  • the present invention relates to an impurity ion removing apparatus in which a bubble discharge promoting portion by pure water is incorporated at both ends in the basic structure described in (1), and the configuration of the additional portion is explained mainly as in (2). To do.
  • the apparatus shown in FIG. 3 is also an apparatus intended to remove cations, and is provided with pure water injection zones at both electrode portions. That is, the pure water injection zone is also provided between the electrode (31b) and the anion exchange membrane (27b) in the anode portion.
  • the cross section is composed of an anion exchange membrane (27b), an anion exchanger (25A) layer, a liquid-permeable cation exchange membrane (28b), and an electrode (31b), and the anion exchanger (25A).
  • a pure water inlet is provided at the top of the bed.
  • the cation exchange membrane imparted with liquid permeability is the same as that used on the cathode side, as described above, which is provided with liquid permeability by subjecting a normal cation exchange membrane to slit processing or the like.
  • pure water is poured from the inlet (21c), passes through the ion exchanger (25A) layer, passes through the cation exchange membrane (28b) imparted with liquid permeability, and is discharged from the outlet (22c).
  • Nafion (registered trademark) NRE-212, 115, 117, 324, 424, 551 manufactured by DuPont
  • Teflon (registered trademark) cation exchange membrane having excellent durability can be preferably used.
  • pure water is always supplied from the pure water supply device 41b.
  • a cation exchanger such as a non-woven fabric ion exchange resin, a mesh-shaped ion exchange resin, or the like exhibiting an equivalent function may be used.
  • the description of the other configuration is omitted because the description overlaps with (1) and (2).
  • the present invention is the invention described in claim 4, and will be described with reference to FIG.
  • the present invention is a device in which a plurality of impurity ion removing devices are connected, and is a device that removes either anions or cations.
  • the invention described in claim 4 is one in which two impurity ion removing devices described in FIG. 3 are connected in series. In other words, a pipe connection is made from the solution outlet of the first device to the solution inlet of the second device to reduce the deionization load in a single device, and two devices try to achieve the desired deionization target. is there.
  • the reason why the load on the apparatus is reduced is that the consumption of the electrode, ion exchange membrane and the like can be reduced, and the lifetime of the impurity ion removing apparatus can be extended.
  • the combination of a plurality of impurity ion removing apparatuses in the present invention includes the apparatus shown in FIGS. 1 and 2 proposed in the present application, and is not limited to two. However, when a plurality of suppressors are used in an ion chromatograph (apparatus), the influence of the diffusion of ions to be detected (the same effect as mixing) appears, and the connection of the two is preferable. Since the description of the other configuration and operation overlaps with the above (1), (2), (3), it will be omitted.
  • the ion analysis system 100 having the same configuration as that of FIG. 9 is used, and the impurity ion removing device 2e for anion removal having the same configuration as that of FIG.
  • the ion removal capability of the impurity ion removal apparatus 9 having the same structure as that shown in FIG. In the experiment, the injector 5 and the separation column 7 were removed from the ion analysis system 100 of FIG.
  • the electrolyte solution generating device 1 is a basic electrolyte solution generating device (manufactured by Nichi Kogyo), the electrolyte solution purifying device 2e is an impurity ion removing device for removing anions (manufactured by Nichi Kogyo), and the impurity ion removing device 9 is for removing cations.
  • Impurity ion removing device manufactured by Niri Kogyo Co., Ltd.
  • pumps 47a and 47b are CCPM (manufactured by Tosoh Corporation)
  • pump 3 is DP-8020 (manufactured by Tosoh Corporation)
  • DC power supply 33 for electrophoresis is EX-375U2 (Takasago Manufacturing Co., Ltd.)
  • the detector 11 was an electrical conductivity detector CM432 (manufactured by Nichi Kogyo).
  • the electrolyte solution generating apparatus 1 has a constant current of 20 mA (about 38 V, about 1604 ⁇ S / cm NaOH solution), the electrolyte solution purifying apparatus 2 e has a constant current of 30 mA (about 44 V), and the impurity ion removing apparatus 9 has a constant current of 2 0.8 mA (about 9 V), a platinum electrode was used as the electrode for electrophoresis, pure water (1.0 ml / min) was supplied from the pumps 47a and 47b, and the flow rate of the pump 3 was 0.75 ml / min.
  • the results are shown in FIG. 12 is divided into 1: the impurity ion removing device 9 having the same structure as in FIG.
  • the electrical conductivity of the eluate (about 1325 ⁇ S / cm), 2: the electrical conductivity of the eluate from the impurity ion removal device 9 when the operation of the impurity ion removal device 9 was stopped (about 1604 ⁇ S / cm).
  • the ion analysis system 100 having the same configuration as that in FIG. 9 is used in the ion analysis system shown in FIGS. 8 and 9, and the anion removing impurity ion removing device 2f having the same configuration as in FIG. 2 is used, and the cation impurity ion removing device 9a having the same configuration as that shown in FIG. 2 is used as the impurity ion removing device 9, and the sodium hydroxide solution (about 12.5 mM, about 1965 ⁇ S / cm) generated by the electrolyte solution generating device 1 is used.
  • the electrical conductivity of the eluate when the suppressor was activated and when it was not activated was compared.
  • the electrolyte solution generator 1 is a basic electrolyte solution generator (manufactured by Nichi Kogyo)
  • the electrolyte solution purifier 2f is an impurity ion removing device for removing anions (manufactured by Nichi Kogyo)
  • the impurity ion removing device 9a is for removing cations.
  • Impurity ion removing device manufactured by Niri Kogyo Co., Ltd.
  • pumps 47a and 47b are CCPM (manufactured by Tosoh Corporation)
  • pump 3 is DP-8020 (manufactured by Tosoh Corporation)
  • DC power supply 33 for electrophoresis is EX-375U2 (Takasago Manufacturing Co., Ltd.)
  • the detector 11 used was CM432 (manufactured by Tosoh Corporation).
  • the electrolyte solution generator 1 has a constant current of 20 mA (about 74.5 V, about 1965 ⁇ S / cm NaOH solution), the electrolyte solution purifier 2 f has a constant current of 30 mA (about 40.6 V), and the impurity ion removing device 9 a A constant current of 40 mA (about 52 V), a platinum electrode as an electrode for electrophoresis, pure water (1.0 ml / min) is supplied from the pumps 47a and 47b, and the flow rate of the pump 3 is 0.75 ml / min. did.
  • the results are shown in FIG. Note that reference numerals 1 and 2 in FIG.
  • the ion analysis system 100 having the same configuration as that in FIG. 9 is used in the ion analysis system shown in FIGS. 8 and 9, and the anion removing impurity ion removing device 2f having the same configuration as in FIG.
  • the impurity ion removing device 9 was used, and the cation removing impurity ion removing device 9a having the same configuration as that shown in FIG.
  • the electrolyte solution generator 1 is a basic electrolyte solution generator (manufactured by Nichi Kogyo), the electrolyte solution purifier 2f is an impurity ion removing device for removing anions (manufactured by Nichi Kogyo), and the impurity ion removing device 9a is for removing cations.
  • Impurity ion removal device manufactured by Nichi Kogyo
  • pumps 47a and 47b are CCPM (manufactured by Tosoh Corporation)
  • pump 3 is DP-8020 (manufactured by Tosoh Corporation)
  • injector is model 7125 (manufactured by RHEODYNE, 20 ⁇ L), for electrophoresis
  • the DC power source 33 used was EX-375U2 (manufactured by Takasago Seisakusho)
  • the separation column 7 was TSKgel superIC Anion AZ (manufactured by Tosoh Corporation)
  • the detector 11 was a non-contact type conductivity detector (manufactured by Nichi Kogyo).
  • the electrolyte solution generating apparatus 1 has a constant current of 20 mA (about 85.6 V, about 2065 ⁇ S / cm NaOH solution), the electrolyte solution purifying apparatus 2 f has a constant current of 30 mA (40.2 V), and the impurity ion removing apparatus 9 a has A constant current was 40 mA (about 55 V), a platinum electrode was used as an electrode for electrophoresis, pure water (1.0 ml / min) was supplied from the pumps 47a and 47b, and the flow rate of the pump 3 was 0.75 ml / min. .
  • the ion analysis system 100 having the same configuration as in FIG. 9 in the ion analysis system shown in FIGS. 8 and 9 is used, and the cation removing impurity ion removing device 2a having the same configuration as in FIG.
  • the anion removal impurity ion removal device 9e having the same configuration as that shown in FIG. 6 was used as the impurity ion removal device 9, and ion analysis of standard cations was performed.
  • the electrolyte solution generator 1 is an acidic electrolyte solution generator (manufactured by Nichi Kogyo)
  • the electrolyte solution purifier 2a is a cation removing impurity ion removing device (manufactured by Nichi Kogyo)
  • the impurity ion removing device 9e is an anion removing impurity.
  • Ion removal device manufactured by Nichi Kogyo
  • pumps 47a and 47b are CCPM (manufactured by Tosoh Corporation)
  • pump 3 is DP-8020 (manufactured by Tosoh Corporation)
  • injector is model 7125 (manufactured by RHEODYNE, 20 ⁇ L), for electrophoresis
  • the DC power source 33 was EX-375U2 (manufactured by Takasago Seisakusho)
  • the separation column 7 was TSKgel superIC-CR (manufactured by Tosoh)
  • the detector 11 was a non-contact electric conductivity detector (manufactured by Nichi Kogyo).
  • the electrolyte solution generator 1 has a constant current of 3.5 mA (about 20 V, about 600 ⁇ S / cm of HNO 3 solution), the electrolyte solution purifier 2 a has a constant current of 40 mA (about 45.4 V), and the impurity ion removing device 9 e.
  • the sample concentrations were: Li + ion; 5 ppb, Na + ion; 20 ppb, NH 3 + ion; 20 ppb, K + ion; 50 ppb, Ca 2+ ion; 50 ppb, Mg 2+ ion; 50 ppb.
  • the measurement results are shown in FIG. In the chart of FIG. 15, peak 1 is Li + ion, peak 2 is Na + ion, peak 3 is NH 3 + ion, peak 4 is K + ion, peak 5 is Ca 2+ ion, peak 6 Are Mg 2+ ions. From this result, it was confirmed that each ion was completely separated and detected for the standard cation.
  • the ion analysis system 100 having the same configuration as that of FIG. 9 is used in the ion analysis system shown in FIGS. 8 and 9, and the anion removing impurity ion removing device 2e having the same configuration as that of FIG.
  • the effect of using a Nafion (registered trademark) NRE-117 membrane as the ion exchange membrane 27b was verified using the anion removal impurity ion removal device 2i having the same configuration as that of FIG.
  • the joint 15, the pump 3, the injector 5, the separation column 7, the impurity ion removing device 9, and the detector were removed from the ion analysis system 100 of FIG.
  • Electrolyte solution generator 1 is a basic electrolyte solution generator (manufactured by Nichi Kogyo), electrolyte solution purifiers 2e and 2i are impurity ion removers for removing anions (manufactured by Nichi Kogyo), and pumps 47a and 47b are CCPM (Tosoh Corporation).
  • EX-375U2 manufactured by Takasago Seisakusho Co., Ltd. was used as the DC power source 33 for electrophoresis.
  • the electrolyte solution generator 1 has a constant current of 20 mA
  • the electrolyte solution purifiers 2e and 2i have a constant current of 30 mA
  • platinum electrodes are used as the electrodes for electrophoresis
  • pure water 1.0 ml / min
  • a graph in which the sodium hydroxide solution generated by the electrolyte solution generator 1 (electrolyte solution generated under the condition of a constant current of 20 mA) is purified by the electrolyte solution purifier under the condition of the constant current of 30 mA, and the time variation of the applied voltage is plotted. As shown in FIG.
  • Neocepta (registered trademark) C66 was used.
  • the applied voltage of the electrolyte solution purifying apparatus 2i has a large slope and rises to the right, whereas the applied voltage of the electrolyte solution purifying apparatus 2e using a Nafion (registered trademark) NRE-117 membrane for the ion exchange membrane 27b.
  • the applied voltage is stable around 39V.
  • the ion analysis system 100 having the same configuration as that shown in FIG. 9 is used in the ion analysis system shown in FIGS. 8 and 9, and the anion removing impurity ion removing device 2e having the same configuration as that shown in FIG.
  • the impurity ion removing device 9 uses the cation removing impurity ion removing device 9b having the same configuration as in FIG. 3 and the cation removing impurity ion removing device 9c having the same configuration as in FIG. 4, and uses two suppressors. The effect of the connected ion analysis system was verified.
  • the electrolyte solution generator 1 is a basic electrolyte solution generator (manufactured by Nichi Kogyo), the electrolyte solution purifier 2e is an impurity ion removing device for removing anions (manufactured by Nichi Kogyo), and the impurity ion removing devices 9b and 9c are cations.
  • Impurity ion removal device for removal (manufactured by Niri Kogyo), pumps 47a and 47b are CCPM (manufactured by Tosoh Corporation), pump 3 is DP-8020 (manufactured by Tosoh Corporation), injector is model 7125 (manufactured by RHEODYNE, 20 ⁇ L), electric
  • the DC power source 33 for electrophoresis is EX-375U2 (manufactured by Takasago Seisakusho), TSKgel superIC Anion AZ (manufactured by Tosoh Corporation) is used as a separation column, and the detector 11 is a non-contact electric conductivity detector (manufactured by Nichi Kogyo). It was used.
  • the electrolyte solution generator 1 has a constant current of 20 mA (about 32.6 V)
  • the electrolyte solution purifier 2 e has a constant current of 30 mA (about 39.4 V)
  • a platinum electrode as an electrode for electrophoresis
  • pumps 47 a and 47 b The pure water (1.0 ml / min) was supplied from each, and the flow rate of the pump 3 was 0.75 ml / min.
  • FIG. 17 shows a chromatogram when an ion analysis system having a configuration in which only one impurity ion removing device is installed (impurity ion removing device 9b having the configuration shown in FIG. 3) and measurement is performed at a constant current of 40 mA (about 45 V).
  • impurity ion removing device 9b having the configuration shown in FIG. 3
  • the first stage impurity ion removing device has a constant current of 20 mA (about 31.9 V)
  • FIG. 18 shows a chromatogram when the second stage impurity ion removing apparatus is measured under the condition of a constant current of 5 mA (about 9.5 V).
  • an ion analysis system having a configuration in which a total of three impurity ion removal devices connected to two impurity ion removal devices 9b configured as shown in FIG. 3 and one impurity ion removal device 9a configured as shown in FIG.
  • the first stage impurity ion removal device 9 has a constant current of 10 mA (about 33.2 V)
  • the second stage impurity ion removal device has a constant current of 5 mA (about 22.2 V)
  • the impurity ion removal device has a constant current.
  • FIG. 19 shows a chromatogram when measured under the condition of 5 mA (about 11.4 V).
  • the first peak is F - ions
  • peak 3 is NO 2 - ions
  • the peak of the 5 NO 3 - ions the peak of the 6 unknown CO 3 - ions and SO 4 2-ions
  • peak 7 is PO 4 3- ions.
  • the eluent can be sufficiently suppressed even though the total current flowing through the impurity ion removal device is 25 mA, which is the smallest amount.
  • the peak height of each sample obtained is the largest, and highly sensitive detection is possible.
  • the amount of current flowing through the system and the amount of ions that can be suppressed are proportional to each other where the amount of current is small.
  • the proportional relationship breaks, and even if an excessive current is passed, ions are left behind in the in-line and the background conductivity cannot be lowered. For this reason, the amount of current flowing through the system is reduced, and another ion that cannot be removed by one impurity ion removing device in a current range in which a proportional relationship exists between the amount of current flowing through the system and the amount of ions that can be suppressed.
  • the eluent By removing it with an impurity ion removal device, the eluent can be efficiently suppressed in a two-stage system. Further, since the amount of current flowing through each system is reduced, the load on the system can be reduced, and the life of the system can be extended. However, if the number of impurity ion removal devices is increased to 3 or more to increase the elution suppression efficiency, the amount of diffusion of the sample in the impurity ion removal device will increase, resulting in signal / noise. Becomes smaller and the detection sensitivity decreases. From the above, it can be seen that it is effective to use two impurity ion removing devices and suppress the eluent in a two-stage system.
  • the ion analysis system 100 having the same configuration as that of FIG. 9 in the ion analysis system shown in FIGS. 8 and 9 is used, and the impurity ion removing device 9 has a cation removing impurity ion removing device 9a having the same configuration as that of FIG.
  • the cation removing impurity ion removing device 9b having the same configuration as in FIG. 3, the anion removing impurity ion removing device 9e having the same configuration as FIG. 6, and the anion removing impurity ion removing device 9i having the same configuration as FIG.
  • the durability of four impurity ion removing devices having different structures was examined.
  • the electrolyte solution generator 1 is a basic electrolyte solution generator (manufactured by Nichi Kogyo), the impurity ion removing devices 9a and 9b are cation removing impurity ion removing devices (manufactured by Nichi Kogyo), and the impurity ion removing devices 9e and 9i are Impurity ion removing apparatus for anion removal (manufactured by Nichi Kogyo), pumps 47a and 47b are CCPM (manufactured by Tosoh Corporation), pump 3 is DP-8020 (manufactured by Tosoh Corporation), and DC power supply 33 for electrophoresis is EX-375U2
  • the detector 11 was an electrical conductivity detector CM432 (manufactured by Nichi Kogyo).
  • the electrolyte solution generator 1 uses a constant current of 20 mA, a platinum electrode as an electrode for electrophoresis, supplies pure water (1.0 ml / min) from the pumps 47a and 47b, and the flow rate of the pump 3 is 0.75 ml / min. It was set to min.
  • the experiment is performed using the electrophoresis DC power source 33 at a constant current of 40 mA, and the impurity ion removing device 9e having the same structure as that shown in FIGS.
  • 9i and 9i the experiment was conducted with the DC power source 33 for electrophoresis at a constant current of 30 mA. The results are shown in FIG.
  • the impurity ion removing device 9a having the same structure as that in FIG. 2 is broken in 1 hour of use, and the impurity ion removing device having a structure in which Neoceptor (registered trademark) C66 is used for the ion exchange membrane 27b in FIG. In 9i, the applied voltage increased as the time passed. It was confirmed that the impurity ion removing devices 9b and 9e having the same structure as in FIGS. 3 and 6 were stable without changing the applied voltage for a long time. The impurity ion removing devices 9b and 9e having the same structure as those in FIGS. 3 and 6 are stable without changing the applied voltage for a long time.
  • the exchange membrane 27b is not in contact with the electrode 31b, the ion exchange resin is filled between the ion exchange membrane 27b and the electrode (anode 31b), the region 52 is provided, and a salt bridge is formed by the ion exchange resin.
  • the electrodes are electrically connected by ionic conduction.
  • a Teflon (registered trademark) -based cation exchange membrane 28b in FIG. 3, 28b in FIG. 6) that is chemically stable to the ion exchanger in contact with the electrode. 27b).
  • the ion analysis system 100 having the same configuration as that shown in FIG. 9 is used in the ion analysis system shown in FIGS. 8 and 9, and the anion removing impurity ion removing device 2e having the same configuration as that shown in FIG.
  • the impurity ion removing device 9 as the impurity ion removing device 9b for cation removal having the same configuration as that shown in FIG. 3
  • the impurity ion removing device 9h for cation removing having the same configuration as that shown in FIG. The effect of was investigated. In the experiment, the injector 5 and the separation column 7 were removed from the ion analysis system 100 of FIG.
  • the electrolyte solution generator 1 is a basic electrolyte solution generator (manufactured by Nichi Kogyo), the electrolyte solution purifier 2e is an anion removing impurity ion removing device (manufactured by Nichi Kogyo), and the impurity ion removing devices 9b and 9h are cations.
  • Impurity ion removing apparatus for removal (manufactured by Nichi Kogyo)
  • pumps 47a and 47b are CCPM (manufactured by Tosoh Corporation)
  • pump 3 is DP-8020 (manufactured by Tosoh Corporation)
  • DC power supply 33 for electrophoresis is EX-375U2 (Takasago) (Manufactured by Seisakusho Co., Ltd.)
  • the detector 11 was an electrical conductivity detector CM432 (manufactured by Nichi Kogyo).
  • the electrolyte solution generator 1 has a constant current of 20 mA (about 37 V, about 1505 ⁇ S / cm NaOH solution), the electrolyte solution purifier 2 has a constant current of 30 mA (about 44 V), and uses a platinum electrode as an electrode for electrophoresis. Pure water (1.0 ml / min) was supplied from the pumps 47a and 47b, and the flow rate of the pump 3 was 0.75 ml / min. The results are shown in FIG.
  • the pump 47a is stopped, and the electric conductivity of the effluent from the impurity ion removing device 9b at a constant current of 10 mA (about 31.5 V) (About 388 ⁇ S / cm) 4:
  • the impurity removal device 9b having the same structure as that shown in FIG. 3, the electric conductivity of the eluate from the impurity ion removal device 9b at a constant current of 10 mA (about 38.5 V) (about 69 ⁇ S / cm) .
  • the impurity ion removing device 9b having the same structure as that in FIG. 3 was used it was confirmed that the highest ion removal efficiency (ion removal amount per energization current amount) was the highest. This is because the bubble discharge promoting means installed at the cathode allows pure water from the pump 47a to flow, discharges cations moving to the vicinity of the cathode 31a out of the system, and lowers the cation concentration near the cathode. This is because it can.
  • the influence on the analysis sensitivity by changing the liquid flow path is examined.
  • the eluate from the separation column 7 is allowed to flow from the first outlet 22a to the first inlet 21a, and the peak height of the standard anion chromatogram obtained at that time is confirmed.
  • the ion analysis system 100 having the same configuration as that shown in FIG. 9 is used in the ion analysis system shown in FIGS. 8 and 9, and the anion removing impurity ion removing device 2e having the same configuration as that shown in FIG.
  • the impurity ion removing device 9b for cation removal having the same configuration as that shown in FIG. Investigate the effect on analysis sensitivity by changing the liquid flow path.
  • the pumps 47a and 47b are CCPM (manufactured by Tosoh Corporation), the pump 3 is DP-8020 (manufactured by Tosoh Corporation), the electrolyte solution generator 1 is a basic electrolyte solution generator (manufactured by Nichi Kogyo), and the electrolyte solution purifier 2e is negative.
  • Impurity ion removal device for ion removal (manufactured by Niri Kogyo)
  • impurity ion removal device 9b is an impurity ion removal device for cation removal (manufactured by Niri Kogyo)
  • the injector is model 7125 (manufactured by RHEODYNE, 20 ⁇ L), for electrophoresis
  • the DC power source 33 used was EX-375U2 (manufactured by Takasago Seisakusho)
  • the separation column 7 was TSKgel superIC Anion AZ (manufactured by Tosoh Corporation)
  • the detector 11 was a non-contact type conductivity detector (manufactured by Nichi Kogyo).
  • the electrolyte solution generator 1 has a constant current of 20 mA (66.5 V, approximately 1836 ⁇ S / cm NaOH solution), the electrolyte solution purifier 2 e has a constant current of 30 mA (approximately 41.2 V), and the impurity ion removing device 9 b has a constant current. 40 mA (about 38.8), a platinum electrode was used as the electrode for electrophoresis, pure water (1.0 ml / min) was supplied from the pumps 47a and 47b, and the flow rate of the pump 3 was 0.75 ml / min. .
  • the first peak is F - ions
  • peak 3 is NO 2 - ions
  • the peaks are unknown CO 3 ⁇ ions and SO 4 2 ⁇ ions
  • the peak 7 is PO 4 3 ⁇ ions. From this result, it was confirmed that the ions were completely separated and detected except that the peaks of carbonate ion and sulfate ion overlapped.
  • the peak height of the standard anion chromatogram obtained when the eluate from the separation column 7 is allowed to flow from the first outlet 22a to the first inlet 21a is confirmed.
  • the experimental conditions and analysis method are the same as in the case of the model except that the eluate from the separation column 7 is allowed to flow from the first outlet 22a to the first inlet 21a.
  • the measurement results are shown in FIG. From this result, it was confirmed that when the eluate from the separation column 7 was flowed from the first outlet 22a to the first inlet 21a, the peak height of the standard anion chromatogram was reduced, that is, the sensitivity was lowered. .
  • the influence of the mixing of the gas contained in the eluate from the impurity ion removing device 9 is electrically conducted. Measure in degrees.
  • the ion analysis system 100 having the same configuration as that shown in FIG. 9 is used in the ion analysis system shown in FIGS. 8 and 9, and the anion removing impurity ion removing device 2e having the same configuration as that shown in FIG. 4 and the impurity ion removing device 9c having the same configuration as that shown in FIG. 4 is used as the impurity ion removing device 9.
  • the injector 5 and the separation column 7 are removed from the ion analysis system 100 shown in FIG. did.
  • the pumps 47a and 47b are CCPM (manufactured by Tosoh Corporation), the electrolyte solution generator 1 is a basic electrolyte solution generator (manufactured by Nichi Kogyo), and the electrolyte solution purifier 2e is an impurity ion removing device for removing anions (manufactured by Nichi Kogyo).
  • the impurity ion removing device 9c is a positive ion removing impurity ion removing device 9c (Nichi Kogyo)
  • the pump 3 is DP-8020 (manufactured by Tosoh Corporation)
  • the DC power supply 33 for electrophoresis is EX-375U2 (Takasago Manufacturing Co., Ltd.)
  • the detector 11 was an electrical conductivity detector CM432 (manufactured by Nichi Kogyo).
  • the electrolyte solution generator 1 has a constant current of 20 mA (about 35.8 V, NaOH solution), the electrolyte solution purifier 2 e has a constant current of 30 mA (about 31.7 V), and the impurity ion removing device 9 c has a constant first stage.
  • the current is 15 mA (about 28.6 V)
  • the second stage is a constant current of 5 mA (17.6 V)
  • a platinum electrode is used as the electrophoresis electrode
  • pure water 1.0 ml / min
  • the flow rate of the pump 3 was 0.75 ml / min.
  • the measurement results are shown in FIG. From FIG. 24, it has been confirmed that spike noise that appears due to gas mixture does not appear.
  • Neoceptor registered trademark
  • AHA is installed in the ion exchange membrane 27b as a comparison.
  • the contamination of foreign impurities was measured using the purified electrolyte solution purifier.
  • the ion analysis system 100 having the same configuration as in FIG. 9 in the ion analysis system shown in FIGS. 8 and 9 is used, and the anion removing impurity ion removing device 2f having the same configuration as in FIG.
  • the influence of the polarity of the ion exchange membrane used in the experiment was investigated.
  • Electrolyte solution generator 1 is a basic electrolyte solution generator (manufactured by Nichi Kogyo)
  • electrolyte solution purifiers 2f and 2j are impurity ion removers for removing anions (Nichiri).
  • impurity ion removing device 9b is an impurity ion removing device for removing cations (Nichi Kogyo)
  • pump 3 is DP-8020 (manufactured by Tosoh Corporation)
  • DC power supply 33 for electrophoresis is EX-375U2 (Takasago Manufacturing Co., Ltd.)
  • the detector 11 was an electrical conductivity detector CM432 (manufactured by Nichi Kogyo).
  • the electrolyte solution generator 1 has a constant current of 20 mA (about 59.3 V, NaOH solution), the impurity ion remover 9 b has a constant current of 40 mA (63 V), platinum electrodes are used as the electrodes for electrophoresis, and the pumps 47 a and 47 b
  • the pure water (1.0 ml / min) was supplied from each, and the flow rate of the pump 3 was 0.75 ml / min.
  • the measurement results are shown in FIG. 25 is divided into 1: the electrolyte solution purification apparatus 2f having the same structure as in FIG. 7, and the ion exchange membrane 27b is replaced with a cation exchange membrane (Nafion (registered trademark) NRE-117).
  • the DC power source 33 for electrophoresis has a constant current of 30 mA (45.3 V), and the electric conductivity of the effluent from the impurity ion removing device 9b when the electrolyte solution is purified, 2: as in FIG.
  • the electrolyte solution purification apparatus 2j having the structure shown in FIG. 5 is used, the ion exchange membrane 27b is Neoceptor (registered trademark) AHA, the electrophoresis DC power source 33 is constant current 30 mA (67.5 V), and the electrolyte solution is purified.
  • the electric conductivity of the eluate from the impurity ion removing device 9b at that time was used.
  • Neoceptor registered trademark
  • the present invention relates generally to a device for removing impurity ions contained in a solution suitable for general use in chemical analysis, synthesis and processing, and in particular, a suppressor (ion removing device) suitably used for an ion chromatograph (device), An eluent purification apparatus is provided.
  • a suppressor ion removing device
  • an ion chromatograph device
  • An eluent purification apparatus is provided.

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Abstract

[Problème] Obtenir, comme moyen pour éliminer les ions d'impureté d'une solution, un dispositif d'élimination d'ions en forme de colonne dans lequel une substance active ou un gaz qui est généré dans le voisinage des électrodes n'entre pas dans le système, et avec lequel les ions à examiner peuvent être retirés avec une sensibilité de détection satisfaisante. [Solution] Une colonne horizontale remplie avec un échangeur d'ions qui adsorbe des ions d'impureté est munie d'une entrée de solution en haut de la colonne et à proximité de l'une des électrodes, et d'une sortie au bas de la colonne et du côté de l'autre électrode pour configurer un canal de liquide étroit. Une membrane échangeuse d'ions et un échangeur d'ions sont utilisés en association afin de former une interface d'ions à chaque extrémité de la colonne, et les ions qui sont générés à la suite d'un glissement par rapport à l'équilibre de dissociation de l'eau peuvent se déplacer vers les électrodes. Les ions d'impureté à retirer sont évacués de la colonne tout en régénérant l'échangeur d'ions qui adsorbe les ions d'impureté. Combiné à cela, de l'eau est introduite extérieurement et est amenée à passer à travers la région entre chaque électrode et la membrane échangeuse d'ions correspondante afin d'accélérer l'évacuation des gaz, des bases et des acides, qui sont des ions d'impureté à éliminer, et des substances actives de la colonne.
PCT/JP2011/070775 2010-09-22 2011-09-13 Dispositif d'élimination d'ions d'impureté WO2012039312A1 (fr)

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