JP4671272B2 - Method and apparatus for detecting anion in liquid - Google Patents

Description

  The present invention relates to an anion detection method and a detection apparatus in a liquid, and more particularly to a detection method for anions typified by chlorine ions capable of sensing leakage of cooling water (seawater) of condensers in thermal power and nuclear power plants. And a detection apparatus.

  Conventionally, in thermal power and nuclear power plants, high-temperature and high-pressure steam generated in a boiler is guided to a steam turbine, and the exhaust steam from the steam turbine is condensed into water by a condenser, and this condensate is used again as boiler feed water. This is a water cycle. Since impurities such as corrosion products accumulate in the circulating water, impurities such as corrosion products are removed during steady operation, and impurities containing sodium chloride as a main component during seawater leaks described below for a certain period of time. A condensate demineralizer is installed to capture and protect the circulating water system. In the condenser in this circulation system, the steam side is depressurized, and seawater is used for cooling water, so if a pinhole occurs in the condenser thin tube, seawater enters the steam side, Salinity increases significantly. As a result, when the load of the condensate demineralizer increases and the amount of seawater leak increases, the allowable range of the demineralizer is exceeded. Therefore, it is necessary to detect seawater leaks with a salt detector. Known methods for detecting seawater leaks include a sodium monitor, an atomic absorption method, and a method for measuring conductivity.

  The sodium monitor uses an ion selective glass electrode. For this reason, the sensitivity in the low-concentration region becomes smaller than the Nernst equation due to a decrease in the electromotive force of the electrode, and a potassium chloride solution is used as the electrode solution for the reference electrode. Ions may give a positive error. In addition, the surface of the electrode is contaminated by iron oxide and hydroxide called clad, and the sensitivity is lowered.

  For analysis such as atomic absorption, there is no portable type that can be installed on-site, so sample water must be sampled and taken back and analyzed. . As a method for quantitative analysis of ions, ion chromatography is generally used, but requires labor such as reagent adjustment, and is an expensive apparatus similar to atomic absorption.

In the method of measuring specific resistance or conductivity, a cation exchange resin is required. In general, in order to suppress corrosion of piping in the system, circulating water should be about 1 mg NH ₃ / l ammonia during steady operation, within a day such as daily start / stop (DSS) or when stopped for about a day. 2mgNH ₃ / l of about ammonia and 50μgN ₂ H ₄ / l of about hydrazine, at the time of 2-3 days about the stop, such as a weekly-start-stop (WSS) is, 2mgNH ₃ / l about ammonia and 10mgN ₂ H ₄ / l of hydrazine is added, and in either case, the resistivity is low and the conductivity is high. Therefore, the change in the measured value is negligible if the salt concentration is slightly increased due to a small amount of seawater leak. It is difficult to know seawater leaks. Therefore, water was passed through the regenerated cation exchange resin to remove the cation components such as ammonia, hydrazine and sodium ions that were mixed in due to seawater leak, and then the acid resistivity or acid conductivity mainly due to HCl. The method of measuring is becoming common. However, in this method, since the cation exchange resin eventually reaches a through-flow capacity, a regeneration operation or a resin replacement operation is required periodically, and the regeneration or replacement operation, resin cost, or the like becomes a problem. Particularly in the PWR nuclear power plant, high pH operation is currently being studied for the purpose of reducing the iron load in the system, and it should be operated at an ammonia or ETA concentration 10 times higher than the conventional condensate quality. Therefore, the frequency of the above-described resin regeneration and replacement work becomes very high, which may cause a problem in actual operation.

  In order to solve this problem, Japanese Patent Application Laid-Open No. 9-210943 discloses a decation chamber in which a cation exchanger partitioned by two cation exchange membranes is filled between an anode chamber and a cathode chamber. The anode chamber, the cathode chamber, and the decation chamber are provided with a water introduction path and a treated water discharge path, respectively, and the treated water discharge path from the decation chamber has a ratio of the treated water. An apparatus for detecting anions in water with a measuring instrument for measuring resistance or conductivity is disclosed. According to this anion detector, it is not necessary to exchange ion exchange resin, etc., and is not affected by contamination by solid suspended matter such as cladding, so that it can be operated easily, stably and accurately. An inexpensive apparatus can be obtained.

  However, in the apparatus for detecting anions in water described in JP-A-9-210943, as an ion exchanger, for example, a particle size of 0.2 to 0.5 mm in which a sulfonic acid group is introduced into a copolymer of styrene and divinylbenzene. When only a spherical cation exchange resin of a certain degree was filled, there were the following problems. That is, when the power plant condensate is used as sample water, the cations to be removed are mostly weak basic components such as ammonia and hydrazine. These weakly basic components are ionized inside the cation exchange resin to form ion pairs with sulfonic acid groups, and can be electrophoresed by a DC voltage applied to the electroregenerative decation apparatus. When the sulfonic acid group is released by the electrophoresis, most of the sulfonic acid group becomes non-dissociated according to the dissociation constant inherent to the weakly basic component, and until it is captured by the sulfonic acid group and ion dissociates again, it depends on the applied DC voltage. It diffuses in sample water without performing electrophoresis. When the diffusion is performed inside the cation exchange resin, since the sulfonic acid groups are present relatively uniformly and densely, the movement of the weak basic component due to the diffusion is limited to a narrow range, At the ion-exchange resin particle interface, the weakly basic component is temporarily removed from the sample water without sulfonic acid groups, and is affected by the DC voltage over a relatively long distance until it is captured again by the ion-exchange resin particles. As a result, the weakly basic component adsorption zone in the cation exchange resin packed bed spreads in the direction of sample water flow. For this reason, in the conventional electric regeneration type decationization apparatus, it is necessary to enlarge the ion exchange resin packed layer in consideration of the expansion of the weak basic component adsorption zone. That is, the conventional electric regenerative decation ion apparatus has a problem that the apparatus is inevitably increased in size and cost.

  In addition, in the electric regeneration type decationization apparatus filled with the conventional spherical ion exchange resin, there is a time during which the weak basic component is not electrophoresed in a non-dissociated state as described above, and the spherical ion exchange resin As a result, the contact area between particles is small, so even in the case of ions that migrate electrophoretically in a dissociated state, the flow concentrates on the contact portion of the particle interface and becomes an inhibitory factor for ion movement, slowing the exclusion of adsorbed ions outside the system. It is a factor. In order to compensate for this, the conventional electric regenerative decationization device needs to be operated at a high current value, and in addition to the movement of the target weak basic component, a large excess of current is dissociated in water. There is a problem that the power consumption increases and the running cost increases.

On the other hand, Japanese Patent Application Laid-Open No. 2002-306976 has an open cell structure having mesopores with an average diameter of 1 to 1,000 μm in the walls of macropores and macropores connected to each other, and the total pore volume is 1 to 50 ml. An electric deionized water production apparatus in which the ion exchange groups are uniformly distributed, the ion exchange capacity is 0.5 mg equivalent / g, and a porous ion exchanger having a dry porous body or more is filled in the desalting chamber. It is disclosed. This organic porous ion exchanger is in the form of a monolithic sponge and has an excellent adsorption capacity due to its extremely large pore volume and specific surface area. However, Japanese Patent Laid-Open No. 2002-306976 does not describe that the monolith is suitable for a cation exchanger of an electric regeneration type decation apparatus used in an anion detection apparatus, and can be downsized. There is no statement to that effect.
Japanese Patent Laid-Open No. 9-210943 (Claim 1) JP 2002-306976 A (Claim 1)

  Therefore, the object of the present invention is to solve the above-mentioned problems of the prior art, the device structure is simple and downsized, the installation cost and the running cost can be reduced, and the operation is simple, stable and accurate constant monitoring. An object of the present invention is to provide a method and an apparatus for detecting an anion in a liquid.

  Under such circumstances, as a result of intensive studies, the present inventors have determined that an organic porous cation exchanger having an open cell structure is one of the cation exchangers in the desalting chamber as means for removing cations in the liquid. If the electric regenerative decation ion device is used as a part or the whole, the structure of the device can be simplified and reduced in size, the installation cost and the running cost can be reduced, and the operation can be performed easily, stably and accurately at all times. The headline and the present invention were completed.

That is, the present invention provides an anion detection in which a sample solution is passed through a desalting chamber of an electric regeneration type decation apparatus, and after removing cations in the sample solution, the anions in the solution are measured. In the method, the cation exchanger filled in the desalting chamber has an open cell structure having macropores connected to each other and mesopores having an average diameter of 1-1000 μm in the walls of the macropores, and the total pore volume is 1 to 50 ml / g, an organic porous cation exchanger having a cation exchange group uniformly distributed and a cation exchange capacity of 0.5 mg equivalent / g dry porous body or more, a granular cation exchanger, The organic porous cation exchanger is disposed on the sample solution inflow side, the granular cation exchanger is disposed on the sample solution outflow side, and the anion in the liquid is characterized in that it is installed in layers. An ion detection method is provided.

The present invention also includes a desalting chamber filled with a cation exchanger between the anode chamber and the cathode chamber, and the anode chamber, the cathode chamber, and the desalting chamber have a liquid inflow pipe and an outflow pipe, respectively. An electric regenerative decation ion device disposed, and a measuring instrument for measuring the conductivity or specific resistance of the treatment liquid disposed in the desalination chamber outflow pipe, The cation exchanger filled in the chamber has an open cell structure having mesopores having an average diameter of 1-1000 μm in the macropores and the walls of the macropores, and the total pore volume is 1-50 ml / g. Yes, an organic porous cation exchanger having a cation exchange group uniformly distributed and a cation exchange capacity of 0.5 mg equivalent / g dry porous body or more, and a granular cation exchanger on the sample solution inflow side The organic porous cation exchanger is disposed, and a granular cation is placed on the sample solution outflow side. The present invention provides an anion detector in a liquid characterized in that an on-exchanger is disposed and installed in a layered manner.

  According to the present invention, the weakly basic component adsorption zone in the porous cation exchanger packed bed is shorter by about 1/3 to 1/2 than when a granular cation exchange resin is used as the cation exchanger. It is compact and can simplify the structure of the device, reduce installation costs and running costs, and is easy to operate, stable and accurate constant monitoring.

  In the present invention, the sample liquid is not particularly limited as long as it is a liquid for detecting and quantifying anions in the liquid. For example, ammonia, hydrazine or ETA such as condensate in thermal power or nuclear power plants is used. It can be suitably used for the measurement of anions in a sample solution containing a large amount of such weakly basic cations. The anion detection device in the liquid of the present invention is an acid conductivity in condensate from the condenser to the condensate demineralizer in the main condensate circulation system for the purpose of constantly monitoring seawater leaks. In addition to this, the main condensate circulation other than the outlet of the condenser such as low-pressure heater, high-pressure heater, deaerator, boiler (steam generator in PWR type electronic power plant) feed water, etc. Water collected from the system and secondary water distribution systems such as low pressure heater drains and high pressure heater drains can also be measured.

  In the electric regeneration type decation apparatus used in the present invention, as an organic porous cation exchanger (hereinafter, also simply referred to as “porous cation exchanger”) filled in at least a part of the desalting chamber, It is not particularly limited, and examples thereof include a monolithic porous cation exchanger (hereinafter also simply referred to as “monolith”), a fibrous porous cation exchanger, a particle aggregation type porous cation exchanger, and the like. Monoliths are preferred because the ion exchange groups are uniformly distributed and ion exclusion is performed promptly.

  The monolith has an open cell structure with mesopores having an average diameter of 1 to 1000 μm, preferably 10 to 100 μm in the macropores and the walls of the macropores, and the total pore volume is 1 to 50 ml / g, preferably Is 4 to 20 ml / g, the ion exchange groups are uniformly distributed, and the ion exchange capacity is 0.5 mg equivalent / g or more of the dried porous body. Other physical properties of the monolith and methods for producing the same are disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-334560.

  If a monolith is used as the cation exchanger, the pore volume and specific surface area can be greatly increased. For this reason, the deionization efficiency of the electric regeneration type decation apparatus is remarkably improved, which is very advantageous. Further, if the total pore volume of the monolith is less than 1 ml / g, the amount of water per unit cross-sectional area becomes small and the treatment capacity is lowered, which is not preferable. On the other hand, if the total pore volume exceeds 50 ml / g, the proportion of the skeleton portion is decreased, and the strength of the porous body is significantly decreased. When a monolith having a total pore volume of 1 to 50 ml / g is used as an ion exchanger of an electroregenerative decation apparatus, both the strength and deionization efficiency of the porous body can be satisfied. Is preferable. Moreover, when the ion exchange capacity of the monolith is less than 0.5 mg equivalent / g dry porous body, the ion adsorption capacity is insufficient, which is not preferable. In addition, if the ion exchange group distribution is non-uniform, the ion movement in the porous cation exchanger becomes non-uniform and the rapid removal of the adsorbed ions is hindered.

  Examples of the fibrous porous ion exchanger include single fibers and woven fabrics and non-woven fabrics that are aggregates of single fibers described in JP-A-5-64726, and further ionized by using radiation graft polymerization for these processed products. Examples thereof include those in which an exchange group is introduced and processed. Further, as the particle aggregation type porous ion exchanger, for example, a mixed polymer or a crosslinkable polymer of a thermoplastic polymer and a thermosetting polymer described in JP-A-10-192716 and JP-A-10-192717 is used. Then, ion-exchange resin particles are combined and processed and molded.

  Further, the cation exchanger may be a mixed bed ion exchanger of the porous cation exchanger and the granular cation exchange resin. In this case, for example, in an electric regeneration type decation apparatus, When a monolith is arranged on the inflow side and a conventional granular ion exchange resin is filled on the downstream side, the exchange capacity per large filling volume of the granular ion exchange resin is provided while providing rapid adsorption and ion exclusion of the monolith. In response to fluctuations in the amount of cation inflow in the treated water during start-up operations after full storage during regular inspections at power plants, daily start / stop (DSS), weekly start / stop (WSS), etc. However, it is preferable in that a more stable decation treatment can be performed and a highly versatile anion detector can be obtained. The filling ratio of the porous cation exchanger and the granular cation exchange resin is not particularly limited, but the volume ratio of monolith: particulate cation exchange resin is 1: 0.5 to 1:10.

  The cation exchanger includes a porous cation through which a cation exchanger part that forms a desalting region and a part of the liquid to be treated that is disposed adjacent to the ion exclusion side of the desalting region. A composite ion exchanger made of an exchanger is preferable in that the ion exchange membrane that partitions the desalting chamber and the electrode chamber can be omitted. Examples of the cation exchanger include monoliths and cation exchange resins. In the composite ion exchanger, the flow resistance of the porous cation exchanger is larger than the liquid resistance of the cation exchanger part forming the desalting region, but a separate special channel distribution means is provided. It is preferable that most of the sample liquid flowing into the desalting region flows out from the desalting region as a decation solution and a part of the liquid to be treated permeates into the liquid permeation region. If flow rate adjusting means is provided in the flow path of the effluent permeated from the liquid permeation region, the flow rate of the permeated liquid and the deionized liquid can be adjusted to a desired ratio by the flow rate adjusting means. When the flow rate adjusting means is provided in the flow path of the effluent permeated from the liquid permeation region, the flow resistance of the porous ion exchanger loaded in the liquid permeation region is determined by the cation exchanger filled in the desalting region. It may be the same as the liquid flow resistance of the part. For example, when a monolith is used for both the desalting region and the liquid permeation region, a single monolith processed into a shape extending over the desalting region and the liquid permeation region can be used. This is advantageous in that it is not necessary to separately manufacture the desalination zone monolith and the liquid permeation zone monolith. The flow rate ratio of the permeate passing through the liquid permeation region to the flow rate of the liquid to be processed is, for example, 2 to 30%, preferably 4 to 30%.

  As the porous cation exchanger filled in at least a part of the desalting chamber, a composite porous ion exchanger described in International Publication WO 02/083770 A1 can be used. The composite porous ion exchanger is formed integrally with the monolith on the surface of at least one of the monoliths. Since the composite porous ion exchanger has an ion exchange group, it can move ions, but substantially transmits water. It has a dense layer that does not. When such a composite porous ion exchanger is used as a cation exchanger, a part or all of the ion exchange membrane is omitted from the configuration of the electric regeneration type decation apparatus, and the apparatus configuration is It can also be simplified.

  An anion detection apparatus according to an embodiment of the present invention will be described with reference to FIG. FIG. 1 is a schematic diagram showing an example of an anion detection device. In FIG. 1, the anion detection device 10 includes an electric regenerative decation ion device 10 a and a measuring instrument 10 b that measures the conductivity or specific resistance of a processing solution disposed in the desalination chamber outflow pipe 32. The electric regenerative decationization apparatus 10a includes a desalination chamber 4 in which a cation exchanger 3 partitioned by two cation exchange membranes 5 and 5 is filled between an anode chamber 1 and a cathode chamber 2. The anode chamber 1, the cathode chamber 2, and the desalting chamber 4 are provided with liquid inflow pipes 11, 21, 31 and outflow pipes 12, 22, 32, respectively.

  In FIG. 1, the desalting chamber 4 is filled with a monolith 35 on the inflow side of the liquid to be treated and a spherical cation exchange resin 36 on the outflow side of the treatment liquid at a filling volume ratio of 1: 1. That is, the monolith 35 and the spherical cation exchange resin 36 are layered bodies in which a monolith phase and a spherical cation exchange resin layer are laminated in the direction of water flow. The layered body of the monolith and the ion exchange resin is a monolithic sponge-like structure, so that the monolith is not mixed with the ion exchange resin and can be filled in phase without using a partition means such as an ion exchange membrane in the room. . Further, the treated water inflow pipe 31 is attached so that the inlet is provided near the cation exchange membrane on the cathode side of the desalting chamber, and the treated water outflow pipe 32 is near the cation exchange membrane on the anode side of the desalination chamber. The outlet is attached to the side far from the inlet. As a result, the application of the DC electric field allows the ions to be eliminated to migrate in the direction opposite to the direction of water flow in the cation exchanger, so that the cations in the liquid to be treated can be reliably removed. Further, the cathode chamber inflow piping 21 is branched from the desalination chamber inflow piping 31, and the anode chamber inflow piping 11 is connected to the measuring device outflow piping 16.

In the anion detection device 10 of FIG. 1, when the liquid to be treated flows into the desalting chamber 4, the ammonia and hydrazine components contained in the sample are captured by the cation exchanger 3 and permeate the cation exchange membrane 5 to form the cathode. It moves to the chamber 2 and is discharged out of the system together with the sample solution which is cathode water. The anode water in the anode chamber 1 is the effluent water of the measuring instrument 10b, which has no cation component other than hydrogen ions and does not move from the anode chamber 1 to the desalting chamber 4 other than hydrogen ions. For this reason, treated water does not contain cation components other than hydrogen ions. Here, when a small amount of sodium chloride is mixed in the sample solution, for example, an increase of several μg NaCl / l in 1 mg NH ₃ / l, the conductivity of the sample solution itself hardly changes. On the other hand, treated water removes cation components such as ammonia and hydrazine, but does not remove Cl ⁻ . Therefore, the conductivity changes by the amount of Cl ⁻ mixed therein. Since this conductivity is a change in acid conductivity, the amount of change is greater than a change in the same equivalent NaCl. The conductivity is the reciprocal of the specific resistance, and either may be measured.

  The anion detection device of the present invention is not limited to the anion detection device of FIG. 1, for example, a composite ion exchanger having the desalting region and the liquid permeation region or a composite porous ion having a dense layer. If an exchanger is used, the installation of two cation exchange membranes can be omitted, and the cost can be further reduced. Further, in the desalting chamber, the flow direction of the liquid to be treated may be a direct electric field applied, and the ions to be excluded may be perpendicular to the water flow direction in the cation exchanger. Further, the anode water may be pure water supplied from a separate pipe instead of the outflow water of the anion measuring device.

  When the entire desalination chamber of the electroregenerative decation apparatus of the anion detector of the present invention is filled with a porous cation exchanger, particularly a monolith, the monolith is a porous body having an open-cell structure. Therefore, in the packed bed, there is no particle interface as in the conventional granular ion exchanger packed bed, and cation exchange groups exist uniformly throughout the packed bed. Therefore, adsorption of cation components such as ammonia and hydrazine in the inflowing treated water to the ion exchanger is rapid, and the adsorbed cation components are present on the cation exchange group continuously present in the entire packed bed. In an almost dissociated state, it electrophoreses and is quickly discharged out of the system. By quickly adsorbing and eliminating the cation component, the anion detector can be constantly and accurately monitored, and has a simple structure, can be miniaturized, and can be manufactured at low cost. In addition, when a monolith is arranged on the treated water inflow side and a conventional granular ion exchange resin is filled on the downstream side, the monolith per a large filling volume of the granular ion exchange resin is provided with quick adsorption and ion exclusion of the monolith. Because of the exchange capacity of the plant, more stable decations are possible even during start-up operations after full water storage during periodic inspections at power stations and fluctuations in the amount of cation inflow in the treated water due to DSS, WSS, etc. Ion processing can be performed.

  EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this is only an illustration and does not restrict | limit this invention.

(Anion detector)
It was confirmed that the apparatus shown in FIG. 1 can stably and accurately detect and quantify anions in test water. A mesh plate made of SUS304 was used as the cathode, and a titanium mesh plate coated with platinum was used as the anode, and was placed in close contact with the two cation exchange membranes 5 and 5. The two cation exchange membranes 5 and 5 were both strongly acidic cation exchange membranes (Neocepta CMX (manufactured by Tokuyama Soda Co., Ltd.)) in which sulfonic acid groups were introduced into a styrene-divinylbenzene copolymer matrix. The opposite sides of both electrodes to the ion exchange membrane contact surface were designated as a cathode chamber 2 and an anode chamber 1, respectively. The decation chamber 4 divided by the two cation exchange membranes 5 and 5 is filled with a monolith 35 on the treated water inflow side and a styrene-divinylbenzene copolymer matrix on the downstream side with a sulfonic acid group. The spherical strong acidic cation exchange resin 36 (Amberlite IR120B) into which was introduced was packed. The shape of the decation chamber was a rectangular parallelepiped of 50 mm × 50 mm × 100 mm, and the monolith 35 and the spherical strong acid cation exchange resin 36 were filled at a volume ratio of 1: 1. The ion exchange capacity of the monolith 35 is 4.0 mg equivalent / g in terms of a dry porous body, and sulfonic acid groups are uniformly introduced into the porous body by mapping of sulfur atoms using EPMA. confirmed. Moreover, as a result of SEM observation, the internal structure of this porous body has an open cell structure, most of the macropores having an average diameter of 30 μm overlap, and the average diameter of the mesopores formed by the overlap of the macropores and the macropores. The value was 5 μm and the total pore volume was 10.1 ml / g. The treated water outflow pipe 32 from the decation chamber 4 is connected to the conductivity meter 10b (Foxboro 875CR (monitor), 871CC (sensor)), and the outflow water from the conductivity meter 10b is supplied to the anode chamber 1 An anion detector 10 was configured by connecting to the inlet.

(Anion detection method)
Using the anion detection device 10, the seawater leak detection ability during steady operation of the power plant was confirmed with simulated water. As the water to be treated, ammonia was dissolved in pure water having a specific resistance of 18.2 MΩ · cm so as to have a concentration of 1 mg NH ₃ / l, and sodium chloride was further added to the ammonia water in order to simulate seawater leak. The concentration was changed as appropriate so that the concentration was 100 μg / l. The flow rate of the water to be treated was 50 l / h, the direct current applied between the anode and the cathode was 1.0 A, and the voltage was 40V. The results are shown in Table 1. From Table 1, it can be seen that the anion detector 10 can detect and quantify 5 μg / l of sodium chloride, and has sufficient performance as a continuous monitoring device for seawater leaks in thermal power and nuclear power plants.

Furthermore, assuming a weekly start / stop (WSS) in a thermal power plant, it was confirmed that the anion detector 10 stably exhibits decation performance even when the cation concentration in the treated water is high. . That is, an anion detection apparatus similar to that of Example 1 except that the cation in the water to be treated was ₂ mg NH ₃ / l ammonia, 10 mg N ₂ H ₄ / l hydrazine, no sodium chloride was added, and the operation time was 1000 hours. And performed in a similar manner. As a result, the conductivity of the treated water is maintained at 0.06 μS / cm or less in 1000 hours of continuous operation, and the anion detector of the present example stably removes the cation even when the cation load increases in the treated water. It was confirmed that ion treatment was possible.

Comparative Example 1
Instead of filling the monolith and the spherical strong acid cation exchange resin at a volume ratio of 1: 1, the negative electrode similar to Example 1 except that the whole chamber was filled with the spherical strong acid cation exchange resin (Amberlite IR120B). Using an ion detector, the operation was performed under the same conditions as the decation performance confirmation when the cation load in the treated water was increased. As a result, the treated water conductivity increased from 50 hours after the start of operation, became 5.2 μS / cm after 70 hours, and stabilized thereafter. When the treated water conductivity is 5.2 μS / cm when water to be treated is added without adding sodium chloride, it is impossible to detect and quantify a slight amount of seawater leak.

  From Examples 1 and 2, it is clear that the anion detection quantification 10 has a simple device structure and can be miniaturized, can reduce the installation cost, is easy to operate, is stable, and can be constantly monitored accurately. In addition, from the results of the comparative example, the anion detection device that does not use the organic porous cation exchanger has a sufficient ability to remove weakly basic cations such as ammonia and hydrazine compared to the anion detection device of the example. It was confirmed that it was not.

It is a schematic block diagram which shows an example of the anion detection apparatus of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Anode chamber 2 Cathode chamber 3 Cation exchanger 4 Decation chamber 5 Cation exchange membrane 10 Anion detector 10a Electric regeneration type decation apparatus 10b Measuring instrument (resistivity meter or conductivity meter)
DESCRIPTION OF SYMBOLS 11 Anode water inflow piping 12 Anode water outflow piping 21 Cathode water inflow piping 22 Cathode water outflow piping 31 Treated water inflow piping 32 Treated water outflow piping

Claims (3)

In the anion detection method for measuring an anion in the liquid after removing the cation in the sample liquid by passing the sample liquid through a desalting chamber of an electric regeneration type decation apparatus, the desalting is performed. The cation exchanger filled in the chamber has an open cell structure having mesopores having an average diameter of 1-1000 μm in the macropores and the walls of the macropores, and the total pore volume is 1-50 ml / g. There, the cation-exchange groups are uniformly distributed, and a cation exchange capacity of 0.5mg equivalent / g dry porous material or organic porous cation exchanger, and a particulate cation exchanger, sample liquid inlet side A method for detecting anions in a liquid , wherein the organic porous cation exchanger is disposed in a layered state, a granular cation exchanger is disposed on the outflow side of the sample liquid, and the organic porous cation exchanger is disposed in a layered manner. Negative ion detection method in a liquid according to claim 1, wherein the measuring the leakage of the cooling water of the condenser of the power plant. An electric regeneration system comprising a desalting chamber filled with a cation exchanger between the anode chamber and the cathode chamber, and an inflow pipe and an outflow pipe for the liquid disposed in the anode chamber, the cathode chamber and the desalting chamber, respectively. A deionization device,
A measuring instrument for measuring the conductivity or specific resistance of the treatment liquid disposed in the desalination chamber outflow pipe;
The cation exchanger filled in the desalting chamber has an open cell structure having macropores connected to each other and mesopores having an average diameter of 1 to 1000 μm in the walls of the macropores. An organic porous cation exchanger having a pore volume of 1 to 50 ml / g, a cation exchange group uniformly distributed, and a cation exchange capacity of 0.5 mg equivalent / g or more of a dry porous body, a granular cation A liquid, characterized in that the organic porous cation exchanger is disposed on the sample liquid inflow side and the granular cation exchanger is disposed on the sample liquid outflow side, and the exchanger is installed in layers. Inside anion detector.

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