An electric ion regeneration method and a water vapor system corrosion monitoring device

Abstract

The present invention relates to the technical field of supercritical units, and in particular to an electric ion regeneration method and a water vapor system corrosion monitoring device, comprising: passing a water sample into an electric regeneration ion exchanger; applying an electric field in the electric regeneration ion exchanger to remove cations; and automatically regenerating an ion exchange resin through the generated hydrogen ions. The electric ion regeneration method and the water vapor system corrosion monitoring device use high voltage at both ends of electrodes to move charged ions in water, and cooperate with ion exchange resins and selective resin membranes to accelerate ion movement and removal, thereby removing NH4 + At the same time, water molecules generate H + The failed resin can be regenerated so that it can be recycled.

Description

Technical Field

[0001] The invention relates to the technical field of supercritical units, and in particular to an ion regeneration method and a water vapor system corrosion monitoring device. Background Art

[0002] When conventional ion exchange resins are used to measure hydrogen conductivity during online hydrogen conductivity monitoring of existing supercritical units, not only does it require frequent resin replacement, increasing manual workload, but the measurement is also subject to a series of interferences such as resin regeneration, resin cracks, unclean resin flushing, resin aging, and resin failure, causing the hydrogen conductivity measurement error to exceed the standard, failing to reflect the true water vapor quality status, misleading chemical supervisors, and in severe cases leading to major corrosion accidents in power plants. Summary of the invention

[0003] In view of the problems existing in the above-mentioned existing ion regeneration method and water vapor system corrosion monitoring device, the present invention is proposed.

[0004] Therefore, one of the objects of the present invention is to provide an ion regeneration method, the purpose of which is to enable the resin to be regenerated for recycling.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions: an electric ion regeneration method, comprising: passing a water sample into an electric regeneration ion exchanger; removing cations by applying an electric field in an electrically regenerated ion exchanger; and, The ion exchange resin is automatically regenerated by the generated hydrogen ions.

[0006] As a preferred solution of the electric ion regeneration method of the present invention, the application of the electric field is achieved through conductivity electrodes, and the conductivity electrodes are arranged at both ends of the electric regeneration ion exchanger.

[0007] As a preferred embodiment of the electric ion regeneration method of the present invention, an ion exchange resin and a selective resin membrane are provided in the electric regeneration ion exchanger.

[0008] As a preferred embodiment of the ion regeneration method of the present invention, the high voltage at both ends of the conductivity electrode causes the charged ions in the water to move, and the ion exchange resin and the selective resin membrane are used to accelerate the movement and removal of ions to remove the cations in the water sample.

[0009] As a preferred embodiment of the electric ion regeneration method of the present invention, water molecules generate hydrogen ions under the action of the electric field to restore the failed resin, so that the resin is re-carried with exchangeable hydrogen ions and the exchange capacity of the resin is restored.

[0010] As a preferred solution of the ion regeneration method of the present invention, it also includes real-time monitoring of the conductivity of the treated water sample by a conductivity sensor, and transmitting the conductivity data to a recording device via a conductivity transmitter.

[0011] As a preferred solution of the ion regeneration method of the present invention, the conductivity monitoring process of the water sample includes filtering out tiny suspended particles and bubbles to ensure the accuracy of the sensor readings.

[0012] The beneficial effect of this ion regeneration method is: using the high voltage at both ends of the electrode to move the charged ions in the water, and cooperating with ion exchange resin and selective resin membrane to accelerate the movement and removal of ions, thereby achieving the removal of NH4 in the water sample. + At the same time, water molecules generate H + The failed resin can be regenerated so that it can be recycled.

[0013] Another object of the present invention is to provide a water vapor system corrosion monitoring device, the purpose of which is to enable the resin to be regenerated for recycling.

[0014] In order to solve the above technical problems, the present invention provides the following technical solutions: a water vapor system corrosion monitoring device, comprising; A bypass system; comprising a conductivity electrode; An exchange system includes an electrically regenerated ion exchanger connected to a conductivity electrode.

[0015] As a preferred solution of the water vapor system corrosion monitoring device of the present invention, the electrically regenerated ion exchanger is provided with ion exchange resin and selective resin membrane.

[0016] As a preferred solution of the water vapor system corrosion monitoring device of the present invention, wherein: the conductivity electrode is connected to a conductivity transmitter.

[0017] The beneficial effects of the present invention are: the high voltage at both ends of the electrodes is used to move the charged ions in the water, and the ion exchange resin and the selective resin membrane are used to accelerate the movement and removal of the ions, thereby achieving the removal of NH4 in the water sample. + At the same time, water molecules generate H + The failed resin can be regenerated so that it can be recycled. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative work.

[0019] Figure 1 It is a schematic diagram of the overall structure of Embodiment 1 and Embodiment 2 of the present invention.

[0020] Figure 2 It is a schematic diagram of the technical principle of the electric regeneration ion exchanger of the present invention.

[0021] Figure 3 It is a schematic diagram of the existing cation resin exchange column measurement technology.

[0022] In the figure: 100, conductivity electrode; 101, conductivity transmitter; 200, electrically regenerated ion exchanger. DETAILED DESCRIPTION

[0023] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the accompanying drawings.

[0024] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein, and those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0025] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The term "in one embodiment" that appears in different places in this specification does not necessarily refer to the same embodiment, nor does it refer to a separate or selective embodiment that is mutually exclusive with other embodiments.

[0026] Secondly, the present invention is described in detail with reference to the schematic diagram. When describing the embodiments of the present invention in detail, for the sake of convenience, the cross-sectional diagrams showing the device structure will not be partially enlarged according to the general scale, and the schematic diagrams are only examples, which should not limit the scope of protection of the present invention. In addition, in actual production, the three-dimensional dimensions of length, width and depth should be included.

[0027] Example 1, reference Figure 1 and 2 , as a first embodiment of the present invention, provides an ion regeneration method, the method comprising: S1. By passing the water sample into the electrically regenerated ion exchanger 200; Therein, the water sample is introduced into the electrically regenerated ion exchanger 200 through a bypass system, and the bypass system is connected to an existing hydrogen conductivity sampling point, allowing sampling without interrupting the operation of the existing system.

[0028] S2. By applying an electric field in the electrically regenerated ion exchanger 200, cations are removed; An electric field is applied in the electric regeneration ion exchanger 200, and the voltage is set through the electrodes to make the cations in the water (such as NH4 + ) Accelerate migration and removal along the direction of the electric field; The application of the electric field is achieved through conductivity electrodes, which are arranged at both ends of the electric regeneration ion exchanger 200, and the electric regeneration ion exchanger 200 is provided with ion exchange resin and selective resin membrane.

[0029] When the high voltage at both ends of the conductivity electrode causes the charged ions in the water to move, the ion exchange resin and selective resin membrane are used to accelerate the movement and removal of ions, thereby removing the cations in the water sample.

[0030] S3. The ion exchange resin is automatically regenerated by the generated hydrogen ions.

[0031] Among them, after the resin completes the exchange with the cations in the water, it changes from hydrogen type to ammonia type and loses the ability to exchange the cations in the water, thus making the resin ineffective.

[0032] At this time, water molecules generate hydrogen ions under the action of the electric field to restore the expired resin, so that the resin can be re-carried with exchangeable hydrogen ions, the exchange capacity of the resin is restored, and the resin can be used again, thus achieving the purpose of regeneration.

[0033] This ion regeneration method can automatically regenerate after power is turned on, does not require replacement, does not have the problem of resin failure, and has high reliability.

[0034] After the existing exchange, the resin changes from hydrogen type to ammonia type, and loses the ability to exchange cations in water. A high concentration of HCl (5%) is passed into the ammonia type resin. At this time, due to the high concentration of hydrogen ions in the solution, the NH4 + The resin is replaced with exchangeable hydrogen ions. This method does not require the use of hydrochloric acid regeneration liquid. After power is applied, water molecules generate H + The expired resin can be regenerated without adding any chemical substances, and it is harmless to humans and does not pollute the environment.

[0035] S4. The conductivity of the treated water sample is monitored in real time through the conductivity sensor, and the conductivity data is transmitted to the recording device through the conductivity transmitter 101.

[0036] A conductivity transmitter 101 is installed at the conductivity electrode 100, and the conductivity sensor inside the conductivity electrode 100 monitors the conductivity of the treated water sample in real time. At the same time, the conductivity data is transmitted to the recording device through the conductivity transmitter 101 to monitor the water quality in real time.

[0037] Furthermore, the conductivity monitoring process of water samples includes filtering out tiny suspended particles and air bubbles to ensure the accuracy of sensor readings.

[0038] Example 2, reference Figure 1-Figure 3 , which is the second embodiment of the present invention, provides a water vapor system corrosion monitoring device: the device includes a bypass system and an exchange system.

[0039] The bypass system includes a conductivity electrode 100, and the exchange system includes an electric regeneration ion exchanger 200, wherein the conductivity electrode 100 is connected to the electric regeneration ion exchanger 200; Furthermore, the electrically regenerated ion exchanger 200 is provided with ion exchange resin and selective resin membrane.

[0040] The conductivity electrodes 100 are arranged at both ends of the electrically regenerated ion exchanger 200. When the water sample enters the electrically regenerated ion exchanger 200, the high voltage at both ends of the conductivity electrodes 100 causes the charged ions in the water to move, wherein the cations react with the exchange resin and the selective resin membrane and are removed. At this time, after the resin completes the exchange with the cations in the water, it changes from hydrogen type to ammonia type and loses the ability to exchange the cations in the water, causing the resin to fail.

[0041] The hydrogen ions in the water will combine with the failed resin, allowing the resin to be re-carried with exchangeable hydrogen ions, restoring the exchange capacity of the resin, and the resin can be used again, thus achieving the purpose of regeneration.

[0042] Furthermore, the conductivity electrode 100 is connected to a conductivity transmitter 101, and the conductivity sensor inside the conductivity electrode 100 monitors the conductivity of the treated water sample in real time, and transmits the conductivity data to a recording device through the conductivity transmitter 101 to monitor the water quality in real time.

[0043] The existing cation exchange column measurement technology is to fill the cation exchange resin in the cation exchange column, which can exchange with the cations in the water, thereby removing the cations in the water in an ionic state. Taking ammonium chloride (NH4Cl) as the inorganic salt in the water, the basic reaction of cation exchange can be expressed by the following equation: R-SO3H+NH4Cl→R-SO3NH4+HCl After the exchange, the resin changes from hydrogen to ammonia and loses its ability to exchange cations in water. If a high concentration of HCl (5%) is passed into the ammonia resin, the H+ If the concentration is high, the NH4 + Replace it and let the resin carry the exchangeable H + , the resin exchange capacity is restored and it can be used again. This process is called regeneration. The equation of the regeneration process is expressed as follows: R-SO3NH4+HCl→R-SO3H+NH4Cl According to the working principle of the above cation resin exchange column, the traditional cation resin exchange column needs to replace the resin from time to time and regenerate the resin.

[0044] The advantages of using an electrically regenerated ion exchanger 200 for steam-water corrosion monitoring are mainly reflected in the following aspects: automatic regeneration after online power-on, no need for replacement, continuous water quality monitoring, and no supervision risks in the operation of the unit; Online power-on continuous automatic regeneration, no resin failure problem, high reliability; no need to use hydrochloric acid regeneration liquid, after power-on, water molecules generate H under the action of the electric field + It can regenerate failed resins without adding any chemical substances, causing no harm to people or environmental pollution. It can automatically regenerate after being powered on online, and the hydrogen conductivity measurement is continuous and stable.

[0045] Electrically regenerated ion exchanger 200 treatment capacity verification test The function of the electric regeneration ion exchanger 200 and the ion exchange resin is to exchange cations such as ammonia in water and convert them into hydrogen ions, which indirectly reflects the concentration of anions in water. Therefore, the ability of the electric regeneration cation exchanger to treat cations such as ammonia was first verified by sampling and analysis. The water samples of the inlet and outlet of 6 sets of equipment were sampled and analyzed by liquid ion chromatography. The analysis data are shown in Table 1.

[0046] Table 1 Test data for the processing capacity verification of the electric regeneration ion exchanger 200 , From the analysis of the test data, it can be seen that a large amount of ammonia and other cations in the influent of the electrically regenerated ion exchanger 200 can be completely replaced and removed, and the cation removal performance of the equipment itself meets the requirements (the processing capacity is higher than 99%).

[0047] The oil and large amount of anions in the water of Unit #1 can be considered as abnormal water quality. Under this water quality condition, the measurement of the electrically regenerated cation exchanger and the cation resin exchange column produced deviations. In order to further confirm the performance of the electrically regenerated cation exchanger, a comparative test of the two devices was carried out under the normal water quality conditions of Unit #3 on site.

[0048] The sample water after the condensate pump was doped was simultaneously passed into the electric regeneration ion exchanger 200 and the cation exchange resin column for comparative testing. The test data is shown in the table.

[0049] Table 2 Hydrogen conductivity of unit #3 under normal water quality conditions , From the comparison data, it can be seen that under normal water quality conditions without oil in unit #3, the deviation of hydrogen conductivity measured by the electrically regenerated ion exchanger 200 and the cationic resin exchange column is relatively small, only 3.69% (it is generally believed that the deviation is less than 5%, and the data is close to the actual situation).

[0050] Most on-site cation exchange resin columns adopt the soaking regeneration method, and the regeneration degree of this regeneration method is generally not high. According to literature records, the regeneration degree of resin in the off-column soaking method is usually less than 70% or even lower, that is, after the cation exchange resin is regenerated, the hydrogen type resin accounts for less than 70% of the total amount, and the rest is ammonium or sodium type resin. + and NH4 + There is a large difference in the molar charge conductivity of aqueous solutions. Insufficient resin regeneration will result in a low hydrogen conductivity measurement value [9]. This deviation will be greater when the on-site water contains a large amount of anions and the ion exchange resin regeneration is insufficient. Compared with the cation exchange resin column, the electrically regenerated ion exchanger 200 is regenerated in real time, and the resin regeneration degree is always maintained at more than 99%. Therefore, the electrically regenerated ion exchanger 200 has a higher measurement value under such a large amount of anion water quality conditions and is more sensitive to anions in the water.

[0051] In order to verify the above error sources, a comparative test was conducted at the high-pressure main steam measuring point of Unit 1. The water samples were separately connected to the electrically regenerated ion exchanger 200 and the ion exchange resin column. The water samples were taken from the equipment and analyzed by liquid ion chromatography. The test data are shown in Table 3.

[0052] Table 3 Anion and cation content of water samples , The test results show that the anion content in the effluent water samples of the electric regeneration ion exchanger 200 and the ion exchange resin column installed at the high-pressure main steam measuring point is similar, but the cation content in the effluent water of the ion exchange resin column is more than 10 times that of the electric regeneration ion exchanger 200. Therefore, it can be judged that the low regeneration degree of the ion exchange resin column leads to the leakage of cations from the resin column, which is the main error source of the low hydrogen conductivity measurement using the ion exchange resin column on site.

[0053] After the thermal system of unit #1 was deoiled, the sample water after the condensate pump was doped was simultaneously passed into the electric regeneration ion exchanger 200 and the cation exchange resin column for comparative testing, and the hydrogen conductivity obtained is shown in the following table.

[0054] Table 4 Hydrogen conductivity of water quality of unit #1 ,

[0055] It can be seen from the data in Table 4 that after the #1 unit is deoiled, the hydrogen conductivity value measured by the electrically regenerated ion exchanger 200 is very close to the hydrogen conductivity value measured by the cation exchange resin column, which is only 2.87% (it is generally believed that the deviation is less than 5%, and the data is close to the actual situation). Therefore, it shows that the electrically regenerated ion exchanger 200 has high reliability.

[0056] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.

Claims

1. An ion regeneration method, characterized in that: include, By passing the water sample into an electrically regenerated ion exchanger (200); removing cations by applying an electric field in an electrically regenerated ion exchanger (200); as well as, Automatically regenerate ion exchange resins through the generation of hydrogen ions; Water molecules generate hydrogen ions under the action of the electric field to restore the failed resin, so that the resin can be re-carried with exchangeable hydrogen ions and the exchange capacity of the resin can be restored; It also includes monitoring the conductivity of the treated water sample in real time through a conductivity sensor, and transmitting the conductivity data to a recording device through a conductivity transmitter (101); The conductivity monitoring process of water samples involves filtering out tiny suspended particles and air bubbles to ensure the accuracy of sensor readings.

2. The ion regeneration method according to claim 1, characterized in that: The application of the electric field is achieved through conductivity electrodes (100), which are arranged at both ends of the electrical regeneration ion exchanger (200).

3. The ion regeneration method according to claim 2, characterized in that: The electric regeneration ion exchanger (200) is provided with ion exchange resin and a selective resin membrane.

4. The ion regeneration method according to claim 3, characterized in that: The high voltage at both ends of the conductivity electrode (100) causes the charged ions in the water to move, and the ion exchange resin and the selective resin membrane are used to accelerate the movement and removal of ions, thereby removing the cations in the water sample.

5. A water vapor system corrosion monitoring device, used to perform the ion regeneration method described in any one of 1-4, characterized in that: include; Bypass system; It includes a conductivity electrode (100); An exchange system includes an electrically regenerated ion exchanger (200) connected to a conductivity electrode (100).

6. The water vapor system corrosion monitoring device according to claim 5, characterized in that: The electrical regeneration ion exchanger (200) is provided with ion exchange resin and a selective resin membrane.

7. The water vapor system corrosion monitoring device according to claim 6, characterized in that: The conductivity electrode (100) is connected to a conductivity transmitter (101).

Images