Method for uniformly mixing nuclear-grade anion-cation resin
By adding lithium hydroxide solution before mixing nuclear-grade lithium cation and hydroxide anion exchange resins and controlling the molar ratio, the problem of resin clumping during mixing was solved, achieving uniform mixing and efficient water treatment, and reducing the risk of equipment corrosion.
Patent Information
- Application Number
- CN202511158391.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-19
- Publication Date
- 2026-01-02
AI Technical Summary
Nuclear-grade lithium-type cation exchange resin and nuclear-grade hydroxide-type anion exchange resin tend to clump together when mixed, resulting in uneven dispersion and affecting the water treatment effect of nuclear power plants.
By adding lithium hydroxide solution before mixing to control the molar ratio of lithium ions to hydroxide ions to 1:1, and using a built-in electric stirrer to mix, the resin is ensured to be uniformly mixed before being filtered, dried, and packaged to remove air impurities.
This method achieves uniform mixing of nuclear-grade anion and cation exchange resins, avoids clumping, ensures effective water treatment, reduces equipment corrosion risk, and improves product purity and production efficiency.
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Figure CN121244034A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of ion exchange resin for adsorption, in particular to a method for uniformly mixing nuclear-grade cation and anion resins. BACKGROUND
[0002] A pressurized water reactor nuclear power plant is generally composed of a primary loop, a secondary loop and a tertiary loop. The lithium-type resin is usually required to be in the lithium-type form under the influence of the radiation field of the primary loop, and needs to be used once. If the nuclear-grade lithium-type cation exchange resin contains impurity cations, the impurity ions will be released under the influence of radiation, high temperature, etc., to pollute the water quality, cause corrosion of the equipment, reduce the service life of the equipment, and affect safe production. Therefore, the nuclear power plant has a higher requirement on the lithium-type conversion rate of the lithium-type cation exchange resin used, and generally requires that the lithium-type rate be not less than 99.5%, and the content of impurity elements be extremely low.
[0003] The nuclear-grade lithium-type cation exchange resin is a cation exchange resin specially used for water treatment of the primary loop of a nuclear power plant, and the exchangeable ions of the exchange group are lithium ions. It is usually mixed with a hydrogen-oxygen type strong alkali anion exchange resin to form a mixed bed with a molar ratio of lithium ions to hydroxyl ions being 1:1 to treat the primary loop water of the nuclear power plant. When other impurity ions are removed, LiOH.H2O is generated, which increases the pH value of the effluent water quality, makes it in a weak alkaline water quality environment, reduces the corrosion of the water quality to the equipment, and reduces the radiation field. 7 OH.H2O, makes the pH value of the effluent water quality increase, makes it in a weak alkaline water quality environment, reduces the corrosion of the water quality to the equipment, and reduces the radiation field.
[0004] The impurity contents of the nuclear-grade lithium-type cation exchange resin and the nuclear-grade hydrogen-oxygen type anion exchange resin after purification treatment are extremely low. When the nuclear-grade lithium-type cation exchange resin and the nuclear-grade hydrogen-oxygen type anion exchange resin are mixed in a certain proportion, the nuclear-grade cation and anion mixed resin obtained after mixing is prone to clumping due to the different charges of the ions on the surfaces of the two resins, which leads to poor dispersion.
[0005] Therefore, there is an urgent need for a method for uniformly mixing nuclear-grade cation and anion resins. So that the nuclear-grade lithium-type cation exchange resin and the nuclear-grade hydrogen-oxygen type anion exchange resin do not clump when mixed, are loose and uniform, and can be uniformly mixed. SUMMARY
[0006] The technical problem to be solved by the present application is to provide a method for uniformly mixing nuclear-grade cation and anion resins, which can avoid clumping of the nuclear-grade lithium-type cation exchange resin and the nuclear-grade hydrogen-oxygen type anion exchange resin when mixed, and ensure that the mixture is loose and uniform.
[0007] To solve the above technical problem, the present application provides a method for uniformly mixing nuclear-grade cation and anion resins, comprising the following steps:
[0008] dissolving lithium hydroxide in water to obtain a lithium hydroxide solution;
[0009] The lithium hydroxide solution is mixed with the nuclear grade hydroxyl type anion exchange resin to obtain a mixed solution;
[0010] The nuclear grade lithium type cation exchange resin is added to the mixed solution and stirred to obtain a nuclear grade mixed anion and cation resin;
[0011] The nuclear grade mixed anion and cation resin is transferred to a packaging container, filtered, dried, packaged, filled with nitrogen to remove air, and then stored.
[0012] Further, the dissolving and mixing are performed in a enamel reaction kettle provided with an internal electric stirrer.
[0013] Further, the concentration of the lithium hydroxide solution is 0.5-2.5 g / L.
[0014] Further, the volume of the lithium hydroxide solution is 0.8-1.0 times the volume of the nuclear grade mixed anion and cation resin.
[0015] Further, the molar ratio of lithium ions to hydroxyl ions in the nuclear grade mixed anion and cation resin is 1:1.
[0016] Further, the nuclear grade lithium type cation exchange resin is stirred and mixed for 15-20 minutes after being added to the mixed solution to obtain the nuclear grade mixed anion and cation resin.
[0017] Further, the nuclear grade lithium type cation exchange resin is a lithium type cation exchange resin converted to high lithium capacity by using a lithium hydroxide solution.
[0018] Further, the lithium type rate of the nuclear grade lithium type cation exchange resin is 99.90-99.99%.
[0019] Further, the nuclear grade hydroxyl type anion exchange resin comprises a cross-linked polystyrene with a quaternary amine group of hydroxyl ions.
[0020] Further, the volume exchange capacity of the nuclear grade hydroxyl type anion exchange resin is 1.10-1.25 mmol / ml, and the volume exchange capacity of the nuclear grade lithium type cation exchange resin is 1.75-2.56 mol / ml.
[0021] The application provides a method for uniformly mixing nuclear-grade anion-cation resin, which comprises the following steps: mixing nuclear-grade anion exchange resin with nuclear-grade lithium-type cation exchange resin, adding a lithium hydroxide solution with a certain concentration in advance, and controlling the volume ratio of the nuclear-grade anion exchange resin and the nuclear-grade lithium-type cation exchange resin according to the volume exchange capacity of the nuclear-grade anion exchange resin and the nuclear-grade lithium-type cation exchange resin, so that the molar ratio of lithium ions to hydroxyl ions in the mixed nuclear-grade anion-cation resin is 1:1, thereby effectively avoiding the problem of agglomeration of the nuclear-grade anion exchange resin and the nuclear-grade lithium-type cation exchange resin during mixing, ensuring that the nuclear-grade anion exchange resin and the nuclear-grade lithium-type cation exchange resin can be uniformly dispersed during mixing, and obtaining the mixed nuclear-grade anion-cation resin.
[0022] In addition, the application provides a method for uniformly mixing nuclear-grade anion-cation resin, which comprises the following steps: uniformly mixing nuclear-grade lithium-type cation exchange resin with nuclear-grade hydroxyl-type strong alkali anion exchange resin according to the molar ratio of anions (hydroxyl ions) to cations (lithium ions) of 1:1 to prepare nuclear-grade anion-cation resin, and using the nuclear-grade anion-cation resin to treat primary loop water of a nuclear power plant, so that LiOH.H2O can be generated when other impurity ions are removed, the pH value of effluent water is increased, and the effluent water is in a weak alkaline water quality environment, thereby reducing the corrosion of water quality on equipment and reducing the radiation field.
[0023] Meanwhile, the application provides a method for uniformly mixing nuclear-grade anion-cation resin, which has a short process flow, is convenient to operate, has low cost, does not introduce impurities in the process, and has high product purity, and belongs to a clean production process. BRIEF DESCRIPTION OF DRAWINGS
[0024] Figure 1 The application provides a method for uniformly mixing nuclear-grade anion-cation resin. DETAILED DESCRIPTION
[0025] Since the nuclear-grade lithium-type cation exchange resin and the nuclear-grade hydroxyl-type anion exchange resin are both subjected to purification treatment and have very low impurity content, when they are mixed according to a certain ratio, the mixed resin will agglomerate and is not easy to disperse because the surfaces of the anion resin and the cation resin respectively carry different charged ions, and it is difficult to obtain the mixed nuclear-grade anion-cation resin, therefore, the application provides a method for uniformly mixing nuclear-grade anion-cation resin.
[0026] Referring to Figure 1 The application provides a method for uniformly mixing nuclear-grade anion-cation resin, which comprises the following steps:
[0027] Step 1) Dissolving lithium hydroxide in water to obtain a lithium hydroxide solution.
[0028] The lithium hydroxide is dissolved in water in a lined reaction kettle provided with an internal electric stirrer.
[0029] The lithium hydroxide is produced by Beijing Boluosi Science and Technology Co., Ltd. 7 OH.H2O).
[0030] The concentration of the obtained lithium hydroxide solution is 0.5-2.5 g / L.
[0031] Step 2) The lithium hydroxide solution is added with a nuclear grade hydroxyl type anion exchange resin under stirring to obtain a mixed solution.
[0032] The nuclear grade hydroxyl type anion exchange resin comprises a cross-linked polystyrene with a quaternary amine group of hydroxyl ions.
[0033] Step 3) The mixed solution is added with a nuclear grade lithium type cation exchange resin under stirring to obtain a nuclear grade anion-cation mixed resin.
[0034] The nuclear grade lithium type cation exchange resin is a lithium type cation exchange resin with high lithium capacity converted from the lithium hydroxide solution.
[0035] The lithium type rate of the nuclear grade lithium type cation exchange resin is 99.90-99.99%.
[0036] The volume exchange capacity of the nuclear grade hydroxyl type anion exchange resin is 1.10-1.25 mmol / ml.
[0037] The volume exchange capacity of the nuclear grade lithium type cation exchange resin is 1.75-2.56 mmol / ml.
[0038] The volume exchange capacities of the nuclear grade hydroxyl type anion exchange resin and the nuclear grade lithium type cation exchange resin are different according to different manufacturers, different types and different batches. Therefore, the volume exchange capacities of the nuclear grade hydroxyl type anion exchange resin and the nuclear grade lithium type cation exchange resin are analyzed according to the national standard, and the mixing ratio of the two resins is determined according to the actually measured volume exchange capacities of the nuclear grade hydroxyl type anion exchange resin and the nuclear grade lithium type cation exchange resin, so as to ensure that the molar ratio of lithium ions to hydroxyl ions in the nuclear grade anion-cation mixed resin obtained by mixing the lithium hydroxide solution, the nuclear grade hydroxyl type anion exchange resin and the nuclear grade lithium type cation exchange resin is 1:1.
[0039] Then, the volume numbers of the nuclear grade hydroxyl type anion exchange resin and the nuclear grade lithium type cation exchange resin are calculated according to the total volume number of the required nuclear grade anion-cation mixed resin.
[0040] The volume of the lithium hydroxide solution is 0.8-1.0 times of the volume of the core-level anion-cation mixed resin.
[0041] The core-level hydrogen-oxygen type anion exchange resin has high chemical exchange capacity, good chemical performance stability and low impurity element content, and can meet the use requirements of nuclear power plants.
[0042] The mixed solution is stirred and mixed for 15-20 minutes to obtain the core-level anion-cation mixed resin.
[0043] The core-level anion-cation mixed resin is transferred to a packaging container, filtered, dried, packaged, and then stored in the warehouse after nitrogen is filled to remove air.
[0044] Step 4) The core-level anion-cation mixed resin is transferred to a packaging container, filtered, dried, packaged, and then stored in the warehouse after nitrogen is filled to remove air.
[0045] Specifically, the core-level anion-cation mixed resin is transferred to a packaging container, filtered and dried quickly, and then the dried core-level anion-cation mixed resin is packaged. After packaging, nitrogen is filled in the container containing the core-level mixed resin to remove air in the core-level anion-cation mixed resin package, and preferably the container is labeled and stored in the warehouse.
[0046] The nitrogen is used to remove air in the core-level anion-cation mixed resin package, and the purpose is to remove carbon dioxide in the air to avoid the combination of carbon dioxide and water to form carbonate ions and react with the core-level hydrogen-oxygen type anion exchange resin to contaminate the resin.
[0047] The nitrogen can also be replaced by other inert gases such as helium, neon, argon, etc.
[0048] The application provides a method for uniformly mixing nuclear-grade cationic and anionic resins, which comprises mixing nuclear-grade lithium cation exchange resin and nuclear-grade hydroxyl strong base anion exchange resin uniformly at a molar ratio of anions (hydroxyl) to cations (lithium ions) of 1:1 to form nuclear-grade cationic and anionic resins, which are used for treating primary loop water of nuclear power plants, and can generate LiOH.H2O when removing other impurity ions, so as to increase the pH value of effluent water and make the effluent water in a weak alkaline water quality environment, thereby reducing the corrosion of water quality to equipment and lowering radiation field.
[0049] In addition, the application provides a method for uniformly mixing nuclear-grade cationic and anionic resins, which has a short process flow, is convenient to operate, has low cost, does not introduce impurities in the process, and has high product purity, and belongs to a clean production process.
[0050] The method for uniformly mixing nuclear-grade cationic and anionic resins provided by the application is specifically described below through examples.
[0051] Example 1
[0052] A nuclear-grade lithium ion exchange resin has a volume exchange capacity of 1.8 mmol / L, and a nuclear-grade hydroxyl ion exchange resin has a volume exchange capacity of 1.2 mmol / L. 300 ml of the mixed resin sample is needed, and 120 ml of lithium cation exchange resin and 180 ml of hydroxyl anion exchange resin are needed according to calculation.
[0053] 240 ml of high-purity deionized water is added into a 1000 ml three-necked flask, and 0.24 g of lithium hydroxide is added under stirring until it is fully dissolved. Then, 180 ml of nuclear-grade anion exchange resin is added, and after stirring for a while, 120 ml of lithium cation exchange resin is slowly added. After stirring for 15 minutes, the mixture is transferred into a clean 500 ml sand core funnel for filtration. After filtration, the mixed resin is filled into a reagent bottle, a small amount of nitrogen is introduced to remove air in the reagent bottle, and the reagent bottle is sealed and stored. The obtained mixed resin is uniformly mixed, has good fluidity, and has no clumping phenomenon.
[0054] Example 2
[0055] A nuclear-grade lithium ion exchange resin has a volume exchange capacity of 2.4 mmol / L, and a nuclear-grade hydroxyl ion exchange resin has a volume exchange capacity of 1.2 mmol / L. 300 ml of the mixed resin sample is needed, and 100 ml of lithium cation exchange resin and 200 ml of hydroxyl anion exchange resin are needed according to calculation.
[0056] In 1000ml three-port bottle, add 250ml high purity deionized water, under stirring conditions, add 0.3g lithium hydroxide, after it is fully dissolved, add 200ml nuclear grade anion exchange resin, after adding, stir for a while, then slowly add 100ml lithium type cation exchange resin, after adding, continue to stir for 15 minutes. Transfer to clean 500ml sand core funnel to filter, after filtering, the mixed resin is loaded into reagent bottle, a small amount of nitrogen is introduced to remove air in the reagent bottle, and is stored in a sealed manner. The obtained mixed resin is mixed uniformly, has good fluidity, and has no clumping phenomenon.
[0057] Example 3
[0058] A nuclear grade lithium type ion exchange resin has a volume exchange capacity of 2.4mmol / L, and a nuclear grade hydroxyl type ion exchange resin has a volume exchange capacity of 1.2mmol / L. It is required to obtain 1500 liters of the mixed resin sample, and it is calculated that 500 liters of lithium type cation exchange resin and 1000 liters of hydroxyl type anion exchange resin are required.
[0059] In 3000 liters of clean enamel reaction kettle, add 1200L high purity deionized water, under stirring conditions, add 610g lithium hydroxide, after it is fully dissolved, add 1000 liters of nuclear grade anion exchange resin, after adding, stir for a while, then slowly add 500 liters of lithium type cation exchange resin, after adding, continue to stir for 15 minutes. Transfer to clean discharge to filter, after filtering, the mixed resin is loaded into 50L plastic barrels with inner membranes, a small amount of nitrogen is introduced to remove air in the resin, and is stored in a sealed manner. The obtained mixed resin is mixed uniformly, has good fluidity, and has no clumping phenomenon.
[0060] Finally, it should be explained that the above specific embodiments are only used to illustrate the technical solutions of the present application and not to limit, although the present application is described in detail with reference to examples, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present application, and they should be covered in the scope of the claims of the present application.
Claims
1. A method for uniformly mixing nuclear-grade anion and cation exchange resins, characterized in that, Includes the following steps: Lithium hydroxide is dissolved in water to obtain a lithium hydroxide solution; Nuclear-grade hydroxide anion exchange resin was added to the lithium hydroxide solution and stirred to obtain a mixed solution; Nuclear-grade lithium-type cation exchange resin was added to the mixed liquid and stirred to obtain nuclear-grade cation-cation mixed resin; The nuclear-grade cation-anion mixed resin is transferred to a packaging container, filtered, dried, packaged, and then stored after nitrogen purging to remove air.
2. The method for uniformly mixing nuclear-grade anion and cation exchange resins according to claim 1, characterized in that, The dissolution and mixing are carried out in an enamel-lined reactor equipped with a built-in electric stirrer.
3. The method for uniformly mixing nuclear-grade anion and cation exchange resins according to claim 1, characterized in that, The concentration of the lithium hydroxide solution is 0.5-2.5 g / L.
4. The method for uniformly mixing nuclear-grade anion and cation exchange resins according to claim 3, characterized in that, The volume of the lithium hydroxide solution is 0.8-1.0 times the volume of the nuclear-grade anion-cation mixed resin.
5. The method for uniformly mixing nuclear-grade anion and cation exchange resins according to claim 4, characterized in that, The molar ratio of lithium ions to hydroxide ions in the nuclear-grade anion-cation mixed resin is 1:
1.
6. The method for uniformly mixing nuclear-grade anion and cation exchange resins according to claim 5, characterized in that, After adding nuclear-grade lithium-type cation exchange resin to the mixture, stir and mix for 15-20 minutes to obtain nuclear-grade cation-cation mixed resin.
7. The method for uniformly mixing nuclear-grade anion and cation exchange resins according to claim 5, characterized in that, The nuclear-grade lithium-type cation exchange resin is a lithium-type cation exchange resin with high lithium capacity converted from lithium hydroxide solution.
8. The method for uniformly mixing nuclear-grade anion and cation exchange resins according to claim 7, characterized in that, The lithium form rate of the nuclear-grade lithium-type cation exchange resin is 99.90-99.99%.
9. The method for uniformly mixing nuclear-grade anion and cation exchange resins according to claim 8, characterized in that, The nuclear-grade hydroxide-type anion exchange resin is composed of cross-linked polystyrene with quaternary ammonium groups containing hydroxide ions.
10. The method for uniformly mixing nuclear-grade anion and cation exchange resins according to claim 9, characterized in that, The nuclear-grade hydroxide-type anion exchange resin has a volume exchange capacity of 1.10-1.25 mmol / ml, and the nuclear-grade lithium-type cation exchange resin has a volume exchange capacity of 1.75-2.56 mol / ml.