阅读说明：本技术 一种核电专用载钯除氧催化树脂的制备方法 (Preparation method of palladium-loaded deoxygenation catalytic resin special for nuclear power ) 是由 沈建华 修慧敏 楼政 汪国周 范赏 吴旭东 姜雷 于 2021-08-06 设计创作，主要内容包括：本发明公开了一种核电专用载钯除氧催化树脂的制备方法,包括如下步骤：(1)取已纯化好的氯型苯乙烯系强碱性阴离子交换树脂于反应釜中,加入已配置好的钯溶液,控制温度20-60℃,低速搅拌反应1-6小时后除去反应残液,降温后用纯水冲洗并用稀碱溶液调节pH至5-10,加入已配置好的水合肼水溶液,20-50℃反应1-5小时,除去反应残液,用纯水洗涤,即得Cl型载钯阴离子交换树脂；(2)将步骤(1)制得的所述Cl型载钯阴离子交换树脂转移至交换柱中,用碱溶液通过将其转成OH型,纯水淋洗后收集,即得OH型载钯强碱阴离子交换树脂。采用本发明方法制备的树脂同时具有除氧效率高、反应速度快、操作简单等优点,特别适合核电用水除氧。(The invention discloses a preparation method of palladium-loaded deoxygenation catalytic resin special for nuclear power, which comprises the following steps: (1) adding a prepared palladium solution into a purified chloro styrene strongly basic anion exchange resin in a reaction kettle, controlling the temperature to be 20-60 ℃, stirring at a low speed for reaction for 1-6 hours, removing reaction residual liquid, cooling, washing with pure water, adjusting the pH to 5-10 with a dilute alkali solution, adding a prepared hydrazine hydrate aqueous solution, reacting for 1-5 hours at 20-50 ℃, removing the reaction residual liquid, and washing with pure water to obtain Cl type palladium-loaded anion exchange resin; (2) and (2) transferring the Cl type palladium-loaded anion exchange resin prepared in the step (1) to an exchange column, converting the Cl type palladium-loaded anion exchange resin into an OH type by using an alkali solution, rinsing with pure water, and collecting to obtain the OH type palladium-loaded strong base anion exchange resin. The resin prepared by the method has the advantages of high deoxidization efficiency, high reaction speed, simple operation and the like, and is particularly suitable for deoxidization of nuclear power water.)

1. A preparation method of palladium-loaded oxygen-removing catalytic resin special for nuclear power is characterized by comprising the following steps:

(1) putting the purified chlorine type styrene strongly basic anion exchange resin into a reaction kettle, adding a prepared palladium solution, controlling the temperature to be 20-60 ℃, stirring at a low speed for reaction for 1-6 hours, removing reaction residual liquid, cooling, washing with pure water, adjusting the pH to 5-10 with a dilute alkali solution, adding a prepared hydrazine hydrate aqueous solution, reacting for 1-5 hours at 20-50 ℃, removing the reaction residual liquid, and washing with pure water to obtain the Cl type palladium-loaded anion exchange resin;

(2) and (2) transferring the Cl-type palladium-loaded anion exchange resin prepared in the step (1) to an exchange column, converting the Cl-type palladium-loaded anion exchange resin into an OH type by using an alkali solution through the Cl-type palladium-loaded anion exchange resin, rinsing with pure water, and collecting to obtain the OH-type palladium-loaded strong base anion exchange resin.

2. The preparation method of the palladium-supported oxygen-removing catalytic resin special for nuclear power as claimed in claim 1, wherein in the step (1), the particle size of the styrene anion exchange resin is 0.30-0.70 mm.

3. The preparation method of the palladium-supported oxygen-removing catalytic resin special for nuclear power as claimed in claim 1, wherein in the step (1), the palladium source in the palladium solution is selected from one or more of palladium chloride, palladium nitrate and palladium acetate.

4. The preparation method of the palladium-loaded oxygen-removing catalytic resin special for nuclear power as claimed in claim 3, wherein in the step (1), the specific preparation process of the palladium solution is as follows: the palladium source solid is dissolved with an acid and heated to form a palladium solution.

5. The preparation method of the palladium-loaded oxygen-removing catalytic resin special for nuclear power as claimed in claim 1, wherein in the step (1), the addition amount of the palladium solution is 1-3 times of the volume of the styrene anion exchange resin.

6. The preparation method of the palladium-loaded oxygen-removing catalytic resin special for nuclear power as claimed in claim 1, wherein in the step (1), the palladium solution adopts H₂PdCl₄Solution of and said H₂PdCl₄The concentration of the solution is 1-2 mol/L.

7. The preparation method of the palladium-supported oxygen-removing catalytic resin special for nuclear power as claimed in claim 1, wherein in the step (1), the addition amount of the hydrazine hydrate aqueous solution is 1-3 times of the volume of the styrene anion exchange resin.

8. The preparation method of the palladium-loaded oxygen-removing catalytic resin special for nuclear power as claimed in claim 1, wherein in the step (2), the addition amount of the alkali solution is 2-4 times of the volume of the styrene anion exchange resin.

9. The preparation method of the palladium-loaded oxygen-removing catalytic resin special for nuclear power as claimed in claim 1, wherein in the step (2), the concentration of the alkali solution is 3-5 wt%.

10. The preparation method of the palladium-loaded oxygen-removing catalytic resin special for nuclear power as claimed in claim 1, wherein in the step (2), the alkali solution adopts NaOH solution and/or NaHCO solution₃And (3) solution.

Technical Field

The invention relates to the technical field of ion exchange resins, in particular to a preparation method of a palladium-loaded oxygen-removing catalytic resin special for nuclear power.

Background

At normal temperature and pressure, water can dissolve certain oxygen, namely dissolved oxygen, and for drinking water, the higher the concentration of the dissolved oxygen in the water is, the better the water quality is, but for many industrial waters, the high concentration of the dissolved oxygen can cause corrosion of equipment or quality reduction of products. Although the dissolved oxygen in water is only about 8mg/L at normal temperature and pressure, the dissolved oxygen has great influence on industrial production. The traditional oxygen removing method mainly comprises thermal oxygen removing, vacuum oxygen removing, desorption oxygen removing and chemical oxygen removing, and any method has certain limitation due to the defects of the method, and the methods can not remove the dissolved oxygen in the water to about 10 mu g/L at all. And at present, the palladium-loaded deoxygenation technology in the water bodies is not suitable for deoxygenation of water for nuclear power plants.

Disclosure of Invention

The invention aims to provide a preparation method of a palladium-loaded uniform-particle oxygen-removing catalytic resin special for nuclear power aiming at the defects in the prior art, and the resin prepared by the method has the advantages of high oxygen-removing efficiency, high reaction speed, simplicity in operation and the like, and is particularly suitable for removing oxygen by water for nuclear power.

In order to achieve the purpose, the invention adopts the technical scheme that:

the invention provides a preparation method of a special palladium-loaded uniform-particle oxygen-removing catalytic resin for nuclear power, which comprises the following steps:

(1) putting the purified homogeneous particle chlorine type styrene strongly-alkaline anion exchange resin into a reaction kettle, adding a prepared palladium solution, controlling the temperature to be 20-60 ℃, stirring at a low speed for reaction for 1-6 hours, removing reaction residual liquid, cooling, washing with pure water, adjusting the pH to 5-10 with a dilute alkali solution, adding a prepared hydrazine hydrate aqueous solution, reacting for 1-5 hours at the temperature of 20-50 ℃, removing the reaction residual liquid, and washing with pure water to obtain the homogeneous particle chlorine type palladium-loaded anion exchange resin;

(2) and (2) transferring the uniform particle chlorine type palladium-loaded anion exchange resin prepared in the step (1) to an exchange column, converting the uniform particle chlorine type palladium-loaded anion exchange resin into an oxyhydrogen type by using an alkali solution, rinsing with pure water, and collecting to obtain the oxyhydrogen type palladium-loaded strong base anion exchange resin.

Preferably, in step (1), the particle size of the styrenic anion exchange resin is 0.6 ± 0.1 mm.

Preferably, in the step (1), the palladium source in the palladium solution is selected from one or more of palladium chloride, palladium nitrate and palladium acetate.

Preferably, in step (1), the specific preparation process of the palladium solution is as follows: the palladium source solid is dissolved with an acid and heated to form a palladium solution. Preferably, in the step (1), the palladium solution is added in an amount of 1 to 3 times by volume of the styrene-based anion exchange resin.

Preferably, in the step (1), the palladium solution adopts H₂PdCl₄Solution of and said H₂PdCl₄The concentration of the solution is 1-2 mol/L.

Preferably, in the step (1), the amount of the hydrazine hydrate aqueous solution added is 1 to 3 times the volume of the styrene-based anion exchange resin.

Preferably, in the step (2), the addition amount of the alkali solution is 2 to 4 times the volume of the styrene-based anion exchange resin.

Preferably, in step (2), the alkali solution has a concentration of 3 to 5 wt%.

Preferably, in step (2), the alkali solution is NaOH solution and/or NaHCO solution₃And (3) solution.

By adopting the technical scheme, compared with the prior art, the invention has the following technical effects:

the prior palladium-loaded catalytic resin in China has unstable performance, and is easy to have the phenomenon of trace Pd shedding in the long-time running process, so that the catalytic effect is reduced, the deoxidation cannot be stably and rapidly carried out, and the Pb concentration in water exceeds the water control requirement of a nuclear power station because the shed Pd enters the effluent, and the use of the nuclear power station cannot be met.

The invention takes the existing nuclear-grade resin (homogeneous styrene anion exchange resin) of Ningbo photo resin Limited company as a carrier, prepares nano Pd with proper size by optimizing and improving the reduction process, so that the nano Pd is just embedded in a three-dimensional cross-linked network framework of the resin, the Pd is prevented from falling off, the performance stability of the palladium-loaded catalytic resin is greatly improved, the purity of the prepared palladium-loaded catalytic resin is high, various performance indexes reach the control requirement of the nuclear-grade resin, the concentration of dissolved oxygen in primary operation water can be reduced to be below 20ug/L, and the water quality requirement of a nuclear power station is met.

Detailed Description

The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.

It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.

Example 1

100g of purified homogeneous particle chlorine type styrene strongly basic anion exchange resin is put into a beaker, and 100mL of 1mol/LH is added₂PdCl₄Controlling the temperature of the solution to be 40 ℃, stirring at a low speed for reaction for 3 hours, removing residual reaction liquid, washing with pure water after cooling, adjusting the pH to 9 with a dilute NaOH solution, pouring 100mL of a 1mol/L hydrazine hydrate aqueous solution into the reaction solution quickly at one time, reacting for 2 hours at 40 ℃, removing the residual reaction liquid, and washing with pure water to obtain chlorine type palladium-loaded resin; transferring to an exchange column, and purifying with 1BV of 4 wt% NaOH, 5BV of pure water, and 3BV of 10 wt% NaHCO₃And sequentially converting 5BV of pure water, 4BV of 4 wt% NaOH and 5BV of pure water into an oxyhydrogen type through the resin, and collecting the oxyhydrogen type palladium-loaded catalytic resin after the pure water is leached.

Example 2

100g of purified homogeneous particle chlorine type styrene strongly basic anion exchange resin is put into a beaker, and 80mL of 1mol/LH is added₂PdCl₄Controlling the temperature of the solution to be 40 ℃, stirring at a low speed for reaction for 3 hours, removing reaction residual liquid, washing with pure water after cooling, adjusting the pH to 9 with a dilute NaOH solution, adding 100mL of 1mol/L hydrazine hydrate aqueous solution into the reaction solution in a spraying manner through a radiation type solution distribution device, reacting for 2 hours at 40 ℃, removing the reaction residual liquid, and washing with pure water to obtain chlorine type palladium-carrying resin; transferring to an exchange column, and purifying with 1BV of 4 wt% NaOH, 5BV of pure water, and 3BV of 10 wt% NaHCO₃And sequentially converting 5BV of pure water, 4BV of 4 wt% NaOH and 5BV of pure water into an oxyhydrogen type through the resin, and collecting the oxyhydrogen type palladium-loaded catalytic resin after the pure water is leached.

Example 3

100g of purified homogeneous particle chlorine type styrene strongly basic anion exchange resin is put into a beaker, and 60mL of 2mol/LH is added₂PdCl₄Controlling the temperature of the solution to be 40 ℃, stirring at a low speed for reaction for 3 hours, removing residual reaction liquid, washing with pure water after cooling, adjusting the pH to 9 with a dilute NaOH solution, adding 100mL of a 3mol/L hydrazine hydrate aqueous solution into the reaction solution in a spraying manner through a radiation type solution distribution device, reacting for 2 hours at 40 ℃, removing the residual reaction liquid, and washing with pure water to obtain chlorine type palladium-loaded resin; transferring to an exchange column, and purifying with 1BV of 4 wt% NaOH, 5BV of pure water, and 3BV of 10 wt% NaHCO₃And sequentially converting 5BV of pure water, 4BV of 4 wt% NaOH and 5BV of pure water into an oxyhydrogen type through the resin, and collecting the oxyhydrogen type palladium-loaded catalytic resin after the pure water is leached.

Comparative example 1

100g of purified homogeneous particle chlorine type styrene strongly basic anion exchange resin is put into a beaker, and 100mL of 1mol/LH is added₂PdCl₄Controlling the temperature of the solution to be 40 ℃, stirring at a low speed for reaction for 3 hours, removing reaction residual liquid, washing with pure water after cooling, adjusting the pH to 9 with dilute NaOH solution, adding 100mL of 3mol/L hydrazine hydrate aqueous solution into the reaction solution by a method with a porous pipeline from top to bottom, reacting for 2 hours at 40 ℃, removing the reaction residual liquid, and washing with pure water to obtain chlorine type palladium-carrying resin; transferring to an exchange column with 1BV of 4 wt% NaOH, 5BV of pure water, 3BV of 10 wt% NaHCO₃5BV of pure water, 4BV of 4 wt% NaOH and 5BV of pure water are sequentially converted into an oxyhydrogen type through the resin, and the pure water isCollecting the hydrogen-oxygen type palladium-supported catalytic resin after water leaching.

Comparative example 2

100g of purified homogeneous particle chlorine type styrene strongly basic anion resin is taken to be put into a beaker, and 100mL of 1mol/LH is added₂PdCl₄Controlling the temperature of the solution to be 40 ℃, stirring at a low speed for reaction for 3 hours, removing reaction residual liquid, washing with pure water after cooling, adjusting the pH to 9 with a dilute NaOH solution, adding 100mL of a 3mol/L hydrazine hydrate aqueous solution into the reaction solution through a disc type pipeline in a rotating mode consistent with the stirring direction, reacting for 2 hours at 40 ℃, removing the reaction residual liquid, and washing with pure water to obtain chlorine type palladium-loaded resin; transferring to an exchange column, and purifying with 1BV of 4 wt% NaOH, 5BV of pure water, and 3BV of 10 wt% NaHCO₃And sequentially converting 5BV of pure water, 4BV of 4 wt% NaOH and 5BV of pure water into an oxyhydrogen type through the resin, and collecting the oxyhydrogen type palladium-loaded catalytic resin after the pure water is leached.

Application example 1

Respectively taking 50ml of the palladium-loaded catalytic resin prepared in the example 1-2, respectively adding the resin into a 250ml triangular flask with a plug, adding 200ml of pure water into the triangular flask, placing one part of the pure water at the room temperature of 25 ℃, placing one part of the pure water at the temperature of 50 ℃, oscillating the pure water all the time, placing the pure water for one month, and taking a soaking water sample every week to test the concentration of palladium ions; meanwhile, the existing catalytic resin is taken for comparison test. The palladium ion concentration (μ g/L) data in the soaking water is shown in Table 1 below:

TABLE 1

As can be seen from the soaking test data of different palladium-loaded resins, the palladium performance of the palladium-loaded catalytic resin is stable, and the phenomenon of palladium falling off does not occur in the soaking process.

Application example 2

The palladium-loaded catalytic resin 5L prepared by the method is placed in a special catalytic resin deoxygenation test device for disputing light, no air bubbles are kept in a resin layer, desalted water and hydrogen gas with saturated oxygen dissolved are repeatedly mixed through a pipeline mixer, the mixture passes through the test device from top to bottom at a certain flow rate, the water dissolved oxygen concentration and the palladium ion concentration are detected, and the deoxygenation performance of the palladium-loaded catalytic resin and the performance stability of the catalytic resin are analyzed. The palladium-loaded catalyzed resin oxygen scavenging operating test data is shown in table 2 below:

TABLE 2

Run time	The oxygen concentration of the effluent solution is mu g/L	The concentration of the palladium ions in the effluent is mu g/L
			1 month	1.6	0
2 months old	1.7	0
			3 months old	1.7	0
4 months old	1.6	0
			For 5 months	1.5	0
6 months old	1.6	0

Through application of test data, the dissolved saturated oxygen demineralized water passes through the catalytic resin, the dissolved oxygen concentration can be rapidly reduced from 8556 mu g/L to 2 mu g/L, the oxygen removal efficiency is very good, and the water consumption requirement of a nuclear power station is completely met.

While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.