Uranium removal method for high-acid high-chlorine associated ore waste liquid and vehicle-mounted device used by uranium removal method

Abstract

The invention discloses a uranium removal method for high-acid and high-chlorine associated ore waste liquid, uranium in the high-acid and high-chlorine associated ore waste liquid can be effectively adsorbed and removed by adopting high-acid and high-chlorine resistant uranium adsorption resin, the resin can be efficiently regenerated and utilized, a vehicle-mounted adsorption device is used, a resin tower adopts a modular drawer type adsorption tower, a tower body is of a drawable structure, the tower falling difficulty is reduced, and the service life of the tower is prolonged. And the resin abrasion is obviously reduced.

Description

Technical Field

[0001] The present invention relates to uranium removal from acidic uranium-containing waste liquid, and particularly to a method for removing uranium from waste liquid of associated minerals with high acid and high chlorine content and a vehicle-mounted device used therefor. Background Art

[0002] During the processing of associated radioactive ores such as zircon sand, highly acidic uranium-containing radioactive waste liquid with high chlorine content is generated, which greatly increases the difficulty of subsequent waste disposal and the risk of environmental control.

[0003] Currently, the neutralization precipitation method is generally used in the associated mineral industry to treat highly acidic wastewater with high chlorine content, but solid waste containing natural radioactive uranium is generated, resulting in a large environmental load.

[0004] Ion exchange method is a traditional uranium recovery technology. By using specific ion exchange resins to adsorb uranium ions in wastewater, this method has high selectivity and adsorption capacity, and can effectively reduce the uranium concentration in wastewater.

[0005] However, associated minerals such as zircon sand need to be leached with concentrated hydrochloric acid. The concentrations of hydrogen ions and chloride ions in the waste liquid of associated minerals are both high, and even the concentrations of hydrogen ions and chloride ions exceed 1 mol / L. When the chloride ion concentration exceeds 10 g / L, common anion exchange resins cannot effectively separate uranium.

[0006] Moreover, associated minerals and smelting sites are generally scattered. When resin adsorption is used, the problem of resin wear is obvious during the process of transporting the saturated resin adsorbed dispersedly to the central hydrometallurgical plant for centralized treatment, and the wear rate is as high as 20%-30%, and the service life is less than 1 year.

[0007] Therefore, there is an actual need for an effective uranium removal technology for waste liquid of associated minerals with high acid and high chlorine content. Summary of the Invention

[0008] To solve the above problems, the present invention provides a method for removing uranium from waste liquid of associated minerals with high acid and high chlorine content. By using a uranium adsorption resin resistant to high acid and high chlorine, it can effectively adsorb and remove uranium therein, and the resin can be efficiently regenerated and reused. A vehicle-mounted adsorption device is used, and the resin tower adopts a modular drawer-type adsorption tower, and the tower body is a pull-out structure, which reduces the difficulty of tower collapse and significantly reduces resin wear, thus completing the present invention.

[0009] The purpose of the present invention is to provide a method for removing uranium from waste liquid of associated minerals with high acid and high chlorine content. A uranium adsorption resin H6 or T1 (China Nuclear Haireg Technology Co., Ltd.) resistant to high acid and high chlorine is used as the adsorption resin to adsorb uranium in the waste liquid.

[0010] The uranium removal method provided by the present invention is applicable to waste liquid of associated minerals with high acid and high chlorine content, especially the following waste liquid of associated minerals with high acid and high chlorine content.

[0011] In a preferred embodiment of the present invention, in the high-acid and high-chloride associated ore waste liquid, the chloride ion concentration is 10 g / L or more, especially 35 g / L or more, more especially 100 g / L or more, and even up to 120 g / L or more.

[0012] In a preferred embodiment of the present invention, in the high-acid and high-chloride associated ore waste liquid, the hydrogen ion concentration is 0.01 g / L or more, especially 0.1 g / L or more, more especially 1 g / L or more.

[0013] In a preferred embodiment of the present invention, in the high-acid and high-chloride associated ore waste liquid, the uranium ion concentration is 0.01 g / L or more, especially 0.1 g / L or more, more especially 1 g / L or more.

[0014] In a preferred embodiment of the present invention, the method for removing uranium from the high-acid and high-chloride associated ore waste liquid comprises the following steps: (1) Resin activation pretreatment: soaking the high-acid and high-chloride resistant anion exchange resin with a resin activation solution; (2) Resin dynamic adsorption: dynamically adsorbing the high-acid and high-chloride associated ore waste liquid through the activated and pretreated high-acid and high-chloride resistant anion exchange resin.

[0015] Among them, the high-acid and high-chloride resistant anion exchange resin is H6 or T1.

[0016] In step (1), as the resin activation solution, a hydrochloric acid-sodium chloride solution is preferably used, especially a (0.5 - 1.5) M hydrochloric acid - (5 - 15)% sodium chloride solution, and especially a 1 M hydrochloric acid - 10% sodium chloride solution.

[0017] In step (1), the soaking time is not particularly limited, but preferably 1 hour or more, more preferably 2 hours or more, to ensure sufficient activation of the resin and then sufficient adsorption of the uranium ions in the high-acid and high-chloride associated ore waste liquid to be treated.

[0018] In step (2), the activated resin for dynamic adsorption is filled into an ion exchange column. In a preferred embodiment, it is filled and installed in series.

[0019] In practice, first obtain the ion exchange resin adsorption curve, then set the breakthrough uranium concentration, and according to the formula: saturation breakthrough ratio = saturated volume number / breakthrough volume number, determine the number of series columns through the saturation breakthrough ratio, and then obtain the resin adsorption saturation capacity in industrial production through the adsorption series column test.

[0020] Among them, the breakthrough uranium concentration ≤ 100 mg / L, such as 10 mg / L.

[0021] Preferably, the hydraulic retention time of the waste liquid for dynamic adsorption is controlled to be 1 - 5 hours, preferably 1 - 2.5 hours.

[0022] Preferably, an activated resin is filled and installed in an ion exchange resin column in a series of three columns. The ion exchange column used is a DN10*800mm ion exchange column (1 resin bed volume 1BV = 50 mL), the resin loading is 50 mL, and the breakthrough uranium concentration is set to 10 mg / L.

[0023] In a preferred embodiment of step (2), a series of three-column mode is adopted, the hydraulic retention time is controlled to be 1 - 2.5 hours, and the upward flow rate is 0.8 - 2.0 m / h. The waste liquid of the high-acid and high-chlorine associated ore is dynamically adsorbed, and the adsorption is stopped when the uranium concentration in the effluent reaches the breakthrough threshold (breakthrough uranium concentration). In a further preferred embodiment, the uranium removal method for the waste liquid of the high-acid and high-chlorine associated ore further comprises the following steps: (3) Resin desorption and regeneration: The high-acid and high-chlorine resistant anion exchange resin saturated with adsorption is desorbed and regenerated with water. Then, the above-mentioned step (2) of resin dynamic adsorption is repeated, and steps (3) and (2) can be cycled multiple times.

[0024] In step (3), pure water is used for resin desorption and regeneration. Preferably, pure water desorbs the saturated adsorption resin at a flow rate of 0.15 - 0.35 mL / min, and the desorption contact time is preferably 2.5 - 5 hours.

[0025] In a further preferred embodiment, the uranium removal method for the waste liquid of the high-acid and high-chlorine associated ore further comprises the following steps: (4) Uranium recovery: The desorbing solution obtained in step (3) is de-ironed by the jarosite process, neutralized to pH 7.0 - 7.5, and a yellow cake product is precipitated.

[0026] The uranium removal method for the waste liquid of the high-acid and high-chlorine associated ore provided by the present invention is preferably carried out by a vehicle-mounted mobile resin tower. The vehicle-mounted mobile resin tower includes a modular drawer-type structural unit, which is a pull-out resin filling module for detachable filling and removal of the resin.

[0027] In a preferred embodiment, the main body structure of the vehicle-mounted mobile resin tower is composed of a plurality of modular drawer-type structural units. The resin filling and disassembly are easy, the resin wear is greatly reduced, the wear rate is lower than 5%, and the service life is significantly extended to 5 years.

[0028] The structure of the vehicle-mounted mobile resin tower is as Figure 1 、 Figure 2As shown in the figure. The resin tower 1 is installed on the movable vehicle base 3 through a rotatable mechanism 2. A bracket 4 for supporting the resin tower 1 is arranged at the rear section of the base. A telescopic support column 5 is arranged at the bottom of the support. When the vehicle moves, the support column 5 retracts to a position where the bottom is higher than the wheels. When the vehicle stops for operations such as adsorbing and loading / unloading resin, the support column 5 extends to a position where the bottom is higher than the wheels, which is suitable for treating waste liquid in scattered mining areas.

[0029] The resin tower is equipped with a negative pressure suction system, and the resin loading and unloading process is operated in a closed manner. The resin tower always maintains the container closed throughout the entire operation process, so the risk of liquid leakage is greatly reduced.

[0030] The present invention has the following beneficial effects: (1) The method of the present invention can efficiently adsorb, separate and remove uranium ions from the waste liquid of high-acid and high-chlorine associated ores, and the removal rate of uranium ions in the waste liquid is as high as over 99%; (2) The resin selected by the method of the present invention is resistant to high acid and high chlorine, can efficiently adsorb uranium ions in a high-acid and high-chlorine environment, and can be efficiently desorbed and regenerated by water after being saturated with adsorbed uranium ions, and can be recycled; (3) The method of the present invention can be carried out by using a vehicle-mounted mobile resin tower, and can be conveniently operated in scattered mining areas; (4) In the method of the present invention, the resin tower used adopts a modular drawer-type adsorption tower, and the tower body is of a pull-out structure, which reduces the difficulty of tower collapse, significantly reduces resin wear, and greatly extends the service life. Description of the Drawings

[0031] Figure 1 Schematic structural diagram of the vehicle-mounted mobile resin tower showing the preferred embodiment of the present invention; Figure 2 Schematic structural diagram of the vehicle-mounted mobile resin tower showing the preferred embodiment of the present invention; Figure 3 Showing the ion exchange resin adsorption curve in Example 2; Figure 4 Showing the ion exchange resin adsorption saturation capacity in Example 2; Figure 5 Showing the elution experiment results in Example 3; Figure 6 Showing the saturation adsorption capacity maintenance rate of resins H6 and T1 after five dynamic adsorption-desorption regeneration cycles in Example 4; Detailed Embodiments The present invention will be described in detail below through specific embodiments, and the features and advantages of the present invention will become clearer and more definite with these descriptions.

[0032] Example 1 Resin Static Adsorption Prepare 7 kinds of resins as shown in Table 1 below. Among them, H6 (ZHONGHE HAIRUI GE TECHNOLOGY CO., LTD., H6), T1 (ZHONGHE HAIRUI GE TECHNOLOGY CO., LTD., T1), SQ (JIANGSU SUQING WATER TREATMENT ENGINEERING GROUP CO., LTD., D204), ZHENGGUANG (NINGBO ZHENGGUANG RESIN CO., LTD., ZGA307FM), H8 (ZHONGHE HAIRUI GE TECHNOLOGY CO., LTD., H8), T2 (ZHONGHE HAIRUI GE TECHNOLOGY CO., LTD., T1) are all soaked in 1M hydrochloric acid - 10% sodium chloride for 2 hours. Respectively measure 2 ml of resin samples and place them in 200 ml Erlenmeyer flasks. Add 100 ml of high-acid and high-chlorine associated ore waste liquid samples (uranium 1.2 g / L, hydrogen 1 g / L, chlorine 120 g / L, iron 9.64 g / L). Place the Erlenmeyer flasks containing the resin and the waste liquid on a shaker for contact adsorption. Take water samples at different adsorption times for analysis and determination of uranium concentration. Based on the analysis results, calculate the relative adsorption amount of uranium adsorbed by each ml of resin. The results are shown in Table 1 below.

[0033]

[0034] As can be seen from Table 1, compared with other commercially available anionic exchange resins, H6 and T1 have outstanding uranium adsorption performance for strong-acid and high-chlorine type cadmium waste liquid.

[0035] Example 2 Resin Dynamic Adsorption Select H6 and T1 resins with higher adsorption capacities for dynamic tests at 2 flow rates (hydraulic residence time 1 h and 2.5 h): High-acid and high-chlorine associated ore waste liquid samples (uranium 1.2 g / L, hydrogen 1 g / L, chlorine 120 g / L, iron 9.64 g / L). Respectively load H6 and T1 resins into DN10*800 mm ion exchange columns (1 resin bed volume 1BV = 50 mL), with a resin loading of 50 mL. Take adsorption tail liquid to detect uranium concentration at different volume numbers. When the uranium concentration in the effluent is equal to the uranium concentration in the original high-acid and high-chlorine associated ore waste liquid, stop the test and draw the ion exchange resin adsorption curve, as Figure 3 shown.

[0036] Set the breakthrough uranium concentration to 10 mg / L, breakthrough saturation ratio = saturated volume number / breakthrough volume number. According to the breakthrough saturation ratio, determine the number of series columns. Through the adsorption series column test, obtain the resin adsorption saturation capacity, as Figure 4 shown.

[0037] Among them, for the dynamic test at a flow rate of 50 ml / h (hydraulic residence time 1 h), the highest adsorption capacity of H6 reaches 23 mgU / ml resin, the breakthrough (uranium concentration < 100 mg / L) bed volume is 12BV, and the saturation is 33BV; for the dynamic test at a flow rate of 20 ml / h (hydraulic residence time 2.5 h), the highest adsorption capacity of H6 reaches 25 mgU / ml resin, the breakthrough bed volume is 17BV, and the saturation is 30BV.

[0038] Example 3 Column Adsorption Test and Elution Desorption Recovery High-acid and high-chlorine associated ore waste liquid sample (uranium 1.2 g / L, hydrogen 1 g / L, chlorine 120 g / L, iron 9.64 g / L), DN10*800 mm ion exchange column (1 resin bed volume 1 BV = 50 mL), resin loading 50 mL, resin is H6, three columns in series, hydraulic retention time controlled at 2.5 h, upward flow rate 0.8 m / h, resin saturation capacity is still 25 mgU / ml resin, adsorption tail liquid concentration: 10 mgU / L, uranium removal rate of the adsorption resin for high-acid and high-chlorine associated ore waste liquid is 99.2%.

[0039] Elution experimental group 1 (contact time 2.5 h group): Immerse 50 ml of H6 saturated resin with pure water, after soaking for 24 hours, with a pump speed of 0.2 r / min and a flow rate of 0.33 ml / min, a total of 500 ml of water is passed, 5 ml per tube every 15 min. After the test, the samples are sent for uranium measurement in separate tubes. The results are as shown in Table 2 and Figure 5 shown below.

[0040]

[0041] Elution experimental group 2 (contact time 5 h group): Immerse 50 ml of H6 saturated resin with pure water, after soaking for 24 hours, with a pump speed of 0.1 r / min and a flow rate of 0.17 ml / min, a total of 500 ml of water is passed, 5 ml per tube every 30 min. After the test, the samples are sent for uranium analysis in separate tubes. The results are as shown in Table 3 and Figure 5 shown below.

[0042]

[0043] Comparing the experimental results of the two elution conditions, it is found that: under the condition of similar final elution rates, which are 69.31% and 70.95% respectively, the elution efficiency is higher when choosing the condition group with a contact time of 2.5 h, and the uranium content in the qualified elution liquid is also higher.

[0044] Example 4 Resin Adsorption, Desorption and Regeneration The H6 and T1 resins that had been soaked in 1M hydrochloric acid and 10% sodium chloride for 2 hours were respectively loaded into the column. With a pump speed of 0.2 r / min and a flow rate of 0.33 ml / min, a total of 500 ml of high-acid and high-chloride associated ore waste liquid samples (uranium 1.2 g / L, hydrogen 1 g / L, chlorine 120 g / L, iron 9.64 g / L) were passed through for adsorption. After the adsorption was completed, the resin column was emptied, and approximately 5 ml of resin at the bottom (i.e., saturated resin) was taken. Then, 5 ml of new H6 and T1 resins that had been soaked in 1M hydrochloric acid and 10% sodium chloride for 2 hours were respectively loaded from the upper part, and the column was sealed. With a pump speed of 0.2 r / min and a flow rate of 0.33 ml / min, a total of 250 ml of pure water was passed through for desorption. After the desorption was completed, the resin column was emptied, and 5 ml of new H6 and T1 resins that had been soaked in 1M hydrochloric acid and 10% sodium chloride for 2 hours were respectively loaded, and the column was sealed. The above experimental steps were repeated five times in total to obtain a total of 20 5-ml resin samples, namely the saturated resins and desorbed resins in the five regeneration processes of H6 and T1. They were uniformly dried and sent for testing.

[0045] The maintenance rate of the saturated adsorption capacity of H6 and T1 resins after five dynamic adsorption-desorption regeneration cycles is as Figure 6 shown.

[0046] Example 5 Adopt a vehicle-mounted mobile resin tower as Figure 1 , Figure 2 shown. The mobile resin tower is a steel tower body, including 10 steel pull-out resin filling module units, with a diameter of 2.5 m and a tower body height of 10 m. The inner lining is polyolefin, and the surface head is EHA2500. The effective resin filling volume is 40 m³. The amount of high-acid and high-chloride associated ore waste liquid (uranium 1.2 g / L, hydrogen 1 g / L, chlorine120 g / L, iron 9.64 g / L) adsorbed and treated by a single tower is 600 m³.

[0047] The present invention has been described in detail above in combination with specific embodiments and / or exemplary examples and the drawings. However, these descriptions should not be construed as limiting the present invention. Those skilled in the art understand that without departing from the spirit and scope of the present invention, various equivalent substitutions, modifications, or improvements can be made to the technical solutions and implementation manners of the present invention, and these all fall within the scope of the present invention. The protection scope of the present invention is subject to the appended claims.

Claims

1. A method for removing uranium from the waste liquid of high-acid and high-chlorine associated ore, which uses a uranium adsorption resin H6 or T1 resistant to high acid and high chlorine as the adsorption resin to adsorb uranium in the waste liquid.

2. The method according to claim 1, wherein In the waste liquid of high-acid and high-chlorine associated ore, the chloride ion concentration is above 10 g / L; The hydrogen ion concentration is above 0.01 g / L; The uranium ion concentration is above 0.01 g / L.

3. The method according to claim 1, comprising the following steps: (1) Resin activation pretreatment: Soak the anion exchange resin resistant to high acid and high chlorine in a resin activation solution, and the anion exchange resin resistant to high acid and high chlorine is H6 or T1; (2) Resin dynamic adsorption: Pass the waste liquid of high-acid and high-chlorine associated ore through the anion exchange resin resistant to high acid and high chlorine pretreated by activation for dynamic adsorption.

4. The method according to claim 3, wherein, In step (1), As the resin activation solution, a hydrochloric acid-sodium chloride solution is used, The soaking time is more than 1 hour.

5. The method according to claim 3, wherein In step (2), the activated resin for dynamic adsorption is filled into an ion exchange column, and the ion exchange columns are installed in series.

6. The method according to claim 3, wherein, In step (2), first obtain the ion exchange resin adsorption curve, then set the breakthrough uranium concentration, and according to the formula: saturation breakthrough ratio = saturation volume number / breakthrough volume number, determine the number of series columns through the saturation breakthrough ratio, and then obtain the saturated adsorption capacity of the resin in industrial production through the adsorption series column test.

7. The method according to claim 3, wherein, In step (2), the hydraulic retention time of the waste liquid for dynamic adsorption is controlled to be 1 - 5 hours.

8. The method according to claim 3, further comprising the following steps: (3) Resin desorption and regeneration: Use water to desorb and regenerate the anion exchange resin resistant to high acid and high chlorine saturated with adsorption; Water desorbs the saturated adsorption resin at a flow rate of 0.15 - 0.35 mL / min, and the desorption contact time is 2.5 - 5 hours.

9. The method according to claim 3, further comprising the following steps: (4) Uranium recovery: After the desorbing solution obtained in step (3) is de-ironed by the jarosite method, it is neutralized to pH 7.0 - 7.5, and yellow cake products are precipitated.

10. The method according to any one of claims 1 - 9 is carried out through a vehicle-mounted mobile resin tower, and the vehicle-mounted mobile resin tower includes a modular drawer-type structural unit, which is a pull-out resin filling module for detachable filling and removal of the resin; Among them, The resin tower (1) is installed on the movable vehicle base (3) through a rotatable mechanism (2), a bracket (4) for supporting the resin tower (1) is arranged at the rear section of the base, and a telescopic support column (5) is arranged at the bottom of the support. When the vehicle moves, the support column (5) retracts to the bottom higher than the wheels, and when the vehicle stops for operations such as adsorption and loading and unloading of the resin, the support column (5) extends to the bottom higher than the wheels.

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