A method for modifying ion exchange resin for lithium resource recovery

Abstract

The present invention discloses a method for modifying a lithium resource recovery ion exchange resin, relating to the field of rare metal recovery technology; comprising the following steps: at room temperature, configuring a 5% mass fraction of hydrochloric acid solution to pickle HYC-100 resin, mechanically stirring the pickling solution after the pickling is completed, washing with pure water until neutral and then drying in a post-incubation oven, tail gas treatment: configuring a saturated NaOH solution, HCl and SO2 gases produced by the chlorination reaction and the triethylene glycol modification reaction need to be passed through this solution for treatment, chlorination reaction of the resin: under ice bath conditions, the reaction vessel is evacuated to vacuum and then passed through dry nitrogen, the outlet pipe is passed through a tail gas treatment device, and thionyl chloride solution is added under nitrogen protection. After the modified resin synthesized by the present invention is used for static adsorption of lithium ions, the adsorption capacity is generally increased by 3-4 times compared to traditional technologies, thereby improving the input and recovery ratio and further reducing costs.

Description

Technical Field

[0001] The present invention relates to the technical field of rare metal recovery, and in particular to a method for modifying an ion exchange resin for lithium resource recovery. Background Art

[0002] With the increasing depletion of lithium-ion battery raw material minerals in my country and the need for environmental protection, the recycling and reuse of resources from waste materials not only offers significant environmental benefits but also offers certain economic and social benefits, making it one of the most promising waste material disposal options in modern society. Recovering and separating the valuable metals from spent lithium batteries and developing and extracting lithium from them using economical and convenient methods are particularly important.

[0003] Lithium recovery methods include solvent extraction, precipitation, electrolysis, adsorption, and salting-out. In recent years, research on separating lithium from solutions using adsorption has been very active, and this method is particularly promising for aqueous phases with low lithium concentrations. The key to adsorption is the development of a high-performance adsorbent that exhibits excellent selectivity for lithium, enabling it to remove the large amounts of alkali metals present in the solution. Furthermore, the adsorbent must exhibit stable adsorption-elution properties to ensure suitability for large-scale operations.

[0004] Ion exchange resin is a functional polymer material with active exchange groups, serving as the material foundation for ion exchange separation operations. It is insoluble in common acidic and alkaline solutions and organic solvents, exhibits excellent chemical stability, and possesses ion exchange capacity. Ion exchange resin molecules can be divided into two parts: one is an immobile, multivalent polymer that forms the resin's backbone, endowing it with these excellent properties. This inert backbone and active groups are integrally linked and cannot move freely; the other is mobile ions, or active ions, which move in and out of the resin backbone, effectively performing ion exchange.

[0005] However, in the prior art, the adsorption efficiency of active ions is low, which leads to increased recovery costs.

[0006] To this end, the present invention proposes a method for modifying ion exchange resin for lithium resource recovery. Summary of the Invention

[0007] The purpose of the present invention is to solve the shortcomings of the prior art and to propose a method for modifying ion exchange resin for lithium resource recovery.

[0008] In order to achieve the above object, the present invention adopts the following technical solutions:

[0009] A method for modifying an ion exchange resin for lithium resource recovery comprises the following steps:

[0010] S1: At room temperature, prepare 5% mass fraction hydrochloric acid solution to pickle the HYC-100 resin. After mechanical stirring, filter out the pickling solution and wash with pure water until neutral, then dry in an oven;

[0011] S2: Tail gas treatment: Prepare saturated NaOH solution. HCl and SO2 gases produced by acyl chlorination reaction and triethylene glycol modification reaction need to be passed into this solution for treatment;

[0012] S3: Acylation reaction of the resin: Under ice bath conditions, the reaction vessel was evacuated to a vacuum and then introduced with dry nitrogen. The outlet pipe was connected to the tail gas treatment device. Under nitrogen protection, thionyl chloride solution was added. Mechanical stirring was started, and dry acid-washed resin was slowly added. Supplementary thionyl chloride was added. After the system stabilized, the ice bath was removed and the system was heated in a water bath for more than 6 hours.

[0013] S4: After the reaction is completed, filter and rinse the excess thionyl chloride on the resin with chloroform during filtration. Spread the filtered resin flat on a glass container and dry it in a fume hood for 1 hour. After drying, transfer it to a sealed glass container and store it in a desiccator for later use.

[0014] S5: Triethylene glycol + lithium chloride mixed DMF solution: Weigh triethylene glycol and lithium chloride, dissolve in anhydrous DMF solution, cover with a lid and magnetically stir to dissolve at 45°C;

[0015] S6: Triethylene glycol modification of acyl chloride resin: Under ice bath conditions, evacuate the reaction vessel to vacuum and introduce dry nitrogen. The outlet pipe is connected to the tail gas treatment device. Anhydrous DMF is transferred to the reaction vessel, and the resin in S4 is added. Triethylamine is added dropwise under mechanical stirring. After the addition of triethylamine is completed, the temperature is raised to 60°C. After the temperature stabilizes, the mixed solution of S5 is added dropwise. After the addition is completed, the reaction is carried out under nitrogen protection.

[0016] S7: Filtration, acid washing and drying S6 resin is washed with pure water during filtration, and then transferred into 0.05M dilute hydrochloric acid solution and stirred magnetically or mechanically for 3 hours; after acid washing, the acid washing solution is filtered out, and the resin is washed with pure water until neutral, and then placed in a 60°C oven for drying.

[0017] S8: Drying DMF: Use an oven to bake the activated 5A molecular sieve to remove water and dry it.

[0018] Preferably, in S1, the ratio of hydrochloric acid to resin is 9-13 ml: 1 g or 40 ml: 1 g.

[0019] Preferably, in S3, the mechanical stirring time is greater than 4 hours, and the oven temperature is 55-65 degrees Celsius.

[0020] Preferably, in S3, the method for determining whether the system is stable is: under ice bath conditions, the liquid surface no longer bubbles.

[0021] Preferably, in S3, the water bath is heated to 60 degrees Celsius at a rate of 2 degrees Celsius / min.

[0022] Preferably, in S5, the mass ratio of triethylene glycol to lithium chloride is 35:11.

[0023] Preferably: in S6, the amount of triethylamine used is half the mass of triethylene glycol.

[0024] Preferably, in S6, the reaction temperature under nitrogen protection is 55-65 degrees Celsius, and the reaction time is greater than 6 hours.

[0025] Preferably: in said S8, the oven temperature is 300-500 degrees Celsius.

[0026] The beneficial effects of the present invention are:

[0027] 1. The experimental synthesis process of the present invention is simple, eliminating complicated separation and purification operations, thereby greatly improving the efficiency of the adsorption process and reducing costs.

[0028] 2. After the modified resin synthesized by the present invention is used for static adsorption of lithium ions, the adsorption capacity is generally increased by 3-4 times compared with traditional technologies, thereby improving the input-recovery ratio and further reducing costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 The present invention provides a flow chart of a method for modifying ion exchange resins for lithium resource recovery. DETAILED DESCRIPTION

[0030] The technical solution of this patent is further described in detail below in conjunction with specific implementation methods.

[0031] In the description of this patent, it should be noted that, unless otherwise expressly specified or limited, the terms "installed," "connected," "connected," and "set" should be understood in a broad sense. For example, they can refer to fixed connection or set, detachable connection or set, or integral connection or set. Those skilled in the art will understand the specific meanings of the above terms in this patent based on the specific circumstances.

[0032] S1: At room temperature, prepare 5% mass fraction hydrochloric acid solution to pickle the HYC-100 resin. After mechanical stirring, filter out the pickling solution and wash with pure water until neutral, then dry in an oven;

[0033] S2: Tail gas treatment: Prepare saturated NaOH solution. HCl and SO2 gases produced by acyl chlorination reaction and triethylene glycol modification reaction need to be passed into this solution for treatment;

[0034] S3: Acylation reaction of the resin: Under ice bath conditions, the reaction vessel was evacuated to a vacuum and then introduced with dry nitrogen. The outlet pipe was connected to the tail gas treatment device. Under nitrogen protection, thionyl chloride solution was added. Mechanical stirring was started and dry acid-washed resin was slowly added. Supplementary thionyl chloride was added. After the system stabilized, the ice bath was removed and heated in a water bath. The reaction was carried out for more than 6 hours. A large amount of HCl and SO2 gas was generated during this process. About 0.3g HCl and 0.26g SO2 were generated for 1g resin.

[0035] S4: After the reaction is completed, filter and rinse the excess thionyl chloride on the resin with chloroform during filtration. Spread the filtered resin flat on a glass container and dry it in a fume hood for 1 hour. After drying, transfer it to a sealed glass container and store it in a desiccator for later use.

[0036] S5: Triethylene glycol + lithium chloride mixed DMF solution: Weigh triethylene glycol and lithium chloride, dissolve in anhydrous DMF solution, cover with a lid and magnetically stir to dissolve at 45°C;

[0037] S6: Triethylene glycol modification of acyl chloride resin: Under ice bath conditions, evacuate the reaction vessel to vacuum and introduce dry nitrogen. The outlet pipe is connected to the tail gas treatment device. Anhydrous DMF is transferred to the reaction vessel, and the resin in S4 is added. Triethylamine is added dropwise under mechanical stirring. After the addition of triethylamine is completed, the temperature is raised to 60°C. After the temperature stabilizes, the mixed solution of S5 is added dropwise. After the addition is completed, the reaction is carried out under nitrogen protection.

[0038] S7: Filtration, acid washing and drying S6 resin is washed with pure water during filtration, and then transferred into 0.05M dilute hydrochloric acid solution and stirred magnetically or mechanically for 3 hours; after acid washing, the acid washing solution is filtered out, and the resin is washed with pure water until neutral, and then placed in a 60°C oven for drying.

[0039] S8: Drying DMF: Use an oven to bake the activated 5A molecular sieve to remove water and dry it.

[0040] In the S1, the ratio of hydrochloric acid to resin is 9-13 ml: 1 g or 40 ml: 1 g.

[0041] In S3, the mechanical stirring time is greater than 4 hours, and the oven temperature is 55-65 degrees Celsius.

[0042] In S3, the method for determining whether the system is stable is: under ice bath conditions, the liquid surface no longer bubbles.

[0043] In S3, the water bath is heated to 60 degrees Celsius at a heating rate of 2 degrees Celsius / min.

[0044] In the S5, the mass ratio of triethylene glycol to lithium chloride is 35:11.

[0045] In the S6, the amount of triethylamine used is half the mass of triethylene glycol.

[0046] In S6, the reaction temperature under nitrogen protection is 55-65 degrees Celsius, and the reaction time is greater than 6 hours.

[0047] In the step S8, the oven temperature is 300-500 degrees Celsius.

[0048] Example 1:

[0049] A method for modifying an ion exchange resin for lithium resource recovery, comprising: step S1: acid-washing 5 g of HYC-100 resin with 200 ml of a 5% by mass hydrochloric acid solution at room temperature, mechanically stirring the solution for 4 hours, filtering out the acid wash solution, washing the resin with pure water until neutral, and drying the resin in an oven at 60 degrees Celsius;

[0050] S2: Tail gas treatment: Prepare saturated NaOH solution. HCl and SO2 gases produced by acyl chlorination reaction and triethylene glycol modification reaction need to be passed into this solution for treatment;

[0051] S3: Acylation reaction of the resin: Under ice bath conditions, the reaction vessel was evacuated to vacuum and then introduced with dry nitrogen. The outlet pipe was connected to the tail gas treatment device. Under nitrogen protection, 100 ml of thionyl chloride solution was added. Mechanical stirring was started and 5 g of dry acid-washed resin was slowly added. After the system stabilized, the ice bath was removed and the system was heated to 60 degrees Celsius in a water bath. The reaction was continued for more than 6 hours.

[0052] S4: After the reaction is completed, filter and rinse the excess thionyl chloride on the resin with chloroform during filtration. Spread the filtered resin flat on a glass container and dry it in a fume hood for 1 hour. After drying, transfer it to a sealed glass container and store it in a desiccator for later use.

[0053] S5: Triethylene glycol + lithium chloride mixed DMF solution: Weigh 14g triethylene glycol and 4.4g lithium chloride, dissolve in 50ml anhydrous DMF solution, cover with a lid and stir with magnetic stirring at 45°C;

[0054] S6: Triethylene glycol modification of acyl chloride resin: Under ice bath conditions, evacuate the reaction vessel to vacuum and then introduce dry nitrogen. The outlet pipe is connected to the tail gas treatment device. Measure 100 mL of anhydrous N,N-dimethylformamide solution and add it to the resin in S4. Add 7 mL of triethylamine dropwise under mechanical stirring. After the addition of triethylamine is complete, heat the mixture to 60°C. After the temperature stabilizes, add the S5 mixed solution dropwise. After the addition is complete, react under nitrogen protection.

[0055] S7: Filtration, acid washing and drying S6 resin is washed with pure water during filtration, and then transferred into 100 ml of 0.05 M dilute hydrochloric acid solution and stirred magnetically or mechanically for 3 hours; after the acid washing is completed, the acid washing solution is filtered out, and the resin is washed with pure water until neutral, and then placed in a 60°C oven for drying.

[0056] S8: Drying DMF: Use an oven to bake the activated 5A molecular sieve to remove water and dry it.

[0057] Example 2:

[0058] A method for modifying an ion exchange resin for lithium resource recovery, comprising: step S1: acid-washing 50 g of HYC-100 resin with 600 ml of a 5% by mass hydrochloric acid solution at room temperature, mechanically stirring the solution for 4 hours, filtering out the acid wash solution, washing the resin with pure water until neutral, and drying the resin in an oven at 60 degrees Celsius;

[0059] S2: Tail gas treatment: Prepare saturated NaOH solution. HCl and SO2 gases produced by acyl chlorination reaction and triethylene glycol modification reaction need to be passed into this solution for treatment;

[0060] S3: Acylation of the resin: Under ice bath conditions, evacuate the reaction vessel to vacuum and introduce dry nitrogen. The outlet pipe is connected to the tail gas treatment device. Under nitrogen protection, add 150 ml of thionyl chloride solution, start mechanical stirring, and slowly add dry acid-washed resin. After the system stabilizes, remove the ice bath and heat to 60 degrees Celsius in a water bath. React for more than 6 hours.

[0061] S4: After the reaction is completed, filter and rinse the excess thionyl chloride on the resin with chloroform during filtration. Spread the filtered resin flat on a glass container and dry it in a fume hood for 1 hour. After drying, transfer it to a sealed glass container and store it in a desiccator for later use.

[0062] S5: Triethylene glycol + lithium chloride mixed DMF solution: Weigh 140g triethylene glycol and 44g lithium chloride, dissolve in 150ml anhydrous DMF solution, cover and magnetically stir to dissolve at 45°C;

[0063] S6: Triethylene glycol modification of acyl chloride resin: Under ice bath conditions, evacuate the reaction vessel to vacuum and then introduce dry nitrogen. The outlet pipe is connected to the tail gas treatment device. Measure 100 mL of anhydrous N,N-dimethylformamide solution and add it to the resin in S4. Add 70 mL of triethylamine dropwise under mechanical stirring. After the addition of triethylamine is complete, heat the mixture to 60°C. After the temperature stabilizes, add the S5 mixed solution dropwise. After the addition is complete, react under nitrogen protection.

[0064] S7: Filtration, acid washing and drying S6 resin is washed with pure water during filtration, and then transferred into 500ml of 0.05M dilute hydrochloric acid solution and stirred magnetically or mechanically for 3h; after acid washing, the acid washing solution is filtered out, and the resin is washed with pure water until neutral, and then placed in a 60℃ oven for drying.

[0065] S8: Drying DMF: Use an oven to bake the activated 5A molecular sieve to remove water and dry it.

[0066] Example 3:

[0067] A method for modifying an ion exchange resin for lithium resource recovery, comprising: step S1: acid-washing 200 g of HYC-100 resin with 2000 ml of a 5% by mass hydrochloric acid solution at room temperature, mechanically stirring the solution for 4 hours, filtering out the acid wash solution, washing the resin with pure water until neutral, and drying the resin in a 60°C oven;

[0068] S2: Tail gas treatment: Prepare saturated NaOH solution. HCl and SO2 gases produced by acyl chlorination reaction and triethylene glycol modification reaction need to be passed into this solution for treatment;

[0069] S3: Acylation of the resin: Under ice bath conditions, evacuate the reaction vessel to vacuum and introduce dry nitrogen. The outlet pipe is connected to the tail gas treatment device. Under nitrogen protection, add 2000 ml of thionyl chloride solution, start mechanical stirring, and slowly add dry acid-washed resin. After the system stabilizes, remove the ice bath and heat to 60 degrees Celsius in a water bath. React for more than 6 hours.

[0070] S4: After the reaction is completed, filter and rinse the excess thionyl chloride on the resin with chloroform during filtration. Spread the filtered resin flat on a glass container and dry it in a fume hood for 1 hour. After drying, transfer it to a sealed glass container and store it in a desiccator for later use.

[0071] S5: Triethylene glycol + lithium chloride mixed DMF solution: Weigh 260g triethylene glycol and 176g lithium chloride, dissolve in 500ml anhydrous DMF solution, cover and magnetically stir to dissolve at 45°C;

[0072] S6: Triethylene glycol modification of acyl chloride resin: Under ice bath conditions, evacuate the reaction vessel to vacuum and introduce dry nitrogen. The outlet pipe is connected to the tail gas treatment device. Measure 100 mL of anhydrous N,N-dimethylformamide solution and add it to the resin in S4. Add 280 mL of triethylamine dropwise under mechanical stirring. After the addition of triethylamine is complete, heat the mixture to 60°C. After the temperature stabilizes, add the S5 mixed solution dropwise. After the addition is complete, react under nitrogen protection.

[0073] S7: Filtration, acid washing and drying The S6 resin is washed with pure water during filtration, and then transferred into 2000 ml of 0.05 M dilute hydrochloric acid solution and stirred magnetically or mechanically for 3 hours; after the acid washing is completed, the acid washing solution is filtered out, and the resin is washed with pure water until neutral, and then placed in a 60°C oven for drying.

[0074] S8: Drying DMF: Use an oven to bake the activated 5A molecular sieve to remove water and dry it.

[0075] The experimental synthesis part of the present invention has a simple process, which eliminates complicated separation and purification operations, thereby greatly improving the efficiency of the adsorption process and reducing costs.

[0076] In addition, after the modified resin prepared by synthesis is used for static adsorption of lithium ions, the adsorption capacity generally increases by 3-4 times compared with traditional technology, thereby improving the input and recovery ratio and further reducing costs.

[0077] The following table shows the adsorption capacity of Examples 1-3 compared with traditional adsorption technology

[0078]

[0079]

[0080] As can be seen from the above table, the maximum adsorption capacity of the present application far exceeds that of the conventional technology, and the adsorption capacity under the various ratios and conditions in Example 3 is optimal.

[0081] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. A method for modifying ion exchange resin for lithium resource recovery, characterized in that: The steps include: S1: At room temperature, prepare 5% mass fraction hydrochloric acid solution to pickle the HYC-100 resin. After mechanical stirring, filter out the pickling solution and wash with pure water until neutral, then dry in an oven; S2: Tail gas treatment: Prepare saturated NaOH solution. HCl and SO2 gases produced by acyl chlorination reaction and triethylene glycol modification reaction need to be passed into this solution for treatment; S3: Acylation reaction of the resin: Under ice bath conditions, the reaction vessel was evacuated to a vacuum and then introduced with dry nitrogen. The outlet pipe was connected to the tail gas treatment device. Under nitrogen protection, thionyl chloride solution was added. Mechanical stirring was started, and dry acid-washed resin was slowly added. Supplementary thionyl chloride was added. After the system stabilized, the ice bath was removed and the system was heated in a water bath for more than 6 hours. S4: After the reaction is completed, filter and rinse the excess thionyl chloride on the resin with chloroform during filtration. Spread the filtered resin flat on a glass container and dry it in a fume hood for 1 hour. After drying, transfer it to a sealed glass container and store it in a desiccator for later use. S5: Triethylene glycol + lithium chloride mixed DMF solution: Weigh triethylene glycol and lithium chloride, dissolve in anhydrous DMF solution, cover with a lid and magnetically stir to dissolve at 45°C; S6: Triethylene glycol modification of acyl chloride resin: Under ice bath conditions, evacuate the reaction vessel to vacuum and introduce dry nitrogen. The outlet pipe is connected to the tail gas treatment device. Anhydrous DMF is transferred to the reaction vessel, and the resin in S4 is added. Triethylamine is added dropwise under mechanical stirring. After the addition of triethylamine is completed, the temperature is raised to 60°C. After the temperature stabilizes, the mixed solution of S5 is added dropwise. After the addition is completed, the reaction is carried out under nitrogen protection. S7: Filtration, acid washing and drying The S6 resin is washed with pure water during filtration, and then transferred to 0.05M dilute hydrochloric acid solution and stirred magnetically or mechanically for 3 hours; after the acid washing is completed, the acid washing solution is filtered out, and the resin is washed with pure water until neutral, and then placed in a 60°C oven for drying; S8: Drying DMF: Use an oven to bake the activated 5A molecular sieve to remove water and dry it.

2. A lithium resource recovery ion exchange resin modification method according to claim 1, characterized in that, In the S1, the ratio of hydrochloric acid to resin is 9-13 ml: 1 g or 40 ml: 1 g.

3. A lithium resource recovery ion exchange resin modification method according to claim 1, characterized in that, In S3, the mechanical stirring time is greater than 4 hours, and the oven temperature is 55-65 degrees Celsius.

4. A lithium resource recovery ion exchange resin modification method according to claim 3, characterized in that, In S3, the method for determining whether the system is stable is: under ice bath conditions, the liquid surface no longer bubbles.

5. A lithium resource recovery ion exchange resin modification method according to claim 4, characterized in that, In S3, the water bath is heated to 60 degrees Celsius at a heating rate of 2 degrees Celsius / min.

6. A lithium resource recovery ion exchange resin modification method according to claim 1, characterized in that, In the S5, the mass ratio of triethylene glycol to lithium chloride is 35:

11.

7. A lithium resource recovery ion exchange resin modification method according to claim 1, characterized in that: In the S6, the amount of triethylamine used is half the mass of triethylene glycol.

8. A lithium resource recovery ion exchange resin modification method according to claim 7, characterized in that: In S6, the reaction temperature under nitrogen protection is 55-65 degrees Celsius, and the reaction time is greater than 6 hours.

9. The method for modifying an ion exchange resin for lithium resource recovery according to claim 1, wherein: In the step S8, the oven temperature is 300-500 degrees Celsius.

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