Novel phosphinic acid extraction agent and preparation method thereof

Abstract

The invention relates to the technical field of extraction solvents, and discloses a novel phosphinic acid extraction agent, which comprises the following components: sodium hypophosphite, diisobutylene, di-tert-butyl peroxide and diisobutylene, and a preparation method of the novel phosphinic acid extraction agent comprises the following steps: weighing 11.04 g of sodium hypophosphite, 8.64 g of acetic acid and 29g of diisobutylene, sequentially adding into a 200mL closed reaction container with a polytetrafluoroethylene lining, and stirring for 20 minutes; 0.63 g of di-tert-butyl peroxide is added under stirring; rapidly raising the temperature to 135 DEG C; the novel phosphinic acid extraction agent provided by the invention has higher extraction efficiency, good selectivity to cobalt, nickel and manganese ions, and excellent separation performance to metals such as cobalt, nickel and manganese, and is applied to the fields of traditional mine wet processes and precious metal recovery; compared with other phosphonic acid extraction agents (P204 and P507), the phosphonic acid extraction agent provided by the invention has remarkable advantages in the process of promoting movement of complexing structure balance from an octahedral complex to a tetrahedral polymer and in the conversion rate and concentration percentage of the tetrahedral structure.

Description

Technical Field

[0001] The invention relates to the technical field of extraction solvents, in particular to a novel phosphinic acid extractant and a preparation method thereof. Background Art

[0002] Solvent extraction is an important method of hydrometallurgy. It has the advantages of high product purity, low consumption of recycling and reuse, relatively simple operation, and low energy consumption. It is widely used in the fields of non-ferrous metal ion liquid purification, chemical separation, etc. Among them, phosphonic acid extractants (P204, P507) are more suitable for extracting cobalt from cobalt-nickel mixtures in acidic environments. Compared with P204 and P507, the new phosphinic acid extractant has higher extraction efficiency and good selectivity for cobalt, nickel, and manganese ions.

[0003] The structure of the cobalt complex in the organic phase can change from a hydrated-solvated pink octahedral complex CoR·2RH to an anhydrous-nonsolvated blue tetrahedral polymer (CoR2)x, thereby increasing the distribution coefficient. With the increase of temperature and cobalt concentration, the equilibrium between the octahedron and tetrahedron moves toward the tetrahedral complex. The separation coefficient of cobalt to nickel increases with the increase of the percentage of conversion to tetrahedron.

[0004] The novel phosphinic acid extractant prepared by the present invention has significant advantages over other phosphonic acid extractants (P204, P507) in promoting the process of complex structure equilibrium moving from octahedral complex to tetrahedral polymer, as well as the conversion rate and concentration percentage of the tetrahedral structure. Summary of the invention

[0005] The object of the present invention is to provide a novel phosphinic acid extractant and a preparation method thereof, so as to solve the problems raised in the above background technology.

[0006] To achieve the above object, the present invention provides the following technical solution: The structural formula of the novel phosphinic acid extractant is as follows:

[0007]

[0008] Ingredients: sodium hypophosphite, diisobutylene, di-tert-butyl peroxide and diisobutylene;

[0009] The mass ratio of the four raw materials is diisobutylene: sodium hypophosphite: acetic acid: di-tert-butyl peroxide = 1.00: 0.38: 0.3: 0.02, and the molar ratio is diisobutylene: sodium hypophosphite: acetic acid: di-tert-butyl peroxide = 1.000: 0.556: 0.452: 0.017.

[0010] A method for preparing a novel phosphinic acid extractant comprises the following steps:

[0011] Step 1: Weigh 11.04 g of sodium hypophosphite, 8.64 g of acetic acid, and 29 g of diisobutylene, add them in order into a 200 mL sealed reaction vessel with a polytetrafluoroethylene liner, add 0.63 g of di-tert-butyl peroxide while stirring, and quickly raise the temperature to 135°C;

[0012] Step 2: After 8 hours of heat preservation, the reaction system turned dark brown and cooled to room temperature. It was dissolved in petroleum ether for 20 minutes and then transferred to a 250 mL separatory funnel. It was washed with deionized water 2 to 3 times and then washed with 4% NaOH solution 3 times. 4 Acidify to pH>2;

[0013] Step 3: Finally, wash with deionized water twice until the pH of the aqueous phase is neutral (≥6), and remove anhydrous Na2SO 4 After drying, 79.2 g of a light amber product was obtained by vacuum distillation at 90°C, which was then refined and purified to obtain the final product.

[0014] The refining and purification in step 3 includes the following steps:

[0015] S1. Put 95g of the product into a 1000mL separatory funnel, add 1mol NaOH and 0.05mol potassium sodium tartrate, take about 460mL of the mixture, shake it to saponify, add 160mL of ether after cooling it slightly, shake it vigorously, and let it stand for phase separation. The water phase is detected to be strongly alkaline, so it is discarded;

[0016] S2. Transfer the extractant sodium soap into a 200mL beaker, heat in a water bath at 70-80℃ to remove ether. When the solution becomes viscous, add 900mL of distilled water and stir to make it a transparent solution. Slowly add the newly prepared CuSO4 solution (78g water) under vigorous stirring to completely precipitate the extractant copper salt, and obtain a fluffy light blue precipitate. Slightly heat to obtain a large particle precipitate, wash it with distilled water 3 times, and remove as much water as possible (the residual water content can be measured using a Karl-Fischer moisture meter);

[0017] S3. The above precipitate is made into a paste with 200 mL of ether, and then 250 mL of acetone is added. Stir vigorously, and add 200 mL of acetone after there are no large particles of precipitate to make the precipitation complete. Stir for 15 minutes and then heat. The precipitate particles become larger, and filter (filtrate recovery). The precipitate is washed with acetone 3 times. Repeat the operation twice to obtain pure copper salt;

[0018] S4. Dry the pure copper salt, grind it and transfer it into a 1000ml separatory funnel, add 200ml of ether and stir to dissolve (not completely dissolved), add 100ml (1:1) HCl to backwash, repeat 4 times until colorless, and then wash 5 times until the aqueous phase is free of Cl;

[0019] S5. Heat the ether solution of the extractant in a water bath to remove most of the ether, add anhydrous Na2SO4 (about 10 g) to remove water, and dry in a vacuum drying oven to obtain 67.4 g of a colorless product.

[0020] In summary, this application includes the following beneficial technical effects:

[0021] The novel phosphinic acid extractant proposed in the present application has higher extraction efficiency and good selectivity for cobalt, nickel and manganese ions. The extractant has excellent separation performance for metals such as cobalt, nickel and manganese, and is applied in the field of traditional mining wet process and precious metal recovery. It has significant advantages in promoting the process of complex structure balance moving from octahedral complex to tetrahedral polymer, as well as the conversion rate and concentration percentage of tetrahedral structure compared with other phosphonic acid extractants (P204, P507). BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 It is a schematic diagram of the structural formula of a novel phosphinic acid extractant of the present invention. DETAILED DESCRIPTION

[0023] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0024] See also Figure 1 The present invention provides a technical solution: the structural formula of the novel phosphinic acid extractant is as follows:

[0025]

[0026] Ingredients: sodium hypophosphite, diisobutylene, di-tert-butyl peroxide and diisobutylene;

[0027] The mass ratio of the four raw materials is diisobutylene: sodium hypophosphite: acetic acid: di-tert-butyl peroxide = 1.00: 0.38: 0.3: 0.02, and the molar ratio is diisobutylene: sodium hypophosphite: acetic acid: di-tert-butyl peroxide = 1.000: 0.556: 0.452: 0.017;

[0028] Physical and chemical properties: colorless or light amber liquid, specific gravity 0.92 (24°C); viscosity 142cP (25°C), 37cP (50°C); solubility in distilled water is 14μg / L (pH2.6), 36μg / L (pH3.7); pour point -36°C, flash point 108°C;

[0029] Weigh 11.04g of sodium hypophosphite, 8.64g of acetic acid, and 29g of diisobutylene, and add them in order to a 200mL sealed reaction vessel with a polytetrafluoroethylene liner, and add 0.63g of di-tert-butyl peroxide under stirring. Rapidly rise to 135°C, and observe from the sight glass that the color of the reaction material becomes darker, and the reaction is more intense. After keeping warm for 8 hours, the reaction system is dark brown. Cool to room temperature, dissolve in petroleum ether for 20 minutes, and then transfer to a 250mL separatory funnel, wash with deionized water 2 to 3 times, then wash with 4% NaOH solution 3 times, acidify with 10% H2SO4 to pH>2, and finally wash with deionized water twice until the pH of the aqueous phase is neutral (≥6), dry with anhydrous Na2SO4, and distill under reduced pressure at 90°C to obtain 79.2g of light amber product;

[0030] Product refining process:

[0031] S1. Put 95g of the product into a 1000mL separatory funnel, add 1mol NaOH and 0.05mol potassium sodium tartrate, take about 460mL of the mixture, shake it to saponify, add 160mL of ether after cooling it slightly, shake it vigorously, and let it stand for phase separation. The water phase is detected to be strongly alkaline, so it is discarded;

[0032] S2. Transfer the extractant sodium soap into a 200mL beaker, heat in a water bath at 70-80℃ to remove ether. When the solution becomes viscous, add 900mL of distilled water and stir to make it a transparent solution. Slowly add the newly prepared CuSO4 solution (78g water) under vigorous stirring to completely precipitate the extractant copper salt, and obtain a fluffy light blue precipitate. Slightly heat to obtain a large particle precipitate, wash it with distilled water 3 times, and remove as much water as possible (the residual water content can be measured using a Karl-Fischer moisture meter);

[0033] S3. The above precipitate is made into a paste with 200 mL of ether, and then 250 mL of acetone is added. Stir vigorously, and add 200 mL of acetone after there are no large particles of precipitate to make the precipitation complete. Stir for 15 minutes and then heat. The precipitate particles become larger, and filter (filtrate recovery). The precipitate is washed with acetone 3 times. Repeat the operation twice to obtain pure copper salt;

[0034] S4. Dry the pure copper salt, grind it and transfer it into a 1000ml separatory funnel, add 200ml of ether and stir to dissolve (not completely dissolved), add 100ml (1:1) HCl to backwash, repeat 4 times until colorless, and then wash 5 times until the aqueous phase is free of Cl;

[0035] S5. Heat the ether solution of the extractant in a water bath to remove most of the ether, add anhydrous Na2SO4 (about 10 g) to remove water, and dry in a vacuum drying oven to obtain 67.4 g of a colorless product.

[0036] Product performance comparison:

[0037] Table 1 Comparison of Cobalt / Nickel Separation Factors

[0038]

[0039] The comparison of product performance tests shows that compared with the other two commonly used phosphonic acid extractants, the refined new phosphinic acid extractant C16H35O2P has a significant advantage in the metal cobalt / nickel separation coefficient. This type of extractant has a relatively stable small-scale test process and excellent product performance, and is worthy of further in-depth research and development.

[0040] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0041] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A novel phosphinic acid extractant, the structural formula of the novel phosphinic acid extractant is as follows: Ingredients: sodium hypophosphite, diisobutylene, di-tert-butyl peroxide and diisobutylene; The mass ratio of the four raw materials is diisobutylene: sodium hypophosphite: acetic acid: di-tert-butyl peroxide = 1.00: 0.38: 0.3: 0.02, and the molar ratio is diisobutylene: sodium hypophosphite: acetic acid: di-tert-butyl peroxide = 1.000: 0.556: 0.452: 0.

017.

2. The method for preparing a novel phosphinic acid extractant according to claim 1, comprising the following steps: Step 1: Weigh 11.04 g of sodium hypophosphite, 8.64 g of acetic acid, and 29 g of diisobutylene, add them in order into a 200 mL sealed reaction vessel with a polytetrafluoroethylene liner, add 0.63 g of di-tert-butyl peroxide while stirring, and quickly raise the temperature to 135°C; Step 2: After 8 hours of heat preservation, the reaction system turns dark brown and cools to room temperature. It is dissolved in petroleum ether for 20 minutes and then transferred to a 250 mL separatory funnel. It is washed with deionized water 2 to 3 times and then washed with 4% NaOH solution 3 times. It is acidified with 10% H2SO4 to pH>2. Step 3: Finally, wash with deionized water twice until the pH of the aqueous phase is neutral (≥6), dry with anhydrous Na2SO4, and distill under reduced pressure at 90°C to obtain 79.2 g of a light amber product, which is then refined and purified to obtain the final product.

3. A novel phosphinic acid extractant and a preparation method thereof according to claim 2, characterized in that: The refining and purification in step 3 includes the following steps: S1. Put 95g of the product into a 1000mL separatory funnel, add 1mol NaOH and 0.05mol potassium sodium tartrate, take about 460mL of the mixture, shake it to saponify, add 160mL of ether after cooling it slightly, shake it vigorously, and let it stand for phase separation. The water phase is detected to be strongly alkaline, and the water phase is discarded; S2. Transfer the extractant sodium soap into a 200mL beaker, heat in a water bath at 70-80℃ to remove ether. When the solution becomes viscous, add 900mL of distilled water and stir to make it a transparent solution. Slowly add the newly prepared CuSO4 solution (78g water) under vigorous stirring to completely precipitate the extractant copper salt to obtain a fluffy light blue precipitate. Slightly heat to obtain a large particle precipitate, wash with distilled water 3 times, and remove water as much as possible (the residual water content can be measured using a Karl Fischer moisture meter); S3, the above precipitate is adjusted into a paste with 200 mL of ether, and then 250 mL of acetone is added. Stir vigorously, and add 200 mL of acetone after there is no large precipitate to make the precipitation complete. Stir for 15 minutes and then heat. The precipitate particles become larger, and filter (filtrate recovery). The precipitate is washed with acetone 3 times, and the operation is repeated twice to obtain pure copper salt; S4. Dry the pure copper salt, grind it and transfer it into a 1000ml separatory funnel, add 200ml of ether and stir to dissolve (not completely dissolved), add 100ml (1:1) HCl to backwash, repeat 4 times until colorless, and then wash 5 times until the aqueous phase is free of Cl; S5. Heat the ether solution of the extractant in a water bath to remove most of the ether, add anhydrous Na2SO4 (about 10 g) to remove water, and dry in a vacuum drying oven to obtain 67.4 g of a colorless product.

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