Regeneration method of hydroxime extraction agent

Abstract

The invention discloses a regeneration method of a hydroxime extraction agent, and relates to the technical field of extraction agent regeneration. The regeneration method comprises the following steps: mixing a failed hydroxime extractant organic phase with a titanium silicalite molecular sieve, tert-butyl alcohol and a solvent, then adding ammonia water and hydrogen peroxide, and reacting to obtain a reactant; and separating reactants to obtain an organic phase, namely the organic phase of the hydroxime extractant. According to the regeneration method of the hydroxime extraction agent, the invalid hydroxime extraction agent can be effectively regenerated, and compared with an invalid organic phase, the obtained regenerated organic phase has the advantages that the copper extraction performance is obviously improved, the copper extraction rate is obviously increased, and the copper / iron separation coefficient is also increased. In addition, the regenerated organic phase also has good stability. Therefore, by adopting the regeneration method disclosed by the invention, the invalid hydroxime extraction agent in the copper extraction process can be regenerated, the regeneration effect is good, and the reduction of the production cost is facilitated.

Description

Technical Field

[0001] The present invention relates to the technical field of extractant regeneration, and particularly relates to a regeneration method for a hydroxime extractant. Background Art

[0002] In the existing zinc smelting system, for gallium-germanium replacement slag, it generally undergoes two-stage oxygen-enriched leaching and one-stage atmospheric pressure leaching. The obtained sulfuric acid solution containing gallium and germanium is used to recover gallium and germanium through extraction, while the raffinate is generally used to extract copper with a hydroxime extractant and electrolyze to obtain copper products, realizing the recovery of gallium, germanium, and copper. However, due to the instability of the oxime group (-C=N-OH), the hydroxime extractant is prone to failure during the copper extraction process, resulting in a decrease in the copper extraction capacity of the organic phase, a reduction in production efficiency, and even an inability to smoothly recover copper. Therefore, during the copper extraction process, the dosage of the hydroxime extractant is often large, and the extraction cost is high.

[0003] In order to solve the problems of large dosage and high cost of the hydroxime extractant, the prior art realizes the reuse of the extractant by regenerating the extraction organic phase, thereby ensuring the stable operation of production and reducing the production cost. However, the current extractant regeneration method has an unsatisfactory regeneration effect on the hydroxime extractant, and the copper extraction rate of the regenerated hydroxime extractant is not significantly improved, and the stability is also poor. Summary of the Invention

[0004] The present invention aims to at least solve the above technical problems existing in the prior art. For this reason, the object of the present invention is to provide a regeneration method for a hydroxime extractant, which reversely synthesizes the degradation products of the failed extractant into effective components through liquid-phase ammoximation to realize the regeneration of the hydroxime extractant. The regenerated hydroxime extractant has a high copper extraction rate and good stability.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0006] The present invention provides a regeneration method for a hydroxime extractant, comprising the following steps:

[0007] Mix the failed hydroxime extractant organic phase with titanium silicalite molecular sieve, tert-butanol, and a solvent, then add ammonia water and hydrogen peroxide, and react to obtain a reaction product; separate the reaction product to obtain the organic phase, which is the hydroxime extractant organic phase.

[0008] The stability of the oxime group in the hydroxime extractant is poor. When it comes into contact with MnO 4- , NO 3- and other plasma in acids and their solutions for a long time, it is prone to degradation reactions such as acid hydrolysis, oxidation, or nitration and fails. Through the analysis of the failed hydroxime extractant organic phase, the present invention finds that its active ingredient oxime compound degrades into aldehyde compounds, resulting in poor extraction effect, low copper extraction rate, and low copper / iron separation coefficient.

[0009] Through the method of liquid-phase ammoximation, the present invention reversely synthesizes the degraded product aldehyde compounds in the hydroxime extractant into the active ingredient oxime compounds, thereby effectively realizing the regeneration of the failed hydroxime extractant. Compared with the organic phase of the failed hydroxime extractant, the copper extraction rate of the obtained regenerated hydroxime extractant organic phase is significantly improved, and the copper / iron separation coefficient is also increased. In addition, the organic phase of the regenerated hydroxime extractant also has good stability and can be reused multiple times.

[0010] In some embodiments of the present invention, the hydroxime extractant is CP150.

[0011] In some embodiments of the present invention, the temperature of the reaction is 55-85 °C.

[0012] In some examples of the present invention, the temperature of the reaction is 60-80 °C.

[0013] In some specific examples of the present invention, the temperature of the reaction is 65-80 °C.

[0014] In some examples of the present invention, the temperature of the reaction is 70-75 °C.

[0015] In some embodiments of the present invention, the time of the reaction is 1-5 h.

[0016] In some examples of the present invention, the time of the reaction is 1-3 h.

[0017] In some specific examples of the present invention, the time of the reaction is 1.5-2.5 h.

[0018] In some embodiments of the present invention, the organic phase of the failed hydroxime extractant contains 5-nonylsalicylaldehyde; based on the molar amount of the 5-nonylsalicylaldehyde, the molar ratio of hydrogen peroxide to the organic phase of the failed hydroxime extractant is (1-2):1.

[0019] In some examples of the present invention, based on the molar amount of the 5-nonylsalicylaldehyde, the molar ratio of hydrogen peroxide to the organic phase of the failed hydroxime extractant is (1-1.6):1.

[0020] In some specific examples of the present invention, based on the molar amount of the 5-nonylsalicylaldehyde, the molar ratio of hydrogen peroxide to the organic phase of the failed hydroxime extractant is (1.2-1.4):1.

[0021] In some embodiments of the present invention, based on the molar amount of the 5-nonylsalicylaldehyde, the molar ratio of ammonia water to the organic phase of the failed hydroxime extractant is (1-3):1.

[0022] In some embodiments of the present invention, based on the molar amount of the 5-nonylsalicylaldehyde, the molar ratio of the ammonia water to the organic phase of the deactivated oxime extractant is (1-2):1.

[0023] In some specific embodiments of the present invention, based on the molar amount of the 5-nonylsalicylaldehyde, the molar ratio of the ammonia water to the organic phase of the deactivated oxime extractant is (1.5-1.7):1.

[0024] The temperature and time of the reaction and the ratio of the reaction raw materials will affect the copper extraction performance of the regenerated organic phase of the oxime extractant, that is, affect the copper extraction rate and the copper / iron separation coefficient.

[0025] In some embodiments of the present invention, the parameters of the titanium silicalite molecular sieve satisfy at least one of the following a)-d):

[0026] a) The specific surface area is 350-450 m 2 / g;

[0027] b) The pore diameter is 0.5-0.6 nm;

[0028] c) The particle size is 750-850 nm;

[0029] d) The silicon-titanium molar ratio is (30-40):1.

[0030] The titanium silicalite molecular sieve is used as a solid catalyst in the preparation method of the present invention, and its characteristic parameters affect its catalytic effect, thereby affecting the regeneration efficiency.

[0031] In some embodiments of the present invention, the hydrogen peroxide is a hydrogen peroxide solution with a mass fraction of 5-15%.

[0032] In some embodiments of the present invention, the mass fraction of the hydrogen peroxide solution is 8-12%.

[0033] In some embodiments of the present invention, the mass fraction of the ammonia water is 20-30%.

[0034] In some embodiments of the present invention, the mass fraction of the ammonia water is 23-27%.

[0035] In some embodiments of the present invention, the volume ratio of the 5-nonylsalicylaldehyde in the organic phase of the deactivated oxime extractant is 10-20%.

[0036] In some embodiments of the present invention, the volume ratio of the 5-nonylsalicylaldehyde in the organic phase of the deactivated oxime extractant is 14-16%.

[0037] To better calculate the dosage ratio of the hydroxime extractant to other raw materials, based on the volume fraction of 5-nonylsalicylaldehyde in the spent organic phase being 10-20%, the dosage ratio is matched according to the molar amount of 5-nonylsalicylaldehyde.

[0038] In some embodiments of the present invention, the solvent is water; the mass ratio of tert-butanol to water is (2-3):1.

[0039] In some embodiments of the present invention, the addition order of ammonia water and hydrogen peroxide is to add ammonia water first.

[0040] In some embodiments of the present invention, ammonia water and hydrogen peroxide are added in a dropwise manner; the total dropwise time is 0.1-2 h.

[0041] In some embodiments of the present invention, the reactants are subjected to solid-liquid separation to remove titanium silicalite molecular sieve, and then the organic phase is separated; the organic phase is also purified, and the purification includes successively washing the organic phase with sulfuric acid and water.

[0042] In some embodiments of the present invention, the method of solid-liquid separation includes filtration.

[0043] In some embodiments of the present invention, the purification step includes: washing with sulfuric acid 1-2 times, and then washing with water 3-4 times; when washing with sulfuric acid or water, the volume ratio of the organic phase to the aqueous phase (O / A) is (5-6):1.

[0044] In some specific embodiments of the present invention, the mass concentration of the sulfuric acid is 4-6%.

[0045] In some embodiments of the present invention, the spent hydroxime extractant organic phase is pretreated, and the pretreatment includes the following steps:

[0046] The spent hydroxime extractant organic phase is back-extracted with sulfuric acid, and the obtained organic phase is successively washed with water and ammonia water.

[0047] In some embodiments of the present invention, the concentration of the sulfuric acid is 180-210 g / L.

[0048] In some embodiments of the present invention, when washing with water, O / A is (5-6):1.

[0049] In some embodiments of the present invention, the ammonia water is dilute ammonia water; the mass fraction of the dilute ammonia water is 5%; when washing with the dilute ammonia water, O / A is (2-3):1

[0050] Compared with the prior art, the present invention has at least the following beneficial effects:

[0051] The regeneration method of the hydroxamic acid extractant of the present invention can effectively regenerate the ineffective hydroxamic acid extractant. Compared with the ineffective organic phase, the copper extraction performance of the regenerated hydroxamic acid extractant organic phase has been significantly improved, the copper extraction rate has been significantly increased, the copper / iron separation coefficient has also been improved, and the regenerated hydroxamic acid extractant organic phase also has good stability. It can be seen that by adopting the regeneration method of the present invention, the ineffective hydroxamic acid extractant in the copper extraction process can be regenerated, with good regeneration effect, simple process, suitable for industrialization, and conducive to reducing production costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 It is the regeneration principle of the hydroxamic acid extractant CP150 in the embodiment of the present invention.

[0053] Figure 2 It is the infrared spectrogram of the ineffective organic phase in the embodiment of the present invention.

[0054] Figure 3 It is the GC-MS analysis chart of the ineffective organic phase in the embodiment of the present invention.

[0055] Figure 4 It is the copper extraction performance chart of the regenerated CP150 organic phase in Examples 1-6 of the present invention.

[0056] Figure 5 It is the copper extraction performance chart of the regenerated CP150 organic phase in Examples 1 and 7-11 of the present invention.

[0057] Figure 6 It is the performance change chart of the regenerated CP150 organic phase in Example 1 of the present invention for repeated copper extraction. DETAILED DESCRIPTION OF THE INVENTION

[0058] The content of the present invention will be further described in detail through specific examples below. Unless otherwise specified, the raw materials, reagents or devices used in the examples and comparative examples can be obtained from conventional commercial channels or can be obtained by existing technical methods. Unless otherwise specified, the test or measurement methods are all conventional methods in the art.

[0059] Some of the raw materials used in the following examples of the present invention are described as follows:

[0060] Titanium silicalite molecular sieve: Conventional commercially available TS-1 molecular sieve, specific surface area 350-450m 2 / g, pore diameter 0.56-0.58nm, particle size 800nm, silicon-titanium molar ratio 30-40;

[0061] Hydrogen peroxide: Conventional commercially available, mass fraction 30%, diluted with deionized water to 10% for use;

[0062] Ammonia water: Conventional commercially available, mass fraction 25%;

[0063] Hydroxamic acid extractant: CP150;

[0064] All the reagents used in the embodiments of the present invention are of analytical purity and do not require further purification.

[0065] The spent organic phase (spent CP150 organic phase) used in the embodiments of the present invention comes from the copper extraction and recovery process of Zhongjin Lingnan Danxia Smelter and is obtained by back-extracting with 200 g / L sulfuric acid. The volume fraction of CP150 in the spent organic phase is 30%.

[0066] The regeneration mechanism of the hydroxamic acid extractant CP150 in the embodiments of the present invention is as Figure 1 shown. The following will be described in detail with specific embodiments.

[0067] Example 1

[0068] A method for regenerating a hydroxamic acid extractant comprises the following steps:

[0069] Pretreatment of the spent organic phase: Back-extract the spent organic phase once with 200 g / L sulfuric acid (O / A = 1:1, 10 min) to eliminate the influence of the loaded metal ions on the regeneration process, and then wash the spent organic phase. The washing process is as follows: First, perform one water wash (O / A = 5:1, 5 min), add 5% dilute ammonia water by mass fraction (O / A = 2:1) to the washed spent organic phase, shake the separating funnel by hand for 1 min and then separate the phases to obtain the organic phase, and then repeat the water wash once (O / A = 5:1, 5 min);

[0070] Regeneration of the spent organic phase: Add TS-1 molecular sieve (1.0 g), spent organic phase (the dosage is 70 mmol calculated according to the molar amount of the degradation product 5-nonylsalicylaldehyde, and the molar amount of 5-nonylsalicylaldehyde is calculated based on 15% of the volume of the spent organic phase), tert-butanol (44 g) and water (20 g) into a 500 mL four-necked round-bottom flask reactor equipped with a thermometer and a mechanical stirrer (200 rpm). When the reaction temperature reaches 70 °C, dropwise add ammonia water (112 mmol) and H2O2 (98 mmol). During the process, add ammonia water first and then H2O2. The total feeding time is controlled within 1 h. After adding, continue the reaction for 2 h; After the reaction is completed, cool down, remove the solid catalyst TS-1 molecular sieve with a microporous filter, and then separate the organic phase and the aqueous phase from the reactants with a separating funnel. The organic phase is first washed once with 5% sulfuric acid by mass fraction (O / A = 5:1), and then washed three times with deionized water (O / A = 5:1) to obtain the regenerated CP150 organic phase.

[0071] Among them, the content of 5-nonylsalicylaldehyde in the spent organic phase is obtained by back-calculating through the saturated adsorption capacity of the fresh extractant.

[0072] Example 2

[0073] A method for regenerating a hydroxime extractant, which is different from Example 1 in that: during the regeneration process of the spent organic phase, the reaction temperature is 55 °C; the rest is the same as in Example 1.

[0074] Example 3

[0075] A method for regenerating a hydroxime extractant, which is different from Example 1 in that: during the regeneration process of the spent organic phase, the reaction temperature is 60 °C; the rest is the same as in Example 1.

[0076] Example 4

[0077] A method for regenerating a hydroxime extractant, which is different from Example 1 in that: during the regeneration process of the spent organic phase, the reaction temperature is 65 °C; the rest is the same as in Example 1.

[0078] Example 5

[0079] A method for regenerating a hydroxime extractant, which is different from Example 1 in that: during the regeneration process of the spent organic phase, the reaction temperature is 75 °C; the rest is the same as in Example 1.

[0080] Example 6

[0081] A method for regenerating a hydroxime extractant, which is different from Example 1 in that: during the regeneration process of the spent organic phase, the reaction temperature is 80 °C; the rest is the same as in Example 1.

[0082] Example 7

[0083] A method for regenerating a hydroxime extractant, which is different from Example 1 in that: during the regeneration process of the spent organic phase, the molar ratio of H2O2 to the spent organic phase (calculated based on the molar amount of 5-nonylsalicylaldehyde) is 1:1, and the molar amount of 5-nonylsalicylaldehyde (i.e., the molar amount of the spent organic phase) is maintained at 70 mmol; the rest is the same as in Example 1.

[0084] Example 8

[0085] A method for regenerating a hydroxime extractant, which is different from Example 1 in that: during the regeneration process of the spent organic phase, the molar ratio of H2O2 to the spent organic phase (calculated based on the molar amount of 5-nonylsalicylaldehyde) is 1:1, and the molar amount of 5-nonylsalicylaldehyde (i.e., the molar amount of the spent organic phase) is maintained at 70 mmol; the rest is the same as in Example 1.

[0086] Example 9

[0087] A regeneration method of a hydroxime extractant, which is different from Example 1 in that: during the regeneration process of the spent organic phase, the molar ratio of H2O2 to the spent organic phase (calculated based on the molar amount of 5-nonylsalicylaldehyde) is 1:1.2, and the molar amount of 5-nonylsalicylaldehyde (i.e., the molar amount of the spent organic phase) is kept at 70 mmol; the rest is the same as in Example 1.

[0088] Example 10

[0089] A regeneration method of a hydroxime extractant, which is different from Example 1 in that: during the regeneration process of the spent organic phase, the molar ratio of H2O2 to the spent organic phase (calculated based on the molar amount of 5-nonylsalicylaldehyde) is 1:6, and the molar amount of 5-nonylsalicylaldehyde (i.e., the molar amount of the spent organic phase) is kept at 70 mmol; the rest is the same as in Example 1.

[0090] Example 11

[0091] A regeneration method of a hydroxime extractant, which is different from Example 1 in that: during the regeneration process of the spent organic phase, the molar ratio of H2O2 to the spent organic phase (calculated based on the molar amount of 5-nonylsalicylaldehyde) is 1:1.8, and the molar amount of 5-nonylsalicylaldehyde (i.e., the molar amount of the spent organic phase) is kept at 70 mmol; the rest is the same as in Example 1.

[0092] Result detection

[0093] 1. Identification and analysis of the spent organic phase (spent CP150 organic phase) in the examples:

[0094] (1) To understand the composition of the spent organic phase in the examples of the present invention, FTIR (Fourier transform infrared spectroscopy analysis) and GC-MS (gas chromatography-mass spectrometry analysis) were performed on the spent organic phase. Among them, during the GC-MS analysis, the spent organic phase was dissolved in dichloromethane solution, helium was used as the carrier gas, and a HP-5MS chromatographic column (30 m × 0.35 mm × 0.25 um) was used to analyze the polar substances in the spent organic phase; the sample inlet temperature was 300 °C, and the split ratio was 50:1; the column temperature was raised to 60 °C and held for 3 min, then raised to 260 °C at a rate of 5 °C / min, and finally raised to 300 °C at a rate of 50 °C / min and held for 1 min; the NIST 14.0 mass spectrometry database was used to compare the mixed organic substances in the spent organic phase.

[0095] The results are as Figure 2 and Figure 3 shown. It can be seen from Figure 2 that the active ingredient 5-nonylsalicylaldoxime in the spent organic phase is severely degraded, and a strong C=O stretching vibration peak appears in its infrared spectrum at 1658 cm -1 . This is related to the degradation products with carbonyl groups such as aldehydes. Further combined with Figure 3It can be seen that in the spent organic phase, the peak of the active ingredient 5-nonylsalicylaldoxime of CP150 (13 - 14 min) is weak, while the peak of the degradation product is strong (11 - 11.8 min). By calculating the peak area, it is found that about 90% of 5-nonylsalicylaldoxime has been degraded. Combining Figure 2 and Figure 3 analysis, its degradation product is 5-nonylsalicylaldehyde.

[0096] (2) The copper extraction performance and phase separation performance of fresh organic phase and spent organic phase were determined through extraction experiments. The extraction experiment process is as follows:

[0097] Mix 30 mL of fresh organic phase or spent organic phase (both containing light white oil and CP150) with a volume fraction of CP150 of 30% with 30 mL of feed liquid (containing Cu 2+ = 20 g / L, Fe 3+ = 2 g / L, pH = 2.5) in a 250 mL separating funnel, place it on an extraction oscillator and carry out the extraction process for 10 min at a rotation speed of 250 rpm. After extraction, phase separation is carried out; record the changes in the phase interface and the phase separation time during the phase separation process; the copper ion concentration in the raffinate is determined by ICP, and the copper extraction rate is calculated. The copper / iron separation coefficient is the ratio of the copper extraction rate to the iron extraction rate.

[0098] The results are shown in Table 1 below.

[0099] It can be seen that compared with the fresh organic phase, the copper extraction rate of the spent organic phase is reduced by about 50%, and the copper / iron separation coefficient decreases sharply, which also shows that due to the degradation of the active ingredient of the hydroxime extractant CP150 in the spent organic phase, the copper extraction ability of the spent organic phase decreases and the phase separation time is greatly extended.

[0100] Table 1 Comparison of the performance of fresh organic phase and spent organic phase

[0101] Copper extraction rate Copper / iron separation coefficient Phase separation time Fresh organic phase 70.44％ 95.15 2 min 3 s Failed organic phase 35.74％ 2.89 8 min 8 s

[0102] 2. Analyze the copper extraction ability of the CP150 organic phase regenerated in Examples 1 - 11:

[0103] The steps of the copper extraction experiment are as follows: Mix 30 mL of fresh organic phase / spent organic phase / regenerated organic phase with a volume fraction of CP150 of 30% with 30 mL of feed liquid (sulfuric acid system, containing Cu 2+ = 20 g / L, Fe 3+ = 2 g / L, pH = 2.5) in a 250 mL separating funnel, place it on an extraction oscillator and carry out the extraction process for 10 min at a rotation speed of 250 rpm. After extraction, phase separation is carried out; the copper ion concentration in the raffinate is determined by ICP, and the copper extraction rate is calculated.

[0104] (1) Analysis of copper extraction ability of regenerated CP150 organic phase in Examples 1 - 6:

[0105] The test results of Examples 1 - 6 are as Figure 4 shown. From Figure 4 it can be seen that the extraction rate of copper by the regenerated CP150 organic phase first gradually increases and then slowly decreases with the increase of the reaction temperature during regeneration. The increase of the reaction temperature enhances the catalytic activity of the TS-1 molecular sieve catalyst, which can, to a certain extent, inhibit the occurrence of non-catalytic oxidation reactions. However, when the temperature is too high, the generated oxime may be re-oxidized into aldehyde, accelerating side reactions such as the oxidation of aldehyde compounds and aldol condensation, resulting in a gradual decrease in the copper extraction rate. In addition, the copper / iron separation coefficient of the regenerated CP150 organic phase is higher than that of the failed organic phase and first increases and then decreases with the increase of the reaction temperature during the regeneration process. This is related to the formation of oxime compounds, and the change trend of the copper / iron separation coefficient is generally consistent with the copper extraction rate.

[0106] (2) Analysis of copper extraction ability of regenerated CP150 organic phase in Examples 1 and 7 - 11:

[0107] The comparative test results of Examples 1 and 7 - 11 are as Figure 5 shown. In the figure, the H2O2 / degradation product molar ratio represents the molar ratio of H2O2 to 5-nonylsalicylaldehyde, that is, the molar ratio of H2O2 to the failed organic phase. According to Figure 5 it can be seen that when the H2O2 / degradation product molar ratio is 1, due to the low yield of the regenerated product oxime, the copper extraction rate is low. With the increase of the molar ratio, the yield of the product increases, manifested as a gradual increase in the copper extraction rate. When the molar ratio increases to 1.6, the copper extraction rate significantly decreases because the excessive H2O2 begins to oxidize the intermediate hydroxylamine and the reaction substrate aldehyde, resulting in a poor selectivity during the regeneration process and an extended phase separation time of the obtained regenerated CP150 organic phase. In addition, the change trend of the copper / iron separation coefficient of the regenerated CP150 organic phase is generally consistent with the copper extraction rate.

[0108] Combining Figure 5 and Figure 6 it can be seen that the regeneration method of the present invention effectively regenerates the hydroxime extractant CP150, and the obtained regenerated CP150 organic phase has a good copper extraction rate, and the copper / iron separation coefficient has also been significantly improved compared with the failed organic phase.

[0109] 3. Analysis of the stability of copper extraction by the regenerated CP150 organic phase in Example 1:

[0110] The experimental process is as follows: 30 mL of the regenerated CP150 organic phase (Example 1) is mixed with 30 mL of the feed solution (sulfuric acid system, containing Cu 2+= 20 g / L, Fe 3+ = 2 g / L, pH = 2.5) was extracted for 10 min at a shaking rate of 250 rpm. After 10 min, the organic phase and the aqueous phase were separated; the loaded organic phase was back-extracted twice with 200 g / L sulfuric acid (O / A = 1.1, 10 min), and then the back-extracted organic phase was washed twice with water (O / A = 5.1, 50 min). The washed organic phase was then extracted with fresh feed solution for 10 min and repeated 5 times. The results are as Figure 6 shown.

[0111] Figure 6 In the figure, after the regenerated CP150 organic phase was repeatedly extracted 5 times, the extraction rate of copper was still significantly higher than that of the spent organic phase. Although the extraction rate decreased to less than 60% at the fourth time, it still remained stable at about 60%. It can be seen that the regeneration method of the present invention can effectively regenerate the hydroxime extractant, and the obtained regenerated CP150 organic phase has good stability.

[0112] In summary, the regeneration method of the hydroxime extractant of the present invention can effectively regenerate the spent hydroxime extractant. Compared with the spent organic phase, the copper extraction performance of the obtained regenerated organic phase has been significantly improved, the copper extraction rate has been significantly increased, and the copper / iron separation coefficient has also been improved. In addition, the regenerated organic phase also has good stability. It can be seen that by adopting the regeneration method of the present invention, the spent hydroxime extractant in the copper extraction process can be regenerated, and the regeneration effect is good, which is beneficial to reducing the production cost.

[0113] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent substitution methods and are all included in the protection scope of the present invention.

Claims

1. A method for regenerating a hydroxamic acid extractant, characterized in that, It includes the following steps: Mix the organic phase of the failed hydroxime extractant with titanium silicalite molecular sieve, tert-butanol and a solvent, then add ammonia water and hydrogen peroxide, and react to obtain a reaction product; separate the reaction product to obtain the organic phase, which is the organic phase of the hydroxime extractant.

2. The regeneration method according to claim 1, characterized in that, The temperature of the reaction is 55 - 85 °C; And / or, the reaction time is 1 - 5 h.

3. The regeneration method according to claim 1, characterized in that, The failed hydroxime extractant organic phase contains 5-nonylsalicylaldehyde; based on the molar amount of the 5-nonylsalicylaldehyde, the molar ratio of the hydrogen peroxide to the failed hydroxime extractant organic phase is (1 - 2):

1.

4. The regeneration method according to claim 3, characterized in that, Based on the molar amount of the 5-nonylsalicylaldehyde, the molar ratio of the ammonia water to the failed hydroxime extractant organic phase is (1 - 3):

1.

5. The regeneration method according to claim 1, wherein, The parameters of the titanium silicalite molecular sieve satisfy at least one of the following a) - d): a) Specific surface area is 350 - 450 m 2 / g; b) The pore diameter is 0.5 - 0.6 nm; c) The particle size is 750 - 850 nm; d) The silicon-titanium molar ratio is (30 - 40):

1.

6. The regeneration method according to claim 3 or 4, characterized in that, The hydrogen peroxide is a hydrogen peroxide solution with a mass fraction of 5 - 15%; And / or, the mass fraction of the ammonia water is 20 - 30%.

7. The regeneration method according to claim 3 or 4, characterized in that, The volume proportion of the 5-nonylsalicylaldehyde in the failed hydroxime extractant organic phase is 10 - 20%.

8. The regeneration method according to claim 1, wherein The solvent is water; the mass ratio of the tert-butanol to the water is (2 - 3):

1.

9. The regeneration method according to claim 1, characterized in that The reaction product is subjected to solid-liquid separation to remove the titanium silicalite molecular sieve, and then the organic phase is separated; the organic phase also undergoes purification, and the purification includes successively washing the organic phase with sulfuric acid and water.

10. The regeneration method according to claim 1, characterized in that, The failed hydroxime extractant organic phase is pretreated, and the pretreatment includes the following steps: Perform back extraction on the failed hydroxime extractant organic phase with sulfuric acid, and the obtained organic phase is successively washed with water and ammonia water.

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