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CN-121992224-A - Method for recovering nickel, cobalt and magnesium from resin analysis liquid containing nickel, cobalt and magnesium

CN121992224ACN 121992224 ACN121992224 ACN 121992224ACN-121992224-A

Abstract

The invention discloses a method for recovering nickel, cobalt and magnesium from nickel, cobalt and magnesium containing resin analysis liquid, which comprises the steps of adding ammonium sulfate into nickel, freezing and crystallizing to recover nickel, removing nickel, crystallizing mother liquor to be used as washing acid liquor in a P507 cobalt extraction process, extracting and recovering cobalt by a P507 organic phase, and removing oil and impurities from magnesium containing raffinate to be subjected to MVR evaporation and crystallization to recover magnesium ammonium sulfate. According to the method for recovering nickel, cobalt and magnesium from the resin analysis liquid containing nickel, cobalt and magnesium, the gradual separation and comprehensive recovery of nickel, cobalt and magnesium are realized by organically combining multiple unit operations such as freezing crystallization, P507 extraction, MVR evaporation and the like. The integrated recovery method and the design of the material flow direction greatly simplify the recovery process, improve the recovery efficiency, reduce the consumption of fresh sulfuric acid by utilizing the original acidity, realize the internal circulation of the material and the reduction of waste, and accord with the ideas of green metallurgy and circular economy.

Inventors

  • FENG ZHIYONG
  • WANG JIAWEI
  • QIN RUYONG
  • HUANG XINRONG
  • WANG SHUWEI
  • YANG HUI
  • HUANG YIFENG
  • XIAO PENG
  • ZHONG CHANGMING

Assignees

  • 赣州寒锐新能源科技有限公司

Dates

Publication Date
20260508
Application Date
20260205

Claims (10)

  1. 1. A method for recovering nickel, cobalt and magnesium from resin analysis liquid containing nickel, cobalt and magnesium is characterized by comprising the following steps: S1, cooling the pretreated nickel-cobalt-magnesium-containing resin analysis liquid to a metastable zone by adopting a freezing crystallization method, adding nickel ammonium sulfate hexahydrate seed crystals, sieving and uniformly spraying on the surface of the dissolved nickel-cobalt-magnesium-containing resin analysis liquid, and then cooling, preserving heat and raising the temperature to recover high-purity nickel ammonium sulfate hexahydrate crystals; s2, enabling the nickel-removing crystallization mother liquor to enter a cobalt P507 line to serve as washing cobalt liquor, and respectively performing cobalt washing in a washing section and cobalt back extraction in an extraction section, wherein the cobalt back extraction process is specifically as follows: A1, adding the crystallization mother liquor for removing nickel into a washing section of a cobalt P507 extraction line for washing a loaded organic phase, wherein the flow ratio of the organic phase to the water phase in the washing section is (6-15): 1; a2, extracting and recovering cobalt through the P507 organic phase in an extraction section, wherein the flow ratio of the organic phase to the water phase in the extraction section is (1.5-4): 1; S3, removing oil and removing impurities from the magnesium-containing ammonium sulfate raffinate produced by the P507 extraction in the step S2, and recovering magnesium ammonium sulfate by MVR, wherein the magnesium-containing ammonium sulfate raffinate obtained by the P507 cobalt extraction is subjected to oil removal, resin adsorption impurity removal and evaporative crystallization in sequence, and a magnesium ammonium sulfate product is recovered.
  2. 2. The method for recovering nickel cobalt magnesium from the resin analysis liquid containing nickel cobalt magnesium according to claim 1, wherein the specific steps of recovering high-purity nickel ammonium sulfate hexahydrate crystals by adopting a freeze crystallization method in the step S1 are as follows: T1, heating a certain volume of analysis liquid to 65-75 ℃ in a water bath, stirring at the speed of 450-550r/min, and then adding solid industrial ammonium sulfate to fully dissolve for 1-1.5h; t2, cooling the analysis liquid fully dissolved in the step T1, and stirring; T3, cooling the fully dissolved analytic solution in the step T1 to a metastable zone through the cooling operation of the step T2, adding nickel ammonium sulfate hexahydrate seed crystals accounting for 0.5% -2% of the expected nickel ammonium sulfate yield, wherein the granularity of the seed crystals is 100-200 meshes, uniformly sprinkling a 100-200-mesh sieve on the surface of the fully dissolved analytic solution in the step T1, and stirring at a speed of 100-200r/min when the seed crystals are added; t4, slowly recovering the stirring speed to 250-350r/min after the seed crystal is added, finally cooling to-5 to-10 ℃, reducing the stirring speed to 100-200r/min, and continuing to keep the temperature for crystal growth for 1-2 hours; And T5, performing centrifugal filtration by adopting a step acceleration method, washing by adopting deionized water at 0-5 ℃ under high-speed centrifugation, spraying the washing liquid in a mist form and uniformly on the surface of a filter cake by using a sprayer or a washing pipe, and discharging to obtain high-purity nickel ammonium sulfate hexahydrate crystals.
  3. 3. The method for recovering nickel, cobalt and magnesium from the resin analysis solution containing nickel, cobalt and magnesium according to claim 2, wherein the analysis solution in the step T1 comprises the components of 25-40g/l of nickel, 3-6g/l of cobalt, 2-4g/l of magnesium and 2-5 g/l of total nitrogen, and the acidity of the analysis solution is 0.8-1.2N.
  4. 4. The method for recovering nickel, cobalt and magnesium from a resin solution containing nickel, cobalt and magnesium according to claim 2, wherein the amount of the solid industrial ammonium sulfate added in the step T1 is 0.95-1.05 times of the nickel content in the solution.
  5. 5. The method for recovering nickel, cobalt and magnesium from the resin analysis liquid containing nickel, cobalt and magnesium according to claim 2, wherein the temperature reduction rate of the analysis liquid fully dissolved in the step T1 in the step T2 is 0.1-0.5 ℃ per minute, and the stirring rate is 250-350r/min.
  6. 6. The method for recovering nickel, cobalt and magnesium from a resin desorption solution containing nickel, cobalt and magnesium according to claim 1, wherein the P507 organic phase extraction in the step a2 is liquid alkali saponification, and the saponification rate is 50% -60%.
  7. 7. The method for recovering nickel, cobalt and magnesium from the resin analysis liquid containing nickel, cobalt and magnesium according to claim 1, wherein the step S3 is carried out by adopting an activated carbon adsorption column for oil removal, and the oil content at the adsorption end point is less than or equal to 20ppm.
  8. 8. The method for recovering nickel, cobalt and magnesium from the resin desorption solution containing nickel, cobalt and magnesium according to claim 1, wherein the resin adsorption impurity removal in the step S3 is to remove and recover nickel and cobalt impurities by adopting nickel and cobalt chelate resin, and the flow rate BV=5-10 is controlled.
  9. 9. The method for recovering nickel, cobalt and magnesium from a resin analysis solution containing nickel, cobalt and magnesium according to claim 1, wherein the evaporative crystallization in the step S3 is MVR evaporative crystallization, and the operation temperature is 50-70 ℃.
  10. 10. The method for recovering nickel, cobalt and magnesium from the resin analysis liquid containing nickel, cobalt and magnesium according to claim 1, wherein the pretreatment in the step S1 is specifically filtering the resin analysis liquid containing nickel, cobalt and magnesium to remove suspended solid impurities, thereby obtaining a clarified liquid.

Description

Method for recovering nickel, cobalt and magnesium from resin analysis liquid containing nickel, cobalt and magnesium Technical Field The invention relates to the technical field of nickel-cobalt wet smelting, in particular to a method for recovering nickel-cobalt-magnesium from resin desorption liquid containing nickel-cobalt-magnesium. Background The magnesium-containing waste liquid produced in the nickel-cobalt wet smelting process mainly contains sodium sulfate and magnesium sulfate, and has the characteristics of high magnesium content, certain recovery value and significance. In the nickel cobalt wet smelting process, the raffinate or the soap-converted liquid containing low-concentration nickel cobalt is generally subjected to resin ion exchange method to recover nickel cobalt valuable metals, the analysis liquid containing nickel cobalt and magnesium is analyzed and recovered through sulfuric acid, and the nickel, cobalt and magnesium are effectively separated and recovered from the resin analysis liquid with complex components, so that the prior art may face the balance problem of product purity, recovery rate or economy. Referring to a method for solving the over-extraction of nickel and magnesium in a P507 cobalt extraction system with the publication number of CN113493871A, P204 raffinate or P507 back-extraction liquid is added into a mixing chamber at the later stage of an extraction stage, and after the P204 raffinate or the P507 back-extraction liquid is added, cobalt in a solution is extracted firstly because the binding capacity of an extractant to cobalt ions is stronger than that of nickel and magnesium ions, and nickel and magnesium ions which are extracted into an organic phase by the extractant are also replaced into a water phase by cobalt ions, so that the problem of over-extraction in the solution is solved rapidly and effectively. Referring to a washing method and a device for a P507 cobalt extraction system, disclosed in Chinese patent publication No. CN111270070A, sulfuric acid is added into an organic phase according to different extraction rates of cobalt, magnesium and nickel, the pH value of a solution is controlled to be 2.0-2.5, most of nickel is separated from the organic phase, meanwhile, part of magnesium is separated, hydrochloric acid is added, the pH value of the solution is controlled to be 1.5-2.0, and the rest of magnesium and the rest of nickel are separated from the organic phase. Comprehensive analysis of the above referenced patents may lead to the following drawbacks: 1) The existing method for recovering nickel, cobalt and magnesium from the resin analysis liquid containing nickel, cobalt and magnesium has poor nickel-cobalt separation effect, low product purity and large wastewater volume, for example, a method for solving the extraction and over-extraction of nickel and magnesium in a P507 cobalt extraction system and a washing method and device for the P507 cobalt extraction system of CN111270070A refer to a method of CN113493871A, which are recovered by adopting the P507 extraction method, and although the nickel-cobalt separation effect is good, the ammonium-containing solution cannot be integrated into the nickel extraction system for treatment, if an extraction line is added for treatment, the investment and treatment cost are obviously high; 2) The existing recovery technology also adopts an ion exchange resin method, is not applicable to the analysis liquid with high nickel and cobalt content, and has the advantages of small treatment capacity, long period and high resin cost. The nickel and magnesium are recovered by adopting a single freezing crystallization method, namely, the nickel-cobalt-magnesium-containing solution is mixed with ammonium sulfate, and the nickel-ammonium sulfate and the magnesium-ammonium sulfate are respectively crystallized by controlling different freezing temperatures, but the solubility difference of the nickel-ammonium sulfate and the magnesium-ammonium sulfate is small, the control difficulty is high, the separation coefficient is low, the product is cross-polluted, and meanwhile, a large amount of waste residues are easy to generate in the conventional recovery method, so that the high-efficiency synchronous recovery of nickel, cobalt and magnesium is difficult to realize. Disclosure of Invention (One) solving the technical problems Aiming at the defects of the prior art, the invention aims to provide a method for synchronously recovering nickel, cobalt and magnesium from a nickel-cobalt-magnesium-containing resin analysis solution in an efficient, economical and environment-friendly way, in particular to realize recycling of materials and reduction of wastes through technological innovation, so as to solve the problems that the existing nickel-cobalt separation effect is poor, the product purity is low, the wastewater quantity is large, the ion exchange resin method is inapplicable to the analysis solution with high