WO2024192575A1 - Procédé de recyclage d'eaux usées de nickel-cobalt-lithium-magnésium à forte dco et utilisation de ce procédé - Google Patents

Procédé de recyclage d'eaux usées de nickel-cobalt-lithium-magnésium à forte dco et utilisation de ce procédé Download PDF

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Publication number
WO2024192575A1
WO2024192575A1 PCT/CN2023/082233 CN2023082233W WO2024192575A1 WO 2024192575 A1 WO2024192575 A1 WO 2024192575A1 CN 2023082233 W CN2023082233 W CN 2023082233W WO 2024192575 A1 WO2024192575 A1 WO 2024192575A1
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Prior art keywords
magnesium
nickel
cobalt
lithium
liquid
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Chinese (zh)
Inventor
彭小聪
张荣荣
刘勇奇
李长东
巩勤学
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Priority to PCT/CN2023/082233 priority Critical patent/WO2024192575A1/fr
Priority to CN202380009013.2A priority patent/CN117083243B/zh
Publication of WO2024192575A1 publication Critical patent/WO2024192575A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/14—Magnesium hydroxide
    • C01F5/20—Magnesium hydroxide by precipitation from solutions of magnesium salts with ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/24—Treatment of water, waste water, or sewage by flotation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention belongs to the technical field of wastewater treatment and metal resource recycling, and specifically relates to a resource recovery method of high-COD nickel-cobalt-lithium-magnesium wastewater and its application.
  • lithium-ion batteries have been widely used due to their large energy storage, fast charge and discharge, long cycle life, and environmental friendliness.
  • Positive and negative electrode materials are the core key materials in lithium-ion batteries.
  • the lower limit of the energy density of lithium-ion batteries depends on the positive and negative electrode materials, and the positive and negative electrode materials account for 60% to 70% of the cost of lithium-ion batteries. Therefore, accelerating the research and development of positive and negative electrode materials and improving production processes will not only help improve the comprehensive performance of lithium-ion batteries, but may also significantly reduce the current high battery costs.
  • the wastewater is then evaporated and concentrated to obtain sodium sulfate and lithium sulfate.
  • This process relies on chemical precipitation to remove metals, and the loss of lithium is large, and the removal capacity is limited, which makes the back-end evaporation and concentration process have a high processing load, which increases the operating cost to a certain extent.
  • the current method of treating magnesium-containing wastewater containing heavy metals, high salinity and high COD uses sodium sulfide to remove nickel and cobalt, and some magnesium will be precipitated and re-enter the system; sodium sulfide is not only easy to cause environmental pollution, but also damages the health of workers in the working environment; sodium hydroxide is used to precipitate magnesium, and the amount of sodium hydroxide is large; the precipitation method also has the problem of high lithium loss. Therefore, there is an urgent need to develop a method for treating high COD nickel-cobalt-lithium-magnesium wastewater and realize resource utilization.
  • the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a resource recovery method and application of high COD nickel-cobalt-lithium-magnesium wastewater, and prepares Surface-modified hexagonal magnesium hydroxide flame retardant, and nickel and cobalt are recovered by precipitation in the rear concentrated liquid to achieve efficient recovery and high-value utilization of metals in wastewater and waste residues.
  • a method for recycling high COD nickel-cobalt-lithium-magnesium wastewater comprising the following steps:
  • the COD content of the high COD nickel-cobalt-lithium-magnesium wastewater is 1000-1500 mg/L, the nickel metal content is 30-100 mg/L, the cobalt metal content is 15-100 mg/L, the lithium metal content is 0.5-10 g/L, and the magnesium metal content is 50-150 mg/L.
  • step S1 the deoiling process is: firstly, a high-pressure CO2 aqueous solution or a high-pressure CO2 liquid is introduced into the high-COD nickel-cobalt-lithium-magnesium wastewater for flotation deoiling, and then the wastewater after flotation deoiling is subjected to adsorption deoiling through a filling column to obtain the deoiled liquid.
  • the high-pressure CO2 aqueous solution is a saturated CO2 pressurized aqueous solution
  • the pressurization pressure is 0.5-7Mpa
  • the dosage of the high-pressure CO2 aqueous solution is 8-12% of the volume of the high-COD nickel-cobalt-lithium-magnesium wastewater.
  • the flotation deoiling time is 2-4h.
  • the use of a high-pressure CO2 aqueous solution for flotation deoiling can utilize the process characteristics of CO2 precipitation from the solution under reduced pressure to gasify or agglomerate and float the micro-emulsified oil substances in the wastewater, and the high-pressure carbon dioxide can be reused by the air compressor after deoiling adsorption treatment, thereby reducing the consumption of auxiliary materials in the production process.
  • the present invention combines high-pressure CO2 aqueous solution for flotation oil removal and packed column adsorption oil removal, which can effectively reduce the COD content in wastewater, reduce the pollution of oil substances to adsorption resins in subsequent work stages, and enhance process stability.
  • step S1 the CO 2 after the flotation oil removal is purified by air filtration, compressed at a pressure of 0.5-1 MPa and reused in the flotation oil removal process.
  • step S1 the oil removal filler of the filling column is activated carbon or vinyl-acrylonitrile copolymer gel-type oil removal resin.
  • step S1 the COD content in the high COD nickel-cobalt-lithium-magnesium wastewater after oil removal is 50-200 mg/L.
  • the hydrogen ion type resin is a polystyrene molecular skeleton chelating resin.
  • step S2 the adsorption conditions of the hydrogen ion resin are: the resin absorption tower is filled with a height-to-diameter ratio of (2-3): 1, a flow rate of 4-5 BV/h, and the solution is controlled at a pH of 5-8.
  • step S2 further includes: desorbing and regenerating the adsorbed hydrogen ion resin with acid to obtain a nickel-cobalt desorption solution.
  • the acid used is sulfuric acid with a mass concentration of 10%-20%, and the pH value is maintained at 3 during the pickling process.
  • the sodium ion type resin is a styrene-divinylbenzene copolymer sulfonyl resin, a styrene-divinylbenzene cross-linked aminophosphonic acid chelating resin or a polystyrene copolymer type I quaternary amine functional resin.
  • step S3 the adsorption conditions of the sodium ion resin are: the resin absorption tower is filled with a height-to-diameter ratio of (2-3): 1, a flow rate of 3-5 BV/h, and the solution is controlled at a pH of 7-9.
  • step S3 sulfuric acid with a mass concentration of 10%-20% is used for desorption, and the pickling flow rate is 2-4 BV/h.
  • step S3 after desorption, the sodium ion resin is regenerated with a 20 wt % -30 wt % sodium hydroxide solution at a flow rate of 2-5 BV/h for 1-2 h.
  • step S3 further includes: performing MVR concentration on the secondary adsorption liquid to obtain sodium sulphate and concentrated liquid, and using sodium carbonate to precipitate lithium in the concentrated liquid to obtain crude lithium carbonate.
  • the secondary adsorption liquid itself has a high salt content, and sodium sulphate can be obtained by evaporating and concentrating it to 1/5-1/3 of the original volume.
  • step S4 the concentration of magnesium ions in the magnesium salt desorption solution is 0.5-2.5 mol/L.
  • step S4 the ammonia gas is introduced to maintain the solution pH at 10-12.
  • the organic phosphine chelating agent is at least one of hexamethylenediaminetetramethylenephosphonic acid (HDTMPA), ethylenediaminetetramethylenephosphonic acid, hydroxyethylidene diphosphonic acid (HEDP), aminotrimethylenephosphonic acid, hexylphosphonic acid or dodecylphosphonic acid.
  • HDTMPA hexamethylenediaminetetramethylenephosphonic acid
  • HEDP hydroxyethylidene diphosphonic acid
  • aminotrimethylenephosphonic acid hexylphosphonic acid or dodecylphosphonic acid.
  • step S4 the amount of the organic phosphine chelating agent added is 1 wt%-5 wt% of the theoretical output of magnesium hydroxide.
  • step S4 the temperature of the magnesium precipitation reaction is 40-80°C.
  • step S4 the aging time is 2-6 hours.
  • the mass concentration of the dilute acid is 1%-5%. Further, the dilute acid is dilute hydrochloric acid.
  • step S4 further includes: evaporating and concentrating the filtrate after the solid-liquid separation, recycling the evaporated ammonia gas to the magnesium precipitation operation, adding alkali to the evaporated and concentrated solution to adjust the pH value for precipitation, and obtaining nickel-cobalt slag. Furthermore, the nickel-cobalt slag is acid-dissolved and then returned to the hydrogen ion resin in step S2 for adsorption, and a nickel-cobalt desorption solution is obtained after desorption, or returned to the front-end extraction process for purification to produce a refined nickel-cobalt solution.
  • the present invention also provides application of the hexagonal magnesium hydroxide solid prepared by the resource recovery method in flame retardant materials.
  • the wastewater after COD removal of the present invention is subjected to the combined adsorption of hydrogen ion resin and sodium ion resin in two stages, which can increase the content of Mg ions in the magnesium salt desorption solution and reduce the content of nickel, cobalt and manganese metals, which is conducive to the subsequent acquisition of a higher purity hexagonal magnesium hydroxide flame retardant solid, and the nickel cobalt salt solution obtained by desorption can be directly reused in the front-end extraction process for purification and production of refined nickel cobalt salt products.
  • the best experimental process is to first adsorb nickel and cobalt, and then adsorb magnesium to achieve the separation of nickel, cobalt and magnesium.
  • nickel and cobalt Since the resin on the market that adsorbs nickel and cobalt has stronger selectivity, magnesium will only be entrained in small amounts due to the concentration difference between nickel, cobalt and magnesium, which does not affect the adsorption capacity of nickel and cobalt; if magnesium in the wastewater is adsorbed first, and then nickel and cobalt are adsorbed, on the one hand, when magnesium is adsorbed, nickel and cobalt will be adsorbed together, affecting the adsorption effect of the resin on magnesium, and on the other hand, increasing the loss of nickel and cobalt.
  • the present invention uses a special selective resin to adsorb nickel, cobalt and magnesium in stages, which can achieve short-range and efficient recycling.
  • the nickel, cobalt and lithium in the wastewater are collected, and the adsorption capacity of the two resins for Li ions is low.
  • the lithium in the liquid can be concentrated to produce sodium sulfate as a by-product, and the concentrated mother liquor is precipitated to obtain crude lithium carbonate, and the comprehensive recovery rate can reach 98%.
  • Organic phosphine chelating agents can chelate with Ni, Co, Ca, and Fe metal ions in the magnesium salt desorption solution. Under the alkaline conditions of ammonia, they will not precipitate or be sandwiched in the magnesium hydroxide precipitate.
  • the chelating agent has multiple phosphate groups, and its molecular chain can be preferentially adsorbed on the (001) and (101) crystal planes of magnesium hydroxide, and the (001) and (101) crystal planes are the main exposed surfaces of the regular hexagonal flakes. Therefore, the chelating agent has the function of regulating the growth direction of the magnesium hydroxide crystal form, and a hexagonal crystal structure suitable for flame retardants can be obtained.
  • the chelating agent can also be grafted onto the surface of the generated hexagonal magnesium hydroxide solid to modify it.
  • the carbon chain of the modified hexagonal magnesium hydroxide solid increases, and the thermal stability and flame retardant properties are improved. It can also improve the surface adhesion between magnesium hydroxide and the flame retardant matrix material and solve the problem of poor compatibility between the two, reaching the standard that can be added to the polymer for flame retardancy.
  • the precipitate obtained after the magnesium precipitation reaction is washed with dilute acid to remove the complex impurity metal ions on the surface and make the phosphate groups grafted on the surface become P(OH). If it is not washed with dilute acid, it may become P-O-M, which is not conducive to the flame retardancy of magnesium hydroxide.
  • the use of low-concentration dilute acid has less impact on the magnesium hydroxide solid.
  • FIG1 is a process flow chart of Example 1 of the present invention.
  • FIG2 is a schematic diagram of the principle of magnesium hydroxide surface modified by hexamethylenediaminetetramethylenephosphonic acid (HDTMPA) of the present invention
  • FIG3 is a SEM image of surface-modified hexagonal magnesium hydroxide with different addition amounts (1%, 3%, 5%) of hexamethylenediaminetetramethylenephosphonic acid (HDTMPA) of the present invention
  • FIG4 is a SEM image of magnesium hydroxide prepared by direct precipitation without using a chelating agent in Comparative Example 2 of the present invention.
  • FIG5 is the DSC curves of magnesium hydroxide before (a) and after (b) modification.
  • a resource recovery method for high COD nickel-cobalt-lithium-magnesium wastewater referring to FIG1, the specific process is as follows:
  • Step (1) after the high COD nickel-cobalt-lithium-magnesium wastewater is allowed to stand, a 0.5MPa CO2 aqueous solution is introduced to perform flotation oil removal operation for 4 hours, wherein the amount of the high-pressure CO2 aqueous solution is 10% of the volume of the high COD nickel-cobalt-lithium-magnesium wastewater, and the COD content of the high COD nickel-cobalt-lithium-magnesium wastewater is 1500mg/L, the nickel metal content is 100mg/L, the cobalt metal content is 35mg/L, the lithium metal content is 10g/L, and the magnesium metal content is 150mg/L;
  • Step (2) the wastewater after flotation oil removal is passed through an activated carbon column for adsorption oil removal again, and the COD of the solution can be reduced to 150 mg/L;
  • Step (3) using a polystyrene molecular skeleton chelating resin (hydrogen ion resin D463 resin of Xi'an Lanxiao Technology Co., Ltd.) to adsorb Ni and Co metal ions on the wastewater obtained in step (2); the resin absorption tower is filled with a height-to-diameter ratio of 2:1, the flow rate is 4BV/h, the solution is controlled to have a pH of 5, and a post-adsorption liquid is obtained after the adsorption operation; using 10% sulfuric acid to desorb and regenerate the polystyrene molecular skeleton chelating resin, and the pH is maintained at 3 during the pickling process to obtain a nickel-cobalt sulfate desorption solution containing 2.4 g/L nickel, 0.9 g/L cobalt, and 0.1 g/L magnesium;
  • a polystyrene molecular skeleton chelating resin hydrogen ion resin D463 resin of Xi'an Lanxiao Technology
  • Step (4) passing the primary adsorption liquid obtained in step (3) into a styrene-divinylbenzene cross-linked aminophosphonic acid chelating resin (Xi'an Lanxiao Technology Co., Ltd. aminophosphonic acid chelating resin LSC-850) for Mg metal ion adsorption, wherein the operating conditions are a resin absorption tower filling height-to-diameter ratio of 3:1, a flow rate of 5 BV/h, and a solution pH controlled at 9, to obtain a secondary adsorption liquid after the operation; the secondary adsorption liquid is subjected to MVR concentration and crystallization to obtain sodium sulfate, and the concentrated mother liquor is subjected to lithium precipitation operation using sodium carbonate to obtain crude lithium carbonate;
  • Step (5) using 10% sulfuric acid at a flow rate of 2 BV/h to desorb the saturated styrene-divinylbenzene copolymer sulfonyl resin in step (4) to obtain a magnesium sulfate desorption solution; then using a 20% sodium hydroxide solution at a flow rate of 5 BV/h to regenerate the styrene-divinylbenzene copolymer sulfonyl resin for 2 hours;
  • Step (6) adding a chelating agent HDTMPA, introducing ammonia gas to the magnesium salt desorption solution to carry out a magnesium precipitation reaction, wherein the concentration of the magnesium salt desorption solution is 0.5 mol/L, and ammonia gas is introduced to maintain the solution pH at 10.
  • the amount of chelating agent added is 1% of the theoretical yield of magnesium hydroxide, the reaction temperature is 40° C., and the precipitation aging reaction time is 2 h; after aging and filtering, washing with water and then washing with 1% dilute hydrochloric acid, and finally washing with water, and drying to obtain a hexagonal magnesium hydroxide solid;
  • Step (7) after filtering the magnesium precipitate in step (6), the filtrate obtained is evaporated and concentrated, the evaporated ammonia is recycled to step (6), and soda ash is added to the concentrated mother liquor for value adjustment and precipitation to obtain nickel-cobalt slag; the nickel-cobalt slag is dissolved with low acid to obtain an acid solution which is returned to step (3) for nickel-cobalt metal adsorption and desorption operations for recovery.
  • a resource recovery method for high COD nickel-cobalt-lithium-magnesium wastewater, the specific process is:
  • Step (1) after the high COD nickel-cobalt-lithium-magnesium wastewater is allowed to stand, a 3MPa CO2 aqueous solution is introduced to perform flotation oil removal operation for 3 hours, wherein the amount of the high-pressure CO2 aqueous solution is 8% of the volume of the high COD nickel-cobalt-lithium-magnesium wastewater, and the COD content of the high COD nickel-cobalt-lithium-magnesium wastewater is 1300 mg/L, the nickel metal content is 50 mg/L, the cobalt metal content is 25 mg/L, the lithium metal content is 5 g/L, and the magnesium metal content is 100 mg/L;
  • Step (2) the wastewater after flotation oil removal is passed through an activated carbon column for adsorption oil removal again, and the COD of the solution can be reduced to 100 mg/L;
  • Step (3) using a polystyrene molecular skeleton chelating resin to adsorb Ni and Co metal ions on the wastewater obtained in step (2); the resin absorption tower is filled with a height-to-diameter ratio of 2.5:1, the flow rate is 4.5 BV/h, the solution pH is controlled at 7, and a primary adsorption liquid is obtained after the adsorption operation; using 15% sulfuric acid to desorb and regenerate the polystyrene molecular skeleton chelating resin, and the pH is maintained at 3 during the pickling process to obtain a nickel-cobalt sulfate desorption solution containing 2.6 g/L nickel, 1.2 g/L cobalt, and 0.15 g/L magnesium;
  • Step (4) passing the primary adsorption liquid obtained in step (3) into a styrene-divinylbenzene copolymer sulfonyl resin for Mg metal ion adsorption, the operating conditions being that the resin absorption tower is filled with a height-to-diameter ratio of 2.5:1, the flow rate is 4BV/h, and the solution is controlled at pH 8, and a secondary adsorption liquid is obtained after the operation; the secondary adsorption liquid is subjected to MVR concentration and crystallization to obtain sodium sulfate, and the concentrated mother liquor is subjected to lithium precipitation operation using sodium carbonate to obtain crude lithium carbonate;
  • Step (5) using 10% sulfuric acid at a flow rate of 2 BV/h to desorb the saturated styrene-divinylbenzene copolymer sulfonyl resin in step (4) to obtain a magnesium sulfate desorption solution; then using a 20% sodium hydroxide solution at a flow rate of 5 BV/h to regenerate the styrene-divinylbenzene copolymer sulfonyl resin for 2 hours;
  • Step (6) adding a chelating agent HDTMPA, introducing ammonia gas to the magnesium salt desorption solution to carry out a magnesium precipitation reaction, wherein the concentration of the magnesium salt desorption solution is 1.5 mol/L, and ammonia gas is introduced to maintain the solution pH at 11.
  • the amount of chelating agent added is 3% of the theoretical yield of magnesium hydroxide, the reaction temperature is 60° C., and the precipitation aging reaction time is 4 h; after aging and filtering, washing with water and then washing with 3% dilute hydrochloric acid, and finally washing with water, and drying to obtain a hexagonal magnesium hydroxide solid;
  • Step (7) after filtering the magnesium precipitate in step (6), the filtrate obtained is evaporated and concentrated, the evaporated ammonia is recycled to step (6), and soda ash is added to the concentrated mother liquor for value adjustment and precipitation to obtain nickel-cobalt slag; the nickel-cobalt slag is dissolved with low acid to obtain an acid solution which is returned to step (3) for nickel-cobalt metal adsorption and desorption operations for recovery.
  • a resource recovery method for high COD nickel-cobalt-lithium-magnesium wastewater, the specific process is:
  • Step (1) after the high COD nickel-cobalt-lithium-magnesium wastewater is allowed to stand, a 7MPa CO2 aqueous solution is introduced to perform flotation oil removal operation for 2 hours, wherein the amount of the high-pressure CO2 aqueous solution is 10% of the volume of the high COD nickel-cobalt-lithium-magnesium wastewater, and the COD content of the high COD nickel-cobalt-lithium-magnesium wastewater is 1000 mg/L, the nickel metal content is 30 mg/L, the cobalt metal content is 15 mg/L, the lithium metal content is 0.5 g/L, and the magnesium metal content is 50 mg/L;
  • Step (2) the wastewater after flotation oil removal is passed through an activated carbon column for adsorption oil removal again, and the COD of the solution can be reduced to 50 mg/L;
  • Step (3) using a polystyrene molecular skeleton chelating resin to adsorb Ni and Co metal ions on the wastewater obtained in step (2); the resin absorption tower is filled with a height-to-diameter ratio of 3:1, the flow rate is 5 BV/h, the solution is controlled to have a pH of 8, and a primary adsorption liquid is obtained after the adsorption operation; using 20% sulfuric acid to desorb and regenerate the polystyrene molecular skeleton chelating resin, and the pH is maintained at >3 during the pickling process to obtain a nickel-cobalt sulfate desorption liquid containing 2.8 g/L nickel, 1.3 g/L cobalt, and 0.25 g/L magnesium;
  • Step (4) passing the primary adsorption liquid obtained in step (3) into a styrene-divinylbenzene copolymer sulfonyl resin for Mg metal ion adsorption, the operating conditions being that the resin absorption tower is filled with a height-to-diameter ratio of 2:1, the flow rate is 3BV/h, and the solution is controlled at a pH of 7, to obtain a secondary adsorption liquid after the operation; the secondary adsorption liquid is subjected to MVR concentration and crystallization to obtain sodium sulfate, and the concentrated mother liquor is subjected to lithium precipitation operation using sodium carbonate to obtain crude lithium carbonate;
  • Step (5) using 10% sulfuric acid at a flow rate of 2 BV/h to desorb the saturated styrene-divinylbenzene copolymer sulfonyl resin in step (4) to obtain a magnesium sulfate desorption solution; then using a 20% sodium hydroxide solution at a flow rate of 5 BV/h to regenerate the styrene-divinylbenzene copolymer sulfonyl resin for 2 hours;
  • Step (6) adding a chelating agent HDTMPA, introducing ammonia gas to the magnesium salt desorption solution to carry out a magnesium precipitation reaction, wherein the concentration of the magnesium salt desorption solution is 2.5 mol/L, and the pH value of the solution is maintained at 12 by introducing ammonia gas.
  • the amount of the chelating agent added is 5% of the theoretical yield of magnesium hydroxide, the reaction temperature is 80° C., and the precipitation aging reaction time is 6 h; after aging and filtering, washing with water and then washing with 5% dilute hydrochloric acid, and finally washing with water, and drying to obtain a hexagonal magnesium hydroxide solid;
  • Step (7) after filtering the magnesium precipitate in step (6), the filtrate obtained is evaporated and concentrated, the evaporated ammonia is recycled to step (6), and soda ash is added to the concentrated mother liquor for value adjustment and precipitation to obtain nickel-cobalt slag; the nickel-cobalt slag is dissolved with low acid to obtain an acid solution which is returned to step (3) for nickel-cobalt metal adsorption and desorption operations for recovery.
  • a method for recycling high COD nickel-cobalt-lithium-magnesium wastewater which differs from Example 1 in that magnesium is adsorbed first and then nickel-cobalt is adsorbed.
  • the specific process is as follows:
  • Steps (1) and (2) are the same as in Example 1;
  • Step (3) passing the wastewater obtained in step (2) into a styrene-divinylbenzene cross-linked aminophosphonic acid chelating resin to adsorb Mg metal ions.
  • the operating conditions are as follows: a resin absorption tower is filled with a height-to-diameter ratio of 3:1, a flow rate of 5 BV/h, and the solution is controlled to have a pH of 9. After the operation, a primary adsorption liquid is obtained;
  • Step (4) passing the primary adsorption liquid obtained in step (3) into a polystyrene molecular skeleton chelating resin to adsorb Ni and Co metal ions, the resin absorption tower is filled with a height-to-diameter ratio of 2:1, the flow rate is 4BV/h, the solution is controlled to have a pH of 5, and a secondary adsorption liquid is obtained after the operation; using 10% sulfuric acid to desorb and regenerate the polystyrene molecular skeleton chelating resin, and the pH is maintained at >3 during the pickling process to obtain a nickel-cobalt sulfate desorption liquid containing 2.1 g/L nickel, 0.5 g/L cobalt, and 0.05 g/L magnesium;
  • Step (5) using 10% sulfuric acid at a flow rate of 2 BV/h to desorb the saturated styrene-divinylbenzene cross-linked aminophosphonic acid chelating resin in step (3) to obtain a magnesium sulfate desorption solution; then using a 20% sodium hydroxide solution at a flow rate of 5 BV/h to regenerate the styrene-divinylbenzene copolymer sulfonyl resin for 2 hours;
  • Step (6) The secondary adsorption liquid obtained in step (4) is subjected to MVR concentration and crystallization to obtain sodium sulphate.
  • the concentrated mother liquor is subjected to lithium precipitation operation using sodium carbonate to obtain crude lithium carbonate.
  • Steps (1) to (5) are the same as those in Example 3.
  • Step (6) without adding a chelating agent, ammonia gas was directly introduced into the magnesium salt solution to precipitate magnesium, the concentration of the magnesium salt solution was 2.5 mol/L, ammonia gas was introduced to maintain the solution pH at 12, the reaction temperature was 80°C, and the precipitation aging reaction time was 6 hours; the aging process After filtration, the product was washed with water and dried to obtain hexagonal magnesium hydroxide solid.
  • the element content wt% refers to the ratio of each metal element to the total metal elements in the magnesium sulfate desorption solution.
  • the Mg content in the magnesium sulfate desorption solution of Comparative Example 1 is significantly reduced, while the nickel and cobalt elements are increased. This is because the styrene-divinylbenzene copolymer sulfonyl resin is not selective enough for magnesium. When adsorbing magnesium, part of the nickel and cobalt will be adsorbed together, affecting the adsorption effect of the resin on magnesium. In Example 1, nickel and cobalt are first adsorbed, and then magnesium is adsorbed. The polystyrene molecular skeleton chelating resin has a stronger selectivity for nickel and cobalt, and only a small amount of magnesium is entrained, which does not affect the adsorption capacity of nickel and cobalt.
  • the impurity elements in the magnesium hydroxide solid prepared in Comparative Example 2 are significantly more than those in Example 3. This is because after the chelating agent is added to Example 3, the chelating agent can ionize the Ni, Co, Ca, and Fe metals in the magnesium sulfate desorption solution. The chelating agent is chelated and basically will not precipitate or be sandwiched in the magnesium hydroxide precipitate, thereby improving the purity of the magnesium hydroxide.
  • the specific surface area of Comparative Example 2 is also significantly higher than that of Example 3, indicating that the magnesium hydroxide crystals generated without the use of a chelating agent have obvious defects and the crystal form is incomplete.
  • the recovery rate of nickel, cobalt and magnesium in Comparative Example 1 is significantly reduced, because the specific selectivity of styrene-divinylbenzene cross-linked aminophosphonic acid chelating resin to magnesium is not strong enough.
  • part of nickel and cobalt will be adsorbed together, affecting the adsorption effect of the resin on magnesium.
  • Example 1 first adsorbs nickel and cobalt, and then adsorbs magnesium.
  • the specific selectivity of the polystyrene molecular skeleton chelating resin to nickel and cobalt is stronger, and only a small amount of magnesium is entrained, which does not affect the adsorption capacity of nickel and cobalt.
  • the recovery rate of nickel, cobalt, lithium and magnesium in Comparative Example 2 is not much different from that in Example 3, because the chelating agent added in Example 3 does not affect the recovery rate of magnesium, but only affects the hexagonal magnesium hydroxide crystal form.
  • the use of a special selective resin for segmented adsorption of nickel, cobalt and magnesium combined process can increase the recovery rate of nickel, cobalt, lithium and magnesium.
  • FIG 3 is an SEM image of hexagonal magnesium hydroxide surface-modified with hexamethylenediaminetetramethylenephosphonic acid (HDTMPA) in different addition amounts (1%, 3%, and 5%);
  • Figure 4 is an SEM image of magnesium hydroxide prepared by direct precipitation without the use of a chelating agent in Comparative Example 2. It can be seen from the figure that the hexagonal magnesium hydroxide prepared under the conditions of adding 1%, 3%, and 5% HDTMPA respectively is significantly different from that without the addition of a chelating agent. The crystal morphology generated without the use of a chelating agent is different, the crystals are staggered and overlapped, the agglomeration is serious, and the crystals have obvious defects.
  • HDTMPA hexamethylenediaminetetramethylenephosphonic acid
  • the resulting crystal form is more complete, the arrangement is more orderly, and the agglomeration is improved.
  • a smaller amount of HDTMPA (1%) is added, the crystal form still has irregular, agglomerated flakes, which is due to insufficient chelating agent molecular chains.
  • more HDTMPA (5%) is added, the excessively long molecular chains may cause the hexagonal flakes to entangle with each other during the growth process. Adding an appropriate amount of HDTMPA (3%) can obtain more successfully modified hexagonal flakes. Square magnesium hydroxide.
  • Figure 5 is a DSC curve of magnesium hydroxide before (a) and after (b) modification corresponding to Example 3 and Comparative Example 2.
  • the carbon chain increases, the thermal stability and flame retardancy are improved, the heat absorption of the modified magnesium hydroxide increases, and the endothermic enthalpy increases. Due to the grafting of the chelating agent HDTMPA, the pyrolysis temperature increases.

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Abstract

L'invention concerne un procédé de recyclage d'eaux usées de nickel-cobalt-lithium-magnésium à forte DCO et l'utilisation de ce procédé. Le procédé comprend : la réalisation d'un traitement de déshuilage sur des eaux usées de nickel-cobalt-lithium-magnésium à forte DCO ; l'adsorption des ions Ni et Co dans le liquide ayant été soumis au déshuilage, avec une résine de type ions hydrogène ; l'adsorption des ions Mg dans le liquide, ayant été soumis à une adsorption primaire, avec une résine de type ions sodium ; puis la désorption de la résine adsorbée de type ions sodium avec un acide pour obtenir une solution de désorption de sel de magnésium ; et l'ajout d'un agent chélatant de phosphine organique à la solution de désorption de sel de magnésium, l'introduction d'ammoniaque dans celle-ci pour effectuer une réaction de précipitation du magnésium, et le lavage du précipité avec de l'eau et un acide dilué pour obtenir un solide d'hydroxyde de magnésium hexagonal. Les eaux usées dont la DCO a été éliminée sont soumises à l'adsorption combinée de deux segments de résines de la résine de type ions hydrogène et de la résine de type ions sodium, ce qui contribue à l'obtention ultérieure d'un solide ignifuge d'hydroxyde de magnésium hexagonal d'une plus grande pureté ; et l'agent chélatant peut être greffé à la surface du solide d'hydroxyde de magnésium hexagonal obtenu pour modifier le solide d'hydroxyde de magnésium hexagonal, de telle sorte que la stabilité thermique et l'ignifugation du solide d'hydroxyde de magnésium hexagonal modifié peuvent être améliorées.
PCT/CN2023/082233 2023-03-17 2023-03-17 Procédé de recyclage d'eaux usées de nickel-cobalt-lithium-magnésium à forte dco et utilisation de ce procédé Ceased WO2024192575A1 (fr)

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CN202380009013.2A CN117083243B (zh) 2023-03-17 2023-03-17 高cod镍钴锂镁废水的资源化方法及其应用

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