WO2023124792A1 - 盐湖提锂方法 - Google Patents

盐湖提锂方法 Download PDF

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Publication number
WO2023124792A1
WO2023124792A1 PCT/CN2022/136482 CN2022136482W WO2023124792A1 WO 2023124792 A1 WO2023124792 A1 WO 2023124792A1 CN 2022136482 W CN2022136482 W CN 2022136482W WO 2023124792 A1 WO2023124792 A1 WO 2023124792A1
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lithium
cleaning
salt lake
adsorbent
flow rate
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English (en)
French (fr)
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韦家亮
林宏业
连俊兰
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BYD Co Ltd
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BYD Co Ltd
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Priority to EP22914047.0A priority Critical patent/EP4394063A4/en
Priority to CA3233544A priority patent/CA3233544A1/en
Priority to AU2022428473A priority patent/AU2022428473B2/en
Publication of WO2023124792A1 publication Critical patent/WO2023124792A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
    • 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 application relates to the fields of environmental protection and resource recycling, in particular to a method for extracting lithium from a salt lake.
  • the current adsorption lithium extraction process has a low adsorption efficiency for lithium, and there is still a problem that it is difficult to produce a qualified desorption solution with high lithium content at low temperature (such as winter).
  • this application provides a method for extracting lithium from salt lakes.
  • the adsorption efficiency of lithium in brine can be greatly improved, and it is difficult to obtain high lithium content at low temperatures.
  • the difficult problem of qualified desorption liquid improves the adsorption efficiency of lithium in brine, so that qualified desorption liquid with high lithium content can be obtained at low temperature, so as to ensure uninterrupted production throughout the year.
  • the application provides a method for extracting lithium from a salt lake, comprising: passing the salt lake brine through a lithium adsorbent at a variable speed, so that lithium ions in the salt lake brine are adsorbed on the lithium adsorbent to obtain a lithium-rich adsorbent; wherein, During the adsorption process, the flow rate of the salt lake brine gradually decreases, and the difference between the initial flow rate and the final flow rate of the salt lake brine is 0.5-3BV/h; the lithium-rich adsorbent is cleaned; and, using lithium The ion eluent desorbs the lithium ions on the cleaned lithium-rich adsorbent to obtain a desorption solution.
  • the adsorption efficiency of lithium in brine can be greatly improved by adopting a specific flow rate change process in which the flow rate of brine gradually decreases during the adsorption stage of salt lake brine, especially at low temperatures (below zero degrees).
  • High-efficiency lithium adsorption can ensure that a desorption solution with a lithium content of more than 500mg/L can be obtained without affecting the production capacity; under the same adsorption time (for example, 180min), under the condition that the production capacity remains unchanged, the application of this application
  • the lithium content in the desorption liquid obtained by the lithium extraction method is much higher than that of the desorption liquid (generally around 400 mg/L) obtained by the lithium extraction method using the brine adsorption process with a fixed flow rate.
  • the initial flow rate is 2.0-3.0 BV/h
  • the final flow rate is 1.2-1.8 BV/h.
  • the total amount of the salt lake brine to be adsorbed is 6-8 BV, and the total duration of the adsorption may be 2.5-4 hours.
  • the cleaning includes in sequence: the first cleaning, the second cleaning, and the third cleaning, wherein, the flow rate of the first cleaning agent during the first cleaning, the second cleaning
  • the flow velocity of the second cleaning agent during cleaning and the flow velocity of the third cleaning agent during the 3rd cleaning are in a magnitude relationship that increases sequentially; the consumption of the second cleaning agent is greater than the consumption of the first cleaning agent, the Describe the dosage of the third cleaning agent.
  • the flow rate of the first cleaning agent is 3-5BV/h, and the dosage is 0.5-1BV; during the second cleaning, the flow rate of the second cleaning agent is 6-8BV/h, The dosage is 1-1.5BV; in the third cleaning, the flow rate of the third cleaning agent is 9-12BV/h, and the dosage is 0.5-1BV.
  • the first cleaning agent includes an aqueous solution containing magnesium ions with a concentration of no more than 50 g/L and lithium ions with a concentration of no more than 300 mg/L; L of magnesium ions and an aqueous solution of lithium ions with a concentration not exceeding 250 mg/L; the third cleaning agent is pure water.
  • the lithium ion eluent is water, and the temperature is 30-50°C.
  • the lithium adsorbent includes an adsorbent material, a binder, and a wetting and dispersing agent, wherein the binder includes vinylidene fluoride-chlorotrifluoroethylene copolymer and fluoroolefin-vinyl ether copolymer
  • the wetting and dispersing agent includes one or more of polyethylene glycol, sodium polyacrylate, polyvinyl alcohol, and formaldehyde condensate.
  • the adsorbent is an aluminum-based adsorbent.
  • the content of the adsorption material is 80-95wt%
  • the content of the binder is 4-17wt%
  • the content of the wetting and dispersing agent It is 1-5wt%.
  • the ratio of the mass of the adsorption material to the sum of the mass of the binder and the wetting and dispersing agent is greater than or equal to 8:1.
  • the mass of the binder is 8%-12.5% of the mass of the adsorption material.
  • the molecular weight of the vinylidene fluoride-chlorotrifluoroethylene copolymer or the fluoroolefin-vinyl ether copolymer is 100,000-800,000.
  • the method before the step of passing the salt lake brine through the lithium adsorbent at a variable speed, the method further includes: filtering the salt lake brine to remove impurities therein.
  • the step of filtering the salt lake brine includes: sequentially performing high-speed centrifugal filtration and backwashing filtration on the salt lake brine.
  • the lithium adsorbent is packed in an exchange column or an adsorption tower.
  • the method before the step of passing the saline lake brine through the lithium adsorbent at a variable speed, the method further includes: performing delithiation on the lithium adsorbent.
  • the flow rate of the lithium ion eluent is 1.5-2.5 BV/h.
  • the desorption time is 2.5-4h.
  • the salt lake lithium extraction method provided by this application can effectively improve the adsorption efficiency of lithium in brine by adopting a specific flow rate change process in the adsorption stage of salt lake brine, and solve the problem of low temperature (brine is at least minus ten degrees Celsius in winter) It is difficult to obtain a qualified desorption liquid with high lithium content, which improves the adsorption efficiency of lithium in the brine, so that a qualified desorption liquid with high lithium content can be obtained at low temperature, so as to ensure all-weather all-year-round intermittent production.
  • the method for extracting lithium from a salt lake has a simple technological process, a high yield of lithium extraction, and is convenient for large-scale industrial production.
  • Fig. 1 is a process flow diagram of a method for extracting lithium from a salt lake provided by an embodiment of the present application.
  • Fig. 2 is a process flow diagram of a method for extracting lithium from a salt lake according to another embodiment of the present application.
  • the application provides a method for extracting lithium from a salt lake, comprising the following steps:
  • the adsorption efficiency of lithium in brine can be greatly improved, especially at low temperatures (below zero degrees).
  • the high-efficiency lithium adsorption can ensure the desorption liquid with a lithium content above 500mg/L without affecting the production capacity; under the same adsorption time (for example, 180min), under the condition that the production capacity remains unchanged, the use of this
  • the lithium content in the desorption liquid obtained by the lithium extraction method applied for is much higher than the desorption liquid (generally around 400 mg/L) obtained by the conventional lithium extraction method using a brine adsorption process with a fixed flow rate.
  • the flow rate of salt lake brine can change according to time, and the overall flow rate gradually decreases with the progress of the adsorption process.
  • the difference between the initial flow velocity and the final flow velocity of salt lake brine is 0.5-3BV/h, which can be 0.8BV/h, 1BV/h, 1.2BV/h, 1.5BV/h, 1.8BV/h, 2BV/h or 2.5 BV/h etc.
  • Appropriate initial and final flow rate difference is conducive to improving the adsorption efficiency of lithium in brine.
  • the definition of the initial flow rate and the final flow rate can be determined according to the specific brine speed change process. If the flow rate of the brine is continuously reduced, the initial flow rate is the brine flow rate that passes through the lithium adsorbent at the beginning of adsorption, and the final flow rate is the brine flow rate that is about to be adsorbed. At the end, the final brine flow rate through the lithium sorbent. If the flow rate of brine is discretely reduced in stages, that is, during the adsorption process, the flow rate of brine has n different values (n is a finite value, and the flow rates can be V1, V2, ...
  • the flow rate segment (the flow rate is V1) is the initial flow rate of the brine
  • the last flow rate segment (that is, the nth flow rate segment, the flow rate is Vn) is the final flow rate.
  • Q unit is Bv
  • the amount of brine passing through the adsorbent at each flow rate stage can be Q/n, wherein the first Q/n BV of the lithium adsorbent passes
  • the flow rate of salt lake brine can be referred to as initial flow rate
  • the flow rate of salt lake brine passing through the last Q/n BV of the lithium adsorbent can be referred to as final flow rate.
  • the brine of each BV passes through the lithium adsorbent at a flow rate of 2.5, 2.3, 2.1, 2.0, 1.8, and 1.6 BV/h respectively, wherein the brine
  • the initial flow rate is 2.5BV/h
  • the final flow rate is 1.6BV/h
  • the adsorption time of each brine is 24min, 26min, 28.6min, 30min, 33min, 37.5min respectively.
  • the initial flow rate is 2.0-3.0 BV/h
  • the final flow rate is 1.2-1.8 BV/h.
  • BV generally refers to the filling volume of the lithium adsorbent
  • 2.0-3.0BV/h (the same below) means that the volume of the brine flow rate is 2-3 times the volume of the lithium adsorbent per hour.
  • the initial flow rate may specifically be 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 or 3.0 BV/h, etc.
  • the final flow rate may specifically be 1.2, 1.3, 1.4, 1.5, 1.6, 1.7 or 1.8 BV/h and the like.
  • the total amount of the salt lake brine to be adsorbed is 6-8 BV, that is, the volume of the salt lake brine to be in contact with the lithium adsorbent is equal to the loading of the lithium adsorbent 6-8 times the volume.
  • the amount of the salt lake brine to be adsorbed can vary according to the lithium content (generally 180-300ppm) in the salt lake brine.
  • the total duration of the adsorption may be 2.5-4h, such as 2.8h, 3h, 3.5h, 3.8h and so on.
  • step (1) before the salt lake brine passes through the lithium adsorbent at a variable speed, it further includes: filtering the brine to remove impurities (such as granular impurities).
  • the filtration may sequentially include: high-speed centrifugal filtration and backwash filtration.
  • High-speed centrifugal filtration is mainly to remove the sediment of large particles. High-speed centrifugal filtration can be carried out in a centrifugal solid-liquid separator with a centrifugal speed of 15000-35000rpm.
  • Backwash filtration is for further precision filtration, so that there are fewer solid impurities in the brine of the salt lake to ensure that the filtered material does not affect the adsorption function of the lithium adsorbent, and the filtered impurities are convenient to backwash, and there is no need to frequently replace the filter consumables.
  • Backwash filtration can be performed with a stainless steel mesh type backwash filter.
  • the salt lake brine realizes lithium extraction through an adsorption method.
  • the lithium adsorbent can be packed in an exchange column (such as a glass column, a stainless steel column) or in a carrier such as an adsorption tower.
  • the salt lake brine flows through the carrier with the lithium adsorbent and contacts with the lithium adsorbent, the lithium ions in it can be adsorbed and fixed by the lithium adsorbent, and at the same time, the lithium adsorbent is also transformed into a lithium-rich adsorbent that absorbs lithium. agent.
  • the lithium adsorbent used may include an adsorbent material and a binder.
  • the adsorbent material can be an aluminum-based adsorbent material, a manganese-based adsorbent material (such as a combination of spinel-type manganese oxide and lithium ions), a titanium-based adsorbent material (such as a metatitanic acid-type lithium ion sieve adsorbent), Iron-based adsorbent materials, etc.
  • the adsorbent material is an aluminum-based adsorbent material.
  • the aluminum-based adsorption material may be a combination of aluminum hydroxide and lithium-containing compounds (such as lithium halide, lithium sulfate, etc.).
  • the aluminum-based adsorption material can absorb lithium ions from a lithium-containing solution, and after the adsorption is saturated, the lithium ions can be decomposed into the solution after being eluted with water at a certain temperature.
  • the lithium adsorbent in order to make the lithium adsorption capacity of the lithium adsorbent of the present application stronger, before using it to extract lithium from salt lakes, the lithium adsorbent can be properly delithiated so that the adsorbent has more lithium vacancies.
  • the aluminum-based adsorbent material after delithiation can be expressed as (1-x)Li a 'X ⁇ mAl(OH) 3 ⁇ nH 2 O, 0 ⁇ x ⁇ 1.
  • aluminum-based adsorption materials can be prepared by mechanochemical synthesis, soaking, acidification conversion, precipitation, etc.
  • LiCl ⁇ mAl(OH) 3 ⁇ nH 2 O As an example, it can be obtained by soaking aluminum hydroxide in LiCl solution, or by soaking aluminum hydroxide in LiOH solution followed by acidification conversion, or by coprecipitation of AlCl3 and LiCl solution , It can also be prepared by LiOH and aluminum hydroxide grinding method.
  • the binder can be epoxy resin, phenolic resin, polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyvinylidene fluoride, ethylene-vinyl acetate copolymer, vinylidene fluoride-trifluorochloroethylene copolymer (referred to as VDF-CTFE) and fluoroolefin-vinyl ether copolymer (also known as FEVE type fluorocarbon resin) and so on.
  • VDF-CTFE vinylidene fluoride-trifluorochloroethylene copolymer
  • FEVE type fluorocarbon resin fluoroolefin-vinyl ether copolymer
  • the binder is at least one of vinylidene fluoride-chlorotrifluoroethylene copolymer and fluoroolefin-vinyl ether copolymer.
  • the lithium adsorbent also includes a wetting and dispersing agent, which may specifically include one or more of polyethylene glycol, sodium polyacrylate, polyvinyl alcohol, and formaldehyde condensate.
  • Exemplary formaldehyde condensates may include, but are not limited to, one of naphthalenesulfonate formaldehyde condensates, methylnaphthalenesulfonate formaldehyde condensates, benzylnaphthalenesulfonate formaldehyde condensates, phenolsulfonate formaldehyde condensates, etc. one or more species.
  • Using vinylidene fluoride-chlorotrifluoroethylene copolymer and/or fluoroolefin-vinyl ether copolymer as binder can not only make the lithium adsorbent have high structural stability, high mechanical strength, and good corrosion resistance, After repeated use of lithium absorption and delithiation, the adsorbent has a low dissolution rate and a long service life.
  • the above-mentioned binder can also make the adsorbent form a surface state with suitable porosity and narrow pore diameter, so that the above-mentioned lithium adsorbent
  • the lithium adsorption efficiency is high, and the effective active area of the lithium adsorbent will not be reduced to affect its adsorption speed and efficiency; the wettability of the above-mentioned wetting and dispersing agent is also conducive to the adsorption efficiency and adsorption capacity of the adsorbent on lithium ions. .
  • the above-mentioned lithium adsorbent is easy to clean and desorb lithium after adsorbing lithium.
  • the process is easier to carry out, thereby saving the water consumption in the cleaning and desorption process, reducing the dissolution rate of the adsorbent in these processes, and reducing the desorption temperature. And obtain the qualified desorption liquid with low magnesium-lithium ratio and high lithium content.
  • the molecular weight of the vinylidene fluoride-chlorotrifluoroethylene copolymer or fluoroolefin-vinyl ether copolymer may be 100,000-800,000.
  • Appropriately high molecular weight binders have a better bonding effect, reduce the risk of cracking and breaking of the lithium adsorbent during use, and increase its service life.
  • the copolymerization ratio of monomer vinylidene fluoride to chlorotrifluoroethylene can be 1:(1-5), preferably 1:4.
  • the binder is vinylidene fluoride-chlorotrifluoroethylene copolymer, or a mixture of vinylidene fluoride-chlorotrifluoroethylene copolymer and fluoroolefin-vinyl ether copolymer.
  • the molecular weight of the formaldehyde condensate is 4000-10000.
  • the molecular weight of the sodium polyacrylate is 5000-10000.
  • the wetting and dispersing agent is polyethylene glycol.
  • Polyethylene glycol has excellent wetting and dispersibility.
  • the polyethylene glycol has a molecular weight of 10,000-30,000. Higher molecular weight polyethylene glycols are less soluble in water with the sorbent, giving the sorbent a longer lifetime.
  • the content of the adsorption material is 80-95wt%
  • the content of the binder is 4-17wt%
  • the content of the wetting and dispersing agent It is 1-5wt%.
  • the overall lithium adsorbent can take into account good structural stability, adsorption effect, and desorption effect.
  • the content of the adsorbent material is 85-92 wt%.
  • the content of the binder is 5-15wt%, more preferably 6-12wt%.
  • the content of the wetting and dispersing agent is 1-3 wt%.
  • the mass of the binder is 8%-12.5% of the adsorption material.
  • An appropriate amount of binder can ensure high structural stability and long service life (not easy to break) of the lithium adsorbent, and also weaken its influence on the reduction of the adsorption capacity of the obtained lithium adsorbent.
  • the mass of the wetting and dispersing agent is 1%-5% of the adsorption material.
  • the wetting and dispersing agent can make the distribution of the adsorption material in the lithium adsorbent particles more uniform, the skeleton is more stable, the wettability of the lithium adsorbent particles is also improved, and the speed of adsorption/desorption of lithium is also changed. high.
  • the wetting and dispersing agent can also be slowly dissolved in brine, so that the porosity of the adsorbent increases slowly, further improving the adsorption efficiency of the adsorbent, and will not have a significant impact on the dissolution rate of the adsorbent. Reduce the service life of the adsorbent.
  • the ratio of the mass of the adsorption material to the sum of the masses of the binder and the wetting and dispersing agent is greater than or equal to 8:1. This is more favorable for the lithium adsorbent to take into account both good structural stability and excellent adsorption and desorption performance.
  • the ratio may be in the range of (8-10):1. Specifically, the ratio may be 8.5, 9:1, 9.5:1, etc.
  • the lithium adsorbent may be columnar particles.
  • the shape of columnar lithium adsorbent particles is simple, and the surface is smooth, which can avoid abrasion or powder falling due to mutual extrusion and friction during use, and reduce loss.
  • the particle diameter of the lithium adsorbent is 1.2mm-1.8mm, and the length is 1.5mm-2.5mm.
  • Lithium adsorbents with such a shape and suitable size can make the diffusion path of liquid and ions more suitable, and when the adsorbents are squeezed, it is easy to leave a certain gap to facilitate the penetration of brine, which is conducive to the improvement of lithium ion adsorption efficiency. Improve and make the ion exchange between lithium ions and water easier to carry out during the desorption process, which is convenient to reduce the delithiation temperature and the amount of desorption water to ensure that the adsorbed lithium is completely desorbed.
  • the cleaning of the lithium-rich adsorbent is mainly to wash away impurities on the surface of the lithium-rich adsorbent that has adsorbed lithium ions.
  • the cleaning is carried out in three steps, including: the first cleaning, the second cleaning and the third cleaning, wherein, the flow rate of the first cleaning agent during the first cleaning, the The flow velocity of the second cleaning agent during the 2nd cleaning and the flow velocity of the third cleaning agent during the 3rd cleaning are in a magnitude relationship that increases sequentially (that is, the flow velocity of the first cleaning agent ⁇ the flow velocity of the second cleaning agent ⁇ the flow rate of the third cleaning agent); the amount of the second cleaning agent is greater than the amount of the first cleaning agent and the third cleaning agent.
  • the amount of the first cleaning agent and the third cleaning agent can be equal or different.
  • the above-mentioned cleaning process for the lithium-rich adsorbent is divided into three steps: slow first and then fast.
  • the flow rate of the first cleaning is low, which can avoid a large amount of high-concentration brine in the carrier containing the lithium-rich adsorbent under the excessively fast cleaning flow rate.
  • the formation of a coagulation layer makes it difficult for impurities in the brine to be discharged, greatly reducing the cleaning effect.
  • the flow rate in the second cleaning is moderate, and the amount of cleaning agent is large, which can ensure sufficient cleaning time to ensure that the impurities such as magnesium adhered to the adsorbent can be fully dissolved and removed.
  • the flow rate in the third cleaning is faster, and the amount of cleaning agent used is lower than that in the second cleaning, which can reduce the desorption of lithium adsorbed on the lithium-rich adsorbent into the cleaning agent, and reduce the loss of lithium in the water washing process. Therefore, the above-mentioned specific cleaning process can clean the impurities on the surface of the lithium-rich adsorbent, so that the quality of magnesium and lithium in the desorption solution obtained by subsequent desorption is relatively low, and the amount of cleaning agent is small, and the lithium loss rate in the cleaning process is relatively low. (That is, the mass ratio of the lithium element dissolved in the cleaning agent to the total lithium element adsorbed by the lithium-rich adsorbent) is within 16%, or even 15%.
  • the difference between the cleaning agent flow rate during the third cleaning process and the cleaning agent flow rate during the first cleaning process may be 5-9 BV/h. In this case, a better cleaning effect as described above can be obtained.
  • the cleaning is carried out in three steps, including: the first cleaning, the flow rate of the first cleaning agent is 3-5BV/h, and the dosage is 0.5-1BV; the second cleaning, the second cleaning agent The flow rate of the cleaning agent is 6-8BV/h, and the dosage is 1-1.5BV; for the third cleaning, the flow rate of the third cleaning agent is 9-12BV/h, and the dosage is 0.5-1BV.
  • this cleaning process can better clean the impurities on the surface of the lithium-rich adsorbent, so that the mass ratio of magnesium to lithium in the desorption solution obtained by subsequent desorption is lower, for example, it can be reduced to below 2:1, and the loss of lithium in the cleaning process The rate is lower, less than 15%, which is far lower than the lithium loss level of about 20% (or even 25% loss rate) brought about by the constant speed cleaning process commonly used in the industry.
  • the amount of the first cleaning agent can be 0.6, 0.7, 0.8 or 0.9 BV, etc.
  • the amount of the second cleaning agent can be 1, 1.2, 1.3, 1.4, 1.5 BV, etc.
  • the amount of the third cleaning agent The dosage can be 0.6, 0.7, 0.8 or 0.9BV, etc.
  • the total amount of cleaning agents used in each cleaning process is controlled to not exceed 2.5BV.
  • the cleaning time of the first road is 6-20min, further can be 7-15min (such as 9min), the time of the second cleaning is 7.5-15min, further can be 9-13min (such as 11min ), the time for the third cleaning is 2.5-6.6min (for example, 4min).
  • the total cleaning time can be controlled within 25 minutes, and further can be within 20 minutes. In this way, the lithium loss rate can be reduced while achieving better cleaning of impurities.
  • the cleaning process specifically includes:
  • the first cleaning agent i.e., the cleaning agent for the first cleaning
  • a second cleaning agent i.e., a cleaning agent for the second cleaning
  • a third cleaning agent ie, a cleaning agent for the third cleaning
  • the third adsorbent here is the lithium-rich adsorbent after cleaning, and the desorption of the aforementioned step (3) is also performed on it.
  • the first cleaning agent, the second cleaning agent, and the third cleaning agent all contain a large amount of water, and each cleaning agent can be pure water or recycled water (containing certain inorganic metal ion impurities), and the composition of each cleaning agent Can be different.
  • the first cleaning agent, the second cleaning agent and the third cleaning agent are all pure water. At this time, the amount of pure water is relatively large, and the loss rate of lithium in the cleaning process will be slightly larger.
  • the first cleaning agent and the second cleaning agent are reused water; the third cleaning agent is pure water instead of reused water, specifically deionized water, distilled water, clean groundwater, tap water, etc.
  • the cleaning agent used in the first two cleanings is recycled water containing lithium, which can inhibit the desorption of lithium during the cleaning process.
  • the last cleaning is pure water.
  • the amount of pure water used is small and can ensure a cleaner cleaning effect.
  • each cleaning agent does not contain organic substances, and has a conductivity of less than 300 ⁇ s/cm, furthermore, a conductivity of less than 200 ⁇ s/cm, preferably less than 50 ⁇ s/cm.
  • the magnesium content in the first cleaning agent, the second cleaning agent, and the third cleaning agent decreases sequentially.
  • the magnesium content in the first cleaning agent is no more than 50g/L, preferably no more than 30g/L, more preferably no more than 10g/L; the magnesium content in the second cleaning agent is no more than 5g/L,
  • the magnesium content in the third cleaning agent does not exceed 100 mg/L.
  • the magnesium ion content in the first cleaning agent does not exceed 50 g/L, and the lithium ion content does not exceed 300 mg/L.
  • the first cleaning agent may also include other respective metal ions (calcium, boron, sodium or potassium) with a concentration not exceeding 10 g/L.
  • the magnesium ion content in the second cleaning agent does not exceed 5g/L, and the lithium ion content does not exceed 250mg/L.
  • the unqualified desorption liquid (produced in the later stage of desorption) obtained in the desorption process of step (3) with a lithium concentration of no more than 250mg/L can be used as the cleaning agent for the second cleaning (that is, the second cleaning agent); in addition, the residual water in the carrier (such as the adsorption column) equipped with the lithium adsorbent after the desorption is completed can also be discharged as the second cleaning agent.
  • the third cleaning solution obtained after the third cleaning or the second cleaning solution obtained after the second cleaning can be used as the cleaning agent for the first cleaning (ie, the first cleaning agent).
  • the first cleaning solution obtained after the first cleaning can be returned and mixed into the brine of the salt lake.
  • the second cleaning solution generally contains magnesium ions with a concentration of no more than 50g/L, and the concentration of other metal ions (calcium, lithium, boron, sodium or potassium) is no more than 10g/L; the concentration of lithium ions can further be 100-200ppm.
  • the third cleaning solution generally contain magnesium ions with a concentration of no more than 10g/L, and other metal ions (such as calcium, lithium, boron, sodium or potassium, etc.) with a concentration of no more than 0.5g/L; further, lithium The ion concentration is lower than 300mg/L.
  • step (3) of the present application the lithium-rich adsorbent after cleaning is eluted with a lithium ion eluent (also called a lithium desorbent), in order to desorb the lithium ions adsorbed on the lithium-rich adsorbent Down, lithium ion is eluted and desorbed into the eluent to obtain a desorption solution, so that the desorption solution is further processed and utilized (generally converted into a lithium carbonate product); at the same time, after desorbing lithium, the lithium-rich adsorbent can be The lithium adsorbent is regenerated, and then used to contact with salt lake brine to adsorb and extract lithium.
  • steps (1)-(3) are one cycle.
  • the temperature of the lithium ion eluent (that is, the "temperature of the desorption process") may be 30-50°C.
  • the temperature can be 30 -40°C, for example, is 28, 30, 32, 35, 38 or 40°C, etc., and further may be 30-35°C.
  • the lithium ion eluent can be deionized water, distilled water, clean ground water or tap water, etc.
  • the flow rate of the lithium ion eluent is 1.5-2.5 BV/h, such as 1.8 BV/h, 2 BV/h, 2.2 BV/h, etc. This can ensure that the lithium ion content in the desorption solution is relatively high, and the desorption time will not be too long.
  • the desorption time is 2.5-4h, such as 2.8h, 3h, 3.5h, 3.8h and so on.
  • the salt lake lithium extraction method provided by this application can effectively improve the adsorption efficiency of lithium in brine by adopting a specific flow rate change process in the adsorption stage of salt lake brine, and solve the problem of low temperature (brine is at least minus ten degrees Celsius in winter) It is difficult to obtain a qualified desorption liquid with high lithium content, which can ensure uninterrupted production throughout the year.
  • the method for extracting lithium from a salt lake has a simple technological process, a high yield of lithium extraction, and is convenient for large-scale industrial production.
  • composition of the salt lake brine used in the following examples to extract lithium is shown in Table 1 below.
  • a method for extracting lithium from a salt lake the process flow chart is as shown in Figure 1, specifically comprising the following steps:
  • the lithium adsorbent (specifically including aluminum-based adsorption material LiCl ⁇ 2Al(OH) 3 ⁇ nH 2 O, binder-polyvinylidene fluoride, the mass ratio of the two is 9:1) is packed in the glass adsorption column, and the loading amount is is 0.9dm 3 ;
  • the salt lake brine to be extracted lithium (hereinafter referred to as "brine”) is subjected to high-speed centrifugal filtration, backwashing and filtration in sequence, and then passes through the adsorption column equipped with the above-mentioned lithium adsorbent at variable speed, so that the lithium ions in it are adsorbed on the lithium adsorbent.
  • the temperature of the adsorption process is 25°C
  • the brine to be adsorbed is 6 BV
  • the flow rate of the brine passing through the first BV of the adsorption column (that is, the initial The flow rate) is 2.5BV/h
  • the adsorption time is 24 minutes.
  • the flow rate of the second BV brine is 2.3BV/h
  • the adsorption time is 26 minutes.
  • the flow rate of the third BV brine is 2.1BV/h, and the adsorption time is In 28 minutes, the flow rate of the 4th BV brine is 2.0BV/h, the adsorption time is 30 minutes, the flow rate of the 5th BV brine is 1.8BV/h, the adsorption time is 33 minutes, the 6th BV brine
  • the flow rate (ie the final flow rate) is 1.3BV/h, the adsorption time is 38 minutes, and the total adsorption time of the above adsorption process is about 3 hours.
  • the first cleaning use the third cleaning solution (composition: Li + content 210mg/L, Mg 2+ content 10g/L) from the third cleaning flow in the previous cycle as the first cleaning agent
  • the third cleaning solution composition: Li + content 210mg/L, Mg 2+ content 10g/L
  • the first cleaning agent is 0.6BV
  • the flow rate is 4.5BV/h
  • the cleaning time is 8 minutes.
  • the first adsorbent and the first cleaning solution are obtained; the first cleaning
  • the liquid can be reused and mixed with salt lake brine;
  • the second cleaning use the unqualified desorption solution collected from the late stage of the desorption stage of the previous cycle (composed of: Li + content is 105mg/L, Mg2 + content is 150mg/L) as the second cleaning agent Clean the first adsorbent, wherein, the volume consumption of the second cleaning agent is 1.3BV (ie 1170mL), the flow rate is 8.5BV/h, and the cleaning time is 9 minutes; after cleaning, the second adsorbent and the second cleaning solution are obtained ;
  • the mass ratio of magnesium to lithium in the second cleaning solution is 206:1, which can be collected and used as brine for re-adsorption to reduce the loss of lithium;
  • the third cleaning pure water is used as the third cleaning agent for this cleaning, the volume dosage is 0.6BV (5400mL), the flow rate is 12BV/h, and the cleaning time is 3 minutes.
  • the third adsorption agent and the third cleaning solution can be stored in the pre-storage tank as the first cleaning agent for the next cycle.
  • the difference between embodiment 2 and embodiment 1 is: in the adsorption process, the flow velocity of bittern according to the adsorption sequence is respectively 2.8BV/h (initial flow velocity), 2.6BV/h, 2.4BV/h, 2.1BV/h, 1.8BV/h, 1.5BV/h (final flow rate), the adsorption time is 21.5min, 23min, 25min, 28.5min, 33min, 40min, the total adsorption time is 171 minutes (ie 2.85h), the remaining process parameters and implementation Example 1 guarantees consistency.
  • embodiment 3 in the adsorption process, the flow rate of brine according to the adsorption sequence is 2BV/h (initial flow rate), 1.8BV/h, 1.6BV/h, 1.4BV/h, 1.3 BV/h, 1.2BV/h (final stage flow rate), adsorption time is respectively 30min, 33.3min, 37.5min, 43min, 46min, 50min, and total adsorption time is about 240min, and all the other process parameters are consistent with embodiment 1.
  • the flow rate of brine according to the adsorption sequence is 2BV/h (initial flow rate), 1.8BV/h, 1.6BV/h, 1.4BV/h, 1.3 BV/h, 1.2BV/h (final stage flow rate)
  • adsorption time is respectively 30min, 33.3min, 37.5min, 43min, 46min, 50min, and total adsorption time is about 240min, and all the other process parameters are consistent with embodiment 1.
  • Example 4 The difference between Example 4 and Example 1 is that the initial flow rate of brine is 3.5BV/h, and the final flow rate is 2.0BV/h.
  • the flow rates of the six BV brines to be adsorbed are respectively It is 3.5BV/h, 3.2BV/h, 3.0BV/h, 2.8BV/h, 2.5BV/h, 2.0BV/h.
  • the adsorption time of each BV brine was 17min, 18.75min, 20min, 21.4min, 24min, 30min, and the total adsorption time was about 240min.
  • Example 5 The difference between Example 5 and Example 1 is that the amount of brine to be adsorbed is 7.5 BV.
  • the flow velocity of the brine increases and decreases, and is divided into 7 different flow velocity sections, and the reduction range of adjacent flow velocity sections is 0.5BV/h
  • the initial flow rate is 5BV/h
  • the final flow rate is 2BV/h
  • the adsorption time of each 1.07 BV brine is 12.9min, 14.3min, 16.1min, 18.4min, 21.4min, 25.7min, 32.1 min
  • the total adsorption time is about 140.9min.
  • Example 6 The difference between Example 6 and Example 1 is that the three-step flow rates of the cleaning process are: 5BV/h, 8BV/h, and 12BV/h, the cleaning time is 7min, 10min, and 3min, respectively, and the total cleaning time is 20 minutes , all the other process parameters are guaranteed to be consistent with Example 1.
  • Example 7 The difference between Example 7 and Example 1 is that the cleaning process adopts a constant-speed cleaning process, and the three-step cleaning is performed at the same flow rate of 7.5BV/h, and the amount of cleaning agent used for each cleaning is 0.8BV and 0.9BV respectively and 0.8BV, the cleaning time is respectively: 384 seconds, 432 seconds, 384 seconds.
  • the total time of the cleaning process was 20min, and the total amount of cleaning agent was 2.5BV remained unchanged.
  • Example 8 The difference between Example 8 and Example 1 is that the cleaning process adopts a constant-speed cleaning process, and the three-step cleaning is cleaned at the same flow rate of 7.5BV/h.
  • the amount of cleaning agent in each cleaning is 0.83BV.
  • the cleaning time is 6.64min.
  • the total time of the cleaning process was 20min, and the total amount of cleaning agent was 2.5BV remained unchanged.
  • Example 9 The difference between Example 9 and Example 1 is that the cleaning process adopts a constant-speed cleaning process, and the three-step cleaning is performed at the same flow rate of 5BV/h.
  • the amount of cleaning agent used for each cleaning is 0.83BV.
  • the time is 10 minutes.
  • the total amount of cleaning agent 2.5BV remains unchanged, and the total time of the cleaning process becomes 30min.
  • Example 10 A method for extracting lithium from a salt lake.
  • the process flow chart is shown in Figure 2.
  • the difference between Example 10 and Example 1 is that in the cleaning process, the cleaning agents used in each cleaning are pure water (unlike Example 1). In 1, the 1st and 2nd cleanings all use recycled water).
  • Example 11 The difference between Example 11 and Example 1 lies in that the lithium adsorbent used is different, the desorption temperature is 30° C., and the rest of the process parameters are the same.
  • the lithium adsorbent used in Example 11 includes the same adsorbent material as in Example 1, but its binder is a vinylidene fluoride-chlorotrifluoroethylene copolymer with a molecular weight of about 20,000, and it also includes a polymer with a molecular weight of 10,000.
  • Polyethylene glycol is used as the wetting and dispersing agent, and the mass ratio of the adsorbent, binder and wetting and dispersing agent (polyethylene glycol) is 9:0.9:0.1.
  • Example 12 The difference between Example 12 and Example 11 is that in the method for extracting lithium from a salt lake, the binder in the lithium adsorbent used is FEVE type fluorocarbon resin.
  • Example 13 The difference between Example 13 and Example 11 is that in the method for extracting lithium from a salt lake, the binder used in the lithium adsorbent is VDF-CTFE and FEVE fluorocarbon resin with a mass ratio of 1:1.
  • Example 14 The difference between Example 14 and Example 11 is that the mass ratio of the adsorption material, binder, and polyethylene glycol is 9.5:0.4:0.1.
  • the difference between the lithium adsorbent of Example 15 and Example 11 is that the molecular weight of the binder (VDF-CTFE) used is 200,000.
  • the difference between the lithium adsorbent of Example 16 and Example 11 is that the molecular weight of the binder (VDF-CTFE) used is 600,000.
  • the lithium adsorbent of Example 17 is different from that of Example 11 in that: the wetting and dispersing agent used is sodium polyacrylate with a molecular weight of 6000.
  • Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the adsorption process adopts a constant-speed adsorption process, and the salt lake brine is passed through the lithium adsorbent at a flow rate of 2.5BV/h, and the adsorption time is still 3 hours.
  • the adsorption process of step (1) adopts a constant-speed adsorption process, and the salt lake brine is passed through the lithium adsorbent at a flow rate of 2.5BV/h, and the adsorption time is still 3 hours; the step ( 2)
  • the cleaning process adopts a constant-speed cleaning process.
  • the three-step cleaning is performed at the same flow rate of 7.5BV/h.
  • the amount of cleaning agent used in each cleaning is 0.83BV, and the cleaning time of each cleaning is 6.64min.
  • the total time of the cleaning process was 20min, and the total amount of cleaning agent was 2.5BV remained unchanged.
  • the amount of lithium adsorption in the adsorption process of each embodiment and the comparative example method were measured. Lithium content, the ratio of magnesium to lithium in the desorption solution, and the amount of pure water used for cleaning.
  • the lithium adsorption amount is expressed by the mass ratio of the lithium element adsorbed by the adsorbent (that is, the mass difference between the adsorbed brine and the lithium element in the pre-absorbed brine) and the adsorbent
  • the adsorption yield is expressed by the mass ratio of the lithium element absorbed by the adsorbent.
  • the ratio of the mass of lithium element adsorbed by the adsorbent to the mass of lithium element in the original brine is expressed.
  • the lithium loss rate in the cleaning process is determined by the mass of lithium element in the cleaning solution obtained after cleaning (if there are multiple steps of cleaning, this refers to the cleaning solution obtained in the last cleaning step) and the total amount of lithium adsorbed by the lithium-rich adsorbent. ratio.
  • the adsorption efficiency represents the overall performance of the example, that is, on the basis of the adsorption yield, other factors are also considered comprehensively, such as the total adsorption time, the amount of cleaning agent and other factors.
  • the variable speed (from slow to fast) cleaning process can effectively reduce the lithium loss rate in the cleaning process (Examples 1, 6); while the constant speed cleaning process (Examples 7-9 ), the lithium loss rate will be slightly higher, and the ratio of magnesium to lithium in the obtained desorption solution will be slightly higher (the comparison of comparative example 2 and comparative example 1 is a similar situation); in addition, the lithium loss rate of the whole process using pure water cleaning (Example 10) is higher than the lithium loss rate (Example 1) when washing together with recycled water and pure water.
  • Example 15-16 Especially tap water, pure water, etc., often cost more than 3-5 times that of other areas.
  • the difference between Examples 15-16 and Example 11 is that the molecular weight of the binder VDF-CTFE is different.
  • the molecular weight of the binder is in the range of 100,000-800,000. Simultaneously, its desorption effect is better than that of Example 11 whose molecular weight of the binder is 20,000.
  • the wetting and dispersing agent of Example 17 is different from that of Example 11.
  • the desorption effect of Example 11 using polyethylene glycol as the wetting and dispersing agent is slightly better than that of Example 17 using sodium polyacrylate as the wetting and dispersing agent.
  • the method for extracting lithium in the embodiment of the present application adopts a specific variable-speed adsorption process, which has a high adsorption efficiency for lithium in brine, which helps to achieve high-efficiency lithium adsorption at low temperature, and thus can ensure reasonable lithium desorption. liquid.

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Abstract

一种盐湖提锂方法，包括：将盐湖卤水变速通过锂吸附剂，以使盐湖卤水中的锂离子吸附在锂吸附剂上，得到富锂吸附剂；其中，在吸附过程中，盐湖卤水的流速逐渐降低，且盐湖卤水的初始流速与末期流速的差值为0.5-3BV/h；对富锂吸附剂进行清洗；采用锂离子洗脱剂将清洗后的富锂吸附剂上的锂离子脱附下来，得到脱附液。

Description

盐湖提锂方法
本申请要求于2021年12月28日提交中国专利局、申请号为202111630401.1、申请名称为“一种盐湖提锂方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及环境保护和资源循环利用领域，具体涉及一种盐湖提锂方法。
背景技术
中国绝大部分锂资源储藏于盐湖卤水中，大都属于高镁锂比的卤水，因此从高镁锂比卤水中提锂成为中国锂资源开发的重点。近年开发的吸附法因具有对锂离子选择性好、工艺简单、可从高镁锂比盐湖卤水中提取锂、成本低等优点而受到广泛青睐。
然而，目前吸附法提锂工艺对锂的吸附效率低，还存在低温下(如冬天)难以生产得到锂含量高的合格脱附液的问题。
发明内容
为解决上述技术问题，本申请提供了一种可用于盐湖提锂方法，通过在卤水吸附阶段采用特定变速吸附工艺，可极大提高卤水中锂的吸附效率，解决在低温下难以得到高锂含量的合格脱附液的难题，提升了吸附卤水中锂的吸附效率，使得低温下也可以得到高锂含量的合格脱附液，从而可保证全年全天候无间断生产。
本申请提供了一种盐湖提锂方法，包括：将盐湖卤水变速通过锂吸附剂，以使所述盐湖卤水中的锂离子吸附在所述锂吸附剂上，得到富锂吸附剂；其中，在所述吸附过程中，所述盐湖卤水的流速逐渐降低，且所述盐湖卤水的初始流速与末期流速的差值为0.5-3BV/h；对所述富锂吸附剂进行清洗；以及，采用锂离子洗脱剂将所述清洗后的富锂吸附剂上的锂离子脱附下来，得到脱附液。
本申请提供的盐湖提锂方法中，通过在盐湖卤水的吸附阶段采用卤水流速逐渐降低的特定流速变化工艺，可以大大提升对卤水中锂的吸附效率，特别是可以实现低温(零度以下)下的高效锂吸附，进而可以保证在不影响产能的情况下得到锂含量在500mg/L以上的脱附液；在相同的吸附时间下(例如180min)，在产能保持不变的条件下，采用本申请的提锂方法所得脱附液中的锂含量远高于常规采用流速固定的卤水吸附工艺的提锂方法制得的脱附液(一般在400mg/L左右)。
在一些实施方式中，所述初始流速为2.0-3.0BV/h，所述末期流速为1.2-1.8BV/h。
在一些实施方式中，所述盐湖卤水的总待吸附量为6-8个BV，所述吸附的总时长可以为2.5-4h。
在一些实施方式中，所述清洗依次包括：第1道清洗、第2道清洗、和第3道清洗，其中，所述第1道清洗时的第一清洗剂的流速、所述第2道清洗时的第二清洗剂的流速、所述第3道清洗时的第三清洗剂的流速呈依次增加的大小关系；所述第二清洗剂的用量大于所述第一清洗剂的用量、所述第三清洗剂的用量。
在一些实施方式中，第1道清洗时，第一清洗剂的流速为3-5BV/h，用量为0.5-1BV；第2道清洗时，第二清洗剂的流速为6-8BV/h，用量为1-1.5BV；第3道清洗时，第三清洗剂的流速为9-12BV/h，用量为0.5-1BV。
在一些实施方式中，所述第一清洗剂包括含浓度不超过50g/L的镁离子，及浓度不超过300mg/L的锂离子的水溶液；所述第二清洗剂包括含浓度不超过5g/L的镁离子，及浓度不超过250mg/L的锂离子的水溶液；所述第三清洗剂为纯水。
在一些实施方式中，所述锂脱附的过程中，所述锂离子洗脱剂为水，温度为30-50℃。
在一些实施方式中，所述锂吸附剂包括吸附材料、粘结剂和润湿分散剂，其中，所述粘结剂包括偏氟乙烯-三氟氯乙烯共聚物和氟烯烃-乙烯基醚共聚物中的至少一种，所述润湿分散剂包括聚乙二醇、聚丙烯酸钠、聚乙烯醇、甲醛缩合物中的一种或多种。
在一些实施方式中，所述吸附材料为铝系吸附材料。
在一些实施方式中，所述铝系吸附材料可表示为Li aX·mAl(OH) 3·nH 2O，其中，X可以是Cl -、SO 4 2-，a＝1或2，m为1-5，n为1-5。
在一些实施方式中，以所述锂吸附剂的重量为基准，所述吸附材料的含量为80-95wt％，所述粘结剂的含量为4-17wt％，所述润湿分散剂的含量为1-5wt％。
在一些实施方式中，所述吸附材料的质量与所述粘结剂和所述润湿分散剂的质量之和的比值大于或者等于8:1。
在一些实施方式中，所述粘结剂的质量为所述吸附材料的质量的8％-12.5％。
在一些实施方式中，所述偏氟乙烯-三氟氯乙烯共聚物或所述氟烯烃-乙烯基醚共聚物的分子量为10万-80万。
在一些实施方式中，在将所述盐湖卤水变速通过锂吸附剂的步骤之前，所述方法还包括：对所述盐湖卤水进行过滤，以除去其中的杂质。
在一些实施方式中，所述对所述盐湖卤水进行过滤的步骤包括：依次对所述盐湖卤水进行高速离心过滤和反冲洗过滤。
在一些实施方式中，所述锂吸附剂装填在交换柱或吸附塔内。
在一些实施方式中，在将盐湖卤水变速通过锂吸附剂的步骤之前，所述方法还包括：对所述锂吸附剂进行脱锂。
在一些实施方式中，所述锂离子洗脱剂的流速为1.5-2.5BV/h。
在一些实施方式中，所述脱附的时间为2.5-4h。
本申请提供的盐湖提锂方法，通过在盐湖卤水的吸附阶段采用特定的流速变化工艺，可以使对卤水中锂的吸附效率得到有效提升，解决了在低温下(卤水在冬天最低零下十几摄氏度一般不结冰)难以得到高锂含量的合格脱附液的难题，提升了吸附卤水中锂的吸附效率，使得低温下也可以得到高锂含量的合格脱附液，从而可保证全年全天候无间断生产。该盐湖提锂方法的工艺流程简单，提锂收率高，便于大规模工业化生产。
附图说明
图1为本申请一实施例提供的盐湖提锂方法的工艺流程图。
图2为本申请另一实施例提供的盐湖提锂方法的工艺流程图。
具体实施方式
本申请提供了一种盐湖提锂方法，包括以下步骤：
(1)将盐湖卤水变速通过锂吸附剂，以使所述盐湖卤水中的锂离子吸附在所述锂吸附剂上，得到富锂吸附剂；其中，在所述吸附过程中，所述盐湖卤水的流速逐渐降低，且所述盐湖卤水的初始流速与末期流速的差值为0.5-3BV/h；
(2)对所述富锂吸附剂进行清洗；
(3)采用锂离子洗脱剂将所述清洗后的富锂吸附剂上的锂离子脱附下来，得到脱附液。
本申请提供的盐湖提锂方法中，通过在盐湖卤水的吸附阶段采用卤水流速逐渐降低的特定流速变化工艺，可以使对卤水中锂的吸附效率大大提升，特别是可以实现低温(零度以下)下的高效锂吸附，进而在不影响产能的情况下可保证得到锂含量在500mg/L以上的脱附液；在相同的吸附时间下(例如180min)，在产能保持不变的条件下，采用本申请的提锂方法所得脱附液中的锂含量远高于常规采用流速固定的卤水吸附工艺的提锂方法制得的脱附液(一般在400mg/L左右)。
本申请中，在吸附过程中，盐湖卤水的流速可根据时间变化，整体流速随吸附过程的进行而逐渐减低。盐湖卤水的初始流速与末期流速的差值为0.5-3BV/h，具体可以是0.8BV/h、1BV/h、1.2BV/h、1.5BV/h、1.8BV/h、2BV/h或2.5BV/h等。合适的初、末期流速差值有利于对卤水中锂的吸附效率的提升。
其中，初始流速与末期流速的界定可根据具体的卤水变速工艺来定，若卤水的流速是连续地降低，则初始流速为开始吸附时最早通过锂吸附剂的的卤水流速，末期流速为吸附即将结束时，最后通过锂吸附剂的盐湖卤水流速。若卤水的流速是分阶段地离散性降低，即，在吸附过程中，卤水的流速有n个不同的值(n为有限值，流速可分别是V1、V2、…Vn)，其中第1个流速段(流速为V1)为卤水的初始流速，最后一个流速段(即，第n个流速段，流速为Vn)为末期流速。若卤水的总待吸附量为Q(单位是Bv)，则每个流速阶段通过吸附剂的卤水的量可以为Q/n，其中，通过所述锂吸附剂的第1个Q/n BV的盐湖卤水的流速可称为初始流速，通过所述锂吸附剂的最后一个Q/n BV的盐湖卤水的流速可称为末期流速。举例来说，当需要吸附6个BV体积量的盐湖卤水时，每个BV的卤水分别依次采用2.5、2.3、2.1、2.0、1.8、1.6BV/h的流速通过锂吸附剂时，其中，卤水的初始流速为2.5BV/h，末期流速为1.6BV/h，每个卤水的吸附时间分别是24min、26min、28.6min、30min、33min、37.5min。
本申请一些实施方式中，所述初始流速为2.0-3.0BV/h，所述末期流速为1.2-1.8BV/h。相较于流速固定的卤水吸附工艺，采用这样的卤水初始流速、末期流速，对卤水中锂的吸附效率可提升5％-20％。其中，BV一般是指锂吸附剂的填充体积，2.0-3.0BV/h(以下相同)代表卤水流速的体积量在每小时内为所述锂吸附剂体积的2-3倍。在一些实施例中，所述初始流速具体可以是2.0、2.1、2.2、2.3、2.4、2.5、2.6、2.7、2.8、2.9或3.0BV/h等。所述末期流速具体可以是1.2、1.3、1.4、1.5、1.6、1.7或1.8BV/h等。
在一些实施方式中，所述吸附过程中，所述盐湖卤水的总待吸附量为6-8个BV，即，待与锂吸附剂接触的盐湖卤水的体积量是所述锂吸附剂的装填体积量的6-8倍。盐湖卤水的待吸附量可根据盐湖卤水中锂含量的高低(一般为180-300ppm)来发生变动。在一些实施方式中，所述吸附的总时长可以为2.5-4h，例如为2.8h、3h、3.5h、3.8h等。
在一些实施方式中，步骤(1)中，在所述盐湖卤水变速通过锂吸附剂之前，还包括：对所述卤水进行过滤，以除去其中的杂质(比如：颗粒状杂质)。其中，过滤可以依次包括：高速离心过滤和反冲洗过滤。高速离心过滤主要是为了除去去除大颗粒的沉淀物，高速离心过滤可以在离心式固液分离机中进行，离心速度为15000-35000rpm。反冲洗过滤是为了进一步精密过滤，以使盐湖卤水中的固态杂质更少以确保过滤得到的物料不影响所述锂吸附剂的吸附功能，且过滤后的杂质反冲洗方便，且不用频繁更换过滤耗材。反冲洗过滤可以采用不锈钢滤网型反冲洗过滤机进行。
本申请中，所述盐湖卤水通过吸附法实现提锂。锂吸附剂可以装填在交换柱内(如玻璃柱、不锈钢柱)或吸附塔等载体内。当盐湖卤水流过装有锂吸附剂的载体，并与锂吸附剂接 触时，其中的锂离子可被锂吸附剂所吸附、固定下来，同时锂吸附剂也转变为吸附有锂的富锂吸附剂。
本申请实施方式中，所用锂吸附剂可以包括吸附材料和粘结剂。其中，吸附材料可以是铝系吸附材料，锰系吸附材料(例如尖晶石型锰氧化物与锂离子形成的结合体)、钛系吸附材料(例如偏钛酸型锂离子筛吸附剂)、铁系吸附材料等。本申请一些实施方式中，吸附材料为铝系吸附材料。铝系吸附材料可以是氢氧化铝和含锂化合物(如卤化锂、硫酸锂等)形成的结合体。该铝系吸附材料可从含锂溶液中吸附锂离子，待吸附饱和后，经一定温度的水洗脱，锂离子可从其上解析到溶液中。在一些实施方式中，所述铝系吸附材料可表示为Li aX·mAl(OH) 3·nH 2O，其中，X可以是Cl -、SO 4 2-等；a＝1或2；m为1-5，优选为2；n为1-5。进一步地，为使本申请的锂吸附剂的锂吸附能力更强，在采用其进行盐湖提锂之前，可对该锂吸附剂进行适当脱锂，以使吸附材料具有较多的锂空位。脱锂后的铝系吸附材料可表示为(1-x)Li a’X·mAl(OH) 3·nH 2O，0＜x＜1。其中，铝系吸附材料可以通过机械化学合成法、浸泡法、酸化转化法、沉淀法等制得。以LiCl·mAl(OH) 3·nH 2O为例，其可通过LiCl溶液浸泡氢氧化铝法制得，或者通过LiOH溶液浸泡氢氧化铝后酸化转化得到，或者通过AlCl3和LiCl溶液共沉淀制得，还可以通过LiOH和氢氧化铝研磨法制得等。
其中，粘结剂可以是环氧树脂、酚醛树脂、聚氯乙烯、聚乙烯、聚丙烯、聚苯乙烯、聚偏氟乙烯、乙烯-醋酸乙烯共聚物、偏氟乙烯-三氟氯乙烯共聚物(简称VDF-CTFE)和氟烯烃-乙烯基醚共聚物(也可称为FEVE型氟碳树脂)等中的一种或多种。
在一些实施方式中，所述粘结剂为偏氟乙烯-三氟氯乙烯共聚物和氟烯烃-乙烯基醚共聚物中的至少一种。此时，所述锂吸附剂还包括润湿分散剂，具体可以包括聚乙二醇、聚丙烯酸钠、聚乙烯醇、甲醛缩合物中的一种或多种。示例性的甲醛缩合物可以包括但不限于萘磺酸盐甲醛缩合物、甲基萘磺酸盐甲醛缩合物、苄基萘磺酸盐甲醛缩合物、酚磺酸盐甲醛缩合物等中的一种或多种。
采用偏氟乙烯-三氟氯乙烯共聚物和/或氟烯烃-乙烯基醚共聚物作粘结剂，不仅可以使锂吸附剂的结构稳定性及机械强度较高、耐腐蚀性好，在循环多次吸锂-脱锂使用后，该吸附剂的溶损率低，使用寿命长，同时上述粘结剂还可使吸附剂形成合适孔隙率和窄孔径的表面状态，使得上述锂吸附剂的锂吸附效率较高、不会使锂吸附剂的有效活性面积变小而影响其吸附速度和效率；上述润湿分散剂的润湿性也有利于吸附剂对锂离子的吸附效率和吸附量提高。此外，在这两种特定粘结剂的出色的表面光滑度和洁净性能及润湿分散剂的润湿性的协同作用下，还使得上述锂吸附剂在吸附锂后易于清洗干净、脱附锂的过程更易进行，进而节省清洗和脱附过程的用水量，降低吸附剂在这些过程中的溶损率，降低脱附温度，对盐湖等高缺少缺能源地区实现工业化提锂具有较大意义，并得到镁锂比低、锂含量高的合格脱附液。
在一些实施方式中，偏氟乙烯-三氟氯乙烯共聚物或氟烯烃-乙烯基醚共聚物的分子量可以为10万-80万。适当高分子量的粘结剂的粘结效果较好，并降低锂吸附剂在使用过程中发生裂纹、破碎的风险，提高其使用寿命。其中，偏氟乙烯-三氟氯乙烯共聚物中，单体偏氟乙烯与三氟氯乙烯的共聚比可以为1：(1-5)，优选为1:4。优选地，所述粘结剂为偏氟乙烯-三氟氯乙烯共聚物，或者为偏氟乙烯-三氟氯乙烯共聚物和氟烯烃-乙烯基醚共聚物的混合。
在一些实施方式中，所述甲醛缩合物的分子量为4000-10000。所述聚丙烯酸钠的分子量为5000-10000。
本申请一些实施方式中，所述润湿分散剂为聚乙二醇。聚乙二醇的润湿、分散性较优异。在一些实施方式中，所述聚乙二醇的分子量为10000-30000。较高分子量的聚乙二醇随吸附剂 在水中的溶解程度较低，使吸附剂的使用寿命较长。
本申请实施方式中，以所述锂吸附剂的重量为基准，所述吸附材料的含量为80-95wt％，所述粘结剂的含量为4-17wt％，所述润湿分散剂的含量为1-5wt％。适量占比的吸附材料、粘结剂、润湿分散剂的配合下，可使整体锂吸附剂能兼顾良好的结构稳定性、吸附效果及脱附效果。优选地，吸附材料的含量为85-92wt％。优选地，粘结剂的含量为5-15wt％，进一步优选为6-12wt％。优选地，润湿分散剂的含量为1-3wt％。
本申请一些实施方式中，所述粘结剂的质量为所述吸附材料的8％-12.5％。适量的粘结剂用量可在保证锂吸附剂的结构稳定性高、使用寿命长(不易破碎)的情况下，还会弱化其对所得锂吸附剂的吸附容量的降低影响。
本申请实施方式中，所述润湿分散剂的质量为所述吸附材料的1％-5％。此时，润湿分散剂可使得吸附材料在锂吸附剂颗粒中的分布情况更均匀、骨架更稳定，锂吸附剂颗粒的润湿性也得到提高，进而其吸附/脱附锂的速度也变高。此外，润湿分散剂也可在卤水中较缓慢地溶解，使吸附剂的孔隙率缓慢增加，进一步提高吸附剂的吸附效率，且不会对吸附剂的溶损率造成明显影响、不会明显减低吸附剂的使用寿命。
本申请一些实施方式中，所述吸附材料的质量与所述粘结剂和所述润湿分散剂的质量之和的比值大于或者等于8:1。这样更利于所述锂吸附剂兼顾良好的结构稳定性及优异的吸附、脱附性能。优选地，该比值可以在(8-10)：1的范围内。该比值具体可以是8.5、9:1、9.5:1等。
本申请实施方式中，所述锂吸附剂可以为柱状颗粒。柱状锂吸附剂颗粒的成型简单，表面光滑程度高，可避免其使用过程中因相互挤压、摩擦等而磨损或者掉粉，降低损耗量。在一些实施方式中，所述锂吸附剂的颗粒直径为1.2mm-1.8mm，长度为1.5mm-2.5mm。这样形貌和合适尺寸的锂吸附剂，可使液体和离子需要扩散的路径更合适，并且吸附剂之间挤压的时候容易留出一定空隙以利于卤水的渗透，有利于锂离子吸附效率的提高，并使脱附过程中锂离子与水之间的离子交换更易进行，便于降低脱锂温度及脱附水的用量以保证吸附的锂完全脱附下来。
本申请的步骤(2)中，对所述富锂吸附剂的清洗主要是洗去已吸附有锂离子的富锂吸附剂表面的杂质。本申请实施方式中，所述清洗分三步进行，依次包括：第1道清洗、第2道清洗和第3道清洗，其中，所述第1道清洗时的第一清洗剂的流速、所述第2道清洗时的第二清洗剂的流速、所述第3道清洗时的第三清洗剂的流速呈依次增加的大小关系(即，第一清洗剂的流速＜第二清洗剂的流速＜第三清洗剂的流速)；所述第二清洗剂的用量大于所述第一清洗剂的用量、所述第三清洗剂的用量。其中，第一清洗剂的用量与第三清洗剂的用量可以相等或者不等。
上述对富锂吸附剂的清洗工序分先慢后快三步进行，其中第1道清洗时的流速较低，可避免装有富锂吸附剂的载体中大量高浓度卤水在过快清洗流速下形成混凝层而使卤水中的杂质不易排出、大大降低清洗效果。第2道清洗时的流速适中，且清洗剂的用量较大，可保证清洗时间充足，以保证吸附剂粘附的镁等杂质能够充分溶解去除。第3道清洗时的流速较快，且清洗剂的用量低于第2道清洗剂的用量，可减少富锂吸附剂上吸附的锂脱附于清洗剂中，降低水洗过程的锂损失。因此，采用上述特定的清洗工艺可以将富锂吸附剂表面的杂质清洗干净，使后续脱附所得脱附液的镁锂质量比较低，且清洗剂的用量较少，清洗过程中的锂损失率(即，溶于清洗剂中的锂元素占被富锂吸附剂吸附的总锂元素的质量比)在16％以内，甚至在15％。
在一些实施方式中，所述第3道清洗时的清洗剂流速与所述第1道清洗时的清洗剂流速的差值可以在5-9BV/h。此时可取得更好的上述清洗效果。
本申请一些实施方式中，所述清洗分三步进行，包括：第1道清洗，第一清洗剂的流速为3-5BV/h，用量为0.5-1BV；第2道清洗，第二清洗剂的流速为6-8BV/h，用量为1-1.5BV；第3道清洗，第三清洗剂的流速为9-12BV/h，用量为0.5-1BV。采用该清洗工艺能更好地将富锂吸附剂表面的杂质清洗干净，使后续脱附所得脱附液的镁锂质量比更低，如可降至2:1以下，清洗过程中的锂损失率更低，低于15％，远低于业界常用的定速清洗工艺带来的约20％左右的锂损失水平(甚至25％的损失率)。
具体地，所述第一清洗剂的用量可以为0.6、0.7、0.8或0.9BV等；所述第二清洗剂的用量可以为1、1.2、1.3、1.4、1.5BV等；第三清洗剂的用量可以为0.6、0.7、0.8或0.9BV等。进一步地，为减少清洗过程中的锂损失率，在一些实施方式中，控制所述清洗过程中各道清洗剂的总用量不超过2.5BV。
在一些实施例中，第1道清洗的时间为6-20min，进一步可以是7-15min(例如是9min)，第2道清洗的时间为7.5-15min，进一步可以是9-13min(例如是11min)，第3道清洗的时间为2.5-6.6min(例如是4min)。在一些实施方式中，步骤(2)中，清洗的总时间可以控制在25min以内，进一步可以是20min以内。这样可以在达到较好的杂质清洗目的同时，还可降低锂损失率。
在具体实施例中，清洗过程具体包括：
i)采用第一清洗剂(即，第1道清洗用清洗剂)对所述富锂吸附剂进行第1道清洗，得到第一清洗液和第一吸附剂；
ii)采用第二清洗剂(即，第2道清洗用清洗剂)对所述第一吸附剂进行第2道清洗，得到第二清洗液和第二吸附剂；
iii)采用第三清洗剂(即，第3道清洗用清洗剂)对所述第二吸附剂进行第3道清洗，得到第三清洗液和第三吸附剂。这里的第三吸附剂即为清洗结束后的富锂吸附剂，前述步骤(3)的脱附也是针对其进行。
本申请中，第一清洗剂、第二清洗剂、第三清洗剂均含大量的水，各清洗剂可以是纯水，或者回用水(含有一定的无机金属离子杂质)，各清洗剂的组成可以不同。在一些实施方式中，第一清洗剂、第二清洗剂、第三清洗剂均为纯水。此时，纯水的用量较大，且清洗过程中锂的损失率会略大。
在另一些实施方式中，第一清洗剂、第二清洗剂为回用水；第三清洗剂为纯水，而非回用水，具体可以是去离子水、蒸馏水、干净地下水、自来水等。前2道清洗用清洗剂为含锂的回用水，可抑制清洗过程中锂的脱附，最后一道清洗为纯水，纯水的用量较小，且可保证较洁净的清洗效果。在一些实施方式中，各清洗剂中不含有机物，且电导率小于300μs/cm，进一步地电导率小于200μs/cm，优选小于50μs/cm。
进一步地，第一清洗剂、第二清洗剂、第三清洗剂中的镁元素含量依次降低。在一些实施方式中，第一清洗剂中的镁含量不超过50g/L，优选不超过30g/L，进一步优选为不超过10g/L；第二清洗剂中的镁含量不超过5g/L，第三清洗剂中的镁含量不超过100mg/L。在一些实施例中，第一清洗剂中的镁离子含量不超过50g/L，锂离子含量不超过300mg/L。在一些实施方式中，所述第一清洗剂还可以包括浓度均不超过10g/L的其他各金属离子(钙、硼、钠或钾)。第二清洗剂中的镁离子含量不超过5g/L，锂离子含量不超过250mg/L。
本申请一些实施方式中，可将步骤(3)的脱附过程中得到的锂浓度不超过250mg/L的 不合格脱附液(脱附后期产生)作为第2道清洗用清洗剂(即，第二清洗剂)；此外，脱附结束后装有锂吸附剂的载体(如吸附柱)中残留的水也可以排出，作为第二清洗剂。第3道清洗后得到的第三清洗液或第2道清洗后得到的第二清洗液可作为第1道清洗用清洗剂(即，第一清洗剂)。第1道清洗后得到的第一清洗液可返回混入所述盐湖卤水中。这样在整个清洗过程中，仅第3道清洗采用纯水，纯水的用量较少，这对在缺水地区进行盐湖卤水提锂工艺具有极大的经济和环保效益。示例性的，第二清洗液中一般含有浓度不超过50g/L的镁离子，其他各金属离子(钙、锂、硼、钠或钾)的浓度均不超过10g/L；锂离子浓度进一步可以为100-200ppm。第三清洗液中，一般含有浓度不超过10g/L的镁离子，以及浓度均不超过0.5g/L的其他各金属离子(如钙、锂、硼、钠或钾等)；进一步地，锂离子浓度低于300mg/L。
本申请的步骤(3)中，采用锂离子洗脱剂(也可称锂脱附剂)对清洗后的富锂吸附剂进行洗脱，是为了将富锂吸附剂上吸附的锂离子脱附下来，使锂离子洗脱解吸至洗脱剂中得到脱附液，以便对脱附液进行进一步处理、利用(一般是转变为碳酸锂产品)；同时富锂吸附剂经脱附锂后，可以再生成所述锂吸附剂，再用来与盐湖卤水接触进行吸附提锂。上述提锂方法，步骤(1)-(3)为一个循环。
本申请实施方式中，锂离子洗脱剂的温度(也即“脱附过程的温度”)可以为30-50℃。在一些实施方式中(如采用上述含偏氟乙烯-三氟氯乙烯共聚物和/或氟烯烃-乙烯基醚共聚物中作粘结剂的锂吸附剂时)，该温度可以是可以为30-40℃，例如为28、30、32、35、38或40℃等，进一步可以是30-35℃。其中，锂离子洗脱剂可以为去离子水、蒸馏水、干净地下水或自来水等。当然，也可可采用未达到锂浓度要求的不合格脱附液(脱附后期产生)按照从锂含量高到低的顺序进行先后脱附，以得到最大量的含锂量合格脱附液。
在一些实施方式中，所述锂离子洗脱剂的流速为1.5-2.5BV/h，例如为1.8BV/h、2BV/h、2.2BV/h等。这样可以保证脱附液中的锂离子含量较高，且脱附时间不致过长。在一些实施方式中，所述脱附的时间为2.5-4h，例如为2.8h、3h、3.5h、3.8h等。
本申请提供的盐湖提锂方法，通过在盐湖卤水的吸附阶段采用特定的流速变化工艺，可以使对卤水中锂的吸附效率得到有效提升，解决了在低温下(卤水在冬天最低零下十几摄氏度一般不结冰)难以得到高锂含量的合格脱附液的难题，可保证全年全天候无间断生产。该盐湖提锂方法的工艺流程简单，提锂收率高，便于大规模工业化生产。
下面分多个实施例对本申请实施例的技术方案进行详细说明。
以下实施例中所用待提锂的盐湖卤水的组成如下表1所示。
表1
Figure PCTCN2022136482-appb-000001
Figure PCTCN2022136482-appb-000002
实施例1
一种盐湖提锂方法，工艺流程图如图1所示，具体包括以下步骤：
(1)吸附：
将锂吸附剂(具体包括铝系吸附材料LiCl·2Al(OH) 3·nH 2O、粘结剂-聚偏氟乙烯，二者质量比为9:1)装填在玻璃吸附柱内，装填量为0.9dm 3；
将待提锂的盐湖卤水(以下简称“卤水”)依次进行高速离心过滤、反冲洗过滤后，使其变速通过装有上述锂吸附剂的吸附柱，使其中的锂离子被吸附在锂吸附剂上并使锂吸附剂转变为富锂吸附剂；其中，吸附过程的温度为25℃，待吸附的卤水为6个BV，共5400mL，通过吸附柱的第1个BV的卤水的流速(即初始流速)为2.5BV/h，吸附时间24分钟，第2个BV的卤水的流速为2.3BV/h，吸附时间为26分钟，第3个BV的卤水的流速为2.1BV/h，吸附时间为28分钟，第4个BV的卤水的流速为2.0BV/h，吸附时间为30分钟，第5个BV的卤水的流速为1.8BV/h，吸附时间为33分钟，第6个BV的卤水的流速(即末期流速)为1.3BV/h，吸附时间为38分钟，上述吸附过程的总吸附时长约为3小时。
(2)富锂吸附剂的清洗：
采用清水对带富锂吸附剂的吸附柱进行清洗以洗去富锂吸附剂表面吸附的杂质；整个清洗过程分3步进行，清洗剂的总用量为2250mL(即，2.5BV)，总清洗时间20分钟，具体包括：
a)第1道清洗：采用来自前一个循环中第3道清洗流出来的第三清洗液(组成为：Li +含量为210mg/L，Mg 2+含量为10g/L)作为第一清洗剂来清洗富锂吸附剂，其中，第一清洗剂的用量为0.6BV，流速为4.5BV/h，清洗时间为8分钟，清洗结束后，得到第一吸附剂和第一清洗液；第一清洗液可回用混入盐湖卤水；
b)第2道清洗：采用来自前一个循环脱附阶段后期收集的不合格脱附液(组成为：Li +含量为105mg/L，Mg 2+含量为150mg/L)作为第二清洗剂来清洗第一吸附剂，其中，第二清洗剂的体积用量为1.3BV(即1170mL)，流速为8.5BV/h，清洗时间为9分钟；清洗结束后，得到第二吸附剂和第二清洗液；第二清洗液的镁锂质量比为206：1，可以收集起来用作卤水再次吸附，减少锂的损失；
c)第3道清洗：采用纯水作为该道清洗的第三清洗剂，其体积用量为0.6BV(5400mL)，流速为12BV/h，清洗时间为3分钟，清洗结束后，得到第三吸附剂和第三清洗液；第三清洗液可存入预储罐中用作下个循环的第一清洗剂。
(3)脱附：
采用50℃的纯水作为锂离子洗脱剂对第三吸附剂进行淋洗脱附以脱去吸附的锂离子，其中，水的用量为3.3BV，流速为1.7BV/h，脱附时间为116min，收集脱附过程中前面2BV的液体作为合格脱附液(Li +含量大于500mg/L)，后面1.3BV作为不合格液回收用作清洗剂。
实施例2
实施例2与实施例1的不同之处在于：吸附过程中，按吸附先后顺序卤水的流速分别是2.8BV/h(初始流速)、2.6BV/h、2.4BV/h、2.1BV/h、1.8BV/h，1.5BV/h(末期流速)，吸附时间分别为21.5min、23min、25min、28.5min、33min、40min，总的吸附时间为171分钟(即2.85h)， 其余工艺参数与实施例1保证一致。
实施例3
实施例3与实施例1的不同之处在于：吸附过程中，按吸附先后顺序卤水的流速分别是2BV/h(初始流速)、1.8BV/h、1.6BV/h、1.4BV/h、1.3BV/h，1.2BV/h(末期流速)，吸附时间分别为30min、33.3min、37.5min、43min、46min、50min，总的吸附时间约为240min，其余工艺参数与实施例1保证一致。
实施例4
实施例4与实施例1的不同之处在于：卤水的初始流速为3.5BV/h，末期流速为2.0BV/h，具体地，按吸附先后顺序，待吸附的6个BV的卤水的流速分别是3.5BV/h、3.2BV/h、3.0BV/h、2.8BV/h、2.5BV/h，2.0BV/h。各1个BV的卤水的吸附时间分别为17min、18.75min、20min、21.4min、24min、30min，总的吸附时间约为240min。
实施例5
实施例5与实施例1的不同之处在于：待吸附的卤水量为7.5个BV，在吸附过程中，卤水的流速增加降低，分为7个不同流速段，相邻流速段的降低幅度为0.5BV/h，其中初始流速为5BV/h，末期流速为2BV/h，各1.07个BV的卤水的吸附时间分别为12.9min、14.3min、16.1min、18.4min、21.4min、25.7min、32.1min，总的吸附时间约为140.9min。
实施例6
实施例6与实施例1的不同之处在于：清洗过程的三步流速分别为：5BV/h、8BV/h、12BV/h，清洗时间分别是7min、10min、3min，总清洗时间为20分钟，其余工艺参数与实施例1保证一致。
实施例7
实施例7与实施例1的不同之处在于：清洗过程采用定速清洗工艺，三步清洗以相同的流速7.5BV/h进行清洗，每道清洗时清洗剂的用量分别为0.8BV、0.9BV和0.8BV，清洗时间分别为：384秒，432秒，384秒。清洗过程的总时间20min、清洗剂的总用量2.5BV保持不变。
实施例8
实施例8与实施例1的不同之处在于：清洗过程采用定速清洗工艺，三步清洗以相同的流速7.5BV/h进行清洗，每道清洗时清洗剂的用量均为0.83BV、各道清洗时间均为6.64min。清洗过程的总时间20min、清洗剂的总用量2.5BV保持不变。
实施例9
实施例9与实施例1的不同之处在于：清洗过程采用定速清洗工艺，三步清洗以相同的流速5BV/h进行清洗，每道清洗时清洗剂的用量均为0.83BV、各道清洗时间均为10min。清洗剂的总用量2.5BV保持不变，清洗过程的总时间变为30min。
实施例10
一种盐湖提锂方法，工艺流程图如图2所示，实施例10与实施例1的不同之处在于：清洗过程中，各道清洗所采用的清洗剂均为纯水(不像实施例1中第1-2道清洗均采用回收水)。
实施例11
实施例11与实施例1的不同之处在于：所用锂吸附剂不同，脱附温度为30℃，其余工艺参数均相同。具体地，实施例11所用锂吸附剂包括与实施例1相同的吸附材料，但其粘结剂是分子量约为2万的偏氟乙烯-三氟氯乙烯共聚物，还包括分子量为1万的聚乙二醇作润湿分散剂，且吸附材料、粘结剂和润湿分散剂(聚乙二醇)的质量比为9:0.9:0.1。
实施例12
实施例12与实施例11的区别在于：盐湖提锂方法中，所用锂吸附剂中的粘结剂为FEVE型氟碳树脂。
实施例13
实施例13与实施例11的区别在于：盐湖提锂方法中，所用锂吸附剂中的粘结剂为质量比1:1的VDF-CTFE和FEVE型氟碳树脂。
实施例14
实施例14与实施例11的区别在于：吸附材料、粘结剂、聚乙二醇的质量比为9.5：0.4：0.1。
实施例15
实施例15的锂吸附剂与实施例11的不同之处在于：所用粘结剂(VDF-CTFE)的分子量为20万。
实施例16
实施例16的锂吸附剂与实施例11的不同之处在于：所用粘结剂(VDF-CTFE)的分子量为60万。
实施例17
实施例17的锂吸附剂与实施例11的不同之处在于：所用润湿分散剂是分子量为6000的聚丙烯酸钠。
为凸出本申请实施例的有益效果，设置以下对比例。
对比例1
对比例1与实施例1的不同之处在于：吸附过程采用定速吸附工艺，将盐湖卤水以2.5BV/h的流速通过锂吸附剂，吸附时间仍为3小时。
对比例2
对比例2与实施例1的不同之处在于：步骤(1)的吸附过程采用定速吸附工艺，将盐湖卤水以2.5BV/h的流速通过锂吸附剂，吸附时间仍为3小时；步骤(2)的清洗过程采用定速清洗工艺，三步清洗以相同的流速7.5BV/h进行清洗，每道清洗时清洗剂的用量均为0.83BV、各 道清洗时间均为6.64min。清洗过程的总时间20min、清洗剂的总用量2.5BV保持不变。
为对本申请实施例的效果进行有力支持，测定各实施例和对比例方法的吸附过程中的锂吸附量、吸附总时长、吸附收率、清洗过程中的锂损失率、最终所得脱附液中的锂含量、脱附液中的镁锂比、以及清洗纯水用量。其中，锂吸附量通过被吸附剂吸附掉的锂元素质量(即，吸附后的卤水与吸附前卤水中锂元素的质量差值)与该吸附剂的质量比来表示，吸附收率通过被锂吸附剂吸附的锂元素质量与原卤水中锂元素质量的比值来表示。清洗过程中的锂损失率是通过清洗完成后得到的清洗液(若有多步清洗，这是指最后一道清洗所得清洗液)中的锂元素质量与被富锂吸附剂所吸附的总锂量的比值。吸附效率表示实施例的综合性能，即在吸附收率的基础上还综合考虑其他因素，例如吸附总时长，清洁剂的用量等因素。
以上结果汇总在下表2中。
表2各实施例和对比例的结果汇总
Figure PCTCN2022136482-appb-000003
一般地，在采用同样的吸附剂在同样温度下进行提锂时，吸附总时长越长，吸附效率越高。从表2可以获知，在吸附剂相同、吸附总时长相同时，变速吸附工艺的吸附效率(实施例 1)要比定速吸附工艺(对比例1-2)的吸附效率的效率高得多。实施例2-5与实施例1的吸附时长不同，虽然实施例2、4、5的总吸附时长比实施例1短，但实施例2、4、5的吸附效率与实施例1的吸附效率相比差距不明显。此外，以清洗剂的流速为变量，采用变速(由慢到快)清洗工艺，可有效降低清洗过程中的锂损失率(实施例1、6)；而定速清洗工艺(实施例7-9)，锂损失率会稍高，且得到的脱附液中镁锂比会略高(对比例2与对比例1的比对是类似的情况)；此外，全程采用纯水清洗的锂损失率(实施例10)高于回用水和纯水共同清洗时的锂损失率(实施例1)。
此外，通过实施例11-14与实施例1的对比可知，采用偏氟乙烯-三氟氯乙烯共聚物和氟烯烃-乙烯基醚共聚物中的至少一种作粘结剂及含润湿分散剂的吸附剂中，其脱附温度可较低，且锂脱附液的锂离子浓度与实施例1基本相当。在锂脱附液的锂离子浓度相当的情况下，实施例的脱附温度越低，越能节约大量能源，对于稀缺水电能源的盐湖地区来说，水电用量对生产成本和产能具有重大意义，特别是自来水，纯水等，往往成本是其余地区的3-5倍以上。此外，实施例15-16与实施例11的区别在于，粘结剂VDF-CTFE的分子量不同，实施例15-16中该粘结剂的分子量在10万-80万的范围，在其它条件相同时，其比粘结剂分子量为2万的实施例11的脱附效果较好。实施例17与实施例11的润湿分散剂不同，采用聚乙二醇作润湿分散剂的实施例11，比采用聚丙烯酸钠作润湿分散剂的实施例17的脱附效果略好。
总的说来，本申请实施例的提锂方法，采用特定的变速吸附工艺，对卤水中锂的吸附效率高，有助于实现低温下的高效锂吸附，进而可保证得到合理的锂脱附液。
以上所述是本申请的示例性实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本申请的保护范围。

Claims (20)

  1. 一种盐湖提锂方法，其特征在于，包括：
    使盐湖卤水变速通过锂吸附剂，以使所述盐湖卤水中的锂离子吸附在所述锂吸附剂上，得到富锂吸附剂；其中，在所述吸附的过程中，所述盐湖卤水的流速逐渐降低，且所述盐湖卤水的初始流速与末期流速的差值为0.5-3BV/h；
    对所述富锂吸附剂进行清洗；以及
    采用锂离子洗脱剂将清洗后的富锂吸附剂上的锂离子脱附下来，得到脱附液。
  2. 根据权利要求1所述的盐湖提锂方法，其特征在于，所述初始流速为2.0-3.0BV/h，所述末期流速为1.2-1.8BV/h。
  3. 根据权利要求1或2所述的盐湖提锂方法，其特征在于，所述盐湖卤水的总待吸附量为6-8个BV，所述吸附的过程的总时长为2.5-4h。
  4. 根据权利要求1-3中任一项所述的盐湖提锂方法，其特征在于，所述清洗依次包括：第1道清洗、第2道清洗、和第3道清洗，且所述第1道清洗时的第一清洗剂的流速、所述第2道清洗时的第二清洗剂的流速、所述第3道清洗时的第三清洗剂的流速呈依次增大；所述第二清洗剂的用量大于所述第一清洗剂的用量、所述第三清洗剂的用量。
  5. 根据权利要求4所述的盐湖提锂方法，其特征在于，
    所述第1道清洗时，第一清洗剂的流速为3-5BV/h，用量为0.5-1BV；
    所述第2道清洗时，第二清洗剂的流速为6-8BV/h，用量为1-1.5BV；以及
    所述第3道清洗时，第三清洗剂的流速为9-12BV/h，用量为0.5-1BV。
  6. 根据权利要求4或5所述的盐湖提锂方法，其特征在于，所述第一清洗剂包括含浓度不超过50g/L的镁离子及浓度不超过300mg/L的锂离子的水溶液；所述第二清洗剂包括含浓度不超过5g/L的镁离子及浓度不超过250mg/L的锂离子的水溶液；所述第三清洗剂为纯水。
  7. 根据权利要求1-6中任一项所述的盐湖提锂方法，其特征在于，所述锂离子脱附的过程中，所述锂离子洗脱剂为水，温度为30-50℃。
  8. 根据权利要求1-7中任一项所述的盐湖提锂方法，其特征在于，所述锂吸附剂包括吸附材料、粘结剂和润湿分散剂，其中，所述粘结剂包括偏氟乙烯-三氟氯乙烯共聚物和氟烯烃-乙烯基醚共聚物中的至少一种，所述润湿分散剂包括聚乙二醇、聚丙烯酸钠、聚乙烯醇、甲醛缩合物中的一种或多种。
  9. 根据权利要求8所述的盐湖提锂方法，其特征在于，所述吸附材料为铝系吸附材料。
  10. 根据权利要求9所述的盐湖提锂方法，其特征在于，所述铝系吸附材料表示为Li aX·mAl(OH) 3·nH 2O，其中，X是Cl -或SO4 2-，a＝1或2，m为1-5，n为1-5。
  11. 根据权利要求8-10中任一项所述的盐湖提锂方法，其特征在于，以所述锂吸附剂的重量为基准，所述吸附材料的含量为80-95wt％，所述粘结剂的含量为4-17wt％，所述润湿分散剂的含量为1-5wt％。
  12. 根据权利要求8-11中任一项所述的盐湖提锂方法，其特征在于，所述吸附材料的质量与所述粘结剂和所述润湿分散剂的质量之和的比值大于或者等于8:1。
  13. 根据权利要求8-12中任一项所述的盐湖提锂方法，其特征在于，所述粘结剂的质量为所述吸附材料的质量的8％-12.5％。
  14. 根据权利要求8-13中任一项所述的盐湖提锂方法，其特征在于，所述偏氟乙烯-三氟氯乙烯共聚物或所述氟烯烃-乙烯基醚共聚物的分子量为10万-80万。
  15. 根据权利要求1-14中任一项所述的盐湖提锂方法，其特征在于，在所述将盐湖卤水变速通过锂吸附剂的步骤之前，所述方法还包括：
    对所述盐湖卤水进行过滤，以除去其中的杂质。
  16. 根据权利要求15所述的盐湖提锂方法，其特征在于，所述对所述盐湖卤水进行过滤的步骤包括：
    依次对所述盐湖卤水进行高速离心过滤和反冲洗过滤。
  17. 根据权利要求1-16中任一项所述的盐湖提锂方法，其特征在于，所述锂吸附剂装填在交换柱或吸附塔内。
  18. 根据权利要求1-17中任一项所述的盐湖提锂方法，其特征在于，在将盐湖卤水变速通过锂吸附剂的步骤之前，所述方法还包括：
    对所述锂吸附剂进行脱锂。
  19. 根据权利要求1-18中任一项所述的盐湖提锂方法，其特征在于，所述锂离子洗脱剂的流速为1.5-2.5BV/h。
  20. 根据权利要求1-19中任一项所述的盐湖提锂方法，其特征在于，所述脱附的时间为2.5-4h。
PCT/CN2022/136482 2021-12-28 2022-12-05 盐湖提锂方法 Ceased WO2023124792A1 (zh)

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