WO2022007662A1 - 带滤机及其在吸附法卤水提锂中的应用 - Google Patents

带滤机及其在吸附法卤水提锂中的应用 Download PDF

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Publication number
WO2022007662A1
WO2022007662A1 PCT/CN2021/103006 CN2021103006W WO2022007662A1 WO 2022007662 A1 WO2022007662 A1 WO 2022007662A1 CN 2021103006 W CN2021103006 W CN 2021103006W WO 2022007662 A1 WO2022007662 A1 WO 2022007662A1
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Prior art keywords
salt
liquid
washing
lithium
desorption
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PCT/CN2021/103006
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English (en)
French (fr)
Inventor
李亦然
沈芳明
马君耀
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浙江衢州明德新材料有限公司
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Publication of WO2022007662A1 publication Critical patent/WO2022007662A1/zh

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    • 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
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • 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 invention belongs to the technical field of lithium extraction from brine, and particularly relates to a belt filter and its application in the extraction of lithium from brine by an adsorption method.
  • Selective adsorption method is currently the main method for extracting lithium from salt lake brine.
  • Selective adsorption method can adsorb and separate lithium from mixed solutions containing various ions, and then elution can achieve the purpose of separating lithium ions from other ions. Since this adsorption method is similar to the traditional water treatment method, the equipment used in the existing brine extraction and adsorption process basically comes from the traditional water treatment industry. It is a molecular sieve or ion sieve type adsorbent such as aluminum series, monoclinic antimonate series, titanate series, manganese oxide series, etc.
  • the crystal structure of this type of selective adsorption material contains a void structure suitable for lithium ions, so in the presence of various ions, it has specific selective adsorption properties for lithium ions.
  • Powder adsorbents do not require granulation, and their adsorption capacity is much higher than that of granular adsorbents, which can greatly reduce the adsorption reaction time and reduce the amount of adsorbents.
  • literature or patent reports using powder adsorbents combined with plate and frame filter presses, centrifuges, precision filtration or ceramic membranes for adsorption and desorption.
  • the purpose of the present invention is to provide a belt filter and its application in the extraction of lithium from brine by adsorption.
  • the belt filter of the present invention is designed for powdery lithium ion selective adsorbents.
  • Lithium extraction from brine can be carried out directly using powdered adsorbents.
  • a belt filter machine comprises a frame, the frame is provided with a filter cloth that reciprocates and rotates, and is sequentially provided along the advancing direction of the filter cloth:
  • a solid-liquid separation zone above the solid-liquid separation zone is provided a mixed adsorption mechanism for transporting the adsorbent brine mixture to the solid-liquid separation zone;
  • the salt washing area above the salt washing area, a washing salt liquid conveying mechanism for conveying the washing salt liquid to the salt washing area is arranged;
  • a desorption liquid conveying mechanism for transporting desorption liquid to the desorption zone is arranged above the desorption zone, and a lithium eluent collection port is arranged below the desorption zone.
  • the total salinity of brine can reach hundreds of grams per liter, while the lithium content is only tens to hundreds of milligrams per liter.
  • the patentee has found through a lot of research and experiments that in the process of extracting lithium from brine by adsorption, how to minimize the salt-to-lithium ratio in the lithium eluent is the key to extracting lithium from brine by adsorption.
  • the lithium eluent with a low salt-to-lithium ratio means that the content of impurities in the adsorption method product is low, the subsequent processing process is simple, the cost is low, and the final lithium carbonate product has high purity.
  • Brine is a high-salt or even salt-saturated solution.
  • various salt ions including lithium ions, will be adsorbed on the adsorbent.
  • the patentee has found that during the adsorption process, lithium ions are in the adsorbent. Intercalation occurs at the interface, while other salt ions do not enter the interlayer of the selective adsorbent, and only interfacial adhesion occurs. This results in different binding strengths between lithium ions and other salt ions and the sorbent.
  • the applicant renovated the traditional belt vacuum filter (ie, belt filter), and applied it to the process of extracting lithium from brine by adsorption method for the first time.
  • the filter cloth is formed with a solid-liquid separation zone, a salt washing zone and a desorption zone which are arranged in sequence along the advancing direction of the filter cloth.
  • the brine is pre-mixed so that the adsorbent can fully absorb the lithium ions in the brine; then the adsorbent brine mixture is transported to the filter cloth in the solid-liquid separation zone to separate the adsorbent from the brine, the adsorbent is left on the filter cloth, and the brine is filtered.
  • the washing salt liquid conveying mechanism conveys the washing salt liquid to the adsorbent on the filter cloth to elute the ions other than lithium adsorbed on the adsorbent;
  • the adsorbent on the filter cloth transports the desorption solution to elute the lithium ions adsorbed on the adsorbent, and the lithium eluate of the filter cloth is collected through the lithium eluent collection port.
  • the contact time between the washing salt solution and the adsorbent is short, and the salt washing solution can take away the salt ions to the maximum and the lithium ions to the minimum through the adsorbent.
  • the salt washing area the salt ions that are weakly bound to the adsorbent are eluted first, and in the desorption area, the lithium ions that are strongly bound to the adsorbent are eluted, thereby Maximize salt-lithium separation.
  • the belt filter of the present invention can obtain a lithium eluent with a magnesium-lithium ratio of less than 1:1 and a salt-to-lithium ratio (TDS/Li) of less than 10:1, and the lithium recovery rate reaches more than 70%, which greatly reduces the subsequent desalting and purification.
  • the investment and production cost of the process reduce the difficulty of the subsequent desalination and purification process, and finally battery-grade lithium carbonate or lithium hydroxide can be stably obtained.
  • powdery lithium ion selective adsorbent is used in the belt filter of the present invention, and it is not necessary to granulate the adsorbent before use.
  • Investment cost, the dosage of adsorbent for 10,000 tons of lithium carbonate production line is only 300-500 t, its cost is only tens of millions of yuan.
  • a brine recovery port is provided below the solid-liquid separation zone, a salt eluent collection port is provided below the salt washing zone, and the brine recovery port, the salt In the eluent collection port and the lithium eluent collection port, at least the salt eluent collection port is connected with a vacuuming mechanism;
  • At least one of the brine recovery port, the salt eluent collection port and the lithium eluent collection port is connected with an adsorbent recovery mechanism.
  • the present invention is provided with a vacuum pumping mechanism at least at the salt eluent collection port, and the vacuum pumping mechanism can speed up the speed of the washing salt liquid passing through the adsorbent, shorten the contact time between the washing salt liquid and the adsorbent, and minimize the contact time between the washing salt liquid and the adsorbent. Reduce the amount of lithium carried away by the wash salt solution.
  • a brine recovery port can also be provided below the solid-liquid separation zone, and a vacuum mechanism can also be provided at the brine recovery port and the lithium eluent collection port to improve the working efficiency of the belt filter.
  • the present invention uses a powder adsorbent, it is difficult for the filter cloth to achieve percent interception. Therefore, the present invention is provided with an adsorbent recovery mechanism at least one of the brine recovery port, the salt eluent collection port and the lithium eluent collection port. , used to recover the adsorbent in brine, salt eluent and lithium eluent, saving the cost of adsorbent.
  • the adsorbent recovery mechanism can use common powder material recovery equipment in the prior art, such as magnetic separators, precision filters, ceramic membranes, and the like.
  • the washing salt liquid conveying mechanism has at least two liquid outlet ends arranged along the advancing direction of the filter cloth. Multiple liquid outlets arranged along the advancing direction of the filter cloth can realize "small dose multiple times of salt washing". Compared with a single liquid outlet, setting multiple liquid outlets can achieve the same salt washing effect while washing salt.
  • the amount of liquid used is less, the loss of lithium is lower, and higher salt washing efficiency can be obtained when the same amount of washing salt solution is used.
  • the applicant has also found that the adsorbent that has trapped lithium ions still has lithium ion loss during the salt washing process, but the higher the salt concentration of the washing salt solution, the lower the lithium ion loss rate. Therefore, in the above-mentioned belt filter, along the reverse direction of the advancing direction of the filter cloth, the salt concentration of the washing salt solution conveyed by the liquid outlet end gradually increases.
  • the present invention also sets the salt concentration of the washing salt solution to a gradient elution from low to high, so as to reduce the amount of lithium ions on the adsorbent as much as possible. loss of lithium ions.
  • the washing salt solution conveying mechanism includes a washing salt solution initial supply component and at least one washing salt solution circulation component, and the washing salt solution initial supply component and the washing salt solution circulation component They are connected in series along the opposite direction of the advancing direction of the filter cloth;
  • the liquid outlet ends of the salt washing liquid initial supply assembly and the washing salt liquid circulation assembly are all located above the salt washing area, and the salt washing liquid collection port corresponding to each liquid outlet end is arranged below the salt washing area, so the The liquid inlet end of the washing salt liquid initial supply assembly is connected with the washing salt liquid storage tank, and the liquid inlet end of the washing salt liquid circulation assembly corresponds to the washing salt liquid initial supply assembly or the previous washing salt liquid circulation assembly
  • the salt eluent collection port is connected.
  • the supply of the washing salt solution is carried out in the opposite direction of the advancing direction of the filter cloth.
  • the washing salt solution of the washing salt solution circulation component is collected from the first washing salt solution supply component or the salt eluent collection port of the previous washing salt solution circulation component. Since the salt has been washed at least once, the salt concentration of the washing salt solution at the outlet end of the washing salt solution circulation component is always higher than that of the first washing salt solution supply component or the last washing salt solution circulation component.
  • the concentration gradient of the wash salt solution is eluted in reverse.
  • the series connection of the initial supply of washing salt solution and at least one washing salt solution circulation component makes the entire washing salt solution transport mechanism only need to set up a washing salt solution storage tank to supply the washing salt solution, which not only simplifies the overall structure, but also saves the amount of washing salt solution. , and can realize one-time collection of salt eluent.
  • the desorption liquid conveying mechanism has at least two liquid outlet ends arranged along the advancing direction of the filter cloth. Multiple liquid discharge ends arranged along the advancing direction of the filter cloth can realize "multiple desorption of small doses". Compared with a single liquid discharge end, setting multiple liquid discharge ends can achieve the same desorption effect while reducing the amount of desorbed liquid. less, and higher desorption efficiency can be obtained with the same amount of desorption liquid.
  • the desorption liquid conveying mechanism includes a desorption liquid initial supply assembly and at least one desorption liquid circulation assembly, and the desorption liquid initial supply assembly and the desorption liquid circulation assembly are along the advancing direction of the filter cloth.
  • the opposite directions are connected in series;
  • the liquid outlet ends of the desorption liquid initial supply assembly and the desorption liquid circulation assembly are all located above the desorption zone, and a lithium eluent collection port corresponding to each liquid outlet end is provided below the desorption zone.
  • the liquid inlet end of the initial supply component is connected with the desorption liquid storage tank, and the liquid inlet end of the desorption liquid circulation component is connected with the lithium eluent collection port corresponding to the desorption liquid initial supply component or the previous desorption liquid circulation component.
  • the desorption liquid initial supply component and the desorption liquid circulation component are connected in series along the opposite direction of the advancing direction of the filter cloth.
  • the concentration of salt ions in the lithium eluent is also getting lower and lower; when the reverse elution is performed, not only "low-salt washing of lithium” is achieved, but also the amount of desorption solution is greatly saved.
  • the present invention also provides the application of the above-mentioned belt filter in the extraction of lithium from the brine by the adsorption method, and the application includes:
  • the filter cake goes to the salt-washing area with the filter cloth.
  • the salt-washing liquid conveying mechanism transports the salt-washing liquid to the filter cake, so that the ions other than lithium adsorbed on the filter cake are absorbed. Elution, collecting the salt eluent;
  • the filter cake goes to the desorption zone with the filter cloth.
  • the desorption liquid conveying mechanism transports the desorption liquid to the filter cake, so that the lithium ions adsorbed on the filter cake are eluted, and the lithium washing is collected. deliquoring;
  • the adsorbent can quickly capture lithium ions in a high-salt concentration solution.
  • a contact time of tens of seconds can reach an adsorption balance of more than 60%. Therefore, in the above-mentioned belt filter, there is also a salt washing backwater zone downstream of the desorption zone, and a salt eluent reflux mechanism is provided above the salt washing backwater zone, and the salt eluent reflux mechanism The liquid inlet end is connected with the described salt eluent collection port;
  • An adsorbent recovery mechanism is arranged downstream of the washing salt water return area, and the adsorbent recovery mechanism is connected with the mixed adsorption mechanism.
  • the salt eluent collected from the salt washing zone is sent to the salt washing water return zone through the salt eluent reflux mechanism, so that the adsorbent that has passed through the salt washing zone and the desorption zone can absorb the salt solution again, so that not only can the salt elution be recovered again Lithium in the liquid, and when this part of the adsorbent is sent back to the mixed adsorption mechanism by the adsorbent recovery mechanism to be mixed with the brine, the adsorbent that has adsorbed high-concentration salt can quickly capture the lithium ions in the brine and implement the next round of adsorption. Lithium extraction from brine.
  • the application of the belt filter in the extraction of lithium from the adsorption brine includes:
  • the filter cake goes to the salt-washing area with the filter cloth.
  • the salt-washing liquid conveying mechanism transports the salt-washing liquid to the filter cake, so that the ions other than lithium adsorbed on the filter cake are absorbed. Elution, collecting the salt eluent;
  • the filter cake goes to the desorption zone with the filter cloth.
  • the desorption liquid conveying mechanism transports the desorption liquid to the filter cake, so that the lithium ions adsorbed on the filter cake are eluted, and the lithium washing is collected. deliquoring;
  • the contact time between the washing salt solution or the desorbing solution and the filter cake is not more than 10 seconds.
  • the contact time between the washing salt solution or the desorbing solution and the filter cake is 1-2 s.
  • the filter cloth is formed with a solid-liquid separation zone, a salt washing zone and a desorption zone which are arranged in sequence along the advancing direction of the filter cloth;
  • the washing salt solution will elute the ions except lithium on the filter cake; in the desorption zone, the desorption solution will elute the lithium ions on the filter cake; It is carried out during the operation, so the contact time between the washing salt solution and the adsorbent is short, and the washing salt solution can take away the salt ions to the maximum and the lithium ions to the minimum through the adsorbent, so as to achieve the purpose of "throwing salt and retaining lithium"; Because in the salt washing zone, the salt ions that are weakly bound to the adsorbent are eluted first, and in the desorption zone, the lithium ions that are strongly bound to the adsorbent are eluted, so as to maximize the separation of salt and lithium.
  • the belt filter of the present invention can obtain a lithium eluent with a magnesium-lithium ratio of less than 1:1 and a salt-to-lithium ratio of less than 10:1, and the lithium recovery rate can reach more than 70%, which greatly reduces the investment and production of the subsequent desalination and purification process. The cost and the difficulty of the subsequent desalination and purification process are reduced, and finally battery-grade lithium carbonate or lithium hydroxide can be stably obtained.
  • Powdered lithium ion selective adsorbent is used in the belt filter of the present invention. It is not necessary to granulate the adsorbent before use.
  • the investment cost of 10,000 tons of lithium carbonate production line is only 300-500 t, its cost is only tens of millions of yuan.
  • a vacuuming mechanism is provided at least at the salt eluent collection port;
  • the contact time of the agent should be reduced as much as possible to reduce the amount of lithium carried away by the washing salt solution.
  • At least one of the brine recovery port, the salt eluent collection port and the lithium eluent collection port is provided with an adsorbent recovery mechanism, and the adsorbent recovery mechanism is used for brine and salt recovery.
  • the adsorbent in the eluent and the lithium eluent is recovered to save the cost of the adsorbent.
  • the washing salt solution conveying mechanism has at least two liquid outlet ends arranged along the advancing direction of the filter cloth; Dosing and washing salt for multiple times", not only improves the efficiency of washing salt, but also compared with a single liquid outlet, setting up multiple liquid outlets can achieve the same salt washing effect, and at the same time, the amount of washing salt solution is less, and lithium is lost. The amount is lower.
  • the salt concentration of the washing salt solution conveyed by the liquid outlet gradually becomes higher, so as to realize the gradient washing of salt, so as to reduce the adsorbent as much as possible. loss of lithium ions.
  • the desorption liquid conveying mechanism has at least two liquid outlet ends arranged along the advancing direction of the filter cloth; a plurality of liquid outlet ends arranged along the advancing direction of the filter cloth can realize “multiple desorption of small doses”. ”, which not only improves the desorption efficiency, but also uses less desorption liquid compared with a single liquid outlet when multiple liquid outlets are provided to achieve the same desorption effect.
  • the belt filter of the present invention there is also a salt washing backwater zone downstream of the desorption zone, and the salt eluent collected from the salt washing zone is sent to the salt washing backwater zone through the salt eluent reflux mechanism, so that the salt eluent has been collected.
  • the adsorbent passing through the salt washing zone and the desorption zone adsorbs the salt solution again, so that not only the lithium in the salt eluent can be recovered, but also when this part of the adsorbent is sent back to the mixed adsorption mechanism through the adsorbent recovery mechanism to be mixed with brine,
  • the adsorbent that has adsorbed high-concentration salts can quickly capture lithium ions in brine, and implement the next round of adsorption method to extract lithium from brine.
  • Fig. 1 is the structural representation of the belt filter of the present invention
  • Fig. 2 is another structural representation of the belt filter of the present invention.
  • Fig. 3 is the second structure schematic diagram of the salt washing zone and the desorption zone in the belt filter of the present invention.
  • Fig. 4 is the third structural schematic diagram of the salt washing zone and the desorption zone in the belt filter of the present invention.
  • this embodiment is a belt filter, which is obtained by improving the existing belt vacuum filter.
  • This embodiment focuses on the detailed description of the improvement points, and the others are not described. Part of the structure is the same as that of the existing commercially available belt vacuum filter, which will not be repeated in this embodiment.
  • the belt filter of this embodiment includes a frame 1 , and a filter cloth 2 for reciprocating rotation is arranged on the frame 1 .
  • the driving mechanism 3 may include conventional: a driving wheel 31 and a driven wheel 32 rotatably connected with the frame 1, wherein the driving wheel 31 is driven by a circumferential driver (not shown in the figure), the filter cloth 2 is Surrounding between the driving wheel 31 and the driven wheel 32 .
  • the filter cloth 2 in this embodiment is preferably a large air volume filter cloth 2, the air volume of the filter cloth 2 is greater than 500 L/m 2 ⁇ s, and the retention rate of the adsorbent is greater than 90%.
  • a liquid collecting box 4 under the filter cloth 2 is fixedly installed on the frame 1, and the top of the liquid collecting box 4 may have an opening or not. Instead, there are several filtration holes on the top of the liquid collection box 4; no matter whether it is open or not, a blocking mechanism (not shown in the figure) should be set on the top of the liquid collection box 4 to prevent liquid from flowing from both sides of the top of the liquid collection box 4. Leak to ensure that all the liquid enters the liquid collection box 4.
  • the frame 1 is formed with a solid-liquid separation zone 100 , a salt washing zone 200 and a desorption zone 300 sequentially arranged along the advancing direction of the filter cloth 2 .
  • the liquid collecting box 4 is also provided with partitions 41 evenly arranged along the advancing direction of the filter cloth 2.
  • the partitions 41 divide the liquid collecting box 4 into several liquid collecting chambers 42;
  • the lengths of the salt washing zone 200 and the desorption zone 300 are all multiples of the length of the liquid collection chamber 42.
  • the specific multiples can be the same or are different, depending on specific design needs.
  • the length of the solid-liquid separation zone 100 is equivalent to the length of the four liquid collection chambers 42
  • the lengths of the salt washing zone 200 and the desorption zone 300 are both equivalent to the length of the three liquid collection chambers 42 .
  • Setting the length of each functional area to be a multiple of the length of the liquid collecting cavity 42 can ensure that the corresponding liquid in each functional area can enter the corresponding liquid collecting cavity 42 .
  • the length of the liquid collecting cavity 42 can be specifically set according to specific needs.
  • a mixed adsorption mechanism 5 is arranged above the filter cloth 2; the mixed adsorption mechanism 5 includes a mixing tank 51, and the top of the mixing tank 51 is A brine feed port 52 and an adsorbent feed port 53 are provided, and the raw material brine and the adsorbent enter the mixing tank 51 through the corresponding feed ports respectively.
  • the adsorbent brine mixture is discharged from the mixing tank 51 and transported to the filter cloth 2 of the solid-liquid separation zone 100; due to the filtering effect of the filter cloth 2, the brine has been adsorbed
  • the adsorbents of various ions in the medium are separated from the brine, the adsorbents remain on the filter cloth 2 , and the brine passes through the filter cloth 2 and enters the corresponding liquid collection chamber 42 .
  • each liquid collecting chamber 42 corresponding to the solid-liquid separation zone 100 has a brine recovery port 43, and each brine recovery port 43 is connected to the brine suction filter barrel 44 through pipelines, and the brine suction filter barrel 44 is connected with a vacuum pumping mechanism (such as a vacuum pump, not shown in the figure). Under the action of the vacuum pumping mechanism, the brine can quickly pass through the filter cloth 2 into the liquid collection chamber 42 and the brine suction filter barrel 44, and the adsorbent can be filtered. A filter cake with a thickness of about 1.5-4 cm is formed on the cloth 2.
  • the discharge end of the mixed adsorption mechanism 5 is located at the beginning of the solid-liquid separation zone 100 (ie, the end away from the salt washing zone 200) to ensure that all brine enters and is separated from the solid-liquid.
  • the liquid collecting chamber 42 corresponding to the zone 100 will not enter the downstream salt washing zone 200 .
  • an adsorbent recovery mechanism 10 connected to the brine suction filter barrel 44 is also provided.
  • the adsorbent recovery mechanism 10 can use screening equipment such as a magnetic separator 101, a precision filter, a ceramic membrane, etc., in order to extract the brine from the collected brine The sorbent is separated and the brine is returned to the salt pan or lake.
  • a washing salt solution conveying mechanism 6 is arranged above the filter cloth 2 , and the washing salt solution conveying mechanism 6 is used for washing the filter cake cloth that enters the salt washing area 200 with the filter cloth 2 .
  • salt solution used in this embodiment may be fresh water, or other solutions with lower salinity.
  • the washing salt solution conveying mechanism 6 adopts the liquid conveying equipment commonly used in the prior art, as long as the uniform infusion in the vertical direction can be ensured, and the washing salt solution transporting mechanism connected to the washing salt solution storage tank (not shown in the figure) may be included.
  • a washing salt liquid delivery pump (not shown in the figure) is installed on the washing salt liquid delivery pipe 61, and a water distribution plate (not shown in the figure) can be installed at the liquid outlet end of the washing salt liquid delivery pipe 61.
  • the water distribution diameter of the water distribution tray is equal to the width of the filter cake to ensure the effect of washing salt.
  • each liquid collection chamber 42 corresponding to the salt washing area 200 has a salt eluent collection port 45, and each salt eluent collection port 45 is connected to the salt eluent suction filter barrel 46 through a pipeline,
  • the salt eluent suction filter barrel 46 is connected with a vacuum pumping mechanism (such as a vacuum pump). Under the action of the vacuum pumping mechanism, the washing salt solution can quickly pass through the filter cake, and the contact time between the washing salt solution and the filter cake is controlled within 10 seconds. within (preferably 1-2 seconds).
  • the liquid outlet end of the salt-washing liquid conveying mechanism 6 is located at the beginning of the salt-washing zone 200 (ie, the end close to the solid-liquid separation zone 100 ) to ensure that all the salt eluate All of them enter the liquid collecting chamber 42 corresponding to the salt washing zone 200 , but will not enter the downstream desorption zone 300 .
  • the brine is a high-salt or even salt-saturated solution
  • a variety of salt ions including lithium ions
  • the adsorption mechanism is different, the salt in the brine will squeeze the lithium ions into the lattice of the amorphous hydroxide adsorbent to form a molecular sieve, while other salt ions will not enter the lattice of the amorphous hydroxide adsorbent, This results in different binding strengths between lithium ions and other salt ions and the sorbent.
  • the filter cake is washed quickly and in a short time with the washing salt solution, which can take away the salt ions to the maximum and the lithium ions to the minimum. Salt to retain lithium" purpose.
  • the collected salt eluent also contains an adsorbent, so this embodiment also sets an adsorbent recovery mechanism 10 connected to the salt eluent suction filter barrel 46, and the adsorbent recovery mechanism 10 can use the magnetic separator 101, Screening equipment such as precision filters, ceramic membranes, etc., to separate the adsorbent from the collected salt eluate, which is then sent to salt lakes or salt pans, or used in other processes.
  • a desorption liquid conveying mechanism 7 is arranged above the filter cloth 2, and the desorption liquid conveying mechanism 7 is used to distribute the desorption liquid to the filter cake entering the desorption area 300 with the filter cloth 2.
  • the desorbent used in this example can be fresh water, or other solutions with lower salinity.
  • the desorption liquid conveying mechanism 7 can adopt the liquid conveying equipment commonly used in the prior art, as long as the uniform infusion in the vertical direction can be ensured, and the same structure as the above-mentioned washing salt liquid conveying mechanism 6 can be used.
  • each liquid collection chamber 42 corresponding to the desorption zone 300 has a lithium eluent collection port 47, and each lithium eluent collection port 47 is connected to the lithium eluent suction filter barrel 48 through a pipeline, and
  • the lithium eluent suction filter barrel 48 is connected with a vacuuming mechanism (such as a vacuum pump). Under the action of the vacuuming mechanism, the desorbed liquid can quickly pass through the filter cake, and the contact time between the desorbed liquid and the filter cake is controlled within 10 seconds. Preferably, 1-2 seconds.
  • the liquid outlet end of the desorption solution conveying mechanism 7 is located at the beginning of the desorption zone 300 (that is, the end close to the salt washing zone 200 ) to ensure that all lithium desorption solution enters and desorbs In the sump 42 corresponding to the zone 300 .
  • the collected lithium eluent also contains an adsorbent
  • this embodiment also provides an adsorbent recovery mechanism 10 connected to the lithium eluent suction filter barrel 48, and the adsorbent recovery mechanism 10 can use magnetic separation Filter 101, precision filter, ceramic membrane and other screening equipment, so as to separate the adsorbent from the collected lithium eluate, and then send the lithium eluate to the next refining and purification process.
  • the adsorbent recovery mechanism 8 is used to collect the desorbed adsorbent, and send it to the mixed adsorption mechanism 5 for recycling.
  • the adsorbent and brine are sent into the mixing tank 51 in proportion, and the stirring component is activated to stir and mix the adsorbent and the brine.
  • the stirring component is activated to stir and mix the adsorbent and the brine.
  • the adsorbent adsorbs various ions in the brine; when the production line is initially started, it is necessary to The adsorbent and brine are stirred in the mixing tank 51 for a period of time (about a few minutes) before discharging to ensure the effective adsorption of the adsorbent; and after the production line starts to run, the adsorbent and brine can be continuously fed, and the adsorbent brine mixture is also Can be discharged continuously.
  • the adsorbent brine mixture is discharged from the mixing tank 51, the discharge end of the mixing tank 51 is at the beginning of the solid-liquid separation zone 100, and the adsorbent brine mixture discharged from the mixing tank 51 gradually falls.
  • the brine passes through the filter cloth 2, enters the corresponding liquid collection chamber 42, and is collected into the brine suction filter barrel 44 through each brine recovery port 43; the recovered brine is adsorbed After the agent is recovered, it can be returned to the salt lake or salt field;
  • the adsorbent discharged at a constant speed forms a filter cake with a thickness of about 1.5-4 cm under the action of the vacuuming mechanism; since it is continuously discharged, the filter cake extends over the entire filter cloth 2. on the run.
  • the filter cake goes to the salt washing area 200 with the filter cloth 2.
  • the washing salt solution conveying mechanism 6 transports the washing salt solution to the filter cake, so that the ions other than lithium adsorbed on the filter cake are eluted , collect the salt eluent;
  • the salt-washing liquid is applied to the filter cake from the beginning of the salt-washing area 200.
  • the salt washing liquid only needs 1-2 seconds to pass through the filter cake, and the salt is thrown away as much as possible to retain lithium;
  • the collected salt eluent can be sent to salt lakes or salt pans, or used in other processes after being recovered by the adsorbent;
  • the filter cake goes to the desorption zone 300 with the filter cloth 2.
  • the desorption liquid conveying mechanism 7 transports the desorption liquid to the filter cake, so that the lithium ions adsorbed on the filter cake are eluted, and the lithium eluent is collected ;
  • the desorption liquid is applied to the filter cloth 2 from the starting end of the desorption zone 300. With the assistance of the vacuuming mechanism, the desorption liquid passes through the filter cake to elute the lithium from the adsorbent; the collected lithium eluent is recovered by the adsorbent. After that, it is sent to the downstream process for refining and purification;
  • the desorbed adsorbent is transported to the mixed adsorption mechanism 5, and the adsorbent recovered by the adsorbent recovery mechanism 10 can also be returned to the mixed adsorption mechanism 5 for new adsorption.
  • the ratio of salt to lithium is less than 10:1, the ratio of magnesium to lithium is less than 1:1, and the lithium concentration is about 0.4 g/l; the amount of washing salt solution is 30% of that of brine. %, and the lithium recovery rate is 70%.
  • the belt filter of this embodiment is basically the same as that of Embodiment 1, except that: along the advancing direction of the filter cloth 2, the frame 1 is formed with a solid-liquid separation zone 100, a salt washing zone 200, a desorption zone Zone 300 and washing salt backwater zone 400, that is, a washing salt backwater zone 400 is also set downstream of the desorption zone 300;
  • the liquid inlet end of the reflux mechanism 9 is connected to the salt eluent suction filter barrel 46, so that the adsorbent that has passed through the salt washing zone 200 and the desorption zone 300 adsorbs the salt eluent again.
  • the adsorbent can quickly capture lithium ions in a high-salt concentration solution, and the adsorption equilibrium of more than 60% can be achieved in a contact time of tens of seconds. Therefore, the adsorbent that has completed the salt washing and desorption will pre-adsorb the salt eluent with higher salt concentration, and then send it back to the mixing adsorption mechanism 5.
  • this part of the adsorbent when this part of the adsorbent enters the mixing tank 51, it can quickly capture Collect lithium ions in raw brine, so as to realize continuous feeding of adsorbent and raw brine, and continuous discharge of adsorbent brine mixture to realize uninterrupted continuous production; in addition, lithium ions in salt eluent can be recovered to further improve lithium Recovery rate.
  • a plurality of liquid collecting cavities 42 are correspondingly arranged in the washing salt water return area 400 for collecting the re-adsorption filtrate through the filter cake and the filter cloth 2; the bottom of each liquid collecting cavity 42 is also provided with a re-adsorption filtrate collection port 49
  • the re-adsorption filtrate collection port 49 is connected with the re-adsorption filtrate suction filter barrel 410 through the pipeline, and the re-adsorption filtrate suction filter barrel 410 is connected with the vacuum pumping mechanism.
  • the adsorbent in the re-adsorption filtrate also needs to be recovered by the adsorbent recovery mechanism 10 such as the magnetic separator 101 .
  • the adsorbent and brine are sent into the mixing tank 51 in proportion, and the stirring component is started, and the adsorbent and brine are stirred and mixed evenly.
  • the adsorbent adsorbs various ions in the brine; when the production line is initially started, it needs to be
  • the adsorbent and brine are stirred in the mixing tank 51 for a period of time for about a few minutes before discharging to ensure the effective adsorption of the adsorbent; and after the production line starts to run, the adsorbent and brine can be continuously fed, and the adsorbent brine mixture can also be continuously Discharge.
  • the adsorbent brine mixture is discharged from the mixing tank 51, the discharge end of the mixing tank 51 is at the beginning of the solid-liquid separation zone 100, and the adsorbent brine mixture discharged from the mixing tank 51 gradually falls.
  • the brine passes through the filter cloth 2, enters the corresponding liquid collection chamber 42, and is collected into the brine suction filter barrel 44 through each brine recovery port 43; the recovered brine is adsorbed After the agent is recovered, it can be returned to the salt lake or salt field;
  • the adsorbent discharged at a constant speed forms a filter cake with a thickness of about 1.5-4 cm under the action of the vacuuming mechanism; since it is continuously discharged, the filter cake extends over the entire filter cloth 2. on the run.
  • the filter cake goes to the salt washing area 200 with the filter cloth 2.
  • the washing salt solution conveying mechanism 6 transports the washing salt solution to the filter cake, so that the ions other than lithium adsorbed on the filter cake are eluted , collect the salt eluent;
  • the salt-washing liquid is applied to the filter cake from the beginning of the salt-washing area 200.
  • the salt washing liquid only needs 1-2 seconds to pass through the filter cake, and the salt is thrown away as much as possible to retain lithium;
  • the filter cake goes to the desorption zone 300 with the filter cloth 2.
  • the desorption liquid conveying mechanism 7 transports the desorption liquid to the filter cake, so that the lithium ions adsorbed on the filter cake are eluted, and the lithium eluent is collected ;
  • the desorption liquid is applied to the filter cloth 2 from the starting end of the desorption zone 300. With the assistance of the vacuuming mechanism, the desorption liquid passes through the filter cake to elute the lithium from the adsorbent; the collected lithium eluent is recovered by the adsorbent. After that, it is sent to the downstream process for refining and purification;
  • step 3 The salt eluent collected in step 3 is transported to the salt washing backwater area 400, so that the adsorbent is pre-adsorbed; the collected re-adsorption filtrate is also sent to the salt field or salt lake after being recovered by the adsorbent;
  • the adsorbent recovery mechanism 8 collects the pre-adsorbed adsorbent and transports it to the mixed adsorption mechanism 5.
  • the adsorbent recovered by the adsorbent recovery mechanism 10 is also recovered. It is sent back to the mixed adsorption mechanism 5 for a new round of extraction of lithium from brine by adsorption.
  • the ratio of salt to lithium is less than 10:1
  • the ratio of magnesium to lithium is less than 1:1
  • the lithium concentration is about 0.4 g/l
  • the amount of washing salt solution is 30% of that of brine. %
  • the lithium recovery rate reaches 80%.
  • the main structure of the belt filter of this embodiment is the same as that of Embodiment 1 or Embodiment 2, except that the salt-washing liquid conveying mechanism 6 of the salt-washing zone 200 has at least two liquid outlet ends (this In the embodiment, three are set), and all the liquid outlet ends are evenly arranged along the advancing direction of the filter cloth 2 .
  • the specific way of setting the three liquid outlet ends can be as follows: three washing salt liquid conveying pipes 61 are arranged, and the three washing salt liquid conveying pipes 61 are connected with the washing salt liquid storage tank through a four-way valve, and the liquid outlet end of each washing salt liquid conveying pipe 61 is All water distribution trays are installed, and the water distribution diameter of each water distribution tray is equal to the width of the filter cake to ensure the effect of washing salt.
  • washing salt liquid transport pump When transporting the washing salt liquid, it is feasible to use one washing salt liquid transport pump to provide power to the three washing salt liquid transport pipes 61 at the same time, or install one washing salt liquid transport pump on each washing salt liquid transport pipe 61 .
  • each liquid outlet end of the salt washing liquid conveying mechanism 6 is evenly arranged with the starting end of the salt washing area 200 as the starting point, and it is ensured that the last liquid outlet end is slightly far from the tail end of the salt washing area 200, so as to filter the salt washing liquid.
  • the filter cake is retained for a certain time to ensure that the salt eluent does not enter the desorption zone 300 .
  • Example 1 Compared with only one liquid outlet in Example 1, the total amount of washing salt solution used by multiple liquid outlets remains unchanged. However, since “small dose multiple washings” are realized during salt washing, the salt washing efficiency is improved. higher.
  • the ratio of salt to lithium is less than 10:1
  • the ratio of magnesium to lithium is less than 1:1
  • the lithium concentration is about 0.4 g/l
  • the amount of washing salt solution is 23% of that of brine. %
  • the lithium recovery rate reaches 85%.
  • the main structure of the belt filter of this embodiment is the same as that of Embodiment 1, Embodiment 2 or Embodiment 3, except that the desorption liquid conveying mechanism 7 of the desorption zone 300 has at least two liquid outlet ends (Three are set in this embodiment), all the liquid outlet ends are evenly arranged along the advancing direction of the filter cloth 2 .
  • the specific arrangement of the desorption liquid conveying mechanism 7 having multiple liquid outlet ends may be the same as that of the washing salt liquid conveying mechanism 6 in Embodiment 3, and a plurality of desorption liquid conveying pipes 71 are also provided.
  • Example 1 Compared with only one liquid outlet in Example 1, the total amount of the desorption liquid used by the multiple liquid outlets remains unchanged, but the desorption efficiency is higher due to the realization of “multiple washings with small doses” during desorption. The lithium recovery rate can be further improved.
  • the ratio of salt to lithium is less than 10:1
  • the ratio of magnesium to lithium is less than 1:1
  • the lithium concentration reaches 0.45 g/l
  • the amount of washing salt solution is 23% of the amount of brine , the lithium recovery rate reached 85%.
  • the main structure of the belt filter of this embodiment is the same as that of Embodiment 1 or Embodiment 2 or Embodiment 4, except that the salt-washing liquid conveying mechanism 6 of the salt-washing area 200 has at least two outlets.
  • the liquid ends (three are set in this embodiment), all the liquid outlet ends are evenly arranged along the advancing direction of the filter cloth 2; and, along the opposite direction of the advancing direction of the filter cloth 2, the salt concentration of the washing salt solution conveyed by each liquid outlet end gradually increases. Becomes high.
  • the specific setting method of the washing salt solution conveying mechanism 6 can be as follows: the washing salt solution conveying mechanism 6 includes a washing salt solution initial supply component 62 and at least one washing salt solution circulation component 63. In this embodiment, two are provided, and the washing salt solution initial supply component 63 is provided. The assembly 62 and each washing salt solution circulation assembly 63 are connected in series in sequence along the opposite direction of the advancing direction of the filter cloth 2 .
  • the structures of the first washing salt solution supply assembly 62 and the washing salt solution circulation assembly 63 are the same, and the same structure as the washing salt solution conveying mechanism 6 in Embodiment 1 can be adopted, and the washing salt solution first supplying assembly 62
  • the liquid outlet end of the salt washing liquid circulation assembly 63 is located above the salt washing zone 200, and the salt washing liquid suction filter bucket 46 corresponding to each liquid outlet end is provided below the salt washing zone 200; 62 and the liquid inlet end of the washing salt liquid circulation assembly 63 are connected in different positions, wherein the liquid inlet end of the washing salt liquid initial supply assembly 62 is connected with the washing salt liquid storage tank, and the liquid inlet end of the washing salt liquid circulation assembly 63 is connected The end is connected to the salt eluent suction and filter bucket 46 corresponding to the first washing salt solution supply assembly 62 , or is connected to the salt eluent suction filter bucket 46 corresponding to the last wash salt solution circulation assembly 63 .
  • the supply of the washing salt solution is carried out in the opposite direction of the advancing direction of the filter cloth 2.
  • the washing salt solution of the washing salt solution circulation assembly 63 is collected from the first washing salt solution supply assembly 62 or the salt elution of the previous washing salt solution circulation assembly 63.
  • the liquid suction filter barrel 46 has undergone at least one salt wash, so the salt concentration of the salt wash at the outlet end of the salt wash circulation assembly 63 is always higher than that of the wash salt liquid initial supply assembly 62 or the previous wash salt solution circulation assembly 63.
  • the salt concentration of the salt solution is high, and the reverse elution of the concentration gradient of the washing salt solution is realized.
  • the applicant's research has found that the adsorbent that has trapped lithium ions still has lithium ion loss during the salt washing process, but the higher the salt concentration of the washing salt solution, the lower the lithium ion loss rate. Therefore, in this embodiment, the above-mentioned reverse elution mode of the concentration gradient of the washing salt solution is set to reduce the loss of lithium ions on the adsorbent as much as possible during the salt washing process.
  • each liquid outlet end of the salt washing liquid conveying mechanism 6 is evenly arranged with the starting end of the salt washing area 200 as the starting point, so as to ensure that the last liquid outlet end is slightly far from the tail end of the salt washing area 200, The filter cake is kept for a certain period of time for washing the salt solution to ensure that the salt eluent does not enter the desorption zone 300 .
  • the ratio of salt to lithium is less than 10:1
  • the ratio of magnesium to lithium is less than 1:1
  • the lithium concentration reaches 0.45 g/l
  • the amount of washing salt solution is 17% of the amount of brine
  • the lithium recovery rate is close to 90%.
  • the main structure of the belt filter of this embodiment is the same as that of Embodiment 1, Embodiment 2, Embodiment 3 or Embodiment 5, except that the desorption liquid conveying mechanism 7 of the desorption zone 300 has at least two There are three liquid outlet ends (three are provided in this embodiment), and all the liquid outlet ends are evenly arranged along the advancing direction of the filter cloth 2;
  • the liquid initial supply assembly 72 and the desorption liquid circulation assembly 73 are connected in series in sequence along the opposite direction of the advancing direction of the filter cloth 2 .
  • the structure of the desorbing liquid conveying mechanism 7 is the same as that of the washing salt liquid conveying mechanism 6 in the fifth embodiment.
  • the ratio of salt to lithium is less than 10:1
  • the ratio of magnesium to lithium is less than 1:1
  • the concentration of lithium reaches 0.5 g/l
  • the amount of washing salt solution is 17% of the amount of brine
  • the lithium recovery rate is close to 90%.

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Abstract

本发明公开了一种带滤机及其在吸附法卤水提锂中的应用，该带滤机包括机架，所述的机架上设有往复回转运行的滤布，沿滤布前进方向依次设有：固液分离区，所述的固液分离区上方设有用于向固液分离区输送吸附剂卤水混合物的混合吸附机构；洗盐区，所述的洗盐区上方布施有用于向洗盐区输送洗盐液的洗盐液输送机构；解吸区，所述的解吸区上方布施有用于向解吸区输送解吸液的解吸液输送机构，所述的解吸区下方设有锂洗脱液收集口。采用本发明的带滤机进行吸附法卤水提锂，成本低，可以获得镁锂比小于1:1、盐锂比小于10:1的锂洗脱液，锂回收率达到70%以上，大幅降低了后续除盐提纯工艺的投资和生产成本。

Description

带滤机及其在吸附法卤水提锂中的应用 技术领域
本发明属于卤水提锂技术领域，特别涉及一种带滤机及其在吸附法卤水提锂中的应用。
 背景技术
当前新能源产业的快速发展带动了锂产品需求的迅猛增长，但全球锂资源的高度集中使全球锂产品生产出现寡头垄断的局面，这就导致在锂产品供应上，我国长期依赖进口。随着我国对锂资源开发越来越重视，我国已探明锂资源储量折合氯化锂为4008万吨，其中盐湖资源约占71%，矿石资源占约29%，因此盐湖卤水提锂对保障我国新能源产业的发展具有重大意义。
 技术问题
选择性吸附法是当前盐湖卤水提锂的主要手段，选择性吸附法能够从含有多种离子的混合溶液中吸附分离锂，再行洗脱即可达到将锂离子与其他离子分离的目的。由于这种吸附方法与传统的水处理方法类似，因此目前已有的卤水提锂吸附工艺所使用的设备基本来源于传统水处理行业，其中最为常见的如吸附塔，而与吸附塔配套使用的是铝系、单斜晶锑酸盐系、钛酸盐系、锰氧化物系等分子筛或离子筛型吸附剂。这类选择性吸附材料的晶体结构中含有与锂离子相适配的空隙构造，因此在多种离子存在的情况下，对锂离子具有特异的选择吸附性。
不过，在将选择性吸附剂用于吸附塔进行卤水提锂时发现了许多现实问题：（1）所使用的选择性吸附剂容量低，工作容量一般小于10 mg/g，造粒后不仅活性大幅缩减，而且易碎、易流失；（2）卤水提锂过程每小时需面对数千立方米的水量，这对吸附塔运行造成了极大的负荷；（3）投产阶段需大量构建填满吸附剂的吸附塔，投资成本高昂，万吨碳酸锂产线投资阶段需备用数千吨吸附剂，价格高达数亿元；（4）获得的锂洗脱液中盐锂比大于30:1，镁锂比大于3:1，这为后续除盐提纯工艺带来了极大困难，最终获得的锂产品极难达到电池级碳酸锂或氢氧化锂对杂质含量的要求；（5）洗涤段中会流失约20%以上的锂离子，这就导致吸附段中锂回收率低于60%，全工艺段锂回收率低于50%，若要获得高锂回收率，需设置多塔串联和功能转换，大幅增加了工业连续生产的难度。
近年来，已有文献报道利用粉体吸附剂进行卤水提锂，粉体吸附剂无需造粒，且其吸附容量远高于颗粒吸附剂，进而可大幅降低吸附反应时间、减少吸附剂用量等。目前已有文献或专利报道利用粉体吸附剂结合板框压滤机、离心机、精密过滤或陶瓷膜进行吸附解吸。然而，已有工作对卤水提锂过程中吸附剂的洗涤过程缺乏认识和关注，因此现有卤水提锂工艺均无法得到低盐锂比的锂洗脱液。
 技术解决方案
本发明的发明目的是提供一种带滤机及其在吸附法卤水提锂中的应用，本发明的带滤机是针对粉状锂离子选择性吸附剂设计的，在该带滤机中，可以直接采用粉状吸附剂进行卤水提锂。
为实现上述发明目的，本发明的技术方案如下：
一种带滤机，包括机架，所述的机架上设有往复回转运行的滤布，沿滤布前进方向依次设有：
固液分离区，所述的固液分离区上方设有用于向固液分离区输送吸附剂卤水混合物的混合吸附机构；
洗盐区，所述的洗盐区上方布施有用于向洗盐区输送洗盐液的洗盐液输送机构；
解吸区，所述的解吸区上方布施有用于向解吸区输送解吸液的解吸液输送机构，所述的解吸区下方设有锂洗脱液收集口。
众所周知，卤水总盐度可达数百克/升，而其中锂含量仅为数十至数百毫克/升。专利权人经大量研究试验发现，在利用吸附法提取卤水中锂的过程中，如何最大限度地降低锂洗脱液中的盐锂比是吸附法卤水提锂的关键。具有低盐锂比的锂洗脱液意味着吸附法产品中杂质含量低，后续加工流程简单、成本低，最终碳酸锂产品纯度高。
卤水为高盐甚至盐饱和溶液，当卤水与吸附剂混合后，包括锂离子在内的多种盐离子都会被吸附到吸附剂上，专利权人研究发现，吸附过程中，锂离子在吸附剂界面发生的是嵌入反应，而其他盐离子则不会进入选择性吸附剂的层间，其仅发生界面沾附。这就导致锂离子和其他盐离子与吸附剂之间的结合强度是不同的。
申请人据此对传统的带式真空过滤机（即带滤机）进行改造，并首次将其应用于吸附法卤水提锂工艺中。依据滤布上方设置的机构不同，滤布上形成有沿滤布前进方向依次设置的固液分离区、洗盐区和解吸区；其中，在固液分离区，混合吸附机构将吸附剂和原料卤水预先混合，使吸附剂充分吸附卤水中锂离子；而后将吸附剂卤水混合物输送到固液分离区的滤布上，使吸附剂与卤水分离，吸附剂留在滤布上，卤水则滤过滤布；在洗盐区，洗盐液输送机构向滤布上的吸附剂输送洗盐液，以将吸附剂上吸附的除锂以外的离子洗脱下来；而在解吸区，解吸液输送机构向滤布上的吸附剂输送解吸液，以将吸附剂上吸附的锂离子洗脱下来，滤过滤布的锂洗脱液经锂洗脱液收集口被收集起来。
由于整个洗盐过程是在滤布动态运行过程中进行的，因此洗盐液与吸附剂的接触时间较短，洗盐液经过吸附剂能够最大限度地带走盐离子、最小限度地带走锂离子，达到“抛盐留锂”的目的；而在洗盐区内，与吸附剂结合较弱的盐离子先被洗脱，在解吸区，与吸附剂结合较强的锂离子后被洗脱，从而最大限度地实现盐锂分离。采用本发明的带滤机可以获得镁锂比小于1:1、盐锂比（TDS/Li）小于10:1的锂洗脱液，锂回收率达到70%以上，大幅降低了后续除盐提纯工艺的投资和生产成本、降低了后续除盐提纯工艺的难度，最终可以稳定地得到电池级碳酸锂或氢氧化锂。
此外，本发明的带滤机中使用的是粉状锂离子选择性吸附剂，使用前无需对吸附剂造粒，使用过程中一次装载的吸附剂量比吸附塔大大降低，大大降低了投产阶段的投资成本，万吨碳酸锂产线吸附剂投加量仅为300-500 t，其耗资仅为数千万元。
在上述的带滤机中，所述的固液分离区下方设有卤水回收口，所述的洗盐区下方设有盐洗脱液收集口，在所述的卤水回收口、所述的盐洗脱液收集口和所述的锂洗脱液收集口中，至少所述的盐洗脱液收集口连接有抽真空机构；
所述的卤水回收口、所述的盐洗脱液收集口和所述的锂洗脱液收集口中至少其一连接有吸附剂回收机构。
申请人研究发现，已捕集锂离子的吸附剂在洗盐过程中仍然存在锂离子流失，但洗涤时间越短，锂离子流失率越低。因此本发明至少在所述的盐洗脱液收集口处设有抽真空机构，抽真空机构能够加快洗盐液穿过吸附剂的速度，缩短洗盐液与吸附剂的接触时间，尽可能地减少洗盐液带走的锂量。
当然，固液分离区的下方也可以设置卤水回收口，在卤水回收口和锂洗脱液收集口处也可以设置抽真空机构，以提高带滤机的工作效率。
由于本发明使用的是粉体吸附剂，因此滤布难以实现百分比截留，因此本发明在卤水回收口、盐洗脱液收集口和锂洗脱液收集口中至少其一处设置了吸附剂回收机构，用以对卤水、盐洗脱液和锂洗脱液中吸附剂进行回收，节约吸附剂成本。
吸附剂回收机构可以采用现有技术中常见的粉状物质回收设备，如磁选机、精密过滤器、陶瓷膜等。
为了提高洗盐效率，在上述的带滤机中，所述的洗盐液输送机构具有沿滤布前进方向布置的至少两个出液端。多个沿滤布前进方向布置的出液端能够实现“小剂量多次洗盐”，与单独一个出液端相比，设置多个出液端在达到同样的洗盐效果的同时，洗盐液的用量更少，锂损失量更低，而在采用等量洗盐液的情况下则能够获得更高的洗盐效率。
同样地，申请人还研究发现，已捕集锂离子的吸附剂在洗盐过程中仍然存在锂离子流失，但洗盐液盐浓度越高，锂离子流失率越低。因此，在上述的带滤机中，沿滤布前进方向的反方向，所述的出液端输送的洗盐液的盐浓度逐渐变高。
沿滤布前进方向的反方向，吸附剂上锂离子的浓度越高，因此本发明也相应地将洗盐液的盐浓度设置成由低至高的梯度洗脱，以尽可能地减少吸附剂上锂离子的流失。
作为优选，在上述的带滤机中，所述的洗盐液输送机构包括洗盐液初供组件和至少一个洗盐液循环组件，所述的洗盐液初供组件和洗盐液循环组件沿滤布前进方向的反方向依次串联；
所述的洗盐液初供组件和洗盐液循环组件的出液端均处于洗盐区上方，所述的洗盐区下方设有与各出液端对应的盐洗脱液收集口，所述的洗盐液初供组件的进液端与洗盐液储罐相连，所述的洗盐液循环组件的进液端与和洗盐液初供组件或上一洗盐液循环组件相对应的盐洗脱液收集口相连。
洗盐液的供给是沿滤布前进方向的反方向进行的，洗盐液循环组件的洗盐液收集自洗盐液初供组件或上一洗盐液循环组件的盐洗脱液收集口，由于至少经过了一次洗盐，因此洗盐液循环组件出液端的洗盐液盐浓度总是比洗盐液初供组件或上一洗盐液循环组件的洗盐液盐浓度要高，实现了洗盐液的浓度梯度逆向洗脱。
洗盐液初供组件和至少一个洗盐液循环组件的串联，使得整个洗盐液输送机构只需设置一个洗盐液储罐供给洗盐液，既简化了整体结构，节约了洗盐液用量，又能够实现盐洗脱液的一次性收集。
同样地，在上述的带滤机中，所述的解吸液输送机构具有沿滤布前进方向布置的至少两个出液端。多个沿滤布前进方向布置的出液端能够实现“小剂量多次解吸”，与单独一个出液端相比，设置多个出液端在达到同样的解吸效果的同时，解吸液的用量更少，而在采用等量解吸液的情况下则能够获得更高的解吸效率。
作为优选，在上述的带滤机中，所述的解吸液输送机构包括解吸液初供组件和至少一个解吸液循环组件，所述的解吸液初供组件和解吸液循环组件沿滤布前进方向的反方向依次串联；
所述的解吸液初供组件和解吸液循环组件的出液端均处于解吸区上方，所述的解吸区下方设有与各出液端对应的锂洗脱液收集口，所述的解吸液初供组件的进液端与解吸液储罐相连，所述的解吸液循环组件的进液端与和解吸液初供组件或上一解吸液循环组件相对应的锂洗脱液收集口相连。
申请人研究发现，解吸液中盐离子浓度越低，锂洗脱效率越高。因此本发明将解吸液初供组件和解吸液循环组件沿滤布前进方向的反方向依次串联，由于沿滤布前进方向，滤饼上盐离子的浓度是越来越低的，因此沿滤布前进方向，锂洗脱液中盐离子的浓度也是越来越低的；当逆向洗脱时不仅实现了“低盐洗锂”，而且大大节约了解吸液的用量。
本发明还提供了上述的带滤机在吸附法卤水提锂中的应用，该应用包括：
（1）将吸附剂与卤水在所述的混合吸附机构中混匀；
（2）将吸附剂卤水混合物输送至固液分离区，使吸附剂与卤水分离并在滤布上将吸附剂制成滤饼；
（3）滤饼随滤布前往洗盐区，在所述的洗盐区内，所述的洗盐液输送机构向滤饼输送洗盐液，使吸附在滤饼上除锂以外的离子被洗脱，收集盐洗脱液；
（4）滤饼随滤布前往解吸区，在所述的解吸区内，所述的解吸液输送机构向滤饼输送解吸液，使吸附在滤饼上的锂离子被洗脱，收集锂洗脱液；
（5）在滤布前进方向的终点处，收集经过解吸的吸附剂并将其输送至混合吸附机构中，进行新一轮的吸附法卤水提锂。
专利权人研究发现，吸附剂在高盐浓度溶液中可快速捕集锂离子，固液比较高时，数十秒的接触时间即可达到60%以上的吸附平衡。因此，在上述的带滤机中，在所述的解吸区下游还设有洗盐回水区，该洗盐回水区的上方设有盐洗脱液回流机构，该盐洗脱液回流机构的进液端与所述的盐洗脱液收集口相连；
在所述的洗盐回水区下游设有吸附剂回收机构，该吸附剂回收机构与混合吸附机构相连。
从洗盐区收集的盐洗脱液经盐洗脱液回流机构送至洗盐回水区，使已经经过洗盐区和解吸区的吸附剂再次吸附盐溶液，如此不仅能够重新回收盐洗脱液中的锂，而且当这部分吸附剂经吸附剂回收机构送回混合吸附机构中与卤水混合时，已吸附高浓度盐的吸附剂能够快速捕获卤水中的锂离子，实施下一轮的吸附法卤水提锂。
在这种情况下，所述的带滤机在吸附法卤水提锂中的应用包括：
（1）将吸附剂与卤水在所述的混合吸附机构中混匀；
（2）将吸附剂卤水混合物输送至固液分离区，使吸附剂与卤水分离并在滤布上将吸附剂制成滤饼；
（3）滤饼随滤布前往洗盐区，在所述的洗盐区内，所述的洗盐液输送机构向滤饼输送洗盐液，使吸附在滤饼上除锂以外的离子被洗脱，收集盐洗脱液；
（4）滤饼随滤布前往解吸区，在所述的解吸区内，所述的解吸液输送机构向滤饼输送解吸液，使吸附在滤饼上的锂离子被洗脱，收集锂洗脱液；
（5）将步骤收集的盐洗脱液输送至洗盐回水区，使吸附剂预吸附；
（6）在滤布前进方向的终点处，收集经预吸附的吸附剂并将其输送至混合吸附机构中，进行新一轮的吸附法卤水提锂。
在上述的带滤机在吸附法卤水提锂中的应用中，所述的洗盐液或解吸液与滤饼的接触时间不超过10秒。
作为优选，在上述的带滤机在吸附法卤水提锂中的应用中，所述的洗盐液或解吸液与滤饼的接触时间为1-2 s。
 有益效果
与现有技术相比，本发明的有益效果体现在：
（1）申请人对锂离子选择性吸附剂的吸附机理进行了重新认识，发现锂离子和其他盐离子与吸附剂之间的结合强度是不同的，并据此对传统的带滤机进行了改造，并首次将其应用于吸附法卤水提锂工艺中。依据滤布上方设置的机构不同，滤布上形成有沿滤布前进方向依次设置的固液分离区、洗盐区和解吸区；在固液分离区，吸附剂与卤水分离并被制成滤饼；在洗盐区，洗盐液将滤饼上除锂以外的离子洗脱下来；在解吸区，解吸液将滤饼上的锂离子洗脱下来；由于整个洗盐过程是在滤布动态运行过程中进行的，因此洗盐液与吸附剂的接触时间较短，洗盐液经过吸附剂能够最大限度地带走盐离子、最小限度地带走锂离子，达到“抛盐留锂”的目的；由于在洗盐区内，与吸附剂结合较弱的盐离子先被洗脱，在解吸区，与吸附剂结合较强的锂离子后被洗脱，从而最大限度地实现盐锂分离。采用本发明的带滤机可以获得镁锂比小于1:1、盐锂比小于10:1的锂洗脱液，锂回收率达到70%以上，大幅降低了后续除盐提纯工艺的投资和生产成本、降低了后续除盐提纯工艺的难度，最终可以稳定地得到电池级碳酸锂或氢氧化锂。
（2）本发明的带滤机中使用的是粉状锂离子选择性吸附剂，使用前无需对吸附剂造粒，使用过程中一次装载的吸附剂量比吸附塔大大降低，大大降低了投产阶段的投资成本，万吨碳酸锂产线吸附剂投加量仅为300-500 t，其耗资仅为数千万元。
（3）本发明的带滤机中，至少在所述的盐洗脱液收集口处设有抽真空机构；抽真空机构能够加快洗盐液穿过吸附剂的速度，缩短洗盐液与吸附剂的接触时间，尽可能地减少洗盐液带走的锂量。
（4）本发明的带滤机中，在卤水回收口、盐洗脱液收集口和锂洗脱液收集口中至少其一处设置了吸附剂回收机构，吸附剂回收机构用以对卤水、盐洗脱液和锂洗脱液中吸附剂进行回收，节约吸附剂成本。
（5）本发明的带滤机中，所述的洗盐液输送机构具有沿滤布前进方向布置的至少两个出液端；多个沿滤布前进方向布置的出液端能够实现“小剂量多次洗盐”，不仅提高了洗盐效率，而且与单独一个出液端相比，设置多个出液端在达到同样的洗盐效果的同时，洗盐液的用量更少、锂流失量更低。
（6）本发明的带滤机中，沿滤布前进方向的反方向，所述的出液端输送的洗盐液的盐浓度逐渐变高，实现梯度洗盐，以尽可能地减少吸附剂上锂离子的流失。
（7）本发明的带滤机中，解吸液输送机构具有沿滤布前进方向布置的至少两个出液端；多个沿滤布前进方向布置的出液端能够实现“小剂量多次解吸”，不仅提高了解吸效率，而且与单独一个出液端相比，设置多个出液端在达到同样的解吸效果的同时，解吸液的用量更少。
（8）本发明的带滤机中，解吸区下游还设有洗盐回水区，从洗盐区收集的盐洗脱液经盐洗脱液回流机构送至洗盐回水区，使已经经过洗盐区和解吸区的吸附剂再次吸附盐溶液，如此不仅能够重新回收盐洗脱液中的锂，而且当这部分吸附剂经吸附剂回收机构送回混合吸附机构中与卤水混合时，已吸附高浓度盐的吸附剂能够快速捕获卤水中的锂离子，实施下一轮的吸附法卤水提锂。
 附图说明
图1为本发明带滤机的结构示意图；
图2为本发明带滤机的另一结构示意图；
图3为本发明带滤机中洗盐区和解吸区的第二种结构示意图；
图4为本发明带滤机中洗盐区和解吸区的第三种结构示意图。
 本发明的最佳实施方式
下面结合附图和具体实施方式对本发明的技术方案做进一步详细说明。
 
 
实施例 1
如图1所示，本实施例一种带滤机，该带滤机是在现有带式真空过滤机的基础上进行改进获得的，本实施例重点对改进点进行详细表述，其他未阐述部分与现有市售带式真空过滤机的结构相同，本实施例不再赘述。
如图1所示，本实施例的带滤机包括机架1，机架1上设有往复回转运行的滤布2，滤布2的往复回转运行是由设置在机架1上的驱动机构3带动的，该驱动机构3可以包括常规的：与机架1转动连接的主动轮31和从动轮32，其中主动轮31由周向驱动器（图中未示出）带动，该滤布2即环绕在该主动轮31和从动轮32之间。
本实施例的滤布2优选为大通气量滤布2，滤布2通气量大于500 L/m 2·s，且对吸附剂的截留率大于90%。
由图1可见，在主动轮31和从动轮32之间，机架1上固定安装有处于滤布2下方的集液盒4，集液盒4的顶部可以是具有开口的，也可以不是开口的，而是在集液盒4顶部设有若干滤过孔；无论是否开口，集液盒4的顶部均应当设置阻挡机构（图中未示出），避免液体从集液盒4顶部两侧泄漏，确保液体全部进入集液盒4内。
如图1所示，依据滤布2上方设置的机构不同，机架1上形成有沿滤布2前进方向依次设置的固液分离区100、洗盐区200和解吸区300。为了与上述分区相适应，集液盒4内也设有沿滤布2前进方向均匀布置的隔板41，隔板41将集液盒4分隔成若干集液腔42；而固液分离区100、洗盐区200和解吸区300的长度均为集液腔42的长度的倍数，当然，对于固液分离区100、洗盐区200和解吸区300，具体的倍数可以是相同的，也可以是不同的，取决于具体的设计需要。
如图1所示，本实施例中，固液分离区100的长度与四个集液腔42的长度相当，洗盐区200和解吸区300的长度均与三个集液腔42的长度相当。将各功能区的长度设置成集液腔42长度的倍数，能够确保各功能区的相应液体均能进入对应的集液腔42。
本实施例中，集液腔42的长度是可以根据具体需要具体设置的。
由图1可见，本实施例的三个功能区中，在固液分离区100，滤布2上方设置有混合吸附机构5；该混合吸附机构5包括一混合罐51，该混合罐51的顶部设有卤水进料口52和吸附剂进料口53，原料卤水和吸附剂分别经过相应的进料口进入混合罐51内，在搅拌组件54的作用下，吸附剂与原料卤水在混合罐51内混合吸附，获得吸附剂卤水混合物；该吸附剂卤水混合物从该混合罐51内出料，被输送至固液分离区100的滤布2上；由于滤布2的滤过作用，已吸附卤水中多种离子的吸附剂与卤水分离，吸附剂留在滤布2上，而卤水则穿过滤布2进入相应的集液腔42。
如图1所示，与固液分离区100对应的每个集液腔42底部均具有卤水回收口43，各卤水回收口43均通过管路与卤水抽滤桶44相连，而卤水抽滤桶44与抽真空机构（如真空泵，图中未示出）相连，在抽真空机构的作用下，卤水能够快速穿过滤布2进入集液腔42和卤水抽滤桶44，且吸附剂能够在滤布2上形成厚1.5-4 厘米左右的滤饼。
由图1可见，为确保对卤水的充分收集，混合吸附机构5的出料端处于固液分离区100的起始端（即远离洗盐区200的一端），确保所有卤水都进入与固液分离区100相对应的集液腔42中，而不会进入下游的洗盐区200内。
由于本实施例采用的吸附剂是粉状吸附剂（粒径为75微米的铝系吸附剂），因此滤布2难以百分百阻挡吸附剂，收集的卤水中或多或少会含有一些吸附剂。因此本实施例还设置了与卤水抽滤桶44相连的吸附剂回收机构10，该吸附剂回收机构10可以采用磁选机101、精密过滤器、陶瓷膜等筛选设备，以便从收集的卤水中分离出吸附剂，而后再将卤水返回盐田或盐湖。
如图1所示，在洗盐区200，滤布2的上方布施有洗盐液输送机构6，该洗盐液输送机构6用于向随滤布2进入洗盐区200的滤饼布施洗盐液。本实施例中采用的洗盐液可以是淡水，或其他盐度较低的溶液。洗盐液输送机构6采用现有技术中常用的液体输送设备，只要确保在竖直方向上均匀输液即可，可以包括与洗盐液储罐（图中未示出）相连的洗盐液输送管61，该洗盐液输送管61上安装有洗盐液输送泵（图中未示出），洗盐液输送管61的出液端可以安装布水盘（图中未示出），该布水盘的布水直径与滤饼宽度相当，确保洗盐效果。
同样地，与洗盐区200对应的每个集液腔42底部均具有盐洗脱液收集口45，各盐洗脱液收集口45均通过管路与盐洗脱液抽滤桶46相连，而盐洗脱液抽滤桶46与抽真空机构（如真空泵）相连，在抽真空机构的作用下，洗盐液能够快速穿过滤饼，将洗盐液与滤饼的接触时间控制在10秒以内（优选为1-2秒）。
同样地，为确保对盐洗脱液的充分收集，洗盐液输送机构6的出液端处于洗盐区200的起始端（即靠近固液分离区100的一端），确保所有盐洗脱液都进入与洗盐区200相对应的集液腔42中，而不会进入下游的解吸区300内。
根据申请人的研究发现，由于卤水为高盐甚至盐饱和溶液，当卤水与吸附剂混合后，包括锂离子在内的多种盐离子都会被吸附到吸附剂上；但锂离子与其他盐离子的吸附机制不同，卤水中的盐会将锂离子挤压到无定型氢氧化物吸附剂的晶格中形成分子筛，而其他盐离子则不会进入无定型氢氧化物吸附剂的晶格中，这就导致锂离子和其他盐离子与吸附剂之间的结合强度是不同的。由于盐离子与吸附剂的结合较弱，因此在洗盐区200，采用洗盐液对滤饼进行短时快速的冲洗，能够最大限度地带走盐离子、最小限度地带走锂离子，达到“抛盐留锂”的目的。
收集到的盐洗脱液中也含有吸附剂，因此本实施例也设置了与盐洗脱液抽滤桶46相连的吸附剂回收机构10，该吸附剂回收机构10可以采用磁选机101、精密过滤器、陶瓷膜等筛选设备，以便从收集的盐洗脱液中分离出吸附剂，而后再送往盐湖或盐田，或用于其他工艺中。
如图1所示，在解吸区300，滤布2的上方布施了解吸液输送机构7，该解吸液输送机构7用于向随滤布2进入解吸区300的滤饼布施解吸液，本实施例中采用的解吸液可以是淡水，或其他盐度较低的溶液。解吸液输送机构7可以采用现有技术中常用的液体输送设备，只要确保在竖直方向上均匀输液即可，可以采用与上述洗盐液输送机构6相同的结构。
同样地，与解吸区300对应的每个集液腔42底部均具有锂洗脱液收集口47，各锂洗脱液收集口47均通过管路与锂洗脱液抽滤桶48相连，而锂洗脱液抽滤桶48与抽真空机构（如真空泵）相连，在抽真空机构的作用下，解吸液能够快速穿过滤饼，将解吸液与滤饼的接触时间控制在10秒以内优选为1-2秒。
同样地，为确保对锂洗脱液的充分收集，解吸液输送机构7的出液端处于解吸区300的起始端（即靠近洗盐区200的一端），确保所有锂解吸液都进入与解吸区300相对应的集液腔42中。
经过洗盐区200对吸附剂上除锂以外的其他离子进行预先洗脱后，吸附剂上的盐锂比已经大大降低，此时采用解吸液将吸附剂上的锂离子洗脱下来，能够获得锂浓度更高的锂洗脱液。
同样地，收集到的锂洗脱液中也含有吸附剂，因此本实施例也设置了与锂洗脱液抽滤桶48相连的吸附剂回收机构10，该吸附剂回收机构10可以采用磁选机101、精密过滤器、陶瓷膜等筛选设备，以便从收集的锂洗脱液中分离出吸附剂，而后再将锂洗脱液送入下一步的精制提纯工序中。
在滤布前进方向的终点处，采用吸附剂回收机构8将经过解吸的吸附剂收集起来，并送入混合吸附机构5中循环使用。
本实施例带滤机在吸附法卤水提锂中的应用方法包括：
（1）将吸附剂与卤水在混合吸附机构5中混匀；
将吸附剂与卤水按比例送入混合罐51中，搅拌组件启动，将吸附剂与卤水搅拌混匀，在搅拌过程中，吸附剂吸附卤水中的各种离子；在生产线初始启动时，需要将吸附剂和卤水在混合罐51中搅拌一段时间（约几分钟）后再出料，以确保吸附剂有效吸附；而在生产线开始运行后，吸附剂和卤水可以连续进料，吸附剂卤水混合物也可以连续出料。
（2）将吸附剂卤水混合物输送至固液分离区100，使吸附剂与卤水分离并在滤布2上将吸附剂制成滤饼；
待吸附剂完成吸附后，将吸附剂卤水混合物自混合罐51中出料，混合罐51的出料端处于固液分离区100的起始端，自混合罐51出料的吸附剂卤水混合物逐渐落在运行的滤布2上，在抽真空机构的辅助下，卤水穿过滤布2、进入相应的集液腔42，经各卤水回收口43收集到卤水抽滤桶44中；回收的卤水经吸附剂回收后，可以返回盐湖或盐田；
在匀速运行的滤布2上，匀速出料的吸附剂在抽真空机构的作用下形成厚约1.5-4厘米的滤饼；由于是连续出料的，因此滤饼是延伸在整个滤布2运行路程上的。
（3）滤饼随滤布2前往洗盐区200，在洗盐区200内，洗盐液输送机构6向滤饼输送洗盐液，使吸附在滤饼上除锂以外的离子被洗脱，收集盐洗脱液；
洗盐液从洗盐区200的起始端向滤饼布施，在抽真空机构的辅助下，洗盐液穿过滤饼只需1-2秒，尽可能地抛盐留锂；
收集到的盐洗脱液经吸附剂回收后，可以送往盐湖或盐田，或用于其他工艺中；
（4）滤饼随滤布2前往解吸区300，在解吸区300内，解吸液输送机构7向滤饼输送解吸液，使吸附在滤饼上的锂离子被洗脱，收集锂洗脱液；
解吸液从解吸区300的起始端向滤布2布施，在抽真空机构的辅助下，解吸液穿过滤饼，将锂从吸附剂上洗脱下来；收集到的锂洗脱液经回收吸附剂后，送往下游工序中，进行精制提纯；
（5）在滤布2前进方向的终点处，将经过解吸的吸附剂输送至混合吸附机构5中，利用吸附剂回收机构10回收的吸附剂也可以送返至混合吸附机构5中，进行新一轮的吸附法卤水提锂。
采用本实施例的带滤机获得的锂洗脱液中，盐锂比小于10:1，镁锂比小于1:1，锂浓度约为0.4 g/l；洗盐液用量为卤水量的30%，锂回收率为70%。
 本发明的实施方式
实施例 2
如图2所示，本实施例的带滤机与实施例1基本相同，不同之处在于：沿滤布2前进方向，机架1上形成有固液分离区100、洗盐区200、解吸区300和洗盐回水区400，即在解吸区300下游还设置了洗盐回水区400；该洗盐回水区400的上方设有盐洗脱液回流机构9，该盐洗脱液回流机构9的进液端与盐洗脱液抽滤桶46相连，使已经经过洗盐区200和解吸区300的吸附剂再次吸附盐洗脱液。
申请人研究发现，吸附剂在高盐浓度溶液中可快速捕集锂离子，数十秒的接触时间即可达到60%以上的吸附平衡。因此将完成洗盐和解吸的吸附剂，预先吸附具有较高盐浓度的盐洗脱液，而后再送回混合吸附机构5，如此，当这部分吸附剂进入到混合罐51内后，能够快速捕集原料卤水中的锂离子，从而能够实现吸附剂和原料卤水连续进料、吸附剂卤水混合物连续出料，实现不间断连续生产；此外，还能回收盐洗脱液中锂离子，进一步提高锂回收率。
同样地，洗盐回水区400也对应设置了若干集液腔42，用于收集经过滤饼和滤布2的复吸附滤液；各集液腔42的底部也开设有复吸附滤液收集口49，复吸附滤液收集口49通过管路与复吸附滤液抽滤桶410相连，复吸附滤液抽滤桶410与抽真空机构相连。复吸附滤液抽滤桶410内的复吸附滤液在进入下游处理工序前，也需要采用磁选机101等吸附剂回收机构10回收其中的吸附剂。
本实施例带滤机在吸附法卤水提锂中的应用方法包括：
（1）将吸附剂与卤水在混合吸附机构5中混匀；
将吸附剂与卤水按比例送入混合罐51中，搅拌组件启动，将吸附剂与卤水搅拌混匀，在搅拌过程中，吸附剂吸附卤水中的各种离子；在生产线初始启动时，需要将吸附剂和卤水在混合罐51中搅拌一段时间约几分钟后再出料，以确保吸附剂有效吸附；而在生产线开始运行后，吸附剂和卤水可以连续进料，吸附剂卤水混合物也可以连续出料。
（2）将吸附剂卤水混合物输送至固液分离区100，使吸附剂与卤水分离并在滤布2上将吸附剂制成滤饼；
待吸附剂完成吸附后，将吸附剂卤水混合物自混合罐51中出料，混合罐51的出料端处于固液分离区100的起始端，自混合罐51出料的吸附剂卤水混合物逐渐落在运行的滤布2上，在抽真空机构的辅助下，卤水穿过滤布2、进入相应的集液腔42，经各卤水回收口43收集到卤水抽滤桶44中；回收的卤水经吸附剂回收后，可以返回盐湖或盐田；
在匀速运行的滤布2上，匀速出料的吸附剂在抽真空机构的作用下形成厚约1.5-4厘米的滤饼；由于是连续出料的，因此滤饼是延伸在整个滤布2运行路程上的。
（3）滤饼随滤布2前往洗盐区200，在洗盐区200内，洗盐液输送机构6向滤饼输送洗盐液，使吸附在滤饼上除锂以外的离子被洗脱，收集盐洗脱液；
洗盐液从洗盐区200的起始端向滤饼布施，在抽真空机构的辅助下，洗盐液穿过滤饼只需1-2秒，尽可能地抛盐留锂；
（4）滤饼随滤布2前往解吸区300，在解吸区300内，解吸液输送机构7向滤饼输送解吸液，使吸附在滤饼上的锂离子被洗脱，收集锂洗脱液；
解吸液从解吸区300的起始端向滤布2布施，在抽真空机构的辅助下，解吸液穿过滤饼，将锂从吸附剂上洗脱下来；收集到的锂洗脱液经回收吸附剂后，送往下游工序中，进行精制提纯；
（5）将步骤3收集的盐洗脱液输送至洗盐回水区400，使吸附剂预吸附；收集到的复吸附滤液经吸附剂回收后，也送往盐田或盐湖；
（6）在滤布2前进方向的终点处，吸附剂回收机构8收集经预吸附的吸附剂，并将其输送至混合吸附机构5中，前述经吸附剂回收机构10回收的吸附剂也被送返至混合吸附机构5中，进行新一轮的吸附法卤水提锂。
采用本实施例的带滤机获得的锂洗脱液中，盐锂比小于10:1，镁锂比小于1:1，锂浓度约为0.4 g/l；洗盐液用量为卤水量的30%，锂回收率达到80%。
实施例 3
如图3所示，本实施例的带滤机主体结构与实施例1或实施例2相同，不同之处在于：洗盐区200的洗盐液输送机构6具有至少两个出液端（本实施例设置了三个），所有出液端沿滤布2前进方向均匀布置。
设置三个出液端的具体方式可以是：设置三根洗盐液输送管61，三根洗盐液输送管61通过四通阀与洗盐液储罐相连，每根洗盐液输送管61的出液端均安装有布水盘，各布水盘的布水直径与滤饼宽度相当，确保洗盐效果。
输送洗盐液时，采用一个洗盐液输送泵同时为三根洗盐液输送管61提供动力，或者在每根洗盐液输送管61上安装一个洗盐液输送泵，均是可实施的。
同样地，洗盐液输送机构6的各个出液端是以洗盐区200起始端为起点均匀布置的，确保最后一个出液端距离洗盐区200的尾端稍远，为洗盐液滤过滤饼保留一定的时间，确保盐洗脱液不进入解吸区300。
与实施例1中只设置一个出液端相比，多个出液端所使用的洗盐液的总量不变，但由于洗盐时实现了“小剂量多次洗涤”，因此洗盐效率更高。
采用本实施例的带滤机获得的锂洗脱液中，盐锂比小于10:1，镁锂比小于1:1，锂浓度约为0.4 g/l；洗盐液用量为卤水量的23%，锂回收率达到85%。
 
实施例 4
如图3所示，本实施例的带滤机主体结构与实施例1、实施例2或实施例3相同，不同之处在于：解吸区300的解吸液输送机构7具有至少两个出液端（本实施例设置了三个），所有出液端沿滤布2前进方向均匀布置。
具有多个出液端的解吸液输送机构7的具体设置方式可以是与实施例3中洗盐液输送机构6相同的，也设置多根解吸液输送管71。
与实施例1中只设置一个出液端相比，多个出液端所使用的解吸液的总量不变，但由于解吸时实现了“小剂量多次洗涤”，因此解吸效率更高，能够进一步提高锂回收率。
采用本实施例的带滤机获得的锂洗脱液中，盐锂比小于10:1，镁锂比小于1:1，锂浓度达到0.45 g/l；洗盐液用量为卤水量的23%，锂回收率达到85%。
实施例 5
如图4所示，本实施例的带滤机主体结构与实施例1或实施例2或实施例4相同，不同之处在于：洗盐区200的洗盐液输送机构6具有至少两个出液端（本实施例设置了三个），所有出液端沿滤布2前进方向均匀布置；并且，沿滤布2前进方向的反方向，各出液端输送的洗盐液的盐浓度逐渐变高。
该洗盐液输送机构6的具体设置方式可以是：洗盐液输送机构6包括洗盐液初供组件62和至少一个洗盐液循环组件63本实施例设置了两个，洗盐液初供组件62和各洗盐液循环组件63沿滤布2前进方向的反方向依次串联。
本实施例中，洗盐液初供组件62和洗盐液循环组件63的结构是相同的，可以采用与实施例1中洗盐液输送机构6相同的结构，且洗盐液初供组件62和洗盐液循环组件63的出液端均处于洗盐区200上方，洗盐区200下方则设有与各出液端对应的盐洗脱液抽滤桶46；但洗盐液初供组件62和洗盐液循环组件63的进液端所对应连接的位置不同，其中，洗盐液初供组件62的进液端与洗盐液储罐相连，而洗盐液循环组件63的进液端则与和洗盐液初供组件62相对应的盐洗脱液抽滤桶46相连，或者，与和上一洗盐液循环组件63相对应的盐洗脱液抽滤桶46相连。
洗盐液的供给是沿滤布2前进方向的反方向进行的，洗盐液循环组件63的洗盐液收集自洗盐液初供组件62或上一洗盐液循环组件63的盐洗脱液抽滤桶46，由于至少经过了一次洗盐，因此洗盐液循环组件63出液端的洗盐液盐浓度总是比洗盐液初供组件62或上一洗盐液循环组件63的洗盐液盐浓度要高，实现了洗盐液的浓度梯度逆向洗脱。
申请人研究发现，已捕集锂离子的吸附剂在洗盐过程中仍然存在锂离子流失，但洗盐液盐浓度越高，锂离子流失率越低。因此，本实施例设置了上述的洗盐液浓度梯度逆向洗脱方式，以尽可能地减少洗盐过程中，吸附剂上锂离子的流失。
同样地，本实施例中，洗盐液输送机构6的各个出液端是以洗盐区200起始端为起点均匀布置的，确保最后一个出液端距离洗盐区200的尾端稍远，为洗盐液滤过滤饼保留一定的时间，确保盐洗脱液不进入解吸区300。
采用本实施例的带滤机获得的锂洗脱液中，盐锂比小于10:1，镁锂比小于1:1，锂浓度达到0.45 g/l；洗盐液用量为卤水量的17%，锂回收率接近90%。
 
实施例 6
如图4所示，本实施例的带滤机主体结构与实施例1、实施例2、实施例3或实施例5相同，不同之处在于：解吸区300的解吸液输送机构7具有至少两个出液端（本实施例设置了三个），所有出液端沿滤布2前进方向均匀布置；该解吸液输送机构7包括解吸液初供组件72和至少一个解吸液循环组件73，解吸液初供组件72和解吸液循环组件73沿滤布2前进方向的反方向依次串联。
本实施例中，解吸液输送机构7的结构与实施例5中洗盐液输送机构6的结构相同。
采用本实施例的带滤机获得的锂洗脱液中，盐锂比小于10:1，镁锂比小于1:1，锂浓度达到0.5 g/l；洗盐液用量为卤水量的17%，锂回收率接近90%。

Claims (10)

  1. 一种带滤机，包括机架（1），所述的机架（1）上设有往复回转运行的滤布（2），其特征在于，沿滤布（2）前进方向依次设有：固液分离区（100），所述的滤布（2）上方设有用于向固液分离区（100）输送吸附剂卤水混合物的混合吸附机构（5）；洗盐区（200），所述的滤布（2）上方布施有用于向洗盐区（200）输送洗盐液的洗盐液输送机构（6）；解吸区（300），所述的滤布（2）上方布施有用于向解吸区（300）输送解吸液的解吸液输送机构（7），所述的解吸区（300）下方设有锂洗脱液收集口（47）。
  2. 如权利要求1所述的带滤机，其特征在于，所述的固液分离区（100）下方设有卤水回收口（43），所述的洗盐区（200）下方设有盐洗脱液收集口（45），在所述的卤水回收口（43）、所述的盐洗脱液收集口（45）和所述的锂洗脱液收集口（47）中，至少所述的盐洗脱液收集口（45）连接有抽真空机构；所述的卤水回收口（43）、所述的盐洗脱液收集口（45）和所述的锂洗脱液收集口（47）中至少其一连接有吸附剂回收机构（10）。
  3. 如权利要求1所述的带滤机，其特征在于，所述的洗盐液输送机构（6）具有沿滤布（2）前进方向布置的至少两个出液端。
  4. 如权利要求3所述的带滤机，其特征在于，沿滤布（2）前进方向的反方向，所述的出液端输送的洗盐液的盐浓度逐渐变高。
  5. 如权利要求4所述的带滤机，其特征在于，所述的洗盐液输送机构（6）包括
    洗盐液初供组件（62）和至少一个洗盐液循环组件（63），所述的洗盐液初供组
    件（62）和洗盐液循环组件（63）沿滤布（2）前进方向的反方向依次串联；
    所述的洗盐液初供组件（62）和洗盐液循环组件（63）的出液端均处于洗盐区（200）上方，所述的洗盐区（200）下方设有与各出液端对应的盐洗脱液收集口（45），所述的洗盐液初供组件（62）的进液端与洗盐液储罐相连，所述的洗盐液循环组件（63）的进液端与和洗盐液初供组件（62）或上一洗盐液循环组件（63）相对应的盐洗脱液收集口（45）相连。
  6. 如权利要求1所述的带滤机，其特征在于，所述的解吸液输送机构（7）具有沿滤布（2）前进方向布置的至少两个出液端。
  7. 在此处如权利要求6所述的带滤机，其特征在于，所述的解吸液输送机构（7）
    包括解吸液初供组件（72）和至少一个解吸液循环组件（73），所述的解吸液初
    供组件（72）和解吸液循环组件（73）沿滤布（2）前进方向的反方向依次串联；
    所述的解吸液初供组件（72）和解吸液循环组件（73）的出液端均处于解吸区（300）上方，所述的解吸区（300）下方设有与各出液端对应的锂洗脱液收集口（47），所述的解吸液初供组件（72）的进液端与解吸液储罐相连，所述的解吸液循环组件（73）的进液端与和解吸液初供组件（72）或上一解吸液循环组件（73）相对应的锂洗脱液收集口（47）相连。
  8. 如权利要求1-7中任意一项所述的带滤机，其特征在于，在所述的解吸区（300）下游还设有洗盐回水区（400），该洗盐回水区（400）的上方设有盐洗脱液回流机构（9），该盐洗脱液回流机构（9）的进液端与所述的盐洗脱液收集口（45）相连；在所述的洗盐回水区（400）下游设有吸附剂回收机构（8），该吸附剂回收机构（8）与混合吸附机构（5）相连。
  9. 如权利要求1-7中任意一项所述的带滤机在吸附法卤水提锂中的应用，其特征在于，包括：（1）将吸附剂与卤水在所述的混合吸附机构（5）中混匀；（2）将吸附剂卤水混合物输送至固液分离区（100），使吸附剂与卤水分离并在滤布（2）上将吸附剂制成滤饼；（3）滤饼随滤布（2）前往洗盐区（200），在所述的洗盐区（200）内，所述的洗盐液输送机构（6）向滤饼输送洗盐液，使吸附在滤饼上除锂以外的离子被洗脱，收集盐洗脱液；（4）滤饼随滤布（2）前往解吸区（300），在所述的解吸区（300）内，所述的解吸液输送机构（7）向滤饼输送解吸液，使吸附在滤饼上的锂离子被洗脱，收集锂洗脱液；（5）在滤布（2）前进方向的终点处，收集经过解吸的吸附剂并将其输送至混合吸附机构（5）中，进行新一轮的吸附法卤水提锂。
  10. 如权利要求8所述的带滤机在吸附法卤水提锂中的应用，其特征在于，包括：
    （1）将吸附剂与卤水在所述的混合吸附机构（5）中混匀；（2）将吸附剂卤水混合物输送至固液分离区（100），使吸附剂与卤水分离并在滤布（2）上将吸附剂制成滤饼；（3）滤饼随滤布（2）前往洗盐区（200），在所述的洗盐区（200）内，所述的洗盐液输送机构（6）向滤饼输送洗盐液，使吸附在滤饼上除锂以外的离子被洗脱，收集盐洗脱液；（4）滤饼随滤布（2）前往解吸区（300），在所述的解吸区（300）内，所述的解吸液输送机构（7）向滤饼输送解吸液，使吸附在滤饼上的锂离子被洗脱，收集锂洗脱液；（5）将步骤（3）收集的盐洗脱液输送至洗盐回水区（400），使吸附剂预吸附；（6）在滤布（2）前进方向的终点处，收集经预吸附的吸附剂并将其输送至混合吸附机构（5）中，进行新一轮的吸附法卤水提锂。
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