WO2022127316A1 - 一种铝基锂离子筛及其制备方法和应用 - Google Patents

一种铝基锂离子筛及其制备方法和应用 Download PDF

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WO2022127316A1
WO2022127316A1 PCT/CN2021/123400 CN2021123400W WO2022127316A1 WO 2022127316 A1 WO2022127316 A1 WO 2022127316A1 CN 2021123400 W CN2021123400 W CN 2021123400W WO 2022127316 A1 WO2022127316 A1 WO 2022127316A1
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aluminum
sulfate
based lithium
lithium ion
ion sieve
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PCT/CN2021/123400
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English (en)
French (fr)
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杨鼎
陈若葵
乔延超
郑显亮
谭枫
李长东
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湖南邦普循环科技有限公司
广东邦普循环科技有限公司
湖南邦普汽车循环有限公司
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Priority to EP21905245.3A priority Critical patent/EP4260935A4/en
Publication of WO2022127316A1 publication Critical patent/WO2022127316A1/zh
Priority to US18/211,587 priority patent/US20230330622A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/045—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing sulfur, e.g. sulfates, thiosulfates, gypsum
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3071—Washing or leaching
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
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    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/02—Processes using inorganic exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/09—Inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/10—Oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/016—Modification or after-treatment of ion-exchangers
    • 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
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • 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
    • C22B7/006—Wet processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the present disclosure belongs to the field of adsorbents, and in particular relates to an aluminum-based lithium ion sieve and a preparation method and application thereof.
  • lithium metal In the field of chemical power supply, lithium metal has high electrochemical potential, light weight and large specific energy. Lithium foil and lithium bar are widely used in rechargeable lithium batteries. Some lithium batteries have long life, high voltage, high energy density, no pollution and can be used at low temperature. Lithium high-energy battery is a promising power battery developed in recent years. Cell phones and computers with long standby time all use lithium-ion batteries. And in the electric vehicle industry, in order to reduce the cost of driving, the use of lithium battery power generation replaces the traditional gasoline engine to start the car.
  • lithium ion adsorption technologies such as adsorption resins, aluminum salt-type adsorbents, lithium-inserting active matrix materials, MnO adsorbents, spodumene concentrates as raw materials, and lithium ion sieves.
  • lithium ion sieves have attracted more and more attention due to their large adsorption capacity and fast adsorption speed.
  • the structure of lithium ion sieves is easily corroded, and it is difficult to accurately control the concentration and purity of lithium in the eluent.
  • Embodiments of the present disclosure provide an aluminum-based lithium ion sieve and a preparation method and application thereof.
  • the aluminum-based lithium ion sieve has the advantages of high adsorption capacity and good stability, and can effectively recover low-concentration lithium in industrial wastewater, while simultaneously
  • the use of aluminum hydroxide cladding can effectively ensure that the structure is not corroded.
  • an embodiment of the present disclosure provides an aluminum-based lithium ion sieve, which is Li 2 SO 4 ⁇ 2Al(OH) 3 ⁇ nH 2 O coated with Al(OH) 3 , and n is 1-4.
  • Embodiments of the present disclosure also provide a method for preparing an aluminum-based lithium ion sieve, comprising the following steps:
  • step (2) adjusting the pH of the aluminum-based lithium adsorbent intermediate obtained in step (1) to be acidic, filtering, and collecting the filter residue to obtain the aluminum-based lithium adsorbent Li 2 SO 4 ⁇ 2Al(OH) 3 ⁇ nH 2 O;
  • step (3) washing the aluminum-based lithium adsorbent obtained in step (2), mixing with the metaaluminate solution, adjusting pH, filtering, taking the filter residue, drying, and grinding to obtain the aluminum-based lithium ion sieve.
  • the aluminum salt is at least one of aluminum sulfate, aluminum chloride, aluminum nitrate and sodium metaaluminate.
  • the lithium salt is at least one of lithium hydroxide, lithium sulfate, lithium chloride and lithium nitrate.
  • step (1) the adjusting pH to alkaline is adjusting pH to 9.0-11.0.
  • the solution used for adjusting pH to alkaline is at least one of the following solutions: sodium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate and ammonia water.
  • the substance used for adjusting pH is at least one of sodium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate and ammonia water.
  • step (1) the temperature of the reaction is 30°C-100°C, and the time is 1-72 h.
  • step (1) the stirring speed of the dispersion is controlled at 100-700 rpm.
  • step (2) the adjusting pH to acidity is adjusting pH to 2.5-5.5.
  • the solution used for adjusting pH to acidity is at least one of sulfuric acid solution, salt solution with sulfate radicals, and mixed solution of sulfuric acid and salt.
  • the sulfuric acid solution is 0.5-2 mol/L.
  • the sulfate-bearing salt solution is a solution of at least one of: aluminum sulfate, nickel sulfate, cobalt sulfate, manganese sulfate, ferric sulfate, and ferrous sulfate.
  • the mixed solution of sulfuric acid and salt is at least one of a mixed solution of sulfuric acid and ferric chloride and a mixed solution of sulfuric acid and ferrous chloride.
  • the metaaluminate is at least one of sodium metaaluminate and potassium metaaluminate.
  • step (3) the pH adjustment is to adjust the pH to 3.5-11.0.
  • the solution used for adjusting pH is at least one of the following solutions: sodium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water, aluminum sulfate, nickel sulfate, cobalt sulfate, Manganese sulfate, permanganic acid, ferric sulfate, ferrous sulfate, ferric chloride and ferrous chloride.
  • the drying temperature is 40°C-100°C.
  • the principles of the embodiments of the present disclosure include: using lithium salts, aluminum salts and a pH-adjusting base to react to obtain an adsorbent intermediate LiOH ⁇ 2Al(OH) 3 ⁇ nH 2 O, where n is 1-4, and then adjusting the pH by dilute sulfuric acid (pH The acid) was adjusted to 2.5-5.5 to obtain an aluminum-based lithium adsorbent Li 2 SO 4 ⁇ 2Al(OH) 3 ⁇ nH 2 O, and n was 1-4.
  • Embodiments of the present disclosure also provide a method for treating industrial wastewater by using an aluminum-based lithium ion screen, comprising the following steps:
  • the industrial wastewater is wastewater with low lithium concentration and high concentration of impurity ions or wastewater with high pH.
  • step (1) when the adsorbed liquid is acidic, it is used to supplement the aluminum salt in the synthesis section, and when it is alkaline, it is used to supplement the metaaluminate in the synthesis section.
  • the standing time is 10-20 min.
  • the clean water used in the analysis of the lithium ion adsorbent is at least one of deionized water and tap water.
  • the embodiment of the present disclosure provides a lithium ion adsorbent different from the usual aluminum salt, because the material coating can be used for industrial wastewater and salt lake brine with high pH, and because during the adsorption and desorption process, the Al ( OH) 3 will play a protective role on its coated lithium sorbent.
  • Industrial wastewater with high pH will first react with acid and alkali through Al(OH) 3 outside the lithium sorbent, while Li ions can penetrate through due to their small ionic radius. After passing through the Al(OH) 3 shell, it is adsorbed by the lithium ion adsorbent as the crystal nucleus, and the aluminum hydroxide is recovered by adjusting the pH of the liquid after adsorption.
  • Embodiment 1 is a process flow diagram of Embodiment 1 of the present disclosure
  • FIG. 2 is the XRD pattern of the aluminum-based lithium ion sieve in Example 1 of the disclosure.
  • the conventional conditions or the conditions suggested by the manufacturer are used.
  • the raw materials, reagents, etc., which are not specified by the manufacturer, are all conventional products that can be purchased from the market.
  • the aluminum-based lithium ion sieve of this embodiment is Li 2 SO 4 ⁇ 2Al(OH) 3 ⁇ 3H 2 O coated with Al(OH) 3 .
  • step (2) (2) adjusting the pH of the aluminum-based lithium adsorbent intermediate obtained in step (1) to 4 through 0.5 mol/L dilute sulfuric acid, aging for 4 h after the reaction, filtering, and washing 2-3 times to obtain aluminum-based lithium adsorption agent Li 2 SO 4 ⁇ 2Al(OH) 3 ⁇ 3H 2 O;
  • step (3) carry out suction filtration with the aluminum-based lithium sorbent obtained in step (2), wash, weigh 100g of NaAlO 2 and dissolve it in 500 ml of water, then mix with the aluminum-based lithium sorbent, adjust the pH to 10.0, filter, and take the filter residue, Dry at 80° C. for 24 h, and grind to obtain an aluminum-based lithium adsorbent Li 2 SO 4 ⁇ 2Al(OH) 3 ⁇ 3H 2 O coated with Al(OH) 3 .
  • the above measured Li + adsorption capacity of the aluminum-based lithium ion sieve is 2.7 mg/g, the pH of the liquid before adsorption is 13, and the liquid after adsorption is 8, and the pH is significantly reduced.
  • the adsorbent has a good adsorption effect on Li in industrial wastewater, and can enrich the pure lithium liquid to more than 500 mg/L through countercurrent analysis, and the Al(OH) 3 shell protects the aluminum during the adsorption process.
  • the base adsorbent itself is not corroded.
  • Fig. 1 is a process flow diagram of Embodiment 1 of the disclosure. From Fig. 1, lithium salt, aluminum salt can be reacted with an alkali for adjusting pH, and then a dilute aluminum sulfate-based lithium sorbent is passed through, and then mixed with metaaluminate to obtain The aluminum-based lithium ion sieve coated with Al(OH) 3 can also supplement the aluminum salt by adjusting the liquid after adsorption.
  • the aluminum-based lithium ion sieve of this embodiment is Li 2 SO 4 ⁇ 2Al(OH) 3 ⁇ 3H 2 O coated with Al(OH) 3 .
  • step (1) (2) adjusting the pH of the aluminum-based lithium adsorbent intermediate obtained in step (1) to 4 by 0.5mol/L dilute sulfuric acid, aging for 6 h after the reaction, filtering, and taking the filter residue to obtain the aluminum-based lithium adsorbent Li 2 SO 4 ⁇ 2Al(OH) 3 ⁇ 3H 2 O;
  • step (3) Wash the aluminum-based lithium adsorbent obtained in step (2) for 2-3 times, weigh 300 g of NaAlO 2 and dissolve it in 500 ml of water, ultrasonically disperse it for 30 min, then mix with the aluminum-based lithium adsorbent, adjust the pH to 8.0, and filter , the filter residue was taken, dried at 80°C for 24 h, and ground to obtain an aluminum-based lithium adsorbent Li 2 SO 4 ⁇ 2Al(OH) 3 ⁇ 3H 2 O coated with Al(OH) 3 .
  • the above measured Li + adsorption capacity of the aluminum-based lithium ion sieve is 2.1 mg/g, the pH of the liquid before adsorption is 12, and the liquid after adsorption is 7.5, and the pH is significantly reduced.
  • the adsorbent has a good adsorption effect on Li in industrial wastewater, and the Al(OH) 3 shell protects the aluminum-based adsorbent itself from corrosion during the adsorption process.
  • the aluminum-based lithium ion sieve of this embodiment is Li 2 SO 4 ⁇ 2Al(OH) 3 ⁇ nH 2 O coated with Al(OH) 3 , and n is 1-4.
  • step (2) (2) adjusting the pH of the aluminum-based lithium adsorbent intermediate obtained in step (1) to 4 by 0.5mol/L dilute sulfuric acid, aging for 6 h after the reaction, filtering, and taking the filter residue to obtain the aluminum-based lithium adsorbent Li 2 SO 4 ⁇ 2Al(OH) 3 ⁇ nH 2 O;
  • step (3) washing the aluminum-based lithium adsorbent obtained in step (2) for 2-3 times, weighing 300 g of NaAlO , dissolved in 500 ml of water, mixed with the aluminum-based lithium adsorbent, ultrasonically dispersed for 30 min, adjusted to pH 6.0, filtered, The filter residue was taken, dried at 80°C for 24 hours, and ground to obtain an aluminum-based lithium adsorbent Li 2 SO 4 ⁇ 2Al(OH) 3 ⁇ nH 2 O coated with Al(OH) 3 .
  • the Li + adsorption capacity of the aluminum-based lithium ion sieve was measured as 2.3 mg/g, the pH of the liquid before adsorption was 13, and the pH of the liquid after adsorption was 8.5, and the pH was significantly reduced.
  • the adsorbent has a good adsorption effect on Li in industrial wastewater.
  • the pure lithium liquid is enriched to more than 500 mg/L through multiple countercurrent analysis, and the Al(OH) 3 shell protects the aluminum during the adsorption process.
  • the base adsorbent itself is not corroded.
  • Fig. 2 is the result graph after carrying out XRD analysis to the product, it can be seen that the peak of Al(OH) 3 is stronger than that of the adsorbent. From the XRD result, the absorption peak of aluminum hydroxide in the prepared product covers the adsorption of lithium ions The absorption peaks of the sorbents showed that the aluminum-based lithium ion adsorbent with aluminum hydroxide coating was synthesized.

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Abstract

一种铝基锂离子筛及其制备方法和应用，该铝基锂离子筛为Al(OH) 3包覆的Li 2SO 4·2Al(OH) 3·nH 2O，n为1～4。该制备方法包括：利用锂盐、铝盐与碱反应得到吸附剂中间体LiOH·2Al(OH) 3·nH 2O，再通过稀硫酸，得到铝基锂吸附剂Li 2SO 4·2Al(OH) 3·nH 2O，将吸附剂过滤洗涤后，再与偏铝酸盐混合，再调pH，得到Al(OH) 3包覆的Li 2SO 4·2Al(OH) 3·nH 2O。所述铝基锂离子筛具有吸附量高、稳定性好的优点，可对工业废水中的低浓度锂进行高效回收，同时使用氢氧化铝包覆，可有效保证结构不受腐蚀。

Description

一种铝基锂离子筛及其制备方法和应用 技术领域
本公开属于吸附剂领域，具体涉及一种铝基锂离子筛及其制备方法和应用。
背景技术
在化工电源领域，金属锂的电化学电位高、质量轻、比能大，锂箔、锂棒材广泛应用于充电锂电池。一些锂电池寿命长、电压高、能量密度高，无污染并可在低温下使用。锂高能电池是近年来发展的一种很有前途的动力电池。待机时间较长的手机、电脑等均采用锂离子电池。并且在电动汽车行业，为了减少行车费用，采用锂电池发电取代传统的汽油发动机发动汽车。
随着动力电池的发展，报废动力电池的处理成为一大难题，当前主要采用粉碎、萃取回收动力电池中有高价金属，但仍有大量的金属锂因为其不易萃取的属性，容易富集在萃余液中无法有效回收。
有关提锂的现有技术中，有采用吸附树脂、铝盐型吸附剂、嵌锂活性基质材料、MnO 2吸附剂、锂辉石精矿为原料的吸附剂、锂离子筛等吸附锂离子技术。这其中又以锂离子筛因其吸附容量很大、吸附速度快等特点越来越受人们重视。目前锂离子筛的结构容易被腐蚀，难以精准实现洗脱液中锂浓度和纯度控制。
发明内容
本公开实施例提供一种铝基锂离子筛及其制备方法和应用，该铝基锂离子筛具有吸附量高、稳定性好的优点，可对工业废水中的低浓度锂进行有效回收，同时使用氢氧化铝包覆，可有效保证结构不受腐蚀。
为实现上述目的，本公开实施例提供了一种铝基锂离子筛，其为Al(OH) 3包覆的Li 2SO 4·2Al(OH) 3·nH 2O，n为1～4。
本公开实施例还提供了一种铝基锂离子筛的制备方法，包括以下步骤：
(1)将铝盐溶于水中，分散，加入锂盐，升温，调节pH至碱性，得到铝基锂吸附剂中间体LiOH·2Al(OH) 3·nH 2O，n为1～4；
(2)对步骤(1)得到的铝基锂吸附剂中间体调节pH至酸性，过滤，取滤渣，得到铝基锂吸附剂Li 2SO 4·2Al(OH) 3·nH 2O；
(3)将步骤(2)得到的铝基锂吸附剂进行洗涤，再与偏铝酸盐溶液混合，调节pH，过滤，取滤渣，烘干，研磨，得到所述铝基锂离子筛。
在一实施例中，步骤(1)中，所述铝盐为硫酸铝、氯化铝、硝酸铝和偏铝酸钠中的至少一种。
在一实施例中，步骤(1)中，所述锂盐为氢氧化锂、硫酸锂、氯化锂和硝酸锂中的至少一种。
在一实施例中，步骤(1)中，所述调节pH至碱性是将pH调至9.0-11.0。
在一实施例中，步骤(1)中，所述调节pH至碱性所用的溶液为以下中的至少一种的溶液：氢氧化钠、氢氧化锂、碳酸钠、碳酸氢钠和氨水。
在一实施例中，步骤(1)中，所述调节pH所用的物质为氢氧化钠、氢氧化锂、碳酸钠、碳酸氢钠和氨水中的至少一种。
在一实施例中，步骤(1)中，所述反应的温度为30℃-100℃，时间为1-72h。
在一实施例中，步骤(1)中，所述分散的搅拌速度控制在100-700rpm。
在一实施例中，步骤(2)中，所述调节pH至酸性是将pH调至2.5-5.5。
在一实施例中，步骤(2)中，所述调节pH至酸性使用的溶液为硫酸溶液、带硫酸根的盐溶液以及硫酸与盐混合溶液中的至少一种。
在另一实施例中，所述硫酸溶液为0.5-2mol/L。
在另一实施例中，所述带硫酸根的盐溶液为以下中的至少一种的溶液：硫酸铝、硫酸镍、硫酸钴、硫酸锰、硫酸铁和硫酸亚铁。
在另一实施例中，所述硫酸与盐混合溶液为硫酸与氯化铁混合溶液和硫酸与氯化亚铁混合溶液中的至少一种。
在一实施例中，步骤(3)中，所述偏铝酸盐为偏铝酸钠和偏铝酸钾中的至少一种。
在一实施例中，步骤(3)中，所述调pH是将pH调至3.5-11.0。
在另一实施例中，所述调节pH使用的溶液为以下中的至少一种的溶液：氢氧化钠、氢氧化锂、碳酸钠、碳酸氢钠、氨水、硫酸铝、硫酸镍、硫酸钴、硫酸锰、高锰酸、硫酸铁、硫酸亚铁、氯化铁和氯化亚铁。
在一实施例中，步骤(3)中，所述烘干的温度为40℃-100℃。
本公开实施例的原理包括：使用锂盐、铝盐与调节pH的碱反应得到吸附剂中间体LiOH·2Al(OH) 3·nH 2O，n为1-4，再通过稀硫酸(调节pH的酸)调值至2.5-5.5得到铝基锂吸附剂Li 2SO 4·2Al(OH) 3·nH 2O，n为1-4，将吸附剂过滤洗涤后，与偏铝酸盐混合，调pH 至3.5-11得到Al(OH) 3包覆的Li 2SO 4·2Al(OH) 3·nH 2O(铝基锂离子筛)。
本公开实施例还提供了一种利用铝基锂离子筛处理工业废水的方法，包括以下步骤：
(1)将铝基锂离子筛填装进树脂柱中，再加入工业废水，进行离子吸附，得到吸附后液和吸附饱和的铝基锂离子筛；
(2)将吸附饱和的铝基锂离子筛进行逆流洗涤，再经过逆流解析，得到纯净的锂液。
在一实施例中，步骤(1)中，所述工业废水为含锂浓度低、杂质离子浓度高的废水或高酸碱度的废水。
在一实施例中，步骤(1)中，所述吸附后液呈酸性时用于补充合成段的铝盐，呈碱性时用于补充合成段的偏铝酸盐。
在一实施例中，步骤(1)中，所述静置时间为10-20min。
在一实施例中，步骤(2)中，所述解析锂离子吸附剂所用清水为去离子水和自来水中的至少一种。
本公开实施例的优点：
(1)本公开实施例提供了不同于通常的铝盐锂离子吸附剂，因为有物料包覆可用于酸碱度较高的工业废水与盐湖卤水中，且因为在吸附解析过程中，外壳的Al(OH) 3将对其包覆锂吸附剂起到保护作用，高酸碱度的工业废水通过锂吸附剂外部的Al(OH) 3首先与酸碱发生反应，而Li离子由于离子半径较小，可穿过Al(OH) 3外壳，从而被作为晶核的锂离子吸附剂吸附，并通过回调吸附后液pH回收氢氧化铝。
(2)本公开实施例的工艺简单，设备要求低，能耗成本低廉，产品价值高(所得产物结构性能良好，选择吸附性高，可以对废弃汽车动力电池正极材料中的锂进行有效的吸附回收)，有助于绿色环保，资源循环再利用，具有可观的经济效益。
附图说明
图1为本公开实施例1的工艺流程图；
图2为本公开实施例1铝基锂离子筛的XRD图。
具体实施方式
为了对本公开进行深入的理解，下面结合实例对本公开若干实验方案进行描述，以进一步地说明本公开的特点和优点，任何不偏离本公开主旨的变化或者改变能够为本领域的技术人员理解，本公开的保护范围由所属权利要求范围确定。
本公开实施例中未注明具体条件者，按照常规条件或者制造商建议的条件进行。所用未注明生产厂商者的原料、试剂等，均为可以通过市售购买获得的常规产品。
实施例1
本实施例的铝基锂离子筛，其为Al(OH) 3包覆的Li 2SO 4·2Al(OH) 3·3H 2O。
本实施例的铝基锂离子筛的制备方法，包括下面步骤：
(1)称取36g LiOH溶于200ml去离子水中，再加入360g Al 2(SO 4) 3，将其超声60min混合均匀，放入水浴锅升温至80℃，用氢氧化钠调节pH至10.0，生成铝基锂吸附剂中间体LiOH·2Al(OH) 3·nH 2O；
(2)将步骤(1)得到的铝基锂吸附剂中间体通过0.5mol/L稀硫酸将pH调至4，反应结束后陈化4h，过滤，洗涤2-3次，得到铝基锂吸附剂Li 2SO 4·2Al(OH) 3·3H 2O；
(3)将步骤(2)得到的铝基锂吸附剂进行抽滤，洗涤，称取100g NaAlO 2溶于500ml水中，再与铝基锂吸附剂混合，调节pH至10.0，过滤，取滤渣，在80℃条件干燥24h，研磨，得到有Al(OH) 3包覆的铝基锂吸附剂Li 2SO 4·2Al(OH) 3·3H 2O。
利用本实施例的铝基锂离子筛处理工业废水的方法，包括以下步骤：
(1)将50g铝基锂离子筛填装进树脂柱中，再加入强碱性工业废水(pH为13，Li +含量)，进行离子吸附，放入恒温水浴锅搅拌60min，用ICP测量废水吸附前后Li +的变化量，并用精明pH计测量吸附前后pH变化，得到吸附后液和吸附饱和的铝基锂离子筛；
(2)将吸附饱和的铝基锂离子筛进行逆流洗涤，再经过逆流解析，得到纯净的锂液。
上述测得铝基锂离子筛对Li +吸附量为2.7mg/g，吸附前液pH为13、吸附后液为8，pH明显降低。
表1
Figure PCTCN2021123400-appb-000001
从表1可得，吸附剂对工业废水中的Li有很好的吸附作用，并可以通过逆流解析将纯净锂液富集到500mg/L以上，吸附过程中Al(OH) 3外壳保护了铝基吸附剂本身不被腐蚀。
图1为本公开实施例1的工艺流程图，从图1中可得锂盐、铝盐与调节pH的碱反应，再通过稀硫酸铝基锂吸附剂，然后与偏铝酸盐混合，得到Al(OH) 3包覆的铝基锂离子筛，还可以通过回调吸附后液补充铝盐。
实施例2
本实施例的铝基锂离子筛，其为Al(OH) 3包覆的Li 2SO 4·2Al(OH) 3·3H 2O。
本实施例的铝基锂离子筛的制备方法，包括下面步骤：
(1)称取48g LiOH溶于200ml去离子水中，再加入180g Al(OH) 3，将其超声120min混合均匀，放入水浴锅升温至60℃，用氢氧化钠调节pH至10.0，生成铝基锂吸附剂中间体LiOH·2Al(OH) 3·3H 2O；
(2)将步骤(1)得到的铝基锂吸附剂中间体通过0.5mol/L稀硫酸将pH调至4，反应结束后陈化6h，过滤，取滤渣，得到铝基锂吸附剂Li 2SO 4·2Al(OH) 3·3H 2O；
(3)将步骤(2)得到的铝基锂吸附剂进行洗涤2-3次，称取300gNaAlO 2溶于500ml水中，超声分散30min，再与铝基锂吸附剂混合，调节pH至8.0，过滤，取滤渣，在80℃条件干燥24h，研磨，得到有Al(OH) 3包覆的铝基锂吸附剂Li 2SO 4·2Al(OH) 3·3H 2O。
利用本实施例的铝基锂离子筛处理工业废水的方法，包括以下步骤：
(1)将50g铝基锂离子筛填装进树脂柱中，再加入强碱性工业废水(pH为12)，进行离子吸附，放入恒温水浴锅搅拌60min，用ICP测量废水吸附前后Li +的变化量，并用精明pH计测量吸附前后pH变化，得到吸附后液和吸附饱和的铝基锂离子筛；
(2)将吸附饱和的铝基锂离子筛进行逆流洗涤，再经过逆流解析，得到纯净的锂液。
上述测得铝基锂离子筛对Li +吸附量为2.1mg/g，吸附前液pH为12、吸附后液为7.5，pH明显降低。
表2
Figure PCTCN2021123400-appb-000002
从表2可得，吸附剂对工业废水中的Li有很好的吸附作用，吸附过程中Al(OH) 3外壳保护了铝基吸附剂本身不被腐蚀。
实施例3
本实施例的铝基锂离子筛，其为Al(OH) 3包覆的Li 2SO 4·2Al(OH) 3·nH 2O，n为1～4。
本实施例的铝基锂离子筛的制备方法，包括下面步骤：
(1)称取21g LiCl溶于200ml去离子水中，再加入210g Al(NO 3) 3，将其超声30min混合均匀，放入水浴锅升温至90℃，用氢氧化钠调节pH至12，搅拌12h，搅拌速度为120rpm， 生成铝基锂吸附剂中间体LiOH·2Al(OH) 3·nH 2O；
(2)将步骤(1)得到的铝基锂吸附剂中间体通过0.5mol/L稀硫酸将PH调至4，反应结束后陈化6h，过滤，取滤渣，得到铝基锂吸附剂Li 2SO 4·2Al(OH) 3·nH 2O；
(3)将步骤(2)得到的铝基锂吸附剂洗涤2-3次，称取300gNaAlO 2溶于500ml水中，再与铝基锂吸附剂混合，超声分散30min，调节pH至6.0，过滤，取滤渣，在80℃条件干燥24h，研磨，得到有Al(OH) 3包覆的铝基锂吸附剂Li 2SO 4·2Al(OH) 3·nH 2O。
利用本实施例的铝基锂离子筛处理工业废水的方法，包括以下步骤：
(1)将50g铝基锂离子筛填装进树脂柱中，再加入强碱性工业废水(pH为13)，进行离子吸附，放入恒温水浴锅搅拌60min，用ICP测量废水吸附前后Li +的变化量，并用精明pH计测量吸附前后pH变化，得到吸附后液和吸附饱和的铝基锂离子筛；
(2)将吸附饱和的铝基锂离子筛进行逆流洗涤，再经过逆流解析，得到纯净的锂液。
上述测得铝基锂离子筛对Li +吸附量为2.3mg/g，吸附前液pH为13、吸附后液为8.5，pH明显降低。
表3
Figure PCTCN2021123400-appb-000003
从表3可得，吸附剂对工业废水中的Li有很好的吸附作用，通过多次逆流解析将纯净锂液富集到500mg/L以上，吸附过程中Al(OH) 3外壳保护了铝基吸附剂本身不被腐蚀。
图2为对产品进行XRD分析后的结果图，可见Al(OH) 3的峰强于吸附剂的峰，由XRD结果来看，制得的产品中氢氧化铝的吸收峰掩盖了锂离子吸附剂的吸收峰，证明合成了具有氢氧化铝包覆的铝基锂离子吸附剂。
以上对本公开提供的一种铝基锂离子筛及其制备方法和应用进行了详细的介绍，本文中应用了具体实施例对本公开的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本公开的方法及其核心思想，包括更好的方式，并且也使得本领域的任何技术人员都能够实践本公开，包括制造和使用任何装置或系统，和实施任何结合的方法。应当指出，对于本技术领域的普通技术人员来说，在不脱离本公开原理的前提下，还可以对本公开进行若干改进和修饰，这些改进和修饰也落入本公开权利要求的保护范围内。本公开专 利保护的范围通过权利要求来限定，并可包括本领域技术人员能够想到的其他实施例。如果这些其他实施例具有不是不同于权利要求文字表述的结构要素，或者如果它们包括与权利要求的文字表述无实质差异的等同结构要素，那么这些其他实施例也应包含在权利要求的范围内。

Claims (10)

  1. 一种铝基锂离子筛，所述铝基锂离子筛为Al(OH) 3包覆的Li 2SO 4·2Al(OH) 3·nH 2O，n为1～4。
  2. 权利要求1所述的铝基锂离子筛的制备方法，包括以下步骤：
    (1)将铝盐溶于水中，分散，加入锂盐，升温，调节pH至碱性，得到铝基锂吸附剂中间体LiOH·2Al(OH) 3·nH 2O，n为1～4；
    (2)对步骤(1)得到的铝基锂吸附剂中间体调节pH至酸性，过滤，取滤渣，得到铝基锂吸附剂Li 2SO 4·2Al(OH) 3·nH 2O；
    (3)将步骤(2)得到的铝基锂吸附剂进行洗涤，再与偏铝酸盐溶液混合，调节pH，过滤，取滤渣，烘干，研磨，得到所述铝基锂离子筛。
  3. 根据权利要求2所述的制备方法，其中，步骤(1)中，所述铝盐为硫酸铝、氯化铝、硝酸铝和偏铝酸钠中的至少一种。
  4. 根据权利要求2所述的制备方法，其中，步骤(1)中，所述锂盐为氢氧化锂、硫酸锂、氯化锂和硝酸锂中的至少一种。
  5. 根据权利要求2所述的制备方法，其中，步骤(1)中，所述调节pH至碱性是将pH调至9.0-11.0；步骤(1)中，所述反应的温度为30℃-100℃，反应的时间为1-72h。
  6. 根据权利要求2所述的制备方法，其中，步骤(1)中，所述调节pH至碱性所用的溶液为以下中的至少一种的溶液：氢氧化钠、氢氧化锂、碳酸钠、碳酸氢钠和氨水。
  7. 根据权利要求2所述的制备方法，其中，步骤(2)中，所述调节pH至酸性使用的溶液为硫酸溶液、带硫酸根的盐溶液以及硫酸与盐混合溶液中的至少一种；所述硫酸溶液的浓度为0.5-2mol/L；所述带硫酸根的盐溶液为以下中的至少一种的溶液：硫酸铝、硫酸镍、硫酸钴、硫酸锰、硫酸铁和硫酸亚铁；所述硫酸与盐混合溶液为硫酸与氯化铁混合溶液和硫酸与氯化亚铁混合溶液中的至少一种。
  8. 根据权利要求2所述的制备方法，其中，步骤(3)中，所述调节pH是将pH调至3.5～11.0；所述调节pH使用的溶液为以下中的至少一种的溶液：氢氧化钠、氢氧化锂、碳酸钠、碳酸氢钠、氨水、硫酸铝、硫酸镍、硫酸钴、硫酸锰、高锰酸、硫酸铁、硫酸亚铁、氯化铁和氯化亚铁。
  9. 根据权利要求2所述的制备方法，其中，步骤(3)中，所述偏铝酸盐为偏铝酸钠和偏铝酸钾中的至少一种。
  10. 用权利要求1所述的铝基锂离子筛处理工业废水的方法，，包括以下步骤：
    (1)将所述铝基锂离子筛填装进树脂柱中，再加入工业废水，进行离子吸附，得到吸附后液和吸附饱和的铝基锂离子筛；
    (2)将吸附饱和的铝基锂离子筛进行逆流洗涤，再经过逆流解析，得到纯净的锂液。
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