WO2024011796A1 - Lithium adsorption material, and preparation method therefor and use thereof - Google Patents

Lithium adsorption material, and preparation method therefor and use thereof Download PDF

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WO2024011796A1
WO2024011796A1 PCT/CN2022/130537 CN2022130537W WO2024011796A1 WO 2024011796 A1 WO2024011796 A1 WO 2024011796A1 CN 2022130537 W CN2022130537 W CN 2022130537W WO 2024011796 A1 WO2024011796 A1 WO 2024011796A1
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lithium
aso
adsorbent material
compound
lithium adsorbent
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PCT/CN2022/130537
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French (fr)
Chinese (zh)
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李军
罗清龙
吴志坚
刘忠
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中国科学院青海盐湖研究所
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    • 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
    • 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
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • 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

Definitions

  • the invention belongs to the technical field of adsorption materials, and specifically relates to a lithium adsorption material and its preparation method and application.
  • Lithium and its compounds are widely used in chemical industry, medicine, aerospace and other fields and have an important strategic position. In recent years, with the rise of energy, battery and other industries, the demand for lithium has been further intensified. At present, the source of lithium mainly comes from lithium-containing solid ores and liquid lithium resources (such as salt lakes, seawater, etc.). Among them, lithium-containing brine deposits account for 60% of global lithium resources. In addition to Li + , there are many other anions and cations coexisting in the salt lake, such as Na + , K + , Mg 2+ , Ca 2+ , Cl - , SO 4 2- , borate and other ions. In the process of extracting lithium resources from salt lakes, other ions in the salt lake will interfere with the extraction and separation of lithium ions, thereby increasing the difficulty of extracting lithium resources.
  • salt lakes are generally located on plateaus, in areas with few people, inconvenient transportation and backward industrial base, adsorption is used The method has obvious advantages.
  • LiAl-LDHs lithium adsorbent has low adsorption capacity, co-adsorption and desorption of borate anions, and poor recycling performance (high dissolution loss, high damage, and structural changes during adsorbent regeneration that can easily cause adsorption capacity attenuation).
  • the preparation process requires a lithium source to first prepare the target compound, and then remove lithium to obtain a lithium-deficient lithium adsorbent, which undergoes an adsorption-desorption (regeneration) cycle.
  • the preparation process is relatively cumbersome and the cost increases. Therefore, new types of lithium adsorbents are needed for industrial production.
  • the present invention provides a lithium hydroxysulfate adsorbent and its preparation method and application to solve the problems of low adsorption capacity, poor recycling performance and co-adsorption of borate anions of the existing lithium adsorbent. Desorption, the problem of high cost of lithium adsorbent.
  • the present invention provides a lithium adsorbent material, which is a hydroxyl synthetic salt with a porous structure, and the molecular formula of the hydroxyl synthetic salt is DG 3 (TO 4 ) 2 (OH) 6 or DG 3 (TO 4 ) 2 (OH,H 2 O) 6 , where D represents a cation with a coordination number greater than or equal to 9, G represents an element that forms an octahedral coordination, and T represents an element that forms a tetrahedral coordination.
  • the synthetic salt is any one of the synthetic salts of the following molecular formulas: KAl 3 (SO 4 ) 2 (OH) 6 , NaAl 3 (SO 4 ) 2 (OH) 6 , (NH) 4 Al 3 ( SO 4 ) 2 (OH) 6 , (H 3 O,Ca)Al 3 (SO 4 ) 2 (OH) 6 , Pb(Al,Cu) 3 (SO 4 ) 2 (OH,H 2 O) 6 , ( Na,Ca) 2 Al 6 (SO 4 ) 4 (OH,H 2 O) 12 , CaAl 6 (SO 4 ) 4 (OH) 12 , Pb(Fe,Cu) 3 (SO 4 ) 2 (OH) 6 , BaAl 6 (SO 4 ) 4 (OH) 12 , KFe 3 (SO 4 ) 2 (OH) 6 , NaFe 3 (SO 4 ) 2 (OH) 6 , (NH) 4 Fe 3 (SO 4 ) 2 (OH) 6 , (H 3 O)F
  • the present invention also provides a method for preparing the lithium adsorbent material as described above, which includes:
  • the mixed inorganic salt solution contains cations corresponding to the cations D and G elements and acid ions containing the T element;
  • the porogen includes surfactant and urea and/or thiourea;
  • reaction solution is placed in a reaction kettle to perform a hydrothermal reaction, and after the reaction is completed, it is filtered to obtain a solid first intermediate product;
  • the second intermediate product is dried to obtain the hydroxyl synthetic salt with a porous structure.
  • the acid ion containing T element is selected from one or more of SO 4 2- , SiO 4 4- , PO 4 3- and AsO 4 3- .
  • the surfactant is selected from one or more than two types of anionic surfactants, cationic surfactants, zwitterionic surfactants and nonionic surfactants; wherein the anionic surfactant is a hard surfactant.
  • anionic surfactant Fatty acid or sodium dodecyl benzene sulfonate; the cationic surfactant is a quaternary ammonium compound; the zwitterionic surfactant lecithin or amino acid type active agent or betaine type active agent; the nonionic surfactant
  • the agent is alkyl glucoside, fatty acid glyceride, fatty acid sorbitan or polysorbate.
  • the temperature of the hydrothermal reaction is 70°C to 180°C, and the reaction time is 3h to 12h.
  • the washing treatment is to use deionized water to wash the first intermediate product multiple times until it becomes neutral.
  • the drying process is constant temperature drying at a temperature of 50°C to 80°C.
  • the hydroxyl synthetic salt is a hydroxysulfate
  • the mixed inorganic salt solution is obtained by dissolving a soluble first compound and a second compound in water
  • the first compound can ionize cation D in water
  • the The second compound is capable of ionizing cations corresponding to the G element in water, and at least one of the first compound and the second compound is capable of ionizing sulfate ions in water
  • the porogen includes urea and surfactant .
  • Another aspect of the present invention is to provide the application of the lithium adsorbent material as described above, wherein the lithium adsorbent material is granulated and used to adsorb and extract lithium ions from a solution containing lithium ions.
  • the lithium adsorbent material provided by the embodiment of the present invention uses hydroxyl synthetic salt with a porous structure as the lithium adsorbent material. It has the advantages of high adsorption capacity, long cycle life, and no adsorption of borate anions, and is particularly suitable for use in Extraction of lithium ions from salt lake brine by adsorption. In addition, the lithium adsorption material does not require the consumption of additional lithium sources during the synthesis process. It has the advantages of mild preparation conditions, simple and easy process flow, low equipment cost requirements and no pollution, and is suitable for large-scale production.
  • Figure 1 is a process flow diagram of a method for preparing a lithium adsorbent material in an embodiment of the present invention
  • Figure 2 is an XRD pattern of the lithium adsorbent material prepared in Example 1 of the present invention.
  • Figure 3 is an SEM image of the lithium adsorbent material prepared in Example 1 of the present invention.
  • Figure 4 is an XRD pattern of the lithium adsorption material prepared in Comparative Example 1 of the present invention.
  • Figure 5 is an XRD pattern of the lithium adsorbent material prepared in Example 3 of the present invention.
  • the term "includes” and variations thereof represent an open term meaning “including, but not limited to.”
  • the terms “based on”, “according to”, etc. mean “based at least in part on”, “based at least in part on”.
  • the terms “one embodiment” and “an embodiment” mean “at least one embodiment.”
  • the term “another embodiment” means “at least one other embodiment”.
  • the terms “first”, “second”, etc. may refer to different or the same object. Other definitions may be included below, whether explicit or implicit. The definition of a term is consistent throughout this specification unless the context clearly indicates otherwise.
  • Embodiments of the present invention first provide a lithium adsorption material.
  • the lithium adsorption material is a hydroxyl synthetic salt with a porous structure.
  • the molecular formula of the hydroxyl synthetic salt is DG 3 (TO 4 ) 2 (OH) 6 or DG 3 ( TO 4 ) 2 (OH,H 2 O) 6 , where D represents a cation with a coordination number greater than or equal to 9, G represents an element that forms an octahedral coordination, and T represents an element that forms a tetrahedral coordination.
  • the molecular formula DG 3 (TO 4 ) 2 (OH) 6 represents that the hydroxyl synthetic salt does not contain crystal water
  • the molecular formula DG 3 (TO 4 ) 2 (OH,H 2 O) 6 represents that the hydroxyl synthetic salt contains Crystal water.
  • the cation D is, for example, H 3 O + , K + , Na + , NH 4 + , Ag + , Ti + , Pb 2+ , Ca 2+ , Ba 2+ , etc.
  • the G element is, for example, Al, Fe, Ga, V, etc.
  • the T element is, for example, S, P, As, Si, etc.
  • the synthetic salt is any one of the synthetic salts of the following molecular formulas: KAl 3 (SO 4 ) 2 (OH) 6 , NaAl 3 (SO 4 ) 2 (OH) 6 , (NH) 4 Al 3 (SO 4 ) 2 (OH) 6 , (H 3 O,Ca)Al 3 (SO 4 ) 2 (OH) 6 , Pb(Al,Cu) 3 (SO 4 ) 2 (OH,H 2 O) 6 , (Na,Ca) 2 Al 6 (SO 4 ) 4 (OH,H 2 O) 12 , CaAl 6 (SO 4 ) 4 (OH) 12 , Pb(Fe,Cu) 3 (SO 4 ) 2 (OH) 6.
  • Embodiments of the present invention provide a method for preparing the lithium adsorbent material as described above.
  • the preparation method includes the following steps:
  • Step S10 Prepare a mixed inorganic salt solution, which contains cations D, cations corresponding to the G element, and acid ions containing the T element.
  • Step S20 Add a porogen to the mixed inorganic salt solution and mix to obtain a reaction liquid; the porogen includes surfactant, urea and/or thiourea.
  • Step S30 Place the reaction solution in a reaction kettle to perform a hydrothermal reaction. After the reaction is completed, filter to obtain a solid first intermediate product;
  • Step S40 Wash the first intermediate product to elute the porogen to obtain a second intermediate product with a porous structure
  • Step S50 Dry the second intermediate product to obtain the hydroxyl synthetic salt with a porous structure, and obtain the lithium adsorption material.
  • step S10 two or more compounds are dissolved in water to obtain the mixed salt solution.
  • At least one of the compounds is a salt, which can ionize in water an acid ion containing the element T and one of the cations corresponding to the cation D or the element G.
  • the other one of the cations corresponding to the element D or G comes from another compound, and the other
  • the compound may be a salt containing an acid ion of the element T.
  • the acid anion containing the T element is an acid anion with a tetrahedral structure, preferably one or two or more selected from SO 4 2- , SiO 4 4- , PO 4 3- and AsO 4 3- .
  • the acid corresponding to the acid ion of the T element can be added to the mixed solution, on the one hand, to adjust the pH value of the mixed salt solution, On the other hand, it is the acid ion containing T element that supplements the mixed salt solution.
  • the molecular formula of the porous structure hydroxyl synthetic salt to be prepared is: NaAl 3 (SO 4 ) 2 (OH) 6 , that is, the cation D is Na + , the G element is Al, and the T element is S. Then one compound can be selected as Na 2 SO 4 , which ionizes into Na + and SO 4 2- in aqueous solution; the other compound can be selected as Al 2 (SO 4 ) 3 , which ionizes into Al 3+ in aqueous solution and SO 4 2- .
  • the molecular formula of the porous structure hydroxyl synthetic salt to be prepared is: NaFe 3 (SO 4 ) 2 (OH) 6 , that is, the cation D is Na + , the G element is Fe, and the T element is S.
  • one compound can be selected as Na 2 SO 4 , which ionizes into Na + and SO 4 2- in aqueous solution; the other compound can be selected as FeCl 3 , which ionizes into Al 3+ and Cl - in aqueous solution, this
  • H 2 SO 4 can be added to the mixed solution, on the one hand, to adjust the pH value of the mixed salt solution, and on the other hand, to supplement the SO 4 2- of the mixed salt solution.
  • the NH 4 + can be directly from the urea in step S20.
  • the mixed salt solution configured in step S10 can only contain cations corresponding to the G element. And acid ions containing T element.
  • the surfactant is selected from one or more than two types of anionic surfactants, cationic surfactants, zwitterionic surfactants and nonionic surfactants; wherein, the anionic surface
  • the active agent is stearic acid or sodium dodecyl benzene sulfonate; the cationic surfactant is a quaternary ammonium compound; the zwitterionic surfactant lecithin or amino acid active agent or betaine active agent; the Nonionic surfactants are alkyl glucosides, fatty acid glycerides, fatty acid sorbitans or polysorbates.
  • the temperature of the hydrothermal reaction is preferably 70°C to 180°C, such as 95°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C or 180°C.
  • the reaction time is preferably 3h to 12h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h.
  • step S40 the washing process is to use deionized water to wash the first intermediate product multiple times until it becomes neutral, that is, wash it multiple times until the pH of the washing liquid is close to 7.
  • step S50 the drying process is preferably constant temperature drying at a temperature of 50°C to 80°C.
  • the hydroxyl synthetic salt is a hydroxysulfate
  • the mixed salt solution is obtained by dissolving a soluble first compound and a second compound in water, and the first compound can ionize cation D in water, The second compound can ionize cations corresponding to the G element in water, and at least one of the first compound and the second compound can ionize sulfate ions in water; the porogen includes urea and surface active agent.
  • one of the first compound and the second compound is selected to be a sulfate or a hydrogen sulfate
  • the other of the first compound and the second compound is selected to be a sulfate, a chloride or a nitrate.
  • sulfuric acid may be further added to adjust the pH of the solution and provide sulfate ions.
  • the lithium adsorbent material provided in the above embodiment is specifically a hydroxyl synthetic salt with a porous structure, which has the advantage of high adsorption capacity. During the process of adsorbing lithium and desorbing lithium and regenerating it, no structural change occurs. Therefore, the structure of the lithium adsorbent material High strength, low dissolution loss and long cycle life. There is no need to consume additional lithium sources during the synthesis process of this lithium adsorption material.
  • the synthetic raw materials are easy to obtain. It has the advantages of mild preparation conditions, simple and easy process flow, low equipment cost requirements and no pollution, and is suitable for large-scale production.
  • Another aspect of the embodiments of the present invention is to provide the application of the lithium adsorbent material as described above, wherein the lithium adsorbent material is granulated and used to adsorb and extract lithium ions from a solution containing lithium ions.
  • the calcium alginate granulation method or the polyacrylonitrile mixed granulation method can be used to granulate the lithium adsorbent material.
  • granulate according to the following steps: add 1.0g sodium alginate and 0.5g chitosan to 150mL deionized water, add 1mL acetic acid, stir evenly, and then add 10g to 12g of the sodium alginate provided by the embodiment of the present invention.
  • Lithium adsorbent material powder is stirred evenly again and dropped into a 4% CaCl2 solution, then aged and left for 6 to 12 hours to obtain granular material; then the granular material is transferred to a solution containing 3 to 8% pentane.
  • granulate according to the following steps: add 1.0 g of polyacrylonitrile and 0.2 g of hydroxylamine hydrochloride to 100 mL of deionized water, add 0.05 g of sodium hydroxide, stir at room temperature for 8 hours, filter and dry. Then add the above mixture and 0.2g of polyacrylonitrile into 20mL of DMSO. After dissolving, add 10g of the lithium adsorbent material powder provided in the embodiment of the present invention, then stir evenly and drop it into deionized water, then age and static. Leave for 6 to 12 hours to prepare a granular lithium adsorbent.
  • the method of adsorbing and extracting lithium ions from a solution containing lithium ions after granulating the lithium adsorbing material mainly includes the following operations:
  • Adsorption operation Select the appropriate pump speed (10ml/h ⁇ 200ml/h) according to the packing height of the adsorption column (10cm ⁇ 50cm), column inner diameter (1cm ⁇ 5cm), and packing particle size (0.05cm ⁇ 0.5cm) , transfer the granular lithium adsorbent obtained by granulation into the adsorption column, adopt the bottom-in-top-out mode, and detect the lithium ion concentration in the effluent. Stop the dynamic when the lithium ions in the feed liquid have just penetrated the adsorption column. Adsorption experiments show that the adsorption capacity is between 6.5 mg/g and 30 mg/g.
  • Desorption operation Select the appropriate pump speed according to the packing height, inner diameter of the column, and packing particle size of the adsorption column, and pump the aqueous solution, low acid (pH between 4-6) eluent, and carbonic acid solution in and out.
  • Pump into the adsorption column collect the eluate, and detect the lithium ion concentration in the outflow eluate. When the lithium ion concentration in the outflow liquid drops to zero, stop pumping the eluent.
  • the white powder product (NH) 4 Al 3 (SO 4 ) 2 (OH) 6 is a lithium hydroxysulfate adsorption material with a porous structure.
  • FIG. 2 is an XRD pattern of the lithium adsorbent material prepared in this embodiment
  • Figure 3 is an SEM image of the lithium adsorbent material prepared in this example. It can be seen from Figures 2 and 3 that the lithium adsorbent material prepared in this embodiment is a hydroxysulfate with a porous structure, and its molecular formula is (NH) 4 Al 3 (SO 4 ) 2 (OH) 6 .
  • the calcium alginate method was used for granulation.
  • the lithium adsorption material obtained in this example was granulated and then put into a customized adsorption column with an inner diameter of 2 cm.
  • a lithium chloride solution with a concentration of 500 mg/L was pumped from the bottom of the adsorption column through a peristaltic pump. Pump in at the end and the pump speed is 45mL/h.
  • the dynamic adsorption experiment is stopped. Then pump the aqueous solution at a flow rate of 2mL/min until no lithium ions flow out.
  • the adsorption capacity of the lithium adsorbent material in this embodiment is 7.16 mg/g.
  • Figure 4 is an XRD pattern of the lithium adsorbent material prepared in Comparative Example 1. It can be seen from Figure 4 that the lithium adsorbent material prepared in Comparative Example 1 is hydroxysulfate, and its molecular formula is also (NH) 4 Al 3 (SO 4 ) 2 (OH) 6 .
  • the calcium alginate method is used for granulation.
  • the lithium adsorbent material obtained in this example is granulated and put into a customized adsorption column with an inner diameter of 2 cm.
  • a 1000 mg/L lithium chloride solution is pumped from the lower end of the adsorption column through a peristaltic pump. Input, pump speed 45mL/h.
  • the dynamic adsorption experiment is stopped. Then pump the aqueous solution at a flow rate of 2mL/min until no lithium ions flow out.
  • the adsorption capacity of the adsorption material of Comparative Example 1 was 6.77 mg/g.
  • the lithium hydroxysulfate adsorbent material synthesized in Comparative Example 1 and Example 1 is the same substance. The difference is that in Comparative Example 1, (NH) 4 Al 3 (SO4) 2 (OH) 6 lithium hydroxysulfate adsorbent was synthesized. No surfactant (porogen) was added during the process, and the adsorption capacity of the prepared lithium adsorbent material was 6.77 mg/g; in Example 1, (NH) 4 Al 3 (SO4) 2 (OH) 6 lithium was synthesized In the process of adsorbing the material, cetyltrimethylammonium bromide was used as a surfactant, and the adsorption capacity of the prepared lithium adsorbent material was 7.16 mg/g. The above comparison shows that adding surfactants to create pores during the synthesis of lithium adsorbent materials for hydroxyl synthetic salts is beneficial to increasing the adsorption capacity of the lithium adsorbent materials for hydroxyl synthetic salts.
  • the white powder product (NH 4 )Fe 3 (SO 4 ) 2 (OH) 6 is a lithium hydroxysulfate adsorption material with a porous structure.
  • the lithium adsorption material obtained in this example was granulated using the polyacrylonitrile method and then put into a custom-made adsorption column with an inner diameter of 2 cm.
  • a 1000 mg/L lithium chloride solution was pumped in from the lower end of the adsorption column through a peristaltic pump. , pump speed 45mL/h.
  • the dynamic adsorption experiment is stopped. Then pump the aqueous solution at a flow rate of 2mL/min until no lithium ions flow out.
  • the adsorption capacity of the lithium adsorbent material in this embodiment is 10.53 mg/g.
  • the white powder product KAl 3 (SO 4 ) 2 (OH) 6 is a lithium hydroxysulfate adsorption material with a porous structure.
  • Figure 5 is an XRD pattern of the lithium adsorbent material prepared in Example 3. It can be seen from Figure 5 that the lithium adsorbent material prepared in Example 3 is hydroxysulfate, and its molecular formula is KAl 3 (SO 4 ) 2 (OH) 6 .
  • the lithium adsorption material obtained in this example was granulated using the calcium alginate method and then put into a custom-made adsorption column with an inner diameter of 2 cm.
  • a 1000 mg/L lithium chloride solution was pumped in from the lower end of the adsorption column through a peristaltic pump. , pump speed 45mL/h.
  • the dynamic adsorption experiment is stopped. Then pump the aqueous solution at a flow rate of 2mL/min until no lithium ions flow out.
  • the adsorption capacity of the lithium adsorption material in this embodiment is 8.36 mg/g.
  • the lithium adsorbent material provided by the embodiments of the present invention, specifically a hydroxyl synthetic salt with a porous structure, has the advantage of high adsorption capacity.
  • the lithium adsorption material has high structural strength, low dissolution loss and long cycle life, and is particularly suitable for adsorption and extraction of lithium ions from salt lake brine.
  • the synthetic raw materials are easy to obtain. It has the advantages of mild preparation conditions, simple and easy process flow, low equipment cost requirements and no pollution, and is suitable for large-scale production.

Abstract

Provided in the present invention is a lithium adsorption material, which is a hydroxyl synthetic salt with a porous structure and a molecular formula of DG3(TO4)2(OH)6 or DG3(TO4)2(OH,H2O)6, where D represents a cation with a coordination number greater than or equal to 9, G represents an element forming octahedral coordination, and T represents an element forming tetrahedral coordination. A preparation method therefor comprises: preparing a mixed inorganic salt solution, which contains a cation D, a cation corresponding to an element G, and an oxygen-containing acid radical ion containing an element T; adding a pore-foaming agent to the mixed inorganic salt solution, and mixing same to obtain a reaction solution; placing the reaction solution into a reaction vessel for a hydrothermal reaction, and then sequentially performing filtering, washing and drying treatments to obtain a hydroxyl synthetic salt with a porous structure, thereby obtaining a lithium adsorption material. The lithium adsorption material provided in the present invention has the advantages of a high adsorption capacity, long cycle life, etc., and does not adsorb a borate; and a lithium source is not needed during the synthesis process thereof, and the advantages of mild preparation conditions, simple and feasible process flow, low equipment cost requirements and no pollution are obtained.

Description

一种锂吸附材料及其制备方法和应用Lithium adsorption material and preparation method and application thereof 技术领域Technical field
本发明属于吸附材料技术领域，具体涉及一种锂吸附材料及其制备方法和应用。The invention belongs to the technical field of adsorption materials, and specifically relates to a lithium adsorption material and its preparation method and application.
背景技术Background technique
锂及其化合物广泛用于化工、医药、航天等领域，具有重要的战略地位，近年来随着能源、电池等行业的兴起，进一步加剧了对锂的需求。目前锂的来源主要来自含锂固体矿石和液态锂资源(如盐湖、海水等)，其中，含锂卤水矿床占全球锂资源的60％。盐湖中除了Li +以外，还有许多其他的阴阳离子共存，如Na +、K +、Mg 2+、Ca 2+、Cl -、SO 4 2-、硼酸盐等离子。在提取盐湖中的锂资源的过程中，盐湖中的其他离子会对锂离子的提取分离造成干扰，从而增加了提取锂资源的难度。 Lithium and its compounds are widely used in chemical industry, medicine, aerospace and other fields and have an important strategic position. In recent years, with the rise of energy, battery and other industries, the demand for lithium has been further intensified. At present, the source of lithium mainly comes from lithium-containing solid ores and liquid lithium resources (such as salt lakes, seawater, etc.). Among them, lithium-containing brine deposits account for 60% of global lithium resources. In addition to Li + , there are many other anions and cations coexisting in the salt lake, such as Na + , K + , Mg 2+ , Ca 2+ , Cl - , SO 4 2- , borate and other ions. In the process of extracting lithium resources from salt lakes, other ions in the salt lake will interfere with the extraction and separation of lithium ions, thereby increasing the difficulty of extracting lithium resources.
目前提取盐湖中的锂资源的方法主要有溶剂萃取法、沉淀法、膜分离法、吸附法和电化学法，由于盐湖一般位于高原、人少、交通不便、工业基础落后的地区，因此采用吸附法具有明显的优势。At present, the main methods for extracting lithium resources in salt lakes include solvent extraction, precipitation, membrane separation, adsorption and electrochemical methods. Since salt lakes are generally located on plateaus, in areas with few people, inconvenient transportation and backward industrial base, adsorption is used The method has obvious advantages.
目前通过吸附法提取盐湖中的锂资源所利用的锂吸附剂一般为铝系锂吸附LiAl-LDHs，所述铝氧锂吸附以多种锂源(氯化锂、碳酸锂、硫酸锂、硝酸锂、氢氧化锂)，以铝源(氯化铝、硫酸铝、碳酸铝、氢氧化铝和无定型三氧化二铝)，按照Li/Al＝1:3～4:1的比例进行制备和合成，经过陈化、过滤、干燥得到白色固体粉末的锂吸附剂LiAl-LDHs。The lithium adsorbent currently used to extract lithium resources in salt lakes through adsorption methods is generally aluminum-based lithium adsorption LiAl-LDHs. , lithium hydroxide), prepared and synthesized with aluminum sources (aluminum chloride, aluminum sulfate, aluminum carbonate, aluminum hydroxide and amorphous aluminum oxide) according to the ratio of Li/Al=1:3~4:1 , after aging, filtration, and drying, the lithium adsorbent LiAl-LDHs as white solid powder is obtained.
LiAl-LDHs锂吸附剂的吸附容量偏低、硼酸盐阴离子共吸脱附、循环使用性能差(溶损高、破损高、吸附剂再生时发生结构变化易造成吸附容量衰减)。此外，制备过程中需要锂源先制备目标化合物，然后脱锂得到欠锂的锂吸附剂，进行吸附-脱附(再生)循环，制备过程相对繁琐，成本上升。因此需要新类型锂吸附剂用于工业生产。LiAl-LDHs lithium adsorbent has low adsorption capacity, co-adsorption and desorption of borate anions, and poor recycling performance (high dissolution loss, high damage, and structural changes during adsorbent regeneration that can easily cause adsorption capacity attenuation). In addition, the preparation process requires a lithium source to first prepare the target compound, and then remove lithium to obtain a lithium-deficient lithium adsorbent, which undergoes an adsorption-desorption (regeneration) cycle. The preparation process is relatively cumbersome and the cost increases. Therefore, new types of lithium adsorbents are needed for industrial production.
发明内容Contents of the invention
鉴于现有技术存在的不足，本发明提供一种羟基硫酸盐锂吸附剂及其制备方法和应用，以解决现有的锂吸附剂吸附容量偏低、循环使用性能差、硼酸盐阴离子共吸脱附，锂吸附剂成本高的问题。In view of the shortcomings of the existing technology, the present invention provides a lithium hydroxysulfate adsorbent and its preparation method and application to solve the problems of low adsorption capacity, poor recycling performance and co-adsorption of borate anions of the existing lithium adsorbent. Desorption, the problem of high cost of lithium adsorbent.
为实现上述目的，本发明提供了一种锂吸附材料，所述锂吸附材料为具有多孔结构的羟基合成盐，所述羟基合成盐的分子式为DG 3(TO 4) 2(OH) 6或DG 3(TO 4) 2(OH,H 2O) 6，其中，D代表配位数大于或等于9的阳离子，G代表形成八面体配位的元素，T代表形成四面体配位的元素。 In order to achieve the above object, the present invention provides a lithium adsorbent material, which is a hydroxyl synthetic salt with a porous structure, and the molecular formula of the hydroxyl synthetic salt is DG 3 (TO 4 ) 2 (OH) 6 or DG 3 (TO 4 ) 2 (OH,H 2 O) 6 , where D represents a cation with a coordination number greater than or equal to 9, G represents an element that forms an octahedral coordination, and T represents an element that forms a tetrahedral coordination.
具体地，所述合成盐为以下分子式的合成盐中的任意一种：KAl 3(SO 4) 2(OH) 6、NaAl 3(SO 4) 2(OH) 6、(NH) 4Al 3(SO 4) 2(OH) 6、(H 3O,Ca)Al 3(SO 4) 2(OH) 6、Pb(Al,Cu) 3(SO 4) 2(OH,H 2O) 6、(Na,Ca) 2Al 6(SO 4) 4(OH,H 2O) 12、CaAl 6(SO 4) 4(OH) 12、Pb(Fe,Cu) 3(SO 4) 2(OH) 6、BaAl 6(SO 4) 4(OH) 12、KFe 3(SO 4) 2(OH) 6、NaFe 3(SO 4) 2(OH) 6、(NH) 4Fe 3(SO 4) 2(OH) 6、(H 3O)Fe 3(SO 4) 2(OH) 6、AgFe 3(SO 4) 2(OH) 6、TiFe 3(SO 4) 2(OH) 6、PbFe 6(SO 4) 4(OH) 12、SrFe 3(PO 4) 2(OH,H 2O) 6、PbFe 3(PO 4) 2(OH,H 2O) 6、PbFe 3[(PO 4SO 4)] 2(OH,H 2O) 6、BiFe 3(PO 4) 2(OH) 6、BaFe 3(AsO 4) 2(OH,H 2O) 6、PbFe 3[(AsO 4SO 4)] 2(OH,H 2O) 6、CaAl 3(PO 4) 2(OH,H 2O) 6、CaAl 3[(PO 4SO 4)] 2(OH,H 2O) 6、SrAl 3(PO 4) 2(OH,H 2O) 6、SrAl 3[(PO 4SO 4)] 2(OH,H 2O) 6、BaAl 3(PO 4) 2(OH,H 2O) 6、PbAl 3(PO 4) 2(OH,H 2O) 6、PbAl 3[(PO 4SO 4)] 2(OH,H 2O) 6、CeAl 3(PO 4) 2(OH) 6、(Bi,Ca)Al 3(PO 4SiO 4) 2(OH) 6、LaAl 3(PO 4) 2(OH) 6、NdAl 3(PO 4) 2(OH) 6、(Th,Pb)Al 3(PO 4SiO 4) 2(OH,H 2O) 6、CaAl 3(AsO 4) 2(OH,H 2O) 6、PbAl 3[(AsO 4SO 4)] 2(OH,H 2O) 6、SrAl 3(AsO 4) 2(OH,H 2O) 6、(Sr,Ce)Al 3[(AsO 4SO 4)] 2(OH,H 2O) 6、CeAl 3(AsO 4) 2(OH) 6、BaAl 3(AsO 4) 2(OH,H 2O) 6、PbAl 3(AsO 4) 2(OH,H 2O) 6、PbGa 3[(AsO 4SO 4)] 2(OH,H 2O) 6、BaV 3(PO 4) 2(OH,H 2O) 6。 Specifically, the synthetic salt is any one of the synthetic salts of the following molecular formulas: KAl 3 (SO 4 ) 2 (OH) 6 , NaAl 3 (SO 4 ) 2 (OH) 6 , (NH) 4 Al 3 ( SO 4 ) 2 (OH) 6 , (H 3 O,Ca)Al 3 (SO 4 ) 2 (OH) 6 , Pb(Al,Cu) 3 (SO 4 ) 2 (OH,H 2 O) 6 , ( Na,Ca) 2 Al 6 (SO 4 ) 4 (OH,H 2 O) 12 , CaAl 6 (SO 4 ) 4 (OH) 12 , Pb(Fe,Cu) 3 (SO 4 ) 2 (OH) 6 , BaAl 6 (SO 4 ) 4 (OH) 12 , KFe 3 (SO 4 ) 2 (OH) 6 , NaFe 3 (SO 4 ) 2 (OH) 6 , (NH) 4 Fe 3 (SO 4 ) 2 (OH) 6 , (H 3 O)Fe 3 (SO 4 ) 2 (OH) 6 , AgFe 3 (SO 4 ) 2 (OH) 6 , TiFe 3 (SO 4 ) 2 (OH) 6 , PbFe 6 (SO 4 ) 4 (OH) 12 , SrFe 3 (PO 4 ) 2 (OH,H 2 O) 6 , PbFe 3 (PO 4 ) 2 (OH,H 2 O) 6 , PbFe 3 [(PO 4 SO 4 )] 2 (OH ,H 2 O) 6 ,BiFe 3 (PO 4 ) 2 (OH) 6 ,BaFe 3 (AsO 4 ) 2 (OH,H 2 O) 6 ,PbFe 3 [(AsO 4 SO 4 )] 2 (OH,H 2 O) 6 , CaAl 3 (PO 4 ) 2 (OH,H 2 O) 6 , CaAl 3 [(PO 4 SO 4 )] 2 (OH,H 2 O) 6 , SrAl 3 (PO 4 ) 2 (OH ,H 2 O) 6 ,SrAl 3 [(PO 4 SO 4 )] 2 (OH,H 2 O) 6 ,BaAl 3 (PO 4 ) 2 (OH,H 2 O) 6 ,PbAl 3 (PO 4 ) 2 (OH,H 2 O) 6 , PbAl 3 [(PO 4 SO 4 )] 2 (OH,H 2 O) 6 , CeAl 3 (PO 4 ) 2 (OH) 6 , (Bi,Ca)Al 3 (PO 4 SiO 4 ) 2 (OH) 6 , LaAl 3 (PO 4 ) 2 (OH) 6 , NdAl 3 (PO 4 ) 2 (OH) 6 , (Th,Pb)Al 3 (PO 4 SiO 4 ) 2 (OH ,H 2 O) 6 ,CaAl 3 (AsO 4 ) 2 (OH,H 2 O) 6 ,PbAl 3 [(AsO 4 SO 4 )] 2 (OH,H 2 O) 6 ,SrAl 3 (AsO 4 ) 2 (OH,H 2 O) 6 , (Sr,Ce)Al 3 [(AsO 4 SO 4 )] 2 (OH,H 2 O) 6 , CeAl 3 (AsO 4 ) 2 (OH) 6 , BaAl 3 (AsO 4 ) 2 (OH,H 2 O) 6 , PbAl 3 (AsO 4 ) 2 (OH,H 2 O) 6 , PbGa 3 [(AsO 4 SO 4 )] 2 (OH,H 2 O) 6 , BaV 3 (PO 4 ) 2 (OH,H 2 O) 6 .
本发明还提供了如上所述的锂吸附材料的制备方法，其包括：The present invention also provides a method for preparing the lithium adsorbent material as described above, which includes:
配制混合无机盐溶液，所述混合无机盐溶液中包含有阳离子D、G元素对应的阳离子以及含有T元素的酸根离子；Preparing a mixed inorganic salt solution, the mixed inorganic salt solution contains cations corresponding to the cations D and G elements and acid ions containing the T element;
向所述混合无机盐溶液加入致孔剂，混合获得反应液；所述致孔剂包括表面活性剂以及尿素和/或硫脲；Add a porogen to the mixed inorganic salt solution and mix to obtain a reaction liquid; the porogen includes surfactant and urea and/or thiourea;
将所述反应液置于反应釜中进行水热反应，反应结束过滤获得固态的第一中间产物；The reaction solution is placed in a reaction kettle to perform a hydrothermal reaction, and after the reaction is completed, it is filtered to obtain a solid first intermediate product;
对所述第一中间产物洗涤处理以洗脱所述致孔剂，获得第二中间产物；Washing the first intermediate product to elute the porogen to obtain a second intermediate product;
将所述第二中间产物进行干燥处理，获得所述具有多孔结构的羟基合成盐。The second intermediate product is dried to obtain the hydroxyl synthetic salt with a porous structure.
优选地，所述含有T元素的酸根离子选自SO 4 2-、SiO 4 4-、PO 4 3-和AsO 4 3-中的一种或两种以上。 Preferably, the acid ion containing T element is selected from one or more of SO 4 2- , SiO 4 4- , PO 4 3- and AsO 4 3- .
优选地，所述表面活性剂选自阴离子表面活性剂、阳离子表面活性剂、两性离子表面活性剂和非离子表面活性剂中的一种或两种以上；其中，所述阴离子表面活性剂为硬脂酸或十二烷基苯磺酸钠；所述阳离子表面活性剂为季铵化物；所述两性离子表面活性剂卵磷脂或氨基酸型活性剂或甜菜碱型活性剂；所述非离子表面活性剂为烷基葡糖苷、脂肪酸甘油酯、脂肪酸山梨坦或聚山梨酯。Preferably, the surfactant is selected from one or more than two types of anionic surfactants, cationic surfactants, zwitterionic surfactants and nonionic surfactants; wherein the anionic surfactant is a hard surfactant. Fatty acid or sodium dodecyl benzene sulfonate; the cationic surfactant is a quaternary ammonium compound; the zwitterionic surfactant lecithin or amino acid type active agent or betaine type active agent; the nonionic surfactant The agent is alkyl glucoside, fatty acid glyceride, fatty acid sorbitan or polysorbate.
优选地，所述水热反应的温度为70℃～180℃，反应时间为3h～12h。Preferably, the temperature of the hydrothermal reaction is 70°C to 180°C, and the reaction time is 3h to 12h.
优选地，所述洗涤处理是使用去离子水对所述第一中间产物进行多次洗涤至中性。Preferably, the washing treatment is to use deionized water to wash the first intermediate product multiple times until it becomes neutral.
优选地，所述干燥处理是在50℃～80℃的温度下进行恒温干燥。Preferably, the drying process is constant temperature drying at a temperature of 50°C to 80°C.
优选地，所述羟基合成盐为羟基硫酸盐，所述混合无机盐溶液是将可溶性的第一化合物和第二化合物溶解于水中获得，所述第一化合物能够在水中电离出阳离子D，所述第二化合物能够在水中电离出G元素对应的阳离子，所述第一化合物和所述第二化合物的至少其中之一能够在水中电离出硫酸根离子；所述致孔剂包括尿素和表面活性剂。Preferably, the hydroxyl synthetic salt is a hydroxysulfate, the mixed inorganic salt solution is obtained by dissolving a soluble first compound and a second compound in water, the first compound can ionize cation D in water, and the The second compound is capable of ionizing cations corresponding to the G element in water, and at least one of the first compound and the second compound is capable of ionizing sulfate ions in water; the porogen includes urea and surfactant .
本发明的另一方面是提供了如上所述的锂吸附材料应用，其中，将所述锂吸附材料造粒后应用于从含锂离子的溶液中吸附提取锂离子。Another aspect of the present invention is to provide the application of the lithium adsorbent material as described above, wherein the lithium adsorbent material is granulated and used to adsorb and extract lithium ions from a solution containing lithium ions.
有益效果：本发明实施例提供的锂吸附材料，采用具有多孔结构的羟基合成盐作为锂吸附材料，其具有吸附量高、循环使用寿命长、不吸附硼酸盐阴离子等优点，特别适合应用于从盐湖卤水中的吸附提取锂离子。另外，该锂吸附材料合成过程中无需消耗额外的锂源，具有制备条件温和、工艺流程简单易行、对设备成本要求低且无污染的优点，适用于大规模生产。Beneficial effects: The lithium adsorbent material provided by the embodiment of the present invention uses hydroxyl synthetic salt with a porous structure as the lithium adsorbent material. It has the advantages of high adsorption capacity, long cycle life, and no adsorption of borate anions, and is particularly suitable for use in Extraction of lithium ions from salt lake brine by adsorption. In addition, the lithium adsorption material does not require the consumption of additional lithium sources during the synthesis process. It has the advantages of mild preparation conditions, simple and easy process flow, low equipment cost requirements and no pollution, and is suitable for large-scale production.
附图说明Description of drawings
通过结合附图进行的以下描述，本发明的实施例的上述和其它方面、特点和优点将变得更加清楚，附图中：The above and other aspects, features and advantages of embodiments of the invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
图1是本发明实施例中的锂吸附材料的制备方法的工艺流程图；Figure 1 is a process flow diagram of a method for preparing a lithium adsorbent material in an embodiment of the present invention;
图2是本发明实施例1制备获得的锂吸附材料的XRD图；Figure 2 is an XRD pattern of the lithium adsorbent material prepared in Example 1 of the present invention;
图3是本发明实施例1制备获得的锂吸附材料的SEM图；Figure 3 is an SEM image of the lithium adsorbent material prepared in Example 1 of the present invention;
图4是本发明对比例1制备获得的锂吸附材料的XRD图；Figure 4 is an XRD pattern of the lithium adsorption material prepared in Comparative Example 1 of the present invention;
图5是本发明实施例3制备获得的锂吸附材料的XRD图。Figure 5 is an XRD pattern of the lithium adsorbent material prepared in Example 3 of the present invention.
具体实施方式Detailed ways
以下，将参照附图来详细描述本发明的具体实施例。然而，可以以许多不同的形式来实施本发明，并且本发明不应该被解释为限制于这里阐述的具体实施例。相反，提供这些实施例是为了解释本发明的原理及其实际应用，从而使本领域的其他技术人员能够理解本发明的各种实施例和适合于特定预期应用的各种修改。Hereinafter, specific embodiments of the present invention will be described in detail with reference to the accompanying drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the specific embodiments set forth herein. Rather, these embodiments are provided in order to explain the principles of the invention and its practical application, thereby enabling others skilled in the art to understand the invention for various embodiments and with various modifications as are suited to the particular use contemplated.
如本文中使用的，术语“包括”及其变型表示开放的术语，含义是“包括但不限于”。术语“基于”、“根据”等表示“至少部分地基于”、“至少部分地根据”。术语“一个实施例”和“一实施例”表示“至少一个实施例”。术语“另一个实施例”表示“至少一个其他实施例”。术语“第一”、“第二”等可以指代不同的或相同的对象。下面可以包括其他的定义，无论是明确的还是隐含的。除非上下文中明确地指明，否则一个术语的定义在整个说明书中是一致的。As used herein, the term "includes" and variations thereof represent an open term meaning "including, but not limited to." The terms "based on", "according to", etc. mean "based at least in part on", "based at least in part on". The terms "one embodiment" and "an embodiment" mean "at least one embodiment." The term "another embodiment" means "at least one other embodiment". The terms "first", "second", etc. may refer to different or the same object. Other definitions may be included below, whether explicit or implicit. The definition of a term is consistent throughout this specification unless the context clearly indicates otherwise.
本发明实施例首先提供了一种锂吸附材料，所述锂吸附材料为具有多孔结构的羟基合成盐，所述羟基合成盐的分子式为DG 3(TO 4) 2(OH) 6或DG 3(TO 4) 2(OH,H 2O) 6，其中，D代表配位数大于或等于9的阳离子，G代表形成八面体配位的元素，T代表形成四面体配位的元素。其中，分子式为DG 3(TO 4) 2(OH) 6代表所述羟基合成盐不含结晶水，分子式为DG 3(TO 4) 2(OH,H 2O) 6代表所述羟基合成盐含有结晶水。 Embodiments of the present invention first provide a lithium adsorption material. The lithium adsorption material is a hydroxyl synthetic salt with a porous structure. The molecular formula of the hydroxyl synthetic salt is DG 3 (TO 4 ) 2 (OH) 6 or DG 3 ( TO 4 ) 2 (OH,H 2 O) 6 , where D represents a cation with a coordination number greater than or equal to 9, G represents an element that forms an octahedral coordination, and T represents an element that forms a tetrahedral coordination. Among them, the molecular formula DG 3 (TO 4 ) 2 (OH) 6 represents that the hydroxyl synthetic salt does not contain crystal water, and the molecular formula DG 3 (TO 4 ) 2 (OH,H 2 O) 6 represents that the hydroxyl synthetic salt contains Crystal water.
其中，阳离子D例如是H 3O +、K +、Na +、NH 4 +、Ag +、Ti +、Pb 2+、Ca 2+、Ba 2+等，G元素例如是Al、Fe、Ga、V等，T元素例如是S、P、As、Si等。 Among them, the cation D is, for example, H 3 O + , K + , Na + , NH 4 + , Ag + , Ti + , Pb 2+ , Ca 2+ , Ba 2+ , etc., and the G element is, for example, Al, Fe, Ga, V, etc., and the T element is, for example, S, P, As, Si, etc.
具体的方案中，所述合成盐为以下分子式的合成盐中的任意一种：KAl 3(SO 4) 2(OH) 6、NaAl 3(SO 4) 2(OH) 6、(NH) 4Al 3(SO 4) 2(OH) 6、(H 3O,Ca)Al 3(SO 4) 2(OH) 6、Pb(Al,Cu) 3(SO 4) 2(OH,H 2O) 6、(Na,Ca) 2Al 6(SO 4) 4(OH,H 2O) 12、CaAl 6(SO 4) 4(OH) 12、Pb(Fe,Cu) 3(SO 4) 2(OH) 6、BaAl 6(SO 4) 4(OH) 12、KFe 3(SO 4) 2(OH) 6、NaFe 3(SO 4) 2(OH) 6、(NH) 4Fe 3(SO 4) 2(OH) 6、 (H 3O)Fe 3(SO 4) 2(OH) 6、AgFe 3(SO 4) 2(OH) 6、TiFe 3(SO 4) 2(OH) 6、PbFe 6(SO 4) 4(OH) 12、SrFe 3(PO 4) 2(OH,H 2O) 6、PbFe 3(PO 4) 2(OH,H 2O) 6、PbFe 3[(PO 4SO 4)] 2(OH,H 2O) 6、BiFe 3(PO 4) 2(OH) 6、BaFe 3(AsO 4) 2(OH,H 2O) 6、PbFe 3[(AsO 4SO 4)] 2(OH,H 2O) 6、CaAl 3(PO 4) 2(OH,H 2O) 6、CaAl 3[(PO 4SO 4)] 2(OH,H 2O) 6、SrAl 3(PO 4) 2(OH,H 2O) 6、SrAl 3[(PO 4SO 4)] 2(OH,H 2O) 6、BaAl 3(PO 4) 2(OH,H 2O) 6、PbAl 3(PO 4) 2(OH,H 2O) 6、PbAl 3[(PO 4SO 4)] 2(OH,H 2O) 6、CeAl 3(PO 4) 2(OH) 6、(Bi,Ca)Al 3(PO 4SiO 4) 2(OH) 6、LaAl 3(PO 4) 2(OH) 6、NdAl 3(PO 4) 2(OH) 6、(Th,Pb)Al 3(PO 4SiO 4) 2(OH,H 2O) 6、CaAl 3(AsO 4) 2(OH,H 2O) 6、PbAl 3[(AsO 4SO 4)] 2(OH,H 2O) 6、SrAl 3(AsO 4) 2(OH,H 2O) 6、(Sr,Ce)Al 3[(AsO 4SO 4)] 2(OH,H 2O) 6、CeAl 3(AsO 4) 2(OH) 6、BaAl 3(AsO 4) 2(OH,H 2O) 6、PbAl 3(AsO 4) 2(OH,H 2O) 6、PbGa 3[(AsO 4SO 4)] 2(OH,H 2O) 6、BaV 3(PO 4) 2(OH,H 2O) 6。 In a specific solution, the synthetic salt is any one of the synthetic salts of the following molecular formulas: KAl 3 (SO 4 ) 2 (OH) 6 , NaAl 3 (SO 4 ) 2 (OH) 6 , (NH) 4 Al 3 (SO 4 ) 2 (OH) 6 , (H 3 O,Ca)Al 3 (SO 4 ) 2 (OH) 6 , Pb(Al,Cu) 3 (SO 4 ) 2 (OH,H 2 O) 6 , (Na,Ca) 2 Al 6 (SO 4 ) 4 (OH,H 2 O) 12 , CaAl 6 (SO 4 ) 4 (OH) 12 , Pb(Fe,Cu) 3 (SO 4 ) 2 (OH) 6. BaAl 6 (SO 4 ) 4 (OH) 12 , KFe 3 (SO 4 ) 2 (OH) 6 , NaFe 3 (SO 4 ) 2 (OH) 6 , (NH) 4 Fe 3 (SO 4 ) 2 ( OH) 6 , (H 3 O)Fe 3 (SO 4 ) 2 (OH) 6 , AgFe 3 (SO 4 ) 2 (OH) 6 , TiFe 3 (SO 4 ) 2 (OH) 6 , PbFe 6 (SO 4 ) 4 (OH) 12 , SrFe 3 (PO 4 ) 2 (OH,H 2 O) 6 , PbFe 3 (PO 4 ) 2 (OH,H 2 O) 6 , PbFe 3 [(PO 4 SO 4 )] 2 (OH,H 2 O) 6 , BiFe 3 (PO 4 ) 2 (OH) 6 , BaFe 3 (AsO 4 ) 2 (OH,H 2 O) 6 , PbFe 3 [(AsO 4 SO 4 )] 2 (OH ,H 2 O) 6 ,CaAl 3 (PO 4 ) 2 (OH,H 2 O) 6 ,CaAl 3 [(PO 4 SO 4 )] 2 (OH,H 2 O) 6 ,SrAl 3 (PO 4 ) 2 (OH,H 2 O) 6 , SrAl 3 [(PO 4 SO 4 )] 2 (OH,H 2 O) 6 , BaAl 3 (PO 4 ) 2 (OH,H 2 O) 6 , PbAl 3 (PO 4 ) 2 (OH,H 2 O) 6 , PbAl 3 [(PO 4 SO 4 )] 2 (OH,H 2 O) 6 , CeAl 3 (PO 4 ) 2 (OH) 6 , (Bi,Ca)Al 3 (PO 4 SiO 4 ) 2 (OH) 6 , LaAl 3 (PO 4 ) 2 (OH) 6 , NdAl 3 (PO 4 ) 2 (OH) 6 , (Th,Pb)Al 3 (PO 4 SiO 4 ) 2 (OH,H 2 O) 6 , CaAl 3 (AsO 4 ) 2 (OH,H 2 O) 6 , PbAl 3 [(AsO 4 SO 4 )] 2 (OH,H 2 O) 6 , SrAl 3 (AsO 4 ) 2 (OH,H 2 O) 6 , (Sr,Ce)Al 3 [(AsO 4 SO 4 )] 2 (OH,H 2 O) 6 , CeAl 3 (AsO 4 ) 2 (OH) 6 , BaAl 3 (AsO 4 ) 2 (OH,H 2 O) 6 , PbAl 3 (AsO 4 ) 2 (OH,H 2 O) 6 , PbGa 3 [(AsO 4 SO 4 )] 2 (OH,H 2 O) 6 , BaV 3 (PO 4 ) 2 (OH,H 2 O) 6 .
本发明实施例提供了如上所述的锂吸附材料的制备方法，参阅图1，所述制备方法包括以下步骤：Embodiments of the present invention provide a method for preparing the lithium adsorbent material as described above. Referring to Figure 1, the preparation method includes the following steps:
步骤S10、配制混合无机盐溶液，所述混合无机盐溶液中包含有阳离子D、G元素对应的阳离子以及含有T元素的酸根离子。Step S10: Prepare a mixed inorganic salt solution, which contains cations D, cations corresponding to the G element, and acid ions containing the T element.
步骤S20、向所述混合无机盐溶液加入致孔剂，混合获得反应液；所述致孔剂包括表面活性剂以及尿素和/或硫脲。Step S20: Add a porogen to the mixed inorganic salt solution and mix to obtain a reaction liquid; the porogen includes surfactant, urea and/or thiourea.
步骤S30、将所述反应液置于反应釜中进行水热反应，反应结束过滤获得固态的第一中间产物；Step S30: Place the reaction solution in a reaction kettle to perform a hydrothermal reaction. After the reaction is completed, filter to obtain a solid first intermediate product;
步骤S40、对所述第一中间产物洗涤处理以洗脱所述致孔剂，获得具有多孔结构第二中间产物；Step S40: Wash the first intermediate product to elute the porogen to obtain a second intermediate product with a porous structure;
步骤S50、将所述第二中间产物进行干燥处理，获得所述具有多孔结构的羟基合成盐，得到所述锂吸附材料。Step S50: Dry the second intermediate product to obtain the hydroxyl synthetic salt with a porous structure, and obtain the lithium adsorption material.
具体地，步骤S10中，将两种以上的化合物溶解于水中获得所述混合盐溶液。其中至少一种化合物为盐，其能够在水中电离出含有T元素的酸根离子以及阳离子D或G元素对应的阳离子的其中一个，D或G元素对应的阳离子的另外一个来自另一化合物，另一化合物可以是包含T元素酸根离子的盐。Specifically, in step S10, two or more compounds are dissolved in water to obtain the mixed salt solution. At least one of the compounds is a salt, which can ionize in water an acid ion containing the element T and one of the cations corresponding to the cation D or the element G. The other one of the cations corresponding to the element D or G comes from another compound, and the other The compound may be a salt containing an acid ion of the element T.
其中，所述含有T元素的酸根离子是具有四面体结构的酸根阴离子，优选是选自SO 4 2-、SiO 4 4-、PO 4 3-和AsO 4 3-中的一种或两种以上。 Wherein, the acid anion containing the T element is an acid anion with a tetrahedral structure, preferably one or two or more selected from SO 4 2- , SiO 4 4- , PO 4 3- and AsO 4 3- .
进一步地，若是D或G元素对应的阳离子的另外一个来自氢氧化物或氯化 物，可以在混合溶液中添加T元素的酸根离子对应的酸，一方面是调节所述混合盐溶液的pH值，另一方面是补充混合盐溶液的含有T元素的酸根离子。Further, if the other cation corresponding to the D or G element comes from hydroxide or chloride, the acid corresponding to the acid ion of the T element can be added to the mixed solution, on the one hand, to adjust the pH value of the mixed salt solution, On the other hand, it is the acid ion containing T element that supplements the mixed salt solution.
例如，所要制备的多孔结构的羟基合成盐的分子式为：NaAl 3(SO 4) 2(OH) 6，即阳离子D为Na +，G元素为Al，T元素为S。则一种化合物可选择为Na 2SO 4，其在水溶液中电离出Na +和SO 4 2-；另一种化合物可选择为Al 2(SO 4) 3，其在水溶液中电离出Al 3+和SO 4 2-。 For example, the molecular formula of the porous structure hydroxyl synthetic salt to be prepared is: NaAl 3 (SO 4 ) 2 (OH) 6 , that is, the cation D is Na + , the G element is Al, and the T element is S. Then one compound can be selected as Na 2 SO 4 , which ionizes into Na + and SO 4 2- in aqueous solution; the other compound can be selected as Al 2 (SO 4 ) 3 , which ionizes into Al 3+ in aqueous solution and SO 4 2- .
例如，所要制备的多孔结构的羟基合成盐的分子式为：NaFe 3(SO 4) 2(OH) 6，即阳离子D为Na +，G元素为Fe，T元素为S。则一种化合物可选择为Na 2SO 4，其在水溶液中电离出Na +和SO 4 2-；另一种化合物可选择为FeCl 3，其在水溶液中电离出Al 3+和Cl -，此时，可以在混合溶液中添加H 2SO 4，一方面是调节所述混合盐溶液的pH值，另一方面是补充混合盐溶液的SO 4 2-。 For example, the molecular formula of the porous structure hydroxyl synthetic salt to be prepared is: NaFe 3 (SO 4 ) 2 (OH) 6 , that is, the cation D is Na + , the G element is Fe, and the T element is S. Then one compound can be selected as Na 2 SO 4 , which ionizes into Na + and SO 4 2- in aqueous solution; the other compound can be selected as FeCl 3 , which ionizes into Al 3+ and Cl - in aqueous solution, this When , H 2 SO 4 can be added to the mixed solution, on the one hand, to adjust the pH value of the mixed salt solution, and on the other hand, to supplement the SO 4 2- of the mixed salt solution.
在一些具体实施例中，当阳离子D为NH 4 +时，NH 4 +可以是直接来自于步骤S20中的尿素，此时步骤S10中的配置的混合盐溶液可以是仅含有G元素对应的阳离子以及含有T元素的酸根离子。 In some specific embodiments, when the cation D is NH 4 + , the NH 4 + can be directly from the urea in step S20. At this time, the mixed salt solution configured in step S10 can only contain cations corresponding to the G element. And acid ions containing T element.
具体地，步骤S20中，所述表面活性剂选自阴离子表面活性剂、阳离子表面活性剂、两性离子表面活性剂和非离子表面活性剂中的一种或两种以上；其中，所述阴离子表面活性剂为硬脂酸或十二烷基苯磺酸钠；所述阳离子表面活性剂为季铵化物；所述两性离子表面活性剂卵磷脂或氨基酸型活性剂或甜菜碱型活性剂；所述非离子表面活性剂为烷基葡糖苷、脂肪酸甘油酯、脂肪酸山梨坦或聚山梨酯。Specifically, in step S20, the surfactant is selected from one or more than two types of anionic surfactants, cationic surfactants, zwitterionic surfactants and nonionic surfactants; wherein, the anionic surface The active agent is stearic acid or sodium dodecyl benzene sulfonate; the cationic surfactant is a quaternary ammonium compound; the zwitterionic surfactant lecithin or amino acid active agent or betaine active agent; the Nonionic surfactants are alkyl glucosides, fatty acid glycerides, fatty acid sorbitans or polysorbates.
具体地，步骤S30中，所述水热反应的温度优选为70℃～180℃，例如是95℃、100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃或180℃。反应时间优选为3h～12h，例如是3h、4h、5h、6h、7h、8h、9h、10h、11h或12h。Specifically, in step S30, the temperature of the hydrothermal reaction is preferably 70°C to 180°C, such as 95°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C or 180℃. The reaction time is preferably 3h to 12h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h.
具体地，步骤S40中，所述洗涤处理是使用去离子水对所述第一中间产物进行多次洗涤至中性，即进行多次洗涤直至洗涤液的pH接近于7。Specifically, in step S40, the washing process is to use deionized water to wash the first intermediate product multiple times until it becomes neutral, that is, wash it multiple times until the pH of the washing liquid is close to 7.
具体地，步骤S50中，所述干燥处理优选是在50℃～80℃的温度下进行恒温干燥。Specifically, in step S50, the drying process is preferably constant temperature drying at a temperature of 50°C to 80°C.
在优选的方案中，所述羟基合成盐为羟基硫酸盐，所述混合盐溶液是将可溶性的第一化合物和第二化合物溶解于水中获得，所述第一化合物能够在水中 电离出阳离子D，所述第二化合物能够在水中电离出G元素对应的阳离子，所述第一化合物和所述第二化合物的至少其中之一能够在水中电离出硫酸根离子；所述致孔剂包括尿素和表面活性剂。In a preferred embodiment, the hydroxyl synthetic salt is a hydroxysulfate, and the mixed salt solution is obtained by dissolving a soluble first compound and a second compound in water, and the first compound can ionize cation D in water, The second compound can ionize cations corresponding to the G element in water, and at least one of the first compound and the second compound can ionize sulfate ions in water; the porogen includes urea and surface active agent.
具体地，第一化合物和第二化合物的其中之一选择为硫酸盐或硫酸氢盐，第一化合物和第二化合物的另一个可选择为硫酸盐、氯化物和硝酸盐。当第一化合物和第二化合物的另一个选择为氢氧化物或氯化物时，可进一步添加硫酸以调节溶液的pH值并提供硫酸根离子。Specifically, one of the first compound and the second compound is selected to be a sulfate or a hydrogen sulfate, and the other of the first compound and the second compound is selected to be a sulfate, a chloride or a nitrate. When another alternative of the first compound and the second compound is a hydroxide or chloride, sulfuric acid may be further added to adjust the pH of the solution and provide sulfate ions.
如上实施例提供的锂吸附材料，具体是具有多孔结构的羟基合成盐，其具有吸附容量高的有点，在吸附锂和脱附锂再生的过程中，不发生结构改变，因此该锂吸附材料结构强度高、溶损低，循环使用寿命长。该锂吸附材料的合成过程中无需消耗额外的锂源，合成原料易得，具有制备条件温和、工艺流程简单易行、对设备成本要求低且无污染的优点，适用于大规模生产。The lithium adsorbent material provided in the above embodiment is specifically a hydroxyl synthetic salt with a porous structure, which has the advantage of high adsorption capacity. During the process of adsorbing lithium and desorbing lithium and regenerating it, no structural change occurs. Therefore, the structure of the lithium adsorbent material High strength, low dissolution loss and long cycle life. There is no need to consume additional lithium sources during the synthesis process of this lithium adsorption material. The synthetic raw materials are easy to obtain. It has the advantages of mild preparation conditions, simple and easy process flow, low equipment cost requirements and no pollution, and is suitable for large-scale production.
本发明实施例的另一方面是提供了如上所述的锂吸附材料应用，其中，将所述锂吸附材料造粒后应用于从含锂离子的溶液中吸附提取锂离子。其中可以使用海藻酸钙造粒法或聚丙烯腈混合造粒法对锂吸附材料进行造粒。Another aspect of the embodiments of the present invention is to provide the application of the lithium adsorbent material as described above, wherein the lithium adsorbent material is granulated and used to adsorb and extract lithium ions from a solution containing lithium ions. The calcium alginate granulation method or the polyacrylonitrile mixed granulation method can be used to granulate the lithium adsorbent material.
(1)海藻酸钙法(1)Calcium alginate method
作为一个示例，按照如下步骤进行造粒：将1.0g的海藻酸钠、0.5g的壳聚糖加入150mL去离子水，加入1mL的乙酸，搅拌均匀后加入10g～12g的本发明实施例提供的锂吸附材料粉末，再次搅拌均匀后滴入至4％的CaCl 2溶液中，然后陈化和静置6～12h，得到颗粒状材料；接着将颗粒状材料转移至含有3～8％的戊二醛/1,4-二(环氧乙烷-2-基)苯/季戊四醇缩水甘油醚混合交联剂，在60℃下交联6小时，制备获得颗粒状的锂吸附剂。 As an example, granulate according to the following steps: add 1.0g sodium alginate and 0.5g chitosan to 150mL deionized water, add 1mL acetic acid, stir evenly, and then add 10g to 12g of the sodium alginate provided by the embodiment of the present invention. Lithium adsorbent material powder is stirred evenly again and dropped into a 4% CaCl2 solution, then aged and left for 6 to 12 hours to obtain granular material; then the granular material is transferred to a solution containing 3 to 8% pentane. Aldehyde/1,4-bis(ethylene oxide-2-yl)benzene/pentaerythritol glycidyl ether mixed cross-linking agent, cross-linked at 60°C for 6 hours, to prepare a granular lithium adsorbent.
(2)聚丙烯腈混合造粒法(2) Polyacrylonitrile mixed granulation method
作为一个示例，按照如下步骤进行造粒：将1.0g的聚丙烯腈、0.2g的盐酸羟胺加入100mL的去离子水中，加入0.05g的氢氧化钠，室温下搅拌8小时，过滤和干燥。然后将以上的混合物和0.2g的聚丙烯腈加入20mL的DMSO中，待溶解后加入10g的本发明实施例提供的锂吸附材料粉末，然后搅拌均匀后滴入去离子水中，然后陈化和静置6～12h，制备获得颗粒状的锂吸附剂。As an example, granulate according to the following steps: add 1.0 g of polyacrylonitrile and 0.2 g of hydroxylamine hydrochloride to 100 mL of deionized water, add 0.05 g of sodium hydroxide, stir at room temperature for 8 hours, filter and dry. Then add the above mixture and 0.2g of polyacrylonitrile into 20mL of DMSO. After dissolving, add 10g of the lithium adsorbent material powder provided in the embodiment of the present invention, then stir evenly and drop it into deionized water, then age and static. Leave for 6 to 12 hours to prepare a granular lithium adsorbent.
本发明实施例中，将锂吸附材料造粒后从含锂离子的溶液中吸附提取锂离子的方法，主要包括以下操作：In the embodiment of the present invention, the method of adsorbing and extracting lithium ions from a solution containing lithium ions after granulating the lithium adsorbing material mainly includes the following operations:
吸附操作：根据采用吸附柱的填料高度(10cm～50cm)、柱内直径(1cm～5cm)、填料粒径(0.05cm～0.5cm)，选择合适的泵速(10ml/h～200ml/h)，将造粒获得的颗粒状的锂吸附剂转入吸附柱中，采用下进上出的模式，并检测流出液中的锂离子浓度，待料液中锂离子刚穿透吸附柱时停止动态吸附实验，其吸附容量在6.5mg/g～30mg/g之间。Adsorption operation: Select the appropriate pump speed (10ml/h~200ml/h) according to the packing height of the adsorption column (10cm~50cm), column inner diameter (1cm~5cm), and packing particle size (0.05cm~0.5cm) , transfer the granular lithium adsorbent obtained by granulation into the adsorption column, adopt the bottom-in-top-out mode, and detect the lithium ion concentration in the effluent. Stop the dynamic when the lithium ions in the feed liquid have just penetrated the adsorption column. Adsorption experiments show that the adsorption capacity is between 6.5 mg/g and 30 mg/g.
脱附操作：根据采用吸附柱的填料高度、柱内直径、填料粒径，选择合适的泵速，将水溶液、低酸(pH在4-6之间)洗脱液、碳酸溶液下进上出泵入吸附柱中，收集洗脱液，并检测流出洗脱液中锂离子浓度，待流出液中锂离子浓度降低为零时，停止泵入洗脱液。Desorption operation: Select the appropriate pump speed according to the packing height, inner diameter of the column, and packing particle size of the adsorption column, and pump the aqueous solution, low acid (pH between 4-6) eluent, and carbonic acid solution in and out. Pump into the adsorption column, collect the eluate, and detect the lithium ion concentration in the outflow eluate. When the lithium ion concentration in the outflow liquid drops to zero, stop pumping the eluent.
依序重复上述吸附处理和脱附处理操作。Repeat the above adsorption treatment and desorption treatment operations in sequence.
实施例1Example 1
称取3mmol Al 2(SO 4) 3·18H 2O、8mmol尿素和1mol十六烷基三甲基溴化铵表面活性剂溶于35mL水中，搅拌均匀后置于50ml的水热反应釜中，在160℃下反应4h。待反应结束后、冷却至室温，过滤，不断地用去离子水洗涤，直到上层水的pH接近7。清洗后将得到湿的白色粉末在60℃的恒温箱干燥，最终得到白色粉末产物(NH) 4Al 3(SO 4) 2(OH) 6，对产物进一步研磨后密封保存备用。 Weigh 3mmol Al 2 (SO 4 ) 3 ·18H 2 O, 8mmol urea and 1mol cetyltrimethylammonium bromide surfactant and dissolve them in 35mL water. Stir evenly and place them in a 50ml hydrothermal reaction kettle. React at 160°C for 4 hours. After the reaction is completed, cool to room temperature, filter, and continuously wash with deionized water until the pH of the upper water is close to 7. After cleaning, the wet white powder is dried in a constant temperature oven at 60°C to finally obtain the white powder product (NH) 4 Al 3 (SO 4 ) 2 (OH) 6 . The product is further ground and sealed for later use.
所述白色粉末产物(NH) 4Al 3(SO 4) 2(OH) 6为具有多孔结构的羟基硫酸盐锂吸附材料。 The white powder product (NH) 4 Al 3 (SO 4 ) 2 (OH) 6 is a lithium hydroxysulfate adsorption material with a porous structure.
图2是本实施例制备获得的锂吸附材料的XRD图，图3是本实施例制备获得的锂吸附材料的SEM图。从图2和图3可获知，本实施例制备获得的锂吸附材料是具有多孔结构的羟基硫酸盐，其分子式为(NH) 4Al 3(SO 4) 2(OH) 6。 Figure 2 is an XRD pattern of the lithium adsorbent material prepared in this embodiment, and Figure 3 is an SEM image of the lithium adsorbent material prepared in this example. It can be seen from Figures 2 and 3 that the lithium adsorbent material prepared in this embodiment is a hydroxysulfate with a porous structure, and its molecular formula is (NH) 4 Al 3 (SO 4 ) 2 (OH) 6 .
利用海藻酸钙法进行造粒，将本实施例得到的锂吸附材料造粒后装入内径为2cm的定制吸附柱内，通过蠕动泵将浓度为500mg/L的氯化锂溶液从吸附柱底端泵入，泵速为45mL/h。待检测到有锂离子流出时，停止动态吸附实验。然后以2mL/min的流速泵入水溶液，至无锂离子流出为止。经过检测，本实施例中的锂吸附材料的吸附容量7.16mg/g。The calcium alginate method was used for granulation. The lithium adsorption material obtained in this example was granulated and then put into a customized adsorption column with an inner diameter of 2 cm. A lithium chloride solution with a concentration of 500 mg/L was pumped from the bottom of the adsorption column through a peristaltic pump. Pump in at the end and the pump speed is 45mL/h. When the outflow of lithium ions is detected, the dynamic adsorption experiment is stopped. Then pump the aqueous solution at a flow rate of 2mL/min until no lithium ions flow out. After testing, the adsorption capacity of the lithium adsorbent material in this embodiment is 7.16 mg/g.
对比例1Comparative example 1
称取1.5mmol Al 2(SO 4) 3·18H 2O、19mmol尿素溶于30mL水中，搅拌均匀后置于50ml的水热反应釜中，在180℃下反应4h。待反应结束后、冷却至室 温，过滤，不断地用去离子水洗涤，直到上层水的pH接近7。清洗后将得到湿的白色粉末在60℃的恒温箱干燥，最终得到白色粉末产物(NH) 4Al 3(SO 4) 2(OH) 6，对产物进一步研磨后密封保存备用。 Weigh 1.5 mmol Al 2 (SO 4 ) 3 ·18H 2 O and 19 mmol urea and dissolve them in 30 mL of water. Stir evenly and place them in a 50 ml hydrothermal reactor. React at 180°C for 4 hours. After the reaction is completed, cool to room temperature, filter, and continuously wash with deionized water until the pH of the upper water is close to 7. After cleaning, the wet white powder is dried in a constant temperature oven at 60°C to finally obtain the white powder product (NH) 4 Al 3 (SO 4 ) 2 (OH) 6 . The product is further ground and sealed for storage.
图4是对比例1制备获得的锂吸附材料的XRD图，从图4可获知，对比例1制备获得的锂吸附材料是羟基硫酸盐，其分子式也是(NH) 4Al 3(SO 4) 2(OH) 6。 Figure 4 is an XRD pattern of the lithium adsorbent material prepared in Comparative Example 1. It can be seen from Figure 4 that the lithium adsorbent material prepared in Comparative Example 1 is hydroxysulfate, and its molecular formula is also (NH) 4 Al 3 (SO 4 ) 2 (OH) 6 .
利用海藻酸钙法进行造粒，将本实施例得到的锂吸附材料造粒后装入内径为2cm的定制吸附柱内，通过蠕动泵将1000mg/L的氯化锂溶液从吸附柱低端泵入，泵速45mL/h。待检测到有锂离子流出时，停止动态吸附实验。然后以2mL/min的流速泵入水溶液，至无锂离子流出为止。经过检测，对比例1的吸附材料的吸附容量为6.77mg/g。The calcium alginate method is used for granulation. The lithium adsorbent material obtained in this example is granulated and put into a customized adsorption column with an inner diameter of 2 cm. A 1000 mg/L lithium chloride solution is pumped from the lower end of the adsorption column through a peristaltic pump. Input, pump speed 45mL/h. When the outflow of lithium ions is detected, the dynamic adsorption experiment is stopped. Then pump the aqueous solution at a flow rate of 2mL/min until no lithium ions flow out. After testing, the adsorption capacity of the adsorption material of Comparative Example 1 was 6.77 mg/g.
对比例1和实施例1中合成的羟基硫酸盐锂吸附材料为同一种物质，区别在于：对比例1中在合成(NH) 4Al 3(SO4) 2(OH) 6羟基硫酸盐锂吸附剂的过程中未添加表面活性剂(致孔剂)，制备得到的锂吸附材料的吸附容量为6.77mg/g；实施例1中在合成(NH) 4Al 3(SO4) 2(OH) 6锂吸附材料的过程中，使用十六烷基三甲基溴化铵作为表面活性剂，制备得到的锂吸附材料的吸附容量为7.16mg/g。上述对比表明，在合成羟基合成盐的锂吸附材料的过程中加入表面活性剂进行造孔，有利于增加所述羟基合成盐的锂吸附材料的吸附容量。 The lithium hydroxysulfate adsorbent material synthesized in Comparative Example 1 and Example 1 is the same substance. The difference is that in Comparative Example 1, (NH) 4 Al 3 (SO4) 2 (OH) 6 lithium hydroxysulfate adsorbent was synthesized. No surfactant (porogen) was added during the process, and the adsorption capacity of the prepared lithium adsorbent material was 6.77 mg/g; in Example 1, (NH) 4 Al 3 (SO4) 2 (OH) 6 lithium was synthesized In the process of adsorbing the material, cetyltrimethylammonium bromide was used as a surfactant, and the adsorption capacity of the prepared lithium adsorbent material was 7.16 mg/g. The above comparison shows that adding surfactants to create pores during the synthesis of lithium adsorbent materials for hydroxyl synthetic salts is beneficial to increasing the adsorption capacity of the lithium adsorbent materials for hydroxyl synthetic salts.
实施例2Example 2
称取4mmol Fe 2(SO 4) 3、6mmol尿素和1.2mol十二烷基苯磺酸钠表面活性剂溶于80mL水中，搅拌均匀后置于50ml的水热反应釜中，在180℃下反应8h。待反应结束后、冷却至室温，过滤，不断地用去离子水洗涤，直到上层水的pH接近7。清洗后将得到湿的粉末在60℃的恒温箱干燥，最终得到粉末产物(NH 4)Fe 3(SO 4) 2(OH) 6，对产物进一步研磨后密封保存备用。 Weigh 4mmol Fe 2 (SO 4 ) 3 , 6mmol urea and 1.2mol sodium dodecylbenzene sulfonate surfactant and dissolve them in 80mL water. Stir evenly and place them in a 50ml hydrothermal reactor to react at 180°C. 8h. After the reaction is completed, cool to room temperature, filter, and continuously wash with deionized water until the pH of the upper water is close to 7. After cleaning, the wet powder is dried in a constant temperature oven at 60°C to finally obtain the powder product (NH 4 )Fe 3 (SO 4 ) 2 (OH) 6 . The product is further ground and sealed for later use.
所述白色粉末产物(NH 4)Fe 3(SO 4) 2(OH) 6为具有多孔结构的羟基硫酸盐锂吸附材料。 The white powder product (NH 4 )Fe 3 (SO 4 ) 2 (OH) 6 is a lithium hydroxysulfate adsorption material with a porous structure.
利用聚丙烯腈法造粒，将本实施例得到的锂吸附材料造粒后装入内径为2cm的定制吸附柱内，通过蠕动泵将1000mg/L的氯化锂溶液从吸附柱低端泵入，泵速45mL/h。待检测到有锂离子流出时，停止动态吸附实验。然后以2mL/min的流速泵入水溶液，至无锂离子流出为止。经过检测，本实施例中的锂吸附材料的吸附容量10.53mg/g。The lithium adsorption material obtained in this example was granulated using the polyacrylonitrile method and then put into a custom-made adsorption column with an inner diameter of 2 cm. A 1000 mg/L lithium chloride solution was pumped in from the lower end of the adsorption column through a peristaltic pump. , pump speed 45mL/h. When the outflow of lithium ions is detected, the dynamic adsorption experiment is stopped. Then pump the aqueous solution at a flow rate of 2mL/min until no lithium ions flow out. After testing, the adsorption capacity of the lithium adsorbent material in this embodiment is 10.53 mg/g.
实施例3Example 3
称取5mmol Al 2(SO 4) 3·18H 2O、3mmol K 2SO 4、8mmol尿素和1mol十二烷基硫酸钠表面活性剂溶于80mL水中，pH值调节到1.6，搅拌均匀后置于，100ml的水热反应釜中，100℃下反应12h。待反应结束后、冷却至室温，过滤，不断地用去离子水洗涤，直到上层水的pH接近7。清洗后将得到湿的粉末在60℃的恒温箱干燥，最终得到粉末产物KAl 3(SO 4) 2(OH) 6，对产物进一步研磨后密封保存备用。 Weigh 5mmol Al 2 (SO 4 ) 3 ·18H 2 O, 3mmol K 2 SO 4 , 8mmol urea and 1mol sodium dodecyl sulfate surfactant and dissolve it in 80mL water. Adjust the pH value to 1.6, stir evenly and place , in a 100ml hydrothermal reactor, react at 100°C for 12h. After the reaction is completed, cool to room temperature, filter, and continuously wash with deionized water until the pH of the upper water is close to 7. After cleaning, the wet powder is dried in a constant temperature oven at 60°C to finally obtain the powder product KAl 3 (SO 4 ) 2 (OH) 6 . The product is further ground and sealed for later use.
所述白色粉末产物KAl 3(SO 4) 2(OH) 6为具有多孔结构的羟基硫酸盐锂吸附材料。图5是实施例3制备获得的锂吸附材料的XRD图，从图5可获知，实施例3制备获得的锂吸附材料是羟基硫酸盐，其分子式为KAl 3(SO 4) 2(OH) 6。 The white powder product KAl 3 (SO 4 ) 2 (OH) 6 is a lithium hydroxysulfate adsorption material with a porous structure. Figure 5 is an XRD pattern of the lithium adsorbent material prepared in Example 3. It can be seen from Figure 5 that the lithium adsorbent material prepared in Example 3 is hydroxysulfate, and its molecular formula is KAl 3 (SO 4 ) 2 (OH) 6 .
利用海藻酸钙法造粒，将本实施例得到的锂吸附材料造粒后装入内径为2cm的定制吸附柱内，通过蠕动泵将1000mg/L的氯化锂溶液从吸附柱低端泵入，泵速45mL/h。待检测到有锂离子流出时，停止动态吸附实验。然后以2mL/min的流速泵入水溶液，至无锂离子流出为止。经过检测，本实施例中的锂吸附材料的吸附容量为8.36mg/g。The lithium adsorption material obtained in this example was granulated using the calcium alginate method and then put into a custom-made adsorption column with an inner diameter of 2 cm. A 1000 mg/L lithium chloride solution was pumped in from the lower end of the adsorption column through a peristaltic pump. , pump speed 45mL/h. When the outflow of lithium ions is detected, the dynamic adsorption experiment is stopped. Then pump the aqueous solution at a flow rate of 2mL/min until no lithium ions flow out. After testing, the adsorption capacity of the lithium adsorption material in this embodiment is 8.36 mg/g.
综上所述，本发明实施例提供的锂吸附材料，具体是具有多孔结构的羟基合成盐，其具有吸附容量高的有点，在吸附锂和脱附锂再生的过程中，不发生结构改变，因此该锂吸附材料结构强度高、溶损低，循环使用寿命长，特别适合应用于从盐湖卤水中的吸附提取锂离子。该锂吸附材料的合成过程中无需消耗额外的锂源，合成原料易得，具有制备条件温和、工艺流程简单易行、对设备成本要求低且无污染的优点，适用于大规模生产。To sum up, the lithium adsorbent material provided by the embodiments of the present invention, specifically a hydroxyl synthetic salt with a porous structure, has the advantage of high adsorption capacity. During the process of adsorbing lithium and desorbing lithium and regenerating it, no structural change occurs. Therefore, the lithium adsorption material has high structural strength, low dissolution loss and long cycle life, and is particularly suitable for adsorption and extraction of lithium ions from salt lake brine. There is no need to consume additional lithium sources during the synthesis process of this lithium adsorption material. The synthetic raw materials are easy to obtain. It has the advantages of mild preparation conditions, simple and easy process flow, low equipment cost requirements and no pollution, and is suitable for large-scale production.
以上结合附图详细描述了本发明的实施例的可选实施方式，但是，本发明的实施例并不限于上述实施方式中的具体细节，在本发明的实施例的技术构思范围内，可以对本发明的实施例的技术方案进行多种简单变型，这些简单变型均属于本发明的实施例的保护范围。The optional implementations of the embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the embodiments of the present invention are not limited to the specific details in the above-mentioned implementations. Within the scope of the technical concept of the embodiments of the present invention, the present invention can be modified. The technical solutions of the embodiments of the invention are subject to various simple modifications, and these simple modifications all belong to the protection scope of the embodiments of the invention.

Claims (10)

  1. 一种锂吸附材料，其特征在于，所述锂吸附材料为具有多孔结构的羟基合成盐，所述羟基合成盐的分子式为DG 3(TO 4) 2(OH) 6或DG 3(TO 4) 2(OH,H 2O) 6，其中，D代表配位数大于或等于9的阳离子，G代表形成八面体配位的元素，T代表形成四面体配位的元素。 A lithium adsorption material, characterized in that the lithium adsorption material is a hydroxyl synthetic salt with a porous structure, and the molecular formula of the hydroxyl synthetic salt is DG 3 (TO 4 ) 2 (OH) 6 or DG 3 (TO 4 ) 2 (OH,H 2 O) 6 , where D represents a cation with a coordination number greater than or equal to 9, G represents an element that forms an octahedral coordination, and T represents an element that forms a tetrahedral coordination.
  2. 根据权利要求1所述的锂吸附材料，其特征在于，所述合成盐为以下分子式的合成盐中的任意一种：KAl 3(SO 4) 2(OH) 6、NaAl 3(SO 4) 2(OH) 6、(NH) 4Al 3(SO 4) 2(OH) 6、(H 3O,Ca)Al 3(SO 4) 2(OH) 6、Pb(Al,Cu) 3(SO 4) 2(OH,H 2O) 6、(Na,Ca) 2Al 6(SO 4) 4(OH,H 2O) 12、CaAl 6(SO 4) 4(OH) 12、Pb(Fe,Cu) 3(SO 4) 2(OH) 6、BaAl 6(SO 4) 4(OH) 12、KFe 3(SO 4) 2(OH) 6、NaFe 3(SO 4) 2(OH) 6、(NH) 4Fe 3(SO 4) 2(OH) 6、(H 3O)Fe 3(SO 4) 2(OH) 6、AgFe 3(SO 4) 2(OH) 6、TiFe 3(SO 4) 2(OH) 6、PbFe 6(SO 4) 4(OH) 12、SrFe 3(PO 4) 2(OH,H 2O) 6、PbFe 3(PO 4) 2(OH,H 2O) 6、PbFe 3[(PO 4SO 4)] 2(OH,H 2O) 6、BiFe 3(PO 4) 2(OH) 6、BaFe 3(AsO 4) 2(OH,H 2O) 6、PbFe 3[(AsO 4SO 4)] 2(OH,H 2O) 6、CaAl 3(PO 4) 2(OH,H 2O) 6、CaAl 3[(PO 4SO 4)] 2(OH,H 2O) 6、SrAl 3(PO 4) 2(OH,H 2O) 6、SrAl 3[(PO 4SO 4)] 2(OH,H 2O) 6、BaAl 3(PO 4) 2(OH,H 2O) 6、PbAl 3(PO 4) 2(OH,H 2O) 6、PbAl 3[(PO 4SO 4)] 2(OH,H 2O) 6、CeAl 3(PO 4) 2(OH) 6、(Bi,Ca)Al 3(PO 4SiO 4) 2(OH) 6、LaAl 3(PO 4) 2(OH) 6、NdAl 3(PO 4) 2(OH) 6、(Th,Pb)Al 3(PO 4SiO 4) 2(OH,H 2O) 6、CaAl 3(AsO 4) 2(OH,H 2O) 6、PbAl 3[(AsO 4SO 4)] 2(OH,H 2O) 6、SrAl 3(AsO 4) 2(OH,H 2O) 6、(Sr,Ce)Al 3[(AsO 4SO 4)] 2(OH,H 2O) 6、CeAl 3(AsO 4) 2(OH) 6、BaAl 3(AsO 4) 2(OH,H 2O) 6、PbAl 3(AsO 4) 2(OH,H 2O) 6、PbGa 3[(AsO 4SO 4)] 2(OH,H 2O) 6、BaV 3(PO 4) 2(OH,H 2O) 6。 The lithium adsorbent material according to claim 1, characterized in that the synthetic salt is any one of the synthetic salts of the following molecular formula: KAl 3 (SO 4 ) 2 (OH) 6 , NaAl 3 (SO 4 ) 2 (OH) 6 , (NH) 4 Al 3 (SO 4 ) 2 (OH) 6 , (H 3 O,Ca)Al 3 (SO 4 ) 2 (OH) 6 , Pb(Al,Cu) 3 (SO 4 ) 2 (OH,H 2 O) 6 , (Na,Ca) 2 Al 6 (SO 4 ) 4 (OH,H 2 O) 12 , CaAl 6 (SO 4 ) 4 (OH) 12 , Pb(Fe,Cu ) 3 (SO 4 ) 2 (OH) 6 , BaAl 6 (SO 4 ) 4 (OH) 12 , KFe 3 (SO 4 ) 2 (OH) 6 , NaFe 3 (SO 4 ) 2 (OH) 6 , (NH ) 4 Fe 3 (SO 4 ) 2 (OH) 6 , (H 3 O)Fe 3 (SO 4 ) 2 (OH) 6 , AgFe 3 (SO 4 ) 2 (OH) 6 , TiFe 3 (SO 4 ) 2 (OH) 6 , PbFe 6 (SO 4 ) 4 (OH) 12 , SrFe 3 (PO 4 ) 2 (OH,H 2 O) 6 , PbFe 3 (PO 4 ) 2 (OH,H 2 O) 6 , PbFe 3 [(PO 4 SO 4 )] 2 (OH,H 2 O) 6 , BiFe 3 (PO 4 ) 2 (OH) 6 , BaFe 3 (AsO 4 ) 2 (OH,H 2 O) 6 , PbFe 3 [ (AsO 4 SO 4 )] 2 (OH,H 2 O) 6 , CaAl 3 (PO 4 ) 2 (OH,H 2 O) 6 , CaAl 3 [(PO 4 SO 4 )] 2 (OH,H 2 O ) 6 , SrAl 3 (PO 4 ) 2 (OH,H 2 O) 6 , SrAl 3 [(PO 4 SO 4 )] 2 (OH,H 2 O) 6 , BaAl 3 (PO 4 ) 2 (OH,H 2 O) 6 , PbAl 3 (PO 4 ) 2 (OH,H 2 O) 6 , PbAl 3 [(PO 4 SO 4 )] 2 (OH,H 2 O) 6 , CeAl 3 (PO 4 ) 2 (OH ) 6 , (Bi,Ca)Al 3 (PO 4 SiO 4 ) 2 (OH) 6 , LaAl 3 (PO 4 ) 2 (OH) 6 , NdAl 3 (PO 4 ) 2 (OH) 6 , (Th,Pb )Al 3 (PO 4 SiO 4 ) 2 (OH,H 2 O) 6 , CaAl 3 (AsO 4 ) 2 (OH,H 2 O) 6 , PbAl 3 [(AsO 4 SO 4 )] 2 (OH,H 2 O) 6 , SrAl 3 (AsO 4 ) 2 (OH,H 2 O) 6 , (Sr,Ce)Al 3 [(AsO 4 SO 4 )] 2 (OH,H 2 O) 6 , CeAl 3 (AsO 4 ) 2 (OH) 6 , BaAl 3 (AsO 4 ) 2 (OH,H 2 O) 6 , PbAl 3 (AsO 4 ) 2 (OH,H 2 O) 6 , PbGa 3 [(AsO 4 SO 4 )] 2 (OH,H 2 O) 6 , BaV 3 (PO 4 ) 2 (OH,H 2 O) 6 .
  3. 根据权利要求1或2所述的锂吸附材料的制备方法，其特征在于，包括：The preparation method of lithium adsorbent material according to claim 1 or 2, characterized in that it includes:
    配制混合无机盐溶液，所述混合无机盐溶液中包含有阳离子D、G元素对应的阳离子以及含有T元素的酸根离子；Preparing a mixed inorganic salt solution, the mixed inorganic salt solution contains cations corresponding to the cations D and G elements and acid ions containing the T element;
    向所述混合无机盐溶液加入致孔剂，混合获得反应液；所述致孔剂包括表面活性剂以及尿素和/或硫脲；Add a porogen to the mixed inorganic salt solution and mix to obtain a reaction liquid; the porogen includes surfactant and urea and/or thiourea;
    将所述反应液置于反应釜中进行水热反应，反应结束过滤获得固态的第一中间产物；The reaction solution is placed in a reaction kettle to perform a hydrothermal reaction, and after the reaction is completed, it is filtered to obtain a solid first intermediate product;
    对所述第一中间产物洗涤处理以洗脱所述致孔剂，获得第二中间产物；Washing the first intermediate product to elute the porogen to obtain a second intermediate product;
    将所述第二中间产物进行干燥处理，获得所述具有多孔结构的羟基合成盐。The second intermediate product is dried to obtain the hydroxyl synthetic salt with a porous structure.
  4. 根据权利要求3所述的锂吸附材料的制备方法，其特征在于，所述含有T元素的酸根离子选自SO 4 2-、SiO 4 4-、PO 4 3-和AsO 4 3-中的一种或两种以上。 The preparation method of lithium adsorbent material according to claim 3, characterized in that the acid ion containing T element is selected from one of SO 4 2- , SiO 4 4- , PO 4 3- and AsO 4 3- One or more species.
  5. 根据权利要求3所述的锂吸附材料的制备方法，其特征在于，所述表面活性剂选自阴离子表面活性剂、阳离子表面活性剂、两性离子表面活性剂和非离子表面活性剂中的一种或两种以上；其中，The method for preparing lithium adsorbent materials according to claim 3, wherein the surfactant is selected from one of anionic surfactants, cationic surfactants, zwitterionic surfactants and nonionic surfactants. or two or more; among them,
    所述阴离子表面活性剂为硬脂酸或十二烷基苯磺酸钠；The anionic surfactant is stearic acid or sodium dodecylbenzene sulfonate;
    所述阳离子表面活性剂为季铵化物；The cationic surfactant is a quaternary ammonium compound;
    所述两性离子表面活性剂卵磷脂或氨基酸型活性剂或甜菜碱型活性剂；The zwitterionic surfactant lecithin or amino acid type active agent or betaine type active agent;
    所述非离子表面活性剂为烷基葡糖苷、脂肪酸甘油酯、脂肪酸山梨坦或聚山梨酯。The nonionic surfactant is alkyl glucoside, fatty acid glyceride, fatty acid sorbitan or polysorbate.
  6. 根据权利要求3所述的锂吸附材料的制备方法，其特征在于，所述水热反应的温度为70℃～180℃，反应时间为3h～12h。The method for preparing a lithium adsorbent material according to claim 3, characterized in that the temperature of the hydrothermal reaction is 70°C to 180°C, and the reaction time is 3h to 12h.
  7. 根据权利要求3所述的锂吸附材料的制备方法，其特征在于，所述洗涤处理是使用去离子水对所述第一中间产物进行多次洗涤至中性。The method for preparing a lithium adsorbent material according to claim 3, wherein the washing treatment is to use deionized water to wash the first intermediate product multiple times until neutral.
  8. 根据权利要求3所述的锂吸附材料的制备方法，其特征在于，所述干燥处理是在50℃～80℃的温度下进行恒温干燥。The method for preparing a lithium adsorbent material according to claim 3, wherein the drying process is constant temperature drying at a temperature of 50°C to 80°C.
  9. 根据权利要求3-8任一项所述的锂吸附材料的制备方法，其特征在于，所述羟基合成盐为羟基硫酸盐，所述混合无机盐溶液是将可溶性的第一化合物和第二化合物溶解于水中获得，所述第一化合物能够在水中电离出阳离子D，所述第二化合物能够在水中电离出G元素对应的阳离子，所述第一化合物和所述第二化合物的至少其中之一能够在水中电离出硫酸根离子；所述致孔剂包括尿素和表面活性剂。The method for preparing a lithium adsorbent material according to any one of claims 3 to 8, wherein the hydroxyl synthetic salt is a hydroxysulfate, and the mixed inorganic salt solution is a mixture of a soluble first compound and a second compound. Obtained by dissolving in water, the first compound can ionize into cation D in water, the second compound can ionize into cation corresponding to G element in water, at least one of the first compound and the second compound Able to ionize sulfate ions in water; the porogen includes urea and surfactants.
  10. 一种如权利要求1或2所述的锂吸附材料应用，其特征在于，将所述锂吸附材料造粒后应用于从含锂离子的溶液中吸附提取锂离子。An application of lithium adsorbent material as claimed in claim 1 or 2, characterized in that the lithium adsorbent material is granulated and used to adsorb and extract lithium ions from a solution containing lithium ions.
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