WO2016184055A1 - 从卤水中提取镁、锂同时生产水滑石的工艺方法 - Google Patents

从卤水中提取镁、锂同时生产水滑石的工艺方法 Download PDF

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WO2016184055A1
WO2016184055A1 PCT/CN2015/094534 CN2015094534W WO2016184055A1 WO 2016184055 A1 WO2016184055 A1 WO 2016184055A1 CN 2015094534 W CN2015094534 W CN 2015094534W WO 2016184055 A1 WO2016184055 A1 WO 2016184055A1
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lithium
brine
hydrotalcite
aluminum
magnesium
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项顼
王瑞瑞
段雪
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/78—Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements
    • C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
    • C01F7/785—Hydrotalcite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/58—Multistep processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/78—Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements
    • C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators or shrinkage compensating agents
    • C04B22/06—Oxides, Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/26—Bituminous materials, e.g. tar, pitch
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM

Definitions

  • the invention relates to a process for extracting magnesium and lithium from brine by a reaction-separation coupling technique and simultaneously producing hydrotalcite.
  • Salt lakes usually refer to lakes with a salt content of more than 50g ⁇ L -1 .
  • China has abundant salt lake resources.
  • the Inner Mongolia area is dominated by carbonate-type salt lakes
  • the Xinjiang area is dominated by sulfate-type salt lakes
  • the Qinghai Qaidam Basin is dominated by sulfate subtypes and chloride-type salt lakes.
  • carbonate-type and sulphate-type salt lakes are the main types.
  • There are many important resources in the salt lake such as potassium, sodium, magnesium, lithium, boron, etc., which are important raw materials for the production of various industrial and agricultural products.
  • the direct development of salt lake mainly refers to the direct extraction and preliminary processing of various natural resources such as potassium, magnesium, lithium and sodium, so as to form chemical basic raw materials.
  • various natural resources such as potassium, magnesium, lithium and sodium
  • the development of potassium resources has been industrialized, providing an important source of potash in China and achieving significant economic benefits.
  • Lithium in brine often coexists with a large amount of alkali metal and alkaline earth metal ions in a trace form. Because of their similar chemical properties, it is very difficult to separate and extract lithium from it, especially the presence of high content of magnesium makes lithium separation more difficult. It is the bottleneck of lithium extraction from brine (Fu Wei, Zhong Hui.
  • the process of separating and extracting lithium is to first separate the sodium and potassium resources to obtain a magnesium/lithium mixed brine, and then separate it. Since the salt lakes in China are mainly high-magnesium/lithium ratio salt lakes, it is very difficult to separate and extract magnesium and lithium by such a process.
  • the main methods for extracting lithium from brine are: precipitation method, extraction method, adsorption method, calcination method, carbonization method, salting out method, etc. (Huang Hao.
  • the carbonization method is easy to extract lithium at a large scale, which has the advantages of continuous, low production cost and good product quality, but the carbon dioxide gas source restricts the development of this method (Wang Baocai. China's brine lithium resources and development technology [J]. Northern Engineering Minerals and Processing, 2000, 10: 13-15.).
  • the selective semi-permeable membrane method mainly utilizes a monovalent selective ion exchange membrane to circulate and concentrate lithium to obtain a lithium-rich low-magnesium brine, and then adds a soda ash precipitate to prepare a lithium carbonate product, and the single extraction rate of lithium can reach 80%.
  • this method is highly dependent on the membrane material, and the related materials are monopolized by foreign manufacturers.
  • Precipitation method is a simple extraction method with low cost.
  • most of the salt lakes in China are high magnesium/lithium ratio salt lakes, and this method is mainly suitable for extracting lithium from salt lake brine with low magnesium/lithium ratio, and a large amount of magnesium salt.
  • the existence of lithium will seriously affect the extraction of lithium, increase the difficulty of lithium extraction, and ultimately affect the development of the salt lake lithium industry.
  • the lithium resources extracted by this method are mainly extracted in the form of lithium carbonate, which lacks a high value-added lithium functional material product. All of the above methods can only extract lithium from the brine, and the remaining magnesium after the lithium extraction has not developed into a high-performance magnesium-based functional material, so that the magnesium resources are not fully utilized after being separated, and the utilization rate of the magnesium resources is low.
  • Magnesium-aluminum hydrotalcite and lithium aluminum hydrotalcite are double-layered hydroxides with a layered structure. Metal elements are alternately arranged on the laminate, and anions can be inserted between the layers to form a large class. Important layered functional materials are widely used in catalysis, adsorption (anion adsorption in solution, carbon dioxide adsorption), functional additives (flame retardants, UV barriers, heat stabilizers, etc.), medicine, etc. (two-dimensional nanometer Composite hydroxide: structure, assembly and function, Duan Xue et al., Beijing: Science Press, 2013).
  • an object of the present invention is to provide a process for simultaneously extracting magnesium and lithium from brine to produce hydrotalcite.
  • the present invention provides a process for simultaneously extracting magnesium and lithium from brine to produce hydrotalcite, and the method comprises the following specific steps:
  • the filtrate is concentrated by evaporation to obtain a lithium-rich brine, and then an aluminum salt is added to prepare a mixed salt solution B for preparing lithium aluminum hydrotalcite, which is added to the alkali solution for precipitation reaction, and the solid-liquid separation is completed after the reaction.
  • step b The filtrate obtained in step b is concentrated by evaporation, and the solution obtained by evaporation and concentration is returned to the lithium-rich brine of step b for recycling.
  • the brine described in step a is a sulfate-type salt lake brine, which is rich in Li + , Mg 2+ , K + .
  • the brine described in step a needs to be filtered out of insoluble impurities before use.
  • the total concentration of the metal ions is 0.9. -1.5 mol/L.
  • the molar ratio of magnesium salt to aluminum salt is 2-4:1.
  • the alkali solution described in the step a is a mixed solution of sodium hydroxide and sodium carbonate, and the volume thereof is mixed with the salt solution A.
  • the volume is the same, and the number of moles of sodium hydroxide is 1.5-2.5 times the sum of the moles of magnesium and aluminum, and the molar ratio of sodium carbonate to aluminum is 1.5-2.5:1.
  • the coprecipitation reaction described in step a is carried out according to the following steps: the preparation of the magnesium-aluminum hydrotalcite
  • the mixed salt solution A is mixed with an alkali solution and rotated at a rotation speed of 1000-5000 rpm for 1-10 minutes to obtain a MgAl-LDH crystal nucleus.
  • the mixing operation of the mixed salt solution A and the alkali solution used for preparing the magnesium aluminum hydrotalcite in the step a is a routine operation in the art.
  • the mixing process can be carried out in any reactor suitable for mixing in the art, but the mixing process needs to be carried out under high speed agitation. In a preferred embodiment of the invention, the above mixing process is carried out in a colloid mill.
  • the crystallization reaction described in step a is carried out according to the following steps: coprecipitation reaction in step a to obtain MgAl-LDH
  • the crystal nucleus is stirred at 60-90 ° C for 6-24 h, and after completion of the reaction, the solid-liquid separation is carried out to obtain a MgAl-LDH filter cake.
  • a method for simultaneously extracting magnesium and lithium from brine to produce hydrotalcite preferably, step After obtaining the MgAl-LDH filter cake in step a, the filter cake is dried to obtain a MgAl-LDH solid product; the drying is dried at 60-80 ° C for 6-12 h.
  • the concentration of lithium ions in the lithium-rich brine described in step b is 0.1-0.5 g/L.
  • the molar ratio of lithium element to aluminum element is 1-6:1.
  • the pH of the alkali solution in step b is 9-12, and the alkali solution includes an aqueous solution of sodium hydroxide or potassium hydroxide. Aqueous solution.
  • the volume of the alkali solution in step b is the same as the volume of the mixed salt solution B used for preparing lithium aluminum hydrotalcite, and
  • the number of moles of sodium hydroxide or potassium hydroxide is 1-1.6 times the sum of the moles of lithium and aluminum.
  • the coprecipitation reaction described in step b is carried out according to the following steps: a mixed salt for preparing lithium aluminum hydrotalcite
  • the solution B is added dropwise to the alkali solution to carry out a coprecipitation reaction, and after the reaction is completed, the solid liquid is separated to obtain a LiAl-LDH filter cake;
  • the dropping speed is 1-5 mL/min
  • the pH of the coprecipitation reaction is 9-12, the reaction temperature is 10-25 ° C, and the reaction time is 8-24 h.
  • the filter cake is dried to obtain a LiAl-LDH solid product;
  • the drying is carried out at 60-80 ° C for 6-12 h.
  • the aluminum salt described in the step a is one of aluminum nitrate, aluminum sulfate, and aluminum chloride.
  • the aluminum salt described in step b is one of aluminum nitrate, aluminum sulfate, and aluminum chloride.
  • the evaporation concentration described in step c is to evaporate and concentrate the filtrate obtained in step b to a concentration of lithium ions of 0.1-0.5. g/L.
  • the object of the present invention is to provide a process for simultaneously extracting magnesium and lithium from brine to produce hydrotalcite.
  • the specific steps are as follows:
  • the filtrate is concentrated by evaporation to obtain a lithium-rich brine, and then an aluminum salt is added to prepare a mixed salt solution B corresponding to lithium aluminum hydrotalcite, which is added to the sodium hydroxide lye to carry out a precipitation reaction, and solid-liquid separation is carried out to obtain LiAl. - LDH solid product and filtrate;
  • step B The filtrate of step B is concentrated by evaporation and returned to the lithium-rich brine for recycling.
  • the brine is filtered to remove insoluble impurities before use.
  • the corresponding mixed salt solution A of the magnesium-aluminum hydrotalcite prepared in the step A wherein the total concentration of the metal ions is 0.9- 1.5 mol / L, the molar ratio of magnesium salt to aluminum salt is 2-4:1; the lye is a mixed solution of sodium hydroxide and sodium carbonate, the volume is the same as the volume of the mixed salt solution A, and the hydroxide
  • the sodium molar concentration is 1.6 times the sum of the molar concentrations of magnesium and aluminum, and the molar concentration of sodium carbonate is twice the molar concentration of aluminum.
  • the coprecipitation reaction described in step A is to simultaneously pour the salt solution and the alkali solution into the colloid mill at 1000-5000 rpm.
  • the lithium-rich brine described in step B is obtained by evaporating and concentrating the filtrate obtained in step A to a lithium ion concentration of 0.1-0.5 g. /L.
  • a method for simultaneously extracting magnesium and lithium from brine to produce hydrotalcite preferably, step
  • the molar concentration of lithium element in the mixed salt solution B described in step B is 1-6 times the molar concentration of the aluminum element; the volume of the sodium hydroxide solution is the same as that of the mixed salt solution B, and the molar concentration of sodium hydroxide is lithium. It is 1-1.6 times the sum of the molar concentrations of aluminum.
  • the coprecipitation reaction described in step B is to add mixed salt solution B to hydrogen at a rate of 1-5 mL/min.
  • the aluminum salt described in steps A and B is one of aluminum nitrate, aluminum sulfate, and aluminum chloride.
  • the object of the present invention is to provide a process for producing MgAl-LDH and LiAl-LDH by using a reaction-separation coupling technique for separating Mg and Li elements in a salt lake brine.
  • FIG. 1 A process for separating Mg and Li elements in brine by simultaneous reaction-separation coupling technology, and simultaneously producing MgAl-LDH and LiAl-LDH, the process flow is shown in FIG. 1; the specific steps are as follows:
  • the filtrate is concentrated by evaporation to obtain a lithium-rich brine, and then an aluminum salt is added to prepare a mixed salt solution B corresponding to lithium aluminum hydrotalcite, which is added to the sodium hydroxide lye to carry out a precipitation reaction, and solid-liquid separation is carried out to obtain LiAl. - LDH solid product and filtrate;
  • step B The filtrate of step B is concentrated by evaporation and returned to the lithium-rich brine for recycling.
  • Step A according to the preparation of magnesium-aluminum hydrotalcite corresponding mixed salt solution A, wherein the total concentration of metal ions is 0.9-1.5mol / L, the molar ratio of magnesium salt to aluminum salt is 2-4:1;
  • the lye is a mixed solution of sodium hydroxide and sodium carbonate, the volume of which is the same as the volume of the mixed salt solution A, and the molar concentration of sodium hydroxide is 1.6 times the sum of the molar concentrations of magnesium and aluminum, and the molar concentration of sodium carbonate is Aluminum element 2 times the molar concentration;
  • the lithium-rich brine described in the step B is obtained by evaporating and concentrating the filtrate obtained in the step A to a lithium ion concentration of 0.1-0.5 g/L; the molar concentration of the lithium element in the mixed salt solution B is 1-1 of the molar concentration of the aluminum element. 6 times; the volume of the sodium hydroxide solution is the same as that of the mixed salt solution B, and the molar concentration of sodium hydroxide is 1-1.6 times the sum of the molar concentrations of lithium and aluminum;
  • the aluminum salt described in the steps A and B is one of aluminum nitrate, aluminum sulfate, and aluminum chloride.
  • the invention utilizes the reaction-separation coupling technology to realize the production of functional materials of magnesium aluminum hydrotalcite and lithium aluminum hydrotalcite while separating the magnesium and lithium resources in the salt lake brine; the method can not only realize the resource separation of the salt lake, but also High value-added functional materials can be obtained, and the method of the present invention opens an important way for the efficient use of salt lake resources.
  • magnesium in the brine is first separated by forming magnesium aluminum hydrotalcite, which solves the problem of separating magnesium and lithium from a high magnesium/lithium ratio solution in the conventional process, thereby making lithium The loss rate is significantly reduced.
  • the present invention extracts lithium by means of lithium aluminum hydrotalcite.
  • the method has mild reaction, simple equipment and small lithium loss. Therefore, the method provided by the invention is suitable for large-scale and high-efficiency utilization of lithium salt resources of salt lake brine.
  • 1 is a flow chart of a process for extracting magnesium and lithium from brine while producing hydrotalcite according to the present invention
  • Example 2 is an X-ray diffraction spectrum of a MgAl-LDH product prepared in Example 1 of the present invention
  • Example 3 is a transmission electron microscope topography of the MgAl-LDH product prepared in Example 1 of the present invention.
  • Example 5 is a scanning electron microscope topography of a LiAl-LDH product prepared in Example 1 of the present invention.
  • the brine used in the examples of the present invention was taken from the Xitai Guiner Salt Lake, which is a sulfate type brine, and the composition of the brine is shown in Table 1.
  • the flow chart of the process for extracting magnesium and lithium from brine by simultaneously producing hydrotalcite is shown in FIG. 1 .
  • the embodiment provides a process for simultaneously extracting magnesium and lithium from brine to produce hydrotalcite, wherein the method comprises the following steps:
  • a weigh MgCl 2 ⁇ 6H 2 O 26.0325g, MgSO 4 ⁇ 7H 2 O 25.7993g, AlCl 3 ⁇ 6H 2 O 18.7290g, KCl 3.3873g, LiCl 1.8768g, NaCl 8.068g, and dissolve the above substances In ionic water, further volume in a 250mL volumetric flask to obtain a mixed salt solution A; weigh 19.5933g of NaOH, 16.433g of NaCO 3 dissolved in deionized water, and then fixed to volume in a 250mL volumetric flask to obtain an alkali solution;
  • the mixed salt solution A and the alkali solution were simultaneously poured into a colloid mill, and rotated at 3000 r/min for 3 minutes to form a MgAl-LDH crystal nucleus; the nucleation solution was transferred to a reactor and dynamically stirred at 80 ° C for 12 hours. , MgAl-LDH growth; filtration, to obtain MgAl-LDH filter cake, and then drying the MgAl-LDH filter cake at 70 ° C for 12 h to obtain a white solid MgAl-LDH product; collecting the filtrate to a container, the molecular formula of the MgAl-LDH is [Mg 0.75 Al 0.25 (OH) 2 ](CO 3 2- ) 0.125 ⁇ 5H 2 O;
  • the MgAl-LDH product prepared in Example 1 was subjected to X-ray diffraction analysis and transmission electron microscopy analysis.
  • the X-ray diffraction spectrum is shown in Fig. 2, and the transmission electron microscope topography is shown in Fig. 3.
  • the LiAl-LDH products prepared in Example 1 were analyzed by X-ray diffraction analysis and scanning electron microscopy.
  • the X-ray diffraction analysis spectrum is shown in Fig. 4, and the scanning electron microscope topography is shown in Fig. 5.
  • the mixed salt solution A and the alkali solution were simultaneously poured into a colloid mill, and rotated at 4000 r/min for 5 minutes to form a MgAl-LDH crystal nucleus; the nucleation solution was transferred to a reactor and dynamically stirred at 80 ° C for 12 hours. , MgAl-LDH growth; filtration, to obtain MgAl-LDH filter cake, and then drying the MgAl-LDH filter cake at 80 ° C for 6 h to obtain a white solid MgAl-LDH product; collecting the filtrate to a container, the molecular formula of the MgAl-LDH is [Mg 0.8 Al 0.2 (OH) 2 ](CO 3 2- ) 0.1 ⁇ 6H 2 O;
  • LiAl-LDH solid LiAl-LDH product
  • the molecular formula of LiAl-LDH is [LiAl 2 (OH) 6 ] 2 CO 3 ⁇ 3H 2 O;
  • the mixed salt solution A and the alkali solution were simultaneously poured into a colloid mill, and rotated at 2000 r/min for 6 minutes to form a MgAl-LDH crystal nucleus; the nucleation solution was transferred to a reactor and dynamically stirred at 70 ° C for 10 hours.
  • MgAl-LDH growth was carried out; filtration was carried out to obtain a MgAl-LDH filter cake, and the MgAl-LDH filter cake was dried at 80 ° C for 8 hours to obtain a white solid MgAl-LDH product; the filtrate was collected into a container, and the molecular formula of the MgAl-LDH was [ Mg 0.744 Al 0.256 (OH) 2 ](CO 3 2- ) 0.128 ⁇ 4H 2 O;
  • the mixed salt solution A and the alkali solution were simultaneously poured into a colloid mill, and rotated at 3000 r/min for 3 minutes to form a MgAl-LDH crystal nucleus; the formed nucleation solution was transferred to a reactor and dynamically stirred at 80 ° C for 24 hours.
  • MgAl-LDH growth MgAl-LDH growth; filtration, to obtain MgAl-LDH filter cake, and then drying the MgAl-LDH filter cake at 70 ° C for 10 h to obtain a white solid MgAl-LDH product; collecting the filtrate to a container, the molecular formula of the MgAl-LDH is [Mg 0.8 Al 0.2 (OH) 2 ](CO 3 2- ) 0.1 ⁇ 7H 2 O;

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Abstract

本发明涉及一种从卤水中提取镁、锂同时生产水滑石的工艺方法。该方法包括以下具体步骤：向卤水中加入铝盐，配成制备镁铝水滑石所用的混合盐溶液A，加入碱液进行共沉淀反应，然后进行晶化反应，反应结束后固液分离，得到MgAl-LDH固体产物和滤液；将滤液进行蒸发浓缩得到富锂卤水，再加入铝盐，配成制备锂铝水滑石所用的混合盐溶液B，将其加入碱液中进行沉淀反应，反应结束后固液分离，得到LiAl-LDH固体产物和滤液；将滤液蒸发浓缩，将蒸发浓缩后得到的溶液返回到富锂卤水中进行循环利用。本发明的方法反应温和，设备简单，锂损失量小，不仅可以实现盐湖的资源分离，还可以获得高附加值的功能材料。

Description

从卤水中提取镁、锂同时生产水滑石的工艺方法 技术领域
本发明涉及一种利用反应-分离耦合技术从卤水中提取镁、锂同时生产水滑石的工艺方法。
背景技术
盐湖通常是指湖水含盐量大于50g·L-1的湖泊。我国具有丰富的盐湖资源，其中，内蒙地区以碳酸盐型盐湖为主，新疆地区以硫酸盐型盐湖为主，青海柴达木盆地则以硫酸盐亚型、氯化物型盐湖为主，而西藏地区则以碳酸盐型、硫酸盐型盐湖为主。盐湖中蕴藏有许多重要资源，例如：钾、钠、镁、锂、硼等，其是生产多种工业、农业产品的重要原料。
盐湖直接开发主要是指对钾、镁、锂、钠等各种自然资源的直接提取和初步加工，使其形成化工基础原料。目前在这些资源的开发中，钾资源的开发已形成产业化，提供了我国钾肥的重要来源，取得了显著的经济效益。卤水中的锂常以微量形式与大量的碱金属、碱土金属离子共存，由于它们的化学性质非常相近，使得从中分离提取锂十分困难，尤其是高含量镁的存在，使分离锂更为困难，是卤水提锂的瓶颈(付烨,钟辉.沉淀法分离高镁锂比盐湖卤水的研究现状[J].矿产综合利用,2010,2:30-32.)。目前分离提取锂的工艺是先分离钠、钾资源，得到镁/锂混合卤水，然后再对其进行分离。由于我国盐湖主要为高镁/锂比类型的盐湖，采用这类工艺分离、提取镁、锂难度很大。目前从卤水提锂的主要方法有：沉淀法、萃取法、吸附法、煅烧法、碳化法、盐析法等(黄浩.青海西台吉乃尔盐湖酸化老卤镁锂分离的技术研究[D].成都:成都理工大学,2009)。其中，离子交换吸附法提取锂的收率可达90％，但是对高选择性吸附剂的要求较高，目前的吸附剂制备方法复杂，交换速率低，不适用于大规模操作使用，且吸附法等方法的工艺条件苛刻，对设备要求条件高。萃取法的工艺条件苛刻，对萃取设备和萃取剂的要求较高，单次萃取回收率较低，低于50％，且方法流程复杂、设备腐蚀严重、成本高，尚不能规模化生产。盐析法设备腐蚀和固体夹带很严重，且以上方法仅在实验室取得了一定效果，未能很好地实现工业化。煅烧法虽然已工业化，但该方法存在能耗高，煅烧不完全，设备腐蚀严重，水蒸发量大且不适合高镁/锂比 卤水等问题(杨建元,夏康明.一种生产高纯镁盐、碳酸锂、盐酸和氯化铵的方法[P].中国专利：CN 1724373，2006)；段烧法的锂回收率通常在80％左右。碳化法易于规模化提取锂，具有连续化、生产成本低、产品质量好等优点，但产生的二氧化碳气源制约了这种方法的发展(王宝才.我国卤水锂资源及开发技术进展[J].北工矿物与加工,2000,10:13-15.)。选择性半透膜法主要是利用一价选择性离子交换膜对锂进行循环浓缩以获得富锂低镁卤水，再加入纯碱沉淀并制取碳酸锂产品，锂的单次提取率可达80％，但是该方法对膜材料的依赖性很强，并且相关材料被国外厂家垄断。沉淀法是一种工艺简单、成本较低的提取方法，但我国盐湖大多是高镁/锂比型盐湖，而此法主要适宜于从低镁/锂比的盐湖卤水中提锂，大量镁盐的存在会严重影响锂的提取，增大提锂的难度，最终影响盐湖锂产业发展进程。而且通过这种方法提取的锂资源主要是以碳酸锂的形式提取得到，其缺乏高附加值锂功能材料产品。以上所有方法都只能从卤水中提取锂，而提锂后剩余的镁并未发展为高性能镁基功能材料，使得镁资源分离出来后未得到充分利用，对镁资源的利用率较低。
镁铝水滑石和锂铝水滑石(MgAl-LDH和LiAl-LDH)是具有层状结构的双金属氢氧化物，金属元素在层板上交替排布，层间可以插入阴离子，形成一大类重要的层状功能材料，在催化、吸附(溶液中阴离子吸附、二氧化碳吸附)、功能助剂(阻燃剂、紫外阻隔剂、热稳定剂等)、医药等领域均有广泛应用(二维纳米复合氢氧化物：结构、组装与功能，段雪等编著，北京：科学出版社，2013年)。
发明内容
为解决上述技术问题，本发明的目的在于提供一种从卤水中提取镁、锂同时生产水滑石的工艺方法。
为实现上述目的，本发明提供了一种从卤水中提取镁、锂同时生产水滑石的工艺方法，该方法包括以下具体步骤：
a、向卤水中加入铝盐，配成制备镁铝水滑石所用的混合盐溶液A，加入碱液进行共沉淀反应，然后进行晶化反应，反应结束后固液分离，得到MgAl-LDH固体产物和滤液；
b、将所述滤液进行蒸发浓缩得到富锂卤水，再加入铝盐，配成制备锂铝水滑石所用的混合盐溶液B，将其加入碱液中进行沉淀反应，反应结束后固液分离，得到LiAl-LDH固体产物和滤液；
c、将步骤b得到的滤液蒸发浓缩，将蒸发浓缩后得到的溶液返回到步骤b的富锂卤水中进行循环利用。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤a中所述的卤水为硫酸盐型盐湖卤水，其中富含Li+、Mg2+、K+及Na+，各离子浓度为[Li+]＝1-3g/L，[Mg2+]＝10-30g/L，[K+]＝5-7g/L，[Na+]＝70-90g/L。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤a中所述的卤水在使用前需要先将不溶性的杂质滤除。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，在步骤a所述的制备镁铝水滑石所用的混合盐溶液A中，金属离子的总浓度为0.9-1.5mol/L。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，在步骤a所述的制备镁铝水滑石所用的混合盐溶液A中，镁盐与铝盐的摩尔比为2-4:1。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤a中所述的碱液是氢氧化钠与碳酸钠的混合溶液，其体积与混合盐溶液A的体积相同，且氢氧化钠的摩尔数是镁和铝元素摩尔数之和的1.5-2.5倍，碳酸钠与铝元素的摩尔比为1.5-2.5:1。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤a中所述的共沉淀反应是按照以下步骤进行的：将所述制备镁铝水滑石所用的混合盐溶液A与碱液混合，以1000-5000转/min的转速旋转1-10分钟，得到MgAl-LDH晶核。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，步骤a中所述制备镁铝水滑石所用的混合盐溶液A与碱液的混合操作为本领域的常规操作，该混合过程可以在本领域任何适用于混合的反应器中进行，但是该混合过程需要在高速搅拌的条件下进行，在本发明优选的实施方式中，上述混合过程是在胶体磨中进行的。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤a中所述的晶化反应是按照以下步骤进行的：将步骤a中共沉淀反应得到MgAl-LDH晶核在60-90℃下搅拌反应6-24h，反应结束后固液分离得到MgAl-LDH滤饼。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步 骤a中得到MgAl-LDH滤饼后，再对该滤饼进行干燥，得到MgAl-LDH固体产物；所述干燥为在60-80℃干燥6-12h。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤a中所述的MgAl-LDH固体产物的化学式为[Mg2+ 1-xAl3+ x(OH)2](CO3 2-)x/2·nH2O，式中，x＝0.2-0.4，n＝1-10。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤b所述的富锂卤水中锂离子的浓度为0.1-0.5g/L。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，在步骤b所述的制备锂铝水滑石所用的混合盐溶液B中，锂元素与铝元素的摩尔比为1-6:1。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤b所述碱液的pH值为9-12，该碱液包括氢氧化钠水溶液或氢氧化钾水溶液。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤b中所述碱液的体积与制备锂铝水滑石所用的混合盐溶液B的体积相同，且氢氧化钠或氢氧化钾的摩尔数是锂和铝元素摩尔数之和的1-1.6倍。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤b中所述的共沉淀反应是按照以下步骤进行的：将制备锂铝水滑石所用的混合盐溶液B滴加到碱液中，进行共沉淀反应，反应结束后固液分离，得到LiAl-LDH滤饼；
所述滴加的速度为1-5mL/min；
所述共沉淀反应的pH值为9-12，反应温度为10-25℃，反应时间为8-24h。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤b中得到LiAl-LDH滤饼后，再对该滤饼进行干燥，得到LiAl-LDH固体产物；所述干燥为在60-80℃干燥6-12h。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤b中所述的LiAl-LDH固体产物的化学式为[LiAl2(OH)6]2CO3·nH2O，式中，n＝1-10。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤a中所述的铝盐为硝酸铝、硫酸铝、氯化铝中的一种。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤b中所述的铝盐为硝酸铝、硫酸铝、氯化铝中的一种。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤c中所述的蒸发浓缩是将步骤b得到的滤液蒸发浓缩至锂离子的浓度为0.1-0.5g/L。
本发明的目的在于提供一种从卤水中提取镁、锂同时生产水滑石的工艺方法，具体步骤为：
A.向卤水中加入铝盐，配成制备镁铝水滑石相应的混合盐溶液A，与共沉淀用的碱液进行共沉淀反应，然后转入反应器继续晶化反应，反应结束后固液分离，得到MgAl-LDH固体产物和滤液；
B.将滤液进行蒸发浓缩得到富锂卤水，再加入铝盐，配成制备锂铝水滑石相应的混合盐溶液B，将其加入氢氧化钠碱液中进行沉淀反应，固液分离，得到LiAl-LDH固体产物和滤液；
C.将步骤B的滤液蒸发浓缩，返回到富锂卤水进行循环利用。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤A所述的卤水为硫酸盐型盐湖卤水，其中富含Li+、Mg2+、K+、Na+离子，各离子浓度为[Li+]＝1-3g/L，[Mg2+]＝10-30g/L，[K+]＝5-7g/L，[Na+]＝70-90g/L；卤水使用前先滤除不溶性杂质。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤A所述的制备镁铝水滑石相应的混合盐溶液A，其中金属离子的总浓度为0.9-1.5mol/L，镁盐与铝盐的摩尔浓度比为2-4：1；所述的碱液是氢氧化钠与碳酸钠的混合溶液，其体积与混合盐溶液A体积相同，且氢氧化钠摩尔浓度是镁和铝元素摩尔浓度之和的1.6倍，碳酸钠摩尔浓度是铝元素摩尔浓度的2倍。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤A所述的共沉淀反应是将盐溶液和碱溶液同时倒入胶体磨，以1000-5000转/min的转速旋转1-10分钟，形成MgAl-LDH晶核；将晶核溶液转移到反应器，在60-90℃下搅拌反应6-24h；过滤得到MgAl-LDH滤饼，在60-80℃干燥6-12h，得到白色固体MgAl-LDH产品，其化学式为[Mg2+ 1-xAl3+ x(OH)2](CO3 2-)x/2·nH2O，x＝0.2-0.33，n＝1-10。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤B所述的富锂卤水是将步骤A得到的滤液蒸发浓缩至锂离子浓度为0.1-0.5g/L。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步 骤B所述的混合盐溶液B中锂元素的摩尔浓度是铝元素摩尔浓度的1-6倍；所述的氢氧化钠溶液的体积与混合盐溶液B相同，且氢氧化钠摩尔浓度是锂和铝元素摩尔浓度之和的1-1.6倍。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤B所述的共沉淀反应是将混合盐溶液B以1-5mL/min的速度滴加到氢氧化钠溶液中，保持pH＝10.5-12，反应在10-25℃进行8-24h，过滤，滤饼在60-80℃干燥6-12h，得到固体LiAl-LDH，其化学式为[LiAl2(OH)6]2CO3·nH2O，n＝1-10。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤A和B中所述的铝盐为硝酸铝、硫酸铝、氯化铝中的一种。
根据本发明所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，优选地，步骤C所述的滤液蒸发浓缩是将滤液蒸发浓缩至锂的浓度[Li+]＝0.1-0.5g/L。
本发明的目的是提供盐湖卤水中Mg、Li元素分离，同时利用反应-分离耦合技术生产MgAl-LDH和LiAl-LDH的工艺方法。
一种利用反应-分离耦合技术分离卤水中Mg、Li元素，同时生产MgAl-LDH和LiAl-LDH的工艺方法，其工艺流程如图1所示；具体步骤为：
A.向卤水中加入铝盐，配成制备镁铝水滑石相应的混合盐溶液A，与共沉淀用的碱液进行共沉淀反应，然后转入反应器继续晶化反应，反应结束后固液分离，得到MgAl-LDH固体产物和滤液；
B.将滤液进行蒸发浓缩得到富锂卤水，再加入铝盐，配成制备锂铝水滑石相应的混合盐溶液B，将其加入氢氧化钠碱液中进行沉淀反应，固液分离，得到LiAl-LDH固体产物和滤液；
C.将步骤B的滤液蒸发浓缩，返回到富锂卤水进行循环利用。
步骤A所述的卤水为硫酸盐型盐湖卤水，其中富含Li+、Mg2+、K+、Na+离子，各离子浓度为[Li+]＝1-3g/L，[Mg2+]＝10-30g/L，[K+]＝5-7g/L，[Na+]＝70-90g/L；卤水使用前先滤除不溶性杂质；
步骤A所述的制备镁铝水滑石相应的混合盐溶液A，其中金属离子的总浓度为0.9-1.5mol/L，镁盐与铝盐的摩尔浓度比为2-4：1；
所述的碱液是氢氧化钠与碳酸钠的混合溶液，其体积与混合盐溶液A体积相同，且氢氧化钠摩尔浓度是镁和铝元素摩尔浓度之和的1.6倍，碳酸钠摩尔浓度是铝元素 摩尔浓度的2倍；
所述的共沉淀反应是将盐溶液和碱溶液同时倒入胶体磨，以1000-5000转/min的转速旋转1-10分钟，形成MgAl-LDH晶核；将晶核溶液转移到反应器，在60-90℃下搅拌反应6-24h；过滤得到MgAl-LDH滤饼，在60-80℃干燥6-12h，得到白色固体MgAl-LDH产品，其化学式为[Mg2+ 1-xAl3+ x(OH)2](CO3 2-)x/2·nH2O，x＝0.2-0.33，n＝1-10。
步骤B所述的富锂卤水是将步骤A得到的滤液蒸发浓缩至锂离子浓度为0.1-0.5g/L；所述的混合盐溶液B中锂元素的摩尔浓度是铝元素摩尔浓度的1-6倍；所述的氢氧化钠溶液的体积与混合盐溶液B相同，且氢氧化钠摩尔浓度是锂和铝元素摩尔浓度之和的1-1.6倍；
所述的混合盐溶液B滴加到氢氧化钠溶液的滴加速度为1-5mL/min，保持pH＝10.5-12，反应在10-25℃进行8-24h，过滤，滤饼在60-80℃干燥6-12h，得到固体LiAl-LDH，其化学式为[LiAl2(OH)6]2CO3·nH2O，n＝1-10。
步骤A和B中所述的铝盐为硝酸铝、硫酸铝、氯化铝中的一种。
将步骤C所述的滤液蒸发浓缩是将滤液蒸发浓缩至锂的浓度[Li+]＝0.1-0.5g/L。
本发明的显著效果：
(1)本发明利用反应-分离耦合技术，在分离盐湖卤水中镁、锂资源的同时，实现镁铝水滑石和锂铝水滑石功能材料的生产；该方法不仅可以实现盐湖的资源分离，还可以获得高附加值的功能材料，本发明的方法为盐湖资源的高效利用开辟了一条重要的途径。
(2)在本发明的方法中卤水中的镁通过形成镁铝水滑石首先被分离出来，解决了目前传统的工艺中从高镁/锂比的溶液中分离镁、锂的难题，从而使得锂的损失率明显降低。
(3)本发明以锂铝水滑石的方式来提取锂，该方法反应温和，设备简单，锂损失量小，因此本发明提供的方法适合对盐湖卤水锂资源的规模化、高效化利用。
附图说明
图1为本发明提供的从卤水中提取镁、锂同时生产水滑石的工艺方法流程图；
图2为本发明实施例1制备得到的MgAl-LDH产品的X射线衍射谱图；
图3为本发明实施例1制备得到的MgAl-LDH产品的透射电镜形貌图；
图4为本发明实施例1制备得到的LiAl-LDH产品的X射线衍射谱图；
图5为本发明实施例1制备得到的LiAl-LDH产品的扫描电镜形貌图。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，以下将通过具体的实施例及说明书附图详细地说明本发明的实施过程和产生的有益效果，旨在帮助阅读者更好地理解本发明的实质和特点，但是不作为对本案可实施范围的限定。
本发明实施例中所用的卤水取自西台吉乃尔盐湖，其为硫酸盐型卤水，该卤水的组成如表1所示。本发明提供的从卤水中提取镁、锂同时生产水滑石的工艺方法流程图如图1所示。
表1
离子名称 Na+ K+ Li+ Mg2+ Cl- SO4 2-
浓度(g/L) 70-90 5-7 1-3 10-30 140-160 20-40
实施例1
本实施例提供了一种从卤水中提取镁、锂同时生产水滑石的工艺方法，其中，该方法包括以下步骤：
a、称取MgCl2·6H2O 26.0325g，MgSO4·7H2O 25.7993g，AlCl3·6H2O 18.7290g，KCl 3.3873g，LiCl 1.8768g，NaCl 8.068g，并将上述物质溶解于去离子水中，再于250mL容量瓶中定容，得到混合盐溶液A；称取NaOH 19.8593g，NaCO316.4443g溶解于去离子水中，再于250mL容量瓶中定容，得到碱溶液；
将混合盐溶液A和碱溶液同时倒入胶体磨中，以3000r/min的转速旋转3分钟，形成MgAl-LDH晶核；将晶核溶液转移到反应器中，在80℃动态搅拌晶化12h，进行MgAl-LDH生长；过滤，得到MgAl-LDH滤饼，再将MgAl-LDH滤饼在70℃干燥12h，得到白色固体MgAl-LDH产品；收集滤液至容器，所述MgAl-LDH的分子式为[Mg0.75Al0.25(OH)2](CO3 2-)0.125·5H2O；
b、将步骤a的滤液在50℃下蒸发浓缩至250mL，此时锂离子浓度达到0.4432g/L，加入AlCl3·6H2O 1.2847g配置混合盐溶液B；另外称量NaOH 16.784g溶解于100mL去离子水中，其摩尔浓度为4mol/L；将混合盐溶液B滴加到氢氧化钠溶液中，滴加速度为1mL/min，保持pH＝11，反应在20℃下进行12h；过滤，滤饼在80℃干燥 10h，得到固体LiAl-LDH产品，所述LiAl-LDH的分子式为[LiAl2(OH)6]2CO3·5H2O；
c、将步骤b的滤液蒸发浓缩至[Li+]＝0.3g/L，返回步骤b循环利用。
对实施例1制备得到的MgAl-LDH产品分别进行X射线衍射分析及透射电镜分析，其X射线衍射谱图如图2所示，透射电镜形貌图如图3所示；
对实施例1制备得到的LiAl-LDH产品分别进行X射线衍射分析及扫描电镜分析，其X射线衍射分析谱图如图4所示，扫描电镜形貌图如图5所示。
实施例2
a、称取MgCl2·6H2O 39.0487g，MgSO4·7H2O 38.6989g，Al(NO3)3·9H2O 32.7187g，KCl 9.1837g，LiCl 1.8768g，NaCl 8.068g，再将上述物质溶解于去离子水中，250mL容量瓶定容，得到混合盐溶液A；称取NaOH 22.3368g，NaCO316.4443g溶解于去离子水中，250mL容量瓶定容，得到碱溶液；
将混合盐溶液A和碱溶液同时倒入胶体磨中，以4000r/min的转速旋转5分钟，形成MgAl-LDH晶核；将晶核溶液转移到反应器中，在80℃动态搅拌晶化12h，进行MgAl-LDH生长；过滤，得到MgAl-LDH滤饼，再将MgAl-LDH滤饼在80℃干燥6h，得到白色固体MgAl-LDH产品；收集滤液至容器，所述MgAl-LDH的分子式为[Mg0.8Al0.2(OH)2](CO3 2-)0.1·6H2O；
b、将步骤a的滤液在50℃下蒸发浓缩至250mL，此时锂离子浓度达到0.4385g/L，加入Al(NO3)3·9H2O 1.9749g配置混合盐溶液B；另外称量NaOH 16.784g溶解于100mL去离子水中，其摩尔浓度为4mol/L；将混合盐溶液B滴加到氢氧化钠溶液中，滴加速度为2mL/min，保持pH＝11，反应在20℃下进行12h；过滤，滤饼在70℃干燥12h，得到固体LiAl-LDH产品，所述LiAl-LDH的分子式为[LiAl2(OH)6]2CO3·3H2O；
c、将步骤b的滤液蒸发浓缩至[Li+]＝0.4g/L，返回步骤b循环利用。
实施例3
a、称取MgCl2·6H2O 39.0487g，MgSO4·7H2O 29.139g，Al2(SO4)3·18H2O 71.2620g，KCl 9.1837g，LiCl 1.8768g，NaCl 8.068g，将上述物质溶解于去离子水中，250mL容量瓶定容，得到混合盐溶液A；称取NaOH 22.3223g，NaCO316.4443g溶解于去离子水中，250mL容量瓶定容，得到碱溶液；
将混合盐溶液A和碱溶液同时倒入胶体磨中，以2000r/min的转速旋转6分钟，形成MgAl-LDH晶核；将晶核溶液转移到反应器，在70℃动态搅拌晶化10h，进行 MgAl-LDH生长；过滤，得到MgAl-LDH滤饼，再将MgAl-LDH滤饼在80℃干燥8h，得到白色固体MgAl-LDH产品；收集滤液至容器，所述MgAl-LDH的分子式为[Mg0.744Al0.256(OH)2](CO3 2-)0.128·4H2O；
b、将步骤a的滤液在50℃下蒸发浓缩至250mL，此时锂离子浓度达到0.4108g/L，加入Al2(SO4)3·18H2O 1.6435g配置混合盐溶液B；另外称量NaOH 16.784g溶解于100mL去离子水中，其摩尔浓度为4mol/L；将混合盐溶液B滴加到氢氧化钠溶液中，滴加速度为3mL/min，保持pH＝10.5，反应在20℃下进行12h；过滤，滤饼在70℃干燥12h，得到固体LiAl-LDH产品，所述LiAl-LDH的分子式为[LiAl2(OH)6]2CO3·6H2O；
c、将步骤b的滤液蒸发浓缩至[Li+]＝0.2g/L，返回步骤b循环利用。
实施例4
a、称取MgCl2·6H2O 39.0487g，MgSO4·7H2O 38.6989g，Al(NO3)3·9H2O 32.6363g，KCl 3.3873g，LiCl 1.8768g，NaCl 8.068g，将上述物质溶解于去离子水中，250mL容量瓶定容，得到混合盐溶液A；称取NaOH 33.472g，NaCO318.4422g溶解于去离子水中，250mL容量瓶定容，得到碱溶液；
将混合盐溶液A和碱溶液同时倒入胶体磨中，以3000r/min的转速旋转3分钟，形成MgAl-LDH晶核；形成的晶核溶液转移到反应器，在80℃动态搅拌晶化24h，进行MgAl-LDH生长；过滤，得到MgAl-LDH滤饼，再将MgAl-LDH滤饼在70℃干燥10h，得到白色固体MgAl-LDH产品；收集滤液至容器，所述MgAl-LDH的分子式为[Mg0.8Al0.2(OH)2](CO3 2-)0.1·7H2O；
b、将步骤a的滤液在50℃下蒸发浓缩至250mL，此时锂离子浓度达到0.4573g/L，加入AlCl3·6H2O 1.3256g配置混合盐溶液B；另外称量NaOH 16.784g溶解于100mL去离子水中，其摩尔浓度为4mol/L；将混合盐溶液B滴加到氢氧化钠溶液中，滴加速度为5mL/min，保持pH＝12，反应在20℃下进行12h；过滤，滤饼在60℃干燥12h，得到固体LiAl-LDH产品，所述LiAl-LDH的分子式为[LiAl2(OH)6]2CO3·7H2O；
c、将步骤b的滤液蒸发浓缩至[Li+]＝0.4g/L，返回步骤b循环利用。

Claims (20)

  1. 一种从卤水中提取镁、锂同时生产水滑石的工艺方法，其特征在于，该方法包括以下具体步骤：
    a、向卤水中加入铝盐，配成制备镁铝水滑石所用的混合盐溶液A，加入碱液进行共沉淀反应，然后进行晶化反应，反应结束后固液分离，得到MgAl-LDH固体产物和滤液；
    b、将所述滤液进行蒸发浓缩得到富锂卤水，再加入铝盐，配成制备锂铝水滑石所用的混合盐溶液B，将其加入碱液中进行沉淀反应，反应结束后固液分离，得到LiAl-LDH固体产物和滤液；
    c、将步骤b得到的滤液蒸发浓缩，将蒸发浓缩后得到的溶液返回到步骤b的富锂卤水中进行循环利用。
  2. 根据权利要求1所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，其特征在于，步骤a中所述的卤水为硫酸盐型盐湖卤水，其中富含Li+、Mg2+、K+及Na+，各离子浓度为[Li+]＝1-3g/L，[Mg2+]＝10-30g/L，[K+]＝5-7g/L，[Na+]＝70-90g/L。
  3. 根据权利要求1所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，其特征在于，步骤a中所述的卤水在使用前需要先将不溶性的杂质滤除。
  4. 根据权利要求1所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，其特征在于，在步骤a所述的制备镁铝水滑石所用的混合盐溶液A中，金属离子的总浓度为0.9-1.5mol/L。
  5. 根据权利要求1所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，其特征在于，在步骤a所述的制备镁铝水滑石所用的混合盐溶液A中，镁盐与铝盐的摩尔比为2-4:1。
  6. 根据权利要求1所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，其特征在于，步骤a中所述的碱液是氢氧化钠与碳酸钠的混合溶液，其体积与混合盐溶液A的体积相同，且氢氧化钠的摩尔数是镁和铝元素摩尔数之和的1.5-2.5倍，碳酸钠与铝元素的摩尔比为1.5-2.5:1。
  7. 根据权利要求1所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，其特征在于，步骤a中所述的共沉淀反应是按照以下步骤进行的：将所述制备镁铝水滑石所用的混合盐溶液A与碱液混合，以1000-5000转/min的转速旋转1-10分钟，得 到MgAl-LDH晶核。
  8. 根据权利要求1所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，其特征在于，步骤a中所述的晶化反应是按照以下步骤进行的：将步骤a中共沉淀反应得到MgAl-LDH晶核在60-90℃下搅拌反应6-24h，反应结束后固液分离得到MgAl-LDH滤饼。
  9. 根据权利要求1所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，其特征在于，步骤a中得到MgAl-LDH滤饼后，再对该滤饼进行干燥，得到MgAl-LDH固体产物；所述干燥为在60-80℃干燥6-12h。
  10. 根据权利要求1所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，其特征在于，步骤a中所述的MgAl-LDH固体产物的化学式为[Mg2+ 1-xAl3+ x(OH)2](CO3 2-)x/2·nH2O，式中，x＝0.2-0.4，n＝1-10。
  11. 根据权利要求1所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，其特征在于，步骤b所述的富锂卤水中锂离子的浓度为0.1-0.5g/L。
  12. 根据权利要求1所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，其特征在于，在步骤b所述的制备锂铝水滑石所用的混合盐溶液B中，锂元素与铝元素的摩尔比为1-6:1。
  13. 根据权利要求1所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，其特征在于，步骤b所述碱液的pH值为9-12，该碱液包括氢氧化钠水溶液或氢氧化钾水溶液。
  14. 根据权利要求1所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，其特征在于，步骤b中所述碱液的体积与制备锂铝水滑石所用的混合盐溶液B的体积相同，且氢氧化钠或氢氧化钾的摩尔数是锂和铝元素摩尔数之和的1-1.6倍。
  15. 根据权利要求1所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，其特征在于，步骤b中所述的共沉淀反应是按照以下步骤进行的：将制备锂铝水滑石所用的混合盐溶液B滴加到碱液中，进行共沉淀反应，反应结束后固液分离，得到LiAl-LDH滤饼；
    所述滴加的速度为1-5mL/min；
    所述共沉淀反应的pH值为9-12，反应温度为10-25℃，反应时间为8-24h。
  16. 根据权利要求1所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，其 特征在于，步骤b中得到LiAl-LDH滤饼后，再对该滤饼进行干燥，得到LiAl-LDH固体产物；所述干燥为在60-80℃干燥6-12h。
  17. 根据权利要求1所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，其特征在于，步骤b中所述的LiAl-LDH固体产物的化学式为[LiAl2(OH)6]2CO3·nH2O，式中，n＝1-10。
  18. 根据权利要求1所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，其特征在于，步骤a中所述的铝盐为硝酸铝、硫酸铝、氯化铝中的一种。
  19. 根据权利要求1所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，其特征在于，步骤b中所述的铝盐为硝酸铝、硫酸铝、氯化铝中的一种。
  20. 根据权利要求1所述的从卤水中提取镁、锂同时生产水滑石的工艺方法，其特征在于，步骤c中所述的蒸发浓缩是将步骤b得到的滤液蒸发浓缩至锂离子的浓度为0.1-0.5g/L。
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