WO2024093930A1 - Silica gel-modified metatitanate-based lithium-ion sieve precursor and method for preparing same - Google Patents

Silica gel-modified metatitanate-based lithium-ion sieve precursor and method for preparing same Download PDF

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WO2024093930A1
WO2024093930A1 PCT/CN2023/127823 CN2023127823W WO2024093930A1 WO 2024093930 A1 WO2024093930 A1 WO 2024093930A1 CN 2023127823 W CN2023127823 W CN 2023127823W WO 2024093930 A1 WO2024093930 A1 WO 2024093930A1
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silica gel
lithium
preparation
product
drying
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蔡建国
石洪雁
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江苏海普功能材料有限公司
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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
    • 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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention belongs to the technical field of lithium ion sieves, and in particular relates to a silica gel-modified metatitanate-type lithium ion sieve precursor and a preparation method thereof.
  • lithium As a key energy element, lithium has developed into a strategic raw material, playing an important strategic role in national economy and national defense construction, and is known as the "new energy of the 21st century". Lithium and its compounds are widely used in chemical industry, nuclear energy, glass, medicine, metallurgy, batteries and other fields due to their excellent performance.
  • the main methods for extracting lithium from salt lake brine include precipitation, calcination leaching, solvent extraction, membrane separation, adsorption, etc.
  • the precipitation method has a simple process and low cost, and is suitable for extracting lithium from salt lake brine with a low magnesium-lithium ratio.
  • the calcination leaching method has a simple process, but hydrated magnesium chloride is difficult to completely decompose, and the generated hydrogen chloride gas is highly corrosive to the equipment, requiring a large amount of water to be evaporated, and the process energy consumption is high.
  • the solvent extraction method is suitable for extracting lithium from brine with a high magnesium-lithium ratio, but the process flow is long, and there are problems of equipment corrosion and dissolution, which significantly increases the cost.
  • the membrane separation method has high cost and is not easy to industrialize.
  • the adsorption method has the advantages of simple process, high recovery rate, and environmental friendliness. Obviously, for low-grade salt lakes, the adsorption method is the most promising method.
  • the method of extracting lithium from salt lake brine by adsorption generally uses an ion sieve adsorbent. The main process is to first prepare a suitable precursor, and then remove Li + in the precursor by acid washing to obtain a lithium ion sieve. Therefore, it is particularly important to adopt a suitable process to synthesize an efficient and inexpensive lithium ion sieve.
  • the preparation process of ion sieve is as follows: first, the target ion (Li + ) is added during the synthesis of inorganic compounds to prepare a composite oxide. Under the condition that the material structure is not affected, the adsorbed ions are separated to obtain a compound lacking the target ion but with a space gap, so it has adsorption memory for the target ion.
  • the most studied ion sieves for lithium extraction are manganese oxide ion sieves, titanium oxide ion sieves, and doped composite ion sieves.
  • Manganese oxide ion sieves have high selectivity, low cost, and fast adsorption rate, but the dissolution rate is large during acid leaching, which is also a prominent problem encountered in current research.
  • the stability of titanium oxide ion sieve acid leaching conditions is higher than that of manganese oxide, and it has broad development prospects.
  • Onodera Y et al. (1988) first discovered that Li 2 TiO 3 can be obtained by high temperature treatment of TiO 2 and Li 2 CO 3. After acid treatment, the titanium oxide ion sieve prepared has good selectivity for Li + .
  • the precursors of lithium ion sieves have problems such as small specific surface area and small adsorption capacity.
  • the present invention provides a silica gel modified metatitanate type lithium ion
  • the sieve precursor and the preparation method thereof can effectively solve the problems of small specific surface area and small adsorption capacity of the existing precursor.
  • the present invention provides a method for preparing a titanium-based high-performance brine lithium extraction adsorbent precursor, comprising the following steps:
  • step S3 heating the solution in step S1 at 50°C, and adding the acidified silica gel particles in step S2 to promote the precipitation of Li 2 TiO 3 in the porous structure of the silica gel until a translucent gel appears;
  • step S4 drying the product obtained in step S3 and sintering it at high temperature in a muffle furnace to obtain.
  • the product of step S2 is filtered, and the filter residue is dried at 80° C. for 5 h to remove the ethanol solvent and small molecule products.
  • the lithium salt is at least one of lithium chloride, lithium acetate, lithium hydroxide, lithium nitrate, lithium sulfate, lithium phosphate, dilithium hydrogen phosphate, and lithium dihydrogen phosphate.
  • the titanium source is at least one of tetrabutyl titanate, titanium sulfate, titanous sulfate and titanyl sulfate.
  • step S1 the molar ratio of the lithium salt to the titanium source is 1-5:1.
  • the acid solution in step S2 is at least one of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and the concentration of the acid solution is 1-6 mol/L.
  • the acidification temperature is 40-80°C, and the acidification treatment time is 6 hours.
  • the amount of silica gel particles added in step S2 is 2-16 g/L.
  • the sintering temperature is 100-600° C.
  • the sintering time is 2-24 h.
  • the present invention also provides a titanium-based high-performance brine lithium extraction adsorbent precursor, which is prepared by the above-mentioned preparation method.
  • the present invention uses soluble lithium salt and soluble titanium source as raw materials to prepare titanium lithium ion sieve precursor sol, then adds acidified silica gel particles thereto, and obtains silica gel-modified metatitanate lithium ion sieve precursor with uniform mesoporous morphology after calcination; the porous structure of silica gel enables it to have a large specific surface area and good adsorption performance, and has high stability and low price; silica gel is applied to the modification of the titanium lithium ion sieve precursor, Li2TiO3 can be loaded in the porous structure of silica gel, the specific surface area of the lithium ion sieve prepared by the precursor is improved, and the nanopores provided by the silica gel have excellent lithium adsorption effect, so the lithium extraction efficiency is also improved.
  • FIG. 1 is a SEM image of the precursor of the titanium lithium ion sieve prepared in Example 1.
  • step (3) Add 2 g of the acidified silica gel particles prepared in step (2) to the solution prepared in step (1), and continue heating and stirring at 50° C. until a translucent gel appears;
  • step (3) The product in step (3) is filtered, and the filter residue is dried at 80° C. for 5 h to remove the ethanol solvent and small molecular products.
  • the dried product is placed in a muffle furnace and sintered at 300° C. for 12 h to obtain a precursor of a titanium lithium ion sieve.
  • step (3) Add 2 g of the acidified silica gel particles prepared in step (2) to the solution prepared in step (1), and continue heating and stirring at 50° C. until a translucent gel appears;
  • step (3) The product in step (3) is filtered, and the filter residue is dried at 80° C. for 5 h to remove the ethanol solvent and small molecular products.
  • the dried product is placed in a muffle furnace and sintered at 300° C. for 12 h to obtain a precursor of a titanium lithium ion sieve.
  • step (3) Add 2 g of the acidified silica gel particles prepared in step (2) to the solution prepared in step (1), and continue heating and stirring at 50° C. until a translucent gel appears;
  • step (3) The product in step (3) is filtered, and the filter residue is dried at 80° C. for 5 h to remove the ethanol solvent and small molecular products.
  • the dried product is placed in a muffle furnace and sintered at 300° C. for 12 h to obtain a precursor of a titanium lithium ion sieve.
  • step (3) Add 2 g of the acidified silica gel particles prepared in step (2) to the solution prepared in step (1), and continue heating and stirring at 50° C. until a translucent gel appears;
  • step (3) The product in step (3) is filtered, and the filter residue is dried at 80° C. for 5 h to remove the ethanol solvent and small molecular products.
  • the dried product is placed in a muffle furnace and sintered at 300° C. for 12 h to obtain a precursor of a titanium lithium ion sieve.
  • step (3) adding 10 g of the acidified silica gel particles prepared in step (2) to the solution prepared in step (1), and continuing to heat and stir at 50° C. until a translucent gel appears;
  • step (3) The product in step (3) is filtered, and the filter residue is dried at 80° C. for 5 h to remove the ethanol solvent and small molecular products.
  • the dried product is placed in a muffle furnace and sintered at 300° C. for 12 h to obtain a precursor of a titanium lithium ion sieve.
  • step (3) Add 2 g of the acidified silica gel particles prepared in step (2) to the solution prepared in step (1), and continue heating and stirring at 50° C. until a translucent gel appears;
  • step (3) The product in step (3) is filtered, and the filter residue is dried at 80° C. for 5 h to remove the ethanol solvent and small molecular products.
  • the dried product is placed in a muffle furnace and sintered at 600° C. for 12 h to obtain a precursor of a titanium lithium ion sieve.
  • step (3) Add 2 g of the acidified silica gel particles prepared in step (2) to the solution prepared in step (1), and continue heating and stirring at 50° C. until a translucent gel appears;
  • step (3) The product in step (3) is filtered, and the filter residue is dried at 80° C. for 5 h to remove the ethanol solvent and small molecular products.
  • the dried product is placed in a muffle furnace and sintered at 300° C. for 24 h to obtain a precursor of a titanium lithium ion sieve.
  • step (3) Add 2 g of the acidified silica gel particles prepared in step (2) to the solution prepared in step (1), and continue heating and stirring at 50° C. until a translucent gel appears;
  • step (3) The product in step (3) is filtered, and the filter residue is dried at 80° C. for 5 h to remove the ethanol solvent and small molecular products.
  • the dried product is placed in a muffle furnace and sintered at 300° C. for 24 h to obtain a precursor of a titanium lithium ion sieve.
  • the precursor of the titanium lithium ion sieve obtained in Example 1-8 is immersed in a 1% hydrochloric acid solution, stirred and eluted, and the pH of the solution is monitored. If the pH is > 3, 1% hydrochloric acid solution is continuously added until the pH stabilizes at ⁇ 3. After washing and drying, a metatitanate lithium ion sieve adsorbent is obtained.
  • the lithium-extracting adsorbent obtained based on the precursor in Examples 1-8 was analyzed by inductively coupled plasma direct reading spectrometry (ICP) to obtain the molar ratio data of lithium to titanium.
  • ICP inductively coupled plasma direct reading spectrometry
  • a certain amount of adsorbent is loaded into the adsorption column, and an adsorption experiment is carried out with a solution containing a certain concentration of Li.
  • the Li + concentration of the inlet and outlet water is detected by ICP, and the saturated adsorption capacity of lithium by the adsorbent is calculated based on the volume of the adsorption solution.

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Abstract

Provided are a silica gel-modified metatitanate-based lithium-ion sieve precursor and a method for preparing same. The method comprises the following steps: S1, drying and dehydrating a lithium salt, and then dissolving the dry lithium salt and a titanium source in ethanol; S2, adding a silica gel particle in an acid solution and heating for acidification, and then drying the product to give an acidified silica gel particle; S3, heating the solution from step S1 at 50 °C, and adding the acidified silica gel particle from step S2 to promote the precipitation of Li2TiO3 in the porous silica gel structure until a semi-transparent gel is observed; and S4, drying the product obtained in step S3, and sintering the dry product in a muffle furnace at a high temperature to give the product. By means of applying silica gel to the modification of titanium-based lithium-ion sieve precursor, Li2TiO3 can be loaded in the porous silica gel structure. Lithium-ion sieves prepared by the precursor feature significantly improved specific surface area and adsorption capacity, as well as improved lithium extraction efficiency.

Description

一种硅胶改性的偏钛酸型锂离子筛前驱体及其制备方法A silica gel modified metatitanate type lithium ion sieve precursor and preparation method thereof 技术领域Technical Field
本发明属于锂离子筛技术领域，具体涉及一种硅胶改性的偏钛酸型锂离子筛前驱体及其制备方法。The invention belongs to the technical field of lithium ion sieves, and in particular relates to a silica gel-modified metatitanate-type lithium ion sieve precursor and a preparation method thereof.
背景技术Background technique
锂作为能源关键元素，已发展成为一种战略性原材料，在国民经济和国防建设中具有重要的战略地位，被誉为“21世纪新能源”。锂及其化合物以其优异的性能而广泛应用于化工、核能、玻璃、医药、冶金、电池等领域。As a key energy element, lithium has developed into a strategic raw material, playing an important strategic role in national economy and national defense construction, and is known as the "new energy of the 21st century". Lithium and its compounds are widely used in chemical industry, nuclear energy, glass, medicine, metallurgy, batteries and other fields due to their excellent performance.
在20世纪80年代中期以前，世界各国主要以锂矿石为原料生产锂盐。该方法历史较长、工艺较成熟，但能耗较高，在一定程度上会污染环境，且锂矿石资源日益匮乏，越发显示出其局限性。另一方面，盐湖卤水中锂资源储量丰富，且成本低于矿石锂的开采，随着南美洲巨大盐湖卤水锂资源的勘探开发，盐湖提锂逐渐成为发展趋势。Before the mid-1980s, countries around the world mainly used lithium ore as raw material to produce lithium salts. This method has a long history and mature technology, but it consumes a lot of energy and pollutes the environment to a certain extent. In addition, the increasing scarcity of lithium ore resources has increasingly shown its limitations. On the other hand, the lithium resources in salt lake brine are abundant and the cost is lower than the mining of lithium ore. With the exploration and development of the huge salt lake brine lithium resources in South America, lithium extraction from salt lakes has gradually become a development trend.
我国是锂资源大国，储量位居世界前列。其中，青海和西藏的盐湖锂资源储量占总储量85％以上。从盐湖卤水提锂工艺简单、能耗低、成本低，因此原卤水提锂已成为全球主流技术和发展趋势。my country is a country with abundant lithium resources, and its reserves are among the highest in the world. Among them, the salt lake lithium resources in Qinghai and Tibet account for more than 85% of the total reserves. The process of extracting lithium from salt lake brine is simple, with low energy consumption and low cost, so extracting lithium from raw brine has become the mainstream technology and development trend in the world.
从盐湖卤水中提锂的方法主要有沉淀法、煅烧浸出法、溶剂萃取法、膜分离法、吸附法等。其中，沉淀法工艺简单、成本较低，适用于低镁锂比的盐湖卤水中提锂。煅烧浸出法工艺简单，但水合氯化镁较难完全分解，且生成的氯化氢气体对设备腐蚀性大，需要蒸发较大的水量，工艺能耗较高。溶剂萃取法，适于从高镁锂比的卤水中提锂，但工艺流程长，存在设备腐蚀和溶损问题，使成本显著增加。膜分离法，成本高，不易工业化。吸附法具有工艺简单、回收率高、环境友好等优点。显然，对于低品位盐湖而言，吸附法是最具应用前景的方法。采用吸附法从盐湖卤水中提锂的方式一般采用离子筛吸附剂进行，其主要工序是先制备出合适的前驱体，再经过酸洗去除前驱体中的Li+得到锂离子筛。因此，采取合适的工艺合成出高效廉价的锂离子筛则尤为重要。The main methods for extracting lithium from salt lake brine include precipitation, calcination leaching, solvent extraction, membrane separation, adsorption, etc. Among them, the precipitation method has a simple process and low cost, and is suitable for extracting lithium from salt lake brine with a low magnesium-lithium ratio. The calcination leaching method has a simple process, but hydrated magnesium chloride is difficult to completely decompose, and the generated hydrogen chloride gas is highly corrosive to the equipment, requiring a large amount of water to be evaporated, and the process energy consumption is high. The solvent extraction method is suitable for extracting lithium from brine with a high magnesium-lithium ratio, but the process flow is long, and there are problems of equipment corrosion and dissolution, which significantly increases the cost. The membrane separation method has high cost and is not easy to industrialize. The adsorption method has the advantages of simple process, high recovery rate, and environmental friendliness. Obviously, for low-grade salt lakes, the adsorption method is the most promising method. The method of extracting lithium from salt lake brine by adsorption generally uses an ion sieve adsorbent. The main process is to first prepare a suitable precursor, and then remove Li + in the precursor by acid washing to obtain a lithium ion sieve. Therefore, it is particularly important to adopt a suitable process to synthesize an efficient and inexpensive lithium ion sieve.
离子筛的制备过程如下：首先在无机化合物合成过程中加入目的离子(Li+)，制备出复合型氧化物，在不影响物质结构的条件下，将所吸附的离子脱离，得到缺少目的离子而有空间间隙的化合物，因而对目的离子具有吸附记忆性。近年来，研究提锂的离子筛最多的是锰氧化物型离子筛、钛氧化物型离子筛、掺杂型复合型离子筛。锰氧化物型离子筛选择性高、成本较低、吸附速率较快，但是在酸浸过程中溶损率较大，也是目前研究遇到比较突出的问题。而钛系氧化物离子筛酸浸条件稳定性比锰氧化物更高，具有广阔的开发前景，Onodera Y等(1988)首先发现由TiO2和Li2CO3经过高温处理可以获得Li2TiO3，其经过酸处理后，制备出的钛氧化物型离子筛Li+有很好的选择性。但是现有技术中，锂离子筛的前驱体存在比表面积小、吸附容量小等问题。The preparation process of ion sieve is as follows: first, the target ion (Li + ) is added during the synthesis of inorganic compounds to prepare a composite oxide. Under the condition that the material structure is not affected, the adsorbed ions are separated to obtain a compound lacking the target ion but with a space gap, so it has adsorption memory for the target ion. In recent years, the most studied ion sieves for lithium extraction are manganese oxide ion sieves, titanium oxide ion sieves, and doped composite ion sieves. Manganese oxide ion sieves have high selectivity, low cost, and fast adsorption rate, but the dissolution rate is large during acid leaching, which is also a prominent problem encountered in current research. The stability of titanium oxide ion sieve acid leaching conditions is higher than that of manganese oxide, and it has broad development prospects. Onodera Y et al. (1988) first discovered that Li 2 TiO 3 can be obtained by high temperature treatment of TiO 2 and Li 2 CO 3. After acid treatment, the titanium oxide ion sieve prepared has good selectivity for Li + . However, in the prior art, the precursors of lithium ion sieves have problems such as small specific surface area and small adsorption capacity.
发明内容Summary of the invention
针对现有技术中存在的上述问题，本发明提供了一种硅胶改性的偏钛酸型锂离子 筛前驱体及其制备方法，能够有效解决现有的前驱体存在的比表面积小、吸附容量小的问题。In view of the above problems existing in the prior art, the present invention provides a silica gel modified metatitanate type lithium ion The sieve precursor and the preparation method thereof can effectively solve the problems of small specific surface area and small adsorption capacity of the existing precursor.
本发明的技术方案为：The technical solution of the present invention is:
本发明提供了一种钛系高性能卤水提锂吸附剂前驱体的制备方法，包括以下步骤：The present invention provides a method for preparing a titanium-based high-performance brine lithium extraction adsorbent precursor, comprising the following steps:
S1、将锂盐烘干脱水，然后将干燥的锂盐与钛源在乙醇中溶解；S1, drying and dehydrating the lithium salt, and then dissolving the dried lithium salt and the titanium source in ethanol;
S2、将硅胶颗粒置于酸液中加热酸化处理，然后将产物烘干得到酸化硅胶颗粒；S2, placing the silica gel particles in an acid solution for heating and acidification treatment, and then drying the product to obtain acidified silica gel particles;
S3、将S1步骤中的溶液在50℃下加热，并加入S2步骤中的酸化硅胶颗粒，促使Li2TiO3在硅胶多孔结构中沉淀，直至出现半透明凝胶；S3, heating the solution in step S1 at 50°C, and adding the acidified silica gel particles in step S2 to promote the precipitation of Li 2 TiO 3 in the porous structure of the silica gel until a translucent gel appears;
S4、将S3步骤中所得产物烘干后置于马弗炉中高温烧结，制得。S4, drying the product obtained in step S3 and sintering it at high temperature in a muffle furnace to obtain.
优选地，将S2步骤的产物过滤，滤渣置于80℃下烘干5h，以去除乙醇溶剂和小分子产物。Preferably, the product of step S2 is filtered, and the filter residue is dried at 80° C. for 5 h to remove the ethanol solvent and small molecule products.
优选地，S1步骤中，锂盐为氯化锂、醋酸锂、氢氧化锂、硝酸锂、硫酸锂、磷酸锂、磷酸氢二锂、磷酸二氢锂中的至少一种。Preferably, in step S1, the lithium salt is at least one of lithium chloride, lithium acetate, lithium hydroxide, lithium nitrate, lithium sulfate, lithium phosphate, dilithium hydrogen phosphate, and lithium dihydrogen phosphate.
优选地，S1步骤中，钛源为钛酸四丁酯、硫酸钛、硫酸亚钛、硫酸氧钛中的至少一种。Preferably, in step S1, the titanium source is at least one of tetrabutyl titanate, titanium sulfate, titanous sulfate and titanyl sulfate.
优选地，S1步骤中，锂盐和钛源的摩尔比为1-5:1。Preferably, in step S1, the molar ratio of the lithium salt to the titanium source is 1-5:1.
优选地，S2步骤中酸液为盐酸、硫酸、硝酸、磷酸中的至少一种，所述酸液的浓度为1-6mol/L。Preferably, the acid solution in step S2 is at least one of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and the concentration of the acid solution is 1-6 mol/L.
优选地，S2步骤中，酸化温度为40-80℃，酸化处理的时间为6h。Preferably, in step S2, the acidification temperature is 40-80°C, and the acidification treatment time is 6 hours.
优选地，S2步骤中的硅胶颗粒的添加量为2-16g/L。Preferably, the amount of silica gel particles added in step S2 is 2-16 g/L.
优选地，S4步骤中，烧结温度为100-600℃，烧结时间为2-24h。Preferably, in step S4, the sintering temperature is 100-600° C., and the sintering time is 2-24 h.
本发明还提供了一种钛系高性能卤水提锂吸附剂前驱体，采用上述制备方法制得The present invention also provides a titanium-based high-performance brine lithium extraction adsorbent precursor, which is prepared by the above-mentioned preparation method.
本发明的有益效果是：The beneficial effects of the present invention are:
本发明以可溶性锂盐和可溶性钛源为原料，制备钛锂离子筛前驱体溶胶，然后向其中加入酸化硅胶颗粒，煅烧后得到具有均匀介孔形貌的硅胶改性的偏钛酸型锂离子筛前驱体；硅胶的多孔结构使其具有较大的比表面积和良好的吸附性能，且稳定性高，价格低廉，将硅胶应用于钛锂离子筛的前驱体改性，Li2TiO3可负载在硅胶的多孔结构中，该前驱体所制得的锂离子筛的比表面积得到提高，并且硅胶所提供的纳米孔道具有优异的锂吸附效果，因此提锂效率也得到提升。The present invention uses soluble lithium salt and soluble titanium source as raw materials to prepare titanium lithium ion sieve precursor sol, then adds acidified silica gel particles thereto, and obtains silica gel-modified metatitanate lithium ion sieve precursor with uniform mesoporous morphology after calcination; the porous structure of silica gel enables it to have a large specific surface area and good adsorption performance, and has high stability and low price; silica gel is applied to the modification of the titanium lithium ion sieve precursor, Li2TiO3 can be loaded in the porous structure of silica gel, the specific surface area of the lithium ion sieve prepared by the precursor is improved, and the nanopores provided by the silica gel have excellent lithium adsorption effect, so the lithium extraction efficiency is also improved.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
下面结合附图及实施例对本发明作进一步描述：The present invention will be further described below in conjunction with the accompanying drawings and embodiments:
图1是是实施例1所制得的钛锂离子筛的前驱体的SEM图。FIG. 1 is a SEM image of the precursor of the titanium lithium ion sieve prepared in Example 1.
具体实施方式Detailed ways
为使本发明的目的、技术方案和优点更加清楚明了，下面结合具体实施方式并参照附图，对本发明进一步详细说明。应该理解，这些描述只是示例性的，而并非要限制本发明的范围。此外，在以下说明中，省略了对公知结构和技术的描述，以避免不必要地混淆本 发明的概念。In order to make the purpose, technical solution and advantages of the present invention more clear, the present invention is further described in detail below in combination with specific implementation methods and with reference to the accompanying drawings. It should be understood that these descriptions are only exemplary and are not intended to limit the scope of the present invention. In addition, in the following description, the description of well-known structures and technologies is omitted to avoid unnecessary confusion. Concept of invention.
实施例1Example 1
(1)在500mL乙醇中加入6.6g乙酸锂，17g钛酸四丁酯，加热至50℃搅拌溶解；(1) Add 6.6 g of lithium acetate and 17 g of tetrabutyl titanate to 500 mL of ethanol, heat to 50° C. and stir to dissolve;
(2)将硅胶颗粒置于5mol/L的盐酸中酸化5h，酸化温度50℃，然后将产物烘干得到酸化硅胶颗粒；(2) placing the silica gel particles in 5 mol/L hydrochloric acid for acidification for 5 h at a temperature of 50° C., and then drying the product to obtain acidified silica gel particles;
(3)在步骤(1)溶液中加入2g步骤(2)的酸化硅胶颗粒，继续以50℃加热搅拌直至出现半透明凝胶；(3) Add 2 g of the acidified silica gel particles prepared in step (2) to the solution prepared in step (1), and continue heating and stirring at 50° C. until a translucent gel appears;
(4)将步骤(3)中的产物过滤，滤渣置于80℃下烘干5h，以去除乙醇溶剂和小分子产物，烘干后的产物置于马弗炉，以300℃烧结12h，制得钛锂离子筛的前驱体。(4) The product in step (3) is filtered, and the filter residue is dried at 80° C. for 5 h to remove the ethanol solvent and small molecular products. The dried product is placed in a muffle furnace and sintered at 300° C. for 12 h to obtain a precursor of a titanium lithium ion sieve.
实施例2Example 2
(1)在500mL乙醇中加入16.5g乙酸锂，17g钛酸四丁酯，加热至50℃搅拌溶解；(1) Add 16.5 g of lithium acetate and 17 g of tetrabutyl titanate to 500 mL of ethanol, heat to 50° C. and stir to dissolve;
(2)将硅胶颗粒置于5mol/L的盐酸中酸化5h，酸化温度50℃，然后将产物烘干得到酸化硅胶颗粒；(2) placing the silica gel particles in 5 mol/L hydrochloric acid for acidification for 5 h at a temperature of 50° C., and then drying the product to obtain acidified silica gel particles;
(3)在步骤(1)溶液中加入2g步骤(2)的酸化硅胶颗粒，继续以50℃加热搅拌直至出现半透明凝胶；(3) Add 2 g of the acidified silica gel particles prepared in step (2) to the solution prepared in step (1), and continue heating and stirring at 50° C. until a translucent gel appears;
(4)将步骤(3)中的产物过滤，滤渣置于80℃下烘干5h，以去除乙醇溶剂和小分子产物，烘干后的产物置于马弗炉，以300℃烧结12h，制得钛锂离子筛的前驱体。(4) The product in step (3) is filtered, and the filter residue is dried at 80° C. for 5 h to remove the ethanol solvent and small molecular products. The dried product is placed in a muffle furnace and sintered at 300° C. for 12 h to obtain a precursor of a titanium lithium ion sieve.
实施例3Example 3
(1)在500mL乙醇中加入6.6g乙酸锂，17g钛酸四丁酯，加热至50℃搅拌溶解；(1) Add 6.6 g of lithium acetate and 17 g of tetrabutyl titanate to 500 mL of ethanol, heat to 50° C. and stir to dissolve;
(2)将硅胶颗粒置于2mol/L的盐酸中酸化5h，酸化温度50℃，然后将产物烘干得到酸化硅胶颗粒；(2) placing the silica gel particles in 2 mol/L hydrochloric acid for acidification for 5 h at a temperature of 50° C., and then drying the product to obtain acidified silica gel particles;
(3)在步骤(1)溶液中加入2g步骤(2)的酸化硅胶颗粒，继续以50℃加热搅拌直至出现半透明凝胶；(3) Add 2 g of the acidified silica gel particles prepared in step (2) to the solution prepared in step (1), and continue heating and stirring at 50° C. until a translucent gel appears;
(4)将步骤(3)中的产物过滤，滤渣置于80℃下烘干5h，以去除乙醇溶剂和小分子产物，烘干后的产物置于马弗炉，以300℃烧结12h，制得钛锂离子筛的前驱体。(4) The product in step (3) is filtered, and the filter residue is dried at 80° C. for 5 h to remove the ethanol solvent and small molecular products. The dried product is placed in a muffle furnace and sintered at 300° C. for 12 h to obtain a precursor of a titanium lithium ion sieve.
实施例4Example 4
(1)在500mL乙醇中加入6.6g乙酸锂，17g钛酸四丁酯，加热至50℃搅拌溶解；(1) Add 6.6 g of lithium acetate and 17 g of tetrabutyl titanate to 500 mL of ethanol, heat to 50° C. and stir to dissolve;
(2)将硅胶颗粒置于2mol/L的盐酸中酸化5h，酸化温度80℃，然后将产物烘干得到酸化硅胶颗粒；(2) placing the silica gel particles in 2 mol/L hydrochloric acid for acidification for 5 h at a temperature of 80° C., and then drying the product to obtain acidified silica gel particles;
(3)在步骤(1)溶液中加入2g步骤(2)的酸化硅胶颗粒，继续以50℃加热搅拌直至出现半透明凝胶；(3) Add 2 g of the acidified silica gel particles prepared in step (2) to the solution prepared in step (1), and continue heating and stirring at 50° C. until a translucent gel appears;
(4)将步骤(3)中的产物过滤，滤渣置于80℃下烘干5h，以去除乙醇溶剂和小分子产物，烘干后的产物置于马弗炉，以300℃烧结12h，制得钛锂离子筛的前驱体。(4) The product in step (3) is filtered, and the filter residue is dried at 80° C. for 5 h to remove the ethanol solvent and small molecular products. The dried product is placed in a muffle furnace and sintered at 300° C. for 12 h to obtain a precursor of a titanium lithium ion sieve.
实施例5Example 5
(1)在500mL乙醇中加入6.6g乙酸锂，17g钛酸四丁酯，加热至50℃搅拌溶解；(1) Add 6.6 g of lithium acetate and 17 g of tetrabutyl titanate to 500 mL of ethanol, heat to 50° C. and stir to dissolve;
(2)将硅胶颗粒置于5mol/L的盐酸中酸化5h，酸化温度50℃，然后将产物烘干得到酸化硅胶颗粒；(2) placing the silica gel particles in 5 mol/L hydrochloric acid for acidification for 5 h at a temperature of 50° C., and then drying the product to obtain acidified silica gel particles;
(3)在步骤(1)溶液中加入10g步骤(2)的酸化硅胶颗粒，继续以50℃加热搅拌直至出现半透明凝胶； (3) adding 10 g of the acidified silica gel particles prepared in step (2) to the solution prepared in step (1), and continuing to heat and stir at 50° C. until a translucent gel appears;
(4)将步骤(3)中的产物过滤，滤渣置于80℃下烘干5h，以去除乙醇溶剂和小分子产物，烘干后的产物置于马弗炉，以300℃烧结12h，制得钛锂离子筛的前驱体。(4) The product in step (3) is filtered, and the filter residue is dried at 80° C. for 5 h to remove the ethanol solvent and small molecular products. The dried product is placed in a muffle furnace and sintered at 300° C. for 12 h to obtain a precursor of a titanium lithium ion sieve.
实施例6Example 6
(1)在500mL乙醇中加入6.6g乙酸锂，17g钛酸四丁酯，加热至50℃搅拌溶解；(1) Add 6.6 g of lithium acetate and 17 g of tetrabutyl titanate to 500 mL of ethanol, heat to 50° C. and stir to dissolve;
(2)将硅胶颗粒置于5mol/L的盐酸中酸化5h，酸化温度50℃，然后将产物烘干得到酸化硅胶颗粒；(2) placing the silica gel particles in 5 mol/L hydrochloric acid for acidification for 5 h at a temperature of 50° C., and then drying the product to obtain acidified silica gel particles;
(3)在步骤(1)溶液中加入2g步骤(2)的酸化硅胶颗粒，继续以50℃加热搅拌直至出现半透明凝胶；(3) Add 2 g of the acidified silica gel particles prepared in step (2) to the solution prepared in step (1), and continue heating and stirring at 50° C. until a translucent gel appears;
(4)将步骤(3)中的产物过滤，滤渣置于80℃下烘干5h，以去除乙醇溶剂和小分子产物，烘干后的产物置于马弗炉，以600℃烧结12h，制得钛锂离子筛的前驱体。(4) The product in step (3) is filtered, and the filter residue is dried at 80° C. for 5 h to remove the ethanol solvent and small molecular products. The dried product is placed in a muffle furnace and sintered at 600° C. for 12 h to obtain a precursor of a titanium lithium ion sieve.
实施例7Example 7
(1)在500mL乙醇中加入6.6g乙酸锂，17g钛酸四丁酯，加热至50℃搅拌溶解；(1) Add 6.6 g of lithium acetate and 17 g of tetrabutyl titanate to 500 mL of ethanol, heat to 50° C. and stir to dissolve;
(2)将硅胶颗粒置于5mol/L的盐酸中酸化5h，酸化温度50℃，然后将产物烘干得到酸化硅胶颗粒；(2) placing the silica gel particles in 5 mol/L hydrochloric acid for acidification for 5 h at a temperature of 50° C., and then drying the product to obtain acidified silica gel particles;
(3)在步骤(1)溶液中加入2g步骤(2)的酸化硅胶颗粒，继续以50℃加热搅拌直至出现半透明凝胶；(3) Add 2 g of the acidified silica gel particles prepared in step (2) to the solution prepared in step (1), and continue heating and stirring at 50° C. until a translucent gel appears;
(4)将步骤(3)中的产物过滤，滤渣置于80℃下烘干5h以去除乙醇溶剂和小分子产物，烘干后的产物置于马弗炉，以300℃烧结24h，制得钛锂离子筛的前驱体。(4) The product in step (3) is filtered, and the filter residue is dried at 80° C. for 5 h to remove the ethanol solvent and small molecular products. The dried product is placed in a muffle furnace and sintered at 300° C. for 24 h to obtain a precursor of a titanium lithium ion sieve.
实施例8Example 8
(1)在500mL乙醇中加入6.6g乙酸锂，8g硫酸氧钛，加热至50℃搅拌溶解；(1) Add 6.6 g of lithium acetate and 8 g of titanyl sulfate to 500 mL of ethanol, heat to 50° C. and stir to dissolve;
(2)将硅胶颗粒置于5mol/L的盐酸中酸化5h，酸化温度50℃，然后将产物烘干得到酸化硅胶颗粒；(2) placing the silica gel particles in 5 mol/L hydrochloric acid for acidification for 5 h at a temperature of 50° C., and then drying the product to obtain acidified silica gel particles;
(3)在步骤(1)溶液中加入2g步骤(2)的酸化硅胶颗粒，继续以50℃加热搅拌直至出现半透明凝胶；(3) Add 2 g of the acidified silica gel particles prepared in step (2) to the solution prepared in step (1), and continue heating and stirring at 50° C. until a translucent gel appears;
(4)将步骤(3)中的产物过滤，滤渣置于80℃下烘干5h以去除乙醇溶剂和小分子产物，烘干后的产物置于马弗炉，以300℃烧结24h，制得钛锂离子筛的前驱体。(4) The product in step (3) is filtered, and the filter residue is dried at 80° C. for 5 h to remove the ethanol solvent and small molecular products. The dried product is placed in a muffle furnace and sintered at 300° C. for 24 h to obtain a precursor of a titanium lithium ion sieve.
将实施例1-8所得的钛锂离子筛的前驱体浸泡于1％盐酸溶液中，搅拌洗脱，同时监测溶液pH，若pH>3则持续加入1％盐酸溶液直至pH稳定在<3，洗净烘干后得到偏钛酸型锂离子筛吸附剂。The precursor of the titanium lithium ion sieve obtained in Example 1-8 is immersed in a 1% hydrochloric acid solution, stirred and eluted, and the pH of the solution is monitored. If the pH is > 3, 1% hydrochloric acid solution is continuously added until the pH stabilizes at < 3. After washing and drying, a metatitanate lithium ion sieve adsorbent is obtained.
以实施例1-8中的前驱体为基础所得到的提锂吸附剂，通过电感耦合等离子直读光谱仪(ICP)分析，得到锂与钛的摩尔比数据。The lithium-extracting adsorbent obtained based on the precursor in Examples 1-8 was analyzed by inductively coupled plasma direct reading spectrometry (ICP) to obtain the molar ratio data of lithium to titanium.
将一定量的吸附剂装入吸附柱，以含有一定浓度Li的溶液进行吸附实验，通过ICP检测进出水Li+浓度，结合吸附溶液体积计算得到吸附剂对锂的饱和吸附量。A certain amount of adsorbent is loaded into the adsorption column, and an adsorption experiment is carried out with a solution containing a certain concentration of Li. The Li + concentration of the inlet and outlet water is detected by ICP, and the saturated adsorption capacity of lithium by the adsorbent is calculated based on the volume of the adsorption solution.
各实施例对应的吸附剂的锂与钛的摩尔比以及对锂的饱和吸附量具体见下表。The molar ratio of lithium to titanium and the saturated adsorption capacity of lithium of the adsorbent corresponding to each embodiment are shown in the table below.
表1
Table 1
应当理解的是，本发明的上述具体实施方式仅仅用于示例性说明或解释本发明的原理，而不构成对本发明的限制。因此，在不偏离本发明的精神和范围的情况下所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。此外，本发明所附权利要求旨在涵盖落入所附权利要求范围和边界、或者这种范围和边界的等同形式内的全部变化和修改例。 It should be understood that the above specific embodiments of the present invention are only used to illustrate or explain the principles of the present invention, and do not constitute a limitation of the present invention. Therefore, any modifications, equivalent substitutions, improvements, etc. made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. In addition, the appended claims of the present invention are intended to cover all changes and modifications that fall within the scope and boundaries of the appended claims, or the equivalent forms of such scope and boundaries.

Claims (10)

  1. 一种硅胶改性的偏钛酸型锂离子筛前驱体的制备方法，其特征在于，包括以下步骤：A method for preparing a silica gel-modified metatitanate-type lithium ion sieve precursor, characterized in that it comprises the following steps:
    S1、将锂盐烘干脱水，然后将干燥的锂盐与钛源在乙醇中溶解；S1, drying and dehydrating the lithium salt, and then dissolving the dried lithium salt and the titanium source in ethanol;
    S2、将硅胶颗粒置于酸液中加热酸化处理，然后将产物烘干得到酸化硅胶颗粒；S2, placing the silica gel particles in an acid solution for heating and acidification treatment, and then drying the product to obtain acidified silica gel particles;
    S3、将S1步骤中的溶液在50℃下加热，并加入S2步骤中的酸化硅胶颗粒，促使Li2TiO3在硅胶多孔结构中沉淀，直至出现半透明凝胶；S3, heating the solution in step S1 at 50°C, and adding the acidified silica gel particles in step S2 to promote the precipitation of Li 2 TiO 3 in the porous structure of the silica gel until a translucent gel appears;
    S4、将S3步骤中所得产物烘干后置于马弗炉中高温烧结，制得。S4, drying the product obtained in step S3 and sintering it at high temperature in a muffle furnace to obtain.
  2. 根据权利要求1所述的制备方法，其特征在于，将S3步骤的产物过滤，滤渣置于80℃下烘干5h，以去除乙醇溶剂和小分子产物。The preparation method according to claim 1 is characterized in that the product of step S3 is filtered and the filter residue is dried at 80° C. for 5 h to remove the ethanol solvent and small molecule products.
  3. 根据权利要求1所述的制备方法，其特征在于，S1步骤中，锂盐为氯化锂、醋酸锂、氢氧化锂、硝酸锂、硫酸锂、磷酸锂、磷酸氢二锂、磷酸二氢锂中的至少一种。The preparation method according to claim 1, characterized in that in step S1, the lithium salt is at least one of lithium chloride, lithium acetate, lithium hydroxide, lithium nitrate, lithium sulfate, lithium phosphate, dilithium hydrogen phosphate, and lithium dihydrogen phosphate.
  4. 根据权利要求1所述的制备方法，其特征在于，S1步骤中，钛源为钛酸四丁酯、硫酸钛、硫酸亚钛、硫酸氧钛中的至少一种。The preparation method according to claim 1, characterized in that in step S1, the titanium source is at least one of tetrabutyl titanate, titanium sulfate, titanous sulfate, and titanyl sulfate.
  5. 根据权利要求1所述的制备方法，其特征在于，S1步骤中，锂盐和钛源的摩尔比为1-5:1。The preparation method according to claim 1, characterized in that in step S1, the molar ratio of the lithium salt to the titanium source is 1-5:1.
  6. 根据权利要求1所述的制备方法，其特征在于，S2步骤中酸液为盐酸、硫酸、硝酸、磷酸中的至少一种，所述酸液的浓度为1-6mol/L。The preparation method according to claim 1 is characterized in that the acid solution in step S2 is at least one of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and the concentration of the acid solution is 1-6 mol/L.
  7. 根据权利要求1所述的制备方法，其特征在于，S2步骤中，酸化温度为40-80℃，酸化处理的时间为6h。The preparation method according to claim 1 is characterized in that in step S2, the acidification temperature is 40-80° C. and the acidification treatment time is 6 hours.
  8. 根据权利要求1所述的制备方法，其特征在于，S2步骤中的硅胶颗粒的添加量为2-16g/L。The preparation method according to claim 1 is characterized in that the amount of silica gel particles added in step S2 is 2-16 g/L.
  9. 根据权利要求1所述的制备方法，其特征在于，S4步骤中，烧结温度为100-600℃，烧结时间为2-24h。The preparation method according to claim 1 is characterized in that in step S4, the sintering temperature is 100-600° C. and the sintering time is 2-24 h.
  10. 一种硅胶改性的偏钛酸型锂离子筛前驱体，其特征在于，采用权利要求1-9任一项所述的制备方法制得。 A silica gel-modified metatitanate-type lithium ion sieve precursor, characterized in that it is prepared by the preparation method described in any one of claims 1 to 9.
PCT/CN2023/127823 2022-10-31 2023-10-30 Silica gel-modified metatitanate-based lithium-ion sieve precursor and method for preparing same WO2024093930A1 (en)

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