Method for producing titanium-based lithium ion exchanger

Abstract

The present invention relates to a method for producing a titanium-based lithium ion exchanger. The method includes the steps of: producing a lithium metatitanate precursor, i.e., uniformly mixing a titanium source, a lithium source and water in equal proportions by ball milling, adding an auxiliary, and reacting by ultrasonic heating and stirring to obtain the lithium metatitanate precursor powder; producing the lithium metatitanate powder by spray drying and microwave firing using the lithium metatitanate precursor; and elution and replacement, i.e., leaching lithium using an eluent to obtain a lithium ion exchanger. The synthesis reaction is accelerated by strengthening it with ultrasound. In addition, the microwave firing effectively reduces energy consumption. By controlling the titanium ratio to be relatively excessive, a lithium metatitanate powder with high porosity and excellent filterability is produced. The produced lithium ion exchanger has excellent lithium extraction performance while having low loss of titanium solution, meeting the requirements for practical use.

Description

Technical Field

[0001] The present invention relates to the technical field of manufacturing novel chemical substances, and particularly to a method for manufacturing a titanium-based lithium ion exchanger.

Background Art

[0002] With the development of science and technology, research on important lithium salts in the chemical industry and pharmaceutical industry has become more in-depth. In addition, lithium has attracted great attention as a new energy source and strategic resource in the 21st century. With the development of lithium battery technology and the development in the field of controlled nuclear fusion, its role will be further expanded. Currently, the international demand continues to grow at a rate of 7-11% per year. Therefore, lithium is also called the "energy metal of the 21st century" and the "clean energy of the 21st century". Lithium is expected in the new energy field. In order to resolve the contradiction between the increasing market demand and the critical shortage of lithium reserves, people are trying to develop lithium salts from scarce liquid resources. Lithium ion sieve adsorbents have excellent adsorption selectivity and can extract and separate lithium ions from salt water and seawater without waste, so they have attracted the attention of industrial stakeholders.

[0003] Conventional synthesis methods of lithium ion sieve precursors include the sol-gel method, the hydrothermal method, and the high-temperature solid-phase method. The first two methods have problems such as high raw material costs, complex processing, and uncontrollability, so it is difficult to apply them to industrialization. On the other hand, the high-temperature solid-phase synthesis method has simple processing and is easy for mass production, but it is necessary to grind the raw material powder many times to mix it. In addition, it is not easy to control the ratio of lithium to titanium during the process, and it is considered that titanium loss is relatively large in the synthesized lithium ion sieve. Moreover, there are problems such as a long firing time and high temperature, and it is difficult to control the particle size of the synthesized powder. Therefore, further research is needed to improve the technology.

Summary of the Invention

[0004] To solve the problems of the prior art, the main object of the present invention is to provide a lithium metatitanate ion exchanger and a method for producing the same. The production method is a solid-liquid contact reaction, which is easy to accurately control the raw material ratio and the reaction process is gentle. To significantly shorten the reaction time, ultrasonic waves are used to enhance the synthesis reaction. Microwave firing effectively reduces the temperature drop during firing and greatly saves energy. By controlling the ratio of titanium to be relatively excessive, lithium metatitanate powder with a uniform size distribution, high porosity, and excellent filtration performance is produced. The produced lithium ion exchanger has a relatively high adsorption activity and low titanium loss. The produced lithium ion sieve (H2TiO3) powder can selectively recognize and adsorb Li ions from salt lake brine, mother liquor in which lithium is precipitated, high-impurity lithium-containing solutions, lithium battery recovery solutions, and other lithium-containing solutions with high selectivity. It also has characteristics such as a large adsorption capacity, a high adsorption rate, low titanium loss, and excellent cycle stability.

[0005] To achieve the above object, the technical solution adopted in the present invention is as follows. A method for producing a titanium-based lithium ion exchanger, comprising: As the production of a lithium metatitanate precursor, a titanium source, a lithium source, water, and a metal dopant which is a salt doped with metal X are uniformly mixed by ball milling, an auxiliary agent is added, a reaction is caused by ultrasonic heating and stirring, and filtration and washing are performed to obtain the lithium metatitanate precursor in Step 1; As the production of lithium metatitanate powder, The lithium metatitanate precursor is mixed at a solid-liquid ratio of 1:2 to 1:5 to obtain a slurry, a pore-forming agent is added to the slurry, and uniform mixing is performed by ball milling in Ball Milling Step A; The uniformly mixed slurry is spray granulated and dried at a temperature of 150 to 200 °C to obtain a powder in Spray Drying Step B; After firing the powder obtained in Step B at 350 to 750 °C for 6 to 12 hours and then rapidly cooling it to room temperature to obtain the lithium metatitanate powder, there is Step 2 having Firing Step C. Regarding the production of the titanium-based lithium ion exchanger, Step 3, which includes a step of mixing and stirring the powder fired in Step 2 with an eluent to leach lithium ions to obtain the titanium-based lithium ion exchanger. A method for producing a titanium-based lithium ion exchanger comprising the above steps is provided.

[0006] In a preferred embodiment of the present application, the titanium source in Step 1 has a primary particle size of 10 to 50 nm, preferably 10 nm, and a specific surface area of 60 to 400 m 2 / g, preferably 300 m 2 / g of metatitanic acid or titanium dioxide.

[0007] In a preferred embodiment of the present application, in Step 1, the metatitanic acid or titanium dioxide is mixed with water in an amount of 20 to 50% (by mass) of the solid content and pulverized to obtain a uniform slurry. Also, the lithium source is solid lithium hydroxide, and its addition amount is a molar ratio of lithium to titanium of 2 to 2.5:1 to 1.5, more preferably a molar ratio of lithium to titanium of 2.01 to 2.50:1.

[0008] In a preferred embodiment of the present application, the metal dopant in Step 1 is a salt doped with metal X, and the dopant element X is any one or more selected from the group consisting of Mn, V, Fe, Nb, Ce, Mo, Mg, and Al. The addition amount of the metal dopant is a molar ratio of titanium to the metal X dopant of 0.8 to 1.0:0 to 0.2, and the metal X doped salt is a soluble salt or an insoluble salt containing any one or more of the group consisting of Mn, V, Fe, Nb, Ce, Mo, Mg, and Al.

[0009] In a preferred embodiment of the present application, more preferably, the auxiliary agent is hydrogen peroxide solution, and its addition amount is 0.5 to 1.5 times the molar mass of titanium, and the concentration of hydrogen peroxide is 10 to 40 wt%.

[0010] In a preferred embodiment of the present application, for the ultrasonic synthesis reaction in Step 1, the ultrasonic frequency is preferably 30 to 60 KHzThe reaction temperature is preferably 40 to 110 °C, and the reaction time is preferably 2 to 8 hours, and the reaction is carried out under these conditions.

[0011] In a preferred embodiment of the present application, the particle size D50 of the lithium metatitanate precursor powder spray granulated in Step 1 is 20 to 60 μm, and the solid content in the sprayed slurry is controlled to 25 to 60 wt%.

[0012] In a preferred embodiment of the present application, the firing in Step 2 is more preferably carried out at a temperature of 400 to 600 °C for 3 to 6 hours in an air atmosphere, and microwave firing is a more preferred option.

[0013] In a preferred embodiment of the present application, the pore-forming agent in the sprayed slurry in Step 1 is any one or more selected from the group consisting of carbon powder, carbon fiber powder, carbon nanotubes, nanocellulose, sucrose, glucose, polyvinyl alcohol, polysulfone, polyallylsulfone, polyethylene powder, and paraffin powder. The addition amount of the pore-forming agent to the sprayed slurry is 3 to 10 wt% of the mass of the slurry, and the solid content in the sprayed slurry is 30 to 60%.

[0014] In a preferred embodiment of the present application, the eluent in Step 3 is any one or more selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, Na2S2O6, and (NH4)2SO4.

[0015] The present invention has the following beneficial effects compared with the prior art. (1) The manufacturing method is a solid-liquid contact reaction, which is easy to accurately control the raw material ratio, and the reaction process is also gentle. To significantly shorten the reaction time, ultrasonic waves are used to enhance the synthesis reaction. Microwave firing effectively reduces the temperature drop during firing and greatly saves energy. By controlling the ratio of titanium to be relatively excessive, lithium metatitanate powder with a uniform size distribution, high porosity, and excellent filterability is produced. (2) When the manufactured lithium ion exchanger is used to extract lithium from the salt water or simulated salt water of a salt lake, it exhibits high adsorption activity and is applicable to simulated salt water containing 0.1 to 2 g / L of lithium. The lithium adsorption capacity of the lithium ion exchanger is 30 to 50 mg / g. (3) The manufactured lithium ion exchanger has high adsorption selectivity, high adsorption and desorption rates, excellent cycle stability, and a titanium loss of less than 0.01%. (4) The presence of an appropriate excess of titanium during the manufacturing process significantly improves the adsorption performance, filterability, and adsorption capacity of the lithium ion sieve.

Brief Description of the Drawings

[0016]

Figure 1

Figure 2

Figure 3

Figure 4

[0017] A method for manufacturing a titanium-based lithium ion exchanger, As the production of the lithium metatitanate precursor, a titanium source, a lithium source, water, and a metal dopant which is a salt doped with metal X are uniformly mixed by ball milling, an auxiliary agent is added, a reaction is caused by ultrasonic heating and stirring, and filtration and washing are performed to obtain the lithium metatitanate precursor in Step 1, As the production of the lithium metatitanate powder, Mix the lithium metatitanate precursor at a solid-liquid ratio of 1:2 to 1:5 to obtain a slurry, add a pore-forming agent to the slurry, and mix uniformly by ball milling. This is ball milling step A. Spray granulate and dry the uniformly mixed slurry at a temperature of 150 to 200 °C to obtain a powder. This is spray drying step B. After firing the powder obtained in step B at 350 to 750 °C for 6 to 12 hours, rapidly cool it to room temperature to obtain the lithium metatitanate powder. This is firing step C. Step 2 has these steps. Regarding the production of the titanium-based lithium ion exchanger, Step 3 has a step of mixing and stirring the powder fired in step 2 with an eluent to leach lithium ions to obtain the titanium-based lithium ion exchanger. A method for producing a titanium-based lithium ion exchanger includes step 3.

[0018] Preferably, the titanium source in step 1 is metatitanic acid or titanium dioxide with a primary particle size of 10 to 50 nm, preferably 10 nm, and a specific surface area of 60 to 400 m 2 / g, preferably 300 m 2 / g.

[0019] Preferably, in step 1, the metatitanic acid or titanium dioxide is mixed with water in an amount of 20 to 50% (by mass) of the solid content and pulverized to obtain a uniform slurry. Also, the lithium source is solid lithium hydroxide, and its addition amount is a molar ratio of lithium to titanium of 2.01 to 2.5:1.

[0020] Preferably, the metal dopant in step 1 is a salt doped with metal X, the dopant element X is any one or more selected from the group consisting of Mn, V, Fe, Nb, Ce, Mo, Mg, and Al, the addition amount of the metal dopant is a molar ratio of titanium to the metal X dopant of 0.8 to 1.0:0 to 0.2, and the metal X-doped salt is a soluble salt or an insoluble salt containing any one or more of the group consisting of Mn, V, Fe, Nb, Ce, Mo, Mg, and Al.

[0021] Preferably, the auxiliary agent is hydrogen peroxide solution, the addition amount thereof is 0.5 to 1.5 times the molar mass of titanium, and the concentration of hydrogen peroxide is 10 to 40 wt%.

[0022] Preferably, the particle size D50 of the lithium metatitanate precursor powder spray granulated in Step 1 is 20 to 60 μm, and the solid content in the sprayed slurry is controlled to 25 to 60 wt%, more preferably 45 to 55 wt%.

[0023] Preferably, the ultrasonic heating and stirring reaction in Step 1 is carried out under the conditions that the ultrasonic frequency is preferably 30 to 60 KHz , the reaction temperature is preferably 40 to 110 °C, and the reaction time is preferably 2 to 8 hours.

[0024] Preferably, the firing in Step 2 is carried out at a temperature of 400 to 600 °C for 3 to 6 hours in an air atmosphere. Also, microwave firing is a more preferred option.

[0025] Preferably, the pore former in the sprayed slurry in Step 1 is any one or more selected from the group consisting of carbon powder, carbon fiber powder, carbon nanotube, nanocellulose, sucrose, glucose, polyvinyl alcohol, polysulfone, polyallyl sulfone, polyethylene powder, and paraffin powder, and the addition amount of the pore former to the sprayed slurry is 3 to 10 wt% of the mass of the slurry.

[0026] Preferably, the eluent in Step 3 is any one or more selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, Na2S2O6, and (NH4)2SO4.

[0027] By freely combining the main solutions in the present invention with their alternatives, a plurality of solutions can be formed, and all of them can be adopted and claimed in the present invention. Further, each alternative can be arbitrarily combined with other compatible alternatives according to the present invention. For those skilled in the art who understand the solutions of the present invention, a plurality of combinations are obvious based on the prior art and common general knowledge. Also, all the solutions of the present invention are technical solutions protected by the present invention and are not all covered herein.

[0028] Hereinafter, the implementation of the present invention will be described through specific examples. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed herein. The present invention can be implemented or applied in other different specific embodiments. Also, various details in this specification can be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that the following embodiments and the features in the embodiments can be combined with each other in a non - conflicting situation.

[0029] It should be noted that in order to clearly understand the object, technical solution, and advantages of the present invention, the technical solution of the embodiment of the present invention is combined with the drawings of the embodiment and is clearly and completely described as follows. Obviously, the embodiments in this specification are only a part, not all of the embodiments of the present invention. Generally, the components of the embodiments of the present invention described and illustrated in this specification can be arranged and designed in various configurations. According to the present invention, the specific operations in stirring including mechanical stirring and high - speed dispersion are not specified, nor is the brine in the present invention specified. Any operations and brine well - known to those skilled in the art can be used.

[0030] In the data analysis in the following examples, K, Ca, Na, Mg, and B are analyzed by ICP analysis, Cl is analyzed by spectrophotometric colorimetry, Li and Ti are measured by atomic absorption analysis, and sulfate is measured by the barium sulfate turbidimetry method (GB 13580.6-92). The % described in this application indicates the mass percentage, i.e., wt%, unless otherwise specified.

[0031] The chemical composition of the simulated saline water used in the following embodiments is as follows.

[0032]

Table 1

[0033] Embodiment 1 Step 1: 40 kg of metatitanic acid and 10 kg of water are mixed by ball milling to obtain a uniform slurry. 10.5 kg of solid lithium hydroxide and 2.5 g of manganese sulfate are added, and the mixture is heated to 80 °C under the condition that the ultrasonic frequency is 40 KHz and stirred at normal pressure to cause a reaction. During the reaction process, hydrogen peroxide solution (0.5% of the molar mass of titanium) is dropped, and after 2.5 hours, lithium metatitanate precursor is obtained by filtration and washing.

[0034] Step 2: Manufacture of lithium metatitanate powder: Ball milling step A: A small amount of water is added to the lithium metatitanate precursor obtained in Step 1 at a solid-liquid ratio of 1:3.5, mixed to obtain a slurry, 3% of starch is added, and the mixture is uniformly mixed by ball milling. Spray drying step B: The slurry obtained in step A is spray dried at a temperature of 180 °C for preliminary granulation and drying to obtain a powder. Firing step C: The powder obtained in step B is subjected to microwave firing at 410 °C for 4 hours to obtain a precursor Li2TiO3 with a measured porosity of up to 82%.

[0035] Step 3: Manufacture of titanium-based lithium ion exchanger: Mix the powder obtained by firing in Process 2 with an eluent, stir, and leach lithium ions to obtain a lithium-ion exchanger (H2TiO3) doped with manganese.

[0036] Perform an adsorption test using simulated saline on the produced titanium-based lithium-ion exchanger (H2TiO3). The lithium-ion exchanger (H2TiO3) can adsorb 30.5 mg / g of lithium within 1 hour and is judged to reach a saturated lithium adsorption capacity of 46.0 mg / g in 24 consecutive hours. The lithium extraction and recovery efficiency is 99.1%, the elution rate is 99.7%, and the titanium loss is less than 0.050%. Figure 4 shows the static adsorption kinetic curve. According to it, the adsorption equilibrium is almost achieved after 2 hours.

[0037] Embodiment 2 The manufacturing method is the same as that of Embodiment 1, but it is different in that the metal-doped salt manganese sulfate in Step 1 of Embodiment 1 is replaced with aluminum sulfate to produce a doped lithium-ion exchanger.

[0038] Embodiment 3 The manufacturing method is the same as that of Embodiment 2, but it is different in that the metal-doped salt manganese sulfate in Step 1 of Embodiment 2 is replaced with vanadium oxalate to produce a doped lithium-ion exchanger.

[0039] Comparative Example 1 The manufacturing method is the same as that of Embodiment 1, but it is different in that the metal-doped salt manganese sulfate in Step 1 of Embodiment 1 is replaced with magnesium sulfate to produce a doped lithium-ion exchanger.

[0040] Comparative Example 2 The manufacturing method is the same as that of Embodiment 1, but it is different in that the metal-doped salt manganese sulfate in Step 1 of Embodiment 1 is replaced with cobalt sulfate to produce a doped lithium-ion exchanger.

[0041] Comparative Example 3 The manufacturing method is the same as that of Embodiment 1, except that the metal-doped salt manganese sulfate is replaced with nickel sulfate in Step 1 of Embodiment 1 to produce a doped lithium ion exchanger.

[0042] An adsorption test is conducted between the exchanger manufactured as described above and the titanium-based lithium ion exchanger (H2TiO3) manufactured in this embodiment. The specific test results are as follows.

[0043]

Table 2

[0044] Embodiment 4 The manufacturing method is the same as that of Example 1, except that ultrasonic waves are omitted from the precursor synthesis reaction process in Embodiment 1, and a reaction time of 12 hours is required to produce a doped lithium ion exchanger. Also, an adsorption test is conducted on the titanium-based lithium ion exchanger (H2TiO3) manufactured in this embodiment. The specific test results are as follows.

[0045]

Table 3

[0046] Embodiment 5 In the case of the titanium-based lithium ion exchanger (H2TiO3), the manufacturing method is the same as that of Embodiment 1, except that microwave firing is replaced with high-temperature furnace firing, and the firing temperature is 600°C. Also, an adsorption test is conducted on the titanium-based lithium ion exchanger (H2TiO3) manufactured in this embodiment. The specific test results are as follows.

[0047]

Table 4

[0048] Comparative Example 4 The manufacturing method is the same as that of Embodiment 2, except that the firing temperature is 500 °C.

[0049] Comparative Example 5 The manufacturing method is the same as that of Embodiment 2, except that the firing temperature is 700 °C. An adsorption test is conducted on the lithium ion exchanger (H2TiO3) produced in Embodiment 2, Comparative Example 2, and Comparative Example 3. The specific test results are as follows.

[0050] [Table 5]

[0051] Embodiment 6 In the case of the titanium-based lithium ion exchanger (H2TiO3), the manufacturing method is the same as that of Embodiment 1, except that the addition amount of solid lithium hydroxide in Step 1 is a molar ratio of lithium to titanium of 2:1.03 (excess titanium). Further, an adsorption test with simulated salt water is conducted on the produced titanium-based lithium ion exchanger (H2TiO3). The specific test results are as follows.

[0052] [Table 6]

[0053] In the case of the titanium-based lithium ion exchanger (H2TiO3) in Embodiments 7 to 9, the manufacturing method is the same as that of Embodiment 6, except that the conditions of the Li / Ti (molar ratio) for producing the titanium-based lithium ion exchanger (H2TiO3) are different. Further, an adsorption test with simulated salt water is conducted on the titanium-based lithium ion exchanger (H2TiO3) produced under different conditions of the Li / Ti (molar ratio). The specific test results are as follows.

[0054] [Table 7]

[0055] Embodiment 10 In the case of the titanium-based lithium ion exchanger (H2TiO3), the manufacturing method is the same as that of Embodiment 3, but the difference is that the pore former is replaced with chitosan. In addition, an adsorption test in simulated salt water is performed on the manufactured titanium-based lithium ion exchanger (H2TiO3). The specific test results are as follows.

[0056]

Table 8

[0057] Embodiment 11 In the case of the titanium-based lithium ion exchanger (H2TiO3), the manufacturing method is the same as that of Embodiment 3, but the difference is that the pore former is replaced with polysulfone powder. In addition, an adsorption test in simulated salt water is performed on the manufactured titanium-based lithium ion exchanger (H2TiO3). The specific test results are as follows.

[0058]

Table 9

[0059] Note: To measure the porosity of the powder, take 50 g of the ion exchange powder dried to a constant weight, put it into a 100 mL graduated cylinder and vibrate it, and read the volume V1. Take another 50 g of the ion exchange powder dried to a constant weight, add it to a 200 mL graduated cylinder, add water to obtain a slurry that is shaken evenly to mix, add another 15 ml of water, then perform ultrasonic treatment for 15 minutes and leave it for 1 hour. After confirming that the adsorbent is saturated with water, read the total volume V. Then, the porosity Φ = (m - V) / V1 × 100%. Note: The percentage ratios of titanium loss, elution rate, and recovery rate are calculated (mass ratio) according to the industry standard calculation formula.

[0060] Cycle stability experiment Using simulated saline 1, adsorb the lithium ion exchanger (H2TiO3) produced in Embodiment 8 over 1.5 hours, wash it, and then filter it. Analyze the solution using 0.22 mol / L sulfuric acid over 1.5 hours, wash it, and then filter it. Repeat the cycle stability experiment 100 times and measure the lithium ion concentration by ICP analysis. The evaluation results are as follows.

[0061]

Table 10

[0062] The lithium ion exchanger circulates 100 times, and the powder adsorbent has excellent stability. The average Li adsorption capacity is stable at over 27 mg / g, and the recovery rate is over 90%. The Li elution rate is over 95%.

[0063] Adsorption experiments with different saline or lithium-containing solutions:

[0064]

Table 11

[0065] The initial Li adsorption capacity is 25.8 mg / g, and the Li recovery rate is 97.7%. The Li adsorption capacity after 50 cycles is 21.5 mg / g, and the Li recovery rate is 95.8%.

[0066]

Table 12

[0067] The initial Li adsorption capacity is 19.8 mg / g, and the Li recovery rate is 98.5%. The Li adsorption capacity after 50 cycles is 18.5 mg / g, and the Li recovery rate is 95.5%.

[0068]

Table 13

[0069] The initial Li adsorption capacity is 30.8 mg / g, and the Li recovery rate is 96.5%. The Li adsorption capacity after 50 cycles is 25.5 mg / g, and the Li recovery rate is 93.5%. From the above table, it can be seen that the titanium-based lithium ion exchanger produced according to the present invention has excellent adsorption performance and cycle stability.

[0070] The above description of the preferred embodiment should not be construed in a limiting sense. Because those skilled in the art can make improvements or changes according to the above description, and all these improvements and changes should be included in the protection scope of the claims of the present invention.

Claims

1. A method for producing a titanium-based lithium ion exchanger, comprising: As a process for producing a lithium metatitanate precursor, a titanium source, a lithium source, water, and a metal dopant are uniformly mixed by ball milling, an auxiliary agent is added, a reaction is caused by ultrasonic treatment, heating, and stirring, and filtration and washing are performed to obtain the lithium metatitanate precursor. Step 1; As a process for producing lithium metatitanate powder, Water is added to the lithium metatitanate precursor at a solid-liquid ratio of 1:2 to 1:5, mixed to obtain a slurry, a pore-forming agent is added to the slurry, and ball milling step A is performed to uniformly mix the slurry by ball milling; Spray drying step B of spray granulating and drying the uniformly mixed slurry at a temperature of 150 to 200 ° C. to obtain a powder; Step 2 having a firing step C of firing the powder obtained in step B at 350 to 750 ° C. for 6 to 12 hours and then rapidly cooling to room temperature to obtain the lithium metatitanate powder; As a process for producing the titanium-based lithium ion exchanger, Step 3 having a step of mixing and stirring the powder fired in step 2 with an eluent to leach lithium ions to obtain the titanium-based lithium ion exchanger; The metal dopant in step 1 is a salt doped with metal X, the salt is a metal salt containing a cation of the metal X, and the metal X is any one or more selected from the group consisting of Mn, V, Fe, Nb, Ce, Mo, Mg, and Al. The addition amount of the metal dopant is a molar ratio of titanium to the metal X dopant (0.8 or more and 1.0 or less): (greater than 0 and 0.2 or less), and the dopant salt of the metal X contains any one or more of the group consisting of Mn, V, Fe, Nb, Ce, Mo, Mg, and Al. The auxiliary agent is any one selected from the group consisting of hydrogen peroxide solution, ammonium hydroxide, citric acid, and oxalic acid, and the addition amount thereof is (greater than 0 and 1.5 or less) times the mass of titanium. The pore-forming agent is any one or more selected from the group consisting of starch, carbon powder, carbon fiber powder, carbon nanotubes, nanocellulose, sucrose, chitosan, glucose, polyvinyl alcohol, polysulfone, polyallyl sulfone, polyethylene powder, and paraffin powder, and the addition amount of the pore-forming agent is 3 to 10% of the mass of the slurry. A method for producing a titanium-based lithium ion exchanger, characterized in that.

2. The titanium source in step 1 is metatitanic acid or titanium dioxide, the primary particle size of the metatitanic acid or the titanium dioxide is 10 to 50 nm, and its nitrogen adsorption specific surface area is 60 to 400 m ２ / g, and the lithium source is lithium hydroxide. The manufacturing method according to claim 1, characterized in that.

3. The titanium source is mixed with water, the addition amount of the water is 20 to 50 wt% of the solid content, the addition amount of lithium hydroxide is a molar ratio of lithium to titanium of 2 to 2.5: 1 to 1.5, and the molar ratio of titanium to the metal dopant is (0.8 or more and 1.0 or less): (greater than 0 and 0.2 or less). The production method according to claim 1 or 2, characterized in that.

4. The reaction caused by ultrasonic treatment, heating and stirring in step 1 is carried out under the parameters of an ultrasonic frequency of 20 to 60 KHz, a reaction temperature of 20 to 120 ° C, and a reaction time of 4 to 24 hours. The production method according to claim 1, characterized in that.

5. The firing method in step 1 is firing in a high-temperature furnace or microwave firing. The production method according to claim 1, characterized in that.

6. The measured value of the particle size D50 of the lithium metatitanate precursor powder spray granulated in step 1 by laser diffraction method is 20 to 60 μm, and the solid content in the sprayed slurry is controlled to 25 to 60 wt%. The production method according to claim 1, characterized in that.

7. The eluent is any one selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, acetic acid, aqueous citric acid solution, Na ２ S ２ O ６ aqueous solution and (NH ４ ) ２ SO ４ aqueous solution, and the production method according to claim 1 is characterized in that it is any one selected from the group consisting of these.

8. A lithium metatitanate ion exchanger, characterized in that it is produced by the production method according to any one of claims 1 to 7.

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