Large-scale synthesized high-capacity titanium-based lithium ion sieve and preparation method of inorganic composite adsorption material of high-capacity titanium-based lithium ion sieve

Abstract

The invention discloses a preparation method of a large-scale synthesized high-capacity titanium-based lithium ion sieve and an inorganic composite adsorption material thereof, which mainly comprises the following steps: (1) mixing a lithium source and a titanium source according to a certain molar ratio, and carrying out secondary grinding and roasting to obtain the titanium-based lithium ion sieve; (2) mixing the obtained titanium-based lithium ion sieve with aluminum ore and SiO2 to obtain forming liquid; and (3) carrying out ball dropping molding on the molding liquid through a pneumatic metering pump, and further roasting to obtain the inorganic composite adsorption material. The method not only solves the problem of poor adsorption performance of large-scale synthesis of the titanium-based lithium ion sieve by a high-temperature solid-phase method, but also solves the problem of batch forming of high-viscosity forming liquid, and realizes batch preparation of an inorganic composite adsorption material. Besides, by ingeniously utilizing the micro solution loss effect of the inorganic composite material, synchronous solution loss of the binder and the titanium-based lithium ion sieve is achieved, and the problem that an adsorbent in an adsorption device is repeatedly replaced in the industrial application process of a traditional organic-inorganic composite material is solved.

Description

Technical Field

[0001] The invention belongs to the technical field of lithium extraction, and in particular relates to a method for preparing a large-scale synthetic high-capacity titanium-based lithium ion sieve and an inorganic composite adsorption material thereof. Background Art

[0002] With the rapid development of industries such as new energy vehicles and portable mobile devices, the global demand for lithium has increased year by year. Due to the high lithium adsorption capacity and cycle stability of titanium-based lithium ion sieves, they have received widespread attention in the field of brine adsorption and lithium extraction. The high-temperature solid-phase method is one of the most common methods for preparing titanium-based lithium ion sieves, but in the process of preparing titanium-based lithium ion sieves by the high-temperature solid-phase method, especially in batch synthesis, the liquefaction and phase separation of the lithium source are prone to insufficient reaction of the reactants because the melting point of the lithium source is much lower than that of the titanium source. In addition, since titanium-based lithium ion sieves have a variety of crystal forms, in the process of high-temperature solid-phase preparation, improper control of conditions may easily lead to mutual conversion between different crystal forms. Due to the significant differences in the adsorption capacity of lithium ion sieves of different crystal forms, the adsorption performance of the prepared material is significantly reduced. However, the current patents or research reports related to the synthesis and adsorption of lithium from titanium-based lithium ion sieves are mainly concentrated on the laboratory scale (the single synthesis amount is only grams or a few grams), and few issues such as the impact of batch synthesis and the synthesis process on the adsorption performance of the material are considered. In batch synthesis, the large amount of raw materials, the uneven mixing of raw materials and the large temperature difference inside the material will affect the performance of the prepared material. Although this problem can be improved to a certain extent by using a rotary furnace and extending the insulation time, this will increase the cost of material production.

[0003] Usually, the titanium-based lithium ion sieve prepared by the high temperature solid phase method is a powder. In order to solve the problems such as poor permeability of powder materials in actual industrial applications, it is necessary to prepare it into a certain shape. The commonly used method is to prepare it into microspheres, filaments or foams with organic polymers as binders (such as polyvinyl chloride, polysulfone, polyacrylonitrile, etc.). For example, Chinese patents CN118719025A, CN117563565B, CN118403619A, CN112619621B, etc. all use organic polymers as binders to over-mold lithium ion sieves. However, due to the low hydrophilicity and low permeability of organic polymers, in particular, organic binders form a dense interface layer on the surface of the material, causing the coverage of the active sites of the lithium ion sieve, and seriously inhibiting the mass transfer of lithium ions at the interface during the adsorption process, thereby causing the double decline problem of the adsorption rate and capacity of organic-inorganic composite materials. In addition, the stability of organic polymer binders is much higher than that of titanium-based lithium ion sieves, that is, the dissolution loss of lithium ion sieves is much higher than that of binders. Therefore, after the composite material has been running in the adsorption device for a certain period of time, it is necessary to replace the material regularly, thereby increasing the workload and maintenance costs. Developing an inorganic-inorganic composite adsorption material with inorganic substances as binders to achieve the synchronous dissolution loss of lithium ion sieves and binders during lithium extraction can effectively solve the above problems.

[0004] In summary, the development of a method for scalable batch synthesis of high-capacity titanium-based lithium ion sieves and their inorganic composite materials is of great significance for the development of lithium resources. Summary of the invention

[0005] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a method for preparing a large-scale synthesis of a high-capacity titanium-based lithium ion sieve and an inorganic composite adsorption material thereof. The large-scale synthesis of a high-capacity titanium-based lithium ion sieve is achieved by secondary grinding and roasting of the lithium source and titanium source for synthesizing the titanium-based lithium ion sieve, and the inorganic composite adsorption lithium extraction material and its batch preparation method are obtained by large-scale drop ball granulation using Al2O3 as a binder combined with a pneumatic metering pump.

[0006] The first aspect of the present invention is to provide a method for preparing a large-scale synthesis of a high-capacity titanium-based lithium ion sieve, the steps of which are as follows:

[0007] The lithium source and the titanium source are mixed in a molar ratio of Li:Ti=4:5-2:1 and fully ground. After being calcined in a muffle furnace at 600-850°C for 1-2 hours, the mixture is cooled and taken out for secondary grinding. After the secondary grinding, the mixture is placed in a muffle furnace and calcined at 600-850°C for 1-2 hours. The secondary calcined material is cooled to room temperature to obtain a titanium-based lithium ion sieve.

[0008] The large-scale synthesis of high-capacity titanium-based lithium ion sieve is achieved by secondary grinding and calcining the lithium source and titanium source for synthesizing the titanium-based lithium ion sieve.

[0009] Furthermore, the lithium source is one or more of lithium carbonate, lithium hydroxide or lithium acetate.

[0010] Furthermore, the titanium source is one or more of anatase titanium dioxide, brookite titanium dioxide, rutile titanium dioxide, and tetrabutyl titanate.

[0011] The second aspect of the present invention provides a method for preparing an inorganic composite adsorption material, comprising the following steps:

[0012] Step (1) dissolving aluminum ore in an acidic solution, and adding SiO2 and a titanium-based lithium ion sieve prepared by the method described in any one of claims 1 to 3 to obtain a molding liquid, wherein the aluminum ore accounts for 50wt% to 70wt%, the SiO2 accounts for 0wt% to 1wt%, and the titanium-based lithium ion sieve accounts for 30wt% to 50wt%;

[0013] Step (2) dripping the obtained forming liquid into the solidifying liquid, taking out the balls after forming the balls, washing the balls and placing them in a muffle furnace for calcination to obtain an inorganic composite adsorption material with Al2O3 as the support.

[0014] By using Al2O3 as a binder and combining it with a pneumatic metering pump for large-scale drop ball granulation, an inorganic composite adsorption and lithium extraction material and a batch preparation method thereof are obtained.

[0015] Furthermore, the aluminum ore in step (1) is one or more of boehmite, diaspore, and pseudo-boehmite.

[0016] Furthermore, the SiO2 is one or both of nano-silicon dioxide dispersion and fumed silicon dioxide.

[0017] Furthermore, the hydrogen ion concentration in the acidic solution is 0.01-0.02 mol / L, and the solid-liquid ratio of the aluminum ore to the acidic solution is 1:2-1:5.

[0018] Furthermore, in step (2), a ball dropping device with a pneumatic metering pump is used to drop the obtained molding liquid into the curing liquid, the working interval of the pneumatic metering pump is 40 to 100 ms, and the discharge port pressure is 0.08 to 0.18 MPa.

[0019] Furthermore, the upper layer of the solidified liquid is one or more of gasoline, diesel or kerosene, and the lower layer of the solidified liquid is an alkaline solution.

[0020] Furthermore, the muffle furnace calcination temperature is 500-800°C.

[0021] The advantages and positive effects of the present invention are:

[0022] (1) The present invention solves the problem of low adsorption capacity in the batch synthesis of titanium-based lithium ion sieves by the traditional high-temperature solid phase method through secondary grinding and roasting, and realizes the batch preparation of high-capacity titanium-based lithium ion sieves.

[0023] (2) By using Al2O3 as a binder and combining it with a pneumatic metering pump for ball drop granulation, not only the batch molding problem of high-viscosity molding liquid is solved, but also inorganic composite adsorption materials can be obtained and batch preparation of composite materials can be realized.

[0024] (3) Since the dissolution loss of Al2O3 matches that of titanium-based lithium ion sieve, which is also an inorganic material, the preparation of inorganic composite materials using Al2O3 as a binder not only solves the problem of polymer binders covering the active adsorption sites of lithium ion sieves, but also solves the problem of replacement of organic-inorganic composite materials in industrial applications due to the mismatch between the dissolution loss of organic binders and titanium-based lithium ion sieves, which is conducive to industrialization. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a process flow chart for synthesizing high-capacity titanium-based lithium ion sieve and its inorganic composite material in Example 1.

[0026] Figure 2 This is the XRD diagram of the titanium-based lithium ion sieve prepared by secondary grinding and calcination in Example 1.

[0027] Figure 3 Schematic diagram of the structure of the pneumatic metering pump for preparing the composite material in Example 1.

[0028] Figure 4 This is a physical picture of the inorganic composite material prepared in Example 1.

[0029] Figure 5 is the XRD pattern of the inorganic composite material prepared in Example 1.

[0030] Figure 6 This is a graph showing the relationship between the adsorption capacity of the inorganic composite material prepared in Example 1 and time.

[0031] Figure 7 It is the titanium and aluminum dissolution diagram of the inorganic composite material prepared in Example 1 in an alkaline solution of pH=12 and a 0.25 mol / L hydrochloric acid solution.

[0032] Figure 8 This is the XRD diagram of the titanium-based lithium ion sieve prepared by secondary grinding and calcination in Example 2.

[0033] Fig. 9 This is a physical picture of the inorganic composite material prepared in Example 2.

[0034] Fig.10This is a graph showing the relationship between the adsorption capacity of the inorganic composite material prepared in Example 2 and time.

[0035] Fig.11 It is the compressive strength of the material prepared by adding different masses of SiO2 in Example 3.

[0036] Fig.12 The particle size change of the material prepared by adjusting the pneumatic metering pump at different working intervals in Example 4.

[0037] Fig.13 This is the XRD diagram of the titanium-based lithium ion sieve prepared by single grinding and calcination in Comparative Example 1.

[0038] Fig.14 This is a comparison chart of the adsorption capacity of the titanium-based lithium ion sieve prepared by single grinding and calcination in Comparative Example 1 and the titanium-based lithium ion sieve prepared by secondary grinding and calcination in Example 1 under the same conditions.

[0039] Fig.15 This is a physical picture of the organic-inorganic composite material prepared using polyvinyl chloride as a binder in Comparative Example 2.

[0040] Fig.16 This is a comparison chart of the adsorption performance of the organic-inorganic composite material prepared with polyvinyl chloride as the binder under the same conditions in Comparative Example 2 and the inorganic-inorganic composite material prepared with Al2O3 as the binder in Example 1.

[0041] Fig.17 This is the XRD pattern of the product obtained by primary grinding and secondary calcination in Comparative Example 3.

[0042] Fig.18 This is a comparison chart of the adsorption capacity of the titanium-based lithium ion sieve in Comparative Example 3 and Example 1 under the same conditions.

[0043] Fig.19 This is the XRD pattern of the product obtained by secondary grinding and primary calcination in Comparative Example 4.

[0044] Fig. 20 This is a comparison chart of the adsorption capacity of the titanium-based lithium ion sieve in Comparative Example 4 and Example 1 under the same conditions.

[0045] Fig.21 This is the XRD pattern of the product obtained by three grindings and three calcinations in Comparative Example 5.

[0046] Fig. 22 It is a comparison chart of the adsorption capacity of the titanium-based lithium ion sieve in Comparative Example 5 and Example 1 under the same conditions. DETAILED DESCRIPTION

[0047] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

[0048] Embodiment 1:

[0049] Li2CO3 and TiO2 were mixed in a molar ratio of Li:Ti=2:1 and ground in an agate mortar for 15 minutes. 54±0.1g of the mixture was weighed and placed in a crucible. The crucible was placed in a muffle furnace, heated to 700℃ at a heating rate of 3℃ / min and kept warm for 1 hour. After the material was cooled, it was taken out for secondary grinding. After grinding, it was placed in a muffle furnace again and kept warm at 700℃ for 2 hours. After cooling, the titanium-based lithium ion sieve was obtained.

[0050] Add 0.6mL of concentrated nitric acid to 11mL of water, and weigh 4g of pseudo boehmite (AlOOH·nH2O) and mix with it. After complete dissolution, add 0.4g of silica aqueous dispersion and 1.7g of titanium-based lithium ion sieve obtained by secondary grinding and calcination respectively to obtain a molding liquid. Measure 40mL of water and add 7mL of ammonia water and a certain amount of kerosene. After standing and stratifying, a solidified liquid is obtained. Adjust the working interval of the pneumatic metering pump of the microsphere forming instrument to 40ms and the discharge port pressure to 0.12Mpa, and drip the molding liquid into the solidified liquid. Take out the small balls, wash them, and dry them. Put them in a muffle furnace and calcine them at 700℃ for 1 hour. After cooling, an inorganic composite adsorption material is obtained. See the material preparation process. Figure 1 The XRD pattern of the lithium ion sieve obtained by secondary grinding and calcination is shown in Figure 2 , the schematic diagram of the pneumatic metering pump is shown in Figure 3 . Figure 2 No diffraction peaks of reactants Li2CO3 and TiO2 were observed, and their characteristic peaks corresponded to the XRD peaks of Li2TiO3, indicating that high-purity titanium-based lithium ion sieve was successfully synthesized.

[0051] Figure 4 and Figure 5 The physical picture and XRD diagram of the prepared inorganic composite material are respectively. Figure 4 The particle size of the inorganic composite material is in the range of 0.8 to 1.2 mm, and the material is uniform in structure size and shape without damage. Figure 5 The XRD characteristic peaks of the material correspond to the diffraction peaks of titanium-based lithium ion sieve and Al2O3, respectively, indicating that the inorganic composite material was successfully synthesized and the two did not react to generate other substances during the synthesis process. After the inorganic composite material was washed with 0.25mol / L hydrochloric acid, it adsorbed 25.78mg / L (pH=12) lithium at a solid-liquid ratio of 1:1000. Figure 6 The results show that the adsorption capacity of the material reaches 22.66 mg / g after only 60 minutes, showing excellent adsorption performance. The prepared material was further placed in an alkaline solution of pH = 12 and 0.25 mol / L hydrochloric acid to measure the aluminum and titanium dissolution of the material. The results are shown in Figure 7 . Figure 7The results show that during the five cycles, the titanium-based lithium ion sieve and the Al2O3 support were in a state of synchronous micro-dissolution, which effectively solved the problem of repeated replacement of adsorbents in the adsorption device during industrial applications of traditional organic-inorganic composite materials.

[0052] Embodiment 2:

[0053] In the material synthesis process of Example 1, Li2CO3 and TiO2 were mixed in a molar ratio of Li:Ti=4:5, and the other steps were exactly the same as in Example 1. The XRD pattern of the obtained titanium-based lithium ion sieve is shown in FIG. Figure 8 The actual picture of the composite material and the graph of adsorption capacity changing with time are shown in Fig. 9 and Fig.10 . Figure 8 The results show that high-purity Li4Ti5O was successfully synthesized 12 . Fig.10 The results show that the equilibrium adsorption capacity of the inorganic composite material for 25.78 mg / L (pH=12) lithium exceeds 9.6 mg / g.

[0054] Embodiment 3:

[0055] In the material synthesis process of Example 1, the amount of SiO2 added was changed from 0.4g to 0g and 0.2g, and the other steps were exactly the same as in Example 1. The compressive strength of the obtained composite material was tested, and the results are shown in Fig.11 The results in the figure show that as the amount of SiO2 added increases, the hardness of the composite material increases proportionally. When the amount of SiO2 added is 0.4g, the compressive hardness can reach 18N.

[0056] Embodiment 4:

[0057] During the material synthesis process of Example 1, the particle size of the composite material was changed by adjusting the working interval (60, 80 ms) of the pneumatic quantitative pump of the microsphere forming apparatus. The other steps were exactly the same as those of Example 1. Fig.12 The results show that the particle size of the prepared inorganic composite material increases with the increase of the working interval of the pneumatic metering pump.

[0058] Comparative Example 1:

[0059] In the synthesis process of the titanium-based lithium ion sieve in Example 1, only one grinding and one calcination were performed.

[0060] Li2CO3 and TiO2 were mixed in a molar ratio of Li:Ti=2:1 and ground in an agate mortar for 15 minutes. 54±0.1g of the mixture was weighed and placed in a crucible. The crucible was placed in a muffle furnace and heated to 700℃ at a heating rate of 3℃ / min and kept warm for 3 hours. After cooling, a titanium-based lithium ion sieve was obtained.

[0061] The XRD pattern of the obtained titanium-based lithium ion sieve is shown in Fig.13 . Since the reactants were not ground twice, the product contained XRD diffraction peaks of Li2CO3 and TiO2, indicating that the reactants were not completely reacted. The materials obtained by the first grinding and calcination and the second grinding and calcination in Example 1 were acid-washed with 0.25 mol / L hydrochloric acid solution to obtain a lithium ion sieve with lithium adsorption performance. Lithium was adsorbed under the same conditions (solid-liquid ratio = 1:1000, pH = 12, lithium concentration = 102.03 mg / L). The results are shown in Table 1. Fig.14 . Fig.14 The adsorption capacity of the titanium-based lithium ion sieve synthesized by secondary grinding and calcination is as high as 27.17 mg / g, while the adsorption capacity of the material obtained by single grinding and calcination is only 16.91 mg / g.

[0062] Comparative Example 2:

[0063] The titanium-based lithium ion sieve prepared in Example 1 was used as the active component for adsorbing lithium, and polyvinyl chloride was used as the binder for drop ball molding. The prepared material is shown in FIG. Fig.15 The prepared organic-inorganic composite material and the inorganic-inorganic composite material prepared in Example 1 were subjected to adsorption and lithium extraction under the same conditions (solid-liquid ratio = 1:1000, pH = 12, lithium concentration = 25.78 mg / L). The results are shown in Fig.16 As can be seen from the figure, under the same conditions, the adsorption performance of the inorganic-inorganic composite material prepared with Al2O3 as a binder is much better than that of the organic-inorganic composite adsorption material prepared with polyvinyl chloride as a binder.

[0064] Comparative Example 3

[0065] In the synthesis process of the titanium-based lithium ion sieve in Example 1, one grinding and two calcinations are performed.

[0066] Li2CO3 and TiO2 were mixed in a molar ratio of Li:Ti=2:1 and ground in an agate mortar for 15 minutes. 54±0.1g of the mixture was weighed and placed in a crucible. The crucible was placed in a muffle furnace, heated to 700℃ at a heating rate of 3℃ / min and kept warm for 1 hour. After cooling, the material was placed in a muffle furnace again and kept warm at 700℃ for 2 hours. After cooling, a titanium-based lithium ion sieve was obtained.

[0067] The XRD pattern of the obtained titanium-based lithium ion sieve is shown in Fig.17. Since the reactants were not ground twice, the product contained XRD diffraction peaks of Li2CO3 and TiO2, indicating that the reactants were not completely reacted. The materials obtained by grinding and calcining once in Comparative Example 3 and grinding and calcining twice in Example 1 were pickled with 0.25 mol / L hydrochloric acid solution to obtain a lithium ion sieve with lithium adsorption performance. Lithium was adsorbed under the same conditions (solid-liquid ratio = 1:1000, pH = 12, lithium concentration = 102.03 mg / L). Fig.18 The adsorption capacity of the material obtained after one grinding and two calcinations is only 16.14 mg / g.

[0068] Comparative Example 4

[0069] In the synthesis process of the titanium-based lithium ion sieve in Example 1, secondary grinding and primary calcination are performed.

[0070] Li2CO3 and TiO2 were mixed in a molar ratio of Li:Ti=2:1 and ground in an agate mortar for 15 minutes. 54±0.1g of the mixture was weighed and placed in a crucible. The crucible was placed in a muffle furnace and heated to 700℃ at a heating rate of 3℃ / min and kept warm for 3 hours. After the material was cooled and ground for 15 minutes, a titanium-based lithium ion sieve was obtained.

[0071] The XRD pattern of the obtained titanium-based lithium ion sieve is shown in Fig.19 Since the second grinding is done after the reaction is completed, agglomeration still occurs during the reaction, and Fig.19 The XRD diffraction peaks of Li2CO3 and TiO2 in the sample were obtained, indicating that the reactants were not completely reacted. The materials obtained by secondary grinding and primary calcination in Comparative Example 4 and secondary grinding and secondary calcination in Example 1 were acid-washed with 0.25 mol / L hydrochloric acid solution to obtain a lithium ion sieve with lithium adsorption performance. Lithium was adsorbed under the same conditions (solid-liquid ratio = 1:1000, pH = 12, lithium concentration = 102.03 mg / L). Fig. 20 The adsorption capacity of the material obtained after secondary grinding and primary calcination was 18.11 mg / g.

[0072] Comparative Example 5

[0073] In the synthesis process of the titanium-based lithium ion sieve in Example 1, three grindings and three calcinations were performed.

[0074] Li2CO3 and TiO2 were mixed in a molar ratio of Li:Ti=2:1 and ground in an agate mortar for 15 minutes. 54±0.1g of the mixture was weighed and placed in a crucible. The crucible was placed in a muffle furnace, heated to 700℃ at a heating rate of 3℃ / min and kept warm for 1 hour. After the material was cooled, it was taken out for secondary grinding. After grinding, it was placed in a muffle furnace again and kept warm at 700℃ for 1 hour. After cooling, the material was taken out for third grinding. After grinding, it was placed in a muffle furnace again and kept warm at 700℃ for 1 hour. After cooling, a titanium-based lithium ion sieve was obtained.

[0075] The XRD pattern of the obtained titanium-based lithium ion sieve is shown in Fig.21 The material that was ground three times and calcined three times did not agglomerate. The product XRD diagram showed a single XRD diffraction peak of Li2TiO3, indicating that the reactants reacted completely. The materials obtained by grinding three times and calcining three times in comparative example 5 and by grinding twice and calcining twice in example 1 were pickled with a 0.25 mol / L hydrochloric acid solution to obtain a lithium ion sieve with lithium adsorption performance. Lithium was adsorbed under the same conditions (solid-liquid ratio = 1:1000, pH = 12, lithium concentration = 102.03 mg / L). The results are shown in Table 1. Fig. 22 . Fig. 22 The adsorption capacities of the two are similar, and the surface only needs two grindings and two calcinations.

[0076] It should be understood that the detailed description of the technical solutions of the present invention by means of the preferred embodiments is illustrative rather than restrictive. Those skilled in the art may modify the technical solutions described in the embodiments, or replace some of the technical features by equivalents, based on reading the specification of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention to be protected, and the scope of the present invention to be protected is defined by the attached claims and their equivalents.

Claims

1. A method for preparing a large-scale synthesis of a high-capacity titanium-based lithium ion sieve, characterized in that: Here are the steps: The lithium source and the titanium source are mixed in a molar ratio of Li:Ti=4:5-2:1 and fully ground. After being calcined in a muffle furnace at 600-850°C for 1-2 hours, the mixture is cooled and taken out for secondary grinding. After the secondary grinding, the mixture is placed in a muffle furnace and calcined at 600-850°C for 1-2 hours. The secondary calcined material is cooled to room temperature to obtain a titanium-based lithium ion sieve.

2. The method for preparing a large-scale synthesis high-capacity titanium-based lithium ion sieve according to claim 1, characterized in that: The lithium source is one or more of lithium carbonate, lithium hydroxide or lithium acetate.

3. The method for preparing a large-scale synthesis high-capacity titanium-based lithium ion sieve according to claim 1, characterized in that: The titanium source is one or more of anatase titanium dioxide, brookite titanium dioxide, rutile titanium dioxide and tetrabutyl titanate.

4. A method for preparing an inorganic composite adsorption material, characterized in that: The steps include: Step (1) dissolving aluminum ore in an acidic solution, and adding SiO2 and a titanium-based lithium ion sieve prepared by the method described in any one of claims 1 to 3 to obtain a molding liquid, wherein the aluminum ore accounts for 50wt% to 70wt%, the SiO2 accounts for 0wt% to 1wt%, and the titanium-based lithium ion sieve accounts for 30wt% to 50wt%; Step (2) dripping the obtained forming liquid into the solidifying liquid, taking out the balls after forming the balls, washing the balls and placing them in a muffle furnace for calcination to obtain an inorganic composite adsorption material with Al2O3 as the support.

5. The method according to claim 4, characterized in that: The aluminum ore in step (1) is one or more of boehmite, diaspore and pseudoboehmite.

6. The method according to claim 4, characterized in that: The SiO2 is one or both of nano-silicon dioxide dispersion and fumed silicon dioxide.

7. The method according to claim 4, characterized in that: The hydrogen ion concentration in the acidic solution is 0.01-0.02 mol / L, and the solid-liquid ratio of the aluminum ore to the acidic solution is 1:2-1:

5.

8. The method according to claim 4, characterized in that: In step (2), a ball dropping device with a pneumatic metering pump is used to drop the obtained molding liquid into the solidifying liquid. The working interval of the pneumatic metering pump is 40 to 100 ms, and the pressure at the discharge port is 0.08 to 0.18 MPa.

9. The method according to claim 4, characterized in that: The upper layer of the solidified liquid is one or more of gasoline, diesel or kerosene, and the lower layer of the solidified liquid is an alkaline solution.

10. The method according to claim 4, characterized in that: The calcination temperature of the muffle furnace is 500-800℃.

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