Method for preparing light energy raw halogen lithium adsorbent by using red mud

Abstract

The application discloses a method for preparing a light energy original halogen lithium adsorbent from red mud, and the red mud is prepared into an adsorbent capable of selectively adsorbing lithium ions in salt lake original halogen by processes such as calcination activation, lithium salt pore expansion and lithium removal. The method uses the red mud as a raw material, realizes high-value comprehensive utilization of the red mud, reduces the environmental pollution caused by the red mud, uses light energy to extract lithium from the salt lake original halogen, effectively reduces the emission of greenhouse gases such as carbon dioxide, and reduces the cost of lithium extraction from the salt lake original halogen in China. The method has important significance for the comprehensive utilization of the red mud and the development and utilization of lithium resources in the salt lake in China.

Description

Technical Field

[0001] This invention relates to the field of lithium extraction technology from salt lakes and utilization of solid waste resources, specifically to a method for preparing a photovoltaic-based lithium extraction adsorbent from red mud. Background Technology

[0002] Red mud is a highly alkaline solid waste generated during the alumina industrial production process, typically producing 1 to 2 tons of red mud for every ton of alumina produced. As the world's largest alumina producer, my country discharges over 100 million tons of red mud annually. With the increasing stockpiles of red mud occupying vast amounts of land and posing environmental and safety risks, maximizing its resource utilization is imperative. Currently, the comprehensive utilization of red mud mainly focuses on valuable metal recovery, soil improvement, and the preparation of concrete cementitious materials, road materials, and building materials. However, at present, the added value of red mud-based products is generally low, resulting in insufficient industrialization momentum. Increasing the added value of red mud-based products can effectively promote the comprehensive utilization of red mud.

[0003] In recent years, the implementation of the national dual-carbon strategy has led to the rapid development of the new energy vehicle industry, which has significantly increased the price of lithium salt raw materials. Although my country possesses abundant brine lithium resources, the actual utilization rate is low. Furthermore, most of my country's salt lakes are located in high-altitude regions such as Qinghai and Tibet, where infrastructure is relatively weak and energy supply is scarce. Traditional salt lake lithium extraction methods are costly and energy-intensive, severely hindering the industrialization of salt lake lithium extraction. Therefore, to overcome these challenges, my country urgently needs to develop a low-cost salt lake brine lithium extraction technology that requires no external energy intervention and relies entirely on local solar energy resources. Utilizing valuable components in red mud to prepare adsorbents for solar energy-based lithium extraction can not only effectively increase the added value of red mud products and solve the problem of comprehensive utilization of red mud, but also reduce the cost of salt lake brine lithium extraction, thereby reducing my country's dependence on imported lithium resources. Summary of the Invention

[0004] This invention provides a method for preparing a photoelectric lithium extraction adsorbent from red mud, which solves the problem of high-value utilization of red mud and reduces the infrastructure requirements for lithium extraction from red mud, thereby reducing the industrialization cost of lithium extraction from red mud.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] A method for preparing a photoelectric lithium-based adsorbent from red mud includes the following steps:

[0007] S01. After drying and crushing the red mud, it is mixed evenly with a lithium salt activator and then calcined to obtain lithium-activated red mud clinker; wherein, the lithium salt activator is one or a mixture of two or more of lithium carbonate, lithium acetate or lithium hydroxide; the calcination temperature is 400~900℃ and the calcination time is 1~12h.

[0008] S02. The clinker obtained in S01 is pulverized and mixed with water to form a suspension. After the reaction is completed, the mixture is filtered and washed to obtain lithium-activated red mud filter cake. The filter cake is dried, ground, and passed through a 200-mesh sieve to obtain lithium-activated red mud concentrate. The mass ratio of lithium-activated red mud clinker to water is 1:(25~100), the reaction temperature is 25~50℃, and the reaction time is 0.5~12h.

[0009] S03. The lithium-activated red mud powder obtained in S02 is mixed evenly with lithium salt porogen, active agent 1 and water, and then subjected to hydrothermal reaction. After the reaction is completed, the precipitate is filtered, washed and dried to obtain the precursor. The lithium salt porogen is one or a mixture of two or more of lithium carbonate, lithium hydroxide, lithium chloride or lithium phosphate; the active agent 1 is one or a mixture of two or more of sodium sulfide, ferric oxalate, ferric acetate, phosphoric acid, lithium silicate or titanium sulfate; the mass ratio of lithium-activated red mud powder to lithium salt porogen, active agent 1 and water is 1:(0.2~2):(0.05~2):(25~85), the reaction temperature is 140~200℃ and the reaction time is 4~18h.

[0010] S04. The precursor obtained in S03 is mixed evenly with active additive 2 and then calcined to obtain a lithium-containing adsorbent; wherein, the active additive 2 is one or a mixture of two or more of bismuth nitrate, titanium nitrate, zinc nitrate, calcium nitrate, bismuth acetate, titanium acetate, zinc acetate, melamine, urea or ferrous sulfide; the calcination temperature is 200~950℃ and the time is 1~12h;

[0011] S05. Add the lithium-containing adsorbent obtained in S04 to the lithium removal solution. After the reaction is completed, filter and wash the precipitate to obtain the light-energy original halide lithium removal adsorbent. The lithium removal solution is one or a mixture of two or more of sulfuric acid, acetic acid, hypochlorous acid, sulfurous acid, sodium persulfate or potassium persulfate.

[0012] In the method for preparing a photoelectric lithium-based adsorbent using red mud as described above, preferably, the lithium salt activator in step S01 is one or a mixture of two or more lithium carbonate or lithium hydroxide.

[0013] In the method for preparing a photoelectric lithium-based adsorbent using red mud as described above, preferably, the calcination temperature in step S01 is 400~900℃ and the calcination time is 1~12h.

[0014] In the method described above for preparing a light-energy lithium-based adsorbent from red mud, preferably, in step S02, the mass ratio of lithium-activated red mud clinker to water is 1:(25~100), the reaction temperature is 25~50℃, and the reaction time is 0.5~4h.

[0015] In the method for preparing a photoelectric lithium-based adsorbent using red mud as described above, preferably, the lithium salt pore-forming agent in step S03 is one or a mixture of two or more of lithium carbonate, lithium hydroxide, lithium chloride, or lithium phosphate.

[0016] In the method for preparing a photoelectric lithium-based adsorbent using red mud as described above, preferably, the active additive 1 in step S03 is one or a mixture of two or more of ferric oxalate, phosphoric acid, lithium silicate, or titanium sulfate.

[0017] In the method described above for preparing a light-energy lithium-based adsorbent using red mud, preferably, in step S03, the mass ratio of lithium-activated red mud powder to lithium salt pore-forming agent, active agent 1, and water is 1:(0.2~2):(0.05~2):(25~85), the reaction temperature is 140~200℃, and the reaction time is 8~18h.

[0018] In the method for preparing a photoelectric lithium extraction adsorbent using red mud as described above, preferably, the active agent 2 in step S04 is one or a mixture of two or more of bismuth nitrate, zinc nitrate, bismuth acetate, titanium acetate, zinc acetate, melamine, urea, or ferrous sulfide.

[0019] In the method for preparing a photoelectric lithium-based adsorbent using red mud as described above, preferably, the calcination temperature in step S04 is 300~800℃ and the time is 1~12h.

[0020] In the method for preparing a photoelectric lithium extraction adsorbent using red mud as described above, preferably, the lithium removal solution in step S05 is one or a mixture of two or more of sulfuric acid, hypochlorous acid, sodium persulfate, or potassium persulfate.

[0021] As described above, in a method for preparing a photo-based lithium extraction adsorbent using red mud, the red mud-based photo-based lithium extraction adsorbent selectively extracts lithium under ultraviolet, visible, or near-infrared light irradiation in step S05, and the adsorbent is then recycled through step S04 after lithium extraction.

[0022] This invention has the following advantages: It enables the high-value comprehensive utilization of red mud, facilitating sustainable resource utilization and reducing environmental pollution. Compared to traditional lithium extraction methods from salt lakes, utilizing solar energy for lithium extraction from salt lake brine can effectively reduce emissions of greenhouse gases such as carbon dioxide, contributing to the achievement of my country's dual-carbon strategy goals. Furthermore, as a distributed energy source, solar energy holds promise as a novel, low-cost lithium extraction technology applicable to various regions, holding significant importance for the development and utilization of lithium resources in my country's salt lakes. Attached Figure Description

[0023] Figure 1The X-ray powder diffraction patterns are those of the red mud-based photoelectric lithium extraction adsorbents provided in Examples 1-3 of this invention. Detailed Implementation

[0024] The following examples are used to illustrate the present invention, but are not intended to limit the scope of the invention. Example

[0025] The chemical composition of red mud from a Bayer process in Shandong Province is shown in Table 1. After drying and crushing, it was mixed with lithium carbonate, ground, and sieved through a 200-mesh sieve. The sieved raw material was calcined at 800℃ for 2 hours to obtain clinker. The clinker was then ground and added to water at 50 times its weight with continuous stirring. The system was heated to 40℃ and reacted for 2 hours. After the reaction, it was filtered and washed three times. The filter cake was dried, crushed, and sieved through a 200-mesh sieve to obtain lithium-activated red mud powder. Then, the lithium-activated red mud powder, lithium hydroxide, phosphoric acid, and water were mixed evenly at a mass ratio of 1:0.45:0.1:80, and subsequently subjected to a hydrothermal reaction at 180℃ for 12 hours. After the reaction, the precipitate was filtered, washed three times, dried, mixed evenly with urea, and calcined at 550℃ for 4 hours to obtain a lithium-containing adsorbent. The lithium-containing adsorbent was then added to a sodium persulfate delithiation solution for delithiation. After delithiation, the precipitate was filtered and washed to obtain the red mud-based photovoltaic lithium extraction adsorbent. The photo-based lithium-extraction adsorbent material was placed in the raw brine of Zabuye Salt Lake, the main components of which are shown in Table 2. Under irradiation with a 300W xenon lamp, the material adsorbed up to 27.8 mg / g of lithium in the brine after 3 days.

[0026] Table 1 Chemical composition of red mud from Shandong

[0027]

[0028] Table 2. Main components of raw brine from Zabuye Salt Lake (g / L)

[0029]

[0030] Example 2

[0031] The chemical composition of red mud from a Bayer process in Henan Province is shown in Table 3. After drying and crushing, lithium hydroxide was added, mixed, ground, and sieved through a 200-mesh sieve. The sieved raw material was calcined at 600℃ for 8 hours to obtain clinker. The clinker was then ground and added to water at 80 times its weight with continuous stirring. The system was heated to 50℃ and reacted for 2 hours. After the reaction, the mixture was filtered and washed three times. The filter cake was dried, crushed, and sieved through a 200-mesh sieve to obtain lithium-activated red mud powder. Then, the lithium-activated red mud powder, lithium phosphate, lithium silicate, and water were mixed evenly at a mass ratio of 1:0.85:0.05:85, and subjected to a hydrothermal reaction at 200℃ for 8 hours. After the reaction, the precipitate was filtered, washed three times, dried, mixed evenly with titanium acetate, and calcined at 500℃ for 4 hours to obtain a lithium-containing adsorbent. Subsequently, the lithium-containing adsorbent was added to a potassium persulfate delithiation solution for delithiation. After delithiation, the precipitate was filtered and washed to obtain the red mud-based photovoltaic lithium extraction adsorbent. The photo-energy lithium adsorbent material was placed in the brine of Yiliping Salt Lake, the main components of which are shown in Table 4. Under natural light irradiation, the material adsorbed up to 25.4 mg / g of lithium in the brine after 7 days.

[0032] Table 3 Chemical composition of red mud from Henan

[0033]

[0034] Table 4. Main components of raw brine in Yiliping Salt Lake (g / L)

[0035]

[0036] Example 3

[0037] The chemical composition of red mud from a Bayer process in Guangdong is shown in Table 5. After drying and crushing, lithium hydroxide was added, mixed, ground, and passed through a 200-mesh sieve. The sieved raw material was calcined at 750℃ for 4 hours to obtain clinker. The clinker was then ground and added to water at 80 times its weight with continuous stirring. The system was heated to 30℃ and reacted for 8 hours. After the reaction, the mixture was filtered and washed three times. The filter cake was dried, crushed, and passed through a 200-mesh sieve to obtain lithium-activated red mud powder. The lithium-activated red mud powder, lithium hydroxide, titanium sulfate, and water were then mixed evenly at a mass ratio of 1:0.85:0.05:85. A hydrothermal reaction was then carried out at 160℃ for 8 hours. After the reaction, the precipitate was filtered, washed three times, dried, mixed evenly with zinc nitrate, and calcined at 250℃ for 4 hours to obtain a lithium-containing adsorbent. The lithium-containing adsorbent was then added to a sulfuric acid solution for delithiation. After delithiation, the precipitate was filtered and washed to obtain the red mud-based photovoltaic lithium extraction adsorbent. The photo-based lithium adsorbent material was placed in the brine of Dongtai Jinaier Salt Lake, the main components of which are shown in Table 6. Under irradiation with a 100W mercury lamp, the material adsorbed up to 24.7 mg / g of lithium in the brine after 5 days.

[0038] Table 5 Chemical composition of red mud from Guangdong

[0039]

[0040] Table 6. Main components of raw brine in Dongtai Jinaier Salt Lake (g / L)

[0041]

[0042] Although the present invention has been described in detail above with general descriptions and specific embodiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. A method for preparing a photoelectric lithium-based adsorbent from red mud, characterized in that... Includes the following steps: S01. After drying and crushing the red mud, it is mixed evenly with a lithium salt activator and then calcined to obtain lithium-activated red mud clinker; wherein, the lithium salt activator is one or a mixture of two or more of lithium carbonate, lithium acetate or lithium hydroxide; the calcination temperature is 400~900℃ and the calcination time is 1~12h. S02. The clinker obtained in S01 is crushed and mixed with water to form a suspension. After the reaction is completed, it is filtered and washed to obtain lithium-activated red mud filter cake. The filter cake is dried, ground and sieved to obtain lithium-activated red mud concentrate. The mass ratio of lithium-activated red mud clinker to water is 1:(25~100), the reaction temperature is 25~50℃, and the reaction time is 0.5~12h. S03. The lithium-activated red mud powder obtained in S02 is mixed evenly with lithium salt porogen, active agent 1 and water, and then subjected to hydrothermal reaction. After the reaction is completed, the precipitate is filtered, washed and dried to obtain the precursor. The lithium salt porogen is one or a mixture of two or more of lithium carbonate, lithium hydroxide, lithium chloride or lithium phosphate; the active agent 1 is one or a mixture of two or more of sodium sulfide, ferric oxalate, ferric acetate, phosphoric acid, lithium silicate or titanium sulfate; the mass ratio of lithium-activated red mud powder to lithium salt porogen, active agent 1 and water is 1:(0.2~2):(0.05~2):(25~85), the reaction temperature is 140~200℃ and the reaction time is 4~18h. S04. The precursor obtained in S03 is mixed evenly with active additive 2 and then calcined to obtain a lithium-containing adsorbent; wherein, the active additive 2 is one or a mixture of two or more of bismuth nitrate, titanium nitrate, zinc nitrate, calcium nitrate, bismuth acetate, titanium acetate, zinc acetate, melamine, urea or ferrous sulfide; the calcination temperature is 200~950℃ and the time is 1~12h; S05. Add the lithium-containing adsorbent obtained in S04 to the lithium removal solution. After the reaction is completed, filter and wash the precipitate to obtain the red mud photovoltaic lithium extraction adsorbent. The lithium removal solution is one or a mixture of two or more of sulfuric acid, acetic acid, hypochlorous acid, sulfurous acid, sodium persulfate or potassium persulfate.

2. The method for preparing a photoelectric lithium-based adsorbent from red mud according to claim 1, characterized in that, In step S01, the calcination temperature is 600~900℃ and the calcination time is 2~12h.

3. The method for preparing a photoelectric lithium-based adsorbent from red mud according to claim 1, characterized in that, In step S04, the calcination temperature is 250~950℃ and the time is 4~12h.

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