CN111250063A - Preparation of conductive manganese-titanium lithium ion sieve/graphene composite hydrogel and application of conductive manganese-titanium lithium ion sieve/graphene composite hydrogel in extraction of lithium from salt lake brine - Google Patents
Preparation of conductive manganese-titanium lithium ion sieve/graphene composite hydrogel and application of conductive manganese-titanium lithium ion sieve/graphene composite hydrogel in extraction of lithium from salt lake brine Download PDFInfo
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Abstract
The invention discloses a preparation method of conductive manganese-titanium lithium ion sieve/graphene composite hydrogel and application of the conductive manganese-titanium lithium ion sieve/graphene composite hydrogel in lithium extraction from salt lake brine. The method adopts an adsorption-electrodeionization exchange method, utilizes MnTi/GNs-LIPs adsorbent to selectively adsorb lithium in salt lake brine, then places the salt lake brine in a single weak acid solution, rapidly desorbs the lithium through electrodeionization exchange, and can achieve the purpose of classifying and recovering the lithium in the salt lake brine after repeated operation.
Description
Technical Field
The invention relates to a material and a method for extracting lithium from salt lake brine, in particular to preparation of conductive manganese-titanium lithium ion sieve/graphene composite hydrogel and application of the conductive manganese-titanium lithium ion sieve/graphene composite hydrogel in extraction of lithium from salt lake brine.
Background
The demand for lithium from clean energy sources is increasingly strong at home and abroad. The salt lake brine has complex components and rich lithium resources, but is difficult to separate. Although the ion exchange adsorption method requires complicated processes such as adsorption, desorption, backwashing, regeneration, metal extraction and the like, the ion exchange adsorption method is often used for extracting lithium from salt lake brine due to simple process (jiaxu macro and the like, guangzhou chemical engineering, 38, 2010, 10). Lithium manganate ion sieves are one of the most preferred adsorbents because of their good lithium adsorption performance and high cost performance (Mapehua et al, application No. 02145582.1; Zhanghui et al, application No. 20101028.648.0; Xiaoguoshu et al, application No. 201010250056.4; Shixingchang et al, application No. 201010285009.3). The study showed that: lithium manganate (LiMnO) (LW. Ma et al, Transactions of non-ferrous Metals Society of China,2011,21:1660) can be prepared by hydrothermal reaction, sol-gel, solid-phase reaction and the like. Acid precipitation of Li in LiMnO+Elution (HMnO), leaving Li behind+Imprinting, HMnO can selectively extract Li from dilute solution+(ii) a However, the stability of HMnO is relatively weak because of Mn during pickling4+Can stay in the spinel structure, Mn2+Soluble in solution, resulting in Mn3+And Mn4+And Mn2+Disproportionate, such that the original structure gradually collapses, eventually leading to a decrease in adsorption performance (LW. Ma et al, Transactions of non-ferrous Metals Society of China,2011,21: 1660; A. Siekiereka et al, Separation and Purification Technology,2018,194: 231). In order to improve the stability of the structure in the acid washing process, researchers respectively adopt a molten salt method and a sol-gel method to prepare a transition metal Ti and other doped lithium manganate compound (Cuiyun et al, application number: 201611191626.0; T.Ryu et al, Hydrometallurgy,2019,184:22) and adopt a reverse suspension polymerization method to prepare a polyacrylamide coated manganese adsorbent compound (JL.Xiao et al, Chemical Engineering Journal 279,2015,659). The structure and the performance of the doped manganese-based lithium ion sieve are improved.
At present, salt lake enterprises adopt an adsorption-acid washing desorption method, manganese-based materials are used as adsorbents, and lithium is extracted from brine after potassium extraction. The method has the advantages of long production period, high acid and water consumption and serious equipment corrosion; furthermore, the structure of the manganese-based sorbent remains inevitably damaged during the continued elution of lithium from the sorbent with strong acids (jiaxu macro et al, guang zhou chemical, 38, 2010, 10). The improvement of the lithium extraction method is imminent. On the other hand, the electrodeionization technology is based on the principle of electric double layer capacitance, takes electrons as driving force, is simple, convenient and quick to operate, clean and environment-friendly, and is widely used for seawater desalination and industrial wastewater desalination (CC. Huang, Chemical Engineering Journal 2013,221: 469; J.Li et al, Carbon,2018,129: 95). However, the salt lake region is wide in margin, the brine stock is huge, the components are complex, and the method cannot be directly adopted for selectively extracting lithium from the salt lake brine by adopting an electrodeionization exchange method. If the conductive manganese-based adsorption material can be prepared, the selective adsorption technology and the electrodeionization exchange technology are combined, the technology for extracting lithium from salt lake brine is expected to be improved, and the lithium separation efficiency is improved.
Disclosure of Invention
The invention provides a preparation method of conductive manganese-titanium lithium ion sieve/graphene composite hydrogel and application of the conductive manganese-titanium lithium ion sieve/graphene composite hydrogel in lithium extraction from salt lake brine. The method adopts a sol-gel method to prepare the manganese-titanium lithium ion sieve, and prepares the manganese-titanium lithium ion sieve/graphene composite hydrogel (MnTi/GNs-LIPs) through an in-situ thermal initiation polymerization method. The method adopts an adsorption-electrodeionization exchange method, utilizes MnTi/GNs-LIPs adsorbent to selectively adsorb lithium in salt lake brine, then places the salt lake brine in a single weak acid solution, rapidly desorbs the lithium through electrodeionization exchange, and can achieve the purpose of classifying and recovering the lithium in the salt lake brine after repeated operation.
The preparation method of the conductive manganese-titanium lithium ion sieve/graphene composite hydrogel (HMnTi/GNs-LIPs) comprises the following steps:
step 1: preparation of manganese-titanium lithium ion sieve (HMnTi) by sol-gel method
1a, adding lithium salt into 100mL of 10-100% ethanol water solution to obtain a solution A; sequentially adding manganese salt, titanate and a complexing agent into 100mL of 10-100% ethanol aqueous solution to obtain solution B;
1B, dropwise adding the solution A into the solution B, adding a catalyst to form a sol solution C, reacting the sol solution C at 10-100 ℃ for 6-24h to form sol gel, and grinding to obtain a precursor D;
1c, roasting the obtained precursor D, heating to 200-600 ℃ by a program of 5-10 ℃/min, and reacting for 6-24 h; and then the temperature is increased to 600-900 ℃ by the program of 5-10 ℃/min, the reaction is carried out for 6-24h, a manganese-titanium lithium compound (marked as LiMnTi) is formed, and the manganese-titanium lithium ion sieve (HMnTi) is formed after the manganese-titanium lithium compound is washed for 2-10h by 5% hydrochloric acid and is dried.
The lithium salt is one of lithium acetate, lithium chloride and lithium sulfate.
The manganese salt is one of manganese carbonate, manganese sulfate and manganese chloride.
The titanate is one of tetrabutyl titanate and tetrapropyl titanate.
The complexing agent is one of ethylenediamine tetraacetic acid, citric acid, triethanolamine and tartaric acid.
The molar ratio of the lithium salt, the manganese salt, the titanate and the complexing agent is 1: 1: 1: 1-5: 5: 2: 1.
the catalyst is one or two of hydrochloric acid, perchloric acid, acetic acid and phosphoric acid, the concentration is 1M, the dosage of the catalyst and the volume ratio of reactants (the volume of the reactants refers to the total volume of the solution A and the solution B) are 1: 50-1: 300.
step 2: in-situ thermal initiation polymerization method for preparing HMnTi/GNs-LIPs
Adding graphene oxide into 100mL of 10-100% ethanol aqueous solution to form a suspension, adding the HMnTi obtained in the step 1, and performing ultrasonic mixing to obtain a mixture E; and adding unsaturated amide, a cross-linking agent and an initiator into the mixture E, carrying out in-situ thermal initiation polymerization reaction for 1-12h at the temperature of 30-100 ℃, then placing the mixture into a reducing agent solution, carrying out reaction for 2-24h at the temperature of 10-100 ℃, crushing and drying the product to obtain the conductive manganese-titanium lithium ion sieve/graphene composite hydrogel (HMnTi/GNs-LIPs).
The graphene oxide used in the present invention is prepared by the conventional method, such as ZL 201510703334X.
The unsaturated amide is one of acrylamide and isopropyl acrylamide, and the concentration is 0.3M-3.0M.
The cross-linking agent is one of N-methylol acrylamide, ethylenediamine and N, N-methylene bisacrylamide.
The initiator is one of ammonium persulfate, potassium persulfate and sodium persulfate.
The molar ratio of the unsaturated amide to the cross-linking agent to the initiator is 100: 1: 1-100: 4: 1; the total mass ratio of HMnTi and the above reactants (acrylamide, crosslinker and initiator) is 1: 1-1: 10.
in the graphene oxide suspension, the content of graphene is 1-4 mg/mL.
The reducing agent is one of sodium nitrite, glucose, ascorbic acid and sodium thiosulfate, the concentration of the reducing agent solution is 1-3M, and the volume ratio of the reducing agent solution to the graphene oxide solution is 1: 10-1: 100.
the application of the conductive manganese-titanium lithium ion sieve/graphene composite hydrogel (HMnTi/GNs-LIPs) prepared by the invention is to recover Li in salt lake brine by adopting an adsorption-electrodeionization exchange desorption method by taking HMnTi/GNs-LIPs as an adsorption material+The method comprises the following steps:
step 1: HMnTi/GNs-LIPs adsorbing Li in salt lake brine+
Adding 5L of salt lake brine into the container, adjusting the pH value to 3-11, and filtering for later use; adding 50g of HMnTi/GNs-LIPs into salt lake brine, and adsorbing Li at 10-50 DEG C+Taking out the mixture for 6 to 24 hours, and then putting the mixture into a conductive packed bed electrode; treating 20 salt lake brine samples by the same method to obtain 20 conductive packed bed electrodes for later use;
step 2: method for recovering Li in salt lake brine by electrodeionization exchange desorption method+
Adopting a three-electrode system, and respectively and sequentially placing the packed bed electrodes in the solution H to be used as working electrodes; adjusting pH to 3-6, sweeping at a sweep rate of 50mV/s and cyclic voltammetry for 20-60min at a potential range of-0.5V to +1.5V to make Li contained in the packed bed electrodes (LiMnTi/GNs-LIPs)+And the positive ions in the solution H are subjected to electrodeionization exchange to desorb Li+Synchronously regenerating the material(HMnTi/GNs-LIP), and can be reused after being taken out. By determining whether the characteristic peak (55.14eV) of Li1s in X-ray photoelectron spectroscopy (XPS) has disappeared+And (4) desorption effect.
And (3) repeating the step (1) and the step (2) for 10 times to obtain the LiCl brine purification solution.
The solution H is an ammonium chloride solution or an ammonium sulfate solution, and the concentration is 1-4M; the pH was adjusted with 2M hydrochloric acid or sulfuric acid.
The composition of the salt lake brine is shown in Table 1, wherein the initial content of LiCl is 0.08-0.13 g/L.
In the three-electrode system, one of silver, silver chloride, carbon fiber cloth or titanium is used as a reference electrode; one of graphite, titanium or carbon fiber cloth is used as a counter electrode.
The pH of the salt lake brine is regulated and controlled by one or two of hydrochloric acid, ammonia water and sodium hydroxide; the concentration is 1-4M.
The packed bed is rectangular and is made of one of carbon fiber cloth (fixed by a titanium frame), stainless steel, a titanium net and a nickel net; the mesh had a pore size of 10 microns, dimensions of 8cm x 3cm x 2cm, and an inlet diameter of 3 cm.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention designs and prepares from multiple angles: manganese-titanium lithium ion sieve and graphene composite hydrogel (HMnTi/GNs-LIPs). In order to protect the stability of the material in strong acid washing, titanium is doped to stabilize the structure of the material, and polyacrylamide hydrogel is coated on the titanium doped to stabilize the structure of the material. In order to improve the desorption process, conductive three-dimensional reticular graphene-polyacrylamide hydrogel is coated on the periphery of HMnTi to form the granular conductive adsorbent (HMnTi/GNs-LIPs) which has good lithium adsorption capacity and stable structure.
2. The invention adopts an adsorption-electrodeionization exchange desorption method, uses conductive HMnTi/GNs-LIPs as an adsorbent, selectively adsorbs lithium, then is placed in a conductive packed bed as a working electrode, is placed in a low-concentration acidic ammonium salt solution, and passes through Li on the adsorbent+And H in solution+And NH4 +Performing electrodeionization exchange, rapidly desorbing lithium, and synchronously making the materialAnd (4) generating. The lithium brine purification solution is formed repeatedly. Compared with the original adsorption-strong acid elution adsorption method, the technology of the invention is convenient to operate and separate, and the time consumption is shortened by 1/3; and the acid consumption is reduced by 50%, the corrosion of equipment is light, and the energy is saved and the consumption is reduced.
Drawings
FIG. 1 is a scanning electron micrograph (FE-SEM) of (A) before acid washing of LiMnTi, (B) after acid washing of HMnTi, after acid washing of (C) before acid washing of HMnTi/GNs-LIPs, (C) after acid washing of (C) and after 5 times of continuous adsorption/desorption of HMnTi/GNs-LIPs. Comparing the structural findings before and after acid pickling of manganese-titanium-lithium complexes (LiMnTi, a): after pickling, the surface gaps of HMnTi (B) become larger, but cubic particles are still distributed, and the structure is basically stable. Before acid pickling (C) of the manganese-titanium lithium ion sieve and graphene composite hydrogel (HMnTi/GNs-LIPs), LiMnTi particles are distributed in a net structure; after acid washing, the hydrogel network presents a dense porous structure, and granular HMnTi is distributed in the pores. After 5 consecutive adsorptions/desorbations of HMnTi/GNs-LIPs (D), the HMnTi particles are still clearly visible, which indicates that the material of the invention is structurally stable during the recovery of lithium.
FIG. 2 shows the adsorption of Li onto LiMnTi before (a), HMnTi (b), HMnTi/GNs-LIPs (c), and HMnTi/GNs-LIPs after acid washing+After (d), and its desorption of Li+X-ray diffraction pattern (XRD) of the latter (e). LiMnTi (a) has main peaks 2 theta at 18.80(111), 36.26(311) and 44.06(400), interplanar spacings (d) of 4.70, 2.47 and 2.05, respectively, characteristic peaks and Li4Mn3.5Ti1.5O12Consensus (MLP Le, et al, Journal of Physics and Chemistry of Solids,2011,72: 124); after acid washing, HMnTi (H) can be obtained4Mn3.5Ti1.5O12B) having main peaks 2 theta at 19.14, 37.00 and 44.96 and interplanar spacings (d) of 4.62, 2.42 and 2.01, respectively. Compared with the prior art, the peak of the HMnTi X-ray after acid cleaning is shifted positively, the interplanar spacing is reduced, and the crystal lattice is contracted. In HMnTi/GNs-LIPs, peaks of HMnTi at 111,311 and 400 are clearly visible, and the peak intensity is relatively reduced due to the coating in the hydrogel; in addition, the characteristic peak 2 θ of reduced graphene oxide is around 19, overlapping with the 111-plane peak of HMnTi (H Jo, et al, Acta biomaterials 2017,48: 100). The investigation shows that: HMnTi/GNs-LIPs adsorbing Li+(d) Then desorb Li+Thereafter, (e) both characteristic peaks were identical to those of HMnTi/GNs-lips (c). This indicates that the material of the present invention is structurally stable during the recovery of lithium.
FIG. 3 shows the adsorption of Li onto LiMnTi before (a), HMnTi (b), HMnTi/GNs-LIPs (c), and HMnTi/GNs-LIPs after acid washing+After (d), and its desorption of Li+Infrared (IR) profile of the latter (e). In curve a, 1632cm-1Is formed by carbon coated on LiMnTi, and has a-C ═ O stretching vibration peak of 625cm-1And 503cm-1With two peaks being MnO6 -Asymmetric stretching vibration peak of functional group. After pickling, 900cm in curve b-1A proton coupling vibration peak of 625cm-1And 503cm-1There was a significant enhancement of the doublet (characteristic peak of lithium ion sieve) indicating HMnTi formation. In curve c, the distance is divided by 900cm-1The peak disappears, and the diffraction peak of HMnTi is visible at 2924cm-1In the long alkyl chain is-CH2Asymmetric stretching vibration peak, 1657 and 1458cm-1Is an asymmetric and symmetric stretching vibration peak of-C ═ O in the carbonate, 1110cm-1The peak is the absorption peak of C-N bond, indicating the formation of HMnTi/GNs-LIPs. Curves d and c are essentially the same, indicating that HMnTi/GNs-LIPs adsorb Li+After that, the structure thereof is not changed. When Li is present+Adsorption of Li from HMnTi/GNs-LIPs+After upper desorption (e), 1650-1The peak becomes wider at 625cm-1And 503cm-1The double peaks are obvious, and other peaks exist, which indicates that the structure of the material is intact.
FIG. 4 shows the adsorption of Li by HMnTi/GNs-LIPs+Front (a), adsorption of Li+After (b), and its desorption of Li+And (c) thereafter, Li (A) and total (B) X-photoelectron spectroscopy (XPS). As can be seen from the figure: adsorption of Li by HMnTi/GNs-LIPs+First is free of Li+Peak (a); when it adsorbs Li+Thereafter, a Li1s peak (b) is exhibited; desorption of Li+After that (c), the peak of Li1s (55.14eV) disappeared and returned to substantially the original shape, which is in accordance with the curve a. The adsorption-electrodeionization exchange method adopted by the invention can be used for Li in salt lake brine+And (4) recovering.
Detailed Description
Example 1:
1. preparation of conductive manganese-titanium lithium ion sieve/graphene composite hydrogel (HMnTi/GNs-LIPs)
(1) Preparation of manganese-titanium lithium ion sieve (HMnTi)
To 100mL of 50% aqueous ethanol, 1.8g of lithium acetate (solution A) was added. To 100mL of 90% ethanol aqueous solution were added 4.5g of manganese chloride, 7.5g of tetrapropyl titanate, and 3.5g of triethanolamine (solution B), in that order. A was added dropwise to B, and 2mL of 1M phosphoric acid was added to form a sol solution C. And reacting the C for 6 hours at 90 ℃ to form sol-gel, and grinding to obtain a precursor D. Roasting the D, firstly, carrying out temperature programming to 300 ℃ at the speed of 5 ℃/min, and reacting for 10 hours; and then the temperature is programmed to 700 ℃ at the speed of 10 ℃/min, and the reaction is carried out for 8 hours, so as to form a manganese-titanium-lithium compound (marked as LiMnTi). And washing LiMnTi with 5% hydrochloric acid for 6h, and drying to form a manganese-titanium lithium ion sieve (HMnTi) for later use.
(2) In-situ thermal initiation polymerization method for preparing HMnTi/GNs-LIPs
After 0.4g of graphene oxide was added to 100mL of a 90% ethanol solution to form a suspension, 6g of HMnTi was added thereto and uniformly mixed by sonication (mixture E). To E were added 15g of acrylamide 0.5g N, N-methylenebisacrylamide and 0.5g of sodium persulfate, and the mixture was mixed by sonication to homogeneity (mixture F). And (3) carrying out in-situ thermal initiation polymerization reaction on the F at the temperature of 45 ℃ for 14h to obtain a product G, putting the product G into 20mL of 2M sodium nitrite solution, reacting at the temperature of 40 ℃ for 3h, crushing and drying the product to form the conductive manganese-titanium lithium ion sieve/graphene composite hydrogel (HMnTi/GNs-LIPs).
2. HMnTi/GNs-LIPs are used as adsorption materials, and an adsorption-electrodeionization exchange desorption method is adopted to recover Li in salt lake brine+
(1) HMnTi/GNs-LIPs adsorbing Li in salt lake brine+
Adding 5L of salt lake brine (LiCl initial content is 0.11 g/L-0.0026M) into a barrel, adjusting pH to 9 with 3M sodium hydroxide, and filtering for later use; 50g of HMnTi/GNs-LIPs was placed in the pretreated brine to adsorb Li at 25 deg.C+After 7h (LiMnTi/GNs-LIPs), it was packed into a titanium packed bed, labeled LiMnTi/GNs-LIPs/Ti. Treating 20 salt lake brine samples by the same method to obtain 20 brine samplesAnd electrically filling the bed electrode for later use.
(2) Method for recovering Li in salt lake brine by electrodeionization exchange desorption method+
5L of 4M ammonium chloride was prepared, and the pH of the solution was adjusted to 4 (solution H) with 2M hydrochloric acid. A three-electrode system is adopted, LiMnTi/GNs-LIPs/Ti is used as a working electrode, a titanium sheet is used as a reference electrode, and a graphite sheet is used as a counter electrode; 20 LiMnTi/GNs-LIPs/Ti are sequentially placed in the solution H, the sweep rate is 50mV/s, and the cyclic voltammetry sweep is 30min within the potential range of +0.1V- + 1.2V. Li being contained in HMnTi/GNs-LIPs/Ni+And H in solution H+And NH4 +Performing electrodeionization exchange to desorb Li+The material is regenerated synchronously (HMnTi/GNs-LIP), and can be reused after being taken out.
After repeating the whole of the steps (1) and (2) 10 times, Li with LiCl content of 19.58g/L (0.46M) can be obtained+The recovery rate of brine purification solution is 89%.
Example 2:
1. preparation of conductive manganese-titanium lithium ion sieve/graphene composite hydrogel (HMnTi/GNs-LIPs)
(1) Preparation of manganese-titanium lithium ion sieve (HMnTi)
To 100mL of 90% aqueous ethanol, 2g of lithium chloride (solution A) was added. To 100mL of 90% ethanol aqueous solution were added 6g of manganese carbonate, 17g of tetrabutyltitanate, and 4g of tartaric acid (solution B) in this order. After A was added dropwise to B, 1mL of 1M hydrochloric acid was added to form a sol solution C. And reacting the C for 10 hours at the temperature of 55 ℃ to form sol-gel, and grinding to obtain a precursor D. Roasting the D, firstly, carrying out temperature programming to 380 ℃ at the speed of 10 ℃/min, and reacting for 15 h; and then the temperature is programmed to 800 ℃ at the speed of 5 ℃/min, and the reaction is carried out for 10 hours, so as to form a manganese-titanium-lithium compound (marked as LiMnTi). And washing LiMnTi with 5% hydrochloric acid for 6h, and drying to form a manganese-titanium lithium ion sieve (HMnTi) for later use.
(2) In-situ thermal initiation polymerization method for preparing HMnTi/GNs-LIPs
After 0.2g of graphene oxide was added to 100mL of 75% aqueous ethanol to form a suspension, 6g of HMnTi was added thereto and mixed by sonication to homogeneity (mixture E). To E, 10g of acrylamide, 0.2g N-methylolacrylamide and 0.35g of ammonium persulfate were added and mixed by sonication (mixture F). And F is subjected to in-situ thermal initiation polymerization reaction for 10h at the temperature of 60 ℃ (mixture G), G is placed in 5mL of 1M ascorbic acid and reacts for 6h at the temperature of 50 ℃, and then the product is crushed and dried to obtain the conductive manganese-titanium lithium ion sieve/graphene composite hydrogel (HMnTi/GNs-LIPs).
2. HMnTi/GNs-LIPs are used as adsorption materials, and an adsorption-electrodeionization exchange desorption method is adopted to recover Li in salt lake brine+
(1) HMnTi/GNs-LIPs adsorbing Li in salt lake brine+
Adding 5L of salt lake brine (LiCl initial content is 0.08 g/L-0.0019M) into a barrel, adjusting pH to 10 with 3M sodium hydroxide, and filtering for later use; 50g of HMnTi/GNs-LIPs was placed in the pretreated brine to adsorb Li at 45 ℃+After 6h (LiMnTi/GNs-LIPs), it was packed into a nickel packed bed, labeled LiMnTi/GNs-LIPs/Ni. And treating 20 salt lake brine samples by the same method to obtain 20 conductive packed bed electrodes for later use.
(2) Method for recovering Li in salt lake brine by electrodeionization exchange desorption method+
5L of 3M ammonium sulfate was prepared, and the pH of the solution was adjusted to 4 (solution H) with 2M hydrochloric acid. A three-electrode system is adopted, LiMnTi/GNs-LIPs/Ni is used as a working electrode, a titanium sheet is used as a reference electrode, and a graphite sheet is used as a counter electrode; 20 LiMnTi/GNs-LIPs/Ni are sequentially placed in the solution H, the sweep rate is 50mV/s, and the cyclic voltammetry sweep is 50min within the potential range of-0.3V- + 1.4V. Li being contained in HMnTi/GNs-LIPs/Ni+And H in solution H+And NH4 +Performing electrodeionization exchange to desorb Li+The material is regenerated synchronously (HMnTi/GNs-LIP), and can be reused after being taken out.
After repeating the whole of the steps (1) and (2) 10 times, Li with a LiCl content of 14.56g/L (0.34M) can be obtained+The recovery rate of brine purification solution is 91%.
Example 3:
1. preparation of conductive manganese-titanium lithium ion sieve/graphene composite hydrogel (HMnTi/GNs-LIPs)
(1) Preparation of manganese-titanium lithium ion sieve (HMnTi)
To 100mL of a 60% ethanol aqueous solution, 5g of lithium sulfate (solution A) was added. To 100mL of 90% ethanol aqueous solution were added 5.4g of manganese carbonate, 5.2g of tetrapropyl titanate, and 1.8g of citric acid (solution B), in that order. A was added dropwise to B, and 2mL of 1M sulfuric acid catalyst was added to form a sol solution C. And reacting the C at 90 ℃ for 3h to form sol-gel, and grinding to obtain a precursor D. Roasting the D, firstly, carrying out temperature programming to 300 ℃ at the speed of 5 ℃/min, and reacting for 10 hours; and then the temperature is programmed to 700 ℃ at the speed of 10 ℃/min, and the reaction is carried out for 8 hours, so as to form a manganese-titanium-lithium compound (marked as LiMnTi). And washing LiMnTi with 5% hydrochloric acid for 6h, and drying to form a manganese-titanium lithium ion sieve (HMnTi) for later use.
(2) In-situ thermal initiation polymerization method for preparing HMnTi/GNs-LIPs
After 0.3g of graphene oxide was added to 100mL of a 100% ethanol solution to form a suspension, 6g of HMnTi was added thereto and uniformly mixed by sonication (mixture E). To E were added 8g of isopropylacrylamide, 0.22g N-methylolacrylamide and 0.2g of potassium persulfate, and the mixture was mixed by sonication to homogeneity (mixture F). And (2) carrying out in-situ thermal initiation polymerization reaction on the F at the temperature of 45 ℃ for 14h to obtain a product G, putting the product G into 10mL of 1M sodium thiosulfate solution, reacting at the temperature of 40 ℃ for 4h, crushing and drying the product to form the conductive manganese-titanium lithium ion sieve/graphene composite hydrogel (HMnTi/GNs-LIPs).
2. HMnTi/GNs-LIPs are used as adsorption materials, and an adsorption-electrodeionization exchange desorption method is adopted to recover Li in salt lake brine+
(1) HMnTi/GNs-LIPs adsorbing Li in salt lake brine+
Adding 5L of salt lake brine (initial LiCl content is 0.13 g/L-0.00307M), adjusting pH to 8 with 3M ammonia water, and filtering; placing 50g HMnTi/GNs-LIPs in the pretreated brine, and adsorbing Li at 35 deg.C+After 10h (LiMnTi/GNs-LIPs), it was packed into a packed bed of carbon fibers, labeled LiMnTi/GNs-LIPs/CF. And treating 20 salt lake brine samples by the same method to obtain 20 conductive packed bed electrodes for later use.
(2) Method for recovering Li in salt lake brine by electrodeionization exchange desorption method+
5L of 4M ammonium chloride was prepared and the pH of the solution was adjusted to 3 with 2M sulfuric acid (solution H)). A three-electrode system is adopted, LiMnTi/GNs-LIPs/Ed is used as a working electrode, silver/silver chloride is used as a reference electrode, and carbon fiber cloth is used as a counter electrode; 20 LiMnTi/GNs-LIPs/CF are sequentially placed in the solution H, and the sweep speed is 50mV/s and the cyclic voltammetry sweep is 40min within the potential range of 0.1V- + 1.3V. By reacting Li contained in HMnTi/GNs-LIPs/CF+And H in solution H+And NH4 +Performing electrodeionization exchange to desorb Li+The material is regenerated synchronously (HMnTi/GNs-LIP), and can be reused after being taken out.
After repeating the whole of the steps (1) and (2) 10 times, Li with LiCl content of 22.62g/L (0.53M) can be obtained+The recovery rate of brine purification solution is 87%.
TABLE 1 variation of Li concentration in salt lake brine treated by the method of the present invention
a*Average recovery after 10 consecutive operations;bconcentration after 10 consecutive operations.
Claims (10)
1. A preparation method of conductive manganese-titanium lithium ion sieve/graphene composite hydrogel is characterized by comprising the following steps:
the method comprises the following steps of preparing a manganese-titanium lithium ion sieve by adopting a sol-gel method, preparing manganese-titanium lithium ion sieve/graphene composite hydrogel MnTi/GNs-LIPs by adopting an in-situ thermal initiation polymerization method, and specifically comprising the following steps:
step 1: preparation of manganese-titanium lithium ion sieve HMnTi by sol-gel method
1a, adding lithium salt into 100mL of 10-100% ethanol water solution to obtain a solution A; sequentially adding manganese salt, titanate and a complexing agent into 100mL of 10-100% ethanol aqueous solution to obtain solution B;
1B, dropwise adding the solution A into the solution B, adding a catalyst to form a sol solution C, reacting the sol solution C at 10-100 ℃ for 6-24h to form sol gel, and grinding to obtain a precursor D;
1c, roasting the obtained precursor D, heating to 200-600 ℃ by a program of 5-10 ℃/min, and reacting for 6-24 h; heating to 600-900 ℃ at the speed of 5-10 ℃/min, reacting for 6-24h to form a manganese-titanium-lithium compound, washing for 2-10h with 5% hydrochloric acid, and drying to form manganese-titanium lithium ion sieve HMnTi;
step 2: in-situ thermal initiation polymerization method for preparing HMnTi/GNs-LIPs
Adding graphene oxide into 100mL of 10-100% ethanol aqueous solution to form a suspension, adding the HMnTi obtained in the step 1, and performing ultrasonic mixing to obtain a mixture E; and adding unsaturated amide, a cross-linking agent and an initiator into the mixture E, carrying out in-situ thermal initiation polymerization reaction for 1-12h at the temperature of 30-100 ℃, then placing the mixture into a reducing agent solution, carrying out reaction for 2-24h at the temperature of 10-100 ℃, crushing and drying the product to obtain the conductive manganese-titanium lithium ion sieve/graphene composite hydrogel HMnTi/GNs-LIPs.
2. The method of claim 1, wherein:
in the step 1, the lithium salt is one of lithium acetate, lithium chloride and lithium sulfate; the manganese salt is one of manganese carbonate, manganese sulfate and manganese chloride; the titanate is one of tetrabutyl titanate and tetrapropyl titanate; the complexing agent is one of ethylenediamine tetraacetic acid, citric acid, triethanolamine and tartaric acid.
3. The method of claim 2, wherein:
the molar ratio of the lithium salt, the manganese salt, the titanate and the complexing agent is 1: 1: 1: 1-5: 5: 2: 1.
4. the method of claim 1, wherein:
the catalyst is one or two of hydrochloric acid, perchloric acid, acetic acid and phosphoric acid, the concentration is 1M, and the volume ratio of the catalyst to reactants is 1: 50-1: 300.
5. the method of claim 1, wherein:
in the step 2, the unsaturated amide is one of acrylamide and isopropyl acrylamide; the cross-linking agent is one of N-methylol acrylamide, ethylenediamine and N, N-methylene bisacrylamide; the initiator is one of ammonium persulfate, potassium persulfate and sodium persulfate.
6. The method of claim 5, wherein:
the molar ratio of the unsaturated amide to the cross-linking agent to the initiator is 100: 1: 1-100: 4: 1; the ratio of the mass of HMnTi to the total mass of acrylamide, crosslinker and initiator is 1: 1-1: 10.
7. the application of any conductive manganese-titanium lithium ion sieve/graphene composite hydrogel prepared by the preparation method of claims 1-6 is characterized in that: HMnTi/GNs-LIPs are used as adsorption materials, and an adsorption-electrodeionization exchange desorption method is adopted to recover Li in salt lake brine+。
8. Use according to claim 7, characterized in that it comprises the following steps:
step 1: HMnTi/GNs-LIPs adsorbing Li in salt lake brine+
Adding 5L of salt lake brine into the container, adjusting the pH value to 3-11, and filtering for later use; adding 50g of HMnTi/GNs-LIPs into salt lake brine, and adsorbing Li at 10-50 DEG C+Taking out the mixture for 6 to 24 hours, and then putting the mixture into a conductive packed bed electrode; treating 20 salt lake brine samples by the same method to obtain 20 conductive packed bed electrodes for later use;
step 2: method for recovering Li in salt lake brine by electrodeionization exchange desorption method+
Adopting a three-electrode system, and respectively and sequentially placing the packed bed electrodes in the solution H to be used as working electrodes; adjusting pH to 3-6, sweeping at a sweep rate of 50mV/s and cyclic voltammetry for 20-60min within a potential range of-0.5V to +1.5V to make Li contained in the packed bed electrode+And the positive ions in the solution H are subjected to electrodeionization exchange to desorb Li+Synchronously regenerating the material, and repeatedly using the material after being taken out;
and (3) repeating the step (1) and the step (2) for 10 times to obtain the LiCl brine purification solution.
9. Use according to claim 8, characterized in that:
the solution H is an ammonium chloride solution or an ammonium sulfate solution, and the concentration is 1-4M; the pH was adjusted with 2M hydrochloric acid or sulfuric acid.
10. Use according to claim 8, characterized in that:
in the three-electrode system, one of silver, silver chloride, carbon fiber cloth or titanium is used as a reference electrode; one of graphite, titanium or carbon fiber cloth is used as a counter electrode.
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