CN109759013B - Cellulose-based lithium extraction material and preparation method thereof - Google Patents
Cellulose-based lithium extraction material and preparation method thereof Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 178
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 61
- 238000000605 extraction Methods 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 74
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 27
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 27
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- 239000000243 solution Substances 0.000 claims description 123
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 111
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- 238000001035 drying Methods 0.000 claims description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 21
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- 238000005406 washing Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000013535 sea water Substances 0.000 claims description 8
- 239000012267 brine Substances 0.000 claims description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 7
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 23
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- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the technical field of chemical separation materials, relates to adsorption and extraction of lithium, and particularly relates to a cellulose-based lithium extraction material which is formed by growing a layer of sodium trititanate whisker on the surface of a cellulose carbon film serving as a substrate in situ by utilizing a hydrothermal process; wherein the mass ratio of the cellulose carbon film to the sodium trititanate whisker is 10: 1-100: 1; the diameter of carbon fibers in the cellulose carbon film is 5-10 mu m, and the length of the carbon fibers is more than 100 mu m; the length of the sodium trititanate whisker is 200 nm-1000 nm, and the diameter of the sodium trititanate whisker is 10-50 nm. The invention also discloses a preparation method and application of the cellulose-based lithium extraction material. The cellulose-based lithium extraction material has a porous carbon fiber structure inside, has a large specific surface area, and is favorable for adsorption; the sodium trititanate crystal whisker growing on the surface of the porous carbon fiber in situ can fully absorb lithium ions and is easy to recover; the defects that pure sodium trititanate powder is easy to agglomerate in a liquid phase due to higher surface energy, is easy to dissolve and damage in a smaller size and the like are avoided. The preparation method is simple and easy to industrialize.
Description
Technical Field
The invention belongs to the technical field of chemical separation materials, relates to adsorption and extraction of lithium, and particularly relates to a cellulose-based lithium extraction material and a preparation method thereof.
Background
The cellulose is a natural polymer material, is rich in carbon elements, has wide sources, abundant reserves and low price, and is an ideal raw material for preparing the carbon fiber. At present, the main source of carbon fiber depends on mineral resources such as petroleum, coal and the like, and the recoverable amount is greatly reduced along with the increasing consumption of non-renewable resources. The high-performance porous carbon fiber is developed by taking renewable resource cellulose as a raw material, so that the demand on non-renewable mineral resources can be relieved, and the high-value utilization of the cellulose is realized. In addition, the carbon film prepared from the cellulose has good thermal stability, high specific surface area and high mechanical strength, and has wide application prospect in the field of adsorption materials.
Lithium is an active metal, has a large charge density and a stable helium type bilayer, and is mainly present in spodumene, lepidolite, phosphate rock, seawater, and salt lake brine. Lithium and lithium compounds are used as strategic resources and widely applied to the fields of batteries, metallurgy, ceramics, medicine, nuclear power, catalysts and the like. In recent years, with the gradual depletion of terrestrial lithium resources and the sharp increase of lithium demand, the recovery of lithium from seawater or salt lake brine has received great attention. To date, recovery of lithium from seawater or salt lake brines by co-precipitation, evaporative crystallization, solvent extraction and adsorption has been developed. However, the coprecipitation method has poor selectivity to lithium, the practical application cost of the evaporative crystallization method is high, and the solvent extraction method causes environmental pollution; the above method is not ideal for recovering lithium from seawater or salt lake brine.
An adsorption method having high selectivity, low cost and environmental friendliness is considered as the most promising method for recovering lithium from seawater or salt lake brine, and the development of a lithium adsorbent having high selectivity and stability is key to the recovery of lithium. Titanium-based materials, particularly sodium trititanate with a hierarchical structure, have significant advantages in lithium recovery due to its high stability and high adsorption capacity. However, pure sodium trititanate is in powder form and is readily soluble and agglomerated in solution, limiting further use in the industry. The compounding of the sodium trititanate and the cellulose carbon film can effectively overcome the defects of pure sodium trititanate powder, and can further improve the adsorption efficiency and the adsorption capacity of the sodium trititanate.
Therefore, the invention provides a cellulose-based lithium extraction material, which is prepared by taking a cellulose carbon film as a substrate and growing a layer of sodium trititanate whisker on the surface of the cellulose carbon film in situ by utilizing a hydrothermal process, has the advantages of large specific surface area, good mechanical property, good thermal stability, good reusability and the like, and has stronger adsorption property on lithium ions.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, it is an object of the present invention to disclose a cellulose-based lithium extraction material.
The technical scheme is as follows:
a cellulose-based lithium extraction material is prepared by taking a cellulose carbon film as a substrate and growing a layer of sodium trititanate whisker on the surface of the cellulose carbon film in situ by utilizing a hydrothermal process; wherein the mass ratio of the cellulose carbon film to the sodium trititanate whisker is 10: 1-100: 1; the diameter of carbon fibers in the cellulose carbon film is 5-10 mu m, the length of the carbon fibers is more than 100 mu m, and the cellulose carbon film has good flexibility; the length of the sodium trititanate whisker is 200 nm-1000 nm, and the diameter of the sodium trititanate whisker is 10-50 nm.
The invention also aims to disclose a preparation method of the cellulose-based lithium extraction material.
A preparation method of a cellulose-based lithium extraction material comprises the following steps:
A. preparing a tetrabutyl titanate ethanol solution with the concentration of 1-10 wt%, adjusting the pH to 2-6 by using dilute nitric acid, preferably adjusting the pH of a tetrabutyl titanate ethanol solution with the concentration of 5wt% to 4, immersing a cellulose carbon film into the solution for 2-6 h, taking out, drying, then immersing again, and repeating the operation for a plurality of times to obtain the cellulose carbon film uniformly wrapping the titanium source;
B. immersing a cellulose carbon film wrapping a titanium source by 1-5 g into 0.5-2 mL of 30% H2O2The method comprises the steps of putting reactants into an autoclave container, and adding 20-100 mL of 1-10 mol/L NaOH solution, preferably 2g of a titanium source-coated cellulose carbon film, 1mL of 30% H2O260 mL of 5mol/L NaOH solution reacts at 120-200 ℃ for 10-20 h, preferably at 140 ℃ for 16 h, the solution is naturally cooled to room temperature, and the product is washed by ethanol and dried to obtain the cellulose-based lithium extraction material.
The cellulose carbon film can be sold in the market or made by the user, and the self-made preparation process comprises the following steps:
a) preparing 1-10 wt% NaOH solution, adding 1-5 g of hemp plant leaves into each 100mL of NaOH solution, preferably adding 2g of 5wt% NaOH solution into each 100mL of NaOH solution, stirring the mixture at 50-100 ℃ for 2-6 h, preferably at 80 ℃ for 3 h, taking out and washing to be neutral, and drying to obtain crude cellulose;
b) preparing NaClO with the concentration of 1-10 wt%2Adjusting the pH of the solution to 2-6, preferably 5wt% NaClO with glacial acetic acid2The solution is subjected to pH4 to obtain bleaching solution, 1-5 g of crude cellulose is added into per 100mL of bleaching solution, the crude cellulose is stirred in the bleaching solution for 1-4 h at the temperature of 60-100 ℃, preferably for 3 h at the temperature of 80 ℃, and the solution is taken out, washed to be neutral and dried to obtain cellulose;
c) stirring cellulose to uniform pasty slurry according to the mass ratio of the cellulose to the deionized water of 5/100-25/100, preferably 15/100, uniformly coating the slurry on a mold, and drying to obtain a cellulose membrane; and under the protection of nitrogen, putting the cellulose membrane into a tube furnace, and carbonizing for 2-6 h at 500-1000 ℃, preferably carbonizing for 4 h at 600 ℃ to obtain the cellulose carbon membrane.
In the preferred embodiment of the present invention, the hemp plant in step a) includes, but is not limited to, sisal, flax, sisal or jute.
Laboratory simulation of lithium extraction from sea water or salt lake brine by adsorption:
adsorbing for 24-72 h at the temperature of 298-338K according to the fact that 5-50 mg of cellulose base lithium extraction material is added into 10 mL of 10-100 mg/L lithium ion solution, filtering the adsorbed solution by using a microfilter, measuring the concentration of lithium ions in the adsorbed solution through ICP (inductively coupled plasma), and calculating the lithium adsorption quantity.
Advantageous effects
The invention takes a cellulose carbon film as a substrate, firstly, the cellulose carbon film is immersed into tetrabutyl titanate ethanol solution for pretreatment, and then H is added2O2And growing a layer of sodium trititanate whisker on the surface of the NaOH solution in situ by using a hydrothermal method to prepare the cellulose-based lithium extraction material. The cellulose-based lithium extraction method has the advantages that the interior of the cellulose-based lithium extraction is of a porous carbon fiber structure, the specific surface area is large, and the adsorption effect is facilitated. The sodium trititanate whisker grown in situ on the surface of the porous carbon fiber can be fully used for absorbing lithium ions and is easy to recover. The defects that pure sodium trititanate powder is easy to agglomerate in a liquid phase due to higher surface energy, is easy to dissolve and damage in a smaller size and the like are overcome. The material combines the high specific surface area and good mechanical property of the cellulose carbon film, and the selective adsorption of the sodium trititanate whisker to lithium ions, and has the advantages ofHas higher lithium ion adsorption effect. The preparation method is simple and easy to industrialize.
Drawings
FIG. 1 is a scanning electron microscope image of a cellulose carbon film and a cellulose-based lithium extraction material under different magnifications, wherein the magnification of a is 230, the magnification of b is 1000, the magnification of c is 5000, the magnification of d is 200, the magnification of e is 1700, and the magnification of f is 25000;
FIG. 2 shows the energy spectrum and element distribution of cellulose-based lithium extraction material.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Unless otherwise defined, terms (including technical and scientific terms) used herein should be construed to have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art, and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Example 1
A preparation method of a cellulose-based lithium extraction material comprises the following steps:
a) preparing a 5wt% NaOH solution, and adding the sisal leaves into the NaOH solution according to the amount of 2g of sisal leaves added into each 100mL of NaOH solution. Stirring for 3 h at 80 ℃, taking out and washing to be neutral, and drying to obtain crude cellulose;
b) NaClO with the concentration of 5wt% is prepared2Adjusting the pH value of the solution to 4 by using glacial acetic acid to obtain bleaching solution. Adding 2g of crude cellulose into per 100mL of bleaching solution, adding the crude cellulose into the bleaching solution at 80 ℃, stirring for 3 h, taking out, washing to be neutral, and drying to obtain cellulose;
c) adding 15 g of cellulose into 100mL of deionized water, stirring to obtain uniform pasty slurry, uniformly coating the pasty slurry on a mold, and drying to obtain the cellulose membrane. Under the protection of nitrogen, putting the cellulose membrane into a tubular furnace, and carbonizing at 600 ℃ for 4 hours to obtain a cellulose carbon membrane;
d) preparing 5wt% tetrabutyl titanate ethanol solution, adjusting pH to 4 with dilute nitric acid, soaking the cellulose carbon film in the solution for 4 h, taking out, drying, and soaking again. Repeating the operation for three times to obtain a cellulose carbon film uniformly wrapping the titanium source;
e) 2g of titanium source-coated cellulose base and 0.5 mL of 30% H2O2Into an autoclave vessel, followed by 60 mL of NaOH (1 mol/L) solution. The autoclave was sealed and allowed to react in an oven at 160 ℃ for 14 h. Then, the autoclave taken out is naturally cooled at room temperature, and the product is washed with ethanol and dried at room temperature to obtain the cellulose-based lithium extraction material.
The solution was adsorbed at 298K for 48 hours based on 10 mL of a lithium ion solution having a concentration of 100 mg/L to which 10 mg of a cellulose-based lithium extraction material was added, the adsorbed solution was filtered by a microfilter, and the concentration of lithium ions in the adsorbed solution was 63.74 mg/L as measured by ICP, to calculate an adsorption amount of 36.26 mg/g.
Example 2
A preparation method of a cellulose-based lithium extraction material comprises the following steps:
a) preparing 4 wt% NaOH solution, and adding the sisal leaves into the NaOH solution according to the proportion that 3 g of sisal leaves are added into each 100mL of NaOH solution. Stirring for 4 hours at 70 ℃, taking out and washing to be neutral, and drying to obtain crude cellulose;
b) NaClO with the concentration of 2 wt% is prepared2Adjusting the pH value of the solution to 4 by using glacial acetic acid to obtain bleaching solution. Adding 3 g of crude cellulose into per 100mL of bleaching solution, adding the crude cellulose into the bleaching solution at 70 ℃, stirring for 3 h, taking out, washing to be neutral, and drying to obtain cellulose;
c) adding 20 g of cellulose into 100mL of deionized water, stirring to obtain uniform pasty slurry, uniformly coating the pasty slurry on a mold, and drying to obtain the cellulose membrane. Under the protection of nitrogen, putting the cellulose membrane into a tubular furnace, and carbonizing at 500 ℃ for 6 hours to obtain a cellulose carbon membrane;
d) preparing a tetrabutyl titanate ethanol solution with the concentration of 10 wt%, adjusting the pH to 3 by using dilute nitric acid, then immersing the cellulose carbon film into the solution for 2 hours, taking out the cellulose carbon film, drying the cellulose carbon film, and then immersing the cellulose carbon film again. Repeating the operation for three times to obtain a cellulose carbon film uniformly wrapping the titanium source;
e) 3 g of a titanium source-coated cellulose carbon film and 1mL of 30% H2O2Into an autoclave vessel, followed by 60 mL of NaOH (2 mol/L) solution. The autoclave was sealed and allowed to react in an oven at 120 ℃ for 20 h. Then, the autoclave taken out is naturally cooled at room temperature, and the product is washed with ethanol and dried at room temperature to obtain the cellulose-based lithium extraction material.
The solution was adsorbed at 298K for 48 hours based on 10 mL of a 50 mg/L lithium ion solution to which 10 mg of a cellulose-based lithium extraction material was added, the adsorbed solution was filtered by a microfilter, and the concentration of lithium ions in the adsorbed solution was 17.44 mg/L as measured by ICP, to calculate the adsorbed amount as 32.56 mg/g.
Example 3
A preparation method of a cellulose-based lithium extraction material comprises the following steps:
a) preparing a 3 wt% NaOH solution, adding flax leaves into the NaOH solution according to the proportion that 1 g of flax leaves are added into each 100mL of NaOH solution. Stirring for 6h at 50 ℃, taking out and washing to be neutral, and drying to obtain crude cellulose;
b) NaClO with the concentration of 2 wt% is prepared2Adjusting the pH value of the solution to 4 by using glacial acetic acid to obtain bleaching solution. Adding 2g of crude cellulose into per 100mL of bleaching solution, adding the crude cellulose into the bleaching solution at the temperature of 60 ℃, stirring for 4 hours, taking out, washing to be neutral, and drying to obtain cellulose;
c) adding 20 g of cellulose into 100mL of deionized water, stirring to obtain uniform pasty slurry, uniformly coating the pasty slurry on a mold, and drying to obtain the cellulose membrane. Under the protection of nitrogen, putting the cellulose membrane into a tube furnace, and carbonizing at 700 ℃ for 2 h to obtain a cellulose carbon membrane;
d) preparing 5wt% tetrabutyl titanate ethanol solution, adjusting pH to 3 with dilute nitric acid, soaking the cellulose carbon film in the solution for 3 h, taking out, drying, and soaking again. Repeating the operation for three times to obtain a cellulose carbon film uniformly wrapping the titanium source;
e) 3 g of a titanium source-coated cellulose carbon film and 1.5 mL of 30% H2O2Into an autoclave vessel, followed by 80 mL of NaOH (2 mol/L) solution. The autoclave was sealed and allowed to react in an oven at 160 ℃ for 12 h. Then, the autoclave taken out is naturally cooled at room temperature, and the product is washed with ethanol and dried at room temperature to obtain the cellulose-based lithium extraction material.
The solution was adsorbed at 298K for 24 hours based on 10 mL of a 10 mg/L lithium ion solution to which 5 mg of a cellulose-based lithium extraction material was added, the adsorbed solution was filtered by a microfilter, and the concentration of lithium ions in the adsorbed solution was 1.24 mg/L as measured by ICP, to calculate an adsorption amount of 17.52 mg/g.
Example 4
A preparation method of a cellulose-based lithium extraction material comprises the following steps:
a) preparing a NaOH solution with the concentration of 7 wt%, and adding flax leaves into the NaOH solution according to the amount that 3 g of flax leaves are added into each 100mL of NaOH solution. Stirring for 4 hours at the temperature of 80 ℃, taking out and washing to be neutral, and drying to obtain crude cellulose;
b) NaClO with the concentration of 3 wt% is prepared2Adjusting the pH value of the solution to 4.5 by using glacial acetic acid to obtain bleaching solution. Adding 5g of crude cellulose into per 100mL of bleaching solution, adding the crude cellulose into the bleaching solution at 90 ℃, stirring for 2 h, taking out, washing to be neutral, and drying to obtain cellulose;
c) adding 15 g of cellulose into 100mL of deionized water, stirring to obtain uniform pasty slurry, uniformly coating the pasty slurry on a mold, and drying to obtain the cellulose membrane. Under the protection of nitrogen, putting the cellulose membrane into a tube furnace, and carbonizing at 800 ℃ for 2 h to obtain a cellulose carbon membrane;
d) preparing a tetrabutyl titanate ethanol solution with the concentration of 10 wt%, adjusting the pH to 2 by using dilute nitric acid, then immersing the cellulose carbon film into the solution for 2 hours, taking out the cellulose carbon film, drying the cellulose carbon film, and then immersing the cellulose carbon film again. Repeating the operation for three times to obtain a cellulose carbon film uniformly wrapping the titanium source;
e) 4 g of a titanium source-coated cellulose carbon film and 2 mL of 30% H2O2Into an autoclave vessel, and then 70 mL of NaOH (4 mol/L) solution was added. The autoclave was sealed and allowed to react in an oven at 150 ℃ for 15 h. Then, the autoclave taken out is naturally cooled at room temperature, and the product is washed with ethanol and dried at room temperature to obtain the cellulose-based lithium extraction material.
The amount of adsorbed lithium ion was 18.288 mg/g as calculated by adding 50 mg of cellulose-based lithium extraction material to 10 mL of 100 mg/L lithium ion solution, adsorbing at 338K for 72 hours, filtering the adsorbed solution with a microfilter, and measuring the concentration of lithium ion in the adsorbed solution by ICP (inductively coupled plasma) to be 8.56 mg/L.
Example 5
A preparation method of a cellulose-based lithium extraction material comprises the following steps:
a) preparing 8 wt% NaOH solution, adding 5g of folium Cannabis into 100mL of NaOH solution, and adding folium Cannabis into NaOH solution. Stirring for 5 h at 60 ℃, taking out and washing to be neutral, and drying to obtain crude cellulose;
b) NaClO with the concentration of 4 wt% is prepared2Adjusting the pH value of the solution to 3.5 by using glacial acetic acid to obtain bleaching solution. Adding 3.5 g of crude cellulose into per 100mL of bleaching solution, adding the crude cellulose into the bleaching solution at 80 ℃, stirring for 3 h, taking out, washing to be neutral, and drying to obtain cellulose;
c) adding 16 g of cellulose into 100mL of deionized water, stirring to obtain uniform pasty slurry, uniformly coating the pasty slurry on a mold, and drying to obtain the cellulose membrane. Under the protection of nitrogen, putting the cellulose membrane into a tubular furnace, and carbonizing at 600 ℃ for 4 hours to obtain a cellulose carbon membrane;
d) preparing a tetrabutyl titanate ethanol solution with the concentration of 7 wt%, adjusting the pH to 3.5 by using dilute nitric acid, then immersing the cellulose carbon film into the solution for 4 hours, taking out the cellulose carbon film, drying the cellulose carbon film, and then immersing the cellulose carbon film again. Repeating the operation for three times to obtain a cellulose carbon film uniformly wrapping the titanium source;
e) 4 g of a titanium source-coated cellulose carbon film and 2 mL of 30% H2O2Into an autoclave vessel, followed by 50 mL of NaOH (3 mol/L) solution. The autoclave was sealed and allowed to react in an oven at 145 ℃ for 14 h. Then, the autoclave taken out is naturally cooled at room temperature, and the product is washed with ethanol and dried at room temperature to obtain the cellulose-based lithium extraction material.
The solution was adsorbed at 298K for 48 hours based on 10 mL of a lithium ion solution having a concentration of 80 mg/L to which 40 mg of a cellulose-based lithium extraction material was added, the adsorbed solution was filtered by a microfilter, and the concentration of lithium ions in the adsorbed solution was 6.56 mg/L as measured by ICP, to calculate an adsorption amount of 18.36 mg/g.
Example 6
A preparation method of a cellulose-based lithium extraction material comprises the following steps:
a) preparing 6 wt% NaOH solution, adding 3 g of jute leaves into each 100mL of NaOH solution, and adding jute leaves into the NaOH solution. Stirring for 4 hours at 75 ℃, taking out and washing to be neutral, and drying to obtain crude cellulose;
b) NaClO with the concentration of 4 wt% is prepared2Adjusting the pH value of the solution to 4 by using glacial acetic acid to obtain bleaching solution. Adding 2.5 g of crude cellulose into per 100mL of bleaching solution, adding the crude cellulose into the bleaching solution at 80 ℃, stirring for 3 h, taking out, washing to be neutral, and drying to obtain cellulose;
c) adding 15 g of cellulose into 100mL of deionized water, stirring to obtain uniform pasty slurry, uniformly coating the pasty slurry on a mold, and drying to obtain the cellulose membrane. Under the protection of nitrogen, putting the cellulose membrane into a tubular furnace, and carbonizing at 500 ℃ for 6 hours to obtain a cellulose carbon membrane;
d) preparing a tetrabutyl titanate ethanol solution with the concentration of 1 wt%, adjusting the pH to 5 by using dilute nitric acid, then immersing a cellulose carbon film into the solution for 6 hours, taking out the cellulose carbon film, drying the cellulose carbon film, and then immersing the cellulose carbon film again. Repeating the operation for three times to obtain a cellulose carbon film uniformly wrapping the titanium source;
e) 5g of a titanium source-coated cellulose carbon film and 2 mL of 30% H2O2Into an autoclave vessel, and then 100mL of NaOH (1 mol/L) solution was added. The autoclave was sealed and allowed to react in an oven at 180 ℃ for 10 h. Then, the autoclave taken out is naturally cooled at room temperature, and the product is washed with ethanol and dried at room temperature to obtain the cellulose-based lithium extraction material.
The solution was adsorbed at 298K for 24 hours based on 10 mL of a lithium ion solution having a concentration of 60 mg/L to which 20 mg of a cellulose-based lithium extraction material was added, the adsorbed solution was filtered by a microfilter, and the concentration of lithium ions in the adsorbed solution was 14.28 mg/L as measured by ICP, to calculate an adsorption amount of 22.86 mg/g.
Example 7
A preparation method of a cellulose-based lithium extraction material comprises the following steps:
a) preparing a 10 wt% NaOH solution, and adding the sisal leaves into the NaOH solution according to the proportion that 5g of sisal leaves are added into each 100mL of NaOH solution. Stirring for 2 h at 100 ℃, taking out and washing to be neutral, and drying to obtain crude cellulose;
b) NaClO with the concentration of 10 wt% is prepared2Adjusting the pH value of the solution to 2 by using glacial acetic acid to obtain bleaching solution. Adding 5g of crude cellulose into per 100mL of bleaching solution, adding the crude cellulose into the bleaching solution at 100 ℃, stirring for 1 h, taking out, washing to be neutral, and drying to obtain cellulose;
c) adding 5g of cellulose into 100mL of deionized water, stirring to obtain uniform pasty slurry, uniformly coating the pasty slurry on a mold, and drying to obtain the cellulose membrane. Under the protection of nitrogen, putting the cellulose membrane into a tube furnace, and carbonizing at 1000 ℃ for 2 h to obtain a cellulose carbon membrane;
d) preparing a tetrabutyl titanate ethanol solution with the concentration of 10 wt%, adjusting the pH to 2 by using dilute nitric acid, then immersing the cellulose carbon film into the solution for 2 hours, taking out the cellulose carbon film, drying the cellulose carbon film, and then immersing the cellulose carbon film again. Repeating the operation for three times to obtain a cellulose carbon film uniformly wrapping the titanium source;
e) 1 g of a titanium source-coated cellulose carbon film and 0.5 mL of 30% H2O2Into an autoclave vessel, followed by 20 mL of NaOH (1 mol/L) solution. The autoclave was sealed and allowed to react in an oven at 200 ℃ for 10 h. Then, the autoclave taken out is naturally cooled at room temperature, and the product is washed with ethanol and dried at room temperature to obtain the cellulose-based lithium extraction material.
10 mg of cellulose-based lithium extraction material was added to 10 mL of a 30 mg/L lithium ion solution, and the mixture was adsorbed at 318K for 48 hours, and the adsorbed solution was filtered through a microfilter, and the concentration of lithium ions in the adsorbed solution was 8.96 mg/L as measured by ICP, and the amount of adsorption was calculated to be 21.04 mg/g.
Figure 1 shows that the whisker structures are uniformly distributed on the surface of the product, and the whisker structures are sodium trititanate whiskers growing on the surface of carbon fibers in situ by a hydrothermal method, and can be used for extracting lithium ions in salt lake brine or seawater by compounding a cellulose carbon film and the sodium trititanate whiskers.
Figure 2 shows that the sodium trititanate whisker is successfully prepared and uniformly distributed on the surface of the carbon fiber.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (5)
1. The preparation method of the cellulose-based lithium extraction material is characterized by comprising the steps of taking a cellulose carbon film as a substrate, and growing a layer of sodium trititanate whisker on the surface of the cellulose carbon film in situ by utilizing a hydrothermal process, wherein the mass ratio of the cellulose carbon film to the sodium trititanate whisker is 10: 1-100: 1; the diameter of carbon fibers in the cellulose carbon film is 5-10 mu m, and the length of the carbon fibers is more than 100 mu m; the length of the sodium trititanate whisker is 200 nm-1000 nm, and the diameter of the sodium trititanate whisker is 10-50 nm; the method comprises the following steps:
A. preparing a tetrabutyl titanate ethanol solution with the concentration of 1-10 wt%, adjusting the pH to 2-6 with dilute nitric acid, immersing a cellulose carbon film into the solution for 2-6 hours, taking out, drying, then immersing again, and repeating the operation for a plurality of times to obtain the cellulose carbon film uniformly wrapping a titanium source;
B. immersing a cellulose carbon film wrapping a titanium source by 1-5 g into 0.5-2 mL of 30% H2O2The method comprises the following steps of putting reactants into an autoclave container, adding 20-100 mL of 1-10 mol/L NaOH solution in proportion, reacting at 120-200 ℃ for 10-20 h, naturally cooling to room temperature, washing the product with ethanol, and drying to obtain the catalyst.
2. The method for preparing the cellulose-based lithium extraction material according to claim 1, wherein: and step A, preparing a tetrabutyl titanate ethanol solution with the concentration of 5wt%, and adjusting the pH to 4 by using dilute nitric acid.
3. The method for preparing the cellulose-based lithium extraction material according to claim 1, wherein: step B immersing a 2g titanium source-coated cellulose carbon film in 1mL of 30% H2O2The reactants are put into an autoclave container, and 60 mL of NaOH solution with the concentration of 5mol/L is added proportionally.
4. The method for preparing the cellulose-based lithium extraction material according to claim 1, wherein: the reaction condition of the step B is that the reaction is carried out for 16 h at 140 ℃.
5. Use of a cellulose-based lithium extraction material prepared according to the method of any one of claims 1 to 4, characterized in that: the method is applied to the adsorption and extraction of lithium from seawater or salt lake brine.
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| CN107921328A (en) * | 2015-08-06 | 2018-04-17 | 因尼威森有限公司 | Lithium is extracted from bittern |
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