CN116510709A - Preparation method of conductive hydrogel adsorption material of metatitanic acid type ion sieve - Google Patents
Preparation method of conductive hydrogel adsorption material of metatitanic acid type ion sieve Download PDFInfo
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- CN116510709A CN116510709A CN202310545502.1A CN202310545502A CN116510709A CN 116510709 A CN116510709 A CN 116510709A CN 202310545502 A CN202310545502 A CN 202310545502A CN 116510709 A CN116510709 A CN 116510709A
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 127
- 239000000017 hydrogel Substances 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 47
- 239000002253 acid Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 150000002500 ions Chemical class 0.000 claims abstract description 42
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002243 precursor Substances 0.000 claims abstract description 38
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000499 gel Substances 0.000 claims abstract description 17
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 15
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 15
- 229940068041 phytic acid Drugs 0.000 claims abstract description 15
- 239000000467 phytic acid Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 12
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 abstract description 47
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 33
- 229910052744 lithium Inorganic materials 0.000 abstract description 33
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- 239000004480 active ingredient Substances 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 description 20
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 230000003068 static effect Effects 0.000 description 15
- 239000012267 brine Substances 0.000 description 10
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 10
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 10
- 238000000926 separation method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000000605 extraction Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 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 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- WWKWZYPOPJIVGF-UHFFFAOYSA-N [Li].[Li].[Mg] Chemical compound [Li].[Li].[Mg] WWKWZYPOPJIVGF-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0211—Compounds of Ti, Zr, Hf
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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Abstract
The invention provides a preparation method of a conductive hydrogel adsorption material of a metatitanic acid type ion sieve, which comprises the steps of rapidly polymerizing and crosslinking aniline under the action of oxidizing agent ammonium persulfate and phytic acid gel to form polyaniline conductive hydrogel; at the same time Li 2 TiO 3 The precursor forms an active ingredient H under the action of acid 2 TiO 3 Embedding polyaniline conductive hydrogel to form the metatitanic acid type ion sieve conductive hydrogel with a three-dimensional network structureAn adsorption material; wherein H is 2 TiO 3 As the efficient lithium adsorption ion sieve, polyaniline has the capability of doping and dedoping lithium ions, is also an active ingredient of lithium adsorption, improves the adsorption capacity of the conductive hydrogel adsorption material of the metatitanic acid type ion sieve, and can improve the contact surface area of the conductive hydrogel adsorption material with a solution, effectively increase the lithium ion adsorption active site, and simultaneously increase the mass transfer rate of the adsorption process and shorten the adsorption balance time of the conductive polyaniline hydrogel under the electrochemical action.
Description
Technical Field
The invention relates to the technical field of adsorption materials, in particular to a preparation method of a conductive hydrogel adsorption material of a metatitanic acid type ion sieve.
Background
According to the development strategy of new energy industry, the demand for lithium resources is continuously increased, the demand for lithium mine resources in China is expected to be increased to 50 ten thousand tons in 2030, the global demand for lithium carbonate is more than 100 ten thousand tons, and the development of lithium resources in China is expected to be totally new. The lithium resources in China mainly comprise brine lithium resources accounting for about 85% of the total amount, and are mainly distributed in western regions such as Qinghai, tibet and Sichuan.
The existing technology for extracting lithium from salt lake brine causes a great deal of lithium loss in the form of entrainment or double salt in the salting-out process, so that the comprehensive recovery rate of lithium is less than 30%, and a great deal of lithium resource waste is caused. The electrochemical adsorption method solves the problems of high lithium-magnesium-lithium ratio and high separation difficulty of the salt lake brine, and is a high-efficiency, energy-saving, safe and environment-friendly technology. Electrochemical lithium extraction technology using Li + The concentration of the obtained lithium-rich liquid can be stabilized at 4-5 g/L based on the principle of intercalation/deintercalation in the electrode material, and the lithium-rich liquid has the characteristics of extremely low energy consumption, less material dissolution loss and high cycle performance. However, the existing electrochemical adsorption lithium extraction technology still has the problems of low adsorption capacity, high dissolution loss rate and long adsorption equilibrium time of the lithium ion sieve. Therefore, providing a lithium ion sieve with high adsorption capacity, low dissolution loss rate and short adsorption equilibrium time is a problem to be solved in the prior art.
Disclosure of Invention
The invention aims to provide a conductive hydrogel adsorption material of a metatitanic acid type ion sieve, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a conductive hydrogel adsorption material of a metatitanic acid type ion sieve, which comprises the following steps:
(1) Mixing lithium acetate, butyl titanate and absolute ethyl alcohol, and then carrying out first stirring in a hot water bath to obtain gel;
(2) Drying and calcining the gel obtained in the step (1) in sequence, and naturally cooling and grinding to obtain Li 2 TiO 3 A precursor.
(3) Mixing phytic acid and aniline to obtain a mixture;
sequentially adding the Li obtained in the step (2) to the mixture 2 TiO 3 Sequentially carrying out second stirring and standing after the precursor and the ammonium persulfate aqueous solution to obtain a precursor;
(4) And (3) washing and vacuum drying the precursor obtained in the step (3) in sequence to obtain the meta-titanic acid type ion sieve conductive hydrogel adsorption material.
Preferably, the ratio of the amounts of the substances of lithium acetate and butyl titanate in the step (1) is (1.9 to 2.4): 1.
preferably, the temperature of the hot water bath in the step (1) is 55-65 ℃.
Preferably, the calcination temperature in the step (2) is 630-780 ℃.
Preferably, the ratio of the amount of aniline to phytic acid in step (3) is (2.8-4.3): 1.
preferably, li in the step (3) 2 TiO 3 The mass ratio of the precursor to the aniline is 1: (0.5-5).
Preferably, the ratio of the aniline in step (3) to the amount of ammonium persulfate in the aqueous solution of ammonium persulfate is 1: (0.9-1.4).
Preferably, the time of standing in the step (3) is 20-28 h.
Preferably, the reagent used for washing in the step (4) is distilled water.
Preferably, the temperature of the vacuum drying in the step (4) is 20-40 ℃, and the time of the vacuum drying is 22-26 hours.
The invention provides a preparation method of a conductive hydrogel adsorption material of a metatitanic acid type ion sieve, which comprises the steps of mixing aniline and phytic acid, and then adding Li 2 TiO 3 Under the action of oxidant ammonium persulfate, the precursor is rapidly polymerized and crosslinked by the existence of phytic acid gel to form polyaniline conductive hydrogel; at the same time Li 2 TiO 3 The precursor forms an active ingredient H of the metatitanic acid type ion sieve under the action of acid 2 TiO 3 Embedding polyaniline conductive hydrogel to finally form the meta-titanic acid type ion sieve conductive hydrogel adsorption material with a three-dimensional network structure; the invention utilizes H 2 TiO 3 The high-efficiency lithium adsorption ion sieve is self, and polyaniline has the capability of doping and dedoping lithium ions, and is also an active ingredient of lithium adsorption, so that the adsorption capacity of the conductive hydrogel adsorption material of the metatitanic acid type ion sieve can be effectively improved; in addition, the invention is characterized by controlling Li 2 TiO 3 The preparation process of the precursor avoids Ti occurrence of the metatitanic acid type ion sieve particles in the repeated adsorption and elution processes +4 The phenomenon of dissolution loss realizes the aim of low dissolution loss rate; the conductive hydrogel adsorption material of the metatitanic acid type ion sieve provided by the invention has a three-dimensional network structure with conductivity, mechanical stability and high flexibility, the three-dimensional network structure can improve the contact surface area of the conductive hydrogel adsorption material with a solution, effectively enlarge lithium ion adsorption active sites, and meanwhile, the mass transfer rate of the polyaniline conductive hydrogel in the adsorption process is increased under the electrochemical action, and the adsorption equilibrium time is shortened, so that the conductive hydrogel adsorption material of the metatitanic acid type ion sieve with high adsorption capacity, low dissolution loss rate and short adsorption equilibrium time when being applied to electrochemical adsorption lithium extraction is obtained; the method provided by the invention does not need to additionally add a binder, and the prepared conductive hydrogel adsorption material of the metatitanic acid type ion sieve has high conductivity and large solid-liquid contact surface, so that the adsorption capacity of the conductive hydrogel adsorption material is improved, the problem of poor flowability and permeability of the traditional lithium ion sieve powder material is solved, and when the conductive hydrogel adsorption material of the metatitanic acid type ion sieve is used for the electrochemical adsorption lithium extraction technology, the mass transfer rate in the adsorption process is high, the conductive hydrogel adsorption material can be used for adsorbing and extracting lithium from low-concentration salt lake brine, and the problem of traditional lithium ion is solvedThe conductive hydrogel adsorption material of the meta-titanic acid type ion sieve can be applied to electrochemical adsorption of salt lake brine with high magnesium-lithium ratio for extracting lithium, and can be applied to underground brine with low lithium ion concentration, seawater and the like. The results of the examples show that H prepared in example 1 of the present invention 2 TiO 3 The static adsorption equilibrium time of the PANI is less than 24 hours, the adsorption capacity is 15-30 mg/g, and the lithium-magnesium separation coefficient is the same as that of the PANIMore than 130, and the dissolution loss rate is less than 0.1 percent; h prepared in example 1 2 TiO 3 The electrochemical adsorption equilibrium time of/PANI is less than 30min, the adsorption capacity is 15-30 mg/g, and the lithium-magnesium separation coefficient is more than 130; the dissolution loss rate is less than 1%.
Drawings
FIG. 1 is a sample of H prepared in comparative example 1 of the present invention 2 TiO 3 PANI prepared in comparative example 2, H prepared in example 1 2 TiO 3 PANI and H prepared in example 1 after static adsorption of lithium 2 TiO 3 SEM image of PANI, wherein (a) in FIG. 1 is H prepared in comparative example 1 2 TiO 3 FIG. 1 (b) is PANI prepared in comparative example 2 and FIG. 1 (c) is H prepared in example 1 2 TiO 3 PANI, FIG. 1 (d) is H prepared in example 1 after static adsorption of lithium 2 TiO 3 /PANI；
FIG. 2 is a diagram of H prepared in comparative example 1 of the present invention 2 TiO 3 PANI prepared in comparative example 2, H prepared in example 1 2 TiO 3 PANI and H prepared in example 1 after static adsorption of lithium 2 TiO 3 XRD pattern of PANI.
Detailed Description
The invention provides a preparation method of a conductive hydrogel adsorption material of a metatitanic acid type ion sieve, which comprises the following steps:
(1) Mixing lithium acetate, butyl titanate and absolute ethyl alcohol, and then carrying out first stirring in a hot water bath to obtain gel;
(2) Drying and calcining the gel obtained in the step (1) in sequenceBurning, naturally cooling and grinding to obtain Li 2 TiO 3 A precursor.
(3) Mixing phytic acid and aniline to obtain a mixture;
sequentially adding the Li obtained in the step (2) to the mixture 2 TiO 3 Sequentially carrying out second stirring and standing after the precursor and the ammonium persulfate aqueous solution to obtain a precursor;
(4) And (3) washing and vacuum drying the precursor obtained in the step (3) in sequence to obtain the meta-titanic acid type ion sieve conductive hydrogel adsorption material.
In the present invention, the raw materials used are all conventional commercial products in the art unless otherwise specified.
According to the invention, lithium acetate, butyl titanate and absolute ethyl alcohol are mixed, and then are subjected to first stirring in a hot water bath to obtain gel.
In the present invention, the ratio of the amounts of the substances of lithium acetate and butyl titanate is preferably (1.9 to 2.4): 1, more preferably (2.0 to 2.2): 1. the invention controls the mole ratio of the lithium acetate and the butyl titanate in the above range to obtain Li with better comprehensive performance 2 TiO 3 The precursor reduces the dissolution loss rate of the conductive hydrogel adsorption material of the meta-titanic acid type ion sieve prepared later.
In the invention, the volume ratio of the tetrabutyl titanate to the absolute ethyl alcohol is preferably 1: (2.0-3.0). The invention controls the volume ratio of tetrabutyl titanate and absolute ethyl alcohol in the above range, thereby being beneficial to obtaining Li with better comprehensive performance 2 TiO 3 A precursor.
In the present invention, the temperature of the hot water bath is preferably 55 to 65 ℃, more preferably 58 to 63 ℃. The invention controls the temperature of the hot water bath in the above range to promote the full reaction of the components.
The invention has no special limit to the time of the first stirring, and can realize the preparation of gel with better performance.
After the gel is obtained, the invention sequentially dries and calcines the gel, and then naturally cools and grinds the gel to obtain Li 2 TiO 3 Precursor body
In the present invention, the temperature of the drying is preferably 105 to 120 ℃, more preferably 110 ℃. The drying time is not particularly limited, and the purpose of removing the solvent can be achieved.
In the present invention, the temperature of the calcination is preferably 630 to 780 ℃, more preferably 650 to 750 ℃; the calcination time is preferably 15 to 20 hours, more preferably 16 to 19 hours, and still more preferably 18 hours. The invention controls the calcination temperature and time in the above range to avoid Ti occurrence in the repeated adsorption and elution process of the meta-titanic acid type ion sieve particles +4 The phenomenon of dissolution loss realizes the aim of low dissolution loss rate.
In the present invention, the Li 2 TiO 3 The particle diameter of the precursor is preferably 0.1 to 2. Mu.m, more preferably 0.2 to 1. Mu.m. The invention controls Li 2 TiO 3 The particle size of the precursor is in the range, so that the meta-titanic acid type ion sieve conductive hydrogel adsorption material with high adsorption capacity, low dissolution loss rate and short adsorption balance time can be obtained.
The invention mixes phytic acid and aniline to obtain a mixture.
In the present invention, the ratio of the amount of the aniline to the amount of the phytic acid is preferably (2.8 to 4.3): 1, more preferably (3.0 to 4.0): 1. the invention controls the ratio of the aniline to the phytic acid in the range so as to promote the aniline to fully react and form polyaniline conductive hydrogel with better performance.
After the mixture is obtained, li is sequentially added into the mixture 2 TiO 3 And (3) after the precursor and the ammonium persulfate aqueous solution, sequentially carrying out second stirring and standing to obtain the precursor.
In the present invention, the Li 2 TiO 3 The mass ratio of the precursor to the aniline is preferably 1: (0.5 to 5), more preferably 1: (0.5-4). The invention controls Li 2 TiO 3 The mass ratio of the precursor and the aniline is in the above range so as to adjust H in the conductive hydrogel adsorption material of the metatitanic acid type ion sieve 2 TiO 3 And polyaniline conductive hydrogel to obtain the metatitanic acid type ion sieve conductive with high adsorption capacity, low dissolution loss rate and short adsorption balance timeHydrogel adsorbent material.
In the present invention, the ratio of the aniline to the amount of the substance of ammonium persulfate in the aqueous solution of ammonium persulfate is preferably 1: (0.9 to 1.4), more preferably 1: (1.0 to 1.3), more preferably 1:1.25. the invention controls the ratio of the aniline to the ammonium persulfate substance in the ammonium persulfate aqueous solution in the above range so as to promote the aniline to fully react and form polyaniline conductive hydrogel with better performance.
In the present invention, the time of the second stirring is preferably 2 to 5 minutes, more preferably 3 minutes. The invention controls the second stirring time in the above range to promote uniform mixing of the components. In the present invention, the time for the standing is preferably 20 to 28 hours, more preferably 22 to 26 hours, and still more preferably 24 hours. The invention controls the standing time in the range so as to promote the aniline to fully react and form polyaniline conductive hydrogel with better performance.
After the precursor is obtained, the precursor is washed and dried in vacuum in sequence, so that the conductive hydrogel adsorption material of the metatitanic acid type ion sieve is obtained.
In the present invention, the reagent used for washing is distilled water. The invention removes redundant ions and oligomers in the precursor by washing, which is favorable for the subsequent preparation of the conductive hydrogel adsorption material of the metatitanic acid type ion sieve with high adsorption capacity, low dissolution loss rate and short adsorption balance time.
In the present invention, the temperature of the vacuum drying is preferably 20 to 40 ℃, more preferably 25 to 35 ℃. In the present invention, the time for the vacuum drying is 22 to 26 hours, more preferably 24 hours. The invention controls the temperature and time of vacuum drying in the above range to prepare the conductive hydrogel adsorption material of the metatitanic acid type ion sieve with high adsorption capacity, low dissolution loss rate and short adsorption equilibrium time.
The preparation method of the conductive hydrogel adsorption material of the meta-titanic acid type ion sieve provided by the invention is simple to operate, mild in reaction condition and suitable for large-scale production.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) Mixing lithium acetate, butyl titanate and absolute ethyl alcohol, and stirring in a hot water bath at 60 ℃ to obtain gel; the molar ratio of the lithium acetate to the butyl titanate is 2.2:1, a step of; the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is preferably 1:2.
(2) Drying the gel obtained in the step (1) in a drying oven at 110 ℃, calcining for 18 hours at 750 ℃, naturally cooling and grinding to obtain Li with the particle size of 0.2-1 mu m 2 TiO 3 A precursor;
(3) Mixing phytic acid and aniline to obtain 10mL of a mixture; the ratio of the amount of aniline to phytic acid material was 3.0:1, a step of;
sequentially adding the Li obtained in the step (2) to the mixture 2 TiO 3 After the precursor and 3mL of ammonium persulfate aqueous solution, carrying out second stirring, and then standing for 24 hours to obtain the precursor;
the Li is 2 TiO 3 The mass ratio of the precursor to the aniline is 1:4.0;
the ratio of the aniline to the amount of ammonium persulfate in the aqueous solution of ammonium persulfate is 1:1.25;
(4) Washing the precursor obtained in the step (3) with distilled water to remove superfluous ions and oligomers. Then vacuum drying is carried out for 24 hours at 30 ℃ to obtain the meta-titanic acid type ion sieve conductive hydrogel adsorption material which is named as H 2 TiO 3 /PANI。
Comparative example 1
(1) Mixing lithium acetate, butyl titanate and absolute ethyl alcohol, and stirring in a hot water bath at 60 ℃ to obtain gel; the molar ratio of the lithium acetate to the butyl titanate is 2.2:1, a step of; the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is preferably 1:2.
(2) Drying the gel obtained in the step (1) in a drying oven at 110 ℃, calcining for 18 hours at 750 ℃, and naturally cooling and grinding to obtain Li 2 TiO 3 Treating the precursor with 0.5mol/L HCl to obtain H 2 TiO 3 ；
Comparative example 2
Mixing phytic acid and aniline to obtain 10mL of a mixture; the ratio of the amount of aniline to phytic acid material was 3.0:1, a step of;
sequentially adding 3mL of ammonium persulfate aqueous solution into the mixture, stirring, and standing for 24 hours to obtain conductive hydrogel named PANI;
the Li is 2 TiO 3 The mass ratio of the precursor to the aniline is 1:4.0;
the ratio of the aniline to the amount of ammonium persulfate in the aqueous solution of ammonium persulfate is 1:1.25;
1. static adsorption detection
150mL of a mixture containing Li + 、Na + 、K + 、Mg 2+ 1g of H prepared in example 1 2 TiO 3 PANI is put into the solution, the pH value is adjusted to 9, the solution is stirred at room temperature until the solution reaches equilibrium, and the supernatant is taken to respectively measure the concentration of each ion in the solution.
Measurement of Li before and after adsorption in solution by inductively coupled plasma atomic emission spectrometry (ICP-OES) + The adsorption capacity (qe), partition coefficient (Kd), and adsorption rate (E) were calculated as follows:
adsorption capacity
Distribution coefficient
Adsorption rate of
Separation coefficient:
wherein: c (C) 0 、C t And C e (mg/L) represents the initial state, adsorption time t (min) and the concentration of lithium ions in the solution at adsorption equilibrium, respectively; m (g) and V (L) represent the mass of the adsorbent and the volume of the solution, respectively.
The static adsorption detection shows that the measurement result is as follows: h prepared in example 1 2 TiO 3 The static adsorption equilibrium time of/PANI is less than 24 hours, the adsorption capacity is 15-30 mg/g, and the lithium-magnesium separation coefficient alpha L M i g Greater than 130; the dissolution loss rate is less than 0.1 percent.
2. Electrochemical adsorption
(1) Three-electrode test system
H prepared in example 1 2 TiO 3 Uniformly coating/PANI on carbon paper, vacuum drying, and cutting into 30X 30mm size for electrochemical adsorption test; working Electrode (WE) was prepared carrying H prepared in example 1 2 TiO 3 A carbon paper electrode of/PANI, sandwiched in the cell using a platinum electrode; the Reference Electrode (RE) is an Ag/AgCl electrode; the Counter Electrode (CE) is a metal platinum sheet; and (3) magnetically stirring the bottom of the electrolytic cell, and stably magnetically stirring the solution when the simulated salt lake brine is used for adsorption test so as to eliminate the influence of concentration polarization in the solution on the adsorption test and keep the concentration of the solution in the electrolytic cell uniform.
(2) Constant potential adsorption test experiment
1) Adsorption isotherm
By adopting the three-electrode testing system, an electrochemical workstation is used as a potentiostat to control the electrode potential of the reaction, and stirring is started to eliminate liquid phase concentration polarization under lower concentration and reduce sampling errors; the solution uses simulated brine with high magnesium-lithium ratio and enough supporting electrolyte to simulate real adsorption conditions, and meanwhile, the adsorption reaction is prevented from being influenced by excessive solution resistance. 1mL of the aqueous solution was drawn from the cell at intervals during the test using a syringe, and its ion concentration was analyzed by inductively coupled plasma atomic emission spectrometry (ICP-OES) to obtain its isothermal adsorption curve.
2) Influence of magnesium-lithium ratio
In the three-electrode test system, a potentiostat is adopted to control the reaction, constant potential adsorption is carried out to extract lithium, and simulated brine (containing 1000mg/LNa is used + 、1000mg/LK + ) Three simulated brines of different magnesium to lithium ratios were used: (a) 100mg/LLi + And 1500mg/LMg 2+ ，Li/Mg＝1:15；(b)10mg/LLi + And 1500Mg/lmg2+, li/mg=1:150; (c) 1mg/LLi + And 1500mg/LMg 2+ The time to reach adsorption equilibrium was measured and the equilibrium adsorption capacity, electrochemical adsorption equilibrium time, lithium magnesium separation coefficient, etc. prepared in example 1 were calculated according to the formula in the above static adsorption detection.
The H prepared in example 1 was measured by the above electrochemical adsorption test 2 TiO 3 The electrochemical adsorption equilibrium time of/PANI is less than 30min, the adsorption capacity is 15-30 mg/g, and the lithium-magnesium separation coefficient is more than 130; the dissolution loss rate is less than 1%.
H prepared in comparative example 1 was observed by electron Scanning Electron Microscopy (SEM), respectively 2 TiO 3 PANI prepared in comparative example 2, H prepared in example 1 2 TiO 3 PANI and H prepared in example 1 2 TiO 3 Micro morphology after static adsorption of lithium by PANI, PANI prepared in comparative example 1 and H prepared in comparative example 1 are obtained 2 TiO 3 H prepared in example 1 2 TiO 3 PANI and H prepared in example 1 2 TiO 3 The SEM image after static adsorption of lithium by PANI is shown in FIG. 1, wherein (a) in FIG. 1 is H prepared in comparative example 1 2 TiO 3 FIG. 1 (b) is PANI prepared in comparative example 2 and FIG. 1 (c) is H prepared in example 1 2 TiO 3 PANI, FIG. 1 (d) is H prepared in example 1 after static adsorption of lithium 2 TiO 3 As can be seen from FIG. 1, the meta-titanic acid type ion sieve conductive hydrogel adsorption material prepared in example 1 is subjected to cyclic static adsorption on H 2 TiO 3 The microscopic morphology of the/PANI composite is not much affected.
H prepared in comparative example 1 by X-ray diffraction (XRD) 2 TiO 3 PANI prepared in comparative example 2, H prepared in example 1 2 TiO 3 PANI and H prepared in example 1 after static adsorption of lithium 2 TiO 3 Analysis of the crystal structure of/PANI gave an XRD pattern as shown in fig. 2, and as can be seen from fig. 2, the meta-titanic acid type ion sieve conductive hydrogel adsorption material prepared in example 1, i.e. H 2 TiO 3 Adsorption of Li by PANI composite material + Diffraction peak after that and Li 2 TiO 3 The PANI precursor is basically consistent, which indicates that H is after static adsorption of lithium 2 TiO 3 The basic structure of the/PANI composite material is unchanged, which indicates that the active exchange sites of the material are relatively stable.
In summary, it can be seen that H prepared in example 1 of the present invention 2 TiO 3 The static adsorption equilibrium time of the PANI is less than 24 hours, the adsorption capacity is 15-30 mg/g, and the lithium-magnesium separation coefficient is the same as that of the PANIMore than 130, and the dissolution loss rate is less than 0.1 percent; h prepared in example 1 2 TiO 3 The electrochemical adsorption equilibrium time of/PANI is less than 30min, the adsorption capacity is 15-30 mg/g, and the lithium-magnesium separation coefficient is more than 130; the dissolution loss rate is less than 1%. According to the method provided by the invention, no additional binder is needed, the prepared conductive hydrogel adsorption material of the metatitanic acid type ion sieve has high conductivity and large solid-liquid contact surface, so that the adsorption capacity of the conductive hydrogel adsorption material is improved, the problem that the traditional lithium ion sieve powder material has poor fluidity and permeability is solved, when the conductive hydrogel adsorption material of the metatitanic acid type ion sieve is used for electrochemical adsorption lithium extraction technology, the mass transfer rate in the adsorption process is high, the conductive hydrogel adsorption material can be used for adsorption lithium extraction of low-concentration salt lake brine, and the problems of low adsorption capacity, high dissolution loss rate and long adsorption balance time of the traditional lithium ion sieve are solved.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A preparation method of a conductive hydrogel adsorption material of a metatitanic acid type ion sieve comprises the following steps:
(1) Mixing lithium acetate, butyl titanate and absolute ethyl alcohol, and then carrying out first stirring in a hot water bath to obtain gel;
(2) Drying and calcining the gel obtained in the step (1) in sequence, and naturally cooling and grinding to obtain Li 2 TiO 3 A precursor.
(3) Mixing phytic acid and aniline to obtain a mixture;
sequentially adding the Li obtained in the step (2) to the mixture 2 TiO 3 Sequentially carrying out second stirring and standing after the precursor and the ammonium persulfate aqueous solution to obtain a precursor;
(4) And (3) washing and vacuum drying the precursor obtained in the step (3) in sequence to obtain the meta-titanic acid type ion sieve conductive hydrogel adsorption material.
2. The method according to claim 1, wherein the ratio of the amounts of the substances of lithium acetate and butyl titanate in the step (1) is (1.9 to 2.4): 1.
3. the method according to claim 1, wherein the temperature of the hot water bath in step (1) is 55 to 65 ℃.
4. The method according to claim 1, wherein the calcination temperature in the step (2) is 630 to 780 ℃.
5. The method according to claim 1, wherein the ratio of the amounts of aniline and phytic acid in the step (3) is (2.8 to 4.3): 1.
6. the method of claim 1Characterized in that Li in the step (3) 2 TiO 3 The mass ratio of the precursor to the aniline is 1: (0.5-5).
7. The method according to claim 1, wherein the ratio of the aniline in the step (3) to the amount of the substance of ammonium persulfate in the aqueous solution of ammonium persulfate is 1: (0.9-1.4).
8. The method according to claim 1, wherein the time of standing in the step (3) is 20 to 28 hours.
9. The method according to claim 1, wherein the reagent for washing in the step (4) is distilled water.
10. The method according to claim 1, wherein the vacuum drying in the step (4) is performed at a temperature of 20 to 40 ℃ for 22 to 26 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102280265A (en) * | 2011-05-25 | 2011-12-14 | 中国科学院过程工程研究所 | Method for preparing metatitanic acid doped polyaniline combined electrode nanomaterial for super capacitor |
| CN103840193A (en) * | 2012-11-21 | 2014-06-04 | 海洋王照明科技股份有限公司 | Gel polymer electrolyte and preparation method thereof |
| JP2016195981A (en) * | 2015-04-06 | 2016-11-24 | 日本化学工業株式会社 | Adsorbent and production method of adsorbent |
| KR20200022231A (en) * | 2018-08-22 | 2020-03-03 | 명지대학교 산학협력단 | LITHIUM ABSORBENT COMPRISING A COMPOSITE NANOSHEET IMPREGNATED WITH H2TiO3 AND METHOD FOR PRODUCING THE SAME |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102280265A (en) * | 2011-05-25 | 2011-12-14 | 中国科学院过程工程研究所 | Method for preparing metatitanic acid doped polyaniline combined electrode nanomaterial for super capacitor |
| CN103840193A (en) * | 2012-11-21 | 2014-06-04 | 海洋王照明科技股份有限公司 | Gel polymer electrolyte and preparation method thereof |
| JP2016195981A (en) * | 2015-04-06 | 2016-11-24 | 日本化学工業株式会社 | Adsorbent and production method of adsorbent |
| KR20200022231A (en) * | 2018-08-22 | 2020-03-03 | 명지대학교 산학협력단 | LITHIUM ABSORBENT COMPRISING A COMPOSITE NANOSHEET IMPREGNATED WITH H2TiO3 AND METHOD FOR PRODUCING THE SAME |
Non-Patent Citations (2)
| Title |
|---|
| ISMAIL ABDULAZEEZ等: "Electrochemical behavior of novel electroactive LaTi4Mn3O12/polyaniline composite for Li+-ion recovery from brine with high selectivity", 《SEPARATION AND PURIFICATION TECHNOLOGY》, pages 1 - 9 * |
| LIYUAN ZHANG等: "Preparation of H2TiO3-lithium adsorbent by the sol-gel process andits adsorption performance", 《APPLIED SURFACE SCIENCE》, pages 82 - 87 * |
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