CN115814761A - Iron-containing feed liquid aluminum ion removal imprinted adsorption material and preparation method thereof - Google Patents
Iron-containing feed liquid aluminum ion removal imprinted adsorption material and preparation method thereof Download PDFInfo
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- CN115814761A CN115814761A CN202211642555.7A CN202211642555A CN115814761A CN 115814761 A CN115814761 A CN 115814761A CN 202211642555 A CN202211642555 A CN 202211642555A CN 115814761 A CN115814761 A CN 115814761A
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- 239000000463 material Substances 0.000 title claims abstract description 61
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 14
- 239000007788 liquid Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000000741 silica gel Substances 0.000 claims abstract description 85
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 85
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 238000010992 reflux Methods 0.000 claims abstract description 52
- 239000002904 solvent Substances 0.000 claims abstract description 51
- 238000010438 heat treatment Methods 0.000 claims abstract description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- -1 aluminum ion Chemical class 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000002791 soaking Methods 0.000 claims abstract description 15
- 238000004132 cross linking Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000020477 pH reduction Effects 0.000 claims abstract description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 66
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 4
- YGJHKCCQWZAUDK-UHFFFAOYSA-N 3-methyl-1-propyl-1-triethoxysilylurea Chemical compound C(CC)N(C(=O)NC)[Si](OCC)(OCC)OCC YGJHKCCQWZAUDK-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 4
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 4
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 229940118662 aluminum carbonate Drugs 0.000 claims description 2
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 15
- 150000002500 ions Chemical class 0.000 abstract description 12
- 238000000926 separation method Methods 0.000 abstract description 8
- 238000010828 elution Methods 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 52
- 238000005576 amination reaction Methods 0.000 description 11
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses an iron-containing feed liquid aluminum ion removal imprinted adsorption material and a preparation method thereof, wherein the method comprises the following steps: (a) silica gel acidification: heating, refluxing and stirring silica gel in an acid solution, cleaning with pure water, and drying for later use; (b) preparing a solvent: preparing a solvent consisting of an alcohol compound and a silane coupling agent; (c) grafting reaction: adding acidified silica gel into the solvent according to a certain proportion, controlling the rotating speed of a stirrer, and heating for reflux reaction; (d) crosslinking reaction: adding a cross-linking agent into the reaction system, heating and refluxing; (e) acidified elution: washing the obtained material with ethanol and pure water, eluting in acid solution, and heating for refluxing; then drying the material after acid washing, and then placing the material in FeLiPO 4 Soaking in the solution. The aluminum ion silica gel imprinted material synthesized by the invention selectively adsorbs aluminumThe ion performance is excellent, and the method is suitable for selective adsorption separation of iron ions and aluminum ions in a complex multi-element heavy metal ion environment.
Description
Technical Field
The invention belongs to the technical field of adsorption materials, and particularly relates to an iron-containing feed liquid aluminum ion removal imprinted adsorption material and a preparation method thereof.
Background
The development of new energy industry has driven the innovation of battery technology. At present, in the process of using and recovering the commonly used lithium iron phosphate battery, aluminum contained in positive and negative electrode materials is electrolyzed into a solution and is mixed with lithium iron phosphate to be difficult to remove. It is particularly important to remove the aluminum from the mixed solution for better recycling of the battery. The mature aluminum removal technology comprises the following steps: precipitation, solvent extraction, ion exchange, liquid membrane separation, and the like. Most of the techniques are mainly precipitation methods, but because the precipitation pH of aluminum ions is close to that of other metal ions, the precipitation methods easily cause the loss of lithium iron phosphate, and consume a large amount of reagents to cause environmental pollution. And, the separation of the settled bottom sludge is difficult.
The adsorption separation method is a green and efficient ion separation method. Researchers in current adsorptive separation processes have developed a series of adsorbent materials: clay minerals, active carbon, polymer adsorbents, microorganism modified adsorption materials, ion imprinting materials and the like. Among them, the ion imprinted material is applied to adsorption separation due to its high selectivity, but when the concentration of other hetero-ions is too high, it will compete with the adsorbed ions for adsorption, thereby affecting the removal of aluminum ions.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of the iron-containing feed liquid aluminum ion removal imprinted adsorption material for industrial production.
The technical scheme of the invention is as follows:
the invention relates to a preparation method of an iron-containing feed liquid aluminum ion removal imprinted adsorption material, which comprises the following steps:
(a) Silica gel acidification: heating, refluxing and stirring silica gel in an acid solution, cleaning with pure water, and drying for later use;
(b) Preparing a solvent: preparing a solvent consisting of an alcohol compound, an aluminum salt and a silane coupling agent;
(c) Grafting (amination): adding the acidified silica gel prepared in the step (a) into the solvent prepared in the step (b) according to a certain proportion, controlling the rotating speed of a stirrer, and heating for reflux reaction;
(d) And (3) crosslinking reaction: adding a cross-linking agent into the reaction system obtained in the step (c), and heating and refluxing;
(e) Acidifying and eluting: washing the material obtained in the step (d) with ethanol and pure water, eluting in an acid solution, and heating and refluxing; then drying the material after acid washing, and then adding the dried material into FeLiPO 4 Soaking in the solution.
Preferably, in the step (a), the size of the silica gel is 0.1-2 mm, the concentration of the acid solution is 1-6 mol/L, and the mass ratio of the silica gel to the acid solution is 1: (3-6); the reflux temperature is 50-80 ℃, the reflux time is 6-12 h, and the drying temperature is 50-80 ℃.
Preferably, in the step (b), the mass ratio of the alcohol compound, the aluminum salt and the silane coupling agent is 1: (0.1-0.8): (0.05-0.25).
Preferably, in step (b), the alcohol compound is one or more of methanol, ethanol, isopropanol, n-butanol and isoamyl alcohol;
the silane coupling agent is one or a mixture of more of gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, 1-propyl-1- (triethoxysilyl) methylurea, gamma-aminopropylmethyldiethoxysilane and N- (beta-aminoethyl) -gamma-aminopropylmethyl-dimethoxysilane;
the aluminum salt is one or a mixture of aluminum chloride, aluminum sulfate, aluminum nitrate and aluminum carbonate.
Preferably, in the step (c), the solvent prepared in the step (b) is mixed according to the mass ratio of 1: (0.05-0.3) adding acidified silica gel; controlling the rotating speed of the stirrer to be 180-300 rpm, and heating the system to 50-70 ℃ for reflux reaction for 12-24 h.
Preferably, in the step (d), the mass ratio of the addition amount of the cross-linking agent to the silica gel is (0.8-2.6): 1; the temperature is increased to 50 ℃ to 70 ℃, and the reflux reaction time is 8 to 16 hours.
Preferably, in step (d), the crosslinking agent is one or more of epichlorohydrin, tetraethyl orthosilicate and dimethylaminopropylamine.
Preferably, in the step (e), the concentration of the elution acid solution is 1-6 mol/L, the temperature is raised to 50-70 ℃, and the reflux is carried out for 4-8 h; drying the acid-washed material at 40-60 ℃, and then adding 5-20% of FeLiPO by mass 4 Soaking in the solution for 12-24 h; wherein the mass ratio of the consumption of the eluting acid solution to the silica gel is (3-6): 1; feLiPO 4 The mass ratio of the dosage to the silica gel is (3-6): 1.
preferably, in step (a), the acid solution is one or more of hydrochloric acid, sulfuric acid and nitric acid; in the step (e), the eluting acid solution is one or a mixture of hydrochloric acid, sulfuric acid and nitric acid.
The invention also relates to an iron-containing feed liquid aluminum ion removal imprinting adsorption material prepared by the preparation method.
The invention has the beneficial effects that:
1) The aluminum ion silica gel imprinted material synthesized by the method disclosed by the invention has excellent performance of selectively adsorbing aluminum ions, can form a cavity to coordinate with aluminum, can form a bidentate or even tridentate complex, and is suitable for selective adsorption and separation of aluminum ions in a complex multi-element heavy metal ion environment.
2) The synthesis of the aluminum ion silica gel imprinted material is more environment-friendly, and the use of toxic reagents and dangerous surface treatment means is reduced.
3) The synthesis of the aluminum ion silica gel imprinted material synthesized by the method is simple in operation, low in reagent cost and mild in reaction conditions.
Drawings
The invention is further described with reference to the following figures and examples:
FIG. 1 is a synthetic scheme of the present invention;
FIG. 2 is an infrared spectrum of the product obtained in example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
Example 1
(a) Silica gel acidification: 100g of silica gel was heated to 60 ℃ in 500mL of 6mol/L hydrochloric acid solution, refluxed and stirred for 12 hours, washed with pure water, and dried at 60 ℃ for use.
(b) Preparing a solvent: the solvent consists of methanol, aluminum sulfate and gamma-aminopropyltriethoxysilane (mass ratio of 1.
(c) Grafting (amination): adding the solvent prepared in the step (b) into a solvent prepared in the step (b) according to a mass ratio of 1:0.15 addition of the acidified silica gel prepared in step (a), control of the stirrer speed at 280rpm and heating to 60 ℃ for reflux reaction for 12h.
(d) And (3) crosslinking reaction: adding silica gel into a reaction system according to the mass ratio: epichlorohydrin =1:1 adding a cross-linking agent, heating to 60 ℃, and carrying out reflux reaction for 12h.
(e) Acidifying and eluting: washing the material obtained by the reaction with ethanol and pure water, and eluting in a 2mol/L hydrochloric acid solution, wherein the mass ratio of the silica gel to the hydrochloric acid is 1:5, heating to 60 ℃, and refluxing for 6h; oven drying the pickled material at 60 deg.C, and then adding 20% FeLiPO 4 Soaking in solution for 24h for standby, the quality of silica gel is equal to FeLiPO 4 The mass ratio of the solution is 1:5; denoted product a.
Example 2
(a) Silica gel acidification: 100g of silica gel was heated to 60 ℃ in 500mL of 6mol/L hydrochloric acid solution, refluxed and stirred for 12 hours, washed with pure water, and dried at 60 ℃ for use.
(b) Preparing a solvent: the solvent consists of methanol, aluminum chloride and gamma-aminopropyltriethoxysilane (mass ratio of 1.
(c) Grafting (amination): adding the solvent prepared in the step (b) into a solvent prepared in the step (b) according to a mass ratio of 1:0.2 addition of the acidified silica gel prepared in step (a), control of the stirrer speed at 280rpm and heating to 60 ℃ for reflux reaction for 12h.
(d) And (3) crosslinking reaction: adding silica gel: tetraethyl orthosilicate =1:1 adding a cross-linking agent, heating to 60 ℃, and carrying out reflux reaction for 12h.
(e) Acidifying and eluting: washing the material obtained by the reaction with ethanol and pure water, and eluting in a 2mol/L hydrochloric acid solution, wherein the mass ratio of the silica gel to the hydrochloric acid is 1:5, heating to 60 ℃, and refluxing for 6h; drying the pickled material at 60 deg.C, and then reducing the content of FeLiPO to 20% 4 Soaking in solution for 24h for standby, the quality of silica gel is equal to FeLiPO 4 The mass ratio of the solution is 1:5; and is marked as product B.
FIG. 2 is an infrared spectrum of the product obtained in example 2, in which 1093cm is indicated -1 ，798.7cm -1 And 465.8cm -1 Shows obvious absorption peaks, and indicates that a special coordination structure formed by amino groups contained on the surface and tetraethyl silicate is successfully synthesized.
Example 3
(a) Silica gel acidification: 100g of silica gel was heated to 60 ℃ in 500mL of 6mol/L hydrochloric acid solution, refluxed and stirred for 12 hours, washed with pure water, and dried at 60 ℃ for use.
(b) Preparing a solvent: the solvent consists of methanol, aluminum sulfate and N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (the mass ratio is 1.
(c) Grafting (amination): adding the solvent prepared in the step (b) into a solvent prepared in the step (b) according to a mass ratio of 1:0.15 adding the acidified silica gel prepared in the step (a), controlling the rotating speed of a stirrer at 280rpm, and heating to 60 ℃ for reflux reaction for 12 hours;
(d) And (3) crosslinking reaction: adding silica gel: tetraethyl orthosilicate =1:1 adding a cross-linking agent, heating to 60 ℃, and carrying out reflux reaction for 12h.
(e) Acidifying and eluting: washing the material obtained by the reaction with ethanol and pure water, eluting in 2mol/L hydrochloric acid solution, the mass of silica gel and hydrochloric acidThe mass ratio of 1:5, heating to 60 ℃, and refluxing for 6h; drying the acid-washed material at 60 ℃, and then adding the dried material into 20% FeLiPO 4 Soaking in solution for 24h for standby, the quality of silica gel is equal to FeLiPO 4 The mass ratio of the solution is 1:5; denoted product C.
Example 4
(a) Silica gel acidification: 100g of silica gel was heated to 60 ℃ in 500mL of 6mol/L hydrochloric acid solution, refluxed and stirred for 12 hours, washed with pure water, and dried at 60 ℃ for use.
(b) Preparing a solvent: the solvent consists of methanol, aluminum chloride and N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (the mass ratio is 1.
(c) Grafting (amination): adding the solvent prepared in the step (b) into a solvent prepared in the step (b) according to a mass ratio of 1:0.15 addition of the acidified silica gel prepared in step (a), control of the stirrer speed at 280rpm and heating to 60 ℃ for reflux reaction for 12h.
(d) And (3) crosslinking reaction: adding silica gel into a reaction system: tetraethyl orthosilicate =1:1 adding a cross-linking agent, heating to 60 ℃, and carrying out reflux reaction for 12h.
(e) Acidifying and eluting: washing the material obtained by the reaction with ethanol and pure water, and eluting in a 2mol/L hydrochloric acid solution, wherein the mass ratio of the silica gel to the hydrochloric acid is 1:5, heating to 60 ℃, and refluxing for 6h; drying the acid-washed material at 60 ℃, and then adding the dried material into 20% FeLiPO 4 Soaking in solution for 24h for standby, the quality of silica gel is equal to FeLiPO 4 The mass ratio of the solution is 1:5; and is marked as product D.
Example 5
(a) Silica gel acidification: 100g of silica gel was heated to 60 ℃ in 500mL of 6mol/L hydrochloric acid solution, refluxed and stirred for 12 hours, washed with pure water, and dried at 60 ℃ for use.
(b) Preparing a solvent: the solvent consists of methanol, aluminum sulfate and 1-propyl-1- (triethoxysilyl) methylurea (mass ratio is 1.
(c) Grafting reaction (amination reaction): adding the solvent prepared in the step (b) into a solvent prepared in the step (b) according to a mass ratio of 1:0.15 addition of the acidified silica gel prepared in step (a), control of the stirrer speed at 280rpm and heating to 60 ℃ for reflux reaction for 12h.
(d) And (3) crosslinking reaction: adding silica gel into a reaction system according to the mass ratio: tetraethyl orthosilicate =1:1 adding a cross-linking agent, heating to 60 ℃, and carrying out reflux reaction for 12h.
(e) Acidifying and eluting: washing the material obtained by the reaction with ethanol and pure water, and eluting in a 2mol/L hydrochloric acid solution, wherein the mass ratio of the silica gel to the hydrochloric acid is 1:5, heating to 60 ℃, and refluxing for 6h; drying the acid-washed material at 60 ℃, and then adding the dried material into 20% FeLiPO 4 Soaking in the solution for 24h for later use, wherein the mass of the silica gel is equal to that of FeLiPO 4 The mass ratio of the solution is 1:5; denoted product E.
Example 6
(a) Silica gel acidification: 100g of silica gel was heated to 60 ℃ in 500mL of 6mol/L hydrochloric acid solution, refluxed and stirred for 12 hours, washed with pure water, and dried at 60 ℃ for use.
(b) Preparing a solvent: the solvent consists of methanol, aluminum chloride and 1-propyl-1- (triethoxysilyl) methylurea (mass ratio of 1.
(c) Grafting (amination): adding the solvent prepared in the step (b) into a solvent prepared in the step (b) according to a mass ratio of 1:0.15 addition of the acidified silica gel prepared in step (a), control of the stirrer speed at 280rpm and heating to 60 ℃ for reflux reaction for 12h.
(d) And (3) crosslinking reaction: adding silica gel: tetraethyl orthosilicate =1:1 adding a cross-linking agent, heating to 60 ℃, and carrying out reflux reaction for 12h.
(e) Acidifying and eluting: washing the material obtained by the reaction with ethanol and pure water, and eluting in a 2mol/L hydrochloric acid solution, wherein the mass ratio of the silica gel to the hydrochloric acid is 1:5, heating to 60 ℃, and refluxing for 6h; drying the acid-washed material at 60 ℃, and then adding the dried material into 20% FeLiPO 4 Soaking in solution for 24h for standby, the quality of silica gel is equal to FeLiPO 4 The mass ratio of the solution is 1:5; denoted product F.
Example 7
(a) Silica gel acidification: 100g of silica gel was heated to 60 ℃ in 500mL of 6mol/L hydrochloric acid solution, refluxed and stirred for 12 hours, washed with pure water, and dried at 60 ℃ for use.
(b) Preparing a solvent: the solvent consists of methanol, aluminum sulfate and gamma-aminopropylmethyldiethoxysilane (mass ratio of 1.
(c) Grafting (amination): adding the solvent prepared in the step (b) into a solvent prepared in the step (b) according to a mass ratio of 1:0.15 addition of the acidified silica gel prepared in step (a), control of the stirrer speed at 280rpm and heating to 60 ℃ for reflux reaction for 12h.
(d) And (3) crosslinking reaction: adding silica gel: tetraethyl orthosilicate =1:1 adding a cross-linking agent, heating to 60 ℃, and carrying out reflux reaction for 12h.
(e) Acidifying and eluting: washing the material obtained by the reaction with ethanol and pure water, and eluting in a 2mol/L hydrochloric acid solution, wherein the mass ratio of the silica gel to the hydrochloric acid is 1:5, heating to 60 ℃, and refluxing for 6h; drying the acid-washed material at 60 ℃, and then adding the dried material into 20% FeLiPO 4 Soaking in solution for 24h for standby, the quality of silica gel is equal to FeLiPO 4 The mass ratio of the solution is 1:5; denoted product G.
Example 8
(a) Silica gel acidification: 100g of silica gel was heated to 60 ℃ in 500mL of 6mol/L hydrochloric acid solution, refluxed and stirred for 12 hours, washed with pure water, and dried at 60 ℃ for use.
(b) Preparing a solvent: the solvent consists of methanol, aluminum chloride and gamma-aminopropylmethyldiethoxysilane (mass ratio of 1.
(c) Grafting (amination): adding the solvent prepared in the step (b) into a solvent prepared in the step (b) according to a mass ratio of 1:0.15 addition of the acidified silica gel prepared in step (a), control of the stirrer speed at 280rpm and heating to 60 ℃ for reflux reaction for 12h.
(d) And (3) crosslinking reaction: adding silica gel: tetraethyl orthosilicate =1:1 adding a cross-linking agent, heating to 60 ℃, and carrying out reflux reaction for 12h.
(e) Acidifying and eluting: washing the material obtained by the reaction with ethanol and pure water, and eluting in a 2mol/L hydrochloric acid solution, wherein the mass ratio of the silica gel to the hydrochloric acid is 1:5, heating to 60 ℃, and refluxing for 6h; drying the acid-washed material at 60 ℃ and then20％ FeLiPO 4 Soaking in solution for 24h for standby, the quality of silica gel is equal to FeLiPO 4 The mass ratio of the solution is 1:5; denoted product H.
Example 9
(a) Silica gel acidification: 100g of silica gel was heated to 60 ℃ in 500mL of 6mol/L hydrochloric acid solution, refluxed and stirred for 12 hours, washed with pure water, and dried at 60 ℃ for use.
(b) Preparing a solvent: the solvent consists of methanol, aluminum sulfate and N- (beta-aminoethyl) -gamma-aminopropylmethyl-dimethoxysilane (mass ratio of 1.
(c) Grafting (amination): adding the solvent prepared in the step (b) into a solvent prepared in the step (b) according to a mass ratio of 1:0.15 addition of the acidified silica gel prepared in step (a), control of the stirrer speed at 280rpm and heating to 60 ℃ for reflux reaction for 12h.
(d) And (3) crosslinking reaction: adding silica gel: tetraethyl orthosilicate =1:1 adding a cross-linking agent, heating to 60 ℃, and carrying out reflux reaction for 12h.
(e) Acidifying and eluting: washing the material obtained by the reaction with ethanol and pure water, and eluting in a 2mol/L hydrochloric acid solution, wherein the mass ratio of the silica gel to the hydrochloric acid is 1:5, heating to 60 ℃, and refluxing for 6h; drying the acid-washed material at 60 ℃, and then adding the dried material into 20% FeLiPO 4 Soaking in solution for 24h for standby, the quality of silica gel is equal to FeLiPO 4 The mass ratio of the solution is 1:5; is marked as product I.
Example 10
(a) Silica gel acidification: 100g of silica gel was heated to 60 ℃ in 500mL of 6mol/L hydrochloric acid solution, refluxed and stirred for 12 hours, washed with pure water, and dried at 60 ℃ for use.
(b) Preparing a solvent: the solvent consists of methanol, aluminum chloride and N- (beta aminoethyl) -gamma-aminopropylmethyl-dimethoxysilane (mass ratio of 1.
(c) Grafting (amination): adding the solvent prepared in the step (b) into a solvent prepared in the step (b) according to the mass ratio of 1:0.15 addition of the acidified silica gel prepared in step (a), control of the stirrer speed at 280rpm and heating to 60 ℃ for reflux reaction for 12h.
(d) And (3) crosslinking reaction: adding silica gel: tetraethyl orthosilicate =1:1 adding a cross-linking agent, heating to 60 ℃, and carrying out reflux reaction for 12h.
(e) Acidifying and eluting: washing the material obtained by the reaction with ethanol and pure water, and eluting in a 2mol/L hydrochloric acid solution, wherein the mass ratio of the silica gel to the hydrochloric acid is 1:5, heating to 60 ℃, and refluxing for 6h; drying the acid-washed material at 60 ℃, and then adding the dried material into 20% FeLiPO 4 Soaking in solution for 24h for standby, the quality of silica gel is equal to FeLiPO 4 The mass ratio of the solution is 1:5; denoted product J.
The products obtained in examples 1 to 10 were tested for their properties as follows: (1) Taking 5-20 g of the iron-containing feed liquid aluminum ion-removing imprinted adsorption material synthesized in the examples 1-10, adding the iron-containing feed liquid aluminum ion-removing imprinted adsorption material into prepared wastewater containing low-concentration aluminum and relatively high-concentration lithium iron phosphate (the mass ratio of the added wastewater to the adsorption material is 10), wherein the contents of aluminum, iron and lithium in raw water are shown in the following table 1; (2) The liquid in the step (1) is contained in a conical flask, and is shaken for 12 to 18 hours in a constant temperature shaker, and the metal ion content is measured by passing through a 0.45 micron membrane, and the obtained results are also shown in the following table 1.
TABLE 1
As is apparent from table 1 above, the performance of the aluminum ion silica gel imprinted material synthesized by the present invention for selectively adsorbing aluminum ions is excellent, and when the concentrations of iron ions and lithium ions are higher, even if the aluminum ions are lower, the product synthesized by the present invention can still effectively remove aluminum. The sample in the example 1 has better actual measurement effect, and can be preferentially used as an aluminum removing material.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.
Claims (10)
1. A preparation method of an iron-containing feed liquid aluminum ion removal imprinted adsorption material is characterized by comprising the following steps:
(a) Silica gel acidification: heating, refluxing and stirring silica gel in an acid solution, cleaning with pure water, and drying for later use;
(b) Preparing a solvent: preparing a solvent consisting of an alcohol compound, an aluminum salt and a silane coupling agent;
(c) Grafting reaction: adding the acidified silica gel prepared in the step (a) into the solvent prepared in the step (b) according to a certain proportion, controlling the rotating speed of a stirrer, and heating for reflux reaction;
(d) And (3) crosslinking reaction: adding a cross-linking agent into the reaction system obtained in the step (c), and heating and refluxing;
(e) Acidifying and eluting: washing the material obtained in the step (d) by using ethanol and pure water, eluting in an acid solution, and heating and refluxing; then drying the material after acid washing, and then adding the dried material into FeLiPO 4 Soaking in the solution.
2. The method according to claim 1, wherein in the step (a), the concentration of the acid solution is 1 to 6mol/L, and the mass ratio of the silica gel to the acid solution is 1: (3-6), the reflux temperature is 50-80 ℃, the reflux time is 6-12 h, and the drying temperature is 50-80 ℃.
3. The production method according to claim 1, wherein in the step (b), the mass ratio of the alcohol compound, the aluminum salt and the silane coupling agent is 1: (0.1-0.8): (0.05-0.25).
4. The preparation method according to claim 1, wherein in the step (b), the alcohol compound is one or more of methanol, ethanol, isopropanol, n-butanol and isoamyl alcohol;
the silane coupling agent is one or a mixture of more of gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, 1-propyl-1- (triethoxysilyl) methylurea, gamma-aminopropylmethyldiethoxysilane and N- (beta-aminoethyl) -gamma-aminopropylmethyl-dimethoxysilane;
the aluminum salt is one or a mixture of aluminum chloride, aluminum sulfate, aluminum nitrate and aluminum carbonate.
5. The method according to claim 1, wherein in the step (c), the solvent prepared in the step (b) is mixed in a mass ratio of 1: (0.05-0.3) adding acidified silica gel; controlling the rotating speed of the stirrer to be 180-300 rpm, and heating the system to 50-70 ℃ for reflux reaction for 12-24 h.
6. The preparation method according to claim 1, wherein in the step (d), the mass ratio of the addition amount of the crosslinking agent to the silica gel is (0.8 to 2.6): 1; the temperature is increased to 50 ℃ to 70 ℃, and the reflux reaction time is 8 to 16 hours.
7. The method of claim 1, wherein in step (d), the cross-linking agent is one or more selected from the group consisting of epichlorohydrin, tetraethyl orthosilicate, and dimethylaminopropylamine.
8. The preparation method according to claim 1, wherein in the step (e), the concentration of the eluting acid solution is 1-6 mol/L, the temperature is raised to 50-70 ℃, and the reflux is carried out for 4-8 h; drying the acid-washed material at 40-60 ℃, and then adding 5-20% of FeLiPO by mass 4 Soaking in the solution for 12-24 h; wherein the mass ratio of the consumption of the eluting acid solution to the silica gel is (3-6): 1; feLiPO 4 The mass ratio of the dosage to the silica gel is (3-6): 1.
9. the method according to claim 1, wherein in the step (a), the acid solution is one or more of hydrochloric acid, sulfuric acid and nitric acid; in the step (e), the eluting acid solution is one or a mixture of hydrochloric acid, sulfuric acid and nitric acid.
10. An iron-containing feed liquid aluminum ion removal imprinted adsorption material, which is characterized by being prepared by the preparation method of any one of claims 1 to 9.
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| CN101711975A (en) * | 2009-11-03 | 2010-05-26 | 厦门大学 | Method for preparing iron ion imprinted silica gel |
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| US20040258986A1 (en) * | 2003-06-23 | 2004-12-23 | Xi Shen | Stacked-type lithium-ion rechargeable battery |
| CN101711975A (en) * | 2009-11-03 | 2010-05-26 | 厦门大学 | Method for preparing iron ion imprinted silica gel |
| US20110114254A1 (en) * | 2009-11-18 | 2011-05-19 | Battelle Memorial Institute | Anodes for lithium ion batteries |
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