CN108607523B - Adsorption material for selectively separating indium and preparation method thereof - Google Patents
Adsorption material for selectively separating indium and preparation method thereof Download PDFInfo
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- 229910052738 indium Inorganic materials 0.000 title claims abstract description 40
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 29
- 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 43
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001449 indium ion Inorganic materials 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 18
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 15
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims abstract description 13
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims abstract description 13
- ULIKDJVNUXNQHS-UHFFFAOYSA-N 2-Propene-1-thiol Chemical compound SCC=C ULIKDJVNUXNQHS-UHFFFAOYSA-N 0.000 claims abstract description 10
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims abstract description 9
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 230000007935 neutral effect Effects 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 5
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims abstract 6
- 239000000243 solution Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- BNKAXGCRDYRABM-UHFFFAOYSA-N ethenyl dihydrogen phosphate Chemical compound OP(O)(=O)OC=C BNKAXGCRDYRABM-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000010881 fly ash Substances 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000002351 wastewater Substances 0.000 description 11
- 238000011084 recovery Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000005272 metallurgy Methods 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000000622 liquid--liquid extraction Methods 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
- 238000000638 solvent extraction Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- QDXBVEACAWKSFL-UHFFFAOYSA-N ethenethiol Chemical compound SC=C QDXBVEACAWKSFL-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses an adsorption material for selectively separating indium, which comprises a substrate and a functional monomer which is modified on the surface of the substrate and can coordinate with indium ions. The invention also discloses a preparation method of the adsorption material for selectively separating indium, which comprises the following steps: 1) modifying carboxyl on the surface of the silicon dioxide, and marking the carboxyl as SG-COOH; 2) dissolving indium sulfate in dimethyl sulfoxide, adding vinylphosphonic acid and allyl mercaptan, and stirring for a period of time to obtain a solution A; 3) mixing SG-COOH obtained in the step 1) with the solution A obtained in the step 2), adding ethylene glycol dimethacrylate and azobisisobutyronitrile, and carrying out polymerization reaction under an anaerobic condition to obtain a polymer B; 4) and removing indium ions from the obtained polymer B by using acid washing, washing the polymer B to be neutral by using deionized water in sequence, and drying to obtain the adsorption material for selectively separating indium. The preparation method of the adsorbing material is simple, and the adsorbing efficiency of the adsorbing material on low-concentration indium ions is high.
Description
Technical Field
The invention belongs to the field of environmental pollution control and rare material recovery, and particularly relates to an adsorption material for selectively separating indium and a preparation method thereof.
Background
Indium, a very low-content rare-earth element in the earth's crust, is widely dispersed in nature, and so far no deposit with indium as an independent or main component has been found to exist in other minerals in the form of impurities. However, indium and its compounds are widely used in the fields of aviation, electronics, and military industry. In addition, indium ions in the aqueous solution are a heavy metal ion which poses serious threats to the environment and human health, so that the method has important significance for selective separation and recovery of indium ions in the aqueous solution from the perspective of resource recycling and the perspective of removing the metal ions in the aqueous solution.
Currently, there are mainly chemical precipitation and liquid-liquid extraction methods for indium separation and recovery. Patent CN 106086410 a discloses a method for separating and recovering indium and zinc from a solution after indium extraction and substitution, which requires that indium and zinc are separated by adjusting the pH value, and then indium is recovered by back extraction. This method of chemical precipitation is often used in systems where the concentration of indium ions is high, and as mentioned above, indium is a very low-dispersion element, and therefore its concentration in aqueous solution is generally low, and other interfering metal ions are also present. The method has certain limitations. Patent CN 103620070 a discloses a method for recovering indium, which adopts a method of strain to recover indium, and this method generally has a small amount of treatment, a long time and a relatively high cost; patent CN 102061398A mentions that indium is recovered by directly adopting a step-by-step extraction method, and although the liquid-liquid extraction method is the main method for recovering indium at present, there are many disadvantages, such as organic phase residue, complex operation, and serious environmental pollution. CN201380050353 discloses a method for producing a complex-forming adsorbent for selective extraction of indium. The technical scheme uses spherical and granular cross-linked macroporous acrylonitrile as a carrier and an organic carrier, and has high cost and complicated modification operation steps.
Therefore, in the field of indium separation and recovery, it is necessary to develop a simpler and easier adsorbent.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide an adsorbent that can efficiently adsorb and recover indium ions when the indium ion concentration is low, and that has a simple preparation method and a high adsorption efficiency for low-concentration indium ions.
In order to achieve the above purpose, the following technical solutions are specifically provided:
1. an adsorption material for selectively separating indium, which comprises a silicon dioxide matrix and a functional monomer modified on the surface of the silicon dioxide matrix and capable of coordinating with indium ions.
2. A preparation method of an adsorption material for selectively separating indium comprises the following steps:
1) modifying carboxyl on the surface of the silicon dioxide, and marking the carboxyl as SG-COOH;
2) dissolving indium sulfate in dimethyl sulfoxide, adding vinylphosphonic acid and allyl mercaptan, and stirring for a period of time to obtain a solution A;
3) mixing SG-COOH obtained in the step 1) with the solution A obtained in the step 2), adding ethylene glycol dimethacrylate and azobisisobutyronitrile, and carrying out polymerization reaction under an anaerobic condition to obtain a polymer B;
4) and removing indium ions from the obtained polymer B by using acid washing, washing the polymer B to be neutral by using deionized water in sequence, and drying to obtain the adsorption material for selectively separating indium.
In a preferred technical scheme, the step 1) is carried out according to the following method: firstly, modifying amino on the surface of silicon dioxide, and marking the amino as SG-NH2And further reacting to obtain SG-COOH.
The technical scheme for modifying amino on the surface of silicon dioxide comprises the following steps: toluene is used as a dispersing agent to prepare silicon dioxide nano-particle turbid liquid with the solid-liquid mass volume ratio of 1-60 percent and the particle size of 40-400 meshes, gamma-aminopropyltriethoxysilane is added into the silicon dioxide nano-particle turbid liquid and is stirred uniformly, and the solid-liquid mass of the gamma-aminopropyltriethoxysilane and the silicon dioxide nano-particle turbid liquid is addedThe volume ratio is 30-100%, the temperature is controlled to be 20-110 ℃ for reaction for 24h, and SG-NH is obtained after filtration and washing2。
Further, SG-COOH was prepared by the following reaction method, and obtained SG-NH250g of the mixture is dispersed in tetrahydrofuran, 15g of maleic anhydride is added, the mixture reacts for 24 hours at room temperature, and SG-COOH is obtained after filtration, washing and drying.
Further, indium sulfate is dissolved in dimethyl sulfoxide, mixed liquid of vinyl phosphoric acid and allyl mercaptan is added, stirring is carried out for reaction for 2 hours, and solution A is obtained, wherein the mass ratio of indium sulfate to dimethyl sulfoxide is 0.1% -20%, vinyl phosphoric acid and allyl mercaptan can be mixed in any ratio, the mass ratio of the mixed liquid to indium sulfate is 0.1% -0.4%, and the reaction temperature of the system is 10-70 ℃.
Further, the synthesis method of the polymer B comprises the following steps: mixing SG-COOH obtained in the step 1) with the solution A obtained in the step 2), adding ethylene glycol dimethacrylate and azobisisobutyronitrile, and carrying out polymerization reaction at the temperature of 20-70 ℃ under an anaerobic condition to obtain a polymer B.
Further, the acid used in the acid washing in the step 4) is one or more of sulfuric acid, hydrochloric acid or nitric acid.
The invention has the beneficial effects that: according to the invention, the adsorption material is prepared by modifying the surface of silicon dioxide into a functional monomer capable of coordinating with indium ions by using a widely-existing inorganic material, and the adsorption material can realize the effect of effectively recovering indium from low-concentration indium ion wastewater. In addition, the preparation method of the adsorption material has the advantages that the cost of all materials is low, the matrix material is widely available, and the price of the used modification material is low; in addition, the preparation process conditions are not harsh, and the operation is simple and easy.
Detailed Description
The present invention will be explained in more detail with reference to specific examples.
Example 1
In a 1000mL flask, 50g of 50 mesh silica was added and dispersed in 350mL of tolueneAdding 50mL of gamma-aminopropyltriethoxysilane, reacting and refluxing for 24h at 70 ℃, filtering, washing and drying to obtain SG-NH2(ii) a The obtained SG-NH2Dispersing 50g of the mixture in tetrahydrofuran, adding 15g of maleic anhydride, reacting for 24 hours at room temperature, and filtering, washing and drying to obtain SG-COOH;
dissolving indium sulfate in dimethyl sulfoxide to prepare a solution with the mass fraction of 10%, adding a mixed solution of 10 wt% of vinylphosphoric acid and allyl mercaptan, and stirring for reacting for 2h to obtain a solution A. Weighing 40g of the obtained SG-COOH, adding the SG-COOH into 150ml of the solution A, then adding 0.4g of ethylene glycol dimethacrylate and 0.4g of azobisisobutyronitrile, introducing nitrogen and discharging oxygen for 20min, and reacting for 24h at the temperature of 60 ℃ to obtain a polymer B; and eluting the obtained polymer A with sulfuric acid to obtain indium ions, sequentially washing with deionized water to neutrality, and drying to obtain the novel adsorption material for selectively separating indium. Weighing 1.50g of the obtained adsorbing material, placing In an adsorbing column with diameter of 1cm and height of 10cm, and using for In3+In the mining and metallurgy wastewater (the wastewater contains a large amount of Fe3+、Zn2+、Ca2+、Mg2+、Al3+K +, Na +, and the like) and selective separation and recovery of In3+, and the result shows that the material can realize In the wastewater3+The adsorption capacity reaches 82.53mg/g and the recovery rate reaches more than 98 percent.
Example 2
Adding 50g of chromatographic silica gel into a 1000mL flask, dispersing the chromatographic silica gel into 350mL of toluene, adding 50mL of gamma-aminopropyltriethoxysilane, reacting and refluxing for 24 hours, filtering, washing and drying to obtain SG-NH2(ii) a The obtained SG-NH2Dispersing 50g of the mixture in tetrahydrofuran, adding 15g of maleic anhydride, reacting for 24 hours at room temperature, and filtering, washing and drying to obtain SG-COOH;
dissolving indium sulfate in dimethyl sulfoxide to prepare a solution with the mass fraction of 10%, adding a mixed solution of 10 wt% of vinyl phosphoric acid and allyl mercaptan into the solution, and stirring at 70 ℃ for reacting for 2 hours to obtain a solution A; 50g of the obtained SG-COO was weighed outAdding H into 240ml of the solution A, then adding 0.5g of ethylene glycol dimethacrylate and 0.5g of azobisisobutyronitrile, introducing nitrogen and discharging oxygen for 20min, and reacting for 24H at the temperature of 60 ℃ to obtain a polymer A; and removing indium ions from the obtained polymer A through nitric acid washing, sequentially washing with deionized water to be neutral, and drying to obtain the novel adsorption material for selectively separating indium. Weighing 1.50g of the obtained adsorbing material, placing In an adsorbing column with diameter of 1cm and height of 10cm, and using for In3+In the mining and metallurgy wastewater (the wastewater contains a large amount of Fe3+、Zn2+、Ca2+、Mg2+、Al3+、K+、Na+Etc.), In3+The result shows that the material can realize In the wastewater3+The adsorption capacity reaches 76.63mg/g and the recovery rate reaches 99.65 percent.
Example 3
Adding 50g of fly ash into a 1000mL flask, dispersing the fly ash into 350mL of toluene, adding 50mL of gamma-aminopropyltriethoxysilane, reacting and refluxing for 24 hours, filtering, washing and drying to obtain SG-NH2(ii) a The obtained SG-NH2Dispersing 50g of the mixture in acetic acid, adding 15g of maleic anhydride, reacting for 24 hours at room temperature, and filtering, washing and drying to obtain SG-COOH;
dissolving indium sulfate in dimethyl sulfoxide to prepare a solution with the mass fraction of 15%, adding a mixed solution of 10 wt% of vinylphosphoric acid and vinylmercaptan, and stirring for reacting for 2 hours to obtain a solution A; weighing 50 parts of SG-COOH obtained above, adding the SG-COOH into the solution A, then adding 0.5 part of ethylene glycol dimethacrylate and 0.5 part of azodiisobutyronitrile, introducing nitrogen and discharging oxygen for 20min, and reacting for 24h at the temperature of 60 ℃ to obtain a polymer A; and removing indium ions from the obtained polymer A through nitric acid washing, sequentially washing with deionized water to be neutral, and drying to obtain the novel adsorption material for selectively separating indium. Weighing 1.50g of the obtained adsorbing material, placing In an adsorbing column with diameter of 1cm and height of 10cm, and using for In3+In the mining and metallurgy wastewater (the wastewater contains a large amount of Fe3+、Zn2+、Ca2+、Mg2+、Al3+、K+、Na+Etc.), In3+The result shows that the material can realize In the wastewater3+The adsorption capacity reaches 25.38mg/g, and the recovery rate reaches 93.61%.
The above examples further illustrate the present invention by modifying the surface of silica component with a functional monomer capable of coordinating with indium ions by using a widely available inorganic material to prepare an adsorbing material, which can achieve the effect of efficiently recovering indium from low-concentration indium ion wastewater.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (8)
1. An adsorption material for selectively separating indium, which is characterized by comprising a substrate and a functional monomer which is modified on the surface of the substrate and can be coordinated with indium ions, wherein the substrate comprises a main component of silicon dioxide;
the preparation method of the adsorption material for selectively separating indium comprises the following steps:
1) firstly, modifying amino on the surface of silicon dioxide, and marking the amino as SG-NH2Further reacting to obtain SG-COOH;
2) dissolving indium sulfate in dimethyl sulfoxide, adding vinylphosphonic acid and allyl mercaptan, and stirring for a period of time to obtain a solution A;
3) mixing SG-COOH obtained in the step 1) with the solution A obtained in the step 2), adding ethylene glycol dimethacrylate and azobisisobutyronitrile, and carrying out polymerization reaction under an anaerobic condition to obtain a polymer B;
4) removing indium ions from the obtained polymer B by using acid washing, washing the polymer B to be neutral by using deionized water in sequence, and drying the polymer B to obtain an adsorption material for selectively separating indium;
the technical scheme for modifying amino on the surface of silicon dioxide comprises the following steps: toluene is used as a dispersing agent to prepare silicon dioxide nano-particle turbid liquid with the solid-liquid mass volume ratio of 1-60 percent and the particle size of 40-400 meshes, gamma-aminopropyltriethoxysilane is added into the silicon dioxide nano-particle turbid liquid and is stirred uniformly, the solid-liquid mass volume ratio of the gamma-aminopropyltriethoxysilane added to the silicon dioxide nano-particle turbid liquid is 30-100 percent, the temperature is controlled to be 20-110 ℃ for reaction for 24 hours, and SG-NH is obtained after filtering and washing2。
2. The adsorption material for selective separation of indium as claimed in claim 1, wherein the substrate is dioxide
Silicon, silica gel and fly ash.
3. A preparation method of an adsorption material for selectively separating indium is characterized by comprising the following steps:
1) modifying carboxyl on the surface of the silicon dioxide, and marking the carboxyl as SG-COOH;
2) dissolving indium sulfate in dimethyl sulfoxide, adding vinylphosphonic acid and allyl mercaptan, and stirring for a period of time to obtain a solution A;
3) mixing SG-COOH obtained in the step 1) with the solution A obtained in the step 2), adding ethylene glycol dimethacrylate and azobisisobutyronitrile, and carrying out polymerization reaction under an anaerobic condition to obtain a polymer B;
4) and removing indium ions from the obtained polymer B by using acid washing, washing the polymer B to be neutral by using deionized water in sequence, and drying to obtain the adsorption material for selectively separating indium.
4. The method for preparing an adsorption material for selective separation of indium as claimed in claim 3, wherein the step 1)
The preparation method comprises the following steps: firstly, modifying amino on the surface of silicon dioxide, and marking the amino as SG-NH2And further reacting to obtain SG-COOH.
5. According to claimThe method for preparing the adsorbing material for selectively separating indium in the claim 4, wherein the SG-COOH is prepared by reacting 50g SG-NH2Dispersing in tetrahydrofuran, adding 15g maleic anhydride, reacting at room temperature for 24 hr, filtering, washing and drying to obtain SG-COOH.
6. The method for preparing the adsorption material for selectively separating indium according to claim 3, wherein the solution A is synthesized by: dissolving indium sulfate in dimethyl sulfoxide, adding a mixed solution of vinyl phosphoric acid and allyl mercaptan, and stirring for reaction for 2 hours to obtain a solution A, wherein the mass ratio of the indium sulfate to the dimethyl sulfoxide is 0.1-20%, the vinyl phosphoric acid and the allyl mercaptan can be mixed in any ratio, the mass ratio of the mixed solution to the indium sulfate is 0.1-0.4%, and the reaction temperature of the system is 10-70 ℃.
7. The method for preparing the adsorption material for selectively separating indium according to claim 3, wherein the polymer B is synthesized by: mixing SG-COOH obtained in the step 1) with the solution A obtained in the step 2), adding ethylene glycol dimethacrylate and azobisisobutyronitrile, and carrying out polymerization reaction at the temperature of 20-70 ℃ under an anaerobic condition to obtain a polymer B.
8. The method for preparing the adsorption material for selectively separating indium according to claim 3, wherein the acid used in the acid washing in the step 4) is one or more of sulfuric acid, hydrochloric acid or nitric acid.
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