CN108607523A - A kind of sorbing material and preparation method thereof of Selective Separation indium - Google Patents
A kind of sorbing material and preparation method thereof of Selective Separation indium Download PDFInfo
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- CN108607523A CN108607523A CN201810562152.9A CN201810562152A CN108607523A CN 108607523 A CN108607523 A CN 108607523A CN 201810562152 A CN201810562152 A CN 201810562152A CN 108607523 A CN108607523 A CN 108607523A
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- 239000000463 material Substances 0.000 title claims abstract description 46
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 41
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000926 separation method Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 22
- 229910001449 indium ion Inorganic materials 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims abstract description 12
- 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 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- ULIKDJVNUXNQHS-UHFFFAOYSA-N 2-Propene-1-thiol Chemical compound SCC=C ULIKDJVNUXNQHS-UHFFFAOYSA-N 0.000 claims abstract description 7
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims abstract description 7
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 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 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- BNKAXGCRDYRABM-UHFFFAOYSA-N ethenyl dihydrogen phosphate Chemical compound OP(O)(=O)OC=C BNKAXGCRDYRABM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 238000005554 pickling Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- -1 γ-aminopropyl Chemical group 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 239000010881 fly ash Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 claims 1
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000002075 main ingredient Substances 0.000 claims 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical group [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 claims 1
- 239000000741 silica gel Substances 0.000 claims 1
- 229910002027 silica gel Inorganic materials 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 20
- 238000011084 recovery Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- 239000002351 wastewater Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006392 deoxygenation reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000005272 metallurgy Methods 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- VNFYMAPAENTMMO-UHFFFAOYSA-N 5-chloro-2-methylquinoline Chemical compound ClC1=CC=CC2=NC(C)=CC=C21 VNFYMAPAENTMMO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 229940008075 allyl sulfide Drugs 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 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
- 239000003463 adsorbent Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- QDXBVEACAWKSFL-UHFFFAOYSA-N ethenethiol Chemical compound SC=C QDXBVEACAWKSFL-UHFFFAOYSA-N 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- 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 a kind of sorbing material of Selective Separation indium, the sorbing material includes matrix and the function monomer that can be coordinated in indium ion modified in stromal surface.The invention also discloses a kind of preparation methods of the sorbing material of Selective Separation indium, include the following steps：1) carboxyl is modified in silica surface, is labeled as SG COOH；2) indium sulfate is dissolved in dimethyl sulfoxide (DMSO), and vinyl phosphoric acid and allyl sulfhydrate is added, stirring a period of time, obtain solution A；3) SG COOH obtained by step 1) are mixed with step 2) acquired solution A, adds ethylene glycol dimethacrylate and azodiisobutyronitrile, under anaerobic, polymerisation occurred, obtains polymer B；4) obtained polymer B is deviate from into indium ion using pickling, be washed with deionized water successively to neutrality, then dry to get the sorbing material of Selective Separation indium.The sorbing material preparation method is simple, and the sorbing material is high for the adsorption efficiency of low concentration indium ion.
Description
Technical field
The invention belongs to control environmental pollution and recycle exotic material field, and in particular to a kind of suction of Selective Separation indium
Enclosure material and preparation method thereof.
Background technology
Indium, the rare and scatter element extremely low as content in a kind of earth's crust, is widely dispersed in nature, is not yet found so far
Using indium as the mineral deposit of independence or main component, it is present in the form of impurity in other mineral.However, indium and its chemical combination
Object is widely used in the fields such as aviation, electronics and military project.In addition, in aqueous solution indium ion as a kind of heavy metal ion,
Environmental and human health impacts are all caused to seriously threaten, thus either from the angle of resource recycling still from aqueous solution it is golden
The removal angle for belonging to ion, it is all significant to the Selective Separation of indium ion, recycling in aqueous solution.
Separation, recycling currently for indium, mainly there is the mode of chemical precipitation and liquid-liquid extraction.Patent CN 106086410
A discloses indium, zinc separation and recovery method in a kind of indium extraction displaced liquid, and the method needs to first pass through adjusting pH value, makes it
Indium and zinc are detached, then the recovery indium by way of back extraction.This method using chemical precipitation is often suitable for system
The middle higher situation of indium ion concentration, as previously mentioned, indium is a kind of extremely low rare and scatter element of content, therefore its in aqueous solution dense
Degree is general very low, and there is also other to interfere metal ion.The method has some limitations.Patent CN 103620070
A discloses a kind of recovery method of indium, uses the method recovery indium of bacterial strain, and the amount that this method is generally handled is smaller and the time
Longer, the cost is relatively high；It is mentioned in 102061398 A of patent CN, directly uses the method recovery indium of fractional extraction, liquid liquid
The method of extraction despite current recovery indium main method, but there are many deficiencies, as organic phase residual, it is complicated for operation,
A series of problems, such as environmental pollution is serious.CN201380050353 discloses a kind of complex compound produced for selective extraction indium
The method for forming adsorbent.It is related to ion exchange and forms polymer by using complex compound to form complex compound or chelate
Field, the technical program is carrier using pelletiod Crosslinked Macroporous acrylonitrile, is organic carrier, of high cost, and to it
Modification is complex for operation step.
Therefore, as separation and recovery indium technical field, it is necessary to develop a kind of more simple and practicable sorbing material.
Invention content
For the above-mentioned problems in the prior art, the purpose of the present invention is to provide one kind for indium ion concentration compared with
To the sorbing material of the effective adsorption recovery of indium ion when low, the sorbing material preparation method is simple, and is directed to low concentration indium
The adsorption efficiency of ion is high.
For achieving the above object, technical solution as described below is specifically provided：
1, a kind of sorbing material of Selective Separation indium, the sorbing material include silica matrix and on its surface
The function monomer that can be coordinated in indium ion of modification.
2, a kind of preparation method of the sorbing material of Selective Separation indium, includes the following steps：
1) carboxyl is modified in silica surface, is labeled as SG-COOH；
2) indium sulfate is dissolved in dimethyl sulfoxide (DMSO), and vinyl phosphoric acid and allyl sulfhydrate is added, when stirring one section
Between, obtain solution A；
3) SG-COOH obtained by step 1) is mixed with step 2) acquired solution A, adds ethylene glycol dimethacrylate
And azodiisobutyronitrile occurs polymerisation, obtains polymer B under anaerobic；
4) obtained polymer B is deviate from into indium ion using pickling, be washed with deionized water successively to neutrality, then dry, i.e.,
Obtain the sorbing material of Selective Separation indium.
Preferred technical solution, step 1) is as follows：Amino is modified in silica surface first, is labeled as
SG-NH2, SG-COOH is further obtained by the reaction.
It is in the technical solution of silica surface modification amino：Using toluene as dispersant, solid-liquid quality volume is prepared
Than for the nano SiO 2 particle turbid that 1%~60% grain size is 40~400 mesh, into nano SiO 2 particle turbid plus
Enter gamma-aminopropyl-triethoxy-silane and stir evenly, gamma-aminopropyl-triethoxy-silane be added and nano SiO 2 particle are turbid
The solid-liquid mass volume ratio of liquid is 30%~100%, and 20 DEG C~110 DEG C of control temperature is reacted for 24 hours, through being filtered, washed up to SG-
NH2。
Further, SG-COOH reacts preparation as follows, obtained SG-NH250g is dispersed in tetrahydrofuran, and is added
Enter 15g maleic anhydrides, reacts at ambient temperature for 24 hours, through being filtered, washed and drying to SG-COOH.
Further, indium sulfate is dissolved in dimethyl sulfoxide (DMSO), and the mixing of vinyl phosphoric acid and allyl sulfhydrate is added
Liquid is stirred to react 2h, obtains solution A, wherein the mass ratio between indium sulfate and dimethyl sulfoxide (DMSO) is 0.1%~20%, second
It can be mixed with arbitrary proportion between alkenyl phosphoric acid, allyl sulfhydrate, the mixed liquor of composition and the mass ratio of indium sulfate are 0.1%
~0.4%, the reaction temperature of system is 10 DEG C~70 DEG C.
Further, the synthetic method of the polymer B is：SG-COOH and step 2) acquired solution A obtained by step 1) is mixed
It closes, ethylene glycol dimethacrylate and azodiisobutyronitrile is added, under anaerobic, under 20~70 DEG C of temperature conditions
Polymerisation occurs, obtains polymer B.
Further, the acid that the step 4) pickling uses is the one or more of sulfuric acid, hydrochloric acid or nitric acid.
The beneficial effects of the present invention are：By the present invention in that the mode that it is modified with the inorganic material being widely present,
It is prepared into sorbing material by being modified into the function monomer that can be coordinated in indium ion in silica surface, the sorbing material can
To realize the effect of effective recovery indium from low concentration indium ion waste water.And from the point of view of the preparation method of the sorbing material,
The cost of its all material is low, and host material is widely present, and used decorative material is cheap；In addition preparation process condition
Not harsh, operation is simple.
Specific implementation mode
More detailed elaboration is carried out to the present invention below in conjunction with specific embodiment.
Embodiment 1
In 1000mL flasks, the silica that 50g50 mesh is added is scattered in 350mL toluene, and 50mL γ-ammonia is added
Propyl-triethoxysilicane, under the conditions of 70 degree celsius temperatures reaction reflux for 24 hours, through being filtered, washed and drying to SG-NH2；
The SG-NH that will be obtained250g is dispersed in tetrahydrofuran, and 15g maleic anhydrides are added, and is reacted at ambient temperature for 24 hours,
Through being filtered, washed and drying to SG-COOH；
Indium sulfate is dissolved in and is configured to mass fraction in dimethyl sulfoxide (DMSO) as 10% solution, and the second of 10wt% is added
Alkenyl phosphoric acid and allyl sulfide mixed alkoxide solution, are stirred to react 2h, obtain solution A.The SG-COOH that 40g is obtained is weighed to be added to
In 150ml solution As, 0.4g ethylene glycol dimethacrylate and 0.4g azodiisobutyronitriles are then added, leads to nitrogen deoxygenation
20min, under the conditions of 60 DEG C, reaction for 24 hours, obtains polymer B；Obtained polymer A is eluted into indium ion by sulfuric acid, with
It is washed with deionized water again successively afterwards to neutral, drying, you can obtain the sorbing material of this new selective separating indium.By gained
To sorbing material weigh 1.50g, a diameter of 1cm is placed in, highly in the adsorption column of 10cm, for containing In3+Mining and metallurgy it is useless
(contain a large amount of Fe in waste water in water3+、Zn2+、Ca2+、Mg2+、Al3+, K+, Na+ etc.), the Selective Separation of In3+, recycling, as a result
Show that the material can realize In in the waste water3+Selective absorption, adsorption capacity reaches 82.53mg/g and the rate of recovery reaches 98%
More than.
Embodiment 2
In 1000mL flasks, 50g chromatographic silica gels are added and are scattered in 350mL toluene, and 50mL γ-aminopropyl three is added
Ethoxysilane, reaction flow back for 24 hours, through being filtered, washed and drying to SG-NH2；The SG-NH that will be obtained250g is dispersed in four
In hydrogen furans, and 15g maleic anhydrides are added, react at ambient temperature for 24 hours, through being filtered, washed and drying to SG-
COOH；
Indium sulfate is dissolved in and is configured to the solution that mass fraction is 10% in dimethyl sulfoxide (DMSO), is added into solution
The vinyl phosphoric acid and allyl sulfide mixed alkoxide solution of 10wt% is stirred to react 2h under 70 degrees celsius, obtains solution A；Claim
It takes the SG-COOH that 50g is obtained to be added in 240ml solution As, then adds 0.5g ethylene glycol dimethacrylate and 0.5g
Azodiisobutyronitrile leads to nitrogen deoxygenation 20min, and under the conditions of 60 DEG C, reaction for 24 hours, obtains polymer A；Obtained polymer A is led to
Pernitric acid elutes indium ion, is then washed with deionized water again successively to neutral, drying, you can obtain this new selective point
Sorbing material from indium.Obtained sorbing material is weighed into 1.50g, is placed in a diameter of 1cm, is highly the adsorption column of 10cm
In, for containing In3+Mining and metallurgy waste water in (in waste water contain a large amount of Fe3+、Zn2+、Ca2+、Mg2+、Al3+、K+、Na+Deng), In3+
Selective Separation, recycling, the results showed that the material can realize In in the waste water3+Selective absorption, adsorption capacity reaches
The 76.63mg/g and rate of recovery reaches 99.65%.
Embodiment 3
In 1000mL flasks, 50g flyash is added and is scattered in 350mL toluene, and 50mL γ-three second of aminopropyl is added
Oxysilane, reaction flow back for 24 hours, through being filtered, washed and drying to SG-NH2；The SG-NH that will be obtained250g is dispersed in acetic acid
In, and 15g maleic anhydrides are added, it reacts at ambient temperature for 24 hours, through being filtered, washed and drying to SG-COOH；
Indium sulfate is dissolved in and is configured to mass fraction in dimethyl sulfoxide (DMSO) as 15% solution, and the second of 10wt% is added
Alkenyl phosphoric acid and vinyl mercaptan mixed solution, are stirred to react 2h, obtain solution A；50 SG-COOH obtained above are weighed to be added
Into solution A, 0.5 ethylene glycol dimethacrylate and 0.5 azodiisobutyronitrile are then added, leads to nitrogen deoxygenation 20min,
Under the conditions of 60 DEG C, reaction for 24 hours, obtains polymer A；Obtained polymer A is eluted into indium ion by nitric acid, then successively again
It is washed with deionized water to neutral, drying, you can obtain the sorbing material of this new selective separating indium.By obtained absorption
Material weighs 1.50g, is placed in a diameter of 1cm, highly in the adsorption column of 10cm, for containing In3+Mining and metallurgy waste water in (waste water
In contain a large amount of Fe3+、Zn2+、Ca2+、Mg2+、Al3+、K+、Na+Deng), In3+Selective Separation, recycling, the results showed that the material
It can realize In in the waste water3+Selective absorption, adsorption capacity reaches 25.38mg/g, and the rate of recovery reaches 93.61%.
It can be further illustrated the present invention by above example and it to be modified by using the inorganic material being widely present
Mode, it is described by being prepared into sorbing material at the function monomer that can be coordinated in indium ion in silica composition surface modification
The effect of effective recovery indium from low concentration indium ion waste water may be implemented in sorbing material.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (10)
1. a kind of sorbing material of Selective Separation indium, which is characterized in that the sorbing material includes matrix and in matrix table
The function monomer that can be coordinated with indium ion of face modification.
2. a kind of sorbing material of Selective Separation indium according to claim 1, which is characterized in that the matrix includes main
Ingredient silica.
3. a kind of sorbing material of Selective Separation indium according to claim 1, which is characterized in that the matrix is titanium dioxide
Silicon, silica gel, flyash.
4. a kind of preparation method of the sorbing material of Selective Separation indium, which is characterized in that include the following steps：
1) carboxyl is modified in silica surface, is labeled as SG-COOH；
2) indium sulfate is dissolved in dimethyl sulfoxide (DMSO), and vinyl phosphoric acid and allyl sulfhydrate is added, stirring a period of time, obtained
To solution A；
3) SG-COOH obtained by step 1) is mixed with step 2) acquired solution A, adds ethylene glycol dimethacrylate and idol
Nitrogen bis-isobutyronitrile occurs polymerisation, obtains polymer B under anaerobic；
4) obtained polymer B is deviate from into indium ion using pickling, be washed with deionized water successively to neutrality, then dry to get choosing
The sorbing material of selecting property separating indium.
5. a kind of preparation method of the sorbing material of Selective Separation indium according to claim 4, which is characterized in that step 1)
Preparation method is：Amino is modified in silica surface first, is labeled as SG-NH2, SG-COOH is further obtained by the reaction.
6. a kind of preparation method of the sorbing material of Selective Separation indium according to claim 5, which is characterized in that in dioxy
The technical solution of SiClx surface modification amino is：Using toluene as dispersant, it is 1%~60% to prepare solid-liquid mass volume ratio
Diameter is the nano SiO 2 particle turbid of 40~400 mesh, and three second of γ-aminopropyl is added into nano SiO 2 particle turbid
Oxysilane simultaneously stirs evenly, the solid-liquid mass body of gamma-aminopropyl-triethoxy-silane be added and nano SiO 2 particle turbid
Product is than being 30%~100%, and 20 DEG C~110 DEG C of control temperature is reacted for 24 hours, through being filtered, washed up to SG-NH2。
7. a kind of preparation method of the sorbing material of Selective Separation indium according to claim 5, which is characterized in that described
SG-COOH reacts preparation as follows, takes 50g SG-NH2It is dispersed in tetrahydrofuran, and 15g maleic anhydrides is added,
It reacts at ambient temperature for 24 hours, through being filtered, washed and drying to SG-COOH.
8. a kind of preparation method of the sorbing material of Selective Separation indium according to claim 4, which is characterized in that described molten
The synthetic method of liquid A is：Indium sulfate is dissolved in dimethyl sulfoxide (DMSO), and the mixing of vinyl phosphoric acid and allyl sulfhydrate is added
Liquid is stirred to react 2h, obtains solution A, wherein the mass ratio between indium sulfate and dimethyl sulfoxide (DMSO) is 0.1%~20%, second
It can be mixed with arbitrary proportion between alkenyl phosphoric acid, allyl sulfhydrate, the mixed liquor of composition and the mass ratio of indium sulfate are 0.1%
~0.4%, the reaction temperature of system is 10 DEG C~70 DEG C.
9. a kind of preparation method of the sorbing material of Selective Separation indium according to claim 4, which is characterized in that described poly-
The synthetic method for closing object B is：SG-COOH obtained by step 1) is mixed with step 2) acquired solution A, adds dimethacrylate
Glycol ester and azodiisobutyronitrile occur polymerisation under 20~70 DEG C of temperature conditions, are polymerize under anaerobic
Object B.
10. a kind of preparation method of the sorbing material of Selective Separation indium according to claim 4, which is characterized in that step
4) pickling uses the one or more that acid is sulfuric acid, hydrochloric acid or nitric acid.
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