CN106824091A - A kind of preparation and its application of magnetic cation hydrogel based composite adsorption material - Google Patents
A kind of preparation and its application of magnetic cation hydrogel based composite adsorption material Download PDFInfo
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- 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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3425—Regenerating or reactivating of sorbents or filter aids comprising organic materials
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
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- 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
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- 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
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- 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
- C02F2101/103—Arsenic compounds
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- 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
- C02F2101/105—Phosphorus compounds
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- 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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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- 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
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The present invention relates to it is a kind of go water removal in inorganic anion pollutant magnetic cation hydrogel based composite adsorption material preparation method its apply.Magnetic cation hydrogel based composite adsorption material of the invention contains the different shape of cationic water gel, magnetisable material and active metal；The preparation method of magnetic cation hydrogel based composite adsorption material of the invention is free-radical polymerized including will be carried out between trimethyl ammonium chloride and methylene-bisacrylamide, magnetisable material is added to be reacted simultaneously, then the load in situ of the active metal of different shape is carried out, synthesized composite adsorbing material has positive surface charge and exclusive adsorption potential high, can be to the F in water‑、PO4 3‑、NO3 ‑And AsO4 3‑、SbO4 3‑Carry out efficiently quick Adsorption.Composite adsorbing material chemical stability prepared by the present invention is good, separated using pH value range is wider, anti-ion interference strong, be easy to magnetic field and repeatedly regeneration, Ion release amount be low, non-secondary pollution, with good application potential.
Description
Technical field
The present invention relates to composite and Environmental science and technology field, more particularly, to a kind of magnetic cation hydrogel
The preparation and its application of based composite adsorption material.
Background technology
With the fast development of social economy, the inorganic anion pollutant kind and quantity into water body are increasing,
Mainly have：Phosphate radical（PO4 3-）, stibate（SbO3 -）, arsenate（AsO3 -）, nitrate anion（NO3 -）, fluoride (F-) etc. its is most
From work/agricultural production, such as：Mining, metallurgy（Aluminium processed）, pharmacy, the processing of leather/rubber/glass/chemical fibre, printing and dyeing, agricultural chemicals/
Chemical fertilizer etc..What is had is then mainly derived from sanitary wastewater, such as：Detergent, wetting agent, foaming agent, soap/medicine/personal care articles
Use.These anionic pollutants are to human body skin（Chromium）, liver（Selenium）, stomach（Nitrate）, etc. have it is potential or aobvious
Animals and plants will be produced and endanger or cause different degrees of water environment by work property toxicity after biological chain runs up to finite concentration
Problem.For example：Long-term Funing tablet of drinking is for the water of 3-6mg/L can cause fluorosis of bone.Fluorine long term accumulation can be generated when human body
CaF2, cause sclerotin crisp, tooth mottled enamels, ligament calcification etc..The long-term personnel of operation under environment containing antimony can trigger antimony chronic
Poisoning, shows as PFT change, chronic bronchitis, pulmonary emphysema, incipient tuberculosis, pleaural adhesion and pneumoconiosis.Additionally, people
Body takes in excessive phosphate can make the internal calcium cannot fully absorb, utilize, and easily cause the change of fracture, loss of tooth and bone
Shape.And the drinking-water containing a large amount of nitrate, vegetables, grain etc. are taken in for a long time, and anoxic poisoning can be made one, cause giddy, palpitaition, vomit
The symptom such as tell.
Absorption method is one of method of removal inorganic anion polluted-water economical and efficient, with flexibility and operation just
Victory, is applicable to multiple-quality water environment, wherein, adsorbent is key factor.In recent years, for the removal of anion in water,
The more active charcoal class material of research, metal oxide and its compound, bio-based materials and ion exchange resin etc..Water-setting
Glue material has caused the concern of industry as a kind of new adsorbent, and it has three-dimensional net structure, high intensity and toughness,
Good shape can be still kept after absorbing water；Wherein cationic water gel can be reached by playing its electrostatic adsorption
The removal of inorganic anion in water.It is mainly made up of cationic monomer, by ion or covalent type cross-linking agents
Propagation, forms the macromolecule hydrogel with high surfaces electric charge.Its surface usually contains more cationic reactive groups, its
In based on amine groups, positive charge characteristic higher is presented in the solution.
Patent of invention（CN201410730897.3）Disclose a kind of preparation of hydrogel composite material and in dye wastewater
Middle application, mainly by radical crosslinking copolymerization method, will acidifying concave convex rod (PS) in acrylamide (AM) and 2- acrylamides-
2- methyl propane sulfonic acids (AMPS) copolymerization, prepares with a large amount of amino and sulfonic hydrogel adsorbent, above-mentioned group enhancing
The specific surface area and recognition performance of the adsorbent, such that it is able to the absorption malachite green in industry or sanitary wastewater.
Patent of invention（CN201510134734.3）Disclose a kind of graphene-based hydrogel adsorbent of visible photo reversal
Preparation method, mainly load glutathione, silver ion and phosphate radical successively in surface of graphene oxide, it is negative so as to prepare
Carry the graphene-based hydrogel adsorbent of silver orthophosphate.The absorption is improved to the adsorption capacity of methyl orange dye, it is possible to follow
Ring is used.
Patent of invention（CN201410300672.4）Disclose a kind of heavy metal ion industrial wastewater handling process and device.
The filler in adsorption tower being directed to is hydrogel sorbing material, can adsorb Pb In Exhausted Water, nickel, chromium ion, it is possible to acid
Wash regeneration.
In the research of above-mentioned hydrogel material, more focus are the modified of hydrogel surface functional group, are such as passed through
Load sulfonic group, amino etc., or supported ionic state noble metal, such as silver ion, adsorption capacity of the enhancing to dyestuff.One side
Face, surface-active functional group's limited amount is in specific surface area, the porosity etc. of adsorbent, it is difficult to a large amount of by graft copolymerization etc.
Obtain, cause its lifting to adsorption effect extremely limited, the Hydrogels adsorbent of another aspect modified with noble metals, due to it
Material cost higher, large-scale popularization and application are restricted.It is many cheap for the removal of anionic pollutant in water
Active metallic ion and its hydrous oxide show excellent absorption property, and such as rare-earth elements of lanthanum, zirconium, cerium are to fluorine ion, phosphorus
The absorption of acid group, nitrate, involved mechanism includes ion/ligand is exchanged, surface is precipitated/is complexed etc..Its absorption feature is
The exclusive effect of feature between active metal and anionic pollutant.At present apparently, the cheap activity of hydrogel sorbent-loaded
The invention of metal is not yet related to, and in water inorganic anion removal aspect application invention also have no report.
The content of the invention
An object of the present invention is to provide a kind of preparation method of magnetic cation hydrogel based composite adsorption material；
The second object of the present invention is that above-mentioned magnetic cation hydrogel based composite adsorption material is used for containing inorganic anion
Drink
With the treatment of water, stain disease or recycled water；The third object of the present invention provides magnetic hydrogel based composite adsorption material and inhales
Regeneration treating method after attached anion.
Technical scheme：
1st, a kind of magnetic cation hydrogel based composite adsorption material, it is characterised in that contain cationic water gel, magnetisable material
With the different shape of active metal, the different shape of supported active metals on magnetic cation hydrogel.
2nd, magnetic cation hydrogel based composite adsorption material as claimed in claim 1, it is characterised in that magnetisable material
It is by Raolical polymerizable single sintering, including the step of be carried out as follows with cationic water gel：
(1) (3- acrylamide propyls) trimethyl ammonium chloride (APTMACl) monomer is added to the water, is subsequently adding friendship
Connection agent N, N'- methylene-bisacrylamide (MBA), after it is completely dissolved, then adds a small amount of pure water, cationic monomer and pure water
Ratio is about 10-500: 1, preferably：10-20：1, generate solution A；
(2) to adding micro accelerator N in solution A, N, N', N'- tetramethylethylenediamine (TEMED) and a small amount of magnetic γ-
Fe2O3Uniformly mixed, be subsequently adding initiator saturation potassium peroxydisulfate (KPS) solution, it is anti-in 10-100 DEG C of stirred in water bath
0-2h is answered, wherein cationic monomer, accelerator, magnetic material, ratio of initiator is 250-500：5-10：50-100：100-
200, generation magnetic cation hydrogel predecessor B；Preferably：25：5：5：10；
(3) magnetic cation hydrogel predecessor B is cured, is generated magnetic cation hydrogel, then replaced container simultaneously
10-100h in pure water is immersed in, a water is changed per 2-10h, particularly changed water spacer and be controlled to 6-8h, wash away unreacted list
Body, crosslinking agent, initiator and accelerator material, then grind the freeze-drying of magnetic cation hydrogel, are prepared as magnetic sun
Aqueous ionomer gel particle.
3rd, magnetic cation hydrogel based composite adsorption material as claimed in claim 1, it is characterised in that active metal
Different shape include in Sr, Zr, Fe one or more in the one or more free hydrated ion or La, Sr, Zr, Fe of metal
The hydrous oxide of metal.
4th, the free hydrated ion of active metal as claimed in claim 3, it is characterised in that active metal is freely hydrated
The load of ion in the following order the step of carry out：
（1）Surface reaction is carried out during magnetic cation hydrogel particle impregnated in into saturated activity metal salt solution, dosage is
0.1-5g/L, preferably 2-4g/L, are continuously stirred with the rotating speed constant temperature of 100-300rpm, until active metallic ion is dense in solution
Degree stabilization, stands, Magneto separate, is filtered dry supernatant, obtains the magnetic cation water-setting of the free hydrated ion of supported active metals
Glue；
（2）The magnetic cation hydrogel of the free hydrated ion of the supported active metals after gained is washed with deionized,
Until the pH value of washing water outlet is neutrality to alkalescent.
5th, the hydrous oxide of active metal as claimed in claim 3, it is characterised in that active metal hydrous oxide
Load in the following order the step of carry out：
（1）Magnetic cation hydrogel particle is immersed in the active metal salt of saturation-organic solvent mixed solution carries out table
Face is reacted, and is thoroughly mixed it；Supernatant is filtered dry, the precipitation that will be leached is added in NaOH solution, is entered at 50-100 DEG C
Row heating water bath, isolating precipitation carries out the deionized water washing of 0-24h；
（2）Washed in the NaCl solution of the precipitation addition 50-500mL after deionized water is washed, until washing water outlet
PH value is for neutral to alkalescent；Finally use deionized water agitator treating；Deposit is carried out 0-60 DEG C of vacuum drying and 50-
110 DEG C of drying,
Particularly, active metal salt described in step 1-alcohol mixed solution concentration is 0-200g/L, and concentration of alcohol is 5-
30wt%；
Particularly, the water-bath heat time is 2-6h in step 2, and washing deionized water used and compound mass ratio are 1：50-
100；
Particularly, it is 0.1-1mol/L that NaCl concentration used is washed in step 3.
6th, magnetic cation hydrogel based composite adsorption material as claimed in claim 1, it is characterised in that go in water removal
Deliquescent inorganic anion pollutant.
7th, inorganic anion pollutant in water as claimed in claim 6, it is characterised in that including F-、PO4 3-、NO3 -With
And AsO4 3-、SbO4 3-Different shape, concentration range is 10-1000mg/L.
8th, magnetic cation hydrogel based composite adsorption material as claimed in claim 1, it is characterised in that absorption it is cloudy from
Son and regeneration process in the following order the step of carry out：
（1）To the magnetic hydrogel based composite adsorption material that 0.1-5g/L is added in the anionic pollutant of 10-1000mg/L；
（2）The adsorption time of 1-48h is kept, and with the rotating speed persistent oscillation of 100-1000rpm in adsorption process；
（3）After the completion of absorption, mixed liquor is staticly settled, the recovery of composite material granular is carried out using permanent magnet；
（4）During reclaimed particle impregnated in the hydrochloric acid solution of 0.01-1M successively, in the sodium hydroxide solution of 0.01-1M, finally
Rinsed with sodium chloride solution, until washing the pH value of water outlet for neutral to alkalescent.
9th, regenerative agent as claimed in claim 8, it is characterised in that including：It is a kind of or many in HCl, NaOH, NaCl
Kind；Particularly hydrochloric acid molar concentration is 0.01-1mol/L, preferably 0.05-0.5mol/L；Particularly NaOH molar concentrations are
0.01-1mol/L, preferably 0.05-0.5mol/L, particularly sodium chloride molar concentration are 0.1-1mol/L；Preferably 0.1-
0.5mol/L。
Advantage：
The present invention uses radical polymerization, can be with single sintering magnetic cation hydrogel based composite adsorption material, method letter
Single, material size shape, mechanical strength, saturation magnetic intensity, swelling character can regulate and control.
Prepared magnetic cation hydrogel based composite adsorption material, surface carries positive charge higher, can pass through
Coulomb active force realizes the efficient quick adsorption to anionic pollutant in water.Additionally, the magnetic cation water-setting matrix is compound
The sorbing material surface also different shape containing active metal, has stronger exclusive adsorptivity to anionic pollutant in water
Energy.Further, the different shape of the active metal in the magnetic cation hydrogel based composite adsorption material obtained by the present invention
Including one or more hydration of metal in the one or more free hydrated ion or La, Sr, Zr, Fe of metal in Sr, Zr, Fe
Oxide, its material source is extensively, with low cost.The reclaiming of magnetic cation hydrogel based composite adsorption material is simple, and two
Secondary pollution is small.
Brief description of the drawings：
Fig. 1 is magnetic cation hydrogel based composite adsorption material preparation method schematic diagram.
Specific embodiment：
Case study on implementation 1
1st, 5g (3- acrylamide propyls) trimethyl ammonium chloride (APTMACl) monomer is weighed, the friendship of 0.5g is added thereto to
Connection agent N, N'- methylene-bisacrylamide (MBA), then add 0.8mL pure water after after crosslinking agent MBA all dissolving, add
0.1ml accelerators N, N, N', N'- tetramethylethylenediamine (TEMED) and 0.5g magnetic γ-Fe2O3When above material mixing is uniform
Afterwards, plus initiator 1.5mL saturations potassium peroxydisulfate (KPS) solution is in 60 DEG C of stirred in water bath reaction 15min.Deng generation gel
Afterwards, the magnetic hydrogel of generation is transferred in vial, is immersed in 5 days in pure water.A water is changed per 8h, to wash away unreacted
Material such as monomer, crosslinking agent, initiator and accelerator etc..Then by magnetic hydrogel freeze-drying, particle is worn into standby.
2nd, cationic water gel particle impregnated in the mixed solution of saturation lanthanum nitrate and zirconium sulfate, dosage is 2g/
100ml, is continuously stirred with the rotating speed constant temperature of 300rpm, until active metal concentrations stabilization in solution, is stood, and Magneto separate is filtered dry
Supernatant, the compound after being loaded.Compound after gained is washed with deionized, until the pH value of washing water outlet is
7.0-7.5。
3rd, particle is obtained to be used to process fluorine-containing water（Fluorinion concentration is in 0-80mg/L in water, equilibrium concentration in 15mg/L,
pH=7）When, the maximal absorptive capacity to fluorine ion is 130mg/g（The i.e. every gram adsorbent adsorbs the fluorine of 130mg）, 24h vibration surveys
Examination lanthanum ion dissolution concentration is less than 10mg/L, and zirconium ion dissolution concentration is less than 7mg/L.
Case study on implementation 2
1st, 5g (3- acrylamide propyls) trimethyl ammonium chloride (APTMACl) monomer is weighed, the friendship of 0.5g is added thereto to
Connection agent N, N'- methylene-bisacrylamide (MBA), then add 0.8mL pure water after after crosslinking agent MBA all dissolving, add
0.1ml accelerators N, N, N', N'- tetramethylethylenediamine (TEMED) and 0.5g magnetic γ-Fe2O3When above material mixing is uniform
Afterwards, plus initiator 1.5mL saturations potassium peroxydisulfate (KPS) solution is in 60 DEG C of stirred in water bath reaction 15min.Deng generation gel
Afterwards, the magnetic hydrogel of generation is transferred in vial, is immersed in 5 days in pure water.A water is changed per 8h, to wash away unreacted
Material such as monomer, crosslinking agent, initiator and accelerator etc..Then by magnetic hydrogel freeze-drying, particle is worn into standby.
2nd, in cationic water gel particle impregnated in into saturation lanthanum nitrate and sulfuric acid zirconium solution, dosage is 0.3g/L, with
The rotating speed constant temperature of 300rpm is continuously stirred, and until active metal concentrations stabilization in solution, is stood, and Magneto separate is filtered dry supernatant, obtains
Compound after must loading.Compound after gained is washed with deionized, until the pH value of washing water outlet is 7.0-7.5.
3rd, particle is obtained for phosphorus acid ion concentration in the water for processing phosphorous acid group in 0-50mg/L, equilibrium concentration exists
21mg/L, pH=7）When, the maximal absorptive capacity to phosphate radical is 70mg/g（The i.e. every gram adsorbent adsorbs the phosphorus of 70mg）, 24h
Vibration test lanthanum ion dissolution concentration is less than 10mg/L, and zirconium ion dissolution concentration is less than 7mg/L.
Case study on implementation 3
1st, 5g (3- acrylamide propyls) trimethyl ammonium chloride (APTMACl) monomer is weighed, the friendship of 0.5g is added thereto to
Connection agent N, N'- methylene-bisacrylamide (MBA), then add 0.8mL pure water after after crosslinking agent MBA all dissolving, add
0.1ml accelerators N, N, N', N'- tetramethylethylenediamine (TEMED) and 0.5g magnetic γ-Fe2O3When above material mixing is uniform
Afterwards, plus initiator 1.5mL saturations potassium peroxydisulfate (KPS) solution is in 60 DEG C of stirred in water bath reaction 15min.Deng generation gel
Afterwards, the magnetic hydrogel of generation is transferred in vial, is immersed in 5 days in pure water.A water is changed per 8h, to wash away unreacted
Material such as monomer, crosslinking agent, initiator and accelerator etc..Then by magnetic hydrogel freeze-drying, particle is worn into standby.
2nd, hydrogel particle is immersed in lanthanum nitrate-alcohol mixed solution（Contain 20g lanthanum nitrates, 20ml second per 100ml
Alcohol）Middle a period of time.It is thoroughly mixed it.Supernatant is filtered dry, the NaOH solution of the 5wt% that will have been configured is added thereto.Water
Bath heating mixed solution is to 60 DEG C.Isolate prepared compound, the agitator treating 1h in deionized water solution.Lasting stirring
Afterwards, supernatant is filtered dry, the NaCl solution washing of equal volume is added, until the pH value of washing water outlet is 7.0-7.5.Finally spend
Ionized water agitator treating.It is vacuum dried at 50 DEG C, is finally taken out, is dried at 60 DEG C.
3rd, particle is obtained is used to process the water of phosphorous acid group（Phosphorus acid ion concentration is in 0-50mg/L, equilibrium concentration in water
In 10mg/L, pH=7）When, the maximal absorptive capacity to phosphate radical is 90.2mg/g（The i.e. every gram adsorbent adsorbs 90.2mg's
Fluorine）, 24h vibration test lanthanum ion dissolutions concentration is less than 10mg/L.
Case study on implementation 4
1st, 5g (3- acrylamide propyls) trimethyl ammonium chloride (APTMACl) monomer is weighed, the friendship of 0.5g is added thereto to
Connection agent N, N'- methylene-bisacrylamide (MBA), then add 0.8mL pure water after after crosslinking agent MBA all dissolving, add
0.1ml accelerators N, N, N', N'- tetramethylethylenediamine (TEMED) and 0.5g magnetic γ-Fe2O3When above material mixing is uniform
Afterwards, plus initiator 1.5mL saturations potassium peroxydisulfate (KPS) solution is in 60 DEG C of stirred in water bath reaction 15min.Deng generation gel
Afterwards, the magnetic hydrogel of generation is transferred in vial, is immersed in 5 days in pure water.A water is changed per 8h, to wash away unreacted
Material such as monomer, crosslinking agent, initiator and accelerator etc..Then by magnetic hydrogel freeze-drying, particle is worn into standby.
2nd, in cationic water gel particle impregnated in into saturation sulfuric acid zirconium solution, dosage is 2g/100ml, with 300rpm
Rotating speed constant temperature continuously stir, until active metal concentrations stabilization in solution, stand, Magneto separate is filtered dry supernatant, loaded
Compound afterwards.Compound after gained is washed with deionized, until the pH value of washing water outlet is 7.0-7.5.
3rd, particle is obtained and contains arsenate, metaantimmonic acid salt solution simultaneously for processing（Arsenic acid radical ion in water, metaantimmonic acid radical ion is dense
, in 0-60mg/L, in 25mg/L, metaantimmonic acid radical ion equilibrium concentration is in 40mg/L, pH=7 for arsenate ionic equilibrium concentration for degree）When,
Maximal absorptive capacity to arsenate is 151mg/g（The i.e. every gram adsorbent adsorbs the arsenate of 151mg）, to the maximum of metaantimmonic acid root
Adsorbance is 62mg/g（The i.e. every gram adsorbent adsorbs the metaantimmonic acid root of 62mg）24h vibration test zirconium ion dissolution concentration is less than
15mg/L。
Case study on implementation 5
1st, 5g (3- acrylamide propyls) trimethyl ammonium chloride (APTMACl) monomer is weighed, the friendship of 0.5g is added thereto to
Connection agent N, N'- methylene-bisacrylamide (MBA), then add 0.8mL pure water after after crosslinking agent MBA all dissolving, add
0.1ml accelerators N, N, N', N'- tetramethylethylenediamine (TEMED) and 0.5g magnetic γ-Fe2O3When above material mixing is uniform
Afterwards, plus initiator 1.5mL saturations potassium peroxydisulfate (KPS) solution is in 60 DEG C of stirred in water bath reaction 15min.Deng generation gel
Afterwards, the magnetic hydrogel of generation is transferred in vial, is immersed in 5 days in pure water.A water is changed per 8h, to wash away unreacted
Material such as monomer, crosslinking agent, initiator and accelerator etc..Then by magnetic hydrogel freeze-drying, particle is worn into standby.
The 2nd, hydrogel particle is immersed in the cerous sulfate-alcohol mixed solution of saturation（Contain 27g cerous sulfates per 100ml,
20ml ethanol）Middle a period of time.It is thoroughly mixed it.Supernatant is filtered dry, the NaOH solution of the 5wt% that will have been configured is added
Wherein.Heating water bath mixed solution is to 60 DEG C.Isolate prepared compound, the agitator treating 1h in deionized water solution.
After lasting stirring, supernatant is filtered dry, adds the NaCl solution washing of equal volume, until the pH value of washing water outlet is 7.0-7.5.
Finally use deionized water agitator treating.It is vacuum dried at 50 DEG C, is finally taken out, is dried at 60 DEG C.
3rd, particle is obtained and contains arsenate, the water of stibate simultaneously for processing（Arsenic acid radical ion in water, metaantimmonic acid radical ion
, in 0-30mg/L, in 15mg/L, metaantimmonic acid radical ion equilibrium concentration is in 10mg/L, pH=7 for arsenate ionic equilibrium concentration for concentration）
When, the maximal absorptive capacity to arsenate is 45mg/g（The i.e. every gram adsorbent adsorbs the phosphate radical of 45mg）, to metaantimmonic acid root most
Big adsorbance is 60mg/g（The i.e. every gram adsorbent adsorbs the metaantimmonic acid root of 60mg）24h vibration test cerium ion dissolution concentration is less than
10mg/L。
Case study on implementation 6
1st, 5g (3- acrylamide propyls) trimethyl ammonium chloride (APTMACl) monomer is weighed, the friendship of 0.5g is added thereto to
Connection agent N, N'- methylene-bisacrylamide (MBA), then add 0.8mL pure water after after crosslinking agent MBA all dissolving, add
0.1ml accelerators N, N, N', N'- tetramethylethylenediamine (TEMED) and 0.5g magnetic γ-Fe2O3When above material mixing is uniform
Afterwards, plus initiator 1.5mL saturations potassium peroxydisulfate (KPS) solution is in 60 DEG C of stirred in water bath reaction 15min.Deng generation gel
Afterwards, the magnetic hydrogel of generation is transferred in vial, is immersed in 5 days in pure water.A water is changed per 8h, to wash away unreacted
Material such as monomer, crosslinking agent, initiator and accelerator etc..Then by magnetic hydrogel freeze-drying, particle is worn into standby.
2nd, in cationic water gel particle impregnated in into saturation lanthanum nitrate-ethanol solution（Contain 132g nitric acid per 100ml
Lanthanum, 20ml ethanol）, dosage is 2g/100ml, is continuously stirred with the rotating speed constant temperature of 300rpm, until active metal in solution
Concentration stabilization, stands, and Magneto separate is filtered dry supernatant, the compound after being loaded.By the compound deionized water after gained
Washing, until the pH value of washing water outlet is 7.0-7.5.
3rd, particle is obtained to be used to process the water containing chromate（Chromate ion concentration is in 0-1000mg/L, pH=in water
7）When, the maximal absorptive capacity to chromate ion is 200mg/g（The i.e. every gram adsorbent adsorbs the chromate of 200mg, balances dense
Degree is in 530mg/L）, 24h vibration test lanthanum ion dissolutions concentration is less than 7mg/L.
Claims (9)
1. a kind of magnetic cation hydrogel based composite adsorption material, it is characterised in that contain cationic water gel, magnetisable material
With the different shape of active metal, the different shape of supported active metals on magnetic cation hydrogel.
2. magnetic cation hydrogel based composite adsorption material as claimed in claim 1, it is characterised in that magnetisable material and sun
Aqueous ionomer gel is by Raolical polymerizable single sintering, including the step of be carried out as follows：
（1）(3- acrylamide propyls) trimethyl ammonium chloride (APTMACl) monomer is added to the water, crosslinking is subsequently adding
Agent N, N'- methylene-bisacrylamide (MBA), after it is completely dissolved, then adds a small amount of pure water, cationic monomer and pure water ratio
Example about 10-500: 1, generates solution A；
（2）To adding micro accelerator N in solution A, N, N', N'- tetramethylethylenediamine (TEMED) and a small amount of magnetic γ-
Fe2O3Uniformly mixed, be subsequently adding initiator saturation potassium peroxydisulfate (KPS) solution, it is anti-in 10-100 DEG C of stirred in water bath
0-2h is answered, wherein cationic monomer, accelerator, magnetic material, ratio of initiator is 250-500：5-10：50-100：100-
200, generation magnetic cation hydrogel predecessor B；
（3）Magnetic cation hydrogel predecessor B is cured, magnetic cation hydrogel is generated, then container is replaced simultaneously
10-100h in pure water is immersed in, a water is changed per 2-10h, wash away unreacted monomer, crosslinking agent, initiator and accelerator thing
Matter, then grinds the freeze-drying of magnetic cation hydrogel, is prepared as magnetic cation hydrogel particle.
3. magnetic cation hydrogel based composite adsorption material as claimed in claim 1, it is characterised in that active metal is not
Include one or more metal in the one or more free hydrated ion or La, Sr, Zr, Fe of metal in Sr, Zr, Fe with form
Hydrous oxide.
4. the free hydrated ion of active metal as claimed in claim 3, it is characterised in that the free hydrated ion of active metal
Load in the following order the step of carry out：
（1）Surface reaction is carried out during magnetic cation hydrogel particle impregnated in into saturated activity metal salt solution, constant temperature is continuous
Stirring, until active metallic ion concentration stabilization in solution, stands, Magneto separate, is filtered dry supernatant, obtains supported active metals
The magnetic cation hydrogel of free hydrated ion；
（2）The magnetic cation hydrogel of the free hydrated ion of the supported active metals after gained is washed with deionized,
Until the pH value of washing water outlet is neutrality to alkalescent.
5. the hydrous oxide of active metal as claimed in claim 3, it is characterised in that active metal hydrous oxide it is negative
The step of carrying in the following order is carried out：
（1）Magnetic cation hydrogel particle is immersed in the active metal salt of saturation-organic solvent mixed solution carries out table
Face is reacted, and is thoroughly mixed it；Supernatant is filtered dry, the precipitation that will be leached is added in NaOH solution, is entered at 50-100 DEG C
Row heating water bath, isolating precipitation carries out the deionized water washing of 0-24h；
（2）Washed in the NaCl solution of the precipitation addition 50-500mL after deionized water is washed, until washing water outlet
PH value is for neutral to alkalescent；Finally use deionized water agitator treating；Deposit is carried out 0-60 DEG C of vacuum drying and 50-
110 DEG C of drying.
6. magnetic cation hydrogel based composite adsorption material as claimed in claim 1, it is characterised in that go in water removal to dissolve
The inorganic anion pollutant of property.
7. inorganic anion pollutant in water as claimed in claim 6, it is characterised in that including F-、PO4 3-、NO3 -And
AsO4 3-、SbO4 3-Different shape, concentration range is 10-1000mg/L.
8. magnetic cation hydrogel based composite adsorption material as claimed in claim 1, it is characterised in that adsorpting anion and
The process of regeneration in the following order the step of carry out：
（1）To the magnetic hydrogel based composite adsorption material that 0.1-5g/L is added in the anionic pollutant of 10-1000mg/L；
（2）The adsorption time of 1-48h is kept, and with the rotating speed persistent oscillation of 100-1000rpm in adsorption process；
（3）After the completion of absorption, mixed liquor is staticly settled, the recovery of composite material granular is carried out using permanent magnet；
（4）During reclaimed particle impregnated in the hydrochloric acid solution of 0.01-1M successively, in the sodium hydroxide solution of 0.01-1M, finally
Rinsed with sodium chloride solution, until washing the pH value of water outlet for neutral to alkalescent.
9. regenerative agent as claimed in claim 8, it is characterised in that can select one or more in HCl, NaOH, NaCl.
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