CN110115983A - A kind of Beta-cyclodextrin-based chelating decolorizing and absorbing material of solid and preparation method thereof - Google Patents
A kind of Beta-cyclodextrin-based chelating decolorizing and absorbing material of solid and preparation method thereof Download PDFInfo
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- CN110115983A CN110115983A CN201910420931.XA CN201910420931A CN110115983A CN 110115983 A CN110115983 A CN 110115983A CN 201910420931 A CN201910420931 A CN 201910420931A CN 110115983 A CN110115983 A CN 110115983A
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- 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
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- 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
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- 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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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Abstract
The present invention discloses a kind of Beta-cyclodextrin-based chelating decolorizing and absorbing material of solid and preparation method thereof.The present invention is using cyclodextrin, epoxychloropropane and polyethylene polyamine as raw material, dialdehyde is crosslinking agent, synthesize polymer microsphere by antiphase emulsifiable method, then make in the presence of a base again carbon disulfide on macromolecular chain active amino or imino group react and modify the dithiocarbonic acid base for having strong sequestering power to contents of many kinds of heavy metal ion to microsphere surface;Not only existing amido, imido grpup and hydroxyl isoreactivity group to contents of many kinds of heavy metal ion with strong effect and the dithiocarbonic acid base-CSS with strong sequestering power in resulting materials structure‑But also contain " internal drainage external hydrophilicity " the cyclodextrin structure unit that can be formed inclusion compound with Some Organic Pollutants and remove it, energy high efficiency synchronous removal heavy metal ions in wastewater and organic pollutant, and make to handle water decolorization, it may be adapted to the processing of heavy metal, organic matter and heavy metal-organic matter combined pollution waste water.
Description
Technical field
The present invention relates to a kind of adsorbent material more particularly to a kind of Beta-cyclodextrin-based chelating decolorizing and absorbing materials of solid and its system
Preparation Method.
Background technique
Combined pollution is that the ingredient that generation interaction is formed when a variety of pollutant components coexist is more complicated, processing difficulty is bigger
Pollution.With the rapid development of industrial and agricultural production, the pollutant kind of discharge is continuously increased, and the combined pollution ingredient of formation is got over
Come more complicated.Wherein, it is a kind of typical multiple that the heavy metal-organic matter combined pollution to be formed, which coexists, in heavy metal and various organic matters
Pollution is closed, the great attention and dense research interest of environmentalist have been caused.Heavy metal is comprehensively considered at present and is had
The method of machine pollutant removal is still few, can be divided by action principle following several: absorption method, ion-exchange, flocculence, light
Catalytic degradation and reduction method etc..Since heavy metal and matter property difference are larger, handled using ion-exchange and flocculence
When heavy metal-organic matter combined pollution, the adsorbent, ion-exchanger and flocculant for designing synthesis need to be to heavy metals and organic
Two substance of object has strong effect, it is clear that and the compatible difficulty in same inorganic agent of two kinds of totally different properties or function is larger,
Preparation process is more complex, higher cost.It is handled using photocatalytic degradation, key is the design and performance of photochemical catalyst, processing
Technique is more complex, inefficient, restricted application;Using reduction treatments such as nano zero valence irons there are restricted application, at
The problems such as this is higher, and the dispersibility of nano zero valence iron, stability and bio-toxicity are all the problems for needing to solve;Tradition
Fenton oxidation technology, there are reactions to carry out under strong acidity environment, Fe2+It is difficult to reuse and generate a large amount of iron dirts
The problems such as mud, and the dissolution rate of heterogeneous Fenton oxidation there are catalyst granules easy to reunite, bad dispersibility, iron is higher etc. asks
Topic.
Compared with other methods, since absorption method is to utilize the solid with porosity, high surface energy or high-specific surface area
It is useless to be adapted to a variety of different heavy metals for the method that material is removed to the suction-operated of heavy metal ions in wastewater and by heavy metal
The advanced treating of water, especially low concentration wastewater and waste water is especially difficult to the severe toxicity being effectively treated and difficulty to using other methods
The pollutant significant effect of degradation, and adsorption rate is very fast, easy to operate, adsorbent material source is wide.Therefore, absorption method is a kind of
Economic, effective and most application value process for treating heavy-metal waste water.Treatment effect of the absorption method to heavy metal wastewater thereby
Depend primarily on the performance of adsorbent material.It is multiple to handle heavy metal-organic matter combined pollution waste water especially heavy metal-organic dyestuff
The adsorbent material for closing pollutant effluents will not only have the ability of strong chelating trap heavy metals ion, it is also desirable to have Adsorption
The ability of organic pollutant.
Cyclodextrin (Cyclodextrin, abbreviation CD) is a kind of first by α -1,4 glycosidic bond by D- glucopyranose units
Tail is connected to form the oligosaccharide compound of cyclic structure.By the D- glucopyranose units number of composition cyclodextrin, common ring
Dextrin has alpha-cyclodextrin (6 glucose units), beta-cyclodextrin (7 glucose units) and gamma-cyclodextrin (8 glucose lists
Member).Cyclodextrin shows as the cone cylinder shape cavity structure of internal drainage external hydrophilicity, and stable inclusion compound can be formed with guest molecule;?
It can be stabilized in aqueous slkali or organic solution, but can release the substance of package under acid condition.Cyclodextrin surface contains
There are three types of various forms of reactive hydroxyls, can realize the hydroxyl of specific position by differential responses form under the conditions of differential responses
Base conversion reaction, to realize the finely regulating to its structure.It can be made to particular size and shape in addition, it bores tubular structure
The lyophobic dust of shape is included, and is advantageously implemented and is carried out selective absorption to Organic Pollutants in Wastewater.And cyclodextrin
With excellent biocompatibility, secondary pollution will not be caused as material for water treatment.But cyclodextrin is soluble easily in water, cannot be direct
As adsorbent material, and thereon, active group is single hydroxyl.Therefore modification need to be carried out to cyclodextrin to increase thereon
Active group, and carry out crosslinking and become insoluble adsorbent material.
Summary of the invention
In view of the above technical problems, the present invention provides a kind of Beta-cyclodextrin-based chelating decolorizing and absorbing material of solid and its preparation side
Method.The ability of the existing very strong heavy-metal ion removal of the adsorbent material has the coloured pollutions such as excellent adsorbing and removing organic matter again
The decoloration performance of object, and safe and non-toxic, wide adaptation range is used, this adsorbent material is the faint yellow spheric granules to yellow,
The cyclodextrin structure unit that inclusion compound is formed compared with multipotency and organic pollutant is contained on its surface, and rich in an a variety of huge sum of moneys
Belong to the dithiocarbonic acid base-CSS that son has strong chelating trapping ability-;Preparation method simple process, reliable, high income, manufacture
It is at low cost, react easily controllable, three waste discharge is few, and easy to spread, universal and realization industrialization.
The technical solution of the present invention is as follows:
A kind of Beta-cyclodextrin-based chelating decolorizing and absorbing material of solid is with cyclodextrin, epoxychloropropane and polyethylene polyamine
Raw material, dialdehyde are crosslinking agent, synthesize polymer microsphere using reverse microemulsion process, then react under alkaline condition with carbon disulfide
It is the faint yellow spheric granules to yellow that appearance, which is made, and particle surface contains the ring for having Inclusion property to organic pollutant simultaneously
Dextrin unit and the dithiocarbonic acid base-CSS to contents of many kinds of heavy metal ion with strong chelating trapping ability-。
The preparation method of the Beta-cyclodextrin-based chelating decolorizing and absorbing material of above-mentioned solid, includes the following steps:
(1) cyclodextrin and deionized water are added to be made into reactor cyclodextrin mass fraction be 15~25% it is molten
Liquid, then pressing cyclodextrin and the molar ratio of alkali is 1: 30~50, and alkali is added in reactor and is dissolved;
(2) emulsifier and oily phase are added in step (1) acquired solution, water phase oil phase volume ratio is 1: 4~12, emulsifier
It is that 1: 15~25g/mL is warming up to 60~70 DEG C after ultrasonic wave auxiliary stirs 30~40min with oily phase mass volume ratio;
(3) mole of cyclodextrin, epoxychloropropane, polyethylene polyamine and dialdehyde 1: 30~50: 20~40: 10~20 is pressed
Than taking polyethylene polyamine to be configured to the polyethylene polyamine aqueous solution that mass fraction is 40~60%;It is molten in step (2) gained
The epoxychloropropane of total amount half is first added dropwise in liquid, 1~2h is reacted after dripping, then the polyethylene polyamine of total amount half is added dropwise
Solution reacts 1~2h after dripping;Remaining epoxychloropropane is added dropwise again, 1~2h is reacted after dripping, then be added dropwise remaining
Polyethylene polyamine solution reacts 1~2h after dripping;4~6h of dialdehyde cross-linking reaction is finally added dropwise, is cooled to room temperature, filters,
It is washed 3~5 times with ethyl alcohol and deionized water respectively;
(4) step (3) obtained solid microballoon is transferred in reactor, adds deionized water, then by sodium hydroxide,
The ratio between amount of substance of carbon disulfide and polyethylene polyamine is 2.2~3.9: 2~3: 1, first weighs sodium hydroxide and is added to instead
It answers in device, measures carbon disulfide again after to be dissolved and be slowly dropped in reactor, the reaction was continued 3~5h after adding;Then it heats up
It to 50~65 DEG C of 30~60min of reaction, is cooled to room temperature, filters, then be washed with deionized 3~5 times, be drying to obtain solid
Beta-cyclodextrin-based chelating decolorizing and absorbing material.
Further, in step (1), the cyclodextrin is alpha-cyclodextrin, beta-cyclodextrin or gamma-cyclodextrin.
Further, in step (1), the alkali is NaOH or KOH.
Further, in step (1), the reactor be three-neck flask, with mechanical stirring, constant pressure funnel and
Condenser pipe.
Further, in step (2), the emulsifier is water-in-oil emulsifier, preferably Span series, including department
Class -60, Span -65 and Span-80.
Further, in step (2), the oil is mutually in atoleine, petroleum ether (90~120 DEG C) and normal octane
It is one or more kinds of.
Further, in step (3), the polyethylene polyamine is diethylenetriamine, triethylene tetramine and four ethylene
One or more of five amine.
Further, in step (3), the dialdehyde is glyoxal or/and glutaraldehyde;Glyoxal preferred mass score is
40% aqueous solution, the aqueous solution that glutaraldehyde preferred mass score is 50%.
Further, in step (3) and step (4), the suction filtration, Suction filtration device is Buchner funnel and bottle,suction, pressure
It is by force -0.1~-0.08 MPa.
Further, drying described in step (3) and step (4) is vacuum drying, and drying temperature is 40~60 DEG C, pressure
For -0.1~-0.08 MPa.
Above-mentioned cyclodextrin, epoxychloropropane, polyethylene polyamine, dialdehyde, sodium hydroxide, emulsifier and curing used
Carbon is that analysis is pure.
Above-mentioned adsorbent material can be widely applied to all kinds of heavy metal wastewater therebies, organic pollutant wastewater or heavy metal-organic matter
The processing of combined pollutant waste water.
The present invention relates to Beta-cyclodextrin-based chelating decolorizing and absorbing materials of a kind of solid and preparation method thereof.With cyclodextrin, epoxy
Chloropropane and polyethylene polyamine are raw material, and dialdehyde is crosslinking agent, synthesize polymer microsphere by antiphase emulsifiable method, then exist again
Alkali exist make carbon disulfide on macromolecular chain active amino or imino group react and will to contents of many kinds of heavy metal ion with by force
The dithiocarbonic acid base modification of chelating trapping ability to Beta-cyclodextrin-based crosslink macromolecule microsphere surface and to generate solid Beta-cyclodextrin-based
Chelate decolorizing and absorbing material;There is only amido, imido grpup and hydroxyls etc. to have to heavy metal ion in gained adsorbent material structure
The active group of stronger adsorption capacity, there are also the dithiocarbonic acid bases to contents of many kinds of heavy metal ion with strong chelation, significantly
Improve the trapping adsorption capacity to heavy metal;And also contain " internal drainage external hydrophilicity " cyclodextrin structure unit, can with it is more
Kind organic pollutant, especially organic dyestuff form inclusion compound and remove.Therefore, product of the present invention has both a strong chelating trapping huge sum of money
Belong to ion and inclusion goes the ability of removal organic polluter especially organic dyestuff, overcoming traditional adsorbent material generally can only be effective
One kind in these two types of pollutants is removed, and treatment effect is poor, the disadvantages of higher cost, efficiency is lower.
Possessed beneficial effect is the present invention compared with prior art:
(I) adsorbent material of the invention is faint yellow or yellow microballoon, and surface is rich in have heavy metal ion
There are the hydroxyl, amino and imino group isoreactivity group of strong effect, and there is strong chelating to trap energy contents of many kinds of heavy metal ion
The dithiocarbonic acid base of power;Simultaneously also inclusion compound can be formed with Some Organic Pollutants especially organic dyestuff etc. containing more
" internal drainage external hydrophilicity " cyclodextrin structure unit.
(II) the preparation method is that using cyclodextrin, epoxychloropropane and polyethylene polyamine as raw material, dialdehyde is
Crosslinking agent synthesizes Beta-cyclodextrin-based crosslink macromolecule microsphere using reverse phase liquid method, then microsphere surface modification to various heavy from
Son has the dithiocarbonic acid base of strong sequestering power, and therefore, material structure obtained and shape are more easily controlled, and are conducive to improve
There is bigger specific surface area to the adsorption dynamics adsorption kinetics characteristic of pollutant, and than isometric other shapes material, increases and dirt
The contact area for contaminating object, enhances its adsorption capacity.
(III) present invention use antiphase emulsifiable method, can be convenient by control raw material, water-oil factor, emulsifier additional amount and
Revolving speed controls the size of microballoon, and the additional amount by controlling carbon disulfide and reaction condition regulate and control dithiocarbonic acid base
Modification amount realizes the controllable preparation to material, to meet the processing requirement of various actual waste waters.
(IV) adsorbent material of the invention has excellent chelating trapping ability to contents of many kinds of heavy metal ion, can be at normal temperature
Hg in quick adsorption waste water2+、Pb2+、Cu2+、Cd2+、Ni2+、Mn2+、Zn2+、Cr3+Etc. contents of many kinds of heavy metal ion;And have excellent
Can with Some Organic Pollutants especially organic dyestuff formed inclusion compound and effectively remove organic pollutant and make handle water
The ability of decoloration;And there is excellent zeolite regeneration performance, service life cycle is long.It is not only adapted to free state heavy metal ion
Processing, is also suitable for the processing of heavy metal-organic matter combined pollution especially heavy metal-organic dyestuff combined pollutant.
(V) easy to operate using the simple process of adsorbent material of the present invention processing waste water.Only need in heavy metal wastewater thereby, have
A certain amount of product of the present invention is added in machine object waste water and heavy metal-organic matter combined pollution object waste water, being sufficiently stirred can be fast
Speed absorption pollutant does not need complicated equipment and process through sedimentation separation and filtering.
(VI) Product formation simple process of the present invention, easily operated, reaction condition is mild, generates without " three wastes ", required to set
Standby is conventional equipment, it is easy to accomplish industrialized production has broad application prospects.
Detailed description of the invention
Fig. 1 is preparation technology flow chart of the invention.
Fig. 2 is the IR spectrogram (sample of embodiment 1) of the Beta-cyclodextrin-based chelating decolorizing and absorbing material of product solid of the present invention.
Fig. 3 is Product scan electron microscope of the present invention.
Specific embodiment
Present invention is further described in detail with reference to the accompanying drawing, and Examples 1 to 7 is product of the present invention solid cyclodextrin
Base chelates the preparation method of decolorizing and absorbing material, and embodiment 8~10 is the application example of product of the present invention.
Embodiment 1
(1) 1.00g mass fraction is added to for 98% beta-cyclodextrin and 5.54mL deionized water with constant pressure addition
The mass percentage concentration that beta-cyclodextrin is made into the 100mL three-neck flask of funnel, mechanical agitator and condensing unit is 15%
Solution is 1: 30 by the molar ratio of beta-cyclodextrin and sodium hydroxide, the sodium hydroxide that 1.08g mass fraction is 96% is added to
It is dissolved in three-neck flask;
(2) 22.18mL atoleine and 1.48g Span-80 are added in step (1) solution, water phase oil phase volume ratio is 1
: 4, emulsifier is 1: 15g/mL with oily phase mass volume ratio, after ultrasonic wave auxiliary stirring 30min, is warming up to 60 DEG C;
(3) by the molar ratio of beta-cyclodextrin, epoxychloropropane, triethylene tetramine and glutaraldehyde 1: 30: 20: 10,2.68 are taken
The triethylene tetramine that mL mass fraction is 96% is configured to 40% triethylene tetramine aqueous solution, first drips in step (2) solution
The epoxychloropropane that aggregation amount half (1.04mL) mass fraction is 98%, reacts 1h, then total amount half is added dropwise after dripping
The triethylene tetramine solution that (3.29 g) mass fraction is 40%, reacts 1h, then remaining epoxychloropropane is added dropwise after dripping
(1.04 mL), reacts 1h after dripping, then remaining triethylene tetramine solution (3.29g) is added dropwise, and 1h is reacted after dripping, then
The glutaraldehyde cross-linking 4h that 1.83mL mass fraction is 50% is added dropwise.It is cooled to room temperature, filters, use ethyl alcohol and deionized water respectively
Washing 3 times.
(4) by step (3) obtained solid microballoon be transferred to 250mL with constant pressure funnel, reflux condensing tube and machine
In the three-neck flask of tool stirring, 100mL deionized water is added, then by sodium hydroxide, carbon disulfide and triethylene tetramine
The ratio between amount of substance is 2.2: 2: 1, first weighs the sodium hydroxide that 1.58g mass fraction is 96% and is added in reactor, to molten
The carbon disulfide that 2.11mL mass fraction is 99% is measured after solution again to be slowly dropped in reactor, the reaction was continued 3h after adding;
Then 50 DEG C of reaction 30min are warming up to, are cooled to room temperature, are filtered, then be washed with deionized 3 times, solid ring paste is drying to obtain
Smart base chelates decolorizing and absorbing material 6.12g.
Embodiment 2
(1) 1.00g mass fraction is added to for 98% beta-cyclodextrin and 3.91mL deionized water with constant pressure addition
The mass percentage concentration that beta-cyclodextrin is made into the 100mL three-neck flask of funnel, mechanical agitator and condensing unit is 20%
Solution is 1: 40 by the molar ratio of beta-cyclodextrin and sodium hydroxide, the sodium hydroxide that 1.44g mass fraction is 96% is added to
It is dissolved in three-neck flask;
(2) 23.45mL atoleine and 1.56g Span-80 are added in step (1) solution, water phase oil phase volume ratio is 1
: 6, emulsifier is 1: 15g/mL with oily phase mass volume ratio, after ultrasonic wave auxiliary stirring 30min, is warming up to 65 DEG C.
(3) by the molar ratio of beta-cyclodextrin, epoxychloropropane, triethylene tetramine and glutaraldehyde 1: 40: 30: 15,4.02 are taken
The triethylene tetramine that mL mass fraction is 96% is configured to 50% triethylene tetramine aqueous solution, first drips in step (2) solution
The epoxychloropropane that aggregation amount half (1.38mL) mass fraction is 98%, reacts 1h, then total amount half is added dropwise after dripping
The triethylene tetramine solution that (3.94 g) mass fraction is 50%, reacts 1h, then remaining epoxychloropropane is added dropwise after dripping
(1.38 mL), reacts 1h after dripping, then remaining triethylene tetramine solution (3.94g) is added dropwise, and 1h is reacted after dripping, then
The glutaraldehyde cross-linking 5h that 2.74mL mass fraction is 50% is added dropwise.It is cooled to room temperature, filters, use ethyl alcohol and deionized water respectively
Washing 4 times;
(4) by step (3) obtained solid microballoon be transferred to 250mL with constant pressure funnel, reflux condensing tube and machine
In the three-neck flask of tool stirring, 120mL deionized water is added, then by sodium hydroxide, carbon disulfide and triethylene tetramine
The ratio between amount of substance is 3: 2.5: 1, first weighs the sodium hydroxide that 3.24g mass fraction is 96% and is added in reactor, to molten
The carbon disulfide that 3.96mL mass fraction is 99% is measured after solution again to be slowly dropped in reactor, the reaction was continued 4h after adding;
Then 55 DEG C of reaction 30min are warming up to, are cooled to room temperature, are filtered, then be washed with deionized 4 times, solid ring paste is drying to obtain
Smart base chelates decolorizing and absorbing material 6.42g.
Embodiment 3
(1) beta-cyclodextrin 1.00g and the 3.91mL deionized water that mass fraction is 98% is added to constant pressure addition
The mass percentage concentration that beta-cyclodextrin is made into the 100mL three-neck flask of funnel, mechanical agitator and condensing unit is 20%
Solution is 1: 50 by the molar ratio of beta-cyclodextrin and sodium hydroxide, the sodium hydroxide that 1.80g mass fraction is 96% is added to
It is dissolved in three-neck flask;
(2) 31.26mL atoleine and 1.56g Span-80 are added in step (1) solution, water phase oil phase volume ratio is 1
: 8, emulsifier is 1: 20g/mL with oily phase mass volume ratio, after ultrasonic wave auxiliary stirring 30min, is warming up to 70 DEG C;
(3) by the molar ratio of beta-cyclodextrin, epoxychloropropane, triethylene tetramine and glutaraldehyde 1: 50: 40: 20,5.36 are taken
The triethylene tetramine that mL mass fraction is 96% is configured to 60% triethylene tetramine aqueous solution, first drips in step (2) solution
The epoxychloropropane that aggregation amount half (1.72mL) mass fraction is 98%, reacts 1h, then total amount half is added dropwise after dripping
The triethylene tetramine solution that (4.38 g) mass fraction is 60%, reacts 1h, then remaining epoxychloropropane is added dropwise after dripping
(1.72 mL), reacts 1h after dripping, then remaining triethylene tetramine solution (4.38g) is added dropwise, and 1h is reacted after dripping, then
The glutaraldehyde cross-linking 6h that 3.65mL mass fraction is 50% is added dropwise.It is cooled to room temperature, filters, use ethyl alcohol and deionized water respectively
Washing 5 times;
(4) by step (3) obtained solid microballoon be transferred to 250mL with constant pressure funnel, reflux condensing tube and machine
In the three-neck flask of tool stirring, 150mL deionized water is added, then by sodium hydroxide, carbon disulfide and triethylene tetramine
The ratio between amount of substance is 3: 2.5: 1, first weighs the sodium hydroxide that 4.32g mass fraction is 96% and is added in reactor, to molten
The carbon disulfide that 5.27mL mass fraction is 99% is measured after solution again to be slowly dropped in reactor, the reaction was continued 4h after adding;
Then 55 DEG C of reaction 30min are warming up to, are cooled to room temperature, are filtered, then be washed with deionized 4 times, solid ring paste is drying to obtain
Smart base chelates decolorizing and absorbing material 7.02g.
Embodiment 4
(1) 1.00g mass fraction is added to for 98% beta-cyclodextrin and 2.93mL deionized water with constant pressure addition
The mass percentage concentration that beta-cyclodextrin is made into the 100mL three-neck flask of funnel, mechanical agitator and condensing unit is 25%
Solution is 1: 30 by the molar ratio of beta-cyclodextrin and potassium hydroxide, the potassium hydroxide that 1.71g mass fraction is 85% is added to
It is dissolved in three-neck flask;
(2) 35.11mL petroleum ether (90~120 DEG C) and Span -60 1.40g, water phase oil phase are added in step (1) solution
Volume ratio is 1: 12, and emulsifier is 1: 15g/mL with oily phase mass volume ratio, after ultrasonic wave auxiliary stirring 30min, is warming up to 65
℃;
(3) by the molar ratio of beta-cyclodextrin, epoxychloropropane, diethylenetriamine and glutaraldehyde 1: 30: 20: 10, quality is taken
The diethylenetriamine 1.92mL that score is 97% is configured to 40% diethylenetriamine aqueous solution, first drips in step (2) solution
The epoxychloropropane that aggregation amount half (1.04mL) mass fraction is 98%, reacts 1h, then total amount half is added dropwise after dripping
The diethylenetriamine solution that (2.29 g) mass fraction is 40%, reacts 1h, then remaining epoxychloropropane is added dropwise after dripping
(1.04 mL), reacts 1h after dripping, then remaining diethylenetriamine solution (2.29g) is added dropwise, and 1h is reacted after dripping, then
The glutaraldehyde cross-linking 4h that 1.83mL mass fraction is 50% is added dropwise, is cooled to room temperature, filters, uses ethyl alcohol and deionized water respectively
Washing 3 times.
(4) by step (3) obtained solid microballoon be transferred to 250mL with constant pressure funnel, reflux condensing tube and machine
In the three-neck flask of tool stirring, 100mL deionized water is added, then by sodium hydroxide, carbon disulfide and diethylenetriamine
The ratio between amount of substance is 3.6: 3: 1, first weighs the sodium hydroxide that 2.59g mass fraction is 96% and is added in reactor, to molten
The carbon disulfide that 3.16mL mass fraction is 99% is measured after solution again to be slowly dropped in reactor, the reaction was continued 5h after adding;
Then 60 DEG C of reaction 30min are warming up to, are cooled to room temperature, are filtered, then be washed with deionized 5 times, solid ring paste is drying to obtain
Smart base chelates decolorizing and absorbing material 6.52g.
Embodiment 5
(1) 1.00g mass fraction is added to for 98% beta-cyclodextrin and 3.91mL deionized water with constant pressure addition
The mass percentage concentration that beta-cyclodextrin is made into the 100mL three-neck flask of funnel, mechanical agitator and condensing unit is 20%
Solution is 1: 30 by the molar ratio of beta-cyclodextrin and sodium hydroxide, the sodium hydroxide that 1.08g mass fraction is 96% is added to
It is dissolved in three-neck flask;
(2) 31.26mL normal octane and Span -20 1.56g are added in step (1) solution, water phase oil phase volume ratio is 1:
8, emulsifier is 1: 20g/mL with oily phase mass volume ratio, after ultrasonic wave auxiliary stirring 30min, is warming up to 70 DEG C.
(3) by beta-cyclodextrin, epoxychloropropane, tetraethylenepentamine and glutaraldehyde 1: 30: 20: 10 molar ratio, take
The tetraethylenepentamine that 3.45mL mass fraction is 95% is configured to 40% tetraethylenepentamine aqueous solution, in step (2) solution
The epoxychloropropane that total amount half (1.04mL) mass fraction is 98% is first added dropwise, 1h is reacted after dripping, then total amount one is added dropwise
The tetraethylenepentamine solution that half (3.69g) mass fraction is 40%, reacts 1h, then remaining epoxy chloropropionate is added dropwise after dripping
Alkane (1.04mL), reacts 1h after dripping, then remaining tetraethylenepentamine solution (3.69g) is added dropwise, and 1h is reacted after dripping, then
The glyoxal that 0.99mL mass fraction is 40% is added dropwise and is crosslinked 4h.It is cooled to room temperature, filters, use ethyl alcohol and deionized water respectively
Washing 3 times;
(4) by step (3) obtained solid microballoon be transferred to 250mL with constant pressure funnel, reflux condensing tube and machine
In the three-neck flask of tool stirring, 100mL deionized water is added, then by sodium hydroxide, carbon disulfide and tetraethylenepentamine
The ratio between amount of substance is 3.6: 3: 1, first weighs the sodium hydroxide that 2.81g mass fraction is 96% and is added in reactor, to molten
The carbon disulfide that 3.16mL mass fraction is 99% is measured after solution again to be slowly dropped in reactor, the reaction was continued 5h after adding;
Then 65 DEG C of reaction 30min are warming up to, are cooled to room temperature, are filtered, then be washed with deionized 5 times, solid ring paste is drying to obtain
Smart base chelates decolorizing and absorbing material 6.62g.
Embodiment 6
(1) 1.00g mass fraction is added to for 98% alpha-cyclodextrin and 5.54mL deionized water with constant pressure addition
The mass percentage concentration that alpha-cyclodextrin is made into the 100mL three-neck flask of funnel, mechanical agitator and condensing unit is 15%
Solution is 1: 30 by the molar ratio of alpha-cyclodextrin and sodium hydroxide, the sodium hydroxide that 1.26g mass fraction is 96% is added to
It is dissolved in three-neck flask;
(2) 22.18mL atoleine and 1.48g Span-80 are added in step (1) solution, water phase oil phase volume ratio is 1
: 4, emulsifier is 1: 15g/mL with oily phase mass volume ratio, after ultrasonic wave auxiliary stirring 30min, is warming up to 60 DEG C;
(3) by the molar ratio of alpha-cyclodextrin, epoxychloropropane, triethylene tetramine and glutaraldehyde 1: 30: 20: 10,3.13 are taken
The triethylene tetramine that mL mass fraction is 96% is configured to 40% triethylene tetramine aqueous solution, first drips in step (2) solution
The epoxychloropropane that aggregation amount half (1.21mL) mass fraction is 98%, reacts 1h, then total amount half is added dropwise after dripping
The triethylene tetramine solution that (3.84 g) mass fraction is 40%, reacts 1h, then remaining epoxychloropropane is added dropwise after dripping
(1.21 mL), reacts 1h after dripping, then remaining triethylene tetramine solution (3.84g) is added dropwise, and 1h is reacted after dripping, then
The glutaraldehyde cross-linking 4h that 1.83mL mass fraction is 50% is added dropwise.It is cooled to room temperature, filters, use ethyl alcohol and deionized water respectively
Washing 3 times.
(4) by step (3) obtained solid microballoon be transferred to 250mL with constant pressure funnel, reflux condensing tube and machine
In the three-neck flask of tool stirring, 100mL deionized water is added, then by sodium hydroxide, carbon disulfide and triethylene tetramine
The ratio between amount of substance is 2.2: 2: 1, first weighs the sodium hydroxide that 1.85g mass fraction is 96% and is added in reactor, to molten
The carbon disulfide that 2.46mL mass fraction is 99% is measured after solution again to be slowly dropped in reactor, the reaction was continued 3h after adding;
Then 50 DEG C of reaction 30min are warming up to, are cooled to room temperature, are filtered, then be washed with deionized 3 times, solid ring paste is drying to obtain
Smart base chelates decolorizing and absorbing material 6.33g.
Embodiment 7
(1) 1.00g mass fraction is added to for 98% gamma-cyclodextrin and 5.54mL deionized water with constant pressure addition
The mass percentage concentration that gamma-cyclodextrin is made into the 100mL three-neck flask of funnel, mechanical agitator and condensing unit is 15%
Solution is 1: 30 by the molar ratio of gamma-cyclodextrin and sodium hydroxide, and the sodium hydroxide that 0.94g mass fraction is 96% is added
It is dissolved into three-neck flask;
(2) 22.18mL atoleine and 1.48g Span-80 are added in step (1) solution, water phase oil phase volume ratio is 1
: 4, emulsifier is 1: 15g/mL with oily phase mass volume ratio, after ultrasonic wave auxiliary stirring 30min, is warming up to 60 DEG C;
(3) by the molar ratio of gamma-cyclodextrin, epoxychloropropane, triethylene tetramine and glutaraldehyde 1: 30: 20: 10,2.34 are taken
The triethylene tetramine that mL mass fraction is 96% is configured to 40% triethylene tetramine aqueous solution, first drips in step (2) solution
The epoxychloropropane that aggregation amount half (0.91mL) mass fraction is 98%, reacts 1h, then total amount half is added dropwise after dripping
The triethylene tetramine solution that (2.88 g) mass fraction is 40%, reacts 1h, then remaining epoxychloropropane is added dropwise after dripping
(0.91 mL), reacts 1h after dripping, then remaining triethylene tetramine solution (2.88g) is added dropwise, and 1h is reacted after dripping, then
The glutaraldehyde cross-linking 4h that 1.60mL mass fraction is 50% is added dropwise.It is cooled to room temperature, filters, use ethyl alcohol and deionized water respectively
Washing 3 times.
(4) by step (3) obtained solid microballoon be transferred to 250mL with constant pressure funnel, reflux condensing tube and machine
In the three-neck flask of tool stirring, 100mL deionized water is added, then by sodium hydroxide, carbon disulfide and triethylene tetramine
The ratio between amount of substance is 2.2: 2: 1, first weighs the sodium hydroxide that 1.39g mass fraction is 96% and is added in reactor, to molten
The carbon disulfide that 1.84mL mass fraction is 99% is measured after solution again to be slowly dropped in reactor, the reaction was continued 3h after adding;
Then 50 DEG C of reaction 30min are warming up to, are cooled to room temperature, are filtered, then be washed with deionized 3 times, solid ring paste is drying to obtain
Smart base chelates decolorizing and absorbing material 5.88g.
The process flow diagram of the method for the present invention is as shown in Figure 1.Embodiment 1 to 7 resulting materials of embodiment is carried out infrared
Spectrum and scanning electron microscope characterization, acquired results are almost the same.By taking 1 resulting materials of embodiment as an example, infrared spectroscopy and scanning electron microscope
It is as shown in Figures 2 and 3 to analyze result.
Each absorption peak can belong to as follows in Fig. 2 infrared spectroscopy: 3430.58cm-1For the stretching vibration peak of-OH and stretching for-NH
Contracting vibration peak;In 2924.22,2853.99cm-1Locate appearance-CH2Symmetrical and asymmetric stretching vibration peak, accordingly exist
1359.98cm-1There is its flexural vibrations peak in place;1634.32cm-1For the stretching vibration of the absorption peak and-C=N of bound water molecule
Peak;1460.39cm-1For-CH2Asymmetric stretching vibration peak;In 1385.64cm-1For aminodithioformic acid group (N-
CSS-) in C-N stretching vibration absworption peak, 970.96cm-1For the stretching vibration peak of C=S in-CSS- and C-S;
1046.97cm-1For the stretching vibration peak of C-O-C, 879.13cm-1For pyranose glycosidic bond characteristic peak;610.54cm-1The peak ring at place
The flexural vibrations peak of cyclic structure in dextrin.The presence of these absorption peaks demonstrates Beta-cyclodextrin-based cross-linked polymer adsorbent material
It has been successfully synthesized.
Fig. 3 scanning electron microscope analysis is the result shows that Beta-cyclodextrin-based cross-linked polymer adsorbent material is about 100~150 μm of diameter
Microballoon, microspherulite diameter is uniform, good dispersion.
Embodiment 8
Using 1~embodiment of embodiment, 5 gained sample as adsorbent material, it is denoted as 1 respectively#、2#、3#、4#With 5#, prepare contain respectively
Cu2+、Zn2+、Cd2+And Pb2+Mass-volume concentration be 100mg/L simulation heavy metal water sample.Adsorption test condition: (1) it inhales
Attached solid measure takes 50mL simulation heavy metal water sample to be placed in 100mL conical flask respectively, weighs the adsorption material of the above-mentioned preparation of 15mg
Material, is placed on constant-temperature table, vibrates 2h at 25 DEG C, is centrifuged (revolving speed 5000r/mim, centrifugation time 5min) with supercentrifuge
Separate microspheres with solid with solution, after taking solution to measure absorption in AA-7000 Atomic Absorption Spectrometer (Japanese Shimadzu Corporation)
The concentration of heavy metal ion calculates the adsorption capacity of adsorbent material;(2) adsorption time measures, by above-mentioned test method, with 5min
Ion concentration is measured by sampling for time interval, determines the time for reaching saturation absorption;(3) heavy metal desorption recycling, with high speed from
Scheming centrifugation (revolving speed 5000r/mim, centrifugation time 5min) separates microspheres with solid with solution, is washed with deionized and sloughs not
The metal ion being adsorbed, is then added in the hydrochloric acid of 0.1mol/L, and 1h is vibrated on shaking table, is centrifuged with supercentrifuge
(revolving speed 5000r/mim, centrifugation time 5min) separates microspheres with solid with solution, then is washed with deionized, measurement elution weight
The amount of metal calculates the rate of recovery of heavy metal, and the results are shown in Table 1.
Absorption property of the product of the present invention of table 1 to heavy metal ion
As it can be seen from table 1 product of the present invention is to free Cu2+、Zn2+、Cd2+And Pb2+Plasma has higher absorption to hold
Amount, the rate of adsorption is fast, short up to time of equilibrium adsorption, and has excellent zeolite regeneration performance.This is because solid is Beta-cyclodextrin-based
Decolorizing and absorbing material surface active group rich in, such as dithiocarbonic acid base, amino, imino group and hydroxyl are chelated, because
This, substantially increases the chelating adsorption capacity to heavy metal ion.
According to above-mentioned test method, consider first to take 100 times of popularization in the loss of test process adsorbent material
1.5g sampling test, gradually reduces experimental scale, and the adsorbent material of zeolite regeneration is reused for the absorption of heavy metal ion,
To Cu2+Absorption investigate regeneration and situation be recycled, table 2 be 5 results of recycling.
The processing of the product of the present invention of table 2 contains Cu2+The recycling situation of waste water
Table 2 the result shows that, zeolite regeneration influences very little to adsorption capacity, and 5 elution cycles are using reaching saturation absorption
Time does not change substantially, and the rate of recovery is substantially unchanged.Therefore, the Beta-cyclodextrin-based chelating decolorizing and absorbing material tool of solid of the invention
Have the advantages that good heavy metal recovery, regneration of adsorbent material, recycling, service life are longer.
Embodiment 9
Using 1~embodiment of embodiment, 5 gained sample as adsorbent material, it is denoted as 1 respectively#、2#、3#、4#With 5#, prepare contain respectively
The simulation organic matter water sample that methyl orange and the mass-volume concentration of methylene blue are 100mg/L.Adsorption test condition: (1) it adsorbs
Solid measure takes 50mL simulation organic matter water sample to be placed in 100mL conical flask respectively, weighs the adsorption material of the above-mentioned preparation of 15mg
Material, is placed on constant-temperature table, vibrates 2h at 25 DEG C, is centrifuged (revolving speed 5000r/mim, centrifugation time 5min) with supercentrifuge
Separate microspheres with solid with solution, the concentration of organic matter after taking solution to measure absorption on visible spectrophotometer is calculated and inhaled
The adsorption capacity of enclosure material;(2) adsorption time measures, and by above-mentioned test method, is measured by sampling using 5min as time interval organic
Object concentration determines the time for reaching saturation absorption;(3) organic matter desorption recycling is centrifuged (revolving speed 5000r/ with supercentrifuge
Mim, centrifugation time 5min) separate microspheres with solid with solution, microspheres with solid, which is washed with deionized, and sloughs unadsorbed has
Machine object, is then added in the hydrochloric acid of 0.1mol/L, and 1h is vibrated on shaking table, is centrifuged (revolving speed 5000r/ with supercentrifuge
Mim, centrifugation time 5min) separate microspheres with solid with solution, then be washed with deionized, the amount of measurement elution organic matter, meter
The rate of recovery of organic matter is calculated, the results are shown in Table 3.
Absorption property of the product of the present invention of table 3 to methyl orange and methylene blue
From table 3 it can be seen that product of the present invention has higher adsorption capacity to organic matters such as methyl orange and methylene blues,
The rate of adsorption is fast, short up to time of equilibrium adsorption, and has excellent zeolite regeneration performance.This is because Beta-cyclodextrin-based crosslinking is high
Molecular Adsorption material has the cone cylinder shape cavity structure of beta-cyclodextrin " internal drainage, external hydrophilicity ", this special construction property makes
It can form stable inclusion compound with guest molecule, and therefore, the Beta-cyclodextrin-based chelating decolorizing and absorbing material of solid has to organic
The stronger adsorption capacity of object.
According to above-mentioned test method, consider first to take 100 times of popularization in the loss of test process adsorbent material
1.5g sampling test, gradually reduces experimental scale, the adsorbent material of zeolite regeneration is reused for the absorption of organic matter, with right
The absorption of methyl orange investigates regeneration and situation is recycled, and table 4 is the result for being recycled 5 times.
The recycling situation of the product of the present invention of table 4 processing Methyl Orange in Wastewater
Table 4 the result shows that, zeolite regeneration influences very little to adsorption capacity, and 5 elution cycles are using reaching saturation absorption
Time does not change substantially, and the rate of recovery is also substantially unchanged.Therefore, the Beta-cyclodextrin-based chelating decolorizing and absorbing material of solid of the invention
Have many advantages, such as that good organic matter recycling, regneration of adsorbent material, recycling, service life are longer.
Embodiment 10
Using 1~embodiment of embodiment, 5 gained sample as adsorbent material, it is denoted as 1 respectively#、2#、3#、4#With 5#, matter is prepared respectively
Amount volumetric concentration is 100-100mg/L Cu2+Methyl orange, Zn2+Methyl orange, Cu2+Methylene blue and Zn2+The mould of methylene blue
Quasi- heavy metal-organic matter water sample.Adsorption test condition: (1) adsorption capacity measures, and 50mL is taken to simulate heavy metal-organic matter respectively
Water sample is placed in 100mL conical flask, is weighed the adsorbent material of the above-mentioned preparation of 15mg, is placed on constant-temperature table, is vibrated at 25 DEG C
2h separates microspheres with solid with solution with supercentrifuge centrifugation (revolving speed 5000r/mim, centrifugation time 5min), solution is taken to exist
The concentration of heavy metal ion and the measurement suction on visible spectrophotometer after measurement absorption on AA-7000 Atomic Absorption Spectrometer
The concentration of attached organic matter calculates adsorbent material to the adsorption capacity of heavy metal ion and organic matter;(2) adsorption time measures,
It by above-mentioned test method, is sampled using 5min as time interval and measures heavy metal ion and organic concentration respectively, determination reaches full
With the time of absorption;(3) organic matter desorption recycling is centrifuged (5000 r/mim of revolving speed, centrifugation time 5min) with supercentrifuge
It separates microspheres with solid with solution, microspheres with solid is washed with deionized and sloughs unadsorbed organic matter, is then added to
In the hydrochloric acid of 0.01mol/L, 1h is vibrated on shaking table, is centrifuged (5000 r/mim of revolving speed, centrifugation time with supercentrifuge
It 5min) separates microspheres with solid with solution, then is washed with deionized, respectively measurement elution heavy metal ion and organic matter
Amount calculates the rate of recovery of heavy metal ion and organic matter, as a result respectively as shown in table 5, table 6 and table 7.
Adsorption capacity of the product of the present invention of table 5 to heavy metal-organic matter combined pollution
Equilibrium adsorption time of the product of the present invention of table 6 to heavy metal-organic matter combined pollution
The rate of recovery of the product of the present invention of table 7 to heavy metal-organic matter combined pollution
From table 5 to table 7 as can be seen that product of the present invention has higher suction to the organic compound contaminated object of heavy metal ion-
Attached capacity, the rate of adsorption is fast, short up to time of equilibrium adsorption, and has excellent zeolite regeneration performance.This is because solid ring is pasted
Smart base chelates decolorizing and absorbing material surface both active groups rich in, such as dithiocarbonic acid base, amino, imino group and hydroxyl
Deng, and the cone cylinder shape cavity structure with beta-cyclodextrin " internal drainage, external hydrophilicity ", this special construction property inhale it both can
Attached heavy metal ion, and stable inclusion compound can be formed with guest molecule, therefore, the Beta-cyclodextrin-based chelating decolorization adsorption material of solid
Material has to the stronger adsorption capacity of heavy metal-organic matter combined pollutant.
According to above-mentioned test method, consider first to take 100 times of popularization in the loss of test process adsorbent material
1.5g sampling test, gradually reduces experimental scale, and the adsorbent material of zeolite regeneration is reused for heavy metal ion and organic matter
Absorption, to Cu2+The absorption of methyl orange investigates regeneration and situation is recycled, and table 8 is the result for being recycled 5 times.
The product of the present invention of table 8 handles Cu2+The recycling situation of methyl orange combined pollution
Table 8 the result shows that, zeolite regeneration influences very little to adsorption capacity, and 5 elution cycles are using reaching saturation absorption
Time does not change substantially, and the rate of recovery is also substantially unchanged.Therefore, Beta-cyclodextrin-based cross-linked polymer adsorbent material of the invention tool
Have the advantages that good organic matter recycling, regneration of adsorbent material, recycling, service life are longer.
The foregoing is merely the preferred embodiments of the present invention, and according to the above-mentioned design, those skilled in the art are also
Can to this, various modification can be adapted and transformation, for example, in the present invention proportion and process condition range that provide, to proportion and work
Skill condition is combined, converts, these similar transformation and modification belong to essence of the invention.
Claims (10)
1. a kind of Beta-cyclodextrin-based chelating decolorizing and absorbing material of solid, which is characterized in that the adsorbent material is with cyclodextrin, epoxy chloropropionate
Alkane and polyethylene polyamine are raw material, using dialdehyde as crosslinking agent, synthesize polymer microsphere using antiphase emulsifiable method, then with curing
Carbon reacts under alkaline condition to be made.
2. the Beta-cyclodextrin-based chelating decolorizing and absorbing material of solid according to claim 1, which is characterized in that adsorbent material appearance
For the faint yellow spheric granules to yellow, particle surface contains the cyclodextrin units for having Inclusion property to organic pollutant simultaneously
With the dithiocarbonic acid base-CSS to contents of many kinds of heavy metal ion with strong chelating trapping ability-。
3. the preparation method of the Beta-cyclodextrin-based chelating decolorizing and absorbing material of solid of any of claims 1 or 2, which is characterized in that packet
Include following steps:
(1) cyclodextrin and deionized water are added to the solution for being made into that the mass fraction of cyclodextrin is 15~25% in reactor,
It is again 1: 30~50 by the molar ratio of cyclodextrin and alkali, alkali is added in reactor and is dissolved;
(2) emulsifier and oily phase are added in step (1) acquired solution, water phase oil phase volume ratio is 1: 4~12, emulsifier and oil
Phase mass volume ratio is that 1: 15~25g/mL is warming up to 60~70 DEG C after ultrasonic wave auxiliary stirs 30~40min;
(3) molar ratio of cyclodextrin, epoxychloropropane, polyethylene polyamine and dialdehyde 1: 30~50: 20~40: 10~20 is pressed,
Polyethylene polyamine is taken to be configured to the polyethylene polyamine aqueous solution that mass fraction is 40~60%, in step (2) acquired solution
It is middle first be added dropwise total amount half epoxychloropropane, after dripping react 1~2h, then be added dropwise total amount half polyethylene polyamine it is molten
Liquid reacts 1~2h after dripping;Remaining epoxychloropropane is added dropwise again, 1~2h is reacted after dripping, is then added dropwise again remaining
Polyethylene polyamine solution, after dripping react 1~2h;4~6h of dialdehyde cross-linking reaction is finally added dropwise, is cooled to room temperature, takes out
Filter, is washed 3~5 times with ethyl alcohol and deionized water respectively;
(4) step (3) obtained solid microballoon is transferred in reactor, adds deionized water, then press sodium hydroxide, two sulphur
Changing the ratio between amount of substance of carbon and polyethylene polyamine is 2.2~3.9: 2~3: 1, first weighs sodium hydroxide and is added to reactor
In, carbon disulfide is measured again after to be dissolved is slowly dropped in reactor, the reaction was continued at room temperature after adding 3~5h;Then
50~65 DEG C of 30~60min of reaction are warming up to, are cooled to room temperature, are filtered, then be washed with deionized 3~5 times, are drying to obtain solid
The Beta-cyclodextrin-based chelating decolorizing and absorbing material of body.
4. the preparation method of the Beta-cyclodextrin-based cross-linked polymer adsorbent material of magnetism according to claim 3, which is characterized in that
In step (1), the cyclodextrin is alpha-cyclodextrin, beta-cyclodextrin or gamma-cyclodextrin.
5. the preparation method of the Beta-cyclodextrin-based chelating decolorizing and absorbing material of solid according to claim 3, which is characterized in that step
Suddenly in (1), the alkali is NaOH or KOH;The reactor is three-neck flask, has mechanical stirring, constant pressure funnel
And condenser pipe.
6. the preparation method of the Beta-cyclodextrin-based chelating decolorizing and absorbing material of solid according to claim 3, which is characterized in that step
Suddenly in (2), the emulsifier is Span series water-in-oil emulsifier.
7. the preparation method of the Beta-cyclodextrin-based chelating decolorizing and absorbing material of solid according to claim 3, which is characterized in that step
Suddenly in (2), the oil is mutually one or more of atoleine, petroleum ether and normal octane.
8. the preparation method of the Beta-cyclodextrin-based chelating decolorizing and absorbing material of solid according to claim 3, which is characterized in that step
Suddenly in (3), the polyethylene polyamine be one or both of diethylenetriamine, triethylene tetramine and tetraethylenepentamine with
On;The dialdehyde is glyoxal or/and glutaraldehyde.
9. the preparation method of the Beta-cyclodextrin-based chelating decolorizing and absorbing material of solid according to claim 3, which is characterized in that step
Suddenly drying described in (3) and step (4) is vacuum drying, and drying temperature is 40~60 DEG C, and pressure is -0.1~-0.08MPa.
10. adsorbent material of any of claims 1 or 2 is multiple in heavy metal wastewater thereby, organic pollutant wastewater or heavy metal-organic matter
Close the application in pollutant wastewater treatment.
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CN114471733A (en) * | 2021-12-16 | 2022-05-13 | 安徽欣创节能环保科技股份有限公司 | Modified sodium alginate-based photocatalytic reducing agent and preparation method and application thereof |
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