CN110115985A - A kind of Beta-cyclodextrin-based cross-linked polymer adsorbent material and preparation method thereof - Google Patents
A kind of Beta-cyclodextrin-based cross-linked polymer adsorbent material and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of Beta-cyclodextrin-based cross-linked polymer adsorbent material and preparation method thereof.The present invention is using cyclodextrin, epoxychloropropane and polyethylene polyamine as raw material, dialdehyde is crosslinking agent, polymer microsphere is synthesized by antiphase emulsifiable method, there is only the amido for having strong effect to contents of many kinds of heavy metal ion, imido grpup and hydroxyl isoreactivity groups in resulting materials structure, and the cyclodextrin structure unit of " internal drainage external hydrophilicity " structure removed is allowed to containing inclusion compound can be formed with Some Organic Pollutants, heavy metal ions in wastewater and organic pollutant, especially heavy metal-organic matter combined pollution object can be effectively removed；Single Pollution object in waste water can only generally be effectively removed by overcoming conventional adsorbent, and treatment effect is poor, efficiency is lower and the defect of higher cost, it can be widely applied to the processing of all kinds of heavy metals, organic pollutant and heavy metal-organic matter combined pollution, be especially suitable for removing the combined pollutant in industrial wastewater and sanitary sewage.
Description
Technical field
The present invention relates to a kind of adsorbent material more particularly to a kind of Beta-cyclodextrin-based cross-linked polymer adsorbent material and its preparations
Method.
Background technique
The heavy metals such as Hg, Pb, Cd, Cr, Mn, Ni, Cu have significant bio-toxicity to people, animals and plants and microorganism etc.,
It is a kind of pollutant very harmful to environment and the mankind, Heavy Metal Pollution is always the difficult point and research of International Environmental Protection circle
Hot spot.As industrial and agricultural production rapid development and people's living standard are continuously improved, to the selecting of heavy metal, smelting, processing, production
Product manufacture and application are increasing, and the discharge amount of heavy metal wastewater thereby is caused to be continuously increased；On the other hand due to easily picking up, processing
Heavy metal mine is increasingly exhausted and counterweight intermetallic composite coating and product manufacturing require to be continuously improved, cause to select smelting, processing technology day
Become complicated, it is required that smelting, processing medicament (or auxiliary agent) type and consumption is selected to increase, cause the heavy metal wastewater thereby pollutant component of discharge
It is increasingly sophisticated.In addition, heavy metal ion is discharged into after environment can also interact with pollutants other in environment.Therefore, real
Heavy metal wastewater thereby pollution in border rarely has with existing for single component, mostly with various heavy, heavy metal-inorganic pollution and a huge sum of money
The combined pollutions form such as category-organic pollutant exists, more universal with heavy metal-organic matter combined pollution, such as heavy metal ion
With the combined pollutant for picking up the formation such as medicament, dyestuff, phenols and antibiotic.Since heavy metal is easily interacted with other ingredients
Effect forms more complicated, the more serious combined pollution of pollution, and therefore, difficulty of governance is bigger.And at the heavy metal wastewater thereby researched and developed
Reason method, as chemical precipitation method, chelating flocculation, ferrite process, ion-exchange, film filtering, floatation, electrochemical method and
Absorption method etc. rarely has to comprehensively consider ingredient coexists primarily directed to the removal of heavy metal ion, and organic pollutant especially coexists
Removal.These processing methods itself are handled for heavy metal, take into account coexisted organic compounds pollution less, therefore, in processing side
Shortcomings in method and conceptual design.This problem leads to the process for treating heavy-metal waste water researched and developed, and effect is owed in practical applications
Good, the practicability is poor.To further increase the treatment effect to practical heavy metal wastewater thereby, heavy metal wastewater thereby pollution is fundamentally solved
Governing problem, need to research and develop from the angle of combined pollution and take into account heavy metal and organic pollutant removal, especially synchronous removal
The new and effective treatment technology of heavy metal and organic pollutant.Therefore, carry out Beta-cyclodextrin-based cross-linked polymer adsorption material
The design of material synthesizes, and realizes removal synchronous with organic pollutant to heavy metal in waste water to the efficient place for promoting heavy metal wastewater thereby
Reason has important practical application value.
Summary of the invention
In view of the above technical problems, the present invention provides a kind of Beta-cyclodextrin-based cross-linked polymer adsorbent material and its preparation side
Method.The ability of the existing excellent Adsorption heavy metal ion of the adsorbent material has the property of good absorption organic pollutant again
Can, it is able to achieve removal synchronous with organic pollutant to heavy metal in waste water, and safe and non-toxic, wide adaptation range；Its preparation side
It is method simple process, reliable, react easily controllable, easy to operate, high income, manufacturing cost is low, and three waste discharge is few, and is easy to push away
Extensively, popularize and realize industrialization.
The technical solution of the present invention is as follows:
A kind of Beta-cyclodextrin-based cross-linked polymer adsorbent material is original with cyclodextrin, epoxychloropropane and polyethylene polyamine
Material, dialdehyde is crosslinking agent, synthesizes polymer microsphere using antiphase emulsifiable method, appearance is the faint yellow spheric granules to yellow.
The preparation method of above-mentioned Beta-cyclodextrin-based cross-linked polymer adsorbent material, 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 30min 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 polyethylene polyamine is first configured to the aqueous solution that mass fraction is 40~60%；Then it is dripped in step (2) acquired solution
The epoxychloropropane of aggregation amount half reacts 1~2h, then the polyethylene polyamine solution of total amount half is added dropwise after dripping, drip
1~2h is reacted after adding；Then remaining epoxychloropropane is added dropwise again, 1~2h is reacted after dripping, then is added dropwise remaining mostly sub-
Polyethylene polyamine solution reacts 1~2h after dripping；4~6h of dialdehyde cross-linking reaction is finally added dropwise；
(4) step (3) acquired solution is cooled to room temperature, respectively with ethyl alcohol and distillation water washing 3~5 times, is filtered, it is dry
Up to Beta-cyclodextrin-based cross-linked polymer adsorbent 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 both of five amine are two or more.
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 (4), the suction filtration, Suction filtration device is Buchner funnel and bottle,suction, and pressure is -0.1
~-0.08 MPa.
Further, in step (4), the drying is vacuum drying, and drying temperature is 40~60 DEG C, and pressure is -0.1
~-0.08MPa.
Above-mentioned cyclodextrin, epoxychloropropane, polyethylene polyamine, dialdehyde and sodium hydroxide and emulsifier used are point
It analyses pure.
It is useless that above-mentioned adsorbent material is suitable for all kinds of heavy metal wastewater therebies, organic wastewater and heavy metal-organic matter combined pollution object
The processing of water.
The present invention relates to a kind of Beta-cyclodextrin-based cross-linked polymer adsorbent materials and preparation method thereof.With cyclodextrin, epoxy chlorine
Propane and polyethylene polyamine are raw material, and dialdehyde is crosslinking agent, synthesizes polymer microsphere by antiphase emulsifiable method；Gained adsorption material
There is only amido, imido grpup and hydroxyls etc. in the structure of material has the active group of strong effect to heavy metal ion, also contains
There is " internal drainage external hydrophilicity " cyclodextrin structure, organic pollutant can be effectively removed；Conventional adsorbent is overcome generally can only
The Single Pollutions objects such as heavy metal or organic pollutant in effective Adsorption waste water, for heavy metal and organic pollutant shape
At combined pollution, the poor processing effect of the stable comple both especially formed, low efficiency, it is at high cost the defects of.
Possessed beneficial effect is the present invention compared with prior art:
(I) adsorbent material of the invention be polymer microsphere, the specific surface area bigger than having with other isometric shapes,
The contact area with pollutant is increased, to enhance the ability of its absorption；It is also beneficial to improve adsorption dynamics adsorption kinetics characteristic simultaneously,
Promote the raising of absorption property.
(II) adsorbent material of the invention is both rich in has the amino of strong effect, Asia to contents of many kinds of heavy metal ion
Amino and hydroxyl isoreactivity group, and the cyclodextrin structure removed is allowed to containing inclusion compound can be formed with Some Organic Pollutants
Therefore unit has both the good ability for removing removing heavy metals and organic pollutant, be able to achieve heavy metal ions in wastewater and organic
The synchronous removal of object.
(III) adsorbent material of the invention is prepared using antiphase emulsifiable method, and structure and performance can be according to actual treatment waste water
The characteristics of easily regulated and controled by control raw material proportioning, water-oil factor, emulsifier additional amount and revolving speed, to realize preparation process
With the optimization of performance.
(IV) adsorbent material of the invention is safe and non-toxic, handles the simple process of waste water, only need to be in heavy metal wastewater thereby, organic
A certain amount of product of the present invention is added in object waste water and heavy metal-organic matter combined pollution waste water, being sufficiently stirred to inhale rapidly
Attached pollutant does not need complicated equipment and process through sedimentation separation and filtering；Wide adaptation range, can be fast at normal temperature
Hg in speed absorption waste water2+、Pb2+、Cu2+、Cd2+、Mn2+And Zn2+Etc. contents of many kinds of heavy metal ion, also can effectively Adsorption it is organic
The organic pollutants such as dyestuff, moreover it is possible to effectively remove heavy metal-organic matter combined pollution object, and there is good zeolite regeneration
Can, service life cycle is long.
(V) synthesis technology of the present invention is simple, easily operated, and reaction condition is mild, technical process environmental protection, and required equipment 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 cross-linked polymer adsorbent material of product 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 the Beta-cyclodextrin-based friendship of product of the present invention
The preparation method of linked polymer adsorbent material, embodiment 8~10 are 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 (1.04mL) that aggregation amount half mass fraction is 98%, reacts 1h, then total amount half matter is added dropwise after dripping
The triethylene tetramine solution (3.29g) that score is 40% is measured, 1h is reacted after dripping, then remaining epoxychloropropane is added dropwise
(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, is cooled to room temperature.
(4) step (3) solution is cooled to room temperature, respectively with ethyl alcohol and distillation water washing 3 times, filters, it is dry to be placed in vacuum
Dry case is dry to constant weight in 40 DEG C, obtains Beta-cyclodextrin-based cross-linked polymer adsorbent material 4.02g.
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 (1.38mL) that aggregation amount half mass fraction is 98%, reacts 1h, then total amount half matter is added dropwise after dripping
The triethylene tetramine solution (3.94g) that score is 50% is measured, 1h is reacted after dripping, then remaining epoxychloropropane is added dropwise
(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, is cooled to room temperature；
(4) step (3) solution is cooled to room temperature, is washed 4 times with ethyl alcohol and deionized water respectively, filtered, be placed in vacuum
Drying box is dry to constant weight in 50 DEG C, obtains Beta-cyclodextrin-based cross-linked polymer adsorbent material 4.52g.
Embodiment 3
(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: 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) it by the molar ratio of beta-cyclodextrin, epoxychloropropane, triethylene tetramine and glutaraldehyde 1: 50: 40: 20, takes
The triethylene tetramine that 5.36mL mass fraction is 96% is configured to 60% triethylene tetramine aqueous solution, in step (2) solution
The epoxychloropropane (1.72mL) that total amount half mass fraction is 98% is first added dropwise, 1h is reacted after dripping, then total amount one is added dropwise
The triethylene tetramine solution (4.38g) that half mass fraction is 60%, reacts 1h, then remaining epoxychloropropane is added dropwise after dripping
(1.72mL) reacts 1h after dripping, then remaining triethylene tetramine solution (4.38g) is added dropwise, and 1h is reacted after dripping, then drip
Adding 3.65mL mass fraction is 50% glutaraldehyde cross-linking 6h, is cooled to room temperature；
(4) step (3) solution is cooled to room temperature, is washed 5 times with ethyl alcohol and deionized water respectively, filtered, be placed in vacuum
Drying box is dry to constant weight in 60 DEG C, obtains Beta-cyclodextrin-based cross-linked polymer adsorbent material 5.31g.
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) it by the molar ratio of beta-cyclodextrin, epoxychloropropane, diethylenetriamine and glutaraldehyde 1: 30: 20: 10, takes
The diethylenetriamine that 1.92mL mass fraction is 97% is configured to 40% diethylenetriamine aqueous solution, in step (2) solution
The epoxychloropropane (1.04mL) that total amount half mass fraction is 98% is first added dropwise, 1h is reacted after dripping, then total amount one is added dropwise
The diethylenetriamine solution (2.30g) that half mass fraction is 40%, reacts 1h, then remaining epoxychloropropane is added dropwise after dripping
(1.04mL) reacts 1h after dripping, then remaining diethylenetriamine solution (2.30g) is added dropwise, and 1h is reacted after dripping, then drip
Adding 1.83mL mass fraction is 50% glutaraldehyde cross-linking 4h, is cooled to room temperature；
(4) step (3) solution is cooled to room temperature, respectively with ethyl alcohol and distillation water washing 3 times, filters, it is dry to be placed in vacuum
Dry case is dry to constant weight in 60 DEG C, obtains Beta-cyclodextrin-based cross-linked polymer adsorbent material 3.76g.
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 3.45
The tetraethylenepentamine that mL mass fraction is 95% is configured to 40% tetraethylenepentamine aqueous solution, first drips in step (2) solution
The epoxychloropropane (1.04mL) that aggregation amount half mass fraction is 98%, reacts 1h, then total amount half matter is added dropwise after dripping
The tetraethylenepentamine solution (3.70g) that score is 40% is measured, 1h is reacted after dripping, then remaining epoxychloropropane is added dropwise
(1.04 mL), reacts 1h after dripping, then remaining tetraethylenepentamine solution (3.70g) 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, is cooled to room temperature；
(4) step (3) solution is cooled to room temperature, respectively with ethyl alcohol and distillation water washing 3 times, filters, it is dry to be placed in vacuum
Dry case is dry to constant weight in 60 DEG C, obtains Beta-cyclodextrin-based cross-linked polymer adsorbent material 4.21g.
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) it by the molar ratio 1: 30: 20: 10 of alpha-cyclodextrin, epoxychloropropane, triethylene tetramine and glutaraldehyde, takes
The triethylene tetramine that 3.13mL mass fraction is 96% is configured to 40% triethylene tetramine aqueous solution, in step (2) solution
The epoxychloropropane (1.21mL) that total amount half mass fraction is 98% is first added dropwise, 1h is reacted after dripping, then total amount one is added dropwise
The triethylene tetramine solution (3.84g) that half mass fraction is 40%, reacts 1h, then remaining epoxychloropropane is added dropwise after dripping
(1.21mL) reacts 1h after dripping, then remaining triethylene tetramine solution (3.84g) is added dropwise, and 1h is reacted after dripping, then drip
Adding 2.13mL mass fraction is 50% glutaraldehyde cross-linking 4h, is cooled to room temperature.
(4) step (3) solution is cooled to room temperature, respectively with ethyl alcohol and distillation water washing 3 times, filters, it is dry to be placed in vacuum
Dry case is dry to constant weight in 40 DEG C, obtains Beta-cyclodextrin-based cross-linked polymer adsorbent material 4.41g.
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) it by the molar ratio 1: 30: 20: 10 of gamma-cyclodextrin, epoxychloropropane, triethylene tetramine and glutaraldehyde, takes
The triethylene tetramine that 2.34mL mass fraction is 96% is configured to 40% triethylene tetramine aqueous solution, in step (2) solution
The epoxychloropropane (0.91mL) that total amount half mass fraction is 98% is first added dropwise, 1h is reacted after dripping, then total amount one is added dropwise
The triethylene tetramine solution (2.87g) that half mass fraction is 40%, reacts 1h, then remaining epoxychloropropane is added dropwise after dripping
(0.91mL) reacts 1h after dripping, then remaining triethylene tetramine solution (2.87g) is added dropwise, and 1h is reacted after dripping, then drip
Adding 2.13mL mass fraction is 50% glutaraldehyde cross-linking 4h, is cooled to room temperature.
(4) step (3) solution is cooled to room temperature, respectively with ethyl alcohol and distillation water washing 3 times, filters, it is dry to be placed in vacuum
Dry case is dry to constant weight in 40 DEG C, obtains Beta-cyclodextrin-based cross-linked polymer adsorbent material 3.75g.
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: 3432.19cm-1For the stretching vibration peak of-OH and stretching for-NH
Contracting vibration peak；In 2924.96,2854.56cm-1Locate appearance-CH2Symmetrical and asymmetric stretching vibration peak, accordingly exist
1384.11cm-1There is its flexural vibrations peak in place；1652.32,1634.50cm-1For the absorption peak and-C=N of bound water molecule
Stretching vibration peak；1461.36cm-1 is-CH2Asymmetric stretching vibration peak；1047.69cm-1For the stretching vibration of C-O-C
Peak, 879.00cm-1For pyranose glycosidic bond characteristic peak；611.84cm-1The bending vibration of cyclic structure in the peak cyclodextrin at place
Peak.The presence of these absorption peaks demonstrates Beta-cyclodextrin-based cross-linked polymer adsorbent material and has been successfully synthesized.
Fig. 3 scanning electron microscope analysis the result shows that Beta-cyclodextrin-based cross-linked polymer adsorbent material is about 150 μm of diameter of 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 (5000 r/mim of revolving speed, centrifugation time with supercentrifuge
It 5min) separates microspheres with solid with solution, solution is taken to measure suction in AA-7000 Atomic Absorption Spectrometer (Japanese Shimadzu Corporation)
The concentration of attached heavy metal ion calculates the adsorption capacity of adsorbent material；(2) adsorption time measures, by above-mentioned test method, with
5min is that ion concentration is measured by sampling in time interval, determines the time for reaching saturation absorption；(3) heavy metal desorption recycling, with height
Fast centrifuge centrifugation (revolving speed 5000r/mim, centrifugation time 5min) separates microspheres with solid with solution, is washed with deionized de-
Unadsorbed metal ion is removed, is then added in the hydrochloric acid of 0.01mol/L, 1h is vibrated on shaking table, uses supercentrifuge
Centrifugation (revolving speed 5000r/mim, centrifugation time 5min) separates microspheres with solid with solution, then is washed with deionized, and measurement is washed
The amount of removing heavy-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 Beta-cyclodextrin-based crosslinking
Therefore polymer adsorbing material surface active group rich in, such as amino, imino group and hydroxyl substantially increase pair
The adsorption capacity of 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 also substantially unchanged.Therefore, Beta-cyclodextrin-based cross-linked polymer adsorbent material of the invention tool
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 0.01mol/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, Beta-cyclodextrin-based cross-linked polymer adsorbent material has to having
The stronger adsorption capacity of machine 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, 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.
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 made with supercentrifuge centrifugation (revolving speed 5000r/mim, centrifugation time 5min)
Microspheres with solid is separated with solution, and 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 (revolving speed 5000r/mim, 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 Beta-cyclodextrin-based
Cross-linked polymer adsorbent material had both had active group abundant, such as amino, imino group and hydroxyl, and had beta-cyclodextrin
The cone cylinder shape cavity structure of " internal drainage, external hydrophilicity ", this special construction property make it that can not only adsorb heavy metal ion, but also can
To form stable inclusion compound with guest molecule, therefore, Beta-cyclodextrin-based cross-linked polymer adsorbent material has organic to heavy metal-
The stronger adsorption capacity of object 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
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 cross-linked polymer adsorbent material, which is characterized in that the adsorbent material is with cyclodextrin, epoxychloropropane
With polyethylene polyamine be raw material, dialdehyde be crosslinking agent using antiphase emulsifiable method synthesize polymer microsphere, appearance be it is faint yellow extremely
The spheric granules of yellow.
2. the preparation method of Beta-cyclodextrin-based cross-linked polymer adsorbent material described in claim 1, which is characterized in that including as follows
Step:
(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 30min；
(3) molar ratio of cyclodextrin, epoxychloropropane, polyethylene polyamine and dialdehyde 1: 30~50: 20~40: 10~20 is pressed,
Polyethylene polyamine is first configured to the aqueous solution that mass fraction is 40~60%；Then it is added dropwise in step (2) acquired solution
The epoxychloropropane of total amount half reacts 1~2h, then the polyethylene polyamine solution of total amount half is added dropwise after dripping, be added dropwise
1~2h is reacted after complete；Then remaining epoxychloropropane is added dropwise again, 1~2h is reacted after dripping, then remaining more sub- second are added dropwise
Quito amine aqueous solution reacts 1~2h after dripping；4~6h of dialdehyde cross-linking reaction is finally added dropwise；
(4) step (3) acquired solution is cooled to room temperature, respectively with ethyl alcohol and distillation water washing 3~5 times, filters, be drying to obtain
Beta-cyclodextrin-based cross-linked polymer adsorbent material.
3. the preparation method of the Beta-cyclodextrin-based cross-linked polymer adsorbent material of magnetism according to claim 2, which is characterized in that
In step (1), the cyclodextrin is alpha-cyclodextrin, beta-cyclodextrin or gamma-cyclodextrin.
4. the preparation method of Beta-cyclodextrin-based cross-linked polymer adsorbent material according to claim 2, which is characterized in that step
(1) in, the alkali is NaOH or KOH；The reactor be three-neck flask, with mechanical stirring, constant pressure funnel and
Condenser pipe.
5. the preparation method of Beta-cyclodextrin-based cross-linked polymer adsorbent material according to claim 2, which is characterized in that step
(2) in, the emulsifier is Span series water-in-oil emulsifier.
6. the preparation method of Beta-cyclodextrin-based cross-linked polymer adsorbent material according to claim 2, which is characterized in that step
(2) in, the oil is mutually one or more of atoleine, petroleum ether and normal octane.
7. the preparation method of Beta-cyclodextrin-based cross-linked polymer adsorbent material according to claim 2, which is characterized in that step
(3) in, the polyethylene polyamine be one or both of diethylenetriamine, triethylene tetramine and tetraethylenepentamine with
On.
8. the preparation method of Beta-cyclodextrin-based cross-linked polymer adsorbent material according to claim 2, which is characterized in that step
(3) in, the dialdehyde is glyoxal or/and glutaraldehyde.
9. the preparation method of Beta-cyclodextrin-based cross-linked polymer adsorbent material according to claim 2, which is characterized in that step
(4) in, the drying 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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| CN115677876A (en) * | 2022-10-10 | 2023-02-03 | 重庆大学 | Bio-based polymer adsorption material and preparation method thereof |
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