CN105664864A - Preparation method and application of vascular plant based porous oxidative polymerization chelating adsorption material - Google Patents
Preparation method and application of vascular plant based porous oxidative polymerization chelating adsorption material Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a vascular plant based porous oxidative polymerization chelating adsorption material. The adsorption material takes a porous vascular plant as the carrier, and is grafted with a lot of amidoxime groups. The preparation method includes: subjecting the vascular plant to oxidation treatment, then conducting coupling with a double-bond equipped silane coupling agent, then carrying out free radical polymerization reaction with acrylonitrile under the action of an initiator, and finally converting part of a nitrile group into an amidoxime group through hydroxylamine, thus obtaining the adsorption material. The adsorption material has strong hydrophilicity, abundant porous structure and numerous amidoxime groups, and can be applied to removal of heavy metals or radioactive metallic elements from wastewater. The adsorption material shows the characteristics of high adsorption capacity, strong adsorption ability, reproducibility and reusability, and good reuse effect, and is especially suitable for adsorption removal of lead, cadmium, uranium and other metals from wastewater.
Description
Technical field
The present invention relates to the preparation method of a kind of vascular plant Quito hole oxidation polymerization chelate adsorption and application, particularly relate to dimension tubing plant as carrier, carry out aoxidizing, surface active, the step such as grafting and polymerization, a kind of novel plant base oxidation polymerization material of preparation, is mainly used in water body and the absorption of heavy metal in soil ion and radioelement; Belong to the modified field of natural organic high-molecular.
Background technology
Heavy Metal Pollution is it is known that water body and heavy metals in soil enter ecological environment and food chain by Transport And Transformation, and then jeopardizes biology and health. Secondly, radioelement uranium has the status do not replaced in national defense safety and national economy. Readjust the energy structure, reduce carbon emission amount and bring unprecedented opportunities to Nuclear Electricity, but simultaneously, also increasingly severe by the uranium radioactive pollution caused in nuclear fuel processing procedure, receive the attention of society. The exploitation of uranium, grinding and smelting process can produce substantial amounts of high concentration uranium-containing waste water, the subsoil water of surrounding, soil and deposit can be caused severe contamination, also the health of the mankind can be produced great radiation damage. The long half time of uranium and have bioaccumulation, in the process such as uranium mining and hydrometallurgy, the discharge of uranium-containing waste water causes radioactive pollution, seeks efficiently, environmental protection, economic uranium-containing waste water treatment technology seem particularly urgent.
The technology processed currently for heavy metal and uranium-containing waste water mainly has following a few class:
(1) chemical precipitation method: chemical precipitation method is the main method of the of a relatively high heavy metal of concentration for the treatment of and uranium-containing waste water, except conventional lime treatment, aluminium hydroxide, basic magnesium carbonate etc. can also be utilized as coprecipitator, form co-precipitation with the low concentration uranium in waste water and reach the purpose of enrichment. Chemical precipitation method have handling with relatively low and also simple to operate a little. But, chemical precipitation method is only suitable to high concentration wastewater treatment, low content harmful ion is processed and has difficulties, and meanwhile, is readily incorporated other foreign ions, impact by the pH value of waste water and temperature, the poor stability of processing procedure in operating process.
(2) synthetic adsorbent processes: the adsorbent in synthetic adsorbent process includes relatively polymorphic type, wherein, Exchange Resin by Adsorption processes low-concentration heavy metal technology relative maturity, most widely used, and ion exchange resin absorption is also the main method of separation and recovery low concentration uranium. But, ion exchange resin adsorption capacity is limited, adsorptive selectivity is not high, is not also suitable for the neutral direct process with meta-alkalescence waste water. At present, the research of chelating resin is the most popular, and its heavy metal ion, rare earth element have very strong coordination ability, have higher selective absorption, is the research emphasis in adsorbing separation recovery field.
(3) membrane separation process: membrane separation process processes the process that heavy metal and uranium-containing waste water are continuous operations, technique simple and need not further chemical treatment, processing procedure environmental protection and economy and effect is fine. But, utilize membrane separation process to process industry uranium-containing waste water technology ripe not enough, also have a lot of problems demand to solve, for instance the selection of membrane material, separate the aspect such as recycling and regenerability, the service life separating film of film.
(4) biosorption process: in recent years, the plant of some rich cellulose classes becomes a study hotspot as the uranium ion processed in waste water. Cellulose contains abundant can form the active group of stable comple with metal ion, and uranium ion is had stronger affinity by these active groups, effectively can be combined with uranium ion and form stable complex. The raw material sources of biological adsorption are extensive, economical and efficient, and adsorbing material generally can repeat regeneration and recycle. Biological adsorption agent is utilized to process uranium-containing waste water technique simple, easy to operate, it is a kind of efficiently feasible method.
Summary of the invention
For the defect that the method for process heavy metal in waste water of the prior art or thorium exists, it is an object of the invention to be in that to provide a kind of using porous vascular plant as carrier, it is grafted with vascular plant Quito hole oxidation polymerization chelate adsorption of a large amount of amidoxime group, vascular plant has abundant fiber multihole structure, specific surface area is big, good hydrophilic property, it is grafted with substantial amounts of amidoxim active function groups simultaneously, can be adsorbed by the mode heavy metal ion such as physical absorption and complexation or thorium, possesses the potential as adsorbing material.
Further object is that and provide a kind of method preparing described vascular plant Quito hole oxidation polymerization chelate adsorption that cost of material is low, simple to operate, reaction condition is gentle, the method is controlled to grafting active function groups number, it is easy to operation.
3rd purpose of the present invention is in that to provide the application of described vascular plant Quito hole oxidation polymerization chelate adsorption, adsorbing material is it can be used as to be applied to remove heavy metal in waste water or thorium, it is big that this adsorbing material shows adsorption capacity, high adsorption capacity, can regenerate and reuse, reuse effective feature, be particularly well-suited to the Adsorption of the metals such as Pb In Exhausted Water, cadmium and uranium.
In order to realize above-mentioned technical purpose, a kind of vascular plant Quito hole oxidation polymerization chelate adsorption, there is formula 1 structure:
Wherein,
For vascular plant matrix;
X is 500～5000;
Y is 500～5000.
Vascular plant Quito hole oxidation polymerization chelate adsorption of the present invention with vascular plant for carrier, the substantial amounts of polymer containing amidoxim active group of surface grafting;Vascular plant itself is porous fibrous structure, specific surface area is big, and there is abundant hole series structure, possibly together with substantial amounts of polar group, good hydrophilic property, heavy metal and thorium have certain absorbability, and amidoxim active group heavy metal and the thorium of grafting on this basis have stronger sequestering power so that the ability of whole adsorbing material Adsorption of Heavy Metals and thorium is highly improved.
Present invention also offers a kind of method preparing described vascular plant Quito hole oxidation polymerization chelate adsorption, the method is by, after oxidation processes, carrying out coupling with the silane coupler with double bond, obtain being grafted with the vascular plant of double bond by vascular plant; The described vascular plant being grafted with double bond carries out Raolical polymerizable with acrylonitrile under initiator effect, obtains being grafted with the vascular plant of polyacrylonitrile; Part itrile group is changed into amidoxime group by azanol by the described vascular plant being grafted with polyacrylonitrile, to obtain final product.
First dimension tubing plant is carried out oxidation processes by technical scheme, the main active group of cellulose surface is hydroxyl, and a small amount of carbonyl, methoxyl group and aldehyde radical etc., the activity of these groups is not high, and the affinity interaction power of surface modifier is not strong, the surface modifying material that grafting degree is significantly high can not be formed, oxidation processes makes the hydroxyl of plant surface be largely converted into carboxyl, improves the activity of plant surface functional group, thus improving the percent grafting that plant surface is modified. On this basis, silane coupler is grafted to oxidized plant surface, introduce polymerisable double bond, radical polymerization thereby through acrylonitrile, at vascular plant surface grafting polyacrylonitrile, carry out amino conversion reaction again, most cyano group on surface are converted into the higher amidoxime group of activity. Logical amidoxime group effective and heavy metal ion and radioelement uranium can form stable complex, thus improve the adsorption effect of this polymeric material heavy metal ion and radioelement uranium.
Preferred scheme, vascular plant, before oxidation processes, is first dried, crushes pretreatment, be crushed to granularity below-100 orders.
Preferred scheme, vascular plant is at least one in pteridophyta (such as Folium Pini orchid class, lycopods, equisetales, true fern etc.), gymnosperm, angiosperm.
Preferred scheme, oxidation processes is: after being mixed homogeneously with oxidizing agent solution by vascular plant, regulate pH value of solution to 1.0～6.5,5～10h is reacted at 40～50 DEG C of temperature, product is after drying, it is placed in NaAc_HAc buffer solution, adds oxidant, at 10～30 DEG C of temperature, react 8～10h.
The mass ratio of more preferably scheme, the oxidant in oxidizing agent solution and vascular plant is 1:0.5～1.
More preferably scheme, the oxidant added in NaAc_HAc buffer solution and the mass ratio of vascular plant are 1:0.8～1.5.
More preferably scheme, oxidant is at least two in sulphuric acid, nitric acid, ozone, sodium chlorite, sodium chlorate, sodium hypochlorite, perchloric acid and sodium metaperiodate.
Preferred scheme, the silane coupler with double bond is at least one in CY-570, CY-571, CY-AGE, CY-3031.
Preferred scheme, the vascular plant volume mass ratio after the described silane coupler with double bond and oxidation is for 1:0.3～1.
Preferred scheme, Raolical polymerizable condition is: under protective atmosphere, reacts 6～12h at 60～80 DEG C of temperature.
Preferred scheme, the mass ratio of the quality of acrylonitrile and the vascular plant being grafted with double bond is 6～10:1.
Preferred scheme, the quality of initiator is the 0.1%～0.8% of acrylonitrile monemer quality.
Preferred scheme, initiator is at least one in sulfate, alkyl peroxide, azodiisobutyronitrile, peroxidating two acyl, alkyl peroxide thing, peroxyester.
Preferred scheme, mixes the described vascular plant being grafted with polyacrylonitrile with free hydroxylamine solution, is 6.0～6.8 at pH, when temperature is 60～80 DEG C, reacts 3～8h, obtains vascular plant Quito hole oxidation polymerization chelate adsorption.
More preferably scheme, free hydroxylamine solution is obtained by reacting by hydroxylamine hydrochloride solution and sodium carbonate liquor.
Present invention also offers the application of described vascular plant Quito hole oxidation polymerization chelate adsorption, be applied to vascular plant Quito hole oxidation polymerization chelate adsorption remove heavy metal in waste water or thorium.
In technical scheme, vascular plant Quito hole oxidation polymerization chelate adsorption of load heavy metal or thorium can adopt the mixed solution of hydrochloric acid and sodium chloride to regenerate; The mixed solution of hydrochloric acid and sodium chloride is 5%NaCl (w/v) and the mixed liquor of 5%HCl (v/v).
The preparation of vascular plant Quito hole oxidation polymerization chelate adsorption of the present invention comprises the following steps:
(1) after vascular plant being made granule, by (1) oxidation processes by major part conversion of hydroxyl be carboxyl obtain product CI;
(2) silane coupler with double bond is grafted on CI and obtains product CIO;
(3) CIO is polymerized acquisition product PAN-CIO with acrylonitrile under the effect of initiator;
(4) cyano group on PAN-CIO is converted into amidoxime group and obtains chelate adsorption PAO-CIO.
Concrete synthetic route is as follows:
Hinge structure, the Advantageous Effects that technical scheme is brought:
1, vascular plant Quito hole oxidation polymerization chelate adsorption of the present invention has that specific surface area is big, hole system is abundant, and the vascular plant matrix containing more active group, surface grafting has substantial amounts of amidoxime group simultaneously, and this adsorbing material good hydrophilic property has very big application potential.
2, the preparation method of vascular plant Quito hole oxidation polymerization chelate adsorption of the present invention adopts vascular plant raw material, raw material is easy to get, cost is low, and the number of vascular plant grafting amidoxime group is controlled, the product that different application requires can be obtained, easy to implement, meet industrialization production requirements.
3, the heavy metal in waste water and thorium are had high adsorption capacity by vascular plant Quito hole oxidation polymerization chelate adsorption of the present invention, the advantage that adsorption capacity is big, and adsorbing material can regenerate, and regeneration efficiency is high, it is possible to reuse; Lot of experiments shows: this adsorbing material is when 50 DEG C, and the saturated extent of adsorption of uranium can be reached 420mg/g by material. When 20 DEG C, to the saturated extent of adsorption of plumbous, cadmium ion more than 100mg/g, be nearly three times of common adsorbing material, and desorption and regenerability good, provide probability for realizing industrialization.
Accompanying drawing explanation
[Fig. 1] is the FT-IR spectrum of different phase product in embodiment 1; A () is product CI; B () is product CIO; C () is product PAN-CIO; D () is product P AO-CIO.
[Fig. 2] is the SEM of different phase product in embodiment 1 and TEM image;A SEM image that () is CI; B SEM image that () is PAO-CIO; C TEM image that () is PAO-CIO.
[Fig. 3] is the XPS spectrum figure of different phase product in embodiment 1; A XPS spectrum figure that () is CI; B XPS spectrum figure that () is PAO-CIO.
PAO-CIO material adsorption uranium that [Fig. 4] is prepared for pteridophyta, lead, cadmium kinetic curve; Adsorption conditions: initial concentration solution=200mg/L, temperature=40 DEG C, absorbent concentration=1.0g/L, time=12h.
The PAO-CIO material that [Fig. 5] is prepared for pteridophyta Adsorption thermodynamics at different temperatures; Adsorption conditions: absorbent concentration=1.0g/L, pH=5.0, time=14h.
The PAO-CIO material that [Fig. 6] is prepared for pteridophyta desorption rate at different conditions: A:1%HCl (v/v); B:3%HCl (v/v); C:5%HCl (v/v); D:5%NaCl (w/v); E:10%NaCl (w/v); F:5%NaCl (m/v) and 5%HCl (v/v) mixed solution.
U (VI) the circulation absorption efficiency of the PAO-CIO material that [Fig. 7] is prepared for pteridophyta: initial concentration=200mg/L, temperature=40 DEG C, absorbent concentration=1.0g/L, pH=5.0, time=12h.
Detailed description of the invention
Following example are intended to present invention is further described, rather than the protection domain of restriction the claims in the present invention.
Embodiment 1
(1) pretreatment of pteridophyta: fresh pteridophyta first flushes three times with deionized water for twice with tap water again, then uses deionized water rinsing twice. Pteridophyta is dried when 65 DEG C, then with ground 100 mesh sieves of plant crusher, stores with valve bag.
(2) pteridophyta oxidation processes: take the pteridophyta after appropriate grinding and mix homogeneously with oxidant, with in acid-alkali accommodation pH value of solution to 1.0～6.5 scopes, under nitrogen atmosphere, putting into stirring reaction 8 hours in 45 DEG C of thermostat water baths, reaction terminates rear filtration washing dries. Taking in the NaAc_HAc buffer solution joining 100mLpH=5.5 of the sample 3.0g after drying, add 3.0g sodium chlorite and 5.0mL hydrogen peroxide, after reacting 24 hours under 20 DEG C of conditions, filtration washing is dried, and prepares oxidation plant product CIO.
(3) surface graft modification: after taking 10.0g oxidation, plant CI joins in the mixed solution of ethanol/water (v/v=1:1), it is subsequently adding 10mL silane coupler, the water-bath of 50 DEG C stirs 24 hours, react after terminating with appropriate alcoholic solution filtration washing, will be attached to the unreacted silane coupler of plant surface rinse well, it is thus achieved that surface modification product.
(4) graft copolymerization: weigh the pteridophyta CIO after 1.5g surface modification and put in there-necked flask, add the N being mixed with 13.5mL acrylonitrile, dinethylformamide (DMF) 100mL, then put in 75 DEG C of thermostat water baths after being sufficiently stirred for 30min under nitrogen atmosphere, add 0.164g initiator, react 8 hours under stirring condition. After having reacted, prepared sample is put into and washs 12 hours equipped with in the apparatus,Soxhlet's of acetone, remove acrylonitrile or the polyacrylonitrile of plant surface attachment, it is thus achieved that product PAN-CIO.
(5) amino converts: mixed homogeneously with the sodium carbonate liquor that 20mL concentration is 1.0mol/L by the hydroxylamine hydrochloride solution that 20mL concentration is 1.0moL/L, with dust technology and dilute sodium hydroxide by the pH regulator of mixed solution to 6.5, add the vascular plant PAN-CIO after 1.0g graft copolymerization, after being filled with nitrogen, put into stirring reaction 5 hours in the thermostat water bath that temperature is 70 DEG C.Reaction is filtered after terminating, and namely prepares final products PAO-CIO by deionized water wash post-drying.
Characterization of The Products:
The product that different phase is prepared has carried out detailed sign by redden external spectrum (FT-IR), surface sweeping Electronic Speculum (SEM), transmission electron microscope (TEM) and electron spectrum (XPS) of fourier, and result is such as shown in accompanying drawing 1～accompanying drawing 3. It is shown that the conclusion that various characterization methods draw has concordance, the characteristic peak of product and ad hoc structure and the elementary composition successful synthesis showing final products PAO-CIO.
By preparation PAO-CIO adsorbing material and to uranium, lead, cadmium absorption:
In a series of 1000mL beaker, it is in the uranium ion of 200mg/L, lead ion, cadmium-ion solution that the material PAO-CIO being prepared from by 1.0g pteridophyta is added separately to 1000mL concentration, with dust technology, pH value of solution is regulated after 5.0, put into stirring reaction 14 hours in thermostat water bath, water-bath temperature is regulated respectively to 50 DEG C, after the sampling filtering of reasonable time interval, measure the instant concentration of uranium ion, lead ion, cadmium ion in solution respectively. Experimental result is shown in accompanying drawing 4, uranium ion, lead ion, cadmium ion adsorption dynamics adsorption kinetics process basically identical. In 0-8 hour, adsorbance enlarges markedly over time, and after 8 hours, adsorbance slowly increases over time, and the equilibrium adsorption time is 12 hours.
Oxidation polymerization chelate adsorption Adsorption thermodynamics research prepared by pteridophyta: weigh 0.05g hair Herba pteridii latiusculi plant base oxidation polymerization material PAO-CIO and add in 50mL conical flask, add a series of Concentraton gradient (50,100 of 50mL, 150,200,250,300,350 and 400mg/L) U3O8Solution, (20,30,40 and 50 DEG C) stirring and adsorbing filtered after 12 hours at different temperatures, takes filtrate and measures uranium ion concentration in solution. Experimental result is shown in accompanying drawing 5, and when solution concentration increases, adsorbance increases, and high temperature is conducive to absorption, and adsorption equilibrium meets Langmuir model, and when 50 DEG C, maximal absorptive capacity reaches 420.2mg/g.
By the regeneration of the PAO-CIO adsorbing material of preparation and cycle performance:
After above-mentioned adsorption process being terminated, the material PAO-CIO collecting load heavy metal or uranium ion carries out detachment assays. The material weighing 0.05g load heavy metal ion joins (A:1%HCl (v/v) in 50mL desorption liquid; B:3%HCl (v/v); C:5%HCl (v/v); D:5%NaCl (w/v); E:10%NaCl (w/v); The mixed solution of F:5%NaCl (m/v) and 5%HCl (v/v)), as shown in accompanying drawing 6 (a). It can be seen that the desorption effect of the mixed solution of 5%NaCl (m/v) and 5%HCl (v/v) is best, desorption rate reaches 92.3%. Utilizing this desorption method to carry out adsorbing/de-adsorption cycle experiment, experimental result is such as shown in accompanying drawing 7 (b). It can be seen that after reusing 6 times, the adsorbance of material does not significantly reduce, after reusing 30 times, adsorbance still keeps more than 80%, it was shown that material has good cycle performance.
Embodiment 2
Shuck (walnut shell etc.) is adopted to prepare oxidation polymerization chelate adsorption and arsenic absorption behavior thereof:
(1) pretreatment of walnut shell: fresh walnut shell first flushes three times with deionized water for twice with tap water again, then uses deionized water rinsing twice. Walnut shell is dried when 65 DEG C, then with ground 100 mesh sieves of plant crusher, stores with valve bag.
(2) walnut shell oxidation processes: take the walnut shell after appropriate grinding and mix homogeneously with oxidant, with in acid-alkali accommodation pH value of solution to 1.0～6.5 scopes, under nitrogen atmosphere, putting into stirring reaction 8 hours in 45 DEG C of thermostat water baths, reaction terminates rear filtration washing dries.Taking in the NaAc_HAc buffer solution joining 100mLpH=5.5 of the sample 3.0g after drying, add 3.0g sodium chlorite and 5.0mL hydrogen peroxide, after reacting 24h under 20 DEG C of conditions, filtration washing is dried, and prepares oxidation plant product NS.
(3) surface graft modification: after taking 10.0g oxidation, plant CI joins in the mixed solution of ethanol/water (v/v=1:1), it is subsequently adding 10mL silane coupler, the water-bath of 50 DEG C stirs 24 hours, react after terminating with appropriate alcoholic solution filtration washing, will be attached to the unreacted silane coupler of plant surface rinse well, it is thus achieved that product NSO.
(4) graft copolymerization: weigh the walnut shell NSO after 1.5g surface modification and put in there-necked flask, add the N being mixed with 13.5mL acrylonitrile, dinethylformamide (DMF) 100mL, then put in 75 DEG C of thermostat water baths after being sufficiently stirred for 30min under nitrogen atmosphere, add 0.164g initiator, under stirring condition, react 8h. After having reacted, prepared sample is put into equipped with the apparatus,Soxhlet's of acetone washs 12h, remove acrylonitrile or the polyacrylonitrile of plant surface attachment, it is thus achieved that product PAN-NSO.
(5) amino converts: mixed homogeneously with the sodium carbonate liquor that 20mL concentration is 1.0mol/L by the hydroxylamine hydrochloride solution that 20mL concentration is 1.0moL/L, with dust technology and dilute sodium hydroxide by the pH regulator of mixed solution to 6.5, add the walnut shell PAN-NSO after 1.0g graft copolymerization, after being filled with nitrogen, put into stirring reaction 5h in the thermostat water bath that temperature is 70 DEG C. Reaction is filtered after terminating, and namely prepares final products PAO-NSO by deionized water wash post-drying.
Characterization of The Products:
The product that different phase is prepared has carried out detailed sign by redden external spectrum (FT-IR), surface sweeping Electronic Speculum (SEM), transmission electron microscope (TEM) and electron spectrum (XPS) of fourier. It is shown that the conclusion that various characterization methods draw has concordance, the characteristic peak of product and ad hoc structure and the elementary composition successful synthesis showing final products PAO-NSO.
Investigate the adsorption dynamics adsorption kinetics of PAO-NSO, in a series of 500mL beaker, respectively the material PAO-NSO that 1.0g walnut shell is prepared from is joined 500mL concentration be 100mg/L containing in trivalent arsenic solution, with dust technology, pH value of solution is regulated after 5.0, put into stirring reaction 10 hours in thermostat water bath, water-bath temperature is regulated respectively to 40 DEG C, after the sampling filtering of reasonable time interval, measure arsenious instant concentration in solution. It is shown that in 0-6 hour, adsorbance enlarges markedly over time, the equilibrium adsorption time is 10 hours, and equilibrium adsorption capacity reaches 154.6mg/g.
By the PAO-NSO adsorption dynamics adsorption kinetics to arsenic ion, continuing to investigate the Adsorption thermodynamics performance of PAO-NSO, result shows that adsorption equilibrium meets Langmuir model, and at 40 DEG C, maximum adsorption capacity can reach 213.7mg/g.
By the regeneration of the PAO-NSO adsorbing material of preparation and cycle performance:
After above-mentioned adsorption process being terminated, the material PAO-NSO collecting load arsenic ion carries out detachment assays. Weighing in the mixing desorption liquid that the material of 0.05g load arsenic ion joins 50mL5%NaCl (m/v) and 5%HCl (v/v), desorption rate reaches 91.3%. After reusing 6 times, the adsorbance of material does not significantly reduce, and after reusing 30 times, adsorbance still keeps more than 83%, it was shown that material has good cycle performance.
Claims (10)
1. vascular plant Quito hole oxidation polymerization chelate adsorption, it is characterised in that: there is formula 1 structure:
Wherein,
For vascular plant matrix;
X is 500～5000;
Y is 500～5000.
2. the method for preparation hole oxidation polymerization chelate adsorption in vascular plant Quito described in claim 1, it is characterised in that: by vascular plant by, after oxidation processes, carrying out coupling with the silane coupler with double bond, obtain being grafted with the vascular plant of double bond; The described vascular plant being grafted with double bond carries out Raolical polymerizable with acrylonitrile under initiator effect, obtains being grafted with the vascular plant of polyacrylonitrile; Part itrile group is changed into amidoxime group by azanol by the described vascular plant being grafted with polyacrylonitrile, to obtain final product.
3. the method for preparation vascular plant Quito hole oxidation polymerization chelate adsorption according to claim 2, it is characterised in that: described vascular plant, before oxidation processes, is first dried, crushes pretreatment, be crushed to granularity below-100 orders; Described vascular plant is at least one in pteridophyta, gymnosperm, angiosperm.
4. the method for preparation vascular plant Quito hole oxidation polymerization chelate adsorption according to claim 2, it is characterized in that: described oxidation processes is: after being mixed homogeneously with oxidizing agent solution by vascular plant, regulate pH value of solution to 1.0～6.5,5～10h is reacted at 40～50 DEG C of temperature, product is after drying, it is placed in NaAc_HAc buffer solution, adds oxidant, at 10～30 DEG C of temperature, react 8～10h.
5. the method for preparation vascular plant Quito hole oxidation polymerization chelate adsorption according to claim 4, it is characterised in that: the mass ratio of the oxidant in oxidizing agent solution and vascular plant is 1:0.5～1;
The oxidant added in NaAc_HAc buffer solution and the mass ratio of vascular plant are 1:0.8～1.5;
Described oxidant is at least two in sulphuric acid, nitric acid, ozone, sodium chlorite, sodium chlorate, sodium hypochlorite, perchloric acid and sodium metaperiodate.
6. the method for preparation vascular plant Quito hole oxidation polymerization chelate adsorption according to claim 2, it is characterised in that: the described silane coupler with double bond is at least one in CY-570, CY-571, CY-AGE, CY-3031; Vascular plant volume mass ratio after the described silane coupler with double bond and oxidation is for 1:0.3～1.
7. the method for preparation vascular plant Quito hole oxidation polymerization chelate adsorption according to claim 2, it is characterised in that: described Raolical polymerizable condition is: under protective atmosphere, reacts 6～12h at 60～80 DEG C of temperature; The mass ratio of the quality of acrylonitrile and the vascular plant being grafted with double bond is 6～10:1; The quality of initiator is the 0.1%～0.8% of acrylonitrile quality; Described initiator is at least one in sulfate, alkyl peroxide, azodiisobutyronitrile, peroxidating two acyl, alkyl peroxide thing, peroxyester.
8. the method for preparation vascular plant Quito hole oxidation polymerization chelate adsorption according to claim 2, it is characterized in that: the described vascular plant being grafted with polyacrylonitrile is mixed with free hydroxylamine solution, it is 6.0～6.8 at pH, when temperature is 60～80 DEG C, reaction 3～8h, obtains vascular plant Quito hole oxidation polymerization chelate adsorption.
9. the method for preparation vascular plant Quito hole oxidation polymerization chelate adsorption according to claim 8, it is characterised in that: free hydroxylamine solution is obtained by reacting by hydroxylamine hydrochloride solution and sodium carbonate liquor.
10. the application of the vascular plant Quito hole oxidation polymerization chelate adsorption described in claim 1, it is characterised in that: it is applied to remove heavy metal in waste water or thorium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610013491.2A CN105664864B (en) | 2016-01-08 | 2016-01-08 | A kind of preparation method of vascular plant Quito hole oxidation polymerization chelate adsorption and application |
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