CN107790104B - Heavy metal available state adsorbed film based on EDTA modified material and preparation method thereof - Google Patents
Heavy metal available state adsorbed film based on EDTA modified material and preparation method thereof Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
The present invention provides a kind of heavy metal available state adsorbed film and preparation method thereof based on EDTA modified material belongs to heavy metal available state absorption detection technique field, comprising the following steps: preparation ZnAl-EDTA modified material；Prepare acrylamide gel solution；It takes EDTA modified material and acrylamide gel solution to be mixed, obtains modified propylene acrylamide gel solution；It takes tetramethylethylenediamine solution and ammonium persulfate solution to be added in modified propylene acrylamide gel solution, mixes in implantation glass plate, glass plate is moved in incubator and is cultivated, the modified propylene acrylamide gel film between two glass plates is taken out in pure water, be hydrated.Absorption film properties provided by the invention are stablized, at low cost, and adsorption rate is high, and large amount of adsorption, adsorption rate is fast, and desorption efficiency is high, and secondary pollution is not generated in preparation process；The various heavies available state such as Cd, Pb, Ni, Cu, As can be adsorbed simultaneously, it is good to trace element adsorption effect, be conducive to the popularization and application of technology.
Description
Technical field
The present invention relates to heavy metal available state absorption detection technique fields more particularly to a kind of based on EDTA modified material
Heavy metal available state adsorbed film and preparation method thereof.
Background technique
Heavy metal pollution of soil not only generates harm to ecological environment, but also can be detrimental to health by food chain,
Environmental behaviour and the ecological effect for grasping heavy metal in soil are particularly important for environmental protection, and the total amount of heavy metal in soil
Its environmental behaviour and ecological effect can not be determined completely, and existing forms and form ratio, which are only, determines its Environmental Chemistry process
And the key factor of biological effectiveness, Speciation Analysis of Heavy Metals technology should agree with biological effectiveness, can accurately mention
Bio-toxicity and biological effectiveness information for the heavy metal of chemical form.Currently, the measurement side of traditional heavy metal available state
Method needs complicated pretreatment, and manual operation is complicated, and sample collection procedure will affect the form and distribution of heavy metal in sample, from
And it be easy to cause analytical error.
Passive sampling technology in situ can collect mesh under the premise of not influencing mother solution concentration and ambient enviroment online
Mark monitoring substance, the concentration for the monitored substance being accumulated in sampler can really reflect that it is true in tested systems
Concentration either time mean concentration, the influence so as to avoid sample collection process to Heavy Metals in sample and distribution.
Diffusive gradients in thin-films (Diffusive gradients in thin films, DGT) technology is in passive sampling technology in situ
One kind, DGT technology being capable of in situ quantitation accumulation and measurement soil, water, heavy metal, nutrient (S, P) in the environment such as deposit
The new method of available state or Manual Suture.
DGT technology is a kind of dynamics sampling technique, using the Fick First Law for describing stable state diffusion as theoretical basis, is led to
The certain thickness diffusion for penetrating into ion is crossed mutually to separate ion exchange resin and solution, it is free using diffusion phase control ion
Diffusion process accomplishes quantitative accumulation and measurement to monitored substance available state, and DGT technology is commonly in conjunction with phase material at present
Chelex-100, such material needs import, expensive and consuming time, and domestic combination phase material can only be to a certain kind
Or two heavy metal species available state adsorbed, various heavy available state cannot be adsorbed simultaneously, and to the trace in environment
Element adsorption effect is poor, becomes time-consuming expense for the quantitative accumulation and measurement of heavy metal available state in pollution complex environment
Power.
Summary of the invention
The purpose of the present invention is to provide adsorbed film and its preparations that one kind can adsorb various heavy available state simultaneously
Method, it is at high cost to solve existing combination phase material in above-mentioned background technique, can only the one or two kinds of heavy metals of specific absorption have
State is imitated, poor to trace element adsorption effect, for polluting complex environment, heavy metal available state, which adsorbs time-consuming and laborious technology, is asked
Topic.
To achieve the goals above, this invention takes following technical solutions:
A kind of heavy metal available state adsorbed film based on EDTA modified material, the constituent of the adsorbed film include:
ZnAl-EDTA modified material, crosslinking agent, acrylamide gel.
Further, the crosslinking agent is modified agarose.
Further, the ZnAl-EDTA modified material is prepared as follows: taking in molar ratio for the ratio of 2:1 suitable
Zinc nitrate and aluminum nitrate are measured, is added in appropriate pure water, is uniformly mixed, obtains solution A；In molar ratio by EDTA and sodium hydroxide
It is added in appropriate pure water for the ratio of 0.25:7~8.4, is uniformly mixed, obtains solution B；Solution B is added in solution A,
It is uniformly mixed, adjusting solution PH with the NaOH solution of 1mol/L is 12, and 20~30min, 60~80min of aging is sufficiently stirred, takes out
Filter, freeze drier is dry, grinds to obtain white powder of the partial size less than 75 μm, and hermetically drying saves modified to get ZnAl-EDTA
Material.
The preparation method of the invention further relates to a kind of heavy metal available state adsorbed film based on EDTA modified material, including with
Lower step:
Step S110: preparation ZnAl-EDTA modified material；
Step S120: crosslinking agent is added in pure water, stirs into uniform solution under the conditions of 60 DEG C of temperature, is added certain
Acrylamide is measured, uniform solution is stirred into, acrylamide gel solution is made；
Step S130: the acrylamide gel of the ZnAl-EDTA modified material and certain volume that take certain mass respectively is molten
10~15min is mixed in liquid, so that ZnAl-EDTA modified material is uniformly dispersed in acrylamide gel solution, must be modified third
Acrylamide gel solution；
Step S140: the pure solution of the tetramethylethylenediamine of certain volume and 10% ammonium persulfate solution is taken to be added to step
In modified propylene acrylamide gel solution made from S131, slowly rocking is uniformly mixed solution, and mixed solution is injected added with U-shaped
In the glass plate of plastic spacer, glass plate is moved in 42~46 DEG C of incubator, cultivates 45~60min, obtain modified propylene acyl
Amine gel film；
Step S150: taking out the modified propylene acrylamide gel film between two glass plates in pure water, hydration for 24 hours, during which changes water 2
~3 times, the heavy metal available state adsorbed film based on EDTA modified material is made.
Further, the step of preparation EDTA modified material includes:
Step S111: taking appropriate zinc nitrate and aluminum nitrate in molar ratio for the ratio of 2:1, is added in appropriate pure water, mixes
It closes uniformly, obtains solution A；
Step S112: the ratio that EDTA and sodium hydroxide are 0.25:7~8.4 in molar ratio is added in appropriate pure water,
It is uniformly mixed, obtains solution B；
Step S113: solution B is added in solution A, is uniformly mixed, and is adjusted solution PH with the NaOH solution of 1mol/L and is
12,20~30min, 60~80min of aging is sufficiently stirred, filters, freeze drier is dry, grind partial size is white less than 75 μm
Color powder, hermetically drying save to get EDTA modified material.
Further, which is characterized in that the molar ratio of the EDTA and the aluminum nitrate is 0.25:1, the sodium hydroxide
Molar ratio with the aluminum nitrate is 7~8.4:1.
Further, the ratio between the quality of the crosslinking agent, the quality of acrylamide, volume of pure water are W (crosslinking agent): W
(acrylamide): V (pure water)=0.3~0.5:15:100.
Further, the crosslinking agent is modified agarose, the method for modifying of the modified agarose are as follows:
Step 1: dissolving by heating agarose: weighing 10g agarose, be added in the boiling water of 490ml and dissolve, and keep 80
DEG C heat preservation；
Step 2: quaternization: weighing 1.67g sodium borohydride and be dissolved in the sodium hydroxide solution of 10ml14mol/L, then
It is added in the agarose solution of step 1, is stirred continuously, sufficiently react；
Step 3: modified-reaction: the sodium hydroxide solution of 100ml10% being added in the solution of step 2, and at 15 points
25ml allyl glycidyl ether is added dropwise in clock, after 1 hour, the allyl of same volume is added dropwise again in 15 minutes
Base glycidol ether reacts 1 hour；
Step 4: neutralizing drying: the solution of step 3 is cooled to 60 DEG C, be added 4mol/l acetum adjust pH value to
6.5~7.5, acetone soln is added and cleans repeatedly, it is dry, it grinds to get modified agarose.
Further, in the step S130, the quality of the EDTA modified material and the body of acrylamide gel solution
The ratio between product is 3~4:10.
Further, in the step S140, the tetramethylethylenediamine solution and the modified propylene acrylamide gel are molten
The volume ratio of liquid is 1:400, and the volume ratio of the ammonium persulfate solution and the modified propylene acrylamide gel solution is 7:1000.
The invention has the advantages that: EDTA modified material performances provided by the invention to stablize, at low cost, easily prepared, with biography
System chelex-100 absorption resin material is compared, and higher to heavy metal available state adsorption rate, adsorbance is bigger, and adsorption rate is more
Fastly, desorption efficiency is higher, and secondary pollution is not generated in preparation process；Adsorbed film of the invention can adsorb simultaneously Cd, Pb, Ni,
The various heavies available state such as Cu, As, and fast, large amount of adsorption, desorption efficiency height is adsorbed, be conducive to the popularization and application of technology.
The additional aspect of the present invention and advantage will be set forth in part in the description, these will become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill of field, without creative efforts, it can also be obtained according to these attached drawings others
Attached drawing.
Fig. 1 is that the heavy metal available state described in the embodiment of the present invention based on EDTA modified material adsorbs membrane preparation method stream
Cheng Tu.
Fig. 2 is the heavy metal available state adsorbed film electron-microscope scanning based on EDTA modified material described in the embodiment of the present invention
Figure.
Fig. 3 is EDTA modified material preparation method flow chart described in the embodiment of the present invention.
Fig. 4 is the method for modifying flow chart of modified agarose described in the embodiment of the present invention.
Fig. 5 be the embodiment of the present invention described in based on the heavy metal available state adsorbed film of EDTA modified material to Ni, Cu,
The adsorbance of five heavy metal species available state of Cd, As, Pb with solution concentration variation diagram.
Fig. 6 is the heavy metal available state adsorbed film DGT combination phase based on EDTA modified material described in the embodiment of the present invention
Device uses structural schematic diagram.
Fig. 7 be the embodiment of the present invention described in based on the heavy metal available state adsorbed film of EDTA modified material to Ni, Cu,
The schematic diagram of five heavy metal species available state adsorption rate of Cd, As, Pb.
Fig. 8 be the embodiment of the present invention described in based on the heavy metal available state adsorbed film of EDTA modified material to Ni, Cu,
The schematic diagram of five heavy metal species available state desorption efficiency of Cd, As, Pb.
Wherein: 1- shell；2- adsorbed film；3- spreads phase；4- filter membrane.
Specific embodiment
Embodiments of the present invention are described below in detail, the example of the embodiment is shown in the accompanying drawings, wherein from beginning
Same or similar element or element with the same or similar functions are indicated to same or similar label eventually.Below by ginseng
The embodiment for examining attached drawing description is exemplary, and for explaining only the invention, and is not construed as limiting the claims.
Those skilled in the art of the present technique are appreciated that unless expressly stated, singular " one " used herein, " one
It is a ", " described " and "the" may also comprise plural form.It is to be further understood that being arranged used in specification of the invention
Diction " comprising " refer to that there are the feature, integer, step, operation, element and/or component, but it is not excluded that in the presence of or addition
Other one or more features, integer, step, operation, element, component and/or their group.
Those skilled in the art of the present technique are appreciated that unless otherwise defined, all terms used herein (including technology art
Language and scientific term) there is meaning identical with the general understanding of those of ordinary skill in fields of the present invention.Should also
Understand, those terms such as defined in the general dictionary, which should be understood that, to be had and the meaning in the context of the prior art
The consistent meaning of justice, and unless defined as here, it will not be explained in an idealized or overly formal meaning.
In order to facilitate understanding of embodiments of the present invention, below in conjunction with attached drawing by taking specific embodiment as an example to the present invention do into
The explanation of one step, and embodiment does not constitute the restriction to the embodiment of the present invention.
Fig. 1 is that the heavy metal available state described in the embodiment of the present invention based on EDTA modified material adsorbs membrane preparation method stream
Cheng Tu, Fig. 2 are the heavy metal available state adsorbed film electron-microscope scanning figure based on EDTA modified material described in the embodiment of the present invention
(500 times), Fig. 3 are EDTA modified material preparation method flow chart described in the embodiment of the present invention, and Fig. 4 is institute of the embodiment of the present invention
The method of modifying flow chart for the modified agarose stated, Fig. 5 are the huge sum of money based on EDTA modified material described in the embodiment of the present invention
Belong to variation diagram of the available state adsorbed film to the adsorbance of five heavy metal species available state of Ni, Cu, Cd, As, Pb with solution concentration, Fig. 6
Structure is used for the heavy metal available state adsorbed film DGT combination phase device described in the embodiment of the present invention based on EDTA modified material
Schematic diagram, Fig. 7 be the embodiment of the present invention described in based on the heavy metal available state adsorbed film of EDTA modified material to Ni, Cu, Cd,
The schematic diagram of five heavy metal species available state adsorption rate of As, Pb, Fig. 8 are described in the embodiment of the present invention based on EDTA modified material
Schematic diagram of the heavy metal available state adsorbed film to five heavy metal species available state desorption efficiency of Ni, Cu, Cd, As, Pb.
Those of ordinary skill in the art will appreciate that: attached drawing is the schematic diagram of one embodiment, module in attached drawing or
Process is not necessarily implemented necessary to the present invention.
As shown in figure 3, the embodiment of the invention provides a kind of heavy metal available state adsorbed film based on EDTA modified material,
The material composi of the adsorbed film includes: ZnAl-EDTA modified material, crosslinking agent, acrylamide gel.The adsorbed film is
Be uniformly distributed in the polyacrylamide gel film of ZnAl-EDTA modified material, the adsorbed film can adsorb simultaneously Ni, Cu, Cd,
The available state of five heavy metal species of As, Pb, the absorption of various heavy available state suitable for water body, soil, deposit.
Above-mentioned ZnAl-EDTA modified material, partial size is less than 75 μm, and the partial size of modified material is smaller, in gel solution more
Uniform suspension easy to form, in this way made of in adsorbed film sorbent material be more evenly distributed, so that contact area is bigger,
Adsorption rate is higher, and desorption effect is also more preferable.The ZnAl-EDTA modified material the preparation method is as follows:
Appropriate zinc nitrate and aluminum nitrate are taken for the ratio of 2:1 in molar ratio, is added in appropriate pure water, is uniformly mixed, obtains
To solution A；The ratio that EDTA and sodium hydroxide are 0.25:7~8.4 in molar ratio is added in appropriate pure water, is uniformly mixed,
Obtain solution B；Solution B is added in solution A, is uniformly mixed, is with the PH that the NaOH solution of 1mol/L adjusts mixed solution
12,20~30min, 60~80min of aging is sufficiently stirred, filters, freeze drier is dry, grind partial size is white less than 75 μm
Color powder, hermetically drying save to get EDTA modified material.
The molar ratio of the EDTA and the aluminum nitrate is 0.25:1, the molar ratio of the sodium hydroxide and the aluminum nitrate
For 7~8.4:1.
EDTA modified material provided in an embodiment of the present invention to heavy metal average adsorption rate 85% or more, 1mol/L nitre
Sour desorption efficiency is average 85% or more, and compared with traditional chelex-100 adsorbs resin material, adsorption rate is higher, and adsorption rate is more
Fastly, desorption efficiency is higher.
As shown in Figure 1 to Figure 2, a kind of heavy metal available state suction based on EDTA modified material described in the embodiment of the present invention
Membrane preparation method, comprising the following steps: preparation ZnAl-EDTA modified material；Crosslinking agent is added in pure water, 60 DEG C of temperature
Under the conditions of stir into uniform solution, add a certain amount of acrylamide, stir into uniform solution, be made acrylamide gel it is molten
Liquid；Take respectively certain mass ZnAl-EDTA modified material and certain volume acrylamide gel solution be mixed 10~
15min makes ZnAl-EDTA modified material be uniformly dispersed in acrylamide gel solution, obtains modified propylene acrylamide gel solution；
The pure solution of the tetramethylethylenediamine of certain volume and 10% ammonium persulfate solution is taken to be added to modified propylene made from step S131
In acrylamide gel solution, slowly rocking is uniformly mixed solution, by mixed solution injection added with the glass plate of U-shaped plastic spacer
In, glass plate is moved in 42~46 DEG C of incubator, cultivates 45~60min, obtain modified propylene acrylamide gel film；In pure water
The modified propylene acrylamide gel film between two glass plates is taken out, hydration for 24 hours, is during which changed water 2~3 times, is made modified based on EDTA
The heavy metal available state adsorbed film of material.
Wherein, the ratio between the quality of EDTA modified material and the volume of acrylamide gel solution are 3~4:10.The tetramethyl
The volume ratio of base ethylenediamine solution and the modified propylene acrylamide gel solution is 1:400, the ammonium persulfate solution with it is described
The volume ratio of modified propylene acrylamide gel solution is 7:1000.
In a specific embodiment of the present invention, the step of preparing acrylamide gel solution includes: that will be crosslinked
Agent is added in pure water, is stirred into uniform solution under the conditions of 60 DEG C of temperature, is added a certain amount of acrylamide, is stirred into uniform molten
Liquid, the ratio between the quality of the crosslinking agent, the quality of acrylamide, volume of pure water are W (crosslinking agent): W (acrylamide): V is (pure
Water)=0.3~0.5:15:100.
As shown in figure 4, in one particular embodiment of the present invention, being used to prepare the crosslinking agent of acrylamide gel solution
For modified agarose crosslinking agent, the method for modifying of the modified agarose are as follows:
Step 1: dissolving by heating agarose: weighing the agarose of certain mass, be added to molten in the boiling water of certain volume
Solution, and keep 80 DEG C of heat preservations；
Step 2: quaternization: weighing certain mass sodium borohydride and be dissolved in the sodium hydroxide solution one of 14mol/L, so
It is added in the agarose solution of step 1, is stirred continuously afterwards, sufficiently react；
Step 3: modified-reaction: 10% sodium hydroxide solution two being added in the solution of step 2, and in 15 minutes
The allyl glycidyl ether of certain volume is added dropwise, after 1 hour, the alkene of same volume is added dropwise again in 15 minutes
Propyl glycidyl ether is reacted 1 hour；
Step 4: neutralizing drying: the solution of step 3 is cooled to 60 DEG C, be added 4mol/l acetum adjust pH value to
6.5~7.5, acetone soln is added and cleans repeatedly, it is dry, it grinds to get modified agarose.
In the step 1, the quality of the agarose is 10g, and the volume of the boiling water is 490ml.
In the step 2, the quality of the sodium borohydride is 1.67g, and the volume of the sodium hydroxide solution one is
10ml；In the step 3, the volume of the sodium hydroxide solution two is 100ml, the volume of the acrylic glycidol ether
For 25ml.
It will be appreciated to those of skill in the art that the above-mentioned heavy metal available state adsorbed film based on EDTA modified material
Preparation flow step is not limited by the sequence of above-mentioned steps, other sequences that those skilled in the art are expected, in this hair
Within bright protection scope.
As shown in fig. 6, adsorbed film described in the embodiment of the present invention is cut into the disk that diameter is 1.9cm, it is placed in DGT device
In, the DGT device includes outmost round plastic shell 1, and 1 one end of shell is equipped with opening, and opening is covered with one layer of filter membrane 4
Lid, to prevent causing mechanical failure and biological pollution to gel, 4 later layer of filter membrane is diffusion phase 3, and diffusion phase 3 is used to control survey
Determine the diffusion flux of component, heavy metal ion reaches adsorbed film 2 by filter membrane 4 and diffusion phase 3 and is fixed against.By ZnAl-
EDTA-LDHs adsorbed film is placed in 10ml centrifuge tube, be added five heavy metal species content of 5mlNi, Cu, Cd, As, Pb be 5,20,
50, the NaNO of the 0.01mol/L of 200,500,1000ug/L3Solution shakes for 24 hours at 25 DEG C, under the conditions of 130r/min, takes out and inhale
Membrane divides solution after taking 1ml to adsorb, uses 1%HNO3Constant volume is to 10ml, solution heavy metal concentration before and after ICP-MS measurement absorption,
Adsorption rate is calculated, obtains the adsorption rate of five heavy metal species available state of Ni, Cu, Cd, As, Pb as shown in fig. 7, each concentration does 3
In parallel, while 1ml stoste 1%HNO is taken3Constant volume measures original liquid concentration to 10ml.By above-mentioned adsorbed film be transferred to another 10ml from
The HNO of 2ml1mol/L is added in heart pipe3, under normal temperature condition, desorption for 24 hours, point takes 1ml stripping liquid, pure water constant volume to 10ml,
ICP-MS measures solution heavy metal concentration, calculates desorption efficiency, obtains the desorption of five heavy metal species available state of Ni, Cu, Cd, As, Pb
Rate is as shown in Figure 8.
As shown in figure 5, under the conditions of various concentration the five heavy metal species available state such as Ni, Cu, Cd, As, Pb average adsorption rate
It is 85%, the average adsorption rate of the five heavy metal species available state such as solution Ni, Cu, Cd, As, Pb of 200ppb or less concentration reaches
90%, it is eluted with 1mol/L nitric acid solution, the average elution rate of the five heavy metal species available state such as Ni, Cu, Cd, As, Pb is equal
85% or more, illustrate that adsorbed film of the present invention can adsorb various heavy available state simultaneously.(a) is adsorbed film to a huge sum of money in Fig. 5
Belong to the adsorbance of Ni ion with the variation diagram of solution concentration, (b) is that adsorbed film is dense with solution to the adsorbance of heavy metal As ion
The variation diagram of degree, (c) for adsorbed film to the adsorbance of heavy metal Cd ion with the variation diagram of solution concentration, (d) be adsorbed film pair
The adsorbance of heavy metal Cu ion with solution concentration variation diagram, (e) for adsorbed film to the adsorbance of heavy metal Pb ion with molten
The variation diagram of liquid concentration.As shown in Figure 7, it in the case where the five heavy metal species ion concentration such as Ni, Cu, Cd, As, Pb is few, inhales
For attached rate close to 1, adsorbed film described in the embodiment of the present invention has higher adsorption rate to the trace element in environment.
In conclusion the present invention is by providing a kind of heavy metal available state absorption film preparation side based on EDTA modified material
Method, is made a kind of heavy metal available state adsorbed film based on EDTA modified material, the adsorbed film can adsorb simultaneously Ni, Cu, Cd,
The various heavies available state such as As, Pb, adsorption rate is high compared with traditional chelex-100 adsorbs resin material, and absorption is fast, inhales
Attached amount is bigger, and secondary pollution is not generated in preparation process, and manufacturing cost is low, and desorption efficiency is high.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with scope of protection of the claims
Subject to.
Claims (8)
1. a kind of heavy metal available state adsorbed film based on EDTA modified material, which is characterized in that the heavy metal available state is inhaled
The preparation method of membrane is as follows；
Step S110: preparation ZnAl-EDTA modified material；
Appropriate zinc nitrate and aluminum nitrate are taken for the ratio of 2:1 in molar ratio, is added in appropriate pure water, is uniformly mixed, obtains molten
Liquid A；
The ratio that EDTA and sodium hydroxide are 0.25:7~8.4 in molar ratio is added in appropriate pure water, is uniformly mixed, obtains
Solution B；
Solution B is added in solution A, is uniformly mixed, adjusting solution PH with the NaOH solution of 1mol/L is 12, is sufficiently stirred 20
~30min, 60~80min of aging are filtered, and freeze drier is dry, grind to obtain white powder of the partial size less than 75 μm, and sealing is dry
Dry preservation is to get EDTA modified material；
Step S120: crosslinking agent is added in pure water, is stirred into uniform solution under the conditions of 60 DEG C of temperature, is added a certain amount of third
Acrylamide stirs into uniform solution, and acrylamide gel solution is made；
Step S130: the acrylamide gel solution of the ZnAl-EDTA modified material and certain volume that take certain mass respectively is mixed
10~15min of stirring is closed, so that ZnAl-EDTA modified material is uniformly dispersed in acrylamide gel solution, obtains modified propylene acyl
Amine gel solution；
Step S140: the pure solution of the tetramethylethylenediamine of certain volume and 10% ammonium persulfate solution is taken to be added to step S130 system
In the modified propylene acrylamide gel solution obtained, slowly rocking is uniformly mixed solution, and mixed solution is injected added with U-shaped plastic mattress
In the glass plate of piece, glass plate is moved in 42~46 DEG C of incubator, cultivates 45~60min, obtain modified propylene acrylamide gel
Film；
Step S150: taking out the modified propylene acrylamide gel film between two glass plates in pure water, hydration for 24 hours, during which changes water 2~3
It is secondary, the heavy metal available state adsorbed film based on EDTA modified material is made.
2. the heavy metal available state adsorbed film according to claim 1 based on EDTA modified material, which is characterized in that described
Crosslinking agent is modified agarose.
3. a kind of preparation method of heavy metal available state adsorbed film of any one of such as claims 1 or 2 based on EDTA modified material,
Characterized by comprising the following steps:
Step S110: preparation ZnAl-EDTA modified material, steps are as follows:
Appropriate zinc nitrate and aluminum nitrate are taken for the ratio of 2:1 in molar ratio, is added in appropriate pure water, is uniformly mixed, obtains molten
Liquid A；
The ratio that EDTA and sodium hydroxide are 0.25:7~8.4 in molar ratio is added in appropriate pure water, is uniformly mixed, obtains
Solution B；
Solution B is added in solution A, is uniformly mixed, adjusting solution PH with the NaOH solution of 1mol/L is 12, is sufficiently stirred 20
~30min, 60~80min of aging are filtered, and freeze drier is dry, grind to obtain white powder of the partial size less than 75 μm, and sealing is dry
Dry preservation is to get EDTA modified material；
Step S120: crosslinking agent is added in pure water, is stirred into uniform solution under the conditions of 60 DEG C of temperature, is added a certain amount of third
Acrylamide stirs into uniform solution, and acrylamide gel solution is made；
Step S130: the acrylamide gel solution of the ZnAl-EDTA modified material and certain volume that take certain mass respectively is mixed
10~15min of stirring is closed, so that ZnAl-EDTA modified material is uniformly dispersed in acrylamide gel solution, obtains modified propylene acyl
Amine gel solution；
Step S140: the pure solution of the tetramethylethylenediamine of certain volume and 10% ammonium persulfate solution is taken to be added to step S130 system
In the modified propylene acrylamide gel solution obtained, slowly rocking is uniformly mixed solution, and mixed solution is injected added with U-shaped plastic mattress
In the glass plate of piece, glass plate is moved in 42~46 DEG C of incubator, cultivates 45~60min, obtain modified propylene acrylamide gel
Film；
Step S150: taking out the modified propylene acrylamide gel film between two glass plates in pure water, hydration for 24 hours, during which changes water 2~3
It is secondary, the heavy metal available state adsorbed film based on EDTA modified material is made.
4. the heavy metal available state according to claim 3 based on EDTA modified material adsorbs membrane preparation method, feature
It is, the molar ratio of the EDTA and the aluminum nitrate is 0.25:1, and the molar ratio of the sodium hydroxide and the aluminum nitrate is 7
~8.4:1.
5. the heavy metal available state according to claim 3 based on EDTA modified material adsorbs membrane preparation method, feature
It is, the ratio between the quality of the crosslinking agent, the quality of acrylamide, volume of pure water are W (crosslinking agent): W (acrylamide): V
(pure water)=0.3~0.5:15:100.
6. the heavy metal available state according to claim 5 based on EDTA modified material adsorbs membrane preparation method, feature
It is, the crosslinking agent is modified agarose, the method for modifying of the modified agarose are as follows:
Step 1: dissolving by heating agarose: weighing 10g agarose, be added in the boiling water of 490ml and dissolve, and keep 80 DEG C of guarantors
Temperature；
Step 2: quaternization: weighing 1.67g sodium borohydride and be dissolved in the sodium hydroxide solution of 10ml14mol/L, be then added
It into the agarose solution of step 1, is stirred continuously, sufficiently reacts；
Step 3: modified-reaction: the sodium hydroxide solution of 100ml10% being added in the solution of step 2, and in 15 minutes
25ml allyl glycidyl ether is added dropwise, after 1 hour, the allyl contracting of same volume is added dropwise again in 15 minutes
Water glycerin ether reacts 1 hour；
Step 4: neutralizing drying: the solution of step 3 being cooled to 60 DEG C, 4mol/l acetum is added and adjusts pH value to 6.5
~7.5, acetone soln is added and cleans repeatedly, it is dry, it grinds to get modified agarose.
7. the heavy metal available state according to claim 3 based on EDTA modified material adsorbs membrane preparation method, feature
Be: in the step S130, the ratio between quality and the volume of acrylamide gel solution of the EDTA modified material are 3~4:
10。
8. the heavy metal available state according to claim 3 based on EDTA modified material adsorbs membrane preparation method, feature
Be: in the step S140, the volume ratio of the tetramethylethylenediamine solution and the modified propylene acrylamide gel solution is
The volume ratio of 1:400, the ammonium persulfate solution and the modified propylene acrylamide gel solution is 7:1000.
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