CN107790104A - Based on heavy metal available state adsorbed film material modified EDTA and preparation method thereof - Google Patents
Based on heavy metal available state adsorbed film material modified EDTA 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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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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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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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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Abstract
The invention provides a kind of heavy metal available state adsorbed film material modified based on EDTA and preparation method thereof, belongs to heavy metal available state absorption detection technique field, comprises the following steps：It is material modified to prepare ZnAl EDTA；Prepare acrylamide gel solution；Take EDTA material modified and acrylamide gel solution mixes, obtain modified propylene acrylamide gel solution；Take tetramethylethylenediamine solution and ammonium persulfate solution to be added in modified propylene acrylamide gel solution, mix in implantation glass plate, glass plate is moved in incubator and cultivated, the modified propylene acrylamide gel film between two glass plates is taken out in pure water, be hydrated.Adsorbed film stable performance provided by the invention, cost is low, and adsorption rate is high, and adsorbance is big, and adsorption rate is fast, and desorption efficiency is high, and secondary pollution is not produced in preparation process；The various heavy available state such as Cd, Pb, Ni, Cu, As can be adsorbed simultaneously, to trace element advantages of good adsorption effect, be advantageous to the popularization and application of technology.
Description
Technical field
The present invention relates to heavy metal available state to adsorb detection technique field, more particularly to a kind of material modified based on EDTA
Heavy metal available state adsorbed film and preparation method thereof.
Background technology
Heavy metal pollution of soil not only produces harm to ecological environment, but also can be detrimental to health by food chain,
It is particularly important for environmental protection to grasp environmental behaviour and the ecological effect of heavy metal in soil, and the total amount of heavy metal in soil
Its environmental behaviour and ecological effect can not be determined completely, and its 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 carry
Bio-toxicity and biological effectiveness information for the heavy metal of chemical form.At present, the measure side of traditional heavy metal available state
Method needs complicated pretreatment, and manual operation is complicated, and sample collection procedure can influence the form of heavy metal and distribution in sample, from
And easily cause analytical error.
Passive sampling technology in situ can collect mesh online on the premise of mother solution concentration and surrounding environment is not influenceed
Mark monitoring material, the concentration for the monitored material being accumulated in sampler can truly reflect that it is true in tested systems
Concentration either time mean concentration, so as to avoid sample collection process to Heavy Metals in sample and the influence of distribution.
Diffusive gradients in thin-films (Diffusive gradients in thin films, DGT) technology is in passive sampling technology in situ
One kind, DGT technologies being capable of heavy metal, nutrients (S, P) in situ quantitation accumulation and measurement soil, water, the environment such as deposit
The new method of available state or Manual Suture.
DGT technologies are a kind of dynamics Sampling techniques, using the Fick First Laws for describing stable state diffusion as theoretical foundation, are led to
The certain thickness diffusion for penetrating into ion is crossed mutually to separate ion exchange resin and solution, it is free using phase control ion is spread
Diffusion process, accomplish quantitative accumulation and measurement to being monitored material available state, the conventional combination phase material of DGT technologies is at present
Chelex-100, such a 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, it is impossible to while adsorb various heavy available state, and to the trace in environment
Element adsorption effect is poor, and the quantitative accumulation and measurement for heavy metal available state in pollution complex environment become time-consuming expense
Power.
The content of the invention
It is an object of the invention to provide a kind of adsorbed film and its preparation that can adsorb various heavy available state simultaneously
Method, to solve existing combination phase material cost height in above-mentioned background technology, specific can only adsorb one or two kinds of heavy metals has
State is imitated, poor to trace element adsorption effect, for polluting complex environment, the technology that the absorption of heavy metal available state is wasted time and energy is asked
Topic.
To achieve these goals, this invention takes following technical scheme：
A kind of heavy metal available state adsorbed film material modified based on EDTA, the constituent of the adsorbed film include：
ZnAl-EDTA is material modified, crosslinking agent, acrylamide gel.
Further, the crosslinking agent is modified agarose.
Further, the ZnAl-EDTA is material modified is prepared as follows：It is 2 in molar ratio：1 ratio takes suitable
Zinc nitrate and aluminum nitrate are measured, is added in appropriate pure water, is well mixed, obtains solution A；By EDTA and sodium hydroxide in molar ratio
For 0.25：7~8.4 ratio is added in appropriate pure water, is well mixed, is obtained solution B；Solution B is added in solution A,
It is well mixed, it is 12 with 1mol/L NaOH solution regulation solution PH, is sufficiently stirred 20~30min, 60~80min of aging, takes out
Filter, freeze drier are dried, and are ground to obtain white powder of the particle diameter less than 75 μm, hermetically drying preservation, are produced ZnAl-EDTA modifications
Material.
The invention further relates to a kind of preparation method of the heavy metal available state adsorbed film material modified based on EDTA, including with
Lower step：
Step S110：It is material modified to prepare ZnAl-EDTA；
Step S120：Crosslinking agent is added in pure water, uniform solution is stirred under 60 DEG C of temperature conditionss, is added certain
Acrylamide is measured, stirs into uniform solution, acrylamide gel solution is made；
Step S130：Take the ZnAl-EDTA of certain mass material modified molten with the acrylamide gel of certain volume respectively
Liquid mixes 10~15min, makes ZnAl-EDTA material modified and is uniformly dispersed in acrylamide gel solution, must be modified third
Acrylamide gel solution；
Step S140：The pure solution of tetramethylethylenediamine and 10% ammonium persulfate solution for taking certain volume are added to step
In modified propylene acrylamide gel solution made from S131, slowly rocking is well 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, cultivate 45~60min, obtain modified propylene acyl
Amine gel film；
Step S150：The modified propylene acrylamide gel film between two glass plates is taken out in pure water, 24h is hydrated, during which changes water 2
~3 times, it is made based on heavy metal available state adsorbed film material modified EDTA.
Further, the material modified steps of EDTA that prepare include：
Step S111：It is 2 in molar ratio：1 ratio takes appropriate zinc nitrate and aluminum nitrate, is added in appropriate pure water, mixes
Close uniformly, obtain solution A；
Step S112：It is 0.25 in molar ratio by EDTA and sodium hydroxide：7~8.4 ratio is added in appropriate pure water,
It is well mixed, obtain solution B；
Step S113：Solution B is added in solution A, is well mixed, is with 1mol/L NaOH solution regulation solution PH
12, be sufficiently stirred 20~30min, 60~80min of aging, filter, freeze drier is dried, grind particle diameter is white less than 75 μm
Color powder, hermetically drying preserve, and it is material modified to produce EDTA.
Further, it is characterised in that the mol ratio of the EDTA and the aluminum nitrate is 0.25：1, the sodium hydroxide
Mol 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, described crosslinking agent is modified agarose, and the method for modifying of the modified agarose is：
Step 1: dissolve by heating agarose：10g agaroses are weighed, is added in 490ml boiling water and dissolves, and keep 80
DEG C insulation；
Step 2: quaternization：Weigh 1.67g sodium borohydrides to be dissolved in 10ml14mol/L sodium hydroxide solution, then
It is added in the agarose solution of step 1, is stirred continuously, fully reaction；
Step 3: modified-reaction：100ml10% sodium hydroxide solution is added in the solution of step 2, and at 15 points
25ml allyl glycidyl ethers are added dropwise in clock, after 1 hour, the allyl of same volume was added dropwise again in 15 minutes
Base glycidol ether, react 1 hour；
Step 4: neutralize drying：The solution of step 3 is cooled to 60 DEG C, add 4mol/l acetums adjust pH value to
6.5~7.5, add acetone soln and clean repeatedly, dry, grinding, produce modified agarose.
Further, in the step S130, the quality material modified EDTA 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, the volume ratio of the ammonium persulfate solution and the modified propylene acrylamide gel solution is 7:1000.
Beneficial effect of the present invention：The material modified stable performances of EDTA provided by the invention, cost is low, easily prepared, with biography
System chelex-100 polymeric adsorbent materials are compared, and heavy metal available state adsorption rate is higher, and adsorbance is bigger, and adsorption rate is more
It hurry up, desorption efficiency is higher, and secondary pollution is not produced in preparation process；The present invention adsorbed film can adsorb simultaneously Cd, Pb, Ni,
The various heavy available state such as Cu, As, and absorption is fast, adsorbance is big, desorption efficiency is high, is advantageous 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, and these will become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Accompanying drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for this
For the those of ordinary skill of field, on the premise of not paying creative work, it can also be obtained according to these accompanying drawings other
Accompanying drawing.
Fig. 1 is that the heavy metal available state material modified based on EDTA described in the embodiment of the present invention adsorbs membrane preparation method stream
Cheng Tu.
Fig. 2 is the heavy metal available state adsorbed film electron-microscope scanning material modified based on EDTA described in the embodiment of the present invention
Figure.
Fig. 3 is the material modified preparation method flow charts of EDTA described in the embodiment of the present invention.
Fig. 4 is the method for modifying flow chart of the modified agarose described in the embodiment of the present invention.
Fig. 5 be the embodiment of the present invention described in the heavy metal available state adsorbed film material modified based on EDTA to Ni, Cu,
The adsorbance of the heavy metal species available state of Cd, As, Pb five with solution concentration variation diagram.
Fig. 6 is the heavy metal available state adsorbed film DGT combination phase material modified based on EDTA described in the embodiment of the present invention
Device uses structural representation.
Fig. 7 be the embodiment of the present invention described in the heavy metal available state adsorbed film material modified based on EDTA to Ni, Cu,
The schematic diagram of the heavy metal species available state adsorption rate of Cd, As, Pb five.
Fig. 8 be the embodiment of the present invention described in the heavy metal available state adsorbed film material modified based on EDTA to Ni, Cu,
The schematic diagram of the heavy metal species available state desorption efficiency of Cd, As, Pb five.
Wherein：1- shells；2- adsorbed films；3- spreads phase；4- filter membranes.
Embodiment
Embodiments of the present invention are described below in detail, the example of the embodiment is shown in the drawings, wherein from beginning
Same or similar element is represented to same or similar label eventually or there is the element of same or like function.Below by ginseng
The embodiment for examining accompanying drawing description is exemplary, is only used for explaining the present invention, and is not construed as limiting the claims.
Those skilled in the art of the present technique are appreciated that unless expressly stated, singulative " one " used herein, " one
It is individual ", " described " and "the" may also comprise plural form.It is to be further understood that what is used in the specification of the present invention arranges
Diction " comprising " refer to the feature, integer, step, operation, element and/or component be present, but it is not excluded that in the presence of or addition
One or more other features, integer, step, operation, element, component and/or their groups.
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 terminology) with the general understanding identical meaning with the those of ordinary skill in art of the present invention.Should also
Understand, those terms defined in such as general dictionary, which should be understood that, to be had and the meaning in the context of prior art
The consistent meaning of justice, and unless defined as here, will not be with idealizing or the implication of overly formal be explained.
For ease of the understanding to the embodiment of the present invention, by taking specific embodiment as an example the present invention is done below in conjunction with accompanying drawing into
The explanation of one step, and embodiment does not form the restriction to the embodiment of the present invention.
Fig. 1 is that the heavy metal available state material modified based on EDTA described in the embodiment of the present invention adsorbs membrane preparation method stream
Cheng Tu, Fig. 2 are the heavy metal available state adsorbed film electron-microscope scanning figure material modified based on EDTA described in the embodiment of the present invention
(500 times), Fig. 3 are the material modified preparation method flow charts of EDTA 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 material modified based on EDTA described in the embodiment of the present invention
Belong to available state adsorbed film to the adsorbance of the heavy metal species available state of Ni, Cu, Cd, As, Pb five with the variation diagram of solution concentration, Fig. 6
Structure is used for the heavy metal available state adsorbed film DGT combination phase device material modified based on EDTA described in the embodiment of the present invention
Schematic diagram, Fig. 7 be the embodiment of the present invention described in the heavy metal available state adsorbed film material modified based on EDTA to Ni, Cu, Cd,
The schematic diagram of the heavy metal species available state adsorption rate of As, Pb five, Fig. 8 are material modified based on EDTA described in the embodiment of the present invention
Schematic diagram of the heavy metal available state adsorbed film to the heavy metal species available state desorption efficiency of Ni, Cu, Cd, As, Pb five.
One of ordinary skill in the art will appreciate that：Accompanying drawing is the schematic diagram of one embodiment, module in accompanying drawing or
Flow is not necessarily implemented necessary to the present invention.
As shown in figure 3, the embodiments of the invention provide a kind of heavy metal available state adsorbed film material modified based on EDTA,
The material composi of the adsorbed film includes：ZnAl-EDTA is material modified, crosslinking agent, acrylamide gel.The adsorbed film is
Be uniformly distributed in the material modified polyacrylamide gel films of ZnAl-EDTA, the adsorbed film can adsorb simultaneously Ni, Cu, Cd,
The available state of the heavy metal species of As, Pb five, the absorption of various heavy available state suitable for water body, soil, deposit.
Above-mentioned ZnAl-EDTA is material modified, and particle diameter is less than 75 μm, and material modified particle diameter is smaller, in gel solution more
Uniform suspension is easily formed, sorbent material is more evenly distributed in so manufactured adsorbed film, so as to which contact area is bigger,
Adsorption rate is higher, and desorption effect is also more preferable.The preparation method material modified ZnAl-EDTA is as follows：
It is 2 in molar ratio：1 ratio takes appropriate zinc nitrate and aluminum nitrate, is added in appropriate pure water, is well mixed, obtains
To solution A；It is 0.25 in molar ratio by EDTA and sodium hydroxide：7~8.4 ratio is added in appropriate pure water, is well mixed,
Obtain solution B；Solution B is added in solution A, is well mixed, the PH that mixed solution is adjusted with 1mol/L NaOH solution is
12, be sufficiently stirred 20~30min, 60~80min of aging, filter, freeze drier is dried, grind particle diameter is white less than 75 μm
Color powder, hermetically drying preserve, and it is material modified to produce EDTA.
The mol ratio of the EDTA and the aluminum nitrate is 0.25：1, the mol ratio of the sodium hydroxide and the aluminum nitrate
For 7~8.4:1.
The material modified heavy metal average adsorption rates of EDTA provided in an embodiment of the present invention are more than 85%, 1mol/L nitre
Sour desorption efficiency is average more than 85%, and compared with traditional chelex-100 polymeric adsorbents material, adsorption rate is higher, and adsorption rate is more
It hurry up, desorption efficiency is higher.
As shown in Figure 1 to Figure 2, a kind of heavy metal available state material modified based on EDTA described in the embodiment of the present invention is inhaled
Membrane preparation method, comprises the following steps：It is material modified to prepare ZnAl-EDTA；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 is material modified and the acrylamide gel solution of certain volume mix 10~
15min, make ZnAl-EDTA material modified and be uniformly dispersed in acrylamide gel solution, obtain modified propylene acrylamide gel solution；
The pure solution of tetramethylethylenediamine and 10% ammonium persulfate solution for taking certain volume are added to modified propylene made from step S131
In acrylamide gel solution, slowly rocking is well mixed solution, the glass plate by mixed solution injection added with U-shaped plastic spacer
In, glass plate is moved in 42~46 DEG C of incubator, cultivate 45~60min, obtain modified propylene acrylamide gel film；In pure water
The modified propylene acrylamide gel film between two glass plates is taken out, 24h is hydrated, during which changes water 2~3 times, is made and is modified based on EDTA
The heavy metal available state adsorbed film of material.
Wherein, the ratio between quality material modified EDTA 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：Will crosslinking
Agent is added in pure water, is stirred into uniform solution under 60 DEG C of temperature conditionss, is added a certain amount of acrylamide, is stirred into homogeneous molten
The ratio between liquid, the quality of the crosslinking agent, the quality of acrylamide, the volume of pure water is 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, for preparing the crosslinking agent of acrylamide gel solution
For modified agarose crosslinking agent, the method for modifying of the modified agarose is：
Step 1: dissolve by heating agarose：The agarose of certain mass is weighed, is added to molten in the boiling water of certain volume
Solution, and keep 80 DEG C of insulations；
Step 2: quaternization：Weigh certain mass sodium borohydride to be dissolved in 14mol/L sodium hydroxide solution one, so
It is added in the agarose solution of step 1, is stirred continuously afterwards, fully reaction；
Step 3: modified-reaction：10% sodium hydroxide solution two is 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 was added dropwise again in 15 minutes
Propyl glycidyl ether, react 1 hour；
Step 4: neutralize drying：The solution of step 3 is cooled to 60 DEG C, add 4mol/l acetums adjust pH value to
6.5~7.5, add acetone soln and clean repeatedly, dry, grinding, produce 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 material modified based on EDTA
Preparation flow step, do not limited by the order of above-mentioned steps, other orders that those skilled in the art are expected, in this hair
Within bright protection domain.
As shown in fig. 6, the adsorbed film described in the embodiment of the present invention to be cut into a diameter of 1.9cm disk, DGT devices are placed in
In, the DGT devices include outmost round plastic shell 1, and the one end of shell 1 is provided with opening, and opening is covered with one layer of filter membrane 4
Lid, to prevent causing mechanical failure and biological pollution to gel, the later layer of filter membrane 4 is diffusion phase 3, and diffusion phase 3 is used for controlling 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 films are placed in 10ml centrifuge tubes, add the heavy metal species content of 5mlNi, Cu, Cd, As, Pb five be 5,20,
50th, 200,500,1000ug/L 0.01mol/L NaNO3Solution, at 25 DEG C, 24h is shaken under the conditions of 130r/min, takes out and inhales
Membrane, point take 1ml adsorb after solution, use 1%HNO3Constant volume is to 10ml, solution heavy metal concentration before and after ICP-MS measure absorption,
Adsorption rate is calculated, obtains the adsorption rate of the heavy metal species available state of Ni, Cu, Cd, As, Pb five as shown in fig. 7, each concentration does 3
It is parallel, while take 1ml stostes 1%HNO3Constant volume determines original liquid concentration to 10ml.By above-mentioned adsorbed film be transferred to another 10ml from
2ml1mol/L HNO is added in heart pipe3, under normal temperature condition, 24h is desorbed, point takes 1ml stripping liquids, pure water constant volume to 10ml,
ICP-MS determines solution heavy metal concentration, calculates desorption efficiency, obtains the desorption of the heavy metal species available state of Ni, Cu, Cd, As, Pb five
Rate is as shown in Figure 8.
As shown in figure 5, under the conditions of various concentrations the heavy metal species available state of Ni, Cu, Cd, As, Pb etc. five average adsorption rate
For 85%, the average adsorption rate of the heavy metal species available state of solution Ni, Cu, Cd, As, Pb of below 200ppb concentration etc. five reaches
90%, eluted with 1mol/L salpeter solutions, the average elution rate of the heavy metal species available state of Ni, Cu, Cd, As, Pb etc. five is equal
More than 85%, 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 ions with the variation diagram of solution concentration, (b) is that the adsorbance of adsorbed film heavy metal As ions is dense with solution
The variation diagram of degree, (c) be adsorbed film heavy metal Cd ions adsorbance with the variation diagram of solution concentration, (d) is adsorbed film pair
For the adsorbance of heavy metal Cu ion with the variation diagram of solution concentration, (e) is the adsorbance of adsorbed film heavy metal Pb ions with molten
The variation diagram of liquid concentration.As shown in Figure 7, in the case where the heavy metal species ion concentration of Ni, Cu, Cd, As, Pb etc. five is few, inhale
For attached rate close to 1, the adsorbed film described in embodiments of the invention has higher adsorption rate to the trace element in environment.
In summary, the present invention adsorbs film preparation side by providing a kind of heavy metal available state material modified based on EDTA
Method, be made a kind of heavy metal available state adsorbed film material modified based on EDTA, the adsorbed film can adsorb simultaneously Ni, Cu, Cd,
The various heavy available state such as As, Pb, adsorption rate is high compared with traditional chelex-100 polymeric adsorbent materials, and absorption is fast, inhales
Attached amount is bigger, and secondary pollution is not produced 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 protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, the change or replacement that can readily occur in,
It should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be with scope of the claims
It is defined.
Claims (10)
- A kind of 1. heavy metal available state adsorbed film material modified based on EDTA, it is characterised in that the composition of the adsorbed film into Dividing includes：ZnAl-EDTA is material modified, crosslinking agent, acrylamide gel.
- 2. the heavy metal available state adsorbed film material modified based on EDTA according to claim 1, it is characterised in that described Crosslinking agent is modified agarose.
- 3. the heavy metal available state adsorbed film material modified based on EDTA according to claim 1, it is characterised in that described ZnAl-EDTA is material modified to be prepared as follows：It is 2 in molar ratio：1 ratio takes appropriate zinc nitrate and aluminum nitrate, adds Into appropriate pure water, it is well mixed, obtains solution A；It is 0.25 in molar ratio by EDTA and sodium hydroxide：7~8.4 ratio adds Enter into appropriate pure water, be well mixed, obtain solution B；Solution B is added in solution A, is well mixed, with 1mol/L's NaOH solution regulation solution PH is 12, is sufficiently stirred 20~30min, 60~80min of aging, filters, freeze drier is dried, and is ground White powder of the particle diameter less than 75 μm is ground to obtain, hermetically drying preservation, it is material modified to produce ZnAl-EDTA.
- 4. a kind of preparation method of the heavy metal available state adsorbed film material modified based on EDTA, it is characterised in that including following Step：Step S110：It is material modified to prepare ZnAl-EDTA；Step S120：Crosslinking agent is added in pure water, uniform solution is stirred under 60 DEG C of temperature conditionss, adds a certain amount of third Acrylamide, uniform solution is stirred into, acrylamide gel solution is made；Step S130：Take the ZnAl-EDTA of certain mass is material modified to be mixed with the acrylamide gel solution of certain volume respectively 10~15min of stirring is closed, makes ZnAl-EDTA material modified and is uniformly dispersed in acrylamide gel solution, obtain modified propylene acyl Amine gel solution；Step S140：The pure solution of tetramethylethylenediamine and 10% ammonium persulfate solution for taking certain volume are added to step S131 systems In the modified propylene acrylamide gel solution obtained, slowly rocking is well 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, cultivate 45~60min, obtain modified propylene acrylamide gel Film；Step S150：The modified propylene acrylamide gel film between two glass plates is taken out in pure water, 24h is hydrated, during which changes water 2~3 It is secondary, it is made based on heavy metal available state adsorbed film material modified EDTA.
- 5. the heavy metal available state absorption membrane preparation method material modified based on EDTA according to claim 4, its feature It is, the material modified steps of EDTA that prepare include：Step S111：It is 2 in molar ratio：1 ratio takes appropriate zinc nitrate and aluminum nitrate, is added in appropriate pure water, and mixing is equal It is even, obtain solution A；Step S112：It is 0.25 in molar ratio by EDTA and sodium hydroxide：7~8.4 ratio is added in appropriate pure water, mixing Uniformly, solution B is obtained；Step S113：Solution B is added in solution A, is well mixed, is 12 with 1mol/L NaOH solution regulation solution PH, 20~30min, 60~80min of aging are sufficiently stirred, is filtered, freeze drier is dried, and grinds to obtain white of the particle diameter less than 75 μm Powder, hermetically drying preserve, and it is material modified to produce EDTA.
- 6. the heavy metal available state absorption membrane preparation method material modified based on EDTA according to claim 5, its feature It is, the mol ratio of the EDTA and the aluminum nitrate is 0.25：1, the mol ratio of the sodium hydroxide and the aluminum nitrate is 7 ~8.4:1.
- 7. the heavy metal available state absorption membrane preparation method material modified based on EDTA according to claim 4, its 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.
- 8. the heavy metal available state absorption membrane preparation method material modified based on EDTA according to claim 7, its feature It is, the crosslinking agent is modified agarose, and the method for modifying of the modified agarose is：Step 1: dissolve by heating agarose：10g agaroses are weighed, is added in 490ml boiling water and dissolves, and keep 80 DEG C of guarantors Temperature；Step 2: quaternization：Weigh 1.67g sodium borohydrides to be dissolved in 10ml14mol/L sodium hydroxide solution, then add Into the agarose solution of step 1, it is stirred continuously, fully reaction；Step 3: modified-reaction：100ml10% sodium hydroxide solution is added in the solution of step 2, and in 15 minutes 25ml allyl glycidyl ethers are added dropwise, after 1 hour, the pi-allyl contracting of same volume was added dropwise again in 15 minutes Water glycerin ether, react 1 hour；Step 4: neutralize drying：The solution of step 3 is cooled to 60 DEG C, 4mol/l acetums is added and adjusts pH value to 6.5 ~7.5, add acetone soln and clean repeatedly, dry, grinding, produce modified agarose.
- 9. the heavy metal available state absorption membrane preparation method material modified based on EDTA according to claim 4, its feature It is：In the step S130, the ratio between volume of the quality material modified EDTA and acrylamide gel solution is 3~4: 10。
- 10. the heavy metal available state absorption membrane preparation method material modified based on EDTA according to claim 4, its feature It is：In the step S140, the volume ratio of the tetramethylethylenediamine solution and the modified propylene acrylamide gel solution is 1:400, the volume ratio of the ammonium persulfate solution and the modified propylene acrylamide gel solution is 7:1000.
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