CN107552008A - A kind of method of corn cob fiber element based aquagel absorption heavy metal ion - Google Patents
A kind of method of corn cob fiber element based aquagel absorption heavy metal ion Download PDFInfo
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- CN107552008A CN107552008A CN201710817499.9A CN201710817499A CN107552008A CN 107552008 A CN107552008 A CN 107552008A CN 201710817499 A CN201710817499 A CN 201710817499A CN 107552008 A CN107552008 A CN 107552008A
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Abstract
The invention discloses a kind of method of corn cob fiber element based aquagel absorption heavy metal ion.First corn cob fiber element is dissolved,Add montmorillonite heating stirring,Make in corn cob fiber element insertion montmorillonite layer,Add tetramethylethylenediamine and ammonium persulfate stirring,Then acrylic acid and N.N ' methylene-bisacrylamides are added,Continue heating stirring and obtain hydrogel,The corn cob fiber element is the pure cellulose extracted using nitric acid Ethanol Method from corncob,By to montmorillonite,N.N ' methylene-bisacrylamides,The optimization of the dosage of acrylic acid has obtained structure,The optimal corn cob fiber element based aquagel of absorption property,Lay equal stress on metal ion solution various concentrations,The optimization of pH value and adsorption time,Confirm the optimal adsorption condition of hydrogel heavy metal ion of the present invention,Preparation method technique of the present invention is simple,The hydrogel absorption property and structural stability of preparation are preferable,The advantages of good adsorption effect of heavy metal ion.
Description
Technical field
The present invention relates to corn cob fiber element based aquagel heavy metal ion (Zn2+, Cd2+And Cr3+) absorption property shadow
Ring, the hydrogel that more particularly to prepared by nitric acid-ethanol corn core cellulose is under the conditions of Different Optimization to Zn2+, Cd2+And Cr3+Weight
The absorption of metal ion.
Technical background
Corn cob fiber element (LNC) is a kind of rich reserves, reproducible natural macromolecular material, has good biology
Degradability, avirulent feature, it is native grass fiber element, lignin and hemicellulose are compared with other wood in preparation process
Matter cellulose is easier to remove.Utilize the hydrogel that reproducible corn cob fiber element Development and Production is degradable, it is possible to achieve its profit
With the maximization of value.Hydroxyl in corn cob fiber element macromolecular, the reaction such as carboxylation, acidifying can be participated in, in corn cob fiber
Various active groups, such as carbonyl, carboxyl are introduced on element, various derivatives can be formed.Because of corn cob fiber element table
Face space is larger, has very strong hydrophobicity and water imbibition, and the high-specific surface area that corn cob fiber element has is advantageous to prepare water
Gel.
In recent years, the heavy metal such as problem of environmental pollution such as cadmium, lead, nickel, zinc, chromium had caused worldwide extensive concern.
Different from organic waste, heavy metal contaminants have the characteristics that strong toxicity, difficult degradation, are easily enriched with, and can be entered by food chain
Enter human body, so as to endanger human health.Therefore, heavy metal pollutant prevention and control turn into research emphasis.Tradition
The method for removing metal ion in the aqueous solution has chemical precipitation method, ion-exchange, chemical oxidation/reduction, counter-infiltration, electric osmose
Analysis, ultrafiltration etc..However, traditional coagulation, chemical precipitation produce substantial amounts of waste residue, secondary pollution is easily caused；Electrolysis and ion are handed over
High energy consumption is changed, cost is high.And the adsorbent advantage such as have strong adsorptivity, simple to operate, small investment, secondary pollution small, therefore, need
Constantly to seek more cheap, efficient, environmental protection the adsorbent of exploitation to improve the removal effect of heavy metal ion in the aqueous solution.
Prior art (mono- acrylic acid of g of lignocellulosic one/montmorillonite hydrogel prepares and Study on adsorption properties) discloses
A kind of preparation method of mono- acrylic acid of g of lignocellulosic one/montmorillonite hydrogel and its methylene is adsorbed in sewage disposal
The effect of blue dyestuff.Lignocellulosic includes cellulose, hemicellulose and lignin, and structure is more complicated, and functional group is more multiple
It is miscellaneous, and hemicellulose easily hydrolyzes in an acidic solution, lignin can also hydrolyze in an acidic solution, and prepared by lignocellulosic
During need to handle by high temeperature chemistry, process is numerous and diverse, and the structure and performance to cellulose cause necessarily to adversely affect.It is existing
Technology needs the degree of neutralization with sodium hydroxide regulation acrylic acid when preparing hydrogel, influences the suction of hydrogel in acid condition
Attached effect.
The content of the invention
In order to solve traditional plant fiber-based heavy metal absorbent exist adsorption capacity is low, the rate of adsorption is slow, structure not
The problems such as stable and adsorption capacity difference, improves the absorption property of hydrogel, improves the adsorption effect of hydrogel heavy metal ion,
The present invention provides a kind of novel corn core cellulose base montmorillonite and is modified hydrogel.
An object of the present invention is to provide a kind of corn cob fiber element based aquagel, the hydrogel structure is stable,
Adsorption capacity is high, the rate of adsorption is fast, recyclability is good and selective adsorption capacity is strong.
The second object of the present invention is to provide a kind of preparation method of corn cob fiber element based aquagel, the preparation side
Method can simply, easily obtain corn cob fiber element based aquagel, be easy to use.
The third object of the present invention is to provide a kind of application of corn cob fiber element based aquagel absorption heavy metal ion
Method, the application process method can determine optimal adsorption condition and maximal absorptive capacity.
To realize above-mentioned technical purpose, specifically, the present invention relates to following technical scheme：
The invention discloses a kind of corn cob fiber element based aquagel preparation method, comprise the following steps：
(1) weigh appropriate corn cob fiber plain (LNC) to be put into three-necked flask, after adding distilled water to dissolve；
(2) montmorillonite (MMT) is added into step (1) resulting solution, in inert gas N2The lower heating stirring of protection；
(3) tetramethylethylenediamine and ammonium persulfate are added into mixing liquid obtained by step (2), is stirring evenly and then adding into third
Olefin(e) acid (AA) and N.N '-methylene-bisacrylamide (MBA) continue heating stirring and obtain hydrogel；
(4) gained hydrogel is added into absolute ethyl alcohol to stand, is cleaned, dried with deionized water.
Preferably, a kind of preparation method of corn cob fiber element based aquagel, comprises the following steps：
(1) weigh appropriate corn cob fiber element to be put into three-necked flask, after adding distilled water to dissolve；
(2) MMT is added into step (1) resulting solution, wherein MMT/LNC mass ratioes are 0.03-0.11, in N2Under protection
Heating stirring, heating-up temperature are 75-90 DEG C, whipping temp 50-70min；
(3) tetramethylethylenediamine (tetramethylethylenediamine/LNC volume/mass is added into mixing liquid obtained by step (2)
Than for 0.2mL/g) and ammonium persulfate (ammonium persulfate/LNC mass ratioes are 0.2), it is stirring evenly and then adding into AA (AA/LNC quality
Than for 8-24) and MBA (MBA/LNC mass ratio is 0.1-0.5) continue heating stirring and obtain hydrogel；
(4) gained hydrogel is added into absolute ethyl alcohol and stands 24h, cleaned with deionized water, 24h is dried at 50-70 DEG C.
Preferably, MMT/LNC mass ratioes are 0.08.
Preferably, AA/LNC mass ratioes are 16.
Preferably, MBA/LNC mass ratioes are 0.2.
The present invention also provides a kind of preparation method of above-mentioned corn cob fiber element, comprises the following steps：
(1) weigh a certain amount of corncob to be put into conical flask, add the mixed solution of nitric acid and ethanol (95%), water-bath adds
Heat is reacted；
(2) it is transferred to step (1) is residue obtained in G2 glass filters, pumps filtrate, above procedure is repeated 2 times；
(3) filtration product obtained by step (2) is finally moved into baking oven, is dried to constant weight.
Preferably, the mass ratio of nitric acid and ethanol (95%) is 1 in step (1):4.
Preferably, water-bath reaction temperature is 75-90 DEG C in step (1), reaction time 1h.
Preferably, drying temperature is 100-120 DEG C in step (3).
Present invention also offers a kind of application process of corn cob fiber element based aquagel absorption heavy metal ion, including：
Corn cob fiber element based aquagel prepared by the method for the invention is added to pH=3.5-6.5, Zn2+, Cd2+
And Cr3+Ion concentration is is adsorbed in the heavy metal solution of (50-800mg/L), adsorption time 60-120min.
Preferably, corn cob fiber element based aquagel prepared by the method for the invention is added to pH=6.5, Zn2+,
Cd2+And Cr3+Concentration is respectively to be adsorbed in 200mg/L, 400mg/L and 800mg/L heavy metal solution, and adsorption time is
60min。
The beneficial effects of the invention are as follows：
(1) it is combined by corn cob fiber element with MMT and prepares hydrogel, corn cob fiber element, which is inserted into sheet and covered, is taken off
In soil, the lamellar structure of montmorillonite is destroyed, cellulose forms baroque tridimensional network with acrylate copolymer again, made
Hydrogel structure is stable, increases the adsorbance of hydrogel, and montmorillonite elementary cell is dispersed in polymeric matrix, can be with
Realize with it is compound on the nanoscale of polymer, add the water imbibition and specific surface area of hydrogel, for hydrogel performance
Research extends new approaches.
(2) the corn cob fiber element of nitric acid-Ethanol Method extraction is pure cellulose, without being passed through as conventional wooden cellulose
High temperature chemical treatment, cellulose purity height and structural integrity are crossed, is prepared into Stability Analysis of Structures after hydrogel.
(3) prepare during hydrogel without the degree of neutralization that use sodium hydroxide regulation acrylic acid, reduce consumption of chemical agent,
The adsorption effect of hydrogel is improved in acid condition.Not adjusting acrylic acid degree of neutralization with sodium hydroxide in preparation process can be with
Improve the structural stability of pure cellulose based aquagel in acid condition, because the carboxylic acid group of polyacrylic acid is weak acid, water-setting
The pH that swelling hop occurs for glue is higher, and the pH sensitiveness of hydrogel is dissociated flat by polyacrylic acid in gel in acid condition
Weighing apparatus, Donnan balance influences are smaller inside and outside ion electrostatic repulsion and gel on network chain, so as to improve the absorption of hydrogel
Effect.
(4) hydrogel is applied to the absorption of heavy metal ion, reduces contaminated wastewater load, and hydrogel is as biology
The repeatable utilization of adsorbent and degraded can reduce cost for wastewater treatment；
(5) a kind of new method and thinking are provided for the application of hydrogel, improves the absorption property of hydrogel, widen water-setting
Glue applies channel；
(6) present invention improve can corn cob fiber element value, expand corn cob fiber element application, enhancing
The absorption property of hydrogel, can solve heavy metal in water ion contamination problems.
Embodiment
It is noted that described further below is all exemplary, it is intended to provides further instruction to the present invention.It is unless another
Indicate, all technologies used herein and scientific terminology are with usual with general technical staff of the technical field of the invention
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe embodiment, and be not intended to restricted root
According to the illustrative embodiments of the present invention.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in this manual using term "comprising" and/or " bag
Include " when, it indicates existing characteristics, step, operation and/or combinations thereof.
Herein, term " corn cob fiber element " refers to the pure cellulose extracted from corncob.
Term " corn cob fiber element based aquagel " refers to corn cob fiber element, montmorillonite, acrylic acid and N.N '-methylene
Base bisacrylamide is hydrogel prepared by primary raw material.
Really as described in the background art, the heavy metal adsorption that prior art is prepared using traditional lignocellulosic as raw material
Hydrogel has that adsorption capacity is low, the rate of adsorption is slow, structural instability and the problems such as adsorption capacity difference, thus the present invention reopening
The preparation method of the good cellulose base hydrogel of Stability Analysis of Structures that to send out a kind of new, recyclability.
A kind of preparation method of corn cob fiber element based aquagel is disclosed in an embodiment of the invention, utilizes nitre
Acid-Ethanol Method extracts corn cob fiber element from corncob, and corn cob fiber element is dissolved in distilled water, adds MMT in N2
The lower heating in water bath for reaction of protection；Reaction adds ammonium sulfate after terminating and tetramethylethylenediamine is stirring evenly and then adding into AA and MBA, adds
Thermal agitation obtains hydrogel.
Preparation method of the present invention selection corn cob fiber element prepares one of primary raw material as hydrogel, in corncob
Content of cellulose is up to 35%, is native grass fiber element, hemicellulose and lignin are easier to remove, so as to obtain
The higher cellulose of purity, needing not move through high temeperature chemistry processing can obtain.
Preparation method of the present invention starts first to make corn cob fiber element with MMT in N2The lower heating water bath of protection carries out anti-
Should, the plain rupture inserted between cheating engaging layer with montmorillonite layer structure of corn cob fiber is promoted, makes montmorillonite elementary cell more
It is tiny, being compounded on corn cob fiber element evenly.
Degree of neutralization of the preparation method of the present invention without use sodium hydroxide regulation AA, the application directly by AA and MBA and
Initiator is added in corn cob fiber element/MMT mixed solutions, the hydroxyl contracting on AA monomers polymerization crosslinking and corn cob fiber element
Close two reactions to carry out simultaneously, AA reduces AA activity with the hydroxyl condensation on corn cob fiber element, so need not pass through tune
The degree of neutralization for saving AA controls reaction speed.AA polymerize and grafting is carried out simultaneously, makes the three-dimensional structure of hydrogel more complicated, structure
It is more stable.Herein described preparation method eliminates the step of adjusting AA degree of neutralization with sodium hydroxide, and AA does not pass through hydroxide
Neutralisation treatment at sodium, the hydrogel structure of preparation are more stable.
In the preferred embodiment of the present invention, preferable, MMT/LNC mass ratioes when preparing corn cob fiber element based aquagel
The mass ratio that mass ratio for 0.08, AA/LNC is 16, MBA/LNC is 0.2.
Inventor find MMT content can not it is very few can not be excessive, MMT contents are very few not to have heavy metal ion
Suction-operated；The excessive MMT of content can not be dispersed in corn cob fiber element well, and cellulose can not intert well with MMT
With reference to MMT interlamellar spacings cannot be modified and particle diameter is larger, and not only adsorptivity cannot improve, and can also influence the structure of hydrogel
The mass ratio of stability, preferable MMT and corn cob fiber element is 0.08.
AA/LNC of the present invention preferred mass ratio, which is that 16, AA contents are too low, can not form stable three-dimensional structure, AA contents
The too high molecular weight increase for easily causing polymerization rear side chain, increases system viscosity, is easily tangled between strand, improve friendship
Connection degree, reduce the absorption property of product.
When MBA/LNC of the present invention preferred mass ratio is that 0.2, MBA contents are relatively low, the degree of cross linking of hydrogel is small, water-soluble
Good, adsorbance is low；During MBA too high levels, cause hydrogel crosslink density too big, the diastole of molecular network is restricted, a huge sum of money
Category ion is difficult to enter from hydrogel surface inside it, and the swellbility of hydrogel diminishes, and causes adsorbance to decline.
It is excellent present invention also offers a kind of application process of the corn cob fiber element based aquagel absorption heavy metal ion
The pH=6.5 of heavy metal solution, Zn in the embodiment of choosing2+, Cd2+And Cr3+Concentration is respectively 200mg/L, 400mg/L and
800mg/L, adsorption time 60min.
The pH=6.5 of application process heavy metal solution of the present invention, when pH value is smaller, substantial amounts of H is contained in solution+, H+
Certain adsorption site is fought for metal ion, on the other hand, the carboxyl, hydroxyl in hydrogel are electric in the larger solution of acidity
From being suppressed, it is unfavorable for generating complex, so causing adsorbance very little；When gradual increase, being gradually reduced in solution,
Comparatively adsorption site increases, carboxyl is ionized into COO-, be advantageous to the generation of complex, so adsorbance increases.
Zn in application process heavy metal solution of the present invention2+, Cd2+And Cr3+Concentration is respectively 200mg/L, 400mg/
L and 800mg/L, when concentration of heavy metal ion is smaller, increase ion concentration adsorbance increases therewith, with concentration of metal ions
Increase, increase the mass transfer force of metal ion, reduce absorption resistance, while increase metal ion and adsorption site
Contact area, gradually increase so as to adsorbance；Continue to increase ion concentration after adsorbance reaches maximum, adsorbance is omited on the contrary
There is reduction, this is due to when ion concentration is excessive, hydrolysis degree increase, is reduced and the combination of active group, while metal
The excessive swelling for being unfavorable for composite of ion concentration, is wrapped the active group on adsorbent, so adsorbance reduces.This
Outside, in the heavy metal solution that different kinds of ions coexists, inhibitory action, different metal ions and the water between different ions be present
The binding ability of gel active group is different, so the optium concentration of different metal ions is also different.
The preferred adsorption time of application process of the present invention is 60min, and absorption of the hydrogel to metal ion is mainly sent out
On the avtive spot of adsorbent outer surface, the rate of adsorption is very fast for life；On the other hand, the absorption of adsorbate may occur at absorption
The endoporus of agent, reaction rate is slower, takes more, and herein described hydrogel is to Zn during 60min2+, Cd2+And Cr3+Absorption reach
To balance, continuing extension adsorption time adsorbance will not increase.
In following examples, in addition to having special instruction, other all percentages are mass percent.
Embodiment 1：
Nitric acid-ethanol corn core cellulose is extracted according to the following steps：
Weigh a certain amount of corncob to be put into conical flask, add nitric acid-ethanol (nitric acid：Ethanol is 1:4) mixed liquor, pass through
Reflux condensate device heats 1h on 85 DEG C of water-bath, and residue is transferred in G2 glass filters, pumps filtrate.Above procedure
It is repeated 2 times.The filter equipped with cellulose is finally moved into baking oven, constant weight is dried at 105 DEG C.
Embodiment 2：
Corn cob fiber element based aquagel is prepared according to the following steps：
The optimization of MMT/LNC mass ratioes：1. weighing appropriate corn cob fiber element to be put into three-necked flask, distilled water is added to dissolve
Afterwards, being put into MMT, (MMT/LNC mass ratioes are respectively 0,0.03,0.05,0.08 and 0.11), and N is passed through at 85 DEG C2Stirring
60min, tetramethylethylenediamine (tetramethylethylenediamine/LNC is 0.2mL/g) and ammonium persulfate (ammonium persulfate/LNC matter are added afterwards
Amount is than for 0.2), stirring 10min, and then adding AA (AA/LNC mass ratio is 16) and MBA, (MBA/LNC mass ratio is
0.2), continue heating stirring and obtain corn cob fiber element based aquagel.Gained hydrogel is added into absolute ethyl alcohol and stands 24h, is used
Deionized water is cleaned, and 24h is dried at 60 DEG C, and stripping and slicing is standby.
2. it is 800mg/L that standby corn cob fiber element based aquagel is put into concentration, the heavy metal ion that pH is 6.5 is molten
Liquid (Zn2+, Cd2+And Cr3+) in stirring and adsorbing 120min.
As a result：By adsorption experiment, the corn cob fiber element based aquagel LNC-g-AA/MMT obtained by above-mentioned processing step
Heavy metal solion (Zn2+, Cd2+And Cr3+) absorption discovery is carried out with the continuous increasing of MMT/LNC mass ratioes (rate of charge)
Add, i.e. the increase of MMT dosages, the adsorption capacity increase of hydrogel, when MMT/LNC mass ratioes are 0.08, hydrogel absorption weight
Metal ion reaches maximum, and when more than 0.08, adsorbance downward trend occurs with the increase of ratio, it is seen that MMT/LNC compared with
Suitable quality ratio is 0.08.Under this mass ratio, corn cob fiber element based aquagel LNC-g-AA/MMT is than conventional wooden cellulose
Based aquagel LNC-g-AA/MMT heavy metal ions (Zn2+, Cd2+And Cr3+) adsorbance improve 16.2%.
Embodiment 3：
Corn cob fiber element based aquagel is prepared according to the following steps：
The optimization of AA/LNC mass ratioes：1. weighing appropriate corn cob fiber element to be put into three-necked flask, distilled water is added to dissolve
Afterwards, MMT (MMT/LNC mass ratioes are 0.08) is put into, N is passed through at 85 DEG C260min is stirred, adds tetramethylethylenediamine (four afterwards
Methyl ethylenediamine/LNC volume/mass ratio is 0.2mL/g) and ammonium persulfate (ammonium persulfate/LNC mass ratioes are 0.2), stirring
10min, then add AA (AA/LNC mass ratio be respectively 8,12,16,20 and 24) and MBA (MBA/LNC mass ratio is
0.2), continue heating stirring and obtain corn cob fiber element based aquagel.Gained hydrogel is added into absolute ethyl alcohol and stands 24h, is used
Deionized water is cleaned, and 24h is dried at 60 DEG C, and stripping and slicing is standby.
2. it is 800mg/L that standby corn cob fiber element based aquagel is put into concentration, the heavy metal ion that pH is 6.5 is molten
Liquid (Zn2+, Cd2+And Cr3+) in stirring and adsorbing 120min.
As a result：By adsorption experiment, the corn cob fiber element based aquagel LNC-g-AA/MMT obtained by above-mentioned processing step
Heavy metal solion (Zn2+, Cd2+And Cr3+) absorption discovery is carried out as the increase of allyl monomer amount, corncob are fine
The adsorbance increase of plain based aquagel (LNC-g-AA) heavy metal ion is tieed up, but when AA/LNC mass ratio is more than 16, water-setting
Downward trend is presented in glue adsorbance, and therefore, AA/LNC mass ratio should control convenient 16.Under this mass ratio, corncob
Cellulose base hydrogel LNC-g-AA/MMT is than conventional wooden cellulose base hydrogel LNC-g-AA/MMT heavy metal ions
(Zn2+, Cd2+And Cr3+) adsorbance improve 13.8%.
Embodiment 4：
Corn cob fiber element based aquagel is prepared according to the following steps：
The optimization of MBA/LNC mass ratioes：1. weighing appropriate corn cob fiber element to be put into three-necked flask, distilled water is added to dissolve
Afterwards, MMT (MMT/LNC mass ratioes are 0.08) is put into, N is passed through at 85 DEG C260min is stirred, adds tetramethylethylenediamine (four afterwards
Methyl ethylenediamine/LNC volume/mass ratio is 0.2mL/g) and ammonium persulfate (ammonium persulfate/LNC mass ratioes are 0.2), stirring
10min, then add AA (AA/LNC mass ratio be 16) and MBA (MBA/LNC mass ratio is respectively 0.1,0.2,0.3,
0.4 and 0.5), continue heating stirring and obtain corn cob fiber element based aquagel.Gained hydrogel is added into absolute ethyl alcohol to stand
24h, cleaned with deionized water, 24h is dried at 60 DEG C, stripping and slicing is standby.
2. it is 800mg/L that standby corn cob fiber element based aquagel is put into concentration, the heavy metal ion that pH is 6.5 is molten
Liquid (Zn2+, Cd2+And Cr3+) in stirring and adsorbing 120min.
As a result：By adsorption experiment, the corn cob fiber element based aquagel LNC-g-AA/MMT obtained by above-mentioned processing step
Heavy metal solion (Zn2+, Cd2+And Cr3+) absorption discovery is carried out with the increase of dosage of crosslinking agent, hydrogel adsorbance
Downward trend after first rising is presented, hydrogel adsorbance reaches maximum when MBA/LNC mass ratio is 0.2.Therefore, MBA/
Volume/mass ratio convenient LNC is 0.2.Under this mass ratio, corn cob fiber element based aquagel LNC-g-AA/MMT is than tradition
Lignocellulosic based aquagel LNC-g-AA/MMT heavy metal ions (Zn2+, Cd2+And Cr3+) adsorbance improve 14.6%.
Embodiment 5：
The absorption of corn cob fiber element based aquagel heavy metal ion is prepared according to the following steps：
The optimization of concentration of heavy metal ion：1. weighing appropriate corn cob fiber element to be put into three-necked flask, add distillation water-soluble
Xie Hou, MMT (MMT/LNC mass ratioes are 0.08) is put into, N is passed through at 85 DEG C260min is stirred, adds tetramethylethylenediamine afterwards
(tetramethylethylenediamine/LNC volume/mass ratio is 0.2mL/g) and ammonium persulfate (ammonium persulfate/LNC mass ratioes are 0.2),
10min is stirred, AA (AA/LNC mass ratio is 16) and MBA (MBA/LNC mass ratio is 0.2) is then added, continues to heat
Stirring obtains corn cob fiber element based aquagel.Gained hydrogel is added into absolute ethyl alcohol and stands 24h, is cleaned with deionized water,
24h is dried at 60 DEG C, stripping and slicing is standby.
2. it is 50,100,200,400,600 and 800mg/L that standby corn cob fiber element based aquagel is put into concentration,
PH is 6.5 heavy metal ion solution (Zn2+, Cd2+And Cr3+) in stirring and adsorbing 120min.
As a result：By adsorption experiment, the corn cob fiber element based aquagel LNC-g-AA/MMT obtained by above-mentioned processing step
Heavy metal ion carries out absorption and finds to work as Zn2+, Cd2+And Cr3+When concentration is respectively 200mg/L, 400mg/L and 800mg/L,
LNC-g-AA/MMT hydrogel adsorption effects are preferable.Under this concentration, corn cob fiber element based aquagel LNC-g-AA/MMT is than passing
Unite lignocellulosic based aquagel LNC-g-AA/MMT heavy metal ions (Zn2+, Cd2+And Cr3+) adsorbance improve
11.7%.
Embodiment 6：
The absorption of corn cob fiber element based aquagel heavy metal ion is prepared according to the following steps：
The optimization of heavy metal ion pH value of solution：1. weighing appropriate corn cob fiber element to be put into three-necked flask, add distilled water
After dissolving, MMT (MMT/LNC mass ratioes are 0.08) is put into, N is passed through at 85 DEG C260min is stirred, it is rear to add tetramethyl second two
(ammonium persulfate/LNC mass ratioes are for amine (tetramethylethylenediamine/LNC volume/mass ratio is 0.2mL/g) and ammonium persulfate
0.2) 10min, is stirred, then adds AA (AA/LNC mass ratio is 16) and MBA (MBA/LNC mass ratio is 0.2), is continued
Heating stirring obtains corn cob fiber element based aquagel.Gained hydrogel is added into absolute ethyl alcohol and stands 24h, it is clear with deionized water
Wash, 24h is dried at 60 DEG C, stripping and slicing is standby.
2. standby corn cob fiber element based aquagel is put into Zn2+、Cd2+、Cr3+Concentration be respectively 200mg/L,
Stirring and adsorbing 120min in 400mg/L and 800mg/L, pH 3.5,4.5,5.5 and 6.5 solution.
As a result：By adsorption experiment, the corn cob fiber element based aquagel LNC-g-AA/MMT obtained by above-mentioned processing step
Heavy metal ion carries out absorption and finds that LNC-g-AA/MMT hydrogels are to Zn when solution ph is 6.52+, Cd2+And Cr3+'s
Adsorption effect is preferable.Under this pH value, corn cob fiber element based aquagel LNC-g-AA/MMT is than conventional wooden cellulose base water-setting
Glue LNC-g-AA/MMT heavy metal ions (Zn2+, Cd2+And Cr3+) adsorbance improve 12.9%.
Embodiment 7：
The absorption of corn cob fiber element based aquagel heavy metal ion is prepared according to the following steps：
The optimization of heavy metal ion solution adsorption time：1. weighing appropriate corn cob fiber element to be put into three-necked flask, add
After distilled water dissolving, MMT (MMT/LNC mass ratioes are 0.08) is put into, N is passed through at 85 DEG C260min is stirred, adds tetramethyl afterwards
Base ethylenediamine (tetramethylethylenediamine/LNC volume/mass ratio is 0.2mL/g) and ammonium persulfate (ammonium persulfate/LNC mass ratioes
0.2), to stir 10min, AA (AA/LNC mass ratio is 16) and MBA (MBA/LNC mass ratio is 0.2) is then added, after
Continuous heating stirring obtains corn cob fiber element based aquagel.Gained hydrogel is added into absolute ethyl alcohol and stands 24h, uses deionized water
Cleaning, dries 24h at 60 DEG C, and stripping and slicing is standby.
2. standby corn cob fiber element based aquagel is put into Zn2+, Cd2+And Cr3+Concentration is respectively 200mg/L,
400mg/L and 800mg/L, pH are stirring and adsorbing 10,20,40,60,90 and 120min in 6.5 solution.
As a result：By adsorption experiment, the corn cob fiber element based aquagel LNC-g-AA/MMT obtained by above-mentioned processing step
Heavy metal ion carries out absorption and finds that when adsorption time is 60min LNC-g-AA/MMT hydrogels are to Zn2+, Cd2+And Cr3+
Adsorption effect it is preferable.Under this time, corn cob fiber element based aquagel LNC-g-AA/MMT is than conventional wooden cellulose base water
Gel LNC-g-AA/MMT heavy metal ions (Zn2+, Cd2+And Cr3+) adsorbance improve 15.6%.
In summary, Zn is worked as2+, Cd2+And Cr3+Concentration is respectively that 200mg/L, 400mg/L and 800mg/L, solution ph are
6.5th, when adsorption time is 60min, corn cob fiber element based aquagel LNC-g-AA/MMT is to Zn2+, Cd2+And Cr3+Adsorbance
It is up to 229.6mg/g, 479.3mg/g and 121mg/g.And adsorbance does not substantially change after being recycled for multiple times.
Corn cob fiber element based aquagel LNC-g-AA/MMT is than conventional wooden cellulose base hydrogel LNC-g-AA/MMT heavy metals
Ion (Zn2+, Cd2+And Cr3+) adsorbance improve 11-16%.
Embodiment 8：
Corn cob fiber element based aquagel adsorption-desorption cycle uses under nitric acid desorption is carried out according to the following steps：
Appropriate dry gel particle is added to preferable Zn2+, Cd2+And Cr3+In solution concentration, in preferable pH value and balance
Between under the conditions of stirring mixture reach adsorption equilibrium, hydrogel particle is washed with deionized 3 times, in salpeter solution (0.5mol/
L stirring immersion desorption 2h in), is then rinsed 8h using 0.01mol/L NaOH, finally, is cleaned using deionized water, by gel
Particle is re-used for adsorption experiment, and absorption-desorption process is repeated 8 times.
As a result：After LNC-g-AA/MMT hydrogels adsorption-desorption cycle uses 8 times, Cr3+、Cd2+And Zn2+Adsorption capacity
Respectively 214.9mg/g, 449.8mg/g and 110.7mg/g, its adsorption capacity is slightly compared with hydrogel first adsorption effect
Reduce, the recycling of this explanation LNC-g-AA/MMT hydrogel is smaller on the influence of its adsorption effect, and reason is in 0.5mol/L
HNO3When being parsed in solution, proton easily produces competition with carboxyl metal ion, due to the presence of electrostatic attraction, causes a huge sum of money
Belong to ionic adsorption on the surface of adsorbent, replaced with originally fixed ion.It can be seen that LNC-g-AA/MMT hydrogels have
There is preferable stability, counterweight after being used 8 times than conventional wooden cellulose base hydrogel LNC-g-AA/MMT adsorption-desorption cycles
Metal ion (Zn2+, Cd2+And Cr3+) adsorbance improve 8-12%.
Embodiment 9：
Corn cob fiber element based aquagel desorption cycle uses under EDTA desorptions is carried out according to the following steps：
Appropriate dry gel particle is added to preferable Zn2+, Cd2+And Cr3+In solution concentration, in preferable pH value and balance
Between under the conditions of stirring mixture reach adsorption equilibrium, hydrogel particle is washed with deionized 3 times, in 0.1M EDTA solution
In, the vibration desorption 3h under normal temperature, then using deionized water cleaning for several times, gel particle is re-used for adsorption experiment, inhaled
Attached-desorption cycle uses 6 times.
As a result：After LNC-g-AA/MMT hydrogels adsorption-desorption cycle uses 6 times, Cr3+、Cd2+And Zn2+Adsorption capacity
Respectively 216.9mg/g, 455.6mg/g and 114.7mg/g, its adsorption capacity is slightly compared with hydrogel first adsorption effect
Reduce, the recycling of this explanation LNC-g-AA/MMT hydrogel is smaller on the influence of its adsorption effect.It can be seen that LNC-g-AA/MMT
Hydrogel has preferable stability, and 6 are used than conventional wooden cellulose base hydrogel LNC-g-AA/MMT adsorption-desorption cycles
Heavy metal ion (Zn after secondary2+, Cd2+And Cr3+) adsorbance improve 11-17%.
Claims (10)
1. a kind of preparation method of corn cob fiber element based aquagel, it is characterised in that comprise the following steps：
(1) weigh appropriate corn cob fiber element to be put into three-necked flask, after adding distilled water to dissolve；
(2) montmorillonite is added into step (1) resulting solution, the heating stirring under inert gas shielding；
(3) tetramethylethylenediamine and ammonium persulfate are added into mixing liquid obtained by step (2), is stirring evenly and then adding into acrylic acid
Continue heating stirring with N.N '-methylene-bisacrylamide and obtain hydrogel；
(4) gained hydrogel is added into absolute ethyl alcohol to stand, is cleaned, dried with deionized water.
2. the preparation method of corn cob fiber element based aquagel as claimed in claim 1, it is characterised in that including following step
Suddenly：
(1) weigh appropriate corn cob fiber element to be put into three-necked flask, after adding distilled water to dissolve；
(2) montmorillonite is added into step (1) resulting solution, the heating stirring under N2 protections, heating-up temperature is 75-90 DEG C, is stirred
It is 50-70min to mix the time；
(3) tetramethylethylenediamine and ammonium persulfate are added into mixing liquid obtained by step (2), is stirring evenly and then adding into acrylic acid
With N.N '-methylene-bisacrylamide, continue heating stirring and obtain hydrogel；
(4) gained hydrogel is added into absolute ethyl alcohol and stands 24h, cleaned with deionized water, 24h is dried at 50-70 DEG C.
3. the preparation method of corn cob fiber element based aquagel as claimed in claim 2, it is characterised in that：Add in step (2)
Hot temperature is 85 DEG C, mixing time 60min.
4. the preparation method of corn cob fiber element based aquagel as claimed in claim 3, it is characterised in that：Each component mass ratio
Respectively：Montmorillonite and corn cob fiber element mass ratio are 0.03-0.11；Acrylic acid and corn cob fiber element mass ratio are 8-
24；N.N '-methylene-bisacrylamide and corn cob fiber element mass ratio are 0.1-0.5；Tetramethylethylenediamine is fine with corncob
The volume/mass ratio of dimension element is 0.2mL/g；Ammonium persulfate is 0.2 with corn cob fiber element mass ratio.
5. the preparation method of corn cob fiber element based aquagel as claimed in claim 4, it is characterised in that：Each component mass ratio
Respectively：Montmorillonite and corn cob fiber element mass ratio are 0.05-0.08；Acrylic acid and corn cob fiber element mass ratio are 12-
20；N.N '-methylene-bisacrylamide and corn cob fiber element mass ratio are 0.2-0.4.
6. the preparation method of corn cob fiber element based aquagel as claimed in claim 5, it is characterised in that：The quality of each component
Than being respectively：Montmorillonite is 0.08 with corn cob fiber element mass ratio；Acrylic acid is 16 with corn cob fiber element mass ratio；
N.N '-methylene-bisacrylamide is 0.2 with corn cob fiber element mass ratio.
7. the preparation method of corn cob fiber element based aquagel as claimed in claim 1, it is characterised in that：The corncob is fine
Tieing up plain extracting method includes：Corncob is put into nitric acid-alcohol mixed solution, reacted in a heated condition, gained is reacted
Product filtering, it is dried to constant weight.
8. the preparation method of corn cob fiber element based aquagel as claimed in claim 7, it is characterised in that：Nitric acid-the second
Nitric acid/ethanol mass ratio is 1 in mixed alkoxide solution：4；The heating condition is heating water bath, and temperature is 85 DEG C, during heating response
Between be 1h；The filtering is filtered using G2 glass filters, is repeated 2 times；Drying temperature is 100-120 DEG C.
9. the application of corn cob fiber element based aquagel absorption heavy metal ion prepared by preparation method described in a kind of claim 1
Method, it is characterised in that：Corn cob fiber element based aquagel is added to pH=3.5-6.5, Zn2+, Cd2+And Cr3+Ion concentration
To be adsorbed in 50-800mg/L heavy metal solution, adsorption time 60-120min.
10. application process as claimed in claim 9, it is characterised in that：Corn cob fiber element based aquagel is added to pH=
6.5, Zn2+, Cd2+And Cr3+Concentration is respectively to be adsorbed in 200mg/L, 400mg/L and 800mg/L heavy metal solution, is inhaled
The attached time is 60min.
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