CN107082894A - A kind of double-network hydrogel adsorbent and preparation method thereof and it is used as the application of heavy metal absorbent - Google Patents
A kind of double-network hydrogel adsorbent and preparation method thereof and it is used as the application of heavy metal absorbent Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- 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
- B01J20/28047—Gels
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/24—Homopolymers or copolymers of amides or imides
- C08J2433/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Abstract
The invention discloses a kind of double-network hydrogel adsorbent and preparation method thereof and as the application of heavy metal absorbent, the preparation method of double-network hydrogel adsorbent is that waste cotton cloth material is dissolved in into sodium hydroxide/urea dicyandiamide solution, obtains cellulose solution；The cellulose solution is well mixed with the solution containing acrylamide, crosslinking agent and initiator and is crosslinked and polymerisation, produce mechanical property it is good, rich in active functional group group, hydrogel with cross-linked cellulose and polyacrylamide dual network and three-dimensional porous structure, this method is simple to operate, low cost, be conducive to large-scale production, the double-network hydrogel adsorbent of preparation is used for heavy metal ion adsorbed in water, have the advantages that addition is small, the rate of adsorption is fast, adsorbance is big, the processing available for various heavy metal ion-containing waste waters.
Description
Technical field
It is more particularly to a kind of that there is cross-linked cellulose and the double nets of polyacrylamide the present invention relates to a kind of double-network hydrogel
Network hydrogel and preparation method thereof, and double-network hydrogel as heavy metal absorbent processing heavy metal polluted waste water in
Using belonging to environment functional material and water process new technical field.
Background technology
Industry mining, heavy metal are smelted, electroplate the chemical process of processing printing and dyeing brush, leather manufacture and some new and high technologies
Fast development to discharge aggravation containing heavy metal industrial effluent, and many natural water bodies, drinking water source are also by different degrees of
Pollution, and eventually affect health.The method of current domestic, international heavy metal pollution of water body repairing and treating mainly has chemistry
The precipitation method, absorption, ion exchange, UF membrane etc..Adsorption separation technology is because its material is cheap and easy to get, removal effect is good, secondary dirt
The advantages of contaminating smaller and energy recycling utilization, is constantly subjected to the favor of people, is that Recent study applies place the most active
Therefore the method for managing Pollutants in Wastewater matter, prepares a kind of low cost, efficiency high, segregative sorbing material with very big
Realistic meaning.
Double-network hydrogel, includes the macromolecule hydrogel material of two kinds of separate network structures.Traditional dual network
Hydrogel preparation process, is usually first to synthesize a strata electrolyte network, then is immersed in the monomer of the second layer network, is being triggered
Agent polymerize with the collective effect of crosslinking agent, obtains double-network hydrogel.The mechanical property of double-network hydrogel not two
Kind of hydrogel mechanical property simple plus and, but show the synergy of two kinds of network structures, therefore, drastically increase
The mechanical property of macromolecule hydrogel.Macromolecule hydrogel has three-dimensional network structure, and soluble small molecular can be in three-dimensional
Free diffusing in network, and diffusion coefficient with approaching in aqueous.Therefore, double-network hydrogel has in terms of sorbing material
Potential application value.At present, existing part double-network hydrogel material is applied to the absorption of heavy metal ion through preparing.
Such as Sodium Polyacrylate/graphene oxide dual network gel (Xu et al., 2015.New doublenetwork hydrogel
adsorbent:highly efficient removal of Cd(II)and Mn(II)ionsin aqueous
Solution.Chem.Eng.J.275,179-188.), but need to carry out functional modification to it after gel is prepared
It can be only achieved ideal adsorption effect.
Currently, duds take-back model is broadly divided into three classes：One be charity organization by way of recruitment, two be environmental sanitation system
By way of refuse classification, three be that returned enterprise relies on government's recycling economy intermediate item to carry out duds recovery.Chinese Resources are comprehensive
Close and shown using an item data of association, about 26,000,000 tons friperies are thrown into dustbin every year for China, and reuse ratio is only
Have less than 1%, most friperies are not all re-worked or carried out harmless treatment.The recycling of discarded clothes is again
Using significant, there is presently no the relevant report for being used to prepare high-performance double-network hydrogel adsorbent on friperie.
The content of the invention
The problem of existing for prior art, the purpose of the present invention is to be that provide one kind is prepared using waste cotton cloth material
Mechanical property is good, rich in active functional group group, with cross-linked cellulose and polyacrylamide dual network and three-dimensional porous structure water
The method of gel, this method is simple to operate, low cost, is conducive to large-scale production.
Another object of the present invention is to be to provide a kind of big with three-dimensional porous structure, adsorption site exposed amount, water
Dissolubility small molecule can free diffusing, and to the double-network hydrogel adsorbent of removal of heavy metal ions efficiency high in water.
Third object of the present invention is to be to provide a kind of double-network hydrogel adsorbent weight in removing waste water
Application in terms of metal ion, its to soluble small molecular can free diffusing, and to removal of heavy metal ions efficiency high in water, and
It is environmentally friendly, can be to be applicable.
In order to realize above-mentioned technical purpose, double-network hydrogel is prepared based on waste cotton cloth material the invention provides one kind and inhaled
Attached dose of method, this method is that waste cotton cloth material is dissolved in into sodium hydroxide/urea dicyandiamide solution, obtains cellulose solution；It is described
Cellulose solution is well mixed with the solution containing acrylamide, crosslinking agent I and initiator, is added crosslinking agent II, is further mixed
After closing uniformly, it is crosslinked and polymerisation, is produced.
Technical scheme prepares stability and dispersiveness preferably by using sodium hydroxide/urea dicyandiamide solution
Cellulose solution, makes cellulose fully unfold in the solution, and it exposes abundant oxygen-containing functional group, is adding acrylamide mixing
After solution, can by interaction of hydrogen bond formation laminated structure, the more functional groups of exposure, and by crosslinking agent after, generation
The increase of cellulose network strength, improves its mechanical performance, while generating three-dimensional net structure, makes it have a stronger absorption huge sum of money
Belong to the function of ion.
It is preferred that scheme, the waste cotton cloth material add to concentration for 10~20wt% sodium hydroxide solution in, -5
~5 DEG C of stirring and dissolvings, add the urea liquid that the pre- concentration for being cooled to -5~5 DEG C is 20~30wt%, and stirring obtains cellulose
Solution；The volume ratio of the sodium hydroxide solution and urea liquid is 1:0.8~1.2.
More preferably scheme, the mass volume ratio of the waste cotton cloth material and sodium hydroxide solution is 1g:10~15mL.
It is preferred that scheme, the solution containing acrylamide, crosslinking agent I and initiator and the cellulose solution press volume
Than 1:1~5 mixing.
It is preferred that scheme, the concentration of acrylamide is 250 in the solution containing acrylamide, crosslinking agent I and initiator
~750g/L, crosslinking agent I concentration are 20~30g/L, and the concentration of initiator is 10~20g/L.
It is preferred that scheme, the concentration of the cellulose solution is 40~50g/L.
More preferably scheme, the crosslinking agent I is N, N- methylene-bisacrylamides.It is mainly used in crosslink propylene acyl
Amine.
More preferably scheme, the initiator is potassium peroxydisulfate and/or ammonium persulfate.
It is preferred that scheme, the crosslinking agent II be epoxychloropropane；It is mainly used in cross-linked cellulose.
It is preferred that scheme, the mass volume ratio of the crosslinking agent II and cellulose solution is 1g:10~30mL.More preferably
1g:15~25mL.
More preferably scheme, temperature is 50~70 DEG C in the crosslinking and polymerization process, and the reaction time is 1~5h.
Present invention also offers a kind of double-network hydrogel adsorbent, it is prepared by method described above.
Present invention also offers the application of the double-network hydrogel adsorbent, it is applied to as heavy metal absorbent
Heavy metal ion in adsorption aqueous solution.
It is preferred that scheme, the heavy metal ion includes at least one of Cd, Cu and Pb ion.
It is preferred that scheme, the double-network hydrogel adsorbent in aqueous consumption be 0.5~1.5g/L.It is described water-soluble
Heavy metal ion initial concentration in liquid is 20~300mg/L.
It is preferred that scheme, the pH value of the aqueous solution for 2.0~8.0 (when containing Pb, pH for 2.0~7.0), adsorption time is
1~120min, temperature is 15~35 DEG C.The pH of the aqueous solution is more preferably 4~7.
The present invention proposes a kind of preparation method of the double-network hydrogel adsorbent using waste cotton cloth material as raw material, will be molten
What is obtained after solution waste cotton cloth is cellulose crosslinked as a layer network, and acrylamide polymerization is used as another layer network, the fibre of preparation
Dimension element/acrylamide double-network hydrogel adsorbent has three-dimensional porous structure, is conducive to the exposure of active function groups.Specific system
Standby step is as follows：
1) cotton shredded is added in sodium hydrate aqueous solution, is placed in low temperature water-bath and is cooled to 0 DEG C in advance and stirs
1min；Aqueous solution of urea is cooled to 0 DEG C in advance and is added to immediately in cotton and sodium hydroxide mixed liquor, 2min is stirred vigorously, obtained
To the sticking cellulose solution of tool；
2) acrylamide, N,N methylene bis acrylamide (MBA) and potassium peroxydisulfate are added in deionized water solution
(KPS), dissolve complete, obtain acrylamide, crosslinking agent and initiator mixed aqueous solution；
3) take cellulose solution to be added in mixed aqueous solution to be well mixed, add epoxychloropropane (ECH), mix again
Close uniform, be placed in 60 DEG C of constant temperature ovens and react 2h, take out, be washed with deionized water to neutrality, dry to constant weight, obtain fiber
Element/acrylamide double-network hydrogel material.
Compared with prior art, the advantage of technical solution of the present invention is：
1st, it is real using discarded cotton cloth as the raw material for preparing cellulose/acrylamide double-network hydrogel material
Existing twice laid, wide material sources, and it is cheap；
2nd, the flow of the invention for preparing cellulose/acrylamide double-network hydrogel material is short, simple to operate, it is not necessary to special
Different chemical industry equipment, can effectively realize industrialized production.
3rd, cellulose/acrylamide double-network hydrogel adsorbent of the invention is provided simultaneously with cross-linked cellulose network and poly-
Acrylamide network, both synergistic functions substantially, produce intermolecular interaction, the more active sites of exposure between the two
Point, and both are built into three-dimensional porous structure, surface area is big, makes it have stronger adsorption capacity, substantially increases to waste water
The removal efficiency of middle heavy metal ion, and both double-network hydrogel mechanical performances for being built into single network mechanicalness relatively
Can be improved significantly.
4th, the heavy metal ion that cellulose/acrylamide double-network hydrogel adsorbent of the invention is used in adsorbing, water
Dissolubility small molecule can in three-dimensional network free diffusing, and heavy metal ion is adsorbed, and double-network hydrogel adsorbent
The advantages of showing that usage amount is small, the rate of adsorption is fast, adsorption capacity is big, and be easily recycled.
5th, cellulose/acrylamide double-network hydrogel adsorbent product of the invention is nontoxic, and two will not be produced after absorption
Secondary pollution, it is environmentally friendly.
Brief description of the drawings
【Fig. 1】It is the ESEM signal of cellulose/acrylamide double-network hydrogel adsorbent of the embodiment of the present invention 1
Figure；
【Fig. 2】It is the swelling curve of cellulose/acrylamide double-network hydrogel adsorbent of the embodiment of the present invention 2；
【Fig. 3】It is the ess-strain song of cellulose/acrylamide double-network hydrogel adsorbent of the embodiment of the present invention 3
Line；
【Fig. 4】It is the zero charge point diagram of cellulose/acrylamide double-network hydrogel adsorbent of the embodiment of the present invention 4；
【Fig. 5】It is the pH influence experiments of cellulose/acrylamide double-network hydrogel adsorbent of the embodiment of the present invention 5
Figure；
【Fig. 6】It is the isothermal adsorption song of cellulose/acrylamide double-network hydrogel adsorbent of the embodiment of the present invention 6
Line；
【Fig. 7】It is the kinetic curve of cellulose/acrylamide double-network hydrogel adsorbent of the embodiment of the present invention 7；
【Fig. 8】It is the aspect graph of cellulose/acrylamide double-network hydrogel adsorbent of the embodiment of the present invention 8.
Embodiment
Present invention is described in further details below with reference to Figure of description and specific embodiment, but the present invention
Claims are not limited by the example.
Embodiment 1：
(1) cotton that 4.0g is shredded is added in 48mL sodium hydrate aqueous solutions (mass fraction is 14%), be placed in low
It is cooled to 0 DEG C in advance in tepidarium and stirs 1min.48mL aqueous solution of urea (mass fraction is 24%) is cooled to 0 DEG C in advance and added immediately
Enter into cotton and sodium hydroxide mixed liquor, be stirred vigorously 2min, obtain having sticking cellulose solution.
(2) 1.0g acrylamides, 0.0434g MBA and 0.0272g KPS, dissolving are added in 2mL deionized water solutions
Completely, acrylamide, crosslinking agent and initiator mixed aqueous solution are obtained.
(3) take 6mL (1) to be added in (2) to be well mixed, add 0.0/0.2/0.3/0.4/0.5/0.6mL ECH,
It is well mixed again, is placed in 60 DEG C of constant temperature ovens and reacts 2h, take out, is washed with deionized water to neutrality, dries to constant weight, obtain
To cellulose/acrylamide double-network hydrogel material of six kinds of different crosslinking degrees.
Six kinds of celluloses obtained above/acrylamide double-network hydrogel material appearance is in three-dimensional structure, is freezed
Dry, be placed under scanning ESEM and observe, its exterior appearance is as shown in figure 1, adsorbent is in three-dimensional cross-linked loose structure.
Embodiment 2：
Six kinds of celluloses prepared by embodiment 1/acrylamide double-network hydrogel material, which takes, a certain amount of is placed in 60 DEG C of perseverances
Dried in warm drying box to constant weight, record mass value.Load weighted material is respectively placed in the beaker for filling deionized water,
Every certain time, the mass value of material is weighed, until quality of materials value tends towards stability.Calculate being swelled for different time points material
Rate, as a result as shown in Figure 2.The final swelling ratio of each material is as shown in table 1：
Table 1：The maximum swelling rate of cellulose/acrylamide material
It can be obtained by table 1, with the increase of cross-linked dosage, the swelling ratio of material is reduced.Swelling ratio is too big, and material can be broken, molten
Swollen rate is too small, and adsorption effect can be not so good, and combination property is it is still further preferred that cellulose/acrylamide -3.
Embodiment 3：
By embodiment 1 prepare without dry six kinds of celluloses/acrylamide double-network hydrogel material with omnipotent examination
The machine of testing is compressed performance test, and stress-strain diagram is as shown in Figure 3.Stress decrease turning point is the break-up point of material in figure,
Corresponding deformation is the largest deformation value of material.As a result show, six kinds of materials all have good mechanical performance.
Embodiment 4：
Six kinds of celluloses prepared by embodiment 1/acrylamide double-network hydrogel material takes a certain amount of (mass/volume
=1g/L) 0.1MNaCl of different initial pH values is placed in, in the constant temperature oscillation bed that 25 DEG C of rotating speeds are 160rpm, react 12h.Instead
After the completion of answering, the pH value and record of supernatant are measured, Δ pH value is calculated, as a result as shown in Figure 4.With the increasing of cross-linked dosage
Greatly, the point of zero electric charge reduction of material, shows that the acidic functionality of material surface and inside is reduced.
Embodiment 5：
Six kinds of celluloses prepared by embodiment 1/acrylamide double-network hydrogel materials application is in heavy metal in waste water
Processing, comprise the following steps (six kinds materials carry out same steps processing)：Configuring each ten parts of initial concentrations of Cd, Cu and Pb is
50mg/L solution, is respectively 2.0,2.5,3.0,3.5,4.0,5.0,6.0,7.0,8.0 with sodium hydroxide or salt acid for adjusting pH.Claim
Take a certain amount of adsorbent to be added in a certain amount of heavy metal ion solution (mass/volume=1g/L), be placed on 25 DEG C
Rotating speed is takes out after reaction 2h in 160rpm constant temperature oscillation bed, standing separation takes out supernatant, uses atomic absorption spectrphotometry
The concentration of heavy metal ion in meter measurement supernatant.Influence of the solution initial pH value to material adsorption effect is as shown in Figure 5.By scheming
5 can obtain, and when pH value is equal to 2, removal of heavy metal ions rate is generally relatively low, as pH rises clearance increase until stable.
Embodiment 6：
Six kinds of celluloses prepared by embodiment 1/acrylamide double-network hydrogel materials application is in heavy metal in waste water
Processing, comprise the following steps (six kinds materials carry out same steps processing)：Configure initial concentration be 20,40,60,80,100,
150th, 200,300mg/L Cd, Cu and Pb solution, the pH value of regulation solution is 5.0.A certain amount of heavy metal solution is taken, is added respectively
Enter a certain amount of adsorbent (mass/volume=1g/L), be placed in the constant temperature oscillation bed that 15 DEG C of rotating speeds are 160rpm and react
Taken out after 2h, standing separation takes out supernatant, the concentration of heavy metal ion in supernatant is measured with atomic absorption spectrophotometer.
And 25 and 35 DEG C of heavy metal adsorption experiments are carried out, operating process is identical with 15 DEG C.Heavy metal ion under the different temperatures of calculating
Adsorbance result is as shown in Figure 6.By Tu Ke get, the removal amount of heavy metal ion increases with the increase of initial concentration, and becomes
In stable.Under same initial concentration, with the rise of temperature, removal amount increase.
Embodiment 7：
Six kinds of celluloses prepared by embodiment 1/acrylamide double-network hydrogel materials application is in heavy metal in waste water
Processing, comprise the following steps：Cd, Cu and Pb solution that initial concentration is 50/100mg/L are configured, regulation pH value is 5.0.Take
A certain amount of heavy metal solution, is separately added into a certain amount of adsorbent (mass/volume=1g/L), is placed on 25 DEG C of rotating speeds and is
In 160rpm constant temperature oscillation bed, take out, standing separation takes out supernatant, use after reaction 1,2,3,4,5,10,15,20,30min
The concentration of heavy metal ion in atomic absorption spectrophotometer measurement supernatant.The heavy metal concentration result of the absorption of calculating is as schemed
Shown in 7.
Embodiment 8：
Cellulose solution prepared by embodiment 1 takes 6.0mL to be added to 2.0mL acrylamide, crosslinking agent and initiator
In mixed aqueous solution, four parts are prepared altogether, is divided into two groups and adds 0 respectively, 0.3mLECH is well mixed, and are respectively placed in 60 DEG C of constant temperature bakings
Case and room temperature, react 2h.Material shape figure is as shown in Figure 8 a, it can be seen that the cellulose/acrylamide -1 for not adding ECH exists
Under room temperature condition, there is no successful polymerization shaping during reaction 2h.Cellulose/acrylamide -3 can gather under the conditions of room temperature and 60 DEG C
Synthesis type, but color is inconsistent, shows that extent of polymerization is different.
Cellulose solution prepared by embodiment 1 takes 6.0mL to be added to 2.0mL acrylamide, crosslinking agent and initiator
In mixed aqueous solution, add such as 0.3mL ECH after being well mixed again, rock mixing, be distributed into three parts, be placed on 60 DEG C of constant temperature bakings
In case, taken out after 1,2,5h are reacted respectively.The form of three parts of materials is observed, as shown in Figure 8 b.As can be seen that the reaction time is 1h
When, material does not have polymerization complete；React after 5h, the form at material two ends is inconsistent, the moisture content reduction of one end；React after 2h, material
Expect that form is good.
Claims (10)
1. a kind of method that double-network hydrogel adsorbent is prepared based on waste cotton cloth material, it is characterised in that：By waste cotton cloth material
Sodium hydroxide/urea dicyandiamide solution is dissolved in, cellulose solution is obtained；The cellulose solution with containing acrylamide, crosslinking agent I and
The solution of initiator is well mixed, and adds crosslinking agent II, after being further well mixed, is crosslinked and polymerisation, produced.
2. the method according to claim 1 that double-network hydrogel adsorbent is prepared based on waste cotton cloth material, its feature is existed
In：In the sodium hydroxide solution that it is 10~20wt% to concentration that the waste cotton cloth material, which is added, in -5~5 DEG C of stirring and dissolvings, then
The urea liquid that the pre- concentration for being cooled to -5~5 DEG C is 20~30wt% is added, stirring obtains cellulose solution；The hydroxide
The volume ratio of sodium solution and urea liquid is 1:0.8~1.2.
3. the method according to claim 2 that double-network hydrogel adsorbent is prepared based on waste cotton cloth material, its feature is existed
In：The mass volume ratio of the waste cotton cloth material and sodium hydroxide solution is 1g:10~15mL.
4. the method that double-network hydrogel adsorbent is prepared based on waste cotton cloth material according to any one of claims 1 to 3,
It is characterized in that：
The solution containing acrylamide, crosslinking agent I and initiator and the cellulose solution by volume 1:1~5 mixing；
The concentration of acrylamide is 250~750g/L, crosslinking agent I in the solution containing acrylamide, crosslinking agent I and initiator
Concentration be 20~30g/L, and initiator concentration be 10~20g/L；
The concentration of the cellulose solution is 40~50g/L.
5. the method according to claim 4 that double-network hydrogel adsorbent is prepared based on waste cotton cloth material, its feature is existed
In：
The crosslinking agent I is N,N methylene bis acrylamide；
The initiator is potassium peroxydisulfate and/or ammonium persulfate.
6. the method according to claim 1 that double-network hydrogel adsorbent is prepared based on waste cotton cloth material, its feature is existed
In：
The crosslinking agent II is epoxychloropropane；
The mass volume ratio of the crosslinking agent II and cellulose solution are 1g:10~30mL.
7. the side that double-network hydrogel adsorbent is prepared based on waste cotton cloth material according to claims 1 to 3,6 any one
Method, it is characterised in that：Temperature is 50~70 DEG C in the crosslinking and polymerization process, and the reaction time is 1~5h.
8. a kind of double-network hydrogel adsorbent, it is characterised in that：Prepared by any one of claim 1~7 methods described.
9. the application of the double-network hydrogel adsorbent described in claim 8, it is characterised in that：It is used as heavy metal absorbent application
Heavy metal ion in adsorption aqueous solution.
10. the application of double-network hydrogel adsorbent according to claim 9, it is characterised in that：
The addition of the double-network hydrogel adsorbent in aqueous is 0.5~1.5g/L；
Heavy metal ion initial concentration in the aqueous solution is 20~300mg/L；
The pH value of the aqueous solution is 2.0~8.0, and temperature is 15~35 DEG C；
The heavy metal ion includes at least one of cadmium ion, copper ion and lead ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710408835.4A CN107082894B (en) | 2017-06-02 | 2017-06-02 | A kind of double-network hydrogel adsorbent and preparation method thereof and application as heavy metal absorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710408835.4A CN107082894B (en) | 2017-06-02 | 2017-06-02 | A kind of double-network hydrogel adsorbent and preparation method thereof and application as heavy metal absorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
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| CN107082894B CN107082894B (en) | 2019-08-06 |
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| CN109485878A (en) * | 2018-11-28 | 2019-03-19 | 五邑大学 | High-intensity and high-tenacity regenerated fiber hydrogel and preparation method thereof |
| CN109865502A (en) * | 2019-04-10 | 2019-06-11 | 广东海洋大学 | Modified water treatment agent of a kind of oyster shell powder and its preparation method and application |
| CN110270317A (en) * | 2019-05-29 | 2019-09-24 | 绍兴文理学院元培学院 | A kind of preparation method of the cellulose base hydrogel adsorbent for heavy metal containing wastewater treatment |
| CN111004353A (en) * | 2019-12-18 | 2020-04-14 | 中国热带农业科学院海口实验站 | Preparation method and application of high-strength double-network hydrogel |
| CN113522251A (en) * | 2021-07-13 | 2021-10-22 | 浙江农林大学 | Heavy metal adsorption material and preparation method thereof |
| CN114672044A (en) * | 2022-04-26 | 2022-06-28 | 中国林业科学研究院林产化学工业研究所 | Cellulose conductive hydrogel and preparation method thereof |
| CN114762821A (en) * | 2021-01-13 | 2022-07-19 | 上海昶法新材料有限公司 | Heavy metal adsorbent, raw material composition, preparation method and application |
| CN115073669A (en) * | 2022-06-30 | 2022-09-20 | 东华大学 | Preparation method of cellulose-based adsorption flocculation material for wastewater treatment |
| CN116970187A (en) * | 2023-04-25 | 2023-10-31 | 常熟威怡科技有限公司 | Preparation method of carboxyl cellulose composite hydrogel containing nitrogen crown ether |
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| CN109126739A (en) * | 2018-08-21 | 2019-01-04 | 浙江理工大学 | It is a kind of for removing the preparation method of the Studies On Preparation And Properties of Cellulose-based Adsorbents of antimony ion in dyeing waste water |
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| CN109865502A (en) * | 2019-04-10 | 2019-06-11 | 广东海洋大学 | Modified water treatment agent of a kind of oyster shell powder and its preparation method and application |
| CN109865502B (en) * | 2019-04-10 | 2022-05-17 | 广东海洋大学 | Oyster shell powder modified water treatment agent and preparation method and application thereof |
| CN110270317B (en) * | 2019-05-29 | 2021-11-09 | 绍兴文理学院元培学院 | Preparation method of cellulose-based hydrogel adsorbent for heavy metal wastewater treatment |
| CN110270317A (en) * | 2019-05-29 | 2019-09-24 | 绍兴文理学院元培学院 | A kind of preparation method of the cellulose base hydrogel adsorbent for heavy metal containing wastewater treatment |
| CN111004353A (en) * | 2019-12-18 | 2020-04-14 | 中国热带农业科学院海口实验站 | Preparation method and application of high-strength double-network hydrogel |
| CN114762821A (en) * | 2021-01-13 | 2022-07-19 | 上海昶法新材料有限公司 | Heavy metal adsorbent, raw material composition, preparation method and application |
| CN113522251A (en) * | 2021-07-13 | 2021-10-22 | 浙江农林大学 | Heavy metal adsorption material and preparation method thereof |
| CN114672044A (en) * | 2022-04-26 | 2022-06-28 | 中国林业科学研究院林产化学工业研究所 | Cellulose conductive hydrogel and preparation method thereof |
| CN115073669A (en) * | 2022-06-30 | 2022-09-20 | 东华大学 | Preparation method of cellulose-based adsorption flocculation material for wastewater treatment |
| CN115073669B (en) * | 2022-06-30 | 2023-10-20 | 东华大学 | Preparation method of cellulose-based adsorption flocculation material for wastewater treatment |
| CN116970187A (en) * | 2023-04-25 | 2023-10-31 | 常熟威怡科技有限公司 | Preparation method of carboxyl cellulose composite hydrogel containing nitrogen crown ether |
| CN116970187B (en) * | 2023-04-25 | 2024-01-23 | 常熟威怡科技有限公司 | Preparation method of carboxyl cellulose composite hydrogel containing nitrogen crown ether |
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