CN110215907A - One kind is for chitosan/γ-AlOOH laminated film of Pb (II) absorption and its preparation method and application in water - Google Patents
One kind is for chitosan/γ-AlOOH laminated film of Pb (II) absorption and its preparation method and application in water 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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- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- 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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- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- 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
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- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a kind of chitosan/γ-AlOOH laminated films and its preparation method and application for Pb (II) absorption in water.This method is specifically: first preparing γ-AlOOH colloidal sol, glutaraldehyde is added after then mixing it with chitosan sol, carry out cross-linking reaction；Chitosan/γ-AlOOH laminated film finally is made after tape casting and drying in complex sol.Compared with single γ-AlOOH film and chitosan film, chitosan prepared by this method/γ-AlOOH laminated film has bigger adsorbance and higher adsorption rate, stronger acid resistance to the Pb (II) in water body, adsorbance to the Pb (II) of 10mg/L is 9.67mg/g, removal rate is up to 96.75%, the residual concentration of Pb (II) can be down to 0.33mg/L in water body, reach the discharge standard of Pb (II) content in national regulation industrial wastewater.
Description
Technical field
The invention belongs to the technical fields of chitosan/γ-AlOOH composite membrane preparation and application, and in particular to Yi Zhongyong
Chitosan/γ-AlOOH laminated film and its preparation method and application of Yu Shuizhong Pb (II) absorption.
Background technique
In recent years, it with industrial rapid development, is produced by fields such as mining, metallurgical industry, chemical fertilizer and machine-building
Raw heavy metal contaminants such as Pb (II), Cd (II), Cu (II), Zn (II), Hg (I) are largely discharged into water body, and agriculture is given
Industry, industry and domestic water bring serious threat.Heavy metal ion cannot be biodegradable because of it and have high toxicity,
So can cause to seriously endanger to human body by the transmitting and enrichment of food chain, wherein Pb (II) will affect the intelligence and bone of people
The development of bone, while indigestion and endocrine disorder are caused, lead to anaemia, hypertension, also destroys renal function and immune function
Energy.Technology currently used for handling heavy metal ion pollutant has absorption method, the precipitation method, membrane separation process, electroosmose process, ion to hand over
Change method, hyperfiltration and bioanalysis etc..Compared to other methods, absorption method is simple with preparation method, it is easy to operate and it is economical can
The advantages that row, it is considered to be one of most suitable technology of heavy metal containing wastewater treatment.
Boehmite (γ-AlOOHxH2O it) is also referred to as class boehmite, is that a kind of composition is unstable, crystallization is imperfect
Thin fold lamella.It has surface area is high, porosity is big, interface Gibbs free energy is high, dispersibility and peptization it is good and
The characteristics such as thixotropic gel, are often applied to field of waste water treatment.CN105107486A discloses a kind of for toxicity Cr (VI) suction
The preparation method and application of attached γ-AlOOH laminated film, precipitate inorganic aluminum salting liquid under alkaline condition, carry out to precipitating
It is centrifuged washing separation；Then add concentrated hydrochloric acid, glacial acetic acid or nitric acid make to precipitate peptization, while add coalescing agent polyvinyl alcohol and
The adsorbent is made after tape casting and drying, the Cr for being 20mg/L to concentration in structure regulator P123 or F127
(VI) eliminating rate of absorption may be up to 99.4%.Zhang et al. (Zhang Y X, Jia Y, Jin Z, Yu X Y, Xu W H,
Luo T,Zhu B J,Liu J H,Huang X J.Self-assembled,monodispersed,flower-likeγ-
AlOOH hierarchical superstructures for efficient and fast removal of heavy
Metal ions from water [J] .CrystEngComm, 2012,14 (9): 2983-3322.) using sodium metaaluminate as silicon source,
Urea is precipitating reagent, polyacrylic acid sodium salt is surfactant, generates monodispersed flower-shaped γ-AlOOH, 5min using hydro-thermal method
When γ-AlOOH be more than 99.0% to the eliminating rate of absorption of Pb (II).But the acid resistance of γ-AlOOH material is poor, in pH=1
There is the shortcomings that being partly dissolved when~5, is easy to cause secondary pollution to water body.
Utilize organic matter and γ-AlOOH is compound forms inorganic-organic composite material, and wherein inorganic matter is formed skeleton
Certain mechanical stability can be provided for composite material, and organic matter is mainly that functional group plays a role, the functional group of carrying (-
NH2,-OH etc.) hydrogen bond or covalent bond can be formed with metal ion, the acidproof of composite material can be improved to a certain extent
Property and absorption property.Chitosan is a kind of linear polymer, be rich in a large amount of hydroxyl and amino, can with metal ion into
Row is effectively compound.CN106853362A discloses a kind of chitosan/aluminium hydroxide compound adsorbent preparation method for adsorbing fluorine,
Chitosan is dissolved in aluminum saline solution, and sodium hydroxide in-situ preparation chitosan/aluminium hydroxide composite particles are added dropwise, are subsequently added into
Glutaraldehyde solution is crosslinked to obtain the adsorbent, and the adsorbance to fluorine ion is 27.23mg/g.Zhang et al. (Zhang H
L,Li P,Wang Z M,Cui W W,Zhang Y,Zhang Y,Zheng S L,Zhang Y.Sustainable
disposal of Cr(VI):adsorption-reduction strategy for treating textile
wastewaters with amino-functionalized boehmite hazardous solid wastes[J].ACS
Sustainable Chemistry and Engineering, 2018,6 (5): 6811-6819.) report a kind of chitosan/
The preparation method of γ-AlOOH composite particles, the material are 81mg/g to the adsorbance of Cr (VI), are γ-AlOOH granular absorptions
3 times of amount.Lyu et al. (Lyu F Y, Yu H Q, Hou T L, Yan L G, Zhang X H, Du B.Efficient and
fast removal of Pb2+and Cd2+from an aqueous solution using a chitosan/Mg-Al-
layered double hydroxide nanocomposite[J].Journal of Colloid and Interface
Science, 2019,539:184-193.) a kind of preparation method of chitosan-magnalium hydrotalcite composite particles, the material are reported
Expect that the maximal absorptive capacity of Pb (II) be 333.3mg/g, removal rate 99.59%.But above-mentioned composite material is powder, absorption
Product after pollutant not only separates difficulty from water body, but also is easy the residual in water body and causes secondary pollution.
To sum up, persistently research preparation condition is mild, has excellent absorption property to toxicity Pb (II) and is easy to from water body
Isolated chitosan/γ-AlOOH laminated film has important scientific meaning.
Summary of the invention
To solve the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is that providing a kind of for Pb in water
(II) chitosan/γ-AlOOH laminated film preparation method adsorbed.
The present invention by sol-gel processing synthesizes uniform and stable γ-AlOOH colloidal sol and chitosan sol carry out it is compound
It is modified, by selecting suitable compound volume ratio and suitable glutaraldehyde additional amount, prepare to Pb (II) pollutant absorption property
Chitosan/γ-AlOOH laminated film that is good, being easy to separate from water body after absorption.
The chitosan for Pb (II) absorption in water obtained another object of the present invention is to provide above-mentioned preparation method/
γ-AlOOH laminated film.
The object of the invention is achieved through the following technical solutions:
Chitosan/γ-AlOOH laminated film preparation method of the one kind for Pb (II) absorption in water, this method be
Using the composite material that sol-gel processing preparation is described under conditions of mild: firstly, at room temperature dissolving ANN aluminium nitrate nonahydrate
In water, ammonium hydroxide is added to be precipitated, obtained precipitate washed with water；Then, by sediment it is evenly dispersed in water and according to
Secondary addition peptizing agent acetic acid and coalescing agent polyvinyl alcohol, carry out aging after mixing evenly at room temperature；Then, uniform by what is obtained
Glutaraldehyde is added in vitreosol after mixing with chitosan sol by certain volume ratio, carry out cross-linking reaction and complex sol is made；
Finally, the complex sol of above-mentioned preparation is uniformly applied on substrate, make its tape casting, and shell is made after being dried at room temperature for
Glycan/γ-AlOOH laminated film.
The preparation method specifically includes the following steps:
(1) 6.3 mass parts ANN aluminium nitrate nonahydrates are dissolved in the water at room temperature, 20 parts by volume are then added, concentration is
The ammonium hydroxide of 5wt% is precipitated；Precipitating, is then dispersed in water by the precipitate washed with water that will be obtained, under stirring condition according to
0.305 parts by volume acetic acid of secondary addition and the poly-vinyl alcohol solution containing 0.5 mass parts polyvinyl alcohol, at room temperature at 90 DEG C after stirring 1h
Under the conditions of aging for 24 hours, be made γ-AlOOH colloidal sol；
(2) γ-AlOOH colloidal sol obtained in step (1) is cooled to room temperature, then presses certain volume with chitosan sol
Than being mixed to prepare mixed sols；
(3) mixed sols in step (2) is taken, glutaraldehyde solution, stirring a period of time, finally by chitosan/γ-is added
AlOOH complex sol is coated in tape casting on substrate, and taking film after being dried at room temperature for off is the chitosan/γ-
AlOOH composite membrane.
The precipitating and the ratio of acetic acid are according to molar ratio: (amount of precipitating is according to nine hydration nitre for acetic acid/precipitating=0.3
Sour aluminium reacts with ammonia water calculating).
The concentration of the poly-vinyl alcohol solution is 5wt%.
The volume ratio of the γ-AlOOH colloidal sol and chitosan sol is 1/9~9；The concentration of the chitosan sol is
2wt%, preparation method are that 2g chitosan is taken to be dissolved in 2v/v% acetic acid aqueous solution.γ-AlOOH the collosol concentration is
2wt%.
The concentration of the glutaraldehyde solution is 5wt%, and the volume of glutaraldehyde solution and the ratio of mixed sols volume are
(0.5~1): 20.
Mixing time in the step (3) is 10h, drying time 48h.
Chitosan/γ-AlOOH laminated film acid resistance that above-mentioned preparation method obtains significantly increases, in the water of pH=2
Massless is lost after impregnating 1h in solution；And under same soaking conditions, the mass loss of γ-AlOOH film 24%, chitosan
The mass loss of film 100%.
The chitosan/γ-AlOOH laminated film can be used for the Pb (II) in adsorbent solution.
The chitosan/γ-AlOOH laminated film, the Pb (II) for adsorbing pH=5, solubility is 10~50mg/L
The residual concentration of the Pb (II) of 10mg/L can be down to 0.33mg/L, reach Pb (II) in national regulation industrial wastewater and contain by solution
The discharge standard of amount.
When adsorbing Pb (II) solution of pH=5, solubility for 50mg/L, wherein single γ-AlOOH film and chitosan are thin
Film is respectively 18.54mg/g and 15.81mg/g to the adsorbance of Pb (II), and the chitosan/γ-AlOOH laminated film is to Pb
(II) adsorbance is 25.00~31.18mg/g.
Principle is based on technical solution of the present invention: can still be formed after γ-AlOOH colloidal sol and chitosan sol mixing
Transparent, uniform and stable complex sol, the addition of glutaraldehyde make to be crosslinked between γ-AlOOH and chitosan, generate new
Covalent bond-C (=O) OAl- group, improve chitosan/γ-AlOOH laminated film acid resistance and stability, and made
Standby chitosan/γ-AlOOH laminated film is rich in functional groups such as hydroxyl and amino, in pH=5 ,-OH and-NH2Easy deprotonation
Change formation-O- and-NH-, it is high to the adsorption efficiency of the positive valence state ion of aqueous solution, be conducive to positive valence state metal ion (such as Pb
(II)) absorption.
Chitosan prepared by the present invention/γ-AlOOH laminated film has following major advantage:
(1) using colloidal sol it is solidifying-glue method and cross-linking method, preparation process it is simple to operation.
(2) chitosan/γ-AlOOH laminated film acid resistance is preferable, and massless is lost in the aqueous solution of pH=2, no
Dissolution.
(3) there is biggish adsorbance (31.18mg/g) and higher eliminating rate of absorption to the Pb (II) in water body
(96.70%), and the residual concentration of the Pb (II) of 10mg/L can be down to 0.33mg/L, reaches Pb in national regulation industrial wastewater
(II) discharge standard of content.
(4) chitosan/γ-AlOOH laminated film after adsorbing Pb (II) is easy to separate from water body, will not generate secondary
Pollution.
Detailed description of the invention
Fig. 1 is chitosan/γ-AlOOH laminated film in embodiment 1-7 to the curve of adsorption kinetics of Pb (II)；
Fig. 2 is the typical chitosan of embodiment 1/γ-AlOOH laminated film, the γ-AlOOH film of embodiment 8 and implementation
The corresponding XRD spectrum of chitosan film sample of example 9；
Fig. 3 is that chitosan/γ-AlOOH laminated film sample of embodiment 1 adsorbs the FT-IR map before and after Pb (II)；
Fig. 4 is γ-AlOOH film, chitosan film, chitosan/γ-AlOOH laminated film acid resistance detection front and back matter
The comparison diagram of amount；
Fig. 5 is chitosan/γ-AlOOH laminated film photo in embodiment 1.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.For not specifically specified technological parameter, routine techniques progress can refer to.
Room temperature, room temperature are at 24-28 DEG C during the test of the embodiment of the present invention.
Embodiment 1:
(1) 6.3g ANN aluminium nitrate nonahydrate is dissolved in the deionized water of 15mL at room temperature, be then slowly added dropwise 20mL,
The ammonium hydroxide of 5wt%；Until by the pH ≈ 7 of obtained sediment deionized water centrifuge washing to filtrate, then precipitating is dispersed
In the deionized water of 30mL (amount of precipitating reacts with ammonia water calculating according to ANN aluminium nitrate nonahydrate), with the rate magnetic of 500r/min
Power stirring, sequentially adds the poly-vinyl alcohol solution of 0.305mL acetic acid and the 5wt% of 10g, at room temperature in 90 DEG C of oil baths after stirring 1h
Under the conditions of aging for 24 hours.
(2) γ-AlOOH colloidal sol obtained in step (1) is cooled to room temperature, then (2wt% dissolves with chitosan sol
In 2v/v% acetic acid aqueous solution) γ-AlOOH colloidal sol by volume: chitosan sol=1 mixing.
(3) the mixed sols 20mL in step (2) is taken, the 5wt% glutaraldehyde of 1mL is added, 10h is stirred, finally gathers shell
Sugar/γ-AlOOH complex sol is applied on 2cm × 6cm ceramic wafer, makes its tape casting, and take off after being dried at room temperature for 48h
Lower film obtains the chitosan/γ-AlOOH laminated film.
(4) Pb (II) solution of 50mL, 50mg/L are adsorbed: adjusting pH to 5 with the NaOH solution that concentration is 0.1mol/L, with
0.05g chitosan/γ-AlOOH laminated film sample is added afterwards, the parameter of setting constant temperature oscillation case is 25 DEG C, 150r/min.Shell
Glycan/γ-AlOOH laminated film is shown in Fig. 1 to the curve of adsorption kinetics of Pb (II), and the eliminating rate of absorption to Pb (II) is
62.36%, adsorbance 31.18mg/g.
It adsorbs Pb (II) solution of 50mL, 10mg/L: adjusting pH to 5 with the NaOH solution that concentration is 0.1mol/L, then
0.05g chitosan/γ-AlOOH laminated film sample is added, the parameter of setting constant temperature oscillation case is 25 DEG C, 150r/min.It is compound
Film is 96.75% to the eliminating rate of absorption of Pb (II), adsorbance 9.67mg/g.
Embodiment 2:
(1) 6.3g ANN aluminium nitrate nonahydrate is dissolved in the deionized water of 15mL at room temperature, be then slowly added dropwise 20mL,
The ammonium hydroxide of 5wt%；Until by the pH ≈ 7 of obtained sediment deionized water centrifuge washing to filtrate, then precipitating is dispersed
In the deionized water of 30mL, with the rate magnetic agitation of 500r/min, 0.305mL acetic acid and the 5wt% of 10g are sequentially added
Poly-vinyl alcohol solution, stirs after 1h that aging is for 24 hours under the conditions of 90 DEG C of oil baths at room temperature.
(2) γ-AlOOH colloidal sol obtained in step (1) is cooled to room temperature, then (2wt% dissolves with chitosan sol
In 2v/v% acetic acid aqueous solution) γ-AlOOH colloidal sol by volume: chitosan sol=1 mixing.
(3) the mixed sols 20mL in step (2) is taken, the 5w% glutaraldehyde of 0.5mL is added, 10h is stirred, finally gathers shell
Sugar/γ-AlOOH complex sol is applied on 2cm × 6cm ceramic wafer, makes its tape casting, and take off after being dried at room temperature for 48h
Lower film obtains the chitosan/γ-AlOOH laminated film.
(4) Pb (II) solution of 50mL, 50mg/L are adsorbed: adjusting pH to 5 with the NaOH solution that concentration is 0.1mol/L, with
0.05g chitosan/γ-AlOOH laminated film sample is added afterwards, the parameter of setting constant temperature oscillation case is 25 DEG C, 150r/min.Shell
Glycan/γ-AlOOH laminated film is shown in Fig. 1 to the curve of adsorption kinetics of Pb (II), and the eliminating rate of absorption to Pb (II) is
49.09%, adsorbance 24.55mg/g.
Embodiment 3:
(1) 6.3g ANN aluminium nitrate nonahydrate is dissolved in the deionized water of 15mL at room temperature, be then slowly added dropwise 20mL,
The ammonium hydroxide of 5wt%；Until by the pH ≈ 7 of obtained sediment deionized water centrifuge washing to filtrate, then precipitating is dispersed
In the deionized water of 30mL, with the rate magnetic agitation of 500r/min, 0.305mL acetic acid and the 5wt% of 10g are sequentially added
Poly-vinyl alcohol solution, stirs after 1h that aging is for 24 hours under the conditions of 90 DEG C of oil baths at room temperature.
(2) γ-AlOOH colloidal sol obtained in step (1) is cooled to room temperature, then (2wt% dissolves with chitosan sol
In 2v/v% acetic acid aqueous solution) γ-AlOOH colloidal sol by volume: chitosan sol=1 mixing.
(3) the mixed sols 20mL in step (2) is taken, is applied on 2cm × 6cm ceramic wafer, makes its tape casting, and
Film is taken off after drying 48h at room temperature, obtains the chitosan/γ-AlOOH laminated film.
(4) Pb (II) solution of 50mL, 50mg/L are adsorbed: adjusting pH to 5 with the NaOH solution that concentration is 0.1mol/L, with
0.05g chitosan/γ-AlOOH laminated film sample is added afterwards, the parameter of setting constant temperature oscillation case is 25 DEG C, 150r/min.Shell
Glycan/γ-AlOOH laminated film is shown in Fig. 1 to the curve of adsorption kinetics of Pb (II), and the eliminating rate of absorption to Pb (II) is
46.20%, adsorbance 23.10mg/g.
Embodiment 4:
(1) 6.3g ANN aluminium nitrate nonahydrate is dissolved in the deionized water of 15mL at room temperature, be then slowly added dropwise 20mL,
The ammonium hydroxide of 5wt%；Until by the pH ≈ 7 of obtained sediment deionized water centrifuge washing to filtrate, then precipitating is dispersed
In the deionized water of 30mL, with the rate magnetic agitation of 500r/min, 0.305mL acetic acid and the 5wt% of 10g are sequentially added
Poly-vinyl alcohol solution, stirs after 1h that aging is for 24 hours under the conditions of 90 DEG C of oil baths at room temperature.
(2) γ-AlOOH colloidal sol obtained in step (1) is cooled to room temperature, then (2wt% dissolves with chitosan sol
In 2v/v% acetic acid aqueous solution) γ-AlOOH colloidal sol by volume: chitosan sol=9 mixing.
(3) the mixed sols 20mL in step (2) is taken, the 5wt% glutaraldehyde of 1mL is added, 10h is stirred, finally gathers shell
Sugar/γ-AlOOH complex sol is applied on 2cm × 6cm ceramic wafer, makes its tape casting, and take off after being dried at room temperature for 48h
Lower film obtains the chitosan/γ-AlOOH laminated film.
(4) Pb (II) solution of 50mL, 50mg/L are adsorbed: adjusting pH to 5 with the NaOH solution that concentration is 0.1mol/L, with
0.05g chitosan/γ-AlOOH laminated film sample is added afterwards, the parameter of setting constant temperature oscillation case is 25 DEG C, 150r/min.Shell
Glycan/γ-AlOOH laminated film is shown in Fig. 1 to the curve of adsorption kinetics of Pb (II), and the eliminating rate of absorption to Pb (II) is
54.92%, adsorbance 27.46mg/g.
Embodiment 5:
(1) 6.3g ANN aluminium nitrate nonahydrate is dissolved in the deionized water of 15mL at room temperature, be then slowly added dropwise 20mL,
The ammonium hydroxide of 5wt%；Until by the pH ≈ 7 of obtained sediment deionized water centrifuge washing to filtrate, then precipitating is dispersed
In the deionized water of 30mL, with the rate magnetic agitation of 500r/min, 0.305mL acetic acid and the 5wt% of 10g are sequentially added
Poly-vinyl alcohol solution, stirs after 1h that aging is for 24 hours under the conditions of 90 DEG C of oil baths at room temperature.
(2) γ-AlOOH colloidal sol obtained in step (1) is cooled to room temperature, then (2wt% dissolves with chitosan sol
In 2v/v% acetic acid aqueous solution) γ-AlOOH colloidal sol by volume: chitosan sol=7/3 mixing.
(3) the mixed sols 20mL in step (2) is taken, the 5wt% glutaraldehyde of 1mL is added, 10h is stirred, finally gathers shell
Sugar/γ-AlOOH complex sol is applied on 2cm × 6cm ceramic wafer, makes its tape casting, and take off after being dried at room temperature for 48h
Lower film obtains the chitosan/γ-AlOOH laminated film.
(4) Pb (II) solution of 50mL, 50mg/L are adsorbed: adjusting pH to 5 with the NaOH solution that concentration is 0.1mol/L, with
0.05g chitosan/γ-AlOOH laminated film sample is added afterwards, the parameter of setting constant temperature oscillation case is 25 DEG C, 150r/min.Shell
Glycan/γ-AlOOH laminated film is shown in Fig. 1 to the curve of adsorption kinetics of Pb (II), and the eliminating rate of absorption to Pb (II) is
55.12%, adsorbance 27.56mg/g.
Embodiment 6:
(1) 6.3g ANN aluminium nitrate nonahydrate is dissolved in the deionized water of 15mL at room temperature, be then slowly added dropwise 20mL,
The ammonium hydroxide of 5wt%；Until by the pH ≈ 7 of obtained sediment deionized water centrifuge washing to filtrate, then precipitating is dispersed
In the deionized water of 30mL, with the rate magnetic agitation of 500r/min, 0.305mL acetic acid and the 5wt% of 10g are sequentially added
Poly-vinyl alcohol solution, stirs after 1h that aging is for 24 hours under the conditions of 90 DEG C of oil baths at room temperature.
(2) γ-AlOOH colloidal sol obtained in step (1) is cooled to room temperature, then (2wt% dissolves with chitosan sol
In 2v/v% acetic acid aqueous solution) γ-AlOOH colloidal sol by volume: chitosan sol=3/7 mixing.
(3) the mixed sols 20mL in step (2) is taken, the 5wt% glutaraldehyde of 1mL is added, 10h is stirred, finally gathers shell
Sugar/γ-AlOOH complex sol is applied on 2cm × 6cm ceramic wafer, makes its tape casting, and take off after being dried at room temperature for 48h
Lower film obtains the chitosan/γ-AlOOH laminated film.
(4) Pb (II) solution of 50mL, 50mg/L are adsorbed: adjusting pH to 5 with the NaOH solution that concentration is 0.1mol/L, with
0.05g chitosan/γ-AlOOH laminated film sample is added afterwards, the parameter of setting constant temperature oscillation case is 25 DEG C, 150r/min.Shell
Glycan/γ-AlOOH laminated film is shown in Fig. 1 to the curve of adsorption kinetics of Pb (II), and the eliminating rate of absorption to Pb (II) is
50.72%, adsorbance 25.36mg/g.
Embodiment 7:
(1) 6.3g ANN aluminium nitrate nonahydrate is dissolved in the deionized water of 15mL at room temperature, be then slowly added dropwise 20mL,
The ammonium hydroxide of 5wt%；Until by the pH ≈ 7 of obtained sediment deionized water centrifuge washing to filtrate, then precipitating is dispersed
In the deionized water of 30mL, with the rate magnetic agitation of 500r/min, 0.305mL acetic acid and the 5wt% of 10g are sequentially added
Poly-vinyl alcohol solution, stirs after 1h that aging is for 24 hours under the conditions of 90 DEG C of oil baths at room temperature.
(2) γ-AlOOH colloidal sol obtained in step (1) is cooled to room temperature, then (2wt% dissolves with chitosan sol
In 2v/v% acetic acid aqueous solution) γ-AlOOH colloidal sol by volume: chitosan sol=1/9 mixing.
(3) the mixed sols 20mL in step (2) is taken, the 5wt% glutaraldehyde of 1mL is added, 10h is stirred, finally gathers shell
Sugar/γ-AlOOH complex sol is applied on 2cm × 6cm ceramic wafer, makes its tape casting, and take off after being dried at room temperature for 48h
Lower film obtains the chitosan/γ-AlOOH laminated film.
(4) Pb (II) solution of 50mL, 50mg/L are adsorbed: adjusting pH to 5 with the NaOH solution that concentration is 0.1mol/L, with
0.05g chitosan/γ-AlOOH laminated film sample is added afterwards, the parameter of setting constant temperature oscillation case is 25 DEG C, 150r/min.Shell
Glycan/γ-AlOOH laminated film is shown in Fig. 1 to the curve of adsorption kinetics of Pb (II), and the eliminating rate of absorption to Pb (II) is
50.00%, adsorbance 25.00mg/g.
Embodiment 8:
In order to compare chitosan/absorption property of the γ-AlOOH laminated film before compound, it is thin to be prepared for γ-AlOOH
Film, step and performance test are as follows:
(1) 6.3g ANN aluminium nitrate nonahydrate is dissolved in the deionized water of 15mL at room temperature, be then slowly added dropwise 20mL,
The ammonium hydroxide of 5wt%；Until by the pH ≈ 7 of obtained sediment deionized water centrifuge washing to filtrate, then precipitating is dispersed
In the deionized water of 30mL, with the rate magnetic agitation of 500r/min, 0.305mL acetic acid and the 5wt% of 10g are sequentially added
Poly-vinyl alcohol solution, stirs after 1h that aging is for 24 hours under the conditions of 90 DEG C of oil baths at room temperature.By γ-AlOOH colloidal sol after being cooled to room temperature
It is applied on 2cm × 6cm ceramic wafer, makes its tape casting, and take film off after being dried at room temperature for 48h.
(2) Pb (II) solution of 50mL, 50mg/L are adsorbed: adjusting pH to 5 with the NaOH solution that concentration is 0.1mol/L, with
After be separately added into 0.05g γ-AlOOH film sample, the parameter of setting constant temperature oscillation case is 25 DEG C, 150r/min.γ-AlOOH
Film is 37.08% to the eliminating rate of absorption of Pb (II), adsorbance 18.54mg/g.
Embodiment 9:
In order to compare chitosan/absorption property of the γ-AlOOH laminated film before compound, it is prepared for chitosan film,
Step and performance test are as follows:
(1) chitosan sol (2wt% is dissolved in 2v/v% acetic acid aqueous solution) is applied on 2cm × 6cm ceramic wafer,
Make its tape casting, and takes film off after being dried at room temperature for 48h.
(2) Pb (II) solution of 50mL, 50mg/L are adsorbed: adjusting pH to 5 with the NaOH solution that concentration is 0.1mol/L, with
After be separately added into 0.05g chitosan film sample, the parameter of setting constant temperature oscillation case is 25 DEG C, 150r/min.Chitosan film
Eliminating rate of absorption to Pb (II) is 31.62%, adsorbance 15.81mg/g.
Embodiment 10:
In order to detect chitosan/γ-AlOOH laminated film acid resistance, to " embodiment 1 ", " embodiment 8 " and " reality
Apply the film sample in example 9 " takes 0.05g to be added in aqueous solution of the 50mL with the HCl solution adjusting pH=2 of 0.1mol/L respectively,
The parameter that constant temperature oscillation case is arranged is 25 DEG C, 150r/min, duration of oscillation 1h.The result shows that: the quality damage of γ-AlOOH film
Lose 24%, the mass loss of chitosan film 100%, chitosan/γ-AlOOH laminated film mass loss 0% can
See it is compound after film acid resistance reinforce.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (9)
1. chitosan/γ-AlOOH laminated film preparation method of the one kind for Pb (II) absorption in water, it is characterised in that packet
It includes following steps: firstly, being at room temperature dissolved in water ANN aluminium nitrate nonahydrate, ammonium hydroxide is added and is precipitated, obtained sediment
It is washed with water；Then, in water and peptizing agent acetic acid and coalescing agent polyvinyl alcohol, room are sequentially added for sediment is evenly dispersed
Aging is carried out under temperature after mixing evenly；Then, obtained homogeneous transparent colloidal sol and chitosan sol are mixed by certain volume ratio
Glutaraldehyde is added after conjunction, carries out cross-linking reaction, complex sol is made；Finally, complex sol is uniformly applied on substrate, make it
Tape casting, and chitosan/γ-AlOOH laminated film is made after being dried at room temperature for.
2. a kind of chitosan/γ-AlOOH laminated film system for Pb (II) absorption in water according to claim 1
Preparation Method, which is characterized in that the preparation method specifically includes the following steps:
(1) 6.3 mass parts ANN aluminium nitrate nonahydrates are dissolved in the water at room temperature, 20 parts by volume are then added, concentration is 5wt%'s
Ammonium hydroxide is precipitated；Precipitating, is then dispersed in water by the precipitate washed with water that will be obtained, and sequentially adds under stirring condition
0.305 parts by volume acetic acid and poly-vinyl alcohol solution containing 0.5 mass parts polyvinyl alcohol are stirred after 1h at room temperature under the conditions of 90 DEG C
For 24 hours, γ-AlOOH colloidal sol is made in aging；
(2) γ-AlOOH colloidal sol obtained in step (1) is cooled to room temperature, then mixed by certain volume ratio with chitosan sol
It closes and mixed sols is made；
(3) mixed sols in step (2) is taken, glutaraldehyde solution, stirring a period of time, finally by chitosan/γ-is added
AlOOH complex sol is coated in tape casting on substrate, and taking film after being dried at room temperature for off is the chitosan/γ-
AlOOH composite membrane.
3. a kind of chitosan/γ-AlOOH laminated film system for Pb (II) absorption in water according to claim 1
Preparation Method, which is characterized in that described precipitate with the ratio of acetic acid is according to molar ratio: acetic acid/precipitating=0.3.
4. a kind of chitosan/γ-AlOOH laminated film system for Pb (II) absorption in water according to claim 1
Preparation Method, which is characterized in that the concentration of the poly-vinyl alcohol solution is 5wt%.
5. a kind of chitosan/γ-AlOOH laminated film system for Pb (II) absorption in water according to claim 1
Preparation Method, which is characterized in that the volume ratio of the γ-AlOOH colloidal sol and chitosan sol is 1/9~9；The chitosan sol
Concentration with γ-AlOOH colloidal sol is 2wt%.
6. a kind of chitosan/γ-AlOOH laminated film system for Pb (II) absorption in water according to claim 1
Preparation Method, which is characterized in that the concentration of the glutaraldehyde solution is 5wt%, the volume and mixed sols volume of glutaraldehyde solution
Ratio be (0.5~1): 20.
7. a kind of chitosan/γ-AlOOH laminated film system for Pb (II) absorption in water according to claim 1
Preparation Method, which is characterized in that the mixing time in the step (3) is 10h, drying time 48h.
8. a kind of chitosan as made from any one of claim 1-7 the method/γ-AlOOH laminated film.
9. application of the chitosan according to any one of claims 8/γ-AlOOH laminated film in the Pb (II) in adsorbent solution.
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