CN112871138A - Chitosan composite film adsorbent material and preparation method and application thereof - Google Patents
Chitosan composite film adsorbent material and preparation method and application thereof Download PDFInfo
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 96
- 239000002131 composite material Substances 0.000 title claims abstract description 85
- 239000000463 material Substances 0.000 title claims abstract description 39
- 239000003463 adsorbent Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000084 colloidal system Substances 0.000 claims abstract description 32
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 31
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 31
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 14
- 150000002500 ions Chemical class 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000000017 hydrogel Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000005266 casting Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 19
- 239000012153 distilled water Substances 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000004809 Teflon Substances 0.000 claims description 13
- 229920006362 Teflon® Polymers 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 1
- 238000004065 wastewater treatment Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 33
- 239000000975 dye Substances 0.000 abstract description 15
- 239000010865 sewage Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 2
- 229940107698 malachite green Drugs 0.000 description 12
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 12
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 11
- PGSADBUBUOPOJS-UHFFFAOYSA-N neutral red Chemical compound Cl.C1=C(C)C(N)=CC2=NC3=CC(N(C)C)=CC=C3N=C21 PGSADBUBUOPOJS-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 9
- 239000002156 adsorbate Substances 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
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- 208000024827 Alzheimer disease Diseases 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 208000018737 Parkinson disease Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000000673 graphite furnace atomic absorption spectrometry Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 210000003932 urinary bladder Anatomy 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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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
-
- 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
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Chemical & Material Sciences (AREA)
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- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a chitosan composite film adsorbent material and a preparation method and application thereof, wherein the preparation method of the material comprises the following steps: (1) preparing chitosan composite colloid: adding polyvinyl alcohol aqueous solution and montmorillonite powder into chitosan hydrogel, and stirring to obtain chitosan composite colloid; (2) and casting the chitosan composite colloid in a mold, drying to obtain the mold containing the chitosan composite film material, then immersing the mold in alkali liquor, and washing, drying and stripping to obtain the chitosan composite film adsorbent material (PCM). The PCM prepared by the invention has good adsorption effect on heavy metal ions and dyes, can be widely applied to sewage purification, has low preparation cost and simple preparation operation, can be industrially produced in large scale, does not cause secondary pollution to the environment, is easy to recover, and is a potential heavy metal ion and dye adsorption material.
Description
Technical Field
The invention belongs to the field of water treatment agents and preparation thereof, and particularly relates to a composite film adsorbent material and a preparation method and application thereof.
Background
In recent years, natural water sources are seriously polluted due to the wild discharge of industrial sewage, and the human health is greatly threatened. Among these industrial sources of contamination, high concentrations of heavy metal ions (e.g., copper, zinc, silver) can seriously threaten our health, including kidney, brain, liver and bladder damage, bowel disease, alzheimer's disease and parkinson's disease; and the chroma of the waste water is very large because the dyes (such as malachite green, neutral red and methyl blue) have chromogenic groups, and the light transmittance is also greatly reduced even if the concentration of the dyes in the water body is very low, so that the photosynthesis of an aquatic ecosystem is influenced, and the damage of the aquatic ecosystem is caused. Therefore, there is a need to find a method for effectively removing heavy metal ions and dyes from polluted water. At present, water pollution treatment methods are various and comprise a chemical method, an ion exchange method, a membrane filtration method and an adsorption method. The adsorption method has high pollution resistance efficiency, easy treatment, low cost and recyclability, thus being one of the best choices for sewage treatment.
The film is a commonly used sewage treatment material, and is mainly prepared by an electrostatic spinning technology and a freeze drying technology at present, but the methods have the defects of low production efficiency, high production cost and the like. Chitosan (CTS) is a product obtained after deacetylation of chitin, and contains a large amount of hydroxyl (-OH) and amino (-NH) on its molecular chain2) The active functional groups can form stable complexes with a plurality of heavy metal ions. Montmorillonite (MMT) is a natural inorganic material with negative charges, which can adsorb most cationic dyes by electrostatic action, and is a well-known excellent cationAn ionic dye adsorbate.
Disclosure of Invention
The invention aims to provide a chitosan composite film adsorbent material and a preparation method and application thereof, and aims to solve the problems that in the prior art, a sewage treatment agent is low in removal rate of heavy metal ions and dyes, high in cost, difficult to recover and the like.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a chitosan composite film adsorbent material comprises the following steps:
(1) preparing chitosan composite colloid: adding polyvinyl alcohol aqueous solution and montmorillonite (MMT) powder into chitosan hydrogel, and stirring to obtain chitosan composite colloid;
(2) preparing a chitosan composite film adsorbent material: casting the chitosan composite colloid in a mould, drying to obtain a mould containing a chitosan composite film material, and then immersing the mould in alkali liquor to neutralize residual acetic acid in the film; and washing the film with distilled water, drying and stripping to obtain the chitosan composite film adsorbent material (PCM).
In the step (1), the chitosan hydrogel is obtained by dissolving Chitosan (CTS) in distilled water, adding glacial acetic acid, and mechanically stirring and uniformly mixing.
Further, in the step (1), the polyvinyl alcohol aqueous solution is obtained by dissolving polyvinyl alcohol (PVA) in hot water and uniformly stirring; the mass ratio of polyvinyl alcohol to water in the polyvinyl alcohol aqueous solution is (1-3): (35-65). Further preferably, the temperature of the hot water is 60-90 ℃.
Further, in the step (1), the stirring is carried out at the temperature of 30-50 ℃ for 5-8 h.
In the further scheme, in the step (1), the mass ratio of polyvinyl alcohol to chitosan in the chitosan composite colloid is (0.40-0.60): 1.
in the step (2), the mold is a teflon mold, and the mass of the chitosan composite colloid cast in the teflon mold is 2-5 g.
In the step (2), the alkali liquor is an aqueous solution of NaOH or KOH, and the concentration of the alkali liquor is 0.05-0.3 mol/L.
The invention also aims to provide the chitosan composite film adsorbent material (PCM) prepared by the preparation method. The MMT in the PCM is uniformly distributed in the PVA/CTS carrier.
The third purpose of the invention is to provide the application of the chitosan composite film adsorbent material in the treatment of heavy metal ions and dye sewage. In particular to the treatment of sewage containing copper ions (Cu (II)), zinc ions (Zn (II)), silver ions (Ag (I)), Malachite Green (MG), Neutral Red (NR) and Methyl Blue (MB).
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts a gel casting method, and prepares the chitosan composite film adsorbent material (PCM) with controllable thickness by controlling the mass of the chitosan colloid added into the mould. The prepared film material has uniform thickness and uniform surface. In the sewage treatment process, after PCM adsorption is finished, the PCM composite film can be directly separated from water, so that the secondary pollution of an adsorption material to a water body is avoided, the recovery and the reutilization of the PCM composite film are realized, the operation is simple, the utilization rate of the PCM is greatly improved, and the investment cost of sewage treatment is reduced while the environment is friendly.
(2) The molecular chain of chitosan contains a large amount of hydroxyl (-OH) and amino (-NH)2) The invention takes polyvinyl alcohol (PVA) enhanced Chitosan (CTS) composite hydrogel (PVA/CTS) as a carrier, and the surface of the prepared PCM composite film contains a large amount of amino (-NH)2) And active functional groups such as hydroxyl (-OH) and the like, can form stable complexes with a plurality of heavy metal ions, and has stronger adsorption capacity to the heavy metal ions in the sewage. Experiments prove that the PCM prepared by the invention has good adsorption effect on heavy metal ions in an aqueous solution.
(3) Montmorillonite (MMT) has negative charges and can effectively adsorb cationic dye. According to the invention, MMT is used as an adsorption enhancer, a large amount of MMT is distributed on the surface and inside of the prepared PCM composite film, and the prepared PCM composite film can adsorb cationic dye in water through electrostatic interaction. Experiments prove that the PCM prepared by the method has good adsorption effect on the dye in the aqueous solution, and can be widely applied to industrial sewage treatment and domestic application water purification.
(4) The PCM provided by the invention has low preparation cost and simple preparation operation, can be industrially produced in a large scale, does not cause secondary pollution to the environment, is easy to recover, and is a potential heavy metal ion and dye adsorption material.
Drawings
FIG. 1 is an SEM image of a PCM composite film prepared in example 1;
FIG. 2 is an FTIR plot of a PCM composite film prepared in example 1;
FIG. 3 is an XRD pattern of a PCM composite film prepared in example 1;
FIG. 4 is an optical photograph of the PCM composite film prepared in example 1 adsorbing distilled water, Malachite Green (MG), Neutral Red (NR), Methyl Blue (MB), copper ions (Cu (II)), zinc ions (Zn (II)), and silver ions (Ag (I)), respectively;
FIG. 5 is a graph of adsorption strength of the PCM composite film prepared in example 1 for MG, NR, MB, Cu (II), Zn (II), and Ag (I) versus adsorption time;
FIG. 6 is a graph of adsorption strength of the PCM composite film prepared in example 1 for MG, NR, MB, Cu (II), Zn (II), and Ag (I) as a function of initial concentration.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Preparing chitosan composite colloid: 4g of Chitosan (CTS) powder and 80g of distilled water were charged into a 250mL three-necked flask, and 2mL of glacial acetic acid was added thereto, and mechanically stirred for 60min to obtain a chitosan hydrogel. Meanwhile, 2g of polyvinyl alcohol powder was added to 50mL of 80 ℃ distilled water and sufficiently stirred to obtain an aqueous polyvinyl alcohol solution. Adding polyvinyl alcohol aqueous solution and 2g of montmorillonite powder into the chitosan hydrogel, and mechanically stirring for 6 hours at 40 ℃ to obtain the chitosan composite colloid.
(2) Preparing a chitosan composite film adsorbent material: taking out 3g of the chitosan composite colloid, casting the chitosan composite colloid into Teflon mold grooves with the length, width and depth of 80 multiplied by 40 multiplied by 3mm respectively, and placing the chitosan composite colloid in an oven at 60 ℃ for drying for 6 hours. And (3) immersing the dried Teflon mould containing the chitosan composite film material into 0.1mol/L NaOH solution for 5min, taking out and fully cleaning with distilled water. And finally, placing the Teflon die containing the chitosan film in a 60 ℃ drying oven for 2h, and stripping the chitosan composite film adsorbent material and naming the material as PCM.
Comparative example 1
4g of Chitosan (CTS) powder and 80g of distilled water were charged into a 250mL three-necked flask, and 2mL of glacial acetic acid was added thereto, and mechanically stirred for 60 min. Meanwhile, 2g of polyvinyl alcohol powder was added to 50mL of 80 ℃ distilled water and sufficiently stirred to obtain an aqueous polyvinyl alcohol solution. Adding polyvinyl alcohol aqueous solution into the chitosan colloid, and mechanically stirring for 6h at 40 ℃ to obtain the chitosan composite colloid. And then the chitosan composite colloid is used for obtaining the chitosan composite film adsorbent material PC without montmorillonite according to the same method in the step (2) of the embodiment 1.
FIG. 1 is SEM images of the surface (A) and cross-section (B) of the PCM composite film prepared in example 1, from which it can be seen that MMT is uniformly distributed in the film and the thickness of the PCM film is 29.49 μm.
FIG. 2 is an FTIR chart showing the PCM, PC composite films prepared in example 1 and comparative example 1, from which it can be seen that the MMT is 844cm-1The characteristic peak at (Si-O-Si) was also found in the PCM composite film, and this result indicates that the PCM composite film does contain the MMT component. Secondly, the FTIR spectrum of PCM also contains characteristic peaks of PC, including 1552cm-1(amino II),1408cm-1(C-N stretching vibration) and 1020cm-1(C-O stretching vibration). FTIR results indicate that the prepared PCM composite film indeed contains MMT, PVA and CTS components.
Fig. 3 is an XRD pattern of the PCM and PC composite films prepared in example 1 and comparative example 1, from which it can be seen that characteristic peaks of MMT at 2 θ of 5.95 ° (d001),19.95 ° (d020),22.05 ° (d100) and 26.9 ° (d101) are substantially disappeared in the XRD pattern of the PCM, indicating that MMT is well intercalated in the PCM composite film.
Heavy metal ion/dye adsorption test
The volume is 20mL, and the initial concentration C is certain0Adding 5mg PCM composite film into 50-1600mg/L solution to be adsorbed, standing at room temperature for a certain time (6-84h), and respectively testing and calculating the concentration (C) of the solution after adsorptione). The concentrations of the dyes (MB, NR and MG) were determined by direct spectrophotometry (UV-1800, Shimadzu, Japan), while the heavy metal ions (Cu (II), Zn (II), Ag (I)) were determined by graphite furnace atomic absorption spectrometry (Varian Spectral-600, Varian Inc., Palo Alto, USA). Equilibrium adsorption Strength (q)e) Calculated by equation 6.1.
Wherein: q. q.se(mg/g) is the adsorption strength of the PCM composite film material to the adsorbate in adsorption equilibrium, C0And Ce(mol/L) is the adsorbate concentration at the onset of adsorption and at the equilibrium of adsorption, respectively, m (g) is the amount of adsorbent material added (dry weight), and V (L) is the solution volume. All adsorption experiments were repeated three times and the average value was taken as the adsorption value.
Fig. 4 is an optical photograph of the PCM composite film prepared in example 1 after adsorbing distilled water, Malachite Green (MG), Neutral Red (NR), Methyl Blue (MB), copper ions (cu), (ii), zinc ions (zn (ii)), and silver ions (ag (i)), respectively, and it can be seen that the film after adsorption exhibits an inherent color of an adsorbate.
Fig. 5 is a graph showing the relationship between the adsorption strength and the adsorption time of the PCM composite film prepared in example 1, and it can be seen from the graph that the adsorption strength of the six adsorbates increases rapidly with the increase of time within 12 hours from the beginning of adsorption, while the adsorption strength increases more slowly from 12h to 72h, and the adsorption equilibrium is substantially reached at 72 h.
FIG. 6 is a graph of the adsorption strength of the PCM composite film prepared in example 1 as a function of the initial concentration of adsorbate, from which it can be seen that the adsorption strength increases with the increase of the initial concentration of adsorbate, and that the adsorption strengths of the PCM composite film to MG, NR, MB, Cu (II), Zn (II), and Ag (I) reach maximum values of 738.0,408.4,2569.3,377.8,650.0 and 567.0MG/g, respectively, when the initial concentration of adsorbate reaches 1200 MG/L.
Example 2
(1) Preparing chitosan composite colloid: 4g of Chitosan (CTS) powder and 100g of distilled water were added to a 250mL three-necked flask, and 2mL of glacial acetic acid was added thereto, and mechanically stirred for 60min to obtain a chitosan hydrogel. Meanwhile, 2g of polyvinyl alcohol powder was added to 30mL of 50 ℃ distilled water and sufficiently stirred to obtain an aqueous polyvinyl alcohol solution. Adding polyvinyl alcohol aqueous solution and 2g of montmorillonite powder into the chitosan hydrogel, and mechanically stirring for 6 hours at 40 ℃ to obtain the chitosan composite colloid.
(2) Preparing a chitosan composite film adsorbent material: taking out 3g of the chitosan composite colloid, casting the chitosan composite colloid into Teflon mold grooves with the length, width and depth of 80 multiplied by 40 multiplied by 3mm respectively, and placing the chitosan composite colloid in an oven at 60 ℃ for drying for 6 hours. And (3) immersing the dried Teflon mould containing the chitosan composite film material into 0.1mol/L KOH solution for 5min, taking out and fully cleaning with distilled water. And finally, placing the Teflon die containing the chitosan film in a 60 ℃ oven for 2h, and stripping the chitosan composite film adsorbent material (PCM). The thickness of the film of the PCM prepared in this example was about 30 μm.
Example 3
(1) Preparing chitosan composite colloid: 4g of Chitosan (CTS) powder and 80g of distilled water were charged into a 250mL three-necked flask, and 2mL of glacial acetic acid was added thereto, and mechanically stirred for 60min to obtain a chitosan hydrogel. Meanwhile, 2g of polyvinyl alcohol powder was added to 50mL of 80 ℃ distilled water and sufficiently stirred to obtain an aqueous polyvinyl alcohol solution. Adding polyvinyl alcohol aqueous solution and 2g of montmorillonite powder into the chitosan hydrogel, and mechanically stirring for 6 hours at 40 ℃ to obtain the chitosan composite colloid.
(2) Preparing a chitosan composite film adsorbent material: taking out 5g of the chitosan composite colloid, casting the chitosan composite colloid into Teflon mold grooves with the length, the width and the depth of 80 multiplied by 40 multiplied by 3mm respectively, and placing the chitosan composite colloid in an oven at 60 ℃ for drying for 4 hours. And (3) immersing the dried Teflon mould containing the chitosan composite film material into 0.2mol/L NaOH solution for 10min, taking out and fully cleaning with distilled water. And finally, placing the Teflon die containing the chitosan film in an oven at 800 ℃ for 2h, and stripping the chitosan composite film adsorbent material (PCM). The thickness of the film of the PCM prepared in this example was about 50 μm.
Claims (10)
1. A preparation method of a chitosan composite film adsorbent material is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing chitosan composite colloid: adding polyvinyl alcohol aqueous solution and montmorillonite powder into chitosan hydrogel, and stirring to obtain chitosan composite colloid;
(2) preparing a chitosan composite film adsorbent material: and casting the chitosan composite colloid in a mold, drying to obtain the mold containing the chitosan composite film material, immersing the mold in alkali liquor, washing the film with distilled water, drying and stripping to obtain the chitosan composite film adsorbent material.
2. The method of claim 1, wherein: in the step (1), the chitosan hydrogel is obtained by dissolving chitosan in distilled water, adding glacial acetic acid, and mechanically stirring and uniformly mixing.
3. The method of claim 1, wherein: in the step (1), the polyvinyl alcohol aqueous solution is obtained by dissolving polyvinyl alcohol in hot water and uniformly stirring; the mass ratio of polyvinyl alcohol to water in the polyvinyl alcohol aqueous solution is (1-3): (35-65).
4. The production method according to claim 3, characterized in that: the temperature of the hot water is 60-90 ℃.
5. The method of claim 1, wherein: in the step (1), the stirring is carried out at the temperature of 30-50 ℃ for 5-8 h.
6. The method of claim 1, wherein: in the step (1), the mass ratio of polyvinyl alcohol to chitosan in the chitosan composite colloid is (0.40-0.60): 1.
7. the method of claim 1, wherein: in the step (2), the mold is a Teflon mold, and the mass of the chitosan composite colloid cast in the Teflon mold is 2-5 g.
8. The method of claim 1, wherein: in the step (2), the alkali liquor is an aqueous solution of NaOH or KOH, and the concentration of the alkali liquor is 0.05-0.3 mol/L.
9. The chitosan composite film adsorbent material prepared by the preparation method as claimed in any one of claims 1 to 8.
10. Use of the chitosan composite membrane adsorbent material of claim 9 in heavy metal ion and dye wastewater treatment.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911206604.0A CN112871138A (en) | 2019-11-29 | 2019-11-29 | Chitosan composite film adsorbent material and preparation method and application thereof |
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