CN111607115A - Preparation method of high-strength hydrogel film capable of continuously treating dyeing sewage - Google Patents
Preparation method of high-strength hydrogel film capable of continuously treating dyeing sewage Download PDFInfo
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- CN111607115A CN111607115A CN202010555728.6A CN202010555728A CN111607115A CN 111607115 A CN111607115 A CN 111607115A CN 202010555728 A CN202010555728 A CN 202010555728A CN 111607115 A CN111607115 A CN 111607115A
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- 238000004043 dyeing Methods 0.000 title claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002131 composite material Substances 0.000 claims abstract description 23
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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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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- B01J20/28047—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
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- 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
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- C08J3/075—Macromolecular gels
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- 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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- C08J2329/00—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 at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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Abstract
The invention belongs to the field of dyeing sewage treatment, and provides a preparation method of a high-strength hydrogel film capable of continuously treating dyeing sewage. The preparation method is based on a tape casting method to prepare a film, adopts polyvinyl alcohol as a base material, and greatly improves the mechanical property of the hydrogel film by introducing nano titanium dioxide. Meanwhile, because the nano titanium dioxide has the property of decomposing the dye through photocatalysis, the obtained film can decompose the adsorbed dye under the condition of natural illumination, and can be recycled without post-treatment. The preparation method is simple to operate and low in cost, the obtained polyvinyl alcohol-titanium dioxide composite hydrogel film has the advantages of high mechanical strength, high dye adsorption speed, large adsorption capacity and in-situ dye decomposition under natural light, continuous treatment of dyeing sewage can be realized without separating dye adsorption films and post-treatment conditions, the cost is reduced, and the efficiency is improved.
Description
Technical Field
The invention belongs to the field of composite material preparation, particularly relates to the field of dyeing sewage treatment, and particularly relates to a preparation method of a high-strength hydrogel film capable of continuously treating dyeing sewage.
Background
In recent years, the problem of wastewater treatment due to dye contamination has attracted much attention. A large amount of dye enters natural water areas along with the discharge of industrial sewage such as textile, printing and dyeing, plastics and the like. Due to the complex components of the dye, the carrying of harmful substances and the difficulty in degradation in natural water, the existence of the dye can cause the imbalance of water ecological civilization and harm the health of human beings, animals and plants. At present, the treatment method of dye wastewater mainly comprises an extraction method, an adsorption method, a biological method, an electrochemical method, a coagulation sedimentation method, a catalytic oxidation method and the like, wherein the adsorption method is one of the most common treatment methods. The research and development of the adsorbent in the adsorption method are crucial, and the efficiency and the cost for treating the dyeing wastewater are directly determined.
The hydrogel film adsorbent not only has the advantages of easy separation, environmental protection and the like of the hydrogel adsorbent, but also has high specific surface area, and is an ideal adsorption material. However, in use, hydrogel film adsorbents still suffer from two problems: (1) the mechanical strength is low. Due to the limitation of the geometrical size, the bearing capacity of the film is weak. However, the film can bear various complicated loads in preparation and application, and the film is easy to break due to low mechanical strength. (2) Dye adsorption and in situ degradation cannot be continued. After the film absorbs the dye and reaches saturation, the film cannot continuously absorb the dye, so that the film cannot be reused, and secondary pollution can be formed on the film absorbing the dye.
The method provides a preparation method of a high-strength hydrogel film capable of continuously treating dyeing sewage. Polyvinyl alcohol (PVA) is taken as a substrate, and nano titanium dioxide (TiO) is added2) The mechanical property of the obtained film is greatly improved, and the complex mechanical load in preparation and application can be resisted. Meanwhile, the nano titanium dioxide has the property of decomposing the dye through photocatalysis, so that the prepared composite hydrogel film can decompose the adsorbed dye under the natural illumination condition, and the film can be directly recycled without separation and post-treatment. The developed polyvinyl alcohol-titanium dioxide composite hydrogel film has the advantages of high mechanical strength, high dye adsorption speed, large adsorption capacity and in-situ dye decomposition under natural light. The preparation method is simple to operate and low in cost, successfully realizes the characteristics of high strength and dye in-situ decomposition of the hydrogel film adsorbent, can realize continuous treatment of dyeing sewage without separating and adsorbing the dye film and under the condition of aftertreatment, reduces the cost and improves the efficiency.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides high-strength polyvinyl alcohol-titanium dioxide (PVA-TiO) for continuously treating dyeing sewage2) A method for preparing a hydrogel film. Adding a small amount of titanium dioxide (TiO) to polyvinyl alcohol (PVA)2) And using the mixed solution of water and dimethyl sulfoxide (DMSO) as precursor solvent, and using acid solution and sodium carbonate (Na)2CO3) As a pore-forming agent, a film is prepared on an aluminum foil by a tape casting method, and a freezing-thawing physical crosslinking method is adopted to prepare the composite hydrogel film. The application of the dye in the field of sustainable adsorption and decomposition of the dye is verified by testing the mechanical property and the dye adsorption property of the dye.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a high-strength hydrogel film capable of continuously treating dyeing sewage comprises the following steps:
firstly, adding polyvinyl alcohol, titanium dioxide and sodium carbonate into a mixed solution of dimethyl sulfoxide and deionized water according to a certain proportion, heating in a constant-temperature water bath at 90-99 ℃, stirring until the polyvinyl alcohol is completely melted and uniformly mixing the rest substances to obtain a mixed solution A.
In the mixed solution A, the mass fraction of polyvinyl alcohol is 10-18 wt.%, the mass fraction of titanium dioxide is 0.05-5 wt.%, and the mass fraction of sodium carbonate is 0.05-5 wt.%. In the mixed solution of the dimethyl sulfoxide and the deionized water, the volume ratio of the dimethyl sulfoxide to the deionized water is 1: 9-9: 1.
And secondly, dropwise adding an acid solution into the mixed solution A, and continuously stirring for 0.5h at 70 ℃ until the sodium carbonate and the acid fully react to generate bubbles to obtain mixed solution B. And adding 0.5-5 mL of acid solution into each 100mL of the mixed solution A.
The acid solution comprises one of acetic acid, hydrochloric acid, citric acid and nitric acid, wherein the mass fraction of the hydrochloric acid and the nitric acid is 15 wt.%, and the mass fraction of the acetic acid and the citric acid is 30 wt.%.
And thirdly, preparing the mixed solution B into a film with the thickness of 50-500 mu m on an aluminum foil by a tape casting method, and performing freezing and unfreezing circulation on the film to obtain the polyvinyl alcohol-titanium dioxide composite hydrogel film. The freezing and thawing cycle refers to that the film is frozen and molded, taken out and thawed, and repeated for many times. The freezing temperature is-18 to-25 ℃, the freezing time is 12 to 20 hours, the unfreezing temperature is 15 to 25 ℃, and the unfreezing time is 4 to 12 hours. The number of cycles is 1 or more.
Based on PVA-TiO obtained by preparation2The composite hydrogel film was subjected to tensile property test at a tensile rate of 100% strain/min.
Based on PVA-TiO obtained by preparation2The composite hydrogel film is used for carrying out dye adsorption and photocatalytic dye decomposition tests, and the method comprises the following specific steps:
1) preparing a methylene blue dye solution or a Congo red dye solution with a certain initial concentration, and taking 100mL of the solution for an adsorption experiment. Adding PVA-TiO with certain mass into the dye solution2The composite hydrogel film is used as an adsorbent;
2) placing the dye solution containing the film adsorbent under sunlight, and simultaneously performing adsorption and photocatalysis until the dye in the solution is completely treated and the film becomes transparent to naked eyes;
3) according to the set time interval, an ultraviolet spectrophotometer is used for testing the concentration of the current dye solution, and PVA-TiO at different time intervals is calculated2The adsorption capacity of the composite hydrogel film to the dye. The experiments have previously determined standard curves for methylene blue and congo red dye solutions.
The invention provides high-strength PVA-TiO for sustainable treatment of dyeing sewage2The formation mechanism of the composite hydrogel film is as follows: the nanometer titanium dioxide particles are introduced into a polyvinyl alcohol gel system, on one hand, the mechanical strength of the material is improved by doping the rigid nanometer particles, and on the other hand, the in-situ decomposition of the dye is realized by utilizing the catalytic decomposition capability of the titanium dioxide on organic matters under the illumination condition. In order to enhance the light transmittance of the hydrogel film, dimethyl sulfoxide is added into the hydrogel precursor solution as a solvent to limit the formation of large-size crystals in the crystallization process, which is macroscopically embodied as that the hydrogel film is transparent, thereby ensuring the photodecomposition efficiency of titanium dioxide to dye. Meanwhile, carbon dioxide generated by the reaction of sodium carbonate and the acid solution is used as a pore-forming agent, so that the porosity and the pore diameter of the material are improved, the adsorption capacity and the adsorption speed are increased, and the dye treatment efficiency is improved.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides high-strength PVA-TiO for sustainable treatment of dyeing sewage2The preparation method of the composite hydrogel film has the advantages of simple use, low cost, easy recovery and the like of the conventional hydrogel film adsorbent, and the mechanical property of the obtained film is greatly improved by introducing the nano titanium dioxide, so that the complex mechanical load in preparation and application can be resisted. Meanwhile, the prepared PVA-TiO has the property of decomposing dye by photocatalysis2The composite hydrogel film has the advantages of high dye adsorption speed, large adsorption capacity and in-situ decomposition of the dye under natural light. The preparation method is simple to operate and low in cost, successfully realizes the characteristics of high strength and dye in-situ decomposition of the hydrogel film adsorbent, and can be continuously applied to various productsThe dye is adsorbed and decomposed in a water area environment.
Drawings
FIG. 1 shows PVA-TiO2Scanning electron microscope topography of the composite hydrogel film;
FIG. 2 shows PVA-TiO2Drawing the tensile property of the composite hydrogel film;
FIG. 3 shows PVA-TiO in light2The effect graph of the composite hydrogel film absorbing dye.
Detailed Description
The following describes in detail a specific embodiment of the invention with reference to fig. 1, 2 and 3 of the technical implementation and the accompanying description.
FIG. 1 shows PVA-TiO prepared in example 12And (3) a topography of the composite hydrogel film, and performing freeze drying treatment on the prepared hydrogel film to keep an original structure from being damaged. The polyvinyl alcohol is observed to be in a regular grid shape through an electron microscope photo, and a large number of holes of about 10 mu m exist in the hydrogel and spherical nano titanium dioxide particles exist in the hydrogel from the amplified section morphology. Wherein (a) is an electron microscope image magnified 100 times and (b) is an electron microscope image magnified 6000 times. FIG. 2 shows PVA-TiO prepared in example 12The tensile strength of the composite hydrogel film is 14.3 +/-1.6 MPa, which is more than ten times higher than that of pure PVA hydrogel. FIG. 3 shows PVA-TiO treated with light in example 12The composite hydrogel film is used as an adsorbent to adsorb the dye in the solution, and the adsorption quantity is continuously increased. Meanwhile, the dye is decomposed by the photocatalysis of titanium dioxide, and the condition that the methylene blue dye solution with blue initial state becomes transparent can be observed, so that the PVA-TiO for dye sewage treatment2The hydrogel film was visually transparent, consistent with that before use, indicating that the hydrogel film had sustained dye handling capability.
Example 1
a) 15g of PVA and 2g of TiO were mixed2、3g Na2CO3Adding into a mixed solution of 80mL of DMSO and deionized waterThe product ratio is 4: and 6, heating in a constant-temperature water bath at 90 ℃, stirring until the PVA is completely melted and uniformly mixing the rest substances to obtain a mixed solution A.
b) And dropwise adding 3mL of acetic acid into the mixed solution A, and continuously stirring at 70 ℃ for 0.5h until the sodium carbonate and the acetic acid fully react to generate bubbles to obtain a mixed solution B. The mass fraction of acetic acid was 30 wt.%.
c) Preparing the mixed solution B into a film with the thickness of 100 mu m on an aluminum foil by a tape casting method, and performing freezing and unfreezing circulation on the film, wherein the freezing temperature is-20 ℃, the freezing time is 16 hours, the unfreezing temperature is 25 ℃, the unfreezing time is 5 hours, and the circulation time is 3 times to obtain PVA-TiO2And (3) compounding the hydrogel film.
PVA-TiO prepared based on the steps2The composite hydrogel film is subjected to dye adsorption and photocatalytic dye decomposition experiments, and comprises the following specific steps:
preparing a methylene blue dye/Congo red solution with the initial concentration of 200mg/mL, and taking 100mL of the solution for an adsorption experiment. To the above dye solution was added 20mg of PVA-TiO2The composite hydrogel film is used as an adsorbent.
2) The dye solution containing the film adsorbent is placed under the sunlight, so that the adsorption and the photocatalysis are simultaneously carried out. After treatment, the methylene blue dye solution which is blue in the initial state becomes transparent, and the PVA-TiO for treating dye sewage is used2The hydrogel film is in a transparent state visible to naked eyes and is consistent with that before use;
3) according to the set time interval, an ultraviolet spectrophotometer is used for testing the concentration of the current dye solution, and PVA-TiO at different time intervals is calculated2The adsorption capacity of the composite hydrogel film to the dye. The experiments have previously determined standard curves for methylene blue and congo red dye solutions.
Example 2
a) 10g of PVA and 0.05g of TiO were mixed2、0.15g Na2CO3And adding 89.8mL of mixed solution of DMSO and deionized water, wherein the volume ratio of the DMSO to the deionized water is 1: and heating in a constant-temperature water bath at the temperature of 9 and 99 ℃, stirring until the PVA is completely melted and uniformly mixing the rest substances to obtain a mixed solution A.
b) And (3) dropwise adding 0.5mL of hydrochloric acid with the mass fraction of 15% into the mixed solution A, and continuously stirring at 70 ℃ for 0.5h until the sodium carbonate and the hydrochloric acid fully react to generate bubbles to obtain a mixed solution B. The mass fraction of hydrochloric acid was 15 wt.%.
c) Preparing the mixed solution B into a film with the thickness of 50 mu m on an aluminum foil by a tape casting method, and performing freezing and unfreezing circulation on the film, wherein the freezing temperature is-25 ℃, the freezing time is 18 hours, the unfreezing temperature is 20 ℃, the unfreezing time is 6 hours, and the circulation time is 5 times to obtain PVA-TiO2And (3) compounding the hydrogel film.
The dye adsorption and photocatalytic dye decomposition experiments were the same as in example 1.
Example 3
a) 18g of PVA and 4g of TiO were mixed2、5g Na2CO3Adding 73mL of mixed solution of DMSO and deionized water, wherein the volume ratio of the DMSO to the deionized water is 8: heating in a constant-temperature water bath at the temperature of 2 and 95 ℃, stirring until the PVA is completely melted and uniformly mixing the rest substances to obtain a mixed solution A.
b) And dropwise adding 5mL of citric acid into the mixed solution A, and continuously stirring at 70 ℃ for 0.5h until the sodium carbonate and the citric acid fully react to generate bubbles to obtain a mixed solution B. The mass fraction of citric acid was 30 wt.%.
c) Preparing the mixed solution B into a film with the thickness of 380 mu m on an aluminum foil by a tape casting method, and performing freezing and unfreezing circulation on the film, wherein the freezing temperature is-18 ℃, the freezing time is 12 hours, the unfreezing temperature is 15 ℃, the unfreezing time is 12 hours, and the circulation time is 4 times to obtain PVA-TiO2And (3) compounding the hydrogel film.
The dye adsorption and photocatalytic dye decomposition experiments were the same as in example 1.
The above-mentioned embodiments only express the embodiments of the present invention, but not should be understood as the limitation of the scope of the invention patent, it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the concept of the present invention, and these all fall into the protection scope of the present invention.
Claims (4)
1. A preparation method of a high-strength hydrogel film capable of continuously treating dyeing sewage is characterized by comprising the following steps:
firstly, adding polyvinyl alcohol, titanium dioxide and sodium carbonate into a mixed solution of dimethyl sulfoxide and deionized water according to a proportion, heating in a constant-temperature water bath at 90-99 ℃, stirring until the polyvinyl alcohol is completely melted and uniformly mixing the rest substances to obtain a mixed solution A; in the mixed solution A, the mass fraction of polyvinyl alcohol is 10-18 wt.%, the mass fraction of titanium dioxide is 0.05-5 wt.%, and the mass fraction of sodium carbonate is 0.05-5 wt.%;
secondly, dropwise adding an acid solution into the mixed solution A, and continuously stirring for 0.5h at 70 ℃ until the sodium carbonate and the acid fully react to generate bubbles to obtain mixed solution B; adding 0.5-5 mL of acid solution into every 100mL of the mixed solution A;
thirdly, preparing the mixed solution B into a film with the thickness of 50-500 mu m on an aluminum foil by a tape casting method, and performing freezing and unfreezing circulation on the film to obtain a polyvinyl alcohol-titanium dioxide composite hydrogel film; the freezing and thawing cycle refers to that the film is frozen and molded, taken out and thawed, and repeated for many times; the freezing temperature is-18 to-25 ℃, the freezing time is 12 to 20 hours, the unfreezing temperature is 15 to 25 ℃, and the unfreezing time is 4 to 12 hours.
2. The preparation method of the high-strength hydrogel film capable of continuously treating the dyeing wastewater according to claim 1, wherein the volume ratio of the dimethyl sulfoxide to the deionized water in the mixed solution of the dimethyl sulfoxide and the deionized water is 1: 9-9: 1.
3. The method of claim 1, wherein the acid solution comprises one of acetic acid, hydrochloric acid, citric acid and nitric acid.
4. The method for preparing a high-strength hydrogel film capable of continuously treating dyed sewage according to claim 3, wherein the mass fraction of the hydrochloric acid and the nitric acid is 15 wt.%, and the mass fraction of the acetic acid and the citric acid is 30 wt.%.
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| CN109762182A (en) * | 2019-01-02 | 2019-05-17 | 大连理工大学 | A kind of high intensity-porous structure polyvinyl alcohol-tannin acid hydrogel preparation method and application |
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| CN109762182A (en) * | 2019-01-02 | 2019-05-17 | 大连理工大学 | A kind of high intensity-porous structure polyvinyl alcohol-tannin acid hydrogel preparation method and application |
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