CN114471469A - Dye recovery material without secondary pollution, preparation method thereof and dye recovery method - Google Patents
Dye recovery material without secondary pollution, preparation method thereof and dye recovery method Download PDFInfo
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- CN114471469A CN114471469A CN202210010611.9A CN202210010611A CN114471469A CN 114471469 A CN114471469 A CN 114471469A CN 202210010611 A CN202210010611 A CN 202210010611A CN 114471469 A CN114471469 A CN 114471469A
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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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3425—Regenerating or reactivating of sorbents or filter aids comprising organic materials
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3441—Regeneration or reactivation by electric current, ultrasound or irradiation, e.g. electromagnetic radiation such as X-rays, UV, light, microwaves
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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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
- C02F2101/00—Nature of the contaminant
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Abstract
The invention discloses a preparation method of a dye recovery material without secondary pollution, which comprises the following steps: adding bismuth nitrate pentahydrate into the mixed solution, and performing ultrasonic treatment and stirring to dissolve the bismuth nitrate pentahydrate; after reaction in a polytetrafluoroethylene hydrothermal reaction kettle, cooling, centrifuging, washing and drying to obtain bismuth formate oxide; adding bismuth oxyformate into the mixed solution, performing ultrasonic treatment and stirring until the bismuth oxyformate is dissolved; dissolving citric acid in water, mixing the two solutions, adjusting the pH value, reacting in a polytetrafluoroethylene hydrothermal reaction kettle, cooling, centrifuging, washing and drying to obtain the dye recovery material. The material prepared by the invention can realize the desorption effect on pollutants only by illumination, and has the outstanding advantages of easy control, no secondary pollution and the like.
Description
Technical Field
The invention relates to the technical field of functional material preparation and water pollution treatment, in particular to a dye recovery material without secondary pollution, a preparation method thereof and a dye recovery method.
Background
The treatment of industrial waste water has been a problem due to the complex and variable composition of the industrial waste water. On the other hand, many substances in the industrial wastewater can be recycled, so that the treatment cost can be reduced, and the environmental pollution can be reduced. The dye wastewater has the characteristics of high chromaticity, salinity, biotoxicity and the like, and a large amount of dye wastewater can not be well treated every year, so that the dye wastewater not only causes great harm to the natural environment and organisms, but also wastes resources due to the waste dye. The dye in the wastewater is recycled and reused, and the national important strategic requirements are met. The adsorption is widely applied due to the advantages of simple operation, high efficiency and the like, and the molecular structure of the adsorbed substance cannot be changed by the adsorption, so that the adsorption is the most suitable treatment mode for dye recovery. The desorption of the adsorbed dye is a difficult problem. Currently, desorption is achieved by adjusting pH, changing temperature or adding chemical agents, but some of these methods cause secondary pollution and some require a large amount of energy.
Therefore, the preparation of a method which is simple and efficient to operate and has no secondary pollution to recover and regenerate the waste dye makes technical problems to be solved urgently for those skilled in the art.
Disclosure of Invention
In view of the above, the present invention provides a dye recycling material without secondary pollution, a preparation method thereof and a dye recycling method.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a dye recovery material without secondary pollution comprises the following steps:
(1) preparing bismuth oxyformate: adding bismuth nitrate pentahydrate into a mixed solution composed of glycerol, water and N, N-dimethylformamide, simultaneously carrying out ultrasonic treatment and stirring on the solution (completely dissolving the bismuth nitrate pentahydrate; putting the dissolved mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting for 15h at 160 ℃, then naturally cooling to room temperature, centrifuging (separating, washing, and drying at 60 ℃ to constant weight) to obtain bismuth oxyformate;
(2) modification of bismuth oxyformate: adding bismuth formate into a mixed solution consisting of glycerol, water and N, N-dimethylformamide, and simultaneously carrying out ultrasonic treatment and stirring on the solution to completely dissolve the bismuth formate, wherein the solution is marked as a solution A; dissolving citric acid into water, and marking as solution B; and dropwise adding the solution B into the solution A, adjusting the pH value of the obtained solution to 0.7 by using nitric acid, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting for 6 hours at 160 ℃, naturally cooling to room temperature, performing centrifugal separation, washing, and drying at 60 ℃ to constant weight to obtain citric acid modified bismuth oxyformate, namely the dye recovery material.
Further, the volume ratio of glycerol, water and N, N-dimethylformamide in the mixed solution in the step (1) and the step (2) is 25:5: 10.
The beneficial effect of adopting the further scheme is that: the proportion is favorable for the formation of the micro-flower structure of the prepared material and the maintenance of the dye recycling performance.
Further, the ultrasonic frequency in the step (1) is 40-50kHz, and the stirring speed is 300-400 r/min;
the centrifugal rate is 10000 r/min;
further, the molar concentration of the bismuth nitrate pentahydrate in the mixed solution in the step (1) is 0.0005 mol/ml.
The beneficial effect of adopting the further scheme is that: the above scheme can fully react with a mixed solution consisting of glycerol, water and N, N-dimethylformamide.
Further, the mass ratio of the bismuth oxyformate to the citric acid in the step (2) is 1: 0.3-2.
Furthermore, the mass concentration of the bismuth oxyformate in the solution A is 0.0125 g/ml; the mass concentration of the citric acid in the solution B is 0.01-0.067 g/ml.
The beneficial effect of adopting the further scheme is that: according to the invention, the adsorption and desorption effects of the prepared material can be enhanced by adding a small amount of citric acid.
Further, the ultrasonic frequency in the step (2) is 40-50kHz, and the stirring speed is 300-400 r/min;
the centrifugation rate is 10000 r/min.
The nitric acid is 65-68 w/% of nitric acid.
Further, the washing methods in the step (1) and the step (2) are washing by sequentially adopting deionized water and ethanol, and repeating for 3 times.
The beneficial effect of adopting the further scheme is that: the operation can effectively remove impurities on the surface of the material.
The invention also provides a dye recovery method, which comprises the following steps: adding the dye recovery material into a solution containing dye, and adjusting the pH value to 5-11; standing and adsorbing under dark condition until adsorption is balanced, centrifuging the solution after adsorption is balanced, collecting the centrifuged material, and drying (centrifugation rate is 10000r/min, drying temperature is 60 ℃); the obtained dried material is placed in clear water, and the dye adsorbed on the surface of the material can be desorbed by 365-630nm illumination, so that the dye recovery is realized.
Further, the dye is methylene blue.
The beneficial effect of adopting the further scheme is that: methylene blue is the most common and harmful dye at present, and has a very wide application range.
Further, the mass ratio of the dye in the dye solution to the dye recovery material is 1: 0.3-0.6.
The beneficial effect of adopting the further scheme is that: according to the scheme, the high-efficiency recovery of the dye can be realized by adding a small amount of materials.
The invention has the beneficial effects that: most of the desorption systems in existence at present realize desorption by adding chemical reagents or changing the temperature of the system, and the methods not only can bring secondary pollution, but also consume a large amount of energy. The material prepared by the invention can realize the desorption effect on pollutants only by illumination, and has the outstanding advantages of easy control, no secondary pollution and the like.
Drawings
FIG. 1 is an XRD pattern of a dye recovery material prepared in example 1 provided by the present invention;
FIG. 2 is an electron micrograph of the dye recovery material prepared in example 1 according to the present invention;
FIG. 3 is a graph showing the influence of different pH values on the adsorption and desorption effects of a dye recovery material according to the present invention;
FIG. 4 is a graph showing the effect of different illumination wavelengths on the adsorption and desorption effects of a dye recovery material according to the present invention;
FIG. 5 is a graph showing the effect of different amounts of dye recovery materials on the adsorption and desorption effects of the dye recovery materials;
FIG. 6 is a comparison of the dye recovery material provided by the present invention before and after adsorption and desorption.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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
A preparation method of a dye recovery material without secondary pollution comprises the following steps:
(1) preparing bismuth oxyformate: 0.97014g of bismuth nitrate pentahydrate is added into a mixed solution consisting of 25ml of glycerol, 5ml of water and 10ml of N, N-dimethylformamide, and the solution is stirred under ultrasonic waves at 45kHz and 300r/min to completely dissolve the bismuth nitrate pentahydrate; putting the dissolved mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting for 15 hours at 160 ℃, then naturally cooling to room temperature, performing centrifugal separation at 10000r/min, sequentially washing with deionized water and ethanol, and repeating for 3 times; drying at 60 ℃ to constant weight to obtain bismuth oxyformate;
(2) modification of bismuth oxyformate: adding 0.5g of bismuth oxyformate into a mixed solution consisting of 25ml of glycerol, 5ml of water and 10ml of N, N-dimethylformamide, and completely dissolving the bismuth oxyformate by performing ultrasonic treatment on the solution at 50kHz and at 400r/min to obtain a solution A; dissolving 0.6g of citric acid into 15ml of water, and marking as a solution B; dropwise adding the solution B into the solution A, adjusting the pH of the obtained solution to 0.7 by using nitric acid with the content of 65 w/% and then transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting for 6 hours at 160 ℃, then naturally cooling to room temperature, carrying out centrifugal separation at 10000r/min, washing by sequentially adopting deionized water and ethanol, and repeating for 3 times; drying at 60 ℃ to constant weight to obtain citric acid modified bismuth oxyformate, namely the dye recovery material.
Example 2
A methylene blue solution having a volume of 50mL and a concentration of 10mg/L was measured, the pH of the methylene blue solution was adjusted to 7 by using a nitric acid or sodium hydroxide solution, 0.025g of the material prepared in example 1 was then weighed, ultrasonically dispersed in a methylene blue dye solution, and subjected to an adsorption reaction in the dark. After the adsorption is balanced (the adsorption rate is 49%), the visible light with the light source of 420nm is turned on for desorption. The desorption rate was 90%.
Example 3
A methylene blue solution having a volume of 50mL and a concentration of 10mg/L was measured, and the pH of the methylene blue solution was adjusted to 9 by using a nitric acid solution. Then 0.025g of the material prepared in example 1 was weighed, ultrasonically dispersed in a methylene blue dye solution, and subjected to an adsorption reaction in the dark. After the adsorption equilibrium (adsorption rate of 60%), respectively using a light source with a wavelength of 420nm to perform desorption. The desorption rate was 90%.
Example 4
A methylene blue solution having a volume of 50mL and a concentration of 10mg/L was measured, and the pH of the methylene blue solution was adjusted to 10 by using nitric acid or a sodium hydroxide solution. Then, 0.030g of the material prepared in example 1 was weighed, and ultrasonically dispersed in a methylene blue dye solution to perform an adsorption reaction under a dark condition. After the adsorption is balanced (the adsorption rate is 87%), the desorption is carried out by turning on the visible light with the light source of 420 nm. The desorption rate was 94%.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. The preparation method of the dye recovery material without secondary pollution is characterized by comprising the following steps:
(1) preparing bismuth oxyformate: adding bismuth nitrate pentahydrate into a mixed solution consisting of glycerol, water and N, N-dimethylformamide, and simultaneously carrying out ultrasonic treatment and stirring on the solution to completely dissolve the bismuth nitrate pentahydrate; putting the dissolved mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting for 15 hours at 160 ℃, then naturally cooling to room temperature, centrifugally separating, washing, and drying at 60 ℃ to constant weight to obtain bismuth oxyformate;
(2) modification of bismuth oxyformate: adding bismuth formate into a mixed solution consisting of glycerol, water and N, N-dimethylformamide, and simultaneously carrying out ultrasonic treatment and stirring on the solution to completely dissolve the bismuth formate, wherein the solution is marked as a solution A; dissolving citric acid into water, and marking as solution B; and dropwise adding the solution B into the solution A, adjusting the pH value of the obtained solution to 0.7 by using nitric acid, transferring the solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting for 6 hours at 160 ℃, naturally cooling to room temperature, performing centrifugal separation, washing, and drying at 60 ℃ to constant weight to obtain citric acid modified bismuth oxyformate, namely the dye recovery material.
2. The method for preparing a dye recycling material without secondary pollution according to claim 1, wherein the volume ratio of glycerol, water and N, N-dimethylformamide in the mixed solution in the step (1) and the step (2) is 25:5: 10.
3. The method for preparing a dye recycling material without secondary pollution as recited in claim 1, wherein the molar concentration of bismuth nitrate pentahydrate in the mixed solution of step (1) is 0.0005 mol/ml.
4. The method for preparing the dye recycling material without secondary pollution according to claim 1, wherein the mass ratio of the bismuth oxyformate to the citric acid in the step (2) is 1: 0.3-2.
5. The method for preparing the dye recycling material without secondary pollution according to claim 4, wherein the mass concentration of bismuth oxyformate in the solution A is 0.0125 g/ml; the mass concentration of the citric acid in the solution B is 0.01-0.067 g/ml.
6. The method for preparing the dye recycling material without secondary pollution according to claim 1, wherein the washing method in step (1) and step (2) is that deionized water and ethanol are sequentially used for washing, and the washing is repeated for 3 times.
7. A dye recycled material free from secondary pollution, which is obtained by the production method according to any one of claims 1 to 6.
8. A method of dye recovery comprising the steps of: adding the dye-recovered material of claim 7 to a solution containing a dye and adjusting the pH to 5-11; standing and adsorbing under dark condition until adsorption is balanced, centrifuging solution after adsorption is balanced at 10000r/min, collecting centrifuged material, and drying at 60 ℃; the obtained dried material is placed in clear water, and the dye adsorbed on the surface of the material can be desorbed by 365-630nm illumination, so that the dye recovery is realized.
9. The dye recovery method of claim 8, wherein the dye is methylene blue.
10. The dye recycling method according to claim 8, wherein the mass ratio of the dye in the dye solution to the dye recycling material is 1: 0.3-0.6.
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| CN202210010611.9A CN114471469A (en) | 2022-01-06 | 2022-01-06 | Dye recovery material without secondary pollution, preparation method thereof and dye recovery method |
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| CN202210010611.9A CN114471469A (en) | 2022-01-06 | 2022-01-06 | Dye recovery material without secondary pollution, preparation method thereof and dye recovery method |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009116181A1 (en) * | 2008-03-21 | 2009-09-24 | 住友金属工業株式会社 | Visible light-responsive photocatalyst and method for producing the same |
| CN106391076A (en) * | 2016-09-14 | 2017-02-15 | 江南大学 | Gray Bi2O2CO3 photocatalyst and preparation method thereof |
| CN106423286A (en) * | 2016-09-14 | 2017-02-22 | 江南大学 | BiOCOOH-Bi2O2CO3 compound photocatalyst and preparation method thereof |
| CN107952480A (en) * | 2017-12-05 | 2018-04-24 | 江南大学 | A kind of Bi/BiOCOOH composite photo-catalysts and preparation method thereof |
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- 2022-01-06 CN CN202210010611.9A patent/CN114471469A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009116181A1 (en) * | 2008-03-21 | 2009-09-24 | 住友金属工業株式会社 | Visible light-responsive photocatalyst and method for producing the same |
| CN106391076A (en) * | 2016-09-14 | 2017-02-15 | 江南大学 | Gray Bi2O2CO3 photocatalyst and preparation method thereof |
| CN106423286A (en) * | 2016-09-14 | 2017-02-22 | 江南大学 | BiOCOOH-Bi2O2CO3 compound photocatalyst and preparation method thereof |
| CN107952480A (en) * | 2017-12-05 | 2018-04-24 | 江南大学 | A kind of Bi/BiOCOOH composite photo-catalysts and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| SHIJIE LI ET AL: "Ag2CO3 Decorating BiOCOOH Microspheres with Enhanced Full-Spectrum Photocatalytic Activity for the Degradation of Toxic Pollutants", 《NANOMATERIALS》, vol. 8, no. 914, pages 1 - 12 * |
| 王冰杰: "光控脱附材料柠檬酸修饰甲酸氧铋的吸脱附性能研究", 《河南省化学会2020年学术年会论文摘要集》, pages 1 * |
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