CN111013553B - Methylene blue and rhodamine B adsorbent and preparation method thereof - Google Patents
Methylene blue and rhodamine B adsorbent and preparation method thereof Download PDFInfo
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- CN111013553B CN111013553B CN201911368027.5A CN201911368027A CN111013553B CN 111013553 B CN111013553 B CN 111013553B CN 201911368027 A CN201911368027 A CN 201911368027A CN 111013553 B CN111013553 B CN 111013553B
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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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention discloses a methylene blue and rhodamine B adsorbent and a preparation method thereof, and belongs to the technical field of wastewater treatment. The invention discloses a methylene blue and rhodamine B adsorbent, which takes beta-cyclodextrin, acryloyl and 2-acrylamido-2-methylpropanesulfonic acid as monomers, ammonium persulfate as an initiator and N, N-methylene bisacrylamide as a cross-linking agent, and adopts an aqueous solution polymerization method to prepare a beta-cyclodextrin graft copolymer; after the reaction is finished, shearing the copolymer, washing the copolymer by using absolute ethyl alcohol, putting the copolymer into a sealed bag filled with a proper amount of sodium hydroxide solid, and putting the sealed bag into an oven to hydrolyze at 90 ℃ to obtain the methylene blue and rhodamine B adsorbent. The methylene blue and rhodamine B adsorbent prepared by the invention has the advantages of large adsorption capacity, high adsorption rate, simple preparation method and low cost.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a methylene blue and rhodamine B adsorbent and a preparation method thereof.
Background
With the development of the dye and printing and dyeing industry, the discharge amount of wastewater is continuously increased, and the production wastewater becomes one of the most main pollution sources of water and soil, thereby causing serious threats to the ecological environment and human health. Most dyes are toxic substances with carcinogenic, teratogenic and mutagenic "triple" effects, such as methylene blue and rhodamine B, which are widely used. The methylene blue is used for dyeing cotton, hemp, silk fabrics and paper, and coloring bamboo and wood. Rhodamine B has been used as a food additive in large quantities, and is prohibited from being used in the food industry because of its carcinogenicity, but rhodamine B is still widely used in industries such as paper making, textile printing and dyeing, leather manufacturing and the like.
Textile printing and dyeing is one of the traditional dominant industries which are the earliest developed in China and have international competitiveness, but is also a typical industry with high energy consumption and high water consumption. The energy consumption of the textile printing and dyeing industry accounts for about 4.4 percent of the total amount of the national industry, the water consumption accounts for about 8.5 percent, and the wastewater discharge amount and the total amount of pollutants are respectively positioned at the second place and the fourth place of the national industrial department. Every 100 m of cloth is dyed in China can generate 4-5 tons of wastewater, about 20-23 hundred million tons of wastewater are generated every year, and the recovery rate of the wastewater is only 7 percent.
The printing and dyeing wastewater has complex components, high organic matter content and difficult biochemical degradation, and belongs to the category of industrial wastewater difficult to treat. Rhodamine B, particularly methylene blue, is a major pollutant in printing and dyeing wastewater. Methylene blue is a phenothiazine dye, rhodamine B is a dibenzo-hexa-oxacyclo dye, the two dyes have poor biodegradability, and if the dyes are discharged into a water body in large quantities without treatment, aquatic plants die and the aerobic environment of the water body is damaged. The pollutants not only cause the pollution of the receiving water body, but also mainly cause the harm to the human health, and have carcinogenic, teratogenic and mutagenic effects.
The prior printing and dyeing wastewater treatment methods used in China comprise a biological method, an extraction method, an adsorption method, a chemical oxidation method and an advanced oxidation method. The adsorption method has simple process and certain advantages in the field of wastewater treatment. The traditional adsorbents for treating dyes mainly comprise carbon materials, alumina, molecular sieves, resins and the like, but the adsorbents have limited adsorption capacity and slow adsorption rate. Therefore, the technical personnel in the field need to solve the problem of providing the methylene blue and rhodamine B adsorbent and the preparation method thereof.
Disclosure of Invention
In view of the above, the invention provides a methylene blue and rhodamine B adsorbent and a preparation method thereof, and the adsorbent is high in adsorption amount and high in adsorption rate.
In order to achieve the purpose, the invention adopts the following technical scheme:
a methylene blue and rhodamine B adsorbent comprises the following raw materials in parts by weight: 0.6-2 parts of beta-cyclodextrin, 15-25 parts of acrylamide, 3-6 parts of 2-acrylamido-2-methylpropanesulfonic acid, 2-5 parts of N, N methylene bisacrylamide and 2-5 parts of ammonium persulfate.
Further, a preparation method of the methylene blue and rhodamine B adsorbent comprises the following specific steps:
(1) adding 0.6-2 parts of beta-cyclodextrin into 50 parts of pure water, and heating and dissolving in a water bath to obtain a beta-cyclodextrin solution;
(2) dissolving 15-25 parts of acrylamide, 3-6 parts of 2-acrylamido-2-methylpropanesulfonic acid and 2-5 parts of N, N methylene bisacrylamide in 50 parts of pure water to obtain a mixed solution;
(3) adding the mixed solution obtained in the step (2) into the beta-cyclodextrin solution obtained in the step (1), adding 2-5 parts of ammonium persulfate, stirring for 5-10 min, reacting for 3h at 50-60 ℃, and taking out the product which is colorless transparent gel;
(4) cutting the gel obtained in the step (3) into pieces, and washing the pieces with absolute ethyl alcohol; putting the mixture and 4-8 parts of NaOH solid into a sealed bag, carrying out hydrolysis reaction for 8-12 h at 90 ℃, taking out, and drying in a vacuum drying oven at 90 ℃ for 24h to obtain methylene blue and rhodamine B adsorbents.
According to the technical scheme, compared with the prior art, the invention discloses and provides a methylene blue and rhodamine B adsorbent and a preparation method thereof, wherein a beta-cyclodextrin (beta-CD), Acrylamide (AM) and 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) are used as monomers, Ammonium Persulfate (APS) is used as an initiator, N, N-Methylene Bisacrylamide (MBA) is used as a cross-linking agent, and an aqueous solution polymerization method is adopted to prepare a beta-cyclodextrin graft copolymer (beta-CD-A-A); after the reaction is finished, shearing the copolymer, washing the copolymer by using absolute ethyl alcohol, putting the copolymer into a sealed bag filled with a proper amount of sodium hydroxide solid, and putting the sealed bag into an oven to hydrolyze at 90 ℃ to obtain methylene blue and rhodamine B adsorbents. The methylene blue and rhodamine B adsorbent prepared by the invention has large adsorption capacity and high adsorption rate, the maximum adsorption capacity for Methylene Blue (MB) can reach 2536mg/g, the maximum adsorption capacity for rhodamine B (RhB) can reach 950mg/g, the adsorption capacity for Methylene Blue (MB) is 850mg/g at 30min, the adsorption capacity for Methylene Blue (MB) is 1380mg/g at 60min, and the adsorbent is simple in preparation method and low in cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a diagram showing a comparison of the forms of methylene blue and rhodamine B adsorbent before and after the adsorption of methylene blue;
wherein a is before methylene blue is adsorbed by an adsorbent; b is after the adsorbent adsorbs methylene blue, and the adsorption process can absorb some water to cause it to swell; c is cutting the adsorbent in b.
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
The preparation method of the methylene blue and rhodamine B adsorbent comprises the following specific steps:
adding 0.8g of beta-cyclodextrin into 50g of pure water, and heating the mixture in a water bath to 60 ℃ for dissolving to obtain a beta-cyclodextrin solution; dissolving 15g of acrylamide, 3g of 2-acrylamido-2-methylpropanesulfonic acid and 2g of N, N methylene bisacrylamide in 50g of pure water to obtain a mixed solution; uniformly mixing the beta-cyclodextrin solution with the mixed solution, adding 2g of ammonium persulfate, stirring for 8min, reacting for 3h at the temperature of 55 ℃, and taking out the product after the product is colorless transparent gel; and cutting the obtained gel into particles of 10-20 meshes, washing with absolute ethyl alcohol, putting the particles and 4g of NaOH solid into a sealed bag, carrying out hydrolysis reaction for 10 hours at 90 ℃, taking out the particles, putting the particles into a vacuum drying oven, and drying the particles for 24 hours at 90 ℃ to obtain the methylene blue and rhodamine B adsorbent.
Example 2
The preparation method of the methylene blue and rhodamine B adsorbent comprises the following specific steps:
adding 1g of beta-cyclodextrin into 50g of pure water, heating the mixture in a water bath to 60 ℃ for dissolving to obtain a beta-cyclodextrin solution; dissolving 20g of acrylamide, 4g of 2-acrylamido-2-methylpropanesulfonic acid and 3g of N, N methylene bisacrylamide in 50g of pure water to obtain a mixed solution; uniformly mixing the beta-cyclodextrin solution with the mixed solution, adding 3g of ammonium persulfate, stirring for 10min, reacting for 3h at 50 ℃, and taking out the product after the product is colorless transparent gel; and cutting the obtained gel into particles of 10-20 meshes, washing the particles by using absolute ethyl alcohol, putting the particles and 5g of NaOH solid into a sealed bag, carrying out hydrolysis reaction for 8 hours at 90 ℃, taking out the particles, putting the particles into a vacuum drying oven, and drying the particles for 24 hours at 90 ℃ to obtain the methylene blue and rhodamine B adsorbent.
Example 3
The preparation method of the methylene blue and rhodamine B adsorbent comprises the following specific steps:
adding 1.5g of beta-cyclodextrin into 50g of pure water, and heating the mixture in a water bath to 60 ℃ for dissolving to obtain a beta-cyclodextrin solution; dissolving 25g of acrylamide, 6g of 2-acrylamido-2-methylpropanesulfonic acid and 5g of N, N methylene bisacrylamide in 50g of pure water to obtain a mixed solution; uniformly mixing the beta-cyclodextrin solution with the mixed solution, adding 4g of ammonium persulfate, stirring for 10min, reacting for 3h at the temperature of 60 ℃, and taking out the product after the product is colorless transparent gel; and cutting the obtained gel into particles of 10-20 meshes, washing with absolute ethyl alcohol, putting the particles and 8g of NaOH solid into a sealed bag, carrying out hydrolysis reaction for 8 hours at 90 ℃, taking out the particles, putting the particles into a vacuum drying oven, and drying the particles for 24 hours at 90 ℃ to obtain the methylene blue and rhodamine B adsorbent.
The method for removing methylene blue and rhodamine B in water by adopting the methylene blue and rhodamine B adsorbent prepared by the invention comprises the following steps: the adsorbent is directly mixed with the dye wastewater, the pH value of the solution is adjusted to 5-10 by NaOH, the adsorbent is separated by centrifugation after oscillation adsorption on an oscillator, and the performances of the adsorbent prepared in examples 1-3 are shown in tables 1-3.
TABLE 1 adsorption capacity of the adsorbents in the three examples for methylene blue and rhodamine B adsorbents
| Examples | MB adsorption amount (mg/g) | RhB adsorption capacity (mg/g) |
| Example 1 | 2354 | 895 |
| Example 2 | 2536 | 950 |
| Example 3 | 2487 | 907 |
TABLE 2 variation of methylene blue adsorption amount with time of the adsorbent in example 2
| Time (h) | 0.5 | 1 | 1.5 | 2 | 6 | 24 |
| Adsorption Capacity (mg/g) | 850 | 1380 | 1622 | 1898 | 2252 | 2524 |
TABLE 3 influence of pH on the amount of methylene blue adsorbed by the adsorbent in example 2
| pH | 5 | 6 | 7 | 8 | 9 | 10 |
| Adsorption Capacity (mg/g) | 2273 | 2394 | 2468 | 2502 | 2522 | 2530 |
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (1)
1. The methylene blue and rhodamine B adsorbent is characterized by comprising the following raw materials in parts by weight: 0.6-2 parts of beta-cyclodextrin, 15-25 parts of acrylamide, 3-6 parts of 2-acrylamido-2-methylpropanesulfonic acid, 2-5 parts of N, N methylene bisacrylamide and 2-5 parts of ammonium persulfate;
the preparation method of the methylene blue and rhodamine B adsorbent comprises the following steps:
(1) adding 0.6-2 parts of beta-cyclodextrin into 50 parts of pure water, and heating and dissolving in a water bath to obtain a beta-cyclodextrin solution;
(2) dissolving 15-25 parts of acrylamide, 3-6 parts of 2-acrylamido-2-methylpropanesulfonic acid and 2-5 parts of N, N methylene bisacrylamide in 50 parts of pure water to obtain a mixed solution;
(3) adding the mixed solution obtained in the step (2) into the beta-cyclodextrin solution obtained in the step (1), adding 2-5 parts of ammonium persulfate, stirring for 5-10 min, reacting for 3h at 50-60 ℃, and taking out the product which is colorless transparent gel;
(4) cutting the gel obtained in the step (3) into pieces, and washing the pieces with absolute ethyl alcohol; putting the mixture and 4-8 parts of NaOH solid into a sealed bag, carrying out hydrolysis reaction for 8-12 h at 90 ℃, taking out, and drying in a vacuum drying oven at 90 ℃ for 24h to obtain methylene blue and rhodamine B adsorbents.
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