CN113321281A - Composite flocculant based on cationic tannin modified clay, preparation method of composite flocculant and treatment method of closed water body - Google Patents
Composite flocculant based on cationic tannin modified clay, preparation method of composite flocculant and treatment method of closed water body Download PDFInfo
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- CN113321281A CN113321281A CN202110601530.1A CN202110601530A CN113321281A CN 113321281 A CN113321281 A CN 113321281A CN 202110601530 A CN202110601530 A CN 202110601530A CN 113321281 A CN113321281 A CN 113321281A
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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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
- C02F7/00—Aeration of stretches of water
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention provides a composite flocculant based on cationic tannin modified clay, which has a core-shell structure with cationic tannin as a shell and a clay material as a core; the cationic tannin is prepared by taking plant tannin as a base material, taking ethanolamine or diethanolamine and formaldehyde as raw materials and carrying out Mannich reaction. The invention also provides a preparation method of the composite flocculant based on the cationic tannin modified clay and a treatment method of a closed water body. The composite flocculant disclosed by the invention is good in settling property, capable of quickly purifying water, green and environment-friendly, small in dosage, low in cost and good in application prospect.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a composite flocculant based on cationic tannin modified clay, a preparation method of the composite flocculant and a treatment method of a closed water body.
Background
The closed water body refers to a naturally or artificially constructed lake, a pond and the like, has certain functionality, and has the characteristics of strong closure, basically no flowing of the water body and poor self-purification function. Because the mobility of water in the closed water body is poor, exogenous pollutants entering the water body and endogenous pollutants generated in the water body can only realize the degradation of the pollutants by means of the self-purification of the water body, and once the total amount of the pollutants exceeds the self-purification capacity of the water body, the water quality is deteriorated.
The treatment of a closed water body with deteriorated water quality in the prior art generally comprises the following steps: a source control and sewage interception; removing bottom mud; thirdly, manual repair. The common techniques for artificial restoration comprise adding biological agents, purifying algae, feeding algae insects, adding aquatic animals, planting aquatic plants, artificially increasing oxygen and the like. Effective water purification techniques often require the use of a combination of the above techniques. Generally speaking, the treatment difficulty of the water body with deteriorated water quality is higher, and the treatment cost is higher.
The clay flocculation method is a common natural water quality purification method, removes water pollutants by adding a large amount of local clay, quickly purifies water, has the advantages of low cost, easy operation and the like, and has the problems of large adding amount, low efficiency and the like. The researchers around the world have taken various research measures with respect to the disadvantages of clay flocculation, and found that the flocculation efficiency can be greatly improved by directly or indirectly modifying clay by combining or applying physical means of clay and other compounds.
At present, clay modification methods are mainly divided into two major types, namely inorganic modification and organic modification, but the modification methods have different advantages and disadvantages. For example, inorganic modification methods such as polyaluminium chloride modified clay flocculants have the characteristics of good flocculation effect, low price and the like, but residual inorganic metal ions can cause environmental risks; the organic modification mode such as the dosage of the polyacrylamide modified clay flocculant is small, the flocculation capability is strong, the particle size of floc is large, but the difficult degradability and the toxicity of residual acrylamide monomer limit the popularization and application of the polyacrylamide modified clay flocculant in water treatment.
Plant tannins, also known as plant polyphenols, are secondary metabolites of plant complex phenols. Plant tannin is abundant in nature, mainly exists in peels, roots, leaves and pulp of plants, and is a fourth forest byproduct inferior to cellulose, lignin and hemicellulose. Naturally extracted plant tannin has low isoelectric point (pH)pzc2.0-3.0), and pollutants caused by natural water body colloid and human activities are mainly electronegative, so that the plant tannin needs to be modified by cationization. However, the tannin modified by cations still has the problem of poor settling property, and when natural water is treated, flocs caused by wind wave disturbance are difficult to settle, so that the flocculation property of the tannin is influenced, and the flocculant cannot be recycled.
Therefore, it is necessary to develop a new flocculant with high efficiency, low cost, environmental protection and strong environmental adaptability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the composite flocculant based on the cationic tannin modified clay, which has the advantages of good sedimentation performance, capability of quickly purifying water, environmental protection, small dosage, low cost and good application prospect.
The invention also aims to provide a preparation method of the composite flocculant based on the cationic tannin modified clay.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a composite flocculant based on cationic tannin modified clay has a core-shell structure with cationic tannin as a shell and a clay material as a core;
the cationic tannin is prepared by taking plant tannin as a base material, taking ethanolamine or diethanolamine and formaldehyde as raw materials and carrying out Mannich reaction.
Preferably, the clay is kaolin, bentonite, diatomaceous earth or montmorillonite.
A preparation method of a composite flocculant based on cationic tannin modified clay comprises the following steps:
dissolving tannin extract powder in water to prepare tannin solution, heating the tannin solution for the first time, adding ethylenediamine alcohol or ethylenediamine with a certain volume into the tannin solution, stirring and mixing for the first time, and adjusting the pH value to obtain a first mixed solution;
heating the first mixed solution for the second time, adding a certain amount of formaldehyde into the first mixed solution to obtain a second mixed solution, heating the second mixed solution for the third time, and continuously carrying out stirring reaction for the second time; after the second stirring is finished, adding pure water into the second mixed solution to obtain the cationic tannin;
weighing a certain amount of cationic tannin and clay, adding pure water, and stirring until the cationic tannin and the clay are fully dissolved and dispersed to obtain a third mixed solution; slowly dripping a cross-linking agent into the third mixed solution for full reaction; and after the reaction is finished, adding ethanol into the reaction product for dehydration and embrittlement, and then performing vacuum drying, crushing and grinding to obtain the cationic tannin modified clay composite flocculant.
Preferably, the tannin content of the tannin extract is 40-70%.
Preferably, the adding volume of the diethanol amine and the adding mass ratio of the tannin extract are (19.4-23.4): 5.
Preferably, the adding mass ratio of the adding volume of the ethanolamine to the adding mass ratio of the tannin extract is (7.8-11.8): 5.
Preferably, the adding volume of the formaldehyde and the adding mass ratio of the tannin extract are (3.8-23.8): 25.
Preferably, the mass ratio of the cationic plant tannin to the clay is 1: 1-10: 1.
Preferably, the cross-linking agent is epichlorohydrin, and the dosage of the cross-linking agent is 0.05-5 wt% of the cationic tannin.
Preferably, the temperature is increased to 65-75 ℃ for the first time, 75-85 ℃ for the second time, and 85-90 ℃ for the third time;
after stirring and mixing for the first time, adjusting the pH value to 6-7 to obtain a first mixed solution; the time for the first stirring and the second stirring is more than or equal to 3 hours; and slowly dripping a cross-linking agent into the third mixed solution, wherein the time for full reaction is more than or equal to 12 hours.
The third aspect of the object of the invention is to provide a treatment method for closed black and odorous water body, which comprises the following steps: arranging a plurality of rows of micro-nano aeration devices at the bottom of a water body to be treated along the vertical direction of water flow, and preparing a treating agent into a treating agent stock solution; then, aerating to ensure dissolved oxygen in the water body, and uniformly adding the treating agent stock solution into the water body to be treated, wherein the adding speed is greater than the water flow speed; wherein the treatment agent is the composite flocculant based on the cationic tannin modified clay.
Preferably, after the treatment agent is added, the conditions of the concentration of the treatment agent in the water body are as follows: the amount of the treating agent in each milliliter of water body is 50-100 mg.
Preferably, each row of the micro-nano aeration devices is provided with one micro-nano aeration head every 20m, each micro-nano aeration device is provided with three micro-nano aeration heads, an interval aeration mode is adopted, each aeration is carried out for 12 hours, and the interval is 2 hours after each two times of aeration, so that the dissolved oxygen of the water body is ensured to be more than 5 mg/L.
The invention has the beneficial effects that:
1. the composite flocculant has a core-shell structure with the cationic tannin as a shell and the clay material as a core, can remove a large amount of pollutants such as suspended matters, algae and the like, quickly purify a water body and obviously improve the water quality of the water body, increases the overall density of the flocculant by using the clay with higher density as the core, increases the particle size of flocs due to the addition of the clay, has a comprehensive effect, increases the sedimentation speed of the flocs and improves the sedimentation performance of the flocs; moreover, after the treatment is finished, the floc can be quickly separated and recycled, so that the solid-liquid separation capacity is improved, and the cost is effectively reduced. Meanwhile, the composite flocculant of the invention has less dosage, thereby reducing the sludge yield and reducing the subsequent treatment cost.
2. The tannin used in the composite flocculant is a biodegradable material, and the clay is an inorganic mineral material, so that the composite flocculant has the advantages of harmlessness, no secondary pollution and the like, is green and environment-friendly in the use process, and has good application prospects in the fields of treatment of natural water bodies such as slightly polluted landscape water bodies, black and odorous water bodies, high algae water bodies and the like and treatment of sewage and wastewater.
3. The preparation method of the composite flocculant has the advantages of simple process, easy operation and low cost, and is suitable for further industrial production and application.
Drawings
FIG. 1 is a ZETA potential diagram of the composite flocculant of tannin, cationic tannin and cationic tannin modified clay in example 1.
FIG. 2 is a graph showing the effect of cationic tannin-modified clay composite flocculant on treating kaolin suspension in example 1.
FIG. 3 is a graph of the effect of cationic tannin modified clay composite flocculant on the treatment of kaolin clay suspension in example 2.
Detailed Description
In order to better understand the technical content of the present invention, specific embodiments are described below with reference to the accompanying drawings.
In this disclosure, aspects of the present invention are described with reference to the accompanying drawings, in which a number of illustrative embodiments are shown. Embodiments of the present disclosure are not necessarily intended to include all aspects of the invention. It should be appreciated that the various concepts and embodiments described above, as well as those described in greater detail below, may be implemented in any of numerous ways.
The composite flocculant based on the cationic tannin modified clay is used for removing pollutants such as suspended matters and algae in water bodies, increases the settling property of flocs through a composite material formed by the clay and the cationic tannin, quickly purifies the water bodies, can be recycled, does not produce secondary pollution, is green and environment-friendly, and has good application prospects in the fields of treatment of natural water bodies such as micro-polluted landscape water bodies, black and odorous water bodies and high-algae water bodies and treatment of sewage and wastewater.
A cationic tannin-modified clay-based composite flocculant according to an exemplary embodiment of the present invention has a core-shell structure with a cationic tannin as a shell and a clay material as a core; the cationic tannin is prepared by taking plant tannin as a base material, taking ethanolamine or diethanolamine and formaldehyde as raw materials and carrying out Mannich reaction.
In a preferred embodiment, the clay is kaolin, bentonite, diatomaceous earth or montmorillonite.
According to the disclosed example, the invention exemplarily provides a preparation method of a composite flocculant based on cationic tannin modified clay, which comprises the following steps:
dissolving tannin extract powder in 5-10 mL of pure water, slowly adding the tannin extract in batches, fully stirring to avoid tannin aggregation, ensuring complete dissolution, preparing a tannin solution, heating the tannin solution for the first time, adding ethylenediamine or ethylenediamine with a certain volume into the tannin solution, stirring and mixing for the first time, and adjusting the pH value to obtain a first mixed solution;
heating the first mixed solution for the second time, adding a certain amount of formaldehyde into the first mixed solution to obtain a second mixed solution, heating the second mixed solution for the third time, and continuously carrying out stirring reaction for the second time; after the second stirring is finished, adding 5-10 mL of pure water into the second mixed solution to obtain the cationic tannin;
weighing a certain amount of cationic tannin and clay, adding 30-70 mL of pure water, and stirring until the cationic tannin and the clay are fully dissolved and dispersed to obtain a third mixed solution; slowly dripping a cross-linking agent into the third mixed solution for full reaction; and after the reaction is finished, adding ethanol into the reaction product for dehydration and embrittlement, and then performing vacuum drying, crushing and grinding to obtain the cationic tannin modified clay composite flocculant.
Preferably, the tannin content of the tannin extract is 40-70%.
Preferably, the adding volume of the diethanol amine and the adding mass ratio of the tannin extract are (19.4-23.4): 5.
Preferably, the adding mass ratio of the adding volume of the ethanolamine to the adding mass ratio of the tannin extract is (7.8-11.8): 5.
Preferably, the adding volume of the formaldehyde and the adding mass ratio of the tannin extract are (3.8-23.8): 25.
Preferably, the mass ratio of the cationic plant tannin to the clay is 1: 1-10: 1.
Preferably, the cross-linking agent is epichlorohydrin, and the dosage of the cross-linking agent is 0.05-5 wt% of the cationic tannin.
Preferably, the temperature is raised to 65-75 ℃ for the first time, 75-85 ℃ for the second time and 85-90 ℃ for the third time.
Preferably, after the first stirring and mixing, adjusting the pH value to 6-7 to obtain a first mixed solution; the time for the first stirring and the second stirring is more than or equal to 3 hours; and slowly dripping a cross-linking agent into the third mixed solution, wherein the time for full reaction is more than or equal to 12 hours.
The invention also provides an in-situ treatment method of the black and odorous water body of the urban river exemplarily, which comprises the following steps: arranging a plurality of rows of micro-nano aeration devices at the bottom of a water body to be treated along the vertical direction of water flow, and preparing a treating agent into a treating agent stock solution; then, aerating to ensure dissolved oxygen in the water body, and uniformly adding the treating agent stock solution into the water body to be treated, wherein the adding speed is greater than the water flow speed; wherein the treatment agent is the composite flocculant based on the cationic tannin modified clay.
In a preferred embodiment, after the treatment agent is added, the conditions of the concentration of the treatment agent in the water body are as follows: the amount of the treating agent in each milliliter of water body is 50-100 mg.
In another preferred embodiment, each row of the micro-nano aeration devices is provided with one micro-nano aeration head every 20m, each micro-nano aeration device is provided with three micro-nano aeration heads, and an interval aeration mode is adopted, wherein each aeration is carried out for 12 hours, and the interval is 2 hours after each two times of aeration, so that the dissolved oxygen of the water body is ensured to be more than 5 mg/L.
It should be understood that the composite flocculant of the present invention includes, but is not limited to, closed water bodies, which satisfy various water body treatments in need, for example, micro-polluted landscape water bodies, natural water bodies such as high algae water bodies, etc.
For better understanding, the present invention is further described below with reference to several specific examples, but the preparation process is not limited thereto and the present disclosure is not limited thereto.
[ example 1 ]
2.5g of tannin extract powder was dissolved in 5mL of pure water. The tannin extract is slowly added in batches, and is fully stirred to avoid the accumulation of tannin and ensure complete dissolution; heating the tannin solution to 70 ℃, adding 10.7mL of diethanolamine, magnetically stirring for 3h to fully mix the materials, and adjusting the pH value of the solution to 6.5 by using concentrated hydrochloric acid with the mass concentration of 37%; heating the tannin mixed solution to 80 ℃, slowly adding 1.38mL of formaldehyde by using a peristaltic pump, then raising the temperature of the solution to 85 ℃ again, and continuously stirring for 3 hours; after stirring, adding 5mL of pure water to stop reaction to obtain the cationic plant tannin; weighing 2g of cationic plant tannin and 20g of clay, putting into a 100mL three-neck flask filled with 50mL of pure water, and stirring for 1h to fully dissolve and disperse the cationic plant tannin and the clay; slowly dripping 0.1g of epoxy chloropropane into the obtained solution, and fully reacting for 12 h; and after the reaction is finished, adding ethanol into the product for dehydration and embrittlement, and then drying in vacuum, crushing and grinding to obtain the cationic tannin modified clay composite flocculant.
Zeta potential diagrams of the acacia negra tannin and the prepared cationic acacia negra tannin flocculants are shown in fig. 1, and it can be seen that the isoelectric point of the cationic acacia negra tannin flocculants is significantly improved compared to acacia negra tannin, the flocculants are both electropositive over a wider pH range, and the wider pH range for removal of electronegative contaminants.
The performance of the composite flocculant in removing kaolin is tested, as shown in fig. 2, the flocculant enables the turbidity of kaolin suspension with initial turbidity of 25.2NTU to be reduced to 2.5NTU under the adding amount of 50mg/L, and the settling time is less than 5min, which indicates that the composite flocculant has better capacity of removing pollutants and good settleability.
[ example 2 ]
2.5g of tannin extract powder was dissolved in 5mL of pure water. The tannin extract is slowly added in batches, and is fully stirred to avoid the accumulation of tannin and ensure complete dissolution; heating the tannin solution to 70 ℃, adding 4.9mL of ethanolamine, magnetically stirring for 3 hours to fully mix the ethanolamine and the tannin solution, and adjusting the pH of the solution to 6.5 by using concentrated hydrochloric acid with the mass concentration of 37%; heating the tannin mixed solution to 80 ℃, slowly adding 1.38mL of formaldehyde by using a peristaltic pump, then raising the temperature of the solution to 90 ℃ again, and continuously stirring for 3 hours; after stirring, adding 5mL of pure water to stop reaction to obtain the cationic plant tannin; weighing 2g of cationic plant tannin and 2g of clay, putting into a 100mL three-neck flask filled with 50mL of pure water, and stirring for 1h to fully dissolve and disperse the cationic plant tannin and the clay; slowly dripping 0.5g of epoxy chloropropane into the obtained solution, and fully reacting for 12 h; and after the reaction is finished, adding ethanol into the product for dehydration and embrittlement, and then drying in vacuum, crushing and grinding to obtain the cationic tannin modified clay composite flocculant.
The flocculant was tested for kaolin removal performance and as shown in figure 3, the flocculant allowed the initial turbidity of a 25NTU kaolin suspension to drop to 2.6NTU at a 25mg/L dosage with a settling time of less than 5 min. The composite flocculant has better capacity of removing pollutants and good settleability.
[ example 3 ]
2.5g of tannin extract powder was dissolved in 5mL of pure water. The tannin extract is slowly added in batches, and is fully stirred to avoid the accumulation of tannin and ensure complete dissolution; then heating the tannin solution to 75 ℃, adding 9.7mL of diethanolamine, magnetically stirring for 3h to fully mix the materials, and adjusting the pH value of the solution to 6.5 by using concentrated hydrochloric acid with the mass concentration of 37%; heating the tannin mixed solution to 85 ℃, slowly adding 2.38mL of formaldehyde by using a peristaltic pump, then raising the temperature of the solution to 90 ℃ again, and continuously stirring for 3 hours; after stirring, adding 5mL of pure water to stop reaction to obtain the cationic plant tannin; weighing 2g of cationic plant tannin and 20g of clay, putting into a 100mL three-neck flask filled with 50mL of pure water, and stirring for 1h to fully dissolve and disperse the cationic plant tannin and the clay; slowly dripping 0.125g of epoxy chloropropane into the obtained solution, and fully reacting for 12 h; and after the reaction is finished, adding ethanol into the product for dehydration and embrittlement, and then drying in vacuum, crushing and grinding to obtain the cationic tannin modified clay composite flocculant.
The flocculant was tested for its kaolin removal performance and at a dosage of 20mg/L, the flocculant allowed the turbidity of a kaolin suspension having an initial turbidity of 50NTU to drop to 4NTU with a settling time of less than 5 min. The composite flocculant has better capacity of removing pollutants and good settleability.
[ example 4 ]
2.5g of tannin extract powder was dissolved in 5mL of pure water. The tannin extract is slowly added in batches, and is fully stirred to avoid the accumulation of tannin and ensure complete dissolution; heating the tannin solution to 65 ℃, adding 3.9mL of ethanolamine, magnetically stirring for 3h to fully mix the ethanolamine and the tannin solution, and adjusting the pH of the solution to 6.5 by using concentrated hydrochloric acid with the mass concentration of 37%; heating the tannin mixed solution to 75 ℃, slowly adding 0.38mL of formaldehyde by using a peristaltic pump, then raising the temperature of the solution to 85 ℃ again, and continuously stirring for 3 hours; after stirring, adding 5mL of pure water to stop reaction to obtain the cationic plant tannin; weighing 2g of cationic plant tannin and 2g of clay, putting into a 100mL three-neck flask filled with 50mL of pure water, and stirring for 1h to fully dissolve and disperse the cationic plant tannin and the clay; slowly dripping 0.0125g of epoxy chloropropane into the obtained solution, and fully reacting for 12 hours; and after the reaction is finished, adding ethanol into the product for dehydration and embrittlement, and then drying in vacuum, crushing and grinding to obtain the cationic tannin modified clay composite flocculant.
The flocculant was tested for its kaolin removal performance and at a dosage of 30mg/L, the flocculant allowed the turbidity of a kaolin suspension having an initial turbidity of 50NTU to drop to 2.3NTU with a settling time of less than 4 min. The composite flocculant has better capacity of removing pollutants and good settleability.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be determined by the appended claims.
Claims (13)
1. The composite flocculant based on cationic tannin modified clay is characterized by having a core-shell structure with cationic tannin as a shell and a clay material as a core;
the cationic tannin is prepared by taking plant tannin as a base material, taking ethanolamine or diethanolamine and formaldehyde as raw materials and carrying out Mannich reaction.
2. The cationic tannin modified clay-based composite flocculant of claim 1, wherein the clay is kaolin, bentonite, diatomaceous earth or montmorillonite.
3. A method for preparing the composite flocculant based on the cationic tannin modified clay according to any one of claims 1 to 2, which is characterized by comprising the following steps:
dissolving tannin extract powder in water to prepare tannin solution, heating the tannin solution for the first time, adding ethylenediamine alcohol or ethylenediamine with a certain volume into the tannin solution, stirring and mixing for the first time, and adjusting the pH value to obtain a first mixed solution;
heating the first mixed solution for the second time, adding a certain amount of formaldehyde into the first mixed solution to obtain a second mixed solution, heating the second mixed solution for the third time, and continuously carrying out stirring reaction for the second time; after the second stirring is finished, adding pure water into the second mixed solution to obtain the cationic tannin;
weighing a certain amount of cationic tannin and clay, adding pure water, and stirring until the cationic tannin and the clay are fully dissolved and dispersed to obtain a third mixed solution; slowly dripping a cross-linking agent into the third mixed solution for full reaction; and after the reaction is finished, adding ethanol into the reaction product for dehydration and embrittlement, and then performing vacuum drying, crushing and grinding to obtain the cationic tannin modified clay composite flocculant.
4. The method for preparing the composite flocculant based on cationic tannin modified clay according to claim 3, characterized in that the tannin content of the tannin extract is 40-70%.
5. The preparation method of the composite flocculant based on cationic tannin modified clay according to claim 3, characterized in that the adding volume of diethanolamine and the adding mass ratio of tannin extract are (19.4-23.4): 5.
6. The preparation method of the composite flocculant based on cationic tannin modified clay according to claim 3, characterized in that the adding volume of ethanolamine and the adding mass ratio of tannin extract are (7.8-11.8): 5.
7. The preparation method of the composite flocculant based on cationic tannin modified clay according to claim 3, characterized in that the adding volume of formaldehyde and the adding mass ratio of tannin extract are (3.8-23.8): 25.
8. The preparation method of the composite flocculant based on cationic tannin modified clay as claimed in claim 3, wherein the mass ratio of the cationic plant tannin to the clay is 1: 1-10: 1.
9. The method for preparing the composite flocculant based on cationic tannin modified clay according to claim 3, characterized in that the cross-linking agent is epichlorohydrin and is used in an amount of 0.05-5 wt.% of the cationic tannin.
10. The preparation method of the cationic tannin modified clay-based composite flocculant as claimed in claim 3, wherein the temperature is raised to 65-75 ℃ for the first time, to 75-85 ℃ for the second time, and to 85-90 ℃ for the third time;
after stirring and mixing for the first time, adjusting the pH value to 6-7 to obtain a first mixed solution; the time for the first stirring and the second stirring is more than or equal to 3 hours; and slowly dripping a cross-linking agent into the third mixed solution, wherein the time for full reaction is more than or equal to 12 hours.
11. A treatment method for closed black and odorous water is characterized by comprising the following steps: arranging a plurality of rows of micro-nano aeration devices at the bottom of a water body to be treated along the vertical direction of water flow, and preparing a treating agent into a treating agent stock solution; then, aerating to ensure dissolved oxygen in the water body, and uniformly adding the treating agent stock solution into the water body to be treated, wherein the adding speed is greater than the water flow speed; wherein the treating agent is the cationic tannin modified clay-based composite flocculant according to any one of claims 1 to 2.
12. The closed black and odorous water body treatment method according to claim 11, wherein after the treatment agent is added, the conditions for satisfying the concentration of the treatment agent in the water body are as follows: the amount of the treating agent in each milliliter of water body is 50-100 mg.
13. The closed black and odorous water body treatment method according to claim 11, wherein each micro-nano aeration device is arranged every 20m, each micro-nano aeration device is provided with three micro-nano aeration heads, and an interval aeration mode is adopted, wherein each aeration is carried out for 12 hours, and the interval is 2 hours after each two times of aeration, so that the dissolved oxygen in the water body is ensured to be more than 5 mg/L.
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| CN113881065A (en) * | 2021-11-05 | 2022-01-04 | 内江师范学院 | Novel tannin-based heavy metal flocculant, preparation method and application thereof |
| CN114956278A (en) * | 2022-06-09 | 2022-08-30 | 河海大学 | Modified plant tannin environment-friendly magnetic flocculant and method for treating high algae water body step by step |
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| CN114956278A (en) * | 2022-06-09 | 2022-08-30 | 河海大学 | Modified plant tannin environment-friendly magnetic flocculant and method for treating high algae water body step by step |
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| CN113321281B (en) | 2023-05-12 |
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