A bactericidal and deodorizing wastewater treatment agent and its preparation method

Abstract

This case involves a bactericidal and deodorizing wastewater treatment agent and its preparation method. Nano-zinc oxide and silver ions are loaded on the surface of attapulgite after acid-base treatment, and then a polymer chain of polyacrylamide and a reactive isothiazolinone derivative is grafted on its surface by in-situ polymerization to obtain the product. Among them, the structural formula of the reactive isothiazolinone derivative is #imgabs0# The present invention provides a bactericidal and deodorizing water treatment agent. When used in combination with a commercially available flocculant, it can effectively remove the COD in the water body. At the same time, at a relatively low dosage, it can quickly deodorize the wastewater, improve the water treatment efficiency, and reduce the cost.

Description

Technical Field

[0001] The present invention relates to the technical field of water treatment agent preparation, and specifically relates to a bactericidal and deodorizing wastewater treatment agent and a preparation method thereof. Background Art

[0002] Water is the source of life. Water treatment is of great significance for the development of industrial production, improvement of product quality, and maintenance of ecological balance. Usually, more attention is paid to the removal rates of COD, SS, heavy metals, etc. in domestic sewage and industrial wastewater treatment. For severely polluted water bodies, it is also necessary to control the odor during the sewage treatment process. The odor comes from compounds with relatively low molecular weights but pungent odors, generally volatile sulfides such as hydrogen sulfide, carbon disulfide, thioethers, thiols, etc., as well as organic compounds such as nitrogen-containing compounds and halogen-containing compounds. Existing deodorization methods include physical deodorization method, biological deodorization method, and chemical deodorization method. The physical deodorization method mainly relies on ventilation or water washing adsorption, which is time-consuming and further wastes water resources; the biological deodorization method mainly uses microorganisms for adsorption and degradation, which is also time-consuming; the chemical deodorization method is to add specific chemical agents, such as strong oxidants like sodium hydroxide and magnesium hydroxide, to treat and prevent the emission of sulfur-containing compounds, etc., but a large amount of chemical agents need to be invested, increasing the cost and there is also potential toxicity. Therefore, combining multiple treatment methods to prepare a composite deodorant with moderate preparation cost and good treatment effect is the research focus of this application. Summary of the Invention

[0003] Aiming at the deficiencies in the prior art, the present invention uses modified attapulgite as a carrier, loads nano-zinc oxide and silver ions on its surface, and simultaneously forms a multi-dimensional network polymer on its surface by in-situ polymerization. It has a large specific surface area of attapulgite and excellent adsorption performance. Metal ions and the polymer chains modified with organic substances are beneficial for bactericidal and deodorizing, and can be used as an auxiliary additive for sewage treatment.

[0004] To achieve the above object, the present invention provides the following technical solutions:

[0005] A preparation method of a bactericidal and deodorizing wastewater treatment agent, comprising the following steps:

[0006] S1. Immerse the acid-base treated attapulgite in zinc acetate solution for 4 - 6 h, heat to 80 °C, add urea solution under stirring, continuously stir for 6 - 8 h, cool down and filter, and calcine the obtained solid at 400 - 600 °C for 2 h;

[0007] S2. Ultrasonically disperse the solid obtained in step S1 in tetrahydrofuran solvent, heat to 50 °C, add KH540 and triethylamine, reflux overnight under condensation, cool to room temperature, add silver nitrate aqueous solution, heat to 100 °C and microwave for 1 min, cool to room temperature and filter, and wash successively with absolute ethanol and deionized water to obtain modified attapulgite;

[0008] S3. Uniformly disperse the modified attapulgite in tetrahydrofuran, introduce nitrogen protection, add an initiator and stir evenly. Heat up to 60 °C. Dissolve the reactive isothiazolinone derivative and acrylamide in the tetrahydrofuran solvent, and then dropwise add it to the attapulgite dispersion. After the dropping is completed, maintain a nitrogen atmosphere and stir and react for 6 - 8 h. After cooling, wash the product with distilled water, soak it, filter it, dry it, pulverize it, and set it aside;

[0009] Among them, the structural formula of the reactive isothiazolinone derivative is

[0010] Furthermore, the preparation process of the attapulgite after acid-base treatment is as follows:

[0011] Soak the attapulgite in 1 M sodium hydroxide solution for 2 h, filter, wash, and calcine it. After cooling, disperse it in deionized water, add sodium chloride to adjust the pH to neutral, filter, and dry it;

[0012] Soak the dried attapulgite in 10% hydrochloric acid solution, heat it in a water bath for 1 h, cool it, filter it by suction, and dry it.

[0013] Furthermore, the solid-liquid ratio of attapulgite in the sodium hydroxide solution and hydrochloric acid solution is both 1:2, and the calcination temperature is 450 °C.

[0014] Furthermore, in the step S1, the concentrations of the zinc acetate solution and the urea solution are 0.5 mol / L and 2 mol / L respectively, and the volume ratio is 1:1.

[0015] Furthermore, in the step S2, the mass ratio of the solid, KH540, and triethylamine is 1:10:1, the concentration of the silver nitrate aqueous solution is 1 M, and the mass-volume ratio with the solid is 1 g:5 ml.

[0016] Furthermore, in the step S3, the molar ratio of the reactive isothiazolinone derivative and acrylamide is 7 - 9:3 - 1, and the ratio of their total mass to the mass of the modified attapulgite is 0.5 - 0.8:1.

[0017] Furthermore, the preparation process of the reactive isothiazolinone derivative is as follows:

[0018]

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows: The present invention provides a water treatment agent with bactericidal and deodorizing functions. When used in combination with a commercially available flocculant, it can effectively remove the COD in water. At the same time, it can quickly deodorize the wastewater at a relatively low dosage, improving the water treatment efficiency and reducing the cost. Specific Embodiments

[0020] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0021] In addition, the technical features involved in different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0022] Embodiment

[0023] A preparation method of a bactericidal and deodorizing wastewater treatment agent includes the following steps:

[0024] S1. Immerse attapulgite in a 1M sodium hydroxide solution for 2 h, with a solid-liquid ratio of 1:2. After filtration, wash it, calcine it at 450 °C, cool it, disperse it in deionized water, add sodium chloride to adjust the pH to neutral, and then filter and dry it.

[0025] Immerse the dried attapulgite in a 10% hydrochloric acid solution, with a solid-liquid ratio of 1:2. Heat it in a water bath for 1 h, cool it, filter it by suction, and dry it to obtain acid-base treated attapulgite.

[0026] S2. Immerse the acid-base treated attapulgite in a zinc acetate solution for 4 - 6 h. Raise the temperature to 80 °C, add a urea solution while stirring, continuously stir for 6 - 8 h, cool it and filter it. The obtained solid is calcined at 400 - 600 °C for 2 h.

[0027] Attapulgite is a natural mineral with a large specific surface area and has a certain adsorption capacity. Natural attapulgite contains a large amount of impurities. Therefore, in this case, purified attapulgite is first obtained through acid-base treatment, which increases the specific surface area and enriches the surface active groups and bonding points. Then, zinc oxide nanoparticles are loaded on its surface by the impregnation calcination method to increase its antibacterial property.

[0028] S3. Ultrasonically disperse the solid obtained in step S1 in a tetrahydrofuran solvent, raise the temperature to 50 °C, add KH540 and triethylamine, reflux overnight, cool to room temperature, add an aqueous silver nitrate solution, raise the temperature to 100 °C, microwave for 1 min, cool to room temperature, filter, and wash successively with absolute ethanol and deionized water to obtain modified attapulgite.

[0029] The purpose of this step is to load silver nanoparticles to further improve the antibacterial property. First, an organic-inorganic bridging connection is carried out through KH540, and at the same time, the abundant amino groups reduce silver ions to obtain silver-loaded attapulgite.

[0030] S4. Uniformly disperse the modified attapulgite in tetrahydrofuran, introduce nitrogen protection, add the initiator and stir evenly, heat up to 60 °C. Dissolve the reactive isothiazolinone derivative and acrylamide in the tetrahydrofuran solvent, and then dropwise add it to the attapulgite dispersion. After the dropping is completed, maintain the nitrogen atmosphere and stir and react for 6 - 8 h. After cooling, wash the product with distilled water, soak it, filter it, dry it, pulverize it, and reserve it for use;

[0031] Among them, the structural formula of the reactive isothiazolinone derivative is

[0032] Based on the surface active sites of the modified attapulgite, polymer chains of polyacrylamide and isothiazolinone derivative are grafted in-situ on its surface. The molar ratio of the reactive isothiazolinone derivative to acrylamide is controlled at 7 - 9:3 - 1. Polyacrylamide is also a commonly used coagulant aid for water treatment. Applying acrylamide as a polymerization monomer to the in-situ polymerization of attapulgite, on the one hand, it can improve the flocculation ability as a coagulant aid itself and has good sedimentation performance; on the other hand, it reduces the steric hindrance effect of the cyclic monomer benzisothiazolinone, forming a macromolecular network polymer on the surface of attapulgite, so that the attapulgite grafted with the organic polymer chain can be used as a microbial immobilization carrier. The microorganisms are used to decompose the substances that produce odors and inhibit the production of odor-causing bacteria, and the isothiazolinone derivative also plays a role in sterilization, and the synergistic effect can remove odors more quickly.

[0033] In the above-mentioned embodiment, the preparation process of the reactive isothiazolinone derivative is as follows. The preparation process refers to the method for synthesizing isothiazolinone derivatives in China Coatings, Vol. 27, No. 05, 2012.

[0034]

[0035] Example 1:

[0036] S1. Immerse 6 g of the attapulgite treated with acid and alkali in 60 ml of 0.5 mol / L zinc acetate solution for 4 - 6 h, heat up to 80 °C, add 60 ml of 2 mol / L urea solution under stirring, continuously stir for 6 - 8 h, cool down and filter. The obtained solid is calcined at 500 °C for 2 h;

[0037] S2. Ultrasonically disperse 5 g of the solid obtained in step S1 in 100 ml of tetrahydrofuran solvent, heat up to 50 °C, add 50 g of KH540 and 5 g of triethylamine, reflux overnight under condensation, cool to room temperature, add 25 ml of 1 M silver nitrate aqueous solution, heat up to 100 °C and microwave for 1 min, cool to room temperature and filter, and wash successively with absolute ethanol and deionized water to obtain the modified attapulgite;

[0038] S3. Uniformly disperse 5 g of modified attapulgite in 100 ml of tetrahydrofuran, introduce nitrogen for protection, add 50 mg of initiator AIBN and stir evenly. Heat up to 60 °C. Dissolve 3.57 g of reactive isothiazolinone derivative and 0.43 g of acrylamide (molar ratio 7:3) in 5 ml of tetrahydrofuran solvent, and then dropwise add it to the attapulgite dispersion. After the dropping is completed, maintain a nitrogen atmosphere and stir for reaction for 6 - 8 h. After cooling, wash the product with distilled water, soak it, filter it, dry it, pulverize it, and set it aside.

[0039] Example 2:

[0040] S1. Immerse 6 g of acid-base treated attapulgite in 60 ml of 0.5 mol / L zinc acetate solution for 4 - 6 h. Heat up to 80 °C and add 60 ml of 2 mol / L urea solution with stirring. Continuously stir for 6 - 8 h, cool down and filter. The obtained solid is calcined at 500 °C for 2 h;

[0041] S2. Ultrasonically disperse 5 g of the solid obtained in step S1 in 100 ml of tetrahydrofuran solvent, heat up to 50 °C, add 50 g of KH540 and 5 g of triethylamine, reflux overnight under condensation. Cool to room temperature, add 25 ml of 1 M silver nitrate aqueous solution, heat up to 100 °C and microwave for 1 min. Cool to room temperature and filter. Wash successively with absolute ethanol and deionized water to obtain modified attapulgite;

[0042] S3. Uniformly disperse 5 g of modified attapulgite in 100 ml of tetrahydrofuran, introduce nitrogen for protection, add the initiator and stir evenly. Heat up to 60 °C. Dissolve 2.41 g of reactive isothiazolinone derivative and 1.59 g of acrylamide (molar ratio 3:7) in 5 ml of tetrahydrofuran solvent, and then dropwise add it to the attapulgite dispersion. After the dropping is completed, maintain a nitrogen atmosphere and stir for reaction for 6 - 8 h. After cooling, wash the product with distilled water, soak it, filter it, dry it, pulverize it, and set it aside.

[0043] Example 3:

[0044] S1. Immerse 6 g of acid-base treated attapulgite in 60 ml of 0.5 mol / L zinc acetate solution for 4 - 6 h. Heat up to 80 °C and add 60 ml of 2 mol / L urea solution with stirring. Continuously stir for 6 - 8 h, cool down and filter. The obtained solid is calcined at 500 °C for 2 h;

[0045] S2. Ultrasonically disperse 5 g of the solid obtained in step S1 in 100 ml of tetrahydrofuran solvent, heat up to 50 °C, add 50 g of KH540 and 5 g of triethylamine, reflux overnight under condensation. Cool to room temperature, add 25 ml of 1 M silver nitrate aqueous solution, heat up to 100 °C and microwave for 1 min. Cool to room temperature and filter. Wash successively with absolute ethanol and deionized water to obtain modified attapulgite;

[0046] S3. Uniformly disperse 5 g of modified attapulgite in 100 ml of tetrahydrofuran, introduce nitrogen for protection, add an initiator and stir evenly. Heat up to 60 °C. Dissolve 2.3 g of reactive isothiazolinone derivative and 0.17 g of acrylamide (total mass is 0.5 g, molar ratio is about 8:2) in 5 ml of tetrahydrofuran solvent, then dropwise add it to the attapulgite dispersion. After the dropping is completed, maintain a nitrogen atmosphere and stir for reaction for 6 - 8 h. After cooling, wash the product with distilled water, soak it, filter it, dry it, crush it, and set it aside.

[0047] Example 4:

[0048] S1. Immerse 6 g of acid-base treated attapulgite in 60 ml of 0.5 mol / L zinc acetate solution for 4 - 6 h. Heat up to 80 °C and add 60 ml of 2 mol / L urea solution while stirring. Continuously stir for 6 - 8 h. Cool down and filter. Calcinate the obtained solid at 500 °C for 2 h.

[0049] S2. Ultrasonically disperse 5 g of the solid obtained in step S1 in 100 ml of tetrahydrofuran solvent. Heat up to 50 °C, add 50 g of KH540 and 5 g of triethylamine, carry out condensation reflux overnight. Cool to room temperature and add 25 ml of 1 M silver nitrate aqueous solution. Heat up to 100 °C and microwave for 1 min. Cool to room temperature and filter. Wash successively with absolute ethanol and deionized water to obtain modified attapulgite.

[0050] S3. Uniformly disperse 5 g of modified attapulgite in 100 ml of tetrahydrofuran, introduce nitrogen for protection, add an initiator and stir evenly. Heat up to 60 °C. Dissolve 3 g of reactive isothiazolinone derivative in 5 ml of tetrahydrofuran solvent, then dropwise add it to the attapulgite dispersion. After the dropping is completed, maintain a nitrogen atmosphere and stir for reaction for 6 - 8 h. After cooling, wash the product with distilled water, soak it, filter it, dry it, crush it, and set it aside.

[0051] Take 0.5 g of the bactericidal and deodorizing wastewater treatment agent prepared in the above example and mix it with 1 g of commercially available flocculant, and put them into 10 L of wastewater for deodorization for 30 min. Detect and compare the wastewater treatment effect. Among them, the evaluation of the deodorization effect: Analyze the odor concentration before and after deodorization by human olfaction. Divide the deodorization effect into 0 - 5 levels. The higher the level, the better the deodorization effect.

[0052] Table 1

[0053] COD removal rate % SS removal rate % Deodorization effect Application Example 1 98.7 99.1 5 Application Example 2 98.4 98.8 3 Application Example 3 97.9 98.4 4-5 Application Example 4 91.5 90.3 3 Application Example 5 77.2 78.1 1

[0054] Application Examples 1 - 4 respectively correspond to the mixed use of Examples 1 - 4 and commercially available flocculants, and Application Example 5 only uses commercially available flocculants.

[0055] It can be seen from Table 1 that the commercially available flocculant has good removal effects on COD and SS in wastewater, but the deodorization effect is poor. Adding a small amount of the bactericidal and deodorizing wastewater treatment agent of the present application can not only improve the COD removal rate and SS removal rate, but also has a good deodorization effect. Among them, the effect of Application Example 1 is the most obvious, that is, a polymer chain of polyacrylamide and isothiazolinone derivative is in-situ polymerized and grafted on the surface of modified attapulgite. The wastewater treatment agent prepared by controlling the molar ratio of the reactive isothiazolinone derivative to acrylamide at 7-9:3-1 can effectively remove the COD in the water body. At the same time, at a low addition amount, it can quickly deodorize the wastewater and improve the water treatment efficiency.

[0056] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and embodiments. It can be fully applied to various fields suitable for the present invention. For those familiar with the field, additional modifications can be easily achieved. Therefore, without departing from the general concept defined by the claims and the equivalent scope, the present invention is not limited to specific details.

Claims

1. A preparation method of a bactericidal and deodorizing wastewater treatment agent, characterized in that, It includes the following steps: S1. Immerse the acid-base treated attapulgite in zinc acetate solution for 4 - 6 h. Heat to 80 °C and add urea solution with stirring. Keep stirring for 6 - 8 h, cool down and filter. Calcinate the obtained solid at 400 - 600 °C for 2 h; S2. Ultrasonically disperse the solid obtained in step S1 in tetrahydrofuran solvent. Heat to 50 °C, add KH540 and triethylamine, carry out reflux condensation overnight. Cool to room temperature and add aqueous silver nitrate solution. Heat to 100 °C and microwave for 1 min. Cool to room temperature and filter. Wash successively with absolute ethanol and deionized water to obtain modified attapulgite; S3. Uniformly disperse the modified attapulgite in tetrahydrofuran and protect it by introducing nitrogen. Add initiator and stir evenly. Heat to 60 °C. Dissolve the reactive isothiazolinone derivative and acrylamide in tetrahydrofuran solvent, and then dropwise add it to the attapulgite dispersion. After the dropping is completed, keep stirring and reacting for 6 - 8 h in a nitrogen atmosphere. After cooling, wash the product with distilled water, soak it, filter it, dry it, crush it and reserve it; Among them, the structural formula of the reactive isothiazolinone derivative is .

2. The preparation method of the bactericidal and deodorizing wastewater treatment agent according to claim 1, characterized in that, The preparation process of the acid-base treated attapulgite is as follows: Immerse attapulgite in 1M sodium hydroxide solution for 2 h, filter, wash, calcinate, cool, disperse in deionized water, add sodium chloride to adjust the pH to neutral, filter and dry; Immerse the dried attapulgite in 10% hydrochloric acid solution, heat it in a water bath for 1 h, cool, filter with suction and dry; 3. The preparation method of the bactericidal and deodorant wastewater treatment agent according to claim 1, wherein, In step S1, the concentrations of zinc acetate solution and urea solution are 0.5 mol / L and 2 mol / L respectively, and the volume ratio is 1:

1.

4. The preparation method of the bactericidal and deodorant wastewater treatment agent according to claim 1, characterized in that, In step S2, the mass ratio of the solid, KH540 and triethylamine is 1:10:1, the concentration of aqueous silver nitrate solution is 1M, and the mass-volume ratio with the solid is 1 g:5 ml.

5. The preparation method of the bactericidal and deodorant wastewater treatment agent according to claim 1, characterized in that, In step S3, the molar ratio of the reactive isothiazolinone derivative and acrylamide is 7 - 9:3 - 1, and the ratio of their total mass to the mass of the modified attapulgite is 0.5 - 0.8:

1.

6. The preparation method of the bactericidal and deodorant wastewater treatment agent according to claim 1, characterized in that, The preparation process of the reactive isothiazolinone derivative is as follows: 。 7. The bactericidal and deodorant wastewater treatment agent prepared by the preparation method according to any one of claims 1 - 6.

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