A special deodorizing composite biological filler for printing and dyeing sewage treatment and its preparation method

Abstract

The present invention provides a special deodorizing composite biological filler for printing and dyeing sewage treatment and a preparation method thereof. The special deodorizing composite biological filler for printing and dyeing sewage treatment of the present invention is mainly prepared from the following raw materials: by mass parts, 10-15 parts of dimethyl phosphonobutanedioic acid, 10-15 parts of acrylic acid, 8-12 parts of ethylene-vinyl acetate, 10-15 parts of calcium carbonate, 20-30 parts of bentonite, and 5-15 parts of sodium hydroxide solution. The special deodorizing composite biological filler for printing and dyeing sewage treatment of the present invention has a large specific surface area and porosity, which is beneficial to the film formation and growth of microorganisms, and can provide certain nutrients for the growth of microorganisms at the same time.

Description

Technical Field

[0001] The present invention relates to the technical field of industrial wastewater treatment, and in particular, to a special deodorizing composite biological filler for printing and dyeing wastewater treatment and a preparation method thereof. Background Art

[0002] Printing and dyeing wastewater refers to the mixed wastewater formed by the wastewater discharged from various processes such as singeing, desizing, boiling, bleaching, and mercerizing during the printing and dyeing process. It mainly includes: wastewater discharged in the pretreatment stage; dyeing wastewater discharged in the dyeing stage; printing wastewater and soaping wastewater discharged in the printing stage; and finishing wastewater discharged in the finishing stage. The composition of printing and dyeing wastewater is complex, mainly based on aromatic hydrocarbons and heterocyclic compounds as the matrix, and with chromogenic groups (such as -N=N-, -N=O) and polar groups (such as -SO3Na, -OH, -NH2). If not treated in time, hydrogen sulfide gas will be generated and emit a pungent odor.

[0003] With the continuous improvement of the national odor emission standards and in order to improve the impact on the atmospheric environment, the collection and treatment of odors in sewage treatment plants have become an urgent task. The original deodorization technologies in sewage treatment plants are difficult to meet the emission requirements of the new standards, and the upgrading and transformation of the deodorization process in sewage treatment plants is an important part of the upgrading and transformation of sewage treatment plants in the new era.

[0004] At present, common odor treatment technologies include physical methods, chemical methods, and biological methods, etc. The biological deodorization method has become the main technical means of deodorization technology for each sewage treatment enterprise at present due to its low investment and operation costs, stable and reliable performance, simple operation, good treatment effect, and little secondary pollution.

[0005] The factors affecting the biological deodorization system include reactor structure, filler, strains, and operating parameters, etc. Among them, as the medium for the growth and attachment of microorganisms, the performance of the filler will directly affect the deodorization effect. Therefore, the filler is the core technology of the deodorization device in the biological deodorization system. Natural organic fillers have the advantages of being cheap, easy for microorganisms to attach and grow, and containing rich organic nutrients, but the disadvantages are easy to rot, poor mechanical properties, and problems such as filler layer collapse and compaction are likely to occur after long-term use. Inorganic fillers are easy to obtain, have high strength, and stable chemical properties, which easily lead to problems such as low biological activity, long reactor startup time, and increased operating costs.

[0006] In view of this, the present invention is specifically proposed. Summary of the Invention

[0007] The first object of the present invention is to provide a special deodorizing composite biological filler for printing and dyeing wastewater treatment, which has a large specific surface area and porosity, is conducive to the film formation and growth of microorganisms, and can provide certain nutrients for the growth of microorganisms.

[0008] The second object of the present invention is to provide a preparation method of the above-mentioned deodorizing composite biological filler for printing and dyeing sewage treatment, and the preparation method has simple process, mild operating conditions, and is safe and environmentally friendly.

[0009] In order to achieve the above objects of the present invention, the following technical solutions are specifically adopted:

[0010] The present invention provides a deodorizing composite biological filler for printing and dyeing sewage treatment, which is mainly prepared from the following raw materials: by mass, 10-15 parts of dimethyl phosphonobutanedioic acid, 10-15 parts of acrylic acid, 8-12 parts of ethylene-vinyl acetate, 10-15 parts of calcium carbonate, 20-30 parts of bentonite, and 5-15 parts of sodium hydroxide solution.

[0011] Preferably, as a further feasible solution, by mass, 10 parts of dimethyl phosphonobutanedioic acid, 10 parts of acrylic acid, 8 parts of ethylene-vinyl acetate, 10 parts of calcium carbonate, 20 parts of bentonite, and 5 parts of sodium hydroxide solution.

[0012] Preferably, as a further feasible solution, by mass, 13 parts of dimethyl phosphonobutanedioic acid, 13 parts of acrylic acid, 10 parts of ethylene-vinyl acetate, 13 parts of calcium carbonate, 25 parts of bentonite, and 10 parts of sodium hydroxide solution.

[0013] Preferably, as a further feasible solution, by mass, 15 parts of dimethyl phosphonobutanedioic acid, 15 parts of acrylic acid, 12 parts of ethylene-vinyl acetate, 15 parts of calcium carbonate, 30 parts of bentonite, and 15 parts of sodium hydroxide solution.

[0014] In the above formula of the deodorizing composite biological filler for printing and dyeing sewage treatment, the high molecular copolymer formed by dimethyl phosphonobutanedioic acid, acrylic acid, and ethylene-vinyl acetate is added with calcium carbonate and bentonite to stretch the copolymer space, forming a larger specific surface area to carry more microorganisms.

[0015] In the above formula, attention needs to be paid to the addition amount relationship between various substances, and the addition amount of each substance needs to be controlled within a reasonable range. Because if the addition amount of a certain component is too large, it will cover up the effect of other components, and although the stability is improved, the oil removal effect will be affected. Therefore, in addition to paying attention to the specific combination between formulas, attention also needs to be paid to the compatibility relationship between dosages.

[0016] The present invention also provides a preparation method of the deodorizing composite biological filler for printing and dyeing sewage treatment, including the following steps:

[0017] Take dimethyl phosphonobutanedioic acid and ethylene-vinyl acetate and add them to the reaction kettle, stir and heat up, and stir evenly after complete dispersion;

[0018] Slowly add acrylic acid, p-toluenesulfonic acid and calcium carbonate, stir, cool down, and add sodium hydroxide solution;

[0019] Add bentonite and continue to stir, then cool.

[0020] Preferably, as a further feasible solution, dimethyl phosphonobutanedioic acid and ethylene-vinyl acetate are added to the reaction kettle, and the temperature is raised to 60-70 °C with stirring.

[0021] Preferably, as a further feasible solution, the stirring temperature after adding acrylic acid, p-toluenesulfonic acid and calcium carbonate is 60-70 °C, and after stirring for 2 h, the temperature is lowered to 30-40 °C.

[0022] Preferably, as a further feasible solution, the mass fraction of sodium hydroxide in the sodium hydroxide solution is 30%.

[0023] By defining each operation parameter in the preparation method, the quality of the special deodorant composite biological filler for printing and dyeing wastewater treatment prepared is improved. The special deodorant composite biological filler for printing and dyeing wastewater treatment has a large specific surface area and porosity, and can effectively enable microorganisms to grow with biofilm attachment.

[0024] In summary, the special deodorant composite biological filler for printing and dyeing wastewater treatment prepared by adopting the above preparation method is green and environmentally friendly and has excellent stability.

[0025] Compared with the prior art, the beneficial effects of adopting the above technical scheme are as follows:

[0026] The polymer copolymer formed by dimethyl phosphonobutanedioic acid, acrylic acid and ethylene-vinyl acetate is added with calcium carbonate and bentonite to stretch the copolymer space, forming a large specific surface area to carry more microorganisms.

[0027] The filler provided by the present invention has the advantages of load resistance, good air permeability, good bioadhesion, etc. The components of the filler can effectively fix the remaining substances in the sludge, so that the sludge can achieve the purpose of harmlessness and resource utilization.

[0028] The raw materials of the present invention are easily available and the process is simple, reducing the production cost; the filler also has the characteristics of large specific surface area, high porosity and high hardness. At the same time, the biological filler prepared by the present invention can provide a certain attachment support for the growth of microorganisms, has good moisture retention performance, fixes and slowly releases nutrients for microorganisms to absorb and utilize, and provides a stable living environment for the growth of microorganisms.

[0029] Compared with inorganic fillers, natural or artificial organic fillers have the advantages of better effect and stable continuous use time, which is beneficial to the application of industrial biological filter deodorization. Specific Embodiments

[0030] The implementation scheme of the present invention will be described in detail below in conjunction with embodiments. However, those skilled in the art will understand that the following embodiments are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. For those not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. For the reagents or instruments not specified for the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0031] Example 1

[0032] The specific preparation process of the special deodorant composite biological filler for printing and dyeing sewage treatment is operated according to the following steps:

[0033] 1. Weigh the following raw materials according to the following mass parts:

[0034] Dimethyl phosphonate succinic acid 10 parts, acrylic acid 10 parts, ethylene-vinyl acetate 8 parts, calcium carbonate 10 parts, bentonite 20 parts, sodium hydroxide solution 5 parts.

[0035] 2. Take dimethyl phosphonate succinic acid and ethylene-vinyl acetate and add them to the reaction kettle, stir and heat up to 60 °C, and stir evenly after complete dispersion;

[0036] Slowly add acrylic acid, p-toluenesulfonic acid, and calcium carbonate, keep at 60 °C, stir for 2 h, cool down to 30 °C, and add sodium hydroxide solution;

[0037] Add bentonite and continue to stir for 1 h, then cool to room temperature;

[0038] Dry to constant weight at 90 °C and crush.

[0039] In the above preparation method of the special deodorant composite biological filler for printing and dyeing sewage treatment, the mass fraction of sodium hydroxide in the sodium hydroxide solution is 30%. The filling density of the filler is measured to be 0.5 - 1.0 g / cm 3 , the particle size range is 15 - 25 mm, and the specific surface area is 256 - 365 m 2 / g.

[0040] Example 2

[0041] The specific preparation process of the special deodorant composite biological filler for printing and dyeing sewage treatment is operated according to the following steps:

[0042] 1. Weigh the following raw materials according to the following mass parts:

[0043] Dimethyl phosphonate succinic acid 15 parts, acrylic acid 15 parts, ethylene-vinyl acetate 12 parts, calcium carbonate 15 parts, bentonite 30 parts, sodium hydroxide solution 15 parts.

[0044] 2. Add dimethyl 2-phosphonobutanedioate and ethylene-vinyl acetate into the reaction kettle, stir and heat up to 70 °C. After complete dispersion, stir evenly.

[0045] Slowly add acrylic acid, p-toluenesulfonic acid, and calcium carbonate, maintain at 70 °C, stir for 2 h, cool down to 40 °C, and add sodium hydroxide solution.

[0046] Add bentonite and continue to stir for 1 h, then cool to room temperature.

[0047] Dry at 80 °C to constant weight and crush.

[0048] In the above preparation method of the deodorant composite biological filler for printing and dyeing wastewater treatment, the mass fraction of sodium hydroxide in the sodium hydroxide solution is 30%. The filling density of this filler is measured to be 0.5 - 1.0 g / cm 3 , the particle size range is 15 - 25 mm, and the specific surface area is 256 - 365 m 2 / g.

[0049] Example 3

[0050] The specific preparation process of the deodorant composite biological filler for printing and dyeing wastewater treatment is operated according to the following steps:

[0051] 1. Weigh each raw material according to the following mass parts:

[0052] The specific preparation process of the deodorant composite biological filler for printing and dyeing wastewater treatment is operated according to the following steps:

[0053] 1. Weigh each raw material according to the following mass parts:

[0054] 13 parts of dimethyl 2-phosphonobutanedioate, 13 parts of acrylic acid, 10 parts of ethylene-vinyl acetate, 13 parts of calcium carbonate, 25 parts of bentonite, 10 parts of sodium hydroxide solution.

[0055] 2. Add dimethyl 2-phosphonobutanedioate and ethylene-vinyl acetate into the reaction kettle, stir and heat up to 65 °C. After complete dispersion, stir evenly.

[0056] Slowly add acrylic acid, p-toluenesulfonic acid, and calcium carbonate, maintain at 65 °C, stir for 2 h, cool down to 45 °C, and add sodium hydroxide solution.

[0057] Add bentonite and continue to stir for 1 h, then cool to room temperature.

[0058] Dry at 85 °C to constant weight and crush.

[0059] In the above preparation method of the deodorant composite biological filler for printing and dyeing wastewater treatment, the mass fraction of sodium hydroxide in the sodium hydroxide solution is 30%. The filling density of this filler is measured to be 0.5 - 1.0 g / cm3 with a particle size range of 15 - 25 mm and a specific surface area of 256 - 365 m 2 / g.

[0060] Example 4

[0061] The specific operation steps are the same as those in Example 3, except that the raw materials are proportioned according to the following parts by mass:

[0062] 15 parts of dimethyl phosphonate succinic acid, 15 parts of acrylic acid, 12 parts of ethylene - vinyl acetate, 15 parts of calcium carbonate, 30 parts of bentonite, and 15 parts of sodium hydroxide solution.

[0063] In the above - mentioned preparation method of the deodorant composite biological filler for printing and dyeing wastewater treatment, the mass fraction of sodium hydroxide in the sodium hydroxide solution is 30%. The measured packing density of this filler is 0.5 - 1.0 g / cm 3 with a particle size range of 15 - 25 mm and a specific surface area of 256 - 365 m 2 / g.

[0064] Comparative Example 1

[0065] The specific operation steps are the same as those in Example 4, except that dimethyl phosphonate succinic acid, acrylic acid, and ethylene - vinyl acetate are not added. The measured packing density of this filler is less than 0.3 g / cm 3 with a particle size range greater than 30 mm and a specific surface area less than 200 m 2 / g.

[0066] Comparative Example 2

[0067] The specific operation steps are the same as those in Example 3, except that calcium carbonate and bentonite are not added. The measured packing density of this filler is less than 0.2 g / cm 3 with a particle size range greater than 30 mm and a specific surface area less than 100 m 2 / g.

[0068] Experimental Example 1

[0069] Carry out the test of carrying bacteria on the deodorant composite biological fillers for printing and dyeing wastewater treatment in Examples 1 - 4 and Comparative Examples 1 - 2.

[0070] Immerse the filler in Example 1 in the deodorant microbial liquid for 48 hours. The amount of bacteria carried by the magnetic filler measured by the casting method is 10 12 cfu / g. Put 3 kg of the filler carrying microorganisms into the sewage. After 45 days, the microbial content in the sewage measured by the casting method is 10 6 cfu / g, and the amount of bacteria carried by the filler is 10 9 cfu / g.

[0071] The sample of Example 2 was immersed in the deodorizing microbial liquid for 48 hours, and the carried amount of bacteria in the magnetic packing was measured by the casting method to be 10 13 cfu / g. 3 kg of the packing carrying microorganisms was put into the sewage. After 45 days, the microbial content in the sewage was measured by the casting method to be 10 7 cfu / g, and the carried amount of bacteria in the packing was 10 8 cfu / g.

[0072] The sample of Example 3 was immersed in the deodorizing microbial liquid for 48 hours, and the carried amount of bacteria in the magnetic packing was measured by the casting method to be 10 13 cfu / g. 4 kg of the packing carrying microorganisms was put into the sewage. After 45 days, the microbial content in the sewage was measured by the casting method to be 10 6 cfu / g, and the carried amount of bacteria in the packing was 10 8 cfu / g.

[0073] The sample of Example 4 was immersed in the deodorizing microbial liquid for 48 hours, and the carried amount of bacteria in the magnetic packing was measured by the casting method to be 10 14 cfu / g. 4 kg of the packing carrying microorganisms was put into the sewage. After 45 days, the microbial content in the sewage was measured by the casting method to be 10 8 cfu / g, and the carried amount of bacteria in the packing was 110 cfu / g.

[0074] The sample of Comparative Example 1 was immersed in the deodorizing microbial liquid for 48 hours, and the carried amount of bacteria in the magnetic packing was measured by the casting method to be 800 cfu / g. 3 kg of the packing carrying microorganisms was put into the sewage. After 45 days, the microbial content in the sewage was measured by the casting method to be 80 cfu / g, and the carried amount of bacteria in the packing was 80 cfu / g.

[0075] The sample of Comparative Example 2 was immersed in the deodorizing microbial liquid for 48 hours, and the carried amount of bacteria in the magnetic packing was measured by the casting method to be 600 cfu / g. 4 kg of the packing carrying microorganisms was put into the sewage. After 45 days, the microbial content in the sewage was measured by the casting method to be 65 cfu / g, and the carried amount of bacteria in the packing was 65 cfu / g.

[0076] As can be seen from the above examples, the packing has an excellent effect of carrying bacteria, can promote the growth of deodorizing microorganisms, and significantly improve the deodorizing effect of the biological filter.

[0077] Although the present invention has been illustrated and described with reference to specific embodiments, it should be appreciated that many other changes and modifications may be made without departing from the spirit and scope of the invention. Therefore, this means that all such changes and modifications that fall within the scope of the present invention are included in the appended claims.

Claims

1. A special deodorizing composite biological filler for printing and dyeing sewage treatment, characterized in that, It is mainly prepared from the following raw materials: by mass, 10-15 parts of dimethyl phosphonobutanedioic acid, 10-15 parts of acrylic acid, 8-12 parts of ethylene-vinyl acetate, 10-15 parts of calcium carbonate, 20-30 parts of bentonite, and 5-15 parts of sodium hydroxide solution.

2. The deodorizing composite biological filler for special use in printing and dyeing sewage treatment according to claim 1, characterized in that By mass, 10 parts of dimethyl phosphonobutanedioic acid, 10 parts of acrylic acid, 8 parts of ethylene-vinyl acetate, 10 parts of calcium carbonate, 20 parts of bentonite, and 5 parts of sodium hydroxide solution.

3. The special deodorizing composite biological filler for printing and dyeing sewage treatment according to claim 1, characterized in that, By mass, 13 parts of dimethyl phosphonobutanedioic acid, 13 parts of acrylic acid, 10 parts of ethylene-vinyl acetate, 13 parts of calcium carbonate, 25 parts of bentonite, and 10 parts of sodium hydroxide solution.

4. The deodorizing composite biological filler special for printing and dyeing sewage treatment according to claim 1, characterized in that, By mass, 15 parts of dimethyl phosphonobutanedioic acid, 15 parts of acrylic acid, 12 parts of ethylene-vinyl acetate, 15 parts of calcium carbonate, 30 parts of bentonite, and 15 parts of sodium hydroxide solution.

5. The preparation method of the special deodorizing composite biological filler for printing and dyeing sewage treatment according to any one of claims 1-4, characterized in that It includes the following steps: Take dimethyl phosphonobutanedioic acid and ethylene-vinyl acetate and add them into a reaction kettle, stir and heat up. After complete dispersion, stir evenly. Slowly add acrylic acid, p-toluenesulfonic acid and calcium carbonate, stir, cool down, and add sodium hydroxide solution. Add bentonite and continue to stir and then cool.

6. The preparation method according to claim 5, characterized in that, Dimethyl phosphonobutanedioic acid and ethylene-vinyl acetate are added into a reaction kettle, and stirred and heated up to 60-70 °C.

7. The preparation method according to claim 5, characterized in that The stirring temperature after adding acrylic acid, p-toluenesulfonic acid and calcium carbonate is 60-70 °C. After stirring for 2 h, cool down to 30-40 °C.

8. The preparation method according to claim 5, characterized in that, The mass fraction of sodium hydroxide in the sodium hydroxide solution is 30%.