CN110563162B - Sewage treatment agent and preparation method and application thereof - Google Patents
Sewage treatment agent and preparation method and application thereof Download PDFInfo
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/342—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the enzymes used
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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
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
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Abstract
The invention relates to a sewage treatment agent. The sewage treatment agent comprises the following components: the chitosan-cured tannin, a sodium bentonite-loaded microbial inoculum, graphene, a biological complex enzyme, an organic-inorganic flocculant, a flocculation auxiliary agent, sodium bisulfite, coconut shell powder and wood dust. The biological active substance of the sewage treatment agent has strong stability and high activity, has good adsorption capacity, flocculation capacity and biodegradation capacity, can effectively remove most heavy metals, complex compounds and organic matters in sewage when being applied to treatment of river sewage and aquaculture wastewater, effectively reduces the content of nitrogen and phosphorus in the sewage, purifies a water body, is efficient and environment-friendly, and does not cause secondary pollution.
Description
Technical Field
The invention relates to a sewage treatment agent and a preparation method and application thereof.
Background
In recent years, intensive aquaculture and livestock-raising are rapidly developed in China, but most of domestic aquaculture adopts closed water areas, the self-purification capacity of water bodies is far lower than the eutrophication speed of the water bodies, and the water area environment is greatly damaged. Due to the application of the feed and the accumulation of animal carcasses and animal excrements, the organic matter and nitrogen-phosphorus ratio in the culture wastewater is extremely high, and the antibiotic in the feed fed for a long time causes the bacteria which resist the drug resistance of animals to invade people and livestock. The livestock breeding wastewater mainly comprises livestock urine, residual excrement, feed residues and the like, and is characterized by high pollutant concentration, more suspended matters, high nitrogen content, large discharged water amount, large residual pathogen and the like. The breeding wastewater causes great harm to the surrounding water area environment and ecological environment, and the problem of high metal content in river sewage is emphasized due to the discharge of industrial wastewater in the river.
At present, the method for treating the aquaculture wastewater can be divided into a physical method, a chemical method and a biological method according to the treatment principle. The physical method is mainly to remove suspended matters and harmful gases in water by mechanical and physical methods, and common methods comprise precipitation, filtration, foam separation, reverse osmosis, adsorption and the like. Wherein, the filtration method can only remove residual feed and excrement in the culture wastewater, and is difficult to remove heavy metal and small particle pollutants which may be contained in the culture wastewater; the foam separation method can only remove surface active substances in the culture wastewater, and is difficult to remove other pollutants. The chemical components mainly comprise oxidation treatment, flocculating agent neutralization coagulation, an electrochemical method and the like. The electrochemical method can remove harmful substances such as ammonia and nitrite, but consumes a large amount of electric energy; the ozone treatment method needs to introduce a large amount of ozone, and has high energy consumption and high cost. Biological methods such as a biological filter have good effects of removing ammonia nitrogen and organic matters, but the content of nitrate in water is increased, national accumulation of nitrate can influence biological growth, and waste water with high nitrogen content is discharged into the environment to cause secondary pollution.
Disclosure of Invention
The invention aims to solve the technical problem of providing a sewage treatment agent, which has strong stability and high activity of bioactive substances, good adsorption capacity, flocculation capacity and biodegradation capacity, can effectively remove most heavy metals, complexes and organic matters in sewage, effectively reduce the content of nitrogen and phosphorus in the sewage, purify a water body, is efficient and environment-friendly, and cannot cause secondary pollution when being applied to treatment of river sewage and aquaculture wastewater.
The technical scheme of the invention is as follows:
a sewage treatment agent comprises the following components in parts by weight: 8-20 parts of chitosan cured tannin, 30-35 parts of sodium bentonite loaded microbial inoculum, 15-23 parts of graphene, 3-10 parts of biological complex enzyme, 28-39 parts of organic-inorganic flocculant, 20-35 parts of flocculation auxiliary agent, 2-3 parts of sodium bisulfite, 12-15 parts of coconut shell powder and 12-20 parts of sawdust.
Further, the chitosan cured tannin is prepared from hydrolyzed tannin, chitosan and glutaraldehyde.
Further, the sodium bentonite-loaded microbial inoculum is prepared from sodium chloride, ethanol, bentonite and a microbial inoculum; the microbial inoculum is at least one of bacillus licheniformis, bacillus subtilis, nitrobacteria, denitrifying bacteria, saccharomycetes and lactic acid bacteria.
Further, the biological complex enzyme comprises amylase, pectinase, cellulase, protease and lipase.
Further, the organic-inorganic flocculant is prepared by compounding an organic flocculant and an inorganic flocculant, wherein the mass ratio of the organic flocculant to the inorganic flocculant is 3-5: 1-2; the organic flocculant is at least one of sodium carboxymethylcellulose, konjac glucomannan, sodium alginate and starch xanthate; the inorganic flocculant is at least one of polymeric ferric sulfate, polymeric aluminum chloride and sodium dihydrogen phosphate.
Further, the flocculation auxiliary agent is at least one of polyacrylamide and polyepichlorohydrin.
The preparation method of the sewage treatment agent comprises the following steps:
s1, preparing chitosan cured tannin: dissolving 32-40 parts of hydrolyzed tannin in 350 parts of water 300-350 parts, adjusting the pH to 7 by using sodium hydroxide, stirring and dissolving, adding 15-20 parts of chitosan, reacting at normal temperature for 1-2h, reacting at 50-55 ℃ for 1-6h, filtering and drying to obtain chitosan cured tannin;
s2, preparing a sodium bentonite-loaded microbial inoculum: dissolving sodium chloride in 50% ethanol water solution, mixing bentonite uniformly, standing for 30-60min to fully wet the bentonite, and performing microwave radiation at power of 2000-; adding 20-30 parts of sodium bentonite into 250 parts of 180-fold microbial inoculum, adjusting the pH value by using sodium hydroxide or glacial acetic acid, stirring at the constant temperature of 35-45 ℃ for 1-1.5h, centrifuging, taking a precipitate, and drying to obtain a sodium bentonite-loaded microbial inoculum;
s3, preparing a sewage treatment agent: uniformly mixing sawdust and coconut shell powder, adding a flocculating aid, soaking for 1-2h, drying and grinding to obtain a mixture a; and (2) after the biological compound enzyme is subjected to microwave radiation for 8-10s at the power of 1000-1200W, adding the biological compound enzyme into the mixture a, adding chitosan solidified tannin, sodium bentonite loaded microbial inoculum, graphene, organic-inorganic flocculant and sodium bisulfite, and uniformly mixing to obtain the sewage treatment agent.
An application of the sewage treatment agent in treating river sewage and aquaculture wastewater.
The invention has the following beneficial effects:
the chitosan solidified tannin is formed by combining chitosan serving as a solidification medium with hydrolyzed tannin in a covalent manner. The chitosan has a plurality of free amino and hydroxyl groups in the molecular structure, has stable coordination effect on transition metal, forms microspheres under the crosslinking effect of glutaraldehyde, has larger specific surface area, and is easy to uniformly fill and stably solidify tannin molecules; two adjacent phenolic hydroxyl groups in the molecular structure of the tannin can perform complex reaction with metal ions in the form of oxygen anions to form a stable five-membered ring chelate. Both can be chelated with metal ions, and the adsorption capacity of the chitosan-cured tannin on the metal ions is improved through the synergy of the two.
In the preparation process of the sodium bentonite-loaded microbial inoculum, 50% ethanol water solution is adopted to dissolve sodium chloride, the characteristics of low viscosity and easy volatilization of ethanol are utilized, the sodium bentonite-loaded microbial inoculum is easy to permeate into bentonite molecules, the product is easy to dry, and Na is used+Replacing Mg with high content in bentonite2+，Ca2+Plasma; adopts a microwave radiation method to accelerate Na in sodium chloride+Speed of ion transmission in bentoniteDegree; the ethanol is vaporized and expanded under microwave heating, so that the space between bentonite layers is increased, the molecular diffusion speed is increased, the ion exchange reaction is accelerated, and the prepared sodium bentonite has high efficiency and good effect. Meanwhile, the expansion of the interlayer spacing of the sodium bentonite increases the pore volume and porosity, is beneficial to the diffusion of the microbial inoculum among the layers and the loading of the microbial inoculum on the surface, can improve the stability of the microbial inoculum while effectively improving the adsorption capacity of the sodium bentonite, and has more efficient and lasting biodegradation capacity.
The organic-inorganic flocculant selected by the invention is matched with the flocculation auxiliary agent and the sodium bisulfite, so that most of suspended matters and metal ions in the sewage can be removed; sodium bentonite loaded microbial inoculum and biological complex enzyme are matched to degrade organic matters, the loading rate and the enzyme activity of the microbial inoculum are improved by utilizing microwave radiation, and the nitrogen and phosphorus content in the anhydrous water is effectively and obviously reduced; and the contents of nitrogen, phosphorus and heavy metals are further reduced by matching with components such as graphene, coconut powder and the like. The components cooperate with each other, so that most heavy metals, complex compounds and organic matters in the sewage can be effectively removed, the nitrogen and phosphorus content in the sewage is effectively reduced, the water body is purified, the efficiency and the environmental protection are realized, and the secondary pollution can not be caused.
Detailed Description
The present invention will be described in detail with reference to examples, which are only preferred embodiments of the present invention and are not intended to limit the present invention.
Examples
The following table is a table of formulations (unit: parts) of 3 examples of the sewage treatment agent of the present invention.
| Components | Example 1 | Example 2 | Example 3 |
| Chitosan-cured tannin | 8 | 11 | 20 |
| Sodium bentonite loading Microbial inoculum | 30, the microbial inoculum is bacillus licheniformis and nitre Bacteria-dissolving | 32, the microbial inoculum is bacillus subtilis, nitrobacteria, Yeast | 35, the microbial inoculum is bacillus subtilis, denitrifying bacteria and yeast Bacteria and lactic acid bacteria |
| Graphene | 15 | 20 | 23 |
| Biological compound enzyme | 3, amylase, pectinase | 5, cellulase and lipase | 10, amylase, pectinase, cellulase, protease, lipase |
| Organic-inorganic flocculant | 20, sodium carboxymethylcellulose: polyaluminum chloride = 3:1 | 28, sodium alginate: polyaluminum chloride, sodium dihydrogen phosphate = 4:1 | 35, starch xanthate, konjac glucomannan: polymeric ferric sulfate =5:2 |
| Flocculation aid | 20, polyacrylamide and polyepichlorohydrin | 28, Polyacrylamide | 35, polyepichlorohydrin |
| Sodium bisulfite | 20 | 22 | 25 |
| Coconut shell powder | 12 | 14 | 15 |
| Wood chip | 12 | 15 | 20。 |
The preparation method of the sewage treatment agent comprises the following steps:
s1, preparing chitosan cured tannin: dissolving 32 parts of hydrolyzed tannin in 300 parts of water, adjusting the pH value to 7 by using sodium hydroxide, stirring and dissolving, adding 15 parts of chitosan, reacting for 1 hour at normal temperature, reacting for 3 hours at 55 ℃, filtering and drying to obtain chitosan cured tannin;
s2, preparing a sodium bentonite-loaded microbial inoculum: dissolving sodium chloride in 50% ethanol water solution, mixing bentonite uniformly, standing for 30min, and performing microwave radiation at 2500W for 2.5min to obtain sodium bentonite; adding 20 parts of sodium bentonite into 220 parts of microbial inoculum, adjusting the pH value by using sodium hydroxide or glacial acetic acid, stirring for 1-1.5h at the constant temperature of 37 ℃, centrifuging, taking a precipitate, and drying to obtain the sodium bentonite-loaded microbial inoculum;
s3, preparing a sewage treatment agent: uniformly mixing sawdust and coconut shell powder, adding a flocculation aid, soaking for 1.5h, drying and grinding to obtain a mixture a; and (2) radiating the biological compound enzyme by microwave with the power of 1200W for 10s, adding the biological compound enzyme into the mixture a, adding chitosan cured tannin, a sodium bentonite-loaded microbial inoculum, graphene, an organic-inorganic flocculant and sodium bisulfite, and uniformly mixing to obtain the sewage treatment agent.
Comparative example
The following table shows the formulation (unit: part) of 3 comparative examples of the sewage treatment agent of the present invention, which were prepared by mixing and drying methods conventional in the art.
| Components | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Chitosan | 8 | 5 | 10 |
| Tannin | / | 6 | 10 |
| Microbial inoculum | 15, Bacillus licheniformis and nitrifying bacteria | 17, bacillus subtilis, nitrobacteria and microzyme | 15, bacillus subtilis, denitrifying bacteria, saccharomycetes and lactic acid bacteria |
| Bentonite clay | 15 | 35 | 20 |
| Graphene | 15 | / | 23 |
| Biological compound enzyme | 3, amylase, pectinase | 5, cellulase and lipase | 10, amylase, pectinase, cellulase, protease, lipase |
| Flocculating agent | 20, polyaluminum chloride | 28, sodium alginate | 35, starch xanthate: polymeric ferric sulfate =5:2 |
| Flocculation aid | 20, polyacrylamide and polyepichlorohydrin | 28, Polyacrylamide | 35, polyepichlorohydrin |
| Sodium bisulfite | 20 | 22 | 25 |
| Coconut shell powder | 12 | 14 | 15 |
| Wood chip | 12 | 15 | 20。 |
Equal-mass sewage treatment agents of examples 1 to 3 and comparative examples 1 to 3 of the sewage treatment agent of the invention were added to 1t of river sewage, and the Chemical Oxygen Demand (COD) removal rate, Biochemical Oxygen Demand (BOD) removal rate, removal rate of suspended matter (SS) in water quality, removal rate of heavy metals, removal rate of turbidity, removal rate of TP and removal rate of liquid nitrogen (NH + 4-N) of the sewage before and after treatment were measured. The test results are shown in the following table.
| Item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| COD removal Rate/%) | 94 | 93 | 96 | 85 | 86 | 89 |
| BOD removal Rate/% | 96 | 96 | 97 | 86 | 82 | 87 |
| SS removal rate/%) | 92 | 95 | 96 | 82 | 79 | 86 |
| Heavy metal removal rate/%) | 93 | 94 | 94 | 78 | 80 | 88 |
| Turbidity removal rate/%) | 93 | 93 | 94 | 81 | 79 | 86 |
| TP removal Rate/%) | 90 | 91 | 93 | 85 | 84 | 87 |
| NH + 4-N removal% | 92 | 91 | 94 | 83 | 84 | 86。 |
Therefore, the sewage treatment agent can effectively improve the COD removal rate, the BOD removal rate, the SS removal rate, the heavy metal removal rate, the turbidity removal rate, the TP removal rate and the NH 4 & lt- & gt-N removal rate before and after sewage treatment.
The biological active substance of the sewage treatment agent has strong stability and high activity, has good adsorption capacity, flocculation capacity and biodegradation capacity, can effectively remove most heavy metals, complex compounds and organic matters in sewage when being applied to treatment of river sewage and aquaculture wastewater, effectively reduces the content of nitrogen and phosphorus in the sewage, purifies a water body, is efficient and environment-friendly, and does not cause secondary pollution.
Claims (7)
1. The sewage treatment agent is characterized by comprising the following components in parts by weight: 8-20 parts of chitosan cured tannin, 30-35 parts of sodium bentonite loaded microbial inoculum, 15-23 parts of graphene, 3-10 parts of biological complex enzyme, 28-39 parts of organic-inorganic flocculant, 20-35 parts of flocculation auxiliary agent, 20-25 parts of sodium bisulfite, 12-15 parts of coconut shell powder and 12-20 parts of sawdust;
the preparation method of the sewage treatment agent comprises the following steps:
s1, preparing chitosan cured tannin: dissolving 32-40 parts of hydrolyzed tannin in 350 parts of water 300-350 parts, adjusting the pH to 7 by using sodium hydroxide, stirring and dissolving, adding 15-20 parts of chitosan, reacting at normal temperature for 1-2h, reacting at 50-55 ℃ for 1-6h, filtering and drying to obtain chitosan cured tannin;
s2, preparing a sodium bentonite-loaded microbial inoculum: dissolving sodium chloride in 50% ethanol water solution, mixing bentonite uniformly, standing for 30-60min, and performing microwave radiation at power of 2000-; adding 20-30 parts of sodium bentonite into 250 parts of 180-fold microbial inoculum, adjusting the pH value by using sodium hydroxide or glacial acetic acid, stirring at the constant temperature of 35-45 ℃ for 1-1.5h, centrifuging, taking a precipitate, and drying to obtain a sodium bentonite-loaded microbial inoculum;
s3, preparing a sewage treatment agent: uniformly mixing sawdust and coconut shell powder, adding a flocculating aid, soaking for 1-2h, drying and grinding to obtain a mixture a; and (2) after the biological compound enzyme is subjected to microwave radiation for 8-10s at the power of 1000-1200W, adding the biological compound enzyme into the mixture a, adding chitosan solidified tannin, sodium bentonite loaded microbial inoculum, graphene, organic-inorganic flocculant and sodium bisulfite, and uniformly mixing to obtain the sewage treatment agent.
2. The wastewater treatment agent of claim 1, wherein the chitosan cured tannin is prepared from hydrolyzed tannin, chitosan, and glutaraldehyde.
3. The sewage treatment agent according to claim 1, wherein the sodium bentonite-loaded microbial inoculum is prepared from sodium chloride, ethanol, bentonite and microbial inoculum; the microbial inoculum is at least one of bacillus licheniformis, bacillus subtilis, nitrobacteria, denitrifying bacteria, saccharomycetes and lactic acid bacteria.
4. The sewage treatment agent according to claim 1, wherein the biological complex enzyme comprises amylase, pectinase, cellulase, protease and lipase.
5. The sewage treatment agent according to claim 1, wherein the organic-inorganic flocculant is prepared by compounding an organic flocculant and an inorganic flocculant, and the mass ratio of the organic flocculant to the inorganic flocculant is 3-5: 1-2; the organic flocculant is at least one of sodium carboxymethylcellulose, konjac glucomannan, sodium alginate and starch xanthate; the inorganic flocculant is at least one of polymeric ferric sulfate, polymeric aluminum chloride and sodium dihydrogen phosphate.
6. The sewage treatment agent according to claim 1, wherein the flocculation aid is at least one of polyacrylamide and polyepichlorohydrin.
7. The use of the sewage treatment agent of any one of claims 1 to 6 in the treatment of river sewage and aquaculture wastewater.
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| CN110563162A (en) | 2019-12-13 |
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