CN113060840A - Method for treating high-concentration nitrate nitrogen in water - Google Patents

Method for treating high-concentration nitrate nitrogen in water Download PDF

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CN113060840A
CN113060840A CN202110358935.7A CN202110358935A CN113060840A CN 113060840 A CN113060840 A CN 113060840A CN 202110358935 A CN202110358935 A CN 202110358935A CN 113060840 A CN113060840 A CN 113060840A
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denitrifying bacteria
denitrification
nitrate nitrogen
water
sulfur
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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
    • 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
    • C02F3/348—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the way or the form in which the microorganisms are added or dosed
    • 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
    • C02F2101/163—Nitrates
    • 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
    • C02F2101/166—Nitrites
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/15—N03-N
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/06—Nutrients for stimulating the growth of microorganisms

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  • Life Sciences & Earth Sciences (AREA)
  • Microbiology (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)

Abstract

The invention provides a denitrification filter material for treating high-concentration nitrate nitrogen in water, which comprises a denitrification filler, sulfur autotrophic denitrifying bacteria and heterotrophic denitrifying bacteria, wherein the denitrification filler comprises sulfur, a slow-release carbon source, carbonate and metal oxides, and the sulfur autotrophic denitrifying bacteria and the heterotrophic denitrifying bacteria form a biological film on the surface of the denitrification filler; the sulfur autotrophic denitrifying bacteria and the heterotrophic denitrifying bacteria are respectively selected from Paracoccus versutus LYM and Pseudomonas stutzeri ATCC 17588. The denitrification filter material has higher treatment efficiency on high-concentration nitrate nitrogen and has wide application prospect.

Description

Method for treating high-concentration nitrate nitrogen in water
Technical Field
The invention relates to the field of water treatment, in particular to a method for treating nitrate nitrogen in water.
Background
Nitrogen is one of the main factors causing water eutrophication, and in the treatment of the problem of water eutrophication, the reduction of the nitrogen content in water is important. The traditional denitrification technology is biological nitrification and denitrification, but the denitrification of the technology needs to consume a large amount of soluble organic matters, namely carbon sources, while the carbon sources of landscape water bodies are seriously insufficient, and the denitrification effect is extremely poor.
With the acceleration of the degree of industrialization, the pollution of underground water and surface water is gradually increased. NO3 -As a water pollutant, the NO in the wastewater is widely existed in surface water and underground water and seriously threatens the health of human bodies along with the improvement of the requirement on the total nitrogen emission of industrial wastewater3 -The removal of-N (nitrate nitrogen) is of increasing concern.
Biological denitrification is always considered as the most economic and effective denitrification mode, but organic matters are required to be used as a denitrification carbon source in the denitrification process, and the defects of high alkalinity yield and high sludge yield exist at the same time, so the problems are particularly obvious when the biological denitrification is applied to high-concentration nitrate nitrogen wastewater. In recent years, the autotrophic denitrification technology attracts much attention, and compared with the traditional denitrification technology, the autotrophic denitrification technology does not need an additional carbon source and has the advantage of saving cost.
In order to improve the treatment efficiency of nitrate nitrogen in water, a mode of combining filter materials and microorganisms is also a common technology in the field. For example, the most studied at home and abroad at present is a sulfur/limestone autotrophic denitrification (SLAD) system, which can utilize reduced sulfur as an electron donor under anoxic or anaerobic conditions, obtain energy by oxidizing the reduced sulfur, and reduce nitrate as an electron acceptor into nitrogen gas, thereby realizing the autotrophic denitrification process; CN107487840A discloses a biological filter material, which comprises sulfur monomers, a slow-release carbon source and carbonate, wherein autotrophic denitrifying bacteria and heterotrophic denitrifying bacteria are adsorbed on the surface of the biological filter material to form a biological membrane, so that high-concentration nitrate nitrogen wastewater can be efficiently treated. CN103232117A discloses that sulfur/limestone/forest waste is used as a denitrification filler and combined with thiobacillus denitrificans to carry out denitrification.
The applicant has found that when nitrate nitrogen is treated by combining biological filter materials and microorganisms, the selection of microorganisms, particularly the selection of autotrophic denitrifying bacteria and heterotrophic denitrifying bacteria, has an important influence on the treatment efficiency of high-concentration nitrate nitrogen, and based on this finding, the applicant has completed the present invention.
Disclosure of Invention
The invention provides a denitrification filter material for treating high-concentration nitrate nitrogen in water, which comprises a denitrification filler, sulfur autotrophic denitrifying bacteria and heterotrophic denitrifying bacteria, wherein the denitrification filler comprises sulfur, a slow-release carbon source, carbonate and metal oxides, and the sulfur autotrophic denitrifying bacteria and the heterotrophic denitrifying bacteria form a biological film on the surface of the denitrification filler.
In one embodiment, the sulphur is present in an amount of 40% to 60%, preferably 50%, by mass; the mass percentage of the carbonate is 10-30%, preferably 25%; the mass percentage of the slow-release carbon source is 10-30%, preferably 20%; the mass percent of the metal oxide is 3% -10%, preferably 5%; the sum of the mass percentages of the components is not more than 100 percent.
In a preferred embodiment, the slow-release carbon source is corncob and the carbonate is calcium carbonate.
Further, the metal oxide is selected from manganese oxide and/or zinc oxide, preferably, zinc oxide.
In a preferred embodiment, the sulfur autotrophic denitrifying bacteria and the heterotrophic denitrifying bacteria are selected from Paracoccus versutus LYM and Pseudomonas stutzeri ATCC17588, respectively.
In one embodiment, the sulfur autotrophic denitrifying bacteria and the heterotrophic denitrifying bacteria are inoculated into the denitrification filler, and the conventional culture medium is continuously introduced to culture and acclimatize the sulfur autotrophic denitrifying bacteria and the heterotrophic denitrifying bacteria until a stable biofilm grows on the surface of the denitrification filler.
In a preferred embodiment, the sulfur autotrophic denitrifying bacteria and the heterotrophic denitrifying bacteria are used in a ratio of 1: 1.
On the other hand, the invention also provides the application of the denitrification filter material in the treatment of nitrate nitrogen in water.
In a preferred embodiment, the content of nitrate nitrogen in water is not less than 400mg/L, more preferably, the content of nitrate nitrogen in water is 400mg/L-1000mg/L, for example, 500mg/L, 600mg/L, 700mg/L, 800mg/L, 900 mg/L.
In another aspect, the invention further provides a method for treating high-concentration nitrate nitrogen in water, which comprises the step of treating the high-concentration nitrate nitrogen in the water by using the denitrification filter material.
In a preferred embodiment, the content of the high concentration nitrate nitrogen is not less than 400mg/L, and more preferably, the content of the high concentration nitrate nitrogen is 400mg/L to 1000mg/L, for example, 500mg/L, 600mg/L, 700mg/L, 800mg/L, 900 mg/L.
The invention optimizes the denitrification filter material, including the optimization of sulfur autotrophic denitrifying bacteria and heterotrophic denitrifying bacteria and the optimization of filler components, thereby improving the treatment efficiency of the denitrification filter material on high-concentration nitrate nitrogen and having wide application prospect.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to the examples. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept and the scope of the appended claims is intended to be protected. The procedures, conditions, reagents, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
EXAMPLE preparation of denitrogenation Filter Material
The application adopts the method of CN107487840A to prepare the denitrification filler. The main components of the prepared filler comprise sulfur simple substance (sulfur), slow-release carbon source (corn cob slow-release carbon source), metal oxide (manganese oxide) and carbonate (calcium carbonate). Wherein the mass percent of the sulfur is 50%, the mass percent of the calcium carbonate is 25%, the mass percent of the corn cob slow-release carbon source is 20%, and the mass percent of the manganese oxide is 5%.
On the surface of the biological filler, sulfur autotrophic denitrifying bacteria and heterotrophic denitrifying bacteria are adsorbed to form a biological film. In the process of treating nitrate nitrogen in water, the elemental sulfur provides electrons for sulfur autotrophic denitrifying bacteria to perform denitrification of the nitrate nitrogen, and nitrogen and sulfate are generated. The slow-release carbon source provides electrons for heterotrophic denitrifying bacteria to perform denitrification of nitrate nitrogen, and a certain alkalinity is generated while nitrogen is generated. The carbonate is used for maintaining the pH value in the denitrification process and preventing the pH value from being too low to influence the growth and the reproduction of bacteria. Because the metal oxide in the biological filter material component has positive charge property, and the surfaces of the sulfur autotrophic denitrifying bacteria and the sulfur heterotrophic denitrifying bacteria have negative charges, the bacteria can be more easily adsorbed on the surface of the filler, thereby forming the biological membrane.
Inoculating sulfur autotrophic denitrifying bacteria and heterotrophic denitrifying bacteria into a denitrification filler, setting the starting hydraulic retention time to be 10h, pumping a water body to be denitrified into the filler, and continuously introducing a conventional culture medium to dynamically culture and acclimate the sulfur autotrophic denitrifying bacteria and the heterotrophic denitrifying bacteria until a stable biological membrane grows on the surface of a denitrification filter material. And continuously pumping into a water body to be denitrified, and carrying out denitrification treatment by the denitrification filler.
The inoculum sizes of the sulfur autotrophic denitrifying bacteria and the heterotrophic denitrifying bacteria are respectively 108-1010cfu, preferably, 109cfu; the ratio of the dosage of the sulfur autotrophic denitrifying bacteria to the dosage of the heterotrophic denitrifying bacteria is 1: 1.
Example verification of denitrification Effect of Secondary denitrification Filter
In this example, based on the first example, it was verified that different sulfur autotrophic denitrifying bacteria and heterotrophic denitrifying bacteria can be used for artificially simulating high-concentration nitrate nitrogen wastewater and nitrate Nitrogen (NO)3 --N) treatment efficiencies at concentrations of 100mg/L, 200mg/L, 300mg/L, 400mg/L, 500mg/L, 600mg/L, 800mg/L, 1000mg/L, respectively.
In this example, the sulfoautotrophic denitrifying bacteria are selected from Thiobacillus denitrificans ATCC 25259 or Paracoccus versatus LYM; the heterotrophic denitrifying bacteria are selected from Paracoccus denitrificans ACCC 10489 or Pseudomonas stutzeri ATCC 17588; the above microorganisms belong to microorganisms known in the art. For example, thiobacillus denitrificans ATCC 25259 is disclosed in CN 103773706A; paracoccus versutus LYM is disclosed in CN 103103147A; the study on aerobic denitrification characteristics of paracoccus denitrificans and the effect of paracoccus denitrificans in water nitrogen conversion discloses paracoccus denitrificans ACCC 10489, and CN101973795A also discloses paracoccus denitrificans ACCC 1048; the 'screening of aerobic denitrifying phosphorus accumulating bacteria and the research of the denitrification and dephosphorization performance' discloses Pseudomonas stutzeri (Pseudomonas stutzeri) ATCC 17588.
In order to verify the effect of the combined treatment of nitrate nitrogen by different sulfur autotrophic denitrifying bacteria and heterotrophic denitrifying bacteria, the following scheme is adopted in the embodiment to verify the treatment efficiency.
Figure BDA0003004684960000041
Figure BDA0003004684960000051
The different experimental groups are adopted to artificially simulate high-concentration nitrate nitrogen wastewater and nitrate Nitrogen (NO)3 --N) concentrations of 100mg/L, 200mg/L, 300mg/L, 400mg/L, 500mg/L, 600mg/L, 800mg/L and 1000mg/L respectively, under the condition that the hydraulic retention time is fixed at 12h, the treatment effect of nitrate nitrogen in each experimental group is as follows:
Figure BDA0003004684960000052
as can be seen from the above table, the experimental groups 1-4 have good treatment efficiency in the low concentration (less than 300mg/L) nitrate nitrogen environment, which also indicates that the combination of the sulfur autotrophic denitrifying bacteria, the heterotrophic denitrifying bacteria and the denitrification filter material can effectively treat the nitrate nitrogen in the water, especially in the low concentration nitrate nitrogen environment.
However, as the concentration of nitrate nitrogen increased, the treatment efficiency of the experimental groups 1-2 decreased significantly beyond 400mg/L, probably because the mechanism and effect of the different sulfur autotrophic denitrifying bacteria and heterotrophic denitrifying bacteria were not completely the same, resulting in significantly different tolerance and treatment efficiency against high concentration of nitrate nitrogen. Even though Paracoccus versutus LYM is used as the sulfur autotrophic denitrifying bacteria, it affects the efficiency of treating high concentration nitrate nitrogen when used in combination with different heterotrophic denitrifying bacteria. As can be seen from experimental groups 3-4, Paracoccus versutus LYM, when used in combination with Pseudomonas stutzeri ATCC17588, had a much higher treatment effect on nitrate nitrogen at high concentrations (over 600mg/L) than when used in combination with Paracoccus denitrificans ACCC 10489.
Although the experimental group 4 showed better efficiency in treating nitrate nitrogen at a high concentration than the other 3 groups, the effect of treating nitrate nitrogen at a high concentration was not good as a whole. To optimize the position of the experimental group 4 for high concentration nitrate nitrogenAnd (5) treating effects. The applicant carries out optimization and adjustment aiming at the components of the denitrification filter material, and particularly, on the basis of the first embodiment, the metal oxide is replaced by different choices, and the influence of the metal oxide on the denitrification efficiency is examined. The other components and the composition are kept unchanged, the manganese oxide in the first embodiment is replaced by CuO, NiO and ZnO to obtain different denitrification filter materials, the influence of the different denitrification filter materials on the denitrification efficiency of Paracoccus versutus LYM in the combined use with Pseudomonas stutzeri ATCC17588 is examined, and the method is adopted in the experimental method. Artificially simulated high-concentration nitrate nitrogen wastewater and high-concentration nitrate Nitrogen (NO)3 --N) are respectively 500mg/L, 600mg/L, 800mg/L and 1000mg/L, and under the condition that the hydraulic retention time is fixed at 12h, the treatment effect of the nitrate nitrogen in each experimental group is as follows:
Figure BDA0003004684960000061
as can be seen from the above table, different metal oxides affect the removal efficiency of nitrate nitrogen at high concentration, which is probably due to the metal dependence of Paracoccus versutus LYM on Pseudomonas stutzeri ATCC17588, which is a phenomenon generally existing in microorganisms, and may have a phenomenon of "poisoning" for some heavy metals, resulting in the inhibition of the denitrification efficiency, for example, CuO and NiO inhibit the removal effect of nitrate nitrogen at high concentration. However, the use of ZnO can improve the denitrification efficiency to some extent.
The above description is only an example of the present application and is not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application. The above description is only an example of the present application and is not intended to limit the present application.

Claims (10)

1. A denitrification filter material for treating high-concentration nitrate nitrogen in water comprises a denitrification filler, sulfur autotrophic denitrifying bacteria and heterotrophic denitrifying bacteria, wherein the denitrification filler comprises sulfur, a slow-release carbon source, carbonate and metal oxides, and the sulfur autotrophic denitrifying bacteria and the heterotrophic denitrifying bacteria form a biological film on the surface of the denitrification filler; the sulfur autotrophic denitrifying bacteria and the heterotrophic denitrifying bacteria are respectively selected from Paracoccus versutus LYM and Pseudomonas stutzeri (Pseudomonas stutzeri) ATCC 17588.
2. The denitrification filter of claim 1, wherein the metal oxide is selected from manganese oxide and/or zinc oxide, preferably zinc oxide.
3. The denitrification filter material of claim 1 or 2, wherein in the denitrification filler, the mass percentage of the sulfur is 40-60%; the mass percentage of the slow-release carbon source is 10-30%; the mass percentage of the carbonate is 10-30%; the mass percentage of the metal oxide is 3% -10%; the sum of the mass percentages of the components is not more than 100%.
4. The denitrification filter material of claim 3, wherein in the denitrification filler, the sulfur accounts for 50% by mass; the mass percentage of the slow-release carbon source is 20%; the mass percentage of the carbonate is preferably 25%; the mass percentage of the metal oxide is 5%.
5. The denitrification filter material of claim 1, wherein the slow-release carbon source is corncob and the carbonate is calcium carbonate.
6. The denitrification filter material of claim 1, wherein the sulfur autotrophic denitrifying bacteria and the heterotrophic denitrifying bacteria are inoculated into the denitrification filler, and a conventional culture medium is continuously introduced to culture and acclimate the sulfur autotrophic denitrifying bacteria and the heterotrophic denitrifying bacteria until a stable biofilm grows on the surface of the denitrification filler.
7. Use of the denitrification filter material of any one of claims 1-6 in the treatment of nitrate nitrogen in water.
8. The method as claimed in claim 7, wherein the content of nitrate nitrogen in water is not less than 400 mg/L; preferably, the nitrate nitrogen content in the water is 400mg/L-1000mg/L, for example, 500mg/L, 600mg/L, 700mg/L, 800mg/L, 900 mg/L.
9. A method for treating high-concentration nitrate nitrogen in water, which comprises the step of treating the high-concentration nitrate nitrogen in water with the denitrification filter material as recited in any one of claims 1 to 6.
10. The method as claimed in claim 9, wherein the content of the high-concentration nitrate nitrogen is not less than 400 mg/L; preferably, the content of the high-concentration nitrate nitrogen is 400mg/L to 1000mg/L, for example, 500mg/L, 600mg/L, 700mg/L, 800mg/L, 900 mg/L.
CN202110358935.7A 2021-04-02 2021-04-02 Method for treating high-concentration nitrate nitrogen in water Withdrawn CN113060840A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116332343A (en) * 2023-05-22 2023-06-27 江苏省环境工程技术有限公司 Sulfur autotrophic denitrification sulfur-based magnetic filler and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116332343A (en) * 2023-05-22 2023-06-27 江苏省环境工程技术有限公司 Sulfur autotrophic denitrification sulfur-based magnetic filler and preparation method and application thereof
CN116332343B (en) * 2023-05-22 2023-08-18 江苏省环境工程技术有限公司 Sulfur autotrophic denitrification sulfur-based magnetic filler and preparation method and application thereof

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