CN114684924B - Denitrification treatment method for salt-containing wastewater - Google Patents

Denitrification treatment method for salt-containing wastewater Download PDF

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CN114684924B
CN114684924B CN202011611562.1A CN202011611562A CN114684924B CN 114684924 B CN114684924 B CN 114684924B CN 202011611562 A CN202011611562 A CN 202011611562A CN 114684924 B CN114684924 B CN 114684924B
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salt
ammonia nitrogen
coenzyme
culture
bacteria
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CN114684924A (en
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陈明翔
高会杰
孙丹凤
王刚
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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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
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/02—Temperature
    • 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
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • 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
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • 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
    • C02F2209/14—NH3-N
    • 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
    • C02F2209/16—Total nitrogen (tkN-N)
    • 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
    • C02F2209/22—O2
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

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  • 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)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)

Abstract

The invention discloses a denitrification treatment method for salt-containing wastewater. The method comprises the following steps: I. introducing the salt-containing wastewater according to 120-180% of the set water inlet load of the salt-containing wastewater, inoculating activated sludge into a wastewater treatment system according to the sludge concentration of 3000-5000mg/L, adding polyethyleneimine into the system, and then carrying out an aeration reaction; II. According to the mass ratio of the nitrosobacteria agent to the inoculated activated sludge of 1-10, adding the nitrosobacteria agent, and adopting an operation mode of changing water in batches and gradually reducing the water inflow of the salt-containing wastewater until a set water inflow load is reached; III, carrying out denitrification treatment on the salt-containing wastewater according to the set water inlet load. The processing method provided by the invention can realize the rapid formation of zoogloea, reduce the loss of nitrosobacteria and realize the stable operation of the system.

Description

Denitrification treatment method for salt-containing wastewater
Technical Field
The invention belongs to the technical field of environmental microorganisms, and particularly relates to a denitrification treatment method for salt-containing wastewater.
Background
With the shortage of water resources and the improvement of the sewage reuse rate, industries such as petroleum, chemical engineering, medicine, chemical fertilizer and the like can generate a large amount of waste water with salt content higher than 1%, and the salt-containing waste water is one of the difficult problems of sewage treatment in the field of environmental protection. At present, the salt-containing wastewater is treated by a physical method, a chemical method or a combination method thereof, such as evaporative crystallization, adsorption, membrane interception and the like, so that the high-salt wastewater can be effectively treated. However, although these methods can remove the salts in the wastewater well, the production and use costs of the equipment and materials are high, and in addition, the methods cannot effectively remove pollutants such as COD, ammonia nitrogen, total nitrogen and the like in the wastewater, and may cause secondary pollution. The traditional biological method has great advantages in treating low-salinity wastewater, but the microbial degradation capability is inhibited in high-salt, high-acid-base, high-temperature or low-temperature environments.
Nitrobacteria are key microorganisms responsible for denitrification, mainly autotrophic propagation is adopted, and the nitrobacteria are suitable for adherent growth, and an accelerant and a suitable carrier in the enrichment culture process are one of key factors for playing a role, so that a large amount of research work is carried out by a plurality of researchers from the aspects of accelerant formula and carrier preparation, and a certain effect is achieved. CN201410585640.3 discloses a nitrobacteria enrichment culture method, the used growth promoter contains hydroxylamine, CN201410585421.5 discloses an ammonia oxidizing bacteria growth promoter and a preparation method and application thereof,the growth promoter is inorganic hydroxylamine and Na 2 SO 3 The hydroxylamine not only can be used as a substrate to directly participate in the metabolic process of ammonia oxidizing bacteria to shorten the enzymatic reaction process, but also can be used as an activator of hydroxylamine oxidoreductase to accelerate cell growth and improve the growth rate of ammonia oxidizing bacteria. The method is mainly used for accelerating the enzymatic reaction and promoting the cell growth by improving the activity of the enzyme for converting hydroxylamine into nitrite.
CN201811255625.7 discloses an accelerant for improving the biological treatment effect of salt-containing wastewater and an application thereof, wherein the accelerant mainly comprises quaternary ammonium hydroxide and humus, and the method can improve the adaptability and the resistance of a treatment system to a high-salt environment and improve the treatment effect of COD, ammonia nitrogen and total nitrogen in the salt-containing wastewater when being used for biological treatment of the salt-containing wastewater through the synergistic effect of the quaternary ammonium hydroxide and the humus. CN201210130657.0 discloses a biological denitrification method for salt-containing sewage, which mainly adds a denitrification microbial inoculum into a sewage biochemical treatment system, can effectively treat the sewage with higher salt content, improves the adsorptivity and flocculation property of sludge, has wide application range for the water quality of the wastewater, has strong impact resistance on the salt-containing sewage, and obviously improves the treatment effect of the sewage while removing pollutants such as ammonia nitrogen, COD and the like. Both the above-mentioned agents and promoters suffer from run-off problems when used alone.
Especially, the microbial inoculum product is directly applied to the denitrification treatment process of salt-containing sewage, the growth and activity of cells can be influenced due to high salinity, meanwhile, the formation of zoogloea is not facilitated, the nitrification efficiency is reduced, sludge is finely crushed, thalli are lost, the treatment effect is not ideal, and the sewage treatment effect can be influenced due to long-period operation.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for denitrifying salt-containing wastewater. The processing method provided by the invention can realize the rapid formation of zoogloea, reduce the loss of nitrosobacteria and realize the stable operation of the system.
The invention provides a denitrification treatment method of salt-containing wastewater, which comprises the following steps:
I. introducing the salt-containing wastewater according to 120-180% of the set water inlet load of the salt-containing wastewater, inoculating activated sludge into a wastewater treatment system according to the sludge concentration of 3000-5000mg/L, adding polyethyleneimine into the system, and then carrying out an aeration reaction;
II. Adding the nitrosation microbial inoculum according to the mass ratio of the nitrosation microbial inoculum to the inoculated activated sludge of 1-10, and adopting an operation mode of changing water in batches and gradually reducing the water inflow of the saline wastewater until a set water inflow load is reached;
III, carrying out denitrification treatment on the salt-containing wastewater according to the set water inlet load.
In the technical scheme, the adopted wastewater treatment system has the aeration and stirring functions and can realize a Sequencing Batch Reactor (SBR) system with intermittent aeration and intermittent stirring.
In the technical scheme, the water quality of the salt-containing wastewater is as follows: COD concentration is 100-500mg/L, ammonia nitrogen concentration is 50-150mg/L, total nitrogen concentration is 50-200mg/L, and salt content is 10000-30000mg/L.
In the technical scheme, the activated sludge in the step I is obtained from excess sludge of a secondary sedimentation tank of a sewage treatment plant, and preferably excess sludge of a high-salt-content series secondary sedimentation tank.
In the technical scheme, the polyethyleneimine in the step I is added according to the volume concentration of the system of 1-5%. The polyethyleneimine is a water-soluble high-molecular polymer, and preferably, the molecular weight of the polyethyleneimine is 1000-16000. The polyethyleneimine can be added into a system in a water solution mode, and the mass concentration of the polyethyleneimine water solution is 20-50%.
In the technical scheme, the aeration reaction conditions in the step I are as follows: the dissolved oxygen is 2-5mg/L, pH with the value of 7-9, the temperature of 20-38 ℃ and the reaction time of 24-72h.
In the above technical scheme, the operation conditions of step II are as follows: the dissolved oxygen is 1-3mg/L, the pH value is 7-9, and the temperature is 20-38 ℃.
In the above technical solution, the step II of replacing the drainage in batches means that when the removal rate of the total nitrogen in each batch reaches 90% or more, the current batch is ended, the salt-containing wastewater in the current batch is discharged, and the salt-containing wastewater is replaced again to enter the next batch of cultivation.
In the technical scheme, in the step II, the water inflow of the salt-containing wastewater is gradually reduced by decreasing the water inflow of the salt-containing wastewater of the current batch by 2-20% compared with that of the salt-containing wastewater of the previous batch. In the step II, the number of times of gradually reducing the water inflow of the salt-containing wastewater is at least more than 2 times.
In the above technical scheme, the mass ratio of the nitrosobacteria agent in step II to the activated sludge is 1-10, preferably 1-5.
In the above technical scheme, the nitrosobacteria agent in step II comprises a nitrite bacteria microorganism and an adsorption carrier, wherein the adsorption carrier comprises calcium carbonate-embedded cross-linked chitosan and heterotrophic bacteria. In the nitrosobacteria agent, the mass content of the nitrite bacteria microorganism is 50-70%, and the mass content of the adsorption carrier is 30-50%. In the adsorption carrier, the heterotrophic bacteria account for 5-50%, preferably 10-30% of the mass of the adsorption carrier, and the calcium carbonate-embedded cross-linked chitosan accounts for 50-95%, preferably 70-90% of the mass of the adsorption carrier. In the calcium carbonate-embedded cross-linked chitosan, the mass ratio of chitosan to calcium carbonate is (1-5): 0.5-5.
In the technical scheme, the nitrite bacteria microorganism is a microorganism capable of converting ammonia nitrogen into nitrite.
In the above technical solution, the heterotrophic bacteria may be at least one selected from yeast, lactic acid bacteria, and sulfate reducing bacteria, and preferably, yeast. The yeast is at least one of candida, cryptococcus, hansenula, pichia, rhodotorula, torulopsis or trichosporon, and is preferably candida tropicalis. The lactobacillus is at least one selected from lactobacillus, bifidobacterium and lactococcus. The sulfate reducing bacteria is at least one selected from desulfomonas and desulfobacterium.
In the technical scheme, the preparation method of the nitrosobacteria agent comprises the following steps: (1) preparing an adsorption carrier; (2) culturing nitrite bacteria microorganisms; (3) Mixing the microorganisms and the adsorption carrier to prepare the nitrosobacteria agent.
In the above technical scheme, the preparation method of the adsorption carrier in step (1) comprises: and (3) adding the calcium carbonate-embedded cross-linked chitosan into a heterotrophic bacteria culture system utilizing an organic carbon source for adsorption growth, stopping culturing until the late logarithmic growth stage, taking out solids, and drying to obtain the calcium carbonate-embedded cross-linked chitosan. The method is characterized in that the calcium carbonate-embedded cross-linked chitosan is added to a heterotrophic bacteria culture system utilizing an organic carbon source for adsorption growth, namely the calcium carbonate-embedded cross-linked chitosan is added at the initial stage of the heterotrophic bacteria culture process for the adsorption growth of the heterotrophic bacteria while culturing. The addition of calcium carbonate-embedded cross-linked chitosan accounts for 20-30% of the total reaction volume. Wherein the organic carbon source required by the heterotrophic bacteria culture is determined according to the specific selected strains, and carbon-containing organic matters cultured by the heterotrophic bacteria conventionally are selected; the organic carbon source is preferably at least one of glucose, hexose, xylose, sucrose, and starch. And the organic carbon source is added according to the mass concentration of 1-5g/L in the system after the organic carbon source is added. The culture conditions of the heterotrophic bacteria are as follows: at a temperature of 20-38 deg.C, preferably 20-30 deg.C, and a pH of 6.0-8.5, preferably 6.0-7.0; standing fermentation (preferably, stirring every 30-60 min) or shaking culture (preferably, shaking culture rotation speed is 200-600 r/min). In the preparation process of the adsorption carrier, the culture is carried out until the late logarithmic growth stage, and the culture is generally carried out for 24-80h. The drying temperature is 25-50 ℃, and the drying time is 1-5h.
In the above technical scheme, in the preparation process of the adsorption carrier, the cross-linked chitosan can be obtained by a conventional preparation method in the art. The crosslinking method mainly adopts direct crosslinking and chemical modification in crosslinking. The crosslinking agent commonly used in the direct crosslinking method is at least one of epoxy chloropropane, glutaraldehyde, formaldehyde, crown ether or genipin, and preferably the crosslinking chitosan carrier prepared by directly crosslinking chitosan by genipin. The cross-linking is the cross-linking reaction between the chitosan and the cross-linking agent molecules, so that the chitosan molecules are changed into a net structure from a straight chain, the physical properties such as the specific surface area, the pore structure and the like of the chitosan can be improved through the cross-linking, and the stability of the chitosan is effectively improved.
In the technical scheme, the calcium carbonate-embedded cross-linked chitosan can be prepared by adopting a conventional method, namely, nano calcium carbonate is introduced when a cross-linking agent reacts with chitosan to prepare the cross-linked chitosan, so that the calcium carbonate-embedded cross-linked chitosan is prepared. The crosslinking method mainly adopts direct crosslinking and chemical modification in crosslinking. The cross-linking agent commonly used in the direct cross-linking method is epichlorohydrin, glutaraldehyde, formaldehyde, crown ether and genipin, and the cross-linked chitosan prepared by directly cross-linking chitosan by genipin is preferred.
In the above technical solution, the heterotrophic bacteria are cultured by using an organic carbon source, and preferably are at least one of yeast, lactic acid bacteria and sulfate reducing bacteria, and more preferably are yeast. The yeast is at least one of candida, cryptococcus, hansenula, pichia, rhodotorula, torulopsis or trichosporon, and is preferably candida tropicalis. The lactobacillus is at least one selected from lactobacillus, bifidobacterium and lactococcus. The sulfate reducing bacteria is at least one selected from desulfomonas and desulfobacterium.
In the above technical solution, preferably, the method for culturing the nitrite bacteria microorganism in step (2) comprises: firstly, inoculating activated sludge rich in nitrobacteria into a reactor with stirring and aeration functions, carrying out enrichment culture on nitrite bacteria by adopting an operation mode of batch feeding and gradually increasing the ammonia nitrogen concentration in the feeding, wherein the conditions for finishing the culture are as follows: the nitrosation rate reaches more than 90 percent, the thallus culture process is finished, and the thallus is harvested; the conditions for terminating the culture are preferably: continuously 3-5 batches of the nitrosation rate reaches more than 90 percent, ending the thallus culture process, and harvesting the thallus;
in the process of culturing the nitrite bacteria, hydroxylamine substances and coenzyme are added at the same time of each batch of fed materials, when the ammonia nitrogen removal rate reaches more than 95 percent, the current batch is ended, and the fed materials enter the next batch for culturing; when the nitrosation rate of the current batch reaches more than 30%, preferably 50% -60%, NO and/or NO is introduced into the culture system from the next batch 2 A gas.
In the technical scheme, in the culture method of the nitrite bacteria microorganism, the activated sludge rich in nitrobacteria is inoculated according to the sludge concentration of 2000-5000 mg/L. The activated sludge can be taken from any sewage treatment plant containing ammonia nitrogen pollutants.
In the above technical solution, in the method for culturing the nitrite bacteria microorganism, the reactor having stirring and aeration functions is used, wherein the nitrite bacteria culture process is performed under stirring conditions, and aeration is used for maintaining dissolved oxygen in the culture system.
In the above technical solution, in the method for culturing a nitrite bacteria microorganism, the coenzyme includes at least one selected from coenzyme i and coenzyme ii and coenzyme Q10, where coenzyme i is NADH (nicotinamide adenine dinucleotide) and coenzyme ii is NADPH (nicotinamide adenine dinucleotide phosphate). Wherein the mass ratio of at least one selected from coenzyme I and coenzyme II to coenzyme Q10 is 8:1-1:8, preferably 5:1-1:5. the hydroxylamine substance is at least one of hydroxylamine, hydroxylamine hydrochloride, hydroxylamine sulfate or hydroxylamine phosphate, and is preferably hydroxylamine phosphate. The hydroxylamine substance is added according to the concentration of 1-5mg/L in the culture system after being added, and the coenzyme is added according to the concentration of 0.001-0.01mg/L in the culture system after being added.
In the above technical scheme, in the method for culturing the nitrite bacteria microorganism, the feeding is to supplement the culture solution, and the batch feeding is to supplement the culture solution once per batch. The culture solution used in the invention is well known to those skilled in the art, wherein the substrate is ammonia nitrogen, and can be ammonium sulfate, urea and other substances containing ammonia nitrogen; the culture medium also contains metal salt. The metal salt can be calcium salt, ferrous salt, copper salt and the like, and the calcium salt can be CaSO 4 Or CaCl 2 (ii) a The ferrous salt is FeSO 4 Or FeCl 2 Preferably FeSO 4 (ii) a The copper salt being CuSO 4 Or CuCl 2 . The metal salt may be Ca 2+ 、Fe 2+ And Cu 2+ The molar ratio of (8-12) to (2-6) to (1-4) is prepared, and the use concentration is 0.01-1.0mg/L.
In the above technical solution, in the method for culturing a nitrite bacteria microorganism, the operation manner for gradually increasing the ammonia nitrogen concentration in the fed material is as follows: the initial ammonia nitrogen concentration is 20-100mg/L, the amplitude for increasing the ammonia nitrogen concentration each time is 10-50mg/L, and the conditions for increasing the ammonia nitrogen concentration are as follows: for the feed supplement with the same ammonia nitrogen concentration, the ammonia nitrogen removal rate reaches more than 95% by 3-5 continuous batches, and the difference between the time used by each batch and the average time used by the batches is within 10%, preferably within 5%, so that the ammonia nitrogen concentration of the feed liquid supplemented in the next batch can be improved.
In the above technical scheme, in the method for culturing the nitrite bacteria microorganism, NO and/or NO is 2 The adding amount of the gas accounts for 0.001-0.01% of the total volume of the introduced gas. In the process of culturing the nitrite bacteria, the introduced gas is usually air and is used for maintaining the dissolved oxygen amount in the system.
In the above technical scheme, in the method for culturing the nitrite bacteria microorganism, the enrichment culture conditions of the nitrite bacteria are as follows: the temperature is 18-40 deg.C, dissolved oxygen is 0.1-3.0mg/L, and pH is 7.0-9.0, preferably as follows: the temperature is 25-35 ℃, the dissolved oxygen is 0.5-2.0mg/L, and the pH value is 7.5-8.5.
In the technical scheme, in the step (3), the product obtained by mixing the microorganism and the carrier is dehydrated to the water content (the water content refers to the percentage of the weight of the water contained in the concentrated solution obtained by mixing the microorganism and the carrier in the total weight of the concentrated solution) of 30-50 wt%, and the product is subjected to vacuum drying under the conditions that the pressure is 1-2kPa and the temperature is 35-50 ℃, so that the prepared solid microbial inoculum is convenient to preserve and transport. The dewatering may be by at least one of gravity settling, centrifugation or filtration.
In the above technical scheme, the denitrification treatment conditions for the salt-containing wastewater according to the set water inlet load in the step III are as follows: the dissolved oxygen is 1-3mg/L, the pH value is 7-9, and the temperature is 20-38 ℃.
In the above technical scheme, step III may adopt intermittent water feeding or continuous water feeding.
In the technical scheme, in the step III, when the ammonia nitrogen concentration is 6-12mg/L, the nitrosation microbial inoculum is supplemented according to the mass ratio of the nitrosation microbial inoculum to the saline wastewater per hour water inflow of 1-5.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the method provided by the invention, firstly, the introduced activated sludge and high-salt-content wastewater are subjected to an aeration reaction in the presence of polyethyleneimine, and due to the high-salt impact and the toxicity effect of the polyethyleneimine, cells of part of microorganisms can be disintegrated to release an outer-protection polymer, so that conditions are created for the formation of zoogloea; and the addition of the nitrosation microbial inoculum protects cells and improves the salt resistance, and accelerates the rapid formation of zoogloea, so that the added nitrosation microbial inoculum can adhere and grow by taking disintegrated sludge fragments as a framework, the loss is reduced, and the treatment effect is further improved.
(2) In the nitrosobacteria agent provided by the invention, hydroxylamine substances and coenzyme are creatively added in the culture process of nitrite bacteria, and NO and/or NO are controlled 2 The addition mode of the gas enables cell division and protein synthesis to be synchronously carried out by regulating and controlling the cell division and protein synthesis rate, thereby realizing the rapid propagation of nitrite bacteria and the rapid preparation of the microbial inoculum. And is beneficial to exerting the effects of strong denitrification capability, stability and difficult loss in the subsequent application process.
(3) In the nitrosobacteria agent provided by the invention, cross-linked chitosan with positive charges and heterotrophic bacteria utilizing an organic carbon source are used as adsorption carriers, and the synergistic effect of the bacteria and the carriers can not only reduce the adverse effect of the cross-linked chitosan on the nitrosobacteria, but also ensure that the nitrosobacteria are easily adsorbed on the carriers to realize rapid growth, so that the prepared microbial agent has high biological concentration and is not easy to lose in the application process.
Detailed Description
The method and effects of the present invention will be described in further detail by examples. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The test materials used in the following examples were purchased from biochemical reagent stores unless otherwise specified.
In the embodiment of the invention, the COD concentration is determined by GB11914-89 bichromate method which is used for determining water quality and chemical oxygen demand; the ammonia nitrogen concentration is measured by GB7478-87 water quality-ammonium measurement-distillation and titration method; the nitrate nitrogen concentration is measured by GB 7480-1987 water quality-nitrate nitrogen determination-phenol disulfonic acid spectrophotometry; the concentration of nitrite nitrogen is measured by GB 7493-1987 determination of water quality-nitrite nitrogen-spectrophotometry; the total nitrogen concentration is measured by GB11894-89 water quality-total nitrogen measurement-alkaline potassium persulfate digestion ultraviolet spectrophotometry.
In the embodiment of the present invention, the total nitrogen removal rate refers to the percentage of the concentration difference between the total nitrogen concentration in the raw material water and the total nitrogen concentration in the effluent water in the total nitrogen concentration in the raw material water, and the total nitrogen removal rate (%) = (total nitrogen concentration in the raw material water-total nitrogen concentration in the effluent water)/total nitrogen concentration in the raw material water × 100%. The nitrosation rate means the percentage of the concentration of nitrite nitrogen oxidized into ammonia nitrogen in the total nitrified product concentration, and the nitrosation rate (%) = nitrite nitrogen concentration in the discharge water/(nitrite nitrogen concentration in the discharge water + nitrate nitrogen concentration in the discharge water) × 100%.
Example 1 preparation of Nitrospirants
(1) Preparation of the adsorption carrier: the preparation process of the cross-linked chitosan comprises the following steps: firstly, 2% (W/V) chitosan is dissolved in 1% (V/V) acetic acid solution for total 500mL, caCO is added 3 10g of nano particles, adding 5 times of edible oil, adding 10mL of span-80, and stirring vigorously. Adding genipin to a final concentration of 20mM in the water phase, continuously stirring for 24 hours, centrifuging to separate the precipitate, and washing with acetone, hot water and cold water for several times to remove the residual oil phase and impurities on the surface of the microsphere. And finally dehydrating for 2 times by using acetone, and airing the obtained product at room temperature to obtain yellowish powder, namely the calcium carbonate-embedded chitosan microcarrier. The chitosan carrier is added into a culture system of candida tropicalis utilizing xylose for adsorption growth, and the mass concentration of the added xylose is 2g/L. The culture conditions were: fermenting at 25 deg.C and pH of 6.0-7.0 in a shaker at 200r/min for 48 hr, taking out solid, and drying at 40 deg.CThe time is 3h, and the adsorption carrier is prepared. Through detection, the heterotrophic bacteria account for 30% of the carrier mass.
(2) Culturing the nitrite bacteria microorganisms: activated sludge rich in nitrifying bacteria was inoculated in a 5L organic glass reactor with stirring and aeration functions at a sludge concentration (MLSS) of 2000 mg/L. Enrichment culture of nitrite bacteria is carried out by adopting a batch feeding mode under the conditions that the temperature is 28 ℃, the dissolved oxygen is 2.0mg/L and the pH value is 8.0. The used culture solution contains ammonia nitrogen and metal salt, wherein the ammonia nitrogen is ammonium sulfate, and the metal salt is CaCl 2 、FeSO 4 And CuSO 4 Wherein Ca is 2+ 、Fe 2+ And Cu 2+ The preparation is carried out according to a molar ratio of 8; the initial ammonia nitrogen concentration of the culture solution is 30mg/L. When the ammonia nitrogen removal rate reaches more than 95 percent, ending the current batch, feeding the culture medium into the next batch, and adding hydroxylamine phosphate according to the concentration of 1mg/L and adding coenzyme I NADH and coenzyme Q10 according to the concentration of 0.001mg/L (the mass ratio is 1:1) while feeding each batch. The time for continuous 3 batches in the culture process to ensure that the ammonia nitrogen removal rate reaches more than 95 percent is basically the same, and the ammonia nitrogen concentration of the next batch is improved by 30mg/L. Culturing until the nitrosation rate of the 10 th batch reaches 56.9%, introducing NO gas accounting for 0.01% of the total volume of the introduced gas from the 11 th batch, continuing culturing until the 20 th batch, wherein the substrate ammonia nitrogen concentration is 180mg/L, the nitrosation rate reaches 95.2%, continuing culturing for three batches, wherein the nitrosation rates are all higher than 90%, ending the thallus culture process to harvest thallus, and analyzing that MLSS is 2800mg/L.
(3) Preparing a nitrosation microbial inoculum: adding the prepared carrier into the thallus according to the mixture ratio of 60% of the mass content of the nitrite bacteria microorganism and 40% of the mass content of the adsorption carrier, uniformly mixing, performing centrifugal dehydration until the water content is 40%, and performing vacuum drying under the conditions that the pressure is 1.5kPa and the temperature is 38 ℃ to prepare the solid microbial agent A.
EXAMPLE 2 preparation of Nitrospirants
The preparation method of the nitrosobacteria agent is the same as that in the example 1, except that in the preparation process of the nitrosobacteria agent, the prepared carrier is added into the bacteria body according to the proportion that the mass content of the nitrosobacteria microorganism is 70 percent and the mass content of the adsorption carrier is 30 percent, the mixture is uniformly mixed, the centrifugal dehydration is adopted until the water content is 35 percent, and the vacuum drying is carried out under the conditions that the pressure is 2kPa and the temperature is 45 ℃ to prepare the solid microbial agent B.
EXAMPLE 3 preparation of Nitrospirants
(1) Preparation of the adsorption carrier: the specific process of preparing cross-linked chitosan was the same as in example 1, except that the culture system of Candida tropicalis using xylose was grown by adsorption, and the mass concentration after addition of xylose was 3g/L. The culture conditions were: the temperature was 30 ℃ and the pH was 6.8. Fermenting and culturing on a shaking table at 200r/min for 48h, taking out the solid, and drying at 42 deg.C for 2h to obtain the adsorption carrier. Through detection, the heterotrophic bacteria account for 27% of the carrier mass.
(2) Culturing nitrite bacteria microorganisms: activated sludge rich in nitrifying bacteria was inoculated in a 5L organic glass reactor with stirring and aeration functions at a sludge concentration (MLSS) of 2000 mg/L. Enrichment culture of nitrite bacteria is carried out by adopting a batch feeding mode under the conditions that the temperature is 28 ℃, the dissolved oxygen is 2.0mg/L and the pH value is 8.0. The culture solution contains ammonia nitrogen and metal salt, wherein the ammonia nitrogen is ammonium sulfate, and the metal salt is CaCl 2 、FeSO 4 And CuSO 4 Wherein Ca is 2+ 、Fe 2+ And Cu 2+ The preparation is carried out according to a molar ratio of 8; the initial ammonia nitrogen concentration of the culture solution is 30mg/L. When the ammonia nitrogen removal rate reaches more than 95 percent, ending the current batch, feeding the culture in the next batch, and adding hydroxylamine phosphate according to the concentration of 1mg/L and adding coenzyme I NADH and coenzyme Q10 according to the concentration of 0.005mg/L (the mass ratio is 3:1) while feeding each batch. The time for continuous 3 batches in the culture process to ensure that the ammonia nitrogen removal rate reaches more than 95 percent is basically the same, and the ammonia nitrogen concentration of the next batch is improved by 30mg/L. Culturing until the nitrosation rate of 10 th batch reaches 55.6%, introducing NO gas in the 11 th batch according to 0.01% of the total volume of the introduced gas, continuously culturing to 20 th batch, wherein the substrate ammonia nitrogen concentration is 180mg/L, the nitrosation rate reaches 93.8%, continuously culturing for three batches, wherein the nitrosation rates are all higher than 90%, and endingThe thalli is harvested in the process of thalli culture, and the analyzed MLSS is 2700mg/L.
(3) The preparation method and process of the nitrosobacteria agent are the same as those of the example 1, and the solid bacteria agent C is prepared.
Example 4 preparation of Nitrospirants
(1) The preparation of the adsorption carrier was the same as in example 1 except that: the organic carbon source adopts sucrose with equal mass to replace xylose, and the heterotrophic bacteria adopt the desulfomonas to replace candida tropicalis.
(2) Culturing nitrite bacteria microorganisms: activated sludge rich in nitrifying bacteria was inoculated in a 5L organic glass reactor with stirring and aeration functions at a sludge concentration (MLSS) of 3000 mg/L. The enrichment culture of the nitrite bacteria is carried out by adopting a batch feeding mode under the conditions that the temperature is 30 ℃, the dissolved oxygen is 1.0mg/L and the pH value is 7.8. The culture solution contains ammonia nitrogen and metal salt, wherein the ammonia nitrogen is ammonium sulfate, and the metal salt is CaCl 2 、FeSO 4 And CuSO 4 Wherein Ca is 2+ 、Fe 2+ And Cu 2+ The preparation is carried out according to a molar ratio of 10; the initial ammonia nitrogen concentration of the culture solution is 50mg/L. When the ammonia nitrogen removal rate reaches more than 95 percent, ending the current batch, feeding the culture in the next batch, and adding hydroxylamine phosphate according to the concentration of 2.5mg/L and adding coenzyme I NADH and coenzyme Q10 according to the concentration of 0.01mg/L (the mass ratio is 5:1) while feeding each batch. The time for continuous 3 batches in the culture process to ensure that the ammonia nitrogen removal rate reaches more than 95 percent is basically the same, and the ammonia nitrogen concentration of the next batch is improved by 30mg/L. Culturing until the nitrosation rate of the 10 th batch reaches 50%, introducing NO gas accounting for 0.001% of the total volume of the introduced gas from the 11 th batch, continuing culturing to the 20 th batch, wherein the substrate ammonia nitrogen concentration is 170mg/L, the nitrosation rate reaches 92.1%, continuing culturing three batches, wherein the nitrosation rates are all higher than 90%, ending the thallus culture process to harvest thallus, and analyzing that MLSS is 2720mg/L.
(3) The preparation method and process of the nitrosobacteria agent are the same as those of the example 1, and the solid bacteria agent D is prepared.
EXAMPLE 5 preparation of Nitrospirants
(1) The calcium carbonate-embedded chitosan microcarriers were prepared as in example 1. The chitosan carrier is added into a culture system of candida tropicalis utilizing xylose for adsorption growth, and the mass concentration of the added xylose is 2g/L. The culture conditions were: standing at 25 deg.C and pH of 6.0-7.0, stirring every 60min, fermenting for 48 hr, taking out solid, and drying at 40 deg.C for 3 hr to obtain adsorption carrier. Through detection, the heterotrophic bacteria account for 30% of the carrier mass.
(2) Culturing nitrite bacteria microorganisms: activated sludge rich in nitrifying bacteria was inoculated in a 5L organic glass reactor with stirring and aeration functions at a sludge concentration (MLSS) of 4000 mg/L. The enrichment culture of the nitrite bacteria is carried out by adopting a batch feeding mode under the conditions that the temperature is 25 ℃, the dissolved oxygen is 3.0mg/L and the pH value is 7.7. The culture solution contains ammonia nitrogen and metal salt, wherein the ammonia nitrogen is ammonium sulfate, and the metal salt is CaCl 2 、FeSO 4 And CuSO 4 Wherein Ca is 2+ 、Fe 2+ And Cu 2+ The preparation is carried out according to a molar ratio of 8; the initial ammonia nitrogen concentration of the culture solution is 50mg/L. When the ammonia nitrogen removal rate reaches more than 95 percent, ending the current batch, feeding the culture in the next batch, and adding hydroxylamine phosphate according to the concentration of 5mg/L and adding coenzyme I NADH and coenzyme Q10 according to the concentration of 0.005mg/L (the mass ratio is 1:5) while feeding each batch. The time for continuous 3 batches in the culture process to ensure that the ammonia nitrogen removal rate reaches more than 95 percent is basically the same, and the ammonia nitrogen concentration of the next batch is improved by 30mg/L. Culturing until the nitrosation rate of the 10 th batch reaches 50%, introducing NO gas accounting for 0.005% of the total volume of the introduced gas from the 11 th batch, continuing culturing to the 20 th batch, wherein the substrate ammonia nitrogen concentration is 190mg/L, the nitrosation rate reaches 90.0%, continuing culturing three batches, wherein the nitrosation rates are all higher than 90%, ending the thallus culture process to harvest thallus, and analyzing that MLSS is 2740mg/L.
(3) The preparation method and process of the nitrosobacteria agent are the same as those of the example 1, and the solid bacteria agent E is prepared.
EXAMPLE 6 preparation of Nitrospirants
The same as example 1, except that: step (3) is to mix the calcium carbonate-embedded chitosan microcarrier and the nitrite bacteria microorganism according to the mass ratio of 6:4, uniformly mixing, performing centrifugal dehydration until the water content is 40%, and performing vacuum drying under the conditions that the pressure is 1.5kPa and the temperature is 38 ℃ to prepare the solid microbial inoculum F.
Example 7 preparation of Nitrosporagen
The difference from example 1 is that: in the process of culturing the nitrite bacteria microorganism, hydroxylamine phosphate is not added while feeding materials in each batch, NO gas is introduced according to 0.01 percent of the total volume of the introduced gas when the nitrosation rate reaches 52 percent after the 14 th batch is cultured, the culture is continued to the 28 th batch, the substrate ammonia nitrogen concentration is 180mg/L, the nitrosation rate reaches 90.3 percent, the nitrosation rates of the three batches are continuously cultured and are all higher than 90 percent, and the thallus culture process is ended to prepare the solid microbial inoculum G.
EXAMPLE 8 preparation of Nitrospirants
The difference from example 1 is that: in the process of culturing the nitrite bacteria microorganism, after the nitrosation rate of the 10 th batch reaches 56.9%, NO NO gas is introduced into the system, the nitrite bacteria is continuously cultured until the substrate ammonia nitrogen concentration of the 20 th batch is 150mg/L, the nitrosation rate is only 70%, the nitrosation rate of the three batches is still only 72%, the process of culturing the thallus is ended, and the thallus is harvested to prepare the solid microbial agent H.
Example 9 Denitrification treatment method of salt-containing wastewater
The water quality of the salt-containing wastewater of a certain sewage treatment plant is as follows: COD concentration is 280mg/L, ammonia nitrogen concentration is 120mg/L, total nitrogen concentration is 150mg/L, and salt content is 10000mg/L.
The total nitrogen volume load of the inlet water of the salt-containing wastewater is designed to be 0.15 kgTN/(m) 3 D), then introducing salt-containing wastewater according to 150% of the set water inlet volume load, inoculating the residual sludge of the secondary sedimentation tank of the salt-containing sewage treatment unit into the wastewater treatment system according to the sludge concentration of 4000mg/L, adding a polyethyleneimine (molecular weight of 4300) water solution with the mass concentration of 25% into the system according to the system volume concentration of 2.5%, and carrying out an aeration reaction under the conditions that the dissolved oxygen is 5mg/L, pH with the value of 7.5-7.8 and the temperature is 30 ℃. After the aeration reaction for 36 hours, the solution is dissolvedAdjusting the oxygen decomposition to 2mg/L, then adding a nitrosobacteria A according to the mass ratio of the nitrosobacteria to the inoculated activated sludge (5). The water inflow is reduced to the set water inflow load after 1 month of operation, and the salt-containing wastewater is treated by adopting a continuous water inflow mode. In the continuous water inlet treatment process of the salt-containing wastewater, when the ammonia nitrogen concentration is below 12mg/L, adding a nitrosobacteria A according to the mass ratio of the nitrosobacteria to the salt-containing wastewater per hour water inlet quantity of 1. The device stably operates for one year, the operation is stable, and the average total nitrogen concentration of the treated effluent is 18.1mg/L.
Example 10 Denitrification treatment method of salt-containing wastewater
The quality of the salt-containing wastewater of a certain sewage treatment plant is as follows: COD concentration is 280mg/L, ammonia nitrogen concentration is 120mg/L, total nitrogen concentration is 150mg/L, and salt content is 10000mg/L.
The total nitrogen volume load of the inlet water of the salt-containing wastewater is designed to be 0.15 kgTN/(m) 3 D), then introducing salt-containing wastewater according to 150% of the set water inlet load, inoculating the residual sludge of the secondary sedimentation tank of the salt-containing sewage treatment unit into the wastewater treatment system according to the sludge concentration of 4000mg/L, adding a polyethyleneimine (molecular weight of 4300) water solution with the mass concentration of 25% into the system according to the system volume concentration of 2.5%, and carrying out aeration reaction under the conditions that the dissolved oxygen is 5mg/L, pH is 7.8-8.0 and the temperature is 32 ℃. After the aeration reaction is carried out for 36 hours, the dissolved oxygen is adjusted to 2mg/L, then, according to the mass ratio of the nitrosobacteria to the inoculated activated sludge (1. The water inflow is reduced to the set water inflow load after 1 month of operation, and the water is treated in a continuous water inflow modeSalt waste water. In the continuous water inlet treatment process of the salt-containing wastewater, when the ammonia nitrogen concentration is below 12mg/L, adding a nitrosobacteria B according to the mass ratio of the nitrosobacteria to the salt-containing wastewater per hour water inlet amount of 1. The device stably operates for one year, the operation is stable, and the average total nitrogen concentration of the treated effluent is 18.8mg/L.
Example 11A Denitrification treatment method of salt-containing wastewater
The quality of the salt-containing wastewater of a certain sewage treatment plant is as follows: COD concentration is 280mg/L, ammonia nitrogen concentration is 120mg/L, total nitrogen concentration is 150mg/L, and salt content is 10000mg/L.
The total nitrogen volume load of the inlet water of the salt-containing wastewater is designed to be 0.15 kgTN/(m) 3 D), then introducing salt-containing wastewater according to 150% of the set water inlet load, inoculating the residual sludge of the secondary sedimentation tank of the salt-containing sewage treatment unit into the wastewater treatment system according to the sludge concentration of 4000mg/L, adding a polyethyleneimine (molecular weight of 4300) water solution with the mass concentration of 50% into the system according to the system volume concentration of 1.0%, and carrying out an aeration reaction under the conditions that the dissolved oxygen is 5mg/L, pH is 7.5-7.8 and the temperature is 30 ℃. After the aeration reaction is carried out for 36 hours, the dissolved oxygen is adjusted to be 2mg/L, then, according to the mass ratio of the nitrosobacteria to the inoculated activated sludge as (5). The water inflow is reduced to the set water inflow load after 1 month of operation, and the salt-containing wastewater is treated by adopting a continuous water inflow mode. In the continuous water inlet treatment process of the salt-containing wastewater, when the ammonia nitrogen concentration is below 12mg/L, adding a nitrosobacteria C according to the mass ratio of the nitrosobacteria to the salt-containing wastewater per hour water inlet quantity of 1. The device stably operates for one year, the operation is stable, and the average total nitrogen concentration of the treated effluent is 18.5mg/L.
Example 12 Denitrification treatment method of salt-containing wastewater
The quality of the salt-containing wastewater of a certain sewage treatment plant is as follows: COD concentration is 280mg/L, ammonia nitrogen concentration is 120mg/L, total nitrogen concentration is 150mg/L, and salt content is 10000mg/L.
The total nitrogen volume load of the inlet water of the salt-containing wastewater is designed to be 0.15 kgTN/(m) 3 D), then introducing salt-containing wastewater according to 150% of the set water inlet load, inoculating the residual sludge of the secondary sedimentation tank of the salt-containing sewage treatment unit into the wastewater treatment system according to the sludge concentration of 4000mg/L, adding a polyethyleneimine (molecular weight of 4300) water solution with the mass concentration of 50% into the system according to the system volume concentration of 5.0%, and carrying out an aeration reaction under the conditions that the dissolved oxygen is 5mg/L, pH is 7.5-7.8 and the temperature is 30 ℃. After the aeration reaction is carried out for 36 hours, the dissolved oxygen is adjusted to 2mg/L, then a nitrosation agent D is added according to the mass ratio of the nitrosation agent to the inoculated activated sludge (5. The water inflow is reduced to the set water inflow load after 1 month of operation, and the salt-containing wastewater is treated by adopting a continuous water inflow mode. In the continuous water inlet treatment process of the salt-containing wastewater, when the ammonia nitrogen concentration is below 12mg/L, adding a nitrosobacteria D according to the mass ratio of the nitrosobacteria to the salt-containing wastewater per hour water inlet quantity of 1. The device stably operates for one year, the operation is stable, and the average total nitrogen concentration of the treated effluent is 19.1mg/L.
Example 13A method for Denitrification of salt-containing wastewater
The quality of the salt-containing wastewater of a certain sewage treatment plant is as follows: the COD concentration is 300mg/L, the ammonia nitrogen concentration is 80mg/L, the total nitrogen concentration is 110mg/L, and the salt content is 20000mg/L.
The total nitrogen volume load of the inlet water of the salt-containing wastewater is designed to be 0.11 kgTN/(m) 3 D), then introducing salt-containing wastewater according to 150% of the set water inlet load, inoculating the residual sludge of the secondary sedimentation tank of the salt-containing sewage treatment unit into the wastewater treatment system according to the sludge concentration of 4000mg/L, adding a polyethyleneimine (molecular weight of 4300) water solution with the mass concentration of 25% into the system according to the system volume concentration of 2.5%, and controlling the temperature to be 30 ℃ under the condition that the dissolved oxygen is 5mg/L, pH is 7.8-8.0The aeration reaction is carried out under the conditions of (1). After the aeration reaction is carried out for 36 hours, the dissolved oxygen is adjusted to 2mg/L, then a nitrosation agent E is added according to the mass ratio of the nitrosation agent to the inoculated activated sludge (5. The water inflow is reduced to the set water inflow load after 1 month of operation, and the salt-containing wastewater is treated by adopting a continuous water inflow mode. In the continuous water inlet treatment process of the salt-containing wastewater, when the ammonia nitrogen concentration is below 12mg/L, adding a nitrosobacteria E according to the mass ratio of the nitrosobacteria to the salt-containing wastewater per hour water inlet of 1. The device stably operates for one year, the operation is stable, and the average total nitrogen concentration of the treated effluent is 18.3mg/L.
Example 14 Denitrification treatment method of salt-containing wastewater
The same as example 9, except that the microbial inoculum F was added to the system. The water inflow is reduced to the set water inflow load after the operation for 2 months, and the salt-containing wastewater is treated by adopting a continuous water inflow mode. The device is operated for one year, fluctuation often occurs, and the average total nitrogen concentration of the treated effluent is 29.1mg/L.
Example 15 Denitrification treatment method of salt-containing wastewater
The same as example 9, except that the microbial inoculum G was added to the system. The water inflow is reduced to the set water inflow load after the operation for 2 months, and the salt-containing wastewater is treated by adopting a continuous water inflow mode. The device is operated for one year, fluctuation often occurs, and the average total nitrogen concentration of the treated effluent is 27.9mg/L.
Example 16A method for Denitrification of salt-containing wastewater
The same as example 9, except that bacterial agent H was added to the system. The water inflow is reduced to the set water inflow load after the operation for 2 months, and the salt-containing wastewater is treated by adopting a continuous water inflow mode. The device is operated for one year, fluctuation often occurs, and the average total nitrogen concentration of the treated effluent is 26.6mg/L.
Comparative example 1A method for Denitrification of salt-containing wastewater
The quality of the treated salt-containing wastewater was the same as that of example 9.
The total nitrogen volume load of the inlet water of the salt-containing wastewater is designed to be 0.15 kgTN/(m) 3 D), then introducing the salt-containing wastewater according to 150% of the set water inlet load, inoculating the residual sludge of the secondary sedimentation tank of the salt-containing serial sewage treatment unit into the wastewater treatment system according to the sludge concentration of 4000mg/L, and carrying out aeration reaction under the conditions that the dissolved oxygen is 5mg/L, pH is 7.5-7.8 and the temperature is 30 ℃. After the aeration reaction is carried out for 36 hours, the dissolved oxygen is adjusted to be 2mg/L, then a nitrosation agent A is added according to the mass ratio of the nitrosation agent to the inoculated activated sludge (5). The water inflow is reduced to the set water inflow load after the operation for 3 months, and the salt-containing wastewater is treated by adopting a continuous water inflow mode. In the continuous water inlet treatment process of the salt-containing wastewater, when the ammonia nitrogen concentration is below 12mg/L, adding a nitrosobacteria A according to the mass ratio of the nitrosobacteria to the salt-containing wastewater per hour water inlet quantity of 1. The device is operated for one year, and the average total nitrogen concentration of the effluent after treatment is 32.3mg/L.
Comparative example 2 Denitrification treatment method of salt-containing wastewater
The same as in example 9. The difference lies in that: after the aeration reaction is carried out for 36 hours, the dissolved oxygen is adjusted to be 2mg/L, and the nitroso agent A is not added according to the mass ratio of the nitroso agent to the inoculated activated sludge (5. The water inflow is reduced to the set water inflow load after 4 months of operation, and the salt-containing wastewater is treated by adopting a continuous water inflow mode. The device runs for one year, the average ammonia nitrogen concentration of the treated effluent is 18mg/L, and the total nitrogen concentration is 37.6mg/L.

Claims (31)

1. A denitrification treatment method for salt-containing wastewater comprises the following steps:
I. introducing the salt-containing wastewater according to 120-180% of the set water inlet load of the salt-containing wastewater, inoculating activated sludge into a wastewater treatment system according to the sludge concentration of 3000-5000mg/L, adding polyethyleneimine into the system, and then carrying out an aeration reaction;
II. According to the mass ratio of the nitrosification microbial inoculum to the inoculated activated sludge of 1-10, adding the nitrosification microbial inoculum, and adopting an operation mode of changing water in batches and gradually reducing the water inflow of the salt-containing wastewater until a set water inflow load is reached;
III, carrying out denitrification treatment on the salt-containing wastewater according to a set water inlet load;
the preparation method of the nitrosation microbial inoculum comprises the following steps: (1) preparing an adsorption carrier; (2) culturing nitrite bacteria microorganisms; (3) Mixing the microorganisms and the adsorption carrier to prepare a nitrosobacteria agent;
wherein the culture method of the nitrite bacteria microorganism in the step (2) comprises the following steps: firstly, inoculating activated sludge rich in nitrobacteria into a reactor with stirring and aeration functions, carrying out enrichment culture on nitrite bacteria by adopting an operation mode of batch feeding and gradually increasing the ammonia nitrogen concentration in the feeding, wherein the conditions for finishing the culture are as follows: the nitrosation rate reaches more than 90 percent, the thallus culture process is finished, and the thallus is harvested;
in the process of culturing the nitrite bacteria, hydroxylamine substances and coenzyme are added at the same time of each batch of fed materials, when the ammonia nitrogen removal rate reaches more than 95 percent, the current batch is ended, and the fed materials enter the next batch for culturing; the nitrosation rate of the current batch reaches more than 30 percent, and NO and/or NO is introduced into the culture system from the next batch 2 A gas.
2. The method according to claim 1, wherein the quality of the salt-containing wastewater is: COD concentration is 100-500mg/L, ammonia nitrogen concentration is 50-150mg/L, total nitrogen concentration is 50-200mg/L, and salt content is 10000-30000mg/L.
3. The method according to claim 1, wherein the activated sludge in step I is obtained from excess sludge in a secondary sedimentation tank of a sewage treatment plant.
4. The method according to claim 1, wherein the activated sludge in step I is obtained from excess sludge from a secondary sedimentation tank of a high salt-containing series in a sewage treatment plant.
5. The method according to claim 1, wherein the polyethyleneimine of step I is added in a concentration of 1% to 5% by volume of the system, and the polyethyleneimine is a water-soluble high-molecular polymer.
6. The method according to claim 1, wherein the polyethyleneimine of step I is added in an amount of 1% -5% by volume of the system, and the polyethyleneimine is a water-soluble high-molecular polymer and has a molecular weight of 1000-16000.
7. The process of claim 1, wherein the aeration reaction conditions in step I are as follows: the dissolved oxygen is 2-5mg/L, pH with the value of 7-9, the temperature of 20-38 ℃ and the reaction time of 24-72h.
8. The method according to claim 1, wherein the step II of replacing the discharge water in batches means that when the total nitrogen removal rate of each batch reaches more than 95%, the current batch is ended, the saline wastewater in the current batch is discharged, and the saline wastewater is replaced to enter the next batch for culture;
and/or in the step II, the water inflow of the salt-containing wastewater of the current batch is gradually reduced by 2-20% compared with the water inflow of the salt-containing wastewater of the previous batch, and the number of times of gradually reducing the water inflow of the salt-containing wastewater is at least more than 2.
9. The process according to claim 1, characterized in that the operating conditions of step II are as follows: the dissolved oxygen is 1-3mg/L, the pH value is 7-9, and the temperature is 20-38 ℃.
10. The method according to claim 1, wherein the nitrosobacteria agent of step II comprises nitrite bacteria microorganism and an adsorption carrier, wherein the adsorption carrier comprises calcium carbonate-embedded cross-linked chitosan and heterotrophic bacteria.
11. The method according to claim 10, characterized in that in the nitrosobacteria agent, the mass content of the nitrite bacteria microorganism is 50% -70%, and the mass content of the adsorption carrier is 30% -50%;
in the adsorption carrier, the heterotrophic bacteria account for 5-50% of the mass of the adsorption carrier, and the cross-linked chitosan embedded with calcium carbonate accounts for 50-95% of the mass of the adsorption carrier;
in the calcium carbonate-embedded cross-linked chitosan, the mass ratio of chitosan to calcium carbonate is (1-5): 0.5 to 5;
the heterotrophic bacteria are selected from at least one of yeast, lactic acid bacteria and sulfate reducing bacteria.
12. The method of claim 10,
in the adsorption carrier, the heterotrophic bacteria account for 10-30% of the mass of the adsorption carrier, and the calcium carbonate-embedded cross-linked chitosan accounts for 70-90% of the mass of the adsorption carrier;
the heterotrophic bacteria are yeasts.
13. The method according to claim 1, wherein the adsorbent carrier in the step (1) is prepared by: and (3) adding the calcium carbonate-embedded cross-linked chitosan into a heterotrophic bacteria culture system utilizing an organic carbon source for adsorption growth, stopping the culture until the later stage of logarithmic growth, taking out the solid and drying to obtain the calcium carbonate-embedded heterotrophic bacteria.
14. The method according to claim 1, wherein the adsorbent carrier in the step (1) is prepared by: adding the calcium carbonate-embedded cross-linked chitosan into a heterotrophic bacteria culture system utilizing an organic carbon source for adsorption growth, namely adding the calcium carbonate-embedded cross-linked chitosan for the heterotrophic bacteria culture while carrying out the culture and the adsorption growth at the initial stage of the heterotrophic bacteria culture process; the addition of the calcium carbonate-embedded cross-linked chitosan accounts for 20-30% of the total reaction volume; the organic carbon source is added according to the mass concentration of 1-5g/L in the system after the organic carbon source is added; the culture conditions of the heterotrophic bacteria are as follows: the temperature is 20-38 ℃, and the pH value is 6.0-8.5; standing for fermentation or shake culture.
15. The method of claim 14, wherein the culture conditions of the heterotrophic bacteria are: the temperature is 20-30 ℃, and the pH value is 6.0-7.0.
16. The method according to claim 1, wherein, in the process of culturing the nitrite bacteria, hydroxylamine and coenzyme are added at the same time of feeding each batch, when the ammonia nitrogen removal rate reaches more than 95%, the current batch is ended, and feeding is carried out for the next batch; when the nitrosation rate of the current batch reaches 50-60%, NO and/or NO is introduced into the culture system from the next batch 2 A gas.
17. A method according to claim 16, wherein the nitrifying bacteria-rich activated sludge is inoculated at a sludge concentration of 2000 to 5000mg/L in the method for culturing the nitrite bacteria-type microorganisms.
18. The method according to claim 16, wherein the nitrite bacteria microorganism is cultured in the presence of a coenzyme selected from the group consisting of coenzyme I, coenzyme II and coenzyme Q10, wherein coenzyme I is nicotinamide adenine dinucleotide and coenzyme II is nicotinamide adenine dinucleotide phosphate; wherein the mass ratio of at least one selected from coenzyme I and coenzyme II to coenzyme Q10 is 8:1-1:8;
and/or the hydroxylamine substance is at least one of hydroxylamine, hydroxylamine hydrochloride, hydroxylamine sulfate or hydroxylamine phosphate;
and/or, adding hydroxylamine substances at a concentration of 1-5mg/L in the culture system after adding, and adding coenzyme at a concentration of 0.001-0.01mg/L in the culture system after adding;
and/or, NO and/or NO 2 The adding amount of the gas accounts for 0.001-0.01% of the total volume of the introduced gas.
19. The method according to claim 16, wherein in the method for culturing the nitrite bacterial microorganism, the coenzyme comprises at least one coenzyme selected from the group consisting of coenzyme I and coenzyme II, and coenzyme Q10, wherein the coenzyme I is nicotinamide adenine dinucleotide, and the coenzyme II is nicotinamide adenine dinucleotide phosphate; wherein the mass ratio of at least one selected from coenzyme I and coenzyme II to coenzyme Q10 is 5:1-1:5;
and/or the hydroxylamine substance is hydroxylamine phosphate.
20. A method according to claim 16, wherein the nitrite bacteria are cultured under the conditions for enrichment culture of the nitrite bacteria as follows: the temperature is 18-40 ℃, the dissolved oxygen is 0.1-3.0mg/L, and the pH value is 7.0-9.0.
21. A method according to claim 16, wherein the nitrite bacteria are cultured under the conditions for enrichment culture of the nitrite bacteria as follows: the temperature is 25-35 ℃, the dissolved oxygen is 0.5-2.0mg/L, and the pH value is 7.5-8.5.
22. The method according to claim 16, wherein the nitrite bacteria microorganism is cultured in a medium supplemented with the medium comprising ammonia nitrogen and a metal salt at a concentration of 0.01 to 1.0mg/L.
23. The method as set forth in claim 16, wherein the feeding is supplemented with a medium comprising ammonia nitrogen and a metal salt selected from the group consisting of calcium salts, ferrous salts and copper salts, wherein the metal salt is Ca 2+ 、Fe 2+ And Cu 2+ The molar ratio of (8-12) to (2-6) to (1-4).
24. A method according to claim 16 or 22, wherein the nitrite bacterial micro-organism is cultivated by gradually increasing the ammonia nitrogen concentration in the feed as follows: the initial ammonia nitrogen concentration is 20-100mg/L, the amplitude of increasing the ammonia nitrogen concentration each time is 10-50mg/L, and the conditions for increasing the ammonia nitrogen concentration are as follows: for the material supplement with the same ammonia nitrogen concentration, the ammonia nitrogen removal rate reaches more than 95% by 3-5 batches continuously, the difference between the time used by each batch and the average time used by the batches is within 10%, and the ammonia nitrogen concentration of the material liquid supplemented by the next batch is improved.
25. A method according to claim 16 or 22, wherein the nitrite bacterial micro-organism is cultivated by gradually increasing the ammonia nitrogen concentration in the feed as follows: the initial ammonia nitrogen concentration is 20-100mg/L, the amplitude for increasing the ammonia nitrogen concentration each time is 10-50mg/L, and the conditions for increasing the ammonia nitrogen concentration are as follows: for the feeding of the same ammonia nitrogen concentration, the ammonia nitrogen removal rate reaches more than 95% by 3-5 continuous batches, and the difference between the time used by each batch and the average time used by the batches is within 5%, namely the ammonia nitrogen concentration of the feed liquid fed in the next batch is improved.
26. The method according to claim 16, wherein the conditions for terminating the culture in the method for culturing the nitrite bacteria microorganism are as follows: and (3) continuously carrying out 3-5 batches with the nitrosation rate reaching more than 90%, finishing the thallus culture process, and harvesting the thallus.
27. The method according to claim 1, wherein the product of the step (3) after mixing the microorganism and the carrier is dehydrated to a water content of 30wt% to 50wt%, and is vacuum-dried under a pressure of 1 to 2kPa and at a temperature of 35 to 50 ℃ to prepare the solid microbial inoculum.
28. The method of claim 1, wherein the denitrification treatment conditions of the saline wastewater according to the set water inlet load in the step III are as follows: the dissolved oxygen is 1-3mg/L, the pH value is 7-9, and the temperature is 20-38 ℃.
29. The process of claim 28 wherein step III is carried out using batch feed or continuous feed.
30. The method as claimed in claim 28, wherein in the step III, when the concentration of ammonia nitrogen is 6-12mg/L, the nitrosation agent is supplemented according to the mass ratio of the nitrosation agent to the saline wastewater per hour water inflow of 1-5.
31. The method according to claim 1, wherein in step II, the nitrosobacteria agent is added according to the mass ratio of the nitrosobacteria agent to the inoculated activated sludge of 1-5.
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