CN115353198B - Synchronous denitrification and dephosphorization method based on sponge iron-sodium thiosulfate autotrophic denitrification biological filter - Google Patents
Synchronous denitrification and dephosphorization method based on sponge iron-sodium thiosulfate autotrophic denitrification biological filter Download PDFInfo
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Abstract
A synchronous denitrification and dephosphorization method based on sponge iron-sodium thiosulfate autotrophic denitrification biological filter belongs to the field of sewage biological treatment. Volcanic rock and sponge filler are uniformly mixed according to the volume ratio of 5:1 and then are filled into a reactor, sulfur autotrophic denitrification sludge is inoculated into the reactor, and water inflow S is controlled 2 O 3 2‑ And NO 3 ‑ The molar ratio of N is 0.86, and the sulfur-iron autotrophic bacteria synergistic denitrification biological filter is gradually formed through enrichment culture. The biological filter has simple structure and short film forming time, and can realize the efficient and synchronous removal of nitrate and phosphate in the wastewater by controlling the hydraulic retention time to be 1.5-3 h, and simultaneously buffer pH and reduce the generation of sulfate.
Description
Technical Field
The application relates to a synchronous denitrification and dephosphorization method based on a sponge iron-sodium thiosulfate autotrophic denitrification biological filter, belonging to the technical field of sewage biological treatment.
Background
In recent years, eutrophication of water has received great attention, and the discharge of nitrogen and phosphorus-rich domestic sewage and industrial wastewater into water in large quantities is a main cause of this phenomenon. Biological denitrification and dephosphorization technology is widely applied to sewage treatment plants as an economic and environment-friendly sewage treatment method. Traditional heterotrophic denitrification requires organic matters to participate in serving as electron acceptors to reduce nitrate to N 2 . However, the sewage in China has the characteristic of low C/N water quality, so that an additional carbon source is often needed to be added by adopting the method. Thus, conventional heterotrophic denitrification can result in higher processing costs.
The sulfur autotrophic denitrification is under the action of sulfur autotrophic denitrification microorganismsNext, use S 2- 、S 2 O 3 2- 、S 0 Etc. as electron donor to reduce nitrate to N 2 No additional carbon source is needed. Wherein S is 2 O 3 2- The bioavailability is highest, and the denitrification can be performed efficiently. At present by S 2 O 3 2- The electron donor is used in the activated sludge system, but compared with the activated sludge system, the biological membrane system (such as a biological filter) has the characteristics of low sludge yield and high stability. Sulfur autotrophic denitrification also faces effluent pH reduction and substantial SO 4 2- Problems with the generation and limited phosphate removal capacity. The sulfur and limestone are used as fillers to buffer pH and efficiently denitrify, but the Ca is generated 2+ The hardness of the effluent is easy to increase, and the dephosphorization capability is limited; the pyrite such as pyrrhotite and pyrite is used as a filler, and has the capability of stably removing phosphorus and buffering pH, but the denitrification rate is slow, so that the engineering application value of the pyrite is affected.
The main component of the sponge iron is Fe 0 Is an environment-friendly material widely applied to the field of sewage treatment, has high specific surface area and porosity, provides good attachment points for microorganism growth, and can remove phosphate through adsorption and precipitation. Iron is also an essential element for microorganism growth, and participates in the synthesis of enzymes such as nitrate reductase in the denitrification process. In addition, sponge iron corrosion can produce significant amounts of alkalinity and Fe 2+ And Fe (Fe) 2+ Can be used as electron donor to participate in biological denitrification process. And the sulfur autotrophic denitrification can generate a large amount of H + Can further promote the release of Fe from the sponge iron 2+ . Sponge iron and S 2 O 3 2- The two substances can cooperatively play the role of denitrification and dephosphorization. Thus, S will be in biological sewage treatment 2 O 3 2- The driven coupling of the sulfur autotrophic denitrification and the sponge iron can strengthen the denitrification and dephosphorization effects, buffer the pH value and reduce the SO of the effluent 4 2- Concentration.
The reaction of sponge iron with nitrate is as follows:
4Fe 0 +NO 3 - +7H 2 O→4Fe 2+ +NH 4 + +10OH - (1)
10Fe 2+ +2NO 3- +12H + →5Fe 3+ +N 2 +6H 2 O (2)
disclosure of Invention
The application relates to a synchronous denitrification and dephosphorization method based on sponge iron-sodium thiosulfate autotrophic denitrification biological filter, which aims to solve the problems of pH reduction and a large amount of SO (SO) in sulfur autotrophic denitrification effluent 4 2- The problems of limited phosphorus removal and the generation can be solved, the denitrification performance can be enhanced, and the water quality of the effluent can be improved.
A synchronous denitrification and dephosphorization method based on sponge iron-sodium thiosulfate autotrophic denitrification biological filter is characterized in that denitrification and dephosphorization are completed in the same filter, and the filter is filled with mixed filler of volcanic rock and sponge iron as a microbial carrier; the outflow of the sodium thiosulfate water tank and the outflow of the waste water tank containing nitrate and phosphate are combined and then used as the inflow of the filter tank; sponge iron and sodium thiosulfate provide electron donor Fe 2+ And S is 2 O 3 2- The method is used for nitrate reduction and strengthening iron and sulfur autotrophic bacteria denitrification; removing phosphate from the sponge iron by adsorption and precipitation; the operation method for synchronous denitrification and dephosphorization comprises the following 4 steps:
(1) Filling with filler
Volcanic rock with the grain diameter of 3-6 mm and sponge iron with the grain diameter of less than 5mm are uniformly mixed according to the volume ratio of 5:1 and then are filled into a filter tank, and the filling height of the filling material is lower than the setting height of a water outlet;
(2) Inoculation sludge and film hanging
Inoculating sulfur autotrophic denitrification sludge, controlling the concentration of the sludge to 2500-3500 mg/L, pumping the inoculated sludge from the bottom of the filter tank by a peristaltic pump, observing that the sludge is trapped on the surface of a filter material, and indicating that the inoculation is successful; culturing sulfur autotrophic denitrification sludge in a 5L sequencing batch reactor, wherein during the culturing period, simulated wastewater is adopted, and S in the wastewater 2 O 3 2- Concentration 400+ -30 mg/L, NO 3 - N concentration 60+ -5 mg/L, PO 4 3- -P concentration 4-6 mg/L; culturingIn the process, the temperature is maintained at 25-27 ℃, and the pH of the inlet water is maintained at 7.0-7.5; one complete operation period of the reactor comprises stirring for 12h, precipitating for 30min and feeding water for 5min; until the nitrate removal rate is maintained at 85+/-5 percent, and the culture of the sulfur autotrophic denitrification sludge is completed;
during the film forming, the simulation of waste water is adopted, S in the waste water 2 O 3 2- Concentration 200+ -20 mg/L, NO 3 - N concentration of 30.+ -.10 mg/L, PO 4 3- -P concentration 4-6 mg/L; the hydraulic retention time is regulated to 48 hours, the pH of the inlet water is 7.0-7.5, the temperature is controlled to be 25-27 ℃ by a temperature control device, and the operation is carried out for 8-10 days;
(3) Enrichment culture of sulfur-iron autotrophic denitrifying bacteria
By S 2 O 3 2- Concentration 200+ -20 mg/L, NO 3 - N concentration of 30.+ -.10 mg/L, PO 4 3- -4-6 mg/L of P concentration of simulated wastewater for enrichment culture of sulfur-iron autotrophic denitrifying bacteria; gradually reducing the hydraulic retention time from 48 hours to 24 hours in the film forming period, and running for 10-15 days; then the temperature is reduced to 12 hours, and the operation is carried out for 25 to 30 days; finally, the temperature is reduced to 6 hours, and the operation is carried out for 15 to 20 days; taking out water sample from the filter tank every day for analysis, and taking out NO as water sample 3 - The concentration of the-N is stabilized at 0.5-1.5 mg/L, and the effluent PO is obtained 4 3- P is stabilized at 0.3-0.5 mg/L, which marks the completion of enrichment culture of sulfur-iron autotrophic denitrifying bacteria;
(4) Stable operation
In the daily operation of the sponge iron-sodium thiosulfate autotrophic denitrification biological filter, S in the wastewater is controlled 2 O 3 2- Concentration of<450mg/L、NO 3 - -N concentration<80mg/L and PO 4 3- P concentration<10mg/L; the hydraulic retention time is controlled to be 1.5-3 hours, so that the efficient synchronous removal of nitrate and phosphate in the wastewater is realized.
Innovation point of the application
(1) Realizing electron donor S with highest bioavailability in sulfur autotrophic denitrification process 2 O 3 2- Applications from activated sludge systems to biofilm systems; the system has the advantages of less sludge production, higher system stability and denitrification performanceThe advantages are that;
(2) Successfully applies the environment-friendly material-sponge iron to a sulfur autotrophic denitrification biological filter system, and rapidly realizes the cooperation of sulfur-iron autotrophic denitrification and efficient denitrification;
(3) Solves the problem that the denitrification performance of the pyrite filter is generally limited by weaker ion dissolution capacity of the filling material; meanwhile, the device has the synchronous denitrification and dephosphorization performance of the pyrite filter.
The beneficial effects of the application are that
(1) Sponge iron and volcanic rock with large specific surface area and high porosity are used as filter materials, so that the film forming time is greatly shortened;
(2) By S 2 O 3 2- The driving of sulfur autotrophic denitrification can improve the denitrification efficiency, and is suitable for treating high-load nitrate wastewater;
(3) The sponge iron filter material is filled, so that the pH value of the effluent is stable, and the effluent has dephosphorization performance;
(4) The iron element in the sponge iron can promote the growth of microorganisms and participate in the synthesis of denitrification related enzymes, so that the microorganisms in the filter tank are enriched in a short time, and the denitrification performance is enhanced;
(5) Fe released by corrosion of sponge iron 2+ The method can be used as an electron donor to participate in denitrification, and can be used for cooperating with sulfur autotrophic denitrification to denitrify, so that the richness of microbial communities in the filter tank and the stability of the filter tank are improved;
(6) Sulfur-iron autotrophic denitrification synergistic denitrification, SO that SO is reduced 4 2- Is generated.
Drawings
FIG. 1 is a schematic diagram of a sponge iron-sodium thiosulfate-based autotrophic denitrification biological filter;
in the figure: 1- -sodium thiosulfate water inlet pool; 2- -a wastewater tank containing nitrates and phosphates; 3- -peristaltic pump; 4- -a water inlet; 5- -a biological filter; 5.1- -a take-out port; 5.2- -a temperature control device; 5.3- -a water outlet; 5.4- -overflow tube; 5.5- -gas collecting port.
FIG. 2 is a graph showing denitrification effect according to an embodiment of the present application;
FIG. 3 illustrates the dephosphorization effect of an embodiment of the present application;
FIG. 4 is an illustration of the pH of the incoming and outgoing water of an embodiment of the present application;
FIG. 5 is a schematic of an actual and theoretical SO of an embodiment of the application 4 2- Creating a situation.
Detailed Description
The application patent is further described with reference to the accompanying drawings and examples: as shown in fig. 1, the application comprises a sodium thiosulfate water tank (1) and a waste water tank (2) containing nitrate and phosphate, wherein the waste water tank is connected with a water inlet (4) through a water inlet peristaltic pump (3), a biological filter (5) is provided with a filter material taking hole (5.1) and a gas collecting hole (5.5) and is provided with a temperature control device (5.2), water is sampled at a water outlet (5.3) for detection, and the effluent of the reactor is discharged through an overflow pipe (5.4).
The water quality of the wastewater used in the specific embodiment is 202-405 mg/L S 2 O 3 2- 、30～60mg/L NO 3 - -N and 4-6 mg/LPO 4 3- P, and the water distribution is always maintained S 2 O 3 2- With NO 3 - The molar ratio of N is 0.86.
The specific implementation process is as follows:
(1) Filling with filler
Volcanic rock with the grain diameter of 3-6 mm and sponge iron with the grain diameter of less than 5mm are uniformly mixed according to the volume ratio of 5:1 and then are filled into a filter tank, and the filling height of the filling material is lower than the setting height of a water outlet;
(2) Inoculation sludge and film hanging
Inoculating sulfur autotrophic denitrification sludge, controlling the concentration of the sludge to be 3200mg/L, pumping the inoculated sludge from the bottom of the filter tank by using a peristaltic pump, and observing that the sludge is trapped on the surface of a filter material, thereby indicating successful inoculation; culturing sulfur autotrophic denitrification sludge in a 5L sequencing batch reactor, wherein during the culturing period, simulated wastewater is adopted, and S in the wastewater 2 O 3 2- Average concentration 410.5mg/L, NO 3 - Average N concentration of 62.1mg/L, PO 4 3- -average concentration of P5.8 mg/L; in the culture process, the temperature is maintained at 25-27 ℃, and the pH of the inlet water is maintained at 7.0-7.5; one complete operation period of the reactor comprises stirring for 12h, precipitating for 30min and feeding water for 5min; nitrate saltsThe removal rate is maintained at 90 percent, and the culture of the sulfur autotrophic denitrification sludge is completed;
during the film forming, the simulation of waste water is adopted, S in the waste water 2 O 3 2- Average concentration 202.7mg/L, NO 3 - Average N concentration of 33.2mg/L, PO 4 3- -average concentration of P6.02 mg/L; the hydraulic retention time is regulated to 48 hours, the pH value of the inlet water is 7.0-7.5, the temperature is controlled to be 25-27 ℃ by a temperature control device, the operation is carried out for 10 days, and the NO of the outlet water is obtained 3 - The N is stabilized at 0.5mg/L and the effluent does not contain NO 2 - N, film formation is successful;
(3) Enrichment culture of sulfur-iron autotrophic denitrifying bacteria
By S 2 O 3 2- Average concentration 197.6mg/L, NO 3 - Average N concentration of 35.3mg/L, PO 4 3- -simulated wastewater enrichment culture of sulfur-iron autotrophic denitrifying bacteria with an average concentration of 5.1mg/L of P; gradually reducing the hydraulic retention time from 48 hours to 24 hours in the film forming period, and running for 10 days; then the temperature is reduced to 12h, and the operation is carried out for 25d; finally, the temperature is reduced to 6h, and 17d is operated; sampling and analyzing every day, wherein the denitrification and dephosphorization performance of the reactor is stable; final water outlet NO 3 - -N is stabilized at 0.7mg/L, PO 4 3- P is stabilized at 0.3mg/L, the nitrate removal rate is more than 99%, and the phosphate removal rate is more than 95%;
(4) Stable operation
S is used in a sponge iron-sodium thiosulfate autotrophic denitrification biological filter 2 O 3 2- Average concentration of 372.8mg/L, NO 3 - Average N concentration of 62.5mg/L, PO 4 3- -simulated wastewater enrichment culture of sulfur autotrophic denitrifying bacteria with an average concentration of 5.01mg/L of P. Firstly, under the condition that the hydraulic retention time is 6 hours, the operation is carried out for 10 days; then the temperature is reduced to 3h, and 13d is operated; finally, the temperature is reduced to 1.5h, and the operation is carried out for 15d; sampling and analyzing every day, wherein the high-load nitrate further strengthens the denitrification and dephosphorization performance of the reactor; final water outlet NO 3 - -N is stabilized at 1mg/L, PO 4 3- P is stabilized at 0.5mg/L, the nitrate removal rate is more than 96%, and the phosphate removal rate is more than 93%.
Nitrate in this exampleThe load removal reaches 3200mg/m 3 And/d, the average nitrate removal rate reaches 97.98%, the average phosphate removal rate reaches more than 93%, and the high-load nitrate removal and the high-efficiency phosphate removal are successfully realized. The constructed reaction system has stable performance, and the common operation of the enrichment culture and stable operation stage is kept for 90 days to always keep stable nitrate and phosphate removal performance. The final pH of the effluent is stabilized at 7.0-7.3, and the sulfate production is reduced by 20-34%. The coupling sponge iron improves the richness of microbial communities and forms a denitrification system with sulfur-iron autotrophic denitrifying bacteria as main dominant bacteria.
Claims (1)
1. The synchronous denitrification and dephosphorization method based on the sponge iron-sodium thiosulfate autotrophic denitrification biological filter is characterized by comprising the following 4 steps:
(1) Filling with filler
Volcanic rock with the grain diameter of 3-6 mm and sponge iron with the grain diameter of less than 5mm are uniformly mixed according to the volume ratio of 5:1 and then are filled into a filter tank, and the filling height of the filling material is lower than the setting height of a water outlet;
(2) Inoculation sludge and film hanging
Inoculating sulfur autotrophic denitrification sludge, controlling the concentration of the sludge to 2500-2500 mg/L, pumping the inoculated sludge from the bottom of the filter tank by using a peristaltic pump, and observing that the sludge is trapped on the surface of the filler, thus indicating successful inoculation; culturing sulfur autotrophic denitrification sludge in a sequencing batch reactor, wherein during the culturing period, simulated wastewater is adopted, and S in the wastewater 2 O 3 2- Concentration 400+ -30 mg/L, NO 3 - N concentration 60+ -5 mg/L, PO 4 3- -P concentration 4-6 mg/L; the temperature is maintained at 25-27 ℃, and the pH of the inlet water is maintained at 7.0-7.5; one complete operation cycle of the sequencing batch reactor comprises stirring for 12 hours, precipitating for 30 minutes and feeding water for 5 minutes; until the nitrate removal rate is maintained at 85+/-5 percent, and the culture of the sulfur autotrophic denitrification sludge is completed;
during the film forming, the simulation of waste water is adopted, S in the waste water 2 O 3 2- Concentration 200+ -20 mg/L, NO 3 - N concentration of 30.+ -.10 mg/L, PO 4 3- -P concentration of 4-6 mgL; the hydraulic retention time is regulated to 48 hours, the pH of the inlet water is 7.0-7.5, the temperature is controlled to be 25-27 ℃ by a temperature control device, and the operation is carried out for 8-10 days;
(3) Enrichment culture of sulfur-iron autotrophic denitrifying bacteria
By S 2 O 3 2- Concentration 200+ -20 mg/L, NO 3 - N concentration of 30.+ -.10 mg/L, PO 4 3- -4-6 mg/L of P concentration of simulated wastewater for enrichment culture of sulfur-iron autotrophic denitrifying bacteria; reducing the hydraulic retention time to 24 hours, and running for 10-15 d; then the temperature is reduced to 12 hours, and the operation is carried out for 25-30 days; finally, the temperature is reduced to 6 hours, and the operation is carried out for 15-20 days; taking out water sample from the filter tank every day for analysis, and taking out NO as water sample 3 - The N is stabilized at 0.5-1.5 mg/L, and the effluent PO is obtained 4 3- P is stabilized at 0.3-0.5 mg/L, and the completion of enrichment culture of the sulfur-iron autotrophic denitrifying bacteria is marked;
(4) Stable operation
In the daily operation of the sponge iron-sodium thiosulfate autotrophic denitrification biological filter, S in the wastewater is controlled 2 O 3 2- Concentration of<450mg/L、NO 3 - -N concentration<80mg/L and PO 4 3- P concentration<10mg/L; controlling the hydraulic retention time to be 1.5-3 hours.
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| 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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