CN116715345A - Autotrophic denitrification bioreactor based on pyrite coupling filler and application - Google Patents
Autotrophic denitrification bioreactor based on pyrite coupling filler and application Download PDFInfo
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- CN116715345A CN116715345A CN202310838520.9A CN202310838520A CN116715345A CN 116715345 A CN116715345 A CN 116715345A CN 202310838520 A CN202310838520 A CN 202310838520A CN 116715345 A CN116715345 A CN 116715345A
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- 230000001651 autotrophic effect Effects 0.000 title claims abstract description 86
- 239000000945 filler Substances 0.000 title claims abstract description 80
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000011028 pyrite Substances 0.000 title claims abstract description 72
- 229910052683 pyrite Inorganic materials 0.000 title claims abstract description 72
- 230000008878 coupling Effects 0.000 title claims abstract description 69
- 238000010168 coupling process Methods 0.000 title claims abstract description 69
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 69
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 72
- 239000011593 sulfur Substances 0.000 claims abstract description 72
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000002351 wastewater Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 34
- 241000894006 Bacteria Species 0.000 claims abstract description 29
- 235000019738 Limestone Nutrition 0.000 claims abstract description 29
- 239000006028 limestone Substances 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 27
- 239000010865 sewage Substances 0.000 claims abstract description 15
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 12
- -1 sulfur ions Chemical class 0.000 claims abstract description 10
- 238000004064 recycling Methods 0.000 claims abstract description 4
- 239000002054 inoculum Substances 0.000 claims description 36
- 230000008569 process Effects 0.000 claims description 27
- 239000001963 growth medium Substances 0.000 claims description 21
- 244000005700 microbiome Species 0.000 claims description 14
- 239000010802 sludge Substances 0.000 claims description 14
- 238000009630 liquid culture Methods 0.000 claims description 12
- 230000014759 maintenance of location Effects 0.000 claims description 12
- 230000002572 peristaltic effect Effects 0.000 claims description 9
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 8
- 238000005086 pumping Methods 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000011081 inoculation Methods 0.000 claims description 6
- 230000009286 beneficial effect Effects 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 150000004763 sulfides Chemical class 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920001021 polysulfide Chemical class 0.000 claims description 4
- 239000005077 polysulfide Chemical class 0.000 claims description 4
- 150000008117 polysulfides Chemical class 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000012258 culturing Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002384 drinking water standard Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 230000007774 longterm Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000010811 mineral waste Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C02F3/28—Anaerobic digestion processes
- C02F3/2806—Anaerobic processes using solid supports for microorganisms
-
- 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
- C02F3/345—Biological treatment of water, waste water, or sewage characterised by the microorganisms used for biological oxidation or reduction of sulfur compounds
-
- 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
- C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
-
- 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
-
- 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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- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Biodiversity & Conservation Biology (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Biological Treatment Of Waste Water (AREA)
Abstract
The autotrophic denitrification bioreactor based on the coupling filler of the pyrite of sulfur comprises a reactor and the coupling filler, wherein the coupling filler is formed by mixing sulfur, pyrite and limestone, the volume ratio of the coupling filler is (1-3), and the average particle size is 1-3mm. The application of the reactor in treating nitrate sewage comprises the following steps: a) Preparing and loading coupling filler; b) Inoculating and film-forming autotrophic denitrifying bacteria; c) And (3) recycling the wastewater. According to the reactor and the application, after the sulfur pyrite limestone is coupled, not only can the negative valence sulfur ions dissolved by pyrite be utilized with Fe 2+ Increase electron transfer rate and generate more Ca 2+ With Fe 2+ The sulfate in the system is neutralized, the film forming period is short, the operation is simple and convenient, the concentration of the sulfate in the water is reduced while the denitrification is performed efficiently, and the sulfur and pyrite are used as fillers, so that the method is low in cost and can be applied to practical engineering.
Description
Technical Field
The invention relates to a bioreactor and application, in particular to a sulfur pyrite coupling filler-based autotrophic denitrification bioreactor and application, and belongs to the field of wastewater treatment.
Background
In recent years, along with the continuous acceleration of urban and industrial processes in China, a large amount of nitrogen-containing wastewater is discharged into water. The out-of-standard emission of nitrogen is a main factor of serious pollution of important water bodies in China, and seriously threatens ecological safety and human health. Therefore, developing a denitrification treatment technology which is economical and efficient and has no secondary pollution has become an important point and a hot spot in the current sewage treatment field in China. Biological denitrification is widely used in many denitrification technologies because of its advantages of high denitrification efficiency, safe treatment and high cost efficiency. Heterotrophic denitrification is a widely applied biological treatment technology at present, but when sewage with low C/N ratio is treated, an additional carbon source is needed, the addition amount is difficult to control, high running cost and secondary pollution are easy to generate, and the sludge yield is large. However, autotrophic denitrification using sulfur, pyrite, etc. as electron donors has been developed gradually because of low price, no secondary pollution, low sludge yield, etc.
The sulfur autotrophic denitrification is widely concerned at home and abroad due to the advantages of low mud yield, low energy consumption, no need of adding an expensive carbon source and no secondary pollution, and is considered to be a traditional denitrification substitution process with potential cost effectiveness. However, the problems of sulfur autotrophic denitrification technology, such as the generation of a large amount of sulfate in the process of reducing nitrate and the consumption of alkalinity of a system, limit the practical engineering application. Pyrite autotrophic denitrification valenceLow cost and can simultaneously provide Fe for denitrifying bacteria 2+ And reducing sulfides as electron donors, but the problems of low denitrification rate, difficulty in long-term continuous denitrification and the like limit the application of the catalyst in sewage treatment. Therefore, in order to solve the problems of low denitrification rate, difficult long-term continuous denitrification, high output of effluent sulfate and the like, it is important to develop a sewage advanced treatment technology which is economical and efficient and can realize continuous denitrification.
Disclosure of Invention
The invention provides an autotrophic denitrification bioreactor based on a coupling filler of pyrite and application thereof, aiming at overcoming the defects of the technical problems.
The invention relates to a sulfur pyrite coupling filler-based autotrophic denitrification bioreactor, which comprises a reactor and coupling fillers filled in an internal cavity of the reactor, wherein the bottom and the upper part of the reactor are respectively provided with a water inlet and a water outlet which are communicated with the internal cavity of the reactor, wastewater to be treated enters through the water inlet, and the treated wastewater is discharged through the water outlet; the method is characterized in that: the coupling filler is formed by mixing sulfur, pyrite and limestone.
The invention relates to a sulfur pyrite coupling filler-based autotrophic denitrification bioreactor, wherein the volume ratio of sulfur to pyrite to limestone is (1-3).
The autotrophic denitrification bioreactor based on the coupling filler of the sulfur pyrite, disclosed by the invention, has the average particle size of 1-3mm.
The application of the autotrophic denitrification bioreactor based on the coupling filler of the pyrite and the sulfur in the treatment of nitrate sewage is characterized by comprising the following steps:
a) Preparing and loading coupling filler; firstly, respectively crushing sulfur, pyrite and limestone by using a crusher, and screening out particles with the particle size of 1-3mm for later use; uniformly mixing particles of sulfur, pyrite and limestone according to a constrained volume ratio to obtain coupling filler, and loading the coupling filler into a reactor;
b) Inoculating and film-forming autotrophic denitrifying bacteria; firstly, enrichment of autotrophic denitrifying bacteria strains is carried out, the enriched strains are added into a liquid culture medium and then pumped into a reactor, so that inoculation of the autotrophic denitrifying bacteria is realized, and the inoculated strains and the culture medium are kept stand for 24 hours in the reactor; after standing, circularly running for 3-5 days to ensure that the biological film is uniformly enriched on the surface of the coupling filler and the biological film is successfully coated;
c) Recycling the wastewater; firstly, introducing high-purity N into a reactor 2 Let N 2 Filling the whole inner cavity of the reactor to provide a proper anoxic environment for denitrifying bacteria so as to ensure the growth of microorganisms; then pumping the wastewater to be treated in the wastewater pool from a water inlet at the bottom of the reactor by utilizing a water inlet pump to realize autotrophic denitrification treatment of the wastewater, and discharging the treated water body through a water outlet;
in the process that the wastewater slowly rises from the bottom in the reactor, the wastewater fully contacts with a biological film on the surface of a coupling filler in the reactor, denitrifying bacteria utilize acidity generated in the sulfur autotrophic denitrification process to dissolve pyrite to generate negative-valence sulfur ions, electrons are easily lost due to the negative-valence sulfur ions, so that the rate of providing electrons by the coupling filler is improved, a series of sulfides and polysulfides are formed to be more easily utilized by autotrophic denitrifying microorganisms, and the denitrification rate is further improved; the acidity generated in the sulfur autotrophic denitrification process causes the limestone to dissolve and produce CO 3 2- 、HCO 3 - 、Ca 2+ ，CO 3 2- And HCO 3 - Providing inorganic carbon source for the growth of autotrophic denitrifying bacteria, and being more beneficial to the growth of autotrophic denitrifying microorganisms; meanwhile, acidity generated in the sulfur autotrophic denitrification process accelerates dissolution of limestone and pyrite, and releases more Ca 2+ And Fe (Fe) 2+ With SO generated in sulfur autotrophic denitrification process 4 2- And calcium sulfate and ferrous sulfate precipitate are generated by combining, so that the purpose of reducing the sulfate of effluent is achieved.
In the step a), pyrite is crushed by a crusher and pyrite particles with the particle size of 1-3mm are screened out, and then the pyrite particles are pickled by using HCl with the concentration of 10% so as to avoid the influence of oxides on the surfaces of the pyrite particles on the performance of the coupling fillers.
The application of the autotrophic denitrification bioreactor based on the coupling filler of the pyrite and the sulfur in the nitrate sewage treatment is realized in the step b), and the inoculation and the film formation of the autotrophic denitrification bacteria are realized by the following steps:
b-1) enrichment of the inoculum; taking anaerobic sludge of a sewage treatment station as seed sludge, inoculating 80mL of anaerobic sludge per liter of liquid culture medium, mixing the culture medium with the anaerobic sludge, and culturing at 28+/-2 ℃; in the culture process, the volume of the generated gas is measured by a water and gas drainage method, and if the volume of the generated gas of a mixture of 1L of culture medium and 80mL exceeds 240.4 mL, the enrichment of autotrophic denitrifying microorganisms is successful;
b-2) inoculating autotrophic denitrifying bacteria; firstly, centrifuging the enriched inoculum obtained in the step b-1) by using a centrifuge, pouring out supernatant after centrifugation, and attaching the inoculum on the wall of a centrifuge tube; the inoculant on the wall of the centrifuge tube is washed for a plurality of times by using sterilized normal saline, so as to eliminate the interference of other ions; then, according to the volume ratio of the liquid culture medium to the inoculum being (85-90): 10-15), the liquid culture medium is mixed with the inoculum to obtain an inoculum solution, and the high-purity N is introduced into the inoculum solution 2 Is washed by a mode of (2);
b-3) coupling the film of the filler; pumping the inoculum solution obtained in the step b-2) into the reactor through a water inlet by utilizing a peristaltic pump, ending pumping after filling the whole inner cavity of the reactor with the inoculum solution, and standing for 24 hours; and then connecting the water outlet of the reactor with the inlet of a peristaltic pump, and circularly flowing the inoculum solution in the reactor for 3-5 days by using the peristaltic pump to ensure that the biological film is uniformly enriched on the surface of the coupling filler, thereby realizing successful film hanging on the surface of the coupling filler.
The invention relates to application of autotrophic denitrification bioreactor based on pyrite coupling filler of sulfur in nitrate sewage treatment, in the step b-2), high-purity N 2 The duration of the washing of the inoculum solution is 15-20min.
The application of the autotrophic denitrification bioreactor based on the sulfur pyrite coupling filler in the nitrate sewage treatment is that in the step c), the hydraulic retention time HRT of the sewage in the reactor is 12-48h.
The beneficial effects of the invention are as follows: according to the autotrophic denitrification bioreactor based on the coupling filler of the sulfur pyrite and the application, the coupling filler formed by mixing the sulfur, the pyrite and the limestone is filled in the inner cavity of the reactor, after the autotrophic denitrification bacteria successfully form a film in the coupling filler, the nitrogenous wastewater to be treated is introduced from the bottom of the reactor, the wastewater is fully contacted with the autotrophic denitrification bacteria in the coupling filler in the process of slowly rising from bottom to top in the reactor, and the autotrophic denitrification organisms utilize the sulfur simple substance of the sulfur as an electron donor to perform denitrification in an anoxic environment, so that the generated acidity enables the pyrite and the limestone to be dissolved to generate Fe 2+ S of negative valence state - 、Fe 2+ 、CO 3 2- 、HCO 3 - The negative valence sulfur ions are easier to lose electrons, so that the rate of providing electrons by the coupling filler is improved, a series of sulfides and polysulfides are formed and are easier to be utilized by autotrophic denitrification microorganisms, and the denitrification rate is further improved; and CO 3 2- And HCO 3 - Providing inorganic carbon source for the growth of autotrophic denitrifying bacteria, and being more beneficial to the growth of autotrophic denitrifying microorganisms; meanwhile, acidity generated in the sulfur autotrophic denitrification process accelerates dissolution of limestone and pyrite, and releases more Ca 2+ And Fe (Fe) 2+ With SO generated in sulfur autotrophic denitrification process 4 2- And calcium sulfate and ferrous sulfate precipitate are generated by combining, so that the purpose of reducing the sulfate of effluent is achieved.
Drawings
FIG. 1 is a schematic structural diagram of a sulfur pyrite-based coupled filler autotrophic denitrification bioreactor of the present invention;
FIG. 2 shows the water inlet and outlet NO of the bioreactor of example 1 of the present invention operated for 40 days 3 - -N and SO 4 2- A concentration profile, wherein the hydraulic retention time HRT is 48h;
FIG. 3 shows the water inlet and outlet NO of the bioreactor of example 2 of the present invention operated for 20 days 3 - -N and SO 4 2- A concentration profile, wherein the hydraulic retention time HRT is 24h;
FIG. 4 shows the water inlet and outlet NO of the bioreactor of example 3 of the present invention operated for 20 days 3 - -N and SO 4 2- Concentration profile, wherein the hydraulic retention time HRT was 12h.
In the figure: 1 reactor, 2 coupling filler, 3 water inlets, 4 water outlets, 5 gas collecting ports, 6 sampling ports, 7 wastewater pools and 8 water inlet pumps.
Description of the embodiments
The invention will be further described with reference to the drawings and examples.
As shown in fig. 1, a schematic structural diagram of the autotrophic denitrification bioreactor based on the coupling filler of sulfur pyrite is provided, which consists of a reactor 1 and a coupling filler 2, wherein the interior of the reactor 1 is a cavity, and the coupling filler 2 is filled in the internal cavity of the reactor 1. The bottom of the reactor 1 is provided with a water inlet 3, the upper part is provided with a water outlet 4, and the water inlet 3 and the water outlet 4 are communicated with the inner cavity of the reactor 1. The top of the reactor 1 is provided with a gas collecting port 5, and nitrogen generated in the wastewater treatment process is discharged through the gas collecting port 5; two sampling ports 6 are provided at different height positions of the reactor 1 for sampling operations. The wastewater to be treated in the wastewater tank 7 is pumped into the reactor 1 through the water inlet pump 8, the wastewater enters from the water inlet 3 at the bottom of the reactor 1, and the wastewater flows out from the water outlet 4 at the upper part after being treated.
The coupling filler 2 filled in the reactor 1 is a mixture of sulfur, pyrite and limestone, the volume ratio of the sulfur, the pyrite and the limestone in the coupling filler 2 is (1-3): (1-3), and the average particle size of the sulfur, the pyrite and the limestone is 1-3mm.
The application of the autotrophic denitrification bioreactor based on the coupling filler of the pyrite and the sulfur in the nitrate sewage treatment is realized by the following steps:
a) Preparing and loading coupling filler; firstly, respectively crushing sulfur, pyrite and limestone by using a crusher, and screening out particles with the particle size of 1-3mm for later use; uniformly mixing particles of sulfur, pyrite and limestone according to a constrained volume ratio to obtain coupling filler, and loading the coupling filler into a reactor;
in the step, after pyrite is crushed by a crusher and pyrite particles with the particle size of 1-3mm are screened out, HCl with the concentration of 10% is utilized to carry out acid washing on the pyrite particles, so that the influence of oxide on the surface of the pyrite particles on the performance of coupling filler is avoided.
b) Inoculating and film-forming autotrophic denitrifying bacteria; firstly, enrichment of autotrophic denitrifying bacteria strains is carried out, the enriched strains are added into a liquid culture medium and then pumped into a reactor, so that inoculation of the autotrophic denitrifying bacteria is realized, and the inoculated strains and the culture medium are kept stand for 24 hours in the reactor; after standing, circularly running for 3-5 days to ensure that the biological film is uniformly enriched on the surface of the coupling filler and the biological film is successfully coated;
in the step, the inoculation and film formation of autotrophic denitrifying bacteria are realized by the following steps:
b-1) enrichment of the inoculum; taking anaerobic sludge of a sewage treatment station as seed sludge, inoculating 80mL of anaerobic sludge per liter of liquid culture medium, mixing the culture medium with the anaerobic sludge, and culturing at 28+/-2 ℃; in the culture process, the volume of the generated gas is measured by a water and gas drainage method, and if the volume of the generated gas of a mixture of 1L of culture medium and 80mL exceeds 240.4 mL, the enrichment of autotrophic denitrifying microorganisms is successful;
b-2) inoculating autotrophic denitrifying bacteria; firstly, centrifuging the enriched inoculum obtained in the step b-1) by using a centrifuge, pouring out supernatant after centrifugation, and attaching the inoculum on the wall of a centrifuge tube; the inoculant on the wall of the centrifuge tube is washed for a plurality of times by using sterilized normal saline, so as to eliminate the interference of other ions; then, according to the volume ratio of the liquid culture medium to the inoculum being (85-90): 10-15), the liquid culture medium is mixed with the inoculum to obtain an inoculum solution, and the high-purity N is introduced into the inoculum solution 2 Is washed by a mode of (2);
in this step, high purity N 2 The duration of the washing of the inoculum solution is 15-20min.
b-3) coupling the film of the filler; pumping the inoculum solution obtained in the step b-2) into the reactor through a water inlet by utilizing a peristaltic pump, ending pumping after filling the whole inner cavity of the reactor with the inoculum solution, and standing for 24 hours; and then connecting the water outlet of the reactor with the inlet of a peristaltic pump, and circularly flowing the inoculum solution in the reactor for 3-5 days by using the peristaltic pump to ensure that the biological film is uniformly enriched on the surface of the coupling filler, thereby realizing successful film hanging on the surface of the coupling filler.
c) Recycling the wastewater; firstly, introducing high-purity N into a reactor 2 Let N 2 Filling the whole inner cavity of the reactor to provide a proper anoxic environment for denitrifying bacteria so as to ensure the growth of microorganisms; then pumping the wastewater to be treated in the wastewater pool from a water inlet at the bottom of the reactor by utilizing a water inlet pump to realize autotrophic denitrification treatment of the wastewater, and discharging the treated water body through a water outlet;
in the process that the wastewater slowly rises from the bottom in the reactor, the wastewater fully contacts with a biological film on the surface of a coupling filler in the reactor, denitrifying bacteria utilize acidity generated in the sulfur autotrophic denitrification process to dissolve pyrite to generate negative-valence sulfur ions, electrons are easily lost due to the negative-valence sulfur ions, so that the rate of providing electrons by the coupling filler is improved, a series of sulfides and polysulfides are formed to be more easily utilized by autotrophic denitrifying microorganisms, and the denitrification rate is further improved; the acidity generated in the sulfur autotrophic denitrification process causes the limestone to dissolve and produce CO 3 2- 、HCO 3 - 、Ca 2+ ，CO 3 2- And HCO 3 - Providing inorganic carbon source for the growth of autotrophic denitrifying bacteria, and being more beneficial to the growth of autotrophic denitrifying microorganisms; meanwhile, acidity generated in the sulfur autotrophic denitrification process accelerates dissolution of limestone and pyrite, and releases more Ca 2+ And Fe (Fe) 2+ With SO generated in sulfur autotrophic denitrification process 4 2- And calcium sulfate and ferrous sulfate precipitate are generated by combining, so that the purpose of reducing the sulfate of effluent is achieved.
In this step, the hydraulic retention time HRT of the wastewater in the reactor is 12-48h.
In example 1, sulfur, pyrite and limestone are uniformly mixed according to the volume ratio of 1:1:1, and three kinds of fillers are filledThe average grain diameter of the material is 2 mm, the coupling filler is filled into the bioreactor 1, the membrane hanging period of the bioreactor is 5 days, the water inlet pump 8 pumps the waste water in the waste water tank 7 into the reactor 1, and the water inlet NO 3 - An average N concentration of 25.23 mg/L, a Hydraulic Retention Time (HRT) of 48h and a water inlet and outlet NO after 40 days of operation 3 - -N and SO 4 2- The concentration profile is shown in FIG. 1, and it can be seen that NO 3 - The average removal rate of N is 98.74 percent, and SO in the effluent is obtained 4 2- The concentration is 207.06mg/L, which is lower than SO generated in the sulfur autotrophic denitrification process 4 2- Concentration of the water meets the national secondary drinking water Standard (SO) established by the United states Environmental Protection Agency (EPA) 4 2- Concentration below 250 mg/L).
Example 2 in this example, the volume ratio and average particle diameter of sulfur, pyrite and limestone in the coupling filler 2 were the same as those in example 1, the coupling filler 2 was charged into the bioreactor 1, after film formation was successful, the water inlet pump 8 pumped the wastewater in the wastewater tank 7 into the reactor 1, and the water inlet NO 3 - An average N concentration of 23.18 mg/L, a Hydraulic Retention Time (HRT) of 24. 24h and a water inlet and outlet NO after 20d of operation 3 - -N and SO 4 2- The concentration change curve is shown in FIG. 2, NO 3 - The average removal rate of N is 97.10 percent, and SO in the effluent is 4 2- The concentration is 152.84mg/L, which is lower than SO generated in the sulfur autotrophic denitrification process 4 2- Concentration of the water meets the national secondary drinking water Standard (SO) established by the United states Environmental Protection Agency (EPA) 4 2- Concentration below 250 mg/L).
Example 3 in this example, the volume ratio and average particle diameter of sulfur, pyrite and limestone in the coupling filler 2 were the same as those in example 1, the coupling filler 2 was charged into the bioreactor 1, after film formation was successful, the water inlet pump 8 pumped the wastewater in the wastewater tank 7 into the reactor 1, and the water inlet NO 3 - An average N concentration of 25.25 mg/L Hydraulic Retention Time (HRT) of 12h, after 20d of operation, NO 3 - -N and SO 4 2- The concentration change curve is shown in FIG. 3, NO 3 - The average removal rate of N is 89.4 percent, and SO in the effluent is realized 4 2- The concentration is 129.36mg/L, which is lower than SO generated in the sulfur autotrophic denitrification process 4 2- Concentration of the water meets the national secondary drinking water Standard (SO) established by the United states Environmental Protection Agency (EPA) 4 2- Concentration below 250 mg/L).
By comparing the water inlet and outlet NO in example 1, example 2 and example 3 3 - -N and SO 4 2- The concentration profile makes it clear that the longer the Hydraulic Retention Time (HRT) of the wastewater in the reactor 1, the NO 3 - The higher the removal of N, but with an increase in the Hydraulic Retention Time (HRT), the SO in the effluent 4 2- The concentration is also increased correspondingly, so that a reasonable Hydraulic Retention Time (HRT) should be specified in the treatment of the wastewater to ensure NO in the wastewater 3 - The removal rate of the-N meets the requirement, and the SO in the effluent is simultaneously carried out 4 2- The concentration also meets the specifications.
Compared with other fillers, the coupling filler autotrophic denitrification bioreactor greatly shortens the film-forming time, and the film-forming success period only needs about 5 days. In addition, pyrite dissolved negative-valence sulfide ions and Fe 2+ The coexistence improves the electron transfer rate, accelerates denitrification and improves the denitrification rate. The acidity generated based on sulfur autotrophic denitrification accelerates the dissolution of limestone and pyrite, generates more calcium ions and iron ions, neutralizes sulfate in the system, greatly reduces the water outlet concentration of the sulfate, and ensures that the water outlet sulfate concentration accords with the national secondary drinking water Standard (SO) formulated by the United states Environmental Protection Agency (EPA) 4 2- Concentrations below 250 mg/L) and all below the theoretical value for sulfate production by sulfur autotrophic denitrification. The method solves the problems of low autotrophic denitrification rate of pyrite and difficult realization of long-term denitrification. In addition, pyrite is used as a mineral waste, and has wide sources and low price.
Claims (8)
1. A coupling filler autotrophic denitrification bioreactor based on pyrite comprises a reactor (1) and a coupling filler (2) filled in an internal cavity of the reactor, wherein a water inlet (3) and a water outlet (4) which are communicated with the internal cavity of the reactor are respectively arranged at the bottom and the upper part of the reactor, wastewater to be treated enters through the water inlet, and treated wastewater is discharged through the water outlet; the method is characterized in that: the coupling filler (2) is formed by mixing sulfur, pyrite and limestone.
2. The sulfur pyrite coupled filler-based autotrophic denitrification bioreactor according to claim 1, wherein: the volume ratio of the sulfur, pyrite and limestone is (1-3).
3. The sulfur pyrite coupled filler-based autotrophic denitrification bioreactor according to claim 2, wherein: the average particle size of the sulfur, pyrite and limestone is 1-3mm.
4. Use of a sulfur pyrite coupled filler based autotrophic denitrification bioreactor according to claim 3 for treating nitrate wastewater, characterized by the following steps:
a) Preparing and loading coupling filler; firstly, respectively crushing sulfur, pyrite and limestone by using a crusher, and screening out particles with the particle size of 1-3mm for later use; uniformly mixing particles of sulfur, pyrite and limestone according to a constrained volume ratio to obtain coupling filler, and loading the coupling filler into a reactor;
b) Inoculating and film-forming autotrophic denitrifying bacteria; firstly, enrichment of autotrophic denitrifying bacteria strains is carried out, the enriched strains are added into a liquid culture medium and then pumped into a reactor, so that inoculation of the autotrophic denitrifying bacteria is realized, and the inoculated strains and the culture medium are kept stand for 24 hours in the reactor; after standing, circularly running for 3-5 days to ensure that the biological film is uniformly enriched on the surface of the coupling filler and the biological film is successfully coated;
c) Recycling the wastewater; firstly, introducing high-purity N into a reactor 2 Let N 2 Filling the whole inner cavity of the reactor to provide a proper anoxic environment for denitrifying bacteria so as to ensure the growth of microorganisms; thenPumping the wastewater to be treated in the wastewater pool from a water inlet at the bottom of the reactor by utilizing a water inlet pump to realize autotrophic denitrification treatment of the wastewater, and discharging the treated water body through a water outlet;
in the process that the wastewater slowly rises from the bottom in the reactor, the wastewater fully contacts with a biological film on the surface of a coupling filler in the reactor, denitrifying bacteria utilize acidity generated in the sulfur autotrophic denitrification process to dissolve pyrite to generate negative-valence sulfur ions, electrons are easily lost due to the negative-valence sulfur ions, so that the rate of providing electrons by the coupling filler is improved, a series of sulfides and polysulfides are formed to be more easily utilized by autotrophic denitrifying microorganisms, and the denitrification rate is further improved; the acidity generated in the sulfur autotrophic denitrification process causes the limestone to dissolve and produce CO 3 2- 、HCO 3 - 、Ca 2+ ，CO 3 2- And HCO 3 - Providing inorganic carbon source for the growth of autotrophic denitrifying bacteria, and being more beneficial to the growth of autotrophic denitrifying microorganisms; meanwhile, acidity generated in the sulfur autotrophic denitrification process accelerates dissolution of limestone and pyrite, and releases more Ca 2+ And Fe (Fe) 2+ With SO generated in sulfur autotrophic denitrification process 4 2- And calcium sulfate and ferrous sulfate precipitate are generated by combining, so that the purpose of reducing the sulfate of effluent is achieved.
5. Use of a sulfur pyrite coupled filler based autotrophic denitrification bioreactor according to claim 4 for treating nitrate wastewater, characterized in that: in the step a), after the pyrite is crushed by a crusher and pyrite particles with the particle size of 1-3mm are screened out, the pyrite particles are pickled by HCl with the concentration of 10 percent, so that the influence of oxides on the surfaces of the pyrite particles on the performance of coupling fillers is avoided.
6. Use of a sulfur pyrite coupled filler based autotrophic denitrification bioreactor according to claim 4 for treating nitrate wastewater, wherein in step b), inoculation and film formation of autotrophic denitrification bacteria are realized by the following steps:
b-1) enrichment of the inoculum; taking anaerobic sludge of a sewage treatment station as seed sludge, inoculating 80mL of anaerobic sludge per liter of liquid culture medium, mixing the culture medium with the anaerobic sludge, and culturing at 28+/-2 ℃; in the culture process, the volume of the generated gas is measured by a water and gas drainage method, and if the volume of the generated gas of a mixture of 1L of culture medium and 80mL exceeds 240.4 mL, the enrichment of autotrophic denitrifying microorganisms is successful;
b-2) inoculating autotrophic denitrifying bacteria; firstly, centrifuging the enriched inoculum obtained in the step b-1) by using a centrifuge, pouring out supernatant after centrifugation, and attaching the inoculum on the wall of a centrifuge tube; the inoculant on the wall of the centrifuge tube is washed for a plurality of times by using sterilized normal saline, so as to eliminate the interference of other ions; then, according to the volume ratio of the liquid culture medium to the inoculum being (85-90): 10-15), the liquid culture medium is mixed with the inoculum to obtain an inoculum solution, and the high-purity N is introduced into the inoculum solution 2 Is washed by a mode of (2);
b-3) coupling the film of the filler; pumping the inoculum solution obtained in the step b-2) into the reactor through a water inlet by utilizing a peristaltic pump, ending pumping after filling the whole inner cavity of the reactor with the inoculum solution, and standing for 24 hours; and then connecting the water outlet of the reactor with the inlet of a peristaltic pump, and circularly flowing the inoculum solution in the reactor for 3-5 days by using the peristaltic pump to ensure that the biological film is uniformly enriched on the surface of the coupling filler, thereby realizing successful film hanging on the surface of the coupling filler.
7. Use of autotrophic denitrification bioreactor based on pyrite coupled filler according to claim 4 for treating nitrate sewage, characterized in that in step b-2), high purity N 2 The duration of the washing of the inoculum solution is 15-20min.
8. Use of a sulfur pyrite coupled filler based autotrophic denitrification bioreactor according to claim 4 for treating nitrate wastewater, wherein in step c) the hydraulic retention time HRT of the wastewater in the reactor is 12-48h.
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