CN114368834A - Method for treating nitrate wastewater - Google Patents
Method for treating nitrate wastewater Download PDFInfo
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- CN114368834A CN114368834A CN202210036483.5A CN202210036483A CN114368834A CN 114368834 A CN114368834 A CN 114368834A CN 202210036483 A CN202210036483 A CN 202210036483A CN 114368834 A CN114368834 A CN 114368834A
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- 229910002651 NO3 Inorganic materials 0.000 title claims abstract description 120
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000002351 wastewater Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 50
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 68
- 241000894006 Bacteria Species 0.000 claims abstract description 57
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 34
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- 238000003672 processing method Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 241000863430 Shewanella Species 0.000 claims description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 241000607528 Aeromonas hydrophila Species 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- 230000005526 G1 to G0 transition Effects 0.000 claims description 3
- 238000012258 culturing Methods 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Inorganic materials [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 3
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- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 238000004064 recycling Methods 0.000 abstract description 10
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 7
- 230000008878 coupling Effects 0.000 abstract description 7
- 238000010168 coupling process Methods 0.000 abstract description 7
- 238000005859 coupling reaction Methods 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 6
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 abstract description 5
- 238000013459 approach Methods 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 description 26
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- 210000002966 serum Anatomy 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 12
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 11
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- 238000009713 electroplating Methods 0.000 description 6
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- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical group OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
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- 230000009286 beneficial effect Effects 0.000 description 4
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- 238000004255 ion exchange chromatography Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 4
- 241001223867 Shewanella oneidensis Species 0.000 description 3
- 239000006172 buffering agent Substances 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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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
- C02F3/28—Anaerobic digestion processes
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The invention belongs to the field of water treatment, and particularly relates to a method for treating nitrate wastewater. The processing method provided by the invention comprises the following processes: under anaerobic conditions, nitrate in the wastewater is converted into ammonia by utilizing zero-valent iron and nitrate reducing bacteria with electric activity. The treatment method provided by the invention utilizes a nitrate reducing bacteria-zero-valent iron coupling system with electric activity to treat nitrate wastewater, and nitrate reducing bacteria and zero-valent iron (ZVI) are directly contacted in the treatment process, so that multiple synergistic effects between the ZVI and nitrate reducing bacteria cells in the aspects of electron transfer, pollutant conversion and the like are exerted. The treatment method can avoid the dependence of nitrate reducing bacteria on an organic carbon source, realizes the high-efficiency and directional conversion of nitrate in the wastewater to produce ammonia, provides a new approach for the economy and high-efficiency synthesis of ammonia nitrogen and the treatment and recycling of wastewater, and particularly provides an effective solution for the denitrification and recycling of wastewater with a low carbon-nitrogen ratio.
Description
Technical Field
The invention belongs to the field of water treatment, and particularly relates to a method for treating nitrate wastewater.
Background
Ammonia is an important industrial raw material and fertilizer. At present, the industrial synthesis of ammonia mainly adopts a haber process: the hydrogen and nitrogen are directly synthesized into ammonia at high temperature and high pressure. However, this technique not only consumes a high amount of energy, but also generates a large amount of greenhouse gases such as carbon dioxide.
The method for producing ammonia by using nitrate in wastewater as a raw material through reduction and conversion is considered to be an alternative way with great development potential, not only can obviously reduce the energy consumption of ammonia nitrogen production, but also can effectively reduce the nitrogen emission of wastewater. The electrochemical technology can realize the high-efficiency reduction of nitrate to produce ammonia, but an expensive catalyst is often used, and the deactivation is easy to occur in the practical application process, so that the activity is reduced. Compared with the chemical synthesis method, the biological method has the obvious advantages of low cost, environmental friendliness, self-regeneration and the like. In particular, dissimilatory nitrate-reducing bacteria can utilize organic pollutants in wastewater as substrates to reduce nitrate to ammonia under mild environmental conditions. However, most nitrate-containing wastewater (including aerobic biological treatment stage effluent) tends to have a low carbon-to-nitrogen ratio and therefore cannot provide sufficient driving force resulting in a slow nitrate reduction rate.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for treating nitrate wastewater, which can avoid the dependence of nitrate reducing bacteria on organic carbon sources, realize the efficient and directional conversion of nitrate in wastewater to produce ammonia, provide a new approach for the economic and efficient synthesis of ammonia nitrogen and the treatment and recycling of wastewater, and particularly provide an effective solution for the denitrification and recycling of wastewater with a low carbon-nitrogen ratio.
The invention provides a method for treating nitrate wastewater, which comprises the following steps:
under anaerobic conditions, nitrate in the wastewater is converted into ammonia by utilizing zero-valent iron and nitrate reducing bacteria with electric activity.
Preferably, the nitrate reducing bacteria having electrical activity are dissimilatory nitrate reducing bacteria.
Preferably, the dissimilatory nitrate-reducing bacteria are Shewanella and/or Aeromonas hydrophila.
Preferably, the zero-valent iron is micron-sized zero-valent iron.
Preferably, the dosage ratio of the zero-valent iron to the wastewater is (0.1-0.5) g:50 mL.
Preferably, the nitrate-reducing bacteria have an initial OD in the wastewater600The concentration is 0.1-0.3.
Preferably, the temperature of the conversion is 25-35 ℃.
Preferably, the specific processing steps include:
mixing the wastewater, zero-valent iron and nitrate reducing bacteria with electric activity, and then culturing under anaerobic conditions.
Preferably, the nitrate-reducing bacteria participating in the mixture are bacteria in a stationary phase.
Preferably, the wastewater also contains a buffering agent, NaOH, KCl and NaH2PO4And NaCl.
Compared with the prior art, the invention provides a method for treating nitrate wastewater. The processing method provided by the invention comprises the following processes: under anaerobic conditions, nitrate in the wastewater is converted into ammonia by utilizing zero-valent iron and nitrate reducing bacteria with electric activity. The treatment method provided by the invention utilizes a nitrate reducing bacteria-zero-valent iron coupling system with electric activity to treat nitrate wastewater, the nitrate reducing bacteria and zero-valent iron (ZVI) are directly contacted in the treatment process, and multiple synergistic effects between the ZVI and nitrate reducing bacteria cells in the aspects of electron transfer, pollutant conversion and the like are exerted: 1) ZVI is used as an extracellular electron donor to input electrons into cells of the nitrate reducing bacteria through a direct electron transfer way for nitrate reduction, so that the problem of insufficient electron donor in the denitrification process of the nitrate reducing bacteria is solved; 2) intermediate product nitrite generated by the nitrate reducing bacteria for reducing nitrate is released to the outside of cells and is further efficiently and selectively converted into ammonia by ZVI, so that the problem that the nitrite accumulation inhibits the activity of the nitrate reducing bacteria is solved; 3) in the wastewater treatment process, the nitrate reducing bacteria can grow on the surface of ZVI and form a biological film to wrap the surface of ZVI, so that the passivation and the side reaction consumption of ZVI are effectively slowed down, and the utilization rate of ZVI for promoting the reduction of nitrate is improved. The treatment method provided by the invention can avoid the dependence of nitrate reducing bacteria on an organic carbon source, realizes the high-efficiency and directional conversion of nitrate in the wastewater to produce ammonia, provides a new approach for the economy and high-efficiency synthesis of ammonia nitrogen and the treatment and recycling of wastewater, and particularly provides an effective solution for the denitrification and recycling of wastewater with a low carbon-nitrogen ratio.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a graph of the catalytic nitrate reduction curves of the experimental group and the control group provided in example 1 of the present invention;
FIG. 2 is a dynamic process diagram of Shewanella and ZVI concerted catalytic nitrate reduction conversion provided in example 1 of the present invention;
FIG. 3 is an SEM photograph of ZVI after wastewater is treated with Shewanella and ZVI in a synergistic manner as provided in example 1 of the present invention;
FIG. 4 is a graph of the catalytic nitrate reduction curves of the experimental group and the control group provided in example 2 of the present invention;
FIG. 5 is a graph of the catalytic nitrate reduction curves of the experimental group and the control group provided in example 3 of the present invention;
FIG. 6 is a diagram showing the dynamic process of the concerted catalytic reduction of nitrate by Aeromonas hydrophila and ZVI according to example 3 of the present invention;
FIG. 7 is a graph showing the effect of Shewanella-ZVI coupling system in removing nitrate from the actual wastewater of electroplating plants in example 4 of the present invention;
FIG. 8 is a graph showing the effect of ammonia generation in the treatment of the actual wastewater from the electroplating plant by the Shewanella-ZVI coupling system according to example 4 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for treating nitrate wastewater, which comprises the following steps:
under anaerobic conditions, nitrate in the wastewater is converted into ammonia by utilizing zero-valent iron and nitrate reducing bacteria with electric activity.
In the treatment method provided by the invention, the nitrate content of the wastewater is preferably 0.1-100 mmol/L, and specifically can be 0.1mmol/L, 0.5mmol/L, 1mmol/L, 1.2mmol/L, 5mmol/L, 10mmol/L, 15mmol/L, 20mmol/L, 30mmol/L, 40mmol/L, 50mmol/L, 57mmol/L, 60mmol/L, 70mmol/L, 80mmol/L, 90mmol/L or 100 mmol/L; the wastewater preferably also contains components suitable for bacterial growth and metabolism, including but not limited to buffer, NaOH, KCl, NaH2PO4And NaCl; the buffering agent is preferably HEPES buffering salt, and the content of the buffering agent in the wastewater is preferably 5-20 g/L, and specifically can be 11.91 g/L; the content of NaOH in the wastewater is preferably 0.1-0.5 g/L, and specifically can be 0.3 g/L; the content of the KCl in the wastewater is preferably 0.05-0.2 g/L, and specifically can be 0.1 g/L; the NaH2PO4The content of the organic silicon compound in the wastewater is preferably 0.4-0.8 g/L, and specifically can be 0.67 g/L; the content of the NaCl in the wastewater is preferably 4-8 g/L, and specifically can be 5.85 g/L; the wastewater preferably does not contain an organic carbon source.
In the treatment method provided by the invention, the zero-valent iron (ZVI) is preferably micron-sized zero-valent iron; the average particle size of the micron-sized zero-valent iron is preferably 5-50 μm, and specifically can be 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50 μm; the dosage ratio of the zero-valent iron to the wastewater is preferably (0.1-0.5) g:50mL, specifically 0.1 g/50 mL, 0.12 g/50 mL, 0.15 g/50 mL, 0.17 g/50 mL, 0.2 g/50 mL, 0.23 g/50 mL, 0.25 g/50 mL, 0.27 g/50 mL, 0.3 g/50 mL, 0.32 g/50 mL, 0.35 g/50 mL, 0.37 g/50 mL, 0.4 g/50 mL, 0.42 g/50 mL, 0.45 g/50 mL, 0.47 g/50 mL, or 0.5 g/50 mL.
In the treatment method provided by the invention, the nitrate with the electrical activity is reducedThe bacteria are preferably dissimilatory nitrate reducing bacteria; the dissimilatory nitrate-reducing bacteria are preferably Shewanella oneidensis MR-1 and/or Aeromonas hydrophila (Aeromonas hydrophylla); initial OD of the nitrate-reducing bacteria in wastewater600The concentration is preferably 0.1 to 0.3, and specifically may be 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29 or 0.3.
In the treatment method provided by the invention, the temperature for converting the nitrate in the wastewater into ammonia by utilizing the zero-valent iron and the nitrate reducing bacteria with electric activity is preferably 25-35 ℃, and specifically can be 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃ or 35 ℃; the conversion time is preferably 6-48 h, and specifically can be 6h, 9h, 12h, 15h, 18h, 21h, 24h, 27h, 30h, 33h, 36h, 39h, 42h, 45h or 48 h.
In the processing method provided by the present invention, the specific processing steps preferably include: mixing the wastewater, zero-valent iron and nitrate reducing bacteria with electric activity, and then culturing under an anaerobic condition; in the culture process, zero-valent iron and nitrate reducing bacteria are used for synergistically catalyzing nitrate in the wastewater to be reduced and converted to produce ammonia. Wherein, the wastewater is preferably aerated and deoxidized before being mixed so as to maintain anaerobic atmosphere; the nitrate-reducing bacteria participating in the mixing are preferably bacteria in a stationary phase to ensure a stable nitrate-reducing effect.
The treatment method provided by the invention utilizes a nitrate reducing bacteria-zero-valent iron coupling system with electric activity to treat nitrate wastewater, the nitrate reducing bacteria and zero-valent iron (ZVI) are directly contacted in the treatment process, and multiple synergistic effects between the ZVI and nitrate reducing bacteria cells in the aspects of electron transfer, pollutant conversion and the like are exerted: 1) ZVI is used as an extracellular electron donor to input electrons into cells of the nitrate reducing bacteria through a direct electron transfer way for nitrate reduction, so that the problem of insufficient electron donor in the denitrification process of the nitrate reducing bacteria is solved; 2) intermediate product nitrite generated by the nitrate reducing bacteria for reducing nitrate is released to the outside of cells and is further efficiently and selectively converted into ammonia by ZVI, so that the problem that the nitrite accumulation inhibits the activity of the nitrate reducing bacteria is solved; 3) in the wastewater treatment process, the nitrate reducing bacteria can grow on the surface of ZVI and form a biological film to wrap the surface of ZVI, so that the passivation and the side reaction consumption of ZVI are effectively slowed down, and the utilization rate of ZVI for promoting the reduction of nitrate is improved. The treatment method provided by the invention can avoid the dependence of nitrate reducing bacteria on an organic carbon source, realizes the high-efficiency and directional conversion of nitrate in the wastewater to produce ammonia, provides a new approach for the economy and high-efficiency synthesis of ammonia nitrogen and the treatment and recycling of wastewater, and particularly provides an effective solution for the denitrification and recycling of wastewater with a low carbon-nitrogen ratio.
The treatment method provided by the invention can avoid the dependence of nitrate reducing bacteria on an organic carbon source, realizes the high-efficiency and directional conversion of nitrate in the wastewater to produce ammonia, provides a new approach for the economy and high-efficiency synthesis of ammonia nitrogen and the treatment and recycling of wastewater, and particularly provides an effective solution for the denitrification and recycling of wastewater with a low carbon-nitrogen ratio. More specifically, the processing method provided by the invention has the following advantages:
1) nitrate is removed in a nitrogen form by a traditional denitrification method, and the product of reducing nitrate by the treatment method provided by the invention is ammonia which can be recycled subsequently; therefore, the process is very suitable for treating high-concentration nitrate wastewater so as to be beneficial to the subsequent recovery of ammonia nitrogen;
2) the nitrate reducing bacteria utilize ZVI as an efficient electron donor, so that the problems of cost increase, secondary pollution and the like caused by adding an organic carbon source in practical application are avoided;
3) the nitrate reducing bacteria and the ZVI are coupled, so that compared with single biological reduction nitrate and single ZVI reduction nitrate, the nitrate reducing bacteria have higher removal rate, can also improve the selectivity of nitrate reduction and ammonia production, and is beneficial to resource utilization of high-concentration nitrate wastewater.
For the sake of clarity, the following examples are given in detail.
Example 1
To a 120mL serum bottle was added 50mL autoclaved without addition of an organic carbon sourceShewanella oneidensis MR-1 mineral salt culture medium (containing 1mM nitrate) mainly contains 11.91g/L HEPES buffer salt, 0.3g/L NaOH, 0.1g/LKCl and 0.67g/L NaH2PO4·2H2O,5.85g/L NaCl; exposing the serum bottle filled with the culture medium in a super-clean workbench for 20 minutes N2Then, 0.25g of micron-sized ZVI (the average particle size is about 20 μm) is weighed and added immediately, a rubber plug is covered and compacted by an aluminum cap, and the serum bottle is ultrasonically dispersed in an ultrasonic machine for 1 minute so that the ZVI is uniformly dispersed in the solution; transferring the serum bottle into an anaerobic glove box, adding Shewanella oneidensis MR-1 (Shewanella oneidensis MR-1) in stable growth phase after cleaning with mineral salt culture medium, and collecting OD600The concentration is controlled to be 0.2; then transferring the mixture to a constant temperature incubator at 30 ℃ for static culture, so that ZVI is directly contacted with Shewanella; taking out the liquid sample at regular time by using an injector at regular time, centrifuging and passing through a membrane, detecting nitrate by using ion chromatography, and detecting nitrite and ammonia by using an enzyme-linked immunosorbent assay.
Referring to the above experimental process, control groups to which micron-sized ZVI and inactivated shiva bacteria were added, to which micron-sized ZVI alone was added, and to which shiva bacteria alone was added were set.
The experimental results are shown in fig. 1 to 3, fig. 1 is a catalytic nitrate reduction curve chart of an experimental group and a control group provided in example 1 of the present invention, fig. 2 is a dynamic process chart of catalytic nitrate reduction and conversion by cooperation of shewanella bacteria and ZVI provided in example 1 of the present invention, and fig. 3 is an SEM image of ZVI after wastewater is treated by cooperation of shewanella bacteria and ZVI provided in example 1 of the present invention.
As can be seen from FIG. 1, the rate of the cooperative catalysis of nitrate reduction by ZVI and Shewanella is obviously higher than that of the control group of Shewanella and ZVI alone, which indicates that ZVI can be used as an electron donor of Shewanella and a cooperative catalysis reaction occurs between the two to enhance the rate of nitrate reduction conversion.
As can be seen from FIG. 2, during the concerted catalytic nitrate reduction of ZVI with Shewanella, the accumulation of nitrite is first observed and then gradually consumed until the reaction is completed for 24 hours with almost complete conversion of nitrate and nitrite to ammonia.
As can be seen from FIG. 3, a dense Shewanella biofilm was formed on the ZVI surface. The close contact is not only beneficial to the direct electron transfer between ZVI and Shewanella, but also beneficial to protecting ZVI, reducing the inactivation of ZVI and generating a large amount of iron mud.
Example 2
A120 mL serum bottle was charged with 50mL autoclaved mineral salt medium (containing 57mM nitrate) of Shewanella oneidensis MR-1 (Shewanella oneidensis) without organic carbon source, the mineral salt medium having the main components of 11.91g/L HEPES buffer salt, 0.3g/L NaOH, 0.1g/L KCl, 0.67g/L NaH2PO4·2H2O,5.85g/L NaCl; exposing the serum bottle filled with the culture medium in a super-clean workbench for 20 minutes N2Thereafter, 0.25g of micron-sized ZVI (average particle diameter about 20 μm) weighed in weight was immediately added, a rubber stopper was covered and compacted with an aluminum cap, the serum bottle was ultrasonically dispersed in an ultrasonic machine for 1 minute to uniformly disperse the ZVI in the solution, the serum bottle was transferred to an anaerobic glove box, Shewanella oneidensis (MR-1) which had been cleaned with a mineral salt medium and had been in a stationary growth phase was added to the anaerobic glove box, and OD was then introduced600The concentration is controlled to be 0.2; then transferring the mixture to a constant temperature incubator at 30 ℃ for static culture, so that ZVI is directly contacted with Shewanella; taking out the liquid sample at regular time by using an injector at regular time, centrifuging and passing through a membrane, detecting nitrate by using ion chromatography, and detecting nitrite and ammonia by using an enzyme-linked immunosorbent assay.
Referring to the above experimental procedure, a control group to which only micron-sized ZVI and only shiva bacteria were added was set.
The experimental results are shown in fig. 4, and fig. 4 is a graph showing the catalytic nitrate reduction curves of the experimental group and the control group provided in example 2 of the present invention. As can be seen from FIG. 4, ZVI and Shewanella may also be used to synergistically catalyze and accelerate the rate of nitrate reduction in high nitrate-containing wastewater.
Example 3
A120 mL serum bottle was charged with 50mL autoclaved mineral salt medium (containing 1mM nitrate) of Aeromonas hydrophila (Aeromonas hydrophylla) without added organic carbon source, mineralThe main components of the salt culture medium are 11.91g/L HEPES buffer salt, 0.3g/L NaOH, 0.1g/LKCl and 0.67g/L NaH2PO4·2H2O,5.85g/L NaCl; exposing the serum bottle filled with the culture medium in a super-clean workbench for 20 minutes N2Then, 0.25g of ZVI (average particle diameter about 20 μm) weighed in mass was immediately added, a rubber stopper was added and immediately compacted with an aluminum cap, the serum bottle was ultrasonically dispersed in an ultrasonic machine for 1 minute to uniformly disperse ZVI in the solution, the serum bottle was transferred to an anaerobic glove box, Aeromonas hydrophila in a stationary growth phase after cleaning with a mineral salt medium was added to the anaerobic glove box, and OD was added600The concentration is controlled to be 0.2; then transferring the mixture to a constant temperature incubator at 30 ℃ for standing culture, so that the ZVI and the aeromonas hydrophila generate a concerted catalytic reaction; taking out the liquid sample at regular time by using an injector at regular time, centrifuging and passing through a membrane, detecting nitrate by using ion chromatography, and detecting nitrite and ammonia by using an enzyme-linked immunosorbent assay.
Referring to the above experimental process, a control group to which micron-sized ZVI and inactivated aeromonas hydrophila were added, to which micron-sized ZVI alone was added, and to which aeromonas hydrophila alone was added was set.
The experimental results are shown in fig. 5 to 6, fig. 5 is a catalytic nitrate reduction curve chart of the experimental group and the control group provided in the embodiment 3 of the present invention, and fig. 6 is a dynamic process chart of the cooperative catalytic nitrate reduction conversion of aeromonas hydrophila and ZVI provided in the embodiment 3 of the present invention. As can be seen from FIG. 5, the rate of the concerted catalytic nitrate reduction of ZVI with Aeromonas hydrophila was significantly higher than that of ZVI alone and that of the bacterial control group alone, demonstrating the concerted catalytic reaction. It can be seen from FIG. 6 that a small accumulation of nitrite occurs during the reaction for up to 24 hours, but is essentially converted to ammonia in the end. The experimental results show that the ZVI-dissimilatory nitrate reducing bacteria synergetic catalytic system can not only accelerate the rate of nitrate reduction, but also realize 100% of conversion rate from nitrate to ammonia.
Example 4
Diluting the collected electroplating plant actual wastewater (main components are shown in Table 1) by 6 times with Shewash mineral salt culture medium containing HEPES buffer salt 11.91g/L, NaOH 0.3g/L and NaOH 0g/L as main components.1g/L KCl，0.67g/L NaH2PO4·2H2O,5.85g/L NaCl; 50mL of diluted wastewater was added to a 120mL serum bottle and exposed to N in a clean bench for 20 minutes2Thereafter, 0.25g of weighed ZVI (average particle diameter about 20 μm) was immediately added, a rubber stopper was added and immediately compacted with an aluminum cap, the serum bottle was ultrasonically dispersed in an ultrasonic machine for 1 minute so that ZVI was uniformly dispersed in the solution, the serum bottle was transferred to an anaerobic glove box, Shewanella oneidensis (MR-1) which was in a stationary growth phase after being washed with a mineral salt medium was added to the anaerobic glove box, OD was then added600The concentration is controlled to be 0.2; then transferring the mixture to a constant temperature incubator at 30 ℃ for standing culture, so that ZVI and Shewanella are subjected to a concerted catalytic reaction; in the reaction process, a liquid sample is taken out at regular time by an injector at regular time and then is centrifuged and filtered, nitrate is detected by ion chromatography, and nitrite and ammonia are detected by an enzyme-linked immunosorbent assay (ELISA); in the reaction process, the nitrate mother liquor is added into the serum bottle every 12 hours, so that the nitrate concentration of the solution is recovered to 1mM, and 1 test cycle is completed after 1 nitrate mother liquor is added.
TABLE 1 main Components and concentrations of electroplating wastewater
The experimental results are shown in fig. 7-8, fig. 7 is a graph of the nitrate removal effect of the shewanella-ZVI coupling system provided in embodiment 4 of the present invention on the actual wastewater of the electroplating plant, and fig. 8 is a graph of the ammonia generation effect of the shewanella-ZVI coupling system provided in embodiment 4 of the present invention on the actual wastewater of the electroplating plant. As can be seen from fig. 7, ZVI synergistically catalyzes the rapid reduction of nitrate to ammonia with shewanella bacteria, and the removal rate of nitrate reached 100% in five test cycles. As can be seen from fig. 8, ammonia gradually accumulated during each cycle of the experiment, and eventually the conversion of nitrate to ammonia reached more than 80%. The above experimental results demonstrate that the ZVI and Shewanella concerted catalytic reaction can be used for treating actual nitrate wastewater.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for treating nitrate wastewater comprises the following steps:
under anaerobic conditions, nitrate in the wastewater is converted into ammonia by utilizing zero-valent iron and nitrate reducing bacteria with electric activity.
2. The process of claim 1, wherein the nitrate-reducing bacteria having electrical activity are dissimilatory nitrate-reducing bacteria.
3. The method according to claim 2, wherein the dissimilatory nitrate-reducing bacteria are Shewanella and/or Aeromonas hydrophila.
4. The process of claim 1, wherein the zero-valent iron is micron-sized zero-valent iron.
5. The treatment method according to claim 1, wherein the dosage ratio of the zero-valent iron to the wastewater is (0.1-0.5) g:50 mL.
6. The treatment method of claim 1, wherein the nitrate-reducing bacteria have an initial OD in the wastewater600The concentration is 0.1-0.3.
7. The process according to claim 1, characterized in that the temperature of the transformation is between 25 and 35 ℃.
8. The processing method according to claim 1, characterized in that the specific processing steps comprise:
mixing the wastewater, zero-valent iron and nitrate reducing bacteria with electric activity, and then culturing under anaerobic conditions.
9. The method according to claim 8, wherein the nitrate-reducing bacteria participating in the mixing are bacteria in a stationary phase.
10. The method according to any one of claims 1 to 9, wherein the wastewater further contains a buffer, NaOH, KCl, NaH2PO4And NaCl.
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| CN115947451A (en) * | 2022-12-30 | 2023-04-11 | 山东大学 | Method for reinforcing nitrate dissimilation reduction to ammonium process by utilizing nanoscale zero-valent iron coupled low-frequency infrared electromagnetic waves |
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