CN1689989A - Denitrogenation technique for waste water containing high concentration ammonia nitrogen - Google Patents
Denitrogenation technique for waste water containing high concentration ammonia nitrogen Download PDFInfo
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Abstract
The high concentration ammonia nitrogen waste water denitrogenating process is completed in the system comprising three units of nitrosating biomembrane reactor, anaerobic ammoxidation biomembrane reactor and soil treating unit. In the nitrosating biomembrane reactor, partial NH4-N in the waste water is oxidized into NO2-N. In the anaerobic ammoxidation biomembrane reactor, nitrite is reduced with NH4-N as electron donor, NH4-N is oxidized with nitrite as electron donor, and ammonia nitrogen and nitrite nitrogen are eliminated simultaneously. In the soil treating unit, water from the anaerobic ammoxidation biomembrane reactor is further treated through the capillary penetration, microbial degradation, soil grain filtering, ion exchange, adsorption and deposition of soil to eliminate the solid grain and dissolved components and to convert organic matter and nitrogen. The present invention can eliminate nitrogen in the condition of low C/N ratio and has low power consumption.
Description
Technical Field
The invention relates to the technical field of environmental protection, and belongs to a denitrification process for treating high-concentration ammonia nitrogen wastewater by using a bioreactor.
Background
High concentration ammonia nitrogen waste water treatment degree of difficulty is high, and environmental hazard is serious, like landfill leachate, mud supernatant and some chemical industry waste water, main quality of water characteristic: the ammonia nitrogen concentration is high, and the carbon nitrogen ratio (C/N) is low. At present, the main technologies for treating nitrogen-containing wastewater at home and abroad comprise biological treatment and physicochemical treatment, although the physicochemical treatment technology has a good treatment effect, the cost is high, the energy consumption is high, secondary pollution is easy to generate, and the biological treatment technology is generally adopted due to the advantages of economy, simplicity and the like.
① under aerobic condition, ammonia nitrogen is converted into nitrate nitrogen through two reactions of nitrosation and complete nitrification, the reaction formula is as follows:
as can be seen from the above formula, 1mgNH4 +Complete nitration of N, consumption of 4.57mg of oxygen and 7.14mg of base (as CaCO)3Meter).
② under anoxic condition, denitrifying bacteria use organic substance as electron donor and nitrate Nitrogen (NO)3 --N) and nitrous Nitrogen (NO)2 --N) is reductively converted to nitrogen (N)2). The reaction formula is as follows:
as can be seen from the above formula, 1mg of NO was converted2 --N or NO3 --N is N2Respectively, require the consumption of organic substances (CODc)r)1.71mg and 2.86 mg.
The conventional biological denitrification process is shown in figure 2.
The traditional biological denitrification technology is applied to treat the wastewater with high ammonia nitrogen and low carbon nitrogen ratio (C/N), and the following main problems exist:
(1) the energy consumption is increased due to the excessively high ammonia nitrogen, and 4.57g of oxygen is required for the complete nitrification of 1g of ammonia nitrogen;
(2) the denitrification process requires sufficient organic carbon source as an electron donor to ensure denitrification rate. For wastewater with high ammonia nitrogen and low carbon nitrogen ratio (C/N), effective denitrification is difficult, so that the denitrification efficiency is low, and an external carbon source not only increases the treatment cost, but also easily causes secondary pollution;
(3) in order to neutralize the acidity generated in the nitration process, alkali is required to be added for neutralization, and the operation cost is increased.
(4) The process flow is complex, and power cost is increased by sludge backflow and mixed liquid backflow.
At present, a biological fluidized bed is mostly adopted for anaerobic ammonia oxidation reactors at home and abroad, and the biological fluidized bed has the following main defects:
(1) the operation is complicated by the need to provide a carrier stripping apparatus and to perform carrier reflux.
(2) A large reflux ratio is required for suspension fluidization of the carrier, and energy consumption is increased.
Disclosure of Invention
Aiming at the characteristics of the water quality and the water quantity of the high ammonia nitrogen wastewater and the typical problems faced by the current treatment technology, the treatment requirements cannot be met by adopting a single treatment method, and the high ammonia nitrogen wastewater can be effectively treated by optimizing and combining different methods. The invention aims to provide an economical and reasonable novel biological denitrification process for high-ammonia nitrogen wastewater, which can efficiently and stably denitrify and save energy consumption by combining a nitrosation-anaerobic ammonia oxidation technology and land treatment by utilizing the denitrification principle of anaerobic ammonia oxidation.
In order to achieve the aim, the technical scheme of the invention is to provide a denitrification process of high-concentration ammonia nitrogen wastewater, the system consists of a nitrosation biofilm reactor, an anaerobic ammonia oxidation biofilm reactor and a land treatment unit, the land treatment unitcomprises a soil infiltration ditch and an underground subsurface wetland, and the denitrification process comprises the following steps:
(1) high-concentration ammonia nitrogen wastewater enters a nitrosation biofilm reactor from the bottom and flows upwards, most of easily biodegradable organic matters in the wastewater are removed through a water distribution device, an aeration device and a biofilm reaction zone, nitrosation reaction is carried out, and part of ammonia nitrogen is converted into Nitrite (NO)2-N) after, overflow from the upper connecting tube;
(2) the wastewater treated in the first step enters an anaerobic ammonia oxidation biomembrane reactor from the bottom through a connecting pipe, flows upwards, passes through a water distribution device and a biomembrane reaction zone, and residual ammonia Nitrogen (NH) in the wastewater4-N) with Nitrite (NO) formed2N) overflowing from the upper connecting pipe after anaerobic ammoxidation denitrification reaction; gas generated in the anaerobic ammonia oxidation biofilm reactor is discharged from the upper part of the reactor;
(3) the wastewater treated in the second step flows into a water distributor of a soil infiltration ditch of the land treatment unit through a connecting pipe, enters the soil infiltration ditch through the water distributor, diffuses and permeates to the surrounding soil, and enters a water collecting pipe at the bottom after being precipitated, filtered, adsorbed and decomposed by a gravel filtering layer and a soil layer;
(4) the wastewater flows into the subsurface flow wetland water distribution pipe of the land treatment unit through the water collection pipe, flows into the bottom layer of the subsurface flow wetland through the water distribution pipe, and is subjected to precipitation, filtration, adsorption and decomposition from bottom to top through the gravel layer, the packing layer and the soil layer, so that particulate matters and odor in the wastewater are effectively removed, the chromaticity is greatly reduced, and the effluent meets the discharge requirement;
(5) the water which can be discharged overflows the ground, is collected in the water outlet weir and is discharged into the nature through the outlet of the water outlet weir.
According to the denitrification process of the high-concentration ammonia nitrogen wastewater, part of wastewater treated in the second step is pumped into the anaerobic ammonia oxidation biomembrane reactor from the bottom through the circulating pump through the circulating pipe, and the circulating water and the inlet water are mixed and enter the reactor, so that the concentration of ammonia nitrogen and nitrite nitrogen in the inlet water is reduced, and the inhibition effect of the ammonia nitrogen and nitrite nitrogen on microorganisms is reduced.
In the first step of the denitrification process of the high-concentration ammonia nitrogen wastewater, the reaction water temperature of a nitrosation biofilm reactor is 33-34 ℃, the hydraulic retention time is 2.0-2.1 d, and the dissolved oxygen DO: 0.8-1.0 mg/L, pH: 8.0 to 8.2.
In the second step, the reaction water temperature of the anaerobic ammonia oxidation biofilm reactor is 30-31 ℃, the hydraulic retention time is 4.0-4.2 d, and the pH value is as follows: 7.9 to 8.1.
In the denitrification process of the high-concentration ammonia nitrogen wastewater, the nitrosation biomembrane reactor adopts a fixed bed biomembrane reactor; the device consists of a biomembrane reaction zone and a solid-liquid separation zone, wherein the biomembrane reaction zone is internally provided with a filler, the top of the biomembrane reaction zone is expanded to slow the ascending flow velocity, the aerated gas is collected in a central cylinder, and the solid-liquid separation zone is arranged at the periphery outside the tube; one side of the upper part of the reactor is provided with a connecting pipe; the aeration pipe, the aeration device and the water distribution device are arranged at the bottom in the reactor; one side of the bottom of the reactor is connected with a wastewater inlet pipe, and an aeration pipe is led out from the other side.
In the denitrification process of the high-concentration ammonia nitrogen wastewater, the anaerobic ammonia oxidation biomembrane reactor adopts a fixed bed biomembrane reactor; the device consists of a biomembrane reaction zone and a solid-liquid separation zone, wherein the biomembrane reaction zone is internally provided with a filler, the top of the biomembrane reaction zone is expanded to slow down the ascending flow velocity, and the solid-liquid separation zone is arranged at the periphery of a central cylinder; one side of the upper part of the reactor is provided with a connecting pipe and a circulating pipe; the circulating pump is arranged in the circulating pipe, the lower end of the circulating pipe is communicated with the lower end of a connecting pipe of the nitrosation biofilm reactor, the outlet of the lower end of the connecting pipe of the nitrosation biofilm reactor is connected to one side of the bottom of the reactor, and the circulating pump enables the effluent of the reactor to enter the reactor again for internal circulation; the water distribution device is arranged at the bottom in the reactor.
In the denitrification process of the high-concentration ammonia nitrogen wastewater, the upper part of the soil infiltration ditch is a soil layer, the middle part of the soil infiltration ditch is a filtering gravel layer, the bottom of the soil infiltration ditch is a water collecting pipe, and the water distributing pipe is arranged on the upper part of the filtering gravel layer; the soil infiltration ditch adopts a dry-wet alternate operation mode to ensure that the soil alternately keeps aerobic and anoxic so as to achieve the aims of aerobic nitrification and anoxic denitrification.
The denitrification process of the high-concentration ammonia nitrogen wastewater comprises the steps that the upper part of the subsurface flow wetland is a soil layer, the middle part of the subsurface flow wetland is a packing layer, the bottom of the subsurface flow wetland is a gravel layer, and a water distribution pipe is arranged in the gravel layer at the bottom.
The denitrification principle of the nitrosation-anaerobic ammonia oxidation technology adopted in the invention is as follows: oxidizing about 50% of ammonia nitrogen in the wastewater into nitrite nitrogen, namely, the nitrification process is only carried out to a nitrosation stage, the microorganisms convert the ammonia nitrogen and the nitrite nitrogen into nitrogen by taking the remaining 50% of ammonia nitrogen as an electron donor and taking the nitrite nitrogen as an electron acceptor under the anaerobic condition, the anaerobic ammonia oxidation technology does not need to add an organic carbon source, and the reaction formula is as follows:
compared with the traditional nitrification-denitrification biological denitrification technology, the biological denitrification technology has the following advantages:
(1) the nitration reaction is only carried out to the nitrosation stage, and only about 50 percent of ammonia nitrogen is required to be oxidized into nitrite nitrogen, so that the aeration energy consumption is reduced. Each 1molof NH removed4 +Only 0.75mol of oxygen is needed to be consumed, and the energy consumption is saved by 62.5 percent. .
(2) Saving 100% of denitrification organic carbon source.
(3) Because only 50 percent of ammonia nitrogen is oxidized into nitrite nitrogen, the acid production is greatly reduced, and 1mol of NH is removed every time4 +Only 1mol of H is produced+Considerable neutralizing agent can be saved.
The nitrosation and anaerobic ammoxidation reactors in the invention both adopt a fixed bed biofilm reactor and have the following main characteristics:
(1) microorganisms are diverse, have long food chain lengths, and survive for longer generations.
(2) Sludge backflow and fluidization are not needed, and energy consumption is greatly reduced; and a sedimentation tank is not required to be arranged independently, so that the operation is simplified.
(3) Impact load resistance and strong adaptability to water quality and water quantity change.
In the invention, the land treatment system is arranged behind the anaerobic ammonia oxidation reactor, so that the whole process has the advantages of good treatment effect, large buffer capacity, investment saving, low operation cost, convenient management and the like. Moreover, the process flow is simple, sludge backflow and mixed liquid backflow are not needed, and the energy consumption is low.
The novel denitrification process has the following advantages:
(1) the denitrification efficiency is high, and organic carbon sources are not required to be added.
(2) Not only removes organic matters difficult to degrade, but also has the functions of decoloring and deodorizing.
(3) The process flow is simple and the operation is simple and convenient.
(4) Reduce power cost, medicament cost and management cost, reduce the running cost.
(5) The capital investment is low.
(6) The ecological technology of land treatment is utilized to treat pollutants and beautify the environment.
The soil infiltration ditch and the subsurface flow wetland are both arranged underground, and flowers, plants and crops can be planted on the soil infiltration ditch and the subsurface flow wetland according to different requirements, and landscapes such as pavilions and the like can be built.
Drawings
FIG. 1 is a process flow diagram of a denitrification process for high-concentration ammonia nitrogen wastewater according to the present invention;
FIG. 2 is a flow chart of a conventional biological denitrification process.
Detailed Description
The process flow of the invention is shown in figure 1. The nitrosation and anaerobic ammoxidation adopt a fixed bed biofilm reactor, and fixed fillers are arranged in a nitrosation biofilm reactor 1 and an anaerobic ammoxidation biofilm reactor 2. The land treatment unit consists of two devices, namely a soil infiltration ditch 3 and a subsurface flow wetland 4, and can be built according to the field topography and the land utilization condition.
The wastewater flows into a nitrosation biomembrane reactor 1 from the bottom, water is uniformly distributed in the reactor 1 through a water distribution device 5, the gas is supplied into the reactor 1 through an aeration pipe and an aeration device 6 by a gas supply facility to provide oxygen required by biological aerobic reaction, the wastewater and bubbles flow from bottom to top, the wastewater and bubbles are contacted with a biomembrane growing on a filler in a biomembrane reaction zone 7, the mixed solution of the wastewater after biodegradation and suspended sludge enters a solid-liquid separation zone 8, the sludge is flocculated and precipitated and enters the biomembrane reaction zone 7, clear water flows out from a connecting pipe 22 at the upper part of the reactor 1 and automatically flows into an anaerobic ammonia oxidation biomembrane reactor 2, the inlet water flows from bottom to top through a water distribution device 9 and is metabolized and degraded by the biomembrane growing on the filler in the biomembrane reaction zone 10, the muddy water mixed solution is separated in the solid-liquid separation zone 11, and the outlet, circulating water and inlet water are mixed and enter the reactor 2, so that the concentration of ammonia nitrogen and nitrite nitrogen in the inlet water is reduced, and the inhibition effect of the inlet water on microorganisms is reduced. Effluent water is prevented from entering the reactor 2 through water seal, gas generated by biological reaction is collected and discharged from the top of the reactor 2, the effluent water flows out from a connecting pipe 23 at the upper part of the reactor 2, flows into the water distribution pipe 13 in the soil infiltration ditch 3, infiltrates and diffuses into the soil layer 15 through the filtering gravel layer 14 around the water distribution pipe 13, wastewater is further purified through the degradation of a biological membrane on the gravel layer 14, the filtration, the adsorption and the biological metabolism of a soil layer, the absorption of surface crops and the like, is collected by the perforated water collection pipe 16 at the bottom, and flows into the water distribution pipe 17 of the subsurface wetland 4 automatically. The soil infiltration ditch 3 adopts a dry-wet alternate operation mode to ensure that the soil keeps alternate aerobic and anoxic. The inlet water of the subsurface wetland 4 flows upwards through the water distribution pipes 17 and the gravel layer 18 around the pipes to enter the packing layer 19, and waste building materials (such as masonry and the like) and other materials can be used as the packing of the subsurface wetland 4. The pollutants in the wastewater are further removed from the wastewater through the utilization of the biomembrane on the packing layer 19, the filtration and biodegradation of the surface soil 20 and the absorption of crops, and the purified effluent is discharged after being collected by the effluent weir 21.
Example 1
Please refer to fig. 1.
The landfill leachate is used as a source for treating wastewater. The whole process flow is continuously and stably operated for nearly four months, and the stable operation conditions and the treatment effect of the whole process are respectively as follows:
nitrosation biofilm reactor: the water temperature is 33-34 ℃, the hydraulic retention time is 2.0-2.1 d, and the dissolved oxygen DO: 0.8-1.0 mg/L, pH: 8.0 to 8.2.
Anaerobic ammonia oxidation biofilm reactor: the water temperature is 30-31 ℃, the hydraulic retention time is 4.0-4.2 d, and the pH is as follows: 7.9 to 8.1.
NH4Feed water concentration of-N: 736.77mg/L, effluent concentration: 58.17mg/L, removal rate: 92.11 percent; feed water concentration of TN: 767.18mg/L, effluent concentration: 68.61mg/L, removal rate: 91.06 percent; feed water concentration of CODcr: 951.50mg/L, effluent concentration: 160.98mg/L, removal rate: 83.08 percent.
Claims (7)
1. The utility model provides a denitrogenation technology of high concentration ammonia nitrogen waste water, the system comprises nitrosation biofilm reactor, anaerobic ammonia oxidation biofilm reactor and three units of land treatment, and the land treatment unit includes two parts of soil infiltration ditch and underground underflow wetland, characterized by: comprises the following steps:
(1) high-concentration ammonia nitrogen wastewater enters a nitrosation biofilm reactor from the bottom and flows upwards, most of easily biodegradable organic matters in the wastewater are removed through a water distribution device, an aeration device and a biofilm reaction zone, nitrosation reaction is carried out, and part of ammonia nitrogen is converted into Nitrite (NO)2-N) after, overflow from the upper connecting tube;
(2) the wastewater treated in the first step enters an anaerobic ammonia oxidation biomembrane reactor from the bottom through a connecting pipe, flows upwards, passes through a water distribution device and a biomembrane reaction zone, and residual ammonia Nitrogen (NH) in the wastewater4-N) with Nitrite (NO) formed2N) overflowing from the upper connecting pipe after anaerobic ammoxidation denitrification reaction; gas generated in the anaerobic ammonia oxidation biofilm reactor is discharged from the upper part of the reactor;
(3) the wastewater treated in the second step flows into a water distributor of a soil infiltration ditch of the land treatment unit through a connecting pipe, enters the soil infiltration ditch through the water distributor, diffuses and permeates to the surrounding soil, and enters a water collecting pipe at the bottom after being precipitated, filtered, adsorbed and decomposed by a gravel filtering layer and a soil layer;
(4) the wastewater flows into the subsurface flow wetland water distribution pipe of the land treatment unit through the water collection pipe, flows into the bottom layer of the subsurface flow wetland through the water distribution pipe, and is subjected to precipitation, filtration, adsorption and decomposition from bottom to top through the gravel layer, the packing layer and the soil layer, so that particulate matters and odor in the wastewater are effectively removed, the chromaticity is greatly reduced, and the effluent meets the discharge requirement;
(5) the water which can be discharged overflows the ground, is collected in the water outlet weir and is discharged into the nature through the outlet of the water outlet weir.
2. The denitrification process of the high-concentration ammonia nitrogen wastewater as set forth in claim 1, which is characterized in that: and pumping part of the wastewater treated in the second step into an anaerobic ammonia oxidation biomembrane reactor from the bottom by a circulating pump through a circulating pipe, mixing the circulating water with the inlet water, and feeding the mixture into the reactor to reduce the concentration of ammonia nitrogen and nitrite nitrogen in the inlet water and reduce the inhibition effect of the mixture on microorganisms.
3. The denitrification process of the high-concentration ammonia nitrogen wastewater as set forth in claim 1, which is characterized in that: in the first step, the reaction water temperature of the nitrosation biofilm reactor is 33-34 ℃, the hydraulic retention time is 2.0-2.1 d, and the dissolved oxygen DO: 0.8-1.0 mg/L, pH: 8.0 to 8.2.
4. The denitrification process of the high-concentration ammonia nitrogen wastewater as set forth in claim 1, which is characterized in that: in the second step, the reaction water temperature of the anaerobic ammonia oxidation biofilm reactor is 30-31 ℃, the hydraulic retention time is 4.0-4.2 d, and the pH value is as follows: 7.9 to 8.1.
5. The denitrification process of the high-concentration ammonia nitrogen wastewater as set forth in claim 1, which is characterized in that: the nitrosation biomembrane reactor adopts a fixed bed biomembrane reactor; the device consists of a biomembrane reaction zone and a solid-liquid separation zone, wherein the biomembrane reaction zone is internally provided with a filler, the top of the biomembrane reaction zone is expanded to slow the ascending flow velocity, the aerated gas is collected in a central cylinder, and the solid-liquid separation zone is arranged at the periphery outside the tube; one side of the upper part of the reactor is provided with a connecting pipe; the aeration pipe, the aeration device and the water distribution device are arranged at the bottom in the reactor; one side of the bottom of the reactor is connected with a wastewater inlet pipe, and an aeration pipe is led out from the other side.
6. The denitrification process of the high-concentration ammonia nitrogen wastewater as set forth in claim 1, which is characterized in that: the anaerobic ammonia oxidation biomembrane reactor adopts a fixed bed biomembrane reactor; the device consists of a biomembrane reaction zone and a solid-liquid separation zone, wherein the biomembrane reaction zone is internally provided with a filler, the top of the biomembrane reaction zone is expanded to slow down the ascending flow velocity, and the solid-liquid separation zone is arranged at the periphery of a central cylinder; one side of the upper part of the reactor is provided with a connecting pipe and a circulating pipe;the circulating pump is arranged in the circulating pipe, the lower end of the circulating pipe is communicated with the lower end of a connecting pipe of the nitrosation biofilm reactor, the outlet of the lower end of the connecting pipe of the nitrosation biofilm reactor is connected to one side of the bottom of the reactor, and the circulating pump enables the effluent of the reactor to enter the reactor again for internal circulation; the water distribution device is arranged at the bottom in the reactor.
7. The denitrification process of the high-concentration ammonia nitrogen wastewater as set forth in claim 1, which is characterized in that: the upper part of the soil infiltration ditch is a soil layer, the middle part of the soil infiltration ditch is a filtering gravel layer, the bottom of the soil infiltration ditch is a water collecting pipe, and the water distributing pipe is arranged on the upper part of the filtering gravel layer; the soil infiltration ditch adopts a dry-wet alternate operation mode to ensure that the soil alternately keeps aerobic and anoxic so as to achieve the aims of aerobic nitrification and anoxic denitrification.
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| CN108163978B (en) * | 2017-12-29 | 2020-09-22 | 华南理工大学 | Method for realizing high-efficiency nitrosation of high-concentration ammonia nitrogen wastewater by using alkalinity provided by sodium carbonate |
| CN108358317A (en) * | 2018-03-26 | 2018-08-03 | 常州大学 | A kind of method of soil filtration processing ammonia nitrogen in high density |
| CN109292974A (en) * | 2018-12-10 | 2019-02-01 | 北京博诚立新环境科技股份有限公司 | A kind of underground water and water-bearing layer soil in-situ anaerobic organism restorative procedure |
| CN109292974B (en) * | 2018-12-10 | 2022-03-29 | 北京博诚立新环境科技股份有限公司 | In-situ anaerobic biological remediation method for underground water and aquifer soil |
| CN109775863A (en) * | 2019-03-06 | 2019-05-21 | 清华大学 | High concentrated organic wastewater anaerobism embrane method water handling reclamation set and technique |
| CN114590900A (en) * | 2022-03-10 | 2022-06-07 | 武汉中科水生环境工程股份有限公司 | Energy-saving and efficient denitrification type subsurface flow wetland process |
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