CN110642373B - Device and method for quickly starting salt-tolerant anaerobic ammonia oxidation - Google Patents
Device and method for quickly starting salt-tolerant anaerobic ammonia oxidation Download PDFInfo
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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
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
-
- 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
- C02F2101/166—Nitrites
Abstract
The invention discloses a device and a method for quickly starting salt-tolerant anaerobic ammonia oxidation. The device comprises an adsorption zone, an anaerobic ammonia oxidation zone and a separation zone; two layers of adsorption fillers are filled in the adsorption area, a water inlet is formed in the bottom of the adsorption area, and a discharge pipe and a feed pipe are respectively arranged in each layer of filler; a diaphragm is arranged between the upper end of the adsorption zone and the bottom of the anaerobic ammonia oxidation zone; the inside of the anaerobic ammonia oxidation zone is filled with high-efficiency anaerobic ammonia oxidation granular sludge, and a sludge inlet pipe and a sludge discharge pipe are arranged in the anaerobic ammonia oxidation zone; an overflow groove communicated with a water outlet pipe is arranged on the side wall of the separation area, one path of the water outlet pipe is mixed with the water inlet pipe in the pipeline mixer through a return pipe, and the other path of water outlet is discharged. The center of the separation area is provided with a three-phase separator, and the upper part of the separation area is provided with a gas collecting connecting pipe and an exhaust pipe; the device is provided with a water storage tank in front and is provided with a conductivity monitor. According to the anaerobic ammonia oxidation reactor, the anaerobic ammonia oxidation granular sludge is inoculated, so that the starting of the reactor can be accelerated, and the stable operation of the anaerobic ammonia oxidation reactor in a high-salt environment is ensured by combining a desalting process of a pre-adsorption zone.
Description
Technical Field
The invention relates to the technical field of sewage biological treatment, in particular to a device and a method for quickly starting salt-tolerant anaerobic ammonia oxidation.
Background
With the continuous progress of society and the rapid development of economy, the eutrophication problem of natural water bodies such as rivers, lakes and the like is increasingly prominent. In order to strengthen the removal of nutrient elements such as nitrogen and phosphorus in sewage and protect the ecological function of a receiving water body, the nitrogen and phosphorus emission standard of sewage treatment in China is continuously improved, the total control of pollutants such as nitrogen and phosphorus is increasingly emphasized, and the defects of the traditional nitrogen and phosphorus removal process are gradually highlighted. Aeration is needed in the traditional biological nitrification process, and the consumed electric energy accounts for more than 60% of the total electric consumption of a sewage plant; the denitrification process needs to consume organic matters, but the concentration of the organic matters in urban sewage in China is generally low, and nitrogen effluent is difficult to reach the standard due to insufficient carbon source. In order to make the effluent reach the standard, exogenous organic matters are required to be added, so that the running cost is increased. Therefore, developing a biological denitrification process technology which is economical, efficient and sustainable has become a hot spot problem in the field of water pollution control engineering.
Anaerobic ammoxidation (Anaerobic ammonium oxidation, anamox) is taken as a novel microbial nitrogen conversion way, so that the knowledge of the traditional nitrogen circulation theory is thoroughly changed, and the anaerobic ammoxidation is an innovation of the traditional nitrification-denitrification biological denitrification technology. The bacteria for performing the anaerobic ammoxidation process are chemolithoautotrophic bacteria, and can be NH 4 + As electron donor, NO 2 - Is an electron acceptor, ultimately producing N 2 The process does not need to add organic carbon source and O 2 . Therefore, the anaerobic ammonia oxidation can effectively save the reagent adding cost and the energy consumption required by the aeration process when being applied to the field of sewage treatment, and is evaluated by domestic and foreign experts as a novel energy-saving pollution-free sustainable sewage biological treatment technology, and is more and more valued by domestic and foreign researchers.
The anaerobic ammonia oxidation process is efficient and economical, is expected to become an upgrading technology for biological denitrification of wastewater, and has good application prospect. However, anaerobic ammonia oxidizing bacteria (AnAOB) have the defects of slow growth, low cell yield, sensitivity to changes of environmental conditions and the like, so that the anaerobic ammonia oxidizing bacteria are frequently plagued by exogenous toxicants in practical application, and the popularization progress is slow. The actual wastewater has complex components, such as pharmaceutical wastewater, leather processing wastewater, food processing wastewater, livestock and poultry breeding wastewater, garbage leakage filtrate, petrochemical wastewater and the like, and contains inorganic salts with different types and concentrations. The high osmotic pressure caused by high concentration inorganic salts (sodium chloride, sodium sulfate, potassium chloride, magnesium sulfate, calcium chloride and the like) in the wastewater can reduce the activity of anammox bacteria, inhibit the metabolism of the bacteria, weaken the metabolism of enzymes and further influence the sedimentation performance of anammox agglomerates and the denitrification performance of a reactor.
The research shows that anaerobic ammonia oxidation is a main contributor to biological denitrification in marine nitrogen circulation, the contribution rate of the anaerobic ammonia oxidation to the marine biological denitrification is about 4-79%, which indicates that the anaerobic ammonia oxidation is anaerobicThe ammonia oxidizing bacteria have certain salt tolerance, and provide theoretical basis for salt tolerance domestication. Of the currently isolated AnAOB, only the genus "Scarindura" is distributed in the marine ecosystem, whereas by domestication, anAOB of the freshwater ecosystem can tolerate a certain concentration of salts. In the prior art, patent CN102952764B discloses a method for culturing salt-tolerant anaerobic ammonium oxidation flora, which mainly comprises the steps of enriching and culturing an activated sludge flora into an anaerobic ammonium oxidation flora, and then carrying out salt-tolerant domestication culture on the enriched anaerobic ammonium oxidation flora. Patent CN 102976489B discloses a method for starting an anaerobic ammoxidation reactor to treat high-salt nitrogen-containing wastewater, which comprises the steps of firstly raising nitrogen concentration, culturing and enriching anaerobic ammoxidation bacteria, gradually raising salinity after the anaerobic ammoxidation function is realized by the reactor, and domesticating the adaptability of the anaerobic ammoxidation bacteria to the salinity, so that the starting process can be divided into two processes of enrichment and domestication. Both of the above patents are inoculated with conventional activated sludge, and because anaerobic ammonium oxidation bacteria (AnAOB) are distributed in the conventional activated sludge slowly, the growth is slow, and the cell yield is low (0.08-0.11 gVSS/gNH) 4 + N), the generation time is as long as 10-25 days, the anaerobic ammonia oxidation reactor can be started for a long time by inoculating conventional activated sludge, and the operation of the reactor is easy to interfere and has weak impact resistance, so that the method has insufficient environment change adaptation capability. In actual production, the uncertainty of the water inlet salinity and the sudden change of the environment can impact an anaerobic ammonia oxidation denitrification system, even the system is unstable and is difficult to recover from paralysis, so that the establishment of a device and a method for quickly starting salt-tolerant anaerobic ammonia oxidation are particularly critical.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a device and a method for rapidly starting salt-tolerant anaerobic ammonia oxidation, which can rapidly improve the starting time of an anaerobic ammonia oxidation reactor in a high-salt environment and the impact resistance of the reactor to the change of the high-salt environment.
The technical solution for achieving the above purpose of the present invention is as follows:
a device for quickly starting salt-tolerant anaerobic ammoxidation comprises an integrated reactor shell, wherein the inside of the integrated reactor shell is sequentially divided into an adsorption zone, an anaerobic ammoxidation zone and a separation zone from bottom to top; the adsorption zone is in a combined shape of an inverted cone and a cylinder, the inner cavity of the adsorption zone is divided into an upper layer and a lower layer by a diaphragm, cation adsorption filler is filled in the lower layer inner cavity, a lower layer filler feeding pipe and a lower layer filler discharging pipe are respectively arranged above and below the cation adsorption filler, anion adsorption filler is filled in the upper layer inner cavity, and an upper layer filler feeding pipe and an upper layer filler discharging pipe are respectively arranged above and below the anion adsorption filler; the bottom of the adsorption zone is provided with a water inlet; a diaphragm is also arranged between the upper end of the adsorption zone and the bottom of the anaerobic ammonia oxidation zone; a plurality of overflow holes are formed in each diaphragm, an upper flow pipe with the top higher than the upper surface of the diaphragm is arranged in each overflow hole, a conical cover is arranged right above each upper flow pipe, and the conical cover, the upper flow pipe and the upper surface of the diaphragm are suspended to form a channel for water flow to flow out;
anaerobic ammonia oxidation granular sludge is filled in the anaerobic ammonia oxidation zone; the top of the anaerobic ammonia oxidation zone is provided with a mud inlet pipe, and the bottom is provided with a mud discharge pipe; an overflow groove is arranged at the upper part of the inner side wall of the separation area, and a water collecting cavity of the overflow groove is connected with one end of a water outlet pipe; the middle of the separation area is provided with an inverted Y-shaped three-phase separator, and the upper part of the separation area is provided with an exhaust pipe; the device is characterized in that a water storage tank is arranged in the front of the device, a conductivity detector is arranged in the water storage tank, the water storage tank is connected with one inlet of a pipeline mixer through a waste water pipe with a waste water metering pump, the other end of the water outlet pipe is divided into two paths, one path of water outlet is discharged, the other path of water outlet is connected with the other inlet of the pipeline mixer through a return pipe with a return metering pump, and an outlet of the pipeline mixer is connected with a water inlet and is used for enabling waste water to be fully mixed with return water and then input into the device from the bottom end of an adsorption zone.
Preferably, the height ratio of the adsorption zone to the upper anaerobic ammoxidation zone is 1: (1-1.5), the volume of the cation adsorption filler filled in the inner cavity of the lower layer of the adsorption zone accounts for 3/4 of the total volume of the inner cavity of the lower layer, the volume of the anion adsorption filler filled in the inner cavity of the upper layer of the adsorption zone accounts for 3/4 of the total volume of the inner cavity of the upper layer, and the volume of the anaerobic ammonia oxidation granular sludge filled in the anaerobic ammonia oxidation zone accounts for 1/4 of the total volume of the anaerobic ammonia oxidation zone.
Preferably, the cation adsorption filler is bentonite, and the anion adsorption filler is hydrotalcite.
Preferably, the diameter of the aperture of the overflow hole on the diaphragm plate is 2-3 mm, and the clearance between the conical cover and the upper surface of the diaphragm plate is 2-3 mm, so that water flow is ensured to pass through the diaphragm plate from bottom to top and upper solid particles are prevented from passing through the diaphragm plate from top to bottom in a countercurrent manner.
Preferably, three sampling ports are arranged on the side wall of the anaerobic ammonia oxidation zone at equal intervals and used for analyzing water quality in the denitrification reactor.
Preferably, the three-phase separator is an inverted Y-shaped cylindrical three-phase separator combination, and the collected nitrogen is discharged through an exhaust pipe at the top.
Preferably, the height of the three-phase separator exposed out of the liquid level is 1/3 to 1/6 of the total height.
Preferably, the automatic control assembly is further provided, and comprises the conductivity detector, a Programmable Logic Controller (PLC) and a liquid flow regulator assembly; the conductivity detector is connected with the programmable PLC controller through a data signal; the liquid flow regulator assembly includes the waste water metering pump and the return metering pump; the liquid flow regulator is in data signal connection with the programmable PLC controller; the programmable PLC is also respectively connected with a waste water inlet valve arranged on the waste water pipe and a backflow inlet valve arranged on the backflow pipe in a control manner; the automatic control assembly further comprises a wireless transceiver connected with the programmable PLC controller, the wireless transceiver is in communication connection with a cloud server through a wireless network, and the cloud server is connected with a remote monitoring center or an intelligent mobile terminal through the wireless network.
Another object of the present invention is to provide a method for treating industrial wastewater containing nitrogen and salt, which uses any one of the above schemes to rapidly start up a salt-tolerant anaerobic ammonia oxidation device, wherein the method comprises the following steps:
fully mixing the salt-containing and nitrogen-containing wastewater to be treated with water outlet backwater water in a pipeline mixer, diluting raw water by using backwater water to reduce the salinity of water inlet in an adsorption zone, and then allowing mixed solution to enter the adsorption zone;
in the process that the wastewater flows upwards through the cation adsorption filler at the lower layer and the anion adsorption filler at the upper layer of the adsorption zone, na in the wastewater solution + 、Mg 2+ 、K + And Ca 2+ Is fully contacted with and adsorbed on the surface of the cation adsorption filling material, and the anion Cl - And SO 4 2- The layered structure entering the anion-adsorbing filler is adsorbed;
the wastewater with partial salinity removed by the adsorption zone continuously rises to enter an anaerobic ammonia oxidation zone, and ammonia nitrogen and nitrite nitrogen are converted into N under the action of anaerobic ammonia oxidation granular sludge 2 ；
The wastewater treated by the anaerobic ammonia oxidation zone continuously enters a separation zone, gas, liquid and solid are separated under the action of a three-phase separator, the gas is discharged through an exhaust pipe, anaerobic ammonia oxidation granular sludge returns to a biological denitrification reaction zone again, clear effluent is directly discharged through a water outlet pipe after passing through an overflow tank, and the other part of the clarified effluent flows back to a pipeline mixer through a return pipe and is fully mixed with salt-containing wastewater in a wastewater pipe;
continuously introducing wastewater into the device according to the flow, and controlling the salinity of mixed water entering the device to be within 1% by controlling the reflux ratio of the reflux water inflow and the wastewater water inflow at the initial start-up period of a reactor for 0-15 days after sludge inoculation; after the device stably operates, gradually reducing the reflux ratio, so as to gradually increase the salinity in the inflow water, and carrying out salt-tolerant domestication on anaerobic ammonia oxidation granular sludge received in the reactor; meanwhile, in the circulation process, based on a conductivity detector and a wastewater metering pump which are arranged in a wastewater storage tank, the total salt content of wastewater entering a reactor is calculated through simulation, the theoretical use days of the filler are calculated by combining the maximum adsorption quantity of the two layers of adsorption fillers, and then the two layers of adsorption fillers are updated regularly, so that the adsorption capacity of the two layers of adsorption fillers is always kept.
Preferably, the anaerobic ammonia oxidation granular sludge is taken from an anaerobic ammonia oxidation reactor which runs stably, wherein the main bacterial strain in the anaerobic ammonia oxidation granular sludge is Candidatus Kuenenia, and the relative abundance is 32.8%; in the domestication process, the water quality in the denitrification reaction zone is analyzed through a sampling port arranged in the anaerobic ammonia oxidation zone at regular intervals, and the reflux ratio is dynamically adjusted to maintain the stability of water output.
Compared with the prior art, the invention has the following advantages: 1) The inoculated sludge is anaerobic ammonia oxidation granular sludge, the relative abundance of anaerobic ammonia oxidation bacteria in the inoculated sludge is improved through a measure of biological enhancement (Bioaugmenting), and the starting of an anaerobic ammonia oxidation reactor is accelerated; 2) The anaerobic ammoxidation granular sludge naturally combines and immobilizes specific biological communities to self-enhance the viability of the clusters in the habitat. The secreted EPS is the key of the skeleton and cell agglomeration of the granular sludge, is also the first defense line of microorganisms against stress, and has stronger salinity impact resistance than the traditional sludge; 3) The desalination process of the pre-adsorption zone can reduce the salinity in the water inlet of the anaerobic ammonia oxidation zone and slow down the inhibition of high-salt impact on anaerobic ammonia oxidation bacteria by developing the adsorption of modified hydrotalcite and bentonite filler to salt ions in the wastewater; 4) The inlet water can be diluted through the water outlet reflux, so that the salinity is lower than the toxicity threshold value, and the influence of the salinity on the biological denitrification treatment process is reduced. The method is simple and easy to operate and manage; 5) The automatic control component can adjust the water outlet reflux ratio according to the conductivity online detector, so that the concentration of the inlet water salt in the anaerobic ammonia oxidation zone is ensured to be within a reasonable threshold range, the impact of the reactor system on the inlet water salt fluctuation is enhanced, and the impact load resistance is strong; 6) And a high-efficiency three-phase separator is arranged to effectively separate three phases of gas, liquid and solid.
Drawings
FIG. 1 is a schematic diagram of a device for rapid start-up of a salt tolerant anaerobic ammonia oxidation;
FIG. 2 is a schematic view of a diaphragm plate of the present invention;
FIG. 3 is a schematic view of the installation of the upflow pipe and cone cover on the diaphragm;
FIG. 4 is a schematic diagram showing the denitrification effect of a rapid start-up salt-tolerant anaerobic ammonia oxidation device according to an embodiment.
In the figure: the device comprises a water storage tank 1, a conductivity meter 2, a reflux metering pump 3, a reflux pipe 4, a diaphragm 5, a sampling port 6, a water outlet pipe 7, a water overflow weir 8, an exhaust pipe 9, a three-phase separator 10, a mud inlet pipe 11, anaerobic ammonia oxidation granular sludge 12, a mud discharge pipe 13, an upper filler inlet pipe 14, anion adsorption filler 15, an upper filler outlet pipe 16, a water inlet pipe 17, a pipe mixer 18, a waste water pipe 19, a waste water metering pump 20, an overflow hole 21, cation adsorption filler 22, a lower filler inlet pipe 23, a lower filler outlet pipe 24, an overflow pipe 25 and a conical cover 26.
Detailed Description
The invention is further illustrated and described below with reference to the drawings and detailed description. The technical features of the embodiments of the invention can be combined correspondingly on the premise of no mutual conflict.
As shown in fig. 1, a reactor device for rapid start-up of salt-tolerant anaerobic ammonia oxidation according to a preferred embodiment of the present invention is provided, wherein the outer shell of the reactor device is an integrated reactor shell, and the interior of the shell is divided into an adsorption zone I, an anaerobic ammonia oxidation zone II and a separation zone III in sequence from bottom to top. The present invention can be constructed with plexiglas and steel plates, and the specific functions and structures of each region are described in detail below.
The main function of the adsorption zone I is to partially remove salt in the inlet water so that the salt concentration is within a reasonable threshold range. The adsorption zone I is in an inverted cone and cylinder combined shape, the inner cavity of the adsorption zone I is divided into an upper layer of inner cavity and a lower layer of inner cavity by a diaphragm 5, and different fillers are respectively filled in the two layers of inner cavities. The lower inner cavity is filled with cation adsorption filler 22, a lower filler feed pipe 23 and a lower filler discharge pipe 24 are respectively arranged above and below the cation adsorption filler 22, the upper inner cavity is filled with anion adsorption filler 15, and an upper filler feed pipe 14 and an upper filler discharge pipe 16 are respectively arranged above and below the anion adsorption filler 15. In addition, a water inlet 17 is arranged at the bottom of the adsorption zone I. The water inlet of the whole reactor device is input through the water inlet 17, and after flowing through the cation adsorption filler 22 in the lower cavity, the water enters the upper cavity through the diaphragm 5, and is continuously adsorbed by the anion adsorption filler 15. Since the adsorption packing has the maximum adsorption capacity, adsorption saturation occurs during use, and thus it is necessary to update it at regular time. The anion adsorption packing 15 of the upper layer can be fed with new packing through the upper layer packing feeding pipe 14, and the adsorption saturated packing is extracted through the upper layer packing discharging pipe 16; similarly, the lower cation-adsorbing filler 22 can be fed with fresh filler via lower filler feed pipe 23 and the adsorption-saturated filler can be withdrawn via lower filler discharge pipe 24. The regeneration of the packing may be a periodic regeneration or a continuous regeneration, preferably the latter, i.e. the new packing is fed while the adsorption-saturated packing is withdrawn, both of which are maintained in an equilibrium state, so that the adsorption capacity of the packing can be utilized as much as possible while ensuring that the continuity of the operation of the reactor is not affected.
A diaphragm plate 5 is also arranged between the upper end of the adsorption zone I and the bottom of the anaerobic ammonia oxidation zone II, and the adsorbed wastewater needs to enter the anaerobic ammonia oxidation zone II above through the diaphragm plate 5. It should be noted that the diaphragm 5 is of the same form as the diaphragm 5 in the adsorption zone I, and that they all need to have the flow capacity of the water flow, while also ensuring that no exchange of solid particles occurs on both sides, since the two sides of the diaphragm are completely different solid particles. The solid particles referred to herein may be filler particles or sludge particles, depending on the particles actually present on both sides of the respective diaphragm. In the invention, the two diaphragm plates 5 are specially designed, as shown in fig. 2, a plurality of overflow holes 21 are uniformly formed in the cross section of each diaphragm plate 5, an overflow pipe 25 with the top higher than the upper surface of the diaphragm plate 5 is arranged in each overflow hole 21, a conical cover 26 is arranged right above each overflow pipe 25, the conical cover 26 is a conical shell, the axis of the conical cover is coaxial with the overflow pipe 25 below, and a channel for water to flow out is formed between the conical cover 26 and the overflow pipe 25 in a suspending way. At the same time, a suspension interval is also arranged between the conical cover 26 and the upper surface of the diaphragm 5, and under the design, water flow below the diaphragm 5 can be input through the upper flow pipe 25 and then flows out to the channels on two sides through the blocking effect of the conical cover 26, so that the flow state shown in fig. 3 is formed. With this construction, the solid particles above the conical hood 26, if they are to enter the up-flow pipe 25, need to overcome the gravity and the thrust of the water flow, so that they generally cannot enter below the diaphragm 5 through the up-flow pipe 25, thereby achieving the effect of ensuring the water flow from bottom to top through the diaphragm 5 while preventing the upward countercurrent flow of the solid particles through the diaphragm 5 from top to bottom.
The anaerobic ammonia oxidation zone II is internally filled with anaerobic ammonia oxidation granular sludge 12, the top of the anaerobic ammonia oxidation zone II is provided with a sludge inlet pipe 11, the bottom of the anaerobic ammonia oxidation zone II is provided with a sludge discharge pipe 13, and the anaerobic ammonia oxidation granular sludge 12 can be input from the sludge inlet pipe 11 and output from the sludge discharge pipe 13. In addition, three sampling ports 6 can be arranged on the side wall of the anaerobic ammonia oxidation zone II at equal intervals and used for analyzing water quality in the denitrification reactor so as to adjust operation parameters such as reflux ratio at any time.
An overflow groove 8 is arranged at the upper part of the inner side wall of the separation zone III, and a water collecting cavity of the overflow groove 8 is connected with one end of a water outlet pipe 7. The center of the separation zone III is provided with an inverted Y-shaped three-phase separator 10, an air outlet at the top of the three-phase separator 10 is connected with an exhaust pipe 9, and the exhaust pipe 9 extends out of the reactor shell.
The reactor device is provided with a water storage tank 1 in front, a conductivity detector 2 is arranged in the water storage tank 1, the water storage tank 1 is connected with one inlet of a pipeline mixer 18 through a waste water pipe 19 with a waste water metering pump 20, the other end of the water outlet pipe 7 is divided into two paths, one path of water outlet is discharged, the other path of water outlet is connected with the other inlet of the pipeline mixer 18 through a return pipe 4 with a return metering pump 3, the outlet of the pipeline mixer 18 is connected with a water inlet 17, and the pipeline mixer 18 is used for fully mixing waste water with return water and then inputting the waste water into the reactor device from the bottom end of an adsorption zone I. The pipe mixer is also called a pipe type static mixer, is very effective in the aspects of adding various coagulants, coagulant aids, ozone, liquid chlorine, acid-base neutralization, gas-water mixing and the like in water supply and drainage and environmental protection projects, is ideal equipment for instantly mixing various medicaments in a treated water area, has the characteristics of quick and efficient mixing, simple structure, energy consumption saving, small volume and the like, can generate three functions of diversion, cross mixing and reverse rotational flow when water flows pass through the pipe mixer without external power, ensures that the added medicaments are quickly and uniformly diffused into the whole water body, achieves the aim of instantly mixing, has the mixing efficiency of 90-95 percent, can save the medicament consumption by about 20-30 percent, and has great significance for improving the water treatment effect and saving the energy.
In this embodiment, the structural parameters of the device can be designed as follows: the height ratio of the adsorption zone I to the upper anaerobic ammoxidation zone II is 1: (1-1.5), the volume of the cation adsorption filler 22 filled in the inner cavity of the lower layer of the adsorption zone I accounts for 3/4 of the total volume of the inner cavity of the lower layer, the volume of the anion adsorption filler 15 filled in the inner cavity of the upper layer of the adsorption zone I accounts for 3/4 of the total volume of the inner cavity of the upper layer, and the volume of the anaerobic ammonia oxidation granular sludge 12 filled in the anaerobic ammonia oxidation zone II accounts for 1/4 of the total volume of the anaerobic ammonia oxidation zone II. The diameter of the pore of the overflow hole 21 on the diaphragm plate 5 is 2-3 mm, the gap between the conical cover 26 and the upper surface of the diaphragm plate 5 is 2-3 mm, and the top of the up-flow pipe 25 is 4-5 cm higher than the upper surface of the diaphragm plate 5, so that particles are prevented from entering the up-flow pipe 25 due to hydraulic turbulence caused by the overlarge gap. The three-phase separator 10 is an inverted Y-shaped cylindrical three-phase separator combination, the collected nitrogen is discharged through the exhaust pipe 9 at the top, and the height of the part of the three-phase separator 10 exposed out of the liquid surface is 1/3-1/6 of the total height of the three-phase separator.
The cation-adsorbing filler 22 and the anion-adsorbing filler 15 of the present invention may be selected as required, as long as the removal of salts can be achieved. In the present embodiment, the cation-adsorbing filler 22 is bentonite, and the anion-adsorbing filler 15 is hydrotalcite. Hydrotalcite can be used for adsorbing Cl in solution - And SO 4 2- While bentonite can adsorb Na + 、Mg 2 + 、K + And Ca 2+ The combination of the two can adsorb various anions or cations in the conventional salt, and the anions and the cations replaced by the adsorbent are OH & lt- & gt and H & lt+ & gt respectively, so that H & lt+ & gt and OH & lt- & gt are combined to generate water, and the aim of desalting is fulfilled.
As a further refinement of the above embodiment, an automatic control assembly may also be provided in the overall device to enable automated control. The automatic control component comprises the conductivity detector 2, a programmable PLC controller and a liquid flow regulator component, wherein the conductivity detector 2 is in data signal connection with the programmable PLC controller, and conductivity data can be transmitted to the programmable PLC controller on line in real time. The liquid flow regulator assembly comprises the waste water metering pump 20 and the backflow metering pump 3, and the two metering pumps are also connected with a Programmable Logic Controller (PLC) through data signals, so that the waste water inflow and the backflow are transmitted in real time. In addition, the programmable PLC is also respectively connected with a waste water inlet valve arranged on the waste water pipe 19 and a backflow inlet valve arranged on the backflow pipe 4 in a control manner, and the two valves can control the opening and closing of corresponding pipelines under the control of the programmable PLC. In order to realize remote automatic control, the automatic control component further comprises a wireless transceiver connected with the programmable PLC controller, the wireless transceiver is in communication connection with the cloud server through a wireless network, and the cloud server is connected with a remote monitoring center or an intelligent mobile terminal through the wireless network, and the automatic control component is specific to the requirements of users.
Based on the rapid starting of the salt-tolerant anaerobic ammonia oxidation device, the invention also provides a method for treating industrial wastewater containing nitrogen and salt by using the device, which comprises the following steps:
firstly, fully mixing the salt-containing and nitrogen-containing wastewater 19 to be treated with effluent backwater water 4 in a pipeline mixer 18, diluting raw water by using backwater water to reduce the salinity of the inlet water of an adsorption zone, and then allowing the mixed solution to enter the adsorption zone I;
during the process that the wastewater flows upwards through the cation adsorption packing 22 at the lower layer and the anion adsorption packing 15 at the upper layer of the adsorption zone I, na in the wastewater solution + 、Mg 2+ 、K + And Ca 2+ Is fully contacted with and adsorbed on the surface of the cation-adsorbing filler 22, and anions Cl - And SO 4 2- The layered structure entering the anion-adsorbing packing 15 is adsorbed;
the wastewater with partial salinity removed by the adsorption zone I continuously rises to enter the anaerobic ammonia oxidation zone II, and ammonia nitrogen and nitrite nitrogen are converted into N under the action of the anaerobic ammonia oxidation granular sludge 12 2 ；
The wastewater treated by the anaerobic ammoxidation zone II continuously enters a separation zone III, gas, liquid and solid are separated under the action of a three-phase separator 10, the gas is discharged from an exhaust pipe 9, the anaerobic ammoxidation granular sludge 12 returns to the biological denitrification reaction zone again, clear effluent 7 is directly discharged from a water outlet pipe after passing through an overflow tank 8, and the other part is returned to a pipeline mixer 18 through a return pipe 4 and is fully mixed with the salt-containing wastewater in a wastewater pipe 19.
The above flow is a circulation flow of wastewater in a reactor device, wastewater is continuously introduced into the device according to the above flow, and at the initial stage of the start-up of the reactor (namely, 0-15 days after sludge inoculation), the salinity of mixed water entering the device is controlled within 1% in a reflux dilution mode by controlling the reflux ratio of the reflux water inflow and the wastewater water inflow, and in the embodiment, the reflux ratio is primarily controlled to be 4:1. after the device stably operates, the reflux ratio is gradually reduced to 3.5:1, 3:1 and 2.5:1, and finally the salinity in the inflow water is gradually increased to be 2:1, and the anaerobic ammonia oxidation granular sludge inoculated in the reactor is subjected to salt-tolerant domestication. After the reflux ratio is reduced each time, a certain time is required to be kept, so that the quality of the effluent is gradually stabilized. In addition, in the domestication process, the water quality in the denitrification reaction zone needs to be analyzed through a sampling port 6 arranged in the anaerobic ammonia oxidation zone at regular intervals, and the reflux ratio is dynamically adjusted according to the fluctuation of the water quality, so that the aim is to maintain the stability of the effluent. Meanwhile, in the circulation process, based on the conductivity detector 2 and the wastewater metering pump 20 which are arranged in the wastewater storage tank, the total salt content of wastewater entering the reactor is calculated through simulation, the theoretical using days of the filler are calculated by combining the maximum adsorption quantity of the two layers of adsorption fillers, and then the two layers of adsorption fillers are updated regularly, so that the adsorption capacity of the two layers of adsorption fillers is always kept.
Since there is a correlation between the ion content in water and the conductivity, the corresponding ion content in water can be reacted by conductivity. Taking the theoretical days of use of hydrotalcite as an example, the calculation formula can be seen in formula 1:
wherein: m is the weight of the added filler, calculated by hydrotalcite, kg; v (V) max For maximum adsorption of filler, hydrotalcite is used for preparing Cl - The maximum adsorption amount of (2) is 48.32 g.kg -1 The method comprises the steps of carrying out a first treatment on the surface of the Q is the originalWaste water flow, m 3 ·d -1 The method comprises the steps of carrying out a first treatment on the surface of the TDS is the salinity (mg.kg) of the raw wastewater -1 ) The average value of 300 groups of conductivity sigma (ms/cm) data in one week is taken, and the average value is converted into TDS through an empirical value formula, wherein the TDS is equal to the conductivity sigma multiplied by 0.5-0.7.
Similarly, the number of theoretical days of bentonite may be calculated by using the above formula 1, and only the difference in coefficients may be found.
In this example, the anaerobic ammonium oxidation granular sludge 12 used for inoculation was taken from a stably operating anaerobic ammonium oxidation reactor, and the anaerobic ammonium oxidation granular sludge was inoculated in a blood red color with a TS concentration of 71.5.+ -. 13.5 g.L -1 VS concentration was 45.8.+ -. 7.6 g.L -1 The VS/TS ratio was 0.64.+ -. 0.01.Candidatus Kuenenia is the main AnAOB in the inoculated sludge, has strong affinity to the matrix and has a relative abundance of 32.8%.
In addition, in a preferred embodiment, the hydrotalcite as the adsorption filler is modified in view of the problem of high operation cost caused by the large amount of the adsorption filler. Namely, the adsorption filler to be filled in the above-mentioned apparatus may be modified clay mineral modified hydrotalcite (LDHs) and Bentonite (Bentonite). In this example, the clay mineral modified hydrotalcite (LDHs) was prepared as follows:
hydrotalcite is prepared by adopting a coprecipitation method: mg (NO) 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 The mol ratio of O to Mg to Al is 3:1 to prepare a mixed salt solution A, wherein Mg (NO 3 ) 2 ·6H 2 O concentration is 10mmol/L, al (NO) 3 ) 3 ·9H 2 The O concentration was 3.3mmol/L. NaOH (2.3 mol/L) and NaNO are prepared 3 (3.5 mol/L) the alkali solution B is mixed. Rapidly mixing salt solution A and alkali solution B, stirring, adjusting pH to 9.5 to obtain white slurry suspension, placing in a constant temperature water bath at 75deg.C, reacting for 12 hr, cooling, vacuum filtering, washing to neutrality, oven drying at 80deg.C, and grinding to obtain clay mineral modified hydrotalcite (LDHs), namely NO 3 --LDH。
The clay mineral modified hydrotalcite is prepared by reacting with activatorImpurities and ions between layers are replaced, so that the modified void volume is higher, the specific surface area is increased, and the adsorption performance is improved. The modified hydrotalcite can be used for adsorbing Cl in solution - And SO 4 2- The corresponding maximum adsorption amount is 48.32 mg.g -1 And 76.54 mg.g -1 . And the modified hydrotalcite has a structural 'memory' effect. The LDHs can be roasted at a certain temperature to remove interlayer anions, the layered structure collapses at the moment, and then the LDHs can adsorb anions in the solution when placed in the solution containing anions, so that the layered structure can be recovered. Therefore, the roasted LDHs can be reused to effectively remove target anions in the wastewater, and the overall operation cost is greatly reduced.
In the preferred embodiment, bentonite is used which adsorbs Na + 、Mg 2+ 、K + And Ca 2+ The corresponding maximum adsorption amounts are 38.21, 5.45, 11.24 and 14.58 mg.g -1 . The adding ratio of the modified hydrotalcite to the bentonite is 1:2. The two adsorption materials are matched with each other, and Cl in the wastewater solution is in the process of the wastewater rising and flowing through the hydrotalcite and bentonite mixed filler layer - And SO 4 2- Fully contacts with hydrotalcite, and anions enter the layered structure of hydrotalcite to be adsorbed. While Na is + 、Mg 2+ 、K + And Ca 2+ Fully contacts with bentonite and is adsorbed on the surface of the bentonite.
The following describes the technical scheme of the invention based on the device for quickly starting salt-tolerant anaerobic ammonia oxidation and the wastewater treatment method in the embodiment, taking simulated nitrogenous wastewater containing sodium chloride as an example, so that the effect of the device can be better understood by a person skilled in the art.
Examples
The device is made of organic glass, the inner diameter of a reaction zone is 60mm, the total height is 550mm, the effective volume is 1.2L, the total volume is 2.2L, and the inoculated sludge volume is 0.8L. The reactor was run for 1h with a gradient of 0, 10, 40, 80, 120, 160, 240, 320, 400, 500, 600mM to gradually increase the NaCl concentration in the feed water. After the reactor is operated stably under a certain salt concentration (TN removal rate > 80%), the NaCl concentration is continuously increased to carry out the next salinity test. The reactor was run in a thermostated chamber (temperature 33.+ -. 1 ℃).
The main flow of the integrated device is as follows: the salt-containing and nitrogen-containing wastewater to be treated is fully mixed with the effluent backwater water in the pipeline mixer, the mixed solution then enters the adsorption zone, and the backwater water is utilized to dilute the raw water, so that the salinity of the inlet water of the adsorption zone can be reduced. In the process of upward flow of wastewater through hydrotalcite and bentonite mixed filler layer, cl in wastewater solution - And SO 4 2- Fully contacts with hydrotalcite, and anions enter the layered structure of hydrotalcite to be adsorbed. While Na is + 、Mg 2+ 、K + And Ca 2+ Fully contacts with bentonite and is adsorbed on the surface of the bentonite. The wastewater with partial salinity removed by the adsorption zone continuously rises to enter an anaerobic ammonia oxidation zone, and ammonia nitrogen and nitrite nitrogen are converted into N under the action of anaerobic ammonia oxidation granular sludge 2 . The wastewater treated by the anaerobic ammonia oxidation zone continuously enters a separation zone, gas, liquid and solid are separated under the action of a three-phase separator, the gas is discharged through an exhaust pipe, the anaerobic ammonia oxidation granular sludge returns to the biological denitrification reaction zone again, and effluent reaching the standard is discharged through an overflow weir and is discharged with filler and sludge periodically. The denitrification effect in the stable operation period of the rapid start-up salt-tolerant anaerobic ammonia oxidation device is shown in fig. 4: during the period from 3.5.2018 to 15.5.2019, the reactor was operated for more than 400 days at different NaCl concentrations. Before adding NaCl, the reactor is discharged with water NH 4 + -N and NO 2 - -N is 5.64+ -6.84 mg.L, respectively -1 And 2.98.+ -. 2.82 mg.L -1 ，NH 4 + -N、NO 2 - The removal rates of N and TN are stabilized at 97.11+ -3.61%, 98.78+ -1.22% and 86.95+ -1.86%, and the NRR of the reactor is 10.43 kg.m -3 ·d -1 . After one month of steady operation, the concentration of the influent matrix and NLR were kept unchanged, and the NaCl concentration was gradually increased to 500mM (0-377 d) in 9 times. Reactor effluent NH during the course of increasing NaCl concentration from 80mM to 120mM (122 d) and from 120mM to 160mM (173 d), respectively 4 + -N、NO 2 - Temporary small increases in the N and TN concentrations;after the operation is continued for a period of time (12-13 d), the effluent quality is recovered; when the NaCl concentration reaches 500mM, water NH is discharged 4 + -N and NO 2 - N concentrations are 17.29.+ -. 10.91 mg.L, respectively -1 And 21.35+ -15.12 mg.L -1 ，NH 4 + -N、NO 2 - The removal rates of N and TN were 91.80.+ -. 5.53%, 92.25.+ -. 5.73% and 80.90.+ -. 7.69%, respectively, and the NRR was 9.72.+ -. 1.15 kg.m -3 ·d -1 . During the course of increasing the NaCl concentration from 500mM to 600mM (377 d), NO in the effluent 2 - The N concentration is greatly increased and stabilized to 256.58 +/-15.04 mg.L -1 TN removal rate was greatly reduced to 7.41.+ -. 2.34% (381-399 d), and reactor efficiency was difficult to recover to the pre-salinity elevation level, thus it was found that the tolerance range of the apparatus to NaCl salinity was 0 to 500mM (2.9% salinity).
The above embodiment is only a preferred embodiment of the present invention, but it is not intended to limit the present invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, all the technical schemes obtained by adopting the equivalent substitution or equivalent transformation are within the protection scope of the invention.
Claims (8)
1. A device for quickly starting salt-tolerant anaerobic ammoxidation is characterized in that: the inside of the integrated reactor shell is sequentially divided into an adsorption zone (I), an anaerobic ammonia oxidation zone (II) and a separation zone (III) from bottom to top; the adsorption zone (I) is in an inverted cone and cylinder combination shape, an inner cavity is divided into an upper layer and a lower layer by a transverse partition plate (5), cation adsorption filler (22) is filled in the lower layer inner cavity, a lower layer filler feed pipe (23) and a lower layer filler discharge pipe (24) are respectively arranged above and below the cation adsorption filler (22), anion adsorption filler (15) is filled in the upper layer inner cavity, and an upper layer filler feed pipe (14) and an upper layer filler discharge pipe (16) are respectively arranged above and below the anion adsorption filler (15); a water inlet (17) is arranged at the bottom of the adsorption zone (I); a diaphragm plate (5) is also arranged between the upper end of the adsorption zone (I) and the bottom of the anaerobic ammonia oxidation zone (II); a plurality of overflow holes (21) are formed in each diaphragm plate (5), an overflow pipe (25) with the top higher than the upper surface of the diaphragm plate (5) is arranged in each overflow hole (21), a conical cover (26) is arranged right above each overflow pipe (25), and the conical cover (26) is suspended from the overflow pipe (25) and the upper surface of the diaphragm plate (5) to form a channel for water to flow out;
anaerobic ammonia oxidation granular sludge (12) is filled in the anaerobic ammonia oxidation zone (II); the top of the anaerobic ammonia oxidation zone (II) is provided with a mud inlet pipe (11), and the bottom is provided with a mud discharge pipe (13); an overflow groove (8) is arranged at the upper part of the inner side wall of the separation zone (III), and a water collecting cavity of the overflow groove (8) is connected with one end of a water outlet pipe (7); the center of the separation zone (III) is provided with an inverted Y-shaped three-phase separator (10), and the upper part of the separation zone is provided with an exhaust pipe (9); the device is characterized in that a water storage tank (1) is arranged in the front of the device, a conductivity detector (2) is arranged in the water storage tank (1), the water storage tank (1) is connected with one inlet of a pipeline mixer (18) through a waste water pipe (19) with a waste water metering pump (20), the other end of the water outlet pipe (7) is divided into two paths, one path of water outlet is discharged, the other path of water outlet is connected with the other inlet of the pipeline mixer (18) through a return pipe (4) with a return metering pump (3), and an outlet of the pipeline mixer (18) is connected with a water inlet (17) and is used for fully mixing waste water with return water and then inputting the mixed water into the device from the bottom end of an adsorption zone (I);
the three-phase separator (10) is an inverted Y-shaped cylindrical three-phase separator combination, and the collected nitrogen is discharged through an exhaust pipe (9) at the top; the height of the part of the three-phase separator (10) exposed out of the liquid level is 1/3-1/6 of the total height of the three-phase separator.
2. A rapid start-up salt tolerant anaerobic ammoxidation apparatus according to claim 1, wherein: the height ratio of the adsorption zone (I) to the upper anaerobic ammonia oxidation zone (II) is 1: (1-1.5), the volume of cation adsorption filler (22) filled in the inner cavity of the lower layer of the adsorption zone (I) accounts for 3/4 of the total volume of the inner cavity of the lower layer, the volume of anion adsorption filler (15) filled in the inner cavity of the upper layer of the adsorption zone (I) accounts for 3/4 of the total volume of the inner cavity of the upper layer, and the volume of anaerobic ammonia oxidation granular sludge (12) filled in the anaerobic ammonia oxidation zone (II) accounts for 1/4 of the total volume of the anaerobic ammonia oxidation zone (II).
3. A rapid start-up salt tolerant anaerobic ammoxidation apparatus according to claim 1, wherein: the cation adsorption filler (22) is bentonite, and the anion adsorption filler (15) is hydrotalcite.
4. A rapid start-up salt tolerant anaerobic ammoxidation apparatus according to claim 1, wherein: the diameter of the pore of the overflow hole (21) on the diaphragm plate (5) is 2-3 mm, and the gap between the conical cover (26) and the upper surface of the diaphragm plate (5) is 2-3 mm, so that water flow is ensured to pass through the diaphragm plate (5) from bottom to top and upward solid particles are prevented from passing through the diaphragm plate (5) from top to bottom in a countercurrent manner.
5. A rapid start-up salt tolerant anaerobic ammoxidation apparatus according to claim 1, wherein: three sampling ports (6) are arranged on the side wall of the anaerobic ammonia oxidation zone (II) at equal intervals and are used for analyzing water quality in the denitrification reactor.
6. A rapid start-up salt tolerant anaerobic ammoxidation apparatus according to claim 1, wherein: the automatic control assembly comprises a conductivity detector (2), a Programmable Logic Controller (PLC) and a liquid flow regulator assembly; the conductivity detector (2) is connected with a Programmable Logic Controller (PLC) through a data signal; the liquid flow regulator assembly comprises the waste water metering pump (20) and the backflow metering pump (3); the liquid flow regulator is in data signal connection with the programmable PLC controller; the programmable PLC is also respectively connected with a waste water inlet valve arranged on the waste water pipe (19) and a backflow inlet valve arranged on the backflow pipe (4) in a control manner; the automatic control assembly further comprises a wireless transceiver connected with the programmable PLC controller, the wireless transceiver is in communication connection with a cloud server through a wireless network, and the cloud server is connected with a remote monitoring center or an intelligent mobile terminal through the wireless network.
7. A method for treating industrial wastewater containing nitrogen and salt by using the rapid start-up salt-tolerant anaerobic ammonia oxidation device according to any one of claims 1 to 6, which is characterized by comprising the following steps:
fully mixing the salt-containing and nitrogen-containing wastewater to be treated with water outlet backwater water in a pipeline mixer (18), diluting raw water by using backwater water to reduce the salinity of water inlet in an adsorption zone, and enabling mixed solution to enter the adsorption zone (I);
in the process that the wastewater flows upwards through the cation adsorption filler (22) at the lower layer and the anion adsorption filler (15) at the upper layer of the adsorption zone (I), na in the wastewater solution + 、Mg 2+ 、K + And Ca 2+ Is fully contacted with and adsorbed on the surface of the cation adsorption filler (22), and anions Cl - And SO 4 2- The layered structure entering the anion-adsorbing filler (15) is adsorbed;
the wastewater with partial salinity removed by the adsorption zone (I) continuously rises to enter the anaerobic ammonia oxidation zone (II), and ammonia nitrogen and nitrite nitrogen are converted into N under the action of the anaerobic ammonia oxidation granular sludge (12) 2 ；
The wastewater treated by the anaerobic ammonia oxidation zone (II) continuously enters a separation zone (III), gas, liquid and solid are separated under the action of a three-phase separator (10), the gas is discharged from an exhaust pipe (9), anaerobic ammonia oxidation granular sludge (12) returns to a biological denitrification reaction zone again, clear effluent is directly discharged from a water outlet pipe after passing through an overflow tank (8), and the other part of the effluent is returned to a pipeline mixer (18) through a return pipe (4) and is fully mixed with salt-containing wastewater in a wastewater pipe (19);
continuously introducing wastewater into the device according to the flow, and controlling the salinity of mixed water entering the device to be within 1% by controlling the reflux ratio of the reflux water inflow and the wastewater water inflow at the initial start-up period of a reactor for 0-15 days after sludge inoculation; after the device stably operates, gradually reducing the reflux ratio, so as to gradually increase the salinity in the inflow water, and carrying out salt-tolerant domestication on anaerobic ammonia oxidation granular sludge received in the reactor; meanwhile, in the circulation process, based on a conductivity detector (2) and a wastewater metering pump (20) which are arranged in a wastewater storage tank, the total salt content of wastewater entering a reactor is calculated through simulation, the theoretical using days of the filler are calculated by combining the maximum adsorption quantity of the two layers of adsorption fillers, and then the two layers of adsorption fillers are updated regularly, so that the adsorption capacity of the two layers of adsorption fillers is always kept.
8. The method for treating industrial wastewater containing nitrogen and salt according to claim 7 wherein said anaerobic ammonium oxidation granular sludge (12) is obtained from a stably operating anaerobic ammonium oxidation reactor, and the main bacterial species in said anaerobic ammonium oxidation granular sludge (12) areCandidatus KueneniaThe relative abundance was 32.8%; in the domestication process, the water quality in the denitrification reaction zone is analyzed through a sampling port (6) arranged in the anaerobic ammonia oxidation zone at regular intervals, and the reflux ratio is dynamically adjusted to maintain the stability of water outlet.
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| CN201911039583.8A CN110642373B (en) | 2019-10-29 | 2019-10-29 | Device and method for quickly starting salt-tolerant anaerobic ammonia oxidation |
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