CN114195261A - Long-term storage and rapid activity recovery method of anaerobic ammonium oxidation sludge - Google Patents
Long-term storage and rapid activity recovery method of anaerobic ammonium oxidation sludge Download PDFInfo
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Abstract
The invention belongs to the technical field of environmental pollution treatment, and provides a long-term storage and rapid activity recovery method for anaerobic ammonium oxidation sludge, which is characterized in that the anaerobic ammonium oxidation sludge is transferred into a biological filter column, and high-concentration synthetic wastewater is added periodically and then is kept stand for storage; the stored anaerobic ammonium oxidation sludge activity recovery method is to gradually adjust the hydraulic retention time and the concentration of a water inlet substrate according to the denitrification performance. The method is simple to operate and low in operation cost, the relative abundance of the anammox bacteria can be kept to 73.6% before storage at the highest level after 1-24 months of storage, the recovery of the anaerobic ammonia oxidation performance can be realized only by adjusting the operation parameters such as hydraulic retention time and the like, the method is quick and efficient, the recovery can be completed within 30 days at the shortest time, the theoretical basis and the technical guidance are provided for the storage and the restart of the idle sludge, and the method is favorable for solving the problems that the anammox sludge cannot be stored for a long time after the stop of a sewage treatment plant and the process performance is difficult to recover quickly.
Description
Technical Field
The invention belongs to the technical field of environmental pollution treatment, and particularly relates to a long-term storage and rapid activity recovery method for anaerobic ammonium oxidation sludge.
Background
With the development of social economy and the gradual deepening of urban construction, the discharge of nitrogen-containing wastewater is gradually increased year by year, which not only can cause direct damage and influence on an ecological system, but also can cause indirect harm to human society. The anaerobic ammonia oxidation process is a biochemical process for generating nitrogen by reacting ammonia nitrogen and nitrite under the action of anaerobic ammonia oxidizing bacteria. The process is proposed since the 90 s of the 20 th century, and is considered to be a denitrification process with great development prospect as the process does not need to add organic carbon sources, saves aeration energy consumption, reduces the emission of greenhouse gases, and conforms to the concept of green development under the current energy crisis and global climate change background. In recent years, anaerobic ammonia oxidation technology has been put into practical use in low C/N ratio wastewater such as landfill leachate, domestic sewage, coking wastewater, sludge digestion liquid, and feed processing wastewater. To date, over 200 anammox facilities have been put into use worldwide. However, in practical applications, biological treatment of industrial wastewater often faces significant challenges in influent water quality characteristics and sludge storage, and sewage treatment plants may be completely shut down for weeks or even months due to industrial downtime, equipment maintenance and repair, downtime during holidays, and external resistance in other emergency situations. In addition, the proliferation cycle of the anammox is slow, and the anammox has strong sensitivity to the environment, and after the anaerobic ammonium oxidation bacteria are starved for a long time, the structure and the stability of the sludge and the activity of microorganisms can be greatly influenced, so that the application and the development of the anammox process in the field of sewage treatment are greatly limited. Therefore, there is a need to develop a rapid recovery strategy for the anammox process performance after storage and long term downtime of the sludge.
In order to solve the above problems, researchers have conducted appropriate studies. The research of Xing and the like shows that the starvation temperature has obvious influence on the shape and physical characteristics of the anaerobic ammonia oxidation granular sludge, and the storage at 4 ℃ has better denitrification performance than that at 20 ℃. Homokiol et al reported that proper storage conditions maximize retention of anammox activity and faster recovery of the stored species at high substrate concentrations. However, the current application is low-temperature storage by means of a refrigerator, which greatly limits the storage space of sludge. In addition, researchers have invented methods for restoring the activity of anammox bacteria: for example, patent No. CN112759065A discloses a method for rapid start of an anammox reactor and recovery of anammox bacteria activity, which activates anammox bacteria activity by increasing the concentration of quorum sensing signal molecules and synergistic action of an external electromagnetic method, the total nitrogen removal rate is stabilized at about 70%, and has a significant difference from the theoretical denitrification rate (89%) of the anammox process, and the additional signal molecules and electromagnetic action increase material consumption and energy consumption, which is not in accordance with the concept of green development. Existing recovery studies on anammox processes require additional materials, which not only increase operating costs, but also introduce new pollution.
Disclosure of Invention
The invention aims to provide a method for long-term storage and rapid activity recovery of anaerobic ammonium oxidation sludge, aiming at the problems of restarting of idle sludge and intermittent production stoppage of the conventional sewage treatment plant. Good storage effect can be obtained only by placing the anaerobic ammonia oxidation sludge in the biological filter column, and the recovery culture of anaerobic ammonia oxidation bacteria is realized by adjusting the operating parameters such as hydraulic retention time, water inlet substrate concentration and the like, so that the stable operation of the anaerobic ammonia oxidation process is realized.
One of the purposes of the invention is to provide a method for long-term storage of anaerobic ammonia oxidation sludge, which comprises the following steps:
s1, standing and precipitating the anaerobic ammonium oxidation sludge in the reactor A, and removing supernatant; then adding high-concentration synthetic wastewater to the original liquid level, wherein the concentrations of ammonia nitrogen and nitrite in the wastewater are respectively 3-5 times of those of the wastewater during the operation of the reactor A, the concentrations of other elements are kept consistent with those of the wastewater during the operation of the reactor A, uniformly stirring, standing for precipitation, removing supernatant, and repeating for 3-5 times;
s2, transferring the sludge obtained in the step S1 to a biological filter column B filled with volcanic rock, fully mixing, wrapping the sludge with black tinfoil paper, and standing for storage;
s3, removing the supernatant at regular intervals, adding the synthetic wastewater with the same concentration to the original liquid level, uniformly stirring, standing for precipitation, removing the supernatant, repeating for 3-5 times, and standing for 1-24 months.
Preferably, in S1 and S3, the standing and precipitating time is 0.5-2 h.
Preferably, in S2, the particle size of the volcanic rock is 6-12 mm, the effective filling rate is less than 30%, the height-diameter ratio of the filter column is 3-10, and the effective volume is 1-5 times of that of the reactor A.
Preferably, in S3, the interval time is 2 to 4 weeks.
The invention also aims to provide a method for quickly recovering the activity of the anaerobic ammonia oxidation sludge stored by the method, which comprises the following steps:
step 1, recovery initial stage: removing the supernatant in the biological filter column B, adding the low-concentration synthetic wastewater to the original liquid level, uniformly stirring, standing for precipitation, removing the supernatant, and repeating for 3-5 times; setting hydraulic retention time, starting inflow water and outflow water to wash out floating aging and shedding biomembranes, providing an autotrophic environment for anaerobic ammonium oxidation bacteria and consuming residual dissolved oxygen;
step 2, recovering the medium term: calculating the ratio of the hydraulic retention time/total nitrogen of inlet water of the reactor A before storage, recording as R, and circularly operating the biological filter column B in the step 1 in the operation mode of the reactor A until the total nitrogen removal rate reaches more than 30% so as to screen active anaerobic ammonium oxidation bacteria; then, adjusting the ratio of R until the total nitrogen removal rate reaches more than 80%;
step 3, final recovery: transferring the biological membrane in the biological filter column B in the step 2 to an original reactor A before storage, operating under the condition of 2R, gradually adjusting R, stopping adjustment and continuing operation when the total nitrogen removal rate is lower than 80%, and continuing to adjust R step by step when the total nitrogen removal rate is higher than 80% for 3 consecutive days until the ratio of the two is recovered to R, recovering the hydraulic retention time and the total nitrogen of inlet water to the values before storage, wherein the ratio of the abundance of the anammox bacteria in the sludge to the abundance of the anammox bacteria in the sludge before storage is greater than or equal to 1, and the ratio of the abundance of the anammox bacteria in the sludge after storage is greater than 1.5, namely the anammox process is successfully recovered.
Preferably, in the step 1, the standing and precipitating time is 0.5-2 h.
Preferably, in the step 1, in the low-concentration synthetic wastewater, the concentration ratio of the nitrite to the ammonia nitrogen in the inlet water is 0.5-1.0, the ammonia nitrogen concentration is 10-30 mg/L, and the concentrations of other elements are consistent with those of the reactor A during operation; setting the hydraulic retention time to be 2-6 h.
Preferably, in the step 2, the R is adjusted in a mode that the hydraulic retention time is 3-20 hours or the concentration ratio of the water inlet nitrite to the ammonia nitrogen is 0.8-1.4.
Preferably, in step 2, the R ratio is adjusted specifically as follows: the ratio is adjusted to 1.5R, the operation is carried out until the total nitrogen removal rate reaches more than 60%, and then the operation is adjusted to 2R until the total nitrogen removal rate reaches more than 80%.
Preferably, in step 3, the step-by-step adjustment of R is as follows: the ratio of the amount of the organic solvent is adjusted to 0.2-0.5R.
Compared with the prior art, the invention has the beneficial effects that:
1. the method for storing the anaerobic ammonium oxidation sludge in the long-term production halt or idle state can realize large-scale storage at normal temperature, and has the advantages of low cost, long storage time and simple operation. Volcanic rock filled by the biological filter column can provide nutrient substances for microorganisms through residual nitrogen adsorbed by pores and internal mineral substances, so that the problem of operation and maintenance of a reactor during intermittent production stoppage or holidays of an anaerobic ammonia oxidation process is effectively solved, and an effective method is provided for the problem of storage of idle sludge.
2. The method for rapidly recovering the activity of the anaerobic ammonia oxidation sludge after long-term production halt or idling has the advantages of low operation cost, no need of adding extra substances, capability of recovering the operation state and the denitrification effect before storage in a short time by only changing the operation conditions, no secondary pollution, rapidness and high efficiency, and capability of providing theoretical support and technical guidance for the recovery of the anaerobic ammonia oxidation process and the restarting of the idling sludge.
Drawings
FIG. 1 is a graph of the total nitrogen removal and total nitrogen removal load for an anammox process prior to storage, after storage and after recovery during example 1 of the present invention; total nitrogen removal (%) (total nitrogen inlet-total nitrogen outlet) 100/total nitrogen inlet, total nitrogen removal load (kg/(m) total nitrogen removal3d) (total nitrogen in water-total nitrogen out) 24/(1000 HRT);
FIG. 2 is a graph showing the relative abundance changes of the main genera of microorganisms before storage, after storage, and after recovery during example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention, which will be limited only by the appended claims, wherein the various materials, reagents, instruments and equipment used in the following examples are commercially available or may be prepared by conventional methods.
Example 1
A method for long term storage of anammox sludge comprising the steps of:
s1, standing and precipitating the anaerobic ammonium oxidation sludge in the reactor A for 0.5h, discarding the supernatant, then adding the high-concentration synthetic wastewater to the original liquid level (1L), uniformly stirring, standing and precipitating again, discarding the supernatant, and repeating the steps for 3 times; the high-concentration synthetic wastewater comprises: (NH)4)2SO4、NaNO2、1200mg/L NaHCO3、68mg/L CaCl2、68mg/L KH2PO4、150mg/L MgSO4The trace element I comprises 5000mg/L EDTA and 5000mg/L FeSO4The trace elements II comprise 15000mg/L EDTA and 430mg/L ZnSO4·7H2O、240mg/L CoCl2·6H2O、990mg/L MnCl2·4H2O、250mg/L CuSO4·5H2O、220mg/L Na2MoO4·2H2O、190mg/L NiCl2·6H2O、210mg/L Na2SeO4·10H2O, wherein the concentrations of ammonia nitrogen and nitrite are respectively 4 times of those of the reactor A during operation, the concentrations of ammonia nitrogen and nitrite are both 200mg/L, and the concentrations of other elements are consistent with those of the reactor A during operation;
s2, transferring the sludge obtained in the step S1 to a biological filter column B filled with volcanic rock, wherein the particle size of the volcanic rock is 6-8 mm, the effective filling rate is less than 30%, the height-diameter ratio of the filter column is 3, the effective volume is 2L which is 2 times that of a reactor A, the outside of the filter column is wrapped by black tinfoil paper, and the sludge and the volcanic rock are fully mixed and then are placed and stored indoors; if the reactor form of the reactor A is the same as that of the reactor B, the reactor A can be directly changed into the reactor B for operation without transfer;
s3, periodically removing the supernatant at intervals of 2 weeks, adding the synthetic wastewater with the same concentration to the original liquid level (1L), uniformly stirring, standing for precipitation for 0.5h, removing the supernatant, repeating the steps for 3 times, and continuously standing and storing in a room. After the operation, the storage time of the anaerobic ammonium oxidation sludge is 4 months.
The method for quickly recovering the activity of the anaerobic ammonia oxidation sludge stored by the method comprises the following steps:
step 1, recovery initial stage: abandon the supernatant in biological filtration column B, add low concentration synthetic waste water to former liquid level (1L), the precipitate of standing after the stirring is even for 0.5h, abandon the supernatant, repeat 3 times so, low concentration synthetic waste water includes: (NH)4)2SO4、NaNO2、1200mg/L NaHCO3、68mg/L CaCl2、68mg/L KH2PO4、150mg/L MgSO4The trace element I comprises 5000mg/L EDTA and 5000mg/L FeSO4The trace elements II comprise 15000mg/L EDTA and 430mg/L ZnSO4·7H2O、240mg/L CoCl2·6H2O、990mg/L MnCl2·4H2O、250mg/L CuSO4·5H2O、220mg/L Na2MoO4·2H2O、190mg/L NiCl2·6H2O、210mg/L Na2SeO4·10H2O, wherein the concentrations of ammonia nitrogen and nitrite are both 20mg/L, and the concentrations of other elements are consistent with those of the reactor A during operation; setting the hydraulic retention time to be 2h, starting inflow water and outflow water, running for 1 day to wash out floating aging shedding biomembranes, providing an autotrophic environment for anaerobic ammonium oxidation bacteria and consuming residual dissolved oxygen;
step 2, recovering the medium term: the hydraulic retention time of the reactor A before storage is 3h, the concentrations of the ammonia nitrogen and the nitrite in the inlet water are both 50mg/L, the ratio of the hydraulic retention time to the total nitrogen in the inlet water is recorded as R, the total nitrogen in the inlet water is the sum of the ammonia nitrogen, the nitrite and the nitrate, and the R value is 30 hL/g; as shown in FIG. 1, the total nitrogen removal rate and the total nitrogen removal load after storage were 23.4% and 0.269 kg/(m)3d) (ii) a Under the condition, the biological filter column B is used for screening active anaerobic ammonium oxidation bacteria, and the total nitrogen removal rate reaches 33.6 percent after 5 days of circulating operation at room temperature. Then, changing the hydraulic retention time to 4.5h, keeping the concentration of the ammonia nitrogen and the nitrite in the inlet water unchanged, adjusting the ratio of the hydraulic retention time to the total nitrogen in the inlet water from 30hL/g to 45hL/g so as to gradually recover the activity of the anaerobic ammonia oxidizing bacteria, and circularly operating at room temperature for 11 days to ensure that the total nitrogen removal rate reaches 62.2 percent; continuously changing the hydraulic retention time to 6h, keeping the concentration of the ammonia nitrogen and the nitrite in the inlet water unchanged, adjusting the ratio of the hydraulic retention time to the total nitrogen in the inlet water from 45hL/g to 60hL/g, and circularly operating at room temperature for 7 days to achieve a total nitrogen removal rate of 82.6 percent;
step 3, final recovery: transferring the biological membrane in the biological filter column B into an original reactor A before storage, and operating for 3 days under the condition that the ratio of hydraulic retention time to total nitrogen of inlet water is 60 hL/g; then reducing the hydraulic retention time to 4.5h, keeping the concentration of the ammonia nitrogen and the nitrite in the inlet water unchanged, adjusting the ratio of the hydraulic retention time to the total nitrogen in the inlet water from 60hL/g to 45hL/g, circularly operating at room temperature for 6 days, and continuously increasing the total nitrogen removal rate to more than 80 percent for more than 3 days. Continuously reducing the hydraulic retention time to 3h, keeping the concentration of the ammonia nitrogen and the nitrite in the inlet water unchanged, and retaining the hydraulic retention timeThe ratio of total nitrogen in the feed water is adjusted from 45hL/g to 30hL/g, the circulating operation is carried out for 5 days at room temperature, the total nitrogen removal rate is higher than 80 percent for more than 3 continuous days, and the total nitrogen removal rate is stabilized at 88.9 percent. As shown in FIG. 1, the total nitrogen removal rate and the total nitrogen removal load before storage were 85.1% and 0.720 kg/(m)3d) After storage, the total nitrogen removal rate and the total nitrogen removal load were 23.4% and 0.269 kg/(m)3d) After recovery, the total nitrogen removal rate and the total nitrogen removal load were 88.9% and 0.758 kg/(m)3d) The total nitrogen removal load after recovery was 1.1 times and 2.8 times the total nitrogen removal load before and after storage, respectively. As shown in figure 2, the relative abundance of the anammox bacteria before and after storage is 23.5% and 17.3%, respectively, after the operation of 38 days, the relative abundance is restored to 32.0%, and the ratio of the relative abundance of the anammox bacteria after restoration to the abundance of the sludge before storage is 1.4>1, the abundance ratio of the sludge after storage is 1.8>1.5, the anaerobic ammonia oxidation process is successfully recovered.
Example 2
A method for long term storage of anammox sludge comprising the steps of:
s1, standing and precipitating the anaerobic ammonia oxidation sludge in the reactor A to be stopped for 0.5h, discarding the supernatant, then adding the high-concentration synthetic wastewater to the original liquid level (2L), standing and precipitating again after uniformly stirring, discarding the supernatant, and repeating the steps for 5 times; the high-concentration synthetic wastewater comprises: (NH)4)2SO4、NaNO2、1200mg/L NaHCO3、68mg/L CaCl2、68mg/L KH2PO4、150mg/L MgSO4The trace element I comprises 5000mg/L EDTA and 5000mg/L FeSO4The trace elements II comprise 15000mg/L EDTA and 430mg/L ZnSO4·7H2O、240mg/L CoCl2·6H2O、990mg/L MnCl2·4H2O、250mg/L CuSO4·5H2O、220mg/L Na2MoO4·2H2O、190mg/L NiCl2·6H2O、210mg/L Na2SeO4·10H2O, wherein the concentration of ammonia nitrogen and the concentration of the nitrite are respectively 4 times of that before the production halt, the concentration of the ammonia nitrogen is 120mg/L, the concentration of the nitrite is 168mg/L,the concentration of other elements is consistent with that before production halt;
s2, transferring the sludge obtained in the step S1 to a biological filter column B filled with volcanic rock, wherein the particle size of the volcanic rock is 6-8 mm, the effective filling rate is less than 30%, the height-diameter ratio of the filter column is 5, the effective volume is 3L, which is 1.5 times of that of a reactor A before production halt, the outside of the filter column is wrapped by black tinfoil paper, and the sludge and the volcanic rock are fully mixed and then are placed and stored indoors; if the reactor form of the reactor A is the same as that of the reactor B, the reactor A can be directly changed into the reactor B for operation without transfer;
s3, periodically removing the supernatant at intervals of 4 weeks, adding the synthetic wastewater with the same concentration to the original liquid level (2L), uniformly stirring, standing for precipitation for 0.5h, removing the supernatant, repeating the steps for 5 times, and continuously standing and storing in a room. The operation is carried out in this way, and the storage period is 24 months.
The method for quickly recovering the activity of the anaerobic ammonia oxidation sludge stored by the method comprises the following steps:
step 1, recovery initial stage: abandoning the supernatant in the biological filter column B, adding low-concentration synthetic wastewater to the original liquid level (2L), standing and precipitating for 0.5h after uniformly stirring, abandoning the supernatant, repeating the steps for 5 times, and including the low-concentration synthetic wastewater: (NH)4)2SO4、NaNO2、1200mg/L NaHCO3、68mg/L CaCl2、68mg/L KH2PO4、150mg/L MgSO4The trace element I comprises 5000mg/L EDTA and 5000mg/L FeSO4The trace elements II comprise 15000mg/L EDTA and 430mg/L ZnSO4·7H2O、240mg/L CoCl2·6H2O、990mg/L MnCl2·4H2O、250mg/L CuSO4·5H2O、220mg/L Na2MoO4·2H2O、190mg/L NiCl2·6H2O、210mg/L Na2SeO4·10H2O, wherein the concentration of ammonia nitrogen is 20mg/L, the concentration of nitrite is 10mg/L, and the concentrations of other elements are consistent with those before production halt; setting the hydraulic retention time to be 4h, starting water inlet and water outlet, running for 1 day to wash out the floating aged and fallen biomembrane, providing autotrophic environment for anaerobic ammonium oxidation bacteria and consuming residual solutionOxygen is decomposed;
step 2, recovering the medium term: the hydraulic retention time of the reactor A before storage is 3h, the concentrations of the ammonia nitrogen and the nitrite in the inlet water are respectively 30mg/L and 42mg/L, the ratio of the hydraulic retention time to the total nitrogen in the inlet water is recorded as R, and the R value is 41.7 hL/g; under the condition, the biological filter column B is used for screening active anaerobic ammonium oxidation bacteria, and the total nitrogen removal rate reaches 31.5 percent after the biological filter column B is circularly operated for 10 days at room temperature. Then, changing the hydraulic retention time to 7.5h, respectively adjusting the concentrations of the ammonia nitrogen and the nitrite in the inlet water to 50mg/L and 70mg/L, and adjusting the ratio of the hydraulic retention time to the total nitrogen in the inlet water from 41.7hL/g to 62.5hL/g so as to gradually recover the activity of the anammox bacteria, wherein the total nitrogen removal rate reaches 60.9 percent after the anaerobic ammonia oxidation bacteria circularly operate at room temperature for 12 days; continuously changing the hydraulic retention time to 16h, respectively adjusting the concentrations of the ammonia nitrogen and the nitrite in the inlet water to 80 mg/L and 112mg/L, adjusting the ratio of the hydraulic retention time to the total nitrogen in the inlet water from 62.5hL/g to 83.3hL/g, circularly operating at room temperature for 8 days, and achieving the total nitrogen removal rate of 81.3 percent;
step 3, final recovery: transferring the biological membrane in the biological filter column B into an original reactor A before storage, and operating for 3 days under the condition that the ratio of hydraulic retention time to total nitrogen of inlet water is 83.3 hL/g; then reducing the hydraulic retention time to 7.5h, respectively adjusting the concentration of the ammonia nitrogen and the nitrite in the inlet water to 50mg/L and 70mg/L, adjusting the ratio of the hydraulic retention time to the total nitrogen in the inlet water from 83.3hL/g to 62.5hL/g, circularly operating at room temperature for 8 days, and continuously increasing the total nitrogen removal rate to be higher than 80 percent for more than 3 days. Continuously reducing the hydraulic retention time to 3h, respectively adjusting the concentration of the influent ammonia nitrogen and the concentration of the nitrite to 30mg/L and 42mg/L, adjusting the ratio of the hydraulic retention time to the total nitrogen of the influent from 62.5hL/g to 41.7hL/g, circularly operating at room temperature for 6 days, continuously increasing the total nitrogen removal rate to more than 80 percent for more than 3 days, and stabilizing the total nitrogen removal rate at 87.8 percent. Before storage, the total nitrogen removal rate and the total nitrogen removal load were 85.1% and 0.490 kg/(m)3d) After storage, the total nitrogen removal rate and the total nitrogen removal load were 12.8% and 0.074 kg/(m)3d) After recovery, the total nitrogen removal rate and the total nitrogen removal load were 87.8% and 0.506 kg/(m)3d) The total nitrogen removal load after recovery was 1.0 times and 6.8 times the total nitrogen removal load before and after storage, respectively. The relative abundance of the anaerobic ammonium oxidation bacteria before and after storage is 21.2 percent and 9.3 percent respectively, and the anaerobic ammonium oxidation bacteria are transported for 48 daysThe relative abundance of the anaerobic ammonium oxidation bacteria is recovered to 23.4 percent, and the ratio of the relative abundance of the anaerobic ammonium oxidation bacteria after recovery to the abundance of the sludge before storage is 1.1>1, the abundance ratio of the sludge after storage is 2.5>1.5, the anaerobic ammonia oxidation process is successfully recovered.
Example 3
A method for long term storage of anammox sludge comprising the steps of:
s1, standing and precipitating the anaerobic ammonia oxidation sludge in the reactor A to be stopped for 1h, discarding the supernatant, then adding the high-concentration synthetic wastewater to the original liquid level (4.5L), standing and precipitating again after uniformly stirring, discarding the supernatant, and repeating the steps for 4 times; the high-concentration synthetic wastewater comprises: (NH)4)2SO4、NaNO2、1200mg/L NaHCO3、68mg/L CaCl2、68mg/L KH2PO4、150mg/L MgSO4The trace element I comprises 5000mg/L EDTA and 5000mg/L FeSO4The trace elements II comprise 15000mg/L EDTA and 430mg/L ZnSO4·7H2O、240mg/L CoCl2·6H2O、990mg/L MnCl2·4H2O、250mg/L CuSO4·5H2O、220mg/L Na2MoO4·2H2O、190mg/L NiCl2·6H2O、210mg/L Na2SeO4·10H2O, wherein the concentrations of ammonia nitrogen and nitrite are respectively 4 times of those before production halt, the concentrations of ammonia nitrogen and nitrite are both 800mg/L, and the concentrations of other elements are consistent with those before production halt;
s2, transferring the sludge obtained in the step S1 to a biological filter column B filled with volcanic rock, wherein the particle size of the volcanic rock is 6-8 mm, the effective filling rate is less than 30%, the height-diameter ratio of the filter column is 7, the effective volume is 4.5L, the effective volume is the same as that of a reactor A before production halt, the outside of the reactor is wrapped by black tinfoil paper, and the sludge and the volcanic rock are fully mixed and then are placed and stored indoors; if the reactor form of the reactor A is the same as that of the reactor B, the reactor A can be directly changed into the reactor B for operation without transfer;
s3, periodically removing the supernatant at intervals of 2 weeks, adding the synthetic wastewater with the same concentration to the original liquid level (4.5L), uniformly stirring, standing and precipitating for 1h, removing the supernatant, repeating for 4 times, and continuously standing and storing in a room. The operation is carried out in this way, and the storage period is 1 month.
The method for quickly recovering the activity of the anaerobic ammonia oxidation sludge stored by the method comprises the following steps:
step 1, recovery initial stage: abandoning the supernatant in the biological filter column B, adding low-concentration synthetic wastewater to the original liquid level (4.5L), standing and precipitating for 1h after uniformly stirring, abandoning the supernatant, repeating for 4 times, wherein the low-concentration synthetic wastewater comprises: (NH)4)2SO4、NaNO2、1200mg/L NaHCO3、68mg/L CaCl2、68mg/L KH2PO4、150mg/L MgSO4The trace element I comprises 5000mg/L EDTA and 5000mg/L FeSO4The trace elements II comprise 15000mg/L EDTA and 430mg/L ZnSO4·7H2O、240mg/L CoCl2·6H2O、990mg/L MnCl2·4H2O、250mg/L CuSO4·5H2O、220mg/L Na2MoO4·2H2O、190mg/L NiCl2·6H2O、210mg/L Na2SeO4·10H2O, wherein the concentrations of ammonia nitrogen and nitrite are both 20mg/L, and the concentrations of other elements are consistent with those before production halt; setting the hydraulic retention time to be 2h, starting inflow water and outflow water, running for 1 day to wash out floating aging shedding biomembranes, providing an autotrophic environment for anaerobic ammonium oxidation bacteria and consuming residual dissolved oxygen;
step 2, recovering the medium term: the hydraulic retention time of the reactor A before storage is 10h, the concentrations of the ammonia nitrogen and the nitrite in the inlet water are both 200mg/L, the ratio of the hydraulic retention time to the total nitrogen in the inlet water is recorded as R, and the R value is 25 hL/g; under the condition, the biological filter column B is used for screening active anaerobic ammonium oxidation bacteria, and the total nitrogen removal rate reaches 30.9 percent after the biological filter column B is circularly operated for 3 days at room temperature. Then, changing the hydraulic retention time to 16.5h, keeping the ammonia nitrogen concentration of the inlet water unchanged, changing the nitrite concentration to 240mg/L, and adjusting the ratio of the hydraulic retention time to the total nitrogen of the inlet water from 25hL/g to 37.5hL/g so as to gradually recover the activity of the anaerobic ammonium oxidation bacteria, wherein the total nitrogen removal rate reaches 61.2 percent after the anaerobic ammonium oxidation bacteria circularly operate at room temperature for 7 days; continuously changing the hydraulic retention time to 22h, keeping the concentration of the ammonia nitrogen and the nitrite in the inlet water unchanged, adjusting the ratio of the hydraulic retention time to the total nitrogen in the inlet water from 37.5hL/g to 50hL/g, circularly operating at room temperature for 7 days, and achieving the total nitrogen removal rate of 81.6 percent;
step 3, final recovery: transferring the biological membrane in the biological filter column B into an original reactor A before storage, and operating for 3 days under the condition that the ratio of hydraulic retention time to total nitrogen of inlet water is 50 hL/g; then reducing the hydraulic retention time to 16.5h, keeping the concentration of the ammonia nitrogen and the nitrite in the inlet water unchanged, adjusting the ratio of the hydraulic retention time to the total nitrogen in the inlet water from 50hL/g to 37.5hL/g, circularly operating at room temperature for 4 days, and continuously increasing the total nitrogen removal rate to be higher than 80 percent after 3 days; continuously reducing the hydraulic retention time to 10h, keeping the ammonia nitrogen concentration of the inlet water unchanged, reducing the concentration of the nitrite to 200mg/L, adjusting the ratio of the hydraulic retention time to the total nitrogen of the inlet water from 37.5hL/g to 25hL/g, circularly operating at room temperature for 4 days, continuously increasing the total nitrogen removal rate to be higher than 80% for more than 3 days, and stabilizing the total nitrogen removal rate to 88.8%. Before storage, the total nitrogen removal rate and the total nitrogen removal load were 88.2% and 0.848 kg/(m)3d) After storage, the total nitrogen removal rate and the total nitrogen removal load were 27.4% and 0.263 kg/(m)3d) After recovery, the total nitrogen removal rate and the total nitrogen removal load were 88.8% and 0.852 kg/(m)3d) The total nitrogen removal load after recovery was 1.0 times and 3.2 times the total nitrogen removal load before and after storage, respectively. The relative abundance of the anaerobic ammonia oxidizing bacteria before and after storage is 19.8% and 13.3% respectively, after 29 days of operation, the relative abundance is recovered to 21.5%, and the ratio of the relative abundance of the anaerobic ammonia oxidizing bacteria after recovery to the abundance of the sludge before storage is 1.1>1, the abundance ratio of the sludge to the sludge after storage is 1.6>1.5, the anaerobic ammonia oxidation process is successfully recovered.
It should be noted that, when the present invention relates to a numerical range, it should be understood that two endpoints of each numerical range and any value between the two endpoints can be selected, and since the steps and methods adopted are the same as those in the embodiment, in order to prevent redundancy, the present invention describes a preferred embodiment. While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A method for long-term storage of anammox sludge, comprising the steps of:
s1, standing and precipitating the anaerobic ammonium oxidation sludge in the reactor A, and removing supernatant; then adding high-concentration synthetic wastewater to the original liquid level, wherein the concentrations of ammonia nitrogen and nitrite in the wastewater are respectively 3-5 times of those of the wastewater during the operation of the reactor A, the concentrations of other elements are kept consistent with those of the wastewater during the operation of the reactor A, uniformly stirring, standing for precipitation, removing supernatant, and repeating for 3-5 times;
s2, transferring the sludge obtained in the step S1 to a biological filter column B filled with volcanic rock, fully mixing, wrapping the sludge with black tinfoil paper, and standing for storage;
s3, removing the supernatant at regular intervals, adding the synthetic wastewater with the same concentration to the original liquid level, uniformly stirring, standing for precipitation, removing the supernatant, repeating for 3-5 times, and standing for 1-24 months.
2. The method for long-term storage of anammox sludge according to claim 1, wherein the standing and settling time in S1 and S3 is 0.5 to 2 hours.
3. The method for long-term storage of anammox sludge according to claim 1, wherein in S2, the volcanic rock has a particle size of 6 to 12mm, an effective packing ratio of less than 30%, a filter column height to diameter ratio of 3 to 10, and an effective volume of 1 to 5 times that of the reactor A.
4. The method for long-term storage of anammox sludge according to claim 1, wherein the interval of time in S3 is 2 to 4 weeks.
5. The method for rapidly recovering the activity of the anaerobic ammonia oxidation sludge stored by the method according to claim 1, which is characterized by comprising the following steps:
step 1, recovery initial stage: removing the supernatant in the biological filter column B, adding the low-concentration synthetic wastewater to the original liquid level, uniformly stirring, standing for precipitation, removing the supernatant, and repeating for 3-5 times; setting hydraulic retention time, starting inflow water and outflow water to wash out floating aging and shedding biomembranes, providing an autotrophic environment for anaerobic ammonium oxidation bacteria and consuming residual dissolved oxygen;
step 2, recovering the medium term: calculating the ratio of the hydraulic retention time/total nitrogen of inlet water of the reactor A before storage, recording as R, and circularly operating the biological filter column B in the step 1 in the operation mode of the reactor A until the total nitrogen removal rate reaches more than 30% so as to screen active anaerobic ammonium oxidation bacteria; then, adjusting the ratio of R until the total nitrogen removal rate reaches more than 80%;
step 3, final recovery: transferring the biological membrane in the biological filter column B in the step 2 to an original reactor A before storage, operating under the condition of 2R, gradually adjusting R, stopping adjustment and continuing operation when the total nitrogen removal rate is lower than 80%, and continuing to adjust R step by step when the total nitrogen removal rate is higher than 80% for 3 consecutive days until the ratio of the two is recovered to R, recovering the hydraulic retention time and the total nitrogen of inlet water to the values before storage, wherein the ratio of the abundance of the anammox bacteria in the sludge to the abundance of the anammox bacteria in the sludge before storage is greater than or equal to 1, and the ratio of the abundance of the anammox bacteria in the sludge after storage is greater than 1.5, namely the anammox process is successfully recovered.
6. The method for rapidly recovering the activity of the anaerobic ammonia oxidation sludge stored by the method according to claim 5, wherein the standing and precipitating time in the step 1 is 0.5-2 h.
7. The method for rapidly recovering the activity of the anaerobic ammonia oxidation sludge stored by the method according to claim 5, wherein in the step 1, in the low-concentration synthetic wastewater, the concentration ratio of the nitrite to the ammonia nitrogen in the inlet water is 0.5-1.0, the ammonia nitrogen concentration in the inlet water is 10-30 mg/L, and the concentrations of other elements are consistent with those of the reactor A during operation; setting the hydraulic retention time to be 2-6 h.
8. The method for rapidly recovering the activity of the anaerobic ammonia oxidation sludge stored by the method according to claim 5, wherein in the step 2, the R is adjusted in a mode that the hydraulic retention time is 3-20 h or the concentration ratio of the nitrite to the ammonia nitrogen in the inlet water is 0.8-1.4.
9. The method for rapidly recovering the activity of the anaerobic ammonia oxidation sludge stored by the method according to claim 5, wherein in the step 2, the R ratio is adjusted by: the ratio is adjusted to 1.5R, the operation is carried out until the total nitrogen removal rate reaches more than 60%, and then the operation is adjusted to 2R until the total nitrogen removal rate reaches more than 80%.
10. The method for rapidly recovering the activity of the anaerobic ammonia oxidation sludge stored according to the method of claim 5, wherein in the step 3, the step-by-step adjustment of R is as follows: the ratio of the amount of the carbon dioxide is 0.2 to 0.5R.
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