CN110723812A - Method for improving pH impact resistance of anaerobic ammonium oxidation particles - Google Patents
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Abstract
A method for improving the pH impact resistance of anaerobic ammonium oxidation particles, belonging to the field of wastewater treatment. The method greatly improves the particle stability and activity under unfavorable pH impact by adding the denitrification sludge EPS subjected to starvation enhanced culture into a reactor and utilizing the high flocculation efficiency of the enhanced denitrification EPS (E-D-EPS) and a large amount of acylhomoserine lactone signal molecules (AHLs) contained in the enhanced denitrification EPS, so that the system can keep stable and higher denitrification efficiency even under extreme acidic or extreme alkaline pH impact.
Description
Technical Field
The invention belongs to the field of wastewater treatment, particularly relates to an anaerobic ammonia oxidation denitrification technology in a wastewater treatment process, and particularly relates to a method for improving the pH impact resistance of anaerobic ammonia oxidation particles.
Background
Anaerobic ammonia oxidation (ANAMMOX) is used as a novel biological denitrification process, and has the advantages of low energy consumption, no need of additional organic carbon source, high denitrification efficiency and the like. However, the ANAMMOX bacteria have long multiplication time and high sensitivity to environmental changes, such as acidic or alkaline pH impact can seriously reduce the stability and activity of ANAMMOX particles, so that the operation performance of the reactor is unstable and the denitrification performance is deteriorated, thereby greatly limiting the wide application of the ANAMMOX process. However, there is currently no effective method for improving the acid or alkaline pH shock resistance of ANAMMOX granules. Most studies currently recover the performance of the ANAMMOX particles and the systematic denitrification performance after pH shock by reducing the concentrations of ammonia nitrogen and nitrite in the influent water, but this method is not suitable for extreme acidic and alkaline pH shock, and for general acidic or alkaline pH shock, it takes a long time to recover the particle performance, and it is not easy to recover the original stability and activity of the particles after alkaline pH shock. Based on this, the invention provides a method for improving the acid resistance and alkaline pH shock of ANAMMOX granules by adding a starvation enhanced denitrification sludge Extracellular Polymer (EPS) method.
Disclosure of Invention
The invention provides a method for improving the pH impact resistance of ANAMMOX particles, which is characterized in that denitrifying sludge EPS subjected to starvation enhanced culture is added into a reactor, and the particle stability and activity under unfavorable pH impact are greatly improved by utilizing the high flocculation efficiency of the enhanced denitrifying EPS (E-D-EPS) and a large amount of acyl homoserine lactone signal molecules (AHLs) contained in the enhanced denitrifying EPS, so that a system can keep stable and higher denitrification efficiency even under extreme acidic or extreme alkaline pH impact.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for improving the pH impact resistance of anaerobic ammonium oxidation particles is characterized in that denitrification sludge EPS subjected to starvation enhanced culture is added into an SBR reactor during pH impact of an ANAMMOX system; the specific operation steps and process conditions are as follows:
(1) obtaining of enhanced denitrification sludge EPS:
and inoculating the denitrification mud of the secondary sedimentation tank to the SBR reactor as seed mud, wherein the ammonia nitrogen concentration of inlet water is 10-60 mg/L, the nitrate nitrogen concentration is 160-380 mg/L, and the COD concentration is 400-1500 mg/L. Feed and reactor use N2-CO2(95/5%) mixed gas scouring to remove oxygen (DO)<0.5mg/L), setting 12 hours as an experimental cycle, wherein the water inlet time is 10min and the water outlet time is 15min per cycle, standing and precipitating for 30min before water outlet, and performing anoxic stirring at 90 +/-10 rpm in other time reactors; the solid retention time is 20 days, the ambient temperature is 23 +/-2 ℃, and the pH value is between 6.5 and 8.5. Sodium acetate as carbon sourcePotassium nitrate was used as a nitrogen source, and the culture was first conducted in a starvation phase in which the C/N ratio was directly decreased from 12.0 (high carbon-nitrogen ratio) to 2.0 (low carbon-nitrogen ratio) for 12 cycles of culture at C/N5.0 and 12.0 cycles of culture at C/N12.0. Culturing for 14 cycles in starvation phase (C/N2.0), and immediately extracting EPS (storing the extract at-20 deg.C for use); the heat treatment method is adopted to extract the denitrifying sludge EPS: firstly, centrifuging a proper amount of the denitrification sludge cultured in the starvation period at a low rotating speed of 100-300r/min, uniformly mixing the centrifuged precipitated sludge with 0.9 wt% NaCl solution again, carrying out heat treatment on the uniformly mixed solution at 100 ℃ for 1h, centrifuging at 3200r/min for 30min, and obtaining the supernatant which is the obtained denitrification sludge EPS (expandable polystyrene), namely E-D-EPS;
(2) enhanced addition of denitrified EPS (E-D-EPS) during pH shock in an ANAMMOX reactor
After the UASB reactor is adopted and ANAMMOX granular sludge is inoculated, the continuous flow is divided into 3 stages in sequence: a stable operation stage, a pH impact stage and a recovery stage;
adding E-D-EPS into the ANAMMOX reactor every day during the period of carrying out extreme acidity or extreme alkalinity pH impact (for example, carrying out 5-25D of extreme acidity pH 5.5-6.5 or extreme alkalinity pH 8.5-9.0 impact) in the ANAMMOX reactor after the stable operation stage, so that the concentration of the E-D-EPS is kept between 1mg/L and 12mg/L until the pH impact is finished; after the impact is stopped, the E-D-EPS is not added into the reactor, and the recovery stage is finally carried out.
And (3) a stable operation stage of the reactor: the operation temperature is 33 +/-2 ℃, the pH value of inlet water is 7.0-7.5, the dissolved oxygen of the inlet water is below 0.5mg/L, the ammonia nitrogen concentration of the inlet water is 40-110 mg/L, the nitrite nitrogen concentration is 60-180 mg/L, and the ratio of the ammonia nitrogen concentration of the inlet water to the nitrite nitrogen concentration is 1: 1.10-1: 1.35.
And (3) pH impact stage: performing 5-25d of extreme acidic pH 5.5-6.5 or extreme basic pH 8.5-9.0 impact. During the pH shock, 1 mg/L-12 mg/L E-D-EPS is added to the reactor every day until the shock is over and other environmental conditions are consistent with those in the stabilization phase.
And (3) a recovery stage: the pH returned to the stationary phase level and the environmental conditions were consistent with the stationary phase.
The E-D-EPS is denitrifying sludge EPS subjected to starvation period enhanced culture;
the denitrification sludge is taken from a secondary sedimentation tank of a sewage treatment plant, and the starvation period enhanced culture refers to that culture is changed from high carbon-nitrogen ratio culture to low carbon-nitrogen ratio culture in an SBR reactor, and the starvation period culture is carried out.
The addition mode of the E-D-EPS is that 1 mg/L-12 mg/L E-D-EPS is added into the reactor every day during the pH impact period of 5-25 h until the impact is finished, and the E-D-EPS is not added continuously after the impact is finished.
The acidic pH impact in the ANAMMOX reactor is 5.5-6.5; the alkaline pH shock is pH 8.5-9.0.
The grain size of the sludge particles inoculated with the ANAMMOX is 0.5-4.5 mm.
The invention has the following function principle: the EPS released by the denitrified sludge after the enhancement of the starvation period has high flocculation performance even under the condition of extreme acid or extreme alkaline, contains more Acyl Homoserine Lactone Substances (AHLs) and less humic acid content, and can also inhibit the growth of certain bacteria (such as hydrophilic bacteria and microorganisms which are not beneficial to flocculation). The addition of denitrifying sludge EPS (E-D-EPS) with high flocculation performance after the enhancement of the starvation period enables ANAMMOX particles to still maintain compact particle structures (namely good stability) even under the pH impact, and meanwhile, effective AHLs contained in the E-D-EPS stimulate the secretion of loose EPS of the particles to change PN/PS, so that the stability of the particles is enhanced from another aspect, and the AHLs also promote the improvement of the microbial activity of the ANAMMOX. In addition, the E-D-EPS contains more hydrophobic groups, so that the hydrophobicity of the surface of the particle is improved. The heterosaccharide (alginate) contained in E-D-EPS is not essential for microbial growth in the granular sludge, but its presence has a significant beneficial effect on the structural stability of the granular sludge. These are the reasons why E-D-EPS is able to improve the pH impact resistance of ANAMMOX particles.
Compared with the prior art, the invention has the following advantages and effects:
(1) the ANAMMOX particle has the advantages that the pH impact resistance of the ANAMMOX particle can be effectively improved, the ANAMMOX particle can still keep good stability and high activity under extreme acidic and extreme alkaline impacts, and therefore the ANAMMOX system can keep stable and high denitrification efficiency under the pH impact.
(2) The denitrification sludge has wide sources, so the technology has low cost.
(3) The method is suitable for various ANAMMOX reactors, hydraulic conditions and the like, and has strong applicability.
(4) The operation process is simple, the realization is easy, and the effect is obvious.
Drawings
FIG. 1 is the change in the strength and activity of ANAMMOX particles after addition of E-D-EPS of example 1; (A) is the particle strength; (B) is the settling velocity of the particles.
FIG. 2 is a graph showing the change in the strength and activity of ANAMMOX particles after the addition of E-D-EPS in example 2; (A) is the particle strength; (B) is the settling velocity of the particles.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples, but the present invention is not limited thereto.
At present, no effective method is available for improving the pH impact resistance of ANAMMOX particles, and the stability of the ANAMMOX particles under pH impact and the operation stability of an activity guarantee system under pH impact are improved by adding denitrifying sludge EPS subjected to starvation reinforced culture.
The specific implementation mode is as follows:
1) culturing of reinforced denitrifying sludge in starvation stage and extraction of EPS
The specific operation steps and the process conditions are the same as the content of the invention.
2) ANAMMOX reactor operation and E-D-EPS addition
After the UASB reactor is adopted and ANAMMOX granular sludge is inoculated, the continuous flow experiment is divided into 3 stages: in a stable operation stage (pH 7.0-7.5, operation for 20-40 d), the operation temperature is 33 +/-2 ℃, the pH of inlet water is 7.0-7.5, the dissolved oxygen of the inlet water is below 0.5mg/L, the ammonia nitrogen concentration of the inlet water is 40-110 mg/L, the nitrite nitrogen concentration is 60-180 mg/L, and the ratio of the ammonia nitrogen concentration of the inlet water to the nitrite nitrogen concentration is 1: 1.10-1: 1.35; in the pH impact stage, carrying out 5-25D of extreme acidic pH5.5 or extreme basic pH9.0 impact, and adding 1-12 mg/L/L E-D-EPS into the reactor every day during the pH impact period until the impact is finished, wherein other environmental conditions are consistent with those in the stabilization stage; in the recovery stage (running for 30-60 d), the pH is recovered to the level of the stationary phase, and the environmental conditions are consistent with those in the stationary stage.
The present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention fall within the protection scope of the present invention. The present invention will be described in further detail with reference to examples.
Example 1:
effect of E-D-EPS on particle Strength and Activity under extreme acidic pH impact
Two sets of UASB reactors were set up, and after inoculation of ANAMMOX granular sludge, a continuous flow experiment was performed (divided into 3 stages). During the stable operation period, in the stable operation stage (pH 7.0-7.5), the operation temperature is 33 +/-2 ℃, the pH of inlet water is 7.0-7.5, the dissolved oxygen of the inlet water is below 0.5mg/L, the ammonia nitrogen concentration of the inlet water is 46mg/L, the nitrite nitrogen concentration is 54mg/L, and the ratio of the ammonia nitrogen concentration of the inlet water to the nitrite nitrogen concentration is 1: 1.32; a pH impact stage, wherein 15D of extreme acidity pH5.5 impact is carried out, 2mg/L E-D-EPS is added into the reactor every day during the pH impact period until the impact is finished, and other environmental conditions are consistent with those in a stable stage; in the recovery stage (running for 30-60 d), the pH is recovered to the level of the stationary phase, and the environmental conditions are consistent with those in the stationary stage.
The experimental water adopts artificial water distribution, and the water quality of the water distribution is as follows (g/L): 0.09KH2PO4，37.92KHCO3，0.44MgSO4·7H2O，0.13CaCl2·2H2O, using NH4Cl and K2NO2Changing NH4 +-N and NO2 —The concentration of N. 1mL/L of each of the trace elements I and II, wherein the trace elements I (g/L): 5.00EDTA, 5.00FeSO4(ii) a Microelement II (g/L): 15.00EDTA, 0.43ZnSO4·4H2O，0.99MnCl2·4H2O，0.014H3BO4，0.25CuSO4·5H2O，0.22Na2MoO4·2H2O，0.21Na2SeO4·10H2O，0.19NiCl2·6H2And O. The influent was flushed with a mixture of 95% nitrogen and 5% carbon dioxide to remove oxygen.
Example 2:
the pH shock phase, which is an extreme alkaline pH9.0 shock of 15D, is carried out, during which 2mg/L E-D-EPS are added daily to the reactor until the end of the shock, and the other experimental procedures are the same as in example 1.
Results and analysis:
1. example 1
As shown in the attached FIG. 1, when E-D-EPS is not added, the granule structure is dense, the stability is good (the strength is high) and the activity is high (the granule strength and the activity are respectively as high as 0.70 F.S and 0.97kg N/(kg VSSd)) in a stable operation period. However, after 15 days of acidic pH shock, the stability and activity of the amammox particles decreased significantly (particle strength and activity were as low as 0.26 fs and 0.68kg N/(kg VSS d), respectively), and the denitrification efficiency of the system also decreased significantly. And even if the pH is restored to the stationary phase level, the particle stability and activity are difficult to restore in a short time. However, after 2mg/L E-D-EPS was added, the strength and activity of ANAMMOX particles after acidic pH shock were increased by 1.54 times and 41% respectively, compared to those without E-D-EPS (FIG. 1a, b), and the stability and activity of the particles could be rapidly restored to the stationary phase level. It was demonstrated that the addition of 2mg/L E-D-EPS effectively improved the acid-resistant pH impact resistance of ANAMMOX granules.
2. Example 2
The addition of 2mg/L E-D-EPS not only can effectively improve the acid-resistant pH impact capacity of ANAMMOX particles, but also can effectively improve the alkaline pH impact resistance of ANAMMOX particles. The strength and activity of the ANAMMOX particles after alkaline pH impact are respectively improved by 3.77 times and 81 percent compared with the strength and activity of the ANAMMOX particles without the addition of E-D-EPS (shown in the attached figures 2a and b), and the stability and activity of the particles can be quickly recovered to the level of a stationary phase.
According to the analysis of the results, the invention can effectively improve the stability and activity of the ANAMMOX particles after pH impact by adding the denitrification sludge EPS strengthened in the hunger stage in the pH impact stage, so that the ANAMMOX particles have stronger pH impact resistance, and the stability and the high efficiency of denitrification of an ANAMMOX system under the pH impact are greatly improved. And the method is easy to implement, simple to operate, low in cost and easy to realize.
Claims (4)
1. A method for improving the pH impact resistance of anaerobic ammonium oxidation particles is characterized in that denitrification sludge EPS subjected to starvation enhanced culture is added into an SBR reactor during the pH impact of an ANAMMOX system; the specific operation steps and process conditions are as follows:
(1) obtaining of enhanced denitrification sludge EPS:
inoculating the denitrification mud of the secondary sedimentation tank to an SBR reactor as seed mud, wherein the ammonia nitrogen concentration of inlet water is 10-60 mg/L, the nitrate nitrogen concentration is 160-380 mg/L, and the COD concentration is 400-1500 mg/L; feed and reactor use N2-CO2(95/5%) mixed gas scouring to remove oxygen (DO)<0.5 mg/L); setting 12 hours as an experimental cycle, wherein the water inlet time is 10min and the water outlet time is 15min in each cycle, standing and precipitating for 30min before water outlet, and performing anoxic stirring at 90 +/-10 rpm on the reactor at other times; the solid retention time is 20 days, the ambient temperature is 23 +/-2 ℃, and the pH value is between 6.5 and 8.5. Adopting sodium acetate as a carbon source and potassium nitrate as a nitrogen source, firstly culturing for 12 circulation periods under C/N5.0, culturing for 12 circulation periods under C/N12.0, directly reducing the C/N ratio from 12.0 to 2.0, and performing starvation-stage culture; culturing for 14 cycles in starvation phase (C/N2.0), and immediately extracting EPS; the heat treatment method is adopted to extract the denitrifying sludge EPS: firstly, centrifuging a proper amount of the denitrification sludge cultured in the starvation period at a low rotating speed of 100-300r/min, uniformly mixing the centrifuged precipitated sludge with 0.9 wt% NaCl solution again, carrying out heat treatment on the uniformly mixed solution at 100 ℃ for 1h, centrifuging at 3200r/min for 30min, and obtaining the supernatant which is the obtained denitrification sludge EPS (expandable polystyrene), namely E-D-EPS; storing the extract at-20 deg.C;
(2) enhanced addition of denitrified EPS (E-D-EPS) during pH shock in an ANAMMOX reactor
After the UASB reactor is adopted and ANAMMOX granular sludge is inoculated, the continuous flow is divided into 3 stages in sequence: a stable operation stage, a pH impact stage and a recovery stage;
adding E-D-EPS into the ANAMMOX reactor every day during the extremely acidic or extremely alkaline pH impact of the ANAMMOX reactor after the stable operation stage, so that the concentration of the E-D-EPS is kept between 1mg/L and 12mg/L until the pH impact is finished; after the impact is stopped, the E-D-EPS is not added into the reactor, and the recovery stage is finally carried out.
2. The method for improving the pH impact resistance of anammox particles according to claim 1, wherein step (2) comprises the following steps: the operation temperature is 33 +/-2 ℃, the pH value of inlet water is 7.0-7.5, the dissolved oxygen of the inlet water is below 0.5mg/L, the ammonia nitrogen concentration of the inlet water is 40-110 mg/L, the nitrite nitrogen concentration is 60-180 mg/L, and the ratio of the ammonia nitrogen concentration of the inlet water to the nitrite nitrogen concentration is 1: 1.10-1: 1.35.
3. The method for improving the pH impact resistance of anammox particles according to claim 1, wherein step (2) comprises the pH impact stage of: performing 5-25d of extreme acidic pH 5.5-6.5 or extreme alkaline pH 8.5-9.0 impact; during the pH shock, 1 mg/L-12 mg/L E-D-EPS is added to the reactor every day until the shock is over and other environmental conditions are consistent with those in the stabilization phase.
4. The method for improving the pH impact resistance of anammox particles according to claim 1, wherein the recovery stage of step (2): the pH returned to the stationary phase level and the environmental conditions were consistent with the stationary phase.
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| CN115520962A (en) * | 2022-07-05 | 2022-12-27 | 济南大学 | With NO 3- Domestication culture method of electroactive anaerobic ammonium oxidation microorganisms serving as single nitrogen source |
| CN115520962B (en) * | 2022-07-05 | 2024-05-03 | 济南大学 | With NO3-Method for domesticating and culturing electroactive anaerobic ammonia oxidizing microorganism serving as single nitrogen source |
| CN117209057A (en) * | 2023-09-19 | 2023-12-12 | 苏州科技大学 | Wastewater treatment method of anaerobic ammonia oxidation system |
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