Method for rapidly recovering activity of anaerobic ammonium oxidation bacteria
Technical Field
The invention belongs to the technical field of environmental microorganisms, and particularly relates to a method for rapidly recovering activity of anaerobic ammonium oxidation bacteria inhibited by heavy metals.
Background
The anaerobic ammonia oxidation phenomenon discovered since the 90 s in the 20 th century provides a new idea for the biological denitrification treatment of high-concentration ammonia-containing wastewater. A batch of novel biological denitrification technologies based on anaerobic ammonia oxidation theory are produced. The anaerobic ammonia oxidation refers to that under the anaerobic or anoxic condition, microorganisms directly react with NH4 +-N is an electron donor, with NO2 --N is an electron acceptor, NH4 +-N and NO2 -Conversion of-N to N2The anaerobic ammonia oxidation process does not need oxygen, and belongs to a complete autotrophic process, so that compared with the traditional nitrification and denitrification process, the oxygen supply cost can be saved by 50 percent, does not need additional organic carbon source, can greatly reduce the capital investment and the running cost of sewage denitrification, and simultaneously can reduce the generation amount of residual sludge to the minimum in the anaerobic ammonia oxidation process, thereby saving a large amount of sludge disposal cost.
The high requirement of anammox on the quality of inlet water is one of the main bottlenecks which limit the industrial application of the anammox technology for a long time. Because the actual wastewater quality is complicated and changeable, when the wastewater contains heavy metals with higher concentration, the activity of anaerobic ammonia oxidizing bacteria can be inhibited to a great extent, which is not beneficial to the proliferation of strains. The inhibition effect of heavy metals on the anaerobic ammonia oxidation process is mainly embodied in the following two aspects: (1) binding to cell wall surfaces and extracellular enzymes, thereby changing their functional structure, the binding sites including hydroxyl, amino and other functional groups of lipids, proteins, carbohydrates; (2) heavy metals destroy the structure and function of proteins by entering cells, and even replace essential metal elements of cells at the position of active groups, resulting in enzyme inactivation. After the wastewater is impacted by high-concentration heavy metal pollutants in actual wastewater, the activity of anammox bacteria can be inhibited or even inactivated, so that the quality of effluent water is deteriorated.
Therefore, the search for a method for recovering the activity of anammox bacteria inhibited by heavy metals is of great practical significance for further promoting the industrialization process of the anammox technology.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for rapidly recovering the activity of anaerobic ammonium oxidation bacteria inhibited by heavy metal. The method can quickly recover the activity of the anaerobic ammonium oxidation bacteria inhibited by the heavy metal, improve the tolerance of the bacteria to the heavy metal and ensure the stable treatment effect.
The method for rapidly recovering the activity of the anaerobic ammonium oxidation bacteria provided by the invention comprises the following steps: in a biological treatment system for treating heavy metal-containing wastewater by using anaerobic ammonium oxidation bacteria, a certain amount of hydroxylamine and ethylene diamine tetraacetic acid are added, so that the concentration of hydroxylamine in inlet water is 1.0-10mg/L, preferably 3.0-6.0mg/L, and the concentration of ethylene diamine tetraacetic acid is 3.0-30mg/L, preferably 5.0-20 mg/L.
In the invention, the anaerobic ammonium oxidation bacteria are NH4 +-N is an electron donor, with NO2 --N is an electron acceptor, NH4 +-N and NO2 -Conversion of-N to N2The mixed cells or/and activated sludge of (1).
In the invention, the heavy metal-containing wastewater contains ammonia nitrogen, nitrite nitrogen and at least one heavy metal ion of cadmium, copper, zinc and the like. In the wastewater, the ammonia nitrogen concentration is 100-150mg/L, the nitrite nitrogen concentration is 100-150mg/L, and the total concentration of heavy metal ions is 10-30 mg/L.
In the invention, the biological treatment system mainly comprises a biochemical reactor with a stirring and pH control system. Wherein the pH value of the reactor is controlled to be 6.5-8.5, the temperature is 25-35 ℃, the dissolved oxygen concentration is not more than 0.05mg/L, and the water conservancy residence time is 4-24 h.
In the invention, furthermore, a certain amount of lysine is added into the biological treatment system at the same time, so that the concentration of the lysine in the inlet water is 0.05-0.5 mug/L, preferably 0.1-0.2 mug/L.
Compared with the prior art, the invention has the following beneficial effects:
(1) by adding a certain amount of hydroxylamine and ethylene diamine tetraacetic acid into the anaerobic ammonia oxidation treatment system inhibited by heavy metals, the tolerance of the bacteria to the heavy metals can be improved, the activity of the bacteria can be quickly recovered, and the stable treatment effect can be ensured.
(2) And a certain amount of lysine is added into the treatment system, so that the wastewater treatment effect is further improved, and the activity recovery time is shortened.
(3) The added materials are easy to obtain, low in price, economical and environment-friendly.
Detailed Description
The method and effects of the present invention will be described in detail with reference to examples. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The test materials used in the following examples were purchased from biochemical reagent stores unless otherwise specified.
In the embodiment of the invention, the ammonia nitrogen concentration is measured by GB7478-87 'determination of water quality-ammonium-distillation and titration method'; the nitrite nitrogen concentration is measured by GB7493-87 water quality-nitrite nitrogen determination-spectrophotometry; the total nitrogen concentration adopts GB 11894-89 'determination of water quality-total nitrogen-alkaline potassium persulfate digestion ultraviolet spectrophotometry'; the metal ions are measured by HJ700-2014 inductively coupled plasma mass spectrometry (inductively coupled plasma mass spectrometry) for measuring water quality-65 elements.
Examples the inoculated anammox sludge was obtained from a laboratory enriched culture of anammox bacteria, and the specific anammox activity SAA (substrate consumption rate divided by sludge concentration, SAA value) of the sludge was about 0.40 kgN/(kgVSS. d), and the total nitrogen removal was higher than 85%. When the wastewater containing no heavy metal ions is treated, the sludge activity is good, and the treatment effect meets the requirements.
The reactor used in the examples was a complete mixing anaerobic reactor, the top of which was equipped with a stirrer, and the feed water was pumped from the bottom of the reactor by a peristaltic pump. The effective volume of the reactor is 2.0L, a temperature, pH and dissolved oxygen control system is arranged, and the sludge concentration (MLSS) of anaerobic ammonia oxidation sludge inoculated in the reactor is about 2000 mg/L. Controlling the temperature at 25-35 deg.C, the dissolved oxygen concentration not more than 0.05mg/L, and the water retention time at 4-24 h.
The experimental water intake formula of the example is shown in Table 1, the wastewater is simulated wastewater, the water intake pH is 7.0-7.3, the ammonia nitrogen concentration is 100-150mg/L, and the nitrite nitrogen concentration is 100-150 mg/L. The heavy metal ions are cadmium ions, copper ions, zinc ions and the like respectively, and the concentration of the heavy metal ions in the inlet water is controlled to be about 10-30 mg/L.
TABLE 1 Experimental quality of influent water
Example 1
The anaerobic ammonium oxidation bacteria are adopted to treat the wastewater containing heavy metal ions, and the water quality of the wastewater is shown in the table 1. Inoculating the anaerobic ammonium oxidation bacteria activated sludge which is enriched and cultured in a laboratory, wherein the initial SAA is 0.40 kgN/(kgVSS.d). Due to the influence of heavy metals, after a period of treatment, the SAA of the strains in the four groups of reactors (four different water inflows) is less than 0.15 kgN/(kgVSS. d), and the activity is reduced by about 70%. Hydroxylamine and ethylene diamine tetraacetic acid are added according to the method of the invention for recovery, so that the concentration of hydroxylamine in the inlet water is 3.0mg/L, and the concentration of ethylene diamine tetraacetic acid is 20 mg/L. After 5 days of operation, the activity of the strains in reactors A, B, C and D gradually recovered, and SAA reached 0.25, 0.29, 0.27 and 0.24 kgN/(kgVSS. D), respectively. After 9 days of operation, SAA all reached the level before inhibition, and the ammonia nitrogen concentration, nitrite nitrogen concentration and total nitrogen concentration in the effluent were as shown in Table 2.
TABLE 2 effluent quality
Example 2
The anaerobic ammonium oxidation bacteria are adopted to treat the wastewater containing heavy metal ions, and the water quality of the wastewater is shown in the table 1. Inoculating the anaerobic ammonium oxidation bacteria activated sludge which is enriched and cultured in a laboratory, wherein the initial SAA is 0.40 kgN/(kgVSS.d). Due to the influence of heavy metals, after a period of treatment, the SAA of the strains in the four groups of reactors (four different water inflows) is less than 0.15 kgN/(kgVSS. d), and the activity is reduced by about 70%. Hydroxylamine and ethylene diamine tetraacetic acid are added according to the method of the invention for recovery, so that the concentration of hydroxylamine in the inlet water is 6.0mg/L, and the concentration of ethylene diamine tetraacetic acid is 5.0 mg/L. After 5 days of operation, the activity of the species in reactors A, B, C and D gradually recovered, and SAA reached 0.23, 0.27, 0.26 and 0.22 kgN/(kgVSS. D), respectively. After 9 days of operation, the SAA was substantially restored to the uninhibited levels, and the ammonia nitrogen concentration, nitrite nitrogen concentration, and total nitrogen concentration in the effluent were as shown in table 3.
TABLE 3 effluent quality
Example 3
The anaerobic ammonium oxidation bacteria are adopted to treat the wastewater containing heavy metal ions, and the water quality of the wastewater is shown in the table 1. Inoculating the anaerobic ammonium oxidation bacteria activated sludge which is enriched and cultured in a laboratory, wherein the initial SAA is 0.40 kgN/(kgVSS.d). Due to the influence of heavy metals, after a period of treatment, the SAA of the strains in the four groups of reactors (four different water inflows) is less than 0.15 kgN/(kgVSS. d), and the activity is reduced by about 70%. Hydroxylamine and ethylene diamine tetraacetic acid are added according to the method of the invention for recovery, so that the concentration of hydroxylamine in the inlet water is 10mg/L, and the concentration of ethylene diamine tetraacetic acid is 30 mg/L. After 5 days of operation, the activity of the strains in the reactors A, B, C and D gradually recovered, and SAA reached 0.21, 0.24, 0.23 and 0.21 kgN/(kgVSS. D), respectively. After 9 days of operation, the SAA was 0.33 kgN/(kgVSS. d) or more, and the ammonia nitrogen concentration, nitrite nitrogen concentration and total nitrogen concentration in the effluent were as shown in Table 4.
TABLE 4 quality of the effluent
Example 4
The anaerobic ammonium oxidation bacteria are adopted to treat the wastewater containing heavy metal ions, and the water quality of the wastewater is shown in the table 1. Inoculating the anaerobic ammonium oxidation bacteria activated sludge which is enriched and cultured in a laboratory, wherein the initial SAA is 0.40 kgN/(kgVSS.d). Due to the influence of heavy metals, after a period of treatment, the SAA of the strains in the four groups of reactors (four different water inflows) is less than 0.15 kgN/(kgVSS. d), and the activity is reduced by about 70%. According to the method, hydroxylamine and ethylene diamine tetraacetic acid are added for recovery, so that the concentration of hydroxylamine in the inlet water is 3.0mg/L, the concentration of ethylene diamine tetraacetic acid is 20mg/L, and lysine with the concentration of 0.15 mug/L is added at the same time. The recovery rates of activity of the strains in reactors A, B, C and D were significantly faster than in example 1, and after 5 days of operation, SAA reached 0.28, 0.32, 0.30 and 0.27 kgN/(kgVSS. D), respectively. After 8 days of operation, the SAA was substantially restored to the uninhibited levels, and the ammonia nitrogen concentration, nitrite nitrogen concentration, and total nitrogen concentration in the effluent were as shown in table 5.
TABLE 5 quality of effluent
Compared with the example 1, the method can show that a certain amount of lysine is additionally added, so that the wastewater treatment effect can be improved, and the activity recovery time can be further shortened.
Example 5
The anaerobic ammonium oxidation bacteria are adopted to treat the wastewater containing heavy metal ions, and the water quality of the wastewater is shown in the table 1. Inoculating the anaerobic ammonium oxidation bacteria activated sludge which is enriched and cultured in a laboratory, wherein the initial SAA is 0.40 kgN/(kgVSS.d). Due to the influence of heavy metals, after a period of treatment, the SAA of the strains in the four groups of reactors (four different water inflows) is less than 0.15 kgN/(kgVSS. d), and the activity is reduced by about 70%. According to the method, hydroxylamine and ethylene diamine tetraacetic acid are added for recovery, so that the concentration of hydroxylamine in the inlet water is 3.0mg/L, the concentration of ethylene diamine tetraacetic acid is 20mg/L, and simultaneously lysine of 0.5 microgram/L is added. The recovery rates of activity of the strains in reactors A, B, C and D were significantly faster than in example 1, and after 5 days of operation, SAA reached 0.29, 0.33, 0.31 and 0.27 kgN/(kgVSS. D), respectively. After 8 days of operation, the SAA was substantially restored to the uninhibited levels, and the ammonia nitrogen concentration, nitrite nitrogen concentration, and total nitrogen concentration in the effluent were as shown in table 6.
TABLE 6 quality of effluent
Comparative example 1
The difference from example 1 is that: after being inhibited by heavy metal, no promoter component is added, and the activity is naturally recovered by the strain. The recovery rates of activity of the strains in reactors A, B, C and D slowed significantly, and after 5 days of operation, SAA reached 0.17, 0.18, 0.19 and 0.16 kg N/kg VSS/D, respectively. After 10 days of operation, the SAA was less than 0.25 kgN/(kgVSSd). The ammonia nitrogen concentration, nitrite nitrogen concentration and total nitrogen concentration in the effluent were as shown in Table 7.
TABLE 7 effluent quality
Comparative example 2
The difference from example 1 is that: only hydroxylamine is added, and ethylenediamine tetraacetic acid is not added. The recovery rates of the activity of the strains in reactors A, B, C and D were relatively slow, and after 5 days of operation, SAA reached 0.19, 0.20, 0.21 and 0.18 kgN/(kgVSSd), respectively. After 10 days of operation, the SAA was almost 0.30 kgN/(kgVSS. d), and the ammonia nitrogen concentration, nitrite nitrogen concentration, and total nitrogen concentration in the effluent were as shown in Table 8.
TABLE 8 effluent quality
Comparative example 3
The difference from example 1 is that: only adding ethylene diamine tetraacetic acid and not adding hydroxylamine. The recovery rates of the activity of the strains in reactors A, B, C and D were relatively slow, and after 5 days of operation, SAA reached 0.20, 0.21, 0.22 and 0.18 kgN/(kgVSSd), respectively. After 10 days of operation, the SAA was almost 0.30 kgN/(kgVSS. d), and the ammonia nitrogen concentration, nitrite nitrogen concentration, and total nitrogen concentration in the effluent were as shown in Table 9.
TABLE 9 quality of effluent
The experimental results of the examples and the comparative examples show that the method has obvious promotion effect on the recovery of the strain activity, relatively short recovery time and good water yielding effect.