CN115159690A - Method for controlling sewage odor by using nitrate and calcium peroxide together - Google Patents
Method for controlling sewage odor by using nitrate and calcium peroxide together Download PDFInfo
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- CN115159690A CN115159690A CN202210724285.8A CN202210724285A CN115159690A CN 115159690 A CN115159690 A CN 115159690A CN 202210724285 A CN202210724285 A CN 202210724285A CN 115159690 A CN115159690 A CN 115159690A
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- 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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/348—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the way or the form in which the microorganisms are added or dosed
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- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- 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
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- 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
- C02F2101/101—Sulfur compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/06—Nutrients for stimulating the growth of microorganisms
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2307/00—Location of water treatment or water treatment device
- C02F2307/08—Treatment of wastewater in the sewer, e.g. to reduce grease, odour
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Abstract
The invention relates to the technical field of sewage treatment, and discloses a method for controlling sewage odor by using nitrate and calcium peroxide in a combined manner, which comprises the following steps: the raw materials containing nitrate and calcium peroxide are added into the sewage of the drainage system, so that the effect of controlling the release of sulfides in the sewage is realized. Can simultaneously greatly reduce the use amount of nitrate and the release flux of carbon dioxide and greenhouse gas in a system, reduce the addition amount of chemical agents and save the dosing cost. Meanwhile, after the dosing is stopped, the system oversulfide still maintains a lower level for 1 to 3 days, and an intermittent dosing mode can be adopted, so that the dosing cost is further reduced. Not only effectively solves the problem of sewage odor, but also can slow down the influence of greenhouse effect, and has great popularization significance in practical application.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a method for controlling sewage odor by using nitrate and calcium peroxide together.
Background
Hydrogen sulfide (H) released from drainage system 2 S) is a major source of the problem of malodor, and for this reason, a liquid-phase chemical dosing control method has become a major point of research in the field of drainage management, and among them, a nitrate dosing method has been widely used in many countries due to advantages such as high solubility and small side effects. The sulfur control mainly involves two mechanisms, namely nitrate stimulates nitrate reduction-sulfur oxidizing bacteria (NR-SOB) to oxidize sulfides, and heterotrophic nitrate reducing bacteria (hNRB) competes with Sulfate Reducing Bacteria (SRB) for an organic electron donor under the stimulation of nitrate to limit the activity of the SRB.
However, the research shows that the sulfur control of the nitrate still has some limitations, the added nitrate is not only consumed by the sulfide oxidation process, but also consumed by the heterotrophic denitrification process, so that the higher nitrate consumption rate is caused, and after the nitrate is exhausted, the sulfide concentration can rebound immediately, so that a large amount of nitrate needs to be added continuously. On the other hand, the organic carbon source in the wastewater is metabolized into carbon dioxide (CO) 2 ) Resulting in a substantial reduction in Chemical Oxygen Demand (COD) and a significant increase in carbon dioxide emissions. Therefore, the exploration of a novel sulfide control strategy for the drainage pipeline is very critical.
Recently, researchers at home and abroad have conducted intensive studies on The improvement of The technology of controlling sulfur based on nitrate addition, such as The research of Chen et al (Chen, C., et al, "Enhanced performance of Density Sulford removal Process under micro-aerobic Condition." Journal of Hazardous materials179.1-3 (2010): 1147-1151), found that micro-aeration conditions contribute to The improvement of The performance of The technology of controlling sulfur by nitrate in The sewage treatment process, however, zhang et al (Zhang, guijiao, et al, "effective of dissolved oxygen on N2O release in The second system under The nitrate controlling moisture, nitrogen concentration is found to exceed that of The NO in 1514. After adding micro-oxygen, dissolved nitrogen, no. 2O release, no. 2O dissolved oxygen, no. 2D 1514. Nitrate dissolved oxygen in The sewage treatment process 2 O) large emissions of greenhouse gases, thereby exacerbating the greenhouse effect. On the other hand, dissolved oxygen in sewage is rapidly consumed by microorganisms, and thus, the wastewater is treatedIn view of the above limitations, the drainage pipeline for transporting sewage over long distances needs to adopt a method of continuously injecting air at multiple points to maintain aerobic conditions all the time, and the problem of how to slowly release oxygen and reduce greenhouse gas emission is receiving more and more attention.
Calcium peroxide (CaO) 2 ) Is a white solid powdery compound with high-energy peroxide covalent bond, and can slowly release oxygen and hydrogen peroxide (H) for a long time when in contact with water 2 O 2 ). For many years, due to CaO 2 The cost is low, and the method is nontoxic and pollution-free, and is widely applied to the remediation of polluted soil and underground water. In view of CaO 2 The addition advantage of (2) can be assumed to be that nitrate and CaO are jointly added 2 The effectiveness of sulfide control in drain pipelines can be improved, but so far, there is no concern about nitrate and CaO 2 In addition, the influence of the proposed combined adding strategy on the emission of greenhouse gases is not clear, so the application technology is worthy of trial and research.
Disclosure of Invention
Aiming at the problems of large dosage, rebound sulfide and high carbon dioxide release amount existing in the process of inhibiting stink by adopting nitrate in a drainage pipeline in the prior art, the invention provides a method for controlling stink in a drainage system by adopting the combined use of nitrate and calcium peroxide, which can reduce the dosage of nitrate by over 50 percent, can effectively reduce the release amount of carbon dioxide and has excellent effect.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for controlling sewage odor by using nitrate and calcium peroxide together comprises the following steps: the raw materials containing nitrate and calcium peroxide are added into the sewage of the drainage system, so that the effect of controlling the release of sulfides in the sewage is realized.
The control mechanism of the method is as follows: the nitrate and calcium peroxide are jointly added to stimulate the activity of NR-SOB in a drainage system, participate in the oxidation process of sulfide with nitrate as an electron acceptor under the anoxic condition, and inhibit the heterotrophic denitrification process, thereby greatly reducing the dosage of the nitrate. In addition, caO 2 Contact with water to produce calcium hydroxide (Ca (OH) 2 ) The alkaline environment formed later greatly reduces CO 2 The release flux of greenhouse gases, and, ca (OH) 2 Interaction with oxygen further inhibits SRB activity. On the other hand, the generation of hydrogen peroxide during the reaction also controls the release of sulfide to some extent. Therefore, under the synergistic effect of the two, the release effect of the sulfide is effectively reduced, the adding amount of the nitrate is greatly reduced (the maximum reduction amount is 57%), and the N is reduced 2 O、CH 4 、CO 2 And the total emission of greenhouse gases, in particular CO 2 The release flux is greatly reduced, and the method is suitable for popularization and application in actual life.
The dosage of the nitrate is more than 30mg-N/L, and the dosage of the calcium peroxide is more than 30 mg/L.
Preferably, the addition amount of the nitrate is more than 30mg-N/L, and the addition amount of the calcium peroxide is more than 50 mg/L. Under the concentration, the best sulfide control effect can be achieved by using the minimum nitrate adding amount, the odor problem of a drainage system is solved, the release flux of greenhouse gases can be reduced, and the greenhouse effect is slowed down.
More preferably, the addition amount of the nitrate is 30-70mg-N/L, and the addition amount of the calcium peroxide is more than 50 mg/L.
The nitrate is water-soluble nitrate.
Preferably, the nitrate salt includes sodium nitrate and potassium nitrate.
The raw materials containing nitrate and calcium peroxide adopt an intermittent feeding mode. Experimental research shows that the compound adding method not only can control sulfur in a coordinated mode, but also can maintain the lower level of the oversulfide of the system within a certain time after the adding is stopped, so that intermittent compound adding can be realized, the using amount of nitrate can be further reduced, the odor problem of a drainage system is effectively solved, and the production cost is reduced to a greater extent.
Preferably, the raw materials containing the nitrate and the calcium peroxide are intermittently added for 10-14h every time at intervals of 1-3 days, and tests show that after the nitrate and the calcium peroxide are compositely added at intervals of 1-3 days, when the addition of the medicament is stopped, the persulfate of the system can be kept at a lower level within 0-2mg-S/L, so that the raw materials are intermittently added at intervals of 1-3 days.
Further preferably, the adding time is 10-12h each time, and the adding time interval is 2-3 days.
The method can reduce the generation amount of sulfide in the system, obviously reduce the release amount of carbon dioxide, and reduce the global warming potential of the total greenhouse gas by about 90 percent.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the sulfide in the drainage system is controlled by adopting the composite addition of the nitrate and the calcium peroxide, so that the odor problem of the sewage is controlled, the use amount of the nitrate and the release flux of the carbon dioxide and greenhouse gas in the system can be greatly reduced, the addition amount of chemical agents is reduced, and the dosing cost is saved.
(2) According to the nitrate and calcium peroxide compound adding method, after the addition of the nitrate and calcium peroxide is stopped, the system persulfate still maintains a lower level for 1-3 days, and an intermittent adding mode can be adopted, so that the medicine cost is further reduced.
(3) The calcium peroxide has good stability, is nontoxic and harmless, is environment-friendly and is suitable for popularization and application in actual life.
Drawings
FIG. 1 is a graph showing the change in the effluent water concentration at the end of the sulfide cycle before and after nitrate addition alone in example 1.
FIG. 2 is a graph showing the change in the effluent concentration at the end of the sulfide cycle before and after nitrate injection with air in example 2.
FIG. 3 is a graph showing the change in the concentration of the effluent at the end of the sulfide cycle before and after the nitrate and calcium peroxide are compositely added in example 3
FIG. 4 is a graph showing the change in the final water concentration of sulfide at the end of a sulfide cycle before and after intermittent combined addition of nitrate and calcium peroxide in example 4
FIG. 5 shows the nitrate addition alone, the nitrate injection with air, and the nitrate and peroxide addition in combination in example 5Before and after calcium conversion, N 2 O、CH 4 、CO 2 And a change in the total greenhouse gas warming potential value.
FIG. 6 is a graph showing the relative abundance of heterotrophic nitrate-reducing bacteria and autotrophic nitrate-reducing sulfide-oxidizing bacteria before and after the combined dosing of example 6.
FIG. 7 is a graph showing the change in copy number of a gene involved in sulfate reduction before and after mixed administration in example 7.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and substitutions without departing from the spirit and scope of the present invention.
The raw materials used in the following embodiments are commercially available, and the nitrate used in the examples is sodium nitrate, which is available at a reasonable price.
Drainage system reactor preparation
The experiment was carried out in 3 drainage system reactors in which the effluent was completely replaced every 12 hours. The reactors had been operated for about 4 months to reach a quasi-steady state before the dosing treatment, and then, a mixture of nitrate, nitrate and air, and nitrate and calcium peroxide was injected into 3 reactors, respectively, at different concentrations; and each dosing is carried out after the water is changed, the effluent concentration at the end of the sulfide period is measured every day, and the influence of different dosing substances and different dosing concentrations on the sulfides in the water is observed. On the other hand, after each water change and dosing, high purity nitrogen gas was injected into the headspace to evacuate residual headspace gas, and a gas sample in the gas phase was collected at the end of the 12 hour pumping cycle each day to analyze methane (CH) 4 ) Dinitrogen monoxide (N) 2 O) and carbon dioxide (CO) 2 ) Monitoring the gas phase composition in the drain line reactor.
Example 1
Nitrate was added separately to the reactor 1 at concentrations of 20mg-N/L, 30mg-N/L, 60mg-N/L, and 70mg-N/L, respectively, and the effluent concentration at the end of the sulfide cycle was examined, with the results shown in Table 1 and FIG. 1.
TABLE 1 average end of cycle water concentration of sulfides in the reactor in example 1
Example 2
Nitrate and air were injected into the reactor 2 at concentrations of 20mg-N/L and 30mg-N/L, respectively, and dissolved oxygen concentrations in the wastewater were 0.1 to 0.3mg/L and 0.4 to 0.6mg/L, and effluent concentrations at the end of the sulfide cycle were measured, and the results are shown in Table 2 and FIG. 2.
Table 2 average end of cycle water concentration of sulfides in the reactor in example 2
Example 3
20mg-N/L or 30mg-N/L nitrate and 30mg/L or 50mg/L calcium peroxide are mixed and added into the reactor 3, and the effluent concentration at the end of the sulfide period is detected, and the results are shown in Table 3 and figure 3.
Table 3 average end of cycle water concentration of sulfides in the reactor in example 3
Example 4
30mg-N/L nitrate and 50mg/L calcium peroxide are intermittently added into the reactor 3, and the effluent concentration at the end of the sulfide period is detected, and the result is shown in figure 4.
As can be seen from the experimental conditions in examples 1 and 2, the data shown in Table 1 and FIG. 1 show that when sodium nitrate was added alone, the formation of sulfides in the reactor was completely suppressed only when the concentration of sodium nitrate reached 70 mg-N/L;
as can be seen from the data in Table 2 and FIG. 2, when trace dissolved oxygen coexists with nitrate in the reactor, the control efficiency of sulfide is significantly improved, and after 30mg-N/L nitrate is added under the condition that the DO concentration is 0.4-0.6mg/L, the removal rate of sulfide reaches 100%, which indicates that the presence of dissolved oxygen is helpful for controlling the generation of sulfide. However, it was also found that after stopping the injection of air with nitrate, the sulfide concentration recovered rapidly, indicating that the addition of nitrate under microaerobic conditions had no long-term inhibitory effect on SRB.
In example 3 in which nitrate and calcium peroxide are mixed and added, namely data in table 3 and fig. 3, when the concentration of sodium nitrate is kept at 30mg-N/L and the concentration of calcium peroxide reaches 50mg/L, the generation of sulfides in the reactor can be completely inhibited; then, the inventor continues to research and find that in the system of 30N-50Ca, when the dosing of the medicine is stopped, the sulfide of the system can still keep a low level within 1-3 days.
Therefore, the inventor tries to implement example 4, after 30mg-N/L nitrate and 50mg/L calcium peroxide are intermittently and compositely added, the system sulfide concentration is rapidly reduced after the first addition for 12 hours on the 5 th day and slightly rebounds after the second day, so the addition is carried out again for 12 hours on the 6 th day, the system sulfide concentration is maintained for about 3 days and rebounds, and the system sulfide concentration is maintained at a low level for about 3-4 days and gradually rises after the addition is carried out again for 12 hours on the 9 th day. Therefore, the method can also realize better sulfide control effect by adopting an intermittent compound feeding mode, and the compound feeding can inhibit the generation of the sulfide for 1 to 3 days at most for 4 days.
Therefore, in the view of comprehensive original points, compared with the prior art of adding 70mg-N/L of sodium nitrate alone, the intermittent compound adding technology has the advantages that the adding times are few, the adding amount is greatly reduced, the adding cost is greatly reduced, and the influence of greenhouse gas emission can be reduced while controlling sulfide through mixed adding.
Example 5 greenhouse gas Release
High-concentration nitrate solutions were fed into the three reactors, respectively, so as to achieve a nitrate concentration of 30mg-N/L in each reactor, while injecting air into the reactor 2 so that the DO concentration in the sewage became 0.4-0.6mg/L, and injecting CaO into the reactor 3 2 CaO in sewage 2 After the concentration reached 50mg/L, the gas phase in the reactor was examined and the results are shown in FIG. 5. Finding N in gas phase after nitrate and calcium peroxide are added compositely 2 O，CH 4 And CO 2 The release flux of the method is obviously reduced, the total warming potential of the greenhouse gas in the system is greatly reduced, and particularly, the release flux effect of the carbon dioxide is very obvious, which shows that the method can reduce the greenhouse effect while removing the sulfide.
Example 6 analysis of microorganisms and functional Gene profiles
The results of observing the microbial heterotrophic nitrate-reducing bacteria and the autotrophic nitrate-reducing sulfide-oxidizing bacteria in the reactor effluent by using a 16s high-throughput sequencing method are shown in FIG. 6.
The initial heterotrophic nitrate-reducing bacteria and the autotrophic nitrate-reducing sulfide-oxidizing bacteria of each reactor are slightly different and are generally at the conventional level. From fig. 6, it can be found that autotrophic nitrate-reducing sulfide-oxidizing bacteria are significantly increased and heterotrophic nitrate-reducing bacteria are significantly decreased when sodium nitrate and calcium peroxide are compositely added, and the difference in the effect is significant compared with the effect obtained by adding sodium nitrate alone or adding sodium nitrate in a mixed manner and the effect obtained by dissolving oxygen. The control pathway of sulfide in the method is mainly through the oxidation process of sulfide with nitrate as an electron acceptor.
Meanwhile, a PICRUST functional gene prediction method is adopted to analyze functional genes related to the sulfate reduction pathway in the reactor, the result is shown in figure 7, and the nitrate and CaO are added in a compounding manner 2 Later, functional genes associated with sulfate reduction were minimized, indicating nitrate and CaO 2 The compound adding strategy can obviously inhibit the activity of sulfate reducing bacteria.
The inventors have tried other nitrate combinations such as potassium nitrate, etc. with similar results as in the case of sodium nitrate.
Claims (10)
1. A method for controlling sewage odor by using nitrate and calcium peroxide together is characterized by comprising the following steps: the raw materials containing nitrate and calcium peroxide are added into the sewage of the drainage system, so that the effect of controlling the release of sulfides in the sewage is realized.
2. The method for controlling foul smell of sewage according to claim 1, wherein the nitrate is added in an amount of 30mg-N/L or more and the calcium peroxide is added in an amount of 30mg/L or more.
3. The method for controlling foul smell of sewage according to claim 1, wherein the nitrate is added in an amount of 30mg-N/L or more and the calcium peroxide is added in an amount of 50mg/L or more.
4. The method for controlling foul smell of sewage according to claim 1, wherein the amount of nitrate added is 30-70mg-N/L and the amount of calcium peroxide added is 50mg/L or more.
5. The method of controlling sewage odor using nitrate in combination with calcium peroxide as claimed in claim 1, wherein the nitrate is a water-soluble nitrate.
6. The method of controlling sewage odor using nitrate in combination with calcium peroxide as claimed in claim 1, wherein the nitrate includes sodium nitrate, potassium nitrate.
7. The method for controlling sewage odor by using nitrate and calcium peroxide in combination according to claim 1, wherein the raw material containing nitrate and calcium peroxide is intermittently added.
8. The method for controlling sewage odor by using nitrate and calcium peroxide together according to claim 1 or 7, wherein the raw material containing nitrate and calcium peroxide is intermittently added for 10-14h every 1-4 days.
9. The method for controlling sewage odor by using nitrate and calcium peroxide together according to claim 7, wherein the raw material containing nitrate and calcium peroxide is intermittently added for 10-12h every 2-3 days.
10. The method of controlling sewage odor of claim 1 wherein said method is capable of reducing total greenhouse gas global warming potential.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050115895A1 (en) * | 2003-12-02 | 2005-06-02 | Simpson Gregory D. | Composition for odor control |
| CN102432078A (en) * | 2011-10-13 | 2012-05-02 | 董文艺 | In-site preparation for rapidly eliminating black and smelly matters in polluting bottom sediment of river and method thereof |
| CN104609548A (en) * | 2015-02-04 | 2015-05-13 | 大连海事大学 | Method for rapidly and stably starting wastewater nitrite type mixotrophic desulfurization and denitrification system |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050115895A1 (en) * | 2003-12-02 | 2005-06-02 | Simpson Gregory D. | Composition for odor control |
| CN102432078A (en) * | 2011-10-13 | 2012-05-02 | 董文艺 | In-site preparation for rapidly eliminating black and smelly matters in polluting bottom sediment of river and method thereof |
| CN104609548A (en) * | 2015-02-04 | 2015-05-13 | 大连海事大学 | Method for rapidly and stably starting wastewater nitrite type mixotrophic desulfurization and denitrification system |
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