CN112408594A - Method for strengthening culture of anaerobic ammonium oxidation bacteria and improving bacterial activity by using ferrous sulfide - Google Patents

Method for strengthening culture of anaerobic ammonium oxidation bacteria and improving bacterial activity by using ferrous sulfide Download PDF

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CN112408594A
CN112408594A CN202011090897.3A CN202011090897A CN112408594A CN 112408594 A CN112408594 A CN 112408594A CN 202011090897 A CN202011090897 A CN 202011090897A CN 112408594 A CN112408594 A CN 112408594A
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倪寿清
郭蓓蓓
邹春榛
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Abstract

The invention relates to a method for strengthening the culture of anaerobic ammonium oxidation bacteria and improving the activity of the bacteria by ferrous sulfide, which comprises the following steps: adding ferrous sulfide particles and anaerobic granular sludge into an upflow anaerobic sludge bed reactor, wherein the adding amount of the ferrous sulfide particles is 1-10 g/L of ammoniacal nitrogen and nitrite nitrogen in wastewater to be treated; stirring under the anaerobic and light-proof condition at the temperature of 30-34 ℃ to enable anaerobic ammonia oxidation sludge in the reactor to fully react with pollutants, and adjusting the inflow velocity to enable the Hydraulic Retention Time (HRT) to be 24-48 hours; according to the invention, the culture of the anaerobic ammonium oxidation bacteria can be accelerated by adding the ferrous sulfide, the starting time of the reactor is shortened, the activity of the anaerobic ammonium oxidation bacteria is improved, and the obtained particles are more compact and have better stability. The method has simple process and mild reaction condition, and can be carried out under the condition of normal anaerobic ammoxidation; is safe and harmless to the environment and is convenient for engineering application.

Description

Method for strengthening culture of anaerobic ammonium oxidation bacteria and improving bacterial activity by using ferrous sulfide
Technical Field
The invention relates to a method for strengthening the culture of anaerobic ammonium oxidation bacteria and improving the activity of the bacteria by ferrous sulfide, belonging to the technical field of environmental microorganisms and wastewater treatment.
Background
The anaerobic ammonia oxidation process is widely concerned as an environment-friendly autotrophic nitrogen removal technology with low energy consumption. The process mainly depends on anaerobic ammonium oxidation bacteria under the anoxic condition to use NO2 --N is an electron acceptor, NH4 +Conversion of-N to N2. Compared with the traditional biological denitrification process, the anaerobic ammonia oxidation process does not need organic matters as a carbon source, simultaneously reduces the oxygen demand by about 60 percent, reduces the excess sludge yield by about 90 percent, occupies a small area and can save the operation cost by about 60 percent. In addition, the anaerobic ammonia oxidation process has higher nitrogen removal rate, is very suitable for treating high ammonia nitrogen wastewater, and reduces the discharge amount of greenhouse gases by about 90 percent compared with the traditional biological denitrification process.
Although industrial anammox reactors have been established around the world, the anammox bacteria have a long generation period, are sensitive to environmental changes, and generate nitrate Nitrogen (NO) during the reaction process3 --N), etc., leading to the current application of this process to the treatment of domestic sewage mainstream wastewater only to a very small extent. Currently, most anammox sewage treatment plants are mainly distributed in europe, china and north america. From the viewpoint of Nitrogen Load Ratios (NLRs), these sewage treatment plants mainly treat wastewater from glutamic acid and amino acid industries and slaughterhouses, anaerobic ammonia oxidation has not become a mainstream process for treating domestic sewage, and many key technologies remain to be solved, especially how to shorten the time for converting anaerobic granular sludge into anaerobic ammonia oxidation granular sludge, so as to cope with problems such as mass production in practical application. Therefore, accelerating the starting process of anaerobic ammonia oxidation is of great significance for the practical application of the technology.
In order to shorten the starting time of the anaerobic ammoxidation reaction and enhance the stability thereof, researchers at home and abroad continuously conduct research and exploration. Among these, a more direct and effective way is to start the reactor quickly by enhancing the activity of anammox bacteria. Yang et al adds a certain amount of nano pyrrhotite (nFe) into the autotrophic denitrification reactor1-xS) successfully domesticate the sulfur autotrophic denitrifying bacteria to realize the removal of nitrate and nitrogen. However, since a long start-up time is still required, it is still a problem to be solved at present how to shorten the time for converting anaerobic granular sludge into anammox granular sludge and improve the activity of anammox bacteria.
Disclosure of Invention
Aiming at the defects of the prior art, especially the problem that the practical application of the anaerobic ammonia oxidation process is seriously hindered due to the long culture time of the anaerobic ammonia oxidation bacteria at present, the invention provides a method for strengthening the culture of the anaerobic ammonia oxidation bacteria and improving the activity of the bacteria by utilizing ferrous sulfide.
The method can promote the rapid start of the anammox, promote the growth of the anammox bacteria, improve the treatment efficiency, is environment-friendly and is easy for engineering application.
In order to solve the problems, the invention is realized by the following technical scheme:
a method for strengthening the culture of anaerobic ammonium oxidation bacteria and improving the bacterial activity by using ferrous sulfide comprises the following steps:
(1) adding ferrous sulfide particles and anaerobic granular sludge into an upflow anaerobic sludge bed reactor, wherein the adding amount of the ferrous sulfide particles is 1-10 g/L of ammoniacal nitrogen and nitrite nitrogen in wastewater to be treated;
(2) introducing wastewater to be treated containing ammoniacal nitrogen and nitrite nitrogen from the bottom of the reactor by using a peristaltic pump, stirring at the anaerobic and light-proof condition of 30-34 ℃ to ensure that anaerobic ammonia oxidation sludge in the reactor fully reacts with pollutants, and adjusting the flow rate of inflow water to ensure that the Hydraulic Retention Time (HRT) is 24-48 hours; the culture time of the anaerobic ammonium oxidation bacteria is shortened, the operation stability is realized, and the activity of the anaerobic ammonium oxidation bacteria is improved; the reactor starts to react after running for 51-59 days.
According to the invention, in the step (1), the addition amount of the ferrous sulfide particles is 3-10 g/L of ammoniacal nitrogen and nitrite nitrogen in the wastewater to be treated.
Preferably, in the step (1), the addition amount of the ferrous sulfide particles is 3-5 g/L of ammoniacal nitrogen and nitrite nitrogen in the wastewater to be treated.
Most preferably, in the step (1), the addition amount of the ferrous sulfide particles is 3g/L of ammoniacal nitrogen and nitrite nitrogen in the wastewater to be treated.
According to the invention, in the step (1), the addition amount of the anaerobic granular sludge is 5450-5550 mgMLSS/L.
The anaerobic granular sludge is the granulated sludge which is generated in the organic wastewater treatment process and is rich in various anaerobic microorganism populations in the prior art, and is taken from the active anaerobic granular sludge of a Yishui sewage treatment plant.
According to the invention, the mol ratio of ammoniacal nitrogen to nitrous nitrogen in the wastewater to be treated containing ammoniacal nitrogen and nitrous nitrogen is 1: 1.2.
According to the invention, the particle size of the ferrous sulfide particles is preferably 1-5 mm.
The upflow anaerobic sludge blanket reactor is in the prior art, and comprises a reactor body, wherein the reactor body is of an inner-layer and outer-layer double-layer structure, is made of organic glass, and has the inner diameter of 10cm, the outer diameter of 12cm, the height of 95cm and the effective volume of 5L; the reactor is characterized in that a three-phase separator is arranged at the upper part in the reactor body, a gravel layer with the particle size of 4mm is laid at the bottom of the reactor, a water distributor is arranged in the gravel layer, filler is filled between the three-phase separator and the gravel layer, nitrogen-containing wastewater (including part of backflow wastewater) enters the reactor through a peristaltic pump through a water inlet hole arranged at the center of the bottom of the reactor, and sewage upwards passes through a sludge bed containing granular sludge. The anammox reaction takes place during the contact between the wastewater and the sludge particles.
The invention uses ferrous sulfide to strengthen the culture of anaerobic ammonium oxidation bacteria and improve the bacterial activity, because the anaerobic ammonium oxidation bacteria contains a plurality of iron storage 'sites', the stored iron element is usually Fe2+The form of (A) is involved in the electron transfer process of anammox bacteria as a coenzyme factor of Fe-S protein and hemoprotein, including NH4 +-N to N2And can promote metabolism of anammox bacteria. Ferrous sulfide (FeS) widely exists in nature, is easy to obtain, and can be partially dissolved in anaerobic water body to release Fe2+And S2-. Ferrous sulfide also has the characteristic of easy oxidation and can react with dissolved oxygen in a water body. Thereby promoting the rapid start of the anaerobic ammonia oxidation. S0、S2-The reduced sulfur can be used as an electron donor to be utilized by sulfur autotrophic denitrifying bacteria, and nitrate nitrogen and nitrite nitrogen are reduced into nitrogen at the same time. The result shows that the activity of the anaerobic ammonium oxidation bacteria is obviously improved,the anaerobic ammonia oxidation starting process is obviously shortened, and the removal rate of ammoniacal nitrogen and nitrite nitrogen in a short time reaches more than 85 percent.
The invention has the following beneficial effects:
1. on the premise of keeping basic treatment conditions, the method strengthens the culture of the anaerobic ammonium oxidation bacteria by using the ferrous sulfide, shortens the time for converting anaerobic granular sludge into the anaerobic ammonium oxidation granular sludge, improves the activity of the anaerobic ammonium oxidation bacteria, can better convert the ferrous sulfide into iron ions and use the iron ions as trace elements for microorganisms, and effectively promotes the starting process of the anaerobic ammonium oxidation. Therefore, the method has the characteristics of high efficiency and safety by using the ferrous sulfide to promote the start of the anaerobic ammonia oxidation.
2. The invention applies ferrous sulfide to strengthening the culture of the anaerobic ammonium oxidation bacteria and improving the bacterial activity, can effectively improve the bacterial activity and shorten the starting time of the anaerobic ammonium oxidation, has low cost, high efficiency, safety and mild condition, and can be used under the conventional anaerobic ammonium oxidation condition. The method of the invention has low operation cost, which is mainly reflected in the consumption of ferrous sulfide. For example, the method can obtain obvious promotion effect by adding 15g of ferrous sulfide into a sewage treatment system with an effective volume of 5L once, and has the advantages of low consumption of ferrous sulfide, low cost, easy purchase of ferrous sulfide, safety and harmlessness to the environment and convenience for engineering application.
Drawings
FIG. 1 is a scanning electron micrograph of ferrous sulfide used in example 1 of the present invention before (a-b) and after (c-f) reaction.
FIG. 2 is a graph showing the effect of the initiation process of anammox in the different treatments of the R1 reactor and the R2 reactor, with time (unit: d) on the abscissa and total nitrogen removal (unit:%); the R1 total nitrogen removal curve is the total nitrogen removal curve over time in the R1 reactor, and the R2 total nitrogen removal curve is the total nitrogen removal curve over time in the R2 reactor.
FIG. 3 is a histogram of the intracellular Heme c content of different treatments in the R1 reactor and the R2 reactor.
Detailed Description
The invention is further illustrated by the following examples, but the scope of the invention as claimed is not limited to the scope described in the detailed description.
The raw materials used in the embodiment of the invention are all commercial products, and the used equipment is conventional equipment.
Examples the reactor used for sewage treatment was an Upflow Anaerobic Sludge Blanket (UASB), which is a commercially available conventional water treatment facility, and practical applications are not limited to the UASB reactor. In the example, the R1 reactor (UASB) was used as a control (no ferrous sulfide added) and the R2 reactor (UASB) was used as a reactor to which ferrous sulfide was added.
Example the contaminant in the Nitrogen-containing wastewater was NH4 +-N and NO2 --N, NH in the feed water4 +the-N is kept between 50 and 100 mg/L.
Example 1
A method for strengthening the culture of anaerobic ammonium oxidation bacteria and improving the bacterial activity by ferrous sulfide comprises the following steps:
(1) ferrous sulfide particles with the particle size of 1-5 mm are shown in the pictures of a scanning electron microscope (A, B) in figure 1, and the color is black brown and the texture is compact; the ferrous sulfide comprises iron and sulfur as main components, wherein the iron is mainly present in the form of ferrous iron.
Taking 2.5-5L of wastewater to be treated containing ammoniacal nitrogen and nitrite nitrogen every day, adding the wastewater into an R2 reactor, and adding 3g/L of ferrous sulfide and anaerobic granular sludge into the reactor at the temperature of 32 +/-1 ℃, wherein the adding amount of the anaerobic granular sludge is 5450-5550 mgMLSS/L;
(2) and aerating for 10 minutes by using a nitrogen bottle, wherein the Hydraulic Retention Time (HRT) is 24-48 hours at the temperature of 30-34 ℃, and the degradation efficiency of pollutants in the wastewater is improved. Through detection and calculation, the total nitrogen removal rate of the R2 reactor reaches more than 85 percent in 51 days.
Scanning electron microscopy is carried out on the ferrous sulfide after the reaction treatment, the scanning electron microscopy photos are shown in fig. 1(c-f), and it can be seen from the pictures that the ferrous sulfide after the reaction treatment has a porous structure, which shows that iron in the ferrous sulfide participates in the culture of the enhanced anaerobic ammonium oxidation bacteria.
The R1 reactor was set up as a control experiment. In the experiment, the nitrogen-containing waste water with the same volume as that of the R2 is added into the R1, and the rest conditions are the same as those of the R2 reactor, except that the ferrous sulfide is not added into the R1.
1. The R1 reactor and the R2 reactor are two reactors, from 13 days after starting to the end, the total nitrogen removal rate of R2 is higher than that of R1, the total nitrogen removal rate of the R2 reactor reaches more than 85% in 51 days, the total nitrogen removal rate of the R1 reactor without ferrous sulfide reaches 85% in 68 days, and the reaction is successfully started, and the comparison shows that the R2 reactor with ferrous sulfide particles shortens the time for converting anaerobic granular sludge into anaerobic ammonium oxidation granular sludge and improves the activity of anaerobic ammonium oxidation bacteria; the starting time is obviously shortened relative to R1, namely, the anaerobic ammonia oxidation starting process can be promoted by adding 3g/L ferrous sulfide particles. As shown in fig. 2.
2. The content of the Heme c on the 50 th day of the two reactors R1 and R2 was tested, and the content of the Heme c in R1 and R2 was 7.2 and 11.8 umol/g-protein, respectively. Iron ions are reported to be involved in the formation of heme c, which is the active center of many enzyme proteins. The conversion of the substrate and the intermediate medium in many biochemical reactions is accomplished by utilizing the catalysis and electron transfer of the type c hemoglobin. amammox contains a large amount of heme, and one subunit of hydroxylamine oxidoreductase (HAO) contains 8 heme c. The positive correlation between ferrous sulfide and intracellular heme c in this experiment demonstrates that heme c synthesis can be promoted by the addition of ferrous sulfide in the reactor.
Since the concentration of heme c is in positive correlation with the nitrogen removal rate, heme c can be used as an index for evaluating the activity of anammox bacteria. Therefore, the invention can improve the activity of the anaerobic ammonium oxidation bacteria.
Example 2
A method for strengthening the culture of anaerobic ammonium oxidation bacteria and improving the bacterial activity by ferrous sulfide comprises the following steps:
(1) ferrous sulfide particles with the particle size of 1-5 mm are black brown in color and compact in texture; the ferrous sulfide comprises iron and sulfur as main components, wherein the iron is mainly present in the form of ferrous iron.
Taking 2.5-5L of wastewater to be treated containing ammoniacal nitrogen and nitrite nitrogen every day, adding the wastewater into an R2 reactor, and adding 1g/L of ferrous sulfide and anaerobic granular sludge into the reactor at the temperature of 32 +/-1 ℃, wherein the adding amount of the anaerobic granular sludge is 5450-5550 mgMLSS/L;
(2) and aerating for 10 minutes by using a nitrogen bottle, wherein the Hydraulic Retention Time (HRT) is 24-48 hours at the temperature of 30-34 ℃, and the degradation efficiency of pollutants in the wastewater is improved.
The R1 reactor was set up as a control experiment. In the experiment, the nitrogen-containing waste water with the same volume as that of the R2 is added into the R1, and the rest conditions are the same as those of the R2 reactor, except that the ferrous sulfide is not added into the R1. By comparison, the starting time of anaerobic ammonia oxidation of R2 is shortened relative to that of R1, namely, the starting process of anaerobic ammonia oxidation can be promoted by adding 1g/L ferrous sulfide particles.
Example 3
A method for strengthening the culture of anaerobic ammonium oxidation bacteria and improving the bacterial activity by ferrous sulfide comprises the following steps:
(1) ferrous sulfide particles with the particle size of 1-5 mm are black brown in color and compact in texture; the ferrous sulfide comprises iron and sulfur as main components, wherein the iron is mainly present in the form of ferrous iron.
Taking 2.5-5L of wastewater to be treated containing ammoniacal nitrogen and nitrite nitrogen every day, adding the wastewater into an R2 reactor, and adding 5g/L of ferrous sulfide and anaerobic granular sludge into the reactor at the temperature of 32 +/-1 ℃, wherein the adding amount of the anaerobic granular sludge is 5450-5550 mgMLSS/L;
(2) and aerating for 10 minutes by using a nitrogen bottle, wherein the Hydraulic Retention Time (HRT) is 24-48 hours at the temperature of 30-34 ℃, and the degradation efficiency of pollutants in the wastewater is improved.
The R1 reactor was set up as a control experiment. In the test, nitrogen-containing wastewater with the same volume as that of R2 is added into R1, and the rest conditions are the same as those of the R2 reactor, except that ferrous sulfide is not added into R1, the starting time of anaerobic ammonia oxidation of R2 is shortened relative to that of R1 by comparison, namely, 5g/L ferrous sulfide particles are added to promote the starting process of anaerobic ammonia oxidation.
Example 4
A method for strengthening the culture of anaerobic ammonium oxidation bacteria and improving the bacterial activity by ferrous sulfide comprises the following steps:
(1) ferrous sulfide particles with the particle size of 1-5 mm are black brown in color and compact in texture; the ferrous sulfide comprises iron and sulfur as main components, wherein the iron is mainly present in the form of ferrous iron.
Taking 2.5-5L of wastewater to be treated containing ammoniacal nitrogen and nitrite nitrogen every day, adding the wastewater into an R2 reactor, and adding 10g/L of ferrous sulfide and anaerobic granular sludge into the reactor at the temperature of 32 +/-1 ℃, wherein the adding amount of the anaerobic granular sludge is 5450-5550 mgMLSS/L;
(2) and aerating for 10 minutes by using a nitrogen bottle, wherein the Hydraulic Retention Time (HRT) is 24-48 hours at the temperature of 30-34 ℃, and the degradation efficiency of pollutants in the wastewater is improved.
The R1 reactor was set up as a control experiment. In the experiment, the nitrogen-containing waste water with the same volume as that of the R2 is added into the R1, and the rest conditions are the same as those of the R2 reactor, except that the ferrous sulfide is not added into the R1. By comparison, the starting time of anaerobic ammonia oxidation of R2 is shortened relative to that of R1, namely the starting process of anaerobic ammonia oxidation can be promoted by adding 10g/L ferrous sulfide particles.
Experimental example:
in examples 1-4, varying the amount of ferrous sulfide material initially charged to the R2 reactor gave the results shown in table 1 below:
TABLE 1 summary of anammox system performance at different ferrous sulfide material dosages
Figure BDA0002722010120000061
As can be seen from Table 1, the R2 reactor added with the ferrous sulfide particles shortens the time for converting anaerobic granular sludge into anaerobic ammonium oxidation granular sludge, improves the activity of anaerobic ammonium oxidation bacteria, and has the advantages of optimal effect and shortest starting time when the addition amount of the ferrous sulfide is 3 g/L.

Claims (7)

1. A method for strengthening the culture of anaerobic ammonium oxidation bacteria and improving the bacterial activity by using ferrous sulfide comprises the following steps:
(1) adding ferrous sulfide particles and anaerobic granular sludge into an upflow anaerobic sludge bed reactor, wherein the adding amount of the ferrous sulfide particles is 1-10 g/L of ammoniacal nitrogen and nitrite nitrogen in wastewater to be treated;
(2) introducing wastewater to be treated containing ammoniacal nitrogen and nitrite nitrogen from the bottom of the reactor by using a peristaltic pump, stirring at the anaerobic and light-proof condition of 30-34 ℃ to ensure that anaerobic ammonia oxidation sludge in the reactor fully reacts with pollutants, and adjusting the flow rate of inflow water to ensure that the Hydraulic Retention Time (HRT) is 24-48 hours; the culture time of the anaerobic ammonium oxidation bacteria is shortened, the operation stability is realized, and the activity of the anaerobic ammonium oxidation bacteria is improved; the reactor starts to react after running for 51-59 days.
2. The method for strengthening the culture of the anaerobic ammonia oxidizing bacteria and improving the bacterial activity by using the ferrous sulfide as claimed in claim 1, wherein in the step (1), the addition amount of the ferrous sulfide particles is 3-10 g/L of the wastewater to be treated containing ammoniacal nitrogen and nitrite nitrogen.
3. The method for strengthening the culture of the anaerobic ammonia oxidizing bacteria and improving the bacterial activity by using the ferrous sulfide as claimed in claim 1, wherein in the step (1), the addition amount of the ferrous sulfide particles is 3-5 g/L of the wastewater to be treated containing ammoniacal nitrogen and nitrite nitrogen.
4. The method for strengthening the culture of the anaerobic ammonia oxidizing bacteria and improving the bacterial activity by using the ferrous sulfide as claimed in claim 1, wherein in the step (1), the addition amount of the ferrous sulfide particles is 3g/L of the wastewater to be treated containing ammoniacal nitrogen and nitrite nitrogen.
5. The method for enhancing the culture and activity of the anaerobic ammonium oxidation bacteria by using the ferrous sulfide as claimed in claim 1, wherein in the step (1), the addition amount of the anaerobic granular sludge is 5450-5550 mgMLSS/L.
6. The method for strengthening the culture of anaerobic ammonia oxidizing bacteria and improving the bacterial activity by using ferrous sulfide as claimed in claim 1, wherein the molar ratio of ammoniacal nitrogen to nitrous nitrogen in the wastewater to be treated containing ammoniacal nitrogen and nitrous nitrogen is 1: 1.2.
7. The method for enhancing the culture and activity of the anaerobic ammonium oxidation bacteria by using the ferrous sulfide as claimed in claim 1, wherein the particle size of ferrous sulfide particles is 1-5 mm.
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CN114853169A (en) * 2022-04-29 2022-08-05 湖南军信环保股份有限公司 Method for regulating and controlling high-iron-concentration nitrogen-containing wastewater in anaerobic ammonia oxidation process

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114853169A (en) * 2022-04-29 2022-08-05 湖南军信环保股份有限公司 Method for regulating and controlling high-iron-concentration nitrogen-containing wastewater in anaerobic ammonia oxidation process
CN114853169B (en) * 2022-04-29 2023-06-06 湖南军信环保股份有限公司 Method for regulating and controlling high-iron concentration nitrogen-containing wastewater in anaerobic ammonia oxidation process

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Application publication date: 20210226