CN114772887A - Method for increasing methane production amount of sludge anaerobic digestion by using ammonium bicarbonate - Google Patents
Method for increasing methane production amount of sludge anaerobic digestion by using ammonium bicarbonate Download PDFInfo
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Abstract
The invention relates to a method for improving the methane production amount of anaerobic digestion of sludge by using ammonium bicarbonate, belonging to the field of sludge treatment and resource utilization. Sludge of a town sewage treatment plant is put into an anaerobic digestion tank, a certain amount of ammonium bicarbonate solution is added to ensure that the initial ammonia nitrogen concentration is 7000mg/L, and anaerobic digestion is carried out for about 30-80 days at the temperature of 30-40 ℃. The result shows that the addition of ammonium bicarbonate can promote the hydrolysis of the excess sludge and improve the yield of methane after anaerobic digestion of the sludge. The method is simple and feasible, is used for recycling, harmlessness and reduction of excess sludge of urban sewage treatment plants, and has good economic and social benefits.
Description
Technical Field
The invention relates to a method for improving the methane yield of anaerobic digestion of sludge by using ammonium bicarbonate, belonging to the technical field of sludge treatment and resource utilization.
Background
In the field of urban sewage treatment, the activated sludge process is the most widely applied biological treatment technology at present, and can generate a large amount of excess sludge while reducing most pollutants in sewage. With the increasing sewage treatment capacity and sludge yield, the traditional sludge landfill can not meet the current requirements of reduction, reclamation and harmlessness of sludge treatment due to space limitation, and the anaerobic digestion is gradually paid attention as a feasible sludge reclamation energy technology. Anaerobic digestion is a degradation process that utilizes microorganisms to convert complex organics into methane and carbon dioxide under anaerobic conditions. After the municipal sludge is subjected to anaerobic digestion, the volume of the municipal sludge is greatly reduced, and simultaneously, the biogas can be generated, so that the sludge reduction is realized, and the biomass energy is recovered. At present, the anaerobic digestion process is mainly divided into four stages, namely hydrolysis, fermentation acidification, hydrogen production and acetic acid production and methane production. However, in the practical application of anaerobic digestion, due to the restriction of various factors such as temperature, pH, carbon-nitrogen ratio, nutrition and the like, the phenomenon that the microbial activity is inhibited to reduce the methane yield often occurs. For anaerobic digestion of municipal sludge, the dewatered high solids sludge has a slow rate of solubilization, and the hydrolysis process is generally considered to be the primary rate-limiting step. In order to solve the problem, various technologies for promoting sludge hydrolysis and improving methane yield are researched and developed at present, including ultrasonic pretreatment, acid-base pretreatment, thermal hydrolysis technology and the like.
In the aspect of pretreatment technology, Chinese patent publication CN109553254A discloses a pretreatment method for improving the dissolution of intracellular substances in excess sludge, which utilizes the combined pretreatment of calcium peroxide and ammonium chloride to adjust the pH value to 8.4-8.6, so that the concentration of free ammonia is 145-155mg/L, the dissolution of organic substances in the excess sludge particles can be improved, and the Soluble Chemical Oxygen Demand (SCOD) and the soluble proteins are respectively improved by nearly 3 times and 5 times. Chinese patent publication CN108821530A discloses a method for improving dissolution of organic matters in excess sludge by combined pretreatment, which utilizes ultrasonic waves and ammonium chloride for combined pretreatment, adjusts the pH value to be between 8.8 and 9.2, enables the concentration of free ammonia to be 40 to 240mg/L, and can also obviously improve SCOD and solubilityProtein and soluble polysaccharide content. Chinese patent publication CN110656133A discloses a pretreatment method for promoting anaerobic fermentation of waste activated sludge to produce medium-chain fatty acids, in the method, ammonium chloride is added and pH is adjusted to carry out free ammonia pretreatment, when the pH is controlled to be 10, the temperature is 25 ℃, and the initial free ammonia concentration is 255mg/L, the n-hexanoic acid concentration after anaerobic digestion for 29 days is 2739-839 mg COD/L, which is obviously improved compared with the blank group of 587-839mg COD/L. Chinese patent publication CN109554399A discloses a pretreatment method for improving the hydrogen production efficiency of the anaerobic fermentation of excess activated sludge, the method also carries out free ammonia pretreatment by adding ammonium chloride and adjusting pH, thereby not only promoting the dissolution of organic matters in the sludge, but also fully inhibiting the activity of hydrogen consuming microorganisms such as homoacetogenic bacteria and methanogenic bacteria, and the hydrogen production rate can reach 14.65mL H when the pH is controlled to be 9, the temperature is 37 ℃, and the initial free ammonia concentration is 300mg/L2VSS, 14.22 times that of the blank.
On one hand, the methods do not refer to the methane production condition after long-term anaerobic digestion, and have incomplete guiding significance on the anaerobic digestion of the sludge in the actual production. On the other hand, the pretreatment of free ammonia is realized by adding ammonium chloride in the various methods, but the ammonium chloride is used as an acidic substance and has a large influence on the pH, and in order to ensure that the desired free ammonia concentration is achieved, alkaline substances such as sodium hydroxide and the like are additionally added to control the pH range of the system to be alkaline (9-10), so that the system components are more complex, the stability is more difficult to control, the cost input of actual operation is increased, and the pH range is not favorable for the growth of methanogens. In addition, in an anaerobic digestion system, excessively high ammonia nitrogen concentration generally affects the activity of microorganisms, and finally shows that the methane yield is reduced, and researches show that when the ammonia nitrogen concentration is 7000mg/L at 1500-.
Therefore, there is a need to find a method for promoting hydrolysis and acidogenesis of sludge and increasing methane yield without long-term pretreatment of sludge and additional pH adjustment.
Disclosure of Invention
In order to overcome the defects of the various technologies, the invention adopts a method of directly adding ammonium bicarbonate in the anaerobic digestion process instead of pretreating sludge, and under the condition of not adjusting pH (the initial pH range is 7-8), the invention not only can promote hydrolysis and acid production of sludge, but also can improve methane yield of anaerobic digestion of sludge, and is a more economic and environment-friendly method. The method is simple and feasible, can effectively realize reclamation, harmlessness and reduction of the sludge, and has engineering application prospect.
In order to achieve the above object, the present invention provides a method for increasing the methane production amount of sludge anaerobic digestion by using ammonium bicarbonate, the method comprising:
taking sludge of a sewage treatment plant as a digestion substrate, adding the sludge into an anaerobic digestion tank, and adding an ammonium bicarbonate solution to ensure that the initial ammonia nitrogen concentration is 2000-7000 mg/L; and sealing the anaerobic digestion tank for anaerobic digestion, wherein the anaerobic digestion temperature is set to be 30-40 ℃, and the anaerobic digestion time is set to be 30-80 days.
In one embodiment of the invention, the sewage treatment plant is a town sewage treatment plant.
In one embodiment of the present invention, the sludge index of the sewage treatment plant is as follows: the sludge concentration is 3-15g/L, the initial pH is 6.8-7.0, the initial ammonia nitrogen concentration is 20-100mg/L, the heavy metal content is lower than 0.0001 mug/L, and the sludge concentration does not influence the microbial activity in the anaerobic digestion process.
In one embodiment of the invention, the pH of the system does not need to be adjusted within the system of the anaerobic digester.
In one embodiment of the invention, the concentration of the ammonium bicarbonate solution is 0.15-0.25 mg/L.
In an embodiment of the present invention, the method specifically includes: taking sludge of a town sewage treatment plant as a digestion substrate, and placing the sludge in an anaerobic digestion tank; adding an ammonium bicarbonate solution into the digestion substrate, and not adjusting the pH value of the system to ensure that the initial ammonia nitrogen concentration is 7000mg/L of 2000-; and sealing the anaerobic digestion tank for anaerobic digestion, setting the temperature at 30-40 ℃ for 30-80d, and collecting and detecting the methane yield.
The invention also provides a town sewage treatment method, which utilizes an activated sludge method to treat municipal sewage and utilizes the method to treat excess sludge.
The invention also provides application of the method in the field of environment.
The beneficial effects of the invention are:
1. according to the invention, ammonium bicarbonate is added into the sludge, so that the dissolution of organic matters in the sludge can be promoted, more usable substrates are released, and compared with the single anaerobic digestion of the sludge, the SCOD (small scale oxygen demand) is improved by 3-5 times
2. According to the invention, ammonium bicarbonate is added into the sludge, so that the methane yield of anaerobic digestion of the sludge can be increased, and compared with the single anaerobic digestion of the sludge, the methane yield is increased by 10-25%.
3. The average price of the current commercial industrial ammonium bicarbonate and ammonium chloride is 1900 yuan/ton and 3500 yuan/ton respectively, and the cost of the ammonium bicarbonate and the ammonium chloride is about 10.7 yuan and 13.3 yuan respectively when 1 kilogram of ammonia nitrogen is added into the sludge by calculation; the method directly adds ammonium bicarbonate into the sludge without adjusting the pH, has simple operation and reduced cost compared with various previous pretreatment methods which utilize ammonium chloride and adjust the pH, and has engineering application prospect.
Drawings
FIG. 1 is a schematic diagram of a process for increasing the methane production of anaerobic sludge digestion by ammonium bicarbonate.
FIG. 2 is a graph showing the SCOD changes in the anaerobic sludge digestion processes in examples 1 to 3 of the present invention.
FIG. 3 is a graph showing the cumulative yield of methane in the anaerobic sludge digestion process according to examples 1 to 3 of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific embodiments and the accompanying drawings. The advantages and features of the present invention will become more apparent in light of the following description. But the embodiments of the present invention are not limited thereto.
The ammonia nitrogen concentration determination method comprises the following steps: the method adopts a Nas reagent spectrophotometry recommended in an urban wastewater quality standard test method (CJ/T51-2018).
SCOD measurement method: a Hash rapid digestion spectrophotometry method is adopted, a sample is digested for 2 hours on a DRB200 intelligent digestion instrument, and then SCOD is measured by using a DR3900 visible spectrophotometer.
The methane determination method comprises the following steps: and measuring various gas components in the biogas by using an Agilent GC 6890 gas chromatograph by adopting a gas chromatography, and calculating according to a standard curve to obtain the yield of the methane.
The municipal sludge is taken from a sewage treatment plant in Shanghai city, the sludge concentration is 10g/L, the initial pH is 6.97, and the initial ammonia nitrogen concentration is 50 mg/L.
Example 1
Adding 200g of dewatered municipal sludge with a solid content of about 12% into an anaerobic digestion tank, adding 13mL of ammonium bicarbonate solution with the concentration of 0.25g/mL to ensure that the ammonia nitrogen concentration in the anaerobic digestion tank is 3g/L, sealing the anaerobic digestion tank, and then placing the anaerobic digestion tank into a constant-temperature oscillation incubator, wherein the set temperature is 35 ℃, the oscillation speed is 200rpm, and the time is 80 days for anaerobic digestion. Meanwhile, municipal sludge from the same source is subjected to anaerobic digestion (ammonium bicarbonate is not added) independently under the same conditions, and the anaerobic digestion is used as a blank control group.
The results show that the highest release SCOD of the sludge added with the ammonium bicarbonate in the anaerobic digestion process is 7265g/mL, which is 3.15 times of that of the blank group (see figure 2). The accumulated methane production amount of the sludge after anaerobic digestion for 80 days added with ammonium bicarbonate is 242.51mL/g VS, which is increased by 24.27 percent compared with the blank group (see figure 3).
Example 2
Adding 200g of dewatered municipal sludge with a solid content of about 12% into an anaerobic digestion tank, adding 22mL of ammonium bicarbonate solution with the concentration of 0.25g/mL to ensure that the concentration of ammonia nitrogen in the anaerobic digestion tank is 5g/L, sealing the anaerobic digestion tank, and then putting the anaerobic digestion tank into a constant-temperature oscillation incubator, setting the temperature to be 35 ℃, the oscillation speed to be 200rpm, and the time to be 80d for anaerobic digestion. Meanwhile, municipal sludge from the same source is subjected to anaerobic digestion independently under the same conditions, and the anaerobic digestion is used as a blank control group.
The results showed that the highest release of SCOD in the anaerobic digestion of the sludge dosed with ammonium bicarbonate was 8810g/mL, which is 4.03 times that of the blank (see FIG. 2). The accumulated methane production amount of the sludge after anaerobic digestion for 80 days added with ammonium bicarbonate is 231.64mL/g VS, which is 18.70 percent higher than that of the blank group (see figure 3).
Example 3
Adding 200g of dewatered municipal sludge with a solid content of about 12% into an anaerobic digestion tank, adding 31mL of ammonium bicarbonate solution with the concentration of 0.25g/mL to ensure that the concentration of ammonia nitrogen in the anaerobic digestion tank is 7g/L, sealing the anaerobic digestion tank, and then putting the anaerobic digestion tank into a constant-temperature oscillation incubator, setting the temperature to be 35 ℃, the oscillation speed to be 200rpm, and the time to be 80d for anaerobic digestion. Meanwhile, municipal sludge from the same source is subjected to anaerobic digestion independently under the same conditions, and the anaerobic digestion is used as a blank control group.
The results show that the highest SCOD released by the sludge added with the ammonium bicarbonate in the anaerobic digestion process is 10185g/mL which is 4.82 times of that of the blank group (see figure 2). The accumulated methane production amount of the sludge after anaerobic digestion for 80 days by adding ammonium bicarbonate is 215.14mL/g VS, which is 10.25 percent higher than that of a blank group (see figure 3).
Comparative example 1
Adding 200g of dewatered municipal sludge with a solid content of 12% into an anaerobic digestion tank, adding 4mL of ammonium bicarbonate solution with the concentration of 0.25g/mL to enable the concentration of ammonia nitrogen in the anaerobic digestion tank to be 1g/L, sealing the anaerobic digestion tank, and then placing the anaerobic digestion tank into a constant-temperature oscillation incubator, setting the temperature to be 35 ℃, the oscillation speed to be 200rpm, and carrying out anaerobic digestion for 80 days. Meanwhile, municipal sludge from the same source is subjected to anaerobic digestion separately under the same conditions, and the anaerobic digestion is used as a blank control group.
The result shows that the highest SCOD released by the sludge added with the ammonium bicarbonate in the anaerobic digestion process is 2815g/mL, which is only improved by 60 percent compared with the blank group. The accumulated methane production amount after 80 days of anaerobic digestion of the sludge added with ammonium bicarbonate is 199.55mL/g VS, which is only 2.05 percent higher than that of the blank group. Compared with the examples 1-3, when the concentration of the additionally added ammonia nitrogen is lower than 2g/L, the promotion effect of the ammonium bicarbonate on the anaerobic digestion of the sludge to generate methane is not obvious.
Meanwhile, high ammonia nitrogen conditions in anaerobic digestion of sludge generally inhibit methane production, but relevant experimental results of the invention show that the methane production is increased under specific high ammonia nitrogen concentration, because the addition of ammonium bicarbonate promotes hydrolytic acidification of the sludge, releases more available substrates, influences the composition and metabolic mechanism of microbial communities and realizes the increase of methane yield.
Comparative example 2
Adding 200mL of municipal sludge with a solid content of about 2% into an anaerobic digestion tank, adding 7mL of ammonium chloride solution with the concentration of 0.3g/mL to ensure that the concentration of ammonia nitrogen in the anaerobic digestion tank is 3g/L, sealing the anaerobic digestion tank, and then placing the anaerobic digestion tank into a constant-temperature oscillation incubator, setting the temperature to be 35 ℃, the oscillation speed to be 200rpm, and carrying out anaerobic digestion for 30 days. Meanwhile, municipal sludge from the same source is subjected to anaerobic digestion independently under the same conditions, and the anaerobic digestion is used as a blank control group.
The result shows that the pH range of the sludge after the ammonium chloride is added is 6.6-6.8, and the pH range of the blank group is 6.8-7.0; the cumulative methane yield after adding the ammonium chloride is 70.03mL/g VS, the cumulative methane yield of the blank group is 68.84mL/g VS, and anaerobic digestion can not be continued after 30 days, which indicates that the acidification of anaerobic digestion conditions is easily caused by adding the ammonium chloride alone, and the effect of promoting anaerobic digestion of sludge to produce methane is not great.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for improving the methane production amount of sludge anaerobic digestion by using ammonium bicarbonate is characterized by comprising the following steps:
taking sludge of a sewage treatment plant as a digestion substrate, adding the sludge into an anaerobic digestion tank, and adding an ammonium bicarbonate solution to ensure that the initial ammonia nitrogen concentration is 2000-7000 mg/L; and sealing the anaerobic digestion tank for anaerobic digestion, wherein the anaerobic digestion temperature is set to be 30-40 ℃, and the anaerobic digestion time is set to be 30-80 d.
2. The method for improving the methane production amount of the sludge in the anaerobic digestion process by using the ammonium bicarbonate according to the claim 1, characterized in that the pH of the system does not need to be adjusted in the system of the anaerobic digestion tank.
3. The method for improving the methane production of the anaerobic digestion of the sludge by using the ammonium bicarbonate as the claimed in claim 1, wherein the concentration of the ammonium bicarbonate solution is 0.15-0.25 mg/L.
4. The method for improving the methane production amount of the anaerobic digestion of the sludge by using the ammonium bicarbonate according to any one of claims 1 to 3, wherein the sewage treatment plant is a town sewage treatment plant.
5. The method for improving the methane production amount of the anaerobic digestion of the sludge by using the ammonium bicarbonate according to claim 4, wherein the concentration of the sludge is 3-15g/L, the initial pH is 6.8-7.0, and the initial ammonia nitrogen concentration is 20-100 mg/L.
6. The method for improving the methane production amount of the anaerobic digestion of the sludge by using the ammonium bicarbonate according to any one of claims 1 to 5, characterized in that an ammonium bicarbonate solution is added to make the initial ammonia nitrogen concentration of 3000-5000 mg/L.
7. The method for improving the methane production amount of the anaerobic digestion of the sludge by using the ammonium bicarbonate according to claim 6, characterized in that an ammonium bicarbonate solution is added to make the initial ammonia nitrogen concentration be 3000 mg/L.
8. The method for improving the methane production amount of the anaerobic digestion of the sludge by using the ammonium bicarbonate according to any one of claims 1 to 7, which is characterized by comprising the following steps: taking sludge of a town sewage treatment plant as a digestion substrate, and placing the sludge in an anaerobic digestion tank; adding ammonium bicarbonate solution into the digestion substrate, and not adjusting the pH of the system to ensure that the initial ammonia nitrogen concentration is 2000-7000 mg/L; and sealing the anaerobic digestion tank for anaerobic digestion, setting the temperature at 30-40 ℃ for 30-80 days, and collecting and detecting the methane yield.
9. A method for treating urban sewage is characterized in that the method utilizes an activated sludge method to treat urban sewage, and utilizes the method for improving the methane production amount of anaerobic sludge digestion by utilizing ammonium bicarbonate to treat excess sludge according to any one of claims 1 to 8.
10. The method for improving the methane production amount of the anaerobic digestion of the sludge by using the ammonium bicarbonate according to any one of claims 1 to 8 or the method for treating the town sewage according to claim 9 is applied to the environmental field.
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