CN111733064A - High-nitrogen-content organic matter anaerobic fermentation system and method for in-situ denitrification through membrane absorption - Google Patents
High-nitrogen-content organic matter anaerobic fermentation system and method for in-situ denitrification through membrane absorption Download PDFInfo
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Abstract
The invention provides a high-nitrogen-content organic matter anaerobic fermentation system and method for in-situ denitrification through membrane absorption, and belongs to the technical field of environmental protection and renewable energy sources. The system comprises high-nitrogen-content organic matters, an anaerobic reactor, a membrane module, absorption liquid, methane and methane liquid, wherein the membrane module is arranged inside the anaerobic reactor and is connected with the absorption liquid, closed-loop circulation is carried out through a circulating pump and a hose, anaerobic fermentation and membrane absorption denitrification are combined, the membrane module is arranged inside the anaerobic reactor, and in-situ denitrification is carried out in real time. The free ammonia is a key factor causing ammonia inhibition, the invention can directly reduce the content of the free ammonia in the fermentation liquor, effectively solve the problem of ammonia inhibition, improve the methane yield, simultaneously, the stable operation of in-situ denitrification and anaerobic fermentation can be further ensured by refluxing and diluting the feed by the biogas slurry with low ammonia nitrogen content, and the ammonia nitrogen can be recovered in the membrane absorption process and reused as the fertilizer raw material.
Description
Technical Field
The invention relates to the technical field of environmental protection and renewable energy, in particular to a high-nitrogen-content organic matter anaerobic fermentation system and method for in-situ denitrification through membrane absorption.
Background
The development of biomass energy is one of the important factors of sustainable development of human society, anaerobic fermentation is a technology for producing renewable energy by utilizing various wastes, is easy to popularize and apply and is environment-friendly, and the produced biogas can be directly used as the renewable energy and can be further extracted to prepare natural gas.
The anaerobic fermentation technology is used for treating the organic waste, so that the environmental problem can be solved, energy can be produced, high nitrogen-containing organic waste such as livestock manure, slaughter wastewater and the like has high methane production potential through anaerobic fermentation, and the methane production rate can be reduced or even the methane production process can be completely inhibited due to the ammonia inhibition problem caused by excessive nitrogen elements. Nitrogen is a necessary nutrient element for the growth and metabolism of microorganisms, and a certain amount of nitrogen can also enhance the buffer capacity of the system and improve the stability of the fermentation system. However, ammonia inhibition by excess ammonia nitrogen is also considered to be a primary problem leading to anaerobic fermentation failure. The organic matter with high nitrogen content can generate a large amount of ammonium ions and free ammonia in the anaerobic fermentation process, and the methane production process can be seriously inhibited due to the overhigh content of the ammonia nitrogen in the fermentation liquor. It is widely believed that the reason for ammonia inhibition is that free ammonia can enter the inside of the microorganism through the cell membrane, causing intracellular pH disorder, inhibiting enzymatic reaction, and thus affecting the growth and metabolism of the microorganism. Furthermore, methanogens are more sensitive to free ammonia and more easily inhibited than hydrolytic bacteria. Therefore, the ammonia nitrogen content in the anaerobic fermentation process is effectively regulated and controlled, and the method is very important for fully utilizing the high-nitrogen organic waste.
In order to solve the problem of ammonia inhibition in anaerobic fermentation, the most common method in practical engineering is to dilute materials, and the problems of excessive ammonia and inhibition can be immediately relieved without adding an additional equipment flow, but the load of anaerobic fermentation is reduced, so that the methane production rate is reduced, more biogas slurry with high water content can be generated by diluting the materials, and the difficulty is increased in the subsequent biogas slurry treatment process. The other practical and more common method is to mix and ferment the biogas slurry with materials with low nitrogen content and high carbon-nitrogen ratio, so that higher organic load can be kept, and the amount of the biogas slurry and the treatment difficulty cannot be increased. However, the research finds that the regulation change process of the accumulated ammonia nitrogen by the mixed fermentation is slow, and the effect of the carbon-nitrogen ratio regulation is uncertain in the case of the excessive nitrogen content. In addition, there are also studies to try to relieve ammonia inhibition by a method of domesticating microorganisms, and domesticate a microbial flora, particularly methanogens, under a condition of high ammonia nitrogen content, so as to improve the tolerance of the microorganisms to free ammonia, and the time is generally 2 months or more, but the domesticated microorganisms cannot fundamentally relieve ammonia inhibition.
Research shows that the problem of ammonia inhibition can be effectively solved by reducing the content of ammonia nitrogen, the stability of the system is improved, and higher methane yield is achieved. The membrane absorption technology can directly remove free ammonia causing ammonia inhibition, and has the advantages of low energy consumption, high selectivity and flexible modular application. Based on the above, the invention provides the high-nitrogen-content organic matter anaerobic fermentation system and method for in-situ denitrification through membrane absorption, wherein the membrane component is arranged in the anaerobic reactor to perform in-situ denitrification on the fermentation liquor in real time, so that free ammonia can be directly removed, the accumulation of the free ammonia in the fermentation liquor is avoided, the activity of methanogens is inhibited, the methane production rate of anaerobic fermentation is improved, and ammonium compounds recovered in the membrane absorption process can be reused as fertilizer raw materials. Compared with pre-treatment denitrification or post-treatment denitrification, the in-situ denitrification has the advantages of higher timeliness, simplified process and reduced equipment cost.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-nitrogen-content organic matter anaerobic fermentation system and method for in-situ denitrification through membrane absorption.
The system comprises high nitrogen-containing organic matters, an anaerobic reactor, a membrane module, absorption liquid, methane and methane liquid, wherein the high nitrogen-containing organic matters enter the anaerobic reactor after being uniformly mixed, the membrane module is arranged inside the anaerobic reactor, the membrane module is connected with the absorption liquid and is in closed-loop circulation with a hose through a circulating pump, a methane outlet is arranged at the upper part of the anaerobic reactor, and a methane liquid outlet is arranged at the lower part of the anaerobic reactor.
The solid content of the high-nitrogen-content organic matter is kept at 4-10%, and the retention time of anaerobic fermentation is 20-40 days.
The membrane material of the membrane component is a hydrophobic hollow fiber membrane; the absorption liquid adopts dilute acid solution.
The method applying the invention comprises the following steps:
s1: uniformly mixing high nitrogen-containing organic matters, then feeding the mixture into an anaerobic reactor, hydrolyzing macromolecular organic matters including protein to release ammonia nitrogen, and generating organic acid, hydrogen and the like;
s2: after the high-nitrogen-content organic matter is hydrolyzed, the ammonia nitrogen content of the fermentation liquor is increased, free ammonia enters the membrane module and enters the inner cavity of the hollow fiber membrane through the membrane hole, and then immediately reacts with absorption liquid to generate an ammonium compound, and the free ammonia is removed;
s3: the content of free ammonia in the fermentation liquor in the anaerobic reactor is low (usually lower than 3000mg/L), ammonia inhibition is avoided, methanogens in the fermentation liquor keep high activity, and organic acid, hydrogen and the like generated by hydrolyzing high-nitrogen-containing organic matters further generate biogas including methane, carbon dioxide and the like under the action of the methanogens;
s4: the ammonia nitrogen content in the biogas slurry generated by anaerobic fermentation is also low (usually lower than 3000mg/L), and high-nitrogen-containing organic matters are diluted through biogas slurry reflux, so that the ammonia nitrogen content of feeding is reduced, the pressure absorbed by a membrane is reduced, and the stable operation of in-situ denitrification and anaerobic fermentation is guaranteed.
The technical scheme of the invention has the following beneficial effects:
the invention designs a method and a system for combining anaerobic fermentation and membrane absorption denitrification, wherein a membrane component is arranged in an anaerobic reactor to carry out in-situ denitrification in real time. Free ammonia is a key factor causing ammonia inhibition, the invention can directly reduce the content of the free ammonia in the fermentation liquor, effectively solves the problem of ammonia inhibition and improves the methane yield. Meanwhile, stable operation of in-situ denitrification and anaerobic fermentation can be further ensured by refluxing and diluting the feed with biogas slurry with low ammonia nitrogen content, and ammonia nitrogen can be recovered in the membrane absorption process and reused as a fertilizer raw material.
Drawings
FIG. 1 is a schematic flow chart of the present invention.
Wherein: 1-high nitrogen-containing organic matter, 2-anaerobic reactor, 3-membrane module, 4-absorption liquid, 5-methane and 6-methane liquid.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
The invention provides a high-nitrogen-content organic matter anaerobic fermentation system and method for in-situ denitrification through membrane absorption.
As shown in figure 1, the system comprises high nitrogen-containing organic matters 1, an anaerobic reactor 2, a membrane module 3, absorption liquid 4, methane 5 and methane liquid 6, wherein the high nitrogen-containing organic matters 1 are uniformly mixed and then enter the anaerobic reactor 2, the membrane module 3 is arranged inside the anaerobic reactor 2, the membrane module 3 is connected with the absorption liquid 4, and closed-loop circulation is carried out through a circulating pump and a hose.
And uniformly mixing the high-nitrogen-content organic matter 1, then feeding the mixed high-nitrogen-content organic matter into an anaerobic reactor 2, keeping the solid content at 4-10%, and keeping the retention time for 20-40 days, wherein macromolecular organic matters including protein are hydrolyzed to release ammonia nitrogen, and organic acid, hydrogen and the like are generated. Then, the content of ammonia nitrogen in the fermentation liquor is increased, free ammonia enters the membrane module 3, passes through the membrane holes and enters the inner cavity of the hollow fiber membrane, and immediately reacts with the circulating absorption liquid 4 to generate ammonium compounds, the absorption liquid 4 is continuously circulated, the ammonium compounds are conveyed away, and the free ammonia is removed. When the pH of the absorbing solution 4 rises to 6 to 7 by absorbing the free ammonia, the absorbing solution 4 needs to be replaced with a new one.
The ammonia nitrogen released by hydrolysis and the ammonia nitrogen absorbed by the membrane gradually reach balance, so that the content of free ammonia in the fermentation liquor is maintained at a lower concentration, the ammonia inhibition can be avoided, methanogenic bacteria in the fermentation liquor keep higher activity, and organic acid, hydrogen and the like generated by the hydrolysis of the high-nitrogen-containing organic matter 1 further generate methane 5 including methane, carbon dioxide and the like under the action of the methanogenic bacteria. Through the process, the ammonia nitrogen content in the biogas slurry 6 generated by anaerobic fermentation is also lower, and the ammonia nitrogen content in the feed can be reduced, the pressure absorbed by the membrane can be reduced, and the stable operation of in-situ denitrification and anaerobic fermentation can be ensured by diluting the feed through biogas slurry reflux.
The following description is given with reference to specific examples.
Example 1
Slaughter wastewater of a certain slaughterhouse is high-nitrogen-content organic matter, and anaerobic fermentation is carried out by adopting the system.
The ammonia nitrogen content of the slaughter wastewater is 7.4g/L, the COD is 58.2g/kg, the slaughter wastewater is evenly mixed and then placed in an anaerobic reactor for anaerobic fermentation, and the hydraulic retention time is 40 days. In the anaerobic fermentation process, macromolecular organic matters including protein are hydrolyzed to release ammonia nitrogen, and the content of the ammonia nitrogen in the fermentation liquor is increased. When the traditional anaerobic reactor is adopted, the content of ammonia nitrogen gradually reaches more than 7.5 g/L. According to the high-nitrogen-content organic matter anaerobic fermentation system and method for in-situ denitrification through membrane absorption, 10mmol/L dilute sulfuric acid is used as absorption liquid, the circulation rate is 360mL/min, free ammonia in fermentation liquid immediately reacts with the circulating absorption liquid after entering a membrane module to generate ammonium sulfate, and the free ammonia is removed. Through continuous operation, the system reaches balance, the ammonia nitrogen content of the fermentation liquor is stabilized at about 2.8g/L, only 10% of ammonia nitrogen in the fermentation liquor in the system exists in a free ammonia form, and about more than 16% of ammonia nitrogen in the fermentation liquor exists in a free ammonia form in the traditional system. Finally, compared with the traditional method, the anaerobic fermentation system and method for the high-nitrogen organic matter through membrane absorption in-situ denitrification have the advantage that the methane production rate is improved by more than 30%.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (4)
1. The utility model provides a high nitrogenous organic matter anaerobic fermentation system of denitrogenation through membrane absorption normal position which characterized in that: the anaerobic reactor comprises high-nitrogen-content organic matters (1), an anaerobic reactor (2), a membrane module (3), absorption liquid (4), methane (5) and methane liquid (6), wherein the high-nitrogen-content organic matters (1) are uniformly mixed and then enter the anaerobic reactor (2), the membrane module (3) is arranged inside the anaerobic reactor (2), the membrane module (3) is connected with the absorption liquid (4), closed-loop circulation is carried out through a circulating pump and a hose, the upper part of the anaerobic reactor (2) is provided with a methane (5) outlet, and the lower part of the anaerobic reactor (2) is provided with a methane liquid (6) outlet.
2. The anaerobic fermentation system for organic matter with high nitrogen content by membrane absorption in-situ denitrification according to claim 1, characterized in that: the solid content of the high-nitrogen organic matter (1) is kept at 4-10%, and the retention time of anaerobic fermentation is 20-40 days.
3. The anaerobic fermentation system for organic matter with high nitrogen content by membrane absorption in-situ denitrification according to claim 1, characterized in that: the membrane material of the membrane component (3) is a hydrophobic hollow fiber membrane; the absorption liquid (4) adopts dilute acid solution.
4. The method for applying the anaerobic fermentation system for nitrogen-rich organic matter by membrane absorption in-situ denitrification according to claim 1, is characterized in that: the method comprises the following steps:
s1: uniformly mixing the high nitrogen-containing organic matters (1), then feeding the mixture into an anaerobic reactor (2), hydrolyzing macromolecular organic matters including protein to release ammonia nitrogen, and generating organic acid and hydrogen;
s2: after the high-nitrogen organic matter (1) is hydrolyzed, the ammonia nitrogen content of the fermentation liquor is increased, free ammonia enters the membrane module (3), enters the inner cavity of the hollow fiber membrane through the membrane hole, immediately reacts with the absorption liquid (4) to generate an ammonium compound, and the free ammonia is removed;
s3: the content of free ammonia in the fermentation liquor in the anaerobic reactor (2) is lower than 3000mg/L, ammonia inhibition is avoided, methanogens in the fermentation liquor keep high activity, and organic acid and hydrogen generated by hydrolysis of the high-nitrogen-content organic matter (1) further generate biogas (5) under the action of the methanogens, wherein the biogas comprises methane and carbon dioxide;
s4: ammonia nitrogen content in the biogas slurry (6) generated by anaerobic fermentation is lower than 3000mg/L, and the high nitrogen-containing organic matter (1) is diluted through backflow of the biogas slurry (6), so that ammonia nitrogen content in feeding is reduced, pressure absorbed by a membrane is relieved, and stable operation of in-situ denitrification and anaerobic fermentation is guaranteed.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112322665A (en) * | 2020-10-30 | 2021-02-05 | 江苏省农业科学院 | Anaerobic fermentation method for organic domestic garbage in villages and towns |
| CN114806858A (en) * | 2022-05-25 | 2022-07-29 | 清研环境科技股份有限公司 | Device and method for recovering volatile fatty acid in anaerobic fermentation system |
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| EP1634946A1 (en) * | 2004-09-13 | 2006-03-15 | RÜTGERS CarboTech Engineering GmbH | Environmentally safe process for generating biological natural gas |
| CN108246051A (en) * | 2018-01-26 | 2018-07-06 | 清华大学 | The device and method of ammonia nitrogen in a kind of removing anaerobic System in situ |
| CN111040936A (en) * | 2019-12-17 | 2020-04-21 | 农业农村部环境保护科研监测所 | Small-scale non-mixed inoculation continuous solid anaerobic fermentation device and fermentation method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1634946A1 (en) * | 2004-09-13 | 2006-03-15 | RÜTGERS CarboTech Engineering GmbH | Environmentally safe process for generating biological natural gas |
| CN108246051A (en) * | 2018-01-26 | 2018-07-06 | 清华大学 | The device and method of ammonia nitrogen in a kind of removing anaerobic System in situ |
| CN111040936A (en) * | 2019-12-17 | 2020-04-21 | 农业农村部环境保护科研监测所 | Small-scale non-mixed inoculation continuous solid anaerobic fermentation device and fermentation method |
Non-Patent Citations (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112322665A (en) * | 2020-10-30 | 2021-02-05 | 江苏省农业科学院 | Anaerobic fermentation method for organic domestic garbage in villages and towns |
| CN114806858A (en) * | 2022-05-25 | 2022-07-29 | 清研环境科技股份有限公司 | Device and method for recovering volatile fatty acid in anaerobic fermentation system |
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Application publication date: 20201002 |