CN111117866A - Denitrification equipment for enriching nitrous oxide and recovering energy - Google Patents
Denitrification equipment for enriching nitrous oxide and recovering energy Download PDFInfo
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- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M21/00—Bioreactors or fermenters specially adapted for specific uses
- C12M21/04—Bioreactors or fermenters specially adapted for specific uses for producing gas, e.g. biogas
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a denitrification device for enriching nitrous oxide and recovering energy, which comprises: the device comprises a gas washing device (4), wherein a gas inlet (1) and a gas outlet (2) are arranged at the top of the gas washing device, a solution injection port (3) is arranged on the side part of the gas washing device, an anaerobic reactor (7) is connected with the gas washing device (4) through a connecting pipeline, a liquid adding port (6) is arranged at the top of the gas washing device, a gas collecting port (9) and a liquid discharging port (10) are arranged on the side part of the gas washing device, and the anaerobic reactor (7) is arranged. Compared with the prior art, the test device has the advantages of simple and convenient operation, stable operation, capability of realizing semi-automatic control, high generation rate of nitrous oxide in the denitrification process, long retention time and highest volume concentration of more than 0.45, and the obtained nitrous oxide gas can be used as an oxidant, a combustion improver and the like.
Description
Technical Field
The invention belongs to the technical field of denitrification treatment in environmental engineering, and particularly relates to denitrification equipment for enriching nitrous oxide and recovering energy.
Background
Nitrous oxide is one of the important intermediates in the denitrification process. Nitrous oxide, a typical greenhouse gas, is often considered a harmful byproduct in the water treatment field to minimize production. However, nitrous oxide is also a potential renewable energy source. Studies have shown that nitrous oxide is a specific oxygen2More powerful oxidants, can increase the energy recovery of CH4 combustion: 1mol of CH4The energy released in the stoichiometric complete combustion reaction with nitrous oxide is 1219kJ, while 1molCH4And O2The complete combustion reaction released 890kJ, which was about 30% more than the latter. On the other hand, nitrous oxide is also an extremely promising combustion improver and propellant. Compared with other oxidants, nitrous oxide is more stable at room temperature and is easy to store. And the products after the decomposition of the nitrous oxide are nontoxic nitrogen and oxygen, have high safety, are often used for pressurizing the engine of a high-performance vehicle, and are often used as a strong oxidant of a hybrid rocket in the aerospace industry.
At present, researches on the accumulation of nitrous oxide in the denitrification process of complex NO exist, but the existing research results have the following problems: (1) to maintain a high level of conversion, the substrate NO concentration is limited, so that the overall denitrification efficiency of the system is limited; (2) the low level NO enables the concentration of nitrous oxide in subsequent gas production to be too low, and the enrichment and recovery cost is increased; (3) nitrous oxide as intermediate product of denitrification can be further reduced into N in short time2Therefore, the residence time in the system is short, which causes difficulty for subsequent recovery; (4) and an experimental device capable of realizing automation is lacked. These problems limit the enrichment and energy recovery of nitrous oxide in the denitrification system.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provide denitrification equipment for enriching nitrous oxide and recovering energy, solve the technical problem that nitrous oxide in a denitrification system is difficult to enrich and recover energy in the prior art, realize semi-automatic control, and achieve high generation rate and long retention time of nitrous oxide in the denitrification process, wherein the maximum volume concentration can reach more than 0.45. The obtained nitrous oxide gas can be used for an oxidant, a combustion improver and the like.
The purpose of the invention can be realized by the following technical scheme:
a denitrification facility for enriching nitrous oxide and recovering energy, comprising:
the top of the gas washing device is provided with a gas inlet and a gas outlet, the side part is provided with a solution filling opening,
the anaerobic reactor is connected with the gas washing device through a connecting pipeline, the top of the anaerobic reactor is provided with a liquid feeding port, the side part of the anaerobic reactor is provided with a gas collecting port and a liquid discharging port,
the denitrifying microorganism in the anaerobic reactor utilizes Fe (II) EDTA-NO prepared by a gas washing device as a nitrogen source, sodium acetate as a carbon source and nutrients required by the microorganism, the pH value is adjusted to 7.2 +/-0.2, headspace gas is removed by utilizing argon gas, then the mixture is placed on a magnetic stirrer, and the reaction is carried out in a sealed constant temperature manner.
The gas washing device is an organic glass container with excellent sealing performance.
The solution injection port is added with Fe (II) EDTA solution which is used for absorbing nitric oxide components in the mixed gas and complexing into Fe (II) EDTA-NO solution.
The concentration of Fe (II) EDTA solution added is between 10mM and 40mM, this concentration being quantified using the original Fe (II) EDTA solution concentration. When the concentrations of NO in the gas inlet flow and the gas outlet flow of the gas washing device are equal, the concentration of Fe (II) EDTA-NO in the solution is considered to be the same as that of the original Fe (II) EDTA solution.
The gas inlet is filled with N2Mixed with NO.
And the gas outlet is also provided with a gas concentration detection device for detecting the concentration of NO contained in the outlet airflow.
The volume of the gas washing device is 3-4 times of the volume of the solution required by a single period of the anaerobic reactor.
A peristaltic pump is arranged on a connecting pipeline between the gas washing device and the anaerobic reactor.
The denitrification microorganism MLVSS in the anaerobic reactor is 4.0-6.0 g/L.
Compared with the prior art, the technical scheme disclosed by the invention has the following advantages:
1. the system has simple process, semi-automatic control and no secondary pollution.
2. The treatment technology has high denitrification load, the highest concentration of Fe (II) EDTA-NO solution can reach 40mM, the conversion rate is maintained between 83 and 87 percent, and the total denitrification efficiency of the system is improved.
3. The generation rate of nitrous oxide in the system is high, the highest point volume concentration can reach about 0.45, the mass concentration of substances is about 20.43mM, the energy of the system can be recovered to a great extent, and the cost of subsequent nitrous oxide gas purification is obviously reduced.
4. The residence time of the nitrous oxide generated by the system is long. When the concentration of Fe (II) EDTA-NO is 40mM, the nitrous oxide can be maintained at a high concentration of more than 10mM (volume concentration of 0.224) for more than 45h, and the enrichment and recovery of nitrous oxide are greatly facilitated.
Drawings
FIG. 1 is a schematic view showing the structure of a denitrification apparatus for enriching nitrous oxide and recovering energy.
In the figure, 1-a gas inlet, 2-a gas outlet, 3-a solution inlet, 4-a gas washing device, 5-a peristaltic pump, 6-a liquid adding port, 7-an anaerobic reactor, 8-a magnetic stirrer, 9-a gas collecting port and 10-a liquid discharging port.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
A denitrification device for enriching nitrous oxide and recovering energy is structurally shown in figure 1 and comprises a gas washing device 4, an anaerobic reactor 7, a magnetic stirrer 8 and the like. The top of the gas washing device 4 is provided with a gas inlet 1 and a gas outlet 2, the lateral part is provided with a solution injection port 3, the anaerobic reactor 7 is connected with the gas washing device 4 through a connecting pipeline, the top is provided with a liquid feeding port 6, the lateral part is provided with a gas collecting port 9 and a liquid discharging port 10, and the connecting pipeline is provided with a peristaltic pump 5 for facilitating sample injection.
The gas washer 4 used may be a plexiglass container having excellent sealing properties. The gas inlet 1 is filled with N2And a gas concentration detection device is arranged at a gas outlet 2 of the NO mixed gas, and Fe (II) EDTA solution is added into a solution injection port 3 and is used for absorbing nitric oxide components in the mixed gas and complexing into Fe (II) EDTA-NO solution. The concentration of Fe (II) EDTA solution added is between 10mM and 40mM, this concentration being quantified using the original Fe (II) EDTA solution concentration. When the concentrations of NO in the inlet gas flow and the outlet gas flow of the gas washing device 4 are equal, the concentration of Fe (II) EDTA-NO in the solution is considered to be the same as the concentration of the original Fe (II) EDTA solution. The volume of the gas washing device 4 is 3-4 times of the solution volume required by a single period of the anaerobic reactor 7.
Denitrifying microorganisms (such as Thauera, Dokdonella, Pseudomonas, Desulfuromonas, Rhizobium, etc., with MLVSS of 4.0-6.0g/L) in the anaerobic reactor 7 are treated with Fe (II) EDTA-NO produced by the gas scrubber 4 as nitrogen source, sodium acetate as carbon source, and other nutrients required by microorganisms, including NaHCO3、KH2PO4、K2HPO4、EDTA、CaCl2·2H2O、MgSO4·7H2O and other trace elements required by the growth of the microorganism, adjusting the pH to 7.2 +/-0.2, removing headspace gas by using argon, placing on a magnetic stirrer 8, and sealing for constant-temperature reaction.
When in use, Fe (II) EDTA solution is added into the gas washing device 4 from the solution injection port 3 to absorb NO in the mixed gas introduced from the gas inlet 1 until the NO content in the gas components of the gas inlet 1 and the gas outlet 2 is consistent, and the gas washing process is stopped. The solution in the gas washing device 4 is pumped into an anaerobic reactor 7 through a peristaltic pump 5, and simultaneously carbon source and other nutrient substances required by microorganisms are added through a liquid adding port 6, and the magnetic stirrer 8 ensures that all parts in the reactor are uniformly mixed. The gas composition is monitored periodically by the gas collection port 9 and headspace gas is collected. After a certain time, stirring is finished, and after settling, the supernatant is discharged from a liquid outlet 10. Then Fe (II) EDTA-NO is pumped in again from the scrubber 4 and the main reactor process is repeated.
The following are more detailed embodiments, and the technical solutions and the technical effects obtained by the present invention will be further described by the following embodiments.
Example 1
Adjusting the original concentration of Fe (II) EDTA in the gas washing device to 10mM, controlling the COD/N value in the reactor to be more than 5, and adjusting the pH value to 7.2 +/-0.2. And continuously purging for 5min by using argon before the reactor runs to keep that no nitrogen and oxygen are left in the reactor, and then sealing for reaction. During the period, the headspace gas composition of the reactor was continuously measured through the gas collection port and collected, while the concentration of Fe (II) EDTA-NO in the liquid phase was measured through the liquid discharge port. After the reaction is finished, the degradation rate of Fe (II) EDTA-NO is 85%, the highest generation concentration of nitrous oxide is 3.26mM, and the duration time of the concentration of the intermediate nitrous oxide which is more than 0.5 times of the highest concentration is 1.0 h.
Example 2
The original concentration of Fe (II) EDTA in the gas washing device is adjusted to be 20mM, the COD/N value in the reactor is controlled to be more than 5, and the pH value is adjusted to be 7.2 +/-0.2. And continuously purging for 5min by using argon before the reactor runs to keep that no nitrogen and oxygen are left in the reactor, and then sealing for reaction. During the period, the headspace gas composition of the reactor was continuously measured through the gas collection port and collected, while the concentration of Fe (II) EDTA-NO in the liquid phase was measured through the liquid discharge port. After the reaction is finished, the degradation rate of Fe (II) EDTA-NO is 87%, the highest generation concentration of nitrous oxide is 9.34mM, and the duration time of the concentration of the intermediate nitrous oxide which is more than 0.5 times of the highest concentration is 2.7 h.
Example 3
The original concentration of Fe (II) EDTA in the gas washing device is adjusted to be 30mM, the COD/N value in the reactor is controlled to be more than 5, and the pH value is adjusted to be 7.2 +/-0.2. And continuously purging for 5min by using argon before the reactor runs to keep that no nitrogen and oxygen are left in the reactor, and then sealing for reaction. During the period, the headspace gas composition of the reactor was continuously measured through the gas collection port and collected, while the concentration of Fe (II) EDTA-NO in the liquid phase was measured through the liquid discharge port. After the reaction is finished, the degradation rate of Fe (II) EDTA-NO is 85%, the highest generation concentration of nitrous oxide is 18.06mM, and the duration time of the concentration of the intermediate nitrous oxide which is more than 0.5 times of the highest concentration is 17.8 h.
Example 4
The original concentration of Fe (II) EDTA in the gas washing device is adjusted to 40mM, the COD/N value in the reactor is controlled to be more than 5, and the pH value is adjusted to 7.2 +/-0.2. And continuously purging for 5min by using argon before the reactor runs to keep that no nitrogen and oxygen are left in the reactor, and then sealing for reaction. During the period, the headspace gas composition of the reactor was continuously measured through the gas collection port and collected, while the concentration of Fe (II) EDTA-NO in the liquid phase was measured through the liquid discharge port. After the reaction is finished, the degradation rate of Fe (II) EDTA-NO is 83%, the highest generation concentration of nitrous oxide is 20.43mM, and the duration time of the concentration of the intermediate nitrous oxide which is more than 0.5 times of the highest concentration is 45.4 h.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. A denitrification plant for enriching nitrous oxide and recovering energy, characterized in that it comprises:
a gas washing device (4), the top of which is provided with a gas inlet (1) and a gas outlet (2), the side of which is provided with a solution filling opening (3),
an anaerobic reactor (7) connected with the gas washing device (4) through a connecting pipeline, the top of the anaerobic reactor is provided with a liquid feeding port (6), the side part of the anaerobic reactor is provided with a gas collecting port (9) and a liquid discharging port (10),
the anaerobic reactor (7) is arranged on the magnetic stirrer (8).
2. The denitrification facility for enriching nitrous oxide and recovering energy according to claim 1, wherein the scrubber (4) is a plexiglas container with excellent sealing property.
3. The apparatus for nitrous oxide enrichment and energy recovery according to claim 1, characterized in that the solution injection port (3) is filled with Fe (II) EDTA solution.
4. The denitrification apparatus for enriching nitrous oxide and recovering energy according to claim 3, wherein the concentration of the Fe (II) EDTA solution is 10mM-40 mM.
5. The denitrification facility for enriching nitrous oxide and recovering energy according to claim 1, wherein said gas inlet (1) is fed with N2Mixed with NO.
6. The denitrification facility for enriching nitrous oxide and recovering energy according to claim 1, wherein a gas concentration detection device is further provided at the gas outlet (2).
7. The denitrification apparatus for enriching nitrous oxide and recovering energy according to claim 1, wherein the volume of the scrubbing means (4) is 3-4 times the volume of the solution required for a single cycle of the anaerobic reactor (7).
8. The denitrification facility for enriching nitrous oxide and recovering energy according to claim 1, characterized in that a peristaltic pump (5) is provided on the connecting pipe between the scrubbing device (4) and the anaerobic reactor (7).
9. The denitrification facility for enriching nitrous oxide and recovering energy according to claim 1, wherein the denitrifying microorganism MLVSS in the anaerobic reactor (7) is 4.0-6.0 g/L.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115487666A (en) * | 2022-08-26 | 2022-12-20 | 福州大学 | High-efficiency conversion of NO in flue gas into N 2 Method of O |
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| CN109351177A (en) * | 2018-12-05 | 2019-02-19 | 大连理工大学 | It is a kind of using nitrous oxide as the microorganism method of denitration of primary product |
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| CN101810983A (en) * | 2010-03-12 | 2010-08-25 | 浙江大学 | Method for regenerating nitrogen oxide complexed absorption liquid in smoke denitration |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115487666A (en) * | 2022-08-26 | 2022-12-20 | 福州大学 | High-efficiency conversion of NO in flue gas into N 2 Method of O |
| CN115487666B (en) * | 2022-08-26 | 2023-09-12 | 福州大学 | Efficient conversion of NO in flue gas to N 2 O method |
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