CN114410706A - Denitrification liquid carbon source and preparation method and application thereof - Google Patents
Denitrification liquid carbon source and preparation method and application thereof Download PDFInfo
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- CN114410706A CN114410706A CN202210017689.3A CN202210017689A CN114410706A CN 114410706 A CN114410706 A CN 114410706A CN 202210017689 A CN202210017689 A CN 202210017689A CN 114410706 A CN114410706 A CN 114410706A
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/02—Monosaccharides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
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- C12P39/00—Processes involving microorganisms of different genera in the same process, simultaneously
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/06—Nutrients for stimulating the growth of microorganisms
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
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Abstract
The invention relates to the technical field of water treatment, and particularly discloses a denitrification liquid carbon source and a preparation method and application thereof. The invention provides a preparation method of a denitrification liquid carbon source, which takes agricultural waste corncobs as main raw materials, can quickly reduce the crystallinity and polymerization degree of cellulose after the corncobs are subjected to alkali liquor soaking and coupling specific microwave heating pretreatment, weaken hydrogen bond acting force between the cellulose and hemicellulose, increase the alkaline hydrolysis effect, facilitate subsequent cellulose degradation bacteria to degrade the cellulose, improve the glucose yield and the quality of the carbon source, and can overcome the problem of accumulation of nitrite caused by different carbon release rates generated in the application process of the traditional solid carbon source.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a denitrification liquid carbon source and a preparation method and application thereof.
Background
The domestic sewage treatment in rural areas plays an important role in the construction of new rural areas, and the conventional treatment process is generally a sewage treatment process of a septic tank, such as a Sequencing Batch Reactor (SBR), a continuous flow nitrification and denitrification reactor (A/O) or a contact oxidation reactor. The discharge requirement of the ecological sensitive rural areas on the domestic sewage is more and more strict, and the requirement is required to reach the first grade A standard of the urban sewage treatment plant. Moreover, most of the existing rural areas are provided with septic tanks, organic matters are consumed in the septic tanks, and a large amount of low-concentration raw water such as vegetable washing water and bath water is mixed, so that the carbon source of the treatment device is insufficient. Meanwhile, the concentration of nitrogen-containing pollutants in the wastewater is getting higher and higher due to the change of the dietary structure consumed by people in recent years. Therefore, rural domestic sewage tends to have the characteristics of high nitrogen and low carbon. Insufficient carbon source supply or unstable supply becomes an important factor for restricting the biological denitrification efficiency, and sufficient carbon source can provide sufficient nutrient source for the growth and metabolism of the microorganisms. Therefore, the solution of the problem of low denitrification efficiency by adding carbon source is becoming a hot point of research in the field of water treatment.
Carbon sources of conventional municipal sewage plants or industrial sewage plants are generally methanol, acetic acid or sodium acetate and the like, have the defects of flammability, high cost, requirement of independent storage conditions and the like, and are not suitable for distributed small sewage devices in rural areas. Agricultural wastes in rural areas, especially wheat straws and corncobs harvested in summer and autumn in northern areas need additional treatment, and treatment cost is increased. Therefore, the raw material for preparing the denitrification carbon source can not only avoid additional treatment on the raw material, but also change waste into valuable, and has wide application prospect. At present, most researches are carried out on the corncobs as the solid carbon source, the solid carbon source generally needs to be pretreated by acid leaching, alkali leaching and the like when being applied, macromolecular chains such as cellulose and the like are not degraded thoroughly, and meanwhile, in the initial application stage, the carbon releasing speed is high, the releasable carbon source in the later stage is less and less, and the denitrification process is blocked due to insufficient carbon source supply, so that the accumulation of nitrite is caused.
Disclosure of Invention
In view of the above technical problems, the present invention provides a denitrification liquid carbon source, a preparation method and applications thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of a denitrification liquid carbon source comprises the following steps:
step a, drying and crushing corncobs, and sieving to obtain corncob particles;
b, adding the corncob particles into alkali liquor to be soaked for 2-6 h, then adopting segmented microwave heating to carry out pretreatment, and cooling to obtain corncob pretreatment liquid;
the specific procedure of the segmented microwave heating is as follows: heating to 55-65 ℃ at the speed of 9-11 ℃/min, heating to 75-85 ℃ at the speed of 4-6 ℃/min, and finally heating to 88-92 ℃ at the speed of 2-3 ℃/min;
and c, adjusting the pH value of the corncob pretreatment solution to 6-9, adding cellulose degrading bacteria, stirring and degrading for 20-40 h, and performing solid-liquid separation to obtain the denitrification liquid carbon source.
Compared with the prior art, the preparation method of the denitrification liquid carbon source provided by the invention has the advantages that the agricultural waste corncob is used as the main raw material, after the corncob is subjected to alkali liquor soaking and coupling specific microwave heating pretreatment, the crystallinity and the polymerization degree of cellulose can be quickly reduced, the hydrogen bond acting force between the cellulose and hemicellulose is weakened, the alkaline hydrolysis effect is increased, and the subsequent cellulose degradation bacteria can be used for degrading the cellulose, so that the effective degradation of macromolecular substances such as cellulose chains in the corncob is realized, the glucose yield and the carbon source quality are improved, the prepared denitrification liquid carbon source can overcome the problem that the nitrite is accumulated due to different carbon release rates generated in the application process of the traditional solid carbon source, the requirement of a denitrification device on an external carbon source can be met, in addition, the resource utilization of the agricultural waste corncob is realized, meanwhile, the denitrification cost of the sewage is greatly reduced, and the method has higher popularization and application values.
Preferably, in the step a, the fineness of the corn cob particles is less than or equal to 40 meshes.
The preferable fineness of the corncob particles is beneficial to increasing the hydrolysis degree of the corncobs in the alkali liquor, thereby being beneficial to improving the saccharification efficiency and the yield of the glucose.
Preferably, in step b, the alkali solution is at least one of a calcium hydroxide solution, a sodium hydroxide solution or a potassium hydroxide solution.
Preferably, in the step b, the mass concentration of the alkali liquor is 1-10%.
Further preferably, the mass ratio of the corncob particles to the alkali liquor is 1: 3-8.
Preferably, when the temperature is increased to 55-65 ℃ at the speed of 9-11 ℃/min, the microwave power is 600W; heating to 75-85 ℃ at the speed of 4-6 ℃/min, wherein the microwave power is 300W; when the temperature is increased to 88-92 ℃ at the speed of 2-3 ℃/min, the microwave power is 150W.
The optimized addition amount of the alkali liquor is matched with the microwave heating pretreatment of a specific program, so that lignin in the corncobs can be fully dissolved in the alkali liquor, reticular macromolecules are changed into branched chain micromolecules, meanwhile, hydrogen bonds between cellulose and hemicellulose are weakened, the polymerization degree and the crystallinity of the cellulose are damaged, the cellulose is swelled, the contact area and the accessibility of cellulose degrading bacteria to the cellulose are increased, the conversion of polysaccharide to monosaccharide is improved, the proportion of saccharide products is improved, and the proportion of substances directly utilized by microbial capacity is improved; in addition, ester bonds between lignin and hemicellulose can be sufficiently broken, so that the lignin is dissolved out in a hydrophilic sodium salt form or is aggregated and precipitated in an alkoxide form, thereby improving saccharification efficiency and glucose yield.
Preferably, in step c, the cellulose-degrading bacteria is at least one of bacteroides succinogenes, ruminococcus bovis, ruminococcus albus, vibrio fibrisolvens, clostridium sp.
Preferably, in the step c, the mass ratio of the cellulose degrading bacteria to the corncob particles is 1: 8-12.
Preferably, in the step c, the rotation speed of stirring degradation is 20 r/min-30 r/min.
Illustratively, in step c, a paddle agitator is used.
In the step c, the pH is adjusted to 6-9 by using a sulfuric acid solution.
For example, in step c, the solid-liquid separation may be performed by precipitation or filtration, which is conventional in the art.
The preferable cellulose degrading bacteria and degrading conditions are favorable for effectively degrading cellulose in the corncobs, improving the yield of glucose, obtaining a high-efficiency carbon source and providing sufficient nutrient components for denitrifying bacteria.
The invention also provides a denitrification liquid carbon source which is prepared by any one of the preparation methods of the denitrification liquid carbon source.
The invention also provides application of the denitrification liquid carbon source in treatment of domestic sewage and industrial wastewater.
The denitrification carbon source prepared by the invention can overcome the problem of accumulation of nitrite nitrogen caused by different carbon release rates generated in the application process of the traditional solid carbon source, can improve the application range of the denitrification carbon source, can supplement the denitrification carbon source as the carbon source of a denitrification device, can provide sufficient and stable carbon source for denitrifying bacteria, obviously improves the denitrification efficiency, has lower production cost, realizes resource utilization of agricultural wastes, can be widely applied to various sewage treatment processes such as A/O, SBR, contact oxidation and the like, is particularly suitable for sewage treatment in rural areas in the north, is also suitable for the treatment of industrial wastewater, and has higher practical application value.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In order to better illustrate the invention, the following examples are given by way of further illustration.
Example 1
A preparation method of a denitrification liquid carbon source comprises the following steps:
step a, drying corncobs at 105 ℃, crushing, and sieving with a 40-mesh sieve to obtain corncob particles;
b, weighing 1Kg of the corncob particles, adding the corncob particles into a microwave heating tank, then adding 3L of 10% calcium hydroxide solution by mass concentration, soaking for 4 hours, starting sectional microwave heating for pretreatment, and cooling to room temperature to obtain corncob pretreatment solution;
the specific procedure of the segmented microwave heating is as follows: the power is 600W, the temperature is increased to 60 ℃ at the speed of 10 ℃/min, the power is 300W, the temperature is increased to 80 ℃ at the speed of 5 ℃/min, and finally the power is 150W, and the temperature is increased to 90 ℃ at the speed of 2.5 ℃/min;
and c, adding a sulfuric acid solution into the corncob pretreatment solution, adjusting the pH value to 6, then adding 0.1Kg of staphylococcus squirrel, stirring and cooling for 30 hours at room temperature, wherein the stirring speed is 25r/min, standing and precipitating, separating supernatant, and detecting the COD of the supernatant to be 12300mg/L to obtain the denitrification liquid carbon source.
Example 2
A preparation method of a denitrification liquid carbon source comprises the following steps:
step a, drying corncobs at 105 ℃, crushing, and sieving with a 40-mesh sieve to obtain corncob particles;
b, weighing 1Kg of the corncob particles, adding the corncob particles into a microwave heating tank, then adding 6L of 6% potassium hydroxide solution by mass concentration, soaking for 6 hours, starting sectional microwave heating for pretreatment, and cooling to room temperature to obtain corncob pretreatment solution;
the specific procedure of the segmented microwave heating is as follows: the power is 600W, the temperature is increased to 65 ℃ at the speed of 11 ℃/min, the power is set to 300W, the temperature is increased to 75 ℃ at the speed of 4 ℃/min, finally the power is set to 150W, and the temperature is increased to 88 ℃ at the speed of 2 ℃/min;
and c, adding a sulfuric acid solution into the corncob pretreatment solution, adjusting the pH value to 7, then adding 0.08Kg of staphylococcus squirrel, stirring and degrading for 40 hours at room temperature, wherein the stirring speed is 20r/min, standing and precipitating, separating supernatant, and detecting that the COD of the supernatant is 9400mg/L to obtain the denitrification liquid carbon source.
Example 3
A preparation method of a denitrification liquid carbon source comprises the following steps:
step a, drying corncobs at 105 ℃, crushing, and sieving with a 40-mesh sieve to obtain corncob particles;
b, weighing 1Kg of the corncob particles, adding the corncob particles into a microwave heating tank, then adding 8L of 1% sodium hydroxide solution by mass concentration, soaking for 2 hours, starting sectional microwave heating for pretreatment, and cooling to room temperature to obtain a corncob pretreatment solution;
the specific procedure of the segmented microwave heating is as follows: the power is 600W, the temperature is increased to 55 ℃ at the speed of 9 ℃/min, then the power is 300W, the temperature is increased to 85 ℃ at the speed of 6 ℃/min, finally the power is 150W, and the temperature is increased to 92 ℃ at the speed of 3 ℃/min;
and c, adding a sulfuric acid solution into the corncob pretreatment solution, adjusting the pH value to 9, then adding 0.12Kg of staphylococcus squirrel, stirring and degrading for 20 hours at room temperature, stirring at the rotating speed of 30r/min, standing and precipitating, separating supernatant, and detecting the COD of the supernatant to be 6200mg/L to obtain the denitrification liquid carbon source.
And measuring the total sugar concentration in the denitrification liquid carbon source by using a DNS method, and measuring the glucose and xylose concentrations in the denitrification liquid carbon source by using a high performance liquid chromatography. The total reducing sugar yield in examples 1-3 was 85% -89%.
The denitrifying liquid carbon source and vinegar prepared in example 1 of the present invention were tested using two identical A/O reactorsThe effect of sodium as carbon source, the total nitrogen conditions of inlet and outlet water of the two reactors are controlled to be completely consistent in the test process, namely the inlet water TN of the reactor is 35mg/L, the outlet water TN is 15mg/L, and the daily throughput is 5m3The results are shown in Table 1.
TABLE 1
As can be seen from the table above, the adoption of two carbon sources can ensure that the total nitrogen of the effluent successfully reaches the standard, but from the aspect of application cost, the cost of the denitrification liquid carbon source prepared by the invention is lower, and the cost advantage is more obvious when the denitrification liquid carbon source is actually applied to large-scale production.
Comparative example 1
The comparative example provides a preparation method of a denitrification liquid carbon source, which has the same steps as the example 1, and is different from the step of adjusting the heating rate of heating to 60 ℃ to be 5 ℃/min, and the other parameters are the same.
The total reducing sugar yield was measured to be 65% according to the same method as described above.
Comparative example 2
The comparative example provides a preparation method of a denitrification liquid carbon source, which has the same steps as the example 1, and is different from the step of adjusting the heating rate of heating to 80 ℃ to 10 ℃/min, and the other parameters are the same.
The total reducing sugar yield was tested to be 75% according to the same method as described above.
Comparative example 3
The comparative example provides a preparation method of a denitrification liquid carbon source, which has the same steps as the example 1, and is different from the step of adjusting the heating rate of heating to 90 ℃ to be 5 ℃/min, and the other parameters are completely the same.
The total reducing sugar yield was tested according to the same method as above to be 72%.
As is clear from the comparison of comparative examples 1 to 3 and example 1, the total reducing sugar yield was decreased by changing the heating rate of the microwave heating. The method obviously improves the yield of the total reducing sugar by controlling a specific microwave heating program, and is beneficial to improving the denitrification rate.
The other cellulose-degrading bacteria defined in the present invention in examples 1 to 3 can also achieve substantially equivalent technical effects to those of the corresponding examples.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a denitrification liquid carbon source is characterized by comprising the following steps:
step a, drying and crushing corncobs, and sieving to obtain corncob particles;
b, adding the corncob particles into alkali liquor to be soaked for 2-6 h, then adopting segmented microwave heating to carry out pretreatment, and cooling to obtain corncob pretreatment liquid;
the specific procedure of the segmented microwave heating is as follows: heating to 55-65 ℃ at the speed of 9-11 ℃/min, heating to 75-85 ℃ at the speed of 4-6 ℃/min, and finally heating to 88-92 ℃ at the speed of 2-3 ℃/min;
and c, adjusting the pH value of the corncob pretreatment solution to 6-9, adding cellulose degrading bacteria, stirring and degrading for 20-40 h, and performing solid-liquid separation to obtain the denitrification liquid carbon source.
2. The method for preparing a denitrifying liquid carbon source according to claim 1, wherein in the step a, the fineness of the corncob particles is less than or equal to 40 mesh.
3. The method for preparing a denitrification liquid carbon source according to claim 1, wherein in the step b, the alkali solution is at least one of a calcium hydroxide solution, a sodium hydroxide solution or a potassium hydroxide solution.
4. The method for preparing the denitrification liquid carbon source according to claim 3, wherein in the step b, the mass concentration of the alkali liquor is 1-10%.
5. The method for preparing the denitrification liquid carbon source as claimed in claim 4, wherein in the step b, the mass ratio of the corncob particles to the alkali liquor is 1: 3-8.
6. The method for preparing a denitrification liquid carbon source according to claim 1, wherein in the step c, the cellulose-degrading bacteria is at least one of Bacteroides succinogenes, Ruminococcus bovis, Ruminococcus albus, Vibrio fibrinolyticus, Clostridium clostridia or Staphylococcus pini.
7. The method for preparing the denitrification liquid carbon source as claimed in claim 6, wherein in the step c, the mass ratio of the cellulose-degrading bacteria to the corncob particles is 1: 8-12.
8. The method for preparing a denitrification liquid carbon source as claimed in claim 1, wherein in the step c, the rotation speed of stirring degradation is 20 r/min-30 r/min.
9. A denitrification liquid carbon source, which is produced by the method for producing a denitrification liquid carbon source according to any one of claims 1 to 8.
10. Use of the denitrified liquid carbon source according to claim 9 in the treatment of domestic sewage and industrial wastewater.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116024272A (en) * | 2023-02-20 | 2023-04-28 | 郑州大学 | A carbon source preparation method for denitrification of sewage and its application |
| CN118420109A (en) * | 2024-04-25 | 2024-08-02 | 中国水产科学研究院黄海水产研究所 | Composition for preparing denitrifying material from plant raw materials and application thereof |
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| EP1498389A1 (en) * | 2002-04-22 | 2005-01-19 | Kuraray Chemical Co., Ltd | Process for producing active carbon, polarizable electrode and electric double layer capacitor |
| CN110540306A (en) * | 2019-09-02 | 2019-12-06 | 安徽舜禹水务股份有限公司 | Preparation method of straw corncob sewage denitrification carbon source |
| CN112408595A (en) * | 2020-10-29 | 2021-02-26 | 南京苏楻生物科技有限公司 | Solid carbon source and preparation process thereof |
| CN112744916A (en) * | 2020-12-29 | 2021-05-04 | 浙江海洋大学 | Method for treating polluted water body by synchronous nitrification and denitrification biological carrier coupling system |
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2022
- 2022-01-07 CN CN202210017689.3A patent/CN114410706A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1498389A1 (en) * | 2002-04-22 | 2005-01-19 | Kuraray Chemical Co., Ltd | Process for producing active carbon, polarizable electrode and electric double layer capacitor |
| CN110540306A (en) * | 2019-09-02 | 2019-12-06 | 安徽舜禹水务股份有限公司 | Preparation method of straw corncob sewage denitrification carbon source |
| CN112408595A (en) * | 2020-10-29 | 2021-02-26 | 南京苏楻生物科技有限公司 | Solid carbon source and preparation process thereof |
| CN112744916A (en) * | 2020-12-29 | 2021-05-04 | 浙江海洋大学 | Method for treating polluted water body by synchronous nitrification and denitrification biological carrier coupling system |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116024272A (en) * | 2023-02-20 | 2023-04-28 | 郑州大学 | A carbon source preparation method for denitrification of sewage and its application |
| CN118420109A (en) * | 2024-04-25 | 2024-08-02 | 中国水产科学研究院黄海水产研究所 | Composition for preparing denitrifying material from plant raw materials and application thereof |
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Application publication date: 20220429 |