CN115925111A - Sulfur autotrophic denitrification slow-release composite filler and preparation method and application thereof - Google Patents
Sulfur autotrophic denitrification slow-release composite filler and preparation method and application thereof Download PDFInfo
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- CN115925111A CN115925111A CN202211674668.5A CN202211674668A CN115925111A CN 115925111 A CN115925111 A CN 115925111A CN 202211674668 A CN202211674668 A CN 202211674668A CN 115925111 A CN115925111 A CN 115925111A
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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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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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- Y02W10/10—Biological treatment of water, waste water, or sewage
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Abstract
The invention discloses a sulfur autotrophic denitrification denitrogenation slow-release composite filler and a preparation method and application thereof, belonging to the field of water pollution control. The preparation method of the composite filler comprises the following steps: mixing and grinding sulfur powder, zinc carbonate powder, active magnesium oxide powder and clay according to a certain proportion, then modulating and granulating by using sodium alginate aqueous solution, and then drying in vacuum to obtain the target product. Wherein sulfur is used as an electron donor; the zinc carbonate is used as a slow-release inorganic carbon source, and zinc ions released by the zinc carbonate can play a role in eliminating hydrogen sulfide; the activated magnesium oxide can ensure that the pH value in the sulfur autotrophic denitrification system is in a proper range. The filler has stable performance and high utilization efficiency, can effectively solve the problem that excessive hydrogen sulfide generated by anti-sulfuration bacteria in a system inhibits the activity of microorganisms, and obtains the effect of deep denitrification. Under the condition that the hydraulic retention time is 1-2h, the nitrate nitrogen can be reduced to below 5mg/L from 30-40mg/L, and the aim of deep denitrification is fulfilled.
Description
Technical Field
The invention belongs to a sulfur autotrophic denitrification nitrogen removal technology in the field of wastewater treatment, and particularly relates to a sulfur autotrophic denitrification nitrogen removal slow-release composite filler as well as a preparation method and an application thereof.
Background
Denitrification is an important link for denitrification in sewage treatment. The traditional denitrifying bacteria take methanol, sodium acetate and the like as carbon sources and serve as electron donors, and if deep denitrification is required, a large amount of carbon sources need to be added, so that the operation cost is high. In recent years, several new denitrification techniques are being developed and applied to practical engineering, wherein the sulfur autotrophic denitrification technique is a new denitrification method capable of replacing the traditional denitrification, and is receiving wide attention. The sulfur autotrophic denitrification technology takes sulfur as an electron donor, can replace the traditional carbon source, carries out denitrification reaction under the action of denitrifying bacteria and enzyme, and has better economy. The sulfur source used in the technology mainly comprises elemental sulfur, thiosulfate or sulfide and the like, and carbonate and the like are used as inorganic carbon sources to realize the denitrification function under the action of desulfurization bacillus and the like. However, the sulfur autotrophic denitrification technology has some problems at present, which prevent the practical wide-range application thereof. Firstly, the problem of sulfur oxidation loss is solved, and in an oxygen environment, sulfur simple substances are easily oxidized and inactivated; secondly, the microbial metabolic environment is unbalanced in acid and alkali, and a large amount of hydrogen ions can be accumulated in the process of sulfur autotrophic denitrification to cause the microbial environment to be acidic; and a large amount of sulfate ions are generated in the microbial environment, and the sulfate ions can generate a large amount of toxic hydrogen sulfide under the action of the anti-sulfuration bacteria, so that the growth and the propagation of microorganisms are inhibited, and the denitrification is hindered. In order to solve the problem that sulfur is easily oxidized and lost, patent CN115028261 proposes to use sodium sulfite and sodium bisulfite as reducing agents to remove dissolved oxygen in water, but the problem of hydrogen sulfide caused by excessive sulfate generation is not solved. In order to solve the problem of microenvironment acid-base imbalance, CN114291900A proposes that sulfur and ferrous ions are jointly used as an electron donor to realize acid-base neutralization, so that the pH value of the system is stabilized, and the effect of deep denitrification of the wastewater is improved. However, no effective solution has been proposed in these techniques to the problem of inhibiting microbial growth by hydrogen sulfide production in the system.
Disclosure of Invention
In order to overcome the defects, the composite filler provided by the invention uses sulfur as an electron donor to be applied to a denitrification nitrogen removal system, simultaneously uses carbonate in zinc carbonate as an inorganic carbon source, and releases zinc ions as a hydrogen sulfide stabilizer, and can react with hydrogen sulfide to generate zinc sulfide, so that the purpose of absorbing hydrogen sulfide is achieved, and the generated zinc sulfide can be used as a sulfur source again to be applied to an autotrophic denitrification nitrogen removal electron donor. In addition, active magnesium oxide is used as a pH regulator, so that the pH value of the system can be effectively stabilized, and deep denitrification is realized.
The purpose of the invention is realized by the following technical scheme:
the invention aims to provide a preparation method of a sulfur autotrophic denitrification slow-release composite filler, which comprises the following steps:
(1) Uniformly mixing sulfur powder, zinc carbonate powder, active magnesium oxide powder and clay, and grinding to obtain grinding powder; preferably, the mass ratio of the sulfur powder, the zinc carbonate powder, the active magnesium oxide powder and the clay is (60-80): (5-15): (5-15): (10-20). Further preferably, the particle size of the sulfur powder is 100-200 meshes; the grain size of the zinc carbonate powder is 100-200 meshes; the particle size of the active magnesium oxide powder is 50-100 meshes; the clay is at least one of kaolin and sodium bentonite, and the particle size of the clay is 100-150 meshes.
(2) Preparing the grinding powder into paste by using a sodium alginate aqueous solution, and granulating to obtain filler particles; preferably, the concentration of the sodium alginate aqueous solution is 1% -2%; the mass ratio of the grinding powder to the sodium alginate aqueous solution is 1:1-2.
(3) And (3) drying the filler particles in vacuum, and cooling to obtain the sulfur autotrophic denitrification slow-release composite filler with the particle size of 8-12mm. Preferably, the temperature of the vacuum drying is 110-120 ℃, and the time is 10-12h; the vacuum degree of vacuum drying is 0.005-0.01Mpa.
The second purpose of the invention is to provide the sulfur autotrophic denitrification nitrogen removal slow-release composite filler, which is prepared by the preparation method in the first purpose.
The third purpose of the invention is to provide the application of the sulfur autotrophic denitrification nitrogen removal slow-release composite filler in sewage treatment according to the second purpose, and the method comprises the following steps: the sulfur autotrophic denitrification slow-release composite filler is placed in an anaerobic reactor and can be used for sewage treatment; the filling ratio of the sulfur autotrophic denitrification slow-release composite filler in the anaerobic reactor is 20-30%, and the concentration of the desulfurization bacillus is 30-40%.
The technical scheme provided by the invention has the following beneficial effects:
(1) The sulfur autotrophic denitrification filler provided by the invention is prepared by mixing sulfur powder, zinc carbonate powder, active magnesium oxide powder, clay, sodium alginate and the like, and can realize deep denitrification in a denitrification system.
(2) The active magnesium oxide powder in the filler can be added with H + And a neutralization reaction is carried out, so that a certain acid-base buffering effect is achieved, and the pH stability in the system is ensured. The sulfur autotrophic denitrification filler is mixed by a sodium alginate solution, so that the stability of the filler is enhanced, the slow release effect of the filler is maintained, the collapse of the filler caused by long-term use is slowed down, the excessive oxidation inactivation of sulfur is avoided, the nitrogen removal effect of a system is further improved, and the operation cost is reduced.
(3) During the sulfur autotrophic denitrification, a large amount of sulfate radicals can be generated along with the reaction, under the action of the denitrifying bacteria, toxic hydrogen sulfide can be generated to inhibit the growth of microorganisms and influence the denitrification effect, and the zinc carbonate added into the filler can react with the hydrogen sulfide to generate water-insoluble zinc sulfide (H) 2 S+ZnCO 3 ＝ZnS+H 2 O+CO 2 ) Thereby inhibiting the concentration of hydrogen sulfide and reducing the toxicity of the hydrogen sulfide to microorganisms.
Detailed Description
The present invention will be further described with reference to the following examples, but the essence of the present invention is not limited to the following examples. The methods are conventional unless otherwise indicated, and the materials may be obtained commercially from published sources, and those skilled in the art will recognize that any simple modification or substitution based on the spirit of the invention is within the scope of the invention as claimed.
Example 1:
a preparation method of a sulfur autotrophic denitrification slow-release composite filler comprises the following steps:
in example 1, sulfur powder and zinc carbonate powder were usedThe method comprises the following steps of taking active magnesium oxide powder, sodium bentonite and sodium alginate as main raw materials, selecting sulfur powder with the particle size of 100 meshes, zinc carbonate powder with the particle size of 100 meshes, active magnesium oxide powder with the particle size of 50 meshes and sodium bentonite with the particle size of 100 meshes, uniformly mixing the raw materials with the mass of 800g, 50g and 100g in a mixer, and grinding to obtain grinding powder; preparing a sodium alginate solution with the mass fraction of 1.5%; and (3) mixing the grinding powder with a sodium alginate solution in a mass ratio of 1.2, and granulating and forming after mixing to prepare filler particles with the diameter of 8 mm. Heating the filler particles in a vacuum drying oven at 110 ℃ for 10h under the vacuum degree of 0.01Mpa to obtain the sulfur autotrophic denitrification and denitrification slow-release composite filler, wherein the bulk density of the composite filler is 1.0g/m 3 The porosity was 5%.
Application example 1:
the composite filler prepared in example 1 was placed in an anaerobic reactor at a filling ratio of 20%. The effective volume of the reactor is 10.8L, and 1L of the inoculated desulfurization bacillus solution with the concentration of 30 percent is used. The influent water is certain domestic sewage, the hydraulic retention time is 2 hours, the average value of the nitrate nitrogen of the raw water is 35.5mg/L, the average value of the nitrate nitrogen of the produced water is 3.2mg/L, and the removal rate is 91 percent.
Example 2:
a preparation method of a sulfur autotrophic denitrification slow-release composite filler comprises the following steps:
in example 2, sulfur, zinc carbonate, active magnesium oxide, sodium bentonite, sodium alginate and the like are used as main raw materials, sulfur powder with the particle size of 200 meshes, zinc carbonate powder with the particle size of 200 meshes, active magnesium oxide powder with the particle size of 100 meshes, sodium bentonite with the particle size of 150 meshes are selected, the mass of the raw materials is 700g, 100g and 100g respectively, the raw materials are uniformly mixed in a mixer, and grinding powder is obtained after grinding; preparing a sodium alginate solution with the mass fraction of 1%; mixing the ground powder and a sodium alginate solution in a mass ratio of 1:2, granulating and molding after mixing, and preparing filler particles with the diameter of 10 mm. Heating the filler particles in a vacuum drying oven at 110 deg.C for 12h under 0.005Mpa to obtain the sulfur autotrophic denitrification nitrogen removal slow-release composite filler with bulk density of 1.3g/m 3 A porosity of8％。
Application example 2:
the composite filler prepared in example 2 was placed in an anaerobic reactor at a filling ratio of 20%. The effective volume of the reactor is 10.8L, and 1L of the desulfurization bacillus solution is inoculated, wherein the concentration of the desulfurization bacillus is 40%. The water inflow is certain domestic sewage, the hydraulic retention time is 1.5h, the average value of the nitrate nitrogen of the raw water is 40mg/L, the average value of the nitrate nitrogen of the produced water is 4.2mg/L, and the removal rate is 89%.
Example 3:
a preparation method of a sulfur autotrophic denitrification slow-release composite filler comprises the following steps:
in example 3, sulfur, zinc carbonate, active magnesium oxide, kaolin, sodium alginate and the like are used as main raw materials, 100-mesh sulfur powder, 200-mesh zinc carbonate powder, 100-mesh active magnesium oxide powder and 100-mesh sodium bentonite are selected, the raw materials are respectively 600g, 150g and 100g in mass, and are uniformly mixed in a mixer to obtain grinding powder after grinding; preparing a sodium alginate solution with the mass fraction of 2%; and (2) mixing the grinding powder with a sodium alginate solution in a mass ratio of 1.5, and granulating and forming after mixing to prepare filler particles with the diameter of 12mm. Heating the filler particles in a vacuum drying oven at 110 deg.C for 12h with a vacuum degree of 0.01Mpa to obtain the sulfur autotrophic denitrification nitrogen removal slow-release composite filler with a bulk density of 1.1g/m 3 The porosity was 10%.
Application example 3:
the composite filler prepared in example 3 was placed in an anaerobic reactor at a packing ratio of 20%. The effective volume of the reactor is 10.8L, and 1L of the desulfurizing bacillus solution is inoculated, and the concentration of the desulfurizing bacillus is 40 percent. The inlet water is certain domestic sewage, the hydraulic retention time is 1.5h, the average value of raw water nitrate nitrogen is 30mg/L, the average value of produced water nitrate nitrogen is 2.2mg/L, and the removal rate is 92.6 percent.
Example 4:
a preparation method of a sulfur autotrophic denitrification slow-release composite filler comprises the following steps:
in example 4, sulfur, zinc carbonate, active magnesium oxide, kaolin, sodium alginate, etc. were used as the main raw materials, and sulfur was selectedThe particle size of the sulfur powder is 200 meshes, the particle size of the zinc carbonate powder is 100 meshes, the particle size of the active magnesium oxide powder is 50 meshes, the particle size of the kaolin is 150 meshes, the mass of the raw materials is 700g, 50g, 100g and 150g respectively, the raw materials are uniformly mixed in a mixer, and grinding powder is obtained after grinding; preparing a sodium alginate solution with the mass fraction of 2%; mixing the ground powder and a sodium alginate solution according to a mass ratio of 1:2, granulating and molding after mixing, and preparing filler particles with the diameter of 10 mm. Heating the filler particles in a vacuum drying oven at 120 deg.C for 12h with a vacuum degree of 0.01Mpa to obtain the sulfur autotrophic denitrification nitrogen removal slow-release composite filler with a bulk density of 1.12g/m 3 The porosity was 12%.
Application example 4:
the composite packing prepared in example 4 was placed in an anaerobic reactor at a packing ratio of 25%. The effective volume of the reactor is 10.8L, and 1L of the desulfurizing bacillus solution is inoculated, and the concentration of the desulfurizing bacillus is 40 percent. The water inflow is certain domestic sewage, the hydraulic retention time is 1.5h, the average value of the nitrate nitrogen of the raw water is 32mg/L, the average value of the nitrate nitrogen of the produced water is 2.8mg/L, and the removal rate is 91.3 percent.
Example 5:
a preparation method of a sulfur autotrophic denitrification slow-release composite filler comprises the following steps:
in example 5, sulfur, zinc carbonate, active magnesium oxide, kaolin, sodium alginate and the like are used as main raw materials, sulfur powder with the particle size of 200 meshes, zinc carbonate powder with the particle size of 200 meshes, active magnesium oxide powder with the particle size of 50 meshes, kaolin with the particle size of 100 meshes are selected, and the raw materials respectively have the mass of 600g, 100g and 200g, are uniformly mixed in a mixer and are ground to obtain ground powder; preparing a sodium alginate solution with the mass fraction of 2%; and mixing the grinding powder and a sodium alginate solution in a mass ratio of 1.5, and granulating and forming after mixing to prepare the filler particles with the diameter of 8 mm. Heating the filler particles in a vacuum drying oven at 110 deg.C for 12h under 0.005Mpa to obtain the sulfur autotrophic denitrification nitrogen removal slow-release composite filler with bulk density of 1.2g/m 3 The porosity was 7%.
Application example 5:
the composite filler prepared in example 5 was placed in an anaerobic reactor at a packing ratio of 30%. The effective volume of the reactor is 10.8L, and 1L of the desulfurization bacillus solution is inoculated, wherein the concentration of the desulfurization bacillus is 40%. The water inflow is certain domestic sewage, the hydraulic retention time is 100min, the average value of the nitrate nitrogen of the raw water is 30mg/L, the average value of the nitrate nitrogen of the produced water is 3.1mg/L, and the removal rate is 90.3 percent.
As can be seen from the application examples, the composite filler prepared in the examples can reduce the nitrate nitrogen in the sewage from 30-40mg/L to below 5mg/L under the condition that the Hydraulic Retention Time (HRT) is 1-2h, and can realize the purpose of deep denitrification.
It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (9)
1. A preparation method of a sulfur autotrophic denitrification slow-release composite filler is characterized by comprising the following steps:
(1) Uniformly mixing sulfur powder, zinc carbonate powder, active magnesium oxide powder and clay, and grinding to obtain grinding powder;
(2) Preparing the grinding powder into paste by using a sodium alginate aqueous solution, and granulating to obtain filler particles;
(3) And (4) drying the filler particles in vacuum, and cooling to obtain the sulfur autotrophic denitrification denitrogenation slow-release composite filler.
2. The preparation method of the sulfur autotrophic denitrification nitrogen removal slow-release composite filler according to claim 1, characterized in that: in the step (1), the mass ratio of the sulfur powder, the zinc carbonate powder, the active magnesium oxide powder and the clay is (60-80): (5-15): (5-15): (10-20).
3. The preparation method of the sulfur autotrophic denitrification nitrogen removal slow-release composite filler according to claim 2, characterized in that: the particle size of the sulfur powder is 100-200 meshes, the particle size of the zinc carbonate powder is 100-200 meshes, the particle size of the active magnesium oxide powder is 50-100 meshes, and the particle size of the clay is 100-150 meshes.
4. The preparation method of the sulfur autotrophic denitrification nitrogen removal slow-release composite filler according to claim 3, characterized in that: the clay is at least one of kaolin and sodium bentonite.
5. The preparation method of the sulfur autotrophic denitrification nitrogen removal slow-release composite filler according to claim 1, wherein the preparation method comprises the following steps: in the step (2), the concentration of the sodium alginate aqueous solution is 1% -2%; the mass ratio of the grinding powder to the sodium alginate aqueous solution is 1:1-2.
6. The preparation method of the sulfur autotrophic denitrification nitrogen removal slow-release composite filler according to claim 1, characterized in that: in the step (3), the temperature of the vacuum drying is 110-120 ℃, and the time is 10-12h; the vacuum degree of vacuum drying is 0.005-0.01Mpa.
7. The preparation method of the sulfur autotrophic denitrification nitrogen removal slow-release composite filler according to claim 1, characterized in that: in the step (3), the particle size of the sulfur autotrophic denitrification slow-release composite filler is 8-12mm.
8. The sulfur autotrophic denitrification slow-release composite filler is characterized in that: which is prepared by the preparation method of any one of claims 1 to 7.
9. The application of the sulfur autotrophic denitrification nitrogen removal slow-release composite filler in sewage treatment according to claim 8 is characterized in that the method comprises the following steps: the sulfur autotrophic denitrification slow-release composite filler is placed in an anaerobic reactor and can be used for sewage treatment; the filling ratio of the sulfur autotrophic denitrification slow-release composite filler in the anaerobic reactor is 20-30%, and the concentration of the desulfurization bacillus is 30-40%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116332329A (en) * | 2023-05-31 | 2023-06-27 | 潍坊学院 | Sustained-release sulfur autotrophic denitrification biological filter material and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116332329A (en) * | 2023-05-31 | 2023-06-27 | 潍坊学院 | Sustained-release sulfur autotrophic denitrification biological filter material and preparation method and application thereof |
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