CN115520955A - Biological filler, preparation method and application thereof, and method for removing nitrate in water - Google Patents
Biological filler, preparation method and application thereof, and method for removing nitrate in water Download PDFInfo
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- CN115520955A CN115520955A CN202211161674.0A CN202211161674A CN115520955A CN 115520955 A CN115520955 A CN 115520955A CN 202211161674 A CN202211161674 A CN 202211161674A CN 115520955 A CN115520955 A CN 115520955A
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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
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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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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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
- C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention provides a biological filler, which comprises an elemental sulfur converting agent, elemental sulfur and a binder, wherein the binder binds the elemental sulfur converting agent and the elemental sulfur; wherein, the elemental sulfur conversion agent comprises protein substances, and the protein substances contain one or more of disulfide bonds and sulfydryl; the binder comprises kaolin; the elemental sulfur can provide an electron donor for sulfur oxidizing bacteria without adding organic matters; the elemental sulfur transforming agent can promote the elemental sulfur to be transformed into polysulfide, thereby improving the utilization rate of sulfur oxidizing bacteria to the elemental sulfur in the process of autotrophic denitrification of sulfur; the biological filler can be used as a carrier for microbial growth and also can be used as an electron donor of sulfur-oxidizing bacteria, so that nitrate in a water body is removed by utilizing the sulfur autotrophic denitrification effect, the time for stabilizing the sulfur autotrophic denitrification rate of the sulfur-oxidizing bacteria is short, the nitrogen removal rate is higher, the biological filler can better adapt to water quality change, and the biological filler has a better application prospect.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a biological filler, a preparation method and application thereof, and a method for removing nitrate in water.
Background
Excessive nitrate in water may cause eutrophication of water, and the presence of nitrate in drinking water poses a threat to human health, and thus it is very important to effectively remove the excessive nitrate from the water. At present, the nitrate in water is mainly removed by adopting a biological treatment technology, the traditional biological treatment technology is heterotrophic denitrification, and organic matters are used as electron donors to reduce the nitrate into nitrogen. However, in the heterotrophic denitrification process, additional organic matters need to be added, the treatment cost is high, and secondary pollution is caused when the organic matters are excessively added.
Sulfur autotrophic denitrification utilizes elemental sulfur as an electron donor, and nitrate is reduced by sulfur autotrophic denitrifying bacteria. The cost of nitrate in unit mass is low in sulfur autotrophic denitrification treatment, and in the denitrification process, solid elemental sulfur is used as an electron donor, so that secondary pollution is not easy to cause. Compared with heterotrophic denitrification, the sulfur autotrophic denitrification process has low sludge yield and low sludge treatment cost. Therefore, the sulfur autotrophic denitrification is widely concerned in the biological denitrification process.
However, the rate of utilization of solid elemental sulfur by microorganisms for denitrifying electron donors is low compared to dissolved organics, resulting in a lower reaction rate for sulfur autotrophic denitrification compared to heterotypic denitrification.
Disclosure of Invention
Based on the above, there is a need for a biological filler, a preparation method and an application thereof, and a method for removing nitrate in water, so as to improve the sulfur autotrophic denitrification reaction rate.
The invention provides a biological filler, which comprises an elemental sulfur converting agent, elemental sulfur and a binder, wherein the binder binds the elemental sulfur converting agent and the elemental sulfur; wherein the elemental sulfur conversion agent comprises a protein material, and the protein material contains one or more of disulfide bonds and sulfydryl; the binder comprises kaolin.
In some embodiments, the proteinaceous material comprises one or more of bovine serum albumin, whey protein, and soy protein.
In some embodiments, the mass ratio of the elemental sulfur converting agent, the binder and the elemental sulfur powder is (5-10): (10-20): (70-85).
In some embodiments, the elemental sulfur converting agent further comprises pyrrhotite;
optionally, the particle size D50 of the pyrrhotite is 0.2 to 0.5mm.
In some embodiments, the mass ratio of the elemental sulfur converting agent, the pyrrhotite, the binder and the elemental sulfur powder is (5-10): (20-30): (10-20): (40-65).
In some embodiments, the biological filler comprises spherical particles having a particle size of 8 to 10 mm.
The second aspect of the invention provides a preparation method of a biological filler, which comprises the following steps:
mixing elemental sulfur transforming agent, adhesive and elemental sulfur, and adding solvent to prepare composite material sticky matter;
and granulating the composite material sticky substance to obtain the biological filler.
In some embodiments, the step of granulating the composite material paste specifically includes:
placing the composite material sticky object in a granulation mould, and carrying out vacuum drying;
optionally, the vacuum drying is performed while satisfying at least one of the following conditions:
(1) The temperature of vacuum drying is 60-80 ℃;
(2) The vacuum drying time is 4-6 h.
A third aspect of the invention provides the use of a biological filler as described in the first aspect in the preparation of a denitrification agent for the treatment of nitrate in water.
The fourth aspect of the invention provides a method for removing nitrate in water, which comprises the following steps:
placing the biological filler in the first aspect in a packed bed reactor, and adding sulfur-oxidizing bacteria liquid for inoculation;
and after the surface of the biological filler is provided with the biological film, introducing water quality to be treated into the packed bed reactor to remove nitrate in the water quality to be treated.
The biological filler, the preparation method and the application thereof and the method for removing nitrate in water are provided, wherein the elemental sulfur can provide an electron donor for sulfur oxidizing bacteria without adding organic matters; the elemental sulfur transforming agent can promote the elemental sulfur to be transformed into polysulfide, thereby improving the utilization rate of sulfur oxidizing bacteria to the elemental sulfur in the process of autotrophic denitrification of sulfur; the biological filler can be used as a carrier for microbial growth and also can be used as an electron donor of sulfur-oxidizing bacteria, so that nitrate in a water body is removed by utilizing the sulfur autotrophic denitrification effect, the time for stabilizing the sulfur autotrophic denitrification rate of the sulfur-oxidizing bacteria is short, the nitrogen removal rate is higher, the biological filler can better adapt to water quality change, and the biological filler has a better application prospect.
Drawings
FIG. 1 is a schematic diagram of the denitrification principle of an elemental sulfur converting agent;
FIG. 2 is a graph showing the results of the denitrification performance test in example 1 and comparative example 1.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In the technical features described in the open-ended form, the closed technical scheme comprising the listed features also comprises the open technical scheme comprising the listed features.
Herein, reference to numerical intervals is deemed continuous within the numerical intervals, unless otherwise stated, and includes the minimum and maximum values of the range, as well as each and every value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
In this context, referring to units of the data range, if only with units after the right end point, the units representing the left end point and the right end point are the same. For example, 8 to 10mm means that the units of the left end point "8" and the right end point "10" are both mm (millimeters).
Only some numerical ranges are specifically disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and similarly any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each separately disclosed point or individual value may itself, as a lower or upper limit, be combined with any other point or individual value or with other lower or upper limits to form ranges not explicitly recited.
The temperature parameter herein is not particularly limited, and is allowed to be either constant temperature treatment or treatment within a certain temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
Excessive nitrate in water can cause eutrophication of water bodies, and the presence of nitrate in drinking water poses a threat to human health, so that effective removal of the excessive nitrate in water bodies is extremely important. At present, the nitrate in water is mainly removed by adopting a biological treatment technology, the traditional biological treatment technology is heterotrophic denitrification, and organic matters are used as electron donors to reduce the nitrate into nitrogen. However, in the heterotrophic denitrification process, additional organic matter needs to be added, the treatment cost is high, and secondary pollution is caused when the added organic matter is excessive.
Sulfur autotrophic denitrification utilizes elemental sulfur as an electron donor, and nitrate is reduced by sulfur autotrophic denitrifying bacteria. The cost of nitrate in unit mass is low in the sulfur autotrophic denitrification treatment, and in the denitrification process, solid elemental sulfur is used as an electron donor, so that secondary pollution is not easy to cause. Compared with heterotrophic denitrification, the sulfur autotrophic denitrification process has low sludge yield and low sludge treatment cost. Therefore, the sulfur autotrophic denitrification has received much attention in the biological nitrogen removal process.
However, the rate of utilization of solid elemental sulfur by microorganisms for denitrifying electron donors is low compared to soluble organics, resulting in a lower reaction rate for sulfur autotrophic denitrification compared to heterogeneous denitrification.
In addition, microorganisms are difficult to attach and grow on the elemental sulfur, so that the time for stabilizing the sulfur autotrophic denitrification rate of sulfur-oxidizing bacteria in practical engineering application is long, and is generally more than 40 days.
In order to solve the above problems, embodiments of the present invention provide a biological filler, which includes an elemental sulfur transforming agent, elemental sulfur, and a binder, where the binder binds the elemental sulfur transforming agent and the elemental sulfur; wherein, the elemental sulfur conversion agent comprises protein substances, and the protein substances contain one or more of disulfide bonds and sulfydryl; the binder comprises kaolin.
The method for utilizing elemental sulfur by sulfur oxidizing bacteria in the process of sulfur autotrophic denitrification comprises the following steps: the sulfur oxidizing bacteria firstly convert the elemental sulfur outside the cells into soluble polysulfide intermediates, and then the soluble polysulfide enters the cells and is oxidized by the sulfur oxidizing bacteria, thereby completing the denitrification process. The elemental sulfur in the biological filler can provide an electron donor for sulfur oxidizing bacteria without adding an organic matter; the elemental sulfur conversion agent comprises protein substances containing disulfide bonds and/or sulfydryl, and the disulfide bonds or the sulfydryl can promote elemental sulfur to be converted into polysulfide, so that the utilization rate of sulfur oxidizing bacteria on the elemental sulfur is improved; the biological filler can be used as a carrier for microbial growth and also can be used as an electron donor of sulfur-oxidizing bacteria, so that nitrate in a water body is removed by utilizing the sulfur autotrophic denitrification effect, the time for stabilizing the sulfur autotrophic denitrification rate of the sulfur-oxidizing bacteria is short, the nitrogen removal rate is higher, the biological filler can better adapt to water quality change, and the biological filler has a better application prospect.
In some embodiments, the proteinaceous material may include one or more of bovine serum albumin, whey protein, and soy protein. Further, the protein substance is bovine serum albumin; bovine serum albumin contains more disulfide bonds and sulfydryl at the same time, and can further promote the conversion of elemental sulfur into polysulfide.
In some embodiments, the mass ratio of the elemental sulfur converting agent, the binder and the elemental sulfur powder is (5-10) to (10-20) to (70-85); for example, the following can be 7. Further optionally, the mass ratio of the elemental sulfur conversion agent, the binder and the elemental sulfur powder is 5.
In some embodiments, the elemental sulfur converting agent further comprises pyrrhotite; the pyrrhotite can generate sulfide under the acidic condition, and the sulfide can react with the elemental sulfur to generate polysulfide, so that the elemental sulfur is promoted to be converted into the polysulfide, and the utilization rate of sulfur oxidizing bacteria to the elemental sulfur is improved.
In some alternative embodiments, the pyrrhotite has a particle size D50 of 0.2 to 0.5mm; for example, it may be 0.23 to 0.5mm, 0.25 to 0.5mm, 0.28 to 0.5mm, 0.3 to 0.5mm, 0.32 to 0.5mm, 0.35 to 0.5mm, 0.38 to 0.5mm, 0.4 to 0.5mm, 0.43 to 0.5mm, 0.45 to 0.5mm, 0.48 to 0.5mm, or 0.2 to 0.4 mm. Further optionally, the particle size D50 of the pyrrhotite is 0.2mm. The smaller the particle size of the pyrrhotite is, the larger the specific surface area of the pyrrhotite is, so that the contact area with the elemental sulfur is larger, and the effect of promoting the conversion of the elemental sulfur is better; however, when the particle size of the pyrrhotite is less than 0.2mm, the process difficulty in preparing the pyrrhotite is increased, and the cost is increased; on the basis of comprehensive consideration of promoting the conversion of elemental sulfur into polysulfide by pyrrhotite and cost, the particle size D50 of the pyrrhotite is selected to be in the range.
In some embodiments, the mass ratio of the elemental sulfur converting agent, the pyrrhotite, the binder and the elemental sulfur powder is (5-10): 20-30): 10-20): 40-65; for example, the following ratio of 7. Further optionally, the mass ratio of the elemental sulfur converting agent, pyrrhotite, the binder and the elemental sulfur powder is 5.
In some embodiments, the biological filler comprises spherical particles having a particle size of 8 to 10 mm; for example, it may be 8.5 to 10mm, 9 to 10mm, 9.5 to 10mm, 8 to 9.5mm, or the like. Further, the particle size of the biological filler is 8mm.
In some embodiments, the elemental sulfur can be industrial sulfur powder, wherein the elemental sulfur content of the industrial sulfur powder is greater than 95%.
FIG. 1 is a schematic diagram illustrating the denitrification principle of an elemental sulfur converting agent, and it can be known from FIG. 1 that disulfide bonds and/or thiol groups in a protein substance can promote elemental sulfur to be converted into soluble polysulfide; the pyrrhotite can generate sulfide under the acidic condition, and the sulfide can react with elemental sulfur to generate soluble polysulfide; because polysulfide is soluble, the polysulfide can be better utilized by sulfur oxidizing bacteria than elemental sulfur, thereby realizing the improvement of denitrification rate; the sulfur oxidizing bacteria oxidize polysulfide into sulfate and simultaneously reduce nitrate into nitrogen, thereby realizing the removal of nitrate.
The embodiment of the invention also provides a preparation method of the biological filler, which comprises the following steps: mixing elemental sulfur transforming agent, adhesive and elemental sulfur, and adding solvent to prepare composite material sticky matter; and granulating the composite material sticky matter to obtain the biological filler.
In some embodiments, the step of pelletizing the composite paste comprises: and (3) placing the sticky composite material in a granulation mould, and performing vacuum drying.
The granulation die is a die for granulation.
For example, when the biological filler is prepared, the protein material, the adhesive and the elemental sulfur are mixed, water accounting for 15-20% of the total mass of the components is added to form a viscous composite material sticky matter, then the composite material sticky matter is placed in a granulating mold, and the granulating mold is placed in a vacuum drying oven to be dried and granulated, so that the biological filler is prepared.
For example, when the biological filler is prepared, the protein substance, the pyrrhotite, the adhesive and the elemental sulfur are mixed, water accounting for 15-20% of the total mass of the components is added to form a sticky composite material sticky substance, then the sticky composite material sticky substance is placed in a granulating mold, and the granulating mold is placed in a vacuum drying oven to be dried and granulated to obtain the biological filler.
In some embodiments, the vacuum drying is performed at a temperature of 60 to 80 ℃, for example, 65 to 80 ℃, 70 to 80 ℃, 75 to 80 ℃, or 60 to 73 ℃. Further optionally, when the vacuum drying treatment is carried out, the temperature of the vacuum drying is 60-65 ℃; further optionally, the vacuum drying treatment is carried out at a temperature of 60 deg.C
In some embodiments, the vacuum drying is performed for 4 to 6 hours, for example, 4.5 to 6 hours, 5 to 6 hours, 5.5 to 6 hours, or 4 to 4.3 hours, and the like, without limitation.
The embodiment of the invention also provides application of the biological filler in preparing a denitrifier for treating nitrate in water.
The embodiment of the invention also provides a method for removing nitrate in water, which comprises the following steps: placing the biological filler into a packed bed reactor, and adding sulfur-oxidizing bacteria liquid for inoculation; after the surface of the biological filler is provided with the biological film, the water quality to be treated is introduced into the packed bed reactor to remove the nitrate in the water quality to be treated.
In some embodiments, the packed bed reactor may be a column reactor; the reactor mainly plays a role in the process of removing nitrate, sulfur oxidizing bacteria are used, and the existence of elemental sulfur in the biological filler provides an electron donor for the sulfur oxidizing bacteria without adding organic matters; meanwhile, the elemental sulfur transforming agent in the biological filler can promote elemental sulfur to be transformed into polysulfide, so that the utilization rate of elemental sulfur by sulfur oxidizing bacteria is improved, the time required for the sulfur autotrophic denitrification of the sulfur oxidizing bacteria to be stable is shortened, and the externalization is represented by the shortened time for starting the reactor.
The technical solution is described in detail with reference to specific examples below.
1. Preparation of biological Filler
Example 1
50g of bovine serum albumin, 200g of pyrrhotite with the particle size D50 of 0.2mm, 150g of kaolin and 600g of elemental sulfur powder are mixed, 150g of water is added and uniformly stirred to form a sticky composite sticky matter, the sticky composite material sticky matter is placed in a granulation die, and the granulation die is placed in a vacuum drying oven at 60 ℃ for 6 hours for drying and granulation to prepare the spherical biological filler with the particle size of 8mm.
Example 2
100g of bovine serum albumin, 300g of pyrrhotite with the particle size D50 of 0.3mm, 200g of kaolin and 650g of elemental sulfur powder are mixed, 250g of water is added and uniformly stirred to form viscous composite material sticky matter, the composite material sticky matter is placed in a granulation mould, and the granulation mould is placed in a vacuum drying oven at the temperature of 80 ℃ for 4 hours for drying and granulating to prepare the spherical biological filler with the particle size of 10 mm.
Example 3
80g of bovine serum albumin, 250g of pyrrhotite with the particle size D50 of 0.5mm, 150g of kaolin and 520g of elemental sulfur powder are mixed, 170g of water is added and stirred uniformly to form a sticky composite material sticky matter, the sticky composite material sticky matter is placed in a granulation die, and the granulation die is placed in a vacuum drying oven at 70 ℃ for 5 hours for drying and granulation to prepare the spherical biological filler with the particle size of 9 mm.
Example 4
50g of bovine serum albumin, 200g of pyrrhotite with the particle size D50 of 0.4mm, 100g of kaolin and 400g of elemental sulfur powder are mixed, 170g of water is added and stirred uniformly to form viscous composite material sticky matter, the composite material sticky matter is placed in a granulation die, and the granulation die is placed in a vacuum drying oven at 70 ℃ for 5 hours for drying and granulation to prepare the spherical biological filler with the particle size of 9 mm.
Example 5
Example 5 differs from example 1 mainly in that: pyrrhotite is not added, and bovine serum albumin is only adopted as an elemental sulfur transforming agent; the specific process is as follows:
50g of bovine serum albumin, 150g of kaolin and 600g of elemental sulfur powder are mixed, 120g of water is added and uniformly stirred to form viscous composite material sticky matter, the composite material sticky matter is placed in a granulation mould, and the granulation mould is placed in a vacuum drying oven at 60 ℃ for 6h for drying and granulation to prepare the spherical biological filler with the particle size of 8mm.
Comparative example 1
Comparative example 1 differs from example 1 mainly in that: in comparative document 1, bovine serum albumin and pyrrhotite were not used, and only elemental sulfur powder and kaolin were prepared into elemental sulfur particles having a particle size of 8mm by the same method as in example 1; the specific process is as follows:
mixing 600g of elemental sulfur powder and 90g of kaolin, adding 100g of water, uniformly stirring to form a thick substance, placing the thick substance in a granulation mould, placing the granulation mould in a vacuum drying oven at 60 ℃ for 6h for drying and granulating to prepare elemental sulfur particles with the particle size of 8mm.
2. Denitrification Performance test
It should be noted that thiobacillus denitrificans mentioned in the following experimental section for performance test belongs to one of the sulfur oxidizing bacteria.
The biological filler prepared in the examples 1 to 5 and the elemental sulfur particles prepared in the comparative example 1 are respectively added into different packed bed reactors, then thiobacillus denitrificans bacterial liquid is added into each packed bed reactor for inoculation, after a biological film is generated on the biological filler or the elemental sulfur particles, the inoculation is completed, nitrate-containing simulated wastewater is introduced into the packed bed reactors through a peristaltic pump, wherein the concentration of nitrate nitrogen in the simulated wastewater is 60mg/L, and the nitrate in the simulated wastewater is removed through the sulfur autotrophic denitrification of the thiobacillus denitrificans. After a certain time of operation, the concentration of nitrate nitrogen in the effluent of the packed bed reactor was measured and based on the formula: denitrification rate = (influent nitrate nitrogen concentration (mg/L) -effluent nitrate nitrogen concentration (mg/L))/hydraulic retention time (d), and denitrification rate results for examples 1-5 and comparative example 1 are shown in table 1 below:
TABLE 1
The denitrification rates of example 1 and comparative example 1 were plotted as shown in FIG. 2. In FIG. 2, R1 represents a denitrification rate time-dependent curve of example 1, and R2 represents a denitrification rate time-dependent curve of comparative example 1. As can be seen from FIG. 2, the denitrification rate of example 1 was stabilized at the 4 th d, while the denitrification rate of comparative example 1 was stabilized at the 6 th d, indicating that biofilm formation on the biofilm filler could be faster, shortening the time required for the thiobacillus denitrificans to stabilize the rate of thioautotrophic denitrification. When the denitrification rates of example 1 and comparative example 1 were stabilized, respectively, the denitrification rate of example 1 was about 1.31 times as high as that of comparative example 1, indicating that the biological filler can increase the rate of thiobacillus denitrificans performing the sulfur autotrophic denitrification and thus increase the denitrification rate, compared with the elemental sulfur particles.
As can be seen from the results of examples 1 to 5 and comparative example 1 in fig. 2 and table 1, when a protein substance containing a disulfide bond and/or a thiol group is used as an elemental sulfur converting agent, or a mixture of a protein substance containing a disulfide bond and/or a thiol group and pyrrhotite is used as an elemental sulfur converting agent, the elemental sulfur can be promoted to be converted into polysulfide, so that the rate of elemental sulfur utilization by thiobacillus denitrificans in the process of thioautotrophic denitrification is increased, the time for stabilizing the rate of thioautotrophic denitrification by thiobacillus denitrificans is shorter, and the denitrification rate is increased.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The biological filler is characterized by comprising an elemental sulfur transforming agent, elemental sulfur and a binder, wherein the binder binds the elemental sulfur transforming agent and the elemental sulfur;
wherein the elemental sulfur conversion agent comprises a protein material, and the protein material contains one or more of disulfide bonds and sulfydryl;
the binder comprises kaolin.
2. The biofilm carrier of claim 1, wherein said proteinaceous material comprises one or more of bovine serum albumin, whey protein and soy protein.
3. The biological filler according to claim 1, wherein the mass ratio of the elemental sulfur converting agent, the binder and the elemental sulfur powder is (5-10): (10-20): (70-85).
4. The biological filler according to any one of claims 1 to 3, wherein the elemental sulphur converting agent further comprises pyrrhotite;
optionally, the particle size D50 of the pyrrhotite is 0.2 to 0.5mm.
5. The biological filler according to claim 4, wherein the mass ratio of the elemental sulfur converting agent, the pyrrhotite, the binder and the elemental sulfur powder is (5-10): (20-30): (10-20): (40-65).
6. The biological filler according to any one of claims 1 to 3 and 5, characterised in that it comprises spherical particles with a diameter of 8 to 10 mm.
7. A method for preparing a biological filler according to any one of claims 1 to 6, characterised in that it comprises the following steps:
mixing elemental sulfur transforming agent, adhesive and elemental sulfur, and adding solvent to prepare composite material sticky matter;
and granulating the composite material sticky substance to obtain the biological filler.
8. The method for preparing the biological filler according to claim 7, wherein the step of granulating the composite material paste comprises:
placing the composite material sticky object in a granulation mould, and carrying out vacuum drying;
optionally, the vacuum drying is performed while satisfying at least one of the following conditions:
(1) The temperature of vacuum drying is 60-80 ℃;
(2) The vacuum drying time is 4-6 h.
9. Use of a biological filler as defined in any one of claims 1 to 6 in the preparation of a denitrification agent for the treatment of nitrate in water.
10. A method for removing nitrate in water is characterized by comprising the following steps:
placing the biological filler as defined in any one of claims 1 to 6 in a packed bed reactor, adding sulfur-oxidizing bacteria liquid for inoculation;
and after the surface of the biological filler is provided with the biological film, introducing water quality to be treated into the packed bed reactor to remove nitrate in the water quality to be treated.
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