CN117105405A - Composite sulfur autotrophic denitrification filler and preparation method thereof - Google Patents
Composite sulfur autotrophic denitrification filler and preparation method thereof Download PDFInfo
- Publication number
- CN117105405A CN117105405A CN202311084158.7A CN202311084158A CN117105405A CN 117105405 A CN117105405 A CN 117105405A CN 202311084158 A CN202311084158 A CN 202311084158A CN 117105405 A CN117105405 A CN 117105405A
- Authority
- CN
- China
- Prior art keywords
- sulfur
- tourmaline
- filler
- autotrophic denitrification
- sublimed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 73
- 239000011593 sulfur Substances 0.000 title claims abstract description 73
- 230000001651 autotrophic effect Effects 0.000 title claims abstract description 48
- 239000000945 filler Substances 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011032 tourmaline Substances 0.000 claims abstract description 44
- 229940070527 tourmaline Drugs 0.000 claims abstract description 44
- 229910052613 tourmaline Inorganic materials 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 11
- 238000005469 granulation Methods 0.000 claims abstract description 4
- 230000003179 granulation Effects 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000008187 granular material Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 230000008569 process Effects 0.000 abstract description 16
- 239000006185 dispersion Substances 0.000 abstract description 6
- 230000033228 biological regulation Effects 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 16
- 244000005700 microbiome Species 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 241000894006 Bacteria Species 0.000 description 8
- 239000010865 sewage Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 102000004190 Enzymes Human genes 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 241001509286 Thiobacillus denitrificans Species 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000004060 metabolic process Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012762 magnetic filler Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 230000014233 sulfur utilization Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- C02F3/2806—Anaerobic processes using solid supports for microorganisms
-
- 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
- C02F3/005—Combined electrochemical biological processes
-
- 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
- C02F3/342—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the enzymes used
-
- 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
- C02F3/348—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the way or the form in which the microorganisms are added or dosed
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Chemical & Material Sciences (AREA)
- Water Supply & Treatment (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Biodiversity & Conservation Biology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Molecular Biology (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The invention relates to a composite sulfur autotrophic denitrification filler and a preparation method thereof. According to the preparation method, sublimed sulfur and tourmaline are subjected to ultrasonic dispersion, mixing and granulation in a sulfur melting state, the dispersion is uniform, the process is simple, the regulation and control are convenient, the obtained product has a good denitrification effect, the treatment load is improved, the pH value of a water sample is stable, and the method can be applied to the field of water treatment.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a composite sulfur autotrophic denitrification filler and a preparation method thereof.
Background
Among the various criteria, removal of total nitrogen is most difficult. If the requirements of higher drainage standards are met, advanced treatment of denitrification is needed, and even limiting denitrification is needed.
The existing deep denitrification technology mainly uses heterotrophic denitrification, a large amount of organic carbon sources are consumed, and meanwhile, the carbon sources are added in a large amount, so that conditions of penetration of the carbon sources, excessive mud production and the like can be caused, secondary pollution is caused to the environment, and therefore, the novel sulfur autotrophic denitrification technology is regarded as a technology capable of replacing the heterotrophic denitrification and is gradually valued.
The sulfur autotrophic denitrification process is a denitrification process for reducing NOx-N into nitrogen by using inorganic carbon sources under the action of autotrophic denitrifying bacteria, taking reducing sulfides (such as sodium sulfide, sodium thiosulfate, elemental sulfur, pyrite and the like) as electron donors, and taking nitrate nitrogen or nitrite nitrogen in sewage as electron acceptors.
In a sulfur autotrophic denitrification process with elemental sulfur as an electron donor, elemental sulfur filler is the core material of the process. On the one hand, compared with the heterotrophic denitrification process using an organic carbon source as an electron donor, the simple substance sulfur is used as a relatively low-cost industrial product, has lower price than the conventional organic carbon source, and can greatly reduce the operation cost of deep denitrification. On the other hand, the sulfur autotrophic denitrification process does not use an organic carbon source, does not have the risk of penetration of the carbon source, does not generate a large amount of excess sludge, and greatly reduces the potential risk of municipal sewage plants, so that the sulfur autotrophic denitrification process has wider application in recent years. However, sulfur autotrophic denitrification is a process of producing acid and consuming alkalinity, and the pH value of water is in a descending trend in the running process; the optimal pH range of the autotrophic denitrification of the elemental sulfur is 6.8-8.2; the scholars found that the sulfur autotrophic denitrification reaction would result in a pH below 5.5 without additional alkalinity, which severely affected the denitrification reaction. The insolubility of the sulfur simple substance in water further influences the utilization rate of sulfur by microorganisms, so that the autotrophic denitrification of sulfur is difficult to be suitable for high-load denitrification deep treatment. Those skilled in the art have made a number of modifications thereto, but they still have drawbacks.
For example, patent document CN116332343a discloses a sulfur autotrophic denitrification sulfur-based magnetic filler, a preparation method and application thereof. The sulfur-based magnetic filler comprises sulfur-containing sludge, biomass, a slow-release inorganic carbon source, an alkaline substance, a metal load, a magnetic material, an adhesive and the like, and has a complex formula. Patent document CN113697950B discloses a sulfur autotrophic denitrification matrix for biological denitrification and a method for using the same, wherein a buffer used in the matrix is calcium carbonate or magnesium carbonate, released calcium and magnesium ions can be recombined with alkalinity in water to form a precipitate, and the autotrophic denitrification reaction can be further inhibited. The sulfur autotrophic filler provided in patent document CN116143281a comprises a porous carrier and elemental sulfur; elemental sulfur is supported on the porous carrier; the porous carrier is mainly prepared from nano calcium carbonate, a binder and a pore-forming agent. However, nano calcium carbonate is used as an alkalinity providing component, and calcium ions have adverse effects on sulfur utilization by microorganisms when calcium carbonate deposits are formed again on the surface.
Disclosure of Invention
Based on the above, in order to solve at least one technical problem in the prior art, the invention provides a composite sulfur autotrophic denitrification filler and a preparation method thereof, so as to improve the sulfur utilization rate, eliminate the adverse effect of the traditional alkalinity buffer calcium carbonate and improve the bacterial activity.
A composite sulfur autotrophic denitrification filler comprises tourmaline and sublimed sulfur.
The sulfur autotrophic denitrification filler is selected from tourmaline and sublimed sulfur to be matched, on one hand, tourmaline can spontaneously generate a micro electric field, the micro electric field can reduce the association degree of water molecules and reduce water molecule clusters, and small molecule clusters are easily absorbed and utilized by cells, so that the metabolism of microorganisms and the enzyme activity of the thiobacillus denitrificans are enhanced. In addition, the method can promote bacteria to produce Extracellular Polymers (EPS) and promote the transfer of sulfur in water, and on the other hand, due to the large specific surface area of sublimed sulfur, the method is easier to cooperate with tourmaline, thereby achieving the effect of improving the utilization rate of the sulfur by microorganisms and the treatment load of the sulfur autotrophic denitrification process.
In one embodiment, the mass ratio of the sublimated sulfur to the tourmaline is (9-7) to (1-3).
In one embodiment, the filler particle size is 3 to 6mm.
In one embodiment, the tourmaline is a ferroelectric tourmaline.
The invention also provides a preparation method of the composite sulfur autotrophic denitrification filler, which comprises the following steps,
s1: heating sublimed sulfur to a molten state;
s2: adding tourmaline into sublimed sulfur in a molten state;
s3: performing ultrasonic dispersion on the mixture of sublimed sulfur and tourmaline;
s4: granulating to obtain the composite sulfur autotrophic denitrification filler.
According to the preparation method, sublimated sulfur and tourmaline are mixed and granulated in a sulfur melting state, so that the raw materials are uniformly dispersed, and the product performance is better.
In one embodiment, the S1-S4 steps are all performed under the condition that sublimed sulfur is heated to 160-170 ℃ in a molten state, so that the sulfur can keep a good fluidity state, and the sulfur is favorable for dispersion.
In one embodiment, in the step S1, the sublimed sulfur particle diameter is less than or equal to 50 micrometers; in the step S2, the particle size of tourmaline is less than or equal to 15 micrometers, the mass ratio of sublimated sulfur to tourmaline is (9-7): (1-3), and the obtained filler has better nitration performance.
In one embodiment, in the step S3, the ultrasonic time is 10-30min, the ultrasonic input power is 20-50W/L, and the dispersion effect is good.
In one embodiment, in the step S4, a water-cooled granulator is used for granulation.
In one embodiment, in the step S4, the particle size of the filler after the granulation is 3 to 6mm.
Compared with the prior art, the invention has the following beneficial effects:
(1) The electrical property of tourmaline can enhance the metabolism of microorganisms and the enzyme activity of thiobacillus denitrificans, and can also promote bacteria to produce Extracellular Polymers (EPS) and promote the transmission of sulfur in water;
(2) The tourmaline has the function of stably regulating the pH value of the sewage, can ensure that the sewage is stable near neutrality for a long time, and does not generate extra hardness ions;
(3) Because the sublimed sulfur has large specific surface area, the sublimed sulfur is easier to cooperate with tourmaline, thereby improving the utilization rate of microorganisms on sulfur and improving the treatment load of the sulfur autotrophic denitrification process;
the preparation method of the sulfur autotrophic denitrification filler has the advantages of simple process, convenient regulation and control, uniform dispersion of the obtained product, good denitrification effect, improved treatment load and stable pH value of the water sample, and can be applied to the field of water treatment.
Drawings
FIG. 1 is a schematic diagram of a composite sulfur autotrophic denitrification filler according to an embodiment of the present invention;
FIG. 2 is a graph showing the denitrification effect of the examples of the present invention and the comparative examples.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended 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 herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The examples do not identify specific experimental procedures or conditions, which may be followed by routine experimental procedures or conditions described in the literature in this field; the materials used in the preparation process are conventional reagent products which are commercially available.
Example 1
A composite sulfur autotrophic denitrification filler,
raw materials: 900g of sublimed sulfur (particle size is less than or equal to 50 microns), 100g of ferroelectric stone powder (particle size is less than or equal to 15 microns),
the preparation method comprises the following steps:
s1: heating sublimed sulfur to 160 ℃ to be in a molten state;
s2: adding tourmaline into sublimed sulfur in 160 deg.c molten state;
s3: performing ultrasonic dispersion on the mixture of sublimed sulfur and tourmaline at 160 ℃, wherein the ultrasonic power is 30W/L, and the ultrasonic dispersion is performed for 30min;
s4: granulating by adopting a water-cooled granulator to obtain the composite sulfur autotrophic denitrification filler, wherein the particle size is 3-6 mm, and the finished product is shown in figure 1.
Example 2
A composite sulfur autotrophic denitrification filler,
raw materials: 800g of sublimed sulfur (particle size is less than or equal to 50 microns), 200g of ferroelectric stone powder (particle size is less than or equal to 15 microns),
the preparation method comprises the following steps:
s1: heating sublimated sulfur to 170 ℃ to be in a molten state;
s2: adding tourmaline into sublimed sulfur in 170 ℃ molten state;
s3: performing ultrasonic dispersion on the mixture of sublimed sulfur and tourmaline at 170 ℃ with ultrasonic power of 20W/L for 25min;
s4: granulating by adopting a water-cooled granulator to obtain the composite sulfur autotrophic denitrification filler, wherein the particle size is 3-6 mm.
Example 3
A composite sulfur autotrophic denitrification filler,
raw materials: 700g of sublimed sulfur (particle size is less than or equal to 50 microns), 300g of ferroelectric stone powder (particle size is less than or equal to 15 microns),
the preparation method comprises the following steps:
s1: heating sublimed sulfur to 160 ℃ to be in a molten state;
s2: adding tourmaline into sublimed sulfur in 160 deg.c molten state;
s3: performing ultrasonic dispersion on the mixture of sublimed sulfur and tourmaline at 160 ℃, wherein the ultrasonic power is 30W/L, and the ultrasonic dispersion is performed for 10min;
s4: granulating by adopting a water-cooled granulator to obtain the composite sulfur autotrophic denitrification filler, wherein the particle size is 3-6 mm.
Comparative example 1
A denitrification filler, which is characterized in that,
raw materials: 900g of sublimed sulfur (particle size is less than or equal to 50 microns), 100g of calcium carbonate (particle size is less than or equal to 15 microns),
the preparation method comprises the following steps:
s1: heating sublimed sulfur to 160 ℃ in a molten state;
s2: adding calcium carbonate into sublimed sulfur in a 160 ℃ molten state;
s3: performing ultrasonic dispersion on the mixture of sublimed sulfur and calcium carbonate at 160 ℃, wherein the ultrasonic power is 30W/L, and the ultrasonic dispersion is performed for 30min;
s4: granulating by adopting a water-cooled granulator, wherein the grain diameter is 3-6 mm.
Comparative example 2
A denitrification filler, which is characterized in that,
raw materials: 900g of sublimed sulfur (particle size is less than or equal to 50 microns), 100g of ferroelectric stone powder (particle size is less than or equal to 15 microns),
the preparation method comprises the following steps:
s1: heating sublimated sulfur to 170 ℃ to be in a molten state;
s2: adding tourmaline into sublimed sulfur in 170 ℃ molten state;
s3: stirring the sublimated sulfur and tourmaline mixture at 170deg.C for 30min;
s4: granulating by adopting a water-cooled granulator to obtain the composite sulfur autotrophic denitrification filler, wherein the particle size is 3-6 mm.
The samples obtained in the examples and comparative examples were placed in a 5L volume biofilter, respectively, and run in continuous flow with an influent nitrate nitrogen of 15mg/L and a phosphate of 2mg/L using artificial simulated wastewater as the experimental wastewater. Taking anaerobic tank sludge of municipal sewage plants as inoculation, wherein the initial residence time of a bed layer is 1h, gradually reducing, and testing the load limit; during the experiment, nitrogen was purged with water twice a day for 20min each. The addition amount of nitrate nitrogen in the artificial simulated wastewater is 15mg/L, no additional inorganic carbon source is added, and the dissolved oxygen is controlled below 1 mg/L; and taking a water sample every day to detect nitrate nitrogen, pH and hardness indexes. The experiment is based on the condition that the nitrate nitrogen in the effluent is lower than 2mg/L, the average pH and hardness indexes of the water inlet and outlet of each example and the comparative example are shown in table 1, and the nitrate nitrogen removal effect is shown in figure 2.
Table 1 pH and hardness values of the Inlet and outlet waters of examples and comparative examples
As can be seen from fig. 2, in the initial film forming stage, examples 1, 2 and 3 can realize that the nitrate nitrogen in the effluent is stably lower than 2mg/L on the 7 th day, while comparative example 1 can meet the requirement that the nitrate nitrogen in the effluent is stably lower than 2mg/L on the 14 th day, which indicates that the rapid film forming of the sulfur autotrophic bacteria is facilitated under the activation of the tourmaline micro electric field.
The ultrasonic dispersion can lead tourmaline to generate piezoelectric effect, the surface of tourmaline powder has repulsive electric property, which is beneficial to more uniform dispersion of powder, while the piezoelectric effect of tourmaline cannot be activated because of common mechanical stirring in the preparation process, thus the tourmaline of comparative example 2 is not uniformly distributed, the activation effect on sulfur autotrophic bacteria is insufficient, and the starting period is slightly longer than that of example 1, but shorter than that of comparative example 1.
After the film forming operation is stable, the average removal rate of nitrate nitrogen in each example and the comparative example is about 95% under the condition that the retention time of the filling area is 60 min. It is shown that the denitrification effect of the two experimental groups is not very different in the case of a sufficient residence time.
When the retention time of the filler is shortened to 45min, the nitrate nitrogen in the effluent of the experimental groups of the comparative example 1 and the comparative example 2 rises, the average removal rate of the nitrate nitrogen of the comparative example 1 and the comparative example 2 is respectively reduced to 85 and 91%, and the examples have no obvious change; when the retention time of the filler was further shortened to 30min, the effluent nitrate nitrogen of the experimental groups of comparative examples 1 and 2 was continuously increased, the nitrate nitrogen removal rate was further reduced to 72% and 78%, the nitrate nitrogen removal rate of example 1 was not significantly changed, the nitrate nitrogen removal rate of example 2 and example 3 was slightly reduced (example 2:89%; example 3: 90%), indicating that the reduction in the sublimated sulfur ratio reduced the contact probability of elemental sulfur with sulfur autotrophic bacteria, thereby affecting the treatment load, but the nitrate nitrogen removal rate of example 2 and example 3 was still higher than that of comparative example.
Experimental results show that the composite sulfur autotrophic denitrification filler provided by the embodiment of the invention has the effect of improving the utilization rate of microorganisms on sulfur, and can realize high-load denitrification reaction. The tourmaline has piezoelectric effect and pyroelectric effect, and generates surface charge when temperature and pressure change, and spontaneously generates micro electric field, so that the association degree of water molecules can be reduced, water molecule clusters are reduced, and small molecule clusters are easily absorbed and utilized by cells, thereby enhancing metabolism of microorganisms and enzyme activity of thiobacillus denitrificans. In addition, the method can promote bacteria to produce Extracellular Polymers (EPS) and promote the transmission of sulfur in water, and on the other hand, the sublimed sulfur has large specific surface area and is easier to be matched with tourmaline, so that the effect of improving the utilization rate of the sulfur by microorganisms and the treatment load of the sulfur autotrophic denitrification process is achieved.
On the other hand, as can be seen from the combination of Table 1, the hardness of the effluent of example 1 is not changed basically, while the average hardness of the effluent of comparative example 1 is increased from the initial 23mg/L to 195mg/L, which indicates that the neutralization reaction between calcium carbonate and acid occurs, so that hardness ions overflow, and the risk of secondary pollution is increased.
In summary, it can be seen that the sulfur autotrophic denitrification filler in the embodiment of the invention has the following beneficial effects that the existing filler containing calcium carbonate is improved, tourmaline and sublimated sulfur which is uniformly mixed with the tourmaline are selected, and the filler has the following advantages:
(1) The electrical property of tourmaline can enhance the metabolism of microorganisms and the enzyme activity of thiobacillus denitrificans, and can also promote bacteria to produce Extracellular Polymers (EPS) and promote the transmission of sulfur in water;
(2) The tourmaline has the function of stably regulating the pH value of the sewage, can ensure that the sewage is stable near neutrality for a long time, and does not generate extra hardness ions;
(3) Because the sublimed sulfur has large specific surface area, the sublimed sulfur is easier to cooperate with tourmaline, thereby improving the utilization rate of microorganisms on sulfur and improving the treatment load of the sulfur autotrophic denitrification process;
the preparation method of the sulfur autotrophic denitrification filler has the advantages of simple process, convenient regulation and control, uniform dispersion of the obtained product, good denitrification effect, improved treatment load and stable pH value of the water sample, and can be applied to the field of water treatment.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A composite sulfur autotrophic denitrification filler is characterized in that the filler comprises tourmaline and sublimed sulfur.
2. The composite sulfur autotrophic denitrification filler according to claim 1, wherein the mass ratio of sublimed sulfur to tourmaline is (9-7): 1-3.
3. The composite sulfur autotrophic denitrification filler according to claim 1, wherein the filler has a particle size of 3-6 mm.
4. A composite sulfur autotrophic denitrification filler according to any one of claims 1-3, wherein the tourmaline is a ferroelectric tourmaline.
5. A preparation method of a composite sulfur autotrophic denitrification filler is characterized by comprising the following steps,
s1: heating sublimed sulfur to a molten state;
s2: adding tourmaline into sublimed sulfur in a molten state;
s3: performing ultrasonic dispersion on the mixture of sublimed sulfur and tourmaline;
s4: granulating to obtain the composite sulfur autotrophic denitrification filler.
6. The method according to claim 5, wherein the S1-S4 steps are performed under the condition that sublimed sulfur is heated to 160-170 ℃ in a molten state.
7. The method according to claim 5, wherein in the step S1, the sublimed sulfur particles have a diameter of 50 μm or less; in the step S2, the particle size of tourmaline is less than or equal to 15 microns, and the mass ratio of sublimated sulfur to tourmaline is (9-7): 1-3.
8. The method according to claim 5, wherein in the step S3, the ultrasonic time is 10-30min and the ultrasonic input power is 20-50W/L.
9. The method according to claim 5, wherein in the step S4, the granules are granulated by using a water-cooled granulator.
10. The method according to claim 5, wherein in the step S4, the particle size of the filler after granulation is 3 to 6mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311084158.7A CN117105405A (en) | 2023-08-25 | 2023-08-25 | Composite sulfur autotrophic denitrification filler and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311084158.7A CN117105405A (en) | 2023-08-25 | 2023-08-25 | Composite sulfur autotrophic denitrification filler and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117105405A true CN117105405A (en) | 2023-11-24 |
Family
ID=88812403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311084158.7A Pending CN117105405A (en) | 2023-08-25 | 2023-08-25 | Composite sulfur autotrophic denitrification filler and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117105405A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117550714A (en) * | 2023-12-21 | 2024-02-13 | 广东卓信环境科技股份有限公司 | Sulfur autotrophic denitrification filler |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229986A (en) * | 2014-09-05 | 2014-12-24 | 南开大学 | Method for improving reduction activity of anaerobic microbes by using electrical mineral |
| CN110078221A (en) * | 2019-04-23 | 2019-08-02 | 南京大学 | A kind of synchronous denitrification dephosphorizing light material and its preparation and application method |
| CN114573103A (en) * | 2022-04-01 | 2022-06-03 | 山东太平洋环保股份有限公司 | Preparation method and application of efficient denitrification composite filler |
| CN115417500A (en) * | 2022-09-29 | 2022-12-02 | 江西零真生态环境集团有限公司 | Sulfur autotrophic denitrification filler and preparation method thereof |
-
2023
- 2023-08-25 CN CN202311084158.7A patent/CN117105405A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229986A (en) * | 2014-09-05 | 2014-12-24 | 南开大学 | Method for improving reduction activity of anaerobic microbes by using electrical mineral |
| CN110078221A (en) * | 2019-04-23 | 2019-08-02 | 南京大学 | A kind of synchronous denitrification dephosphorizing light material and its preparation and application method |
| US20200338485A1 (en) * | 2019-04-23 | 2020-10-29 | Nanjing University | Method for preparing simultaneous nitrogen and phosphorus removal lightweight material and the use thereof |
| CN114573103A (en) * | 2022-04-01 | 2022-06-03 | 山东太平洋环保股份有限公司 | Preparation method and application of efficient denitrification composite filler |
| CN115417500A (en) * | 2022-09-29 | 2022-12-02 | 江西零真生态环境集团有限公司 | Sulfur autotrophic denitrification filler and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117550714A (en) * | 2023-12-21 | 2024-02-13 | 广东卓信环境科技股份有限公司 | Sulfur autotrophic denitrification filler |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Start-up and bacterial community compositions of partial nitrification in moving bed biofilm reactor | |
| CN110104760B (en) | Preparation and application method of calcium/magnesium carbonate powder material modified sulfur light material | |
| Yan et al. | Enhanced nitrogen removal in an aerobic granular sequencing batch reactor under low DO concentration: Role of extracellular polymeric substances and microbial community structure | |
| CN101054236A (en) | Denitrogenation method for nitrosation-anaerobic ammoxidation single stage organism | |
| Gao et al. | Biofilm carriers for anaerobic ammonium oxidation: Mechanisms, applications, and roles in mainstream systems | |
| Wei et al. | Enhanced aerobic granulation and nitrogen removal by the addition of zeolite powder in a sequencing batch reactor | |
| CN117105405A (en) | Composite sulfur autotrophic denitrification filler and preparation method thereof | |
| Shayegan et al. | The effect of influent COD and upward flow velocity on the behaviour of sulphate-reducing bacteria | |
| CN105217901A (en) | A kind of method of wastewater biochemical removing total nitrogen | |
| CN114573103A (en) | Preparation method and application of efficient denitrification composite filler | |
| CN113480002B (en) | Denitrifying denitrification biological filler and preparation method and application thereof | |
| Montalvo et al. | Autotrophic denitrification with sulfide as electron donor: Effect of zeolite, organic matter and temperature in batch and continuous UASB reactors | |
| Wang et al. | Impact of hydraulic retention time on swine wastewater treatment by aerobic granular sludge sequencing batch reactor | |
| Woo et al. | Removal of nitrogen from municipal wastewater by denitrification using a sulfur-based carrier: a pilot-scale study | |
| CN111470714A (en) | Environment-friendly recycling method for aquaculture wastewater | |
| CN114409065B (en) | Composite carbon source material and preparation method thereof | |
| Xu et al. | Effect of magnetic powder on denitrification using the sludge alkaline fermentation liquid as a carbon source | |
| Wang et al. | Fe-loaded biochar facilitates simultaneous bisphenol A biodegradation and efficient nitrate reduction: Physicochemical properties and biological mechanism | |
| CN114735831A (en) | Novel sulfur autotrophic and heterotrophic synergetic denitrification and denitrification material and preparation method thereof | |
| Shi et al. | Enhanced biological phosphorus and nitrogen removal by high-concentration powder carriers: extracellular polymeric substance, microbial communities, and metabolic pathways | |
| CN116813079A (en) | Biological composite filler for generating polysulfide to realize deep denitrification and preparation method thereof | |
| Jalali et al. | Rapid start-up and improvement of granulation in SBR | |
| Sharma et al. | Aerobic granulation in wastewater treatment: a general overview | |
| KR101179049B1 (en) | Nitrite removal processes from waters using sulfur-oxidizing denitrifying bacteria | |
| CN112723523A (en) | Carbon-source-free synchronous nitrogen and phosphorus removal filler based on composite sulfur component, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |