CN114291900A - Sulfur autotrophic denitrification particle and preparation method and application thereof - Google Patents
Sulfur autotrophic denitrification particle and preparation method and application thereof Download PDFInfo
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- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 177
- 239000011593 sulfur Substances 0.000 title claims abstract description 177
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 230000001651 autotrophic effect Effects 0.000 title claims abstract description 145
- 239000002245 particle Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 241000894006 Bacteria Species 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 23
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims abstract description 22
- 235000019345 sodium thiosulphate Nutrition 0.000 claims abstract description 22
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 17
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 61
- 238000006243 chemical reaction Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 16
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- 239000000661 sodium alginate Substances 0.000 claims description 11
- 235000010413 sodium alginate Nutrition 0.000 claims description 11
- 229940005550 sodium alginate Drugs 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
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- 230000000694 effects Effects 0.000 abstract description 9
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- 239000003673 groundwater Substances 0.000 description 6
- 239000004005 microsphere Substances 0.000 description 6
- 238000004065 wastewater treatment Methods 0.000 description 4
- 238000010170 biological method Methods 0.000 description 3
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- 230000000593 degrading effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- 239000011028 pyrite Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910021646 siderite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- 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 1
- 238000007664 blowing Methods 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
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- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 238000000053 physical method Methods 0.000 description 1
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- Biological Treatment Of Waste Water (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The invention relates to a sulfur autotrophic denitrification particle and a preparation method and application thereof, wherein the sulfur autotrophic denitrification particle comprises the following raw materials: sulfur autotrophic denitrifying bacteria liquid, biological sulfur, sodium thiosulfate, active carbon and embedding agent. The prepared sulfur autotrophic denitrification particles have a porous structure and a large specific surface area, and are beneficial to removing nitrate; the sulfur autotrophic denitrification bacteria liquid, the biological sulfur, the sodium thiosulfate and the active carbon are fixedly embedded, the problem that the biological sulfur is difficult to fluidize in the sulfur autotrophic denitrification process is solved, the prepared sulfur autotrophic denitrification particles can be applied to a fluidized bed reactor, the denitrification rate is greatly improved, the floor area is reduced, and the activity and the hydraulic shock resistance of the sulfur autotrophic denitrification bacteria liquid are improved.
Description
Technical Field
The invention belongs to the technical field of treatment of underground water and drinking water, and particularly relates to a sulfur autotrophic denitrification particle, and a preparation method and application thereof.
Background
Due to the overuse of agricultural nitrogen fertilizers, nitrogen accumulates in large amounts in surface soils in the form of nitrates. And the nitrate in the surface water is promoted to be leached downwards due to rainfall and irrigation, so that the pollution of the underground water is caused. The problem of nitrate contamination of groundwater is a ubiquitous environmental problem, and therefore, nitrogen removal is an important process in wastewater treatment.
The biological method is to convert nitrate into nitrogen by adding organic or inorganic carbon source by using heterotrophic or autotrophic denitrifying microorganisms. Compared with physical methods and chemical methods, biological methods are widely researched and applied because of the fact that the biological methods can thoroughly remove nitrates, and have the advantages of mild reaction conditions, simple equipment, easy maintenance, low operation cost and the like.
CN107176702B discloses a sewage treatment method for enhancing synchronous nitrogen and phosphorus removal in a sulfur autotrophic denitrification process, which comprises the following steps: uniformly mixing pyrite, sulfur and siderite particles, adding the mixture into a reaction vessel, adding wastewater into the reaction vessel, then adding sulfur autotrophic denitrifying bacteria liquid, blowing protective gas into the mixed culture solution, covering and sealing the mixed culture solution, and carrying out autotrophic denitrification reaction. According to the treatment method, pyrite and sulfur are used as sulfur sources, siderite is used as a carbon source, the strain of the sulfur autotrophic denitrifying bacteria is strengthened, but an organic carbon source is required to be added, so that secondary pollution is easily caused, and the operation cost is increased.
Different from the traditional biological denitrification, the sulfur autotrophic denitrification is a novel denitrification technology which uses low-valence sulfur to replace a carbon source as an electron donor and realizes denitrification by autotrophic denitrification, does not need an additional carbon source, has low cost, does not have secondary pollution and the like, and becomes a hotspot in the denitrification field.
CN111484129A discloses a sulfur autotrophic denitrification filler, a preparation method and application thereof, wherein the sulfur autotrophic denitrification filler is prepared by uniformly mixing a sulfur-containing substance obtained by reducing phosphogypsum, ethyl cellulose, span 80 and sodium bicarbonate, then adding ethanol for dissolving and stirring to obtain a paste, pouring the paste into a mold, and drying and molding to obtain the sulfur autotrophic denitrification filler. But the filler is powdery, has large mass transfer resistance and is not beneficial to recycling.
Therefore, there is a need to develop a sulfur autotrophic denitrification granule with low cost, resistance to breakage and fast denitrification rate.
Disclosure of Invention
In order to solve the technical problems, the invention provides sulfur autotrophic denitrification particles and a preparation method and application thereof, the invention solves the problem that biological sulfur is difficult to fluidize in a sulfur autotrophic denitrification process, the prepared sulfur autotrophic denitrification particles can be applied to a fluidized bed reactor, the denitrification rate is greatly improved, the floor area is reduced, and meanwhile, the activity and the hydraulic shock resistance of sulfur autotrophic denitrification bacteria liquid are improved by burying the sulfur autotrophic denitrification bacteria liquid.
In order to achieve the technical effect, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a sulfur autotrophic denitrification granule, comprising the following raw materials: sulfur autotrophic denitrifying bacteria liquid, biological sulfur, sodium thiosulfate, active carbon and embedding agent.
In the invention, the sulfur autotrophic denitrification particles have a porous structure and a large specific surface area, can be directly used, and improve the hydraulic impact resistance of the sulfur autotrophic denitrification bacteria liquid.
As a preferable technical scheme of the invention, the embedding medium comprises polyethylene glycol, polyvinyl alcohol and sodium alginate.
Preferably, the sulfur autotrophic denitrification particles further comprise a solvent.
Preferably, the solvent comprises water.
Preferably, the sulfur autotrophic denitrification particles are based on a solvent, and the mass ratio of each component is as follows: 10-80 wt% of sulfur autotrophic denitrifying bacteria liquid, 10-70 wt% of biological sulfur, 10-20 wt% of sodium thiosulfate, 1-10 wt% of activated carbon, 0.1-50 wt% of polyethylene glycol, 0.1-50 wt% of polyvinyl alcohol and 0.1-20 wt% of sodium alginate.
The mass ratio of the sulfur autotrophic denitrifying bacteria liquid is 10 to 80 wt%, and may be, for example, 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, or 80 wt%, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
The mass ratio of the biological sulfur is 10 to 70 wt%, and may be, for example, 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, or 70 wt%, etc., but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
The mass ratio of the sodium thiosulfate is 10 to 20 wt%, and for example, it may be 10 wt%, 12 wt%, 14 wt%, 16 wt%, 18 wt%, or 20 wt%, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
The mass ratio of the activated carbon is 1 to 10 wt%, and may be, for example, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
The mass ratio of the polyethylene glycol is 0.1 to 50 wt%, and may be, for example, 0.1 wt%, 1 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt%, or 50 wt%, etc., but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
The polyvinyl alcohol may be contained in an amount of 0.1 to 50% by weight, for example, 0.1%, 1%, 10%, 20%, 30%, 40% or 50% by weight, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned numerical range are also applicable.
The sodium alginate is contained in an amount of 0.1 to 20 wt%, for example, 0.1 wt%, 1 wt%, 3 wt%, 5 wt%, 7 wt%, 10 wt%, 15 wt%, 18 wt%, or 20 wt%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned values are also applicable.
In a second aspect, the present invention provides a process for the preparation of a sulfur autotrophic denitrification granule according to the first aspect, comprising the steps of:
(1) mixing embedding agent and water, heating and dissolving to obtain gel;
(2) uniformly mixing sulfur autotrophic denitrifying bacteria liquid, biological sulfur, sodium thiosulfate, active carbon and the gel in the step (1) to obtain a mixed solution;
(3) and (3) dripping the mixed solution obtained in the step (2) into a cross-linking agent solution, carrying out cross-linking reaction, and washing to obtain the sulfur autotrophic denitrification particles.
As a preferred embodiment of the present invention, the heating temperature in the step (1) is 50 to 110 ℃ and may be, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ or 110 ℃ or the like, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
In a preferred embodiment of the present invention, the time for the crosslinking reaction in step (3) is 18 to 48 hours, for example, 18 hours, 20 hours, 22 hours, 24 hours, 26 hours, 28 hours, 30 hours, 32 hours, 34 hours, 36 hours, 38 hours, 40 hours, 42 hours, 44 hours, 46 hours, or 48 hours, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
As a preferred technical scheme of the invention, the cross-linking agent solution comprises a mixed solution of calcium chloride and boric acid.
Preferably, the calcium chloride solution has a mass concentration of 1-50%, for example, 1%, 10%, 20%, 30%, 40%, or 50%, etc., but is not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the boric acid solution has a mass concentration of 1 to 50%, for example, 1%, 10%, 20%, 30%, 40%, or 50%, etc., but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) mixing polyethylene glycol 0.1-50 wt%, polyvinyl alcohol 0.1-50 wt%, sodium alginate 0.1-20 wt% and water, and heating to dissolve at 50-110 deg.C to obtain gel;
(2) uniformly mixing 10-80 wt% of sulfur autotrophic denitrifying bacteria liquid, 10-70 wt% of biological sulfur, 10-20 wt% of sodium thiosulfate, 1-10 wt% of activated carbon and the gel in the step (1) to obtain a mixed solution;
(3) and (3) dripping the mixed solution obtained in the step (2) into a mixed solution of 1-50% of calcium chloride and 1-50% of boric acid, carrying out crosslinking reaction for 18-48h, and washing to obtain the sulfur autotrophic denitrification particles.
In the invention, the sulfur autotrophic denitrifying bacteria liquid, the biological sulfur, the sodium thiosulfate and the active carbon are embedded in the polyethylene glycol, the polyvinyl alcohol and the sodium alginate gel, and the density of the biological sulfur is 2.1g/cm3On the left and right sides, the massive sulfur can not be fluidized, and the powdered sulfur is easy to run off along with water; meanwhile, the prepared sulfur autotrophic denitrification particles do not need to be inoculated with a biofilm, can quickly start sulfur autotrophic denitrification, and greatly promote the application of sulfur autotrophic denitrification.
In a third aspect, the present invention provides a sulfur autotrophic denitrification process, comprising: a sulfur autotrophic fluidized bed reactor is used as a reaction tank body to carry out sulfur autotrophic denitrification on the underground water containing the nitrate.
The packing of the packing reaction zone of the sulfur autotrophic fluidized bed reactor comprises the sulfur autotrophic denitrification particles produced in the second aspect.
As a preferable technical scheme of the invention, a water inlet pipeline is arranged at the bottom of the sulfur autotrophic fluidized bed reactor.
Preferably, a water outlet pipeline is arranged at the top of the sulfur autotrophic fluidized bed reactor.
Preferably, the sulfur autotrophic fluidized bed reactor is provided with a packing reaction zone.
Preferably, the sulfur autotrophic fluidized bed reactor is provided with a circulating water pump.
As a preferred technical solution of the present invention, the method comprises: the method comprises the following steps: and (3) the underground water containing nitrate flows into the sulfur autotrophic fluidized bed reactor from the water inlet pipe, the sulfur autotrophic denitrification particles are fluidized by the circulating water pump and stay in the filler reaction zone, the underground water is subjected to denitrification degradation denitrification by the sulfur autotrophic denitrification particles, and the treated underground water flows out from the water outlet pipe.
In the present invention, the nitrate is used at a concentration of 30 to 70mg/L, for example, 30mg/L, 35mg/L, 40mg/L, 45mg/L, 50mg/L, 55mg/L, 60mg/L, 65mg/L or 70mg/L, but is not limited to the values listed above, and other values not listed above within the numerical range are also applicable.
In the present invention, the residence time is 2 to 10 hours, and for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours, etc., but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Compared with the prior art, the invention has the following beneficial effects:
(1) the sulfur autotrophic denitrification particles prepared by the invention have a porous structure and a large specific surface area, and the hydraulic impact resistance of the sulfur autotrophic denitrification bacteria liquid is improved;
(2) the preparation method has the advantages of low production cost, simple process, low energy consumption and good industrial application prospect;
(3) the invention solves the problem that biological sulfur is difficult to fluidize in the traditional sulfur autotrophic denitrification process, improves the speed of sulfur autotrophic denitrification, shortens the hydraulic retention time and effectively reduces the wastewater treatment cost.
Drawings
FIG. 1 is a sulfur autotrophic fluidized bed reactor in the sulfur autotrophic denitrification nitrogen removal method of the present invention;
FIG. 2 is a graph showing the nitrate nitrogen concentrations of influent and effluent water in the sulfur autotrophic denitrification nitrogen removal according to example 1 of the present invention;
FIG. 3 is a scanning electron micrograph (200 μm) of sulfur autotrophic denitrification particles prepared in example 1 of the present invention;
FIG. 4 is a scanning electron micrograph (50 μm) of sulfur autotrophic denitrification particles prepared in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The structure schematic diagram of the sulfur autotrophic fluidized bed reactor is shown in figure 1, and a water inlet pipeline is arranged at the bottom of the sulfur autotrophic fluidized bed reactor; and a water inlet pump is arranged on the water inlet pipeline.
And a water outlet pipeline is arranged at the top of the sulfur autotrophic fluidized bed reactor.
And a filler reaction zone is arranged in the middle of the sulfur autotrophic fluidized bed reactor.
The sulfur autotrophic fluidized bed reactor is provided with a circulating water pump.
Example 1
The embodiment provides a preparation method and application of sulfur autotrophic denitrification particles, wherein the preparation method comprises the following steps:
(1) mixing 10g of polyethylene glycol, 10g of polyvinyl alcohol, 20g of sodium alginate and 100g of water, heating and dissolving at 90 ℃ to obtain gel, and cooling to 25 ℃;
(2) uniformly mixing 50g of sulfur autotrophic denitrifying bacteria liquid, 30g of biological sulfur, 5g of activated carbon, 10g of sodium thiosulfate and the gel in the step (1) to obtain a mixed solution;
(3) dripping the mixed solution obtained in the step (2) into a mixed solution of 50% calcium chloride and 1% boric acid, carrying out crosslinking reaction for 24 hours, taking out the immobilized microspheres, and washing the immobilized microspheres with deionized water for multiple times to obtain the sulfur autotrophic denitrification particles;
(4) and (3) allowing the underground water containing 30mg/L of nitrate to flow into the sulfur autotrophic fluidized bed reactor from a water inlet pipe, fluidizing the sulfur autotrophic denitrification particles through a circulating water pump, staying for 2 hours in a filler reaction zone, denitrifying and degrading the underground water by the sulfur autotrophic denitrification particles for denitrification, and allowing the treated underground water to flow out of a water outlet pipe.
Example 2
The embodiment provides a preparation method of sulfur autotrophic denitrification particles, which comprises the following steps:
(1) mixing 50g polyethylene glycol, 0.1g polyvinyl alcohol, 1g sodium alginate and 100g water, heating and dissolving at 110 deg.C to obtain gel, and cooling to 25 deg.C;
(2) uniformly mixing 80g of sulfur autotrophic denitrifying bacteria liquid, 10g of biological sulfur, 1g of activated carbon, 20g of sodium thiosulfate and the gel in the step (1) to obtain a mixed solution;
(3) dripping the mixed solution obtained in the step (2) into a mixed solution of 20% calcium chloride and 30% boric acid, carrying out crosslinking reaction for 48 hours, taking out the immobilized microspheres, and washing the immobilized microspheres with deionized water for multiple times to obtain the sulfur autotrophic denitrification particles;
(4) and (2) allowing underground water containing 40mg/L nitrate to flow into the sulfur autotrophic fluidized bed reactor from a water inlet pipe, fluidizing the sulfur autotrophic denitrification particles through a circulating water pump, staying for 4 hours in a filler reaction zone, denitrifying and degrading the underground water by the sulfur autotrophic denitrification particles for denitrification, allowing the treated underground water to flow out of a water outlet pipe, and collecting generated nitrogen through a three-phase separator.
Example 3
The embodiment provides a preparation method of sulfur autotrophic denitrification particles, which comprises the following steps:
(1) mixing 0.1g polyethylene glycol, 50g polyvinyl alcohol, 1g sodium alginate and 100g water, heating and dissolving at 50 deg.C to obtain gel, and cooling to 25 deg.C;
(2) uniformly mixing 50g of sulfur autotrophic denitrifying bacteria liquid, 10g of biological sulfur, 10g of activated carbon, 15g of sodium thiosulfate and the gel in the step (1) to obtain a mixed solution;
(3) dripping the mixed solution obtained in the step (2) into a mixed solution of 1% calcium chloride and 50% boric acid, carrying out a crosslinking reaction for 18h, taking out the immobilized microspheres, and washing the immobilized microspheres with deionized water for multiple times to obtain the sulfur autotrophic denitrification particles;
(4) and (2) allowing groundwater containing 70mg/L of nitrate to flow into the sulfur autotrophic fluidized bed reactor from a water inlet pipe, fluidizing the sulfur autotrophic denitrification particles through a circulating water pump, staying for 8 hours in a filler reaction zone, denitrifying and degrading the groundwater by the sulfur autotrophic denitrification particles for denitrification, allowing the treated groundwater to flow out of a water outlet pipe, and collecting generated nitrogen through a three-phase separator.
Example 4
This example differs from example 3 only in that "10 g of the bio-sulfur" in step (2) was replaced with "5 g of the bio-sulfur", and the other conditions were the same as in example 1.
Example 5
This example differs from example 3 only in that "10 g of the bio-sulfur" in step (2) was replaced with "75 g of the bio-sulfur", and the other conditions were the same as in example 1.
Example 6
This example differs from example 3 only in that "50 g of the sulfur autotrophic denitrifying bacteria liquid" in step (2) was replaced with "8 g of the sulfur autotrophic denitrifying bacteria liquid", and the other conditions were the same as in example 1.
Example 7
This example differs from example 3 only in that "50 g of the sulfur autotrophic denitrifying bacteria liquid" in step (2) was replaced with "85 g of the sulfur autotrophic denitrifying bacteria liquid", and the other conditions were the same as in example 1.
Example 8
This example differs from example 3 only in that "10 g of activated carbon" in step (2) was replaced with "15 g of activated carbon", and the other conditions were the same as in example 1.
Example 9
This example differs from example 3 only in that "15 g of sodium thiosulfate" in step (2) was replaced with "7 g of sodium thiosulfate", and the other conditions were the same as in example 1.
Example 10
This example differs from example 3 only in that "15 g of sodium thiosulfate" in step (2) was replaced with "25 g of sodium thiosulfate", and the other conditions were the same as in example 1.
Comparative example 1
This comparative example differs from example 1 only in that 30g of biosulphur was not added in step (2) and the other conditions were the same as in example 1.
Comparative example 2
This comparative example differs from example 1 only in that 50g of the sulfur autotrophic denitrifying bacteria solution was not added in step (2), and the other conditions were the same as in example 1.
Comparative example 3
In the comparative example, 50g of sulfur autotrophic denitrifying bacteria liquid, 30g of biological sulfur, 1g of activated carbon and 10g of sodium thiosulfate are directly mixed to obtain the sulfur autotrophic denitrifying particles.
The sulfur autotrophic denitrification particles prepared in examples 1 to 10 and comparative examples 1 to 3 were applied to sulfur autotrophic denitrification nitrogen removal in a sulfur autotrophic fixed bed reactor, which was different from the sulfur autotrophic fluidized bed reactor only in that a circulating water pump was not provided and the other conditions were the same as those in the sulfur autotrophic fluidized bed reactor.
The water sample was filtered through a 0.45 μm filter membrane and tested. NO3 --N、NO2 --N was determined using a Headean chromatograph (ICS2000, USA). The eluent is KOH solution, the flow rate is 1.0mL/min, the concentration is 30mM, the sample injection amount is 20 μ L, and the determination time is 0-20 min.
Experimental data of the sulfur autotrophic denitrification particles prepared in examples 1 to 10 and comparative examples 1 to 3 applied to the sulfur autotrophic fluidized bed reactor and the sulfur autotrophic fixed bed reactor are shown in tables 1 and 2, respectively.
TABLE 1
TABLE 2
| NO of inlet water3 --N(mg/L) | NO of effluent3 --N(mg/L) | NO of effluent2 --N(mg/L) | |
| Example 1 | 30 | 15.07 | 0 |
| Example 2 | 40 | 22.32 | 0 |
| Example 3 | 70 | 25.62 | 0 |
| Example 4 | 70 | 46.64 | 5.638 |
| Example 5 | 70 | 23.62 | 3.628 |
| Example 6 | 70 | 60.38 | 3.3285 |
| Example 7 | 70 | 30.25 | 0.62 |
| Example 8 | 70 | 60.35 | 3.62 |
| Example 9 | 70 | 20.36 | 0.3581 |
| Example 10 | 70 | 21.68 | 0.62 |
| Comparative example 1 | 30 | 30 | 0 |
| Comparative example 2 | 30 | 30 | 0 |
| Comparative example 3 | 30 | 25.72 | 2.24 |
As can be seen from Table 1, the sulfur autotrophic denitrification particles prepared by the invention have good treatment effect on nitrate-containing groundwater and high sulfur autotrophic denitrification rate when being applied to a sulfur autotrophic fluidized bed reactor, and can reduce the wastewater treatment cost.
Examples 2 and 3 resulted in NO in the effluent due to higher nitrate concentration in the influent3 --N has a partial residue; the embedding amount of biological sulfur in example 4 is less, the embedding amount of the sulfur autotrophic denitrifying bacteria liquid in example 6 is less, and the embedding amount of the sodium thiosulfate in example 9 is less, and each componentThe concentration is low, the effect of the prepared sulfur autotrophic denitrification particles is reduced when the particles are applied to underground water treatment, and NO in effluent is caused3 --N has a residue; in example 5, the embedding amount of biological sulfur is high, in example 7, the embedding amount of the sulfur autotrophic denitrification bacteria liquid is high, in example 8, the embedding amount of activated carbon is high, in example 10, the embedding amount of sodium thiosulfate is high, the concentration of each component is high, the structure of the prepared sulfur autotrophic denitrification particles is damaged, and the effect is reduced when the particles are applied to groundwater treatment.
The sulfur autotrophic denitrification particles prepared by the comparative example 1 without embedded biological sulfur and the comparative example 2 without embedded sulfur autotrophic denitrification bacteria liquid have no treatment effect; in comparative example 3, only the sulfur autotrophic denitrifying bacteria liquid and the sulfur were mixed, and were not embedded and fixed, the treatment effect of the sulfur autotrophic denitrifying bacteria liquid that was not embedded was poor, resulting in NO in the effluent3 -The residue of-N is relatively high.
As can be seen from Table 2, the sulfur autotrophic denitrification particles prepared by the invention can also remove nitrate in underground water when being applied to a sulfur autotrophic fixed bed reactor, but the treatment effect is not as good as that of a sulfur autotrophic fluidized bed reactor.
As can be seen from figure 2, the sulfur autotrophic denitrification particles prepared by the method can remove nitrate in wastewater within 30min, have high sulfur autotrophic denitrification rate, can shorten hydraulic retention time, and effectively reduce wastewater treatment cost.
As can be seen from the graphs in FIGS. 3 to 4, the sulfur autotrophic denitrification particles prepared by the invention have porous structures on the surfaces and large specific surface areas, and are beneficial to the removal of nitrates.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The sulfur autotrophic denitrification particle is characterized by comprising the following raw materials: sulfur autotrophic denitrifying bacteria liquid, biological sulfur, sodium thiosulfate, active carbon and embedding agent.
2. The sulfur autotrophic denitrification particle of claim 1, wherein the embedding agent comprises polyethylene glycol, polyvinyl alcohol, and sodium alginate;
preferably, the sulfur autotrophic denitrification particles further comprise a solvent;
preferably, the solvent comprises water;
preferably, the sulfur autotrophic denitrification particles are based on a solvent, and the mass ratio of each component is as follows: 10-80 wt% of sulfur autotrophic denitrifying bacteria liquid, 10-70 wt% of biological sulfur, 10-20 wt% of sodium thiosulfate, 1-10 wt% of activated carbon, 0.1-50 wt% of polyethylene glycol, 0.1-50 wt% of polyvinyl alcohol and 0.1-20 wt% of sodium alginate.
3. A process for the preparation of the sulfur autotrophic denitrification particles according to claim 1 or 2, characterized in that it comprises the following steps:
(1) mixing embedding agent and water, heating and dissolving to obtain gel;
(2) uniformly mixing sulfur autotrophic denitrifying bacteria liquid, biological sulfur, sodium thiosulfate, active carbon and the gel in the step (1) to obtain a mixed solution;
(3) and (3) dripping the mixed solution obtained in the step (2) into a cross-linking agent solution, carrying out cross-linking reaction, and washing to obtain the sulfur autotrophic denitrification particles.
4. The method according to claim 3, wherein the heating temperature in the step (1) is 50 to 110 ℃.
5. The method according to claim 3 or 4, wherein the time for the crosslinking reaction in step (3) is 18 to 48 hours.
6. The production method according to any one of claims 3 to 5, wherein the crosslinking agent solution comprises a mixed solution of calcium chloride and boric acid;
preferably, the mass concentration of the calcium chloride solution is 1-50%;
preferably, the mass concentration of the boric acid solution is 1-50%.
7. The method according to any one of claims 4 to 6, characterized in that it comprises the following steps:
(1) mixing polyethylene glycol 0.1-50 wt%, polyvinyl alcohol 0.1-50 wt%, sodium alginate 0.1-20 wt% and water, and heating to dissolve at 50-110 deg.C to obtain gel;
(2) uniformly mixing 10-80 wt% of sulfur autotrophic denitrifying bacteria liquid, 10-70 wt% of biological sulfur, 10-20 wt% of sodium thiosulfate, 1-10 wt% of activated carbon and the gel in the step (1) to obtain a mixed solution;
(3) and (3) dripping the mixed solution obtained in the step (2) into a mixed solution of 1-50% of calcium chloride and 1-50% of boric acid, carrying out crosslinking reaction for 18-48h, and washing to obtain the sulfur autotrophic denitrification particles.
8. A sulfur autotrophic denitrification process, comprising: a sulfur autotrophic fluidized bed reactor is used as a reaction tank body to carry out sulfur autotrophic denitrification on the underground water containing the nitrate;
the packing of the packing reaction zone of the sulfur autotrophic fluidized bed reactor comprises the sulfur autotrophic denitrification particles produced according to any one of claims 4-7.
9. The sulfur autotrophic denitrification nitrogen removal method according to claim 8, wherein a water inlet pipe is provided at the bottom of the sulfur autotrophic fluidized bed reactor;
preferably, a water outlet pipeline is arranged at the top of the sulfur autotrophic fluidized bed reactor;
preferably, the sulfur autotrophic fluidized bed reactor is provided with a packing reaction zone;
preferably, the sulfur autotrophic fluidized bed reactor is provided with a circulating water pump.
10. The sulfur autotrophic denitrification process according to claim 8 or 9, wherein the process comprises: and (3) the underground water containing the nitrate flows into the sulfur autotrophic fluidized bed reactor from the water inlet pipeline, the sulfur autotrophic denitrification particles are fluidized by the circulating water pump and stay in the filler reaction zone, the underground water is subjected to denitrification degradation and denitrification by the sulfur autotrophic denitrification particles, and the treated underground water flows out from the water outlet pipeline.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115385522A (en) * | 2022-08-19 | 2022-11-25 | 浙江巨能环境工程有限公司 | Comprehensive treatment method for circulating cooling water in chemical industrial park |
| CN116715357A (en) * | 2023-08-11 | 2023-09-08 | 上海勘测设计研究院有限公司 | Composite filler, denitrification filter and denitrification method for sulfur autotrophic denitrification biological denitrification |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103723893A (en) * | 2014-01-10 | 2014-04-16 | 中国科学院生态环境研究中心 | Method for removing nitrate nitrogen from water |
| CN108913623A (en) * | 2018-07-23 | 2018-11-30 | 中国地质大学（北京） | A kind of preparation method of sulphur autotrophic denitrification bacteria immobilized particle |
| WO2019027377A1 (en) * | 2017-08-03 | 2019-02-07 | Hasan Kalyoncu Üni̇versi̇tesi̇ | Elemental sulfur-based mixotrophic denitrifying membrane bioreactor |
| CN110819564A (en) * | 2019-11-19 | 2020-02-21 | 云南大学 | Autotrophic denitrification and denitrification microbial inoculum and preparation method thereof |
| CN111072132A (en) * | 2020-01-09 | 2020-04-28 | 北京恩菲环保股份有限公司 | Sulfur-iron autotrophic denitrification suspended filler and preparation method thereof |
| CN111944799A (en) * | 2020-07-24 | 2020-11-17 | 河北科技大学 | Preparation method and application of immobilized particles embedded with thiobacillus denitrificans |
| CN111943351A (en) * | 2020-08-17 | 2020-11-17 | 河北科技大学 | Biological filler embedded with anthraquinone and thiobacillus denitrificans and sulfur autotrophic denitrification method |
-
2021
- 2021-12-31 CN CN202111662711.1A patent/CN114291900A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103723893A (en) * | 2014-01-10 | 2014-04-16 | 中国科学院生态环境研究中心 | Method for removing nitrate nitrogen from water |
| WO2019027377A1 (en) * | 2017-08-03 | 2019-02-07 | Hasan Kalyoncu Üni̇versi̇tesi̇ | Elemental sulfur-based mixotrophic denitrifying membrane bioreactor |
| CN108913623A (en) * | 2018-07-23 | 2018-11-30 | 中国地质大学（北京） | A kind of preparation method of sulphur autotrophic denitrification bacteria immobilized particle |
| CN110819564A (en) * | 2019-11-19 | 2020-02-21 | 云南大学 | Autotrophic denitrification and denitrification microbial inoculum and preparation method thereof |
| CN111072132A (en) * | 2020-01-09 | 2020-04-28 | 北京恩菲环保股份有限公司 | Sulfur-iron autotrophic denitrification suspended filler and preparation method thereof |
| CN111944799A (en) * | 2020-07-24 | 2020-11-17 | 河北科技大学 | Preparation method and application of immobilized particles embedded with thiobacillus denitrificans |
| CN111943351A (en) * | 2020-08-17 | 2020-11-17 | 河北科技大学 | Biological filler embedded with anthraquinone and thiobacillus denitrificans and sulfur autotrophic denitrification method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115385522A (en) * | 2022-08-19 | 2022-11-25 | 浙江巨能环境工程有限公司 | Comprehensive treatment method for circulating cooling water in chemical industrial park |
| CN115385522B (en) * | 2022-08-19 | 2024-05-14 | 浙江巨能环境工程有限公司 | Comprehensive treatment method for circulating cooling water in chemical industry park |
| CN116715357A (en) * | 2023-08-11 | 2023-09-08 | 上海勘测设计研究院有限公司 | Composite filler, denitrification filter and denitrification method for sulfur autotrophic denitrification biological denitrification |
| CN116715357B (en) * | 2023-08-11 | 2023-10-31 | 上海勘测设计研究院有限公司 | Composite filler, denitrification filter and denitrification method for sulfur autotrophic denitrification biological denitrification |
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