CN114620832B - Sulfur-based autotrophic microorganism denitrification material and preparation and application methods thereof - Google Patents
Sulfur-based autotrophic microorganism denitrification material and preparation and application methods thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2806—Anaerobic processes using solid supports for microorganisms
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/36—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing sulfur, sulfides or selenium
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/02—Selection of the hardening environment
- C04B40/0231—Carbon dioxide hardening
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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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- 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
- C02F2101/166—Nitrites
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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 discloses a sulfur-based autotrophic microorganism denitrification material and a preparation method and an application method thereof. The autotrophic nitrogen removal material is used as the filler of the anaerobic biological filter to construct a deep anaerobic biological filter bed, and can reduce the nitrate and nitrite nitrogen of 25mg/L to below 5mg/L at proper temperature for 40-60min, and the material replaces organic carbon sources such as sodium acetate and the like to denitrify and denitrify, thereby saving the denitrification cost by more than 50%.
Description
Technical Field
The invention relates to the technical field of environmental functional materials and sewage treatment, in particular to a preparation and application method of an autotrophic microorganism denitrification material.
Background
Nitrogen is one of the most important elements leading to eutrophication of water bodies, however, in the past the focus of attention in water treatment and surface water environments has been mainly the control of ammonia nitrogen. In recent years, as water eutrophication becomes more serious, particularly urban black and odorous rivers are widely developed, nitrate nitrogen and total nitrogen have been brought into pollution discharge and water control indexes, and stricter nitrogen control standards are formulated in various places.
The nitrification-heterotrophic denitrification is always a mainstream process technology for denitrification of wastewater, and is characterized in that organic nitrogen and ammonia nitrogen in the wastewater are converted into nitrate nitrogen through an aerobic process, then the wastewater is returned to an anoxic tank, and the nitrate nitrogen is converted into nitrogen through heterotrophic denitrification microorganisms by using organic matters in the wastewater as electron donors. The heterotrophic denitrification technology meets a plurality of barriers for reaching the stricter and stricter total nitrogen water quality standard of the drainage: firstly, a very high reflux ratio is needed to enable the total nitrogen to reach the emission standard, so that the energy consumption of water treatment is excessive and the water treatment is uneconomical; secondly, as the retention time of the wastewater in the septic tank and the drainage pipeline is long, partial carbon sources are consumed in the degradation process of microorganisms on organic matters, so that the carbon sources in the wastewater entering the sewage treatment plant are insufficient, the carbon-nitrogen ratio is too low, and the requirement of heterotrophic denitrification on organic carbon cannot be met; thirdly, under the condition of insufficient carbon source, an anaerobic biological filter is added after a secondary sedimentation tank at present, organic carbon is added to denitrify by means of heterotrophic denitrifying bacteria, but the addition of sodium acetate and other medicaments causes the problem of excessively high denitrification cost, the addition amount is not controlled in place, and the problem of secondary pollution caused by excessively high COD of effluent is caused.
In order to make up for the deficiency of heterotrophic denitrification and meet the requirement of advanced denitrification in water treatment, the sulfur autotrophic denitrification technology is rapidly developed as a representative autotrophic denitrification technology in recent years. Sulfur autotrophic denitrification is a facultative anaerobic microorganism such as thiobacillus denitrificans which utilizes inorganic carbon as a carbon source to complete anabolism, and simultaneously sulfur and a reducing sulfur compound (thiosulfate, sulfite and sulfide) are used as electron donors to reduce nitrate into nitrogen, wherein the denitrification by taking sulfur as the electron donor is the main direction of development. The sulfur autotrophic denitrification technology is widely focused by students at home and abroad because no additional carbon source is needed, has the advantages of abundant and low-cost sulfur resources, small mud production, low treatment cost and the like, and is a hot spot for research in the current denitrification field. In autotrophic denitrification process using sulfur as electron donor, water is acidified, and carbonate such as limestone is generally used as medium with stable pH. The existing sulfur-limestone autotrophic denitrification system is characterized in that limestone and elemental sulfur particles are mixed according to a certain proportion and then used as a filler, the filler is filled into a reaction filter column for sewage treatment, and the limestone is continuously dissolved in the treatment process, so that the reduction of pH is buffered. For example: patent CN201910887769.2 is a biological detention pond filler based on sulfur autotrophic denitrification, namely, sulfur particles and carbonate mineral quartz sand or crushed stone are mixed according to a proportion and filled into a filter pond for autotrophic microorganism denitrification. Patent CN202110289081.1, a denitrification material based on sulfur autotrophic denitrification, a preparation method and application thereof, wherein the denitrification material is obtained by heating and melting sulfur (35-65%), carbonate powder (25-50%), slow-release phosphorus material (5-15%) and foaming agent (0.5-5%) at 115-180 ℃, uniformly mixing, molding and cooling molding. Patent CN202010863127.1, a novel denitrification dephosphorization sulfur-based composite material and a preparation method thereof, is obtained by mixing and processing sulfur-rich solution, calcined dolomite, gypsum powder and siderite powder. The patent CN201910332916.X, a preparation method and application method of a calcium/magnesium carbonate powder material modified sulfur light material, wherein sulfur and calcium/magnesium carbonate powder are mixed and then melted at high temperature, then the melted mixture is foamed under stirring, and then the melted mixture is cooled and molded to obtain the light material. The existing sulfur-based denitrification material only considers the problem of neutralization of acid produced by oxidizing sulfur in the autotrophic microorganism denitrification process, so that a certain proportion of carbonate mineral is added into the sulfur particles and the composite material prepared by sulfur, and the pH of the system is stabilized within the acceptable range of microorganisms by neutralizing the sulfur to oxidize the acid. The existing sulfur autotrophic nitrogen removal material has the following outstanding problems:
(1) The existing sulfur-based sulfur autotrophic nitrogen removal material has a low nitrogen removal rate, so that the occupied land area of the treatment pool is overlarge. The electron transfer process of the interaction of sulfur and microorganisms for reducing nitrate nitrogen is needed, the sulfur belongs to insoluble solid substances, and the electron transfer between sulfur particles and microorganisms is a key factor for limiting the denitrification reaction speed and is also a root cause of low autotrophic denitrification speed of sulfur. The heterotrophic denitrification anaerobic biological deep filter with sodium acetate is usually added, the control requirements of nitrate nitrogen and total nitrogen can be stably met when the hydraulic retention time is 25-40min, and the hydraulic retention time of autotrophic denitrification of sulfur particles is more than 100 min. How to improve the biological reaction speed of the sulfur autotrophic denitrification material by the material preparation method, so that the hydraulic retention time of the denitrification reaction reaches or approaches to the hydraulic retention time of heterotrophic denitrification is a key technical problem which needs to be solved urgently at present.
(2) The sulfur autotrophic denitrification process is divided into two steps, nitrate is reduced to nitrite, and nitrite is reduced to nitrogen, which are respectively completed by different microorganisms. The sulfur autotrophic anammox microorganism is very sensitive to pH, the optimal pH is 7-7.5, and too high and too low pH can affect the denitrification reaction rate of the microorganism. Due to the difference of metabolic rates of nitrate-reducing microorganisms and nitrite-reducing microorganisms and the difference of sensitivity to pH, a biofilter constructed by sulfur particles and carbonate particles often has nitrite accumulation, thereby affecting denitrification efficiency. How to construct the material composition, structure and reactivity, and creating microenvironment which is favorable for microorganism attachment, proliferation and metabolism are key to the preparation of the material.
(3) The sulfur autotrophic nitrogen removal material is generally filled into the anaerobic nitrogen removal filter as particles, and how to prevent the filler from blocking is also the key of the water treatment operation. The current denitrification biological filter adopts regular back flushing to solve the blockage problem. But the back flushing process not only washes out the particles causing the blockage, but also causes the falling of the biological film, and the recovery of the biological film requires a certain period of time, which affects the water quality of the effluent in the recovery stage of the biological film. In addition, the density and strength of the sulfur particles are low, the density and strength difference between the sulfur particles and carbonate minerals is large, the back flushing is easy to cause abrasion and loss increase of the sulfur particles, and separation of the sulfur particles and carbonate particles is also caused.
Disclosure of Invention
The invention provides a sulfur-based autotrophic microorganism denitrification material and a preparation and application method thereof through a large number of static and dynamic denitrification experimental researches, so as to solve the problems existing in the prior art and provide materials and technical support for the application of sulfur autotrophic denitrification in the field of sewage treatment.
The technical scheme adopted by the invention is as follows:
a sulfur-based autotrophic microorganism denitrification material is characterized in that: the sulfur-based autotrophic microorganism denitrification material is a particulate matter obtained by mixing a sulfur-containing raw material with lime powder, and then melting, forming and surface carbonation. In the sulfur-based autotrophic microorganism denitrification material, the mass percentage of sulfur is not less than 70%, the mass percentage of lime is not less than 10%, and the material also contains a small amount of calcium carbonate, iron compounds and organic compounds.
The preparation method of the sulfur-based autotrophic microorganism denitrification material comprises the following steps:
step 1, uniformly mixing a sulfur-containing raw material and lime powder according to a dry basis mass ratio of 3-9:1 to obtain a mixed material;
step 2, adding the mixed material into a hopper of a forming machine, heating to 125-140 ℃ to melt sulfur, and enabling the mixed material to be in a viscous plastic flowing state; extruding the materials by a forming machine, cutting and cooling to obtain spherical or rod-shaped particles with the diameter of 2-50 mm;
or: heating and melting the mixed material, cooling the mixed material into blocks, and crushing the blocks into particles with the particle size of 2-50 mm;
step 3, spraying water to the surface of the particles obtained in the step 2, and introducing CO-containing gas 2 The calcium oxide on the surface of the particles is hydrated into calcium hydroxide, then the calcium hydroxide is carbonated into calcium carbonate, and finally the pH value of the aqueous solution for immersing the particles is not more than 10, thus obtaining the sulfur-based autotrophic microorganism denitrification material.
The phase composition of the sulfur-based autotrophic microorganism denitrification material comprises elemental sulfur, calcium hydroxide, calcium oxide, calcite, a small amount of ferro-manganese compound and organic matters; the bulk density of the sulfur-based autotrophic microorganism denitrification material is 0.8-1.3 g/cm 3 The stacking porosity is 40-60%.
The application method of the sulfur-based autotrophic microorganism denitrification material comprises the following steps:
(1) Uniformly mixing the sulfur-based autotrophic microorganism denitrification material with limestone particles or dolomite particles with the same particle size according to a mass ratio of 1-2:1 to obtain a biological filter filler; uniformly filling the filler into a biological filter for sewage treatment;
(2) Introducing nitrate-containing wastewater to be treated into a biological filter tank, and inoculating the nitrate-containing wastewater to the concentration>2*10 7 cfu/mL of thiobacillus denitrificans anaerobic microbial liquid, wherein the volume of the added microbial liquid is 0.1% -1% of the volume of pool water;
(3) The pond water is driven by a pump to circulate according to the hydraulic retention time of 2-6 h, and the anaerobic denitrification microorganism is promoted to form a film on the surface of the filler at the water temperature of more than 15 ℃; when the denitrification efficiency reaches more than 80%, the microbial film is mature, and normal operation is started;
(4) In normal operation, the hydraulic retention time parameter of the biological filter is 40-60min according to the requirements of water inlet and water discharge on nitrate nitrogen and total nitrogen.
Further, the effective thickness of the filler layer is designed to be larger than 2m in practical engineering application so as to ensure that the flow rate of the gaps in the filler layer meets the requirement.
Further, with the consumption of sulfur-based autotrophic microorganism denitrification materials, limestone or dolomite particles in the biological filter, the height of the filler layer is gradually reduced, and when the height of the filler layer is reduced by more than 10cm, the filler in the step (1) is added into the biological filter.
Compared with the prior art, the invention has the beneficial effects that:
(1) And (3) carbonating the surface after compounding sulfur and lime to construct a large-particle core-shell structure material with alkalinity gradient. The sulfur and lime are compounded to prepare the material through melting and carbonating, the particle size is adjustable, the particle strength is high, calcium hydroxide and calcium oxide exist in particles, strong alkalinity exists in the particles, and the surface of the particles is kept neutral due to carbonating. The strong alkalinity in the particles enhances the formation of polysulfide species and the release of sulfur dissolution into water, and improves the availability of sulfur and the electron transfer efficiency in the autotrophic microorganism denitrification process, so that the speed of reducing nitrate nitrogen and nitrite nitrogen by sulfur by the thiobacillus denitrificans can be greatly improved. In the biological filter, calcium hydroxide, calcium oxide and carbonate ions in water which are exposed on the surface of denitrification material particles due to reaction act, a thin calcite layer always exists, and a long-term stable pH value condition which is favorable for microbial metabolism denitrification is ensured to be maintained by a filler system in the water treatment process.
(2) The mechanical strength of the particles is improved by melt compounding of the sulfur and the lime, so that the particle material with the strength far greater than that of the pure sulfur particles and the sulfur sheets is obtained, and the strength requirement of the water treatment filler is met. Moreover, not only the sintering of sulfur and lime carbonation are relied on to form high-strength granular materials, but also the biological reaction activity is improved due to fusion compounding. The compounding of sulfur and lime powder on the micron scale is favorable for maintaining a pH microenvironment favorable for the proliferation and metabolism of the thiobacillus denitrificans on the micron scale, and the microenvironment more suitable for the attached growth and metabolism denitrification of denitrifying microorganisms is formed. Compared with sulfur particles and the composite material of the sulfur particles and carbonate, the denitrification reaction rate of the material is greatly improved.
(3) Solves the problem of blockage of a filler layer of the biological filter, and omits frequent back flushing and negative effects thereof. The main components of the material of the invention are elemental sulfur, calcium hydroxide, calcium oxide and calcite, and the minerals are all bioactive components in the denitrification process of sulfur autotrophic microorganisms, and SO is generated due to oxidation-reduction reaction and neutralization reaction 4 2- 、Ca 2+ Dissolved in water and lost in the denitrification process. The acid insoluble content of the selected lime and carbonate particulate matter raw materials is required to be less than 2%, so that the risk of blockage of a filter bed caused by accumulation of insoluble solid particulate matters is reduced. The prepared autotrophic nitrogen removal material has coarse particles (2-50 mm) and large inter-particle gaps, and the fine particles are dissolved and disappear preferentially due to the dissolution kinetic effect, so that the inter-particle gaps of the bed layer are continuously regenerated. In engineering application, the depth of the autotrophic denitrification biological bed is more than 2m, the hydraulic retention time is less than 40min, the inter-particle flow velocity is more than 5cm/min, the accumulation of suspended matters in particle gaps is eliminated, the blockage of the denitrification filter bed is avoided, and the back flushing and the negative problems caused by the back flushing are avoided. Experimental study shows that the sulfur-based autotrophic microorganism denitrification material is suitable for heterotrophic bacteria and sulfate reductionThe bacteria grow in an attached mode, and in the biological film biochemical reaction process taking thiobacillus as a main part, aged and dead microorganism residues can be degraded and utilized by microorganisms such as sulfate reduction and the like to form hydrogen sulfide which can be utilized by autotrophic denitrification microorganisms. This process avoids the accumulation of aged biofilm and also prevents clogging of the packing layer. The dynamic experimental column constructed by the material of the invention runs for 1 year, and the water outlet flow is not obviously changed, which indicates that the blocking phenomenon can not occur.
(4) The proper proportion and structure of the material components are optimized, the pH value of the stable system is in the optimum range, and the biological denitrification rate is improved. The characteristics of different acid reactivity and balanced pH values of dolomite and limestone are utilized, the sulfur-based autotrophic microorganism denitrification material is properly selected to be matched with limestone or dolomite for use according to different water qualities required to be denitrified, the matching proportion of the autotrophic denitrification composite material and the limestone or dolomite is regulated, and the pH value of the system is controlled to be stabilized in a range most suitable for the proliferation and metabolism of the thiobacillus denitrificans for a long time. For wastewater with high nitrate nitrogen and low COD, the acid production rate of sulfur oxide in the autotrophic microorganism denitrification process is high, and the calcite with high neutralization reaction rate is selected to be matched with the wastewater. For wastewater with low nitrate nitrogen and high COD, partial nitrate is heterotrophically denitrified and generates corresponding alkali, the acid production rate of autotrophic microorganism denitrification and oxidation sulfur is reduced, the amount of consumed carbonate for neutralization is correspondingly reduced, dolomite mineral with low neutralization reaction rate is selected to be matched with the waste water, and the ratio of the sulfur lime composite material to dolomite is properly improved when a filter tank is filled.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
The following raw materials were used in the examples below:
25kg of industrial sulfur is purchased, the purity is more than 95%, and no toxic or harmful substances are contained; industrial lime 25kg, acid insoluble matter in lime less than 5%. Collecting 25kg of limestone for metallurgy, crushing and screening to obtain 3-6mm particles, wherein the acid insoluble matters of the limestone are less than 5%. Collecting 25kg of dolomite for the flux, crushing and screening to obtain 3-6mm particles, wherein the content of dolomite acid insoluble matters is less than 2%.
Example 1
Uniformly mixing sulfur and lime powder according to a dry basis mass ratio of 8:1 to obtain a mixed material; adding the mixed material into a hopper of a forming machine, heating to 125-140 ℃ in the forming machine to melt sulfur, and enabling the mixed material to be in a viscous plastic flowing state; then, the material was extruded by a molding machine, cut, and cooled to obtain pellets having a diameter of about 5mm and a length of about 10 mm. And (3) placing the formed particles into a tray, spraying water to keep a continuous wetting state, and naturally carbonating in the air for 20 days, wherein the pH value of the particle soaking water solution is 6.8 according to the detection, so as to obtain the sulfur-based autotrophic microorganism denitrification material.
Uniformly mixing the prepared sulfur-based autotrophic microorganism denitrification material with limestone particles with the particle size of 3-6mm according to the mass ratio of 1:1, and filling the mixture into a dynamic column with the inner diameter of 10cm and the effective height of 50 cm; preparing 1L of simulated wastewater with nitrate nitrogen concentration of 100mg/L, TOC mg/L by tap water, removing dissolved oxygen by blowing nitrogen for 10min, and adding directionally enriched thiobacillus denitrificans bacterial liquid (bacterial liquid concentration)>2*10 7 cfu/mL) 50mL; driving water in the column to circulate according to the hydraulic retention time of 6h through a peristaltic pump, so as to promote anaerobic denitrification microorganisms to form a film on the surface of the filler; after the denitrification efficiency reaches more than 80%, the microbial biofilm is mature. Then, a long-term dynamic test is carried out by using simulated wastewater with the nitrate concentration of 25mg/L, TOC and 10mg/L, and the nitrate nitrogen concentration of the water outlet with the water temperature of more than 15 ℃ is less than 5mg/L and is far lower than the wastewater discharge standard.
Example 2
Uniformly mixing sulfur and lime powder according to a dry basis mass ratio of 7:1 to obtain a mixed material; adding the mixed material into a hopper of a forming machine, heating to 130-140 ℃ in the forming machine to melt sulfur, and enabling the mixed material to be in a viscous plastic flowing state; then, the material was extruded by a molding machine, cut, and cooled to obtain pellets having a diameter of about 5mm and a length of about 10 mm. And (3) placing the formed particles into a tray, spraying water to keep a continuous wetting state, and naturally carbonating in the air for 20 days, wherein the pH value of the particle soaking water solution is 6.8 according to the detection, so as to obtain the sulfur-based autotrophic microorganism denitrification material.
Uniformly mixing the prepared sulfur-based autotrophic microorganism denitrification material with dolomite particles with the particle size of 3-6mm according to the mass ratio of 2:1, and filling the mixture into a dynamic column with the inner diameter of 10cm and the effective height of 50 cm; preparing nitrate nitrogen concentration 100mg/L, TOC mg/L simulated wastewater 1L with tap water, blowing nitrogen gas to remove dissolved oxygen for 10min, adding directionally enriched thiobacillus denitrificans bacterial liquid (bacterial liquid concentration)>2*10 7 cfu/mL) 50mL; driving water in the column to circulate according to the hydraulic retention time of 6h through a peristaltic pump, so as to promote anaerobic denitrification microorganisms to form a film on the surface of the filler; after detecting that the denitrification efficiency reaches more than 80%, the microbial film is mature; then, carrying out long-term dynamic test by using simulated wastewater with nitrate concentration of 15mg/L, TOC =20mg/L, wherein the nitrate nitrogen concentration of the water outlet with the water temperature of more than 15 ℃ is less than 4mg/L and is far lower than the wastewater discharge standard.
The above description of the specific embodiments of the present invention has been given by way of example only, and the present invention is not limited to the above described specific embodiments. Any equivalent modifications and substitutions for the present invention will occur to those skilled in the art, and are also within the scope of the present invention. Accordingly, equivalent changes and modifications are intended to be included within the scope of the present invention without departing from the spirit and scope thereof.
Claims (5)
1. A sulfur-based autotrophic microorganism denitrification material is characterized in that: the sulfur-based autotrophic microorganism denitrification material is a particulate matter obtained by mixing a sulfur-containing raw material with lime powder, and then melting, forming and surface carbonation; the preparation method of the sulfur-based autotrophic microorganism denitrification material comprises the following steps:
step 1, uniformly mixing a sulfur-containing raw material and lime powder according to a dry basis mass ratio of 3-9:1 to obtain a mixed material;
step 2, adding the mixed material into a hopper of a forming machine, heating to 125-140 ℃ to melt sulfur, and enabling the mixed material to be in a viscous plastic flowing state; extruding the materials by a forming machine, cutting and cooling to obtain spherical or rod-shaped particles with the diameter of 2-50 mm;
or: heating and melting the mixed material, cooling the mixed material into blocks, and crushing the blocks into particles with the particle size of 2-50 mm;
step 3, spraying water to the surface of the particles obtained in the step 2, and introducing CO-containing gas 2 The calcium oxide on the surface of the particles is hydrated into calcium hydroxide, then the calcium hydroxide is carbonated into calcium carbonate, and finally the pH value of the aqueous solution for immersing the particles is not more than 10, thus obtaining the sulfur-based autotrophic microorganism denitrification material.
2. The sulfur-based autotrophic microbial denitrification material according to claim 1, wherein: in the sulfur-based autotrophic microorganism denitrification material, the mass percentage of sulfur is not less than 70%, and the mass percentage of lime is not less than 10%.
3. A method of using the sulfur-based autotrophic microorganism denitrification material as claimed in claim 1 or 2, comprising the steps of:
(1) Uniformly mixing the sulfur-based autotrophic microorganism denitrification material with limestone particles or dolomite particles with the same particle size according to a mass ratio of 1-2:1 to obtain a biological filter filler; uniformly filling the filler into a biological filter for sewage treatment;
(2) Introducing nitrate-containing wastewater to be treated into a biological filter tank, and inoculating the nitrate-containing wastewater to the concentration>2*10 7 cfu/mL of thiobacillus denitrificans anaerobic microbial liquid, wherein the volume of the added microbial liquid is 0.1% -1% of the volume of pool water;
(3) The pond water is driven by a pump to circulate according to the hydraulic retention time of 2-6 h, and the anaerobic denitrification microorganism is promoted to form a film on the surface of the filler at the water temperature of more than 15 ℃; when the denitrification efficiency reaches more than 80%, the microbial film is mature, and normal operation is started;
(4) In normal operation, the hydraulic retention time parameter of the biological filter is 40-60min according to the requirements of water inlet and water discharge on nitrate nitrogen and total nitrogen.
4. A method of application according to claim 3, characterized in that: the effective thickness of the filler layer is designed to be more than 2m in practical engineering application so as to ensure that the flow rate of the gaps in the filler layer meets the requirement.
5. A method of application according to claim 3, characterized in that: and (3) gradually reducing the height of the filler layer along with the consumption of the sulfur-based autotrophic microorganism denitrification material, limestone or dolomite particles in the biological filter, and supplementing the filler in the step (1) to the biological filter when the height of the filler layer is reduced by more than 10 cm.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0055967A1 (en) * | 1980-12-31 | 1982-07-14 | SOCIETE GENERALE POUR LES TECHNIQUES NOUVELLES S.G.N. Société anonyme dite: | Process and apparatus for the treatment of nitrogen compounds containing waste water |
| EP1419996A1 (en) * | 2002-11-05 | 2004-05-19 | Nippon Steel Chemical Co., Ltd. | Nitrate nitrogen denitrifying treatment material, method of producing the same, and method of removing nitrate nitrogen |
| JP2007044589A (en) * | 2005-08-08 | 2007-02-22 | Nippon Steel Chem Co Ltd | Waste water treatment method, and sulfur-containing denitrification material |
| US7455773B1 (en) * | 2007-08-14 | 2008-11-25 | Earth Renaissance Technologies, Llc | Package wastewater chemical/biological treatment method |
| CN109468307A (en) * | 2018-11-01 | 2019-03-15 | 上海水源地建设发展有限公司 | Immobilization microorganism particles and preparation method thereof and the method that black and odorous water is efficiently administered with immobilization microorganism particles |
| CN110104760A (en) * | 2019-04-24 | 2019-08-09 | 南京大学 | A kind of preparation of calcium/magnesium carbonate powder body material modified sulfur light material and its application method |
| CN212894081U (en) * | 2020-07-01 | 2021-04-06 | 泉州南京大学环保产业研究院 | Based on enhanced denitrification device of sulphur autotrophy denitrification |
Family Cites Families (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2455002A1 (en) * | 1979-04-23 | 1980-11-21 | Omnium Assainissement | Biological denitrification of water by autotrophic microorganisms - on substrate of a carbonate and a sulphur cpd. |
| EP1129996A4 (en) * | 1998-09-25 | 2004-04-21 | Nitchitsu Co Ltd | Denitrifying composition for removing nitrate nitrogen and process for producing the same |
| JP4474690B2 (en) * | 1998-11-09 | 2010-06-09 | Ｊｆｅスチール株式会社 | Porous stone for water purification and water purification method |
| WO2004031084A1 (en) * | 2002-09-30 | 2004-04-15 | Nippon Steel Chemical Co., Ltd. | Method of removing nitrate nitrogen and device used for the method |
| JP2004175848A (en) * | 2002-11-25 | 2004-06-24 | Taiho Ind Co Ltd | Biodegradable resin molding having denitrifying action |
| JP4608851B2 (en) * | 2003-06-10 | 2011-01-12 | 株式会社大林組 | Construction method of water purification structure |
| JP4517593B2 (en) * | 2003-06-17 | 2010-08-04 | 株式会社大林組 | Water purification jar |
| JP2007054732A (en) * | 2005-08-24 | 2007-03-08 | Clion Co Ltd | Sewage treatment material and its production method |
| JP2007075716A (en) * | 2005-09-14 | 2007-03-29 | Jfe Steel Kk | Method for sinking carbonated/solidified body in water |
| CN101269875A (en) * | 2007-03-23 | 2008-09-24 | 宝山钢铁股份有限公司 | Application of carbonatation steel scoria in wastewater treatment |
| CN101353201A (en) * | 2007-07-24 | 2009-01-28 | 宝山钢铁股份有限公司 | Novel wastewater treatment method |
| KR101009713B1 (en) * | 2010-11-04 | 2011-01-19 | 이상범 | Treatment method of food waste leachate by anaerobic digestion device |
| JP6274426B2 (en) * | 2013-04-15 | 2018-02-07 | 新日鉄住金エンジニアリング株式会社 | Method and apparatus for denitrification of nitrate nitrogen |
| KR20160010794A (en) * | 2014-07-18 | 2016-01-28 | 주식회사 루트제이제이 | Consolidation body for treating waste water |
| CN105621609B (en) * | 2016-04-05 | 2018-11-09 | 中国地质大学（北京） | A kind of autotrophic microbe denitrification method removes nitrate material in water removal |
| JP6935653B2 (en) * | 2016-12-14 | 2021-09-15 | 一般財団法人畜産環境整備機構 | Sulfur material for denitrification |
| CN106745718A (en) * | 2016-12-14 | 2017-05-31 | 云南大学 | The drop of effectively removal nitrate nitrogen filters technology and its device under a kind of nitrogen low-carbon (LC) environment high |
| CN208980406U (en) * | 2018-09-21 | 2019-06-14 | 中国科学院生态环境研究中心 | Autotrophic denitrification bio-carrier |
| CN109384309A (en) * | 2018-11-09 | 2019-02-26 | 深圳市市政设计研究院有限公司 | The method of waste water synchronous denitrification dephosphorizing |
| CN211999044U (en) * | 2019-08-22 | 2020-11-24 | 南京华创环境技术研究院有限公司 | Composite artificial wetland system for nitrogen and phosphorus removal |
| CN111547839A (en) * | 2020-04-07 | 2020-08-18 | 水艺控股集团股份有限公司 | Composite sulfur-based porous filler |
| CN112390380A (en) * | 2020-11-16 | 2021-02-23 | 合肥工业大学 | Functional material for removing nitrate nitrogen in water and preparation and application methods thereof |
| CN112978912B (en) * | 2021-05-06 | 2021-11-05 | 臻和慧联(浙江)环境科技有限公司 | Sewage treatment agent, autotrophic denitrification microorganism carrier and preparation method thereof |
| CN113860518A (en) * | 2021-11-03 | 2021-12-31 | 威海百克环保工程有限公司 | Sulfur autotrophic composite filter material and preparation method and application thereof |
| CN114634247A (en) * | 2022-04-15 | 2022-06-17 | 合肥工业大学 | Sulfur autotrophic nitrogen removal material prepared from sulfur paste or sulfur slag and preparation and application methods thereof |
-
2022
- 2022-04-15 CN CN202210399675.2A patent/CN114620832B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0055967A1 (en) * | 1980-12-31 | 1982-07-14 | SOCIETE GENERALE POUR LES TECHNIQUES NOUVELLES S.G.N. Société anonyme dite: | Process and apparatus for the treatment of nitrogen compounds containing waste water |
| EP1419996A1 (en) * | 2002-11-05 | 2004-05-19 | Nippon Steel Chemical Co., Ltd. | Nitrate nitrogen denitrifying treatment material, method of producing the same, and method of removing nitrate nitrogen |
| JP2007044589A (en) * | 2005-08-08 | 2007-02-22 | Nippon Steel Chem Co Ltd | Waste water treatment method, and sulfur-containing denitrification material |
| US7455773B1 (en) * | 2007-08-14 | 2008-11-25 | Earth Renaissance Technologies, Llc | Package wastewater chemical/biological treatment method |
| CN109468307A (en) * | 2018-11-01 | 2019-03-15 | 上海水源地建设发展有限公司 | Immobilization microorganism particles and preparation method thereof and the method that black and odorous water is efficiently administered with immobilization microorganism particles |
| CN110104760A (en) * | 2019-04-24 | 2019-08-09 | 南京大学 | A kind of preparation of calcium/magnesium carbonate powder body material modified sulfur light material and its application method |
| CN212894081U (en) * | 2020-07-01 | 2021-04-06 | 泉州南京大学环保产业研究院 | Based on enhanced denitrification device of sulphur autotrophy denitrification |
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