CN110002610B - Siderite modified sulfur light material and preparation method and application thereof - Google Patents
Siderite modified sulfur light material and preparation method and application thereof Download PDFInfo
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- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- 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
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Abstract
The invention discloses a siderite modified sulfur light material and a preparation method and application thereof, belonging to the technical field of environmental functional materials and sewage treatment. The siderite modified sulfur light material is prepared by mixing siderite and sulfur, heating for melting, foaming the obtained siderite and sulfur molten mixture in a physical foaming or chemical foaming mode, and cooling for forming. The siderite modified sulfur light material prepared by the invention has the characteristics of large specific surface area, light weight, high reaction activity, easy microorganism attachment, slow-release electron donor denitrification, iron ion dephosphorization and the like, can be used as a filler of a sewage treatment fluidized bed and a fixed bed reactor, and deeply removes pollutants such as nitrogen, phosphorus and the like in sewage through the action of microorganisms.
Description
Technical Field
The invention belongs to the technical field of environmental functional materials and sewage treatment, and particularly relates to a siderite modified sulfur light material, and a preparation method and application thereof.
Background
In recent years, environmental protection has become a focus of society, and countries invest a lot of funds to research, develop and apply environmental protection technologies. Wherein, the upgrading and reconstruction of the sewage treatment are performed as fiercely as possible, and various technologies are continuously emerged. However, these techniques have problems of high cost, limited effect, and consumption of a large amount of materials and energy when applied. With the deep research on siderite, the application value of siderite in the field of sewage denitrification is also explored.
The invention discloses a denitrification and dephosphorization material based on siderite and a using method thereof through retrieval and discovery of a Chinese patent application No. CN201410063868.6, wherein the application date is 2/25/2014. However, the efficiency of the invention in biological denitrification is limited due to the low rate of direct utilization of siderite by microorganisms.
Chinese patent application No. CN201710636553.X, filed 2017, 7 and 31 discloses a siderite/sulfur biofilter and a method for synchronously removing nitrate nitrogen and phosphorus in water by using the same, belonging to the field of sewage deep treatment. The method comprises the following steps: (1) preparing and constructing a biological filter filler; (2) starting the biological filter; (3) and (5) operating the biological filter. In the method, sulfur autotrophic denitrifying bacteria take sulfur as an electron donor to reduce nitrate radical in water into nitrogen gas and remove nitrate nitrogen in water; siderite provides an inorganic carbon source to support the autotrophic denitrification reaction and simultaneously releases iron ions for chemical phosphorus removal, thereby realizing the synchronous nitrogen and phosphorus removal of the filter tank. The biological filter has simple structure, convenient start, stable operation and high nitrogen and phosphorus removal efficiency, but siderite and sulfur particles have larger granularity and smaller specific surface area; siderite and sulfur are not uniformly distributed, which is not beneficial to the utilization of electron donors and inorganic carbon sources by microorganisms; the density difference between the siderite particles and the sulfur particles is large, the formed fixed bed has poor mass transfer and is not beneficial to back washing, thereby limiting the further improvement of the nitrogen and phosphorus removal efficiency.
Chinese patent application No. CN201811113486.4, the patent application document with the application date of 2018, 9, 21 discloses a nitrogen and phosphorus removal active biological carrier, a preparation method and application thereof, the nitrogen and phosphorus removal active biological carrier is formed by the prior sulfur and siderite through a physical process, the substrate is sulfur, a large amount of siderite particles are embedded in the surface and the inside, under the condition of not changing the composition, an integrated composite biological carrier with a novel structure is prepared, the sulfur in the novel structure can participate in the denitrification process to realize deep nitrogen removal, the siderite can assist in realizing the automatic regulation of pH, and the generated ferrous ions can be used for the removal of phosphorus and the denitrification process. However, the biological carrier still has the defects of large specific gravity, small specific surface area and unfavorable utilization of microorganisms.
In addition, the chinese patent application No. CN201410063868.6, filed on 2014, 25.2 discloses a nitrogen and phosphorus removal material based on siderite and a use method thereof, the preparation method is that siderite ore is crushed and sieved by a 40-mesh sieve, and porous granular material using siderite as a main body is obtained by adding a foaming agent according to a proper proportion of siderite ore powder, a bonding agent and a pore-forming agent or according to a proper proportion of siderite powder and the bonding agent, and the material has the characteristics of high granular strength, high void ratio, large specific surface area, large microorganism loading capacity and the like. The material is a carrier of microorganism, and is an electron donor of anaerobic microorganism and a dephosphorizing adsorbent. The fixed bed is filled to treat the wastewater in a filtering mode, anaerobic bacteria liquid mainly containing nitrate-dependent iron oxidizing bacteria is inoculated, the microorganisms reduce the nitrate into nitrogen by taking ferrous iron in the siderite as an electron donor under the anaerobic condition, the adsorption effect on phosphorus is enhanced, and the method is mainly used for synchronously removing nitrate nitrogen and phosphate from the wastewater. However, the anaerobic iron-oxidizing bacteria used in the invention have high requirements on the ecological environment, have poor viability competitiveness, are difficult to apply efficiently, and have complex whole operation flow.
Therefore, the need still exists for a sewage deep nitrogen and phosphorus removal technology with low energy consumption, low cost and high efficiency.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems that the denitrification and dephosphorization efficiency of a siderite-based denitrification and dephosphorization material in the prior sewage treatment technology is limited, the specific gravity is high, the siderite-based denitrification and dephosphorization material is not easy to be applied efficiently and the like, the siderite-modified sulfur light material is creatively provided, the mass of the material is reduced through high fusion of the sulfur and the siderite and foaming, the specific surface area of the material is greatly increased, more microorganisms are attached, the utilization rate of the microorganisms is increased, and the removal rate of nitrogen and phosphorus pollutants is increased.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention discloses a preparation method of a siderite modified sulfur light material, which comprises the following steps:
s1, mixing siderite and sulfur, and heating and melting to obtain a siderite and sulfur molten mixture;
and S2, foaming the siderite and sulfur molten mixture obtained in the step S1 in a physical foaming or chemical foaming mode, and cooling and forming to obtain the siderite modified sulfur light material.
Preferably, the mass ratio of the sulfur to the siderite in the step S1 is 10: 1-1: 5; more preferably, 3:1 to 1: 2.
Preferably, when the mass ratio of the sulfur to the siderite in the step S1 is less than 2:1, foaming is performed in a physical foaming manner in the step S2; and when the mass ratio of the sulfur to the siderite in the step S1 is more than or equal to 2:1, foaming in a chemical foaming manner in a step S2.
Preferably, the heating and melting temperature in the step S1 is 115-200 ℃; more preferably 140 to 160 ℃.
Preferably, the cooling molding in step S2 includes wet granulation, steel belt granulation, or crushing granulation after solidification.
Preferably, the physical foaming means comprises foaming using air or carbon dioxide or nitrogen; the chemical foaming mode comprises foaming by using a chemical foaming agent, wherein the chemical foaming agent comprises one or more of sodium bicarbonate, azodicarbonamide or 4,4' -oxybis-benzenesulfonylhydrazide; more preferably the chemical blowing agent is sodium bicarbonate.
Preferably, the grain size of the siderite is less than or equal to 0.3 mm.
The siderite modified sulfur light material is prepared by the preparation method of the siderite modified sulfur light material, wherein the density of the light material is 0.81-2.5 g/cm3The porosity is 20-65%.
The invention relates to a method for carrying out nitrogen and phosphorus removal treatment on sewage by adopting siderite modified sulfur light material, which comprises the following steps:
s10, filling the siderite modified sulfur light material into a reactor;
s20, inoculating microorganisms to carry out biofilm formation, and starting the reactor;
s30, introducing sewage into the started reactor to perform nitrogen and phosphorus removal treatment.
Preferably, the reactor comprises a fluidized bed reactor or a fixed bed reactor; the inoculated microorganisms include anaerobic sludge containing sulfur autotrophic denitrifying bacteria or microbial agents.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the preparation method of the siderite modified sulfur light material, the sulfur and the siderite are highly fused by mixing the sulfur and the siderite and heating and melting the mixture, and the light material is obtained by foaming the molten mixture in a physical or chemical foaming manner, so that the quality of the material is reduced by foaming, the specific surface area of the material is greatly increased, and the light material has the characteristics of large specific surface area, light weight, high reaction activity, easiness in microorganism attachment, slow-release electron donor denitrification and iron ion dephosphorization, can realize more microorganism attachment amount, and improve the utilization rate of microorganisms, thereby improving the removal rate of nitrogen and phosphorus pollutants;
(2) the density of the siderite modified sulfur light material prepared by the invention can be 0.81-2.5 g/cm3The porosity is 20-65%, the siderite modified sulfur light material in the density and porosity range can be suitable for fillers of a sewage treatment fluidized bed and a fixed bed reactor, and the siderite modified sulfur light material can be applied to fillers of a sewage treatment fluidized bed and a fixed bed reactor under the action of microorganismsAnd pollutants such as nitrogen, phosphorus and the like in the sewage are deeply removed.
Drawings
FIG. 1 is a diagram of a siderite modified sulfur lightweight material of the invention;
FIG. 2 is a diagram of the effect of denitrification and dephosphorization in a batch reactor of siderite modified sulfur light material.
Detailed Description
The invention is further described with reference to specific examples.
The following detailed description of exemplary embodiments of the invention refers to the accompanying drawings, which, although described in sufficient detail to enable those skilled in the art to practice the invention, it is to be understood that other embodiments may be realized and that various changes to the invention may be made without departing from the spirit and scope of the invention. The following more detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is presented for purposes of illustration only and not limitation to describe the features and characteristics of the invention, to set forth the best mode of carrying out the invention, and to sufficiently enable one skilled in the art to practice the invention. Accordingly, the scope of the invention is to be limited only by the following claims.
The invention discloses a preparation method of a siderite modified sulfur light material, which comprises the following steps:
s1, mixing the fine siderite with the particle size of less than or equal to 0.3mm and sulfur according to the mass ratio of 10: 1-1: 5, more preferably 3: 1-1: 2, heating to 115-200 ℃, more preferably 140-160 ℃, and carrying out high-temperature melting to obtain a molten mixture of the siderite and the sulfur;
and S2, foaming the molten mixture of the siderite and the sulfur obtained in the step S1 by adopting a physical foaming or chemical foaming mode, and cooling and forming to obtain the siderite modified sulfur light material, wherein the cooling and forming method comprises wet granulation, steel belt granulation or crushing and granulation after solidification.
Wet granulation refers to dropping a molten mixture of siderite and sulfur into water, and cooling to form a solid material; steel belt granulation refers to dripping the melted mixture of the siderite and the sulfur on a steel belt and cooling to form a solid material; crushing and granulating after solidification refers to that a molten mixture of the siderite and the sulfur is cooled by air and solidified into a solid material.
It should be noted that in step S1, during the heating and melting process after mixing the sulfur and siderite, the sulfur is also required to be continuously crushed, so that a highly fused and uniform siderite and sulfur molten mixture is obtained.
The physical foaming method adopted in the step S2 includes dispersing the gas into the high-temperature molten mixture of siderite and sulfur by physical aeration method using air or carbon dioxide or nitrogen to foam. Particularly, it is noted that in experiments, if gas is dispersed in the high-temperature melting mixture of the siderite and the sulfur at normal temperature, the partial solidification of the siderite and the sulfur occurs because the melting mixture of the siderite and the sulfur is at a high temperature of 115-200 ℃, so that the melting state of the melting mixture of the siderite and the sulfur is affected, and the sufficient and uniform foaming cannot be ensured. Therefore, in order to avoid the influence of the temperature of the gas to be dispersed on the high-temperature melting mixture of the siderite and the sulfur and ensure the final foaming effect, the gas can be preheated before being dispersed in the high-temperature melting mixture, and the preheated temperature is more than or equal to 50 ℃.
In addition, the chemical foaming means includes foaming using a chemical foaming agent, wherein the chemical foaming agent includes sodium bicarbonate, azodicarbonamide, or 4,4' -oxybis-benzenesulfonylhydrazide; more preferably the chemical blowing agent is sodium bicarbonate. It is particularly noted that when sodium bicarbonate is used for chemical foaming, the added sodium bicarbonate cannot completely enter into the melted mixture of the siderite and the sulfur due to the light weight of the sodium bicarbonate, so that the foaming effect cannot be fully exerted. To address this challenge, a small amount of siderite (less than 5% of the initially weighed siderite from step S1) was used in the experiment mixed with sodium bicarbonate and added to the molten mixture, which, because of the heavier weight of siderite, was completely dispersed in the molten mixture along with the sodium bicarbonate to achieve adequate foaming.
It is further noted that, in the present invention, when the mass ratio of the sulfur to the siderite in step S1 is <2:1, the foaming is performed in step S2 by a physical foaming method; and when the mass ratio of the sulfur to the siderite in the step S1 is more than or equal to 2:1, foaming in a chemical foaming manner in a step S2.
Multiple experiments show that as the mass ratio of the sulfur to the siderite is more than or equal to 2:1, the viscosity of the molten mixture of the sulfur and the siderite is smaller when the amount of the sulfur is larger, the foaming effect of dispersing air or carbon dioxide or nitrogen in the molten mixture by adopting a physical foaming mode is not good, and the gas can quickly escape and cannot play a role in full foaming. According to the invention, a proper foaming mode is flexibly selected according to the viscosity of the molten mixture obtained under a specific mass ratio of the sulfur to the siderite, so that the foaming effect is ensured, and the purposes of reducing the mass of the material and increasing the specific surface area of the material are achieved.
The siderite modified sulfur light material is prepared by the preparation method of the siderite modified sulfur light material, wherein the density of the light material is 0.81-2.5 g/cm3The porosity is 20-65%. The siderite modified sulfur light material has the characteristics of large specific surface area, light weight, high reaction activity, easiness in microorganism attachment, slow-release electron donor denitrification, iron ion dephosphorization and the like, can be used as a filler of a sewage treatment fluidized bed and a fixed bed reactor, and can deeply remove nitrogen and phosphorus pollutants in water through the action of microorganisms.
The invention relates to a method for carrying out nitrogen and phosphorus removal treatment on sewage by adopting siderite modified sulfur light material, which comprises the following steps:
s10, filling filler: taking the siderite modified sulfur light material, crushing, screening and filling into a reactor;
s20, inoculating sludge: inoculating microorganisms into the reactor in the step S10, adding nutrient solution for culture, starting the reactor after the microorganisms finish biofilm formation, and starting to operate;
s30, operation and debugging: and sewage is introduced into the reactor after the start-up, nitrogen and phosphorus removal treatment is carried out, the hydraulic retention time of the sewage is adjusted according to the concentration of the inlet nitrogen and phosphorus and the requirement of the outlet index, and the effective removal of the nitrogen and phosphorus is realized, so that the discharge reaches the standard.
Notably, the reactor comprises a fluidized bed reactor or a fixed bed reactor; the inoculated microorganisms include anaerobic sludge containing sulfur autotrophic denitrifying bacteria or microbial agents.
Example 1
In the embodiment, sulfur and siderite are uniformly mixed according to the mass ratio of 1:1, and the mixture is heated to 150 ℃ for high-temperature melting to obtain a siderite and sulfur molten mixture; blowing nitrogen into the molten mixture under the condition of physical aeration to foam the molten mixture of the siderite and the sulfur, and mechanically stirring the molten mixture in the foaming process, wherein the stirring speed is 200-300 rpm, and the stirring time is 20 minutes, so that bubbles are uniformly dispersed in the molten mixture; finally, the siderite modified sulfur light material is prepared by cooling and forming, and the obtained material is shown in figure 1. The siderite modified sulfur lightweight material prepared in this example had a density greater than water, measured at about 2.13g/cm3The porosity was 30.8%.
10g of the broken siderite modified sulfur light material is put into a batch reaction container, and 50mL of NO with the concentration of 28mg/L is added into the batch reaction container3 --N、15mg/L PO4 3--P. Then 3.5mL of sulfur autotrophic denitrifying bacteria liquid with the mass fraction of 10% (the volume of the bacteria liquid accounts for 7% of the volume of the wastewater) is added into the batch reaction container, the mixed solution is subjected to nitrogen blowing to remove oxygen, then the mixed solution is covered and sealed to carry out the denitrification reaction process, the mixed solution is cultured for 10 days, and NO in the wastewater is treated in 0.5 th, 1 th, 2 th, 3 th, 5 th, 7 th and 10 th days respectively3 --N、PO4 3--P concentration was measured. The specific denitrification and dephosphorization data are shown in figure 2.
Example 2
The basic contents of this embodiment are the same as embodiment 1, except that: in the embodiment, the mass ratio of the sulfur to the siderite is 10: 1; weighing 95% of siderite by mass and mixing with all sulfur to obtain a mixture in the specific mixing process, and heating the mixture to 120 ℃ for high-temperature melting to obtain a siderite and sulfur molten mixture; at the mass ratioThe viscosity of the obtained fused mixture of the siderite and the sulfur is low, and a chemical foaming agent sodium bicarbonate is required to be added for foaming. Mixing the remaining 5% of siderite and sodium bicarbonate according to the mass ratio of the sulfur to the siderite to the foaming agent of 300:30:2, adding the mixture of the siderite and the sodium bicarbonate into the siderite and sulfur molten mixture, and simultaneously carrying out magnetic stirring on the molten mixture, wherein the stirring speed is 50-100 rpm, and the stirring time is 5 minutes; finally, the siderite modified sulfur light material is prepared by cooling and forming. The resulting material had a density less than water, measured at about 0.81g/cm3The porosity was 59.8%.
Example 3
The basic content of this embodiment is different from embodiment 2 in that: in the embodiment, the mass ratio of the sulfur to the siderite is 2:1, the sulfur and the siderite are uniformly mixed, and the mixture is heated to 160 ℃ for high-temperature melting to obtain a siderite and sulfur molten mixture; adding a chemical foaming agent sodium bicarbonate for foaming, wherein the mass ratio of sulfur to siderite to the foaming agent is 300:150:2, mechanically stirring the molten mixture in the foaming process, wherein the stirring speed is 300-350 rpm, and the stirring time is 15 minutes, so that bubbles are uniformly dispersed; finally, the siderite modified sulfur light material is prepared by cooling and forming. The resulting material was measured to have a density of about 1.08g/cm3The porosity was 61.9%.
Crushing the siderite modified sulfur light material, screening out a material with the average particle size of about 2.3mm as a filler, filling the filler into a fluidized bed reactor, inoculating anaerobic sludge, adding a culture solution, culturing for 5 days, finishing film formation, and starting the reactor. And (3) introducing inlet water into the started reactor, wherein the flow rate is 60mL/min, the hydraulic retention time is 2.5h, the average nitrate nitrogen of the inlet water is 32.3mg/L, the average nitrate nitrogen of the outlet water is 0.06mg/L, the average phosphate phosphorus of the inlet water is 1.81mg/L, and the average phosphate phosphorus of the outlet water is 0.02mg/L in the 127d operation process.
Example 4
The basic contents of this embodiment are the same as embodiment 3, except that: in the embodiment, the mass ratio of the sulfur to the siderite is 1:1.2, and the sulfur and the siderite are mixedAfter the ores are uniformly mixed, heating the mixture to 145 ℃ for high-temperature melting to obtain a mixture of melted siderite and sulfur; blowing nitrogen into the molten mixture under the condition of physical aeration, foaming the molten mixture of the siderite and the sulfur, and mechanically stirring the molten mixture in the foaming process, wherein the stirring speed is 150-200 rpm, and the stirring time is 25 minutes, wherein the stirring time is the foaming time, so that the bubbles are uniformly dispersed; finally, the siderite modified sulfur light material is prepared by cooling and forming. The resulting material was measured to have a density of about 1.86g/cm3The porosity was 40.9%.
Crushing the siderite modified sulfur light material, screening out a material with the average particle size of about 3mm as a filler, filling the filler into a fixed bed reactor, inoculating anaerobic sludge, adding a culture solution, culturing for 8 days, finishing film formation, and starting the reactor. And (3) introducing inlet water into the started reactor, wherein the flow rate is 60mL/min, the hydraulic retention time is 2h, and nitrogen and phosphorus removal of inlet and outlet water is stable in the 99d operation process, wherein the nitrogen removal rate is stable at about 98%, and the phosphorus removal rate is also over 85%.
The invention has been described in detail hereinabove with reference to specific exemplary embodiments thereof. It will, however, be understood that various modifications and changes may be made without departing from the scope of the invention as defined in the appended claims. The detailed description and drawings are to be regarded as illustrative rather than restrictive, and any such modifications and variations are intended to be included within the scope of the present invention as described herein. Furthermore, the background is intended to be illustrative of the state of the art as developed and the meaning of the present technology and is not intended to limit the scope of the invention or the application and field of application of the invention.
Claims (7)
1. The preparation method of the siderite modified sulfur light material is characterized by comprising the following steps:
s1, mixing sulfur and siderite in a mass ratio of 10: 1-1: 5, and heating and melting at 115-200 ℃ to obtain a siderite and sulfur molten mixture;
s2, foaming the siderite and sulfur molten mixture obtained in the step S1 by adopting a physical foaming or chemical foaming mode, and cooling and forming to obtain the siderite modified sulfur light material, wherein the physical foaming mode comprises foaming by using air or carbon dioxide or nitrogen; the chemical foaming mode comprises foaming by using a chemical foaming agent, wherein the chemical foaming agent comprises one or more of sodium bicarbonate, azodicarbonamide or 4,4' -oxybis-benzenesulfonylhydrazide.
2. The method for preparing the siderite modified sulfur lightweight material according to the claim 1, which is characterized in that: when the mass ratio of the sulfur to the siderite in the step S1 is less than 2:1, foaming is performed in a physical foaming manner in a step S2; and when the mass ratio of the sulfur to the siderite in the step S1 is more than or equal to 2:1, foaming in a chemical foaming manner in a step S2.
3. The method for preparing the siderite modified sulfur lightweight material according to the claim 1, which is characterized in that: the cooling molding in step S2 includes wet granulation, steel belt granulation or crushing granulation after solidification.
4. The method for preparing the siderite modified sulfur lightweight material according to the claim 1 or 2, characterized in that: the grain size of the siderite is less than or equal to 0.3 mm.
5. An siderite modified sulfur lightweight material, which is characterized by being prepared by the preparation method of the siderite modified sulfur lightweight material according to any one of claims 1 to 4.
6. A method for carrying out nitrogen and phosphorus removal treatment on sewage by adopting siderite modified sulfur light material is characterized by comprising the following steps:
s10, filling the siderite modified sulfur light material of claim 5 into a reactor;
s20, inoculating microorganisms to carry out biofilm formation, and starting the reactor;
s30, introducing sewage into the started reactor to perform nitrogen and phosphorus removal treatment.
7. The method for removing nitrogen and phosphorus from sewage by using the siderite modified sulfur light material as claimed in claim 6, wherein the method comprises the following steps: the reactor comprises a fluidized bed reactor or a fixed bed reactor; the inoculated microorganisms include anaerobic sludge containing sulfur autotrophic denitrifying bacteria or microbial agents.
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| CN111977787A (en) * | 2020-08-10 | 2020-11-24 | 深圳市播绿者生态科技股份有限公司 | Self-activated denitrification carrier material and preparation method and application thereof |
| CN112142208B (en) * | 2020-09-23 | 2022-11-15 | 北京林业大学 | Nitrogen and phosphorus removal active biological carrier and application thereof |
| CN114057283A (en) * | 2021-09-10 | 2022-02-18 | 南京华创环境技术研究院有限公司 | Light nitrogen and phosphorus removal filler utilizing pyrite to modify waste polyurethane and preparation method thereof |
| CN113620414A (en) * | 2021-10-11 | 2021-11-09 | 黄河三角洲京博化工研究院有限公司 | Composite slow-release filler, preparation method and application thereof |
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| CN107176702A (en) * | 2017-07-31 | 2017-09-19 | 南京大学 | A kind of sewage water treatment method for strengthening sulphur autotrophic denitrification process synchronous denitrification dephosphorizing |
| CN109019877A (en) * | 2018-09-21 | 2018-12-18 | 中国科学院生态环境研究中心 | Denitrogenation dephosphorizing active bio carrier, preparation method and its application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010067161A (en) * | 1999-12-09 | 2001-07-12 | 이준상 | Manufacturing method of bioceramic media for native microorganisms and disposal system of sewage and waste water using the same |
| CN103801254A (en) * | 2014-02-25 | 2014-05-21 | 合肥工业大学 | Siderite-based nitrogen and phosphorus removal material and application method thereof |
| CN107176702A (en) * | 2017-07-31 | 2017-09-19 | 南京大学 | A kind of sewage water treatment method for strengthening sulphur autotrophic denitrification process synchronous denitrification dephosphorizing |
| CN109019877A (en) * | 2018-09-21 | 2018-12-18 | 中国科学院生态环境研究中心 | Denitrogenation dephosphorizing active bio carrier, preparation method and its application |
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