CN107512771B - Siderite/sulfur biofilter and method for synchronously removing nitrogen and phosphorus in water by using siderite/sulfur biofilter - Google Patents

Siderite/sulfur biofilter and method for synchronously removing nitrogen and phosphorus in water by using siderite/sulfur biofilter Download PDF

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CN107512771B
CN107512771B CN201710636553.XA CN201710636553A CN107512771B CN 107512771 B CN107512771 B CN 107512771B CN 201710636553 A CN201710636553 A CN 201710636553A CN 107512771 B CN107512771 B CN 107512771B
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sulfur
siderite
water
phosphorus
nitrogen
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CN107512771A (en
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李睿华
李甫昌
张永威
王卫
葛志斌
李爱民
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NANJING UNIVERSITY & YANCHENG ACADEMY OF ENVIRONMENTAL PROTECTION TECHNOLOGY AND ENGINEERING
Nanjing University
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NANJING UNIVERSITY & YANCHENG ACADEMY OF ENVIRONMENTAL PROTECTION TECHNOLOGY AND ENGINEERING
Nanjing University
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/28Anaerobic digestion processes
    • C02F3/2826Anaerobic digestion processes using anaerobic filters
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/105Phosphorus compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/16Nitrogen compounds, e.g. ammonia

Abstract

The invention discloses a siderite/sulfur biofilter and a method for synchronously removing nitrate nitrogen and phosphorus in water by using the siderite/sulfur biofilter, and belongs to the field of advanced wastewater 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 disclosed by the invention is simple in structure, convenient to start, stable to operate, high in nitrogen and phosphorus removal efficiency and suitable for advanced treatment of sewage.

Description

Siderite/sulfur biofilter and method for synchronously removing nitrogen and phosphorus in water by using siderite/sulfur biofilter
Technical Field
The invention belongs to the field of advanced sewage treatment, and particularly relates to a siderite/sulfur biofilter and a method for synchronously removing nitrate nitrogen and phosphorus in water by using the siderite/sulfur biofilter.
Background
In the traditional water treatment biological denitrification process, microorganisms convert ammonia nitrogen into nitrate nitrogen under an aerobic condition, and heterotrophic denitrifying bacteria gradually convert the nitrate nitrogen into nitrogen by taking an organic carbon source as an electron donor under an anoxic condition. The traditional biological phosphorus removal is completed by utilizing microorganisms such as phosphorus-accumulating bacteria and the like to absorb phosphorus under aerobic conditions and release phosphorus under anoxic conditions, and both processes need organic carbon sources. The A2/O and other processes formed by combining biological denitrification and biological dephosphorization in series can achieve the purpose of denitrification and dephosphorization, but the processes are complex. And the biological denitrification and dephosphorization process is realized on the basis of the biological activities of the denitrifying bacteria and the dephosphorizing bacteria, so when the denitrifying bacteria and the dephosphorizing bacteria are connected in series and combined for denitrifying and dephosphorizing, the problem of living environment of the two microorganisms is inevitably considered: sludge age, aerobic-anaerobic equilibrium, competition of dissolved oxygen and organic matter, etc. Therefore, the process is difficult to efficiently and synchronously remove nitrogen and phosphorus, and the process control difficulty is high. In addition, the traditional biological nitrogen and phosphorus removal series process depends on organic matters in water, when the organic matters in the inlet water are insufficient or the carbon-nitrogen ratio in the water is low, the organic matters (usually methanol) need to be added additionally, so that the treatment cost is increased, and the secondary pollution can be caused.
Aiming at the problem of denitrification of sewage with low carbon-nitrogen ratio, a sulfur/limestone autotrophic denitrification System (SLAD) based on sulfur autotrophic denitrification bacteria is developed, and the system can realize denitrification without organic carbon source. However, the system has the problems of unobvious dephosphorization effect, high effluent hardness and the like. Aiming at the problems of SLAD, the Chinese patent application number: ZL2010105243393, application date: the invention is invented and created in the year 2010, 10 and 29, and the name is: the application relies on the biochemical process denitrification and denitrification of sulfur autotrophic denitrifying bacteria by taking the pyrite as an electron donor, and the thiobacillus denitrificans carries out synchronous denitrification and dephosphorization by taking the pyrite as a sulfur source, but the problem of low denitrification capability due to long treatment time caused by low denitrification rate of the sulfur autotrophic denitrifying bacteria by taking the pyrite as the sulfur source is solved; the application uses limestone, calcite or dolomite, increases the operation cost, has influence on the effluent quality, and has higher hardness of the effluent quality. As another example, application No.: 2012100953709, filing date: 4, 1/2012, the name of the invention is: the application realizes the natural fusion of a thiobacillus denitrificans nitrogen removal technology and an iron ion phosphorus removal technology, has lower reaction cost, also has the problem of low nitrogen removal capability with long treatment time, does not have a filler for neutralizing pH, has low pH of a system, and is not beneficial to the efficient and stable operation of the system.
Again as in patent application No.: 2014100638686, filing date: in 2014, 2, 25 and 25 days, the invention and creation name is as follows: a denitrifying and dephosphorizing material based on siderite and its application method are disclosed, wherein the preparation method comprises crushing siderite ore, sieving with 40 mesh sieve, and adding foaming agent according to proper proportion of siderite ore powder, binder and pore-forming agent, or according to proper proportion of siderite ore powder and binder, to obtain porous granular material with siderite ore powder as main body, and the material has the characteristics of high granular strength, high porosity, large specific surface area, large microorganism loading capacity, etc. The material is used as a carrier of microorganism, and is also used as 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. The application uses natural siderite as the filler, so that the complexity of the process is reduced, but the anaerobic iron-oxidizing bacteria used in the application have high requirements on the ecological environment, have poor viability competitiveness and are difficult to be applied efficiently.
Disclosure of Invention
1. Technical problem to be solved by the invention
When the traditional biological water treatment process is used for treating sewage with low carbon-nitrogen ratio, the nitrogen and phosphorus removal effect is poor and the cost is high; the sulfur/limestone system has good denitrification effect, but can not effectively remove phosphorus, and the hardness of effluent is too high; the pyrite system can effectively remove nitrogen and phosphorus, but the reaction speed is slow, and the problem of overhigh calcium ions in the effluent is also existed. Aiming at the defects, the invention provides the siderite/sulfur biofilter and the method for synchronously removing nitrate nitrogen and phosphorus in water by using the siderite/sulfur biofilter.
2. Technical scheme
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the invention discloses a method for synchronously removing nitrate nitrogen and phosphorus in water by using a siderite/sulfur biofilter, which is characterized by comprising the following steps of:
step one, preparing and constructing a filler of a biological filter: preparing siderite and sulfur into granular materials with the granularity of 0.5-5mm respectively, cleaning, and then uniformly mixing the siderite and the sulfur and filling the mixture into a reactor;
step two, starting the biological filter: mixing the enriched bacterial liquid with a culture medium, pumping the mixed liquid into a reactor, statically culturing for 3-5d, pumping a new culture medium again, repeating the steps until the film hanging of the reactor is mature, and detecting that the concentration of nitrate and nitrogen in water is stable;
step three, the operation of the biological filter: and after the concentration of nitrate and nitrogen in the effluent of the reactor is kept stable, pumping the sewage to be treated into the reactor, adjusting the hydraulic retention time to synchronously remove nitrogen and phosphorus in the sewage, and discharging the effluent after the effluent reaches the discharge standard of urban sewage.
Further, in the first step, the siderite and the sulfur are mixed according to the ratio of (2-4): 1 volume ratio was mixed homogeneously.
Further, in step one, the particulate material made from siderite and sulfur is washed with clear water prior to charging, the pH of the wash water being from 7 to 8.
Furthermore, the reactor in the first step is an up-flow reactor with water inlet at the bottom and water outlet at the top.
Further, the enriched bacterial liquid in the second step is screened and enriched from anaerobic sludge.
Furthermore, in the second step, the enriched bacterial liquid and the culture medium are mixed, and the inoculation amount is 7-10%.
Furthermore, the enriched bacterial liquid in the second step is sulfur autotrophic denitrifying bacteria enriched bacterial liquid.
Furthermore, the medium components in the second step are as follows: na (Na)2S2O35g/L,KNO32g/L,KH2PO42g/L,NaHCO32g/L,FeSO40.01g/L,NH4Cl 0.5g/L,MgCl20.5g/L。
Furthermore, the hydraulic retention time in the third step is 6-48 h.
The siderite/sulfur biofilter comprises the reactor treated in the first step and the reactor treated in the second step.
The invention has the technical principle that the physiological and biochemical characteristics of sulfur autotrophic denitrifying bacteria are utilized, and the start parameter items such as granularity, filler ratio, inlet water hydraulic retention time and the like of a biological filter tank are controlled, so that the sulfur autotrophic denitrifying bacteria use nitrate as an electron acceptor, sulfur as an electron donor and siderite as a carbon source to perform autotrophic denitrification so as to achieve the aim of nitrogen removal, and meanwhile, the metabolic products of the siderite are used for chemical phosphorus removal to realize the coupling of biological nitrogen and phosphorus removal and chemical phosphorus removal; the invention uses the sulfur source as an electron donor, has faster autotrophic denitrification speed, and simultaneously hydrogen ions generated in the reaction process act on siderite to release an inorganic carbon source supporting autotrophic denitrification and Fe participating in chemical phosphorus removal.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:
(1) the invention discloses a method for synchronously removing nitrate nitrogen and phosphorus in water by using a siderite/sulfur biofilter, which is characterized in that siderite and sulfur are prepared into particles with the particle size of 0.5-5mm according to the siderite/sulfur volume ratio of (2-4): 1, the reactor is filled, and the reactor can synchronously remove nitrogen and phosphorus in wastewater with low carbon-nitrogen ratio after being started, so that the method is suitable for advanced treatment of sewage nitrogen and phosphorus removal and purification of underground water, and the effect of nitrogen and phosphorus removal is obvious.
(2) The method for synchronously removing nitrate nitrogen and phosphorus in water by using the siderite/sulfur biofilter has the advantages of wide distribution of natural siderite and sulfur, low price, easy obtainment, simple and practical method and high reactor treatment capacity.
Drawings
FIG. 1 shows the effect of simultaneous denitrification and dephosphorization with artificial water distribution in example 1;
FIG. 2 shows the effect of simultaneous denitrification and dephosphorization with artificial water distribution in example 2;
FIG. 3 shows the effect of simultaneous denitrification and dephosphorization of actual wastewater in example 3;
FIG. 4 shows the effect of simultaneous denitrification and dephosphorization with artificial water distribution in example 4.
Detailed Description
For a further understanding of the invention, reference should be made to the following detailed description taken in conjunction with the accompanying drawings.
The present invention will be further described with reference to the following examples.
Example 1
In the method for synchronously removing nitrate nitrogen and phosphorus in water by using the siderite/sulfur biofilter, the treatment object is artificial water distribution consisting of tap water, monopotassium phosphate, ammonium chloride and potassium nitrate, wherein NO is contained in the artificial water distribution3 --N28mg/L,PO4 3-P3.1mg/L, NH4 +-N2mg/L, water temperature 20 ℃, and other processing steps:
(1) preparing and constructing a filler of the biological filter: preparing siderite and sulfur into 2mm granules respectively, washing with clear water before filling siderite and sulfur granules, and adjusting pH of the washing water to 7-8. Mixing siderite and sulfur particles according to the volume ratio of 3: 1, filling the mixture into a reactor, wherein the reactor is an upflow reactor with water inlet at the bottom and water outlet at the top, and the shape of the reactor is the best cylindrical. The volume ratio of siderite to sulfur has great influence on the synchronous denitrification and dephosphorization effect of the system, and when the volume ratio is too large, the specific surface area of the electron donor sulfur is reduced, and the denitrification rate is reduced; when the volume ratio is too small, the nitrogen source of the system is insufficient, the denitrification capability is inhibited, and the dephosphorization capability is reduced due to the reduction of iron ions.
(2) Starting the biological filter: mixing the enriched bacterial liquid with a culture medium (the inoculation amount is 10%), pumping the mixed liquid into a reactor by a pump, statically culturing for four days, then pumping a new culture medium again to replace the original culture medium, repeating the steps until the biofilm formation of the reactor is mature, and the concentration of the effluent nitrate nitrogen is stable;
it should be noted that in this embodiment, the enriched bacterial liquid is selected and enriched from the common anaerobic sludge, and the enriched bacterial liquid is an enriched bacterial liquid of sulfur autotrophic denitrifying bacteria, and is culturedThe nutrient comprises the following components: na (Na)2S2O35g/L,KNO32g/L,KH2PO42g/L,NaHCO32g/L,FeSO40.01g/L,NH4Cl 0.5g/L,MgCl20.5g/L。
(3) Operation of the biological filter: after the concentration of nitrate and nitrogen in effluent of the reactor is kept stable, pumping the sewage to be treated into the reactor, adjusting the hydraulic retention time to 24 hours according to the concentration of nitrate and nitrogen in the sewage according to the concentration rule of removing nitrate and nitrogen in a culture medium during enrichment culture, operating for one month, and sampling once a day. And (3) synchronously removing nitrate nitrogen and phosphorus in the sewage, and discharging the effluent after the effluent reaches the urban sewage discharge standard, wherein the result is shown in figure 1, the nitrate nitrogen concentration and the phosphate concentration of the final effluent are lower than detection limits, and the nitrate nitrogen removal rate and the phosphate removal rate both reach 100%.
Example 2
The method for synchronously removing nitrate nitrogen and phosphorus in water by using the siderite/sulfur biofilter is basically the same as that in example 1, except that siderite and sulfur are respectively prepared into granular materials with the granularity of 0.5mm and washed in the step one of the example, and then the siderite and the sulfur are mixed in a volume ratio of 2: 1, uniformly mixing and filling the mixture into a reactor; mixing the enriched bacterial liquid with a culture medium, wherein the inoculation amount is 7%, statically culturing for 3d, and pumping a new culture medium again until the biofilm formation of the reactor is mature; and in the third step, the wastewater to be treated is pumped into a reactor, the hydraulic retention time is 48 hours, the operation is carried out for one month, the sampling is carried out once every day, the synchronous removal of nitrate nitrogen and phosphorus in the wastewater is completed, the effluent is discharged after reaching the standard, the result is shown in figure 2, the nitrate nitrogen concentration and the phosphate concentration of the final effluent are lower than the detection limit, and the removal rates of the nitrate nitrogen and the phosphate are both 100%.
Example 3
The method for synchronously removing nitrate nitrogen and phosphorus in water by using the siderite/sulfur biofilter is basically the same as that in the embodiment 2, except that the inlet water in the embodiment is 2-stage outlet water from a certain sewage treatment plant in Changzhou, and the comprehensive indexes of the inlet water are as follows: COD68mg/L, PO4 3--P0.35mg/L,NO3 --N8.498mg/L,NH4 --N0.326mg/L,SO4 2--S324.857mg/L. In this example, the operation is performed for 10 days, sampling is performed every two days, the sampling result is shown in fig. 3, the final effluent nitrate nitrogen is lower than the detection limit, the nitrate nitrogen removal rate is 100%, the effluent phosphate is gradually reduced, and the phosphate removal capacity is gradually recovered.
Example 4
The method for synchronously removing nitrate nitrogen and phosphorus in water by using the siderite/sulfur biofilter is basically the same as that in example 2, except that siderite and sulfur are respectively prepared into granular materials with the granularity of 5mm and washed in the first step of the example, and then the siderite and the sulfur are mixed in a volume ratio of 4: 1, uniformly mixing and filling the mixture into a reactor; mixing the enriched bacterial liquid with a culture medium, wherein the inoculation amount is 8%, statically culturing for 5 days, and pumping a new culture medium again until the biofilm formation of the reactor is mature; in the third step, the wastewater to be treated is pumped into the reactor, the hydraulic retention time is 6 hours, the operation is carried out for one month, the sampling is carried out once a day, the result is shown in figure 4, the concentration of the nitrate and the nitrogen in the effluent water in the anesthesia is 3.86mg/L, the concentration of the phosphate is 0.41mg/L, the removal rate of the nitrate and the nitrogen is 86.22%, and the removal rate of the phosphate is 86.78%.
The present invention and its embodiments have been described above schematically, without limitation, and what is shown in the drawings is only one of the embodiments of the present invention, and the actual structure is not limited thereto. Therefore, if the person skilled in the art receives the teaching, without departing from the spirit of the invention, the person skilled in the art shall not inventively design the similar structural modes and embodiments to the technical solution, but shall fall within the scope of the invention.

Claims (10)

1. A method for synchronously removing nitrate nitrogen and phosphorus in water by using a siderite/sulfur biofilter is characterized by comprising the following steps:
step one, preparing and constructing a filler of a biological filter: preparing siderite and sulfur into granular materials with the granularity of 0.5-5mm respectively, cleaning, and then uniformly mixing the siderite and the sulfur and filling the mixture into a reactor;
step two, starting the biological filter: mixing the enriched bacterial liquid with a culture medium, pumping the mixed liquid into a reactor, statically culturing for 3-5d, pumping a new culture medium again, repeating the steps until the film hanging of the reactor is mature, and detecting that the concentration of nitrate and nitrogen in water is stable;
step three, the operation of the biological filter: after the concentration of nitrate and nitrogen in the effluent of the reactor is kept stable, pumping the sewage to be treated into the reactor, adjusting the hydraulic retention time, completing the synchronous removal of nitrogen and phosphorus in the sewage, and discharging the effluent after reaching the standard.
2. The method for synchronously removing nitrate nitrogen and phosphorus in water by using the siderite/sulfur biofilter according to claim 1, which is characterized in that: in the first step, siderite and sulfur are mixed according to the ratio of (2-4): 1 volume ratio was mixed homogeneously.
3. The method for synchronously removing nitrate nitrogen and phosphorus in water by using the siderite/sulfur biofilter according to claim 2, which is characterized in that: in the first step, the granular material prepared from siderite and sulfur is washed by clear water before filling, and the pH value of the washing water is 7-8.
4. The method for synchronously removing nitrate nitrogen and phosphorus in water by using the siderite/sulfur biofilter according to claim 1, which is characterized in that: the reactor in the first step is an up-flow reactor with water inlet at the bottom and water outlet at the top.
5. The method for synchronously removing nitrate nitrogen and phosphorus in water by using the siderite/sulfur biofilter according to claim 1, which is characterized in that: and screening the enriched bacterial liquid in the step two to enrich the anaerobic sludge.
6. The method for synchronously removing nitrate nitrogen and phosphorus in water by using the siderite/sulfur biofilter according to claim 5, wherein the method comprises the following steps: and step two, mixing the enriched bacterial liquid with a culture medium, wherein the inoculation amount is 7-10%.
7. The method for synchronously removing nitrate nitrogen and phosphorus in water by using the siderite/sulfur biofilter according to claim 5, wherein the method comprises the following steps: and the enriched bacterial liquid in the second step is sulfur autotrophic denitrifying bacteria enriched bacterial liquid.
8. The method for synchronously removing nitrate nitrogen and phosphorus in water by using the siderite/sulfur biofilter according to claim 7, which is characterized in that: the components of the culture medium in the second step are as follows: na (Na)2S2O35g/L,KNO32g/L,KH2PO42g/L,NaHCO32g/L,FeSO40.01g/L,NH4Cl 0.5g/L,MgCl20.5g/L。
9. The method for synchronously removing nitrate nitrogen and phosphorus in water by using the siderite/sulfur biofilter according to any one of claims 1 to 8, which is characterized by comprising the following steps: the hydraulic retention time in the third step is 6-48 h.
10. A siderite/sulphur biofilter comprising the reactor according to any one of claims 1 to 9 after treatment in steps one and two.
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CN109019877B (en) * 2018-09-21 2020-04-17 中国科学院生态环境研究中心 Nitrogen and phosphorus removal active biological carrier, and preparation method and application thereof
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