CN112875857B - Denitrification filter material, and preparation method and application thereof - Google Patents
Denitrification filter material, and preparation method and application thereof Download PDFInfo
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- CN112875857B CN112875857B CN202110094665.3A CN202110094665A CN112875857B CN 112875857 B CN112875857 B CN 112875857B CN 202110094665 A CN202110094665 A CN 202110094665A CN 112875857 B CN112875857 B CN 112875857B
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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
- 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
Abstract
The invention discloses a preparation method of a denitrification filter material, which comprises the steps of cleaning bagasse as a raw material by using deionized water, then drying the bagasse by air, then uniformly mixing the bagasse with siderite and ordinary portland cement according to a certain mass ratio to obtain a mixed material, then adding water into the mixed material, uniformly mixing, granulating into a sphere, and drying at room temperature to obtain the denitrification filter material. The denitrification filter material is an organic matter-ferrous matrix composite system, is based on a mixed nutritional type denitrification mode, can realize high-efficiency denitrification of the tail water of a sewage plant without an external carbon source, has the advantages of low cost, simplicity in preparation, good hydraulic performance and the like, can be applied to deep denitrification of the tail water of the sewage plant, can also be used for denitrification of wastewater with low C/N ratio, provides a brand-new approach for resource utilization of bagasse, and achieves the aim of treating waste with waste.
Description
Technical Field
The invention belongs to the field of sewage treatment, and the technical field of ecology and environment, relates to a preparation method and application of a denitrification filter material, and particularly relates to a denitrification filter material for efficiently denitrifying tail water in a town sewage plant, and a preparation method and application thereof.
Background
The healthy water environment is an important component of urban sustainable development. Since the official promulgation of the action plan for preventing and treating water pollution in 2015, the requirements for the discharge standard of urban sewage plants are increasingly strict, and particularly, the requirements for implementing the strict special discharge limit of pollutants in the sewage plants in key drainage basin areas are more strict, wherein how to meet the discharge standard of Total Nitrogen (TN) in sewage under the high discharge standard becomes a hot spot and a difficult point of concern in the field of water treatment. The main nitrogen form in the tail water (secondary effluent) of a sewage treatment plant is nitrate nitrogen, and a denitrification filter tank is the most common deep denitrification process at present. After the sewage is subjected to the whole biological treatment process, tail water almost has no carbon source available for the traditional denitrification, so that a large amount of organic carbon sources (sodium acetate, glacial acetic acid and the like) are usually added into a denitrification filter to meet the denitrification requirement. However, the external addition of carbon sources not only greatly increases the operating cost, but also increases the complexity of the operation and maintenance.
As a core part of the denitrification filter tank, the development and the modification of filter materials are concerned by more and more researchers. At present, the research and development of the denitrification filter material mainly focuses on two aspects: one is the optimization of the material, the particle size and the configuration of a filter material based on the improvement of the hydraulic characteristic of the filter, and the currently adopted filter material mainly comprises quartz sand, ceramsite, volcanic rock and the like; on the other hand, the development of the filter material for enhancing the autotrophic denitrification process without carbon source mainly comprises the development of filter materials using sulfur, zero-valent iron or ferrous iron as electron donors, such as compound pyrite + limestone (3-10). However, the filter materials developed based on the autotrophic nitrogen removal process alone have the problems of low nitrogen removal efficiency, sulfate increase in effluent, and the like.
Disclosure of Invention
In order to solve the defects and defects of the existing denitrification filter material, the invention aims to provide a preparation method and application of a novel denitrification filter material based on a mixed nutrition type denitrification mode (heterotrophic denitrification-ferrous anoxic denitrification).
In addition, the material has the advantages of low cost, simple preparation, no need of external carbon source addition, good hydraulic performance, excellent denitrification effect and the like, can be used as a denitrification filter material for deep denitrification of tail water of a sewage plant, and simultaneously provides a novel approach for resource utilization of bagasse.
The invention provides a novel denitrification filter material, which is characterized in that an organic matter-ferrous matrix composite system is prepared by compounding bagasse, siderite and ordinary portland cement serving as raw materials.
Wherein, the mass fractions of bagasse, siderite and ordinary portland cement in the denitrification filter material are respectively 30% -40%, 50% -70% and 10% -15%; preferably, the mass fractions of the bagasse, the siderite and the ordinary portland cement are 40%, 50% and 10%, respectively.
The bagasse is a byproduct of a sucrose production plant, is cleaned by deionized water, is naturally air-dried at room temperature, is crushed, and is sieved by a 100-mesh sieve;
the siderite is common iron ore and is selected from mining areas of Bijie city, guizhou province, and the siderite is sieved by a 40-mesh sieve after being crushed;
the portland cement is common ordinary portland cement.
The denitrification filter materials existing in the prior art mainly comprise two types: 1) Filter materials (quartz sand, ceramsite, volcanic rock and the like) taking heterotrophic denitrification as a main denitrification way usually need a large amount of additional carbon sources to maintain the denitrification function; 2) The filter material (iron-based and sulfur-based material, etc.) with autotrophic denitrification as the main denitrification path often has the technical bottleneck of low denitrification efficiency. The denitrification filter material developed by the invention is an organic matter-ferrous matrix composite system, organic matters not only can provide a carbon source for heterotrophic denitrification, but also can provide a carbon source and an energy source for the growth of iron matrix denitrifying bacteria, and can promote electron transfer between ferrous and nitrate.
The invention also provides a preparation method of the denitrification filter material, which comprises the following specific steps:
uniformly mixing bagasse, siderite and ordinary portland cement according to a certain mass ratio to obtain a mixed material, adding water into the mixed material, uniformly mixing, granulating into balls, and then air-drying to obtain the denitrification filter material.
The bagasse is a by-product of a sucrose production plant.
The bagasse also comprises a pretreatment step before use: washing with deionized water, naturally drying at room temperature, crushing, sieving, and sieving.
The siderite is common iron ore and is sieved by a 40-mesh screen after being crushed before use.
The bagasse, the siderite and the ordinary portland cement are in the mass ratio: 30% -40%: 50% -70%: 10% -15%; preferably, it is 40%:50%:10 percent.
The mass ratio of the water to the mixed materials is (60-100): 100; preferably, 4.
The sphere diameter d =80 ± 20mm.
The air drying is preferably carried out at room temperature.
The air drying time is 5-7 days; preferably, it is 7 days.
In one embodiment, the method comprises the following specific steps:
1) Selection and pretreatment of raw materials
Bagasse is a byproduct of a sucrose production plant, is cleaned by deionized water, is naturally dried at room temperature, is crushed and is sieved by a 100-mesh sieve; the siderite is common iron ore, and is sieved by a 40-mesh screen after being crushed; portland cement is common ordinary Portland cement.
2) Raw material compounding
The raw materials are uniformly mixed according to the mass fractions of bagasse, siderite and ordinary portland cement of 30-40%, 50-70% and 10-15% respectively to obtain a mixed material, then water is added into the mixed material according to the mass ratio of 80g of water to 100g of the mixed material, and the mixed material is fully stirred uniformly and granulated into a sphere (the sphere diameter d =80 +/-20 mm). The formed filter material is placed in a ventilation place and air-dried for 5-7 days at room temperature. And obtaining the denitrification filter material.
According to the invention, different compounding experiments are carried out to obtain an optimized proportioning range, batch experiments with bagasse mass fractions of 10%, 20%, 30%, 40% and 50% are respectively carried out, 40% -80% of siderite and 10% -20% of ordinary portland cement are simultaneously added, and finally the performance of the mixture is evaluated to obtain the optimized compounding ratio of different raw materials.
The invention also provides application of the denitrification filter material in deep denitrification of tail water of a sewage plant or denitrification of wastewater with low C/N ratio.
The wastewater with the low C/N ratio is wastewater with the C/N less than 3.
The invention develops a novel denitrification filter material by combining the current research situation at home and abroad and considering the actual requirement of upgrading and modifying deep denitrification in sewage plants in China. The beneficial effects are as follows: the denitrification filter material is an organic matter-ferrous matrix composite system, organic matters not only can provide a carbon source for heterotrophic denitrification, but also can provide a carbon source and an energy source for the growth of iron matrix denitrifying bacteria, and can promote electron transfer between ferrous iron and nitrate.
Drawings
FIG. 1 is a process flow of the denitrification filter material developed by the present invention.
FIG. 2 shows denitrification performance of a denitrification filter (a) and internal release of ammonia nitrogen and COD (b)
FIG. 3 is a graph based on the comparison of denitrification performance of ceramsite and self-made filter material denitrification columns under different hydraulic retention time.
Detailed Description
The present invention will be described in further detail with reference to the following examples and the accompanying drawings. The procedures, conditions, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
Example 1 optimized compounding experiment of different raw materials of denitrification filter material
According to the invention, different compounding experiments are carried out to obtain the optimized proportioning range of the raw materials, batch experiments with bagasse mass fractions of 10%, 20%, 30%, 40% and 50% are respectively carried out, 40% -80% of siderite and 10% -20% of ordinary portland cement are simultaneously added, and finally the performance of the materials is evaluated to obtain the optimized compounding ratio of different raw materials. Table 1 summarizes the denitrification performance under different compounding ratios.
TABLE 1 Total nitrogen removal of filter materials prepared at different material ratios
Application example 1:
50g of the denitrification filter material prepared according to the formula 7 of the invention in example 1 was placed in a 500mL Erlenmeyer flask and 250mL of simulated wastewater treatment plant tail water (nitrate nitrogen formulated with potassium nitrate, about 12 mg/L) was added. Placing the conical flask in a constant temperature shaking table (25 deg.C; 100 r/min) after plugging for 3 days, continuously oscillating, changing water once and replenishing fresh simulated tail water again; then continuously oscillating for 3 days, changing water and replenishing fresh simulation tail water again; then changing water once a day and detecting the quality of the outlet water (figure 1) to judge the denitrification performance of the prepared denitrification filter material. After the system is stable, the total nitrogen removal rate is higher than 80%, the ammonia nitrogen concentration in effluent is lower than 0.5mg/L, and the COD concentration is lower than 20mg/L.
Application example 2:
the denitrification filter material prepared according to the formula 7 in the embodiment 1 of the invention is filled in a self-made denitrification column (the diameter is 20cm, the height is 120 cm) and compared with a control group (ceramsite is used as the filter material) to verify the denitrification effect of the filter material. The denitrification column adopts an up-flow type operation mode, and water enters from bottom to top to sequentially pass through a water distribution area (5 cm), a pebble supporting layer (15 cm), a filter material layer (100 cm) and a super-high layer (30 cm). The tail water of the simulated sewage plant is circulated in the denitrification column for 8 days through the peristaltic pump, and fresh simulated tail water is supplemented to maintain the nitrate nitrogen concentration in the period, so that the microorganisms are promoted to form a film on the surface and in the interior of the filter material. Then, normal water inflow is started, and the denitrification effects of the filter material and the ceramsite prepared under different hydraulic retention times are compared (figure 2). The denitrification efficiency of the denitrification filter is relatively best (the total nitrogen removal rate is more than 80%) under the condition that the Hydraulic Retention Time (HRT) is 5 h.
The above examples can show that the denitrification filter material developed in the invention can realize the high-efficiency denitrification of the tail water of the sewage plant by more than 80% without an external carbon source (the denitrification removal rate of the denitrification filter material is about 80% under the condition of an external large amount of carbon source in the existing common technology), and the whole manufacturing process of the filter material is simple, the raw materials are cheap, and a novel approach is provided for the resource utilization of bagasse.
The above-described embodiments of the present invention are not intended to be limiting. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept.
Claims (6)
1. A denitrification filter material is characterized in that the denitrification filter material is an organic matter-ferrous matrix composite system, and is prepared by compounding bagasse, siderite and ordinary portland cement as raw materials; the denitrification filter material is used for deep denitrification of tail water of a sewage plant or denitrification of wastewater with a low C/N ratio, wherein the wastewater with the low C/N ratio is wastewater with a C/N ratio less than 3; the mass fractions of bagasse, siderite and ordinary portland cement in the denitrification filter material are respectively 30-40%, 50-70% and 10-15%, and the sum of the components is 100%.
2. A preparation method of a denitrification filter material is characterized by comprising the following steps: uniformly mixing bagasse, siderite and ordinary portland cement according to a certain mass ratio to obtain a mixed material, adding water into the mixed material, uniformly mixing, granulating into balls, and then air-drying to obtain the denitrification filter material;
the bagasse also comprises a pretreatment step before use: washing with deionized water, naturally drying at room temperature, crushing, sieving, and screening;
the bagasse, the siderite and the ordinary portland cement are in the mass ratio: 30% -40%: 50% -70%: 10% -15%, and the sum of all the components is 100%.
3. The method according to claim 2, wherein the mass ratio of water to mixed material is (60-100): 100.
4. The method of claim 2, wherein the sphere diameter d =80 ± 20mm.
5. The method according to claim 2, wherein the air-drying is performed at room temperature; the air drying time is 5 to 7 days.
6. The use of the denitrification filter material of claim 1 for deep denitrification of wastewater from a wastewater treatment plant or denitrification of wastewater with a low C/N ratio, wherein the wastewater with a low C/N ratio is a wastewater with a C/N ratio of less than 3.
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| CN113511728B (en) * | 2021-07-26 | 2022-09-30 | 河北地势坤环保工程有限公司 | Constructed wetland denitrification system and sewage denitrification method thereof |
| CN114275896B (en) * | 2021-12-23 | 2022-10-11 | 江西挺进环保科技股份有限公司 | Percolation biochemical treatment system applied to denitrification of enhanced percolation system |
| CN115093035A (en) * | 2022-06-21 | 2022-09-23 | 上海太和水科技发展股份有限公司 | Methyl cinnamate complexing agent for controlling propagation of filamentous algae in tail water wetland and preparation and use methods thereof |
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| CN110642338A (en) * | 2019-10-30 | 2020-01-03 | 深圳杜尔环境科技有限公司 | Sewage nitrogen and phosphorus removal filler and preparation method thereof |
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| CN103801254B (en) * | 2014-02-25 | 2015-12-09 | 合肥工业大学 | A kind of denitrogenation dephosphorizing material based on siderite and using method thereof |
| CN104129850B (en) * | 2014-08-14 | 2016-09-28 | 合肥工业大学 | A kind of method of azotate pollution in in-situ remediation of underground water |
| CN108862574A (en) * | 2018-06-22 | 2018-11-23 | 河海大学 | Denitrifying artificial wet land system and its sewage denitrification method are cooperateed with based on reduction-state Fe autotrophy/sawdust heterotrophism |
| CN110330115A (en) * | 2019-06-05 | 2019-10-15 | 中国矿业大学 | A kind of composite filling of intensified denitrification and dephosphorization and its application in sewage treatment |
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| CN111646578B (en) * | 2020-05-28 | 2021-05-11 | 河海大学 | Method for removing nitrate in sewage through synergetic denitrification of iron autotrophic bacteria and heterotrophic bacteria |
| CN111362405B (en) * | 2020-05-28 | 2020-09-08 | 北京涞澈科技发展有限公司 | Material for denitrification by autotrophic heterotrophic synergetic biological denitrification method, preparation method and application |
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| CN106396097A (en) * | 2016-11-22 | 2017-02-15 | 南京大学宜兴环保研究院 | Autotrophic/heterotrophic denitrification-based integrated nitrogen removal apparatus and nitrogen removal method thereof |
| CN110642338A (en) * | 2019-10-30 | 2020-01-03 | 深圳杜尔环境科技有限公司 | Sewage nitrogen and phosphorus removal filler and preparation method thereof |
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