CN113511728B - Constructed wetland denitrification system and sewage denitrification method thereof - Google Patents
Constructed wetland denitrification system and sewage denitrification method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of sewage treatment, and provides an artificial wetland denitrification system which is characterized in that a soil layer, a limestone packing layer, a synergetic autotrophic heterotrophic packing layer and a zeolite packing layer are sequentially arranged from top to bottom, and the layers play a synergistic role, so that the denitrification effect of the artificial wetland system on sewage is remarkably improved. The autotrophic heterotrophic packing layer synergistically improves the denitrification effect of the polluted water through the rice bran heterotrophic effect and the siderite autotrophic effect, and the siderite is activated to remarkably increase the adsorption capacity of iron autotrophic microorganisms, so that the autotrophic denitrification efficiency in the system is improved, and the denitrification effect of the constructed wetland denitrification system is remarkably improved.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to an artificial wetland denitrification system and a sewage denitrification method thereof.
Background
With the continuous increase of the population quantity of China, the rapid increase of water consumption and the change of living habits of people, the discharge of low-concentration domestic sewage is continuously increased, so that the quality of the domestic sewage in cities and towns of China, particularly the sewage in cities and towns of south China, is continuously developed towards the trend of low carbon resource. Therefore, the trend of low carbon source of urban sewage water quality brings greater challenges to the conventional denitrification process which has certain difficulty in realizing the synchronous denitrification and dephosphorization of the conventional C/N ratio sewage. When the artificial wetland technology is used for treating low organic carbon sewage, an organic carbon source is usually directly supplemented into a system to promote heterotrophic denitrification, but the method is high in cost, and the addition of the organic carbon source can generate by-product ammonia nitrogen, so that the effluent is turbid and the like.
The autotrophic denitrification does not need additional organic carbon source, and mainly refers to that inorganic substances (such as hydrogen and sulfur) are used as electron donors and inorganic carbon compounds (such as CO) 2 、HCO 3- ) As a carbon source for metabolism by the microorganism. A class of iron autotrophic denitrifying bacteria is now discovered that can convert NO under anaerobic conditions 3- As electron acceptors, elemental iron and various forms of Fe 2+ The compound is used as an electron donor, and NO is added 3- Reduction to N 2 And removing the nitrogen, thereby realizing the aim of removing the nitrogen from the polluted water, but the nitrogen removal efficiency is lower when the nitrogen is independently applied.
In order to improve the efficiency of the denitrification of the polluted water, at present, many researchers at home and abroad combine the heterotrophic denitrification and the autotrophic denitrification to perform the denitrification treatment on the polluted water in a synergistic manner, so that the inherent defects of the heterotrophic denitrification and the autotrophic denitrification when the heterotrophic denitrification and the autotrophic denitrification are used independently are overcome, and the denitrification efficiency is improved. Patent application CN112694169A discloses an autotrophic-heterotrophic denitrification integrated denitrification device and method, in which autotrophic denitrifying bacteria and heterotrophic denitrifying bacteria are coupled in different parts of the same reactor, and the circulation promotes the autotrophic denitrification reaction zone and the heterotrophic denitrification reaction zone to have good mass transfer effect, so that the coordinated and stable operation of the autotrophic-heterotrophic denitrification process is realized, and nitrogen in nitrogen-containing wastewater can be continuously and efficiently removed.
Disclosure of Invention
The invention provides a denitrification system with better effect, which is used for carrying out heterotrophic-autotrophic denitrification sewage denitrification treatment after mixing rice bran and siderite and carrying out related treatment on components in the system, thereby not only realizing resource utilization of wastes, but also solving the problems of complex denitrification process and poor effect in the prior art.
The technical scheme of the invention is as follows:
an artificial wetland denitrification system is sequentially provided with a soil layer, a limestone packing layer, a synergetic autotrophic heterotrophic packing layer and a zeolite packing layer from top to bottom.
Further, the soil layer is selected from one or more of brick red soil, red soil, red soil and brown soil.
Further, the thickness of the soil layer is 50-100 cm.
Further, the limestone filler layer is a mixture of limestone and sodium hydrosulfite in a mass ratio of 5-8:1, the particle size of the limestone is 8-15mm, and the filling thickness is 20-25 cm.
Further, the synergistic autotrophic heterotrophic packing layer is prepared from rice bran and siderite according to a volume ratio of 1: 0.5-3, and the filling thickness is 35-45 cm.
Further, the rice bran is washed, dried, crushed and filled.
Further, after being crushed, the siderite is sequentially treated by sodium fluosilicate, alpha-starch, hydroximic acid and ammonium citrate and then mixed with rice bran for filling.
Further, the hydroximic acid is one or more of C5-9 hydroximic acid, benzohydroxamic acid, salicylhydroxamic acid and benzohydroxamic acid.
Furthermore, the siderite is crushed into the particle size of 3.5-4mm, water is added to form siderite slurry with the concentration of 35-45%, then 1000-3000g/t sodium fluosilicate and 50-80mg/t alpha-starch are sequentially added, the pH of the slurry is adjusted to 6.5-7.5, and then 100-800g/t benzohydroxamic acid and 200-600g/t ammonium citrate are added for treatment and then mixed with rice bran for filling.
Further, the rice bran and the siderite are wrapped by gauze and then filled.
Further, the gauze is absorbent gauze of 100mm × 100 mm.
Further, the particle size of zeolite in the zeolite filler layer is 5-10mm, the zeolite filler layer is soaked by NaCl solution with the concentration of 1-1.5mol/L and hydrochloric acid with the concentration of 0.1-1.0mol/L in sequence, then washed by clear water until the pH value of washing liquid is 6.5-7.5, and the washing liquid is dried and filled to the thickness of 8-10 cm.
The invention also provides a sewage denitrification method of the constructed wetland denitrification system, which comprises the following steps:
(1) and (3) starting a biofilm culturing stage: adding an iron autotrophic microorganism culture solution into the artificial wetland system, and replacing the culture solution every 2-3 days for 10-17 times;
(2) and (3) a stable operation stage: and (2) adding the sewage into the artificial wetland system in the step (1) to perform sewage denitrification.
Further, the iron autotrophic microorganism culture solution comprises the following components in percentage by weight: 6g/L FeSO 4 ·7H 2 O、0.5g/L MgSO 4 ·7H 2 O、2.0g/L NaHCO 3 、0.01g/L CaCl 2 、0.73g/L NaNO 3 、0.25g/L KNO 3 。
Further, the addition amount of the iron autotrophic microorganism culture solution is based on submerging a soil layer.
The working principle and the beneficial effects of the invention are as follows:
1. the invention takes a soil layer, a limestone packing layer, a synergic autotrophic heterotrophic packing layer and a zeolite packing layer as a complete system, wherein iron autotrophic denitrifying bacteria are provided in the soil layer; the limestone layer can consume dissolved oxygen in water through the reaction of limestone and sodium hydrosulfite in water, an anoxic environment is provided for the growth of iron autotrophic microorganisms in the subsequent synergic autotrophic packing layer, and excessive heat generated by reaction is avoided to kill the iron autotrophic microorganisms by strictly controlling the mass ratio of the limestone to the sodium hydrosulfite; the autotrophic heterotrophic packing layer synergistically improves the denitrification effect of the polluted water through the heterotrophic effect of the rice bran and the autotrophic effect of the siderite; the zeolite filler layer can further adsorb nitrogen, phosphorus and other substances in the sewage, and can also adsorb Fe 3+ To purify the color of the polluted water.
2. The siderite in the autotrophic filling layer is activated, pores of the siderite treated by the sodium fluosilicate, the alpha-starch, the benzohydroxamic acid and the ammonium citrate are increased, the adhesion of the siderite to the iron autotrophic microorganisms is improved, the iron autotrophic microorganisms can better utilize iron electron donors in the siderite when needed, and the nitrogen removal efficiency of the siderite is obviously improved. When the carbon source released by the rice bran is less, the treated siderite can efficiently realize the nitrogen removal effect, meanwhile, the decomposed nutrient substances in the rice bran can be utilized by the iron autotrophic microorganisms, the reproduction and activity of the microorganisms are further improved, the metabolites of the iron autotrophic microorganisms promote the decomposition of the rice bran, and a virtuous cycle denitrification system is realized.
3. The invention also carries out activation treatment on the zeolite in the zeolite filler layer, and after the zeolite is treated by sodium chloride and hydrochloric acid, a series of micropores are formed in the zeolite, so that the Fe generated by the zeolite on the adsorption autotrophic and heterotrophic filler layer can be improved 3+ Ability to avoid Fe in water 3+ In the presence of (B) and shows yellow, furtherThe sewage purification treatment is realized.
4. The siderite and the rice bran adopted in the invention are cheap and easily available, and both are wastes, so that the wastes can be recycled, byproducts are not generated, and secondary environmental pollution is avoided.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any inventive step, are intended to be within the scope of the present invention.
Example 1
The constructed wetland denitrification system is sequentially provided with a soil layer, a limestone packing layer, a synergetic autotrophic heterotrophic packing layer and a zeolite packing layer from top to bottom.
Wherein the soil layer is red soil with the thickness of 100 cm;
in the limestone filler layer, the mass ratio of the mixture of limestone and sodium hydrosulfite is 6:1, the particle size of the limestone is 10mm, and the paving thickness is 22 cm.
The synergistic autotrophic heterotrophic packing layer is prepared by mixing rice bran and siderite according to a volume ratio of 1: 1, and the thickness is 40 cm.
Specifically, (1) the rice bran is cleaned, dried and crushed for later use;
(2) the siderite is crushed into particles with the particle size of 4mm, water is added to form siderite slurry with the concentration of 40%, 2000g/t of sodium fluosilicate and 60mg/t of alpha-starch are sequentially added to adjust the pH of the slurry to be 7.0, and then 500g/t of benzohydroxamic acid and 400g/t of ammonium citrate are added to treat the siderite for later use;
(3) the rice bran and siderite are mixed and wrapped in absorbent gauze of 100mm × 100mm and then filled into the synergistic autotrophic heterotrophic packing layer.
The particle size of zeolite in the zeolite filler layer is 8mm, the zeolite filler layer is soaked by NaCl solution with the concentration of 1.0mol/L and hydrochloric acid with the concentration of 0.5mol/L in sequence, then washed by clear water until the pH value of washing liquid is 7.0, and the washing liquid is dried and filled, wherein the filling thickness is 8 cm.
The embodiment also provides a sewage denitrification method of the artificial wetland denitrification system, which comprises the following steps:
(1) and (3) starting a biofilm formation stage: adding an iron autotrophic microorganism culture solution into the artificial wetland system until the culture solution submerges the soil layer, and replacing the culture solution every 2 days for 17 times;
(2) and (3) a stable operation stage: and (3) adding the sewage into the artificial wetland system in the step (1) to perform sewage denitrification.
Wherein the iron autotrophic microorganism culture solution comprises the following components in percentage by weight: 6g/L FeSO 4 ·7H 2 O、0.5g/L MgSO 4 ·7H 2 O、2.0g/L NaHCO 3 、0.01g/L CaCl 2 、0.73g/L NaNO 3 、0.25g/L KNO 3 。
Example 2
The constructed wetland denitrification system is sequentially provided with a soil layer, a limestone packing layer, a synergetic autotrophic heterotrophic packing layer and a zeolite packing layer from top to bottom.
Wherein the soil layer is brick red soil with the thickness of 70 cm;
in the limestone filler layer, the mass ratio of the mixture of limestone and sodium hydrosulfite is 5:1, the particle size of the limestone filler is 8mm, and the paving thickness is 20 cm.
The synergic autotrophic heterotrophic packing layer is prepared from rice bran and siderite according to a volume ratio of 1: 0.5 to 35cm thick.
Specifically, (1) the rice bran is cleaned, dried and crushed for later use;
(2) crushing the siderite into particles with the particle size of 3.5mm, adding water to form siderite slurry with the concentration of 35%, then sequentially adding 1000g/t of sodium fluosilicate and 50mg/t of alpha-starch, adjusting the pH of the slurry to 6.5, and then adding 100g/t of benzohydroxamic acid and 200g/t of ammonium citrate for treatment for later use;
(3) the rice bran and siderite are mixed and wrapped in absorbent gauze of 100mm × 100mm and then filled into the synergistic autotrophic heterotrophic packing layer.
The particle size of zeolite in the zeolite filler layer is 10mm, the zeolite filler layer is sequentially soaked in NaCl solution with the concentration of 1.5mol/L and hydrochloric acid with the concentration of 0.1mol/L, then washed by clean water until the pH value of washing liquid is 7.5, and the washing liquid is dried and filled with the thickness of 10 cm.
The embodiment also provides a sewage denitrification method of the artificial wetland denitrification system, which comprises the following steps:
(1) and (3) starting a biofilm formation stage: adding an iron autotrophic microorganism culture solution into the artificial wetland system until the culture solution submerges the soil layer, and replacing the culture solution every 3 days for 10 times;
(2) and (3) a stable operation stage: and (3) adding the sewage into the artificial wetland system in the step (1) to perform sewage denitrification.
Wherein the iron autotrophic microorganism culture solution comprises the following components in percentage by weight: 6g/L FeSO 4 ·7H 2 O、0.5g/L MgSO 4 ·7H 2 O、2.0g/L NaHCO 3 、0.01g/L CaCl 2 、0.73g/L NaNO 3 、0.25g/L KNO 3 。
Example 3
The constructed wetland denitrification system is sequentially provided with a soil layer, a limestone packing layer, a synergetic autotrophic heterotrophic packing layer and a zeolite packing layer from top to bottom.
Wherein the soil layer is brown soil with the thickness of 50 cm;
the mass ratio of the mixture of limestone and sodium hydrosulfite in the limestone filler layer is 8:1, the particle size of the limestone filler is 15mm, and the paving thickness is 25 cm.
The synergistic autotrophic heterotrophic packing layer is prepared by mixing rice bran and siderite according to a volume ratio of 1: 3 and the thickness is 45 cm.
Specifically, (1) the rice bran is cleaned, dried and crushed for later use;
(2) crushing the siderite into particles with the particle size of 4mm, adding water to form siderite slurry with the concentration of 45%, then sequentially adding 3000g/t of sodium fluosilicate and 80mg/t of alpha-starch, adjusting the pH of the slurry to 7.5, and then adding 800g/t of benzohydroxamic acid and 600g/t of ammonium citrate for treatment for later use;
(3) the rice bran and siderite are mixed and wrapped in absorbent gauze of 100mm × 100mm and then filled into the synergistic autotrophic heterotrophic packing layer.
The grain size of zeolite in the zeolite filler layer is 5mm, the zeolite filler layer is sequentially soaked by NaCl solution with the concentration of 1.0mol/L and hydrochloric acid with the concentration of 1.0mol/L, then washed by clear water until the pH value of washing liquid is 6.5, and the zeolite filler layer is filled after being dried, wherein the filling thickness is 8 cm.
The embodiment also provides a sewage denitrification method of the constructed wetland denitrification system, which comprises the following steps:
(1) and (3) starting a biofilm formation stage: adding an iron autotrophic microorganism culture solution into the constructed wetland system until the culture solution submerges the soil layer, and replacing the culture solution once every 2 days for 15 times;
(2) and (3) a stable operation stage: and (3) adding the sewage into the artificial wetland system in the step (1) to perform sewage denitrification.
Wherein the iron autotrophic microorganism culture solution comprises the following components in percentage by weight: 6g/L FeSO 4 ·7H 2 O、0.5g/L MgSO 4 ·7H 2 O、2.0g/L NaHCO 3 、0.01g/L CaCl 2 、0.73g/L NaNO 3 、0.25g/L KNO 3 。
Comparative example 1
The mass ratio of limestone to sodium hydrosulfite in the limestone packing layer is 4:1, and the rest is the same as that in example 1.
In this scheme, since the mass ratio of limestone to sodium dithionite was 4:1, the proportion of sodium dithionite increased compared to examples 1-3, and it reacted with limestone in water to generate excessive heat, resulting in the killing of iron autotrophic microorganisms in the system and failure of subsequent experiments.
Comparative example 2
The siderite in the synergic autotrophic heterotrophic packing layer is treated as follows, and the rest is the same as the example 1:
crushing the siderite into particles with the particle size of 4mm, soaking the siderite for 60min by using dilute hydrochloric acid to remove impurities on the surface of the siderite, and then washing the siderite by using clear water until the pH value of the washing water is 7.0 for later use;
comparative example 3
The siderite in the layer of the synergistically autotrophic heterotrophic packing is treated as follows, with the remainder being as in example 1:
the siderite is crushed into particles with the particle size of 4mm, water is added to form siderite slurry with the concentration of 40%, 2000g/t of sodium fluosilicate and 60mg/t of common starch are sequentially added, the pH of the slurry is adjusted to 7.0, and 300g/t of sodium dodecyl sulfate and 400g/t of ammonium citrate are added for treatment and later use;
comparative example 4
The zeolite in the zeolite packing layer was treated as follows, as in example 1.
The zeolite in the zeolite packing layer has a particle size of 8mm, and NaNO with a concentration of 1.0mol/L is sequentially used 3 Soaking the solution in 0.5mol/L nitric acid, washing with clear water until the pH value of the washing liquid is 7.0, drying, and filling to a thickness of 8 cm.
The water treated in examples 1-3 and comparative examples 2-4 was collected separately, placed in a nano-scale colorimetric tube with 10mL per tube, placed on a white background, and the color of each tube was observed vertically from top to bottom, wherein only the water collected in comparative example 4 appeared yellow.
Examples of the experiments
According to the constructed wetland denitrification system provided by the embodiment 1-3 and the comparative example 2-4, the nitrate nitrogen, ammonia nitrogen and total nitrogen concentration in the sewage before treatment are measured, the nitrate nitrogen, ammonia nitrogen and total nitrogen concentration in the sewage are measured after the sewage is treated in the system for 10 days, and the nitrogen removal rate is calculated. Removal rate (concentration before treatment-concentration after treatment)/concentration before treatment × 100%
Wherein, the total nitrogen is determined by alkaline potassium persulfate digestion ultraviolet spectrophotometry, the ammonia nitrogen is determined by a distilled Nashinou reagent colorimetry, the nitrate nitrogen is determined by the spectrophotometry, and the results are shown in the following tables 1-3.
TABLE 1 effect of removing nitrate and nitrogen in sewage by different artificial wetland systems
TABLE 2 Ammonia nitrogen removing effect of different constructed wetland systems
TABLE 3 Total effect of total nitrogen in sewage removal of different constructed wetland systems
The data in tables 1-3 show that the removal rate of the constructed wetland system on nitrate nitrogen in sewage reaches more than 87%, the removal rate on ammonia nitrogen reaches 95% and the removal rate on total nitrogen reaches more than 83% through the synergistic action of the soil layer, the limestone filler layer, the synergetic autotrophic heterotrophic filler layer and the zeolite filler layer; while the comparative example 2 only treats the surface impurities of the siderite, the removal rate of nitrate nitrogen is only 59.4%, the removal rate of ammonia nitrogen is only 68.6%, and the removal rate of total nitrogen is only 57.8%, which are all obviously reduced, thus the siderite is a potential electron donor of iron autotrophic microorganisms, but the siderite has limited capability of providing the electron donor when being directly applied, and the siderite needs to be activated. Compared with the comparative example 2, the system of the comparative example 3 has 73% of the removal rate of nitrate nitrogen in sewage, 82.5% of the removal rate of ammonia nitrogen and 77.9% of the removal rate of total nitrogen, but the removal rate of the comparative example 3 is still lower compared with that of the comparative example 3, which shows that after the siderite is treated by sodium fluosilicate, alpha-starch, benzohydroxamic acid and ammonium citrate, pores are increased, the adhesion force to iron autotrophic microorganisms is improved, the nitrogen removal efficiency is obviously improved, and the change of the activating agent influences the N removal effect of the final system on the sewage. Comparative example 4 the zeolite treatment agent was changed, and the removal rate of N from the wastewater by the system was also somewhat reduced compared to examples 1-3, although the main effect of the zeolite was to eliminate Fe 3+ The effect on the color of water, but the treated zeolite also has a certain denitrification effect, and the denitrification effect of the treatment reagent is changed.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The constructed wetland denitrification system is characterized in that a soil layer, a limestone packing layer, a synergetic autotrophic heterotrophic packing layer and a zeolite packing layer are sequentially arranged from top to bottom;
the limestone packing layer is a mixture of limestone and sodium hydrosulfite, the mass ratio is 5-8:1, the particle size of the limestone is 8-15mm, and the packing thickness is 20-25 cm;
the synergic autotrophic heterotrophic packing layer is prepared from rice bran and siderite according to a volume ratio of 1: 0.5-3, and the filling thickness is 35-45 cm;
after being crushed, the siderite is sequentially treated by sodium fluosilicate, alpha-starch, hydroximic acid and ammonium citrate and then mixed with rice bran for filling;
the particle size of zeolite in the zeolite filler layer is 5-10mm, the zeolite filler layer is soaked in NaCl solution with the concentration of 1-1.5mol/L and hydrochloric acid with the concentration of 0.1-1.0mol/L in sequence, then washed by clear water until the pH value of washing liquid is 6.5-7.5, and the washing liquid is dried and filled with the filling thickness of 8-10 cm.
2. The constructed wetland denitrification system of claim 1, wherein the soil layer is selected from one or more of brick red soil, red soil, red soil and brown soil.
3. The constructed wetland denitrification system according to claim 1, wherein the rice bran is washed, dried, crushed and filled.
4. The constructed wetland denitrification system of claim 1, wherein the siderite is crushed to 3.5-4mm particle size, water is added to form siderite slurry with the concentration of 35-45%, then 1000-3000g/t sodium fluosilicate and 50-80mg/t alpha-starch are sequentially added to adjust the pH of the slurry to 6.5-7.5, and then 100-800g/t benzohydroxamic acid and 200-600g/t ammonium citrate are added for treatment and then mixed with rice bran for filling.
5. The sewage denitrification method of the constructed wetland denitrification system according to any one of claims 1 to 4, characterized by comprising the following steps:
(1) and (3) starting a biofilm culturing stage: adding an iron autotrophic microorganism culture solution into the constructed wetland system of any one of claims 1 to 4, and replacing the culture solution every 2 to 3 days for 10 to 17 times;
(2) and (3) a stable operation stage: and (3) adding the sewage into the artificial wetland system in the step (1) to perform sewage denitrification.
6. The sewage denitrification method of the constructed wetland denitrification system according to claim 5, wherein the iron autotrophic microorganism culture solution comprises the following components in percentage by weight: 6g/L FeSO 4 •7H 2 O、0.5g/L MgSO 4 •7H 2 O、2.0g/L NaHCO 3 、0.01g/L CaCl 2 、0.73g/L NaNO 3 、0.25g/L KNO 3 。
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