Preparation method and use method of denitrification solid carbon source
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a preparation method and a use method of a denitrification solid carbon source. A modified poly-3-hydroxybutyrate-hydroxyvalerate (PHBV) by sodium bicarbonate, anhydrous ferric chloride and anhydrous manganese chloride is used as a denitrification device filler and a specific use method.
Background
In recent years, due to the change of economic industry of China, a large amount of nitrogenous domestic sewage and agricultural sewage are discharged into water bodies. The content of nitrate nitrogen in surface water systems of various regions and underground water of partial regions is increased sharply, and the method becomes a field needing to be developed intensively in the current water treatment technology.
At present, the main means for removing nitrate nitrogen in town sewage treatment is to convert nitrate nitrogen into nitrogen to be discharged into the atmosphere by the action of denitrifying bacteria. In order to be able to ensure sufficient activity of the denitrifying bacteria, it is necessary to have a sufficient carbon source as an energy supply in their reaction environment.
The existing sewage treatment process in China generally has the condition of insufficient carbon source in the denitrification link, and on the other hand, the discharge standard of total nitrogen is increasingly raised along with the improvement of the water treatment standard. Therefore, under the condition of ensuring the water conditions, the research on novel external carbon sources has become an urgent key problem in the water treatment process.
The existing external carbon sources can be generally divided into two major types, namely traditional soluble carbon sources and novel solid carbon sources (Shao stay, Xu Zu Xin, Yi sea dragon, research progress of external carbon sources in denitrification process of polluted water body, industrial water treatment 27(12) (2007) 10-14).
The traditional soluble carbon source mainly comprises liquid organic matters such as methanol, acetic acid, glucose and the like. However, such soluble organics generally have some problems, such as: the carbon-nitrogen ratio is difficult to control; the method has the operating problems that the nitrate nitrogen in water is difficult to regulate and control when fluctuation occurs, the COD (chemical oxygen demand) of effluent water quality is increased when excessive carbon source addition is carried out, and the generation of nitrite is accumulated when insufficient addition is carried out.
The above conditions can cause the quality of the effluent to be poor, and influence is caused. And the solid carbon source can be utilized by denitrifying bacteria only by decomposing the filler by using enzyme in the microorganism under the condition that the microorganism is attached. On one hand, the control problem of carbon source addition is avoided, and on the other hand, the effluent quality is not influenced.
In recent years, many researchers at home and abroad search for a nontoxic and cheap slow-release carbon source to replace the traditional carbon source through many ways, and most of the slow-release carbon source is natural solid organic matter rich in cellulose substances and some biodegradable artificial materials, such as cotton, rice hulls, paper, degradable meal boxes, PCL, starch and the like. However, such materials generally have the disadvantages of hydrophobicity, easy crystallization, long degradation time and the like.
Poly-3-hydroxybutyrate valerate (PHBV) is biological polyester which is produced by using starch as a raw material and applying a fermentation engineering technology. The application of the composite material in the technical field of water treatment has proved to be effective, but the material has the defects of stronger hydrophobicity, large particle density, difficulty in providing a microorganism living place and the like, and can influence the use in practical engineering. Therefore, the PHBV raw material is modified, and the problems are solved.
Disclosure of Invention
In order to solve the problems of long film forming time, small number of microorganisms per unit volume, low biological film strength, poor impact resistance and the like of the traditional solid carbon source, a preparation method and a use method of the denitrification solid carbon source are provided.
The specific scheme of the invention is as follows: a preparation method of a denitrification solid carbon source is characterized by comprising the following steps:
(1) putting poly (3-hydroxybutyrate-hydroxyvalerate) (PHBV) powder into a beaker, and heating for 3-5 min at 160-175 ℃; after the poly 3-hydroxybutyrate-hydroxyvalerate is melted, the mass ratio of poly 3-hydroxybutyrate-hydroxyvalerate: sodium bicarbonate: anhydrous ferric chloride: anhydrous manganese chloride = 100: 5-10: 0.005-0.020: adding 0.001-0.010 reagent into a beaker, and stirring for 30-60 s at the speed of 60-120 rpm/min to prepare the denitrification solid carbon source.
(2) Cooling the denitrification solid carbon source, taking out, and filling into a mesh-shaped filler bag with the aperture of 1.0-2.0 mm to obtain the filler porosity of 55-65%; placing the filling bag into a container filled with 1-6% of beta-glucan water solution, and oscillating for 15-30 s on a table oscillator; taking out the filling bag and drying in the air; putting the mixture into a reactor, wherein the filling rate of the reactor is 50%; the filler soaked by the beta-glucan aqueous solution can enhance the interception capability on microorganisms and improve the film hanging speed; through oscillation, the air content in the modified PHBV material is reduced, and the influence on an anaerobic environment can be reduced; the filling bag can be taken out at any time, so that the reactor and the filling are convenient to clean, replace and test, and the filling bag is prevented from floating upwards;
(3) mixing the prepared sewage (formula shown in table 1) and activated sludge according to the volume ratio of = 1: 3 and stirring at a speed of 60rpm/min to form a mixed liquid. KH in 50L sewage2PO4The content is 1.00 g; MgSO (MgSO)4The content is 0.55 g; CaCl2The content is 0.14 g; MnSO4The content is 0.13 g; FeCl3·6H2The O content is 0.18 g; ZnCl2The content is 0.11 g; NaNO3The content was 12.14 g.
(4) The mixed liquid enters from the lower part of the reactor through a peristaltic pump, flows out from the top and continuously runs for 36-48 h; then preparing sewage and continuously operating the reactor, keeping the hydraulic retention time at 1.5h, and carrying out rapid film formation; taking effluent liquid of the reactor every 24 hours, filtering, measuring the content of nitrate nitrogen and DOC and the pH value, and maintaining the operation of the reactor.
The activated sludge is from anaerobic pond sludge of a sewage treatment plant.
The modified PHBV material is used as a solid carbon source of a reactor and a microorganism attachment carrier. The method has the advantages that the microorganism attachment space is greatly increased, and the quantity of denitrifying bacteria is increased; the start-up time of the reactor is shortened; the wettability of the material is improved; the absorption of the microorganism to nutrient substances is accelerated, and the propagation of the microorganism is strengthened; the concentration of the effluent nitric acid nitrogen is stable and meets the sewage discharge requirement; the operation is simple and the control is easy.
The invention has the beneficial effects that:
(1) the modified PHBV has improved porosity and viscosity, greatly improves the attachment of microorganisms and improves the denitrification efficiency;
(2) the modified PHBV is more suitable for the survival of denitrifying microorganisms and the propagation of the microorganisms is strengthened;
(3) the modified PHBV greatly enhances the denitrification capability of the PHBV and shortens the starting time of the reactor;
(4) the modified PHBV filler does not have obvious influence on the pH environment in the reactor.
Drawings
FIG. 1 is a flow chart of the manufacturing process of the modified PHBV filler of the present invention.
FIG. 2 is a process flow diagram of a method of use of the present invention.
Reference numbers in the figures: 1-a water inlet barrel; 2-a peristaltic pump; 3-a water inlet; 4-a reactor; 5-filling mesh bags; 6-water outlet; 7-water outlet; 8-a filler; 9-a stirrer.
Detailed description of the preferred embodiments
The invention provides a method for modifying PHBV raw material and removing nitric acid and nitrogen in water by using the PHBV raw material as reactor filler, and the invention is further explained by combining the attached drawings and a specific embodiment. Wherein, the commercial PHBV, beta-glucan, laboratory sodium bicarbonate, anhydrous ferric chloride and anhydrous manganese chloride reagents are selected and analyzed to be pure.
In the invention, KH is contained in 50L of prepared sewage2PO4 1.00 g; MgSO (MgSO)40.55 g; CaCl20.14 g; MnSO40.13 g; FeCl3·6H2O is 0.18 g; ZnCl20.11 g; NaNO3It was 12.14 g.
The reactor of the invention is a packed bed reaction column.
Example 1
(1) Putting the PHBV powder into a beaker, and heating for 5min at 160-175 ℃. After the PHBV is melted, the mass ratio of PHBV: sodium bicarbonate: anhydrous ferric chloride: anhydrous manganese chloride = 100: 5: 0.010: adding 0.005 reagent into a beaker, stirring at the speed of 100rpm/min for 60s, and naturally cooling to prepare a filler;
(2) cooling the filler, taking out, filling the filler into a mesh bag with the aperture of 1.0-2.0 mm, then putting the mesh bag into a container filled with 1% beta-glucan water solution, and oscillating the mesh bag on a table oscillator for 30 s; taking out the packing bag, airing, and putting the packing bag into a reactor, wherein the filling rate of the reactor is 50%;
(3) the prepared sewage is not added with any organic carbon source. Preparing sewage and activated sludge according to a volume ratio of 1: 3, mixing; a stirring device is additionally arranged and is stirred at the speed of 60 rpm/min; the activated sludge comes from anaerobic tank sludge of sewage treatment plants in Taiyuan city;
(4) the reactor is made of organic glass and is cylindrical, the inner diameter is 5cm, the height is 45cm, and the effective volume is 0.88L, as shown in figure 2; and pumping the mixed water sample from the bottom, allowing the mixed water sample to flow out from the top, continuously running for 48 hours, and controlling the temperature to be 15-17 ℃. Continuously injecting the prepared sewage into the reactor by using a peristaltic pump, wherein the hydraulic retention time is 1.5 h;
(5) then taking effluent every 24 hours, filtering the effluent through a 0.45-micrometer filter membrane, and testing the content of nitrate nitrogen and DOC and the pH value; ensuring enough sewage preparation and maintaining the operation of the reactor;
(6) after 3 days, the nitrogen content of nitrate in the effluent of the reactor can be stably reduced from 40mg/L to below 0.5mg/L, the DOC content is continuously maintained at 0.1-5 mg/L, and the pH value is changed between 6.89-7.21.
Example 2
(1) PHBV in mass ratio: sodium bicarbonate: anhydrous ferric chloride: anhydrous manganese chloride = 100: 10: 0.020: 0.010 to prepare a modified material.
(2) The oscillation time is 15s, and the mixed water sample is continuously injected for 36 h; the rest of the filler treatment, wastewater formulation, reactor specifications, operating conditions, test methods, etc. were the same as in example 1.
(3) After 3 days, the nitrogen content of nitrate in the effluent of the reactor can be stably reduced from 40mg/L to below 2.5mg/L, the DOC content is continuously kept at 2.5-5.5 mg/L, and the pH value is changed between 6.71-7.33.
Example 3
(1) PHBV in mass ratio: sodium bicarbonate: anhydrous ferric chloride: anhydrous manganese chloride = 100: 10: 0.015: 0.070 to modify the material.
(2) The oscillation time is 15s, and the mixed water sample is continuously injected for 36 h; the rest of the filler treatment, wastewater preparation, reactor specifications, operating conditions, and test methods were the same as in example 1.
(3) After 3 days, the nitrogen content of nitrate in the effluent of the reactor can be stably reduced from 40mg/L to below 2.0mg/L, the DOC content is continuously kept at 5.0-7.0 mg/L, and the pH value is changed between 6.95-7.25.
The measured data results of the examples can meet the ideal requirements. Reactor mean NO3 -The N removal rate is more than 95 percent and the highest rate is 98 percent; the DOC concentration does not influence the COD of the effluent; the pH value is in the range suitable for the growth of the denitrifying bacteria; the film forming speed is 1 day faster than that of a PHBV raw material reactor. Therefore, the modified PHBV can be used as a more excellent solid carbon source.
The foregoing description of the examples is provided to enable any person skilled in the art to make and use the present invention. It will be apparent to those skilled in the art that modifications may be made to the described examples of the invention and the general principles of the technology may be applied to other examples. Therefore, the present invention is not limited to the above examples, and modifications and improvements made without departing from the scope of the invention should fall within the protection scope of the invention.