CN111099787A - Total nitrogen treatment process for desulfurization wastewater of coal-fired power plant - Google Patents
Total nitrogen treatment process for desulfurization wastewater of coal-fired power plant Download PDFInfo
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Abstract
The invention relates to a total nitrogen treatment process for desulfurization wastewater of a coal-fired power plant, which comprises the following steps: chemical precipitation treatment; treating nitrogen and sulfur compounds; and (4) treating the microorganisms. The invention further processes the nitrogen compound which is difficult to degrade and is generated in the coal-fired process through chemical precipitation, nitrogen-sulfur compound treatment and biological treatment, thereby effectively reducing the total nitrogen in the coal-fired power generation process to meet the stricter total nitrogen control requirements of different countries and regions.
Description
Technical Field
The invention relates to a wastewater treatment process, in particular to a total nitrogen treatment process for desulfurization wastewater of a coal-fired power plant.
Background
China, as a large power energy consumption country, relies on coal-fired power plants to generate electricity as a main power source, and coal-fired power generation accounts for 65% in the national power generation structure until 2016. The main pollutant generated by coal-fired power generation is sulfur dioxide (SO)2) It is the main cause of acid rain. At present, the wet limestone-gypsum process is mostly adopted for domestic flue gas desulfurization. The process is the flue gas desulfurization process which is most widely applied and has the most mature technology in the world at present, and has the advantages of high desulfurization efficiency, quick load response, wide range of coal used, mature gypsum utilization technology, low operation cost and the like. The wastewater produced by the process has complex water quality components, mainly contains calcium and magnesium ions, heavy metals and chemical oxygen demand (CO)D) And Total Nitrogen (TN). Among them, nitrogen and sulfur compounds synthesized by nitrogen oxygen ions and sulfur oxygen ions in the flue gas desulfurization process are the main reasons for the rise of COD and TN. And after the nitrogen-sulfur compound is formed, the chemical property is stable.
At present, the treatment method aiming at the desulfurization wastewater at home and abroad mainly realizes zero emission of the desulfurization wastewater through a chemical precipitation-microfiltration membrane method, a fluidized bed method and an evaporative crystallization method. However, because the removal efficiency of the nitrogen and sulfur compounds by a common treatment method is extremely low, the nitrogen and sulfur compounds are accumulated continuously with the increase of the cycle number, the COD and TN contents are increased, and if a power plant does not adopt an effective treatment method for the wastewater, the discharge of the wastewater can cause serious harm to the environment. Therefore, the removal of nitrogen and sulfur compounds in the desulfurization wastewater is a difficult point of the discharge of the desulfurization wastewater.
Total Nitrogen (TN) is one of the examination indexes of sewage. Excessive TN can cause abnormal proliferation of algae and microorganisms in water bodies, and has more chance to cause toxic action on aquatic organisms and human bodies if the concentration of TN reaches a certain value. The TN ratio of the nitrogen-sulfur compound (NS compound) in the desulfurization waste water is high. The concentration of the single NS compound is already above the emission requirement of TN. The general sewage treatment method adopted in the industry cannot effectively remove the total nitrogen because nitrogen and sulfur compounds are difficult to degrade by a biological treatment method. Therefore, effective treatments for degrading NS compounds are of considerable importance.
Disclosure of Invention
In view of the above, the present invention aims to provide a total nitrogen treatment process for desulfurization wastewater of coal-fired power plants.
In order to achieve the aim, the invention provides a total nitrogen treatment process for desulfurization wastewater of a coal-fired power plant, which comprises the following steps:
1) chemical precipitation treatment;
2) treating nitrogen and sulfur compounds;
3) and (4) treating the microorganisms.
Further, in step 1), the chemical precipitation treatment specifically includes:
s11, coagulation: adjusting the pH value of the desulfurization wastewater to 11-12 by alkali liquor, and adding a sodium carbonate solution to further enhance the removal of calcium and magnesium ions;
s12, flocculation: adding a flocculating agent to form floccules;
s13, precipitation: and (4) sending the floccule into a mud-water separator for mud-water separation.
Further, in step S11, the alkali solution is 10 wt% -40 wt% NaOH solution, the concentration of the sodium carbonate solution is 10 wt% -40 wt%, and the adding amount of the sodium carbonate is 1000-3000 mg/L; in step S12, the flocculant is 0.1 wt% -0.5 wt% of polyacrylamide aqueous solution, and the dosage of polyacrylamide is 0.5 mg/L; in step S13, the mud-water separator is a filter press or a centrifuge.
Further, in step 2), the nitrogen-sulfur compound treatment specifically includes:
s21, disassembling nitrogen sulfur compounds: adding the filtrate after chemical precipitation treatment into a reaction cylinder, adjusting the pH value of the supernatant to 2-3 by using 10-40 wt% sulfuric acid solution, heating the reaction cylinder to 55-60 ℃, adding 10-40 wt% sodium nitrite solution into the reaction cylinder, reacting for 2-3 hours, and decomposing the nitrogen-sulfur compound into nitrogen or nitrous oxide gas.
S22, adjusting pH value and cooling: and (4) adjusting the pH value of the wastewater subjected to the decomposition of the nitrogen and sulfur compounds back to neutral by using alkali liquor, and cooling to room temperature for subsequent microbial treatment.
Further, in step S21, the adding amount of the sodium nitrite is 1000-3000 mg/L; in step S22, the alkali solution is 10 wt% -40 wt% NaOH solution.
Further, in step 3), the microbial treatment specifically comprises:
s31, a first aerobic reaction stage: carrying out a first nitrification reaction by using autotrophic nitrifying bacteria on the premise that an air blower provides oxygen so as to convert organic nitrogen and ammonia nitrogen in the wastewater into nitrate nitrogen and nitrite nitrogen;
s32, anoxic reaction stage: carrying out denitrification reaction for 24 hours by using heterotrophic denitrifying bacteria to convert nitrate nitrogen and nitrite nitrogen in the aerobic reaction wastewater into nitrogen;
s33, a second aerobic reaction stage: and (3) carrying out secondary nitration reaction by using autotrophic nitrifying bacteria on the premise that the blower provides oxygen to remove carbon sources not consumed in water so as to meet the requirement of yielding water.
Further, in step S31, the concentration of the oxygen is 4-6mg/L, and the first nitrification reaction is carried out in the submerged biological aerated filter; the immersed biological aerated filter is an up-flow fixed film biochemical reactor; the immersed biological aerated filter is filled with a volume load of>0.15NH3kg/m3D, the immersed filler is a honeycomb porous wavy plastic plate; the pH value of the first nitration reaction is 8-9, the dissolved oxygen is 4-6mg/L, and the hydraulic retention time is 24 h; the equation of the first nitration reaction is NH4 ++2O2→NO3 -+2H++H2O, the reaction time is 24 hours; conversion rate of organic nitrogen and ammonia nitrogen in wastewater to nitrate nitrogen and nitrite nitrogen>90％。
Further, in step S32, the denitrifying bacteria are heterotrophic bacteria; a carbon source is additionally added in the denitrification reaction; the denitrification reaction is carried out in a moving bed bioreactor; 30-60 wt% of suspension carrier is added into the moving bed bioreactor; the equation for the denitrification reaction is 2NO3 -+10e-+12H+→N2+6H2O, the reaction time is 24 hours; conversion rate of converting nitrate nitrogen and nitrite nitrogen in wastewater into nitrogen>90％。
Further, in step S32, the denitrification reaction has a pH value of 8-9, an oxidation-reduction potential of-50, a carbon-nitrogen ratio of 4:1 to 6:1, and a hydraulic retention time of 24 h.
Further, in step S33, the second nitrification reaction is performed in the submerged biological aerated filter; the immersed biological aerated filter is an up-flow fixed film biochemical reactor; the immersed biological aerated filter is filled with immersed fillers (the filling amount needs to be calculated according to different conditions, and the volume load is generally selected to be>0.15NH3kg/m3D), the immersed filler is a honeycomb-shaped porous wavy plastic plate; the equation of the second nitration reaction is NH4 ++2O2→NO3 -+2H++H2O, the reaction time is 24 hours; removal rate of the carbon source not consumed in water>95 percent; the pH value of the second nitration reaction is 6-8, the dissolved oxygen is 4mg/L, and the hydraulic retention time is 24 h.
The invention has the beneficial effects that:
the total nitrogen treatment process realizes standard discharge of desulfurization wastewater through chemical precipitation, nitrogen-sulfur compound treatment and biological treatment.
The total nitrogen treatment process further treats the refractory nitrogen compounds generated in the coal-fired process, effectively reduces the total nitrogen in the coal-fired power generation process to a great extent, and meets the stricter total nitrogen control requirements of different countries and regions.
Detailed Description
To further illustrate the technical means and effects of the present invention for achieving the predetermined objects, the following detailed description will be given to the specific implementation, features and effects of the total nitrogen treatment process for desulfurization wastewater of coal-fired power plant according to the present invention with reference to the preferred embodiments.
The invention provides a total nitrogen treatment process for desulfurization wastewater of a coal-fired power plant. The whole process comprises three main treatment parts: chemical precipitation treatment, nitrogen and sulfur compound treatment and microorganism treatment. The effluent of the treatment part enters nitrogen and sulfur compound treatment, and the nitrogen and sulfur compound and sodium nitrite are decomposed and removed under the heating condition. After the reaction, the effluent enters biological treatment, and ammonia nitrogen, nitrate nitrogen and residual COD are gradually removed through three stages of aerobic reaction-anoxic reaction-aerobic reaction, so that the total nitrogen is removed. The following is a detailed description of each part of the process:
firstly, chemical precipitation treatment:
the processing unit is configured to process the data by:
s11, coagulation: adjusting the pH value of the desulfurization wastewater to 11-12 by 10-40 wt% of NaOH solution, and adding 10-40 wt% of sodium carbonate solution (the adding amount of sodium carbonate is 1000-3000mg/L) to further enhance the removal of calcium and magnesium ions;
s12, flocculation: adding a flocculating agent (0.1-0.5 wt% of polyacrylamide aqueous solution, wherein the adding amount of polyacrylamide is 0.5mg/L) to form a floccule; the flocculating agent is polyacrylamide;
s13, precipitation: the floc is sent to a sludge-water separator such as a filter press to separate sludge from water.
II, nitrogen and sulfur compound treatment:
s21, disassembling nitrogen sulfur compounds: adding the supernatant subjected to chemical precipitation treatment into a reaction cylinder, adjusting the pH value of the supernatant to 2-3 by using 10-40 wt% sulfuric acid solution, heating the reaction cylinder to 55-60 ℃, adding 10-40 wt% sodium nitrite solution (the adding amount of sodium nitrite is 1000-3000mg/L) into the reaction cylinder, wherein the reaction time is 2-3 hours, and decomposing the nitrogen-sulfur compound into nitrogen or nitrous oxide gas in the reaction process.
S22, adjusting pH value and cooling: and (3) adjusting the pH value of the wastewater subjected to the decomposition of the nitrogen and sulfur compounds back to neutral by using 10-40 wt% of NaOH solution, and cooling to room temperature for subsequent microbial treatment.
Thirdly, treating the microorganisms:
s31, a first aerobic reaction stage: the autotrophic nitrifying bacteria are utilized to carry out the first nitrification reaction under the premise that the blower supplies oxygen (the concentration is 4-6mg/L) so as to convert organic nitrogen and ammonia nitrogen in the wastewater into nitrate nitrogen and nitrite nitrogen (the conversion rate is>90%). The first nitration reaction is carried out in an immersed aeration biological filter which is an up-flow type fixed film biochemical reactor. The immersed biological aerated filter is filled with immersed fillers (the filling amount needs to be calculated according to different conditions, and the volume load is generally selected to be>0.15NH3kg/m3D). The immersed filler is a cellular porous wavy plastic plate, and the action of the immersed filler is to attach and grow microorganisms (autotrophic nitrosobacteria, with the load of 0.15/m) on the filler by virtue of field domestication3Day) to reduce biofilm formationAnd removing the pollutants in the water. Compared with the traditional activated sludge method, the method has the advantages of small occupied area, high microorganism quantity and strong impact load resistance. The above equation for the first nitration reaction is NH4++2O2→NO3-+2H++H2And O, the reaction time is 24 h.
The nitration reaction conditions at this stage are as follows:
| pH value | 8-9 |
| Dissolved oxygen DO | 4mg/L |
| Hydraulic retention time HRT | 24h |
S32, anoxic reaction stage: converting nitrate nitrogen and nitrite nitrogen in the aerobic reaction wastewater into nitrogen gas (conversion rate) by using heterotrophic denitrifying bacteria to perform denitrification reaction>90%), so as to achieve the denitrification effect. The denitrification reaction is carried out in a moving bed bioreactor. As the denitrifying bacteria are heterotrophic bacteria, the reaction process requires an additional carbon source to meet the carbon-to-nitrogen ratio (C/N ratio) required by the denitrifying reaction. The carbon-nitrogen ratio (mass ratio) required by the anoxic reaction of the wastewater is 6:1, the moving bed bioreactor is selected as the reactor, and 30-60 wt% of suspension carriers are added into the reactor, so that the attached phase and the suspended phase living things can survive simultaneously, the biomass and the biological species in the reactor are improved, and the treatment efficiency of the reactor is improved. The above equation for the denitrification reaction is 2NO3 -+10e-+12H+→N2+6H2And O, the reaction time is 24 h.
The conditions of the denitrification reaction in the stage are as follows:
| pH value | 8-9 |
| Oxidation reduction potential ORP | -50 |
| Carbon to nitrogen ratio C/N | 4:1～6:1 |
| Hydraulic retention time HRT | 24h |
S33, a second aerobic reaction stage: as an external carbon source is required to be added in the anoxic stage to meet the requirement of the nitrogen ratio of the denitrifying carbon, in order to avoid overhigh COD (chemical oxygen demand) of the effluent, aerobic reaction in the stage is set, autotrophic nitrifying bacteria are utilized to carry out secondary nitrification reaction on the premise of providing oxygen by an air blower, and the aim of removing the consumed carbon source (removal rate) in the water is fulfilled>95 percent) that it meets the effluent requirement (COD)<150 mg/L). The second nitration reaction is carried out in the immersed aeration biological filter, and the filling is the same as the first nitration reaction. The above equation for the second nitration reaction is NH4 ++2O2→NO3 -+2H++H2And O, the reaction time is 24 h.
The reaction conditions in this stage are:
| pH value | 6-8 |
| Dissolved oxygen DO | 4mg/L |
| Hydraulic retention time HRT | 24h |
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (10)
1. A total nitrogen treatment process for desulfurization wastewater of a coal-fired power plant is characterized by comprising the following steps of:
1) chemical precipitation treatment;
2) treating nitrogen and sulfur compounds;
3) and (4) treating the microorganisms.
2. The process for treating total nitrogen in desulfurization wastewater of coal-fired power plant according to claim 1, wherein in the step 1), the chemical precipitation treatment specifically comprises:
s11, coagulation: adjusting the pH value of the desulfurization wastewater to 11-12 by alkali liquor, and adding a sodium carbonate solution to further enhance the removal of calcium and magnesium ions;
s12, flocculation: adding a flocculating agent to form floccules;
s13, precipitation: and (4) sending the floccule into a mud-water separator for mud-water separation.
3. The process as claimed in claim 2, wherein in step S11, the alkali solution is 10 wt% -40 wt% NaOH solution, the concentration of the sodium carbonate solution is 10 wt% -40 wt%, and the amount of sodium carbonate added is 3000mg/L of 1000-; in step S12, the flocculant is 0.1 wt% -0.5 wt% of polyacrylamide aqueous solution, and the dosage of polyacrylamide is 0.5 mg/L; in step S13, the mud-water separator is a filter press or a centrifuge.
4. The total nitrogen treatment process for desulfurization wastewater of coal-fired power plant according to claim 3, wherein in the step 2), the nitrogen-sulfur compound treatment specifically comprises:
s21, disassembling nitrogen sulfur compounds: adding the filtrate subjected to chemical precipitation treatment into a reaction cylinder, adjusting the pH value of the supernatant to 2-3 by using 10-40 wt% sulfuric acid solution, heating the reaction cylinder to 55-60 ℃, adding 10-40 wt% sodium nitrite solution into the reaction cylinder, reacting for 2-3 hours, and decomposing nitrogen-sulfur compounds into nitrogen or nitrous oxide gas;
s22, adjusting pH value and cooling: and (4) adjusting the pH value of the wastewater subjected to the decomposition of the nitrogen and sulfur compounds back to neutral by using alkali liquor, and cooling to room temperature for subsequent microbial treatment.
5. The total nitrogen treatment process for desulfurization wastewater of coal-fired power plant as claimed in claim 4, wherein in step S21, the adding amount of sodium nitrite is 1000-3000 mg/L; in step S22, the alkali solution is 10 wt% -40 wt% NaOH solution.
6. The process for treating total nitrogen in desulfurization wastewater of coal-fired power plant according to claim 1, wherein in the step 3), the microbial treatment specifically comprises:
s31, a first aerobic reaction stage: carrying out a first nitrification reaction by using autotrophic nitrifying bacteria on the premise that an air blower provides oxygen so as to convert organic nitrogen and ammonia nitrogen in the wastewater into nitrate nitrogen and nitrite nitrogen;
s32, anoxic reaction stage: carrying out denitrification reaction for 24 hours by using heterotrophic denitrifying bacteria to convert nitrate nitrogen and nitrite nitrogen in the aerobic reaction wastewater into nitrogen;
s33, a second aerobic reaction stage: and (3) carrying out secondary nitration reaction by using autotrophic nitrifying bacteria on the premise that the blower provides oxygen to remove carbon sources not consumed in water so as to meet the requirement of yielding water.
7. The process of claim 6, wherein in step S31, the concentration of oxygen is 4-6mg/L, and the first nitrification reaction is performed in the submerged biological aerated filter; the immersed biological aerated filter is an up-flow fixed film biochemical reactor; the immersed biological aerated filter is filled with a volume load of>0.15NH3kg/m3D, the immersed filler is a honeycomb porous wavy plastic plate; the pH value of the first nitration reaction is 8-9, the dissolved oxygen is 4-6mg/L, and the hydraulic retention time is 24 h; the equation of the first nitration reaction is NH4 ++2O2→NO3 -+2H++H2O, the reaction time is 24 hours; conversion rate of organic nitrogen and ammonia nitrogen in wastewater to nitrate nitrogen and nitrite nitrogen>90％。
8. The process for treating total nitrogen in desulfurization wastewater of coal-fired power plant according to claim 6, wherein in step S32, the denitrifying bacteria are heterotrophic bacteria; a carbon source is additionally added in the denitrification reaction; the denitrification reaction is carried out in a moving bed bioreactor; 30-60 wt% of suspension carrier is added into the moving bed bioreactor; the equation for the denitrification reaction is 2NO3 -+10e-+12H+→N2+6H2O, the reaction time is 24 hours; conversion rate of converting nitrate nitrogen and nitrite nitrogen in wastewater into nitrogen>90％。
9. The process of claim 8, wherein in step S32, the denitrification reaction has a pH of 8-9, an oxidation-reduction potential of-50, a carbon-nitrogen ratio of 4:1 to 6:1, and a hydraulic retention time of 24 h.
10. The process for treating total nitrogen in desulfurization wastewater of coal-fired power plant according to claim 6, wherein in step S33, the second nitrification reaction is performed in a submerged biological aerated filter; the immersed biological aerated filter is an up-flow fixed film biochemical reactor; the immersed biological aerated filter is filled with immersed fillers, and the immersed fillers are honeycomb porous wavy plastic plates; the equation of the second nitration reaction is NH4 ++2O2→NO3 -+2H++H2O, the reaction time is 24 hours; removal rate of the carbon source not consumed in water>95 percent; the pH value of the second nitration reaction is 6-8, the dissolved oxygen is 4mg/L, and the hydraulic retention time is 24 h.
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| CN1212898A (en) * | 1997-09-19 | 1999-04-07 | 三菱重工业株式会社 | Processes for treatment of flue gas desulfurization waste water |
| US20080050801A1 (en) * | 2006-08-25 | 2008-02-28 | Infilco Degremont, Inc., A Corporation Of New York | Methods and systems for biological treatment of flue gas desulfurization wastewater |
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