CN108455790B - A kind of biochemical and advanced treatment method of coking wastewater - Google Patents
A kind of biochemical and advanced treatment method of coking wastewater Download PDFInfo
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- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C02F2101/00—Nature of the contaminant
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- C02F2101/16—Nitrogen compounds, e.g. ammonia
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Abstract
本发明涉及一种焦化废水的生化和深度处理方法，生化处理过程采用厌氧‑缺氧‑膜曝气生物膜组合工艺，深度处理过程采用焦粉过滤‑臭氧催化氧化‑厌氧氨氧化组合工艺；出水水质指标为：COD≤50mg/L、氨氮≤5mg/L、挥发酚≤0.2mg/L、总氰≤0.1mg/L。本发明将预处理后的焦化废水再经生化处理和深度处理，有效去除氨氮和难降解类的有机污染物，强化出水水质，减少焦化废水对环境的危害，并使处理后的焦化废水水质达到相关标准的要求。The invention relates to a biochemical and advanced treatment method for coking wastewater. The biochemical treatment process adopts an anaerobic-anoxic-membrane aeration biofilm combined process, and the advanced treatment process adopts a coke powder filtration-ozone catalytic oxidation-anaerobic ammonia oxidation combined process ; The effluent quality indicators are: COD≤50mg/L, ammonia nitrogen≤5mg/L, volatile phenols≤0.2mg/L, total cyanide≤0.1mg/L. In the method, the pretreated coking wastewater is subjected to biochemical treatment and advanced treatment, so as to effectively remove ammonia nitrogen and refractory organic pollutants, strengthen the effluent quality, reduce the harm of the coking wastewater to the environment, and make the treated coking wastewater meet the requirements of relevant standards.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a biochemical and advanced treatment method for coking wastewater.
Background
The steel industry is the prop industry of national economy in China, the problem of environmental pollution is more and more emphasized by people along with the continuous development of the industry, and especially the standard discharge and the recycling of coking wastewater become the hot point of research. Coking wastewater is wastewater generated in the coal coking and chemical product refining processes, and has the advantages of complex components, large fluctuation range, toxicity and harm. At present, more treatment methods are divided into two stages, wherein the first-stage treatment refers to the recycling of pollutants in high-concentration wastewater and comprises ammonia dephenolization, ammonia distillation, final cold water decyanation and the like. The secondary treatment mainly refers to the harmless treatment of phenol-cyanogen wastewater, mainly adopts an activated sludge process, and also comprises some biological strengthening technologies. Because the coking wastewater contains a large amount of polycyclic and azacyclo-aromatic compounds which are difficult to biodegrade, pollutants such as COD, ammonia nitrogen and the like in the wastewater after secondary treatment are difficult to discharge up to the standard and cannot meet the increasingly improved environmental protection requirement.
Chinese patent No. CN 101224936 discloses a process for treating coking wastewater, which adopts a first-stage anoxic and two-stage aerobic biofilter as biological treatment and is coupled with an aeration micro-electrolysis physicochemical treatment technology to treat the coking wastewater, the treatment effect of the method is not ideal, and the effluent index can only reach the secondary standard of sewage comprehensive discharge. Chinese patent No. CN 200610005557.X discloses a coking wastewater zero-discharge treatment system, which adopts advanced deamination nitrogen membrane separation technology to separate ammonia nitrogen from water after the coking wastewater is deeply treated on the basis of the primary treatment. The method has the defects that the membrane pollution is easy to generate and the back washing is difficult because the organic matters which are difficult to degrade in the wastewater are not completely removed. Chinese patent No. CN 101215068A discloses "a biological treatment process for coking wastewater", in which a biological treatment part is formed by connecting an anaerobic tank, an anoxic tank and an aerobic tank in series, and sludge and suspended solids accumulated in a filter tank are removed by regular backwashing, which improves the biochemical treatment effect of coking wastewater to a certain extent, but a biological fluidized bed has the disadvantages of complex structure, difficult three-phase separation, high power consumption, and the like. Chinese patent No. CN101195513 discloses an energy-saving high ammonia nitrogen wastewater treatment method, wherein wastewater is firstly pretreated to convert Kjeldahl nitrogen into ammonia nitrogen, then the ammonia nitrogen enters a short-cut nitrification tank, the nitrification of the ammonia nitrogen is controlled at a nitrite nitrogen stage, a micro-electrolysis reactor is used for denitrification treatment, and then a biological method or a Fenton oxidation method and a physicochemical oxidation method are used for subsequent treatment, so that the total nitrogen removal rate reaches 60-75%. The method is mainly used for treating high ammonia nitrogen, and is not ideal for treating refractory organics.
In order to further enhance the effluent quality of the coking wastewater, a method of additionally arranging three-stage treatment is generally adopted. Common methods include a flocculent film separation method, an adsorption method, a coagulation method, a chemical oxidation method and the like. The physical method has the advantages of simple equipment, investment saving and convenient operation, but has very limited removal effect. The chemical oxidation method has obvious removal effect and can convert organic matters into inorganic matters, but the chemical agent has large dosage and has certain dangers in transportation, storage and use.
The highest allowable discharge concentration of COD in wastewater in Liaoning province wastewater discharge Standard (DB 21/1627-2008) is 50mg/L, and the traditional two-stage coking wastewater treatment process is difficult to reach the discharge standard. Therefore, the economic and efficient three-stage advanced treatment process for the coking wastewater is developed, and has important practical significance.
Disclosure of Invention
The invention provides a biochemical and advanced treatment method of coking wastewater, which is characterized in that the pretreated coking wastewater is subjected to biochemical treatment and advanced treatment, so that ammonia nitrogen and refractory organic pollutants are effectively removed, the water quality of effluent is enhanced, the harm of the coking wastewater to the environment is reduced, and the water quality of the treated coking wastewater meets the requirements of relevant standards.
In order to achieve the purpose, the invention adopts the following technical scheme:
a biochemical and advanced treatment method of coking wastewater comprises the following steps:
1) the biochemical treatment process adopts an anaerobic-anoxic-membrane aeration biological membrane combined process, and comprises the following specific steps:
the pretreated coking wastewater enters an anaerobic tank, the coking wastewater and activated sludge in the anaerobic tank carry out biochemical reaction, anaerobic bacteria are utilized to degrade partial harmful substances in the coking wastewater, and meanwhile, the biodegradability of the coking wastewater is improved;
the effluent of the anaerobic tank flows into an anoxic tank, and the coking wastewater and the activated sludge in the anoxic tank carry out biochemical reaction to further degrade and remove ammonia nitrogen and COD in the wastewater;
the effluent of the anoxic tank flows into a membrane aeration biomembrane reaction tank, the membrane aeration biomembrane adopts a hollow fiber membrane component, the generated biomembrane has a double-layer structure, the inner surface is an aerobic zone, the coking wastewater mainly performs nitration reaction at the inner surface, the outer surface is in an anaerobic state, and the coking wastewater mainly performs denitrification reaction at the outer surface; the biological membrane which is continuously dropped back to the anoxic tank along with the sludge;
2) a deep treatment process; adopting a coke powder filtering-ozone catalytic oxidation-anaerobic ammonia oxidation combined process; the specific process is as follows:
the effluent of the membrane aeration biomembrane reaction tank enters a coke powder filter tank for physical adsorption reaction, and the effluent of the coke powder filter tank enters an ozone catalytic oxidation reaction tower;
in the ozone catalytic oxidation reaction tower, an ozone generator converts oxygen into ozone, hydroxyl radicals with high oxidation potential are generated under the catalytic action, and organic matters remained in the waste water are selectively oxidized;
the effluent of the ozone catalytic oxidation reaction tower enters an anaerobic ammonia oxidation reaction tank for anaerobic ammonia oxidation reaction;
3) the raw water quality of the coking wastewater is as follows: 3000-4600 mg/L of COD, 80-160 mg/L of ammonia nitrogen, 700-1400 mg/L of volatile phenol and 25-35 mg/L of total cyanogen; after the treatment of the step 1) and the step 2), the effluent quality indexes are as follows: COD is less than or equal to 50mg/L, ammonia nitrogen is less than or equal to 5mg/L, volatile phenol is less than or equal to 0.2mg/L, and total cyanogen is less than or equal to 0.1 mg/L.
In the step 1), the concentration of the activated sludge in the anaerobic tank is 8500-9500 mg/L, and the retention time of the coking wastewater is 24-36 h.
In the step 1), the concentration of the activated sludge in the anoxic tank is 4000-5000 mg/L, and the retention time of the coking wastewater is 18-24 h.
In the step 1), the retention time of the coking wastewater in the membrane aeration biomembrane reaction tank is 4-8 h, and the sludge reflux amount is 5-10% of the treatment amount.
In the step 2), the retention time of the coking wastewater in the coke powder filtering tank is 1-2 h.
In the step 2), the ozone inlet gas concentration of the ozone catalytic oxidation reaction tower is 20-30 mg/L, and the hydraulic retention time is 0.4-0.8 h.
In the step 2), the hydraulic retention time in the anaerobic ammonia oxidation reaction tank is 8-16 h, and the sludge concentration is 1000-2000 mg/L.
Compared with the prior art, the invention has the beneficial effects that:
1) the coking wastewater treatment method combining biochemical treatment and advanced treatment is adopted, the coking wastewater after biochemical treatment still contains various nonbiodegradable aromatic compounds such as indole, carbazole, quinoline and the like, the existence of pollutants is the main reason causing the COD of the effluent of biochemical treatment to be higher, and the ammonia nitrogen in the coking wastewater can be efficiently removed by the advanced treatment process;
2) in the advanced treatment process, the effluent of the ozone catalytic oxidation reaction tower enters an anaerobic ammonia oxidation tank for treatment because the concentration of organic matters in the water after ozone oxidation is very low, the traditional denitrification reaction can not be carried out, but a certain amount of ammonia nitrogen and nitrate nitrogen are remained in the water, so that necessary conditions are provided for anaerobic ammonia oxidation; by combining the two, organic pollutants which are difficult to degrade in the coking wastewater can be thoroughly removed;
3) the process flow is short, the effluent quality can meet the requirements of 'Liaoning province integrated wastewater discharge standard' (DB 21/1627-2008), the ecological environment is protected, and the method has important practical significance for the sustainable development of coking enterprises.
Detailed Description
The invention relates to a biochemical and advanced treatment method of coking wastewater, which comprises the following steps:
1) the biochemical treatment process adopts an anaerobic-anoxic-membrane aeration biological membrane combined process, and comprises the following specific steps:
the pretreated coking wastewater enters an anaerobic tank, the coking wastewater and activated sludge in the anaerobic tank carry out biochemical reaction, anaerobic bacteria are utilized to degrade partial harmful substances in the coking wastewater, and meanwhile, the biodegradability of the coking wastewater is improved;
the effluent of the anaerobic tank flows into an anoxic tank, and the coking wastewater and the activated sludge in the anoxic tank carry out biochemical reaction to further degrade and remove ammonia nitrogen and COD in the wastewater;
the effluent of the anoxic tank flows into a membrane aeration biomembrane reaction tank, the membrane aeration biomembrane adopts a hollow fiber membrane component, the generated biomembrane has a double-layer structure, the inner surface is an aerobic zone, the coking wastewater mainly performs nitration reaction at the inner surface, the outer surface is in an anaerobic state, and the coking wastewater mainly performs denitrification reaction at the outer surface; the biological membrane which is continuously dropped back to the anoxic tank along with the sludge;
2) a deep treatment process; adopting a coke powder filtering-ozone catalytic oxidation-anaerobic ammonia oxidation combined process; the specific process is as follows:
the effluent of the membrane aeration biomembrane reaction tank enters a coke powder filter tank for physical adsorption reaction, and the effluent of the coke powder filter tank enters an ozone catalytic oxidation reaction tower;
in the ozone catalytic oxidation reaction tower, an ozone generator converts oxygen into ozone, hydroxyl radicals with high oxidation potential are generated under the catalytic action, and organic matters remained in the waste water are selectively oxidized;
the effluent of the ozone catalytic oxidation reaction tower enters an anaerobic ammonia oxidation reaction tank for anaerobic ammonia oxidation reaction;
3) the raw water quality of the coking wastewater is as follows: 3000-4600 mg/L of COD, 80-160 mg/L of ammonia nitrogen, 700-1400 mg/L of volatile phenol and 25-35 mg/L of total cyanogen; after the treatment of the step 1) and the step 2), the effluent quality indexes are as follows: COD is less than or equal to 50mg/L, ammonia nitrogen is less than or equal to 5mg/L, volatile phenol is less than or equal to 0.2mg/L, and total cyanogen is less than or equal to 0.1 mg/L.
In the step 1), the concentration of the activated sludge in the anaerobic tank is 8500-9500 mg/L, and the retention time of the coking wastewater is 24-36 h.
In the step 1), the concentration of the activated sludge in the anoxic tank is 4000-5000 mg/L, and the retention time of the coking wastewater is 18-24 h.
In the step 1), the retention time of the coking wastewater in the membrane aeration biomembrane reaction tank is 4-8 h, and the sludge reflux amount is 5-10% of the treatment amount.
In the step 2), the retention time of the coking wastewater in the coke powder filtering tank is 1-2 h.
In the step 2), the ozone inlet gas concentration of the ozone catalytic oxidation reaction tower is 20-30 mg/L, and the hydraulic retention time is 0.4-0.8 h.
In the step 2), the hydraulic retention time in the anaerobic ammonia oxidation reaction tank is 8-16 h, and the sludge concentration is 1000-2000 mg/L.
The following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation processes are given, but the scope of the invention is not limited to the following examples. The methods used in the following examples are conventional methods unless otherwise specified.
[ examples ] A method for producing a compound
In this embodiment, the main water quality indexes of the coking wastewater inlet water are as follows: COD: 4560mg/L, ammonia nitrogen: 150mg/L, volatile phenol: 950mg/L, total cyanogen: 28mg/L, the biochemical and advanced treatment method of the coking wastewater comprises the following steps:
1) biochemical treatment of coking wastewater:
the biochemical treatment adopts an anaerobic-anoxic-membrane aeration biomembrane combination process, the anaerobic treatment and the anoxic treatment both adopt an activated sludge method, and the activated sludge and the membrane aeration biomembrane are both inoculated with the sludge from a secondary sedimentation tank of a coking wastewater treatment plant.
The pretreated coking wastewater is firstly injected into an anaerobic tank by a pump, the sludge concentration of the anaerobic tank is controlled to be 8500mg/L, and the retention time is controlled to be 24 h; the effluent of the anaerobic tank flows into an anoxic tank, the sludge concentration of the anoxic tank is controlled to be 4000mg/L, and the retention time is controlled to be 18 h; the effluent of the anoxic tank flows into a membrane aeration biomembrane reaction tank, the retention time is controlled to be 4h, and the sludge reflux amount is 5 percent of the treatment amount;
2) advanced treatment of coking wastewater:
the coking wastewater after biochemical treatment is injected into a coke powder filtering tank by a pump, and the retention time is 1 h; and the effluent is injected into an ozone catalytic oxidation reaction tower by a pump, the ozone inlet concentration is 20mg/L, and the hydraulic retention time is 0.4 h. The effluent flows into an anaerobic ammonia oxidation reaction tank, the hydraulic retention time is 8h, and the sludge concentration is 1000 mg/L.
The embodiment includes 3 specific embodiments, the process of the 3 embodiments is the same, and the process parameters in each embodiment are shown in table 1.
TABLE 1 Process parameters for the examples
The main indexes of the effluent after the biochemical treatment and the advanced treatment in each example are shown in table 2.
TABLE 2 Water discharge index of each example
As can be seen from Table 2, the coking wastewater after the biochemical treatment and the advanced treatment in the embodiment has COD less than or equal to 50mg/L, ammonia nitrogen less than or equal to 5mg/L, volatile phenol less than or equal to 0.2mg/L and total cyanogen less than or equal to 0.1mg/L, and the quality of the process effluent is stable and meets the requirements of the "Liaoning province Integrated wastewater discharge Standard" (DB 21/1627-2008).
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
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