CN115536206A - Advanced treatment combined process for chemical degradation-resistant sewage - Google Patents
Advanced treatment combined process for chemical degradation-resistant sewage Download PDFInfo
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- CN115536206A CN115536206A CN202110744308.7A CN202110744308A CN115536206A CN 115536206 A CN115536206 A CN 115536206A CN 202110744308 A CN202110744308 A CN 202110744308A CN 115536206 A CN115536206 A CN 115536206A
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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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
- C02F2101/30—Organic compounds
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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
- C02F3/30—Aerobic and anaerobic processes
- C02F3/302—Nitrification and denitrification treatment
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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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- Life Sciences & Earth Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to a chemical wastewater advanced treatment technology, in particular to a chemical degradation-resistant wastewater advanced treatment combined process, belonging to the technical field of industrial wastewater treatment. The combined process comprises the following steps: iron-carbon micro-electrolysis, homogeneous regulation, ultraviolet light catalytic oxidation, activated carbon adsorption, biological denitrification treatment, flocculation sedimentation and engineering bacteria biofilter. The process has safe and reliable operation and stable effluent quality, and the treated sewage can reach COD less than or equal to 40mg/L and NH 3 The N is less than or equal to 5mg/L, the total nitrogen is less than or equal to 40mg/L, the TOC is less than or equal to 30mg/L, and the investment cost is low.
Description
Technical Field
The invention relates to a chemical wastewater advanced treatment technology, in particular to a chemical degradation-resistant wastewater advanced treatment combined process, belonging to the technical field of industrial wastewater treatment.
Background
The chemical industry is the prop industry of national economy and has a great position in the modern construction of China. With the rapid development of economy, the production scale of chemical enterprises is continuously enlarged, the processing depth is continuously improved, and the quality of the produced sewage shows the trend of increasing the types of pollutants and complex water quality. Typical petrochemical wastewater contains conventional pollutants such as petroleum, ammonia nitrogen, sulfur, phenol, cyanide and the like. Different enterprises have different products, and the produced sewage also contains various characteristic pollutants related to organic chemical products thereof, such as difficultly biodegradable organic matters such as polycyclic aromatic hydrocarbon compounds, aromatic amine compounds, heterocyclic compounds and the like, so that the sewage quality is complex, and the difficultly degradable substances are various. In addition, the fluctuation of production such as start-stop, overhaul, change of raw material sources and the like of enterprises can cause the change of the sewage quantity and the content and the property of pollutants, and the impact load of sewage treatment facilities is increased. From the current oil refining chemical sewage treatment practices, most of the oil refining chemical sewage treatment practices adopt an oil separation-air flotation-biochemical treatment process, and on the basis of the oil separation-air flotation-biochemical treatment process, an anaerobic treatment technology or an advanced oxidation technology is introduced, and meanwhile, advanced treatment measures such as membrane separation and the like are combined to carry out advanced treatment on the sewage.
In recent years, with the increasing shortage of water resources and the enhancement of the awareness of environmental protection of people, national governments and local governments put forward stricter control standards for industrial enterprise drainage, and in some areas, even the COD concentration of the drained water is required to be controlled below 40mg/L, and the standard-reaching discharge pressure of the sewage is higher. Therefore, the research on the efficient, economic and energy-saving treatment technology and the system development combined process are the main contents and development directions of the research on the sewage treatment technology.
Chinese patent CN207483539U discloses a chemical wastewater micro-electrolysis treatment system, provides a chemical wastewater micro-electrolysis treatment system and a biochemical system microorganism domestication method, and is suitable for the treatment of pharmaceutical and chemical wastewater. Comprises an iron-carbon pool, a primary sedimentation pool, a photocatalytic oxidation device, a homogeneous regulating pool, an anaerobic pool, a facultative pool, an aerobic pool and a secondary sedimentation pool. In the combined process, the wastewater is pretreated by the steps of micro-electrolysis, coagulating sedimentation, photocatalytic oxidation and the like before biochemical treatment, wherein the micro-electrolysis treatment removes chromophoric groups and color-assisting groups in the wastewater to achieve the aim of color removal. The photocatalytic oxidation uses hydrogen peroxide as an oxidant, tiO2 is used for carrying out oxidation treatment on the wastewater by adopting a heterogeneous method, the removal rate of organic matters in the wastewater reaches more than 40%, and the B/C is improved to more than 0.4. The pretreated wastewater is treated by a biochemical system and then is discharged after reaching the standard.
Chinese patent CN105271605A discloses a method for treating acrylonitrile wastewater, which comprises the steps of homogenizing, acidifying, denitrifying, nitrifying and precipitating the acrylonitrile wastewater. And TMPD waste water with very good biodegradability is used as a carbon source and is supplemented into the acrylonitrile waste water treatment system from the homogenizing tank according to the proportion of BOD/TN =20 to 1, so that the treatment effect of the acrylonitrile waste water COD and total nitrogen is improved, the problem that the TMPD waste water is difficult to directly reach the standard and discharge is solved, and the purpose of treating waste with waste is achieved.
In practical application, the pollutants such as cyanogen substances, pyridine substances and the like contained in the acrylonitrile wastewater are biotoxic, can inhibit the nitration reaction of a biochemical system, and influence the biological denitrification effect, and if effective pretreatment is not carried out, the pollutants directly enter the biochemical system, and the operation effects of nitrification and denitrification of the biochemical system cannot be improved simply by adding a denitrification filler and optimizing the adding type and mode of a carbon source, so that the good effect of removing total nitrogen and ammonia nitrogen is achieved.
Chinese patent CN101955305A discloses a method for treating papermaking sewage by adopting a combined process of pretreatment, hydrolytic acidification, efficient biological strengthening tank and Fenton oxidation tower. Wherein the pretreatment unit adopts the processes of precipitation, grid filtration and the like to remove large granular substances, and the powdered activated carbon is added into the high-efficiency biological strengthening tank to improve the treatment effect of the aerobic unit. The combined process can reduce the COD value of the papermaking sewage from more than 450mg/L to 100mg/L and has obvious COD removing effect. The Fenton reagent oxidation process can selectively oxidize most organic matters in water, and is particularly suitable for the oxidation treatment of organic wastewater which is difficult to biodegrade or difficult to achieve effect by common chemical oxidation. The chemical sewage has the characteristics of various types, complex water quality and poor biodegradability, so that the process for treating the sewage has certain limitation, and the treatment depth cannot meet increasingly strict discharge requirements, so that the whole set of treatment process needs to be further optimized.
Chinese patent CN105174644A discloses a high-efficiency treatment combined process for acrylonitrile wastewater, wherein the production wastewater subjected to four-effect evaporation and steam stripping in the acrylonitrile production process enters a catalytic oxidation tower to be subjected to oxidation treatment of a supported catalyst and hydrogen peroxide, and effluent and factory domestic sewage are fully mixed and then enter a biochemical treatment system and sequentially pass through an anaerobic hydrolysis tank, an anoxic tank and an MBR tank; the biochemical effluent is treated by adopting a membrane separation technology. In the treatment process, domestic sewage and effluent of a catalytic oxidation tower are fully mixed according to the proportion of 4-6, and then enter an anaerobic hydrolysis acidification tank, so that the effect of dilution is mainly achieved, the time for hydrolysis acidification of nitrile-containing nitrogen-containing organic matters in acrylonitrile wastewater is shortened, and microorganisms preferentially degrade the domestic sewage with strong biodegradability to influence the stable operation of a subsequent biochemical system.
In summary, most of the existing chemical wastewater treatment processes have the defects of complex process, poor effluent quality, harsh and difficult control of reaction conditions of treatment units, low treatment efficiency, high investment cost, difficult realization of industrialization and the like.
Disclosure of Invention
The invention aims to solve the technical problems of complex process, low treatment efficiency, high treatment cost, unstable treatment effect and the like in the prior art and provide the combined process for the advanced treatment of the chemical degradation-resistant sewage, which has the advantages of safe and reliable operation, stable effluent quality and low investment cost.
The invention provides a combined process for advanced treatment of chemical degradation-resistant sewage. The process flow is shown in figure 1, and the technical scheme for solving the technical problem comprises the following steps: iron-carbon micro-electrolysis, homogeneous regulation, ultraviolet light catalytic oxidation, activated carbon adsorption, biological denitrification treatment, flocculation sedimentation and engineering bacteria biofilter.
Specifically, the method comprises the following steps:
step 1: iron-carbon micro-electrolysis pretreatment unit
The refractory wastewater is firstly subjected to iron-carbon micro-electrolysis treatment. The micro-electrolysis technology is based on the metal corrosion electrochemical principle, metal and metal (or nonmetal) with different electrode potentials are directly contacted in industrial sewage with better conductivity, and the industrial sewage is treated by the battery effect generated by a formed macro battery and a micro battery. The action mechanism comprises oxidation reduction, flocculation precipitation and micro-electrolysis, and various mechanisms are combined in the industrial sewage treatment process to achieve the aims of removing COD and improving the biodegradability of the wastewater.
The invention adopts a micro-electrolysis reaction tower to pretreat the wastewater, the wastewater to be treated is firstly subjected to pH adjustment, enters the tower from the bottom of the micro-electrolysis tower, goes upward to pass through a packed bed and is discharged from a water collecting tank at the top of the tower. The tower is filled with micro-electrolysis filler, and the upper part of the tower is provided with a screen mesh pressing plate to prevent the filler from losing. The filler is preferably high-temperature sintered iron-carbon micro-electrolysis filler, so that the conditions of hardening and passivation are avoided in the using process. The filler is placed on a bearing layer of the reaction tower, a perforated plate is used as a support, and the continuous water feeding and continuous aeration mode is adopted for operation.
The main technological parameters are as follows: pH is 2 to 7, preferably pH 3 to 6.5; the reaction time is 20-60 min, preferably 30-50 min; fe/C (volume ratio) is about 0.5 to 3, preferably 1 to 2; the gas-water ratio is about 1.
And 2, step: homogeneous precipitation treatment unit
The refractory wastewater after iron-carbon micro-electrolysis treatment flows into a homogenizing tank, and an online pH monitor and an acid-base agent adding device are installed on a pipeline connecting the homogenizing tank and the iron-carbon micro-electrolysis reaction unit, so that the automatic adjustment of pH is realized. The wastewater naturally settles in the homogenizing tank to remove the iron-carbon filler flowing out along with the water. The supernatant fluid after the impurities are removed enters an ultraviolet light catalytic oxidation treatment unit, so that the influence on the irradiation efficiency of ultraviolet light due to the impurities is avoided. And iron ions dissolved in water are used as a catalyst to enter the photocatalytic oxidation treatment unit.
The main technological parameters are as follows: the size of the homogenizing tank is determined according to the size of the water quantity to be treated, and the hydraulic retention time is 2-6 h, preferably 3-5 h; the pH value of the effluent of the homogenizing tank is controlled to be 2-6, preferably 2.5-5.5. Adding acid or alkaline substance, and adjusting to obtain the pH value range required by the process. The acid or alkali is added, the acid can be sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and acetic acid, preferably sulfuric acid, and the alkali can be sodium hydroxide and potassium hydroxide, preferably sodium hydroxide. And a slag scraping and sludge discharging system is arranged at the bottom, and impurities at the bottom are jointly treated with the saturated active carbon adsorbed in the active carbon adsorption tower in the step 4.
And step 3: ultraviolet light catalytic oxidation treatment unit
The most effective oxidant with the strongest oxidizing capability on refractory organic matters is hydroxyl radical OH, and the best mode for generating the hydroxyl radical is Fenton reagent, namely hydrogen peroxide can generate the hydroxyl radical under the catalysis of ferrous iron under the acidic condition. However, the Fenton reagent generates a large amount of iron oxide precipitates after being used, and the disposal cost is high. To improve the efficiency of the fenton reaction and to significantly reduce the amount of sludge, the photo-Fenton reaction is currently the most efficient and economical method.
Different from Fenton oxidation which adopts ferrous iron ions as a catalyst, the ultraviolet light catalytic oxidation technology is carried out within a certain pH value range, the photo-promoted Fenton oxidation adopts ferric iron ions as a catalyst, hydrogen peroxide is used as an oxidant under an acidic condition, and the ultraviolet light high-efficiency catalysis hydrogen peroxide is decomposed to generate hydroxyl radicals. Fe 3+ Under the condition of ultraviolet irradiation, the Fe (OH) can be hydrolyzed to generate hydroxyl radical under the acidic condition 2+ ，Fe(OH) 2+ Can be converted into Fe under the action of ultraviolet light 2+ Simultaneously, OH is produced. Fe 2+ And H 2 O 2 Then, fenton reaction is carried out. OH generated by the reaction can react with organic matters, thereby achieving the purposes of removing COD concentration, reducing the biological toxic substances of pollutants and improving the biodegradability of wastewater.
The main technological parameters are as follows: the pH value range of the invention is adjusted in a homogenization tank, and the pH value is controlled to be 2-6, preferably 2.5-5.5 under the condition of weak acidity; the ultraviolet light used in the light band comprises ultraviolet light emitted by a low-pressure lamp tube and a high-pressure lamp tube, the ultraviolet light is selected according to the property of the wastewater to be treated, and the high-pressure ultraviolet lamp tube is preferably selected for the wastewater with high toxicity and high COD; the ferric salt as the catalyst is derived from an iron-carbon micro-electrolysis process, the ratio of the amount of the iron element in ferric iron or ferrous iron salt to the amount of water is 1-200 mg/L, preferably 10-100 mg/L, and if the concentration of the iron ions is low, the iron ions need to be supplemented, preferably: ferric sulfate, ferric chloride, ferrous sulfate, ferrous chloride; the hydrogen peroxide is an oxidant, the dosage is about 100-10000mg/L, preferably 1000-8000mg/L, and the dosage can be adjusted according to the water quality of the incoming water. The time of the ultraviolet light catalytic oxidation is 0.5 to 6 hours, preferably 40min to 5.5 hours; the ratio of B to C is increased to more than 0.35.
And 4, step 4: activated carbon adsorption unit
The iron element belongs to one of mineral nutrient elements necessary for microorganisms. However, if the influent water contains excessive iron compounds, the activated sludge in the biochemical tank is poisoned, and the activated sludge is manifested by fine flocs, abnormal color and difficult sedimentation. Therefore, it is necessary to remove the excess iron ions in the effluent from the photocatalytic oxidation. The outlet water after photocatalytic oxidation is conveyed to an active carbon adsorption tower through a pipeline, an online pH monitor and an acid-base medicament adding device are arranged on the pipeline, the pH is adjusted to be more than 5, and iron ions in the water are converted into Fe (OH) 3 Precipitating, and adsorbing with activated carbon. In addition, the concentration of the iron ions in the water adsorbed by the activated carbon is greatly reduced, the phenomenon that excessive iron ions enter a biochemical treatment unit to cause activated sludge to sink is avoided, the activated carbon is adsorbed and saturated and then is recovered together with the iron and carbon powder precipitated at the bottom of the homogenizing tank, the iron and carbon powder is processed and refined back to prepare micro-electrolysis iron and carbon filler, the micro-electrolysis iron and carbon filler is periodically supplemented to the iron and carbon micro-electrolysis treatment unit for recycling, and the running cost of water treatment can be greatly reduced.
The main technological parameters are as follows: the pH is adjusted to 4.5-8, preferably 5-7.5, by adding an alkaline chemical agent, and the retention time of the activated carbon adsorption tower is 20 min-3 h, preferably 0.5-2.5 h. When the iron ion in the water discharged from the activated carbon adsorption tower is less than 10mg/L, the sludge poisoning can not be caused.
And 5: biochemical treatment unit
The biochemical treatment of the invention comprises anaerobic hydrolytic acidification, an anoxic reaction tank and an aerobic reaction tank in turn.
Introducing the degradation-resistant sewage treated in the step 4 into a hydrolysis acidification tank, hydrolyzing the granular substances into soluble substances in the hydrolysis acidification tank, and simultaneously converting macromolecular substances and substances which are difficult to biodegrade into micromolecular substances which are easy to biodegrade under the synergistic action of acid-producing bacteria; improving the biodegradability of the waste water. Meanwhile, the impact load influence which may occur can be buffered and adjusted, sludge bulking or excessive growth of filamentous bacteria which may occur in the subsequent activated sludge method treatment process can be prevented and overcome, the operation stability and reliability of the treatment system can be enhanced, and very favorable conditions can be provided for the subsequent aerobic treatment.
The main technological parameters are as follows: in the hydrolysis acidification tank, DO (dissolved oxygen) is controlled to be less than or equal to 0.5mg/L, MLSS (sludge concentration) is controlled to be 4-12 g/L, and 6-10 g/L is preferred. The retention time of the wastewater in the hydrolysis acidification tank is 4 to 55 hours, preferably 6 to 53 hours. The temperature in the pool is 20-40 ℃, preferably 25-35 ℃, and the pH value is 5.5-7.5.
The nondegradable sewage subjected to hydrolytic acidification and supposed clean sewage including circulating water sewage in a plant area, concentrated water of chemical water production, domestic sewage, ground washing water, rain drainage and other wastewater are mixed at the inlet of the tank A of the denitrification tank and enter the anoxic reaction tank for denitrification treatment, so that the content of total nitrogen in the sewage is reduced.
The treatment method of the invention is obviously different from the treatment method of entering the sewage treatment system from the foremost end of the sewage treatment plant after the mixed treatment method of the clear sewage and the chemical sewage to be treated is completely mixed with the sewage commonly used in the current sewage treatment plant. The beneficial effects produced include the following two aspects: after all the sewage generated in the plant area is completely treated, the indexes of total nitrogen, ammonia nitrogen, COD, TOC and the like are all discharged up to the standard, thereby not only meeting the increasingly strict environmental protection discharge requirement, but also solving the problem that the hydraulic retention time of the production sewage is insufficient in the hydrolysis acidification stage, and being beneficial to deep hydrolysis acidification of organic matters in the production sewage of chemical plants. In addition, domestic sewage with good biochemical property can be added in the denitrification stage to serve as an external source denitrification carbon source, so that the purpose of treating waste by waste is achieved, the COD which is easy to degrade improves the denitrification efficiency, and the use cost of the carbon source is reduced.
The mixing ratio of the refractory production wastewater to the supposed clean sewer is 1-1. Hydraulic retention time: 10 to 60 hours, preferably 12 to 55 hours; the pH value of the anoxic pond is controlled to be 6.0-8.0, and preferably: 6.5 to 7.5; dissolved oxygen: less than 0.5mg/L; sludge concentration: 3500-5000 mg/L.
The effluent of the anoxic tank automatically flows to the aerobic tank, the COD is further removed by the activated sludge in the aeration tank, and the nitrification reaction is carried out in the aerobic reaction tank, so that the aim of removing the ammonia nitrogen in the water is fulfilled. DO in water is 2-10 mg/L, preferably 4-6 mg/L; MLSS:2000 to 8500mg/L, preferably: 3000-8000 mg/L; hydraulic retention time: 15 to 60 hours, preferably 18 to 58 hours; pH value of O pool: 7.0 to 9.0, preferably: 7.5 to 8.5; return flow of nitrifying liquid: 200 to 300 percent.
And 6: flocculation precipitation unit
The flocculation precipitation unit mainly comprises a precipitation tank and a filtration system.
After the whole biochemical treatment, the removal rate of COD reaches more than 80%, but TOC still can not meet the emission requirement and needs to be subjected to advanced treatment. After biochemical treatment, the sewage usually contains suspended matters with higher concentration, so that the effluent quality is turbid, the COD is higher, and adverse effects are brought to subsequent treatment. Filtration is an effective method for removing suspended matter, particularly fine particles in a suspension having a relatively low concentration.
The effluent of the aerobic tank automatically flows to a secondary sedimentation tank, and the supernatant of the sedimentation tank automatically flows to a flocculation filtration system. PAC is added into the sewage, and the content of the PAC in the sewage is 20-1000 mg/L, preferably 50-900 mg/L. The combined process can adopt a plurality of processes such as a lamination filter, a quicksand filter, an SSF (sludge suspension purifier) and the like to purify the sewage according to the water quality condition of the effluent, and ensures that the concentration SS of suspended matters is less than or equal to 2mg/L. The biochemical effluent is treated in engineering bacteria biological filter after eliminating suspended matter, and has the advantages of reduced organic matter load and capacity of eliminating COD and TOC. In addition, the device can prevent suspended matters from entering the bed layer of the engineering bacteria biological filter to cause the increase of the bed layer resistance, can ensure the stable operation of the engineering bacteria biological filter, reduces the backwashing frequency and reduces the energy consumption.
And 7: engineering bacteria biofilter (ABR) unit
The ABR high-efficiency bioreactor is a novel aerobic bioreactor for advanced treatment of refractory industrial wastewater. The technology mainly depends on that ABR specific flora forms a biomembrane on an ABR efficient carrier, and utilizes and decomposes the nondegradable COD in the wastewater under aerobic conditions to maintain the activity of cells, thereby removing the nondegradable COD in the water. The specific flora can be used as a nutrient source besides degrading COD, and nutrients do not need to be added in the subsequent operation process except the starting stage, so that the operation cost is greatly reduced.
The ABR high-efficiency engineering bacteria filter is used as a final treatment link, and not only can nondegradable organic matters still remained in water after the traditional primary and secondary biochemical treatment be stably and effectively treated, but also ammonia nitrogen can be further removed, and high-quality effluent can be directly discharged.
The method adopts a running mode of bottom-in and top-out, fills solid fillers which take active carbon as a carrier and load denitrifying bacteria and decarbonizing microorganisms, and independently fills the denitrifying fillers or the decarbonizing fillers or the mixture of the denitrifying fillers and the decarbonizing fillers according to the quality of incoming water. The height of the filter material is as follows: 1.5 to 4m, preferably: 2.0 to 3.5; hydraulic retention time: 1 to 10h, preferably: 2-8 h; micro-aeration is carried out in the operation process.
In conclusion, the beneficial effects of the invention are as follows:
1. the combined process is adopted to treat the chemical wastewater difficult to degrade, the organic matter removal efficiency is high, the effluent quality is stable, the treated sewage can reach COD less than or equal to 40mg/L and NH 3 N is less than or equal to 5mg/L, total nitrogen is less than or equal to 40mg/L, and TOC is less than or equal to 30mg/L, so that the emission requirement of a higher standard is met.
2. The mixed treatment mode of the supposed clean sewage and the chemical sewage to be treated in the invention is different from the mixed mode commonly used in the current sewage treatment plant, the production sewage is directly pumped into the anaerobic tank after being pretreated, and the supposed clean sewage is pumped into the denitrification tank. The two strands of sewage are mixed at the inlet end of the denitrification tank, so that the requirement on environmental protection is met, the problem that the hydraulic retention time of the production sewage in the anaerobic tank is insufficient is solved, and the deep hydrolysis and acidification of the production sewage are facilitated.
3. The combined process provided by the invention has low cost, and achieves the purpose of treating wastes with processes of wastes against one another. The catalyst of the photocatalytic oxidation unit is derived from the effluent of iron-carbon micro-electrolysis, so that the adding cost of the catalyst is reduced, and the iron-carbon can be recycled by performing adsorption treatment on the photocatalytic oxidation effluent through activated carbon adsorption; the domestic sewage serving as the denitrification carbon source greatly reduces the adding cost of the exogenous denitrification carbon source.
Drawings
FIG. 1 is a schematic view of the combined process flow of advanced treatment of chemical degradation-resistant sewage.
Detailed Description
In order that those skilled in the art will understand the invention in more detail, the invention is described in detail below by way of specific examples, with reference to the drawings of the process flow.
Example 1
COD of the production wastewater of a certain acrylonitrile device: 2111.6mg/L, total nitrogen 479.8mg/L, TOC:1148.6mg/L of 150m 3 The flow rate of/h enters the treatment flow shown in figure 1, and the main process parameters of each treatment unit are as follows:
adjusting the pH value of acrylonitrile production wastewater to 3.0, entering the tower from the bottom of the micro-electrolysis tower, ascending through a packed bed, and then discharging from a water collecting tank at the top of the tower, wherein the reaction time is 30min, and iron-carbon micro-electrolysis filler is filled in the micro-electrolysis reaction tower. The filling amount is 80 percent of the volume of the reaction tower, and the Fe/C (volume ratio) is 1; the gas-water ratio is 5. Micro-electrolysis effluent COD:1761.2mg/L, total nitrogen 429.8mg/L, TOC:920.6mg/L.
The refractory wastewater after the acrylonitrile production wastewater is subjected to iron-carbon micro-electrolysis treatment flows into a homogenizing tank, the pH value is adjusted to 3.5-4.5 through an automatic dosing system, the wastewater naturally settles in the homogenizing tank, and the iron-carbon filler flowing out along with water is removed. The homogeneous settling tank adopts a mode of water inlet from the top and water outlet from the middle, supernatant liquid after impurities are removed enters an ultraviolet light catalytic oxidation treatment unit, iron ions dissolved in water by a micro-electrolysis unit are used as a catalyst, and the concentration of the iron ions is 60mg/L; adding hydrogen peroxide as oxidant with concentration of 1000mg/L, deep oxidizing refractory organic matter in water by means of homogeneous oxidation reaction and light energy strength of 15Kw.m -3 Reduction of biotoxicity and improvement of biodegradability, B/C>0.35, catalytic oxidation by ultraviolet lightThe time is 30min. COD:1284.3mg/L, total nitrogen 351.6mg/L, TOC:720.3mg/L.
Adjusting the pH of the acrylonitrile production wastewater subjected to photocatalytic oxidation to 6.0, and then introducing the wastewater into an activated carbon adsorption tower for adsorption treatment to remove suspended impurities and generated Fe (OH) in the water 3 Precipitating, reducing the concentration of iron ions to 8mg/L, allowing the effluent to enter a biochemical treatment system, and allowing the wastewater to stay in a hydrolysis acidification pool for 40.0h under the conditions that dissolved oxygen DO is not more than 0.5mg/L, sludge concentration MLSS is 7g/L, temperature is 30 ℃ and pH value is 6.5-7.0. Effluent COD concentration 728.5mg/L, total nitrogen 249.2mg/L, ammonia nitrogen: 83.8mg/L, TOC:349.2mg/L.
The difficultly degraded production wastewater and supposed clean sewage including other wastewater such as circulating water sewage in a plant area, concentrated water of chemical water production, domestic sewage, ground washing water, rain drainage and the like are mixed according to the proportion of 1.5, and then flow into an A/O reaction tank for COD reduction and denitrification treatment. The COD concentration of the mixed water is 491.5mg/L, the total nitrogen is 133.2mg/L, and the ammonia nitrogen: 20mg/L, TOC:110.2mg/L. Hydraulic retention time of mixed water in the anoxic pond: controlling the pH value of the anoxic tank to be 6.5-7.5 within 50h; dissolved oxygen: less than 0.5mg/L; sludge concentration: 4500mg/L. The effluent of the anoxic tank automatically flows to the aerobic reaction tank, the retention time of the sewage in the aeration tank is 60 hours, and DO in the water is 4-6 mg/L; MLSS:6000mg/L; pH value: 7.5 to 8.5; return flow of nitrifying liquid: 200%, COD concentration of effluent of the aeration tank is 70mg/L, total nitrogen is 22.6mg/L, ammonia nitrogen: 1.47mg/L, TOC:57.5mg/L.
The effluent of the aerobic biochemical tank enters an engineering bacteria biological filter after suspended matters need to be removed, the PAC dosage of a flocculation sedimentation unit is 200mg/L, and the SS content is 2mg/L after the effluent is filtered by a quicksand filter. The sewage automatically flows to an engineering bacteria biological filter, and the biological filter is filled with filler for removing COD, thereby further removing COD and TOC. The retention time of the sewage in the biological filter is 2.5h. The final effluent quality is COD concentration 38mg/L, total nitrogen 20.6mg/L, ammonia nitrogen: not detected, TOC:30.0mg/L.
Example 2
COD of certain dyeing production wastewater: 3020.0mg/L, ammonia nitrogen 500.5mg/L, total nitrogen: 830.1mg/L, TOC:920.6mg/L at 150m 3 The flow rate of/h enters the treatment flow shown in FIG. 1, and each treatment unitThe main process parameters are as follows:
the pH value of the printing and dyeing wastewater is adjusted to 4, the printing and dyeing wastewater enters the tower from the bottom of the micro-electrolysis tower, goes up to pass through a packed bed and is discharged from a water collecting tank at the top of the tower, the reaction time is 50min, and iron-carbon micro-electrolysis filler is filled in the micro-electrolysis reaction tower. The filling amount is 80 percent of the volume of the reaction tower, and the Fe/C (volume ratio) is 1.5; the gas-water ratio is 3. Micro-electrolysis effluent COD:2501.8mg/L, total nitrogen 500.8mg/L, TOC:732.5mg/L, ammonia nitrogen: 370.3mg/L.
The non-degradable wastewater after the printing and dyeing wastewater is subjected to iron-carbon micro-electrolysis treatment flows into a homogenizing tank, the pH value is adjusted to 4.5 through an automatic dosing system, the wastewater naturally settles in the homogenizing tank, and iron-carbon filler flowing out along with water is removed. The homogeneous settling tank adopts a mode of feeding water from the top and discharging water from the middle, supernatant liquid after impurities are removed enters an ultraviolet light catalytic oxidation treatment unit, iron ions dissolved in water by a micro-electrolysis unit are used as a catalyst, and the concentration of the iron ions is 50mg/L; adding hydrogen peroxide as oxidant with concentration of 3500mg/L, and deep oxidizing refractory organics in water by using homooxidation reaction, wherein light energy intensity is 10Kw.m -3 Reducing biotoxicity, increasing biodegradability, B/C>0.5, the time of the ultraviolet light catalytic oxidation is 2h. COD:1284.8mg/L, total nitrogen 351.6mg/L, TOC:500.3mg/L, ammonia nitrogen: 200.8mg/L.
Adjusting the pH value of the printing and dyeing wastewater after photocatalytic oxidation to 6.5, and then entering an activated carbon adsorption tower for adsorption treatment to remove suspended impurities and generated Fe (OH) in the wastewater 3 Precipitating, reducing the concentration of iron ions to 3mg/L, leading the effluent to enter a biochemical treatment system, leading the wastewater to have hydraulic retention time of 40.0h in a hydrolytic acidification tank, leading the dissolved oxygen DO to be less than or equal to 0.2mg/L, leading the sludge concentration MLSS to be 6000mg/L, leading the temperature to be 30 ℃ and leading the pH value to be 6.5-7.0. Effluent COD concentration 908.7mg/L, total nitrogen 299.2mg/L, ammonia nitrogen: 283.8mg/L, TOC:349.2mg/L.
The nondegradable production wastewater and supposed clean sewage including circulating water and sewage in a plant area, concentrated water of chemical water production, domestic sewage, ground washing water, rain drainage and the like are mixed according to the proportion of 1. The COD concentration of the mixed water is 321.0mg/L, the total nitrogen is 153.5mg/L, and the ammonia nitrogen: 35.4mg/L, TOC:80.2mg/L. Hydraulic retention time of mixed water in the anoxic pond: controlling the pH value of the anoxic tank to be 6.5-7.5 after 20 hours; dissolved oxygen: less than 0.5mg/L; sludge concentration: 3500mg/L. The effluent of the anoxic tank flows to the aerobic reaction tank automatically, the retention time of the sewage in the aeration tank is 30h, and DO in the water is 4-6 mg/L; MLSS:4000mg/L; pH value: 7.0 to 9.0; return flow of nitrifying liquid: 200%, COD concentration of effluent of the aeration tank is 50.1mg/L, total nitrogen is 19.6mg/L, ammonia nitrogen: 8.0mg/L, TOC:20.5mg/L.
The effluent of the aerobic biochemical tank enters an engineering bacteria biological filter after suspended matters need to be removed, the PAC dosage of a flocculation sedimentation unit is 200mg/L, and the SS content is 2mg/L after the effluent is filtered by a quicksand filter. Sewage flows to an engineering bacteria biological filter automatically, COD removal and denitrification fillers are filled in the biological filter according to the proportion of 2. The retention time of the sewage in the biological filter is 3 hours. The final effluent quality is COD concentration 38.2mg/L, total nitrogen 13.4mg/L, ammonia nitrogen: 3.2mg/L, TOC:15.2mg/L.
Example 3
High-concentration nitrogen-containing wastewater COD of a certain chemical production plant: 4100.0mg/L, total nitrogen: 2230.4mg/L, ammonia nitrogen: 1200.5mg/L, TOC:1640.7mg/L at 200m 3 The flow rate of/h enters the treatment flow shown in figure 1, and the main process parameters of each treatment unit are as follows:
adjusting the pH value of the wastewater to 4.5, entering the tower from the bottom of the micro-electrolysis tower, ascending through a packed bed, and then discharging from a water collecting tank at the top of the tower, wherein the reaction time is 30min, and iron-carbon micro-electrolysis filler is filled in the micro-electrolysis reaction tower. The filling amount is 80 percent of the volume of the reaction tower, and the Fe/C (volume ratio) is 2; the gas-water ratio is 2. Micro-electrolysis effluent COD:2661.2mg/L, total nitrogen: 1600.7mg/L, 1080.5mg/L ammonia nitrogen, TOC:1066.6mg/L
The refractory wastewater after iron-carbon micro-electrolysis treatment flows into a homogenizing tank, the pH value is adjusted to 4.5 through an automatic dosing system, the wastewater naturally settles in the homogenizing tank, and iron-carbon fillers flowing out along with water are removed. The homogeneous settling tank adopts a mode of water inlet from the top and water outlet from the middle, supernatant liquid after impurities are removed enters an ultraviolet light catalytic oxidation treatment unit, iron ions dissolved in water by a micro-electrolysis unit are used as a catalyst, and the concentration of the iron ions is 80mg/L; adding is carried outHydrogen peroxide as oxidant with concentration of 4000mg/L, and through homogeneous oxidation reaction to deeply oxidize refractory organic matter in water and with light energy intensity of 20Kw.m -3 Reduction of biotoxicity and improvement of biodegradability, B/C>0.6, the time of the ultraviolet light catalytic oxidation is 5.5h. COD:2057mg/L, total Nitrogen: 605.7mg/L, ammonia nitrogen 474mg/L, TOC:822.8mg/L.
Adjusting pH of the wastewater after photocatalytic oxidation to 6.5, and adsorbing in an activated carbon adsorption tower to remove suspended impurities and Fe (OH) generated in the wastewater 3 Precipitating, reducing the concentration of iron ions to 8mg/L, leading the effluent to enter a biochemical treatment system, leading the wastewater to have hydraulic retention time of 15.0h in a hydrolysis acidification pool, leading the dissolved oxygen DO to be less than or equal to 0.3mg/L, leading the sludge concentration MLSS to be 6.5g/L, leading the temperature to be 30 ℃ and leading the pH value to be 6.5-7.0. COD concentration of effluent is 811mg/L, total nitrogen is 390.9mg/L, ammonia nitrogen: 135.9mg/L, TOC:324.4mg/L.
The difficultly degraded production wastewater is mixed with supposed clean sewage comprising circulating water sewage in a plant area, concentrated water of chemical water production, domestic sewage, ground washing water, rain drainage and other wastewater according to the proportion of 1, and then flows into an A/O reaction tank for COD reduction and denitrification treatment. The COD concentration of the mixed water is 354mg/L, the total nitrogen is 190mg/L, and the ammonia nitrogen is as follows: 68.9mg/L, TOC:140.2mg/L. Hydraulic retention time of mixed water in the anoxic pond: 50h; the pH value of the anoxic pond is controlled to be 6.5-7.5; dissolved oxygen: less than 0.5mg/L; sludge concentration: 4500mg/L. The effluent of the anoxic tank flows to the aerobic reaction tank automatically, the retention time of the sewage in the aeration tank is 60 hours, and DO in the water is 4-6 mg/L; MLSS:6000mg/L; pH value: 7.5 to 8.5; return flow of nitrifying liquid: 200%, COD concentration of effluent of the aeration tank is 60mg/L, total nitrogen is 22.6mg/L, ammonia nitrogen: 15.9mg/L, TOC:24mg/L.
And (3) after suspended matters are required to be removed from the effluent of the aerobic biochemical tank, feeding the effluent into an engineering bacteria biological filter, wherein the PAC dosage of a flocculation sedimentation unit is 200mg/L, and the SS content is 2mg/L after the effluent is filtered by a quicksand filter. Sewage flows to an engineering bacteria biological filter automatically, COD removal and denitrification fillers are filled in the biological filter according to the proportion of 1. The retention time of the sewage in the biological filter is 2.5h. The final effluent quality is COD concentration 26.7mg/L, total nitrogen 13.9mg/L, ammonia nitrogen: 2.0mg/L, TOC:12.0mg/L.
Claims (10)
1. A chemical industrial degradation-resistant sewage advanced treatment combined process is characterized in that: the method comprises the following steps:
1) Iron-carbon micro-electrolysis pretreatment unit
Firstly, carrying out pH adjustment on wastewater to be treated, entering the tower from the bottom of the micro-electrolysis tower, ascending the wastewater to pass through a packed bed, and then discharging the wastewater from a water collecting tank at the top of the tower;
filling a microelectrolysis filler in the tower, wherein the filler is a high-temperature sintered iron-carbon microelectrolysis filler; the filler is placed on a bearing layer of the reaction tower, a perforated plate is used as a support, and the continuous water feeding and continuous aeration mode is adopted for operation;
2) Homogeneous precipitation treatment unit
After the pH value of the refractory wastewater subjected to iron-carbon micro-electrolysis treatment is adjusted, the wastewater flows into a homogenizing tank, naturally settles in the homogenizing tank, removes iron-carbon filler flowing out along with water, and the supernatant enters an ultraviolet catalytic oxidation treatment unit;
3) Ultraviolet light catalytic oxidation treatment unit
Adding hydrogen peroxide as an oxidant, and carrying out ultraviolet light catalytic oxidation on the degradation-resistant wastewater;
4) Activated carbon adsorption unit
Adjusting the pH value of the difficultly degraded wastewater subjected to ultraviolet catalytic oxidation, and then putting the difficultly degraded wastewater into an activated carbon adsorption tower for adsorption treatment;
5) Biochemical treatment unit
Introducing the difficultly degraded wastewater subjected to adsorption treatment into a hydrolysis acidification tank for treatment;
mixing the nondegradable wastewater subjected to hydrolytic acidification with supposed clean sewage comprising circulating water sewage in a plant area, concentrated water of chemical water production, domestic sewage, ground washing water and rain drainage at the inlet of a tank A of a denitrification tank, and allowing the mixture to enter an anoxic reaction tank for denitrification treatment;
the effluent of the anoxic reaction tank automatically flows into an aeration tank to carry out nitration reaction;
6) Flocculation precipitation unit
The effluent of the aeration tank automatically flows to a secondary sedimentation tank, the supernatant of the sedimentation tank automatically flows to a flocculation filtration system, and PAC is added into the supernatant;
7) Engineering bacteria biological filter unit
The difficultly degraded wastewater after the flocculation precipitation automatically flows to an engineering bacteria biological filter, and a filler for removing COD is filled in the biological filter to further remove COD and TOC.
2. The advanced treatment combined process for chemical degradation-resistant sewage as claimed in claim 1, which is characterized in that: in the step 1), the pH value is 2-7, the reaction time is 20-60 min, the Fe/C volume ratio of the iron-carbon micro-electrolysis filler is 0.5-3, and the gas-water ratio is 1-5.
3. The advanced treatment combined process for chemical degradation-resistant sewage as claimed in claim 1, which is characterized in that: in the step 2), the hydraulic retention time of the homogenizing tank is 2-6 h, and the pH of the outlet water of the homogenizing tank is controlled to be 2-6.
4. The advanced treatment combined process for chemical degradation-resistant sewage as claimed in claim 1, which is characterized in that: in the step 3), the concentration of iron ions in the water is controlled to be 1-200 mg/L, the dosage of hydrogen peroxide is 100-10000mg/L, and the time of ultraviolet light catalytic oxidation is 0.5-6 h.
5. The advanced treatment combined process for chemical degradation-resistant sewage as claimed in claim 1, which is characterized in that: in the step 4), the pH value is adjusted to 4.5-8, and the retention time of the activated carbon adsorption tower is 20 min-3 h.
6. The advanced treatment combined process for chemical degradation-resistant sewage as claimed in claim 1, which is characterized in that: in the step 5), controlling DO not more than 0.5mg/L and MLSS 4-12 g/L in a hydrolysis acidification tank, wherein the retention time of the wastewater in the hydrolysis acidification tank is 4-55 h, the temperature in the tank is 20-40 ℃, and the pH value is 5.5-7.5.
7. The advanced treatment combined process for chemical degradation-resistant sewage as claimed in claim 1, which is characterized in that: in the step 5), the mixing ratio of the refractory wastewater to the supposed clean sewer is 1-1: 10-60 h, controlling the pH value of the anoxic reaction tank to be 6.0-8.0, dissolving oxygen: less than 0.5mg/L, sludge concentration: 3500-5000 mg/L.
8. The advanced treatment combined process for chemical degradation-resistant sewage as claimed in claim 1, which is characterized in that: in the step 5), DO in water is 2-10 mg/L, MLSS: 2000-8500 mg/L, hydraulic retention time: 15-60h, and the pH value of an O pool: 7.0-9.0, nitrifying liquid reflux: 200 to 300 percent.
9. The advanced treatment combined process for the chemical degradation-resistant sewage as claimed in claim 1, wherein: in the step 6), the PAC content in the refractory wastewater is 20-1000 mg/L.
10. The advanced treatment combined process for chemical degradation-resistant sewage as claimed in claim 1, which is characterized in that: in the step 7), the engineering bacteria biofilter adopts a running mode of bottom-in-top-out, and is filled with solid fillers which take activated carbon as a carrier and load denitrifying bacteria and/or decarburized microorganisms, wherein the height of the fillers is as follows: 1.5-4 m, hydraulic retention time: 1-10 h, and micro-aeration in the operation process.
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