CN115321764B - Coking wastewater treatment system and method - Google Patents
Coking wastewater treatment system and method Download PDFInfo
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Abstract
The invention provides a system and a method for treating coking wastewater, which belong to the technical field of wastewater treatment, wherein the treatment system comprises an oil separation tank, a first air floatation tank, an adjusting tank, a composite hydrolysis acidification tank, a second air floatation tank, an anoxic tank, an aerobic tank, a secondary sedimentation tank, a denitrification filter tank and a coagulation reaction system which are sequentially connected in series from front to back; the secondary sedimentation tank is respectively communicated with the composite hydrolysis acidification tank and the anoxic tank through a nitration liquid return pipeline; a flow control device is arranged on the nitrifying liquid return pipeline; controlling the volume flow of the nitrifying liquid which flows back to the composite hydrolytic acidification tank to be 0.5 to 1.5 times of the volume flow of the wastewater flowing out of the regulating tank by using a flow control device; the method is to treat the coking wastewater by using the system. According to the invention, the nitrifying liquid in the secondary sedimentation tank is controlled to flow back to the composite hydrolysis acidification tank at a specific flow rate, so that the inhibition effect of toxic substances and water quality fluctuation in the coking wastewater on hydrolytic bacteria and acidification bacteria can be reduced, the hydrolysis acidification effect is enhanced, and the biodegradability is improved.
Description
Technical Field
The invention relates to a coking wastewater treatment technology, in particular to a system and a method for treating coking wastewater.
Background
The coking wastewater contains a large amount of inorganic substances such as ammonia salts, thiocyanide, sulfide, cyanide and the like, organic substances such as phenols, monocyclic and polycyclic aromatic compounds, heterocyclic compounds containing nitrogen, sulfur and oxygen and the like, and heavy metals such as zinc, chromium, lead and the like, the problem that the total nitrogen reaches the standard can be met in the treatment process, and most coking plants cannot meet the requirement that the total nitrogen in the middle row of table 2 of the discharge standard of pollutants for coking chemical industry (GB 16171-2012) is less than 50mg/L, and cannot meet the standard of direct discharge. Part of the coke-oven plants are additionally provided with secondary AO or denitrification filters to reach the intermediate discharge standard in the table 2, but after all nitrates are removed, the standard requirement that the total nitrogen in the direct discharge of the table 3 is less than 10mg/L can not be met. After research, nitrates in the total nitrogen components in the effluent of the secondary AO or denitrification filter are completely removed, but more quinoline, pyridine and other complex nitrogen-containing heterocyclic substances are still contained, and the total nitrogen in the effluent is overproof due to the pollutants. The pollutants can be subjected to ring opening and chain breaking by hydrolytic fermentation bacteria in an anaerobic environment to generate inorganic compounds such as ammonia nitrogen and the like with simple structures, but a large number of engineering practices and research reports show that the anaerobic technology has little effect on the treatment of coking wastewater.
The hydrolysis acidification treatment method is a process of hydrolyzing insoluble organic matters into soluble organic matters under the action of a large amount of hydrolytic bacteria and acidification bacteria and converting macromolecular substances which are difficult to biodegrade into micromolecular substances which are easy to biodegrade, so that the biodegradability of the wastewater is improved, and a good foundation is laid for subsequent treatment. However, the coking wastewater belongs to typical high-concentration refractory toxic industrial organic wastewater, contains organic pollutants such as phenols, benzene series, polycyclic aromatic hydrocarbons, nitrogen heterocyclic compounds, oils and the like, and inorganic pollutants such as ammonia, cyanogen, thiocyanide and the like, and the toxic substances can inhibit the activity of hydrolytic bacteria and acidifying bacteria, so that the hydrolytic acidification tank cannot take effect. Meanwhile, the water quality of the coking wastewater has strong fluctuation, and can impact microorganisms in a hydrolysis acidification tank, so that the hydrolysis acidification tanks of many coking enterprises basically have no treatment effect, and are abandoned.
According to the growth mode of microorganisms, the hydrolysis acidification tank is divided into a mud method mixed precipitation type hydrolysis tank and a membrane method non-precipitation type hydrolysis tank. A mud method is adopted to realize the circular flow of mixed liquid and promote the mud-water mixing in a pool with a sedimentation type hydrolysis pool by adopting an underwater stirrer; the water outlet system is provided with a precipitation unit and a sludge reflux system to maintain the sludge concentration in the hydrolysis acidification tank. This type of pond of hydrolysising need set up solitary sedimentation tank, and area is great, and when the incoming water fluctuated or the operation was unusual, the sedimentation tank took place easily and floats the mud phenomenon, influences follow-up biochemical treatment system operation. The membrane method non-precipitation type hydrolysis tank is characterized by that it uses up-flow water inlet, uses water distributor to implement uniform water inlet of every corner in the reactor, and adds filling material in the tank, and utilizes the growth of anaerobic microorganism attached to the filling material to degrade organic material. The filler is usually soft filler and elastic filler, wherein the soft filler is easy to form a film, but a biological film on the surface of the filler is not easy to update after long-time operation, so that the treatment efficiency is reduced; the elastic filler is not easy to be filmed, and the attachable microorganisms are small, so that the treatment efficiency is not high, and the problems of filler replacement, operation cost increase and the like exist.
Disclosure of Invention
In order to solve the problems, the invention provides a system and a method for treating coking wastewater.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a treatment system for coking wastewater comprises an oil separation tank, a first air floatation tank, an adjusting tank, a composite hydrolysis acidification tank, a second air floatation tank, an anoxic tank, an aerobic tank, a secondary sedimentation tank, a denitrification filter tank and a coagulation reaction system which are sequentially connected in series from front to back;
the secondary sedimentation tank is respectively communicated with the composite hydrolysis acidification tank and the anoxic tank through a nitrifying liquid return pipeline; a flow control device is arranged on the nitrifying liquid return pipeline; controlling the volume flow of the nitrifying liquid which flows back to the composite hydrolytic acidification tank to be 0.5 to 1.5 times of the volume flow of the wastewater flowing out of the regulating tank by using a flow control device;
a first sludge return pipe is arranged between the second air flotation tank and the hydrolysis acidification tank;
a second sludge return pipe is arranged between the aerobic tank and the secondary sedimentation tank.
Further, the secondary sedimentation tank comprises a sedimentation area and a water outlet tank;
the bottom of the settling zone is provided with a sludge collecting device; the sludge collecting device is communicated with the aerobic tank through a second sludge return pipe; the top of the settling zone is provided with a three-phase separator; the outer diameter of the section of the three-phase separator in the vertical direction is equal to that of the section of the settling zone; the water outlet of the three-phase separator is arranged in the water outlet pool; a water inlet device is arranged between the three-phase separator and the sludge collecting device; the water inlet device is communicated with the aerobic tank.
A method for treating coking wastewater is characterized in that the coking wastewater treatment system carries out treatment, and the specific method comprises the following steps:
s1) coking wastewater separates the heavy oil through the oil interceptor, and light oil and suspended solid are detached to first flotation tank, and the balanced quality of water of equalizing basin controls the volume flow of outflow waste water, and the outflow waste water of control equalizing basin is with 1 with the liquid of nitrifying: mixing the sludge and the water in the front end of the composite hydrolysis acidification pool at a volume flow ratio of 0.5 to 1.5, mixing the sludge and the water with the sludge flowing out of the first sludge return pipe, and then allowing the mixture to enter the composite hydrolysis acidification pool for hydrolysis acidification reaction and denitrification reaction;
s2) the wastewater flowing out of the composite hydrolysis acidification tank enters a second air floatation tank for mud-water separation, and the sludge enters the composite hydrolysis acidification tank again through a first sludge return pipe;
s3) the wastewater flowing out of the second air floatation tank enters an anoxic tank, is mixed with a nitrifying liquid at the front end of the anoxic tank, is subjected to denitrification reaction, then enters an aerobic tank, is subjected to heterotrophic bacteria degradation and nitrifying bacteria conversion, and is subjected to sludge-water separation in a secondary sedimentation tank, so that the nitrifying liquid for backflow is obtained;
the obtained nitrified liquid flows into a composite hydrolysis acidification tank, an anoxic tank and a denitrification filter tank respectively; the volume flow of the nitrifying liquid entering the denitrification filter tank is equal to the volume flow of the effluent wastewater of the regulating tank;
s4) carrying out denitrification reaction on the nitrified liquid entering the denitrification filter tank, and then entering a coagulation reaction system to remove soluble organic matters and heavy metals to obtain directly discharged clear water reaching the standard.
Furthermore, the residence time in the composite hydrolytic acidification tank is 12 to 24h, and the oxidation-reduction potential is less than or equal to 50mV.
Further, the concentration of the sludge in the composite hydrolysis acidification pool is 6000 to 8000mg/L; the sludge reflux ratio of the sludge flowing into the composite hydrolytic acidification tank from the first sludge reflux pipe is 0.8 to 1.2.
Furthermore, the composite hydrolysis acidification tank is provided with at least one hyperboloid stirrer and at least one submersible stirrer.
Furthermore, the volume flow ratio of the wastewater flowing out of the second air flotation tank to the nitrifying liquid flowing into the anoxic tank is 1.5 to 3.5.
Further, the dissolved oxygen concentration of the aerobic pool is 0.8 to 5mg/L, and the sludge reflux ratio flowing into the aerobic pool from the second sludge reflux pipe is 0.8 to 1.2.
Furthermore, the denitrification filter adopts an upward flow filter with the flow speed of 4 to 8m 3 /h。
Further, the compound medicament added into the coagulation reaction system is prepared from the following raw materials in a weight ratio of 1:0.8 to 1.2 of cross-linked starch-polyacrylamide-xanthate and high-polymer aluminum complex silicon flocculant.
The coking wastewater treatment system and the method have the beneficial effects that:
according to the invention, the nitrifying liquid in the secondary sedimentation tank is controlled to flow back to the composite hydrolysis acidification tank at a specific flow rate, so that the inhibition effect of toxic substances such as thiocyanide, cyanide, phenolic substances and sulfide in the coking wastewater and water quality fluctuation on hydrolysis bacteria and acidification bacteria can be reduced, the growth of the hydrolysis bacteria and the acidification bacteria is promoted, the hydrolysis acidification effect is enhanced, and the biodegradability is improved;
the nitrifying liquid entering the composite hydrolysis acidification tank can also utilize volatile fatty acid generated by the hydrolysis bacteria and the acidification bacteria as a carbon source to carry out rapid denitrification reaction, so that products of the hydrolysis bacteria and the acidification bacteria are consumed, and the hydrolysis and acidification reactions are further promoted to be carried out;
because the hydrolytic bacteria and the acidizing bacteria in the sludge are influenced by the oxidation-reduction potential (the growth of the hydrolytic bacteria and the acidizing bacteria can be inhibited if the pH value exceeds 50 mV), the nitrate in the nitrifying liquid can improve the oxidation-reduction potential in the composite hydrolytic acidification tank, and the oxidation-reduction potential of the liquid entering the composite hydrolytic acidification tank is controlled to be below 50mV by controlling the volume flow ratio of the nitrifying liquid to the coking wastewater, so that the hydrolysis and acidification reactions are effectively promoted;
the composite hydrolysis acidification tank can lead complex organic matters such as polycyclic aromatic hydrocarbon, benzopyrene, nitrogen-containing and sulfur-containing heterocycles and the like contained in coking wastewater to generate ring opening and chain breaking phenomena through hydrolysis and acidification reactions, and decompose the complex organic matters into micromolecular substances such as ammonia nitrogen, volatile fatty acid and the like, thereby improving the biodegradability of the coking wastewater, leading a subsequent biochemical system to have better treatment effect, saving the medicament cost of a coagulation reaction system, simultaneously reducing the COD value, and leading indexes such as polycyclic aromatic hydrocarbon, benzopyrene and the like to reach the standard;
because part of the nitrified liquid flows back to the composite hydrolytic acidification tank for denitrification reaction, the flow of the nitrified liquid flowing back to the anoxic tank is reduced, and the denitrification pressure of the anoxic tank is reduced, so that the floor area of the anoxic tank can be reduced to 2/3 of the original floor area, and the production cost is reduced;
meanwhile, the composite hydrolysis acidification tank converts the organic matters into soluble micromolecular organic matters, and the micromolecular organic matters which are not consumed in the composite hydrolysis acidification Chi Zhongxiao can provide a carbon source for the anoxic tank, so that the anoxic tank can perform complete denitrification reaction without adding a new carbon source;
according to the invention, the second air flotation tank is arranged behind the composite hydrolysis acidification tank, so that high-concentration return sludge can be provided for the composite hydrolysis acidification tank, the sludge concentration in the hydrolysis acidification tank is improved, and the influence of the water quality fluctuation of the coking wastewater on hydrolysis, acidification and denitrification reactions is further inhibited;
according to the invention, the hyperboloid stirrer and the submersible stirrer are arranged in the composite hydrolysis acidification tank, so that the mud and water on the horizontal plane and the vertical plane can be fully mixed, and the mixing ratio of the mud and water is improved; meanwhile, the submersible stirrer can also adjust the water flow direction, prevent sludge deposition of the composite hydrolysis acidification tank, realize full utilization of activated sludge and promote hydrolysis, acidification and denitrification reactions;
according to the invention, the three-phase separator with the outer diameter equal to that of the sedimentation zone is arranged at the top of the secondary sedimentation tank, so that gas, liquid and sludge are effectively separated, fine suspended sludge particles are prevented from being taken away by effluent, the recovery rate of sludge is improved, the influence of the suspended sludge particles on the denitrification filter tank is reduced, the number of suspended sludge particles to be treated by a coagulation reaction system is reduced, and the dosage of a medicament of the coagulation reaction system is reduced;
according to the invention, by adding the compound medicament in a specific ratio, water-soluble organic matters which are not completely degraded, suspended solid particles and heavy metals contained in the coking wastewater can be effectively removed.
Drawings
FIG. 1 is a schematic view showing the construction of a system for treating coking wastewater in example 1 of the present invention;
FIG. 2 is a sectional view of a secondary sedimentation tank in example 1 of the present invention.
Wherein, 1, a sludge collecting device; 2. a three-phase separator; 3. a water inlet device; 4. a second sludge return pipe; 5. a waste water outlet of the secondary sedimentation tank; 6. a mud scraper.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as specifically described herein, and it will be appreciated by those skilled in the art that the present invention may be practiced without departing from the spirit and scope of the present invention and that the present invention is not limited by the specific embodiments disclosed below.
Embodiment 1 coking wastewater treatment system
As shown in fig. 1, a treatment system for coking wastewater comprises 11 treatment tanks, namely an oil separation tank, a first air flotation tank, an adjusting tank, a composite hydrolysis-acidification tank, a second air flotation tank, an anoxic tank, an aerobic tank, a secondary sedimentation tank, a denitrification filter tank, a coagulation reaction system and a clean water tank, which are sequentially connected in series from front to back, wherein the clean water tank can be arranged or not arranged for directly discharging treated clean water.
The front end of the composite hydrolysis acidification tank is provided with three inlets, namely a wastewater inlet for wastewater flowing out of the regulating tank, a nitrifying liquid inlet and a sludge inlet, and the rear end of the composite hydrolysis acidification tank is provided with a wastewater outlet for wastewater flowing into the second air floatation tank.
The front end of the second air flotation tank is provided with a wastewater inlet of wastewater flowing out of the composite hydrolysis acidification tank, and the wastewater inlet of the second air flotation tank is communicated with the wastewater outlet of the composite hydrolysis acidification tank; the rear end of the second air floatation tank is provided with a wastewater outlet and a sludge return outlet for flowing into the anoxic tank wastewater;
a first sludge return pipe is arranged between the second air floatation tank and the hydrolysis acidification tank, and two ends of the first sludge return pipe are respectively communicated with a sludge return outlet of the second air floatation tank and a sludge inlet of the hydrolysis acidification tank; the first sludge return pipe is provided with a return pump, and sludge precipitated and flocculated in the second air floatation tank can be pumped into a sludge inlet of the composite hydrolysis acidification tank again;
the front end of the anoxic tank is provided with a wastewater inlet and a nitrifying liquid inlet for wastewater flowing out of the second air floatation tank, and the wastewater inlet of the anoxic tank is communicated with the wastewater outlet of the second air floatation tank; the rear end of the anoxic tank is provided with a wastewater outlet for flowing wastewater into the aerobic tank;
the front end of the aerobic tank is provided with a wastewater inlet and a sludge inlet for wastewater flowing out of the anoxic tank, and the wastewater inlet of the aerobic tank is communicated with the wastewater outlet of the anoxic tank; the rear end of the aerobic tank is provided with a wastewater outlet for flowing into the secondary sedimentation tank;
the front end of the secondary sedimentation tank is provided with a wastewater inlet for wastewater flowing out of the aerobic tank, and the wastewater inlet of the secondary sedimentation tank is communicated with the wastewater outlet of the aerobic tank. The rear end of the secondary sedimentation tank is provided with a wastewater outlet, a sludge outlet and at least one nitrifying liquid outlet for the wastewater flowing into the denitrification filter.
The self-nitration liquid outlet of the secondary sedimentation tank is respectively communicated with the composite hydrolysis acidification tank and the anoxic tank through nitration liquid return pipelines. A flow control device is arranged on the nitrifying liquid return pipeline; the flow control devices are generally respectively arranged near a nitrifying liquid inlet close to the composite hydrolytic acidification tank and near a nitrifying liquid inlet close to the anoxic tank, and the volume flow of nitrifying liquid flowing back to the composite hydrolytic acidification tank is controlled by the flow control devices to be 0.5 to 1.5 times of the volume flow of wastewater flowing out of the regulating tank; generally, the flow control device comprises a flow meter and a control valve, and the volume flow of the nitrified liquid flowing into the composite hydrolytic acidification tank and the anoxic tank is controlled by adjusting the control valve.
Wherein, the secondary sedimentation tank can be provided with a nitrifying liquid outlet communicated with the nitrifying liquid return pipeline, and can also be provided with two nitrifying liquid outlets communicated with the nitrifying liquid return pipeline. When the secondary sedimentation tank is provided with a nitrifying liquid outlet, the nitrifying liquid return pipeline is respectively communicated with the composite hydrolysis acidification tank and the anoxic tank through a tee joint. At this time, nitrifying liquid return pipelines behind the tee joint in the flowing direction of nitrifying liquid are respectively marked as a composite hydrolytic acidification Chi Xiaohua liquid branch and an anoxic Chi Xiaohua liquid branch, and flow devices are respectively arranged on a composite hydrolytic acidification Chi Xiaohua liquid branch and an anoxic Chi Xiaohua liquid branch. When two nitrifying liquid outlets are arranged, two nitrifying liquid return pipelines are respectively communicated with the composite hydrolysis acidification tank and the anoxic tank, and at the moment, the flow devices are respectively arranged on the two nitrifying liquid return pipelines.
A second sludge return pipe 4 is arranged between the aerobic tank and the secondary sedimentation tank, and two ends of the second sludge return pipe 4 are respectively communicated with a sludge outlet of the secondary sedimentation tank and a sludge inlet of the aerobic tank; the second sludge return pipe 4 is provided with a return pump, and sludge precipitated and flocculated in the secondary sedimentation tank can be pumped into the sludge inlet of the aerobic tank again.
The outlet of the secondary sedimentation tank is communicated with the front end of the denitrification filter tank, and the denitrification filter tank generally adopts a DNBF denitrification filter tank. The back end of the denitrification filter tank is communicated with the front end of the coagulation reaction system, and the back end of the coagulation reaction system can be provided with an outer discharge pipe or a clean water tank.
In the use process, because sludge still exists in the secondary sedimentation tank, denitrifying bacteria utilize nitrate generated by the aerobic tank to perform denitrification reaction with a carbon source contained in wastewater to generate nitrogen, and the nitrogen drives the sludge to float upwards, while the sludge scraper 6 used in the prior art cannot well solve the problem of sludge floating in the secondary sedimentation tank, in the embodiment, the three-phase separator 2 with the same size as a sedimentation area of the secondary sedimentation tank is arranged at the top of the secondary sedimentation tank.
As shown in fig. 2, in this embodiment, the secondary sedimentation tank includes a sedimentation zone and a water outlet tank, and a sludge collection device 1 is disposed at the bottom of the sedimentation zone; the rear end of the sludge collecting device 1, namely the bottom end of the sedimentation zone, is provided with a sludge outlet of the secondary sedimentation tank, namely the sludge collecting device 1 is communicated with the aerobic tank through a second sludge return pipe 4, and at the moment, the sludge collected by the sludge collecting device 1 is conveyed into the aerobic tank through the second sludge return pipe 4; the top of the settling zone is provided with a three-phase separator 2; the external diameter of the section of the three-phase separator 2 in the vertical direction is equal to that of the section of the settling zone; the three-phase separator 2 comprises a water outlet and an air outlet, and the water outlet of the three-phase separator 2 is positioned in the water outlet pool and outside the sedimentation zone. The gas outlet is positioned at the top end of the three-phase separator 2, and waste gas generated in the secondary sedimentation tank is discharged through the gas outlet. The outer end of the water outlet tank is provided with a waste water outlet 5 and at least one nitrified liquid outlet which are close to the ground. A mud scraper 6 and a water inlet device 3 are sequentially arranged between the three-phase separator 2 and the sludge collecting device 1 from top to bottom; the water inlet device 3 is communicated with a wastewater outlet of the aerobic tank through a wastewater inlet of the secondary sedimentation tank by a pipeline.
Example 2A method for treating coking wastewater
In this embodiment, the coking wastewater treatment system in embodiment 1 is used to treat coking wastewater, and the specific method includes the following steps:
s1) the coking wastewater enters an oil separation tank, heavy oil is separated by utilizing the gravity settling effect, and no agent is added; the retention time of the oil separation tank is 6 to 8 hours, and the retention time of the oil separation tank in the embodiment is 6 hours.
Enabling the wastewater flowing out of the oil separation tank to enter a first air flotation tank to remove light oil and suspended matters, then entering a regulating tank, staying for 12 to 24h (staying for 12h in the embodiment), balancing the water quality, and controlling the volume flow of the flowing-out wastewater; simultaneously, the volume flow of the nitrifying liquid entering the composite hydrolysis acidification tank is adjusted, and the outflow wastewater and the nitrifying liquid of the adjusting tank are controlled to be mixed according to the ratio of 1: mixing the sludge and the water in the front end of the composite hydrolytic acidification tank at a volume flow ratio of 0.5 to 1.5, and allowing the mixture to enter the composite hydrolytic acidification tank for hydrolytic acidification reaction and denitrification reaction after mixing the sludge and the water flowing out of the first sludge return pipe; the effluent wastewater of the regulating reservoir flows into the composite hydrolytic acidification tank from a wastewater inlet of the composite hydrolytic acidification tank, the nitrified liquid flows into the composite hydrolytic acidification tank from a nitrified liquid inlet of the composite hydrolytic acidification tank, and the sludge flows into the composite hydrolytic acidification tank from a sludge inlet of the composite hydrolytic acidification tank. In this example, the volume flow ratio of the effluent wastewater of the adjusting tank to the nitrifying liquid is 1:1, and at this time, the oxidation-reduction potential of the sludge water in the composite hydrolysis-acidification tank is +50mV.
At least one hyperboloid stirrer and at least one submersible stirrer are arranged in the composite hydrolysis acidification tank, and the hyperboloid stirrer can fully mix muddy water on a horizontal plane and a vertical plane, so that the mixing ratio effect of the muddy water is improved; the submersible stirrer with adjustable direction effectively prevents sludge deposition in the composite hydrolysis acidification tank, and realizes full utilization of activated sludge; the muddy water is fully mixed (namely, the waste water, the nitrifying liquid and the sludge flowing into the self-regulating tank are fully mixed), so that toxic substances and water quality fluctuation in the mixed muddy water can be reduced, the growth of hydrolytic bacteria and acidifying bacteria is promoted, and the hydrolysis and acidification reactions can be promoted.
The wastewater and the nitrifying liquid flowing out of the self-regulating pool enter a composite hydrolysis acidification pool and then stay for 12 to 24h for hydrolysis reaction, acidification reaction and denitrification reaction, and stay for 12h in the embodiment;
the sludge reflux ratio of the sludge flowing into the composite hydrolytic acidification tank from the first sludge reflux pipe is 0.8 to 1.2, and the concentration of the sludge in the corresponding composite hydrolytic acidification tank is 6000 to 8000mg/L. In this example, the sludge reflux ratio was 1, and the concentration of sludge in the composite hydrolytic acidification tank was 7000mg/L.
And S2) the wastewater flowing out of the composite hydrolysis acidification tank enters a second air floatation tank for mud-water separation (the second air floatation tank replaces the existing sedimentation tank for mud-water separation), and in the embodiment, the second air floatation tank is treated by adopting a water outlet part reflux pressurization dissolved air floatation process. The sludge with high concentration and concentration generated by the air flotation enters the front end of the composite hydrolysis acidification tank again through the first sludge return pipe, namely enters the first sludge return pipe through the sludge return outlet of the second air flotation tank and is pumped into the sludge inlet of the composite hydrolysis acidification tank through the return pump. The residence time of the second air floatation tank is 1.5 to 2.5 hours, and the residence time of the second air floatation tank is 2 hours in the embodiment.
And S3) the wastewater flowing out of the second air flotation tank enters the anoxic tank and is mixed with the nitrifying liquid at the front end of the anoxic tank, the volume flow of the nitrifying liquid entering the anoxic tank is adjusted, the volume flow ratio of the wastewater flowing out of the second air flotation tank to the nitrifying liquid is controlled to be 1.5 to 3.5, and denitrification reaction is carried out. In this embodiment, the volume flow ratio of the wastewater flowing out of the second flotation tank to the nitrified liquid is 1:2.
wherein, the outflow waste water of second air supporting pond flows into the oxygen deficiency pond from the waste water entry of oxygen deficiency pond, and the liquid of nitrifying flows into the oxygen deficiency pond from the liquid entry of nitrifying of oxygen deficiency pond.
Because the nitrifying liquid partially flows back into the composite hydrolytic acidification tank and only partially flows back into the anoxic tank, the content of nitrate to be treated in the anoxic tank is greatly reduced by about 1/3, and therefore, when the anoxic tank is newly built, the area of the anoxic tank can be reduced by about 1/3, and the denitrification reaction to be finished by the anoxic tank can be achieved. The embodiment is an improvement of the prior art, and the anoxic pond is built, so the area of the anoxic pond is not reduced.
Meanwhile, macromolecular organic matters are fully degraded into easily biodegradable micromolecular organic matters in the composite hydrolysis acidification tank, so that the carbon source content of denitrifying bacteria in the wastewater entering the anoxic tank is increased, and the rapid occurrence of denitrification reaction is facilitated.
After the denitrification reaction is completed, the wastewater flowing out of the anoxic tank enters the front end of the aerobic tank from a wastewater inlet of the aerobic tank, and is mixed with the sludge flowing out of the second sludge return pipe 4, and meanwhile, oxygen is introduced to maintain the concentration of the dissolved oxygen in the aerobic tank to be always kept at 0.8-5mg/L, wherein the concentration of the dissolved oxygen is maintained at 3mg/L in the embodiment. In an oxygen environment, heterotrophic bacteria and nitrobacteria are used for converting organic matters and ammonia nitrogen in the wastewater flowing into the aerobic tank, the heterotrophic bacteria degrade COD (chemical oxygen demand) in the wastewater by using a self reaction, and the nitrobacteria convert the ammonia nitrogen into nitrate. As the nitrifying bacteria can generate hydrogen ions in the process of converting ammonia nitrogen into nitrate, an alkaline pH regulator is also required to be added into the aerobic pool, the pH value is controlled to be maintained at 7.5 +/-1, and the pH regulator can be sodium carbonate under the general condition.
The retention time of the aerobic pool is 28 to 32h, and the retention time of the aerobic pool is 30h.
The waste water flowing out of the aerobic tank enters a secondary sedimentation tank for mud-water separation, namely the waste water flows out of the aerobic tank and then enters a water inlet device 3 through a pipeline through a waste water inlet of the secondary sedimentation tank, then flows into the secondary sedimentation tank through the water inlet device 3, sludge is settled to the bottom in the secondary sedimentation tank, is collected by a sludge collection device 1 and flows into a second sludge return pipe 4; the gas is discharged from the gas outlet after being collected by the three-phase separator 2, the liquid flows into the water outlet pool from the water outlet after being collected by the three-phase separator 2, and the liquid in the water outlet pool is the nitrified liquid. Nitrifying liquid in the water outlet tank flows into the composite hydrolysis acidification tank, the anoxic tank and the denitrification filter tank respectively; a flow control device (namely a flowmeter and a control valve) is arranged on a pipeline between the secondary sedimentation tank and the denitrification filter tank, the volume flow of the nitrifying liquid entering the denitrification filter tank is adjusted, and the volume flow of the nitrifying liquid entering the denitrification filter tank is controlled to be equal to the volume flow of the effluent wastewater of the adjusting tank;
the residence time in the secondary sedimentation tank is 18 to 22h, and the residence time in the secondary sedimentation tank is 20h.
S4) carrying out denitrification reaction on the nitrified liquid entering the denitrification filter, wherein a proper amount of carbon source can be added according to the content of the carbon source in the nitrified liquid, and when the content of the carbon source in the nitrified liquid is higher, the carbon source can not be added, so that the composite carbon source is added in the embodiment.
The denitrification filter tank adopts an upward flow filter tank, and the flow speed is 4 to 8m 3 H, flow rate of 6m in this example 3 /h。
And (3) allowing the wastewater flowing out of the denitrification filter tank to enter a coagulation reaction system, adding a compound medicament into the coagulation reaction system, and staying for 0.5-1.5 h (staying for 1h in the embodiment), so as to adsorb residual soluble organic matters, suspended solids and heavy metals in the wastewater, thereby obtaining the directly discharged clear water reaching the standard. The clear water up to standard can directly discharge, can get into recycle in the clean water basin, and the clear water up to standard flows into the clean water basin in this embodiment for recycle.
Wherein 800ppm activated carbon, 2000ppm polyaluminium chloride (PAC)/polyferric sulfate, 5ppm polyacrylamide and 15ppm complexing agent are added.
The compound medicament is prepared from the following components in percentage by weight: 0.8 to 1.2 of crosslinked starch-polyacrylamide-xanthate and a flocculant of highly polyaluminium silica (in this example, the weight ratio of the crosslinked starch-polyacrylamide-xanthate to the flocculant of highly polyaluminium silica is 1:1).
The effect after each treatment pond handles among the above-mentioned coking wastewater treatment process is seen as the following table:
TABLE 1 list of treated wastewater treatment tanks (unit: mg/L)
Example 8978 method of treating coking wastewater with zxft 8978
Examples 3~6 are processes for treating coking wastewater, respectively, which are substantially the same as in example 2 except for the differences in process parameters, as detailed in table 2:
TABLE 2 summary of the process parameters of example 3~6
The process parameters, steps and treatment effects of the other parts of the 3~6 embodiment are substantially the same as those of the 531 embodiment.
Comparative example 1 treatment method of coking wastewater in prior art
In the embodiment, the coking wastewater is sequentially treated by an oil separation tank, an air flotation tank, a regulating tank, an anaerobic tank, an anoxic tank, an aerobic tank, a secondary sedimentation tank, a DNBF denitrification filter, a coagulation reaction system and a clean water tank, wherein the retention time of the oil separation tank is 8 hours, the retention time of the air flotation tank is 2 hours, the retention time of the regulating tank is 24 hours, the retention time of the anaerobic tank is 12 hours, the retention time of the anoxic tank is 18 hours, the retention time of the aerobic tank is 30 hours, the retention time of the secondary sedimentation tank is 20 hours, the retention time of the coagulation reaction system is 1 hour, and the retention time of the clean water tank is 50 hours. The dosage of the compound medicament added into the coagulation reaction system is 15ppm. The specific treatment results are shown in the following table:
TABLE 3 general list of treated wastewater treatment tanks in comparative example 1 (unit: mg/L)
Because coking wastewater contains toxic substances such as volatile phenol, sulfide, cyanide, thiocyanide and the like, the conventional anaerobic tank is in an idle state, no hydrolysis and acidification reaction of the system occurs, and complex organic matters such as polycyclic aromatic hydrocarbon, benzopyrene, nitrogen-containing and sulfur-containing heterocycles and the like cannot be subjected to ring opening and chain scission in an anaerobic stage, so that COD index of a subsequent biochemical system is high, the using amount of a compound medicament in a coagulation reaction system is increased, and the operation cost is increased. In addition, indexes such as TN index, polycyclic aromatic hydrocarbon and benzopyrene also have the problem of exceeding standards and cannot be directly discharged.
Comparative example 2 method for treating coking wastewater
Comparative example 2 is a comparative experiment of the method for treating coking wastewater of example 2, differing only in that: nitrified liquid only flows back to the anoxic tank and does not flow back to the composite hydrolysis acidification tank, and specific treatment results are shown in the following table:
TABLE 4 general table of treated wastewater treatment tanks in comparative example 2 (unit: mg/L)
In comparative example 2, the wastewater flowing into the composite hydrolysis acidification tank contained toxic substances such as thiocyanide, cyanide, phenolic substances and sulfides, and the water quality fluctuation was large, the hydrolysis bacteria and the acidification bacteria were inhibited and could not grow well, and the composite hydrolysis acidification tank could not function.
Comparative example 3 method for treating coking wastewater
Comparative example 3 is a comparative experiment of the method for treating coking wastewater of example 2, differing only in that: the volume flow ratio of the effluent wastewater of the control adjusting tank to the nitrified liquid in the composite hydrolysis acidification tank is 1:3, and the specific treatment results are shown in the following table:
TABLE 5 general list of treated wastewater treatment tanks in comparative example 3 (unit: mg/L)
In the comparative example 3, the redox potential in the composite hydrolysis acidification tank exceeds 50mV, the hydrolysis bacteria, the acidification bacteria and the nitrobacteria can not grow well, and the composite hydrolysis acidification tank can not play a role.
Comparative example 4 method for treating coking wastewater
Comparative example 4 is a comparative experiment of the method for treating coking wastewater of example 2, differing only in that: the cross-linked starch-polyacrylamide-xanthate is not added into the compound preparation, but the total dosage of the compound preparation is not changed, and the specific treatment results are shown in the following table:
TABLE 6 general list of treated wastewater treatment tanks in comparative example 4 (unit: mg/L)
The complex agent used in comparative example 4 could not remove heavy metals in the coking wastewater well.
Comparative example 5 method for treating coking wastewater
Comparative example 5 is a comparative test of the method for treating coking wastewater of example 2, differing only in that: the high-polyaluminium silicon flocculant is not added into the compound preparation, but the total dosage of the compound preparation is unchanged, and the specific treatment result is shown in the following table:
TABLE 7 summary of the results of treatment in comparative example 5 on each wastewater treatment tank (unit: mg/L)
The complex reagent used in comparative example 5 also failed to remove heavy metals from coking wastewater well.
It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. The coking wastewater treatment system is characterized by comprising an oil separation tank, a first air floatation tank, an adjusting tank, a composite hydrolysis acidification tank, a second air floatation tank, an anoxic tank, an aerobic tank, a secondary sedimentation tank, a denitrification filter tank and a coagulation reaction system which are sequentially connected in series from front to back;
the secondary sedimentation tank is respectively communicated with the composite hydrolysis acidification tank and the anoxic tank through a nitrifying liquid return pipeline; a flow control device is arranged on the nitrifying liquid return pipeline; controlling the volume flow of the nitrifying liquid which flows back to the composite hydrolytic acidification tank to be 0.5 to 1.5 times of the volume flow of the wastewater flowing out of the regulating tank by using a flow control device;
the oxidation-reduction potential in the composite hydrolysis-acidification tank is less than or equal to 50mV;
a first sludge return pipe is arranged between the second air flotation tank and the hydrolysis acidification tank;
a second sludge return pipe is arranged between the aerobic tank and the secondary sedimentation tank.
2. The coking wastewater treatment system of claim 1, wherein the secondary sedimentation tank includes a settling zone and an effluent tank;
the bottom of the settling zone is provided with a sludge collecting device; the sludge collecting device is communicated with the aerobic tank through a second sludge return pipe; the top of the settling zone is provided with a three-phase separator; the outer diameter of the section of the three-phase separator in the vertical direction is equal to that of the section of the settling zone; the water outlet of the three-phase separator is arranged in the water outlet pool; a water inlet device is arranged between the three-phase separator and the sludge collecting device; the water inlet device is communicated with the aerobic tank.
3. A method for treating coking wastewater by using the coking wastewater treatment system of claim 1 or 2, which is characterized by comprising the following steps:
s1) coking wastewater passes through oil separation tank separation heavy oil, and light oil and suspended solid are detached to first air supporting pond, and the equalizing water quality of equalizing basin controls the volume flow of outflow waste water, and the outflow waste water of control equalizing basin and nitrify liquid with 1: mixing the sludge and the water in the front end of the composite hydrolytic acidification tank at a volume flow ratio of 0.5 to 1.5, and allowing the mixture to enter the composite hydrolytic acidification tank for hydrolytic acidification reaction and denitrification reaction after mixing the sludge and the water flowing out of the first sludge return pipe;
s2) the wastewater flowing out of the composite hydrolysis acidification tank enters a second air floatation tank for mud-water separation, and the sludge enters the composite hydrolysis acidification tank again through a first sludge return pipe;
s3) the wastewater flowing out of the second air floatation tank enters an anoxic tank, is mixed with a nitrifying liquid at the front end of the anoxic tank, is subjected to denitrification reaction, then enters an aerobic tank, is subjected to heterotrophic bacteria degradation and nitrifying bacteria conversion, and is subjected to sludge-water separation in a secondary sedimentation tank, so that the nitrifying liquid for backflow is obtained;
the obtained nitrified liquid flows into a composite hydrolysis acidification tank, an anoxic tank and a denitrification filter tank respectively; the volume flow of the nitrifying liquid entering the denitrification filter tank is equal to the volume flow of the effluent wastewater of the regulating tank;
s4) carrying out denitrification reaction on the nitrified liquid entering the denitrification filter tank, and then entering a coagulation reaction system to remove soluble organic matters and heavy metals to obtain directly discharged clear water reaching the standard.
4. The method for treating coking wastewater according to claim 3, characterized in that the residence time in the composite hydrolysis acidification pool is 12 to 24h.
5. The method for treating coking wastewater according to claim 3 or 4, wherein the concentration of the sludge in the composite hydrolytic acidification tank is 6000 to 8000mg/L; the sludge reflux ratio of the sludge flowing into the composite hydrolytic acidification tank from the first sludge reflux pipe is 0.8 to 1.2.
6. The method for treating coking wastewater according to claim 3 or 4, characterized in that the composite hydrolytic acidification tank is provided with at least one hyperboloid stirrer and at least one submersible stirrer.
7. The method for treating the coking wastewater according to claim 3 or 4, wherein the volume flow ratio of the wastewater flowing out of the second air flotation tank to the nitrifying liquid flowing into the anoxic tank is 1.5 to 3.5.
8. The method for treating coking wastewater according to claim 3 or 4, characterized in that the dissolved oxygen concentration of the aerobic pool is 0.8 to 5mg/L, and the sludge reflux ratio flowing into the aerobic pool from the second sludge reflux pipe is 0.8 to 1.2.
9. The method for treating coking wastewater according to claim 3 or 4, characterized in that the denitrification filter tank adopts an upward flow filter tank, and the flow speed is 4 to 8m 3 /h。
10. The method for treating coking wastewater according to claim 3 or 4, characterized in that the compound medicament added into the coagulation reaction system is mixed with the raw materials in a weight ratio of 1:0.8 to 1.2 of cross-linked starch-polyacrylamide-xanthate and a high polyaluminium silicon flocculant.
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