CN116062931A - Wastewater multi-pollutant cooperative removal regulation and control method taking adsorption enhancement as core - Google Patents
Wastewater multi-pollutant cooperative removal regulation and control method taking adsorption enhancement as core Download PDFInfo
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- CN116062931A CN116062931A CN202211713852.6A CN202211713852A CN116062931A CN 116062931 A CN116062931 A CN 116062931A CN 202211713852 A CN202211713852 A CN 202211713852A CN 116062931 A CN116062931 A CN 116062931A
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Classifications
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
-
- 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
- C02F1/72—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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a method for cooperatively removing and regulating multiple pollutants in wastewater with adsorption enhancement as a core, which comprises the steps of firstly enabling wastewater after biochemical treatment to flow through an ozone pre-oxidation system, enabling effluent to flow into a coagulating sedimentation system, and then adding a coagulant to perform coagulating sedimentation treatment; the treated effluent flows into a resin adsorption system for adsorption treatment; regenerating the used resin and collecting desorption liquid; the collected desorption liquid flows into an ozone catalytic oxidation system for strengthening treatment of the desorption liquid, and the effluent flows into an electric flocculation system; and refluxing the treated effluent. The invention enhances the treatment effect of the ozone catalytic oxidation system through resin adsorption, enhances the resin adsorption effect through ozone oxidation treatment, reduces energy consumption, improves the deep removal capacity of organic matters, can realize the self circulation of resin regeneration liquid, simplifies the process flow, shortens the reaction time and reduces the cost.
Description
Technical Field
The invention relates to the technical field of sewage purification, in particular to a method for cooperatively removing and regulating multiple pollutants in wastewater by taking adsorption enhancement as a core.
Background
The waste water from petrochemical coking contains benzene series, esters, phenols, aldehydes, ketones, alcohols, nitriles, amines, alkanes, polycyclic aromatic hydrocarbons, organic acids and other toxic and refractory organic matters, and belongs to typical refractory industrial waste water. At present, the domestic treatment technology taking ozone catalytic oxidation as a core is widely applied to the advanced treatment of the wastewater tail water, but the subsequent treatment of the wastewater is greatly influenced by a front-end process, and the treatment difficulty and the pertinence requirements are higher. Tail water after biochemical treatment of industrial wastewater is difficult to directly reach the standard and be difficult to deeply purify, the treatment cost of directly adopting an ozone catalytic oxidation method is high, the traditional direct ozone oxidation/catalytic oxidation treatment mode is often short in contact time between ozone, active oxygen free radicals generated by catalysis and the like and organic molecules because of lower initial concentration of pollutants in the advanced treatment, insufficient contact, low ozone utilization rate, and the need of a large amount of absorption liquid to independently absorb excessive ozone, so that ozone is ineffective and lost, and the treatment cost is increased. Tail water after biochemical treatment of industrial wastewater has large water quality fluctuation and is difficult to deeply purify, the treatment cost is high by directly adopting an ozone catalytic oxidation technology, and the resin adsorption technology faces the problems of difficult regulation and control of inflow load, difficult treatment of desorption liquid and the like.
The coagulating sedimentation method is one of the most common advanced treatment methods in sewage treatment in China, but is limited in organic matter removal efficiency due to the influence of complex water quality and low concentration of tail water. Ozone oxidation is reported to enhance coagulation efficiency in tail water, and is more common in the coupling technology of practical application of a coagulation sedimentation method and an ozone catalytic oxidation, chinese patent CN207391147U discloses a wastewater treatment system based on the ozone catalytic oxidation and the coagulation sedimentation method, the removal effect of the method on organic matters is only simple superposition of the ozone catalytic oxidation and the coagulation sedimentation method, the synergistic removal effect on the organic matters is not seen, and the method has no obvious advantage in cost. Chinese patent CN105800758A discloses an ozone coagulation interaction synergistic method for improving the efficiency of removing organic matters, and simultaneously realizes oxidation and coagulation in the same system, and the method needs to perform oxidation operation under the condition of ph=3, has a complex process, and is mainly suitable for advanced treatment of low-concentration biochemical tail water/drinking water.
The adsorption resin also has wide application in the aspect of deeply treating industrial wastewater tail water. For example, the catalyst has good adsorption, recovery and purification effects on various organic matters such as benzene or phenol compounds, organic acids and the like in the wastewater. The adsorption resin is used for highly treating the organic industrial wastewater which is difficult to biochemically degrade and is valued in various countries around the world. The method has great progress in the aspects of efficiently adsorbing and recovering phenols, amines, organic acids, nitro compounds, halogenated hydrocarbons and the like from chemical production wastewater. Compared with the prior adsorbents (active carbon, molecular sieve, alumina and the like), the adsorbent resin has the advantages of outstanding performance, large adsorption capacity, easy elution, certain selectivity and good strength, and can be reused. However, aiming at complex waste water types, such as biochemical tail water, the treatment depth of a single resin adsorption technology is limited, desorption liquid needs to be treated independently, modes of distillation, evaporative crystallization and the like are utilized, the recycling treatment flow of regeneration liquid is complex, the cost is high, and the application of the resin adsorption technology faces the problems of difficult regulation and control of inflow load, difficult treatment of desorption liquid and the like. Chinese patent CN108147591B discloses a method for treating high-concentration alkaline resin desorption liquid by catalytic ozonation technology, which improves the biodegradability of the high-concentration alkaline resin desorption liquid after catalytic ozonation treatment, but needs to repeatedly adjust pH to neutral before entering biochemistry, consumes a large amount of chemicals, and the treatment unit is only resin adsorption, so that the treated water quality and treatment depth are limited, ozone gas is not fully utilized, and safety absorption is still required to be carried out independently.
Disclosure of Invention
Aiming at the problems in the background art, the invention aims at the problems that the treatment difficulty of tail water of wastewater in the industries of petrifaction, coking and the like is high, the cost of a traditional direct ozone oxidation treatment mode is too high, the utilization rate of an oxidant caused by low concentration is low, the treatment depth of a single adsorption technology is limited, the desorption liquid needs to be treated independently, the circulating treatment flow of a regeneration liquid is complex, the cost is high and the like, and specifically provides a multi-process coupling regulation method for deep purification of wastewater with adsorption enhancement as a core. The method is suitable for advanced treatment of industrial wastewater biochemical tail water, effectively plays the advantage of multi-process coupling reinforcement, can realize multi-pollutant cooperative removal, and simultaneously realizes efficient treatment and cyclic utilization of resin desorption liquid, cascade utilization of oxidant, efficient utilization of coagulant and functional enhancement of adsorbent. The method has the advantages of good stability, low medicine consumption, capability of greatly reducing the operation cost and wide application and popularization prospect.
The technical aim of the invention is realized by the following technical scheme:
a method for cooperatively removing and regulating multiple pollutants in wastewater by taking adsorption enhancement as a core comprises the following steps:
step S1: firstly, flowing the wastewater after biochemical treatment through an ozone pre-oxidation system, flowing the effluent into a coagulating sedimentation system, then adding a coagulant to perform coagulating sedimentation treatment, and discharging coagulated and precipitated sludge;
step S2: enabling the effluent water treated in the step S1 to flow into a resin adsorption system for adsorption treatment;
step S3: regenerating the resin used in the step S2, and collecting desorption liquid;
step S4: the desorption liquid collected in the step S3 flows into an ozone catalytic oxidation system for strengthening treatment of the desorption liquid, the effluent flows into an electric flocculation system, and then coagulant is added for coagulating sedimentation treatment again;
step S5: carrying out reflux on the effluent treated in the step S4 to realize reutilization or reprocessing, wherein one part of the effluent is used for preparing a regenerant, and the other part of the effluent is mixed with the effluent treated in the step S1 by coagulating sedimentation and then further enters a resin adsorption system to realize deep purification treatment by enhancing adsorption; after one backflow, the water body is treated by the resin adsorption system and then discharged from the effluent.
The steps S1 to S5 are sequentially carried out according to the sequence.
Preferably, in the step S1 and the step S4, the coagulant in the coagulating sedimentation treatment is one or more of aluminum series, iron series and aluminum-iron series inorganic coagulants, and the adding amount of the coagulant is 20-80mg/L. The coagulant dosage is any value in the range of 20-80mg/L, such as 20mg/L,30mg/L,40mg/L,50mg/L,60mg/L,70mg/L and 80mg/L.
In any of the above schemes, it is preferable that when the wastewater in step S1 is treated by the ozone pre-oxidation system, the ozone oxidation contact time is 10-40min, the ozone initial flux is 1-2mg/min, the ozone oxidation contact time is any value within the range of 10-40min, such as 10min,20min,30min,40min, and the ozone initial flux is any value within the range of 1-2mg/min, such as 1mg/min,2mg/min. In the step S4, the collected desorption liquid flows into an ozone catalytic oxidation system, the ozone catalytic oxidation contact time is 10-60min, the ozone initial flux is 1-4mg/min, and the ozone oxidation contact time is any value within the range of 10-60min, such as 10min,20min,30min,40min,50min and 60min; the initial flux of ozone is any value in the range of 1-4mg/min, such as 1mg/min,2mg/min,3mg/min,4mg/min.
In any of the above schemes, preferably, in step S2, the resin in the resin adsorption system includes one or more of ammonia nitrogen removal adsorption resin, ion exchange resin, magnetic resin and chelating resin. After the treatment of the step S2, the removal rate of various pollutants is effectively improved, and the adsorbed effluent is deeply purified.
In any of the above schemes, it is preferable that in the step S2, the flow rate of the wastewater in the resin adsorption system is 1-8 BV/h, and the adsorption volume is 50-150 BV. The flow rate of the wastewater in the resin adsorption system is any value in the range of 1-8 BV/h, such as 1BV/h,2BV/h,3BV/h,4BV/h,5BV/h,6BV/h,7BV/h and 8BV/h. The adsorption volume is any value in the range of 50 to 150BV, such as 50BV,80BV,100BV,120BV,140BV,150BV.
In any of the above embodiments, in step S3, the resin used in step S2 is preferably desorbed and regenerated by a regenerating agent. The used resin is desorbed and regenerated through the regenerant, the resin is cleaned by the cleaning water after the desorption liquid is discharged, the next batch is ready for use, and meanwhile, the wastewater flows through other resins, so that the continuous operation of the whole system is ensured.
In any of the above-mentioned embodiments, in step S3, the regenerant is preferably 2 to 15% NaCl and/or NaOH solution at a flow rate of 1 to 6BV/h during the resin regeneration treatment. The regenerant in the step can be 2% of NaCl and/or NaOH solution, 5% of NaCl and/or NaOH solution, 6% of NaCl and/or NaOH solution, 8% of NaCl and/or NaOH solution, 10% of NaCl and/or NaOH solution, 12% of NaCl and/or NaOH solution and 15% of NaCl and/or NaOH solution; the flow rates were 1BV/h,2BV/h,3BV/h,4BV/h,5BV/h,6BV/h. In the step S3, organic matters on the surface and inside of the resin material are desorbed through backwashing, the flow rate is 1-4 BV/h, the regeneration liquid amount is 1.5-3 BV, the resin after backwashing is cleaned through a large amount of cleaning water, the cleaning water amount is 1.5-3 BV, residual liquid remained on the surface and inside of the resin is washed away, and then flushing water is emptied and is ready for the next use.
In any of the above schemes, in step S4, the catalyst in the ozone catalytic oxidation system is preferably one or more of an aluminum catalyst, an iron catalyst, a biochar catalyst and a supported catalyst thereof.
In any of the above embodiments, preferably, in step S4, the electric current density in the electric flocculation system is 1 to 50mA/cm 2 The distance between the anode and the cathode is 1-10 cm, and the hydraulic retention time is 1-20 min. The current density is 1-50 mA/cm 2 Any value within the range, e.g. 1mA/cm 2 ，10mA/cm 2 ，20mA/cm 2 ，30mA/cm 2 ，40mA/cm 2 ，50mA/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The distance between the anode and the cathode can be 1cm,3cm,5cm and 6cm.
In any of the above schemes, preferably, in the step S4, the ozone catalytic oxidation system performs efficient ozone catalytic oxidation treatment on the desorption liquid after concentration in the step S3 through ozone generated by an ozone generator and further catalytic action of a catalyst in the ozone catalytic oxidation system, and overflowed ozone gas directly enters the ozone pre-oxidation system in the step S1 to perform ozone oxidation pretreatment on inflow water of the ozone pre-oxidation system without performing absorption treatment on the overflowed ozone gas by a separate absorption liquid, so that the resin absorption system outflow water is used as ozone absorption liquid while pollutants are degraded, and the process cost is reduced.
In any of the above schemes, preferably, in step S5, the effluent treated in step S4 is refluxed for reuse or reprocessing, wherein 20% of the effluent is used for preparing a regenerant, and 80% of the effluent is mixed with the effluent treated in step S1 by coagulating sedimentation and then further enters a resin adsorption system to achieve deep purification treatment by enhancing adsorption; after one backflow, the water body is treated by the resin adsorption system and then discharged from the effluent.
The invention also discloses application of the wastewater multi-pollutant cooperative removal regulation and control method taking adsorption enhancement as a core to deep degradation treatment of organic wastewater.
In summary, the invention has the following advantages:
the application discloses a wastewater multi-pollutant collaborative removal regulation and control method taking adsorption enhancement as a core, through selecting a proper resin material, a large number of active sites and charged groups on the surface of the resin material are utilized in a resin adsorption system, and various soluble organic matters such as benzene or phenol compounds, organic acids and the like in tail water are adsorbed and removed and enriched together. The high-concentration desorption liquid generated after separation has higher initial concentration, and can obviously improve the efficiency of ozone catalytic oxidation and the ozone utilization rate. The excessive unused ozone can be effectively reused and absorbed by pre-oxidation treatment before resin adsorption, so that the cost is greatly reduced, and the resin adsorption effect is enhanced. After the desorption liquid is subjected to ozone catalytic oxidation treatment, the coagulation effect is greatly enhanced, and the regeneration and the cyclic utilization of the desorption liquid can be further realized through the coagulation treatment, so that the targeted combined resin adsorption and ozone catalytic oxidation technology forms good technical coupling and economical coupling advantages. Specific:
(1) The adsorption effect of the resin is enhanced by ozone pre-oxidation and coagulation, a large amount of soluble organic matters in tail water are removed by resin adsorption, concentration and enrichment are carried out, high-concentration desorption liquid is formed after desorption, ozone catalytic oxidation treatment is carried out on the high-concentration desorption liquid, and the utilization efficiency of ozone can be greatly improved.
(2) The overflow ozone is introduced into the resin to adsorb the front end of water inflow for pretreatment, so that the overflow ozone is used as an absorption liquid of ozone, and meanwhile, the redundant ozone is reused, so that the soluble organic matters are decomposed, the subsequent resin adsorption effect is enhanced, the extra occupation area and equipment investment are reduced, the cost is greatly reduced, and the safety is improved.
(3) The desorption liquid is subjected to ozone catalytic oxidation treatment, the coagulating sedimentation treatment capacity of the desorption liquid is greatly enhanced, a good coupling effect is formed, a proper amount of a re-rising agent can be supplemented after the coagulating treatment, the regeneration and recycling of the regenerating agent are realized, the self-circulation of the resin regenerating liquid can be realized, the process flow is simplified, the occupied area is reduced, and the good technical coupling characteristic and economic coupling advantage are embodied.
(4) The method can effectively treat biochemical tail water of waste water such as petrifaction, coking and the like under weak alkaline pH, does not introduce new metal, does not need to adjust pH, can effectively exert the advantage of multi-process interaction reinforcement, and simultaneously realizes the efficient treatment and recycling of resin desorption liquid, the cascade utilization of oxidant, the efficient utilization of coagulant and the functional reinforcement of adsorbent, thereby greatly reducing the cost of an integrated process.
(5) The sodium salt solution is adopted to carry out backwashing regeneration of the resin, so that the equipment requirement is low, and the operation is simple and safe;
(6) The method has the advantages of simple reaction process, low-cost and easily-obtained related raw materials, no dangerous and expensive chemical, high safety performance and environmental protection.
(7) The invention is suitable for advanced treatment of industrial wastewater biochemical tail water, effectively plays the advantage of multi-process coupling reinforcement, can realize the cooperative removal of multiple pollutants, and simultaneously realizes the efficient treatment and recycling of resin desorption liquid, the cascade utilization of oxidizing agent, the efficient utilization of coagulant and the functional enhancement of adsorbent. The method has the advantages of good stability, low medicine consumption, capability of greatly reducing the operation cost and wide application and popularization prospect.
Drawings
FIG. 1 is a process flow diagram of a wastewater multi-pollutant cooperative removal regulation and control method with adsorption enhancement as a core;
FIG. 2 is a three-dimensional fluorescent projection view of raw water (biochemical tail water secondary sedimentation tank effluent of petrochemical wastewater) of the invention;
FIG. 3 is a three-dimensional fluorescent projection of effluent from an ozone pre-oxidation system according to the present invention;
FIG. 4 is a three-dimensional fluorescent projection of effluent from a resin adsorption system according to the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention, and it is apparent that the described embodiments are merely all other embodiments that a person skilled in the art may obtain without making any inventive effort, and are all within the scope of protection of the present invention.
Example 1
The method for cooperatively removing and regulating the multiple pollutants in the wastewater by taking adsorption enhancement as a core comprises the following steps of:
firstly, enabling effluent of the secondary sedimentation tank to flow through an ozone pre-oxidation system for pretreatment, wherein the ozone flux is 2mg/L, the treatment time is 20min, continuing to carry out a coagulating sedimentation system, adding 20mg/L of polymeric ferric sulfate and 50mg/L of polyaluminium chloride, pumping supernatant into a resin adsorption system to remove soluble organic matters, selecting ND-2 resin as resin for adsorption experiments, and discharging effluent at an adsorption flow rate of 2 BV/h.
And (II) desorbing the resin used by the resin adsorption system by using 10% NaCl solution, wherein the flow rate is 1BV/h, and the desorption liquid amount is 2BV.
And (III) the desorption liquid flows into an ozone catalytic oxidation system for treatment, and the reaction conditions are as follows: the catalyst is alumina pellets with the diameter of 5mm, the adding amount of the catalyst is 20g/L, the ozone flux is 4mg/L, the treatment time of the ozone oxidation process is 30min, and overflowed ozone is connected with an ozone pre-oxidation system at the front end for absorption and reutilization; the effluent enters an electric flocculation system, and the current density is 30mA/cm 2 The distance between the anode and the cathode is 6cm, and the hydraulic retention time is 20min.
And (IV) carrying out reflux recycling on the electric flocculation effluent, wherein 20% of the effluent is supplemented according to the loss proportion of 10% of the regenerant, then enters the resin adsorption system as the regenerant for repeated use, and the remaining 80% of the effluent flows back to the front end to be mixed with the inflow water of the resin adsorption system, and after one-time reflux, the water body is treated by the resin adsorption system and then is discharged from the effluent.
And fifthly, sampling at the water outlet end of each working section, standing for 3 hours, taking supernatant, filtering, and performing index detection analysis.
The comparative conditions of the effluent treatment effect and stability of each working section obtained in this example are shown in table 1 and fig. 2 to 4:
table 1 Water output index for each section
As can be seen from Table 1, the method for regulating and controlling the multi-pollutant synergistic removal of wastewater with adsorption enhancement as a core can successfully realize efficient treatment and direct discharge of biochemical tail water of petrochemical wastewater by the constructed resin adsorption coupling ozone oxidation process, has stable multi-batch water outlet effect and high treatment depth, wherein the COD removal efficiency of an ozone pre-oxidation system can reach 66.40%, the removal efficiency of residual COD of effluent of the resin adsorption system can reach 85.71%, and the removal rate of TN and TP of the resin adsorption section is 55.55% and 53.84%, thereby playing a main role. Obviously, the method has obvious enhancement effect on removing residual organic matters, the spectrum intensity is obviously reduced in the treatment process, and the method shows that the method has good process coupling effect.
As shown in figures 2-4, after ozone pre-oxidation, the high intensity peaks corresponding to Ex/Em of about 290.0/390.0 and 280.0/391.0 disappear, which indicates that the organic pollutants can be effectively removed by the pre-oxidation section, and mainly humic acid-like organic matters can be seen, while a peak with Ex/Em of 245.0/384.0 appears in a fluorescence spectrum, and the peak mainly corresponds to carbonyl-like, carboxyl-like and phenolic-like matters, which can be generated by microorganisms or plankton, and the substances exist in a large amount due to the biochemical treatment section in the pre-treatment process. The peak value is obviously reduced in the adsorption water of the resin, which indicates that the organic pollutants can be effectively removed in the adsorption section. Further, a possible blue shift is observed on the excitation and emission axes, which may be related to a reduction of the bond or to the removal of carbonyl and hydroxyl groups. After adsorption treatment with resin, the fluorescence intensity of the peak is obviously reduced, which indicates that under the action of high-intensity ozone catalytic oxidation, the organic macromolecules are completely degraded into small molecules and are absorbed by the resin. The coexistence system of some small molecular organic matters remained in the working section can reach the standard on the effluent index without completely mineralizing the organic matters.
Example 2
The method for cooperatively removing and regulating the multiple pollutants of the wastewater by taking adsorption enhancement as a core comprises the following specific steps of:
firstly, enabling effluent of the secondary sedimentation tank to flow through an ozone pre-oxidation system for pretreatment, wherein the ozone flux is 2mg/L, the treatment time is 20min, coagulating sedimentation is continuously carried out, 20mg/L of polymeric ferric sulfate and 50mg/L of polymeric aluminum chloride are added, supernatant fluid is pumped into a resin adsorption system to remove soluble organic matters, ND-2 resin is selected as resin for adsorption experiments, the adsorption flow rate is 2BV/h, and effluent is discharged.
And (II) desorbing the resin used by the resin adsorption system by using 10% NaCl solution, wherein the flow rate is 1BV/h, and the desorption liquid amount is 2BV.
And (III) the desorption liquid flows into an ozone catalytic oxidation system for treatment, and the reaction conditions are as follows: the catalyst is alumina pellets with the diameter of 5mm, the adding amount of the catalyst is 20g/L, the ozone flux is 4mg/L, the treatment time of the ozone oxidation process is 30min, and overflowed ozone is connected with an ozone pre-oxidation system for absorption and reutilization; the effluent enters an electric flocculation system, and the current density is 30mA/cm 2 The distance between the anode and the cathode is 6cm, and the hydraulic retention time is 20min.
And fourthly, carrying out reflux recycling on the effluent of the electric flocculation system, wherein after the 20% of the effluent is supplemented according to the loss proportion of 10% of the regenerant, the regenerant is reused, and the remaining 80% of the effluent is refluxed to the front end and mixed with the resin water.
And fifthly, sampling at the water outlet end of each working section, standing for 3 hours, taking supernatant, filtering, and performing index detection analysis.
The results of the experiment of the effluent treatment effect and the stability of each section in this example are shown in Table 2.
Table 2 Water output index for each section
As can be seen from Table 2, the method for regulating and controlling the multi-pollutant synergistic removal of wastewater with adsorption enhancement as a core can successfully realize the efficient treatment of biochemical tail water by adopting the resin-enhanced ozone catalytic oxidation coupling electric flocculation system, wherein the removal efficiency of ozone catalytic oxidation coupling electric flocculation on COD of concentrated desorption liquid can reach 92.01%, and the electric flocculation technology has better TP and TN removal effects on effluent water after ozone catalytic oxidation.
Example 3
The method for cooperatively removing and regulating the multiple pollutants of the wastewater by taking adsorption enhancement as a core comprises the following specific treatment steps of:
firstly, enabling effluent of the secondary sedimentation tank to flow through an ozone pre-oxidation system for pretreatment, wherein the ozone flux is 2mg/L, the treatment time is 20min, continuing to carry out a coagulating sedimentation system, adding 20mg/L of polymeric ferric sulfate and 50mg/L of polyaluminium chloride, pumping supernatant into a resin adsorption system to remove soluble organic matters, selecting ND-2 resin as resin for adsorption experiments, and discharging effluent at an adsorption flow rate of 2 BV/h.
And (II) desorbing the resin used by the resin adsorption system by using 10% NaCl solution, wherein the flow rate is 1BV/h, and the regeneration liquid amount is 2BV.
And (III) the desorption liquid flows into an ozone catalytic oxidation system for treatment, and the reaction conditions are as follows: the catalyst is alumina pellets with the diameter of 5mm, the adding amount of the catalyst is 20g/L, the ozone flux is 4mg/L, the treatment time of the ozone oxidation process is 30min, and overflow ozone is connected with an ozone pre-oxidation system for absorption and reutilization; the effluent enters an electric flocculation system, and the current density is 30mA/cm 2 The distance between the anode and the cathode is 6cm, and the hydraulic retention time is 20min.
And fourthly, the electric flocculation effluent is recycled, wherein 20% of the effluent is supplemented according to the loss proportion of 10% of the regenerant and is reused as the regenerant, and the remaining 80% of the effluent is recycled to the front end and mixed with the resin inflow.
And fifthly, carrying out 5 batches of resin regeneration experiments in an accumulated way, sampling at the water outlet end in each working section, standing for 3 hours, taking the supernatant, filtering, and carrying out index detection analysis.
The COD treatment effect and the stability of the effluent of each section of the resin adsorption coupling ozone oxidation process obtained in this example are shown in Table 3.
TABLE 3 COD treatment effect of effluent from each section
As shown in Table 3, the wastewater multi-pollutant synergistic removal regulation and control method with adsorption enhancement as a core, constructed by the invention, can successfully realize the efficient treatment of petrochemical wastewater biochemical tail water, has stable multi-batch water outlet effect and high treatment depth, and has good stability after regeneration.
Example 4
A method for controlling the synergistic removal of multiple pollutants in wastewater with adsorption enhancement as a core is similar to that of example 1, except that the current density in the electric flocculation system is 0mA/cm 2 The distance between the anode and the cathode can be 6cm.
In the effluent of the electric flocculation system of the desorption liquid obtained in the embodiment, the COD removal efficiency of the desorption liquid of the resin is 73.1%, the removal rates of TN and TP are 8.1% and 5%, and the COD is 17mg/L, and the removal rates of TN and TP are 2.4mg/L and 0.3mg/L respectively in the effluent of the resin. In the back flow desorption liquid, ozone catalytic oxidation plays a main role in removing COD, and the electric flocculation system is mainly beneficial to removing TP and TN in the desorption liquid, so that accumulation of pollutants of the type can be effectively avoided, and the emission values of various pollutants of the effluent of the system are ensured to reach the standard.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A method for cooperatively removing and regulating multiple pollutants in wastewater by taking adsorption enhancement as a core is characterized by comprising the following steps of: the method comprises the following steps:
step SI: firstly, flowing the wastewater after biochemical treatment through an ozone pre-oxidation system, flowing the effluent into a coagulating sedimentation system, then adding a coagulant to perform coagulating sedimentation treatment, and discharging coagulated and precipitated sludge;
step S2: enabling the effluent water treated in the step S1 to flow into a resin adsorption system for adsorption treatment;
step S3: regenerating the resin used in the step S2, and collecting desorption liquid;
step S4: the desorption liquid collected in the step S3 flows into an ozone catalytic oxidation system for strengthening treatment of the desorption liquid, and the effluent flows into an electric flocculation system for further treatment;
step S5: carrying out reflux on the effluent treated in the step S4 to realize reutilization or reprocessing, wherein one part of the effluent is used for preparing a regenerant, and the other part of the effluent is mixed with the effluent treated by the coagulating sedimentation in the step S1 and then further enters a resin adsorption system to realize deep purification treatment by enhancing adsorption, and the water body after the reflux is treated by the resin adsorption system and is discharged from the effluent;
the steps S1 to S5 are sequentially carried out according to the sequence.
2. The method for regulating and controlling the multi-pollutant cooperative removal of wastewater by taking adsorption enhancement as a core according to claim 1, which is characterized by comprising the following steps of: in the step S1 and the step S4, the coagulant in the coagulating sedimentation treatment is one or more of aluminum series, iron series and aluminum-iron series inorganic coagulants, and the adding amount of the coagulant is 20-80mg/L.
3. The method for regulating and controlling the multi-pollutant cooperative removal of wastewater by taking adsorption enhancement as a core according to claim 1, which is characterized by comprising the following steps of: when the wastewater in the step S1 is treated by an ozone pre-oxidation system, the ozone oxidation contact time is 10-40min, and the initial flux of ozone is 1-2mg/min; in the step S4, the collected desorption liquid flows into an ozone catalytic oxidation system, the ozone catalytic oxidation contact time is 10-60min, and the ozone initial flux is 1-4 mg/min.
4. The method for regulating and controlling the multi-pollutant cooperative removal of wastewater by taking adsorption enhancement as a core according to claim 1, which is characterized by comprising the following steps of: in step S2, the resin in the resin adsorption system includes one or more of ammonia nitrogen removal adsorption resin, ion exchange resin, magnetic resin and chelating resin.
5. The method for regulating and controlling the multi-pollutant cooperative removal of wastewater by taking adsorption enhancement as a core according to claim 1, which is characterized by comprising the following steps of: in the step S2, the flow rate of the wastewater in the resin adsorption system is 1-8 BV/h.
6. The method for regulating and controlling the multi-pollutant cooperative removal of wastewater by taking adsorption enhancement as a core according to claim 1, which is characterized by comprising the following steps of: in step S3, the resin used in step S2 is desorbed and regenerated by the regenerating agent.
7. The method for regulating and controlling the multi-pollutant cooperative removal of wastewater by taking adsorption enhancement as a core according to claim 1, which is characterized by comprising the following steps of: in the step S3, the regenerant adopts 2-15% NaCl and/or NaOH solution in the resin regeneration treatment, the flow rate is 1-6 BV/h, and the regeneration liquid amount is 1.5-3 BV.
8. The method for regulating and controlling the multi-pollutant cooperative removal of wastewater by taking adsorption enhancement as a core according to claim 1, which is characterized by comprising the following steps of: and S4, the catalyst in the ozone catalytic oxidation system is one or more of an aluminum catalyst, an iron catalyst, a biochar catalyst and a supported catalyst thereof.
9. The method for regulating and controlling the multi-pollutant cooperative removal of wastewater by taking adsorption enhancement as a core according to claim 1, which is characterized by comprising the following steps of: s4, the current density in the electric flocculation system is 1-50 mA/cm 2 The distance between the anode and the cathode is 1-10 cm, and the hydraulic retention time is 1-20 min.
10. The adsorption-enhanced wastewater multi-pollutant cooperative removal regulation and control method according to any one of claims 1-9 is applied to deep degradation treatment of organic wastewater.
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