CN112939294A - Electrolytic oxidation method and system for synchronous denitrification and decarbonization - Google Patents
Electrolytic oxidation method and system for synchronous denitrification and decarbonization Download PDFInfo
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Abstract
The invention relates to an electrolytic oxidation method and system for synchronous denitrification and decarbonization, which mainly generate strong oxidizing substances such as hydroxyl free radicals, chlorine free radicals, hypochlorite radicals and the like in the electrolytic process in a weak alkali environment to perform direct oxidation and indirect oxidationWhen the method is used, ammonia nitrogen in water is oxidized into nitrogen, and organic pollutants are converted into easily degradable, low-toxicity or non-toxic micromolecular substances and CO2And H2And O, the final effluent ammonia nitrogen is less than 8mg/L, CODcr and less than 60mg/L, and the requirements of the discharge in table 3 of the control standard of pollutants for domestic waste landfill (GB16889-2008) are met, so that the synchronous denitrification and carbon removal are realized. The invention has the advantages of high deamination and decarbonization efficiency, low operation cost, convenient electrode cleaning, effective treatment of waste gas generated in the system, no secondary pollution and safe and reliable operation.
Description
Technical Field
The invention belongs to the technical field of landfill leachate treatment, and particularly relates to an electrolytic oxidation method and system for synchronous denitrification and decarbonization.
Background
The landfill leachate has the characteristics of complex pollutant components, large water quality fluctuation, high organic pollutant concentration, high ammonia nitrogen concentration, high heavy metal ion concentration, high salt content, imbalance proportion of nutrient elements and the like, and is difficult to treat. At present, the landfill leachate is mainly a combined treatment process of 'biochemical treatment and membrane treatment'. However, the salinity of the aged landfill leachate is usually over 20000mg/L, the content of ammonia nitrogen is over 2500mg/L, and the content of refractory organic matters is high, so that the biochemical treatment efficiency is extremely low, and even the leachate can not normally operate, and therefore, how to efficiently remove the ammonia nitrogen and the organic matters in the high-salinity wastewater is an industrial problem.
The electrochemical advanced oxidation technology has good development prospect as one of advanced oxidation technologies, is widely applied in the field of wastewater treatment, but generally has the following problems:
(1) the probability of generating chlorine gas by side reaction of electrolyzed water in the electrolytic reaction process is high, so that the environment is polluted, and the efficiency of removing target pollutants by electrolysis is reduced;
(2) after the electrolysis system runs for a long time, the scaling problem of the cathode is serious, and the cathode is not easy to clean after scaling.
Disclosure of Invention
In order to simultaneously carry out the oxidation process onThe invention provides an electrolytic oxidation method and system for synchronous denitrification and decarbonization of landfill leachate, wherein ammonia nitrogen in water is oxidized into nitrogen by direct oxidation and indirect oxidation in the electrolytic process in a weak alkali environment, and organic pollutants are converted into easily degradable, low-toxicity or non-toxic small molecular substances, CO2And H2O, the ammonia nitrogen of the final effluent is less than 8mg/L, CODcrLess than 60mg/L, meets the requirement of standard discharge, thereby realizing the purpose of synchronously removing nitrogen and carbon (namely synchronously removing ammonia nitrogen and organic matters). The invention has the advantages of high deamination and decarbonization efficiency, low operation cost, convenient electrode cleaning, effective treatment of waste gas generated in the system and no secondary pollution.
The technical scheme adopted by the invention is as follows:
an electrolytic oxidation method for synchronously removing nitrogen and carbon comprises the following steps:
1) introducing the landfill leachate to be treated into a filter, removing suspended matters, and adjusting the pH value of the landfill leachate to be alkalescent by using an acid-base regulator to obtain pretreated leachate;
2) introducing the pretreated percolate obtained in the step 1) into an electrolytic oxidation system, so that hydroxyl free radicals, chlorine free radicals and strong-oxidizing substances of hypochlorite are generated in the electrolytic oxidation system, ammonia nitrogen and organic pollutants are removed, and water and tail gas produced by electrolytic oxidation are obtained;
3) the water produced by the electrolytic oxidation in the step 2) flows out of the electrolytic oxidation system and then flows in three ways, one way directly flows into the water production tank, the other way flows back to the electrolytic oxidation system as defoaming water through a circulating water pump, and the other way flows to the front end of the pretreatment system through the circulating water pump and is mixed with the landfill leachate to be treated;
4) and (3) washing and absorbing the tail gas generated after the reaction in the step 2) by a tail gas recovery system, and then discharging the tail gas at high altitude.
Due to the technical scheme, the anode electrode with high oxygen evolution potential of 2.0-2.8V is arranged, the pH value of the landfill leachate is adjusted to be alkalescent, so that molecular ammonia is easier to be oxidized, and the method combines a weak base environment with hydroxyl radicals to realize the purpose of landfill leachate infiltrationThe direct oxidation and indirect oxidation of the liquid lead chloride ions in the wastewater to generate Cl-→Cl2→ClO-→Cl-The oxidation-reduction reaction is circulated, so that chloride ions are effectively utilized and Cl is not generated2And escape in large quantities; meanwhile, under the alkalescent condition, ammonia nitrogen mostly exists in the form of neutral molecules, and is more than ammonium ions (NH)4 +) The oxidation is easier, pollutants such as ammonia nitrogen, COD and the like in the wastewater react with strong oxidizing ions generated by electrolytic oxidation: harmless nitrogen N generated by ammonia nitrogen2And H2O, high molecular organic pollutant is converted into easily degradable, low-toxicity or non-toxic small molecular substance, even inorganic ion and CO2、H2And O, achieving the treatment effect of synchronous denitrification and decarbonization. In the invention, the waste gas generated in electrolytic oxidation is effectively treated, the chlorine generated in electrolytic oxidation is absorbed through chemical reaction, and nitrogen is flushed into the gas after absorption treatment, so that the volume fraction of hydrogen is reduced, and the occurrence of accidents is reduced.
Preferably, the pH value of the landfill leachate in the step 1) is adjusted to 8-10; before the electrolytic oxidation in the step 2), adding hydrogen peroxide into the electrolytic oxidation system, wherein the adding amount is 2-5 per mill.
Due to the technical scheme, a large number of experiments show that the effect of removing nitrogen and carbon in the landfill leachate is best when the pH value of the landfill leachate reaches the range of 8-10, and the pH value is within the range<At 7, the free ammonia is converted into ammonium ion (NH)4 +) (ii) a When the pH is higher>11, the ammonia exists only in the form of free ammonia, is not beneficial to removing ammonia nitrogen under the strong acid or strong alkaline condition, and can cause the anode to generate ClO under the strong alkaline condition3 -So that the concentration of free chlorine is reduced, the indirect oxidation efficiency is reduced, and the quality of effluent is deteriorated; in order to avoid secondary pollution, a large amount of hydroxyl radicals are generated by adding hydrogen peroxide under the electrolysis of an electrode, the hydroxyl radicals (OH & ltcng & gt) have extremely strong electron obtaining capacity, namely oxidation capacity, the oxidation potential is 2.8V, and the hydroxyl radicals are second only to fluorine in nature and oxidize ammonia nitrogen and organic matters.
Preferably, in the electrolytic oxidation water production in the step 3), the water content ratio flowing into the water production tank is 20-40%, the water content ratio serving as defoaming water flowing back to the electrolytic oxidation system is 5-10%, and the rest of water flows to the front end of the filter and is mixed with the landfill leachate to be treated.
Due to the technical scheme, the water produced by electrolytic oxidation flows in three ways, one part of the water directly enters the water production tank, and a small part of circulating water is used as defoaming water and flows back to the electrolytic oxidation system, so that the overflow of foams in the electrolytic process is prevented. And the rest flows to the front end of the pretreatment system to be mixed with the landfill leachate to be treated, and then enters the electrolytic oxidation system again to be subjected to further electrolytic oxidation, so that the removal effect of ammonia nitrogen and organic matters in the landfill leachate is improved.
Preferably, the filtration precision of the filter is 5 μm, the scale inhibitor is added before the landfill leachate to be treated is introduced into the filter, and the ratio of the added scale inhibitor to sulfate and carbonate in the leachate to be treated is 1:6-15 by mass fraction.
According to the technical scheme, large particle impurities and suspended matters in the landfill leachate are removed through the filter, the pH value of the landfill leachate is adjusted to be alkalescent through the acid-base regulator, a reaction condition of alkalescence is created, the synchronous denitrification and carbon removal effects are improved, the adding amount of the acid-base regulator is determined according to the actually measured pH value of the landfill leachate, and the general dosage is 5-10 g/L.
Preferably, the electrolytic oxidation system is provided with a cleaning system, the cleaning period is 12-20 days, the outlet valve of the water produced by electrolytic oxidation is closed during cleaning, the electrolytic oxidation system is aerated in the electrolytic reactor by using a blower while being cleaned circularly, and the cleaning is carried out by combining water and gas, so that the dirt remained on the surface of the electrode is removed, and the automatic cleaning function of the electrolytic oxidation system is realized. The aeration intensity of the blower is 10-25L/(m)2S), the operating pressure is 1-3bar, the cleaning time is 10-30 min.
Due to the technical scheme, the operation of the circulating water pump and the aeration in the electrolytic bath are used for carrying out the water-gas combined cleaning operation, so that the dirt remained on the surface of the electrode is removed, and the automatic cleaning function of the electrolytic oxidation system is realized.
Preferably, in the electrolytic oxidation system, the oxygen evolution potential of the anode electrode is 2.0-2.8V, the voltage between the anode and the cathode of the electrode is 3-7V, and the current density passing through the electrode is 200-2(ii) a When the electrolytic oxidation system is in operation, the flow velocity of liquid in the system is 5-15 m/h; the electrolytic oxidation system is characterized in that two electrolytic reactors are arranged, and the two electrolytic reactors can be connected in parallel or in series for electrolytic oxidation.
Due to the technical scheme, the electrolytic reactors are connected in parallel or in series by using pipelines and valves according to the treatment conditions of different water qualities or different water quantities; when the water inlet amount is 50m3When the ammonia nitrogen concentration is 100mg/L, COD to 2000mg/L, two electrolytic reactors can be connected in series for use; when the water inlet amount is 100m3And d, when the ammonia nitrogen 50mg/L, COD is 1000mg/L, the closing state of partial valves is changed, two electrolytic reactors are connected in parallel for use, and the treatment process is more flexible and more efficient and energy-saving according to different water inlet states.
An electrolytic oxidation system for synchronous denitrification and carbon removal comprises a water inlet tank, wherein the outlet end of the water inlet tank is connected with a filter, the outlet end of the filter is connected with the electrolytic oxidation system, and the outlet end of the electrolytic oxidation system is connected with a circulating system and a produced water collecting system; an electrolytic reactor is arranged in the electrolytic oxidation system, and a plurality of electrolytic electrodes are arranged in the electrolytic reactor; the inner layer of the electrolysis electrode is a cylindrical electrode of an anode electrode, and the outer layer of the electrolysis electrode is a cathode electrode; the circulating system is provided with a dosing box, and an acid-base regulator is arranged in the dosing box.
Due to the technical scheme, the pH value of the landfill leachate is adjusted through the adjusting tank, so that the landfill leachate is alkalescent, a alkalescent reaction environment is created, favorable conditions are provided for subsequent electrolytic oxidation treatment, and the synchronous denitrification and carbon removal effects are improved. The anode electrode and the cathode electrode are wrapped on the same electrode column and are evenly and orderly arranged in the electrolytic reactor, the anode electrode is connected with the positive pole of the direct-current power supply, the cathode electrode is connected with the negative pole of the direct-current power supply and is fully distributed in the whole electrolytic reactor, a high-frequency pulse direct-current power supply is provided through a power cabinet, a stable power supply is provided for the electrolytic oxidation reaction device, and the control cabinet monitors and controls the running state of the electrolytic oxidation reaction device in real time, so that leachate in an electrolytic cell is subjected to electrolytic oxidation treatment.
Preferably, the number of the electrolytic reactors in the electrolytic oxidation system is two, and the two electrolytic reactors are connected through a valve and a pipeline; the two electrolytic reactors are respectively connected with the outlet end of a water collector through a valve and a pipeline, and the water collector is connected with the outlet end of a filter; the electrolytic reactor is characterized in that a plurality of electrolytic electrodes are uniformly distributed in the electrolytic reactor, and the hollow part of each electrolytic electrode is connected with the water collector through an electrode water inlet.
Because above technical scheme, electrolytic oxidation system is the box structure of sealed equipment, and inside the box, the top is the water collector of connecting the inlet channel, goes up to have the gas vent (open during the washing, normally operation during operation sealed closing always) that conveniently opens on the cap, and the below is a plurality of orderly electrolysis electrodes of range. The electrolytic reactors can be connected in parallel or in series according to actual requirements, water in the water collector enters the electrolytic reactors through the electrode water inlet, the flow speed in the system is 0.2-0.5m/s when the system runs, the voltage between the anode and the cathode is 4-7V when the electrolytic oxidation reaction occurs, and the current density passing through the electrodes is 200 plus materials of 500A/m2And electrolytic oxidation reaction is realized.
Preferably, the electrolytic reactor is provided with a water production outlet and a circulating water outlet, and the water production outlet is connected with a water production tank through a water production pump; a dosing tank on the circulating system is connected with a dosing metering pump, a circulating water outlet is connected with an inlet of a circulating water pump, and an outlet of the circulating water pump is respectively connected with a water inlet of the electrolytic reactor and a water inlet of the filter through pipelines; and the acid-base regulator in the dosing box is pumped into the circulating pipeline through a dosing metering pump.
Due to the technical scheme, the electrolyzed oxidizing water after the reaction is finished is repeatedly treated by three paths, so that the standard reaching rate of the final water is ensured.
Preferably, the electrolytic oxidation system is connected with a tail gas purification system, the tail gas purification system comprises an induced draft fan, the induced draft fan is connected with an absorption washing tower, and an air outlet communicated with the outside is formed in the absorption washing tower.
Due to the technical scheme, hydrogen (H) is generated by water ionization in the electrolytic oxidation reaction process2) The ionization of chloride ions generates chlorine gas (Cl)2) The tail gas purification system is provided with a hydrogen detection alarm and a chlorine detection alarm for monitoring the concentration of hydrogen and chlorine in the air around the device and increasing the safety performance of the device. Conveying tail gas (mixed gas) generated in the electrolytic oxidation treatment process to a washing absorption tower, absorbing chlorine in the mixed gas through chemical reaction, and discharging the residual gas into the air; hydrogen may be present in the gas discharged into the air, and when the hydrogen is mixed with the air and the volume fraction of the hydrogen is between 4.0% and 75.6%, an explosion may be caused when encountering fire. To reduce the occurrence of such accidents, the gas tank is used to fill the exhausted gas with sufficient nitrogen to reduce the volume fraction of hydrogen.
The invention has the following beneficial effects:
1) according to the invention, the anode electrode with high oxygen evolution potential is arranged, the probability of side reaction in the electrolytic process is reduced, the pH value of the electrolytic reaction is controlled to be alkalescent, and meanwhile, hydrogen peroxide is added into the treatment solution, so that a large amount of hydroxyl radicals and hypochlorite are generated in the electrolytic oxidation process, the generation of chlorine is reduced or avoided, the risk of environmental pollution is reduced, and the efficiency of degrading target pollutants (ammonia nitrogen and organic matters) by electrolytic oxidation is improved;
2) the invention utilizes strong oxidizing substances such as hydroxyl free radical, chlorine free radical, hypochlorite and the like generated in electrochemical reaction to generate direct or indirect oxidation reaction, and the direct or indirect oxidation reaction reacts with organic pollutants, ammonia nitrogen and the like which are difficult to degrade, so that the ammonia nitrogen is converted into nitrogen, and the organic pollutants are converted into micromolecular substances, CO, which are easy to degrade, have low toxicity or no toxicity2And H2O, efficiently removing ammonia nitrogen and COD, and achieving the purpose of synchronous denitrification and carbon removal;
3) before electrolytic oxidation, the pH value of the liquid to be treated is adjusted to be alkalescent, hydrogen peroxide is added into the treatment liquid, so that a large amount of hydroxyl radicals are generated in the subsequent electrolytic oxidation process, and favorable conditions are provided for the subsequent electrolytic oxidation process through the synergistic effect of the alkalescent reaction environment and the hydroxyl radicals;
4) the invention controls the water inlet mode by changing the pipeline and the valve, realizes the series or parallel operation among the electrolytic reactors, effectively controls the degradation and conversion rate of pollutants, and achieves the purposes of high efficiency and energy saving; the system is also provided with a tail gas treatment system and a nitrogen safety protection measure, so that the system can be ensured to run safely and stably;
5) the invention can periodically carry out water-gas combined automatic cleaning on the electrode by arranging the blast aeration device, removes dirt on the surface of the electrode, thoroughly solves the problem that the electrode is difficult to clean, ensures the normal operation of a system, prolongs the service life of the electrode and reduces the operation cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a schematic view of the overall structure of the present invention;
FIG. 2 is a schematic view of an arrangement of electrolysis electrodes inside an electrolysis reactor according to the present invention;
FIG. 3 is a cross-sectional view of an electrolytic reactor.
In the figure: 1-a water inlet tank; 2-a water inlet lift pump; 3-a filter; 4-an electrolytic oxidation system; 5-a circulation system; 6-produced water collection system; 7-a tail gas purification system; 8-a blower; 9-hydrogen detection alarm; 10-chlorine gas detection alarm; 11-a power supply cabinet; 12-a control cabinet; 13-a circulating water outlet; 14-water production outlet; 15-a water collector; 16-electrode water inlet; 17-an anode electrode; 18-a cathode electrode; 4-1-electrolytic reactor A; 4-2-electrolysis reactor B; 5-1-dispensing box; 5-2-dosing metering pump; 5-3-circulating water pump; 6-1-water production pump; 6-2-producing a water tank; 7-1-induced draft fan; 7-2-absorption scrubber; 7-3-nitrogen gas tank.
Detailed Description
It is worth to say that the reaction principle of the present invention is that the contaminants are mainly subjected to direct oxidation or indirect oxidation during the conversion or degradation process. Wherein ammonia nitrogen is represented by NH3, macromolecular organic pollutants are represented by R, and micromolecular organic matters are represented by R.
1. Direct oxidation:
the pollutants are directly converted into harmless substances. Such as: at the anode electrode, ammonia nitrogen directly loses 3 electrons to generate nitrogen (N)2) As shown in the reaction formula (1); the high molecular organic pollutant is directly converted into harmless small molecular organic matter or CO at the anode electrode2And water as shown in the reaction formula (2).
2NH3-6·-+6OH-→N2↑+6H2O (1)
2. Indirect oxidation:
firstly, the polluted molecules react with hydroxyl free radicals (OH) generated under the high potential of the anode to generate harmless micromolecular organic matters or CO2And water. Such as: the ammonia nitrogen reacts with OH to generate nitrogen (N)2) And water, as shown in reaction formula (3); OH generates dehydrogenation, electrophilicity and electron transfer effects on organic polluted organic matters of macromolecules to form activated organic free radicals, and generates chain free radical reaction to rapidly degrade the organic matters, as shown in a reaction formula (4).
2NH3+6OH·→N2↑+6H2O (3)
Secondly, the chloride ions are firstly oxidized into free chlorine at the anode and dissolved in the wastewater to form active chlorine which is used as a strong oxidant to react with pollutants, and finally the pollutants are removed. As shown in reaction formulas (5) to (8).
Cl2+2OH-→ClO-+Cl-+H2O (5)
2NH3+3ClO-→N2^+3Cl-+3H2O (6)
The general reaction formula is as follows: 2NH3-3Cl2+6OH-→N2^+6Cl-+6H2O (7)
③ the hydroxyl radical (OH) reacts with the chlorine radical (Cl) in the wastewater to generate hypochlorous acid with strong oxidizing property and oxidize pollutants. As shown in reaction formulas (9) to (14).
OH·+Cl·→HOCl (9)
HClO+OH-→ClO-+H2O (10)
Cl·+Cl-→Cl2· (11)
Cl2+2OH-→ClO-+C-+H2O (12)
2NH3+3ClO-→N2^+3Cl-+3H2O (13)
Example 1
As can be seen from fig. 1, 2 and 3, an electrolytic oxidation system for synchronous denitrification and decarbonization comprises a water inlet tank 1, wherein an outlet end of the water inlet tank 1 is connected with a filter 3 through a water inlet lift pump 2, the filter 3 can adopt a core filter, the outlet end of the filter 3 is connected with a water collector 15, a water outlet end of the water collector 15 is connected with an electrolytic oxidation system 4, two electrolytic reactors are arranged in the electrolytic oxidation system 4, the two electrolytic reactors are connected through a pipeline and a valve to realize series connection or parallel connection, and the two electrolytic reactors are respectively connected with the water collector 15; the electrolytic oxidation system 4 is a sealed and assembled box structure, a water collector 15 (shown in figure 3) connected with a water inlet pipeline is arranged above the box structure, a plurality of electrolytic electrodes which are arranged orderly are arranged below an exhaust port which is conveniently opened on an upper cover, the electrolytic electrodes are cylindrical electrodes with an inner layer being an anode electrode 17 and an outer layer being a cathode electrode 18, and the outlet end of the electrolytic oxidation system 4 is connected with the circulating system 5 and the produced water collecting system 6. It can be understood that a gap exists between the anode electrode 17 and the cathode electrode 18, the leachate directly enters the gap between the anode electrode 17 and the cathode electrode 18 through the electrode water inlet 16 to perform electrolytic oxidation, the electrolysis electrode is communicated with the electrolysis reactor, and after the leachate completes the electrolytic oxidation in the electrolysis electrode, the leachate directly flows into the electrolysis reactor (outside the electrolysis electrode) from the peripheral side wall of the electrode and fills the whole electrolysis reactor.
The hydrogen detection alarm 9, the chlorine detection alarm 10, the power cabinet 11 and the control cabinet 12 are arranged outside the box body, and the hydrogen detection alarm 9 and the chlorine detection alarm 10 are used for detecting whether the content exceeds the standard or not because hydrogen and chlorine are generated in the electrolytic oxidation process. The power supply cabinet 11 provides a high-frequency pulse direct-current power supply to provide a stable power supply for the electrolytic oxidation reaction device, and the control cabinet 12 monitors and controls the running state of the electrolytic oxidation reaction device in real time.
Furthermore, a circulating water outlet 13 and a produced water outlet 14 are arranged on the electrolytic reactor, a dosing tank 5-1, a dosing metering pump 5-2 and a circulating water pump 5-3 are arranged in the circulating system 5, the circulating water outlet 13 is connected with an inlet of the circulating water pump 5, and an outlet of the circulating water pump 5-3 is respectively connected with a water inlet of the electrolytic reactor and a water inlet of the filter 3 through pipelines; the water production outlet 14 is connected with the water production tank 6-2 through the water production pump 6-1. A part of circulating water serving as defoaming water is returned to the electrolytic oxidation system 4 by the circulating water pump 5-3, and the rest water enters the electrolytic oxidation system 4 again together with inlet water before being conveyed to the filter 3 along a pipeline; the circulating water pipeline is also connected with a circulating water electromagnetic flowmeter and a circulating water float flowmeter. An acid-base regulator is arranged in the dosing box 5-1, and the acid-base regulator in the dosing box 5-1 is pumped into the circulating pipeline through the dosing metering pump 5-2 to regulate the pH value of liquid on the circulating pipeline.
Furthermore, a tail gas purification system 7 is connected to the electrolytic oxidation system 4, the tail gas purification system 7 comprises an induced draft fan 7-1, the induced draft fan 7-1 is connected with a washing tower 7-2, the washing tower 7-2 is further connected with a nitrogen gas tank 7-3, and a gas outlet communicated with the outside is formed in the washing tower 7-2. Negative pressure is formed under the action of the induced draft fan 7-1, tail gas (mixed gas) generated in the electrolytic oxidation treatment process is conveyed to the washing tower 7-2, chlorine in the mixed gas is absorbed through chemical reaction, and the residual gas is discharged in high altitude; for safety, a certain amount of nitrogen may be charged into the mixed gas by using a nitrogen gas tank 7-3.
Based on the system, the adopted processing method comprises the following steps:
1) the method comprises the steps of introducing the landfill leachate to be treated into a filter, wherein the filtering precision is 5-10 mu m, removing suspended matters, simultaneously adding an acid-base regulator on a pipeline, and regulating the pH value of the landfill leachate to be alkalescent by using the acid-base regulator, wherein the pH value is regulated within the range of 8-10, so that alkalescent reaction conditions are created, the synchronous denitrification and decarbonization effects are improved, and the pretreated landfill leachate is obtained.
2) Introducing the pretreated percolate obtained in the step 1) into an electrolytic oxidation system, wherein strong oxidizing substances such as hydroxyl radicals, chlorine radicals, hypochlorite radicals and the like can be generated in the electrolytic oxidation system, ammonia nitrogen and organic pollutants are removed, and electrolytic oxidation water is obtained and discharged through a pipeline; the wastewater enters an electrolytic oxidation system after passing through a filter, an adjusting agent in a dosing box is pumped into a pipeline in front of an inlet of the circulating water pump through a dosing metering pump, the pH value is adjusted to be within the range of 8-10, the alkalescent reaction condition is maintained, and the synchronous denitrification and decarbonization effects are improved; adding hydrogen peroxide into the landfill leachate to ensure that a large amount of hydroxyl radicals (OH) are obtained after the hydrogen peroxide is electrolyzed, ammonia nitrogen and organic matters are oxidized, the adding amount of the hydrogen peroxide is determined according to the actually measured water quality of inlet water, and the adding amount of the hydrogen peroxide is 2-5 per mill of the hydrogen peroxide generally; ammonia nitrogen in the waste water,COD and other pollutants react with the strong oxidizing substances generated by electrolytic oxidation to convert ammonia nitrogen into nitrogen N2And H2O, high molecular organic pollutant is converted into easily degradable, low-toxicity or non-toxic small molecular substance, even inorganic ion and CO2And H2And O, achieving the treatment effect of synchronous denitrification and decarbonization.
When the electrolysis system is in operation, the flow rate of liquid in the system is 5-15m/h, the oxygen evolution potential of the anode in the electrolytic oxidation system is up to 2.0-2.8V, the high oxygen evolution potential can inhibit the self electrolysis of water and promote the electrolysis process to proceed towards the direction of degrading ammonia nitrogen and organic pollutants, the voltage between the anode and the cathode is 3-7V, and the current density passing through the electrode is 200-500A/m-2(ii) a One electrolytic reactor can be adopted in the electrolytic oxidation system, two electrolytic reactors are preferably selected in the invention, and the two electrolytic reactors can be used in series or in parallel according to different water quality and water quantity, so that the treatment efficiency is improved.
During electrolytic oxidation treatment, leachate enters the electrodes from the electrode water inlets 16 through the water collectors 15 to fill the whole electrolytic reactor A4-1 and the electrolytic reactor B4-2; turning on the power supply of the power supply cabinet 11, adjusting the operation parameters through the control cabinet, and starting the electrolytic oxidation reaction; a water production outlet 14 and a circulating water outlet 13 are arranged on each of the electrolytic reactor A4-1 and the electrolytic reactor B4-2, a circulating water pump 5 and a water production pump 6-1 are started, a part of the treated wastewater enters a water production tank 6-2 through the water production pump 6-1, and a part of the treated wastewater enters a circulating water pipeline through the circulating water pump 5; a small part of circulating water in the circulating water pipeline is taken as defoaming water to flow back to the electrolytic reactor A4-1 and the electrolytic reactor B4-2, and the rest of circulating water is mixed with inlet water before being conveyed to the filter 3 along the pipeline and enters the electrolytic oxidation system 4 again.
3) And (3) washing and absorbing tail gas generated after the reaction in the step 2) by a tail gas recovery system, and then discharging the tail gas into the air.
4) And after the electrolytic oxidation device runs for about 12-20 days, cleaning operation is carried out. When cleaning, the water production outlet 14 is closed, water inlet is stopped, the circulating water outlet 13 is opened, and the water in the whole electrolytic reactor A4-1 and the electrolytic reactor B4-2 is in a flowing state by using the circulating water pump 5; turning on the blastAnd the machine 8 is used for aerating the whole electrolytic reactor and carrying out water-gas combined cleaning operation to remove dirt remained on the surface of the electrode. After the cleaning is finished, the produced water outlet 14 is opened, the water inlet lifting pump 2 is started, the exhaust port on the water collector 15 is closed, and the electrolytic oxidation device continues to operate normally. The aeration intensity of the blower is 10-25L/(m)2S), the operating pressure is 1-3bar, the cleaning time is 10-30 min.
Example 2
The difference from the embodiment 1 is that no regulating agent is added in the embodiment to regulate the pH value, and other methods and steps are consistent.
Example 3
The difference from the embodiment 1 is that hydrogen peroxide is not added in the embodiment, and other methods and steps are consistent.
The following table shows statistics of ammonia nitrogen and COD in each examplecrThe removal effect of (1).
Taking the landfill leachate pretreated by a certain project of the Chengdu as an example, a test sample is taken to return to the factory area of an enterprise for testing, the ammonia nitrogen content of the landfill leachate is 1150mg/L, the COD content is 950mg/L, and after the landfill leachate is treated by the synchronous denitrification decarbonization electrolytic oxidation system, the treatment effect of each embodiment is as follows.
As can be seen from the table above, the removal effect of the implementation 1 is best, the ammonia nitrogen in the effluent is less than 8mg/L, COD and less than 60mg/L, and the requirements of the discharge in table 3 of the Standard for controlling pollutants in municipal solid waste landfill (GB16889-2008) are met; example 2 when the pH was not adjusted to alkalinity, the COD of the effluent of the system could reach the requirement below 60mg/L, but the ammonia nitrogen removal effect was poor and could not reach the discharge requirement, indicating that the removal effect of the present invention was affected by not adjusting the pH to alkalinity; in the embodiment 3, hydrogen peroxide is not added, the ammonia nitrogen in the effluent can reach below 8mg/L, and the COD is less than 60mg/L, so that the discharge requirement is met, but the ammonia nitrogen and COD concentration in the effluent are higher than those in the embodiment 1, which shows that the effluent standard problem is not influenced by the fact that hydrogen peroxide is not added, but the effect is slightly poor.
According to the invention, the wastewater in the electrolytic oxidation system is alkalescent, and meanwhile, the hydrogen peroxide is added, so that the removal rate of ammonia nitrogen in the leachate during electrolytic oxidation can reach 99.7%, and the removal rate of COD can reach 95.6%.
It should be understood by those skilled in the art that the above embodiments are only for illustrating the present invention and are not to be used as a limitation of the present invention, and that suitable changes and modifications of the above embodiments are within the scope of the claimed invention as long as they are within the spirit and scope of the present invention.
Claims (10)
1. An electrolytic oxidation method for synchronously removing nitrogen and carbon is characterized in that: the method comprises the following steps:
1) introducing the landfill leachate to be treated into a filter, removing suspended matters, and adjusting the pH value of the landfill leachate to be alkalescent by using an acid-base regulator to obtain pretreated leachate;
2) introducing the pretreated percolate obtained in the step 1) into an electrolytic oxidation system, so that hydroxyl free radicals, chlorine free radicals and strong-oxidizing substances of hypochlorite are generated in the electrolytic oxidation system, ammonia nitrogen and organic pollutants are removed, and water and tail gas produced by electrolytic oxidation are obtained;
3) the water produced by the electrolytic oxidation in the step 2) flows out of the electrolytic oxidation system and then flows in three ways, one way directly flows into the water production tank, the other way flows back to the electrolytic oxidation system as defoaming water through a circulating water pump, and the other way flows to the front end of the pretreatment system through the circulating water pump and is mixed with the landfill leachate to be treated;
4) and (3) washing the tail gas generated after the reaction in the step 2) by a tail gas purification system, and then discharging the tail gas at high altitude.
2. The electrolytic oxidation method for simultaneous denitrification and decarbonization as claimed in claim 1, wherein: adjusting the pH value of the landfill leachate in the step 1) to 8-10; before the electrolytic oxidation in the step 2), adding hydrogen peroxide into the electrolytic oxidation system, wherein the adding amount is 2-5 per mill.
3. The electrolytic oxidation process for simultaneous denitrification and decarbonization according to claim 1 or 2, characterized in that: in the electrolytic oxidation water production in the step 3), the water content flowing into the water production tank is 20-40%, the water content returned to the electrolytic oxidation system as defoaming water is 5-10%, and the rest water flows to the front end of the filter and is mixed with the landfill leachate to be treated.
4. The electrolytic oxidation method for simultaneous denitrification and decarbonization according to claim 3, wherein: the filtration precision of the filter is 5-10 mu m, the scale inhibitor is added before the landfill leachate to be treated is introduced into the filter, and the weight ratio of the added scale inhibitor to sulfate and carbonate in the leachate to be treated is 1: 6-15.
5. The electrolytic oxidation method for simultaneous denitrification and decarbonization as claimed in claim 1, wherein: the electrolytic oxidation system is provided with a cleaning system, the cleaning period is 12-20 days, an electrolytic oxidation water production outlet valve is closed during cleaning, circulating cleaning is carried out, an air blower is used for carrying out aeration on the inside of an electrolytic reactor in the electrolytic oxidation system, and cleaning is carried out through water-gas combination to remove dirt remained on the surface of an electrode; the aeration intensity of the blower is 10-25L/(m)2S), the operating pressure is 1-3bar, the cleaning time is 10-30 min.
6. The electrolytic oxidation method for simultaneous denitrification and decarbonization as claimed in claim 1, wherein: in the electrolytic oxidation system, the oxygen evolution potential of the anode electrode is 2.0-2.8V, the voltage between the anode and the cathode of the electrode is 3-7V, and the current density passing through the electrode is 200-2(ii) a When the electrolytic oxidation system is in operation, the flow velocity of liquid in the system is 5-15 m/h; the electrolytic oxidation system is characterized in that two electrolytic reactors are arranged, and the two electrolytic reactors can be connected in parallel or in series for electrolytic oxidation.
7. The utility model provides an electrolytic oxidation system of synchronous denitrogenation decarbonization, includes into water tank (1), its characterized in that: the outlet end of the water inlet tank (1) is connected with a filter (3), the outlet end of the filter (3) is connected with an electrolytic oxidation system (4), and the outlet end of the electrolytic oxidation system (4) is connected with a circulating system (5) and a produced water collecting system (6); an electrolytic reactor is arranged in the electrolytic oxidation system (4), and a plurality of electrolytic electrodes are arranged in the electrolytic reactor; the inner layer of the electrolysis electrode is a cylindrical electrode of an anode electrode (17) and the outer layer is a cathode electrode (18); a dosing box (5-1) is arranged on the circulating system (5), and an acid-base regulator is arranged in the dosing box (5-1).
8. The electrolytic oxidation system for simultaneous denitrification and decarbonization of claim 7, wherein: the electrolytic oxidation system (4) is characterized in that two electrolytic reactors are arranged, and the two electrolytic reactors are connected through a valve and a pipeline; the two electrolytic reactors are respectively connected with the outlet end of a water collector (15) through a valve and a pipeline, and the water collector (15) is connected with the outlet end of the filter (3); a plurality of electrolysis electrodes are uniformly distributed in the electrolysis reactor, and the hollow part of each electrolysis electrode is connected with a water collector (15) through an electrode water inlet (16).
9. The electrolytic oxidation system for simultaneous denitrification and decarbonization according to claim 7 or 8, wherein: the electrolytic reactor is provided with a water production outlet (14) and a circulating water outlet (13), and the water production outlet (14) is connected with a water production tank (6-2) through a water production pump (6-1); a dosing tank (5-1) on the circulating system (5) is connected with a dosing metering pump (5-2), a circulating water outlet (13) is connected with an inlet of a circulating water pump (5-3), and an outlet of the circulating water pump (5-3) is respectively connected with a water inlet of the electrolytic reactor and a water inlet of the filter (3) through pipelines; and the acid-base regulator in the dosing tank (5-1) is pumped into the circulating pipeline through a dosing metering pump (5-2).
10. The electrolytic oxidation system for simultaneous denitrification and decarbonization of claim 9, wherein: connect tail gas clean system (7) on electrolytic oxidation system (4), tail gas clean system (7) are including draught fan (7-1), draught fan (7-1) are connected with absorption scrubbing tower (7-2), be provided with the gas outlet with outside intercommunication on absorption scrubbing tower (7-2).
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