CN114735863A - Method and system for treating landfill leachate in later period - Google Patents
Method and system for treating landfill leachate in later period Download PDFInfo
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- CN114735863A CN114735863A CN202210485446.2A CN202210485446A CN114735863A CN 114735863 A CN114735863 A CN 114735863A CN 202210485446 A CN202210485446 A CN 202210485446A CN 114735863 A CN114735863 A CN 114735863A
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- oxidation
- electrochemical oxidation
- landfill leachate
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- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- RBLWMQWAHONKNC-UHFFFAOYSA-N hydroxyazanium Chemical compound O[NH3+] RBLWMQWAHONKNC-UHFFFAOYSA-N 0.000 description 1
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- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
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Images
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
- C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46128—Bipolar electrodes
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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
- 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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
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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
- 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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46152—Electrodes characterised by the shape or form
- C02F2001/46157—Perforated or foraminous electrodes
- C02F2001/46161—Porous electrodes
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- 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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46152—Electrodes characterised by the shape or form
- C02F2001/46171—Cylindrical or tubular shaped
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- 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
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
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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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
- C02F2201/007—Modular design
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4612—Controlling or monitoring
- C02F2201/4615—Time
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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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4618—Supplying or removing reactants or electrolyte
- C02F2201/46185—Recycling the cathodic or anodic feed
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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Abstract
The invention discloses a method and a system for treating landfill leachate in a later period. The processing method comprises the following steps: s1, first, performing electrochemical oxidation treatment of a ruthenium electrode; s2 step, carrying out double oxidation treatment on the effluent of S1; the double oxidation treatment comprises a step of combined oxidation treatment of electrocatalytic Fenton oxidation and electrochemical oxidation; s3 step, the step of performing electrochemical oxidation advanced treatment on the effluent of S2. The step of electrochemical oxidation treatment of the ruthenium electrode in the step S1 is added before the steps S2 and S3, so that the problem that COD and total nitrogen of the landfill leachate in the later period are difficult to reduce due to the step of directly carrying out double oxidation treatment can be effectively avoided, and the content of COD and total nitrogen in the landfill leachate in the later period is effectively reduced.
Description
Technical Field
The invention belongs to the technical field of landfill leachate treatment processes, and particularly relates to a method and a system for treating later-stage landfill leachate.
Background
COD and salinity are higher, and the biodegradability is poor, and the local COD and the salinity that the rainwater is many are lower, and landfill leachate that the biodegradability is relatively stronger is because rainwater oozes the waste layer of landfill and produces, mainly is the complicated mixture of constituteing by Dissolving Organic Matter (DOM), inorganic compound, heavy metal and exogenous compound etc.. This rain water may enter the soil and then the ground water and drain into the surface water, which adversely affects human health and the environment. The quality of landfill leachate is affected by various factors such as the type of garbage, operating conditions, climate, hydrogeology, the age of landfill, etc. For example, higher temperatures in summer, lower concentrations of COD and Dissolved Organic Carbon (DOC), and higher proportions of aromatic structures of DOM in landfill leachate in summer, while pH, total nitrogen, and conductivity are generally higher in winter than in summer; the COD content is generally higher in places with less rain.
The landfill leachate can be divided into early, middle and late landfill leachate according to the landfill time of the landfill leachate. The landfill time of the early landfill leachate is within 5 years, the landfill leachate in the middle period is 5-10 years, and the landfill leachate in the later period is more than 10 years. As landfill time varies, the composition of landfill leachate also varies. The early landfill leachate mainly comprises low molecular organic matters such as unsaturated fatty acid and the like, the COD and the BOD of the landfill leachate are high, but the B/C ratio is more than 0.3, the landfill leachate belongs to wastewater which is easy to be biologically treated, and the landfill leachate can be treated by a biological method; at the later stage, the landfill leachate mainly comprises heterocyclic substances, aromatic compounds and humic acid substances which are generated by the reaction of straight-chain substances and are dissolved in from an external source, the total COD (chemical oxygen demand) of the landfill leachate is greatly reduced compared with that at the early stage, but the landfill leachate has extremely complex components, high toxic and harmful effects and B/C ratio of less than 0.1 and is difficult to biochemically treat. At the same time, the landfill time increases, resulting in higher salinity compared to early landfill leachate, and also very high total nitrogen (ammonia nitrogen, nitrate nitrogen and organic nitrogen) content (see table 1). In addition, substances such as micromolecular organic nitrogen contained in the landfill leachate are difficult to degrade by OH in the traditional advanced oxidation method, for example, hydroxyl radicals are more stable to oxidize hydroxylammonium generated by micromolecular organic nitrogen, so that the landfill leachate treatment by advanced oxidation cannot be carried out, and an effective method for treating later-stage landfill leachate is not available at present.
TABLE 1 landfill leachate parameters at different periods
The subject group discloses a double oxidation-electrochemical oxidation combined process for deeply treating landfill leachate in the prior art with Chinese patent publication No. CN112960819A, which comprises the following steps: a) electro-catalytic Fenton treatment: taking an iron electrode as an anode and stainless steel as a cathode, and adding Fe in a dissolved iron form2+Slowly adding hydrogen peroxide after iron dissolution; b) after the iron dissolution is finished, carrying out electrocatalytic oxidation reaction, and carrying out repeated cycle treatment on the electrocatalytic oxidation reaction in the step b) and the electrocatalytic Fenton in the step a); c) Adjusting the effluent after the cyclic treatment of a) and b) to be alkaline so as to precipitate iron mud; d) carrying out electrochemical oxidation treatment on the effluent treated in the step c): adding a certain amount of sodium chloride, and removing ammonia nitrogen in the percolate by utilizing a tubular membrane electrode chlorine evolution reaction. Although the total nitrogen removal rate in the prior artMore than 90 percent, the COD removal rate reaches more than 95 percent, but when the total COD and the total nitrogen concentration are higher, the COD and the total nitrogen with higher content are still difficult to be completely degraded. The prior art adopts a double oxidation technology and electrochemical oxidation of a rear ruthenium electrode, so that indexes such as COD, ammonia nitrogen, total nitrogen and the like in early-stage landfill leachate can be effectively removed, but subsequent researches find that the effluent index is relatively high when the later-stage landfill leachate is treated by adopting the method in the prior art.
Based on the complex composition of the later-stage landfill leachate, the later-stage landfill leachate is difficult to treat, and an efficient method for the later-stage landfill leachate is urgently needed to be developed.
Disclosure of Invention
1. Problems to be solved
Aiming at the technical problem that COD and total nitrogen are difficult to reduce after landfill leachate is subjected to double-oxidation combined ruthenium electrode electrochemical oxidation advanced treatment in the later period, the method adopts a ruthenium electrode electrochemical oxidation-double-oxidation-ruthenium electrode electrochemical oxidation advanced treatment combined process for synergistic treatment, and a biological treatment method is not adopted, so that COD and total nitrogen are efficiently and synchronously removed. According to researches, when the later-stage landfill leachate is directly subjected to double oxidation treatment, micromolecular organic nitrogen in the later-stage landfill leachate continuously reacts with OH free radicals formed in double oxidation to generate nitrogen-containing substances (such as hydroxylamines) difficult to oxidize, the nitrogen-containing substances difficult to oxidize are difficult to further degrade in double oxidation and subsequent electrochemical oxidation deep treatment of a ruthenium electrode, the substances contribute to COD and total nitrogen, so that the COD and the total nitrogen are difficult to reduce after reaction when the double oxidation and electrochemical oxidation deep treatment of the ruthenium electrode are only adopted.
The method further aims at the problem of high nitrate nitrogen content in the landfill leachate in the later period, the copper-nickel mesh cathode and the ruthenium oxide coating tubular anode are introduced for cooperative treatment in the advanced treatment step, the reducing cathode reduces nitrate and ammonia nitrogen generated in the reduction, and active chlorine generated by the anode can be used for oxidation removal, so that the aim of further reducing the nitrate nitrogen in the landfill leachate in the later period is fulfilled.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
in order to solve the problems, the invention provides a method for treating landfill leachate at a later stage, which comprises a ruthenium electrode electrochemical oxidation treatment step, a double oxidation treatment step and a ruthenium electrode electrochemical oxidation advanced treatment step, wherein the ruthenium electrode electrochemical oxidation treatment step can effectively remove micromolecular organic nitrogen in wastewater, the double oxidation treatment step can effectively degrade organic pollutants by using a large amount of generated OH, reduce COD (chemical oxygen demand) and release organic nitrogen, and finally, through the ruthenium electrode electrochemical oxidation advanced treatment, the cathode and anode are cooperatively treated to remove nitrate nitrogen, ammonia nitrogen, reduce total nitrogen and further remove residual organic matters in the wastewater.
A treatment method for post-stage landfill leachate comprises the following steps:
s1, first, performing electrochemical oxidation treatment of a ruthenium electrode;
s2 step S1 step of carrying out double oxidation treatment on the effluent; the double oxidation treatment comprises a step of combined oxidation treatment of electrocatalytic Fenton oxidation and electrochemical oxidation;
s3 step S2 effluent water is further processed by ruthenium electrode electrochemical oxidation advanced treatment. Preferably, 5-20g/L of sodium chloride can be added into the effluent water of the step S2, and then the electrochemical oxidation advanced treatment of the ruthenium electrode is carried out.
Preferably, the total nitrogen TN content of the later-stage landfill leachate is greater than or equal to 2000 mg/L. The later-stage landfill leachate has the characteristics of high COD, high salinity, high ammonia nitrogen, high total nitrogen and poor biodegradability of organic matters in the later-stage landfill leachate.
Preferably, in the electrochemical oxidation treatment of ruthenium electrode in the step S1, Ti/RuO is adopted2The coating tubular anode, the stainless steel cathode and the electrochemical oxidation direct-current power supply form a ruthenium electrode electrochemical oxidation module; the current density of the ruthenium electrode in electrochemical oxidation treatment is 5-20mA/cm2Later stage ofThe retention time of the landfill leachate treated in the step S1 is 4-12 h.
Preferably, in the step S2, the electrochemical oxidation is performed by Ti/PbO2The coating tube type anode, the stainless steel cathode and the electrochemical direct current power supply, and the Ti/PbO2The current density of the coating tube type anode electrochemical oxidation reaction is 5-20mA/cm2(ii) a The electrocatalytic Fenton oxidation is carried out by a composite iron electrode and an electrocatalytic direct-current power supply under the condition of adding hydrogen peroxide, and the composite iron electrode is used for dissolving Fe in wastewater when electrified2+The size of the iron dissolving current is 1-2A, the iron dissolving time is 4-12h, and hydrogen peroxide is added to start the electro-catalytic Fenton oxidation after the iron dissolving is finished.
Preferably, the composite iron electrode is a porous composite iron electrode, and the preparation method comprises the steps of mixing raw iron powder (45%) and cooked iron powder (55%), grinding to 80-160 meshes, placing the mixture in a flat template, pressing, and sintering at 350 ℃ for 1-3h for forming, wherein the electrode has a large active potential and strong oxidation performance.
Preferably, in the step S2, H in the landfill leachate2O2(27.5% wt) the mass ratio of the addition amount to the COD is (1-2.5): 1; fe2+Amount of addition and H2O2The molar ratio of the added amount is 1 (8-20).
Preferably, the retention time of the double oxidation treatment of the landfill leachate in the step S2 is 5-20h (excluding the iron dissolving time).
Preferably, in the electrochemical oxidation depth treatment of the ruthenium electrode in the step S3, Ti/RuO is adopted2The coating tubular anode, the copper-nickel mesh cathode and the electrochemical oxidation direct-current power supply form a ruthenium electrode electrochemical oxidation advanced treatment module; the current density of the electrochemical oxidation advanced treatment is 10-30mA/cm2The current density of the copper-nickel mesh cathode in the electrocatalytic oxidation reaction is 10-30mA/cm2(ii) a The retention time of the landfill leachate treated in the step S3 is 4-16 h. The copper-nickel mesh cathode in the step plays a role in nitrate reduction and is used for advanced treatment.
Preferably, the copper-nickel mesh cathode (Cu-Ni/TiO)2Electrode) the preparation method comprises:
1) pretreatment: cleaning a titanium sheet with deionized water, polishing the titanium sheet with 500-mesh, 800-mesh, 1000-mesh, 1200-mesh and 1500-mesh sand paper respectively until the surface is bright, and cleaning the polished titanium sheet with deionized water; then placing the cleaned titanium sheet in 10 wt% oxalic acid solution for heating in water bath at the temperature of 70-80 ℃, and then placing the titanium sheet in acetone for ultrasonic cleaning for 30 minutes;
2) anodic oxidation: when the titanium sheet pretreated in the step 1) is used for anodic oxidation treatment, the electrolyte solution is a mixed solution of ethylene glycol, ultrapure water and ammonium fluoride, wherein the mass ratio of the ethylene glycol to the ultrapure water is 4-10: 1, the mass fraction of ammonium fluoride in the mixed solution is 0.5%, the voltage is 20-50V, and the time is 1-4 h. During annealing treatment, the heating/cooling rate is 1-5 ℃/min, the annealing temperature is 600-650 ℃, and the annealing time is 1-2 h. When high-temperature gas-phase reduction is carried out, the reduction temperature is 750-950 ℃; the heating rate is 1-5 ℃/min; the reduction time is 20-50 min; reducing the gas to H2And N2The mixture gas of (1) and (B) in the ratio of H2： N21: (1-10), the gas flow rate is 100-150 mL/min.
3) Plating by an electrodeposition method: TiO prepared by anodic oxidation2The electrode was used as a cathode and the anode was a ruthenium oxide electrode. The electrodeposition solution is prepared by CuSO with the molar ratio of 3:14·5H2O and NiSO4·7H2O supply and introduction of 0.03M H3BO4To stabilize the pH of the solution. The electrodeposition experiment is carried out at the current density of 10-20mA cm-2Is carried out under the condition of (1) and is powered by a direct current power supply.
Preferably, a pretreatment step is further included before step S1, the pretreatment step includes performing flocculation precipitation on the post-stage landfill leachate; and/or
Before the double oxidation treatment in the step S2, firstly, adjusting the pH value of the landfill leachate to 3-4; and/or
Before the electrochemical oxidation advanced treatment of the ruthenium electrode in the step S3, firstly, the pH of the effluent in the step S2 is adjusted to 9-14, and the effluent is kept stand for precipitation.
Preferably, after the landfill leachate is flocculated and precipitated, taking the supernatant and carrying out the following steps:
s1 ruthenium electrode electrochemical oxidation treatment step: turning on the electrochemical oxidation DC power supply, and utilizing Ti/RuO2An electrochemical oxidation device formed by a coating tubular anode carries out electrochemical oxidation reaction, and the step is mainly set for removing micromolecular organic nitrogen substances through active chlorine generated by a ruthenium electrode and simultaneously carrying out preliminary degradation on organic matters and ammonia nitrogen in water; adjusting the pH of the effluent to be acidic, and then performing double oxidation treatment;
s2 double oxidation treatment step:
(a) electrocatalytic fenton oxidation: taking a composite iron electrode (for example, a porous composite iron electrode) as an anode and stainless steel as a cathode, turning on an electrocatalytic direct current power supply, and adding Fe in a form of dissolving iron by the anode2+Meanwhile, the dissolved iron can generate an electric floating effect to remove suspended matters in the leachate, and hydrogen peroxide is slowly added after the iron is dissolved to start the electro-catalytic Fenton oxidation;
(b) electrochemical oxidation: when the electro-catalytic Fenton oxidation is started, an electrochemical oxidation direct current power supply is turned on, and Ti/PbO is utilized2An electrochemical oxidation device consisting of a tubular electrode performs electrochemical oxidation reaction;
(c) performing repeated circulating treatment on the landfill leachate entering the double-oxidation treatment step in the electrochemical oxidation of the step (b) and the electrocatalytic Fenton oxidation treatment of the step (a), so as to realize the synergistic effect of the electrocatalytic Fenton and the electrochemical oxidation, strengthen the oxidation effect and efficiently remove COD;
(d) adjusting the effluent water after the circulating treatment in the steps (a) and (b) to be alkaline so as to precipitate iron mud; the effluent enters a ruthenium electrode electrochemical oxidation advanced treatment step;
and S3 electrochemical oxidation advanced treatment step of the ruthenium electrode: from Ti/RuO2Carrying out electrochemical oxidation advanced treatment on an electrochemical oxidation device consisting of a coating tubular anode and a copper-nickel mesh cathode; the nitrate is reduced into nitrogen and ammonia nitrogen by the cathode, and the generated ammonia nitrogen and the ammonia nitrogen in the water utilize Ti/RuO2The coating tube type anode chlorine evolution reaction is removed, and the generated active chlorine can effectively oxidize low molecular organic acid to achieve the deep degradation of pollutants. This step is mainly a deep process, generalReducing nitrate nitrogen into ammonia nitrogen through reduction reaction of the cathode, removing the ammonia nitrogen by using active chlorine, and further removing COD; preferably, 5-20g/L of sodium chloride can be added into the effluent water of the step S2, and then the electrochemical oxidation advanced treatment of the ruthenium electrode is carried out.
A treatment system for later-stage landfill leachate comprises a ruthenium electrode electrochemical oxidation module, a double oxidation module and a ruthenium electrode electrochemical oxidation advanced treatment module which are sequentially connected;
the ruthenium electrode electrochemical oxidation module comprises Ti/RuO2A coated tubular anode and a stainless steel cathode;
the double oxidation module comprises a combination of an electro-catalytic Fenton oxidation device and an electrochemical oxidation device, wherein the electro-catalytic Fenton oxidation device comprises a composite iron anode and a stainless steel cathode; the electrochemical oxidation device comprises Ti/PbO2A coated tubular anode and a stainless steel cathode;
the ruthenium electrode electrochemical oxidation advanced treatment module comprises Ti/RuO2A coated tubular anode and a copper-nickel mesh cathode.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, through researching the composition characteristics of the later-stage landfill leachate and the post-stage landfill leachate after double oxidation, the finding is that when the later-stage landfill leachate is directly subjected to double oxidation treatment, the micromolecular organic nitrogen in the later-stage landfill leachate can continuously react with OH free radicals formed in the double oxidation to generate nitrogen-containing substances difficult to oxidize, the nitrogen-containing substances difficult to oxidize are difficult to further degrade in the double oxidation and subsequent electrochemical oxidation deep treatment of a ruthenium electrode, so that COD and total nitrogen after reaction are difficult to reduce when only the double oxidation and the electrochemical oxidation deep treatment of the ruthenium electrode are adopted; based on the method, the electrochemical oxidation step of the front ruthenium electrode is added, the generated active chlorine is utilized to firstly degrade micromolecular organic nitrogen in the garbage percolate at the later stage, and nitrogen-containing substances difficult to oxidize are not generated when the double oxidation is carried out, so that the COD and the total nitrogen are reduced after the reaction.
(2) Compared with the traditional advanced oxidation technology which mainly utilizes OH to oxidize pollutants, the method introduces active chlorine before advanced oxidation, can avoid the problem of generating nitrogen-containing substances which are difficult to oxidize when directly treated by OH, and effectively reduces COD and total nitrogen content after the later-stage landfill leachate treatment.
(3) Compared with the traditional biochemical method for treating nitrate, the method has the limitations that the treatment time is long and the number of influencing factors for strain culture is large, the method introduces the copper-nickel mesh cathode to reduce nitrate in the electrochemical oxidation advanced treatment step of the ruthenium electrode, ammonia nitrogen and nitrogen are generated, the generated ammonia nitrogen and the original ammonia nitrogen in the wastewater are removed by using the active chlorine generated by the ruthenium oxide anode, and the purpose of efficient denitrification is realized.
(4) The ruthenium electrode electrochemical oxidation module, the double oxidation module and the ruthenium electrode electrochemical oxidation advanced treatment module are combined and used according to the corresponding sequence, the front ruthenium electrode electrochemical oxidation module firstly degrades micromolecular organic nitrogen in garbage leachate at the later stage by utilizing generated active chlorine, and the double oxidation module degrades refractory organic pollutants by the synergistic action of two oxidation methods; the electrochemical oxidation advanced treatment module utilizes the copper-nickel mesh cathode to carry out nitrate reduction, and realizes decarburization and denitrification of the garbage leachate at the later stage.
Drawings
FIG. 1 is a flowchart of a processing method according to embodiment 1 of the present invention.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs; as used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
As used herein, the term "about" is used to provide the flexibility and inaccuracy associated with a given term, measure or value. The degree of flexibility for a particular variable can be readily determined by one skilled in the art.
Concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such a range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a numerical range of about 1 to about 4.5 should be interpreted to include not only the explicitly recited limit values of 1 to about 4.5, but also include individual numbers (such as 2, 3, 4) and sub-ranges (such as 1 to 3, 2 to 4, etc.). The same principle applies to ranges reciting only one numerical value, such as "less than about 4.5," which should be construed as including all such values and ranges. Moreover, such an interpretation should apply regardless of the breadth of the range or feature being described.
Example 1
The method for removing COD, ammonia nitrogen and total nitrogen in the landfill leachate at the later stage by adopting the ruthenium electrode electrochemical oxidation-double oxidation-ruthenium electrode electrochemical oxidation advanced treatment method comprises the following specific steps:
step 1, electrochemical oxidation treatment of a ruthenium electrode: taking 3L of later-stage landfill leachate, adopting flocculation precipitation to pretreat a water sample, taking supernate, and utilizing Ti/RuO2The electrochemical oxidation device formed by the coating tubular anode and the stainless steel tubular cathode carries out electrochemical oxidation reaction, and the current density is 15mA/cm3Reacting for 4 hours; adjusting the pH value of the wastewater after reaction to 3.0-4.0 by using sulfuric acid;
step 2, double oxidation treatment:
electrocatalytic fenton oxidation: dissolving iron for 36min under the current of 2A by using a porous composite iron electrode as an anode (10cm multiplied by 20cm) and stainless steel as a cathode (10cm multiplied by 20cm), and slowly adding 20mL (27.5% wt) of hydrogen peroxide after the iron is dissolved;
electrochemical oxidation: after the iron dissolution is finished, starting an electrochemical oxidation process, and selecting Ti/PbO2Anode with a set current density of 15mA/cm2(electrode area 100 cm)2) The voltage is 3.8V, and the landfill leachate is electrochemically oxidized and electro-catalyzed FentonSynchronously and circularly performing, and staying for 18 h; after the reaction is finished, adjusting the pH to 9-11 by using caustic soda flakes, standing for 1h, and taking supernatant for the next reaction;
step 3, electrochemical oxidation advanced treatment of the ruthenium electrode: opening by Ti/RuO2Carrying out electrochemical oxidation advanced treatment on an electrochemical oxidation device consisting of a tubular coating anode and a copper-nickel mesh cathode;
the influent water utilizes the cathode to reduce nitrate, the anode carries out chlorine evolution reaction, and the current density is 20mA/cm2And reacting for 10 hours. The degradation effect of the treatment of example 1 is shown in Table 2.
TABLE 2 summary of the degradation effects of example 1
Comparative example 1
The method for removing COD, ammonia nitrogen and total nitrogen in the landfill leachate by adopting a dual-ruthenium-electrode electrochemical oxidation advanced treatment method comprises the following specific steps:
step 1, double oxidation treatment:
electrocatalytic fenton oxidation: taking 3L of later-stage landfill leachate, pretreating a water sample by adopting flocculation precipitation, taking supernatant, adjusting the pH value to 3.0-4.0 by using sulfuric acid, dissolving iron for 36min under the current of 2A by using a porous composite iron electrode as an anode (10cm multiplied by 20cm) and stainless steel as a cathode (10cm multiplied by 20cm), and slowly adding 20mL (27.5% wt) of hydrogen peroxide after the iron is dissolved;
electrochemical oxidation: after the iron dissolution is finished, starting an electrochemical oxidation process, and selecting Ti/PbO2Anode with a set current density of 15mA/cm2(electrode area 100 cm)2) The voltage is 3.8V, the landfill leachate is synchronously circulated in electrochemical oxidation and electro-catalytic Fenton and stays for 18 h; after the reaction is finished, adjusting the pH to 9-11 by using caustic soda flakes, standing for 1h, and taking supernatant for the next reaction;
step 2, electrochemical oxidation treatment of ruthenium electrode: using Ti/RuO2Electrochemical oxidation is carried out by an electrochemical oxidation device consisting of a coated tubular anode and a stainless steel tubular cathodeChemical reaction, current density 15mA/cm3And reacting for 4 hours.
Step 3, electrochemical oxidation advanced treatment of the ruthenium electrode: opening by Ti/RuO2Carrying out electrochemical oxidation advanced treatment on an electrochemical oxidation device consisting of a tubular coating anode and a copper-nickel mesh cathode; the influent water utilizes the cathode to reduce nitrate, the anode carries out chlorine evolution reaction, and the current density is 20mA/cm2And reacting for 10 hours. Comparative example 1 a list of the effect of treatment degradation is shown in table 3.
TABLE 3 summary of the degradation effects of comparative example 1
From example 1 and comparative example 1, it can be seen that the final effluent water content of COD and total nitrogen in comparative example 1 is increased compared with example 1, because part of the small molecular organic nitrogen reacts with OH in the double oxidation reaction to form hydroxylamine structure, which is more stable, and part of COD and organic nitrogen remain, so the final effluent water COD and ammonia nitrogen content are higher.
Comparative example 2
The method for removing COD, ammonia nitrogen and total nitrogen in the landfill leachate by adopting a ruthenium electrode electrochemical oxidation-ruthenium electrode electrochemical oxidation advanced treatment-double oxidation method comprises the following specific steps:
step 1, electrochemical oxidation treatment of a ruthenium electrode: taking 3L of later-stage landfill leachate, adopting flocculation precipitation to pretreat a water sample, taking supernate, and utilizing Ti/RuO2The electrochemical oxidation device formed by the coating tubular anode and the stainless steel tubular cathode carries out electrochemical oxidation reaction, and the current density is 15mA/cm3Reacting for 4 hours;
step 2, electrochemical oxidation advanced treatment of the ruthenium electrode: opening by Ti/RuO2Carrying out electrochemical oxidation advanced treatment on an electrochemical oxidation device consisting of a tubular coating anode and a copper-nickel mesh cathode; the effluent water in the step 1 is subjected to nitrate reduction by using a cathode, chlorine evolution reaction is carried out at an anode, and the current density is 20mA/cm2Reacting for 10 hours; adjusting the pH value of the wastewater after the reaction in the step 2 to 3.0-4.0 by using sulfuric acid;
step 3, double oxidation treatment:
electrocatalytic fenton oxidation: dissolving iron for 36min under the current of 2A by using a porous composite iron electrode as an anode (10cm multiplied by 20cm) and stainless steel as a cathode (10cm multiplied by 20cm), and slowly adding 20mL (27.5% wt) of hydrogen peroxide after the iron is dissolved;
electrochemical oxidation: after the iron dissolution is finished, starting an electrochemical oxidation process, and selecting Ti/PbO2Anode with a set current density of 15mA/cm2(electrode area 100 cm)2) The voltage is 3.8V, the landfill leachate is synchronously circulated in electrochemical oxidation and electro-catalytic Fenton and stays for 18 h; after the reaction is finished, adjusting the pH value to 9-11 by using caustic soda flakes, and standing for 1 h.
Comparative example 2a list of the effect of treatment degradation is shown in table 4.
TABLE 4 summary of the degradation effects of comparative example 2
From the embodiment 1 and the comparative example 2, the COD, ammonia nitrogen and total nitrogen effluent values in the comparative example 2 are all improved compared with those in the embodiment 1, because part of micromolecular organic matters generated by the reaction of macromolecular organic matters in the double oxidation module, OH cannot be degraded and needs active chlorine to be degraded, and in the double oxidation link, part of organic nitrogen is released into ammonia nitrogen, and the ammonia nitrogen is higher without subsequent treatment.
Example 2
Aiming at arid regions with high concentrations of COD, ammonia nitrogen and the like, a ruthenium electrode electrochemical oxidation-double oxidation-ruthenium electrode electrochemical oxidation advanced treatment method is adopted to remove COD, ammonia nitrogen and total nitrogen in garbage leachate at the later stage, and the method comprises the following specific steps:
step 1, electrochemical oxidation treatment of a ruthenium electrode: taking 3L of later-stage landfill leachate, adopting flocculation precipitation to pretreat a water sample, taking supernate, and utilizing Ti/RuO2The electrochemical oxidation device formed by the coating tubular anode and the stainless steel tubular cathode carries out electrochemical oxidation reaction, and the current density is 20mA/cm3Reacting for 8 hours; regulating the waste water after reaction with sulfuric acidThe pH value is 3.0-4.0;
step 2, double oxidation treatment:
electrocatalytic fenton oxidation: taking a porous composite iron electrode as an anode (10cm multiplied by 20cm), stainless steel as a cathode (10cm multiplied by 20cm), dissolving iron for 100min, carrying out current 2A, and slowly adding 70mL (27.5% wt) of hydrogen peroxide after the iron dissolution is finished;
electrochemical oxidation: after the iron dissolution is finished, starting an electrochemical oxidation process, and selecting Ti/PbO2Anode with a set current density of 20mA/cm2(electrode area 100 cm)2) The voltage is 4.3V, the landfill leachate is synchronously circulated in electrochemical oxidation and electro-catalytic Fenton and stays for 18 h; after the reaction is finished, adjusting the pH to 9-11 by using caustic soda flakes, standing for 1h, and taking supernatant for the next reaction;
step 3, electrochemical oxidation advanced treatment of the ruthenium electrode: opening by Ti/RuO2Carrying out electrochemical oxidation advanced treatment on an electrochemical oxidation device consisting of a tubular coating anode and a copper-nickel mesh cathode; the influent water utilizes the cathode to reduce nitrate, the anode carries out chlorine evolution reaction, and the current density is 25mA/cm2And reacting for 14 h. The degradation effect of the treatment of example 2 is shown in Table 5.
TABLE 5 summary of the degradation effects of example 2
The above description is illustrative of the present invention and its embodiments, and is not to be construed as limiting, and the embodiments shown in the examples are only one embodiment of the present invention, and the actual embodiments are not limited thereto. Therefore, if the person skilled in the art receives the teaching, the embodiment and the embodiment similar to the technical solution should be designed without creativity without departing from the spirit of the invention, and shall fall within the protection scope of the invention.
Claims (10)
1. A treatment method for post-stage landfill leachate is characterized by comprising the following steps:
s1, first, performing electrochemical oxidation treatment of a ruthenium electrode;
s2 step, carrying out double oxidation treatment on the effluent of S1; the double oxidation treatment comprises a step of combined oxidation treatment of electrocatalytic Fenton oxidation and electrochemical oxidation;
s3 step, the step of performing electrochemical oxidation advanced treatment on the effluent of S2.
2. The method for treating the late-stage landfill leachate according to claim 1, wherein the total nitrogen TN content of the late-stage landfill leachate is greater than or equal to 2000 mg/L.
3. The method for treating post-landfill leachate according to claim 1, wherein in the ruthenium electrode electrochemical oxidation treatment in step S1, Ti/RuO is used to treat the post landfill leachate2The tubular coating anode, the stainless steel cathode and the electrochemical oxidation direct-current power supply form a ruthenium electrode electrochemical oxidation module; the current density of the ruthenium electrode in electrochemical oxidation treatment is 5-20mA/cm2The retention time of the landfill leachate treated in the step S1 is 4-12 h.
4. The method for treating post-landfill leachate according to claim 1, wherein in step S2, the electrochemical oxidation is performed by Ti/PbO2A coated tubular anode, a stainless steel cathode and an electrochemical DC power supply, wherein the Ti/PbO2The current density of the coating tubular anode in electrochemical oxidation reaction is 5-20mA/cm2(ii) a The electrocatalytic Fenton oxidation is carried out by a composite iron electrode and an electrocatalytic direct-current power supply under the condition of adding hydrogen peroxide, and the composite iron electrode is used for dissolving Fe in wastewater when electrified2+The size of iron dissolving current is 1-2A, the iron dissolving time is 4-12h, and after the iron dissolving is finished, hydrogen peroxide is added to start the electro-catalytic Fenton oxidation.
5. The method for treating post-stage landfill leachate according to claim 1, wherein in step S2, H in the landfill leachate is added2O2The mass ratio of the added amount to the COD is(1-2.5): 1, said H2O2Is 27.5 percent wt; fe2+Amount of addition and H2O2The molar ratio of the adding amount is 1 (8-20).
6. The method for treating post-stage landfill leachate according to claim 1, wherein the retention time of the double oxidation treatment of landfill leachate in step S2 is 5-20 h.
7. The method for treating post-stage landfill leachate according to claim 1, wherein in the ruthenium electrode electrochemical oxidation advanced treatment in step S3, Ti/RuO is used as the oxidizing agent2The tubular coating anode, the copper-nickel mesh cathode and the electrochemical oxidation direct-current power supply form a ruthenium electrode electrochemical oxidation module; the current density of the electrochemical oxidation advanced treatment is 10-20mA/cm2The current density of the copper-nickel mesh cathode in the electrocatalytic oxidation reaction is 10-20mA/cm2(ii) a The retention time of the landfill leachate treated in the step S3 is 4-16 h.
8. The method for treating post-stage landfill leachate according to claim 1, further comprising a pretreatment step before step S1, wherein the pretreatment step comprises flocculation precipitation of the landfill leachate; and/or
Before the double oxidation treatment in the step S2, firstly, adjusting the pH value of the landfill leachate to 3-4; and/or
Before the electrochemical oxidation advanced treatment of the ruthenium electrode in the step S3, firstly, the pH of the effluent in the step S2 is adjusted to 9-14, and the effluent is kept stand for precipitation.
9. The method for treating post-stage landfill leachate according to claim 1, wherein the method comprises the following steps of performing flocculation precipitation on the landfill leachate, and taking supernatant fluid:
s1 ruthenium electrode electrochemical oxidation treatment step: turning on the electrochemical oxidation DC power supply, and utilizing Ti/RuO2The electrochemical oxidation device consisting of the coating tubular anode and the stainless steel tubular cathode carries out electrochemistryCarrying out oxidation reaction, adjusting the pH value of the effluent to be acidic, and then carrying out double oxidation treatment;
s2 double oxidation treatment step:
(a) electrocatalytic fenton oxidation: taking a composite iron electrode (for example, a porous composite iron electrode) as an anode and stainless steel as a cathode, turning on an electrocatalytic direct current power supply, and adding Fe in a form of dissolving iron by the anode2+Meanwhile, the dissolved iron can generate an electric floating effect to remove suspended matters in the leachate, and hydrogen peroxide is slowly added after the iron is dissolved to start the electro-catalytic Fenton oxidation;
(b) electrochemical oxidation: when the electro-catalytic Fenton oxidation is started, an electrochemical oxidation direct current power supply is turned on, and Ti/PbO is utilized2An electrochemical oxidation device consisting of a tubular electrode performs electrochemical oxidation reaction;
(c) the landfill leachate entering the double-oxidation treatment step is repeatedly and circularly treated in the electrochemical oxidation of the step (b) and the electro-catalytic Fenton oxidation treatment of the step (a), so that the synergistic effect of the electro-catalytic Fenton and the electrochemical oxidation is realized, the oxidation effect is enhanced, and COD is efficiently removed;
(d) adjusting the effluent water after the circulating treatment in the steps (a) and (b) to be alkaline so as to precipitate iron mud; the effluent enters a ruthenium electrode electrochemical oxidation advanced treatment step;
s3 ruthenium electrode electrochemical oxidation advanced treatment step: from Ti/RuO2Carrying out electrochemical oxidation advanced treatment on an electrochemical oxidation device consisting of a tubular coating anode and a copper-nickel mesh cathode; the nitrate is reduced into nitrogen and ammonia nitrogen by the cathode, and the generated ammonia nitrogen and the ammonia nitrogen in the water utilize Ti/RuO2The tubular coating anode is removed by chlorine evolution reaction, and the generated active chlorine can effectively oxidize low-molecular organic acid to achieve deep degradation of pollutants.
10. A treatment system for later-stage landfill leachate is characterized by comprising a ruthenium electrode electrochemical oxidation module, a double oxidation module and a ruthenium electrode electrochemical oxidation advanced treatment module which are sequentially connected;
the ruthenium electrode electrochemical oxidation module comprises Ti/RuO2A coated tubular anode and a stainless steel cathode;
the double oxidation module comprises a combination of an electro-catalytic Fenton oxidation device and an electrochemical oxidation device, wherein the electro-catalytic Fenton oxidation device comprises a composite iron anode and a stainless steel cathode; the electrochemical oxidation device comprises Ti/PbO2Coating a tubular anode and a titanium tube cathode;
the ruthenium electrode electrochemical oxidation advanced treatment module comprises Ti/RuO2A coated tubular anode and a copper-nickel mesh cathode.
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| CN112960819A (en) * | 2021-03-05 | 2021-06-15 | 南京理工大学 | Double oxidation-electrochemical oxidation combined process for advanced treatment of landfill leachate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1412124A (en) * | 2002-11-28 | 2003-04-23 | 武汉大学 | Treatment method of waste water and its equipment |
| CN101914782A (en) * | 2010-07-27 | 2010-12-15 | 武汉大学 | Metallic oxide anode suitable for Fenton system and preparation method thereof |
| CN105923850A (en) * | 2016-05-17 | 2016-09-07 | 浙江工商大学 | Treatment technology of refuse leachate membrane concentration liquid |
| CN112960819A (en) * | 2021-03-05 | 2021-06-15 | 南京理工大学 | Double oxidation-electrochemical oxidation combined process for advanced treatment of landfill leachate |
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