CN112723653A - Garbage leachate full-scale harmless treatment method and system - Google Patents

Garbage leachate full-scale harmless treatment method and system Download PDF

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CN112723653A
CN112723653A CN202011423593.4A CN202011423593A CN112723653A CN 112723653 A CN112723653 A CN 112723653A CN 202011423593 A CN202011423593 A CN 202011423593A CN 112723653 A CN112723653 A CN 112723653A
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treatment
module
membrane
leachate
tank
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邹巍
黄昭玮
李红
高本修
顾磊
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Wuhan Tianyuan Environmental Protection Co ltd
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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
    • C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2203/00—Apparatus and plants for the biological treatment of water, waste water or sewage
    • C02F2203/006—Apparatus and plants for the biological treatment of water, waste water or sewage details of construction, e.g. specially adapted seals, modules, connections
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/30—Aerobic and anaerobic processes
    • C02F3/302—Nitrification and denitrification treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F7/00—Aeration of stretches of water

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Abstract

The invention belongs to the technical field of sewage treatment, and particularly provides a full-scale harmless treatment method and a full-scale harmless treatment system for garbage leachate. According to the method and the system, on the basic premise of ensuring that the final produced water is qualified and reaches the standard, the water production rate is close to 95%, secondary pollutants such as membrane-free concentrated solution and the like are generated, zero discharge of leachate treatment is realized, and the method and the system are green and environment-friendly; the independent treatment modules can respond to the change of the water quality and the water quantity of the wastewater to be treated in real time, and can increase or decrease core equipment elements, adjust the dosage and other measures to control the pollutant removal efficiency; the whole process has strong control and regulation capability and strong impact load resistance capability, and can meet the treatment requirements of the landfill leachate on water quality and water quantity fluctuation at different periods; and the process running cost is low.

Description

Garbage leachate full-scale harmless treatment method and system
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a full-scale harmless treatment method and system for landfill leachate.
Background
The landfill leachate is a secondary pollutant generated by compacting and fermenting garbage wastes in the stacking, landfill and incineration processes, is in a liquid form of organic or inorganic harmful components, generally has the main characteristics of complex components, high concentration of ammonia nitrogen (NH4-N) and organic pollutants (CODcr), poor biodegradability, high Total Dissolved Solids (TDS), high content of heavy metal substances, high toxicity, malodor and the like, and is one of the most difficult-to-treat wastewater recognized at home and abroad.
The material composition and concentration of landfill leachate greatly fluctuate, and depend on the type, property, landfill mode, dissolution rate and chemical action of pollutants, rainfall condition, landfill age, landfill structure and the like, but the main influence factors are the service life and design structure of the landfill. At present, according to the length of the landfill years, the landfill sites in China are mainly divided into initial landfill sites (less than or equal to 5 years), mature landfill sites (5-10 years) and old landfill sites (more than or equal to 10 years). The water quality conditions of landfill leachate of landfill sites at different periods are greatly changed, and the treatment difficulty is increased year by year along with the increase of the landfill age.
At present, independent leachate treatment stations are set in most domestic landfill sites, and a mainstream treatment process of "pretreatment + biochemical treatment + membrane advanced treatment" proposed by technical specification (trial) of leachate treatment engineering in domestic landfill sites (HJ564-2010) is usually adopted and issued by the ministry of environmental protection of China, and mainly comprises the following steps: (1) pretreatment, wherein slag and suspended substances in the leachate are primarily removed by physical methods such as solid-liquid separation, grating, coagulating sedimentation and the like; (2) biochemical treatment, namely performing biodegradation on pollutants in the percolate by utilizing the synergistic action of nitrobacteria and denitrifying bacteria, wherein an A/O + UF Membrane Bioreactor (MBR) module is usually adopted; (3) and (3) performing membrane advanced treatment, namely intercepting pollutants by utilizing a membrane separation device aiming at the pollutants which can not be biochemically treated in the percolate, and discharging qualified produced water which reaches the standard after treatment, wherein a nanofiltration and reverse osmosis combined membrane separation process is usually adopted.
Several major problems have long been associated with mainstream leachate treatment processes:
(1) the ability to resist water quality and water fluctuation is weak. The water quality and the water quantity of the landfill leachate fluctuate along with the seasons, the climate, the landfill age and other factors, and particularly for the old landfill site with the landfill age more than 10 years, the landfill leachate generally has the characteristics of water quantity reduction, organic pollutant concentration reduction, ammonia nitrogen pollutant concentration increase and the like, if a mainstream treatment process is continuously adopted, a large amount of carbon sources are required to be added in a biochemical treatment stage, the operation cost is increased suddenly, the water yield of membrane advanced treatment is low, and the risk that the on-site water quality and the water quantity do not reach the standard at any time is realized;
(2) secondary pollutants that are harmful to the environment are generated. The membrane advanced treatment technology essentially only separates pollutants in the percolate from a liquid phase in a physical interception mode, and the concentration of each pollutant in the produced membrane concentrated solution is higher, so that the treatment is more difficult. At present, most of operating percolate treatment stations recycle membrane concentrated solution to a reservoir area and then circularly flow into a regulating reservoir, so that the quality of raw water is continuously deteriorated, and finally, the whole treatment module is crashed;
(3) the controllable regulating ability is weak. Generally, the main treatment process of landfill leachate is difficult to realize the change of pollutant removal efficiency by adjusting a single or a plurality of independent process units in the operation process, the controllable adjustment capability of the combined treatment process is weak, the combined treatment process cannot adapt to the complex water quality change of the leachate, and the requirement of treatment scale is difficult to meet on the premise of ensuring the qualified water production index.
Disclosure of Invention
The invention aims to provide a full-amount harmless treatment method and system for landfill leachate. The problem of weak ability to resist water quality and water fluctuation is solved.
Therefore, the invention provides a full-scale harmless treatment method of landfill leachate, which comprises the following steps:
s1: the pretreatment comprises the steps of performing pre-aeration and pre-coagulating sedimentation on leachate stock solution of a regulating reservoir of the refuse landfill;
s2: catalytic wet oxidation (CWAO) treatment, including in particular the pretreatment of effluentConverting organic matters and nitrogen-containing substances in the leachate into CO through high-temperature high-pressure wet catalytic oxidation2，H2O and N2And the like;
s3: membrane Bioreactor (MBR) treatment, which specifically comprises removing biodegradable organic matters and ammonia nitrogen pollutants in the percolate after CWAO treatment by two-stage nitrification-denitrification;
s4: performing Membrane Fenton Reactor (MFR) treatment, specifically performing advanced treatment on organic pollutants which are not biochemically degradable in the leachate after the MBR treatment through a Fenton-like catalytic oxidation system to meet the COD index discharge requirement;
s5: the deamination treatment of the degassing membrane specifically comprises the steps of extracting ammonia nitrogen from residual ammonia nitrogen pollutants in leachate after the MBR and MFR treatment by utilizing the combined action of strong acid and a gaseous membrane, and deeply treating tail water to NH4N and TN target emission requirements.
Preferably, the pretreatment comprises the steps of firstly introducing compressed air into the landfill leachate stock solution, changing a liquid phase buffer system under the conditions of preset retention time and aeration rate, and then adding sodium carbonate (Na)2CO3) And adjusting the pH value of the wastewater to 8-9.5 by using sodium hydroxide (NaOH), so that calcium and magnesium ions in the wastewater form precipitates, adding polyaluminum chloride (PAC) and Polyacrylamide (PAM), uniformly stirring, and settling calcium and magnesium floccules and suspended substances in the wastewater through a coagulating sedimentation effect to improve the quality of leachate.
Preferably, the catalytic wet oxidation (CWAO) comprises the steps of introducing the pretreated landfill leachate into a specific CWAO catalytic oxidation module, heating the wastewater by a heat exchanger, uniformly mixing compressed air and the heated wastewater by a steam-water mixer, introducing the mixture into a main reaction tower of an intermittent stirred tank, and respectively oxidizing and decomposing organic matters and nitrogen-containing substances in the leachate into substances containing CO by air and an oxidizing agent under the action of preset temperature, pressure and a catalyst through combined oxidation of air and an oxidizing agent2，H2O and N2The substance of (1).
Preferably, the Membrane Bioreactor (MBR) comprises a biochemical treatment module and an external tubular membrane ultrafiltration module; the biochemical treatment module comprises a primary denitrification tank, a primary nitrification tank, a secondary denitrification tank and a secondary nitrification tank, wherein submersible mixers are arranged in the primary denitrification tank and the secondary denitrification tank for continuous stirring, so that the sludge concentration in the tanks is ensured to be uniform; jet aeration devices are arranged in the primary nitrification tank and the secondary nitrification tank for blast aeration, so that the concentration of dissolved oxygen in the tanks is maintained at 2-5 mg/L; pumping the CWAO effluent into a primary denitrification tank, then respectively flowing into a primary nitrification tank, a secondary denitrification tank and a secondary nitrification tank along with the overflow direction, lifting the effluent of the secondary nitrification tank to an external tubular ultrafiltration membrane module by a water pump, and refluxing ultrafiltration concentrate to the primary denitrification tank; meanwhile, a mixed liquid reflux pump is arranged between the first-stage denitrification tank and the first-stage nitrification tank to reflux the nitrified liquid in the first-stage nitrification tank to the first-stage denitrification tank.
Preferably, the Membrane Fenton Reactor (MFR) comprises a fenton-like catalytic oxidation module and an internal microfiltration membrane module;
the MBR discharges water and then enters an MFR reactor, and the pH is adjusted to 4-4.5, so that the organic pollutants which cannot be biochemically degraded are further mineralized and decomposed into CO under the combined action of the Fenton-like composite catalyst and the oxidizing agent2And H2O; meanwhile, the built-in microfiltration membrane is used for replacing the traditional secondary sedimentation tank to intercept suspended substances in the wastewater.
Preferably, step S5 specifically includes: and adjusting the pH value of the MFR effluent to 9-11, adjusting the temperature to 35 ℃, converting free ammonia nitrogen pollutants in the wastewater into ammonia gas under the action of a hydrophobic hollow fiber membrane, and converting the ammonia gas into ammonium salt to be discharged after the ammonia gas is absorbed by a strong acid side.
Preferably, the chemical sludge generated in the steps S1 and S4 and the biochemical sludge generated in the step S3 are collected into a sludge conditioning tank together, dehydrated by a sludge filter pressing module and sent to a designated landfill site for landfill.
Preferably, step S4 further includes: and converting the residual organic nitrogen after the MBR treatment into an ammonia nitrogen form.
The invention also provides a system for harmless treatment of the total quantity of the landfill leachate, and the module is used for treating the leachate stock solution of the regulating reservoir of the landfill site by the method for harmless treatment of the total quantity of the landfill leachate.
Preferably, the system comprises a pretreatment module, a CWAO catalytic wet oxidation module, an MBR membrane bioreactor module, an MFR membrane Fenton reactor module, a degassing membrane deamination module, a clean water tank, a sludge concentration tank and a sludge treatment module which are sequentially connected through a pipeline.
The invention has the beneficial effects that: the full-amount harmless treatment method and the system for the landfill leachate provided by the invention are used for sequentially carrying out pre-aeration and pre-coagulating sedimentation treatment, catalytic wet oxidation treatment, membrane bioreactor treatment, membrane Fenton reactor treatment and degassing membrane deamination treatment on the leachate stock solution of the regulating reservoir of the landfill to obtain standard water quality. According to the method and the system, on the basic premise of ensuring that the final produced water is qualified and reaches the standard, the water production rate is close to 95%, secondary pollutants such as membrane-free concentrated solution and the like are generated, zero discharge of leachate treatment is realized, and the method and the system are green and environment-friendly; the plurality of independent processing modules can immediately respond according to the change of the water quality and the water quantity of the wastewater to be processed, and the modules such as the CWAO module, the MFR module, the degassing membrane deamination module and the like can control the pollutant removal efficiency by controlling reaction conditions, increasing and decreasing core equipment elements, adjusting the dosage and the like; the whole process has strong control and regulation capability and strong impact load resistance capability, and can meet the treatment requirements of the landfill leachate on water quality and water quantity fluctuation at different periods; and the process running cost is low.
The present invention will be described in further detail below with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic flow chart of the method for harmless treatment of landfill leachate in full scale according to the present invention;
FIG. 2 is a schematic diagram of the overall structure of the landfill leachate total innocent treatment system of the present invention;
FIG. 3 is a schematic diagram of the top view of the MFR membrane Fenton reactor configuration of the landfill leachate full scale detoxification treatment system of the present invention;
FIG. 4 is a schematic front view of the MFR membrane Fenton reactor structure of the landfill leachate full-scale detoxification treatment system of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that the terms "center", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention.
The terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature; in the description of the present invention, "a plurality" means two or more unless otherwise specified.
The embodiment of the invention provides a full-scale harmless treatment method for landfill leachate, which comprises the following steps:
s1: the pretreatment comprises the steps of performing pre-aeration and pre-coagulating sedimentation on leachate stock solution of a regulating reservoir of the refuse landfill;
s2: catalytic wet oxidation (CWAO) treatment, which comprises converting organic matters and nitrogen-containing substances in the leachate into CO by high-temperature high-pressure wet catalytic oxidation of the pretreated effluent2，H2O and N2And the like;
s3: membrane Bioreactor (MBR) treatment, which specifically comprises removing biodegradable organic matters and ammonia nitrogen pollutants in the percolate after CWAO treatment by two-stage nitrification-denitrification;
s4: performing Membrane Fenton Reactor (MFR) treatment, specifically performing advanced treatment on organic pollutants which are not biochemically degradable in the leachate after the MBR treatment through a Fenton-like catalytic oxidation system to meet the COD index discharge requirement;
s5: the deamination treatment of the degassing membrane specifically comprises the steps of extracting ammonia nitrogen from residual ammonia nitrogen pollutants in leachate after the MBR and MFR treatment by utilizing the combined action of strong acid and a gaseous membrane, and deeply treating tail water to NH4N and TN target emission requirements.
The scheme aims to overcome the defects of the prior art and provide the full-amount harmless treatment process for landfill leachate, which utilizes a combined advanced oxidation technology to replace a membrane separation advanced treatment module. The process integrates the advanced technology in the aspect of treating high-concentration organic wastewater at home and abroad and is combined with the Fenton-like catalytic oxidation technology which is independently researched and developed, a set of novel garbage leachate treatment process route is developed, the current mainstream treatment process can be completely replaced, the defects and the problems of the mainstream process are solved on the premise of ensuring the treatment to reach the standard, the impact load resistance and the operation stability of a module are improved, no secondary pollutant is generated, and the process is green and environment-friendly.
The specific technical scheme provided by the invention is as follows:
as shown in fig. 1, a process for the complete harmless treatment of landfill leachate comprises the following steps:
(1) pretreatment: the method mainly comprises the steps of pre-aerating, pre-coagulating and precipitating leachate stock solution of a regulating reservoir of the refuse landfill, removing suspended matters in the leachate, and regulating an acid-base buffer system through an aeration effect while calcium and magnesium ions are removed;
(2) catalytic wet oxidation (CWAO): mainly converting organic matters and nitrogen-containing substances in the leachate into CO by the high-temperature high-pressure wet catalytic oxidation of the pretreated effluent2，H2O and N2And the like, so as to achieve the purpose of reducing the concentration of pollutants in the landfill leachate;
(3) membrane Bioreactor (MBR): biodegradable organic and ammonia nitrogen pollutants in the percolate after the CWAO treatment are removed mainly through two-stage nitrification-denitrification; an external ultrafiltration membrane is used for removing suspended matters and realizing sludge circulation, so that the biochemical reaction efficiency is improved;
(4) membrane Fenton Reactor (MFR): the method mainly aims at the advanced treatment of organic pollutants which cannot be biochemically degraded in the leachate after the MBR treatment through a Fenton-like catalytic oxidation system, and achieves the COD index discharge requirement. In addition, converting residual organic nitrogen after MBR treatment into an ammonia nitrogen form;
(5) and (3) degassing membrane deamination treatment: mainly aiming at residual ammonia nitrogen pollutants in leachate after MBR and MFR treatment, ammonia nitrogen is extracted by utilizing the combined action of strong acid and a gaseous membrane, so that tail water is deeply treated to reach NH4N and TN target emission requirements.
The pretreatment in the step (1) comprises the steps of firstly introducing compressed air into the raw liquid of the landfill leachate, changing a liquid-phase buffer system under the conditions of certain retention time and aeration rate, and then adding sodium carbonate (Na)2CO3) And adjusting the pH value of the wastewater to 8-9.5 by using sodium hydroxide (NaOH), so that calcium and magnesium ions in the wastewater form precipitates, adding polyaluminum chloride (PAC) and Polyacrylamide (PAM), uniformly stirring, and settling calcium and magnesium floccules and suspended substances in the wastewater through a coagulating sedimentation effect to improve the quality of leachate.
The catalytic wet oxidation (CWAO) in the step (2) comprises the steps of introducing the pretreated landfill leachate into a specific CWAO catalytic oxidation module, heating the wastewater by a heat exchanger, uniformly mixing compressed air and the heated wastewater by a steam-water mixer, introducing the mixture into a main reaction tower of an intermittent stirring kettle, and respectively oxidizing and decomposing organic matters and nitrogen-containing substances in the leachate into CO by air and an oxidizing agent under the action of certain temperature, pressure and a catalyst through combined oxidation of air and an oxidizing agent2，H2O and N2And the like, so as to achieve the effect of reducing the concentration of the pollutants in the wastewater; meanwhile, macromolecular complex organic groups are decomposed, and the biodegradability of the wastewater is improved.
And (3) the Membrane Bioreactor (MBR) comprises a biochemical treatment module and an external tubular membrane ultrafiltration module. The biochemical treatment module comprises a primary denitrification tank, a primary nitrification tank, a secondary denitrification tank and a secondary nitrification tank, wherein submersible mixers are arranged in the primary denitrification tank and the secondary denitrification tank for continuous stirring, so that the sludge concentration in the tanks is ensured to be uniform; jet aeration devices are arranged in the primary nitrification tank and the secondary nitrification tank for blast aeration, so that the concentration of dissolved oxygen in the tanks is maintained at 2-5 mg/L; pumping the CWAO effluent into a primary denitrification tank, then respectively flowing into a primary nitrification tank, a secondary denitrification tank and a secondary nitrification tank along with the overflow direction, lifting the effluent of the secondary nitrification tank to an external tubular ultrafiltration membrane module by a water pump, and refluxing ultrafiltration concentrate to the primary denitrification tank; meanwhile, a mixed liquid reflux pump is arranged between the first-stage denitrification tank and the first-stage nitrification tank to reflux the nitrified liquid in the first-stage nitrification tank to the first-stage denitrification tank.
And (4) the Membrane Fenton Reactor (MFR) comprises a Fenton-like catalytic oxidation module and a built-in microfiltration membrane module. Pumping MBR effluent into an MFR reactor, regulating the pH to 4-4.5, and further completely mineralizing and decomposing non-biodegradable organic pollutants into CO under the combined action of Fenton-like composite catalyst and oxidizing agent2And H2O; meanwhile, the built-in microfiltration membrane is used for replacing the traditional secondary sedimentation tank to intercept suspended substances in the wastewater. The step thoroughly reduces the organic pollutants in the landfill leachate to the emission standard value, converts the organic nitrogen pollutants into an ammonia nitrogen form, and reduces the suspended matter concentration (SS) to the acceptance value of a subsequent treatment module.
And (5) adjusting the pH value of the MFR effluent to 9-11, adjusting the temperature to 35 ℃, converting free ammonia nitrogen pollutants in the wastewater into ammonia gas under the action of a hydrophobic hollow fiber membrane, absorbing the ammonia gas by a strong acid side, and converting the ammonia nitrogen pollutants into ammonium salts to be discharged. The concentration of the ammonia nitrogen pollutants in the landfill leachate can be completely reduced to the standard discharge value through the steps, and the generated ammonium salt solution flows back to the regulating tank to participate in biochemical cycle reaction, so that no secondary pollutants are generated.
And (3) collecting the chemical sludge generated in the step (1) and the biochemical sludge generated in the step (4) and the biochemical sludge generated in the step (3) to a sludge conditioning tank, dehydrating by a sludge filter-pressing module, and then conveying to a specified landfill site for landfill.
Compared with the traditional mainstream landfill leachate treatment process of pretreatment, biochemical treatment and membrane advanced treatment, the invention adopts the combined process of pretreatment, catalytic wet oxidation (CWAO), Membrane Bioreactor (MBR), Membrane Fenton Reactor (MFR) and degassing membrane treatment to carry out full-quantitative harmless treatment on the landfill leachate, and the advancement is as follows:
(1) the CWAO has the characteristics of wide organic matter treatment range, good effect, short reaction time, small reaction container volume, almost no secondary pollution, capability of recovering useful substances and energy and the like; the method is particularly suitable for treating high-concentration refractory organic wastewater (COD is more than or equal to 15000mg/L) such as landfill leachate, can utilize self reaction heat to maintain the reaction process, reduce the concentration of organic and ammonia nitrogen pollutants in the wastewater, decompose macromolecular benzene ring organic matters simultaneously, and greatly improve the biodegradability of the wastewater;
(2) the MBR adopts a two-stage nitrification-denitrification (A/O) biochemical treatment module to be matched with an external cross-flow ultrafiltration membrane component to form a membrane bioreactor, and the biodegradability of the CWAO produced water is better, so that compared with the traditional process, the two-stage A/O treatment in the invention has the advantages of low pollutant load, high reaction efficiency and no need of secondary carbon source addition;
(3) the MFR + degassing membrane deamination combined process replaces the traditional membrane separation process to be used as a leachate advanced treatment process module, and the Fenton-like catalytic oxidation technology is utilized to thoroughly decompose the non-biodegradable part of organic pollutants in the leachate into CO through the strong oxidation of hydroxyl free radicals2And H2O, simultaneously converting residual ammonia nitrogen pollutants in the leachate into ammonia gas by adopting a hydrophobic degassing membrane, absorbing the ammonia gas by using strong acid, and circularly entering a CWAO module for secondary treatment; the combined advanced treatment process fundamentally overcomes the defects of low water yield and membrane concentrated solution generation of the traditional membrane separation module, and realizes the deep full-quantitative harmless treatment of the landfill leachate in a real sense.
The first embodiment is as follows: referring to fig. 1 to 4, the system mainly comprises a pretreatment module (comprising an adjusting tank 1 and an aeration coagulating sedimentation device 2), a CWAO catalytic wet oxidation module 3, an MBR membrane bioreactor module (comprising a primary nitrification-denitrification tank 4, a secondary nitrification-denitrification tank 5 and an external tubular ultrafiltration membrane component 6), an MFR membrane fenton reactor module 7, a degassing membrane deamination module 8, a clear water tank 9, a sludge concentration tank 10 and a sludge treatment module 11 which are sequentially connected through pipelines. Wherein, the aeration coagulating sedimentation device 2, the MBR membrane bioreactor module and the sludge generated by the MFR membrane Fenton reactor module 7 are connected with the sludge concentration tank 10.
The leachate in the landfill area of the refuse landfill is collected by a pipeline and then flows into a pretreatment module adjusting tank 1, the retention time of the leachate in the adjusting tank is 25-30 days, the leachate is subjected to preliminary anaerobic hydrolysis acidification reaction, and part of slag is precipitated. The landfill leachate stoste promotes to pretreatment module aeration coagulating sedimentation device 2 through the immersible pump in the equalizing basin, and this device design adopts integrated carbon steel anticorrosion structure, utilizes the baffle to separate the box for different functional areas, realizes the treatment such as the preliminary aeration to the leachate, thoughtlessly congeals, deposits, improves waste water quality of water.
Effluent of the pretreatment module is lifted to a CWAO catalytic wet oxidation module 3 by a pretreatment device 2 through a filter, a water storage tank and a water pump, and the module comprises a shell-and-tube heat exchanger, a blower, a steam-water mixer, an intermittent stirred tank main reaction tower, a gas-liquid separator and other main components. The method comprises the steps of heating wastewater to a reaction temperature (200-220 ℃) through a tube pass of a tube-in-tube heat exchanger, then fully mixing compressed air generated by a steam-water mixer and an air blower, injecting the mixture into a main reaction tower of an intermittent stirred tank, filling composite solid catalysts in the tower in a layered mode, fully reacting for 60-90 minutes in a sealed high-temperature (200-220 ℃) and high-pressure (1.5-2.5MPa) state, separating residual air and nitrogen in the wastewater through a steam-water separator, and then refluxing the separated residual air and nitrogen into the tube pass of the tube-in-tube heat exchanger for cooling, so that the process module treatment is completed. It should be noted that, the CWAO is operated for the first time by heating the inlet water to the required reaction temperature through the external heater, and after the CWAO is operated continuously and stably, the inlet water is heated up through the outlet water reflux without adding an additional heat source. It should be noted that, the CWAO module can adjust the pollutant removal efficiency of the module at a proper time by changing the reaction conditions (temperature, pressure, type of chemical agent) according to the overall process requirements, thereby improving the water and mass impact load resistance of the process module.
The effluent of the CWAO module is lifted to an MBR membrane bioreactor module. The MBR is composed of a primary nitrification-denitrification tank 4, a secondary nitrification-denitrification tank 5 and an external tubular ultrafiltration membrane component 6. Wherein, the first-stage denitrification tank and the second-stage denitrification tank are internally provided with submersible stirring devices, the first-stage nitrification tank and the second-stage nitrification tank are internally provided with jet aeration devices, and the outer parts of the first-stage nitrification tank and the second-stage nitrification tank are provided with matched jet circulating pumps; in addition, the first-stage nitrification tank is also connected with the first-stage denitrification tank through a pipeline and a reflux pump, and an external ultrafiltration membrane is used for intercepting the concentrated water and returning the concentrated water to the first-stage denitrification tank. The leachate is degraded by aerobic bacteria in the primary nitrification tank and the secondary nitrification tank to biochemically treat partial organic pollutants, simultaneously converts the ammonia nitrogen pollutants into nitrate nitrogen forms, converts the nitrate nitrogen forms into nitrogen under the action of flora in the denitrification tank through the reflux action, realizes the removal of total nitrogen, and finally separates muddy water through the action of an external ultrafiltration membrane to complete the treatment of the leachate in the MBR module. It should be noted that most of the organic pollutants in the leachate in the MBR module, such as ammonia nitrogen, total nitrogen, suspended matters and biodegradable parts, are removed, and the leachate serves as a core function module for leachate treatment.
MBR effluent enters a leachate advanced treatment module, which comprises an MFR membrane Fenton reactor module 7 and a degassing membrane deamination module 8. Wherein, the MFR membrane Fenton reactor module 7 adopts an integrated carbon steel anticorrosion structure, and a box body is divided into different functional areas by using a partition plate, as shown in figure 2; the device includes: an acid conditioning zone 71; a liquid dosing zone 72; a catalytic oxidation reaction zone 73; a base conditioning zone 74; 75 a coagulation dosing zone 75; 76 vertical flow settling zone 76; 77 solid-liquid separation zone 77; 78 out of the water zone 78. MBR effluent is firstly pumped into an acid adjusting area 71, the pH value of wastewater is adjusted to 4-4.5 by adding sulfuric acid, the wastewater overflows into a drug adding area 72, an adding liquid awakens a catalyst and hydrogen peroxide, the catalyst and the hydrogen peroxide are uniformly mixed and then overflow into a catalytic oxidation reaction area 73, wherein a Fenton-like composite catalyst filler layer is arranged in the drug adding area 73, and the filler density is 35-50 kg/m3. The bottom of the reaction zone 73 is provided with a perforated aerator, compressed air is uniformly distributed in the reaction zone to ensure that the medicaments are fully mixed and reacted, then the compressed air flows into a vertical flow settling zone through a guide pipe, the settled effluent flows into a solid-liquid separation zone 77 through a triangular weir, and the bottom of the solid-liquid separation zone 77 is provided with a built-in microfiltration membrane component to reduce the concentration of suspended matters in the effluent under the action of the built-in microfiltration membrane component. The water produced in the solid-liquid separation zone is pumped into the solid-liquid separation zone by a self-priming pumpAnd (4) discharging the water zone to finish the Fenton-like catalytic oxidation process. It should be noted that, compared with the traditional fenton technology, the fenton-like catalytic oxidation technology adopted by the process module has the advantages of low reaction activation energy, high reaction efficiency, COD removal rate of more than or equal to 85 percent and sludge production of less than or equal to 15 percent, and can reduce the COD concentration value of MBR produced water to the qualified discharge standard, convert organic nitrogen pollutants into ammonia nitrogen pollutants, and treat the ammonia nitrogen pollutants in the subsequent module.
MFR effluent zone 78 is connected to degassing membrane deamination module 8, which contains a gaseous deamination membrane core module and a strong acid absorption module. Firstly, adjusting the pH of the wastewater to 9-11, passing the wastewater through a hollow fiber hydrophobic membrane module shell pass, introducing strong acid into a membrane module tube pass, and under a strong alkaline environment, introducing free NH in the wastewater4 +Conversion to NH3The water-repellent film layer is absorbed by strong acid on the other side and then changed into ammonium salt, and the ammonium salt is refluxed to a regulating reservoir for secondary treatment, and the specific reaction process is as follows:
a.NH4++OH-＝NH3·H2O＝NH3↑+H2O
b.2NH3↑+H2SO4＝(NH4)2SO4
the water produced by the degassing membrane deamination module 8 enters a clean water tank 9, and the main pollutant indexes of the water quality of the water produced by the clean water tank 9 can meet the standard requirements of table 2 in the standard for controlling pollution of domestic garbage landfill (GB 16889-2008).
The pretreatment aeration coagulation device 2, the external tubular ultrafiltration membrane module 6 and the MFR membrane Fenton reactor 7 are used for producing sludge, the sludge is conveyed to a sludge concentration tank 10, the sludge is concentrated and then conveyed to a sludge dewatering module 11 by a screw pump, and the sludge is treated by a screw-stacking dewatering machine or a plate-and-frame filter press and then is transported to a designated place for landfill treatment.
Example two:
the source of the wastewater is as follows: the concentration values of main pollutants in water quality of a large-scale domestic waste field regulating reservoir percolate in Wuhan city, Hubei province are shown in the following table:
table 1: analysis of water quality condition of leachate in regulating reservoir of large domestic refuse field in Wuhan City of Hubei province
Figure BDA0002823663840000141
As can be seen from Table 1, the indexes of main pollutants, conductivity, suspended matter concentration and the like of the leachate of the regulating reservoir of the refuse landfill exceed normal values, the C/N ratio of the leachate is disordered, the biodegradability is poor, and the water quality and the water quantity can hardly reach the standard by adopting the conventional pretreatment, biochemical treatment and membrane advanced treatment processes.
The garbage leachate is treated by adopting the full-amount harmless treatment process module for the leachate provided by the embodiment 1 of the invention, and the treatment scale is 100m3And d, the single-day running time of the module is 20 h.
The landfill leachate in the adjusting tank 1 is firstly pumped into the pretreatment aeration coagulation device 2 through a submersible sewage pump. The pretreatment aeration coagulation device 2 is designed to adopt an integrated carbon steel cubic structure. Wherein the retention time of the aeration zone is 8-12h, and the aeration air volume is 4.85m3Min, the wind pressure is 0.05 Mpa; the residence time of the settling zone is 6-8h, the dosage of the coagulating agent PAC is 250ppm, and the dosage of PAM is 105 ppm; and adjusting the pH of the produced water to about 6.0-6.5 by using NaOH.
The water produced by the pretreatment aeration coagulation device 2 enters a CWAO catalytic wet oxidation module 3. Wherein the gas-water mixed gas supply amount is 7.75m3And/min, the reaction temperature of the main reaction tower is 220 ℃, the pressure is 2.1Mpa, the reaction time is 150min, the temperature of effluent water is reduced to 20-25 ℃ through a heat exchanger after the reaction is finished, and the residual gas components are removed through a gas-liquid separation device, so that the treatment at the stage is finished.
The effluent of the CWAO catalytic wet oxidation module 3 enters an MBR membrane bioreactor, and the leachate removes most of biodegradable organic, ammonia nitrogen and total nitrogen pollutants under the biochemical treatment action of two-stage nitrification-denitrification; meanwhile, the biological activated sludge is separated by an ultrafiltration membrane. The total retention time of the MBR is about 6-7 days, the dissolved oxygen concentration of the denitrification tank is maintained below 0.1mg/L, and the dissolved oxygen concentration of the nitrification tank is maintained at 2-5 mg/L.
MBR effluent enters a leachate advanced treatment module, wherein the design of the MFR membrane Fenton reactor 7 adopts an integrated carbon steel structure. A dosing zone, a coagulation zone with a retention time of 15 min; in the reaction zonePartially filled with a Fenton-like special composite catalyst, filled in two layers and filled at a filling density of 25kg/m3(ii) a The residence time of the reaction zone is 8.0h, and the residence time of the vertical flow settling zone is 10.0 h; the core medicament adding comprises the following steps: 300ppm of special Fenton-like liquid catalyst and oxidizing agent H2O2825 ppm. The produced water in the vertical flow sedimentation area flows into the membrane tank through the triangular weir, suspended matters are separated under the action of the built-in microfiltration membrane, and the quality of the produced water is improved. Meanwhile, partial sludge in the sedimentation zone and the membrane tank flows back to the reaction zone through the reflux pump, so that the concentration of effective reaction components is ensured.
Water produced by the MFR membrane Fenton reactor 7 enters a degassing membrane deamination module 8; adjusting the pH value of the inlet water to 9.5, and controlling the reaction temperature to 25 ℃; the core membrane component adopts hollow fiber hydrophobic membrane filaments, the material is PVDF or PTEF, and the total membrane area is 125m2The membrane component is operated in two stages in series, and the single-stage operation pressure is 1.0-1.2 Mpa; the strong acid absorption adopts concentrated sulfuric acid with the concentration of 98 percent, and the pH value of the drawing side is maintained to be about 0.2.
The water produced by the degassing membrane deamination module 8 enters a clean water tank 9, namely a complete process chain for the full-scale harmless treatment of the landfill leachate in the embodiment is completed, and the removal effect of each process module is shown in the following table:
table 2: module removal rate analysis of leachate treatment process in large domestic refuse field in Wuhan city, Hubei province
Figure BDA0002823663840000151
Figure BDA0002823663840000161
As can be seen from the above table, in example 2, by using the garbage leachate total harmless treatment process module and the treatment method of the present invention, the produced water can meet the standard requirements in table 2 of the pollution control standard for landfill of domestic waste (GB16889-2008), the water production rate is greater than 95%, and no concentrated solution or other secondary pollutants are generated. The whole process module has strong water quality and water quantity load resistance, and is economical, efficient, green and environment-friendly.
The invention has the following outstanding characteristics and obvious benefits:
(1) the process combination is reasonable and efficient. On the basic premise of ensuring that the final produced water is qualified and reaches the standard, the water production rate is close to 95 percent, secondary pollutants such as membrane concentrated solution and the like are not generated, zero discharge of leachate treatment is realized, and the method is green and environment-friendly;
(2) the whole process has strong water quality and water fluctuation resistance. In the process, a plurality of independent treatment modules can immediately respond according to the water quality and water quantity change of the wastewater to be treated, for example, the modules such as CWAO, MFR, degassing membrane deamination and the like can control the pollutant removal efficiency by controlling the reaction conditions, increasing or decreasing core equipment elements, adjusting the dosage and the like; the whole process has strong control and regulation capability and strong impact load resistance capability, and can meet the treatment requirements of the landfill leachate on water quality and water quantity fluctuation in different periods.
(3) The process has low operation cost, reduces the consumption of carbon sources and medicaments in the traditional treatment process, can reduce the operation cost of 80-100 yuan ton of water to within 55 yuan, and has obvious economic and social benefits.
The invention aims to overcome the defects of the prior art and provide a full-scale harmless treatment process for landfill leachate, which utilizes a combined advanced oxidation technology to replace a membrane separation advanced treatment unit. The process integrates the advanced technology in the aspect of treating high-concentration organic wastewater at home and abroad and is combined with the Fenton-like catalytic oxidation technology which is independently researched and developed, a set of novel garbage leachate treatment process route is developed, the current mainstream treatment process can be completely replaced, the defects and the problems of the mainstream process are solved on the premise of ensuring the treatment to reach the standard, the impact load resistance and the operation stability of a module are improved, no secondary pollutant is generated, and the process is green and environment-friendly.
The above examples are merely illustrative of the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims and any design similar or equivalent to the scope of the invention.

Claims (10)

1. A full-scale harmless treatment method for landfill leachate is characterized by comprising the following steps:
s1: the pretreatment comprises the steps of performing pre-aeration and pre-coagulating sedimentation on leachate stock solution of a regulating reservoir of the refuse landfill;
s2: catalytic wet oxidation (CWAO) treatment, which comprises converting organic matters and nitrogen-containing substances in the leachate into CO by high-temperature high-pressure wet catalytic oxidation of the pretreated effluent2，H2O and N2And the like;
s3: membrane Bioreactor (MBR) treatment, which specifically comprises removing biodegradable organic matters and ammonia nitrogen pollutants in the percolate after CWAO treatment by two-stage nitrification-denitrification;
s4: performing Membrane Fenton Reactor (MFR) treatment, specifically performing advanced treatment on organic pollutants which are not biochemically degradable in the leachate after the MBR treatment through a Fenton-like catalytic oxidation system to meet the COD index discharge requirement;
s5: the deamination treatment of the degassing membrane specifically comprises the steps of extracting ammonia nitrogen from residual ammonia nitrogen pollutants in leachate after the MBR and MFR treatment by utilizing the combined action of strong acid and a gaseous membrane, and deeply treating tail water to NH4N and TN target emission requirements.
2. The method for harmless treatment of full quantity of landfill leachate according to claim 1, wherein the method comprises the following steps: the pretreatment comprises the steps of firstly introducing compressed air into the raw liquid of the landfill leachate, changing a liquid-phase buffer system under the conditions of preset retention time and aeration rate, and then adding sodium carbonate (Na)2CO3) And adjusting the pH value of the wastewater to 8-9.5 by using sodium hydroxide (NaOH), so that calcium and magnesium ions in the wastewater form precipitates, adding polyaluminum chloride (PAC) and Polyacrylamide (PAM), uniformly stirring, and settling calcium and magnesium floccules and suspended substances in the wastewater through a coagulating sedimentation effect to improve the quality of leachate.
3. The method for harmless treatment of full quantity of landfill leachate according to claim 1, wherein the method comprises the following steps: the catalytic wet oxidation (CWAO) comprises the step of introducing the pretreated landfill leachate into a specific CWAO for catalytic oxidationThe module heats up the wastewater through the heat exchanger, uniformly mixes the compressed air and the heated wastewater through the steam-water mixer, then introduces the mixture into the main reaction tower of the batch type stirring kettle, and respectively oxidizes and decomposes organic matters and nitrogenous substances in the leachate into substances containing CO through the combined oxidation of air and an oxidizing agent under the action of preset temperature, pressure and catalyst2，H2O and N2The substance of (1).
4. The method for harmless treatment of full quantity of landfill leachate according to claim 1, wherein the method comprises the following steps: the Membrane Bioreactor (MBR) comprises a biochemical treatment module and an external tubular membrane ultrafiltration module; the biochemical treatment module comprises a primary denitrification tank, a primary nitrification tank, a secondary denitrification tank and a secondary nitrification tank, wherein submersible mixers are arranged in the primary denitrification tank and the secondary denitrification tank for continuous stirring, so that the sludge concentration in the tanks is ensured to be uniform; jet aeration devices are arranged in the primary nitrification tank and the secondary nitrification tank for blast aeration, so that the concentration of dissolved oxygen in the tanks is maintained at 2-5 mg/L; pumping the CWAO effluent into a primary denitrification tank, then respectively flowing into a primary nitrification tank, a secondary denitrification tank and a secondary nitrification tank along with the overflow direction, lifting the effluent of the secondary nitrification tank to an external tubular ultrafiltration membrane module by a water pump, and refluxing ultrafiltration concentrate to the primary denitrification tank; meanwhile, a mixed liquid reflux pump is arranged between the first-stage denitrification tank and the first-stage nitrification tank to reflux the nitrified liquid in the first-stage nitrification tank to the first-stage denitrification tank.
5. The method for harmless treatment of full quantity of landfill leachate according to claim 1, wherein the method comprises the following steps: the Membrane Fenton Reactor (MFR) comprises a Fenton-like catalytic oxidation module and an internal microfiltration membrane module;
the MBR discharges water and then enters an MFR reactor, and the pH is adjusted to 4-4.5, so that the organic pollutants which cannot be biochemically degraded are further mineralized and decomposed into CO under the combined action of the Fenton-like composite catalyst and the oxidizing agent2And H2O; meanwhile, the built-in microfiltration membrane is used for replacing the traditional secondary sedimentation tank to intercept suspended substances in the wastewater.
6. The method for harmless treatment of full quantity of landfill leachate according to claim 1, wherein the method comprises the following steps: step S5 specifically includes: and adjusting the pH value of the MFR effluent to 9-11, adjusting the temperature to 35 ℃, converting free ammonia nitrogen pollutants in the wastewater into ammonia gas under the action of a hydrophobic hollow fiber membrane, and converting the ammonia gas into ammonium salt to be discharged after the ammonia gas is absorbed by a strong acid side.
7. The method for harmless treatment of full quantity of landfill leachate according to claim 1, wherein the method comprises the following steps: and (4) collecting the chemical sludge generated in the steps S1 and S4 and the biochemical sludge generated in the step S3 to a sludge conditioning tank, dehydrating the chemical sludge and the biochemical sludge by a sludge filter-pressing module, and then sending the chemical sludge and the biochemical sludge to a designated landfill site for landfill.
8. The method for harmless treatment of full quantity of landfill leachate according to claim 1, wherein the method comprises the following steps: step S4 further includes: and converting the residual organic nitrogen after the MBR treatment into an ammonia nitrogen form.
9. The utility model provides a landfill leachate total innocent treatment system which characterized in that: the module is used for treating the leachate stock solution of the landfill conditioning tank according to the full-scale harmless treatment method of landfill leachate of any one of claims 1 to 8.
10. The landfill leachate total innocent treatment system of claim 9, wherein: the system comprises a pretreatment module, a CWAO catalytic wet oxidation module, an MBR membrane bioreactor module, an MFR membrane Fenton reactor module, a degassing membrane deamination module, a clean water tank, a sludge concentration tank and a sludge treatment module which are sequentially connected through a pipeline.
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