CN117509979A - System and method for classifying and treating garbage percolate concentrate pollutants - Google Patents
System and method for classifying and treating garbage percolate concentrate pollutants Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 33
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 33
- 239000012141 concentrate Substances 0.000 title claims description 16
- 238000011282 treatment Methods 0.000 claims abstract description 96
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 64
- 230000003647 oxidation Effects 0.000 claims abstract description 33
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 33
- 238000004062 sedimentation Methods 0.000 claims abstract description 26
- 230000001112 coagulating effect Effects 0.000 claims abstract description 23
- 239000012528 membrane Substances 0.000 claims abstract description 20
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- 230000008878 coupling Effects 0.000 claims abstract description 10
- 238000010168 coupling process Methods 0.000 claims abstract description 10
- 238000005859 coupling reaction Methods 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 70
- 238000006243 chemical reaction Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 230000001105 regulatory effect Effects 0.000 claims description 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 16
- 239000010439 graphite Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 238000005516 engineering process Methods 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 15
- 239000006228 supernatant Substances 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 10
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 239000004571 lime Substances 0.000 claims description 10
- 239000004902 Softening Agent Substances 0.000 claims description 9
- 239000000701 coagulant Substances 0.000 claims description 8
- 238000001728 nano-filtration Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000001223 reverse osmosis Methods 0.000 claims description 7
- 238000005189 flocculation Methods 0.000 claims description 6
- 230000016615 flocculation Effects 0.000 claims description 6
- 238000006385 ozonation reaction Methods 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 208000034699 Vitreous floaters Diseases 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000005518 electrochemistry Effects 0.000 claims description 3
- 239000008394 flocculating agent Substances 0.000 claims description 3
- 230000002195 synergetic effect Effects 0.000 claims description 3
- 238000011369 optimal treatment Methods 0.000 claims description 2
- 239000007793 ph indicator Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 17
- 239000000149 chemical water pollutant Substances 0.000 abstract description 14
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 238000009303 advanced oxidation process reaction Methods 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 238000004904 shortening Methods 0.000 abstract 1
- 239000000725 suspension Substances 0.000 abstract 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 9
- 239000011575 calcium Substances 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 238000005374 membrane filtration Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000004021 humic acid Substances 0.000 description 2
- 229910001410 inorganic ion Inorganic materials 0.000 description 2
- 231100001240 inorganic pollutant Toxicity 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000005842 biochemical reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910021432 inorganic complex Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- -1 salt ions Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- 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
- C02F1/5281—Installations for water purification using chemical 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
- C02F1/66—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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/05—Conductivity or salinity
- C02F2209/055—Hardness
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
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- 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
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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
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/02—Softening water by precipitation of the hardness
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Abstract
The invention discloses a system and a method for classifying and treating garbage leachate concentrated solution pollutants, wherein inorganic matters and a part of organic pollutants are removed by utilizing softening and coagulating sedimentation; the softening treatment unit not only can be used for reducing the problems of scaling of a subsequent pipeline and scaling of a membrane, but also can improve the treatment efficiency of a subsequent advanced oxidation process, so that the degradation of organic matters in the concentrated solution is more thorough; the purpose of coagulating sedimentation after softening: removing suspended matters formed after softening, accelerating the precipitation of the suspension and shortening the precipitation time; removing excessive medicament added in the softening process and carrying the excessive medicament to remove a part of other pollutants; solves the problem of poor precipitation performance in the softening process. In this embodiment, the purpose of the electrochemical coupling ozone advanced oxidation treatment process is: and removing the degradation-resistant DOM in the concentrated solution. The technical scheme of the application can well realize the grading treatment of the landfill leachate concentrated solution, so that the COD removal rate in the concentrated solution reaches more than 80%, and the hardness removal rate reaches more than 90%.
Description
Technical Field
The invention relates to the technical field of pollutant classification treatment, in particular to a system and a method for classifying and treating garbage percolate concentrate pollutants.
Background
The landfill leachate is wastewater which is complex in components and high in humic acid content and is difficult to biochemically degrade, a combined process of pretreatment, biochemical treatment and membrane advanced treatment is mainly adopted to solve a large amount of landfill leachate, a better leachate treatment effect can be achieved through the combined use of different treatment technologies, and concentrated solution accounting for about 13-30% of the volume of the leachate after advanced treatment is generated in the treatment process. The concentrated solution has the characteristics of high hardness, high salinity, poor biodegradability, complex pollutant components, difficult degradation, large production quantity and the like. The existing evaporation and recharging technology has the problems of high cost, great environmental hazard and the like, and the concentrated solution still cannot be treated effectively finally. Therefore, an effective concentrated solution treatment system is developed, and the system has great significance for the treatment of the existing percolate concentrated solution.
Based on the existing treatment process, a system for treating the percolate concentrated solution in a grading manner is developed, pollutant components in the percolate concentrated solution are classified, and are not treated simultaneously as a whole, and a treatment method conforming to different pollutants is constructed in a targeted manner, so that the key point that the pollutants are difficult to degrade and are not completely treated is solved.
The invention provides a grading treatment mode, which mainly comprises a chemical softening unit aiming at hardness ions, a coagulating sedimentation unit for macromolecular substances, a high-grade oxidation unit aiming at refractory organic pollutants, and a membrane separation unit aiming at high-grade oxidative degradation of micromolecular substances and refractory substances. The invention has the advantages of strong pertinence to remove different pollutants, good removing effect, wide application and the like.
At the present stage, the main treatment technologies are recharging, evaporating, advanced oxidation and the like due to the characteristics of various pollutants, complex water quality components, high humic acid, high salt ions and the like of the percolate concentrated solution;
the treatment difficulty of the percolate concentrated solution generated by the conventional technology of biochemical and membrane filtration is mainly that the treatment efficiency is low due to the mixing of the Dissolved Organic Matters (DOM), inorganic salt ions and metal ions. Based on the characteristics, the prior art comprises 'biochemical reaction, fenton reaction, electrolysis, membrane advanced treatment', 'membrane separation, softening, reverse osmosis' and the like.
Aiming at the prior art of percolate concentrate treatment, inorganic ions and complexes formed by the inorganic ions have quenching effect on free radicals in the advanced oxidation process, and meanwhile, the efficiency in the advanced oxidation process is reduced. Meanwhile, inorganic salt ions in the landfill leachate concentrated solution can be deposited on a polar plate of an electrochemical system in the treatment process, so that the current effect of the polar plate is blocked, and the efficiency of the electrode is reduced. In addition, the high-concentration hardness ions can aggravate the problems of scaling of a percolate conveying pipeline, scaling of a subsequent advanced treatment film and the like;
aiming at the conventional combined process of percolate concentrate, the main principle is that an advanced oxidation technology converts refractory organic matters into small molecular organic matters, and the small molecular organic matters enter a membrane advanced treatment unit for separation. The advanced oxidation technology is only effective for organic matters, and cannot remove inorganic pollutants, wherein the inorganic pollutants such as heavy metal ions of calcium, magnesium and the like can be enriched on the surface of an electrode, and become key components for limiting the efficiency of an electrochemical device.
Therefore, the pollutant classification refinement in the percolate concentrated solution is not carried out as a whole research, the development of classification treatment measures aiming at different pollutants in the concentrated solution is a key for solving the problem of difficult degradation of pollutants in the percolate treatment process by constructing a classification treatment technology conforming to the difficulty in the percolate treatment process. The invention provides a percolate concentrated solution grading treatment system which mainly comprises a chemical softening unit aiming at hardness ions, a coagulating sedimentation unit aiming at macromolecular substances, a high-grade oxidation treatment unit aiming at refractory organic substances and a membrane separation system aiming at micromolecular substances, so as to achieve the aim of stable standard-reaching treatment of the percolate concentrated solution.
Disclosure of Invention
The invention aims to provide a system and a method for classifying and treating garbage leachate concentrated solution pollutants, which solve the problems that pollutants are difficult to degrade and incomplete to remove in the existing garbage leachate treatment process.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a method for classifying and treating garbage leachate concentrated solution pollutants, which comprises the following steps:
s1, adding a softening agent into garbage percolate for softening to obtain a softening liquid;
s2, adding a flocculating agent into the softening liquid obtained in the step 1, performing flocculation precipitation to obtain flocculation liquid, and obtaining supernatant after precipitation;
s3, mixing the supernatant obtained in the step 2 with ozone, and then passing through a reactor provided with an electrochemical device from bottom to top to perform advanced oxidation treatment, wherein oxidized water is treated by a nanofiltration/reverse osmosis system and then discharged;
wherein the electrochemical plate in step 3 is reusable.
Preferably, wherein the softening agent used in S1 is selected according to the nature of the percolate concentrate, it comprises at least two of:
(1) For concentrates with hardness values (calculated as calcium ions) higher than alkalinity values (calculated as carbonate ions), softening with sodium hydroxide alone;
(2) The concentrated solution with hardness value (calculated by calcium ion) lower than alkalinity value (calculated by carbonate ion) is treated by adopting a double-alkali softening method of sodium hydroxide and sodium carbonate.
Preferably, the flocculant in S2 is preferably PAFC; the PAFC can not only precipitate macromolecular substances or colloids in the softened suspended matters and concentrated solution, but also promote the reaction of unsaturated hydrocarbons and ozone in a subsequent advanced oxidation treatment unit, or change the structure of the unsaturated hydrocarbons to enable the unsaturated hydrocarbons to react with ozone more easily, so that the ozonization treatment efficiency is improved.
Preferably, the supernatant in S3 is mixed with ozone into water and the residence time in the ozone reactor is 60 to 120min.
Preferably, in S3 the electrochemical plate of the ozone reactor: the anode is Ti 4 O 7 The cathode is graphite;
wherein Ti is 4 O 7 As an anode, the electrochemical device has higher efficiency;
the graphite cathode is part of the electrochemical device and acts as a catalyst and adsorbent in the ozone reactor, respectively.
The treatment method can well treat the landfill leachate concentrated solution, so that the COD removal rate in the concentrated solution is more than 80%, and the hardness removal rate is more than 90%.
Preferably, it includes a softening treatment unit, a coagulating sedimentation unit, a high-grade oxidation treatment unit, and a membrane treatment unit.
Preferably, the softening treatment unit comprises a sodium hydroxide regulating tank, a sodium carbonate reaction chamber and a lime reaction chamber;
the pH value of the inlet water is regulated to 11.5-12.5 by the sodium hydroxide regulating tank so as to ensure the optimal treatment condition of the softening treatment unit, and the inlet water is stirred and mixed by the sodium carbonate and lime reaction chamber, and the mixture is left to stand after full reaction, so that the separation of hardness ions is realized.
Preferably, the advanced oxidation treatment unit comprises an ozone reactor and a gas-liquid mixing pump;
wherein Ti is 4 O 7 As anodeThe graphite is used as an electrochemical device of a cathode, is arranged in a reactor, and is mixed with ozone water entering the reactor to form an advanced oxidation technology of electrochemical coupling micro-nano ozone;
the ozone and percolate concentrated solution is changed into concentrated solution rich in ozone microbubbles after passing through the gas-liquid mixing pump, and then enters the ozone reactor, catalytic ozonation reaction occurs under the synergistic effect of electrochemistry, the gas-liquid mixing pump and the ozone reactor are connected in sequence, and the two electrodes are arranged in the ozone reactor.
Preferably, the membrane treatment unit comprises a nanofiltration/reverse osmosis membrane for separating and removing small molecular substances and residual substances;
the front end of the sodium hydroxide regulating tank is connected with raw water, and a screen is arranged at the raw water inlet end so as to filter large-scale floaters; an automatic pH indicator is arranged in the sodium hydroxide regulating tank, a set of alkali liquor dosing system is arranged outside the sodium hydroxide regulating tank, alkali liquor is added into the sodium hydroxide regulating tank, and the pH is regulated to 11.5-12.5;
the three reaction chambers of the softening treatment unit are respectively provided with an oil stirrer and a baffle, wherein the stirrer is used for accelerating the mixing of the administered agent and the concentrated solution, and the baffle is used for accelerating the separation of the precipitate and the concentrated solution after the reaction and preventing the stirrer from carrying the precipitate again;
the coagulating sedimentation system is provided with a pH meter, a stirrer and two sets of dosing systems outside, wherein one set of dosing systems is used for dosing acid liquor for adjusting pH, and the other set of dosing systems is used for dosing coagulating agents.
Compared with the prior art, the invention has the following beneficial technical effects:
1) The system for classifying different types of pollutants of the percolate concentrate is developed, and the key for solving the problem of difficult treatment is to pertinently construct a classification technology which meets the complex characteristic of the pollutant components of the concentrate.
2) Softening and coagulating sedimentation are key to improving the performance of the subsequent advanced oxidation treatment technology, and scale ions and part of other metal ions in the advanced oxidation treatment technology are removed by using softening, so that the influence of inorganic metal ions and complexes thereof on the advanced oxidation process is reduced. Meanwhile, the scaling problem in the pipeline and the subsequent film advanced treatment process can be greatly reduced by softening, and the service life of the device is prolonged.
3) The phenomenon that hardness ions scale on the surface of an electrode in the electrochemical coupling ozone treatment process can be effectively relieved by removing the hardness ions, and the degradation efficiency of the electrochemical coupling ozone on DOM in the landfill leachate concentrated solution is improved. The coagulating sedimentation can improve the sedimentation performance, quicken the sedimentation of colloid and suspended matters, and simultaneously remove excessive softening agent and partial organic pollutants. Ti (Ti) 4 O 7 The electrode can promote the generation of electrode surface adsorptivity OH, and compared with the traditional OH, the free radical has stronger oxidizing capability and can degrade organic matters more thoroughly. Meanwhile, the electrochemical and ozone coupling can greatly improve the degradation efficiency of organic matters.
Graphite is used as a cathode to form a part of an electrochemical device, can be used as a catalyst of ozone to improve the efficiency of converting ozone into free radicals, and can be used as an adsorbent to adsorb and remove a part of micromolecular organic matters generated after advanced oxidation. When obvious scaling substances are generated on the surface of the graphite electrode, desorption is completed by immersing the graphite electrode in 1mol/L hydrochloric acid solution for 6 hours.
Drawings
The invention is further described with reference to the following description of the drawings.
FIG. 1 is a block diagram of a system for classifying the contaminants in a landfill leachate concentrate according to the present invention.
Detailed Description
Softening, coagulating sedimentation is utilized to remove inorganic matters and a part of organic pollutants;
the softening treatment unit is used for reducing the problems of scaling of a subsequent pipeline and scaling of a membrane, so that the efficiency of subsequent advanced oxidation treatment is improved, and the membrane filtration concentrated solution is subjected to reduction treatment by a plurality of stages of membranes after being treated;
the purpose of coagulating sedimentation after softening: excessive medicament in the softening process softens other inorganic matters which are not removed, and improves the precipitation problem of poor precipitation performance in softening;
in this example, the purpose of the electrochemical coupling ozone treatment process is: and removing the degradation-resistant DOM in the concentrated solution.
In order to achieve the technical aim, the invention provides a treatment method of landfill leachate concentrated solution, which can effectively remove hardness, heavy metal ions, COD, macromolecular suspended substances, colloid and organic matters in the leachate concentrated solution, has simple operation and low treatment cost, and can recycle a catalyst in the advanced oxidation process; the method comprises the following steps:
adding a softening agent into the landfill leachate to soften the landfill leachate to obtain a softened solution;
adding a flocculating agent into the softening liquid obtained in the step 1, performing flocculation precipitation to obtain flocculation liquid, and obtaining supernatant after precipitation;
mixing the supernatant obtained in the step 2 with ozone, then passing through an ozone reactor filled with a catalyst from bottom to top, performing advanced oxidation treatment, and discharging water after the oxidized water is treated by a nanofiltration/reverse osmosis system.
The electrochemical plate in step 3 can be reused.
In this example, the softening agent in step 1 is selected according to the nature of the percolate concentrate, and there are mainly two types: firstly, for concentrated solution with high hardness and low alkalinity, sodium hydroxide is singly used for softening; and secondly, treating the concentrated solution with low hardness and high alkalinity by adopting a double-alkali softening method of sodium hydroxide and sodium carbonate.
Preferably, the flocculant in the step 2 selects PAFC, and the addition of PAFC not only can precipitate the softened suspended matters and macromolecular substances or colloids in the concentrated solution, but also can promote the reaction of unsaturated hydrocarbons and ozone in the subsequent advanced oxidation treatment unit, or change the structure of the unsaturated hydrocarbons to make the unsaturated hydrocarbons more easily react with ozone, thereby improving the ozonization efficiency.
Preferably, the residence time of the supernatant liquid and the ozone mixed water in the step 3 in the ozone reactor is 60-120min.
Preferably, the plate is shown with anode of Ti 4 O 7 The cathode is graphite. Ti (Ti) 4 O 7 The graphite cathode can be part of the electrochemical device, and the graphite can also be used as a catalyst and an adsorbent in an ozone reactor.
The treatment method can well treat the landfill leachate concentrated solution, so that the COD removal rate in the concentrated solution is more than 80%, and the hardness removal rate is more than 90%.
The invention provides a system and a method for classifying and treating pollutants in landfill leachate concentrated solution, which comprise a softening treatment unit, a coagulating sedimentation unit, an advanced oxidation treatment unit and a membrane treatment unit.
The softening treatment unit comprises a sodium hydroxide regulating tank, a sodium carbonate reaction chamber and a lime reaction chamber, wherein the pH value of the inlet water is regulated to 11.5-12.5 by the sodium hydroxide regulating tank to ensure the optimal softening treatment condition, and the inlet water is stirred and mixed by the sodium carbonate and the lime reaction chamber, and the inlet water is left stand after full reaction, so that the separation of main hardness ions such as calcium, magnesium and the like is realized, the pipeline scaling in the subsequent treatment unit and the membrane scaling of the membrane treatment unit can be effectively prevented, and the treatment efficiency of the subsequent advanced oxidation is improved. The addition of the softening agent can remove part of other inorganic metal cations, so that the removal efficiency of the metal ions is improved, and the effluent is discharged up to the standard.
The coagulating sedimentation unit not only can remove excessive softening agent added in the softening process and solve the problem of poor sedimentation performance in the softening process, but also can remove other pollutants. The coagulant PAFC is mainly added in coagulating sedimentation, so that pollutants can be precipitated by adding the coagulant, and meanwhile, the reaction of unsaturated hydrocarbon and ozone in a subsequent advanced oxidation treatment unit can be promoted, or the structure of the unsaturated hydrocarbon is changed to enable the unsaturated hydrocarbon to react with ozone more easily, so that the ozonization treatment efficiency is improved.
The supernatant after coagulating sedimentation does not need to carry out additional pH adjustment before entering an ozone reactor, and the alkalescent supernatant is beneficial to improving the oxidation efficiency of the subsequent ozone treatment.
The advanced oxidation treatment unit comprises an ozone reactor and a gas-liquid mixing pump (a micro-bubble generator)Green device), ti 4 O 7 As an anode, graphite is used as a cathode to form an electrochemical coupling advanced oxidation technology of micro-nano ozone. Ti (Ti) 4 O 7 The graphite as the cathode not only forms part of the electrochemical device, but also can be used as a catalyst and an adsorbent in ozone reaction. In addition, ti 4 O 7 In an electrochemically coupled ozone treatment system as an anode, ti 4 O 7 The existence of the electrode can generate a physical OH which is adsorbed on the surface of the anode, and the free radical can thoroughly degrade organic matters, so that the removal efficiency of the organic matters in the percolate concentrated solution is improved. Ozone and percolate concentrated solution are changed into concentrated solution rich in ozone microbubbles after passing through a gas-liquid mixing pump, catalytic ozonation reaction is carried out under the synergistic effect of electrochemistry after entering an ozone reactor, the gas-liquid mixing pump and the ozone reactor are connected in sequence, and electrodes are arranged in the ozone reactor.
The membrane treatment unit comprises a nanofiltration/reverse osmosis membrane, so as to realize separation and removal of small molecular substances and other residual substances.
The front end of the sodium hydroxide regulating tank is connected with raw water, a screen is arranged at the raw water inlet end for filtering large-scale floaters, an automatic pH display is arranged in the sodium hydroxide regulating tank, a set of alkali liquor dosing system is arranged outside the sodium hydroxide regulating tank, and alkali liquor is added into the regulating tank to regulate the pH to 11.5-12.5. The three reaction chambers of the softening treatment unit are respectively provided with a stirrer and a baffle, the stirrer accelerates the mixing of the chemical dosing agent and the concentrated solution, and the baffle is used for accelerating the separation of the precipitate and the concentrated solution after the reaction and preventing the stirrer from rolling up the precipitate again.
The coagulating sedimentation system is provided with a pH meter, a stirrer and two sets of dosing systems outside, one set of dosing system is used for dosing acid liquor for adjusting pH, the other set of dosing system is used for dosing a coagulating agent, and the coagulating agent is PAFC.
Application example 1
The embodiment discloses a system and a method for classifying and treating garbage leachate concentrated solution pollutants,
the landfill leachate concentrated solution is obtained from nanofiltration concentrated solution of a landfill in Shanghai, and has COD concentration of 4500-6000mg/L and total hardness of 10000-15000mg/L.
Through softening treatment unit, naOH is used to regulate pH value to 11.5-12.5, and then the water enters sodium carbonate reaction chamber, according to the relation between alkalinity and hardness of water, ca (OH) is added if the alkalinity is high and the hardness is low 2 Softening. If the hardness is high and the alkalinity is low, caCO is selected 3 +Ca(OH) 2 Softening by double alkali method.
Firstly, the water in the regulating tank enters a sodium carbonate reaction chamber, and the adding amount is CaCO (CaCO) determined according to the hardness-alkalinity 3 Stirring at 100rpm for 2min, stirring at 60rpm for 18min, standing for 30min, and feeding into lime reaction chamber to obtain residual Ca 2+ 、Mg 2+ The required amount of complete precipitation is firstly stirred for 2min at the speed of 100rpm, then stirred for 18min at the speed of 60rpm, and stood for 30min, so that the removal rate of the hardness ions above 90% and the removal rate of COD of 5-20% can be finally realized. And (5) allowing the supernatant after precipitation to enter a subsequent coagulating sedimentation treatment unit.
And through a coagulating sedimentation treatment unit, PAFC is taken as a coagulant, the adding amount of the PAFC is 4g/L, stirring is carried out for 30min after the adding, and standing is carried out for 30min, so that the COD removal rate is more than 10%. And (5) allowing the supernatant after coagulating sedimentation to enter a subsequent advanced oxidation treatment unit.
The ozone generator is treated by an electrochemical coupling micro-nano ozone advanced oxidation technology treatment unit, the air inlet of the ozone generator is high-purity oxygen, the ozone flow is 1L/min, the ozone concentration is 80-100mg/L, and the electrochemical device part is made of Ti 4 O 7 Graphite as anode and cathode with electrochemical current of 30-40mA/cm 2 The COD removal rate can reach more than 70%.
After the effluent of the advanced oxidation treatment unit passes through the membrane filtration treatment unit, the COD (chemical oxygen demand) of the final effluent is less than 100mg/L, and Ca 2+ 、Mg 2+ Less than 10mg/L.
Application example 2
The landfill leachate concentrated solution is obtained from nanofiltration concentrated solution of a landfill of Shanghai, and has COD concentration of 4500-6000mg/L and total hardness of 10000-15000mg/L.
The garbage percolate concentrate is directly used in a softening treatment unitNaOH is used for regulating the pH value to 12.0, the stirring is firstly carried out for 2min at the speed of 100rpm, then the stirring is carried out for 18min at the speed of 60rpm, the mixture is stood for 30min, then the mixture enters a lime reaction chamber, and the lime adding amount is the rest Ca 2+ 、Mg 2+ The required amount of complete precipitation is firstly stirred for 2min at the speed of 100rpm, then stirred for 18min at the speed of 60rpm, and stood for 30min, so that the removal rate of the hardness ions above 90% and the removal rate of COD of 5-20% can be finally realized. And (5) allowing the supernatant after precipitation to enter a subsequent coagulating sedimentation treatment unit. The sodium carbonate and lime reaction chambers do not need to be added with medicaments.
And through a coagulating sedimentation treatment unit, PAFC is taken as a coagulant, the adding amount of the PAFC is 4g/L, stirring is carried out for 30min after the adding, and standing is carried out for 30min, so that the COD removal rate is more than 10%. And (5) allowing the supernatant after coagulating sedimentation to enter a subsequent advanced oxidation treatment unit.
The ozone generator is treated by an electrochemical coupling micro-nano ozone advanced oxidation technology treatment unit, the air inlet of the ozone generator is high-purity oxygen, the ozone flow is 1L/min, the ozone concentration is 80-100mg/L, and the electrochemical device part is made of Ti 4 O 7 Graphite as anode and cathode with electrochemical current of 30-40mA/cm 2 The COD removal rate can reach more than 70%.
After the effluent of the advanced oxidation treatment unit passes through the membrane filtration treatment unit, the COD (chemical oxygen demand) of the final effluent is less than 100mg/L, and Ca 2+ 、Mg 2+ Less than 10mg/L.
The foregoing embodiments are merely illustrative of the preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to which the present invention pertains should fall within the scope of the invention as defined in the appended claims without departing from the spirit of the invention.
Claims (9)
1. A method for classifying and treating garbage percolate concentrate pollutants is characterized by comprising the following steps of: the method comprises the following steps:
s1, adding a softening agent into garbage percolate for softening to obtain a softening liquid;
s2, adding a flocculating agent into the softening liquid obtained in the step 1, performing flocculation precipitation to obtain flocculation liquid, and obtaining supernatant after precipitation;
s3, mixing the supernatant obtained in the step 2 with ozone, and then passing through a reactor provided with an electrochemical device from bottom to top to perform advanced oxidation treatment, wherein oxidized water is treated by a nanofiltration/reverse osmosis system and then discharged;
wherein the electrochemical plate in step 3 is reusable.
2. The method for classifying the garbage leachate concentrated solution pollutants according to claim 1, which is characterized in that: wherein the softening agent used in S1 is selected according to the nature of the percolate concentrate, and comprises at least two of:
(1) For concentrates with hardness values (calculated as calcium ions) higher than alkalinity values (calculated as carbonate ions), softening with sodium hydroxide alone;
(2) The concentrated solution with hardness value (calculated by calcium ion) lower than alkalinity value (calculated by carbonate ion) is treated by adopting a double-alkali softening method of sodium hydroxide and sodium carbonate.
3. The method for classifying the garbage leachate concentrated solution pollutants according to claim 1, which is characterized in that: the flocculant in S2 is preferably PAFC.
4. The method for classifying the garbage leachate concentrated solution pollutants according to claim 1, which is characterized in that: the supernatant liquid in S3 is mixed with ozone into water, and the residence time in the reactor is 60-120min.
5. The method for classifying the garbage leachate concentrated solution pollutants according to claim 1, which is characterized in that: in S3, electrochemical plates of the ozone reactor: the anode is Ti 4 O 7 The cathode is graphite;
wherein Ti is 4 O 7 As an anode, the ozone mixed water has higher efficiency after entering the reactor;
the graphite cathode is not only part of the electrochemical device, but also serves as a catalyst and adsorbent during the reaction.
6. The method for classifying the garbage leachate concentrated solution pollutants according to claim 1, which is characterized in that: which comprises a softening treatment unit, a coagulating sedimentation unit, an advanced oxidation treatment unit and a membrane treatment unit.
7. The method for classifying the garbage leachate concentrated solution pollutants according to claim 6, which is characterized in that: the softening treatment unit comprises a sodium hydroxide regulating tank, a sodium carbonate reaction chamber and a lime reaction chamber;
the pH value of the inlet water is regulated to 11.5-12.5 by the sodium hydroxide regulating tank so as to ensure the optimal treatment condition of the softening treatment unit, and the inlet water is stirred and mixed by the sodium carbonate and lime reaction chamber, and the mixture is left to stand after full reaction, so that the separation of hardness ions is realized.
8. The method for classifying the garbage leachate concentrated solution pollutants according to claim 6, which is characterized in that: the advanced oxidation treatment unit comprises an ozone reactor and a gas-liquid mixing pump;
wherein Ti is 4 O 7 An electrochemical device which is used as an anode and graphite is used as a cathode is arranged in a reactor, and is mixed with ozone water entering the reactor to form an advanced oxidation technology of electrochemical coupling micro-nano ozone;
the ozone and percolate concentrated solution is changed into concentrated solution rich in ozone microbubbles after passing through the gas-liquid mixing pump, and then enters the ozone reactor, catalytic ozonation reaction occurs under the synergistic effect of electrochemistry, the gas-liquid mixing pump and the ozone reactor are connected in sequence, and the two electrodes are arranged in the ozone reactor.
9. The method for classifying the garbage percolate concentrate pollutant according to claim 7, which is characterized in that: the membrane treatment unit comprises a nanofiltration/reverse osmosis membrane and is used for separating and removing small molecular substances and residual substances;
the front end of the sodium hydroxide regulating tank is connected with raw water, and a screen is arranged at the raw water inlet end so as to filter large-scale floaters; an automatic pH indicator is arranged in the sodium hydroxide regulating tank, a set of alkali liquor dosing system is arranged outside the sodium hydroxide regulating tank, alkali liquor is added into the sodium hydroxide regulating tank, and the pH is regulated to 11.5-12.5;
the three reaction chambers of the softening treatment unit are respectively provided with an oil stirrer and a baffle, wherein the stirrer is used for accelerating the mixing of the administered agent and the concentrated solution, and the baffle is used for accelerating the separation of the precipitate and the concentrated solution after the reaction and preventing the stirrer from carrying the precipitate again;
the coagulating sedimentation system is provided with a pH meter, a stirrer and two sets of dosing systems outside, wherein one set of dosing systems is used for dosing acid liquor for adjusting pH, and the other set of dosing systems is used for dosing coagulating agents.
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