CN103936201B - Fenton method associating supercritical water oxidation method treating refuse percolate - Google Patents
Fenton method associating supercritical water oxidation method treating refuse percolate Download PDFInfo
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- CN103936201B CN103936201B CN201410179876.7A CN201410179876A CN103936201B CN 103936201 B CN103936201 B CN 103936201B CN 201410179876 A CN201410179876 A CN 201410179876A CN 103936201 B CN103936201 B CN 103936201B
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Abstract
The invention discloses a kind of Fenton method associating supercritical water oxidation method treating refuse percolate, first Fenton method pretreating waste percolate is adopted, supercritical water oxidation method will be adopted to carry out advanced treatment through pretreated percolate, react the rear purification realizing percolate.The present invention can make the pollutents such as the COD in percolate, ammonia nitrogen, colourity all can efficiently be removed, and Pollutant Treatment is comparatively thorough, is swift in response, water outlet water white transparency; Processing cost is adjusted, and average removal 1 ton of COD, Fenton method associating supercritical water oxidation method treatment process is than adopting separately supercritical water oxidation method running cost saving 15-25%, and application prospect is very wide.
Description
Technical field
The present invention relates to environmental science, especially a kind of Fenton method associating supercritical water oxidation method treating refuse percolate.
Background technology
The innoxious process for treating of percolate is the difficult problem that annoying domestic and international each refuse landfill always, if dealt with improperly, will cause severe contamination to the surrounding environment of refuse landfill, basement soil and underground water.At present, the methods such as chemical oxidation, chemical coagulation, charcoal absorption, reverse osmosis, photoxidation, catalyzing and electrolyzing oxidation are mainly contained to the process of percolate both at home and abroad.But these methods still can not be completely efficient, economical removal pollutent, also there is many problems in actual applications.Research and development percolate efficient treatment technology is a focus in current wastewater processing technology research field and difficult point.
From bibliographical information situation, Fenton reagent method and supercritical water oxidation method all have separately significantly advantage and defect.Fenton reagent method, due to H
2o
2the high cost restriction that reagent place produces, is difficult to drop into large-scale industrial application, is generally used as Wastewater Pretreatment and advanced treatment at present; Supercritical water oxidation method reacts under tying up to special high temperature, high pressure conditions, requires that high, power consumption is greatly that it mainly limits to reactor material.But above-mentioned two kinds of methods have again applied widely simultaneously, processing efficiency is high and all do not cause the total advantage of secondary pollution.
Summary of the invention
The object of the invention is: provide a kind of Fenton method to combine supercritical water oxidation method treating refuse percolate, the percolate of high density, difficult degradation can effectively be degraded and remove pollutent, overcome the deficiencies in the prior art by it.
The present invention is achieved in that Fenton method associating supercritical water oxidation method treating refuse percolate, comprises the steps:
1) regulate the pH of percolate to 3 ~ 5, add hydrogen peroxide and ferrous sulfate, adopt Fenton method pretreating waste percolate, react 0.5 ~ 3 hour, pH is transferred to 8 termination reactions, and staticly settles 1 hour;
2) get the supernatant liquor after staticly settling in step 1) and enter supercritical water oxidation system, take cupric nitrate as catalyzer, hydrogen peroxide adds in reactor by 2 ~ 4 times of percolate theoretical oxygen demand, control temperature is 360 ~ 480 DEG C, pressure is react 1 ~ 5 minute under the agitation condition of 20 ~ 28MPa, has reacted the purification realizing percolate.
In step 1), the mol ratio of hydrogen peroxide and ferrous sulfate is 4:1, adds 7.5ml hydrogen peroxide and 5.2g ferrous sulfate in often liter of percolate.
In step 1), the pH of percolate is 4, and the reaction times is 2 hours.This is optimum reaction condition.
Step 2) in, the concentration after the adding of cupric nitrate is 40-50mgL
-1, the add-on of hydrogen peroxide is 3.0 times of percolate theoretical oxygen demand, and temperature of reaction is 420 ~ 440 DEG C, and pressure is 24 ~ 26MPa, and the reaction times is 3 ~ 5 minutes.This is optimum reaction condition.
The comprehensive Fenton reagent method of the present invention and the feature both supercritical water oxidation method, as first adopted supercritical water oxidation method to landfill leachate treatment to a certain extent, Fenton reagent method is adopted to carry out successive depths process again, or first adopt Fenton reagent method to carry out pre-treatment, supercritical water oxidation method is adopted to process further again, all can realize shortening conversion unit reaction times under high-temperature and high-pressure conditions, reduce equipment corrosion, reduce Fenton reagent usage quantity, reduce costs, significantly improve processing efficiency, its combined utilization has good prospect.But, first adopt supercritical water oxidation method to landfill leachate treatment to a certain extent through experimental verification, then adopt Fenton reagent method to carry out successive depths treatment effect not as the former.
Owing to have employed technique scheme, compared with prior art, the present invention first adopts Fenton method pretreating waste percolate, then adopts supercritical water oxidation method to carry out advanced treatment to percolate; By carrying out in a kettle. through the pretreated percolate of Fenton method and hydrogen peroxide heating, compressive reaction, take cupric nitrate as catalyzer, the pollutents such as the COD in percolate, ammonia nitrogen, colourity can be made all efficiently to be removed, Pollutant Treatment is more thorough, be swift in response, water outlet water white transparency; Processing cost is adjusted, average removal 1 ton of COD, Fenton method associating supercritical water oxidation method treatment process saves 15-25% than adopting separately supercritical water oxidation method running cost, be a kind of method that high-level efficiency and pollution reduction cost are better than adopting separately Fenton method and supercritical water oxidation method, application prospect is very wide.The present invention is simple, and the apparatus structure adopted is simple, and cost-effective, result of use is good.
Accompanying drawing explanation
Accompanying drawing 1 is the structural representation of device of the present invention;
1-Fenton reactor, 2-settling pond, 3-waste water tank, 4-dioxygen water pot, 5-plunger type metering pump, 6-T-valve, 7-autoclave, 8-thermocouple thermometer, 9-tensimeter, 10-water cooler, 11-agitator, 12-back pressure valve, 13-process furnace, 14-temperature regulator, 15-gas-liquid separator.
Embodiment
Embodiments of the invention 1:Fenton method associating supercritical water oxidation method treating refuse percolate, comprises the steps:
1) COD be 2000 ~ 30000mg/L, the salinity percolate that is less than 5%, regulate the pH of this percolate to 4, add hydrogen peroxide and ferrous sulfate, the mol ratio of hydrogen peroxide and ferrous sulfate is 4:1, adopt Fenton method pretreating waste percolate, react 2 hours, pH is transferred to 8 termination reactions, and staticly settles 1 hour;
2) get the supernatant liquor after staticly settling in step 1) and enter supercritical water oxidation system, take cupric nitrate as catalyzer, cupric nitrate adds rear Cu
2+concentration be 45mgL
-1, hydrogen peroxide adds in reactor by 3 times of percolate theoretical oxygen demand, and control temperature is 440 DEG C, and pressure is react 4 minutes under the agitation condition of 26MPa, has reacted the purification realizing percolate.
The device of supercritical water oxidation as shown in Figure 1, first carry out hydrostatic test and air tight test, then the heater switch on open temp controller 14, start to heat up, with plunger type metering pump 5, distilled water is squeezed into autoclave 7 simultaneously, regulation system temperature, after pressure reaches preset value, the distilled water of charging is switched to through the pretreated percolate 3 of Fenton method and hydrogen peroxide 4, a certain amount of cupric nitrate is added after dissolving in the percolate 3 that Fenton method is pretreated and squeeze into autoclave 7 with hydrogen peroxide 4 respectively by plunger type metering pump 5, and fully reaction in autoclave 7, reacted water cools through water cooler 10, gas-liquid separator 15 is entered again after back pressure valve 12 reduces pressure, system pressure is controlled by back pressure valve 12, is heated reactor 7 by process furnace 13, carrys out control temperature by temperature regulator 14, quit work after reactive system is stable.
In embodiment 1, Fenton method reaction conditions: pH=4, n(H
2o
2): n(Fe
2+)=4:1, the reaction times is 2h, supercritical water oxidation method reaction conditions: temperature 440 DEG C, and pressure 26MPa, oxidant ratio K are 3.0, and copper ion concentration is 45mgL
-1, result is as shown in table 3:
Embodiment 2: the Fenton method process of percolate, reaction conditions: pH=4, n(H
2o
2): n(Fe
2+)=4:1, the reaction times is 2h, and result is as shown in table 2:
Embodiment 3: the supercritical water oxidation method process of percolate, reaction conditions: temperature 500 DEG C, pressure 26MPa, oxidant ratio K are 3.0, and copper ion concentration is 45mgL
-1, result is as shown in table 2:
Claims (4)
1. a Fenton method associating supercritical water oxidation method treating refuse percolate, is characterized in that: comprise the steps:
1) regulate the pH of percolate to 3 ~ 5, add hydrogen peroxide and ferrous sulfate, adopt Fenton method pretreating waste percolate, react 0.5 ~ 3 hour, pH is transferred to 8 termination reactions, and staticly settles 1 hour;
2) get the supernatant liquor after staticly settling in step 1) and enter supercritical water oxidation system, take cupric nitrate as catalyzer, hydrogen peroxide adds in reactor by 2 ~ 4 times of percolate theoretical oxygen demand, control temperature is 360 ~ 480 DEG C, pressure is react 1 ~ 5 minute under the agitation condition of 20 ~ 28MPa, has reacted the purification realizing percolate.
2. Fenton method associating supercritical water oxidation method treating refuse percolate according to claim 1, it is characterized in that: in step 1), the mol ratio of hydrogen peroxide and ferrous sulfate is 4:1, adds 7.5ml hydrogen peroxide and 5.2g ferrous sulfate in often liter of percolate.
3. Fenton method associating supercritical water oxidation method treating refuse percolate according to claim 1 and 2, it is characterized in that: in step 1), the pH of percolate is 4, and the reaction times is 2 hours.
4. Fenton method associating supercritical water oxidation method treating refuse percolate according to claim 1, is characterized in that: step 2) in, cupric nitrate adds rear Cu
2+concentration be 40-50mgL
-1, the add-on of hydrogen peroxide is 3.0 times of percolate theoretical oxygen demand, and temperature of reaction is 420 ~ 440 DEG C, and pressure is 24 ~ 26MPa, and the reaction times is 3 ~ 5 minutes.
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| CN106746485A (en) * | 2016-12-21 | 2017-05-31 | 北京科技大学 | A kind of SCWO technologies steel rolling oily sludge decrement method for innocent treatment |
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| CN106698780A (en) * | 2015-11-18 | 2017-05-24 | 中国科学院大连化学物理研究所 | Combined landfill leachate treatment process |
| CN114790029B (en) * | 2022-04-29 | 2024-02-06 | 西安交通大学 | Pollutant harmless regulation and control system and method based on supercritical water oxidation technology |
| CN117105492B (en) * | 2023-10-25 | 2024-02-23 | 常熟理工学院 | Method for purifying high-concentration landfill leachate by utilizing supercritical water generator and product thereof |
Citations (1)
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| CN101979337A (en) * | 2010-10-27 | 2011-02-23 | 南京工业大学 | System and method for treating landfill leachate by using supercritical water oxidation method |
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| CN101979337A (en) * | 2010-10-27 | 2011-02-23 | 南京工业大学 | System and method for treating landfill leachate by using supercritical water oxidation method |
Non-Patent Citations (1)
| Title |
|---|
| "超临界水氧化法处理焦化废水的模拟试验";李晶晶等;《净水技术》;20131231;第32卷(第5期);第26-30页 * |
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| CN106746485A (en) * | 2016-12-21 | 2017-05-31 | 北京科技大学 | A kind of SCWO technologies steel rolling oily sludge decrement method for innocent treatment |
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