CN101774678A - Treatment method of garbage percolate - Google Patents
Treatment method of garbage percolate Download PDFInfo
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- CN101774678A CN101774678A CN201010113937A CN201010113937A CN101774678A CN 101774678 A CN101774678 A CN 101774678A CN 201010113937 A CN201010113937 A CN 201010113937A CN 201010113937 A CN201010113937 A CN 201010113937A CN 101774678 A CN101774678 A CN 101774678A
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- percolate
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- garbage percolate
- free radical
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Abstract
The invention provides a treatment method of garbage percolate, which belongs to a novel wet type garbage percolate oxidation treatment method based on sulfate radical free radicals (SO4<2->). The method comprises the following steps: pretreating the garbage percolate; injecting the pretreated garbage percolate into a reaction kettle; adding catalysts and sulfate free radical evocating agents for oxidizing and degrading the garbage percolate under the conditions of the moderate temperature between 80 and 250 DEG C, the moderate pressure between 0.5 and 10 MPa and the oxygen partial pressure between 0.2 and 5 MPa. The invention lowers the wet type oxidation reaction conditions, the reaction conditions are mild, the free radical generation speed of the invention is fast, the garbage percolate treatment efficiency is high (the COD removal rate can reach more than 85 percent), the garbage percolate can be effectively treated, the organic matter residue quantity of outlet water can be reduced, the wet type oxidation operation conditions can be lowered, and the invention is favorable for the popularization of the wet type oxidation technology, and has good economic and environmental benefits.
Description
Technical field
The present invention relates to a kind of advanced oxidation treatment technology and method of percolate.
Background technology
Percolate is one of modal in garbage collecting and transferring, processing and the disposal process " secondary pollution ", be that universally acknowledged pollution hazard is big, composition is complicated, change of water quality greatly, one of the most unmanageable high concentrated organic wastewater, mainly contain a large amount of organic pollutants, nitrogen, phosphorus and miscellaneous heavy metal class material.The treatment technology of percolate is international research focus, receives much concern all the time.
At present, the technology that is used for the treating refuse percolate mainly contains: the combination of biologic treating technique, materialization treatment technology, soil treatment technology and these technologies etc.Biologic treating technique is easy and simple to handle, working cost is lower, but owing to contain some toxicants (as polycyclic aromatic hydrocarbons, polychlorobiphenyl etc.) and biorefractory material (as humic acid, tensio-active agent etc.) in the percolate, therefore the biological process treatment effect is relatively poor, the residual height of COD makes its application be subjected to tangible restriction.Soil treatment technology relative cost is lower, but can cause soil and phreatic pollution, the penetrating power of soil also can be along with the prolongation of time descends gradually in addition, also can decrease the processing efficiency of percolate, can not satisfy the environment protection emission requirement of increasingly stringent.The physico-chemical process that is used for the treating refuse percolate at present mainly contains chemical oxidization method, absorption method, chemical precipitation method and membrane filter method etc., but all exists separately deficiency and defective.For example the greatest problem of film processing is a Film impurity, can stop up fenestra, and processing efficiency is had a significant impact; The chemical precipitation rule is subject to the restriction of conditions such as pH value; Absorption method is just transferred to solid phase to pollutent from water, causes secondary pollution easily.
High-level oxidation technology is to grow up on the basis of single chemical oxidization method over nearly 20 years, utilizes the strong oxidizing property free radical that generates in the reaction, organic pollutant degradation is become small-molecule substance, even mineralising becomes CO
2, H
2O and corresponding mineral ion.Wet oxidation (WAO) is a kind of high-level oxidation technology of handling organic waste water, mainly is under high temperature, condition of high voltage, utilizes air to be organic a kind of treatment technology in the oxygenant oxidation water.Adopt wet oxidation treating refuse percolate can remove high concentration of COD, and the biodegradability of raising waste water, decolouring, deodorizing do not produce secondary pollutants such as oxynitride, sulfurous gas, Dioxins and furans, and not influenced by the pH, toxic substance, ammonia nitrogen etc. of percolate.Traditional wet oxidation needs higher temperature and pressure, and the relatively long residence time, reaction conditions is comparatively harsh, thereby the actual popularization of this method is restricted.
In the last few years, people had carried out some improvement on the basis of traditional wet oxidation technology, for example catalytic wet air oxidation process (CWAO) and wet type peroxide oxidation (WPO) technology.CWAO adds suitable catalyzer to reduce the temperature and pressure of reaction in traditional wet type air oxidation processing technique, reduce reaction activity, improves oxidative decomposition capacity, shortens the reaction times, reduces running cost.Traditional catalytic wet air oxidation still needs comparatively high temps (180～315 ℃), elevated pressures, and (2～25Mpa) reaction conditions, working cost is higher, and equipment is all had very high requirement, thereby limits it and further apply.The WPO technology is to add oxygenant in reaction system, as hydrogen peroxide (H
2O
2), ozone etc., and make organic pollutant accelerate decomposition and mineralising.H
2O
2Be eco-friendly oxygenant, it is the initiator of hydroxyl radical free radical (OH), but H
2O
2Itself be liquid, should not store and transport, and since actual waste water complicated various often join and easily be decomposed into O in the reaction system
2And H
2O greatly reduces treatment effect.
Persulphate and S
2O
8 2-With single peroxosulphuric hydrogen salt (HSO
5 -) be sulphuric acid free radical (SO
4 -) initiator, in the catalytic wet oxidation process, add these oxygenants and can produce a large amount of strong oxidizing property sulphuric acid free radicals, under certain conditions, SO
4 -The redox potential ratio
OH is taller, and most organic pollutants can both be by SO
4 -Degraded fully.
Summary of the invention
The object of the present invention is to provide a kind of rubbish leachate treatment method, it is based on sulfate radical free radical (SO
4 -) the method for novel wet oxidation treating refuse percolate, can remedy the deficiency of existing WPO technology, to avoid hydroxyl radical free radical initiator H
2O
2The problem that should not store and transport.For this reason, the present invention is by the following technical solutions: it carries out pre-treatment with percolate, inject reactor through pretreated percolate, 80～250 ℃ of middle Wen Wendu, middle pressure pressure 0.5～10Mpa, the dividing potential drop of oxygen is under 0.2～5Mpa condition, adds catalyzer and sulphuric acid free radical initiator, the oxidative degradation percolate.Under the condition of technical scheme of the present invention, can reach quick decomposing organic matter, reach the advanced treatment of landfill leachate purpose.
Know-why of the present invention: in filling the reactor of percolate, in liquid-phase system, 80～250 ℃ of catalyzer and middle temperature, middle 0.5～the 10Mpa that presses, the dividing potential drop of oxygen is under 0.2～5Mpa condition, the sulphuric acid free radical initiator that adds some amount, as persulphate or single peroxosulphuric hydrogen salt, one side catalyzer energy catalysis persulphate or single peroxosulphuric hydrogen salt, in addition on the one hand, High Temperature High Pressure also can generate sulphuric acid free radical by accelerate decomposition initiator persulphate (or single peroxosulphuric hydrogen salt), cause a series of free radical reaction, concrete reaction formula is as follows:
M
n++S
2O
8 2-→M
(n+1)++SO
4 ·-+SO
4 2-
M
n++HSO
5 -→M
(n+1)++SO
4 ·-+OH
-
2SO
4 ·-+RH→R
·+HSO
4 -
The sulphuric acid free radical that is produced by above-mentioned reaction has very high oxidation activity, can react with the materials such as organic pollutant in the percolate, causes free radical reaction, organic pollutant degradation is become small-molecule substance, even mineralising becomes CO
2, H
2O and corresponding mineral ion, thus reach the purpose of advanced treatment.
The invention has the beneficial effects as follows: (1) has reduced the reaction conditions of wet oxidation, the reaction conditions gentleness.The present invention adds radical initiator on the basis of catalytic wet oxidation, make reaction system produce the extremely strong novel living radical-SO of a large amount of oxidisability
4 -, the free radical formation speed is fast, increases wet oxidation advanced treatment effect greatly, great raising is also arranged, percolate processing efficiency height (the COD clearance can reach more than 85%) for the processing rate of the COD of percolate.(2) add environmental friendliness reagent, can not cause secondary pollution, reduce the organic substance residues amount of water outlet, help the popularization of wet oxidation technology, have good economy and environmental benefit.
Embodiment
A kind of rubbish leachate treatment method of the present invention is based on sulphuric acid free radical strengthening wet treatment by catalytic oxidation, it is specially: the pre-treatment of (1) percolate: percolate is removed the macrobead foreign material after filtration, add the particulate matter that flocculation agent precipitation coagulation is removed suspended state again; (2) inject reactor through the percolate of pre-treatment, seal, adjust stirring velocity (100rpm～800rpm), heat up, arrive 80～250 ℃ of design temperatures after, charge into oxygen, oxygen partial pressure is 0.2～5Mpa.After reaching the temperature and pressure of setting, inject sulphuric acid free radical initiator persulphate S by injection port
2O
8 2-Or Oxone (KHSO
5KHSO
4K
2SO
4) (determining the consumption of oxygenant according to the concentration of percolate), (0.5h～4h), finish after the cooling behind the reaction certain hour.
Below in conjunction with embodiment the present invention is further detailed, protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Percolate (COD concentration is about 1100mg/L) is degraded,, get this percolate of 500mL and add in the reactor, add CATALYST Co SO after filtration with the pre-treatment of ferrous sulfate flocculation sediment
4(0.05g) and CuO (0.5g), inject initiator Oxone (KHSO
5KHSO
4K
2SO
4) 6g, aerating oxygen 0.5MPa, stirring velocity 600rpm heats up, reach 200 ℃ of preset temps and preset pressure 5Mpa after, reaction 4h begins to cool down, remove throw out after, measurement result shows that the COD clearance of percolate is 85.4%; Repeat this experiment, adopt to add initiator H
2O
2Replace Oxone (KHSO
5KHSO
4K
2SO
4), it is 51.4% only that final COD removes rate, shows based on the Catalytic Wet Oxidation method of sulfate radical free radical to compare based on hydroxyl radical free radical initiator H
2O
2Wet type peroxide oxidation method, can improve organic clearance in the percolate significantly.
Adopting temperature in the present embodiment is 200 ℃, pressure 5Mpa, and the condition of oxygen 0.5MPa can effectively be removed the COD in the percolate, and the clearance of COD is higher in the percolate.Under the ordinary test condition, when temperature is 80～250 ℃, pressure 0.5～10Mpa, the dividing potential drop of oxygen is under 0.2～5Mpa condition, all can reach the purpose of the COD in effective removal percolate.
Embodiment 2
Percolate (COD concentration is about 1100mg/L) is degraded,, get the percolate of this concentration of 500mL and put into reactor, add catalyst Fe SO through filtering and the pre-treatment of ferrous sulfate flocculation sediment
4(0.05g) and CuO (0.5g), add initiator persulphate K
2S
2O
85g, aerating oxygen 0.5MPa, stirring velocity 600rpm heats up, reach 200 ℃ of preset temps and preset pressure 5Mpa after, reaction 4h begins to cool down, remove throw out after, measurement result shows that the COD clearance of percolate is 87.2%; Repeat this experiment, adopt to add oxygenant H
2O
2Replace K
2S
2O
8, it is 64.4% only that final COD removes rate, shows based on the Catalytic Wet Oxidation method of sulfate radical free radical to compare based on hydroxyl radical free radical initiator H
2O
2Wet type peroxide oxidation method, can improve organic clearance in the percolate significantly.
The catalyzer that the above embodiment of the present invention adopts is respectively CoSO
4, FeSO
4And CuO, general catalyzer transiting state metal salt commonly used such as cupric salt, manganous salt, and transiting state metal oxide compound Co
3O
4, Fe
2O
3And MnO
2Also can be used for the treating refuse percolate as the catalyzer among the present invention.
Claims (5)
1. rubbish leachate treatment method, it is characterized in that: it carries out pre-treatment with percolate, inject reactor through pretreated percolate, 80～250 ℃ of middle Wen Wendu, middle pressure pressure 0.5～10Mpa, the dividing potential drop of oxygen is under 0.2～5Mpa condition, adds catalyzer and sulphuric acid free radical initiator, the oxidative degradation percolate.
2. a kind of rubbish leachate treatment method as claimed in claim 1 is characterized in that: described pre-treatment is filtration treatment and precipitation process.
3. a kind of rubbish leachate treatment method as claimed in claim 1 is characterized in that: described catalyzer is transiting state metal salt or transiting state metal oxide compound.
4. a kind of rubbish leachate treatment method as claimed in claim 3 is characterized in that: described transiting state metal salt catalyst is selected from divalent cobalt, cupric salt, divalent iron salt, manganous salt, and described transiting state metal oxide catalyst is selected from Co
3O
4, CuO, Fe
2O
3And MnO
2
5. a kind of rubbish leachate treatment method as claimed in claim 1 is characterized in that: described sulphuric acid free radical initiator is persulphate or single peroxosulphuric hydrogen salt, and the acid ion of described persulphate is S
2O
8 2-, the acid ion of described single peroxosulphuric hydrogen salt is HSO
5 -
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|---|---|---|---|
| CN201010113937A CN101774678A (en) | 2010-02-24 | 2010-02-24 | Treatment method of garbage percolate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010113937A CN101774678A (en) | 2010-02-24 | 2010-02-24 | Treatment method of garbage percolate |
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|---|---|
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ID=42511303
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020350A (en) * | 2011-01-04 | 2011-04-20 | 华中师范大学 | Processing method of heterocatalysis persulfate Fenton oxidation water |
| CN102701313A (en) * | 2012-06-20 | 2012-10-03 | 哈尔滨工业大学 | Method for removing organic pollutants with persulfate strengthened cobalt ferrite under catalysis of visible light |
| CN103570118A (en) * | 2013-11-22 | 2014-02-12 | 湖南大学 | Method for degrading humic pollutants by catalytic wet cooxidation |
| CN104163539A (en) * | 2013-05-17 | 2014-11-26 | 中国科学院生态环境研究中心 | Processing method of wastewater in coal chemistry industry |
| CN104211158A (en) * | 2014-09-29 | 2014-12-17 | 镇江华域环保设备制造有限公司 | Landfill leachate treatment method |
| CN104529078A (en) * | 2014-12-30 | 2015-04-22 | 浙江大学 | Refuse landfill leachate treatment method |
| CN104876363A (en) * | 2015-05-27 | 2015-09-02 | 华南理工大学 | Catalytic wet oxidation method for up-to-standard discharge of refuse leachate |
| CN105439250A (en) * | 2015-12-16 | 2016-03-30 | 复旦大学 | Method for degrading humic acid in water through activating persulfates by electric synergistic ferrous iron |
| CN106747482A (en) * | 2017-01-24 | 2017-05-31 | 福州大学 | A kind of method that utilization percolate prepares thinning type ceramic additive |
| CN107082507A (en) * | 2017-04-26 | 2017-08-22 | 四川吉奥安欣环保科技有限公司 | A kind of method for handling percolate |
| CN108726640A (en) * | 2017-04-20 | 2018-11-02 | 华中科技大学 | A kind of method of electrochemistry collaboration persulfate removal Organic Pollutants in Wastewater |
| CN110550686A (en) * | 2018-05-31 | 2019-12-10 | 中国科学院过程工程研究所 | treatment method of heterocyclic organic matter-containing wastewater and obtained adsorption material |
| CN112876292A (en) * | 2021-01-14 | 2021-06-01 | 生态环境部南京环境科学研究所 | Pretreatment method for enhancing extraction of nitrogen in landfill leachate |
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2010
- 2010-02-24 CN CN201010113937A patent/CN101774678A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020350A (en) * | 2011-01-04 | 2011-04-20 | 华中师范大学 | Processing method of heterocatalysis persulfate Fenton oxidation water |
| CN102701313A (en) * | 2012-06-20 | 2012-10-03 | 哈尔滨工业大学 | Method for removing organic pollutants with persulfate strengthened cobalt ferrite under catalysis of visible light |
| CN104163539A (en) * | 2013-05-17 | 2014-11-26 | 中国科学院生态环境研究中心 | Processing method of wastewater in coal chemistry industry |
| CN103570118A (en) * | 2013-11-22 | 2014-02-12 | 湖南大学 | Method for degrading humic pollutants by catalytic wet cooxidation |
| CN104211158A (en) * | 2014-09-29 | 2014-12-17 | 镇江华域环保设备制造有限公司 | Landfill leachate treatment method |
| CN104529078A (en) * | 2014-12-30 | 2015-04-22 | 浙江大学 | Refuse landfill leachate treatment method |
| CN104876363A (en) * | 2015-05-27 | 2015-09-02 | 华南理工大学 | Catalytic wet oxidation method for up-to-standard discharge of refuse leachate |
| CN105439250A (en) * | 2015-12-16 | 2016-03-30 | 复旦大学 | Method for degrading humic acid in water through activating persulfates by electric synergistic ferrous iron |
| CN106747482A (en) * | 2017-01-24 | 2017-05-31 | 福州大学 | A kind of method that utilization percolate prepares thinning type ceramic additive |
| CN106747482B (en) * | 2017-01-24 | 2019-10-08 | 福州大学 | A method of it is prepared using landfill leachate and type ceramic additive is thinned |
| CN108726640A (en) * | 2017-04-20 | 2018-11-02 | 华中科技大学 | A kind of method of electrochemistry collaboration persulfate removal Organic Pollutants in Wastewater |
| CN107082507A (en) * | 2017-04-26 | 2017-08-22 | 四川吉奥安欣环保科技有限公司 | A kind of method for handling percolate |
| CN110550686A (en) * | 2018-05-31 | 2019-12-10 | 中国科学院过程工程研究所 | treatment method of heterocyclic organic matter-containing wastewater and obtained adsorption material |
| CN110550686B (en) * | 2018-05-31 | 2020-12-29 | 中国科学院过程工程研究所 | Treatment method of heterocyclic organic matter-containing wastewater and obtained adsorption material |
| US11760673B2 (en) | 2018-05-31 | 2023-09-19 | Institute Of Process Engineering, Chinese Academy Of Sciences | Treatment method of wastewater containing heterocyclic organics and adsorbing material obtained therefrom |
| CN112876292A (en) * | 2021-01-14 | 2021-06-01 | 生态环境部南京环境科学研究所 | Pretreatment method for enhancing extraction of nitrogen in landfill leachate |
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| CB03 | Change of inventor or designer information |
Inventor after: Chen Xiaoyang Inventor after: Xue Zhiyong Inventor after: Wang Weiping Inventor after: Zhu Fengxiang Inventor after: Hong Chunlai Inventor after: Wu Chuanzhen Inventor after: Xiao Hua Inventor before: Chen Xiaoyang |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: CHEN XIAOYANG TO: CHEN XIAOYANG XUE ZHIYONG WANG WEIPING ZHU FENGXIANG HONG CHUNLAI WU CHUANZHEN XIAO HUA |
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Application publication date: 20100714 |