CN102068782A - Method for treating persistent organic pollutants through microwave hydrothermal reaction - Google Patents
Method for treating persistent organic pollutants through microwave hydrothermal reaction Download PDFInfo
- Publication number
- CN102068782A CN102068782A CN2009102238314A CN200910223831A CN102068782A CN 102068782 A CN102068782 A CN 102068782A CN 2009102238314 A CN2009102238314 A CN 2009102238314A CN 200910223831 A CN200910223831 A CN 200910223831A CN 102068782 A CN102068782 A CN 102068782A
- Authority
- CN
- China
- Prior art keywords
- hydrothermal reaction
- organic pollutant
- persistence organic
- alkali
- microwave hydrothermal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Processing Of Solid Wastes (AREA)
- Fire-Extinguishing Compositions (AREA)
Abstract
The invention discloses a method for treating persistent organic pollutants (POPs) through microwave hydrothermal reaction. In the method, an iron oxide and/or a ferrite is generated and simultaneously hydrogen is released by reducing iron powder and sodium hydroxide or performing the hydrothermal reaction on potassium hydroxide solution under a microwave irradiation condition to realize rapid dechlorination of the POPs substances in wastes to be treated. The method can be used for treating waste organic chlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) oil in a transformer, soils and deposits which are seriously polluted by the OCPs or the PCBs, garbage incineration fly ash containing high-concentration dioxins (PCDD/Fs), chlorine-alkali industrial brine sludge and the like; besides, the method is short in treatment time and high in dechlorination efficiency, and can realize rapid treatment of various wastes containing the POPs.
Description
Technical field
The present invention relates to a kind of organic pollution treatment technology, relate in particular to a kind of method of utilizing microwave hydrothermal reaction treatment persistence organic pollutant.
Background technology
Persistence organic pollutant (Persistent Organic Pollutants, be called for short " POPs "), be meant have extended residual, biological accumulation, half volatile and high toxicity, and can long-distance migration and human health and environment are had an organic pollution materials of serious harm by various surrounding mediums (atmosphere, water, organism etc.).Even when very low degree of exposure, POPs is harmful to human body and animal, POPs pollutes has become global environmental problem.For reducing environmental risk; the human environment of depending on for existence of protection; urgent need is developed the refuse that technical finesse fast and effectively contains POPs, as De bioxin (PCDD/Fs) in PCBs, blast furnace/house refuse/medical refuse burning flyash and the chlorine industry salt slurry in discarded organo-chlorine pesticide (OCPs), the Polychlorinated biphenyls (PCBs) in the transformer oil, near the soil of transformer landfill point etc.
Use the Zero-valent Iron reduction dechlorination technology of reduced iron powder once to be used to the processing of low concentration chloro-alkenes and alkane in the underground water, but as if the processing that this technology is used for to high concentration POPs class material, need under the condition of high temperature and high pressure, carry out (as overcritical or subcritical), this has increased processing cost undoubtedly, has also increased the difficulty that technology realizes.
Be gas chemistry reduction (GPCR) for the more effective treatment technology of POPs class refuse in the world at present, promptly utilize hydrogen, under higher temperature and condition of normal pressure, POPs class refuse is carried out reduction dechlorination, realize harmless treatment as reducing agent.But this technology is higher to the security requirement of device, if easily blast because of misoperation enters then air.But if can progressively provide hydrogen by gentle relatively chemical reaction, be used for the reduction dechlorination of POPs class refuse, then reaction is with safer and controlled.
At material science, reduced iron powder is used to prepare ferriferous oxide under hydrothermal reaction condition, and one of accessory substance of this reaction is exactly a hydrogen.But it is slower that conventional hydro-thermal reaction is carried out, and the present invention utilizes microwave (MW) radiation that the effect of reduced iron powder and aqueous slkali is produced high temperature, and concurrent unboiled water thermal response discharges hydrogen, realizes the reduction dechlorination of POPs class refuse is handled.The microwave hydrothermal reaction produces the process of hydrogen and can explain with following equation:
Summary of the invention
The purpose of this invention is to provide the method for utilizing microwave hydrothermal reaction treatment persistence organic pollutant that a kind of reaction time is short, treatment effeciency is high, energy consumption is low.
The objective of the invention is to be achieved through the following technical solutions:
The method of utilizing microwave hydrothermal reaction treatment persistence organic pollutant of the present invention comprises hydro-thermal reaction, and in described hydro-thermal reaction, reduced iron powder and aqueous slkali generate ferriferous oxide and/or ferrite under microwave irradiation effect, and discharge hydrogen.
As seen from the above technical solution provided by the invention, the method of utilizing microwave hydrothermal reaction treatment persistence organic pollutant of the present invention, because in hydrothermal reaction process, there is hydrogen to continue to generate, and system temperature is higher, can realize the reduction dechlorination of POPs class refuse is handled, the reaction time is short, energy consumption is low.
The specific embodiment
The method of utilizing microwave hydrothermal reaction treatment persistence organic pollutant of the present invention, its preferable specific embodiment be, comprises hydro-thermal reaction and dechlorination reaction, in course of reaction, reactant carried out the microwave radiation.
Reactant comprises reduced iron powder, alkali, water and treated waste etc.Reduced iron powder wherein, alkali and water are microwave absorbing material, and the principle by dipole polarization or interfacial polarization absorbs microwave energy to improve system temperature.Reduced iron powder and aqueous slkali generation hydro-thermal reaction generate ferriferous oxide and/or ferrite with this understanding, and discharge hydrogen, and POPs class material in the treated waste and hydrogen at high temperature react the dechlorination degraded takes place.
Concrete steps comprise:
To mix with reduced iron powder and aqueous slkali through the pending POPs of the containing refuse of pre-treatment step, start microwave device and carry out hydro-thermal reaction and dechlorination reaction, in the course of reaction, continue to feed the nitrogen of 100～1000mL/min flow.Microwave frequency is 2450MHz or 915MHz.
Described alkali comprises NaOH and potassium hydroxide, and the addition of alkali can be the 1%-20% of treated waste weight; The 0.2-5 that described reduced iron powder addition is the alkali addition doubly; The 1-10 that described water addition is the alkali addition doubly.The amount of the reduced iron powder of concrete required adding, alkali and water can be according to the kind and the concentration adjustment of POPs class material in the treated waste.
The handled refuse that contains persistence organic pollutant of the present invention can comprise following one or more:
Discarded organo-chlorine pesticide, the PCBs oil in the transformer, be subjected to organo-chlorine pesticide or PCBs oil contaminated soil and deposit, the incineration of refuse flyash that contains bioxin and chlorine industry salt slurry etc.
Above-mentioned pre-treatment step can comprise:
For the refuse that contains the low concentration persistence organic pollutant, concentrate by modes such as thermal desorptions earlier; For solid waste, carry out fragmentation earlier, make its uniform particles; For the useless transformer or the capacitor of filling PCBs oil, earlier with its fragmentation, and with solvent extraction PCBs oil wherein.
The present invention utilizes the microwave radiation to provide energy for hydro-thermal reaction, effect by several reactants such as microwave and reduced iron powder, alkali and water (also being microwave absorbing material simultaneously), improve system temperature, promote the carrying out of hydro-thermal reaction, produce hydrogen, realization is to the reduction dechlorination of POPs pollutant, and the HCl that dechlorination generates is neutralized by aqueous slkali.
The present invention can be directly used in and handle the refuse that contains high concentration POPs, or concentrates by the POPs of certain pre-treatment step (as thermal desorption) with low concentration in the refuse earlier, and then handles with the present invention.For the processing of solid waste such as OCPs refuse that contains OCPs or PCBs soil, the flying dust that contains PCDD/Fs and production or circulation department, can be earlier will be wherein bulk crushing, foreign material such as removal brick, tile fragment and branch make its uniform particles.For the useless transformer or the capacitor of filling PCBs oil, should be earlier with its fragmentation, and with solvent extraction PCBs oil wherein.
To mix and start microwave with reduced iron powder, alkali and the water of proper proportion through the solid waste of pre-treatment or transformer wet goods liquid wastes and carry out irradiation, determine the processing time according to the amount and the parameters such as concentration and microwave power of processing refuse.The nitrogen that course of reaction continues to feed 100～1000ml/min flow is to prevent breaking out of fire, and the steam of generation is condensed, collects and emptying after activated-charcoal column absorption.
Selected microwave frequency is 2450MHz or 915MHz etc., and mini-reactor can be used 2450MHz, and large-scale reactor can be used 915MHz;
Described alkali comprises NaOH and potassium hydroxide, and the addition of alkali can be the 1%-20% of treated waste weight; Alkali can the aqueous solution form add, form that also can solid particle adds, the alkali that adds with aqueous solution form can mix with treated waste better;
Used reduced iron powder available hydrogen is before use handled to improve treatment effect, also can not treated direct use, and the 0.2-5 that described reduced iron powder addition is the alkali addition is doubly;
The 1-10 that described water addition is the alkali addition doubly;
The amount of the reduced iron powder of concrete required adding, alkali and water can be according to the kind and the concentration adjustment of POPs class material in the treated waste.
Processing procedure mainly is dechlorination, but the dechlorination meeting causes increasing in the homologue concentration of low chloro of a certain stage, and promptly high chloro changes into low chloro.This has no problem for the pollutant as PCBs, and for PCDD/Fs, the homologue of some low chloro may have higher toxicity, and (as 2,3,7,8-tetrachloro dibenzodioxin English TCDD), therefore needs monitoring reaction course to guarantee complete dechlorination.
Among the present invention, microwave cavity can be one-mode cavity or multimode cavity; The power bracket of microwave generator is regulated according to the amount and the concentration of processing refuse from several hectowatts to tens kilowatt;
Reactor can be made by the material that quartz glass, pottery, polytetrafluoroethylene (PTFE), polystyrene etc. can see through microwave and can tolerate uniform temperature, accept equal microwave radiation equal angles consideration everywhere from processing and easy to operate, reactor, determine the cylindrical shape that is shaped as of reactor;
Periphery at reactor and microwave generator is provided with radome, and connects ground wire, prevents that microwave energy from leaking;
The mensuration of the interior temperature of charge of reactor can adopt armouring K-type thermocouple and electron temperature indicator in the microwave processing process, also can adopt fibre optic temperature sensor or infrared radiation thermometer.
Specific embodiment:
Utilize the PCBs in the microwave hydrothermal reaction treatment analogue transformer oil:
Choose Aroclor1254 as model compound, the storing solution with toluene preparation Aroclor1254 joins in a certain amount of hexadecane, fully mixes, and obtaining concentration is the analogue transformer oil of 100mg/L.Here adopt hexadecane analogue transformer oil to be because the boiling point of hexadecane and transformer oil is approaching, and be convenient to analyze.
Adopt the microwave hydrothermal reaction unit among the present invention, carry out the processing of analogue transformer oil, step is:
The first step, reactant mixes, and takes by weighing the analogue transformer oil that 0.3g reduced iron powder, 0.3g sodium hydrate particle, 0.6mL water and 10mL concentration are 100mg/L respectively, fully mixes;
In second step, the reactor of quartz glass material is selected in charging for use, quartz reactor internal diameter 5cm, and height 30cm is with the said mixture material reactor of packing into;
The 3rd step started the microwave hydrothermal reaction unit, and the microwave frequency of selecting for use is 2450MHz, and power is 700W, radiation treatment 3min.Continue to feed the nitrogen of 100mL/min flow in the microwave irradiation process, prevent that reactant from being lighted, the steam that processing procedure produces is by condenser system, fluid collection vials and solvent absorption bottle, emptying after active-carbon bed absorption again;
The 4th step repeated the experiment of first to the 3rd step, and microwave irradiation time is respectively 6min, 10min, 20min and 30min;
The 5th step, treatment effect detects, to utilize after the microwave hydrothermal reaction treatment analogue transformer oil after filtration, carry out GC/ECD after the washing, centrifugation, dilution and analyze, generate low chloro-product after finding to handle 3min and 6min, can realize complete dechlorination substantially more than handling 10min; Solution after handling is extracted and has found through ion chromatography the chlorion of quantitative generation with diluted sodium hydroxide solution; Reacted solid residue is carried out X-ray diffraction (XRD) analysis confirmation generated sodium ferrite (NaFeO2).According to above-mentioned testing result, can determine that reduced iron powder and aqueous slkali issue the unboiled water thermal response at microwave action and generated hydrogen, and in this device, realize reduction dechlorination Aroclor1254.
Among the present invention, because heating using microwave is interior heating, microwave energy directly acts on the microwave absorbing materials such as reduced iron powder, alkali and water as reactant, shortens the processing time greatly, saves energy, reduces processing cost; Microwave frequency, resonator form, the kind of alkali, reactant add key element such as ratio multiple choices, is convenient to select suitable response parameter at different type of wastes; Control is convenient in heating using microwave, starts microwave, immediately with reactor in the material effect, carry out hydro-thermal reaction and dechlorination reaction, close microwave, reaction stops very soon, hysteresis effect is little.
The above; only for the preferable specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, and anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.
Claims (8)
1. a method of utilizing microwave hydrothermal reaction treatment persistence organic pollutant comprises hydro-thermal reaction, it is characterized in that, in described hydro-thermal reaction, reactant is carried out the microwave radiation.
2. the method for utilizing microwave hydrothermal reaction treatment persistence organic pollutant according to claim 1 is characterized in that described reactant comprises reduced iron powder, alkali and water.
3. the method for utilizing microwave hydrothermal reaction treatment persistence organic pollutant according to claim 2 is characterized in that described alkali comprises NaOH and potassium hydroxide.
4. according to claim 1, the 2 or 3 described methods of utilizing microwave hydrothermal reaction treatment persistence organic pollutant, it is characterized in that, comprise step:
To mix with reduced iron powder, alkali and water through the pending POPs of the containing refuse of pre-treatment step, and start the microwave radiation and react, in the described course of reaction, continue to feed the nitrogen of 100～1000mL/min flow.
5. the method for utilizing microwave hydrothermal reaction treatment persistence organic pollutant according to claim 4 is characterized in that, described microwave frequency is 2450MHz or 915MHz.
6. the method for utilizing microwave hydrothermal reaction treatment persistence organic pollutant according to claim 4, it is characterized in that, the addition of described alkali is the 1%-20% of described treated waste weight, the 0.2-5 that described reduced iron powder addition is the alkali addition times, the 1-10 that described water addition is the alkali addition doubly.
7. the method for utilizing microwave hydrothermal reaction treatment persistence organic pollutant according to claim 4 is characterized in that, the refuse that contains described persistence organic pollutant comprises following one or more materials:
Polychlorinated biphenyls oil in organo-chlorine pesticide, the transformer, be subjected to organo-chlorine pesticide or Polychlorinated biphenyls oil contaminated soil and deposit, the incineration of refuse flyash that contains bioxin and chlorine industry salt slurry.
8. the method for utilizing microwave hydrothermal reaction treatment persistence organic pollutant according to claim 4 is characterized in that, described pre-treatment step comprises:
For the refuse that contains the low concentration persistence organic pollutant, concentrate by modes such as thermal desorptions earlier; For solid waste, carry out fragmentation earlier, make its uniform particles; For the useless transformer or the capacitor of filling Polychlorinated biphenyls oil, earlier with its fragmentation, and with solvent extraction Polychlorinated biphenyls oil wherein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102238314A CN102068782A (en) | 2009-11-24 | 2009-11-24 | Method for treating persistent organic pollutants through microwave hydrothermal reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102238314A CN102068782A (en) | 2009-11-24 | 2009-11-24 | Method for treating persistent organic pollutants through microwave hydrothermal reaction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102068782A true CN102068782A (en) | 2011-05-25 |
Family
ID=44027663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009102238314A Pending CN102068782A (en) | 2009-11-24 | 2009-11-24 | Method for treating persistent organic pollutants through microwave hydrothermal reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102068782A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775080A (en) * | 2012-08-08 | 2012-11-14 | 常州市环境科学研究院 | Treatment method of organochlorine pesticide polluted soil |
| CN106077031A (en) * | 2016-06-22 | 2016-11-09 | 浙江大学 | A kind of method of disposal that microwave-hydrothermal method is applied to domestic garbage incineration flyash |
| CN109430268A (en) * | 2018-12-06 | 2019-03-08 | 江苏新河农用化工有限公司 | A kind of preparation method of low hexachlorobenzene content chlorothalonil suspending agent |
| CN109663557A (en) * | 2018-12-24 | 2019-04-23 | 环境保护部华南环境科学研究所 | Remove the single mold microwave reaction unit and method of incineration of refuse flyash dioxin |
| CN112620329A (en) * | 2020-11-30 | 2021-04-09 | 桂林电子科技大学 | Soil organic matter pollution treatment device |
| CN115055479A (en) * | 2022-05-13 | 2022-09-16 | 中国城市建设研究院有限公司 | Decoration garbage treatment device and method |
-
2009
- 2009-11-24 CN CN2009102238314A patent/CN102068782A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775080A (en) * | 2012-08-08 | 2012-11-14 | 常州市环境科学研究院 | Treatment method of organochlorine pesticide polluted soil |
| CN102775080B (en) * | 2012-08-08 | 2013-11-06 | 江苏常环环境科技有限公司 | Treatment method of organochlorine pesticide polluted soil |
| CN106077031A (en) * | 2016-06-22 | 2016-11-09 | 浙江大学 | A kind of method of disposal that microwave-hydrothermal method is applied to domestic garbage incineration flyash |
| CN109430268A (en) * | 2018-12-06 | 2019-03-08 | 江苏新河农用化工有限公司 | A kind of preparation method of low hexachlorobenzene content chlorothalonil suspending agent |
| CN109663557A (en) * | 2018-12-24 | 2019-04-23 | 环境保护部华南环境科学研究所 | Remove the single mold microwave reaction unit and method of incineration of refuse flyash dioxin |
| CN109663557B (en) * | 2018-12-24 | 2024-05-14 | 生态环境部华南环境科学研究所 | Single-mode microwave reaction device and method for removing dioxin in waste incineration fly ash |
| CN112620329A (en) * | 2020-11-30 | 2021-04-09 | 桂林电子科技大学 | Soil organic matter pollution treatment device |
| CN115055479A (en) * | 2022-05-13 | 2022-09-16 | 中国城市建设研究院有限公司 | Decoration garbage treatment device and method |
| CN115055479B (en) * | 2022-05-13 | 2022-12-20 | 中国城市建设研究院有限公司 | Decoration garbage treatment device and method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101461990A (en) | Method for analyzing and processing persistent organic pollutants by microwave assisted base catalysis | |
| Falciglia et al. | A review on the microwave heating as a sustainable technique for environmental remediation/detoxification applications | |
| US7491861B2 (en) | In-drum pyrolysis | |
| Kulkarni et al. | Dioxins sources and current remediation technologies—a review | |
| CN102068782A (en) | Method for treating persistent organic pollutants through microwave hydrothermal reaction | |
| EP1836008B1 (en) | In-container mineralization | |
| Pan et al. | Detoxifying PCDD/Fs and heavy metals in fly ash from medical waste incinerators with a DC double arc plasma torch | |
| KR100300143B1 (en) | Steam-Regeneration Systems and Methods of Liquid or Slurry Injections | |
| Xie et al. | Emissions investigation for a novel medical waste incinerator | |
| CN101513643A (en) | In situ microwave repairing method and apparatus of contaminated soil | |
| Ajorloo et al. | Heavy metals removal/stabilization from municipal solid waste incineration fly ash: a review and recent trends | |
| Amend et al. | Critical evaluation of PCB remediation technologies | |
| CN103234209A (en) | Device and method for processing chloro-containing organic industrial waste | |
| Yang et al. | Coupled microwave hydrothermal dechlorination and geopolymer preparation for the solidification/stabilization of heavy metals and chlorine in municipal solid waste incineration fly ash | |
| Kamarehie et al. | Dechlorination and decomposition of Aroclor 1242 in real waste transformer oil using a nucleophilic material with a modified domestic microwave oven | |
| JP4087657B2 (en) | Waste treatment method and cement raw material manufacturing method | |
| Liu et al. | Comparison of dioxin destruction in the fly ash and froths under microwave irradiation | |
| JP2007209364A (en) | Method and device for decomposition of asbestos | |
| Ojovan et al. | Thermochemical processing using powder metal fuels of radioactive and hazardous waste | |
| El-Amaireh et al. | Hospital waste incinerator ash: characteristics, treatment techniques, and applications (A review) | |
| Kuo et al. | Pollution characteristics of thermal treatments for elutriated ashes. Part 2: comparison with incineration system and plasma melting system | |
| AU2020427285A1 (en) | Recycling system for general waste including waste plastic, recycling method for general waste, and far-infrared catalytic reduction apparatus for use in recycling system for general waste | |
| CN100509647C (en) | Chlorohydrocarbon waste liquid treating method | |
| Rubin et al. | Noncombustion technologies for remediation of persistent organic pollutants in stockpiles and soil | |
| Fülöp et al. | Combination of methods of thermal and radiation treatment of sediments associated with PCBs–the Delor type |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110525 |