CN1344685A - Organic waste water treaitng magnetic field and supersonic wave method - Google Patents
Organic waste water treaitng magnetic field and supersonic wave method Download PDFInfo
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- CN1344685A CN1344685A CN 01134044 CN01134044A CN1344685A CN 1344685 A CN1344685 A CN 1344685A CN 01134044 CN01134044 CN 01134044 CN 01134044 A CN01134044 A CN 01134044A CN 1344685 A CN1344685 A CN 1344685A
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Abstract
In a water treating reactor, industrial organic waste water or domestic sewage is irradiated with supersonic wave and magnetic field simultaneously. The supersonic wave has a frequency range of 16 kHz to 10 MHz and a strength of 0.1-12 W/sq cm. The magnetic flux density is 0.008-2 T, and the combined irradiation time is over 5 min. The present invention utilizes magnetochemical effect to prevent and reduce the recombination of OH and H free radical pair produced in supersonic cavitation and this raise greatly the supersonic treatment effect of waste water. The method of the present invnetion is easy to control, high in efficiency and low in power consumption, and may be used widely.
Description
Technical Field
The invention relates to a method for treating organic wastewater.
Background
At present, high-concentration toxic organic wastewater in some key industries such as printing and dyeing, medicine, chemical industry, papermaking and the like is one of the main reasons for aggravation of water pollution in China. The waste water has the common characteristics of difficult degradation in the environment, long-term stable existence, biological accumulation, serious influence on the health of human beings and obstruction of the sustainable development of economy in China. Therefore, research and application of high-concentration refractory toxic organic wastewater is a hot spot in the wastewater treatment technology of today.
Aiming at high-concentration refractory toxic organic wastewater, people develop a plurality of high-efficiency advanced treatment processes, which are typified by activated carbon adsorption, macroporous resin adsorption, various membrane bioreactors, photocatalytic oxidation and the like. The activated carbon adsorption, macroporous resin adsorption and ozone oxidation are partially popularized, but the cost is high, and the popularization has certain difficulty; photocatalytic oxidation has also progressed in stages, but industrialization is difficult to achieve due to high cost, treatment effect, and the like. Therefore, it is necessary to develop a novel advanced treatment process which is efficient and inexpensive.
In recent years, ultrasonic cavitation technology is adopted to treat refractory toxic organic wastewater to attract attention. Research on the application of ultrasonic sonochemistry to degradation of non-degradable toxic organicmatters in water is carried out in 90 years by Mason at the university of Coventry in England and Luche at the university of pure Sabat in France, and good effects are obtained. In 1994, Tersere in the United states of America combined with ultrasound and ozone studies the kinetics of humic acid oxidation of natural organic substances and determines whether the scheme can be expanded to be applied to degrading refractory electrolytes, and the result is satisfactory. A great deal of work is carried out on researches on ultrasonic cavitation degradation of various refractory toxic organic matters in water bodies by colleges, laboratories and research institutes such as Japan, France, Canada and Germany. Research results show that the effect of degrading the refractory toxic organic matters in the water body by adopting the ultrasonic cavitation technology is obvious. Calculated, the laboratory cost (in terms of electricity consumption)Much lower than ozone oxidation. Since 1996, there were also a few national research institutes who started such laboratory studies, but the comparison was limited to the use of ultrasound and oxidizing agents (H)2O2、O3) The combined processes for degrading several toxic organic matters which are difficult to biodegrade have also made progress to a certain extent in this respect. General description of the inventionAt present, the laboratory research stage is still in the home and abroad.
But the treatment effect and energy consumption of the ultrasonic cavitation technology for degrading the organic matters are not ideal. Theoretically, the organic matters in the wastewater can be mineralized completely by long-time ultrasonic irradiation, but the energy consumption is obviously large, and the economy in engineering practice cannot be allowed, so that the ultrasonic treatment performance is mostly inspected by adopting an ultrasonic combined process. Currently, ultrasonic-oxidizing agents (H) are mainly used2O2、O3) The effect of the two major combined treatment processes of oxidation, ultrasonic and photocatalytic oxidation is obviously higher than that of a single ultrasonic cavitation treatment technology. However, in the meantime, the first type of combination process uses a large amount of oxidant with higher cost, which results in significantly increased operation cost, and the second type of combination process also uses various artificial light sources, which requires a large amount of electric energy during operation. Practice proves that the operation cost of the two major combined processes in unit time is twice of that of a single ultrasonic cavitation technology, so that the two major combined processes are difficult to industrialize at present and are main obstacles for practical engineering application.
Disclosure of Invention
The invention aims to solve the problems and provides a method for treating organic wastewater by using magnetic field and ultrasonic wave, which can effectively and economically purify industrial organic pollutants and realize industrial application.
The technical solution of the invention is as follows:
a method for treating organic waste water by magnetic field and ultrasonic wave features that the ultrasonic wave radiation and magnetic field radiation are simultaneously performed to industrial organic waste water or domestic sewage in water treating reactor, the frequency range of ultrasonic wave is 16kHz-10MHz, and the sound intensity is 0.1-12W/cm2The magnetic flux density is 0.008-2T, and the synergistic radiation time is more than 5 min.
The invention organically combines the magnetochemistry effect and the ultrasonic cavitation effect for the first time, and greatlyenhances the effect of ultrasonic degradation of organic matters. The mechanism of the ultrasonic degradation of the organic matters is that non-selective OH free radicals with strong oxidation capacity are generated to oxidize the organic matters, and the compounding of OH and H in the process can be effectively prevented or reduced under the action of a magnetic field, so that the concentration of OH is improved, and the capacity of ultrasonic degradation of the organic matters is greatly improved. The magnetic field can be generated in a direct current mode or a permanent magnetic substance mode, so that only a small amount of electric energy is consumed, even no energy is needed, no medicament is added, and compared with other ultrasonic cavitation processes, the operation cost is greatly reduced. The magnetic field generating device of the invention is simpler than an oxidant generator or a light source generating device, is convenient to manufacture and has low cost, so the fixing cost of the device of the invention is greatly reduced.
The invention not only provides a brand-new ultrasonic cavitation and magnetization combined process for treating high-concentration, difficult-degradation and toxic organic wastewater for the first time at home and abroad, but also opens up a new application field for the magnetics. Because the generation of the magnetic field and the sound field is mature technology, compared with a single ultrasonic process and the current ultrasonic combined process, the operation parameters are convenient to operate and easy to control in actual engineering, and the industrial production is easy to realize.
The process has the advantages of high efficiency and low consumption in treating high-concentration refractory toxic organic wastewater, thereby having great popularization and application values and very wide prospects. The invention is applicable to halocarbons (CH)2Cl2、CCl4CFC series), phenols (phenol, chlorophenol and p-nitrophenol), alcohols, polymers, polycyclic aromatic compounds, malathion pesticide and griseofulvin, and the compounds are widely present in domestic wastewater of chemical industry, medicine, electronics, food and other important industries.
The method is more effective for other easily degradable organic wastewater.
Drawings
FIG. 1 is a schematic diagram of an embodiment of the present invention.
Detailed Description
The method of the invention is that industrial organic wastewater or domestic sewage is treated in a water treatment reactor simultaneouslyUltrasonic irradiation and magnetic field irradiation, wherein the frequency range of the ultrasonic is 16kHz-10MHz, and the sound intensity is 0.1-12W/cm2The magnetic flux density is 0.008-2T, and the synergistic radiation time is more than 5 min.
There are optimum values for the above process parameters for a particular organic wastewater. For different types of organic wastewater, the cavitation bubbles are generated and the molecular polarization conditions are different due to different types of organic matters, and the optimal values of the process parameters are also different. Generally, the preferred frequency range of the ultrasonic waves is 20kHz-1MHz, and the sound intensity is 0.5-3W/cm2The magnetic flux density is 0.020-1.0T, and the radiation time is more than 15 min.
Since the sound field and the magnetic field can exist in the same space, the organic wastewater can be simultaneously subjected to ultrasonic wave and magnetic field irradiation. The generator of magnetic field and sound field can be any one of the existing markets, and can also be self-made according to the needs. The water flow running mode of the industrial organic wastewater and the domestic sewage in the water treatment reactor can be static or dynamic. The water flow operation mode is preferably dynamic. The ultrasonic waves may be generated by any of various electromechanical or mechanical means. The ultrasonic sound field preferably uses reverberant fields to achieve low power consumption and high intensity. The magnetic field is realized by adopting a stable magnetic field which can be generated by adopting stable current or a permanent magnetic substance (such as a permanent magnet and the like), and the magnetic field is preferably generated by adopting direct current to generate the stable magnetic field so as to ensure that the process is easy to control.
The method of the invention mainly relates to the basic principles of two aspects: ultrasonic cavitation effect and magnetic chemical effect. Briefly described as follows:
the mechanism of ultrasonic cavitation: when the solution is irradiated by ultrasonic wave with certain frequency and sound intensity, cavitation bubbles are generated under the action of sound wave negative pressure phase, and then the solution is quickly collapsed under the action of sound wave positive pressure phase, the whole process is carried out within ns-mus time, and abnormal high temperature (higher than 5000K) and high pressure (higher than 5 multiplied by 10) are generated in the liquid environment with normal temperature and pressure7Pa), so-called "hot spots" are formed. The water vapor entering the cavitation bubbles is subjected to cracking and chain reaction at high temperature and high pressure,the reaction formula is as follows:
collapse of cavitation bubbles to generate shock waves and jet flow to make OH and H2O2And the solution enters the whole solution, and provides a very special physical and chemical environment for chemical reaction. Since the radical contains an unpaired electron, it is active and can be easily converted into a stable molecule by further reaction. The free radicals can recombine at the interface around the cavitation bubbles or react with volatile solutes in the gas phase or with soluble solutes in the bubble interface region, even in bulk solution, to form the final product. In a multi-phase system containing organic matters, carbon bonds on a main chain of macromolecules can be broken due to strong hydrodynamic shearing force when cavitation bubbles collapse, and radicals are generated to initiate various reactions.
Chemical effect of magnetism: the study of the kinetics of magnetization is currently mainly focused on the radical reactions and the "radical theory" has been established accordingly. In chemical reactions, free radicals are always generated in pairs. The nascent pair of radicals forms a "cage". During the reaction, the initial free radical can derive new free radical, and these free radicals may still exist in pairs to constitute new cage. Whether the free radical reaction occurs inside or outside the cage directly affects the reaction rate and the reaction products. For example, two radicals react within a cage, known as "recombination". Recombination occurs at two initial radicals, which means that the reaction is terminated and initiated inefficiently, and the reaction rate must be influenced. In general, the extra-cage reactions of free radicals are more significant, and thus itis always desirable in practical studies to increase the fraction of the extra-cage reactions in the overall reaction.
Recombination of radicals can only occur between singlet radical pairs. As long as the presence of the radical pair in a singlet state is prevented as much as possible, the radical pair cannot recombine, and the radical reaction can only proceed outside the cage. To prevent or reduce the presence of free radical pairs in the singlet state, the intersystem transition of the free radical pair is controlled. While the magnetic field effects may influence the intersystem transition. In some chemical reactions, an external magnetic field is applied to control intersystem transition, so that the free radical pair keeps a triplet state as much as possible, and the possibility of extra-cage reaction is increased from the surface. The main role of the magnetochemistry is also here.
Based on the basic principle, the compounding of OH and H free radical pairs generated by ultrasonic cavitation is effectively prevented or reduced by utilizing the chemical effect of magnetism, and the effect of ultrasonic treatment on organic wastewater is greatly enhanced. In fact, the mechanism of ultrasonic-oxidant oxidation is not that the oxidant directly oxidizes the organic matter, but the H is captured to reduce the compounding of OH, thereby improving the concentration of OH and strengthening the ultrasonic treatment effect, so that the ultrasonic-oxidant oxidation method has the same work and different curves with the ultrasonic-magnetic field combined process. The generation of the magnetic and acoustic fields can be in any steady state manner.
In the embodiment, as shown in fig. 1, the present invention can adopt a rectangular water treatment device 1, in which a plurality of ultrasonic transducers 4 (commercially available electromechanical ultrasonic transducers) are mounted on upper and lower cover plates 2, 3and permanent magnet beads 5 are filled therein. The ultrasonic transducer 4 generates an ultrasonic reverberation field in the water treatment device 1, organic wastewater continuously flows from one side of the water treatment device 1 to the other side, the size of the water treatment device 1 can be changed according to the treated water quantity, and the power and the number of the ultrasonic transducer 4 and the material of the magnetic small balls 5 are determined according to the treated water quality and quantity.
If the treated organic wastewater is wastewater mainly containing o-chlorophenol, the water amount is 184m3D, the concentration of the o-chlorophenol is 1500mg/L, the sound field frequency of the ultrasonic transducer 4 is 32kHz, and the sound intensity is 2.8W/cm2The magnetic flux density generated by the magnetic small ball 5 is 80mT, the irradiation time is 30min, and the removal rate of the o-chlorophenol can reach more than 96%.
If the treated organic wastewater is easily degradable domestic sewage, the water amount is 1500m3D, the biochemical oxygen demand COD is 200mg/L, the sound field frequency of the ultrasonic transducer 4 is 20kHz, and the sound intensity is 0.12W/cm2The magnetic flux density generated by the magnetic small ball 5 is 10mT, the irradiation time is 5min, and the COD removal rate can reach more than 98%.
If the treated organic wastewater is refractory naphthol-containing organic wastewater, the water amount is 20m3D, the concentration of naphthol is 300mg/L, the sound field frequency of the ultrasonic transducer 4 is 8MHz, and the sound intensity is 10W/cm2The magnetic flux density generated by the magnetic small ball 5 is 1.8T, the irradiation time is 45min, and the naphthol removal rate can reach more than 90%.
If the treated organic wastewater is alcohol wastewater mainly containing ethanol, the water amount is 300m3D, the biochemical oxygen demand COD is 800mg/L, the sound field frequency of the ultrasonic transducer 4 is 750kHz, and the sound intensity is 4.0W/cm2The magnetic flux density generated by the magnetic small ball 5 is 0.8T, the irradiation time is 60min, and the COD removal rate can reach more than 99%.
If the organic wastewater to be treated is organic wastewater mainly containing chlorohydrocarbon, the water amount is 200m3D, the biochemical oxygen demand COD is 1100mg/L, the sound field frequency of the ultrasonic transducer 4 is 1MHz, and the sound intensity is 0.5W/cm2The magnetic flux density generated by the magnetic small ball 5 is 0.5T, the irradiation time is 20min, and the COD removal rate can reach more than 95%.
Claims (6)
1. A method for treating organic waste water by magnetic field and ultrasonic wave features that the ultrasonic wave radiation and magnetic field radiation are simultaneously performed to industrial organic waste water or domestic sewage in water treating reactor, the frequency range of ultrasonic wave is 16kHz-10MHz, and the sound intensity is 0.1-12W/cm2The magnetic flux density is 0.008-2T, and the synergistic radiation time is more than 5 min.
2. The method for treating organic wastewater by using magnetic field in combination with ultrasonic waves according to claim 1, wherein the ultrasonic waves have a preferred frequency range of 20kHz to 1MHz and an acoustic intensity of 0.5 to 3W/cm2The magnetic flux density is 0.020-1.0T, and the radiation time is more than 15 min.
3. The method of claim 1, wherein the water treatment reactor is operated in a static or dynamic manner by the flow of industrial organic wastewater or domestic wastewater.
4. The method for treating organic wastewater using magnetic field in combination with ultrasonic waves according to claim 1, wherein the ultrasonic waves are generated by any one of various electromechanical types or mechanical types.
5. The method of claim 4, wherein the ultrasonic field is preferably a reverberant field.
6. The method for treating organic wastewater by using magnetic field in combination with ultrasonic wave according to claim 1, wherein the magnetic field is a steady magnetic field, or is generated by using a steady electric current, or is generated by using a permanent magnetic substance.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100537461C (en) * | 2006-12-20 | 2009-09-09 | 中国科学院成都生物研究所 | Handling method for refractory waste water |
| CN101543740A (en) * | 2009-04-09 | 2009-09-30 | 姚明勤 | Emulsifier for supersonic ferromagnetic cavity effect control |
| CN102173524A (en) * | 2011-03-23 | 2011-09-07 | 哈尔滨工业大学 | Water treatment method for ultrasonically improving oxidation of pollutant with permanganate |
| CN102225820A (en) * | 2011-05-30 | 2011-10-26 | 安徽师范大学 | Cycle utilization method of engine ultrasonic cleaning agent / liquid |
| CN103539212A (en) * | 2013-10-10 | 2014-01-29 | 彭伟明 | Water activating method and device by combination of acoustic field/electromagnetic field/magnetic field and double-vortex-body vortex |
| CN103539220A (en) * | 2013-10-10 | 2014-01-29 | 彭伟明 | Water activating method and device by combination of acoustic field and double-vortex-body vortex |
| CN106542621A (en) * | 2015-09-18 | 2017-03-29 | 中国石油化工股份有限公司 | Polyacrylamide equipment in magnetic field, ultrasound wave and laser treatment oil field mining liquid |
| CN106542605A (en) * | 2015-09-18 | 2017-03-29 | 中国石油化工股份有限公司 | Laser and ultrasonication oil field waste petrochina kind equipment |
| CN110844983A (en) * | 2019-11-26 | 2020-02-28 | 北京航空航天大学 | Method for treating organic wastewater through magnetic catalysis |
-
2001
- 2001-10-15 CN CN 01134044 patent/CN1120807C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100537461C (en) * | 2006-12-20 | 2009-09-09 | 中国科学院成都生物研究所 | Handling method for refractory waste water |
| CN101543740A (en) * | 2009-04-09 | 2009-09-30 | 姚明勤 | Emulsifier for supersonic ferromagnetic cavity effect control |
| CN102173524A (en) * | 2011-03-23 | 2011-09-07 | 哈尔滨工业大学 | Water treatment method for ultrasonically improving oxidation of pollutant with permanganate |
| CN102225820A (en) * | 2011-05-30 | 2011-10-26 | 安徽师范大学 | Cycle utilization method of engine ultrasonic cleaning agent / liquid |
| CN102225820B (en) * | 2011-05-30 | 2012-11-21 | 安徽师范大学 | Cycle utilization method of engine ultrasonic cleaning agent / liquid |
| CN103539212A (en) * | 2013-10-10 | 2014-01-29 | 彭伟明 | Water activating method and device by combination of acoustic field/electromagnetic field/magnetic field and double-vortex-body vortex |
| CN103539220A (en) * | 2013-10-10 | 2014-01-29 | 彭伟明 | Water activating method and device by combination of acoustic field and double-vortex-body vortex |
| CN106542621A (en) * | 2015-09-18 | 2017-03-29 | 中国石油化工股份有限公司 | Polyacrylamide equipment in magnetic field, ultrasound wave and laser treatment oil field mining liquid |
| CN106542605A (en) * | 2015-09-18 | 2017-03-29 | 中国石油化工股份有限公司 | Laser and ultrasonication oil field waste petrochina kind equipment |
| CN110844983A (en) * | 2019-11-26 | 2020-02-28 | 北京航空航天大学 | Method for treating organic wastewater through magnetic catalysis |
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