CN105819539A - Method for processing organic contaminated waste water - Google Patents
Method for processing organic contaminated waste water Download PDFInfo
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- CN105819539A CN105819539A CN201510009227.7A CN201510009227A CN105819539A CN 105819539 A CN105819539 A CN 105819539A CN 201510009227 A CN201510009227 A CN 201510009227A CN 105819539 A CN105819539 A CN 105819539A
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Abstract
The invention discloses a method for processing organic contaminated waste water. The method is characterized by comprising the following steps: under effect of microwave radiation and supersonic wave, under existence of a photocatalyst, processing the organic contaminated waste water through ultraviolet irradiation, wherein, the microwave frequency of microwave radiation is 900-2500 MHz; the supersonic wave frequency is 20-60 kHz; and the ultraviolet light wavelength is 250-370 nm. In the method for processing the organic contaminated waste water, through combination of the microwave radiation, the supersonic wave and photocatalysis, the synergism is obvious, photocatalysis oxidation treatment is carried out on organic pollutants of the organic contaminated waste water can be better carried out, so that COD and BOD5 of the organic contaminated waste water are reduced to low values, and the processing time is short.
Description
Technical field
The present invention relates to the processing method of a kind of organic polluting water.
Background technology
Along with city and the fast development of modern industry, the organism kinds of synthetic is increasing and consumption increases day by day, and this also brings serious problem of environmental pollution.Generally use traditional biological degradation method that the organic pollution in organic polluting water is carried out degradation treatment, but for the organic pollutant degradation that toxicity is the biggest, traditional biological degradation method poor performance, and need to carry out under suitable ambient temperature, cause being difficult to more thoroughly be converted into organic pollution CO2And water, and its process time is relatively long；Especially for for the brine waste that salt content is high, it is not suitable for the existence of microorganism thus is difficult to use biological degradation method that the organic pollution of brine waste is processed.Although additionally, chemical method can more fully process organic pollution, however it is necessary that and add substantial amounts of chemically reactive substance, such as H2O2、ClO2Deng, processing cost is higher.
Summary of the invention
It is an object of the invention to overcome existing organic polluting water, the organic pollution that particularly processing method of brine waste exists is difficult to remove and the time-consuming defect such as long, is to provide a kind of organic pollution that can remove in organic polluting water efficiently and the processing method of process time shorter organic polluting water.
The present inventor finds through further investigation, compared with traditional heating means, uses microwave heating technique to process Organic Pollutants in Wastewater and has the advantages such as quick, efficient, free from environmental pollution.At present, microwave technique application mainly has three kinds in the mode that organic polluting water processes: the first is first to be adsorbed onto on absorbing material by the pollutant in organic polluting water, is then taken out by absorbing material and is placed in microwave field radiation, makes the contaminant degradation of absorption；The second is that the organic polluting water that direct microwave radiation contains absorbing material is degraded；The third is and being used in combination of other technologies, including with the combining of NaClO, Fenton etc..Said method all there are organic pollutants for the process of the process particularly brine waste of organic polluting water to be difficult to remove and the time-consuming defect such as long.
Additionally, ultrasound wave is so that produce ultrasound cavitation effect in waste water, i.e. make waste water localized hyperthermia high pressure, free radical, shock wave and jet such that it is able to effectively the organic pollution in waste water is processed.The technical operation mild condition of ultrasonic degradation organic pollutants, degradation speed is fast, applied widely.
And, photocatalytic oxidation is a kind of advanced oxidation processes, its principle is under the irradiation of ultraviolet light, the internal electron of used photocatalyst (such as titanium dioxide) migrates, produce hole and electronics, owing to electronics has reproducibility, and hole has the extremely strong ability obtaining electronics, can be by the OH in water-And H2The chemical conversion of O molecular oxygen has the hydroxyl radical free radical (OH) of extremely strong oxidisability, promotes the generation of redox reaction, thus contributes to the degraded of the organic pollution in organic polluting water.
But, inventor finds first, microwave technology, ultrasonic technology and photocatalysis oxidation technique is combined for processing organic polluting water, especially for the process to brine waste.Wherein, the combination of microwave radiation and ultrasound wave can improve heating effectively and energy shifts, and improves energy ecology；Ultraviolet cooperating microwave radiation can form inducing catalysis Oxidation in photocatalyst surface, thus preferably the organic pollution of catalyst surface is removed, and keeps the activity of photocatalyst higher；Further, the addition of ultrasound wave can effectively prevent photocatalyst surface from producing the polymeric film of organic pollution, and can reduce the particle size of the organic pollution being attached to its surface, strengthens reaction mass transfer process；It addition, ultrasound wave and UV light combined are contributed to photocatalysis produce greater concentrations of OH free radical, improve the degradation efficiency of organic pollutants.The present invention is also based on what this completed.
To achieve these goals, the present invention provides the processing method of a kind of organic polluting water, the method includes: under the effect of microwave radiation and ultrasound wave, organic polluting water is injected row process through ultraviolet lighting in the presence of photocatalyst, wherein, the microwave frequency of described microwave radiation is 900-2500MHz；The frequency of described ultrasound wave is 20-60kHz；The wavelength of described ultraviolet light is 250-370nm.
In the processing method of the organic polluting water of the present invention, by microwave radiation, ultrasound wave and light-catalysed combination, its synergism is notable, it is possible to preferably the organic pollution of organic polluting water is carried out Treatment by Photocatalysis Oxidation so that COD and BOD of organic polluting water5It is down to lower value, process especially for brine waste, can not affected by its salinity is higher, and also be there is the advantages such as floor space is little, the process time is short, organic matter degradation is thorough, energy consumption is low, non-secondary pollution, be had broad application prospects.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, is used for explaining the present invention, but is not intended that limitation of the present invention together with detailed description below.In the accompanying drawings:
Fig. 1 be the present invention a kind of preferred embodiment in the schematic diagram of processing means of organic polluting water.
Description of reference numerals
1 microwave reactor；
2 supersonic generators；
3 ultrasonic transducers；
4 uviol lamps；
5 quartz ampoules；
6 water inlets；
7 outlets.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
The present invention provides the processing method of a kind of organic polluting water, the method includes: under the effect of microwave radiation and ultrasound wave, through ultraviolet lighting, organic polluting water is injected row process in the presence of photocatalyst, and wherein, the microwave frequency of described microwave radiation is 900-2500MHz；The frequency of described ultrasound wave is 20-60kHz；The wavelength of described ultraviolet light is 250-370nm.
According to the present invention, the source of described organic polluting water is not particularly limited, can be the waste water polluted by organic pollution from commercial production, it can be especially the organic polluting water that salinity is higher, such as, can be directly using sea water as the waste water produced after water for industrial use, can be the strong brine of discharge after reverse osmosis units.Wherein, the salinity of described organic polluting water is not particularly limited by the present invention, the organic polluting water in the range of wider salinity can be processed, especially process the organic polluting water that salinity is high, preferably, described organic polluting water is the salinity brine waste at more than 2000mg/L.It is highly preferred that described organic polluting water is the salinity brine waste at 2000-5000mg/L.Above-mentioned salinity is mainly determined by the amount of the inorganic salt contained in waste water, such as, can be NaCl, Na2SO4、CaCl2、MgSO4Deng.
Wherein, owing to described organic polluting water is mainly derived from containing being difficult to the industrial wastewater of organic pollution that removes, although the organic polluting water of any organic pollution content can be processed by the processing method of the organic polluting water of the present invention, but method of the invention is particularly suitable for processing COD is 50-300mg/L, BOD5For the organic polluting water of 5-30mg/L, it is highly preferred that the COD of described organic polluting water is 60-250mg/L, BOD5For 6-20mg/L.It is further preferred that the COD of described brine waste is 100-205mg/L, BOD5For 10-20mg/L.
According to the present invention, the microwave frequency of described microwave radiation is 900-2500MHz, in order to obtain the degradation effect of more preferable organic pollution, under preferable case, the microwave frequency of described microwave radiation is 915-2450MHz, and particularly preferably using microwave frequency is the microwave of 2450MHz.
According to the present invention, owing to microwave radiation can improve energy ecology together with ultrasound wave synergistically, and, the photocatalyst used has the strongest absorbability to microwave radiation, this makes to adsorb the organic pollution in photocatalyst surface and can degrade quickly, it is thus possible to improve the activity of photocatalyst, complete the short time treatment of organic pollution to organic polluting water (particularly brine waste).
Therefore, the source of microwave radiation is not particularly limited by the present invention, as long as enabling to ultrasonic reaction carry out under microwave radiation and be capable of above-mentioned degradation effect, such as, Vltrasonic device can be placed in the environment of microwave radiation, can by as described in Vltrasonic device be placed in microwave reactor.If employing microwave reactor, the power that can set is as 20-80W, and sets the microwave frequency launching microwave as 900-2500MHz.
Additionally, the process of organic polluting water is also carried out under the effect of ultrasound wave by the present invention.Owing to have employed ultrasound wave, it is possible not only to jointly act on microwave radiation, the more important thing is, so that the surface of described photocatalyst will not be covered by organic pollution and form polymeric film, and the particle size of the organic pollution being attached to its surface can be reduced, strengthen reaction mass transfer process, thus more contribute to the photocatalyst absorption to microwave radiation, activated again photocatalyst, it is possible to more efficiently organic pollution is carried out photocatalytic oxidation degradation simultaneously.
Preferably, the frequency of the ultrasound wave that the present invention uses is 20-60kHz, it is highly preferred that the frequency of described ultrasound wave is 20-40kHz, more preferably 20-30kHz.
The source of ultrasound wave is not particularly limited by the present invention, as long as being capable of above-mentioned degradation effect, for example, it is possible to the reaction system of photocatalysis oxidation reaction is arranged in ultrasonic generator so that the reaction system of photocatalysis oxidation reaction is in the environment of ultrasound wave.If in the case of using ultrasonic generator, the power of described ultrasonic generator is preferably 30-100W.
Additionally, the present invention is to carry out under ultraviolet light irradiates the process of organic polluting water.Wherein, the photocatalyst used, first can be under the irradiation of ultraviolet light so that organic pollution carries out photocatalytic oxidation degradation on the surface of photocatalyst；Second the photocatalyst used also has stronger Absorption to microwave, it is possible to use organic pollution is degraded by microwave radiation；Under the effect of ultrasound wave, the mass transfer of photocatalyst surface can be strengthened, the generation of OH can be promoted for three.In other words, owing to present invention employs microwave radiation, ultrasound wave and ultraviolet light, its synergism is very beneficial for the photocatalysis oxidation reaction process to the organic pollution of organic polluting water, especially for the process of brine waste, will not be affected by its high salinity character.
Preferably, the wavelength of the ultraviolet light that the present invention uses is 250-370nm, and in order to obtain more preferable water treatment efficiency, the wavelength of the most described ultraviolet light is 254-365nm, such as, can be the ultraviolet light of the wavelength of 254nm, 305nm or 365nm.
The source of ultraviolet light is not particularly limited by the present invention, as long as being capable of above-mentioned degradation effect, such as, can can produce the uviol lamp of ultraviolet light by configuration in photocatalysis oxidation reaction system, and also quartz ampoule can be used to entangle this uviol lamp to prevent the damage to uviol lamp.If in the case of using uviol lamp, the power of described uviol lamp is preferably 30-150W.
In order to play the effect of ultraviolet light more preferable Synergistic degradation organic pollution, under preferable case, the exposure rate of described ultraviolet light is 300-600mW/cm2。
Wherein, described photocatalysis is not particularly limited by the present invention, if be capable of the effect above all can, under preferable case, described photocatalyst is TiO2Nano-particle, ZnO nano granule, SnO2Nano-particle, ZrO2One or more in nano-particle and CdS nano-particle, more preferably TiO2One or more in nano-particle, ZnO nano granule and CdS nano-particle.
In order to preferably degrade the organic pollution in brine waste, under preferable case, the grain graininess of described photocatalyst is 5-20nm.
The consumption of described photocatalyst can change in wider scope, suitable adjustment can be carried out according to the water quality situation of concrete organic polluting water, under preferable case, on the basis of the total amount of described organic polluting water, the consumption of described photocatalyst is 1-6 weight %, more preferably 2-5 weight %.
In order to obtain more preferable degradation effect, under preferable case, the condition of described process includes: pH is 3-10, and temperature is 15-50 DEG C, and the time is 5-15min.It is highly preferred that the condition of described process includes: pH is 3-9, temperature is 20-40 DEG C, and the time is 5-10min.It is further preferred that the condition of described process includes: pH is 5-7, temperature is 25-35 DEG C, and the time is 6-8min.
The present invention one preferred embodiment in, as shown in Figure 1, organic polluting water is sent to supersonic generator 2 from water inlet 6, and this supersonic generator 2 is placed in the environment of making reaction system be in microwave radiation in microwave reactor 1, and in this supersonic generator 2, it is provided with the uviol lamp 4 entangled by quartz ampoule 5 so that under reaction system is irradiated also in ultraviolet light；Additionally, this supersonic generator 2 bottom is additionally provided with ultrasonic transducer 3 produces ultrasound wave to coordinate.Organic pollution in organic polluting water, under the synergism of microwave radiation, ultrasound wave and ultraviolet light, carries out photocatalytic oxidation degradation by photocatalyst.After completing degraded, discharge from outlet 7.
By means of the invention it is also possible to by microwave radiation, ultrasound wave and the synergism of ultraviolet light, the organic pollution of organic polluting water is down to lower value, especially, COD is reduced to below 50mg/L, BOD5It is reduced to below 10mg/L, the reusing sewage standard that GB18918-2002 " urban wastewater treatment firm pollutant emission standard " specifies can be reached.
Hereinafter will be described the present invention by embodiment.
In following example and comparative example,
Described organic polluting water is taken from the strong brine of Yanshan Petrochemical company wastewater reusing device reverse osmosis units scene discharge, and its water quality situation is: COD is 205mg/L, BOD5Being 7.2 for 16mg/L, pH, salinity is 2200mg/L, and electrical conductivity is 4.07ms/cm；
The COD value of water quality is by using the dichromate titration in GB11914-89 to be measured, BOD5Value is by using the method in GB7488-87 to be measured, and salinity is by using the method in HJ/T51-1999 to be measured.
Embodiment 1
The present embodiment is for illustrating the processing method of the organic polluting water of the present invention.
As it is shown in figure 1, by organic polluting water described in 1L and photocatalyst TiO2Nano-particle (10nm, purchased from Haitai Nano Material Co., Ltd., Nanjing, on the basis of the total amount of described brine waste, the consumption of this photocatalyst is 2 weight %) join in supersonic generator, and this supersonic generator is configured with the uviol lamp being cased with quartz ampoule, and this supersonic generator is placed in microwave reactor.Under the effect of microwave radiation, ultrasound wave and ultraviolet light, at the reaction of pH to be 3 times carried out at 30 DEG C 5min, COD and BOD of its water outlet5As shown in table 1.
Wherein, microwave reactor: be MCR-3 purchased from Ke Rui Instrument Ltd. of Gongyi City model；Microwave frequency is 2450MHz；Power is 20W；
Supersonic generator: Shanghai Sheng Xi ultrasonic instrument company limited model is FS-600N；Frequency is 20KHz, and power is 30W；
Uviol lamp: fly up to Science and Technology Ltd. purchased from Shenzhen is rich；Wavelength is 365nm, and power is 30W.
Embodiment 2
The present embodiment is for illustrating the processing method of the organic polluting water of the present invention.
As shown in Figure 1, by organic polluting water described in 1L and light-catalyst ZnO nano-particle (20nm, purchased from Haitai Nano Material Co., Ltd., Nanjing, on the basis of the total amount of described brine waste, the consumption of this photocatalyst is 5 weight %) join in supersonic generator, and this supersonic generator is configured with the uviol lamp being cased with quartz ampoule, and this supersonic generator is placed in microwave reactor.Under the effect of microwave radiation, ultrasound wave and ultraviolet light, at the reaction of pH to be 6 times carried out at 20 DEG C 10min, COD and BOD of its water outlet5As shown in table 1.
Wherein, microwave reactor: be MCR-3 purchased from Ke Rui Instrument Ltd. of Gongyi City model；Microwave frequency is 2450MHz；Power is 80W；
Supersonic generator: Shanghai Sheng Xi ultrasonic instrument company limited model is FS-600N；Frequency is 40KHz, and power is 90W；
Uviol lamp: fly up to Science and Technology Ltd. purchased from Shenzhen is rich；Wavelength is 254nm, and power is 120W.
Embodiment 3
The present embodiment is for illustrating the processing method of the organic polluting water of the present invention.
As shown in Figure 1, by organic polluting water described in 1L and photocatalyst CdS nano-particle (5nm, purchased from quantum source, Hefei nanosecond science and technology limited company, on the basis of the total amount of described brine waste, the consumption of this photocatalyst is 3 weight %) join in supersonic generator, and this supersonic generator is configured with the uviol lamp being cased with quartz ampoule, and this supersonic generator is placed in microwave reactor.Under the effect of microwave radiation, ultrasound wave and ultraviolet light, at the reaction of pH to be 9 times carried out at 40 DEG C 8min, COD and BOD of its water outlet5As shown in table 1.
Wherein, microwave reactor: be MCR-3 purchased from Ke Rui Instrument Ltd. of Gongyi City model；Microwave frequency is 2450MHz；Power is 50W；
Supersonic generator: Shanghai Sheng Xi ultrasonic instrument company limited model is FS-600N；Frequency is 30KHz, and power is 60W；
Uviol lamp: fly up to Science and Technology Ltd. purchased from Shenzhen is rich；Wavelength is 305nm, and power is 80W.
Embodiment 4
The present embodiment is for illustrating the processing method of the organic polluting water of the present invention.
According to the method described in embodiment 2, except that, the photocatalyst of employing is SnO2Nano-particle (20nm, purchased from quantum source, Hefei nanosecond science and technology limited company, on the basis of the total amount of described brine waste)；COD and BOD of its water outlet5As shown in table 1.
Embodiment 5
The present embodiment is for illustrating the processing method of the organic polluting water of the present invention.
According to the method described in embodiment 2, except that, under the effect of microwave radiation, ultrasound wave and ultraviolet light, in the reaction of pH to be 10 times carried out at 50 DEG C 15min；COD and BOD of its water outlet5As shown in table 1.
Embodiment 6
The present embodiment is for illustrating the processing method of the organic polluting water of the present invention.
According to the method described in embodiment 2, except that, microwave reactor is for being FSQ purchased from Beijing Jie Nengda Electronics Equipment Co., Ltd model, and microwave frequency is 915MHz, and power is 60W；COD and BOD of its water outlet5As shown in table 1.
Embodiment 7
The present embodiment is for illustrating the processing method of the brine waste of the present invention.
According to the method described in embodiment 1, except that, the frequency of supersonic generator is 60KHz, and power is 80W；COD and BOD of its water outlet5As shown in table 1.
Comparative example 1
According to the method described in embodiment 2, except that, do not carry out ultraviolet light irradiation, COD and BOD of its water outlet5As shown in table 1.
Comparative example 2
According to the method described in embodiment 2, except that, do not carry out ultrasonic Treatment, COD and BOD of its water outlet5As shown in table 1.
Comparative example 3
According to the method described in embodiment 2, wherein, except that, do not carry out microwave radiation processing, COD and BOD of its water outlet5As shown in table 1.
Table 1
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can be carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that, each concrete technical characteristic described in above-mentioned detailed description of the invention, in the case of reconcilable, can be combined by any suitable means, in order to avoid unnecessary repetition, various possible compound modes are illustrated by the present invention the most separately.
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. the processing method of an organic polluting water, it is characterized in that, the method includes: under the effect of microwave radiation and ultrasound wave, and through ultraviolet lighting, organic polluting water is injected row process in the presence of photocatalyst, wherein, the microwave frequency of described microwave radiation is 900-2500MHz；The frequency of described ultrasound wave is 20-60kHz；The wavelength of described ultraviolet light is 250-370nm.
Method the most according to claim 1, wherein, the wavelength of described ultraviolet light is 254-365nm.
Method the most according to claim 1, wherein, the microwave frequency of described microwave radiation is 915-2450MHz.
Method the most according to claim 1, wherein, the frequency of described ultrasound wave is 20-40KHz.
Method the most according to claim 1, wherein, described photocatalyst is TiO2Nano-particle, ZnO nano granule, SnO2Nano-particle, ZrO2One or more in nano-particle and CdS nano-particle, preferably TiO2One or more in nano-particle, ZnO nano granule and CdS nano-particle.
6. according to the method described in any one in claim 1-5, wherein, on the basis of the total amount of described organic polluting water, the consumption of described photocatalyst is 1-6 weight %, preferably 2-5 weight %.
7. according to the method described in any one in claim 1-6, wherein, the condition of described process includes: pH is 3-10, and temperature is 15-50 DEG C, and the time is 5-15min.
Method the most according to claim 7, wherein, the condition of described process includes: pH is 3-9, and temperature is 20-40 DEG C, and the time is 5-10min.
9. according to the method described in any one in claim 1-8, wherein, the COD of described organic polluting water is 50-300mg/L, BOD5For 5-30mg/L.
10. according to the method described in any one in claim 1-9, wherein, the salinity of described organic polluting water is more than 2000mg/L.
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| CN109734569A (en) * | 2019-03-08 | 2019-05-10 | 合肥工业大学 | A kind of method that intensified by ultrasonic wave photocatalysis continuously prepares acetylacetone metallic compound |
| CN113000585A (en) * | 2021-02-01 | 2021-06-22 | 生态环境部南京环境科学研究所 | Composite catalytic oxidation degradation method and device for organochlorine pesticide contaminated soil |
| CN114656078A (en) * | 2022-01-25 | 2022-06-24 | 昆明理工大学 | Method for removing organic matters in solution through spray catalysis in multi-field coupling high-energy field |
| CN116177637A (en) * | 2023-02-20 | 2023-05-30 | 长安大学 | Repairing system and method for ultrasonic-assisted reinforced underground water circulating well |
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| CN102826698A (en) * | 2012-09-11 | 2012-12-19 | 宁波大学 | Wastewater-degradation microwave photocatalytic device beneficial to inhibiting energy unnecessary dissipation |
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| CN109734569A (en) * | 2019-03-08 | 2019-05-10 | 合肥工业大学 | A kind of method that intensified by ultrasonic wave photocatalysis continuously prepares acetylacetone metallic compound |
| CN113000585A (en) * | 2021-02-01 | 2021-06-22 | 生态环境部南京环境科学研究所 | Composite catalytic oxidation degradation method and device for organochlorine pesticide contaminated soil |
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