CN1544346A - Ultrasonic wave and oxidation sewage treatment method - Google Patents
Ultrasonic wave and oxidation sewage treatment method Download PDFInfo
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Abstract
The invention relates to a ultrasonic oxidization sewage treatment process which is aimed at solving the problem of unsatisfactory treatment effects to COD, BOD, SS, N, P, chromaticity and various hard-degradable organics in the conventional sewage treatment methods, the process according to the invention comprises the steps of, (1) water pretreatment, (2) subjecting the pretreated water to ultrasonic treatment, (3) subjecting the treated water to post-treatment, high-grade oxidation treatment can be added to each or any one of the steps.
Description
The technical field is as follows:
the invention relates to a sewage treatment method, in particular to a sewage treatment method by adopting ultrasonic and advanced oxidation treatment.
Background art:
with the rapid development of fine chemical industry, pharmaceutical industry, printing and dyeing and other industries, the treatment of some high-concentration refractory toxic and harmful organic wastewater is a difficult problem which troubles environmental protection workers, and meanwhile, the micro-pollution of drinking water is also directly related to the drinking water health problem of human beings. Meanwhile, with the improvement of living standard, people's environmental awareness is continuously strengthened, and the migration and change of refractory organic matters in the environment are concerned more and more, however, the treatment of high-concentration refractory organic pollutants is always a difficult point of wastewater treatment and is difficult to treat by the conventional process. Because the concentration of the wastewater is high, the COD is generally tens of thousands mg/l, in addition, the contained pollutants are mainly aromatic compounds, the molecular weight is very large, the biodegradability is poor, the toxicity of the wastewater is high, the content of inorganic salts is high, the method for treating the high-concentration refractory organic wastewater by adopting the chemical oxidation method is one of the more effective methods at present, but the method for treating the high-concentration refractory organic wastewater by adopting the chemical oxidation method has the defects of long reaction time, incomplete reaction, large using amount of oxidant and the like.
The ultrasonic wave is used for degrading chemical pollutants in water, particularly organic pollutants which are difficult to degrade, and is a novel water treatment technology developed in recent years. A large number of experimental studies show that the ultrasonic frequency is increased, cavitation bubbles in a liquid medium are reduced, the cavitation strength is reduced, and the ultrasonic chemical effect is correspondingly reduced. When the ultrasonic frequency is high, the time of the expansion and compression cycles is very short, since the time of the expansion cycle is too short to wait until the microbubbles are long enough to cause the liquid medium to collapse, forming cavitation bubbles, which collapse much longer than the time required for the compression half-cycle, even if cavitation bubbles are generated during the expansion. Therefore, when the intensity of the ultrasonic wave is constant, the higher the frequency is, the smaller the cavitation is. Recent studies have shown that high frequency ultrasound contributes to increased rates of sonication. The acoustic source frequency is too low, the yield of OH radicals is not high, and the sonochemical degradation effect is reduced.
Disclosure of Invention
In order to solve the above disadvantages, the present invention aims to provide a method with good treatment effect and good removal effect on COD, BOD, SS, N, P, chromaticity and various refractory organics.
The invention relates to a method for treating sewage by ultrasonic oxidation, which comprises the following steps:
a. pretreating water;
b. then the pretreated water is subjected to ultrasonic treatment;
c. post-treating the water after ultrasonic treatment;
an advanced oxidation treatment is added to any one or each of the above steps.
After the method is adopted, the generation amount of hydroxyl free radicals in the sewage can be greatly increased through an advanced oxidation technology, the chemical reaction speed is accelerated, and meanwhile, the heat release effect generated by the oxidation reaction can further strengthen the high-temperature pyrolysis reaction in the cavitation bubbles or on the cavitation bubble interface. The presence of metal ions or metal compounds in the solution will have some catalytic effect on the degradation process of the contaminants. By adding catalysts such as metal salt or oxide, the concentration of metal ions in water can be increased, on one hand, the chemical oxidation speed is accelerated, and on the other hand, the efficiency of ultrasonic sewage treatment is improved. The ultrasonic cavitation effect should produce a strong mechanical shearing action. In a multiphase system containing polymers with water content, mass points of a sound transmission medium generate large instantaneous speed and acceleration when cavitation bubbles collapse to cause violent vibration, and the vibration macroscopically shows strong hydrodynamic shear force and can break carbon bonds on a main chain of macromolecules, so that the action of degrading macromolecules is achieved. Therefore, the ultrasonic technology can degrade macromolecules of the sewage into micromolecules, and is beneficial to further and thoroughly oxidizing the subsequent oxidation treatment. The high temperature generated by the ultrasonic cavitation effect also accelerates the oxidation reaction. The exothermic effect of the oxidation reaction increases the temperature and the vapor pressure, so that the cavitation is easier to realize, and the products of the oxidation reaction are inorganic gases dissolved in water, thereby reducing the cavitation area and being beneficial to the formation of the cavitation effect. In addition, the contact probability of the sewage and the oxide is enhanced by the violent vibration effect of the ultrasonic waves, the mass transfer effect between the organic matters and the free radicals is enhanced, the efficiency and the effect of ultrasonic sewage treatment can be effectively enhanced, and COD, BOD, SS, N, P, chromaticity and various organic matters which are difficult to degrade can be well removed.
Drawings
FIG. 1 is a schematic view of a method for treating sewage by ultrasonic oxidation according to the present invention.
FIG. 2 is a schematic view of the method for treating sewage by ultrasonic photocatalytic oxidation according to the present invention.
Detailed Description
Referring to fig. 1, the general sewage treatment process includes the necessary pretreatment of regulation, coagulating sedimentation, filtration, pre-oxidation, biochemical treatment, etc., and then enters the ultrasonic reactor for ultrasonic treatment, and the water enters the post-treatment after being treated by the ultrasonic reactor, and the post-treatment process may include the residence of the effluent in a water storage tank, the regulation treatment, or the micro-filtration, coagulation, sedimentation, filtration, membrane filtration, etc., and the control of part of the water to flow back to the pretreatment stage to reduce the organic load of the ultrasonic and oxidation stages. The reflux ratio is controlled to be 0-300%. The present invention incorporates advanced oxidation treatment in any or each of the steps described above. In the advanced oxidation treatment process, free radicals (OH radicals) with strong oxidation capacity can be generated, the free radicals have high oxidation-reduction potential and strong oxidizability, so that the oxidation capacity and the reaction rate can be greatly improved, a plurality of difficultly-degraded pollutants which cannot be decomposed by an oxidant alone can be oxidized, and the defect that the yield of the free radicals is low due to the influence of the sound source frequency and the power in the ultrasonic technology can be greatly overcome.
As a further improvement of the present invention, the above-mentioned oxidation treatment is added to the ultrasonic treatment step.
Ultrasonic sewage treatment is based on the following effects: (1) cavitation effect: the ultrasonic wave is composed of a series of longitudinal waves with alternate density and is transmitted to the periphery through a liquid medium. When the acoustic energy is high enough, the attractive force between liquid phase molecules is broken in the loose half period, and cavitation nuclei are formed. The lifetime of the cavitation core is about 0.1 mus, it can generate local high temperature and high pressure environment of about 4000K and 100MPa at the moment of explosion, and generate microjet with strong impact force at the speed of about 110m/s, and this phenomenon is called ultrasonic cavitation. The organic matter is subjected to chemical bond breakage, water phase combustion, pyrolysis or free radical reaction in the cavitation bubbles. (2) Free radical reaction: at high temperature and pressure generated by cavitation, water molecules are cleaved to generate free radicals:
Therefore, the oxidation treatment process is added to the ultrasonic treatment step, and the ultrasonic oxidation treatment can remarkably improve the sewage treatment effect. The generation amount of hydroxyl free radicals in the sewage can be greatly increased through oxidation treatment, the chemical reaction speed is accelerated, and meanwhile, the heat release effect generated by the oxidation reaction can further strengthen the high-temperature pyrolysis reaction in cavitation bubbles or on a cavitation bubble interface. The presence of metal ions or metal compounds in the solution will have some catalytic effect on the degradation process of the contaminants. By adding catalysts such as metal salt or oxide, the concentration of metal ions in water can be increased, on one hand, the chemical oxidation speed is accelerated, and on the other hand, the efficiency of ultrasonic sewage treatment is improved. The ultrasonic cavitation effect should produce a strong mechanical shearing action. In a multiphase system containing polymers with water content, mass points of a sound transmission medium generate large instantaneous speed and acceleration when cavitation bubbles collapse to cause violent vibration, and the vibration macroscopically shows strong hydrodynamic shear force and can break carbon bonds on a main chain of macromolecules, so that the action of degrading macromolecules is achieved. The high temperature generated by the ultrasonic cavitation effect also accelerates the oxidation reaction. The exothermic effect of the oxidation reaction increases the temperature and the vapor pressure, so that the cavitation is easier to realize, and the products of the oxidation reaction are inorganic gases dissolved in water, thereby reducing the cavitation area and being beneficial to the formation of the cavitation effect. In addition, the contact probability of the sewage and the oxide is enhanced by the violent vibration action of the ultrasonic waves, and the mass transfer effect between the organic matters and the free radicals is enhanced. The ultrasonic sewage treatment technology and the advanced oxidation technology are organically combined, the respective technical advantages are fully exerted, and the treatment effect of the organic sewage is superior to that of a single ultrasonic and advanced oxidation system.
The advanced oxidation treatment may be one or a combination of several of optical oxidation, chemical oxidation, wet oxidation and supercritical oxidation, such as photochemical oxidation.
The chemical oxidation in the advanced oxidation treatment of the invention comprises adopting O3、H2O2、KMnO4、ClO2And ferrate, the dosage of the oxidant is determined according to the specific sewage condition.
The wet oxidation in the advanced oxidation treatment of the invention comprises oxidizing organic matters in the sewage by using oxygen or air as an oxidant under the operating conditions of high temperature of 150-350 ℃ and high pressure of 5-20 MPa.
The supercritical oxidation in the advanced oxidation treatment according to the present invention includes decomposing organic substances contained in wastewater into simple and harmless small molecular compounds such as water and carbon dioxide with oxygen in a supercritical water state.
The optical oxidation in the advanced oxidation treatment of the invention refers to the treatment of sewage by ultraviolet irradiation in the sewage. When the ultraviolet lamp tube is added in the ultrasonic oxidation treatment, the ultraviolet lamp tube can be cleaned to a certain degree, and the photocatalytic oxidation efficiency is enhanced.
The photochemical oxidation is a combination of optical oxidation and chemical oxidation, and comprises irradiating with ultraviolet light while using O3、H2O2Or Fenton reagent or O3And H2O2Or Fenton as an oxidant (UV/H)2O2、UV/O3、UV/O3/H2O2). Wherein, the Fenton reagent can adopt bivalent or trivalent iron.
In order to obtain better oxidation effect, according to different sewage quality, a catalyst can be added in the oxidation treatment process.
For example, the photocatalytic oxidation includes irradiation with ultraviolet light and simultaneous addition of a catalyst, and can adopt two forms of homogeneous phase and heterogeneous phase, the homogeneous photocatalytic oxidation includes a UV/Fenton reagent method, and the Fenton reagent can adopt ferrous or ferric salts. Heterogeneous photocatalytic oxidation is carried out by using a semiconductor, such as TiO2ZnO, etc. degrade organic substances by photocatalysis. The heterogeneous photocatalytic oxidation catalyst can adopt modified TiO2Or modified other metal oxides or metal salts or mixtures of each.
In order to obtain better treatment effect, a catalyst can be added in photochemical oxidation, namely photocatalytic chemical oxidation, including ultraviolet irradiation and O3、H2O2Or Fenton reagent or O3And H2O2Or Fenton as an oxidant (UV/H)2O2、UV/O3、UV/O3/H2O2) And simultaneously adding a catalyst. The catalyst can adopt modified TiO2Or modified other metal oxides or metal salts or mixtures of each.
The wet catalytic oxidation comprises adding a proper catalyst into the conventional wet oxidation treatment to reduce the temperature and pressure required for the reaction, improve the oxidative decomposition capability, shorten the time, prevent the corrosion of equipment and reduce the cost. The catalyst adopts transition metal and its oxide, composite oxide and salt.
The supercritical catalytic oxidation in the advanced oxidation treatment of the invention is a method for treating sewage by adding a proper catalyst on the basis of the supercritical oxidation treatment.
The catalyst added in the advanced oxidation treatment adopts oxide composite oxides and salts of transition metals and noble metals. Such as TiO2, ZnO, CdS, WO3, Pb2O3, SnO2，In2O3，SrTiO3，Co2O3，MoO，Ni2O3，Cr2O3And the like.
Photocatalytic oxidation (UV/TiO) in advanced oxidation treatment according to the present invention2UV/Fenton), photochemical oxidation (UV/H)2O2、UV/O3、UV/O3/H2O2) Photocatalytic chemical oxidation (UV/TiO)2/H2O2、UV/TiO2/O3、UV/TiO2/O3/H2O2) The wavelength of the ultraviolet light is 200-300 nm, and a broad-spectrum ultraviolet lamp can be used as a light source.
Because the invention adopts advanced oxidation treatment, no secondary pollution is caused. Of course, the invention can also be used for removing refractory organic matters and Ternary Substances (THMs) in the advanced treatment of drinking water.
The following are comparative data of 5 groups of examples when the method for treating sewage by ultrasonic oxidation is adopted to treat the water quality of landfill leachate and the comparison data when ultrasonic waves are singly used and advanced oxidation treatment is singly used.
Example 1
Ultrasonic wave and photocatalytic oxidation are combined. As shown in figure 2, the ultraviolet lamp 1 is a broad-spectrum UV lamp, a quartz tube is sleeved outside the lamp tube, a catalyst carrier is coated outside the quartz tube, and the catalyst 2 is TiO2The ultraviolet lamp is placed in an ultrasonic generator.
Example 2
The sewage is treated by adopting ultrasonic and ultraviolet light-assisted Fenton reagent (Fenton) in a combined way. Ultraviolet rays adopt a broad-spectrum UV lamp with the wavelength of 20O-280nm, and Fenton reagent is added into a reactor.
Example 3
Using ultrasonic and ozone/ultraviolet (UV/O)3) And (4) combining. The ultraviolet lamp is a broad-spectrum UV lamp. Ozone is added into the reactor, and the concentration of the ozone is mg/l.
Example 4
Using ultrasonic waves and ozone/ultraviolet light/H2O2(UV/O3/H2O2) And (4) combining.
Example 5
Using ultrasonic waves and ozone/ultraviolet light/H2O2(UV/O3/H2O2) And (4) combining. The ultrasonic sound source adopts 80KHz and the power is 9.5w/cm2. The ultraviolet lamp adopts a broad-spectrum UV lamp with the wavelength of 200-280nm, 150mg/l of ozone is added into the reactor, and 250mg/l of Fenton reagent is added at the same time.
| Measurement items | COD (mg/l) | BOD (mg/l) | NH3-N (mg/l) | PH | |
| Fruit of Chinese wolfberry Applying (a) to Example (b) | Example one | 3180 | 1240 | 2550 | 7.2 |
| Example two | 4320 | 1553 | 2438 | 7.2 | |
| EXAMPLE III | 2845 | 1165 | 2374 | 7.2 | |
| Example four | 2550 | 1028 | 2256 | 7.1 | |
| EXAMPLE five | 1576 | 603 | 2035 | 7.0 | |
| Raw water | 31600 | 6250 | 2700 | 7.3 | |
| Ultrasonic wave | 23300 | 8530 | 2857 | 7.5 | |
| UV/TiO2 | 28650 | 6190 | 2753 | 7.4 | |
From the data, the ultrasonic sewage treatment technology and the advanced oxidation technology are organically combined, respective technical advantages are fully exerted, the advanced oxidation technology generates a large number of hydroxyl free radicals (. OH groups), the defect that the yield of the free radicals is not high due to the influence of sound source frequency and power on the ultrasonic technology is overcome, and the long chain of the macromolecular organic matter can be fully broken and converted into small molecular substances due to the cavitation effect, the mechanical shearing effect and the condensation effect of ultrasonic treatment, so that the consumption of an oxidant is greatly reduced, and the sewage treatment cost is saved.
Claims (6)
1. A method for treating sewage by ultrasonic oxidation comprises the following steps:
a. pretreating sewage;
b. then carrying out ultrasonic treatment on the pretreated sewage;
c. carrying out post-treatment on the sewage treated by the ultrasonic wave; the method is characterized in that: an advanced oxidation treatment is added to any one or each of the above steps.
2. The method of ultrasonic oxidation sewage treatment as set forth in claim 1, wherein: the advanced oxidation treatment is added in the ultrasonic treatment step.
3. The method for ultrasonic oxidation sewage treatment according to claim 1 or 2, characterized in that: the advanced oxidation comprises one or more of optical oxidation, chemical oxidation, wet oxidation and supercritical oxidation.
4. The method of ultrasonic oxidation sewage treatment as set forth in claim 3, wherein: the light source of the optical oxidation is a broad-spectrum ultraviolet lamp, and the wavelength of the ultraviolet light is 200-300 nm.
5. The method for ultrasonic oxidation sewage treatment according to claim 1 or 2, characterized in that: the advanced oxidation treatment process is also added with a catalyst.
6. The method of ultrasonic oxidation sewage treatment as set forth in claim 5, wherein: the catalyst comprises one or a combination of more of transition metal, oxide, composite oxide, salt and composite salt of noble metal.
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| CN102417283A (en) * | 2010-09-27 | 2012-04-18 | 财团法人工业技术研究院 | Organic solid hydrolyzing method and device thereof |
| CN103180252A (en) * | 2010-08-24 | 2013-06-26 | A.史策有限公司 | Enhanced advanced oxidation procedure |
| CN103395920A (en) * | 2013-07-10 | 2013-11-20 | 贵州长城环保科技有限公司 | Ultrasonic synergistic oxidation wastewater treatment equipment |
| CN103880150A (en) * | 2014-04-04 | 2014-06-25 | 厦门理工学院 | Water treatment device for enhancing chloramine disinfection and treatment method thereof |
| CN104193038A (en) * | 2014-09-17 | 2014-12-10 | 长沙威保特环保科技有限公司 | Method for treating landfill leachate through combination of simulative Fenton reaction and ultrasonic as well as simulative Fenton-ultrasonic reactor |
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| CN103180252B (en) * | 2010-08-24 | 2016-01-27 | A.史策有限公司 | The advanced oxidization method strengthened |
| US9169135B2 (en) | 2010-09-03 | 2015-10-27 | Industrial Technology Research Institute | Method and apparatus for hydrolyzing organic solid |
| CN102417283B (en) * | 2010-09-27 | 2014-09-03 | 财团法人工业技术研究院 | Organic solid hydrolyzing method and device thereof |
| CN102417283A (en) * | 2010-09-27 | 2012-04-18 | 财团法人工业技术研究院 | Organic solid hydrolyzing method and device thereof |
| CN103395920A (en) * | 2013-07-10 | 2013-11-20 | 贵州长城环保科技有限公司 | Ultrasonic synergistic oxidation wastewater treatment equipment |
| CN103880150A (en) * | 2014-04-04 | 2014-06-25 | 厦门理工学院 | Water treatment device for enhancing chloramine disinfection and treatment method thereof |
| CN103880150B (en) * | 2014-04-04 | 2015-07-15 | 厦门理工学院 | Water treatment device for enhancing chloramine disinfection and treatment method thereof |
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| CN104193038B (en) * | 2014-09-17 | 2016-01-20 | 长沙威保特环保科技有限公司 | The method of simulation Fenton's reaction combining ultrasonic ripple treating refuse percolate and simulation Fenton-ultrasonic reactor |
| CN104193038A (en) * | 2014-09-17 | 2014-12-10 | 长沙威保特环保科技有限公司 | Method for treating landfill leachate through combination of simulative Fenton reaction and ultrasonic as well as simulative Fenton-ultrasonic reactor |
| CN105439337A (en) * | 2014-09-30 | 2016-03-30 | 天津科技大学 | Method for treating food industry wastewater through ultrasonic waves and supercritical water oxidation |
| CN108147499A (en) * | 2015-11-20 | 2018-06-12 | 安溪县景宏技术咨询有限公司 | Sewage disposal system |
| CN108147499B (en) * | 2015-11-20 | 2021-05-25 | 广东万绿环保集团有限公司 | Sewage treatment system |
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| CN107029697A (en) * | 2017-05-26 | 2017-08-11 | 河海大学 | A kind of method of supersonic synergic zinc oxide/graphene photocatalysis combined pretreatment mature landfill leachate |
| CN109085673A (en) * | 2017-06-14 | 2018-12-25 | 重庆海扶医疗科技股份有限公司 | Light transmission assembly and sonoluminescence detection system |
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| CN108218065A (en) * | 2017-12-29 | 2018-06-29 | 浙江水知音环保科技有限公司 | A kind of method that polluted river water quickly removes low-concentration ammonia-nitrogen |
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| CN110697976A (en) * | 2019-10-09 | 2020-01-17 | 桂润环境科技股份有限公司 | Treatment method of percolate concentrated solution of household garbage landfill |
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