CN111138057A - E+Device and method for deep treatment of oily sludge by micro-nano bubble ozone - Google Patents
E+Device and method for deep treatment of oily sludge by micro-nano bubble ozone Download PDFInfo
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- CN111138057A CN111138057A CN202010015306.XA CN202010015306A CN111138057A CN 111138057 A CN111138057 A CN 111138057A CN 202010015306 A CN202010015306 A CN 202010015306A CN 111138057 A CN111138057 A CN 111138057A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/06—Treatment of sludge; Devices therefor by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/006—Electrochemical treatment, e.g. electro-oxidation or electro-osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention discloses a method for preparing a compound+-a device and a method for deep treatment of oily sludge by micro-nano bubble ozone; the device comprises a vibrating screen E+-micro-nano bubble ozone device, power supply; the oily sludge treated by the vibrating screen enters the step E+-micro-nano bubble ozone device to destroy oily sludge emulsification structure by ozone oxidation, using E at the upper end of the device+Electrolyzing to further demulsify; e+O brought in during aeration by the coupling effect of micro-nano bubble ozone2And O not consumed in time as organic matter3Conversion to H2O2OH and the like to realize deep oxidation of oil substances and convert the oil substances into carbon dioxide and water; the micro-nano ozone floating bubbles bring the demulsified oil drops to the liquid level and are recovered by an oil scraper. Book (I)Invention adopts E+The micro-nano bubble ozone coupling method realizes air floatation, ozone and electrochemical synergistic oxidation, and simultaneously achieves multiple effects of recycling, reducing, harmlessness and the like of the oily sludge.
Description
Technical Field
The invention belongs to the field of hazardous waste treatment, and particularly relates to an E+A device and a method for deep treatment of oily sludge by micro-nano bubble ozone.
Background
The sludge of the oil separation tank, the floating tank scum, the crude oil tank bottom sludge and the like generated by the sewage treatment of the oil refining sewage treatment plant are commonly called as 'three sludge', the sludge is composed of water, oil and solid matters with different contents, contains benzene series, phenols, anthracene, pyrene, heavy metals and other substances with foul smell and toxicity, and has the characteristics of complex components, strong emulsion stability, larger viscosity, difficult thorough sedimentation of solid phase components and the like. As a national hazardous waste, the recycling, reduction and harmless treatment of oily sludge become a difficult problem to be solved urgently for various chemical enterprises.
China mainly depends on landfill or drying incineration treatment on the reduction treatment of oily sludge. Although the landfill treatment is low in cost, the landfill treatment does not bring economic benefits for a long time, and also brings unnecessary harm to ecology, for example, the change of the form of soil is caused, the soil is barren, and the vegetation withers. The drying incineration releases high-concentration toxic gas in the oily sludge to the nature, so that not only air is polluted, but also ecology is influenced by invisibility. Therefore, aiming at the oily sludge with different compositions and properties, a new oily sludge treatment technology with stronger pertinence needs to be developed, and important guarantee is provided for realizing the win-win situation of economy and environment.
In the traditional ozone treatment process, because the concentration of ozone is low and the solubility in water is poor, the energy consumption in the production process is high, the ozone utilization efficiency is low, and partial organic matters are difficult to mineralize. How to improve the treatment efficiency of ozone and improve the degradation and even mineralization of organic matters becomes a key. At present, relevant patents report on the treatment of oil-containing sludge by ozone, and 2016 (CN 106186609A) mentions that the oxidation of oil-containing sludge by ozone under the action of a catalyst can effectively separate oil, mud and water in the oil-containing sludge, reduce the pollution of the oil-containing sludge to the environment, recycle part of crude oil and use less chemical agents. However, the addition of the agent itself poses environmental hazards and affects the quality properties of the recovered crude oil.
Disclosure of Invention
The invention aims to solve the problems of poor utilization rate and poor mass transfer efficiency of pure ozone+A device and a method for deep treatment of oily sludge by micro-nano bubble ozone.
The purpose of the invention is realized by the following technical scheme:
in a first aspect, the invention relates to a method of+-micro-nano bubble ozone coupling oil-containing sludge advanced treatment unit mainly includes: vibrating screens 1, E+-a micro-nano bubble ozone device 2, a power supply 3;
the vibrating screens 1 and E+-the oily sludge inlet of the micro-nano bubble ozone device is connected;
said E+An aeration disc 4 is arranged at the bottom of the micro-nano bubble ozone device 2, and an ozone generator 5 is connected with the aeration disc 4 through an ozone concentration meter 6, a flow meter 7 and a fluid pump 8;
said E+A stirrer 9 is arranged inside the micro-nano bubble ozone device 2, and an oil wiper 10 is arranged at the upper end part;
said E+Electrodes are respectively arranged on two sides inside the micro-nano bubble ozone device 2 and are respectively connected with the positive electrode and the negative electrode of the power supply 3;
said E+The micro-nano bubble ozone device 2 is provided with an ozone outlet, and ozone discharged from the ozone outlet is absorbed by the tail gas absorption tank 12 and then discharged from the tail gas outlet 13;
said E+The micro-nano bubble ozone device 2 is further provided with a reflux device 14, and an oily sludge reflux outlet of the reflux device 14 is positioned at E+Upper part of micro-nano bubble ozone apparatus 2, return inlet of oily sludge located at E+The lower part of the micro-nano bubble ozone device 2; the upper end of the reflux device 14 is also provided with an oily sludge outlet 11; the reflux device 14 is used for reflux and pH adjustment of the oily sludge.
Further, the power supply 3 is a direct current power supply or a pulse power supply, the power supply mode is constant voltage power supply, the control voltage is 1V-15V, and the control current is 2A-10A.
Further, the electrode is titanium-based ruthenium dioxide, is of a grid structure and is 1-2mm thick; the distance between the anode electrode and the cathode electrode is 40-300 mm.
Further, the bottom end of the electrode and E+The ratio of the distance from the bottom of the micro-nano bubble ozone device to the total height of the device is 1-1.8: 2. When the height ratio is lower than 1:2, the electrochemistry destroys the free radicals generated in the ozone oxidation process, and when the height ratio is higher than 1: at 1.8, the coupled oxidation of ozone and electrochemistry is less effective than between this height (1-1.8: 2).
Further, a micro-nano bubble aeration head is arranged on the aeration disc 4; the micro-nano bubble aeration head is made of titanium, the aperture is 0.2-0.5 mu m, the micro-nano bubble aeration head is shaped like a flat plate or an umbrella-shaped aeration head, and the size of generated micro-nano bubbles is less than 50 mu m. If the generated bubbles are higher than 50 μm, the bubbles do not belong to micro-nano bubbles, the mass transfer area is reduced, the rising speed is too high, and the contact time with pollutants is short.
Further, the height ratio of the oily sludge return outlet of the return device 14 to the device is 1-3: 10. The position of the oil-containing sludge backflow outlet is too high, which can affect the process of recovering upper-layer floating oil by the upper-end oil wiper, and the position of the oil-containing sludge backflow outlet is too low, which easily causes the system to be uneven and insufficient backflow.
In a second aspect, the invention relates to a method E+The micro-nano bubble ozone coupling oil-containing sludge advanced treatment method comprises the following steps:
s1, screening the oily sludge by using a vibrating screen 1 to obtain the treated oily sludge;
s2, feeding the treated oily sludge into E+Micro-nano bubble ozone device 2, breaking the oily sludge emulsifying structure by ozone oxidation, said E+Electrodes built into the micro-nano bubble ozone device 2 (device upper end E)+) Further demulsification is realized by utilizing the electrolytic performance of the emulsion breaker;
S3、E+coupling of micro-nano bubble ozone, O brought in during aeration2And O not consumed in time as organic matter3Conversion to H2O2OH and the like to realize deep oxidation of oil substances and convert the oil substances into carbon dioxide and water;
s4, micro-nano ozone floating bubbles (the bubbles pass through E)+Generated by a micro-nano bubble aeration head at the bottom of the micro-nano bubble ozone device) to bring the demulsified oil drops to the liquid level and recover the oil drops by using an oil scraper 10;
s5, warp E+After the micro-nano bubble ozone device is used for treatment, the oil content of the oily sludge is less than or equal to 3 per mill, and the oily sludge can be directly discharged to farmlands or used for paving;
s6, the discharged ozone is absorbed by the tail gas absorption tank 12 and then discharged from the tail gas outlet 13.
Further, step S1 is to separate large-particle solids from the oily sludge by using a vibrating screen. The diameter of the oil sludge is less than or equal to 28mm after the oil-containing sludge is screened by a vibrating screen.
Further, the oil wiper 10 intermittently recovers the upper layer of oil slick.
Further, the pH value of the oily sludge after being screened by the vibrating screen is controlled below 5.0 by an external circulating device.
According to the reaction route described below, a pH greater than 5 produces radicals in much smaller amounts than those produced under extreme acid conditions, while the ozone molecules present in the system are also in much smaller amounts than under extreme acid conditions, so that their oxidizing properties are strongest at a pH less than 5.
O+H2O→2HO· (2)
·OH+O3→HO2·+O2k＝1.1×(10)^8dm^3mol^(-1)s^(-1) (3)
HO2·+O3→·OH+2O2k<(10)^4dm^3mol^(-1)s^(-1) (4)
·O3^-+H^+→·OH+O2k＝9×(10)^10dm^3mol^(-1)s^(-1) (6)
·OH+HO2·→H2O+O2k＝7×(10)^9dm^3mol^(-1)s^(-1) (7)
Further, in step S1, the oily sludge refers to oil separation tank bottom sludge, flotation tank scum, crude oil tank bottom sludge, and the like generated by the sewage treatment in the oil refinery.
Furthermore, the water content of the oily sludge before treatment is controlled to be 75-95%, and the oil content is controlled to be 5-20%.
Further, said E+Ozone in the oily sludge discharged tail gas treated by the micro-nano bubble ozone device is treated and purified by the tail gas absorption tank 12, and the concentration of the ozone is lower than 1 ppm.
Compared with the prior art, the invention has the following beneficial effects:
1. through ozone oxidation, destroy the oily sludge emulsification structure, E on the upper end of the device+Further demulsification is realized by utilizing the electrolytic performance of the emulsion breaker;
2. the invention fully utilizes the ozone which can not be consumed by the organic matters in time and brings in a large amount of oxygen in the aeration process, and the ozone is further activated into H in the environment of electrochemical oxidation2O2OH and the like, and deeply oxidize and remove or decompose pollutants in the oily sludge;
3. the micro-nano bubbles are adopted to replace the traditional aeration mode, the large specific surface area of the micro-nano bubbles can be utilized, the adhesion efficiency between pollutants and the micro-nano bubbles is improved, the utilization rate of ozone is improved, the oil sludge separation efficiency is improved by utilizing the air floatation effect of the bubbles, meanwhile, the continuous contraction and collapse of the micro-nano bubbles can generate strong pressure waves and high mechanical shearing force, and the pollutants on the surface of the oil sludge are further removed;
4. a large amount of oil drops are brought to the liquid level by the micro-nano ozone floating bubbles and are recovered by an oil scraper;
5. the oily sludge treated by the device reaches the discharge or recycling standard, and the deep treatment of the oily sludge is realized.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is the invention E+-micro-nano bubble ozone coupled oily sludge advanced treatment flow diagram;
wherein: 1. vibrating sieves, 2, E+-micro-nano bubble ozone means, 3, power supply, 4, aeration disc, 5, ozone generator, 6, ozone concentration meter, 7, flow meter, 8, fluid pump, 9, stirrer, 10, oil scraper, 11, oily sludge outlet, 12, tail gas absorption tank, 13, tail gas outlet, 14, reflux means.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
The first embodiment is as follows: one kind of this embodiment E+-micro-nano bubble ozone coupled oily sludge advanced treatment unit, as shown in figure 1; the method mainly comprises the following steps: vibrating screens 1, E+-a micro-nano bubble ozone device 2, a power supply 3;
the vibrating screens 1 and E+-the oily sludge inlet of the micro-nano bubble ozone device is connected;
said E+ An aeration disc 4 is arranged at the bottom of the micro-nano bubble ozone device 2, and an ozone generator 5 is connected with the aeration disc 4 through an ozone concentration meter 6, a flow meter 7 and a fluid pump 8;
said E+A stirrer 9 is arranged inside the micro-nano bubble ozone device 2, and an oil wiper 10 is arranged at the upper end part;
said E+Electrodes are respectively arranged on two sides inside the micro-nano bubble ozone device 2 and are respectively connected with the positive electrode and the negative electrode of the power supply 3;
said E+The micro-nano bubble ozone device 2 is provided with an ozone outlet, and ozone discharged from the ozone outlet is absorbed by the tail gas absorption tank 12 and then discharged from the tail gas outlet 13;
said E+The micro-nano bubble ozone device 2 is further provided with a reflux device 14, and an oily sludge reflux outlet of the reflux device 14 is positioned at E+Upper part of micro-nano bubble ozone apparatus 2, return inlet of oily sludge located at E+The lower part of the micro-nano bubble ozone device 2 and the upper end of the reflux device 14 are provided with an oily sludge outlet 11; the reflux device 14 is used for reflux and pH adjustment of the oily sludge.
The method is implemented according to the following steps:
screening the oily sludge by using a vibrating screen to obtain the treated oily sludge; the treated oily sludge enters the step E+Micro-nano bubble ozone device to destroy the oily sludge emulsifying structure by ozone oxidation, E at the upper end of the device+Further demulsification is realized by utilizing the electrolytic performance of the emulsion breaker; e+Coupling of micro-nano bubble ozone, O brought in during aeration2And O not consumed in time as organic matter3Conversion to H2O2OH and the like to realize deep oxidation of oil substances and convert the oil substances into carbon dioxide and water; the micro-nano ozone floating bubbles bring the demulsified oil drops to the liquid level and recover the oil drops by using an oil scraper.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the water content of the oily sludge is controlled to be 75-95%, the oil content is controlled to be 5-20%, the actual action intensity of current is controlled, the control voltage is 1-15V, and the control current is 2-10A.
Other steps and parameters are the same as those in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the diameter of the oil sludge is less than or equal to 28mm after the oil-containing sludge is screened by the vibrating screen.
Other steps and parameters are the same as those in the first or second embodiment.
The fourth concrete implementation mode: the present embodiment differs from the first to third embodiments in that: the anode and the cathode used in electrochemistry are titanium-based ruthenium dioxide, the electrodes are of a grid structure, the thickness is 1-2mm, and the distance between the anode and the cathode is 40-300 mm.
Other steps and parameters are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the first to fourth differences of this embodiment from the first to fourth embodiments are: the pH value of the oily sludge after sieving treatment is controlled below 5.0 by an external circulating device.
Other steps and parameters are the same as those in the first to fourth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1
In the embodiment, the oily sludge is taken from a certain oil refinery in Shanghai, the water content is controlled to be 95 percent, and the oil content is controlled to be 5 percent; the micro-nano bubble aeration head is made of titanium, the aperture is 0.2 mu m, and the micro-nano bubble aeration head is in an umbrella shape; a direct-current power supply is adopted, the power supply mode is constant-voltage power supply, the control voltage is 1V, and the control current is 2A; the adopted anode and cathode electrodes are titanium-based ruthenium dioxide, the electrodes are in a grid structure, the thickness of the electrodes is 1mm, and the distance between the anode electrode and the cathode electrode is 40 mm; the pH value of the oily sludge is controlled to be 5.0 before treatment, the ozone concentration is 60ppm, the aeration flow rate is 0.5L/min, and the oil content of the oily sludge after treatment is 2.0 per mill, so that the requirement of discharge or recycling is met.
Example 2
In the embodiment, the oily sludge is taken from a certain oil refinery in Shanghai, the water content is controlled to be 85 percent, and the oil content is controlled to be 10 percent; the micro-nano bubble aeration head is made of titanium, the aperture is 0.45 mu m, and the micro-nano bubble aeration head is shaped as a flat plate aeration head; a pulse power supply is adopted, the power supply mode is constant voltage power supply, the control voltage is 10V, and the control current is 5A; the adopted anode and cathode electrodes are titanium-based ruthenium dioxide, the electrodes are in a grid structure, the thickness is 1.5mm, and the distance between the anode electrode and the cathode electrode is 200 mm; the pH value of the oily sludge is controlled to be 4.0 before treatment, the ozone concentration is 60ppm, the aeration flow rate is 0.5L/min, and the oil content of the oily sludge after treatment is 2.4 per mill, so that the requirement of discharge or recycling is met.
Example 3
In the embodiment, the oily sludge is obtained from a certain oil refinery in Shanghai, the water content is controlled to be 75 percent, and the oil content is controlled to be 20 percent; the micro-nano bubble aeration head is made of titanium, the aperture is 0.5 mu m, and the micro-nano bubble aeration head is shaped as a flat plate aeration head; a pulse power supply is adopted, the power supply mode is constant voltage power supply, the control voltage is 15V, and the control current is 10A; the adopted anode and cathode electrodes are titanium-based ruthenium dioxide, the electrodes are of a grid structure and have the thickness of 2mm, and the distance between the anode electrode and the cathode electrode is 300 mm; the pH value of the oily sludge is controlled to be 4.0 before treatment, the ozone concentration is 60ppm, the aeration flow rate is 0.5L/min, and the oil content of the oily sludge after treatment is 2.9 per mill, so that the requirement of discharge or recycling is met.
In summary, the present invention employs E+The micro-nano bubble ozone coupling method realizes air floatation, ozone and electrochemical synergistic oxidation, and simultaneously achieves multiple effects of recycling, reducing, harmlessness and the like of the oily sludge.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. E+-micro-nano bubble ozone advanced treatment device of oily sludge, characterized in that it comprises a vibrating screen (1), E+Micro-nano bubble odorAn oxygen device (2) and a power supply (3);
the vibrating screen (1) and E+-the oily sludge inlet of the micro-nano bubble ozone device is connected;
said E+An aeration disc (4) is arranged at the bottom of the micro-nano bubble ozone device (2), and an ozone generator (5) is connected with the aeration disc (4) through an ozone concentration meter (6), a flowmeter (7) and a fluid pump (8);
said E+A stirrer (9) is arranged in the micro-nano bubble ozone device (2), and an oil wiper (10) is arranged at the upper end part;
said E+Electrodes are respectively arranged on two sides inside the micro-nano bubble ozone device (2), and the electrodes are respectively connected with the positive electrode and the negative electrode of the power supply (3);
said E+The micro-nano bubble ozone device (2) is provided with an ozone outlet, and ozone discharged from the ozone outlet is absorbed by the tail gas absorption tank (12) and then discharged from the tail gas outlet (13);
said E+The micro-nano bubble ozone device (2) is also provided with a reflux device (14), and an oily sludge reflux outlet of the reflux device (14) is positioned at E+-the upper part of the micro-nano bubble ozone device (2) and the return inlet of the oily sludge is positioned at E+-the lower part of the micro-nano bubble ozone device (2); the upper end of the reflux device (14) is also provided with an oily sludge outlet (11); the backflow device (14) is used for backflow and pH adjustment of oily sludge.
2. E according to claim 1+The device for deep treatment of oily sludge by micro-nano bubble ozone is characterized in that the power supply (3) adopts a direct current power supply or a pulse power supply, the power supply mode is constant voltage power supply, the control voltage is 1-15V, and the control current is 2-10A.
3. E according to claim 1+-micro-nano bubble ozone advanced treatment device for oily sludge, characterized in that the electrode is titanium-based ruthenium dioxide, the electrode is of a grid structure and the thickness is 1-2 mm; the distance between the two electrodes is 40-300 mm.
4. According to claimE as described in claim 1+-micro-nano bubble ozone advanced treatment device for oily sludge, characterized in that the distance E of the bottom ends of the electrodes+Height of micro-nano bubble ozone device bottom and E+-the height ratio of the micro-nano bubble ozone device is 1-1.8: 2.
5. E according to claim 1+-micro-nano bubble ozone advanced treatment oil-containing sludge's device, characterized by, there are micro-nano bubble aeration heads on the said aeration disc (4); the micro-nano bubble aeration head is made of titanium, the aperture is 0.2-0.5 mu m, the micro-nano bubble aeration head is shaped like a flat plate or an umbrella-shaped aeration head, and the size of generated micro-nano bubbles is less than 50 mu m.
6. E according to claim 1+-device for deep treatment of oily sludge by micro-nano bubble ozone, characterized in that the ratio of the height of the oily sludge return outlet of the return device (14) from the bottom to the device height is 1-3: 10.
7. E+-micro-nano bubble ozone coupled oily sludge advanced treatment method, characterized in that the method comprises the following steps:
s1, screening the oily sludge by adopting a vibrating screen (1) to obtain the treated oily sludge;
s2, feeding the treated oily sludge into E+-a micro-nano bubble ozone device (2) to break the oily sludge emulsification structure by ozone oxidation, said E+The electrodes arranged in the micro-nano bubble ozone device (2) realize further demulsification by utilizing the electrolytic performance of the electrodes;
S3、E+coupling of micro-nano bubble ozone, O brought in during aeration2And O not consumed in time as organic matter3Conversion to H2O2OH, realizing deep oxidation of oil substances and converting the oil substances into carbon dioxide and water;
s4, carrying the demulsified oil drops to the liquid level by the micro-nano ozone floating bubbles, and recovering the oil drops by an oil scraper (10);
s5, warp E+After the micro-nano bubble ozone device (2) is used for treatment, the oil content of the oily sludge is less than or equal to 3 per thousand, and the oily sludge can be directly discharged to farmlands or used for paving;
s6, the discharged ozone is absorbed by the tail gas absorption tank (12) and then discharged from the tail gas outlet (13).
8. E according to claim 7+The deep treatment method of the oil-containing sludge by coupling micro-nano bubble ozone is characterized in that large-particle solids in the oil-containing sludge are separated by adopting a vibrating screen in step S1; the diameter of the oily sludge after sieving treatment is less than or equal to 28 mm.
9. E according to claim 7+-micro-nano bubble ozone coupled oily sludge advanced treatment method, characterized in that the oil scraper (10) recovers upper layer oil slick in an intermittent manner.
10. E according to claim 7+The deep treatment method of the oil-containing sludge by coupling micro-nano bubble ozone is characterized in that the pH value of the oil-containing sludge after being screened by a vibrating screen is regulated and controlled below 5.0 by a reflux device (14).
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| CN111792809A (en) * | 2020-07-03 | 2020-10-20 | 中国石油天然气集团有限公司 | Oil-containing sludge advanced treatment process and treatment equipment |
| CN112358014A (en) * | 2020-11-01 | 2021-02-12 | 广东蓝绿科技有限公司 | Flocculation treatment process based on electric field |
| CN113233651A (en) * | 2021-06-02 | 2021-08-10 | 大庆腾辉石油工程技术服务有限公司 | Efficient environment-friendly harmless treatment system for oil-containing sludge, slurry and oil field waste liquid |
| CN114292005A (en) * | 2021-12-31 | 2022-04-08 | 同济大学 | Method and system for strengthening air flotation concentration reduction and harmlessness of sludge by using ozone |
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