CN100480190C - Ultrasonic ozone treating technique of chlorophenol-containing wastewater - Google Patents
Ultrasonic ozone treating technique of chlorophenol-containing wastewater Download PDFInfo
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Abstract
The present invention provides a chlorophenol-containing wastewater treatment technology by ultrasonic ozonation, wherein a stainless steel ultrasonic wave reaction tank is adopted, the ozone contacts with the waste water through a pore diffuser fixed at the bottom of the reaction tank, the chlorophenol of the waste water is removed under the condition of a sound wave frequency of 40 kHz, a sound energy density of 50~150 W/L, a ozone amount of 10~30 mg/L.h, a pH value of 8.0~8.2 and a water power residence time in the tank of 60~90 min. In the present invention, by optimizing the technological parameters, the purpose of lower energy consumption, high removing efficiency is realized, and the technology is adapted to the practical chlorophenol-containing wastewater treatment and has excellent market development prospect.
Description
(1) technical field
The present invention relates to a kind of technology of ultrasonic ozonize chlorophenol-containing wastewater.
(2) background technology
Chlorinated organics is extensive use of in chemical industry, petrochemical industry, agricultural chemicals etc. are produced, and is disposed to environment with forms such as gaseous state, liquid state, produces " three cause effect ".Senior oxidation technologies such as sound, ozone are because of having good environment compatibility, the class of being known as " environmental friendliness " technology (Environmental friendlytechnology), for the pollution of chlorinated organics control provides wide prospect, relevant research and application have caused the extensive concern of going together both at home and abroad, particularly the coupling oxidation technology can form synergistic effect, has represented the development trend of high-level oxidation technology in this field.
Chlorophenol is the pollutent of a class to the toxic effect of human body, extensively is present among the various industrial sewage, is listed in emphasis control pollutent class.Owing to the existence of itself benzene ring structure and chloro atom has very strong toxicity and anti-degradation capability, chlorophenol is difficult for oxidized and hydrolysis at nature, on the contrary, easily rich long-pending in animal and plant body by food chain, human body and animal are produced carcinogenic, mutagenesis and teratogenic effect.
The processing that is applied to chlorophenol-containing wastewater at present mainly contains physics method, chemical oxidization method and biological oxidation process.Wherein the physics method only is applicable to the recovery of high concentration cl phenol; Chemical oxidization method needs high temperature, high pressure (as wet oxidation), adds medicament (as Fenton reagent etc.), and investment is big, the processing cost height; Biological oxidation process degraded chlorophenol only is applicable to extremely low concentration, and can not obtain satisfied treatment effect with conventional activated sludge process.The above analysis, the main drawback of these technologies are to need to add pharmaceutical chemicals, equipment requirements height, loaded down with trivial details, the low aftertreatment complexity etc. that reaches of efficient of operation.
Ozonation technology is strong because of ozone oxidation, speed of response soon, advantage such as non-secondary pollution generally, use extensive gradually at aspects such as drinking water disinfection, Industrial Wastewater Treatment.But ozone hangs down diffusivity in water treatment and high working cost is restricted its application in wastewater treatment.Utilization ratio (as ultrasonic oxidation) with other technology couplings raising ozone is just becoming a focus (Zhao Chaocheng, oil-gas field environment protection, 2001,11 (3): 26～29; Shi Xinjun, 2006,9 (3): 51～55).Numerous studies show that, there is the obvious synergistic effect in ultrasonic ozonation technology.Ozone decomposes fast that to produce the strong oxidizing property free radical be major cause (Shi Huixiang, chemical industry journal, 2006,57 (2): 390～396) of ultrasound-enhanced ozone oxidation ability under the ultrasonic cavitation effect.Xu Xianwen etc. (2005, J.ZhejiangSCI 6B (6)) reported under frequency of sound wave 22kHz, acoustic density 625W/L, the ozone amount 41.9mg/Lh experiment condition, P-Chlorophenol concentration 46.22mg/L waste water is carried out 120min handle experiment, P-Chlorophenol is removed efficient 78.78%, COD
CrRemove efficient 97.028%.This proves absolutely and adopts ultrasonic ozone technology can effectively carry out the chlorophenols wastewater treatment, but the processing condition that adopt are less economical, energy consumption is high, is difficult to be fit to actual waste water polycomponent occasion.
(3) summary of the invention
The present invention just is being based on above-mentioned present situation, from improving ozone utilization rate, optimizing frequency of sound wave and acoustic density angle, provide a kind of energy consumption low, remove the efficient height, be fit to the ultrasonic ozonize technology of actual chlorophenol wastewater treatment.
For reaching goal of the invention, the technical solution used in the present invention is:
A kind of technology process of ultrasonic ozonize chlorophenol-containing wastewater, described technology process is to adopt stainless steel ultrasonic response groove, ozone contacts with waste water by the microporous diffuser that is fixed on the reactive tank bottom surface, under the processing parameter of frequency of sound wave 40kHz, acoustic density 50～150W/L, ozone amount 10～30mg/Lh, pH8.0～8.2, the trough inner water power residence time 60～90min, carry out the removal of chlorophenol in the waste water.
The principle of this treatment process is: under the ultrasonic wave effect, ozone is decomposed rapidly, and discharges the O free radical:
O
3→O
2+O·
O+O
3→ 2O
2(side reaction)
The O that the ozone pyrolysis produces produces OH with the water vapour reaction in cavitation bubble
O·+H
2O→2·OH
Meanwhile, water vapour pyrolysis in cavitation bubble produces OH
H
2O→·OH+·H
The OH of above-mentioned generation is incorporated into H in cavitation bubble gas-liquid circle
2O
2
2·OH→H
2O
2
The OH group and the H that form
2O
2All have strong oxidizing property, especially OH radical oxidation electropotential compares O up to 2.80V
3(2.07V) high by 35%, oxidation capacity is only second to fluorine; In addition, this group has high electronegativity (Electron Affinities), and its electron affinity is 569.3kJ, easily the high cloud density point of attack.H
2O
2Oxidizing electrode current potential 1.76V.Therefore, OH group and H
2O
2Can play two synergies, realize the deep oxidation of pollutent is decomposed, and then reach processing intent.
With chlorophenesic acid, Trichlorophenol is example, and the exhaustive oxidation decomposition reaction is:
C
6H
4Cl
2+28·OH+2e→6CO
2+16H
2O+2Cl
-
C
6H
3Cl
3+27·OH+3e→6CO
2+15H
2O+3Cl
-
2C
6H
4Cl
2+28H
2O
2+4e→12CO
2+32H
2O+4Cl
-
2C
6H
3Cl
3+27H
2O
2+6e→12CO
2+30H
2O+6Cl
-
As from the foregoing, in ultrasonic ozone oxidation system, ozone is all decomposed rapidly, and 1mol O
3Can produce 2molOH, and in independent ozone oxidation system, 1mol O
3Only produce 1molOH.Therefore, ultrasonic ozone oxidation system exists synergistic effect mainly to produce more OH by ozone pyrolysis in cavitation bubble to cause.
Described chlorophenol is one of following or two or more mixture wherein: 1. ortho chloro phenol, 2. para-chlorophenol, 3. m-Chlorophenol, 4. 2,4 dichloro phenol, 5. 2,5-chlorophenesic acid, 6. 2,4,5-Trichlorophenol, 7. 2,4,6-Trichlorophenol, 8. pentachlorophenol.
Preferably, described chlorophenol is a para-chlorophenol, and concentration is 30～250mg/L in waste water.
Further, described processing parameter is: acoustic density 100W/L, ozone amount 10mg/Lh, trough inner water power residence time 60min.
Concrete, described technology is as follows: process object is the waste water that contains para-chlorophenol 40～60mg/L, adopt the stainless steel reaction groove, ozone contacts with waste water by the microporous diffuser that is fixed on the reactive tank bottom surface, under the processing parameter of acoustic density 100W/L, ozone amount 10mg/Lh, pH value 8.0, trough inner water power residence time 60min, carry out the removal of para-chlorophenol in the waste water.
The technology beneficial effect of ultrasonic ozonize chlorophenol-containing wastewater of the present invention is mainly reflected in: by to parameters Optimization, reach energy consumption low, remove the efficient height, be fit to the purpose of actual chlorophenol wastewater treatment, it is very high that P-Chlorophenol is removed efficient, reach more than 90%, have the very great prospect of marketing.
(4) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:
Embodiment: the ultrasonic ozone Oxidation Treatment technology that contains para-chlorophenol 50.02mg/L waste water, adopt the stainless steel reaction groove, the ozone input contacts with waste water by the microporous diffuser that is fixed on the reactive tank bottom surface, under the processing condition of frequency of sound wave 40kHz, acoustic density 100W/L, ozone amount 10mg/Lh, pH value 8.0, trough inner water power residence time 60min, O
3Pyrolysis in cavitation bubble produces OH with water vapour, realization is decomposed the deep oxidation of 2-chlorophenol pollutent, thereby reach containing the purpose of the ultrasonic ozone Oxidation Treatment of para-chlorophenol waste water, wastewater treatment the results are shown in Table 1, make comparisons with (2005, J.Zhejiang SCI 6B (6)) bibliographical information results such as Xu Xianwen.
Table 1: wastewater treatment result
Monitoring method: the liquid-phase chromatographic analysis detection method of stipulating in " water and effluent monitoring analytical procedure " that chlorophenol adopts State Environmental Protection Administration to write.
Table 1 is the result show, under the processing condition of frequency of sound wave 40kHz, acoustic density 100W/L, ozone amount 10mg/Lh, trough inner water power residence time 60min, the clearance of the ultrasonic ozone Oxidation Treatment technology of the present invention para-chlorophenol reaches 90.32%, is higher than the experimental result (78.78%) of (2005) reports such as Xu Xianwen.Find relatively that from process parameter value acoustic density, treatment time and ozone concn that the present invention adopts are less than the bibliographical information value, only frequency of sound wave is higher than bibliographical information (22kHz), and this explanation frequency of sound wave role is relatively more crucial.In fact, ultrasonic wave plays two effects here: the one, and pyrolysis water generates OH, the 2nd, strengthen the ozone pyrolysis and produce OH (1mol O
3Can produce 2molOH), and infrasonic wave's frequency is difficult to play this respect effect, therefore, suitably improving frequency of sound wave needs.When frequency of sound wave is increased to 100kHz, test and find that the clearance of para-chlorophenol only improves 4 percentage points.Therefore, consider that from actual effect and equipment cost the removal of frequency of sound wave 40kHz para-chlorophenol waste water is suitable.
Embodiment 2:
Other condition is with embodiment 1, waste water chlorinated phenol (mixture of ortho chloro phenol, para-chlorophenol, m-Chlorophenol) 200mg/L, under the processing condition of frequency of sound wave 40kHz, ozone amount 10mg/Lh, trough inner water power residence time 60min and 90min, relatively investigate acoustic density (50,100,150W/L) and ortho chloro phenol is removed imitated effect, result sees Table 2.
Table 2: wastewater treatment result under the different acoustic densities
Table 2 is the result show, ultrasonic acoustic density increase helps the removal of para-chlorophenol, and behind the 90min, chlorophenol is removed and increased to 80.4% from 77.9%.But chlorophenol clearance increasing degree descends to some extent, and when 50W/L increased to 100W/L, chlorophenol is removed had increased by 5.2 percentage points, and when 100W/L increased to 150W/L, the chlorophenol clearance had only increased by 2.5 percentage points.In addition, increase hydraulic detention time (60min increases to 90min), help the removal of para-chlorophenol, come water for the waste water of higher concentration, it is necessary prolonging the residence time.
Embodiment 3:
Other condition is with embodiment 2, and acoustic density is 100W/L, and trough inner water power residence time 90min compares ozone amount (10mg/Lh, 20mg/Lh, 30mg/Lh) para-chlorophenol removal effect, and result sees Table 3.
Table 3: wastewater treatment result under the different ozone amounts
Table 3 is the result show, the ozone amount increase helps the removal of chlorophenol, and chlorophenol is removed and increased to 94.4% from 90.7%.But chlorophenol clearance increasing degree descends to some extent, and when ozone amount increased to 20mg/Lh from 10mg/Lh, chlorophenol is removed had increased by 12.8 percentage points, and when 20mg/Lh increased to 30mg/Lh, chlorophenol is removed had increased by 3.7 percentage points.Chlorophenol waste water for higher concentration comes water, needs suitably to increase ozone amount.
Embodiment 4:
Other condition is with embodiment 3, and acoustic density is 100W/L, trough inner water power residence time 90min, and ozone amount 20mg/Lh relatively investigates and installs and do not install ozone scatterer para-chlorophenol removal effect effect, and result sees Table 4.
Table 4: scatterer is to wastewater treatment result's influence
Table 4 is the result show, scatterer is very big to the result influence.Scatterer is installed, and ozone utilization rate improves greatly, processing efficiency height (reaching 90.7%).Therefore, previous embodiment 1 and bibliographical information result's difference also has much relations (data in literature is to obtain under the no scatterer) with the installation scatterer.The scatterer that the present invention adopts is the micro-hole aerator that water treatment aeration uses, and coefficient of oxygen utilization 14～16% under the clear water condition.Can infer the aerator that coefficient of oxygen utilization is high more, the suitable more ozone scatterer of doing.
Embodiment 5:
Chlorinated phenol class actual waste water, chlorophenol concentration 34.3mg/L wherein, phenol concentration 6.1mg/L, COD
Cr420mg/L, the slightly inclined to one side alkali of wastewater pH neutrality (8.2) adopts ultrasonic ozone Oxidation Treatment technology.At the stainless steel reaction groove, the ozone input contacts with waste water by the microporous diffuser that is fixed on the reactive tank bottom surface, under the processing condition of frequency of sound wave 40kHz, acoustic density 100W/L, ozone amount 10mg/Lh, trough inner water power residence time 60min, and O
3Pyrolysis in cavitation bubble produces OH with water vapour, realizes the oxygenolysis of pollutents such as para-chlorophenol, and the wastewater treatment result reduces to 4.3mg/L for chlorophenol concentration, and clearance is 87.5%; Phenol concentration is reduced to 1.7mg/L, and clearance is 72.1%; COD
CrReduce to 47.6mg/L, clearance is 88.7%.
In sum, the ultrasonic ozonize technology of the present invention can effectively be handled chlorophenol-containing wastewater.Adopt stainless steel ultrasonic response groove, the ozone input contacts with waste water by the microporous diffuser that is fixed on the reactive tank bottom surface, under the processing condition of acoustic frequency 40kHHz, acoustic density 50～150W/L, ozone amount 10～30mg/Lh, the trough inner water power residence time 60～90min, the slightly inclined to one side alkali of pH value neutrality (8.0～8.2), the ultrasonic ozonize technology of the present invention reaches 72.7～94.4% to concentration less than the chlorophenol clearance of 200mg/L, also can effectively remove other pollutents simultaneously.
Compared with prior art, ultrasonic ozone of the present invention is processed the technology tool of chlorophenol-containing wastewater The advantages such as energy consumption is low, removal efficient height, suitable actual chlorinated phenol class wastewater treatment are arranged, have very The great prospect of marketing.
Claims (5)
1. the technology of a ultrasonic ozonize chlorophenol-containing wastewater, described technology is to adopt stainless steel ultrasonic response groove, ozone contacts with waste water by the microporous diffuser that is fixed on the reactive tank bottom surface, under the processing parameter of frequency of sound wave 40kHz, acoustic density 50～150W/L, ozone amount 10～30mg/L.h, pH8.0～8.2, the trough inner water power residence time 60～90min, carry out the removal of chlorophenol in the waste water.
2. the technology of ultrasonic ozonize chlorophenol-containing wastewater as claimed in claim 1 is characterized in that described chlorophenol is one of following or two or more mixture wherein: 1. ortho chloro phenol, 2. para-chlorophenol, 3. m-Chlorophenol, 4. 2,4 dichloro phenol, 5. 2,5-chlorophenesic acid, 6. 2,4, the 5-Trichlorophenol, 7. 2,4,6-Trichlorophenol, 8. pentachlorophenol.
3. the technology of ultrasonic ozonize chlorophenol-containing wastewater as claimed in claim 2 is characterized in that described chlorophenol is a para-chlorophenol, and concentration is 30～250mg/L in waste water.
4. as the technology of the described ultrasonic ozonize chlorophenol-containing wastewater of one of claim 1～3, it is characterized in that: described processing parameter is: acoustic density 100W/L, ozone amount 10mg/Lh, trough inner water power residence time 60min.
5. the technology of ultrasonic ozonize chlorophenol-containing wastewater as claimed in claim 1, it is characterized in that described technology is as follows: process object is the waste water that contains para-chlorophenol 40～60mg/L, adopt the stainless steel reaction groove, ozone contacts with waste water by the microporous diffuser that is fixed on the reactive tank bottom surface, under the processing parameter of acoustic density 100W/L, ozone amount 10mg/Lh, pH value 8.0, trough inner water power residence time 60min, carry out the removal of para-chlorophenol in the waste water.
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| CN101985371A (en) * | 2010-11-02 | 2011-03-16 | 南京工业大学 | Method of ultrasonic degradation of chlorophenols waste water |
| CN102134133B (en) * | 2011-04-25 | 2012-07-04 | 南京师范大学 | Method for treating 2,4-dichlorophenol wastewater by ozone oxidation in organic solvent |
| CN102358636B (en) * | 2011-09-19 | 2013-01-16 | 哈尔滨工业大学 | System for treating dye wastewater and method for treating triphenylmethane dye wastewater |
| CN102491491A (en) * | 2011-12-09 | 2012-06-13 | 哈尔滨工业大学 | Method for ultrasonically treating nitro-containing phenol waste water with ozone |
| CN103112924B (en) * | 2013-03-06 | 2014-02-26 | 河海大学常州校区 | Experimental device and method for degrading farm chemicals by utilizing synergy of ultrasound and ozone |
| CN103523856B (en) * | 2013-09-09 | 2015-06-24 | 河海大学常州校区 | Water mist discharge and ultrasound synergetic degradation wastewater treatment device and running method thereof |
| CN103570099B (en) * | 2013-09-13 | 2015-05-06 | 上海大学 | Method for inhibiting production of bromated in ozonization process |
| CN104649489B (en) * | 2015-01-28 | 2017-10-03 | 六合天地（武汉）环境有限公司 | A kind of micro- aeration of ultrasonic wave active oxygen decomposes profit device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5087374A (en) * | 1990-03-05 | 1992-02-11 | Ding Lambert L | Removal of contaminates from granular solids |
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| US5087374A (en) * | 1990-03-05 | 1992-02-11 | Ding Lambert L | Removal of contaminates from granular solids |
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|---|
| 声电协同氧化氯酚的实验研究. 陈霞等.环境工程学报，第1卷第1期. 2007 * |
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