CN1594146A - Ultrasonic catalytic oxidation-biological treatment method for poor-degradable organic water - Google Patents
Ultrasonic catalytic oxidation-biological treatment method for poor-degradable organic water Download PDFInfo
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
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- 238000005457 optimization Methods 0.000 description 2
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- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention relates to an ultrasonic catalytic oxidation-biological treatment method for poor-degradable organic water, wherein the three effects of free radical oxidization, high temperature thermal dissociation and hypercritical water oxidization generated in the ultrasonic cavitation procedure are employed, the process conditions including dissolved oxygen concentration, pH and reaction time are controlled simultaneously, thus directly converting the organics in the waste water into carbon dioxide, water or micromolecular organics, as a result, the biological toxicity of the waste water is removed, and the microorganism load is reduced substantially.
Description
(1) technical field: wastewater treatment
(2) background technology: organic wastewater with difficult degradation thereby comprises coking water waste water, percolate, agricultural chemicals waste water, dyeing waste water etc.Hardly degraded organic substance mainly is under normal residence time condition, the organism that microorganism can not be degraded.These organism have bio-toxicity, mutagenicity or carinogenicity etc. mostly, and the transformation period in environment is very long, has very high environmental correclation, so handle before need entering water body, atmosphere or soil to it.
Hardly degraded organic substance mainly comprises and contains two key triple-linked hydro carbons, halogen compounds, ether compound, nitro-azo compounds, water-soluble high-molecular compounds, has the compound of germicidal action etc., these still not difficult compounds that fall, and be to be difficult to resolve factor, in case a molecule has been introduced these factors, all can cause biodegradable difficulty.
Known at the different waste water characteristics of hardly degraded organic substance, industrial processing to this waste water mainly contains chemical oxidization method, exchange resin method, absorption method etc.
The deficiency that above-mentioned treatment process exists is:
1) chemical oxidization method need add a large amount of oxygenants in waste water, and oxygenant form a complete production network or store comparatively complicated, thereby increased processing cost and management difficulty.The dosage that the treatment of Organic Wastewater of middle and high concentration is added oxygenant is excessive, and economy is not good enough.
2) resin price of exchange resin method is higher, and one-time investment is excessive, and for the waste water that contains a large amount of suspended matters or colloidalmaterial in the waste water, also needs to increase the pre-treatment facility, could guarantee normally carrying out of resins exchange.
3) absorption method can be adsorbed hardly degraded organic substance, but this method does not fundamentally transform hardly degraded organic substance, eliminate its potential threat, and adsorbed gac of a large amount of hardly degraded organic substances etc., formed new solid waste again environment.
In view of present various used water difficult to degradate are handled the various deficiencies that exist, and ultrasonic cavitation has the characteristics of degradation efficiency height and removal bio-toxicity material, biological treatment has the low characteristics of cost, water outlet can reach the emission standard of national correlation water, both are unified in conjunction with the optimization of the efficiency cost of having realized treatment system, have impelled formation of the present invention.
(3) summary of the invention:
1, the objective of the invention is to be intended to free-radical oxidn, high temperature pyrolysis and three kinds of effects of supercritical water oxidation of utilizing the ultrasonic cavitation process to be produced, control processing condition such as treating processes dissolved oxygen concentration, pH value, temperature, reaction times simultaneously, form rapidly effectively degraded hardly degraded organic substance of a degraded environment, set up a kind of treatment process of new organic wastewater with difficult degradation thereby.
2, the present invention relies on following technical scheme to realize.
After organic wastewater with difficult degradation thereby at first needs to remove macrobead suspended matter in the waste water, introduce in the ultrasonic reactor, regulate the frequency and the power of ultrasonic reactor, regulate the pH value and the temperature of waste water, add catalyzer, carrying out ultrasound wave irradiation handles, control pH value and temperature variation in treating processes, the maintenance catalyzer fully contacts with cavitation bubble, through the organic wastewater with difficult degradation thereby after the ultrasonically catalyzing oxidation pre-treatment, feed in the SBR biological treatment reactor, carry out a biological disposal upon.
The important indicator that ultrasonically catalyzing oxide treatment hardly degraded organic substance generally need be considered is the degradation rate (characterizing the removal of total organic matter) of COD, BOD/COD is than factors such as (characterize the biodegradability of waste water, also characterize hardly degraded organic substance simultaneously and transform and removal effect).Find that through experimental study the principal element (processing condition) that influences treatment effect has factors such as dissolved oxygen concentration, pH value, starting point concentration, temperature, the sound intensity, catalyst type, catalyzer existence form, the control of pH value.Each processing condition to the hardly degraded organic substance degradation effect to influence rule as follows:
(1) higher dissolved oxygen concentration assists in removing the raising of rate;
(2) condition of neutral slant acidity assists in removing the raising of rate;
(3) lower starting point concentration assists in removing the raising of rate, and higher starting point concentration has higher degraded total amount;
(4) temperature raises and helps to contain the raising of hardly degraded organic substance clearance in the colloid waste water, and is little to not rhagiocrin waste water influence;
(5) sound intensity improves the raising of the rate that assists in removing, and the size of treatment capacity is regulated with the frequency and the sound intensity;
(6) keep the raising that fully contacts the rate of assisting in removing of catalyzer and cavitation bubble;
(7) keep the pH value stabilization to assist in removing the raising of rate in the reaction process.
According to above-mentioned rule, the ultrasonically catalyzing oxidizing process condition after the optimization is: ultrasonic frequency is at 20～500kHz, and the sound intensity is at 5～65W/cm
2, dissolved oxygen concentration is controlled at 1～4mg/L in the waste liquid, and the pH value is controlled between 4～8, and temperature is controlled at 15～75 ℃, and catalyzer is FeSO
4, CuO, catalyzer is required to be fluidized state, the reaction times is at 40～30min.
3, compare advantage and the positively effect that the present invention has with known technology
(1) can thoroughly hardly degraded organic substance in the waste water be converted into carbonic acid gas and water or Degradation and Transformation small organic molecule, eliminate bio-toxicity, not produce secondary pollution for easily degrading.
(2) technical process unit, catalyzer is inexpensive, and the influence factor condition is controlled easily;
(3) organic wastewater with difficult degradation thereby to high, normal, basic concentration all has good removal degradation effect, wide adaptability, resistance to overload shock;
(4) catalyzer is difficult for poisoning and losing efficacy, and catalytic effect is stable and reliable;
(5) conversion unit is simply compact, and equipment is convenient to arrange and dismounting;
(6) the ultrasonically catalyzing oxidation pre-treatment has improved wastewater biodegradability, has guaranteed the stable and high effective operation of subsequent biological treatment.
(4) embodiment:
The processing of a pair of coking chemical waste water of embodiment
Mainly contain phenols in the coking chemical waste water and (comprise phenol, ortho-cresol, p-cresol, meta-cresol, 3,4 one xylenols, 2,3 one xylenols, Resorcinol), mononuclear aromatics (comprising benzene,toluene,xylene), polycyclic aromatic hydrocarbons (comprising biphenyl, naphthalene, methylnaphthalene, anthracene, phenanthrene, fluorenes), organic compounds containing nitrogen (comprising that quinoline, isoquinoline 99.9, toluquinoline, pyrrole form sediment, the methyl pyrrole forms sediment), Oxygenic heterocyclic compounds (dibenzofuran) etc.
The above-mentioned coking chemical waste water 100L that gets COD concentration and be 2000～2500mg/L puts into ultrasonic reactor, and the frequency of regulating ultra-sonic generator is 100KHz, and the sound intensity is 12W/cm
2In the process, add soluble metallic salt FeSO
4Make catalyzer, its concentration is the 3mmol/L waste liquid, and temperature is controlled at 25 ℃, and the pH value is 8, controls simultaneously that dissolved oxygen concentration is 1-2mg/L in the liquid, reaction times 240min.
The BOD/COD of process ultrasonically catalyzing oxidation pre-treatment coking chemical waste water is greater than 0.75, and the biodegradability of waste water improves, and satisfies the biological process processing requirements fully.Subsequent biological treatment adopts SBR technology, and technology controlling and process MLSS is 3500mg/L, and sludge loading is 0.3kg/kgd, exposes to the sun to adopting unrestricted aeration, and last treat effluent reaches sewage comprehensive discharge primary standard (GB8978-1996).
The processing of two pairs of alkaline straw pulp paper black liquids of embodiment
Contain a large amount of xylogen and colloid in the alkaline straw pulp paper black liquid, xylogen is then extremely difficult to be decomposed by Institute of Micro-biology.
The alkaline straw pulp paper black liquid of getting COD concentration and be 12000mg/L is 100L, and regulating the pH value is 5, adds FeSO
4Be catalyzer, its concentration 5mmol/L waste liquid, regulating the ultra-sonic generator frequency is 200kHz, the sound intensity is 12W/cm
2, temperature of reaction is controlled at 15-25 ℃, the reaction times is 180min, in the process control reaction solution in dissolved oxygen at 3mg/L.
The BOD/COD of process ultrasonically catalyzing oxidation pre-treatment alkaline straw pulp paper black liquid is greater than 0.45, and the biodegradability of waste water improves, and satisfies the biological process processing requirements fully.Subsequent biological treatment is identical with example one, and last treat effluent reaches sewage comprehensive discharge secondary standard (GB8978-1996).
Embodiment three, to the processing of agricultural chemicals waste water
Get methamidophos pesticide waste water 50L and put into ultrasonic reactor, the frequency of regulating ultra-sonic generator is 24kHz, and the sound intensity is 65W/cm
2, the concentration of methamidophos pesticide waste water is that temperature is controlled at 30～35 ℃ in 3mmol/L, the process, the pH value remains on 6～7, dissolve under the oxygen-saturated condition in the waste liquid, reaction times 90min, the clearance of acephatemet reaches more than 99%, and the clearance of COD also reaches more than 99%.
The BOD/COD of process ultrasonically catalyzing oxidation pre-treatment methamidophos pesticide waste water is greater than 0.45, and the biodegradability of waste water improves greatly, satisfies the biological process processing requirements fully.Subsequent biological treatment adopts SBR technology, and last treat effluent reaches sewage comprehensive discharge primary standard (GB8978-1996).
Four pairs of processing that contain Pentachlorophenol waste water of embodiment
When getting the trade effluent that contains Pentachlorophenol (PCP) and carrying out ultrasonic degradation, with three grades of identical ultrasonic reactors series connection, the frequency of every stage reactor is 500kHz, and the sound intensity is 45W/cm
2, reactor volume is 100L, and the entire reaction system is a Continuous Flow, and flow is 6～7L/min, and the concentration of PCP is 1mmol/L, adds the Al of Supported CuO in the reaction process
2O
3As catalyzer, 7～8 of pH value control, temperature is controlled at 30～40 ℃, dissolved oxygen concentration 3～4mg/L in the reaction solution, reaction times 35～45min, its degradation rate are more than 80%.
The BOD/COD ratio of process ultrasonically catalyzing oxidation pre-treatment Pentachlorophenol (PCP) trade effluent is greater than 0.55, the biodegradability of waste water improves, satisfy the biological process processing requirements fully, subsequent biological treatment adopts SBR technology, and last treat effluent reaches sewage comprehensive discharge primary standard (GB8978-1996).
The processing of five pairs of percolates of embodiment
The more hard-degraded substance of content mainly contains hydro carbons and derivative, esters of gallic acid, pure phenols, keto-aldehyde class and amides etc. in the percolate of selecting for use in this enforcement, wherein lists have 5 kinds of China's environment priority pollutants in.
The percolate 10L that gets COD concentration and be 37000mg/L puts into ultrasonic reactor, and the frequency of regulating ultra-sonic generator is 20kHz, and the sound intensity is 7.5W/cm
2, adding concentration is the soluble metallic salt FeSO of 3mmol/L waste liquid
4Make catalyzer, temperature is controlled at 55～75 ℃, in the reaction process pH value be controlled at 5～5.5 and liquid in dissolved oxygen concentration under the condition of 3-4mg/L, reaction times 300min.
The clearance of the COD of the percolate of process ultrasonically catalyzing oxidation pre-treatment reaches 81%, and the BOD/COD ratio is greater than 0.6, and the biological process processing requirements is satisfied in can biochemically improving of waste water fully.
Claims (6)
1, the method of a kind of ultrasonically catalyzing oxidation-biological treatment organic wastewater with difficult degradation thereby, after the removal of the macrobead suspended matter in the organic waste water of difficult degradation, introduce ultrasonic reactor, regulate the frequency and the sound intensity of ultrasonic reactor, regulate the pH value and the temperature of waste water, and add catalyzer and carry out ultrasound wave irradiation and handle, dissolved oxygen concentration in control pH value and temperature variation and the waste liquid in treating processes, the maintenance catalyzer fully contacts with cavitation bubble, carry out the pre-treatment of used water difficult to degradate, used water difficult to degradate feeds the SBR bio-reactor after the pre-treatment, carries out a biological disposal upon, it is characterized in that: control ultrasonic frequency 20～500kHz in ultrasonic reactor, the sound intensity 5～65W/cm
2, dissolved oxygen concentration 1～4mg/L, pH value 4～8,15～65 ℃ of temperature, reaction times 40～300min.
2, the method for processing organic wastewater with difficult degradation thereby according to claim 1 is characterized in that: described waste water is the coking chemical waste water 100L of 2000～2500mg/L for COD concentration, control ultrasonic frequency 100kHz, sound intensity 12W/cm
2, FeSO
4Make catalyzer, its concentration is the 3mmol/L waste liquid, 25 ℃ of temperature, and the pH value is 8, dissolved oxygen concentration 1-2mg/L in the waste liquid, reaction times 240min.
3, the method for processing organic wastewater with difficult degradation thereby according to claim 1 is characterized in that: described waste water is the alkaline straw pulp paper black liquid 100L control ultrasonic frequency 200kHz of 12000mg/L for COD concentration, sound intensity 12W/cm
2, FeSO
4Make catalyzer, its concentration is the 5mmol/L waste liquid, temperature 15-25 ℃, and waste liquid dissolved oxygen concentration 3mg/L, reaction times 180min.
4, the method for processing organic wastewater with difficult degradation thereby according to claim 1 is characterized in that: described waste water is that concentration is the methamidophos pesticide waste water 50L of 3mmol/L, control ultrasonic frequency 25kHz, sound intensity 65W/cm
2, temperature 30-35 ℃, pH value 6-7, dissolved oxygen is saturated in the waste liquid, reaction times 90min.
5, the method for processing organic wastewater with difficult degradation thereby according to claim 1, it is characterized in that: described waste water is that concentration is the Pentachlorophenol trade effluent of 1mmol/L, with three identical ultrasonic reactor series connection, every reactor volume is 100L, reactive system is a Continuous Flow, flow 6～7L/min, every reactor frequency 500kHz, sound intensity 45W/cm
2, the Al of load C nO
2O
3Make catalyzer, pH7-8, temperature 30-40 ℃, dissolved oxygen concentration 3-4mg/L in the waste liquid, reaction times 35-40min.
6, the method for processing organic wastewater with difficult degradation thereby according to claim 1 is characterized in that: described waste water is the percolate 10L of 37000mg/L for COD concentration, control ultrasonic frequency 20kHz, sound intensity 7.5W/cm
2, concentration is the 3mmol/L waste liquid, FeSO
4Make catalyzer, 55～75 ℃ of temperature, pH value 5-5.5, dissolved oxygen concentration 3-4mg/L in the waste liquid, reaction times 300min.
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| CN103180252B (en) * | 2010-08-24 | 2016-01-27 | A.史策有限公司 | The advanced oxidization method strengthened |
| CN103180252A (en) * | 2010-08-24 | 2013-06-26 | A.史策有限公司 | Enhanced advanced oxidation procedure |
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| CN103043871A (en) * | 2013-01-18 | 2013-04-17 | 信发集团有限公司 | Phenol-contained wastewater treatment method and phenol-contained wastewater treatment system |
| CN103043871B (en) * | 2013-01-18 | 2014-10-22 | 信发集团有限公司 | Phenol-contained wastewater treatment method and phenol-contained wastewater treatment system |
| CN103739133A (en) * | 2014-01-24 | 2014-04-23 | 鼎泰（湖北）生化科技设备制造有限公司 | Method for deep treatment of printing and dyeing waste water by low-frequency ultrasonic waves and spherical active carbon |
| 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 |
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