CN103864250A - Treatment method of high-concentration organic wastewater - Google Patents
Treatment method of high-concentration organic wastewater Download PDFInfo
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- CN103864250A CN103864250A CN201410092447.6A CN201410092447A CN103864250A CN 103864250 A CN103864250 A CN 103864250A CN 201410092447 A CN201410092447 A CN 201410092447A CN 103864250 A CN103864250 A CN 103864250A
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Abstract
The invention discloses a treatment method of high-concentration organic wastewater. The method has a favorable treatment effect on high-concentration organic wastewater of which the COD (Chemical Oxygen Demand) concentration is larger than 50000mg/L and the chromaticity is larger than 10000 times. The hardly degradable substances in the treated wastewater can be degraded, so that the biodegradability of the treated wastewater is improved and the treated wastewater reaches the biochemical treatment requirement. The treatment method smartly combines ultrasonic splitting, micro-electrolytic decomposition and high-grade oxidation, and the problem that the high-concentration organic wastewater which has high COD and large toxicity and is difficulty biochemically degraded is solved.
Description
Technical field:
The invention belongs to sewage treatment area, be specifically related to a kind for the treatment of process of high concentrated organic wastewater.
Background technology:
Along with the fast development of the industry such as oil, chemical industry and pharmacy, produce the organic industrial sewage of a large amount of high-concentration hardly-degradables, this type of waste water has that organic pollutant content is high, colourity is high, toxicity is large, the features such as difficult degradation, even microorganism is still difficult to cultivate after dilution hundreds of times, can not directly carry out biochemical treatment.For this kind of water quality characteristics that wastewater biodegradability is poor, can adopt corresponding pretreatment process, improve the biodegradability of waste water, thereby ensured the treatment effect of follow-up biochemical system, therefore choosing applicable pretreatment process is the key of processing this kind of waste water.At present mainly contain electrolytic process, advanced oxidation, catalyzed oxidation, wet oxidation etc. for the pretreatment process of this high concentrated organic wastewater, because every kind of oxidation technology has different relative merits, use and have its limitation separately, multiple treatment technology simply piece together stack tend to again bring added amount of chemical is high, energy consumption is high and processing efficiency without problems such as obvious raisings, and appropriate optimum combination and the compound coupling of multiple treatment technology can obtain optimum handling effect and minimum processing cost.Therefore the efficient treatment technology that develops the organic industrial sewage of high density, poisonous, difficult degradation has become a Current Domestic external environment resist technology field difficult problem in the urgent need to address.
Summary of the invention:
The object of the invention is to overcome the deficiencies in the prior art, a kind for the treatment of process of high concentrated organic wastewater is provided, not only can be by hardly degraded organic substance and toxicant cracking and decomposition, and greatly reduce waste water COD concentration and colourity, improve biodegradability, make it adapt to the water quality requirement of biochemical treatment.
To achieve these goals, the present invention adopts following combination process to carry out pre-treatment to high concentrated organic wastewater waste water:
(1) ultrasonic treatment;
(2) micro-electrolytic decomposition;
(3) gac Fenton oxidation;
(4) coagulating sedimentation.
The pretreatment technology of ammonium sulfate waste water as above, it specifically can comprise the following steps:
(1) high concentrated organic wastewater enters ultrasound reactor through water inlet pipe, and power-on is carried out ultrasonic treatment to waste water, and ultrasonic frequency is 20-50KHz, and intensity is 5-20W/cm
2, preferred ultrasonic popin rate is 40-50KHz, preferably ultrasonic intensity is 10-20W/cm
2, the ultrasonic reaction time is 5-30 minute, preferably the ultrasonic reaction time is 10-20 minute, and powered-down after completion of the reaction, waste water is discharged through rising pipe.
(2) in step (1), draining enters micro-electrolysis reactor through water inlet pipe, and in reactor, iron carbon mass ratio is 1:1.Open aerating apparatus, dissolved oxygen is 2-4mg/L.Add several times the vitriol oil, reaction adds once while beginning, and every cadmium adds once for 30 minutes, regulates waste water ph to 1-5, and preferably pH value is 2-4.React after 60-180 minute, the preferred reaction time is 120-180 minute.Close after completion of the reaction aerating apparatus, waste water is discharged through rising pipe.
(3) in step (2), draining enters oxidizing reaction pond, opens and stirs, and adds Powdered Activated Carbon 1-6g/L, and preferably Powdered Activated Carbon dosage is 1-3g/L.Add ferrous sulfate 2-12g/L, the ferrous dosage of preferably sulfuric acid is 2-6g/L.Add several times hydrogen peroxide, reaction adds once while beginning, and every cadmium adds once for 30 minutes, and hydrogen peroxide dosage is 1-6g/L, and preferably hydrogen peroxide dosage is 1-3g/L.React after 60-120 minute, close stirring, waste water is discharged through rising pipe.
(4) in step (3), draining enters coagulative precipitation tank, adds sodium hydroxide to regulate waste water ph to 8-12, and preferably pH value is 8-9, opens and stirs, reaction 1-5 minute.Add polyacrylamide 0.2-2g/L, optimization polypropylene acid amides dosage is 0.5-1g/L, and reaction 0.5-2 minute, closes stirring, staticly settles 30-60 minute, discharges supernatant liquor.
For the pretreatment process of explanation the present invention directly perceived to high concentrated organic wastewater, incorporated by reference to Fig. 1, be process flow diagram of the present invention.High concentrated organic wastewater enters ultrasound reactor through water inlet pipe, power-on is carried out ultrasonic treatment to waste water, waste water is discharged and is entered micro-electrolysis reactor through rising pipe after completion of the reaction, open aerating apparatus, add several times the vitriol oil to regulate waste water ph, after completion of the reaction, close aerating apparatus, waste water is discharged and is entered oxidizing reaction pond through rising pipe, Xiang Chizhong adds ferrous sulfate, hydrogen peroxide, Powdered Activated Carbon, open and stir, after completion of the reaction, close stirring, waste water is discharged and is entered coagulative precipitation tank through rising pipe, add sodium hydroxide to regulate waste water ph, open and stir, after completion of the reaction, after adding polyacrylamide stirring reaction, staticly settle, discharge supernatant liquor.
The present invention compared with prior art, has obtained following unforeseeable technique effect:
(1) after ultrasonic wave and micro-electrolysis coupling and micro-electrolysis are placed in ultrasonic wave, the processing of high concentrated organic wastewater has been obtained to beyond thought effect.This combination is high to hardly degraded organic substance decomposition efficiency, and ultrasonic time is short, and micro-electrolysis stuffing loss is few, has greatly saved energy consumption and material consumption.For same waste water, carry out again ultrasonication if first carry out microelectrolysis processing, processing efficiency declines 20%, and micro-electrolysis stuffing loss is serious, still can not obtain desirable treatment effect even if carry out long supersound process.
(2) in micro-electrolysis reaction process, the employing gradation of the invention adds the mode of the vitriol oil, advantage that can the micro-electrolysis process of high efficiency performance iron charcoal, high to stripping iron unilization, high to organic substance decomposing efficiency, the vitriol oil is fewer than disposable throwing acid mode consumption, and gradation acid adding mode has ensured content ferrous in micro-electrolysis water outlet and lower pH value, for follow-up Fenton's reaction provides suitable condition of water quality.
(3) after micro-electrolysis and Fenton coupling and Fenton are placed in micro-electrolysis, Fenton's reaction process is directly utilized the ferrous ion of stripping in micro-electrolysis water outlet, and therefore, without adding in addition ferrous salt, vitriol oil consumption also reduces 50%, has saved processing cost.
(4) in Fenton's reaction, the introducing Powdered Activated Carbon of the invention and employing gradation add the mode of hydrogen peroxide, and gac plays the effect of catalyzed oxidation, and the catalysed oxidn of Fenton reagent is improved, compared with not adding the Fenton technology of Powdered Activated Carbon, processing efficiency improves 30%; Gradation adds hydrogen peroxide and had both ensured to have in water enough stable hydroxyl radical free radicals with efficient degradation organism, avoid again the disposable hydrogen peroxide that adds to cause consuming the hydroxyl radical free radical having discharged, cause processing efficiency to decline, the usage quantity of simultaneously having saved hydrogen peroxide.
(5) the present invention adopts ultrasonic treatment, micro-electrolytic decomposition, Fenton oxidation, coagulating sedimentation combination process to be greater than 50000mg/L to COD concentration, colourity is greater than the high concentrated organic wastewater of 10000 times and has good treatment effect, COD clearance is greater than 90%, chroma removal rate is greater than 95%, waste water hard-degraded substance after treatment is decomposed, biodegradability improves, and meets the requirement of biochemical treatment.
Brief description of the drawings
Fig. 1 is the schematic flow sheet that uses the inventive method to carry out wastewater treatment.Wherein 1-ultrasound reactor, 2-micro-electrolysis reactor, 3-oxidizing reaction pond, 4-coagulative precipitation tank,
Embodiment
Below will further illustrate the present invention by specific embodiment, but it should be appreciated by those skilled in the art that the specific embodiment of the invention and do not limit the present invention in any way.Within taking up an official post and how all fall into protection scope of the present invention with replacement on basis of the present invention.
Embodiment 1::
Certain pharmaceutical factory's antibiotic pharmaceutical wastewater mother liquor, water-quality guideline is in table one.This waste water of 2L is imported to ultrasound reactor through water inlet pipe, and power-on is carried out ultrasonic treatment, and ultrasonic wave is set as 20KHz, and intensity is 10W/cm
2, ultrasonic reaction 30 minutes, powered-down after completion of the reaction, waste water is discharged and is entered micro-electrolysis reactor through rising pipe, reactor internal volume 4L, the quality of iron and carbon is 1K, open aerating apparatus, dissolved oxygen is 2mg/L, reaction adds the vitriol oil once while beginning, regulate waste water ph to 1.0, reacting added the vitriol oil once after 30 minutes, regulate waste water ph to 1.0, react and close aerating apparatus after 60 minutes, waste water is discharged and is entered oxidizing reaction pond through rising pipe, open and stir, add Powdered Activated Carbon 12g, add ferrous sulfate 24g, reaction adds hydrogen peroxide 3g while beginning, react and add hydrogen peroxide 3g after 30 minutes, react after 60 minutes and add and react hydrogen peroxide 3g, react after 90 minutes and add and react hydrogen peroxide 3g, react and close stirring after 120 minutes, waste water is discharged and is entered coagulative precipitation tank through rising pipe, add sodium hydroxide to regulate waste water ph to 12, open and stir, react 5 minutes, add polyacrylamide 4g, react and close stirring after 2 minutes, staticly settle 30 minutes, discharge supernatant liquor.Detect various processes effluent index in table one.
The treatment effect of table one the present invention to pharmacy waste water
| Index | Water inlet | Ultrasonic wave water outlet | Micro-electrolysis water outlet | Fenton water outlet | Final outflow water |
| COD（mg/L） | 55600 | 44500 | 22200 | 7530 | 7250 |
| Colourity (doubly) | 10000 | 8000 | 2000 | － | 500 |
| Pyridine (mg/L) | 8000 | 2400 | 0 | － | － |
Embodiment 2::
Certain agricultural chemicals waste water, water-quality guideline is in table two.This waste water of 5L is imported to ultrasound reactor through water inlet pipe, and power-on is carried out ultrasonic treatment, and ultrasonic frequency is set as 50KHz, and intensity is 5W/cm
2, ultrasonic reaction 5 minutes, powered-down after completion of the reaction, waste water is discharged and is entered micro-electrolysis reactor through rising pipe, reactor internal volume 10L, the quality of iron and carbon is 3Kg, open aerating apparatus, dissolved oxygen is 4mg/L, reaction adds the vitriol oil once while beginning, regulate waste water ph to 5.0, reacting added the vitriol oil once after 30 minutes, regulate waste water ph to 3.0, react and close aerating apparatus after 60 minutes, waste water is discharged and is entered oxidizing reaction pond through rising pipe, open and stir, add Powdered Activated Carbon 5g, add ferrous sulfate 10g, reaction adds hydrogen peroxide 3g while beginning, react and add hydrogen peroxide 2g after 30 minutes, react after 60 minutes and add and react hydrogen peroxide 2g, react and close stirring after 90 minutes, waste water is discharged and is entered coagulative precipitation tank through rising pipe, add sodium hydroxide to regulate waste water ph to 8, open and stir, react 1 minute, add polyacrylamide 1g, react and close stirring after 0.5 minute, staticly settle 60 minutes, discharge supernatant liquor.Detect various processes effluent index in table two.
The treatment effect of table two the present invention to agricultural chemicals waste water
| Index | Water inlet | Ultrasonic wave water outlet | Micro-electrolysis water outlet | Fenton water outlet | Final outflow water |
| COD（mg/L） | 61300 | 49700 | 15000 | 6000 | 5860 |
| Colourity (doubly) | 10000 | 6000 | 2000 | － | 500 |
| Chlorobenzene (mg/L) | 5300 | 1620 | 0 | － | － |
Embodiment 3::
Certain pharmaceutical factory's antibiotic pharmaceutical wastewater mother liquor, water-quality guideline is in table three.Following experimental group is identical with control group water quality.Experimental group: this waste water of 1L is imported to ultrasound reactor through water inlet pipe, and power-on is carried out ultrasonic treatment, ultrasonic frequency is 40KHz, intensity is 20W/cm2
,ultrasonic reaction 10 minutes, powered-down after completion of the reaction, waste water is discharged and is entered micro-electrolysis reactor through rising pipe, reactor internal volume 2L, the quality of iron and carbon is 0.5Kg, open aerating apparatus, dissolved oxygen is 3mg/L, reaction adds the vitriol oil once while beginning, regulate waste water ph to 2.0, reacting added the vitriol oil once after 30 minutes, regulate waste water ph to 1.0, react and close aerating apparatus after 60 minutes, waste water is discharged and is entered oxidizing reaction pond through rising pipe, open and stir, add Powdered Activated Carbon 2g, add ferrous sulfate 6g, reaction adds hydrogen peroxide 2g while beginning, react and add hydrogen peroxide 1g after 30 minutes, react and close stirring after 60 minutes, waste water is discharged and is entered coagulative precipitation tank through rising pipe, add sodium hydroxide to regulate waste water ph to 9, open and stir, react 2 minutes, add polyacrylamide 1g, react and close stirring after 1 minute, staticly settle 30 minutes, discharge supernatant liquor.Control group: by this waste water of 1L regulate pH value to 2.0 laggard enter micro-electrolysis reactor, reactor internal volume 2L, the quality of iron and carbon is 0.5Kg, open aerating apparatus, dissolved oxygen is 3mg/L, reacts and closes aerating apparatus after 60 minutes, waste water imports ultrasound reactor through water inlet pipe, power-on is carried out ultrasonic treatment, and ultrasonic frequency is 40KHz, and intensity is 20W/cm
2ultrasonic reaction 10 minutes, powered-down after completion of the reaction, waste water is discharged and is entered oxidizing reaction pond through rising pipe, opens and stirs, and adds Powdered Activated Carbon 2g, add ferrous sulfate 6g, reaction adds hydrogen peroxide 3g while beginning, reacts and closes stirring after 60 minutes, and waste water is discharged and entered coagulative precipitation tank through rising pipe, add sodium hydroxide to regulate waste water ph to 9, open and stir, react 2 minutes, add polyacrylamide 1g, react and close stirring after 1 minute, staticly settle 30 minutes, discharge supernatant liquor, comparing result is as table three
Table three the present invention and the comparison of controlled trial treatment effect
Claims (7)
1. a treatment process for high concentrated organic wastewater, is characterized in that comprising the following steps:
(1) ultrasonic treatment;
(2) micro-electrolytic decomposition;
(3) gac Fenton oxidation;
(4) coagulating sedimentation.
2. the treatment process of high concentrated organic wastewater as claimed in claim 1, is characterized in that the device of implementing above-mentioned treatment process is: ultrasound reactor, micro-electrolysis reactor, oxidizing reaction pond, coagulative precipitation tank.
3. the treatment process of high concentrated organic wastewater as claimed in claim 2, is characterized in that comprising the following steps:
(1) high concentrated organic wastewater enters ultrasound reactor through water inlet pipe, and power-on is carried out ultrasonic treatment to waste water, and ultrasonic frequency is 20-50KHz, and intensity is 5-20W/cm
2, reacting powered-down after 5-30 minute, waste water is discharged through rising pipe;
(2) in step (1), draining enters micro-electrolysis reactor through water inlet pipe, opens aerating apparatus, and dissolved oxygen is 2-4mg/L, adds the vitriol oil to regulate waste water ph to 1-5; React after 60-180 minute, close aerating apparatus, waste water is discharged through rising pipe;
(3) in step (2), draining enters oxidizing reaction pond, adds ferrous sulfate 2-12g/L, hydrogen peroxide 1-6g/L, and Powdered Activated Carbon 1-6g/L, opens and stirs, and reacts after 60-120 minute, closes stirring, and waste water is discharged through rising pipe;
(4) in step (3), draining enters coagulative precipitation tank, adds sodium hydroxide to regulate waste water ph to 8-12, opens and stirs, react after 1-15 minute, add polyacrylamide 0.2-2g/L, stirring reaction 0.5-2 minute, close stirring, staticly settle 30-60 minute, discharge supernatant liquor.
4. the treatment process of high concentrated organic wastewater as claimed in claim 3, is characterized in that in step (1), ultrasonic frequency is 40-50KHz, and intensity is 10-20W/cm
2, the ultrasonic reaction time is 10-20 minute; In step (2), waste water ph is to 2-4; Reaction 120-180 minute; Ferrous sulfate 2-6g/L in step (3), hydrogen peroxide 1-3g/L, Powdered Activated Carbon 1-3g/L; Waste water ph is to 8-9 in step (4), polyacrylamide 0.5-1g/L.
5. the treatment process of high concentrated organic wastewater as claimed in claim 4, is characterized in that in step (2), the vitriol oil adds several times; In step (3), hydrogen peroxide adds several times.
6. the treatment process of high concentrated organic wastewater as claimed in claim 4, is characterized in that high concentrated organic wastewater COD concentration is greater than 100000mg/L, and colourity is greater than 10000 times.
7. the treatment process of high concentrated organic wastewater as claimed in claim 4, is characterized in that the supernatant liquor of discharging in step (4) carries out activated sludge biochemical processing.
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| CN104326611A (en) * | 2014-10-24 | 2015-02-04 | 苏州富奇诺水治理设备有限公司 | Method for processing organic wastewater by electro-fenton |
| CN104386868A (en) * | 2014-10-24 | 2015-03-04 | 苏州富奇诺水治理设备有限公司 | Method for treating waste water through Fenton oxidation by utilizing ultrasonic catalysis |
| CN106044811A (en) * | 2016-05-31 | 2016-10-26 | 贵州大学 | Method for removing organic substances in aluminum oxide production process with hydrogen peroxide through multiple stages |
| CN106045147A (en) * | 2016-08-05 | 2016-10-26 | 山东明泰环保科技有限公司 | Organic waste water MT polyphase catalytic oxidation device |
| WO2016189363A1 (en) * | 2015-05-26 | 2016-12-01 | Aqua Dyn Auroville | An apparatus to produce high frequency waves and light rays and sound waves to increase efficiency of bio-dynamised water |
| CN106396242A (en) * | 2015-07-28 | 2017-02-15 | 江苏吉华化工有限公司 | Difficultly-degradable wastewater treatment method |
| CN106396053A (en) * | 2016-09-21 | 2017-02-15 | 湖北君集水处理有限公司 | Method for removing pollutants by using ultrasonic enhanced coagulation |
| CN106565053A (en) * | 2016-08-26 | 2017-04-19 | 长兴县夹浦污水处理有限公司 | Textile printing and dyeing wastewater and domestic sewage mixed treatment system |
| CN108862870A (en) * | 2018-07-17 | 2018-11-23 | 四川意龙科纺集团有限公司 | A kind for the treatment of method of printing and dying wastewater |
| CN108862871A (en) * | 2018-07-17 | 2018-11-23 | 四川意龙科纺集团有限公司 | A kind of method for the treatment of of dyeing wastewater and reuse |
| CN108862731A (en) * | 2018-07-17 | 2018-11-23 | 四川意龙科纺集团有限公司 | A kind of processing method of dyeing waste water regeneration |
| CN109809601A (en) * | 2019-03-19 | 2019-05-28 | 青岛科技大学 | Batch-type electricity for degradation of organic waste water promotees iron reduced form Fenton oxidation method |
| CN110395818A (en) * | 2019-07-25 | 2019-11-01 | 苏州湛清环保科技有限公司 | The processing method of secondary phosphorous waste liquid |
| CN111646616A (en) * | 2020-06-30 | 2020-09-11 | 广东源控环保科技有限公司 | Hydrodynamic cavitation treatment process for high-concentration organic wastewater |
| CN113371881A (en) * | 2021-06-22 | 2021-09-10 | 中石化南京化工研究院有限公司 | Treatment method of process wastewater generated in one-step synthesis of N-phenylmaleimide |
| CN115010239A (en) * | 2022-06-28 | 2022-09-06 | 哈尔滨工业大学（深圳） | Method and system for treating wastewater by ozone-advanced oxidation |
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| CN104326611A (en) * | 2014-10-24 | 2015-02-04 | 苏州富奇诺水治理设备有限公司 | Method for processing organic wastewater by electro-fenton |
| CN104386868A (en) * | 2014-10-24 | 2015-03-04 | 苏州富奇诺水治理设备有限公司 | Method for treating waste water through Fenton oxidation by utilizing ultrasonic catalysis |
| WO2016189363A1 (en) * | 2015-05-26 | 2016-12-01 | Aqua Dyn Auroville | An apparatus to produce high frequency waves and light rays and sound waves to increase efficiency of bio-dynamised water |
| CN106396242A (en) * | 2015-07-28 | 2017-02-15 | 江苏吉华化工有限公司 | Difficultly-degradable wastewater treatment method |
| CN106044811A (en) * | 2016-05-31 | 2016-10-26 | 贵州大学 | Method for removing organic substances in aluminum oxide production process with hydrogen peroxide through multiple stages |
| CN106045147A (en) * | 2016-08-05 | 2016-10-26 | 山东明泰环保科技有限公司 | Organic waste water MT polyphase catalytic oxidation device |
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| CN109809601A (en) * | 2019-03-19 | 2019-05-28 | 青岛科技大学 | Batch-type electricity for degradation of organic waste water promotees iron reduced form Fenton oxidation method |
| CN109809601B (en) * | 2019-03-19 | 2022-06-21 | 青岛科技大学 | Sequencing batch type electro-promoting iron reduction type Fenton oxidation method for degrading organic wastewater |
| CN110395818A (en) * | 2019-07-25 | 2019-11-01 | 苏州湛清环保科技有限公司 | The processing method of secondary phosphorous waste liquid |
| CN111646616A (en) * | 2020-06-30 | 2020-09-11 | 广东源控环保科技有限公司 | Hydrodynamic cavitation treatment process for high-concentration organic wastewater |
| CN113371881A (en) * | 2021-06-22 | 2021-09-10 | 中石化南京化工研究院有限公司 | Treatment method of process wastewater generated in one-step synthesis of N-phenylmaleimide |
| CN115010239A (en) * | 2022-06-28 | 2022-09-06 | 哈尔滨工业大学（深圳） | Method and system for treating wastewater by ozone-advanced oxidation |
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