CN1075471C - Method for treating high concentration waste water difficult to be bio-oxidized - Google Patents
Method for treating high concentration waste water difficult to be bio-oxidized Download PDFInfo
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- CN1075471C CN1075471C CN 96110517 CN96110517A CN1075471C CN 1075471 C CN1075471 C CN 1075471C CN 96110517 CN96110517 CN 96110517 CN 96110517 A CN96110517 A CN 96110517A CN 1075471 C CN1075471 C CN 1075471C
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Abstract
The present invention relates to a new treatment technology for organic waste water of high concentration and difficult biological oxidation. In the technology, hydroxyl free radicals generated in a catalytic oxidation reaction process are used for a chain coupling reaction so that pollutants are separated out; after the treatment of coagulation and sedimentation, the purpose of pollutant removal is reached. The present invention is suitable for poisonous and harmful organic auxiliary agents with high concentration, complicated components and difficult biological degradation and organic waste water in textile industry, printing and dyeing industry, pharmacy industry, etc. After waste water is treated, the CODcr removing rate reaches more than 50%, the daily operating cost of the present invention is decreased by half as compared with the daily operating cost of the prior art, and basic construction requires low investment.
Description
The present invention relates to the particularly treatment by catalytic oxidation of chemical industry organic additive industry waste water of a kind of organic industry.
Catalytic oxidation is that recent two decades grows up and is applied to a kind of new and effective treatment process of field of waste water treatment, is improvement and reinforcement to the traditional chemical oxidation style, and it utilizes the katalysis of catalyzer to accelerate efficiency.The flat 2-63595 of JP has reported a kind of strong oxidizing property of utilizing hydroxyl radical free radical, handle the treatment process that contains organic owner's inner complex waste liquid if make organic oxygenolysis: waste liquid is remained under the acidic conditions (PH=3), in reaction vessel, supply waste liquid continuously, with iron ion and (or) cupric ion is catalyzer, near under the boiling temperature, add hydrogen peroxide, organism in the oxygenolysis waste liquid, concentrating spent liquor, when the salt density in the waste liquid reaches the solubleness boundary, be cured processing, this method is because reaction is to carry out under PH is 3 condition, so equipment material has relatively high expectations, and will heat system, the consumption of hydrogen peroxide is also higher, is 30L hydrogen peroxide/40L waste liquid.
The object of the present invention is to provide a kind of treatment process that is applicable to the organic waste water of high density, composition complexity, difficult for biological degradation, and it is simple to make it have technology, need not corrosion resistant apparatus, the pressurization of heating, characteristics that working cost is low.
For realizing the object of the invention, the method that adopts is that the pH value with actual industrial production waste water transfers to below 8.0, add iron, copper wherein one or both simple substance or ion as catalyzer, add hydrogen peroxide simultaneously, carry out oxidative coupling, this reaction is carried out at normal temperatures and pressures, be generally the multi-stage oxidizing reaction, solubility pollutent in the waste water becomes insoluble pollutent by link and separates out, transfer PH to 6.0～8.0 again, coagulating treatment is carried out in water outlet, and is settlement separate by vertical sedimentation basin, and water outlet enters the secondary biochemical treatment system.
Adoptable catalyzer can be ferrous sulfate, iron nitrate and copper sulfate, cupric nitrate, cupric chloride etc. among the present invention.Determine the consumption of iron ion and cupric ion according to the concentration of waste water, the difference of composition.General consumption is: iron ion, as: 0.8～1.2Kg ferrous sulfate/m
3Waste water; Cupric ion is as 0.2～0.6Kg cupric nitrate/m
3Waste water.
Bubbling air in oxidizing reaction of the present invention not only can utilize the stripping effect of air, and also can participate in chain reaction, oxygen in the postreaction process, the consumption of hydrogen peroxide is reduced greatly, reduce processing cost, the air add-on is generally at 4L～6L/L waste water.When having air to add, the add-on of hydrogen peroxide can be lower than 0.8ml hydrogen peroxide/L waste water.
Advantage of the present invention is: (1). all oxidizing reactions are all carried out at normal temperatures and pressures, need not high-temperature high-pressure apparatus, and facility investment is low; (2). the present invention adopts iron, cupric ion or simple substance to carry out catalyzed oxidation as catalyzer, and reaction can be carried out under the partial neutral condition, does not need corrosion resistant apparatus, and initial cost reduces significantly, and the soda acid consumption of regulating PH is reduced, and working cost reduces; (3). the present invention utilizes the hydroxyl radical free radical that produces in the catalytic oxidation process to carry out the chain type coupled reaction, making solubility pollutent in the waste water become insoluble pollutent by connection separates out, be aided with coagulation, sedimentation processing again, thereby reach the purpose of removing pollutent, hydrogen peroxide plays action of evocating in reaction process, be different from and in reaction process, play oxygenant, thereby its consumption is reduced greatly; (4). bubbling air in reaction process, the add-on of hydrogen peroxide can be lower than 0.8ml hydrogen peroxide/L waste water, reduce processing cost; (5). method for processing organic wastewater of the present invention, hydraulic detention time is short, and the plant area area is little; (6). the method for processing organic wastewater of the present invention pressurization that need not to heat, power consumption is low.
The difficult oxidized organic wastewater New Process for Treatment of high-concentration biological of the present invention is applicable to the organic waste water of the industries such as organic additive, weaving, printing and dyeing, pharmacy of high density, composition complexity, poisonous and harmful, difficult for biological degradation.After the wastewater treatment, the clearance of CODcr can reach more than 50%, and the day-to-day operation expense reduces more than one times than prior art, and initial cost is low.
Embodiment 1
Organic factory auxiliary agent COD value of waste water is 3795.2mg/l, and oil of mirbane is 147.8mg/l, and aniline is 220.9mg/l, and sulfide is 102.42mg/l, and Sulfothiorine is 304.82 mg/l.Transfer to 6～7 with sour pH value earlier with waste water, squeeze into the stair oxidation groove with pump then, dominant discharge is 100 liters/hour, in oxidation trough, add composite catalyst, be that iron ion 800mg/l and copper sludge (for the mixture of copper simple substance and mantoquita) cupric ion amount is 300mg/l, add hydrogen peroxidase 10 .3ml/l, and logical people's air, the gas catalyzed reaction is after 15 minutes, flow into the secondary oxidation groove, add iron ion 400mg/l and cupric ion 200mg/l to wherein serving as a contrast, and add hydrogen peroxidase 10 .5ml/l and bubbling air, catalyzed reaction is after 15 minutes, after water outlet is transferred pH to 7.0 with calcium oxide, squeeze into collection surface by pump, add poly-iron and carry out aggregation after 5 minutes, coagulation basin is gone in overflow, and add polyacrylamide therein, behind the coagulating 10 minutes, vertical-flow settling bowl is gone in overflow, carries out settlement separate, clear liquid enters the secondary biochemical treatment system, behind the mud concentration and settlement 12 hours, carry out mud modified after, filter press.
After using the present invention's processing, the COD clearance is 61.2%, and the oil of mirbane clearance is 89.7%, and the aniline clearance is 47.6%, and sulphur thing clearance is 100%, and Sulfothiorine is 100%, and total hrt is 2 hours.
Embodiment 2
Organic factory auxiliary agent COD value of waste water is 3532mg/l, and oil of mirbane is 140mg/l, and aniline is 179.18mg/l, and sulfide is 66.43mg/l, and thiosulfuric acid acid sodium is 348.37mg/l.Transfer to 6-7 with sour pH value earlier with waste water, squeeze into the stair oxidation groove with pump then, dominant discharge is 100 liters/hour, in oxidation trough, add iron ion 800mg/l and cupric ion 300mg/l as composite catalyst, add hydrogen peroxidase 10 .3ml/l, and bubbling air, after the catalyzed reaction 15 minutes, after water outlet is transferred pH to 7.0 with sodium hydroxide, squeeze into collection surface by pump, add poly-iron and carry out aggregation after 5 minutes, coagulation basin is gone in overflow, and add polyacrylamide therein, behind the coagulating 10 minutes, the vertical-flow settling bowl of one-level is gone in overflow, carries out settlement separately, and clear liquid is squeezed into the secondary oxidation groove by pump, to wherein adding iron ion 200mg/l and cupric ion 100mg/l, and adding hydrogen peroxidase 10 .5ml/l and bubbling air, catalyzed reaction is after 15 minutes, after water outlet is transferred pH to 7.5 with calcium hydroxide, squeeze into collection surface by pump, add poly-iron and carry out aggregation after 5 minutes, coagulation basin is gone in overflow, and adds polyacrylamide therein, behind the coagulating 10 minutes, the vertical-flow settling bowl of secondary is gone in overflow, carries out settlement separately, and clear liquid enters the secondary biochemical treatment system.The mud concentration and settlement that the vertical-flow settling bowl of one-level and secondary is discharged is after 12 hours, carry out mud modified after, filter press.
After using the present invention's processing, the COD clearance is 59.1%, and the oil of mirbane clearance is 64.86%, and the aniline clearance is 68.0%, and the sulfide clearance is 100%, and Sulfothiorine is 100%, and total hrt is 2 hours.
Claims (2)
1. a catalytic oxidation is handled the method for difficult oxidized organic wastewater, it is characterized in that the pH value of actual industrial production waste water is transferred to below 8.0, add iron, copper wherein one or both simple substance or ion as catalyzer, add hydrogen peroxide simultaneously, carry out the catalyzed oxidation coupled reaction, this reaction is carried out at normal temperatures and pressures, solubility pollutent in the waste water becomes insoluble pollutent by link and separates out, transfer PH to 6.0～8.0 again, coagulating treatment is carried out in water outlet, settlement separate by settling tank, water outlet enters the secondary biochemical treatment system.
2. the treatment process of organic waste water according to claim 1 is characterized in that bubbling air in the catalyzed oxidation coupled reaction process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96110517 CN1075471C (en) | 1996-07-12 | 1996-07-12 | Method for treating high concentration waste water difficult to be bio-oxidized |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96110517 CN1075471C (en) | 1996-07-12 | 1996-07-12 | Method for treating high concentration waste water difficult to be bio-oxidized |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1148032A CN1148032A (en) | 1997-04-23 |
| CN1075471C true CN1075471C (en) | 2001-11-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96110517 Expired - Lifetime CN1075471C (en) | 1996-07-12 | 1996-07-12 | Method for treating high concentration waste water difficult to be bio-oxidized |
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| CN (1) | CN1075471C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100436346C (en) * | 2006-11-16 | 2008-11-26 | 五邑大学 | Multiple phase catalytic oxidation-coagulation precipitation method for processing active dye printing waste water |
| CN101723485B (en) * | 2008-10-23 | 2011-12-21 | 中国石油化工股份有限公司 | Method for processing reverse osmosis concentrated water |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY143602A (en) * | 2003-01-24 | 2011-06-15 | Teoh Eng-Chye | Methods for the removal of organic nitrogen, organic and inorganic contaminants from an aqueous liquid |
| CN101659467B (en) * | 2008-08-29 | 2013-01-09 | 中国石油化工股份有限公司 | Method for treating sewage by Fenton process |
| CN101734812B (en) * | 2008-11-06 | 2012-07-18 | 中国石油化工股份有限公司 | Method for applying flue gas to waste water treating process by catalytic oxidation |
| CN102040308B (en) * | 2009-10-22 | 2012-08-01 | 中国石油化工股份有限公司 | Method for treating wastewater by combining catalytic oxidation with biological aerated filter |
| CN102050533B (en) * | 2009-10-29 | 2012-07-25 | 中国石油化工股份有限公司 | Method for treating and recycling circulating water and sewage |
| CN101955275B (en) * | 2010-09-07 | 2012-07-04 | 华泰(天津)集装箱服务有限公司 | Wet catalytic oxidation based method for treating liquid container cleaning waste water |
| CN102010085B (en) * | 2010-11-11 | 2012-08-29 | 上海集惠环保科技发展有限公司 | Method for treating high-concentration organic wastewater by P450 bionic normal-temperature normal-pressure catalytic oxidation |
| CN102351349A (en) * | 2011-09-15 | 2012-02-15 | 广东工业大学 | Treatment method for high-stability complexing heavy metal waste water |
| CN102583814B (en) * | 2012-01-18 | 2013-10-02 | 马放 | Method for processing heavy alkylbenzene sulfonate waste water |
| CN102627360B (en) * | 2012-03-16 | 2013-12-25 | 同济大学 | Method for pretreatment on industrial wastewater by nascent state ferrous iron reduction |
-
1996
- 1996-07-12 CN CN 96110517 patent/CN1075471C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100436346C (en) * | 2006-11-16 | 2008-11-26 | 五邑大学 | Multiple phase catalytic oxidation-coagulation precipitation method for processing active dye printing waste water |
| CN101723485B (en) * | 2008-10-23 | 2011-12-21 | 中国石油化工股份有限公司 | Method for processing reverse osmosis concentrated water |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1148032A (en) | 1997-04-23 |
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