CN102381788A - Electrolytic oxidation process for raising aromatic alcohol waste water biodegradability - Google Patents
Electrolytic oxidation process for raising aromatic alcohol waste water biodegradability Download PDFInfo
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- CN102381788A CN102381788A CN2011102597795A CN201110259779A CN102381788A CN 102381788 A CN102381788 A CN 102381788A CN 2011102597795 A CN2011102597795 A CN 2011102597795A CN 201110259779 A CN201110259779 A CN 201110259779A CN 102381788 A CN102381788 A CN 102381788A
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Abstract
The invention discloses an electrolytic oxidation process for raising aromatic alcohol waste water biodegradability, and relates to the environment sewage treatment field. In the process of aromatic alcohol waste water oxidation treatment, a catalyst of 0.1-10% (wt) is added for regulating the pH value between 6-12. O3 is introduced, the introduction amount is 2-20g/h, then an oxidizing agent H2O2 of 0.5-10% (wt) is added, and is introduced in an electrolytic bath for oxidation and electrolyzation, the current density of the electrolytic bath reaction system is 0-25mA/cm<2>, the electrolyzing time is 0.5-4 hours, the specific pollutant aromatic alcohol compound in waste water is conversed to a micromolecule poly fatty acid substance with easy biochemical degradation. The effluent of secondary settling tank in urban sewage treatment plants is taken as dilutial water for testing and evaluating the BOD5/CODcr value of waste water, the BOD5/CODcr value of waste water is increased from less than 0.3 to 0.4-0.6.
Description
Technical field
The present invention relates to the environmental wastewater process field, relate to a kind of method that improves aromatic alcohol wastewater biochemical degradability, specifically belong to a kind of O
3-H
2O
2-electrolytic oxidation combination process.This combination process transforms the characteristic pollutent in the waste water through chemical reaction, can biodegradability is poor, BOD
5/ COD
CrValue is converted into good biodegradability at the organic waste water that contains the aromatic alcohol pollutent below 0.3, BOD
5/ COD
CrValue is at 0.4～0.6 organic waste water.
Background technology
The aromatic alcohol compound kind is numerous, mainly comprises phenylcarbinol, phenylethyl alcohol, 1-phenylglycol, 1-phenyl-1-propyl alcohol, 1-phenyl-2-propyl alcohol, 2-phenyl-1-propyl alcohol, 1-phenyl-2-butanols, 2-phenyl-1-butanols etc.Aromatic alcohol compound is of many uses in industrial chemical is produced.Can be used for making spices and seasonings (most is fatty ester), be widely used in the allotment soap simultaneously and use and cosmetic essence.
The aromatic alcohol compound demand progressively increases both at home and abroad at present.Commercial process at aromatic alcohol compound can give off great amount of wastewater, and concentration is high, toxicity is big, and it is very high in wherein aromatic alcohol compound content to run off, and biodegradability is very poor, generally is difficult to directly carry out biochemical treatment.
For the processing of aromatic alcohol waste water, so far, be generally in the existing both at home and abroad technical process: pre-treatment → physical/chemical processing → biochemical degradation processing → qualified discharge.In actually operating, the water outlet BOD before biochemical degradation
5/ COD
CrBe worth lowly, make that the biochemical device operational efficiency is low, the degraded fluctuation is big, big to biochemical device influence.But the development of As market, the aromatic alcohol compound industrial scale constantly enlarges, thereby improves the BOD of aromatic alcohol compound factory effluent
5/ COD
CrValue, the work of efficient that improves follow-up biochemical treatment is also urgent day by day.
Improve the method for the biodegradability of organic pollutant; Can be divided into two types from the character of process method; The one, the physico-chemical pretreatment method, exactly the organism of these complex constructions is decomposed into simple in structure, the form of being utilized by mikrobe easily; Improve the biodegradability of hardly degraded organic substance, get into biochemical treatment system again; And utilize oxygenant that these organic pollutant oxygenolysis have been proved to be a feasible method for small molecules, organism simple in structure; The 2nd, cultivate efficient bacterial strain, through screening or make up multi-functional super bacterium and change molecular structure and introduce special groups and strengthen their the degrade ability of this type of material.But the screening of various efficient degrading bacterias and purification ratio be blindness, at random.
CN101948163A discloses a kind of process method that improves the trade effluent biodegradability; The waste water of secondary biochemical treatment is earlier settlement separate through settling tank; Wastewater flow rate adopts the metering of water inlet volume pump after water-in gets into, and the water after the separation gets in the main reactor through recycle pump, venturi tube and ozone with reactor drum internal recycle water and carries out oxidizing reaction.The biodegradability of processed waste water is brought up to the highest by 0.282 by original 0.131.But DeGrain, complex operation, equipment requirements is high, and processing cost is higher.
CN2910917Y has proposed a kind of anaerobic reactor that improves wastewater biodegradability, after the question response device is stable, and the containing the thick-oil waste water biodegradability and can improve about 40% of processing.But because this structure of reactor is complicated, specific aim is not strong, so limited its application in improving wastewater biodegradability.
CN101456639A has mentioned a kind of device and method of handling organic wastewater with difficult degradation thereby, adopts ozone～ultrasonic～nano-TiO
2The photochemical catalysis coupling technique is handled organic wastewater with difficult degradation thereby, promptly with gas-liquid mixing pump waste water and ozone is attracted, mixes, dissolves, and directly send in ultrasonic～nano-photo catalytic reaction column the waste water BOD after the processing
5/ COD
CrValue reaches 0.63.Though and this method can improve the biodegradability of waste water to a great extent, complex technical process, catalyzer is made loaded down with trivial details, and cost is high.
Summary of the invention
Key problem in technology to be solved by this invention; Comprise and overcome high, the problems such as processing cost is high, complicated operation, treatment effect is not obvious, specific aim is not strong of aforesaid device requirement; Simultaneously in order to improve the biochemical degradability of waste water; Carry out follow-up biological degradation more easily, proposed the combination oxidizing process method that a kind of raising contains the biochemical degradability of aromatic alcohol waste water, be converted into the good organic waste water of biodegradability with the aromatic alcohol waste water that reaches the biodegradability difference; Improve biodegradability, alleviate the purpose of follow-up biodegradable burden.
The used technical scheme of the present invention is: with O
3Oxidation, H
2O
2Oxidation, oxidization electrolysis technology are coupled together, and form a kind of combination oxidizing process method that improves the biochemical degradability of aromatic alcohol waste water, carry out according to following step:
⑴ add catalyzer in the aromatic alcohol waste water at normal temperatures, the catalyzer add-on accounts for handles 0.1～10% of wastewater quality, and the preferred catalyst add-on is 2.5～4%;
⑵ add a certain amount of alkali, and the pH value of regulating waste water is between 6～12;
⑶ feed oxygenant O
3, O
3The feeding amount be 2～20g/h, preferred O
3The feeding amount be 8～14g/h;
⑷ add oxygenant H
2O
2, H
2O
2Add-on account for the waste water of handling quality 0.5～10%, preferred H
2O
2Add-on 3.5～6.5%;
⑸ feed waste water in the electrolyzer, and electrolyzer reactive system current density is controlled to be 0～25mA/cm
2Electrolysis time is 0.5～4h.
Wherein the described catalyzer of step 1 is ferrous sulfate, zinc sulfate, Xiao Suangu, manganous nitrate, and wherein the described aromatic alcohol waste water of step 1 is phenylcarbinol waste water or phenylethyl alcohol waste water.
Alkali in the step 2 is sodium hydroxide, sodium hydrogencarbonate.
Use H in the step 4
2O
2Be H
2O
2The aqueous solution, massfraction is: 20～90%.
The present invention at first adds the catalyzer of 0.1～10% (wt) in oxide treatment aromatic alcohol waste water process, regulate between pH to 6～12.Feed O
3, the feeding amount is 2～20g/h, adds oxygenant 0.5～10% (wt) H then
2O
2After, feeding electrolyzer and carry out oxidization electrolysis, electrolyzer reactive system current density is 0～25mA/cm
2, electrolysis time is 0.5～4h, and the characteristic pollutent aromatic alcohol compound in the waste water is converted into the small molecules polyhydric aliphatic acid that is prone to biochemical degradation at this moment, and wherein the massfraction of maleic acid is the highest, the BOD of water outlet
5/ CODcr value is the highest.The massfraction of handling the back maleic acid brings up to 0～50% from 0%, and is wherein preferred 20～50%, serves as the BOD of inoculation water test evaluation waste water with municipal sewage plant's second pond water outlet
5/ COD
CrValue, the BOD of waste water
5/ COD
CrValue brings up to 0.4～0.6.Waste water after treatment, characteristic pollutent wherein is converted into small molecules polyhydric aliphatic acid (typical product is a maleic acid) by aromatic alcohol compound, serves as the BOD of inoculation water test evaluation waste water with municipal sewage plant's second pond water outlet
5/ COD
CrValue, the BOD of waste water
5/ COD
CrValue is by bringing up to 0.4～0.6 below 0.3.
The present invention has the following advantages:
1. the present invention utilizes the combination oxidizing process to improve a kind of method of the biochemical degradability of aromatic alcohol waste water, and wherein oxygenant is O
3, H
2O
2, and collaborative electrolysis, have characteristics such as dosage is low, processing cost is low, operational condition is simple, low for equipment requirements.It is low that processing cost is handled aromatic alcohol waste water than absorption method.
2. the present invention can handle aromatic alcohol waste water efficiently; Adopt the combination oxidizing process to handle aromatic alcohol waste water; Make through after the processing of combination oxidizing process; Characteristic pollutent aromatic alcohol compound conversion in the waste water is small molecules polyhydric aliphatic acid (typical product is a maleic acid), and the massfraction of the maleic acid behind chemical reaction in the waste water is the highest, is 0～50%; Preferred 20%～50%, serve as the BOD of inoculation water test evaluation waste water with municipal sewage plant's second pond water outlet
5/ COD
CrValue, the BOD of waste water
5/ COD
CrValue brings up to 0.4～0.6, has improved the biochemical degradability of organic waste water, can more effectively carry out follow-up biological degradation.
3. the present invention has characteristics such as technology is simple, treatment effect is good.
The practical implementation method
Following embodiment will further explain the present invention, but therefore not limit the present invention.
Embodiment 1
Get the phenylcarbinol waste water that needs to handle and drop in the treating pond, adding accounts for and handles wastewater quality is the catalyst sulfuric acid cobalt of 0.1% (wt), and the back that stirs adds a certain amount of sodium hydrogencarbonate, and regulating waste water ph is 6.0.5% the mass concentration that adds the quality account for the waste water of handling then is 20% H
2O
2The aqueous solution, O
3The feeding amount is 2g/h, and cell current density remains on 2mA/cm
2, electrolysis time is 0.5h.Sedimentation 2h, small molecules polyhydric aliphatic acid propanedioic acid massfraction brings up to 2% from 0% in the waste water supernatant liquid, and the massfraction of Succinic Acid brings up to 3.8% from 0%, and the maleic acid massfraction brings up to 22.19% from 0%.With municipal sewage plant's second pond water outlet is the BOD of inoculation water test evaluation waste water
5/ COD
CrValue, the COD of former water
CrBe 4200mg/L, BOD
5Be 880mg/L, BOD
5/ COD
CrValue is 0.21, the COD of water outlet
CrBe 1560mg/L, BOD
5Be 640mg/L, BOD
5/ COD
CrValue reaches 0.41.
Embodiment 2
Get the phenylcarbinol waste water that needs to handle and drop in the treating pond, adding accounts for and handles wastewater quality is the catalyst sulfuric acid cobalt of 1.0% (wt), and the back that stirs adds a certain amount of sodium hydrogencarbonate, and regulating waste water ph is 8.1.5% the mass concentration that adds the quality account for the waste water of handling then is 40% H
2O
2The aqueous solution, O
3The feeding amount is 6g/h, and cell current density remains on 4 mA/cm
2, electrolysis time is 1h.Sedimentation 2h, small molecules polyhydric aliphatic acid propanedioic acid massfraction brings up to 2.9% from 0% in the waste water supernatant liquid, and the massfraction of Succinic Acid brings up to 4.2% from 0%, and the maleic acid massfraction mentions 25.83% from 0%.With municipal sewage plant's second pond water outlet is the BOD of inoculation water test evaluation waste water
5/ COD
CrValue, the COD of former water
CrBe 4200mg/L, BOD
5Be 880mg/L, BOD
5/ COD
CrValue is 0.21, the COD of water outlet
CrBe 1310mg/L, BOD
5Be 590mg/L, BOD
5/ COD
CrValue reaches 0.45.
Embodiment 3
Get the phenylcarbinol waste water of need handling and drop in the treating pond, add and account for that to handle wastewater quality be that the catalyst sulfuric acid of 2.5% (wt) is ferrous, the back that stirs adds a certain amount of sodium hydroxide, and regulating waste water ph is 7.3.5% the mass concentration that adds the quality account for the waste water of handling then is 50% H
2O
2The aqueous solution, O
3The feeding amount is 8g/h, and cell current density remains on 8 mA/cm
2, electrolysis time is 1.5h.Sedimentation 2h, small molecules polyhydric aliphatic acid propanedioic acid massfraction brings up to 3.3% from 0% in the waste water supernatant liquid, and the massfraction of Succinic Acid brings up to 4.6% from 0%, and the maleic acid massfraction brings up to 29.17% from 0%.With municipal sewage plant's second pond water outlet is the BOD of inoculation water test evaluation waste water
5/ COD
CrValue, the COD of former water
CrBe 4200mg/L, BOD
5Be 880mg/L, BOD
5/ COD
CrValue is 0.21, the COD of water outlet
CrBe 1100mg/L, BOD
5Be 520mg/L, BOD
5/ COD
CrValue reaches 0.48.
Embodiment 4
Get the phenylcarbinol waste water of need handling and drop in the treating pond, add and account for that to handle wastewater quality be that the catalyst sulfuric acid of 0.8% (wt) is ferrous, the back that stirs adds a certain amount of sodium hydroxide, and regulating waste water ph is 8.5% the mass concentration that adds the quality account for the waste water of handling then is 30% H
2O
2The aqueous solution, O
3The feeding amount is 10g/h, and cell current density remains on 15 mA/cm
2, electrolysis time is 2.5h.Sedimentation 2h, small molecules polyhydric aliphatic acid propanedioic acid massfraction brings up to 3.5% from 0% in the waste water supernatant liquid, and the massfraction of Succinic Acid brings up to 5.1% from 0%, and the maleic acid massfraction brings up to 48.19% from 0%.With municipal sewage plant's second pond water outlet is the BOD of inoculation water test evaluation waste water
5/ COD
CrValue, the COD of former water
CrBe 4200mg/L, BOD
5Be 880mg/L, BOD
5/ COD
CrValue is 0.21, the COD of water outlet
CrBe 860mg/L, BOD
5Be 480mg/L, BOD
5/ COD
CrValue reaches 0.56.
Embodiment 5
Get the phenylethyl alcohol waste water that needs to handle and drop in the treating pond, adding accounts for and handles wastewater quality is the catalyst sulfuric acid zinc of 4% (wt), and the back that stirs adds a certain amount of sodium hydroxide, and regulating waste water ph is 9.6.5% the mass concentration that adds the quality account for the waste water of handling then is 60% H
2O
2The aqueous solution, O
3The feeding amount is 14g/h, and cell current density remains on 10 mA/cm
2, electrolysis time is 2.0h.Sedimentation 2h, small molecules polyhydric aliphatic acid propanedioic acid massfraction brings up to 3.2% from 0% in the waste water supernatant liquid, and the massfraction of Succinic Acid brings up to 4.9% from 0%, and the maleic acid massfraction brings up to 41.32% from 0%.With municipal sewage plant's second pond water outlet is the BOD of inoculation water test evaluation waste water
5/ COD
CrValue, the COD of former water
CrBe 4200mg/L, BOD
5Be 880mg/L, BOD
5/ COD
CrValue is 0.21, the COD of water outlet
CrBe 1010mg/L, BOD
5Be 515mg/L, BOD
5/ COD
CrValue reaches 0.51.
Embodiment 6
Get the phenylethyl alcohol waste water that needs to handle and drop in the treating pond, adding accounts for and handles wastewater quality is the catalyst sulfuric acid zinc of 6% (wt), and the back that stirs adds a certain amount of sodium hydroxide, and regulating waste water ph is 10.7.5% the mass concentration that adds the quality account for the waste water of handling then is 70% H
2O
2The aqueous solution, O
3The feeding amount is 16g/h, and cell current density remains on 18 mA/cm
2, electrolysis time is 3.0h.Sedimentation 2h, small molecules polyhydric aliphatic acid propanedioic acid massfraction brings up to 2.9% from 0% in the waste water supernatant liquid, and the massfraction of Succinic Acid brings up to 4.7% from 0%, and the maleic acid massfraction brings up to 36.28% from 0%.With municipal sewage plant's second pond water outlet is the BOD of inoculation water test evaluation waste water
5/ COD
CrValue, the COD of former water
CrBe 4200mg/L, BOD
5Be 880mg/L, BOD
5/ COD
CrValue is 0.21, the COD of water outlet
CrBe 1020mg/L, BOD
5Be 512mg/L, BOD
5/ COD
CrValue reaches 0.5.
Embodiment 7
Get the phenylethyl alcohol waste water that needs to handle and drop in the treating pond, adding accounts for and handles wastewater quality is the catalyst sulfuric acid manganese of 8% (wt), and the back that stirs adds a certain amount of sodium hydrogencarbonate, and regulating waste water ph is 11.8.5% the mass concentration that adds the quality account for the waste water of handling then is 80% H
2O
2The aqueous solution, O
3The feeding amount is 18g/h, and cell current density remains on 21mA/cm
2, electrolysis time is 3.5h.Sedimentation 2h, small molecules polyhydric aliphatic acid propanedioic acid massfraction brings up to 2.6% from 0% in the waste water supernatant liquid, and the massfraction of Succinic Acid brings up to 4.4% from 0%, and the maleic acid massfraction brings up to 35.66% from 0%.With municipal sewage plant's second pond water outlet is the BOD of inoculation water test evaluation waste water
5/ COD
CrValue, the COD of former water
CrBe 4200mg/L, BOD
5Be 880mg/L, BOD
5/ COD
CrValue is 0.21, the COD of water outlet
CrBe 1140mg/L, BOD
5Be 558mg/L, BOD
5/ COD
CrValue reaches 0.49.
Embodiment 8
Get the phenylethyl alcohol waste water that needs to handle and drop in the treating pond, adding accounts for and handles wastewater quality is the catalyst sulfuric acid manganese of 10% (wt), and the back that stirs adds a certain amount of sodium hydrogencarbonate, and regulating waste water ph is 12.10% the mass concentration that adds the quality account for the waste water of handling then is 90% H
2O
2The aqueous solution, O
3The feeding amount is 20g/h, and cell current density remains on 25mA/cm
2, electrolysis time is 4.0h.Sedimentation 2h, small molecules polyhydric aliphatic acid propanedioic acid massfraction brings up to 2.3% from 0% in the waste water supernatant liquid, and the massfraction of Succinic Acid brings up to 3.8% from 0%, and the maleic acid massfraction brings up to 32.79% from 0%.With municipal sewage plant's second pond water outlet is the BOD of inoculation water test evaluation waste water
5/ COD
CrValue, the COD of former water
CrBe 4200mg/L, BOD
5Be 880mg/L, BOD
5/ COD
CrValue is 0.21, the COD of water outlet
CrBe 1420mg/L, BOD
5Be 610mg/L, BOD
5/ COD
CrValue reaches 0.43.
The present invention is through regulating the pH value, adding catalyzer, through changing oxygenant O
3, H
2O
2, regulate its add-on, the current densities of electrolyzer etc. are to the influence of the biochemical degradability of raising organic waste water.Transform the characteristic pollutent in the waste water through chemical reaction, can biodegradability is poor, BOD
5/ COD
CrOrganic waste water at 0.3 following aromatic alcohol pollutent is converted into good biodegradability, BOD
5/ COD
CrOrganic waste water 0.4～0.6 has been optimized reaction conditions.With cheap price, operate a large amount of characteristic pollutent aromatic alcohol compounds easily and be converted into small molecules polyhydric aliphatic acid (typical product is a maleic acid) in the waste water, promptly improve the BOD of waste water
5/ COD
Cr, improved the biodegradability of waste water, for follow-up biological degradation reduces the heavy burdens, good economic benefit is arranged again.
Claims (3)
1. combination oxidizing process method that improves the biochemical degradability of aromatic alcohol waste water is characterized in that carrying out according to following step:
⑴ add catalyzer in the aromatic alcohol waste water at normal temperatures, the catalyzer add-on accounts for handles 0.1～10% of wastewater quality, and the preferred catalyst add-on is 2.5～4%;
⑵ add a certain amount of alkali, and the pH value of regulating waste water is between 6～12;
⑶ feed oxygenant O
3, O
3The feeding amount be 2～20g/h, preferred O
3The feeding amount be 8～14g/h;
⑷ add oxygenant H
2O
2, H
2O
2Add-on account for the waste water of handling quality 0.5～10%, preferred H
2O
2Add-on 3.5～6.5%;
⑸ feed waste water in the electrolyzer, and electrolyzer reactive system current density is controlled to be 0～25mA/cm
2Electrolysis time is 0.5～4h.
2. a kind of combination oxidizing process method that improves the biochemical degradability of aromatic alcohol waste water according to claim 1; It is characterized in that wherein the described catalyzer of step 1 is ferrous sulfate, zinc sulfate, Xiao Suangu or manganous nitrate, wherein the described aromatic alcohol waste water of step 1 is phenylcarbinol waste water or phenylethyl alcohol waste water; Alkali in the step 2 is sodium hydroxide or sodium hydrogencarbonate, uses H in the step 4
2O
2Be H
2O
2The aqueous solution, massfraction are 20～90%.
3. a kind of combination oxidizing process method that improves the biochemical degradability of aromatic alcohol waste water according to claim 1 is characterized in that wherein the described catalyzer add-on of step 1 is 2.5～4%; The described O of step 3 wherein
3The feeding amount be 8～14g/h; The described H of step 4 wherein
2O
2Add-on 3.5～6.5%.
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|---|---|---|---|
| CN2011102597795A CN102381788A (en) | 2011-09-05 | 2011-09-05 | Electrolytic oxidation process for raising aromatic alcohol waste water biodegradability |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011472A (en) * | 2013-01-09 | 2013-04-03 | 杭州诚洁环保有限公司 | Pretreatment method for enhancing BOD (biochemical oxygen demand) absolute value of chemical waste acid |
| CN104211233A (en) * | 2014-09-26 | 2014-12-17 | 昆山美淼环保科技有限公司 | Electrooxidation process for treating water-based ink waste water |
| CN105174561A (en) * | 2015-09-10 | 2015-12-23 | 陕西省石油化工研究设计院 | Treatment process of high-salinity concentrated water difficult to biodegrade |
-
2011
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011472A (en) * | 2013-01-09 | 2013-04-03 | 杭州诚洁环保有限公司 | Pretreatment method for enhancing BOD (biochemical oxygen demand) absolute value of chemical waste acid |
| CN103011472B (en) * | 2013-01-09 | 2014-01-15 | 杭州诚洁环保有限公司 | Pretreatment method for enhancing BOD (biochemical oxygen demand) absolute value of chemical waste acid |
| CN104211233A (en) * | 2014-09-26 | 2014-12-17 | 昆山美淼环保科技有限公司 | Electrooxidation process for treating water-based ink waste water |
| CN105174561A (en) * | 2015-09-10 | 2015-12-23 | 陕西省石油化工研究设计院 | Treatment process of high-salinity concentrated water difficult to biodegrade |
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