CN101186402B - Fenton two-stage method oxidation processing technique for paper-making and pulping waste water - Google Patents
Fenton two-stage method oxidation processing technique for paper-making and pulping waste water Download PDFInfo
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- CN101186402B CN101186402B CN2007101148877A CN200710114887A CN101186402B CN 101186402 B CN101186402 B CN 101186402B CN 2007101148877 A CN2007101148877 A CN 2007101148877A CN 200710114887 A CN200710114887 A CN 200710114887A CN 101186402 B CN101186402 B CN 101186402B
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Abstract
The invention relates to a Fenton two-step oxidation treatment technique for wastewater of pulp and paper making in the field of treatment techniques for wastewater of pulp and paper making. The technical proposal is that Fe<2+> is first added into pulping effluent, which is then added with acid to regulate the PH value to 4-5, next entering a reactor with H2O2 added; the mixture obtained after oxidation for 15-20 minutes is added with alkalizers to regulate the PH value and then is treated with flocculent settling and supernatant separation. The Fe<2+> adopts ferrous sulphate and the ratio of addition amount of ferrous sulphate and H2O2 and COD in the wastewater is 0.6 to 1 to 2.25; the alkalizers consist of metallic catalyst and alkali which are added into the mixture for twice after the oxidation and a first precipitation to finally regulate the PH value to 7. The Fenton two-step oxidation treatment technique for wastewater of pulp and paper has the effects that the removal rate of COD can be increased to 90-95 percent from 80-85 percent by a conventional method with an increase of about 10 percent while the removal rate of chromaticity can be increased to 98-99 percent from 70-75 percent by the conventional method with an increase of about 25 percent and the wastewater treatment cost has no addition and slightly decreases on the contrary.
Description
Technical field
The present invention relates to the Fenton two-stage method oxidation processing technique for paper-making pulping waste water in a kind of paper-making pulping waste water treatment process field.
Background technology
In general, the oxidation capacity of oxygenant is consistent with its standard potential, and hydroxyl free radical (OH) has higher standard potential than other common oxygenants, also just has higher oxidation capacity.Hashimoto Herens etc. are to nano level TiO
2The OH that produced by optical excitation studies show that the photon energy on the OH active group is equivalent to 3327 ℃ of pyritous heat energy, be enough to make organism " burning " rapidly under this high temperature, and final oxygenolysis is CO
2And H
2O reduces the COD value of organic sewage greatly, reaches the purpose of water treatment.High-level oxidation technology claims the deep oxidation technology again, utilizes this characteristic of OH to reach the purpose of oxygenolysis exactly.It comprises Fenton method, O oxidation style, wet oxidation technology, supercritical water oxidation method, nano-photo catalytic oxidation style, electrochemical catalysis edman degradation Edman and ultrasonic degradation method etc., nowadays becomes the focus of various countries' water technology research gradually.Fenton reagent is a kind of advanced oxidation agent commonly used, other advanced oxidation agent relatively, the Fenton method has that operating process is simple, reactant is easy to get, expense cheap, need not complex apparatus, follow-up biochemical treatment is not had toxic action and advantage such as environmentally friendly, be applied to gradually in the waste water treatment engineerings such as pulping and paper-making, dyestuff, sanitas, photographic developer, agricultural chemicals, and have good application prospects.
1, the oxidation mechanism of Fenton oxidation style
Fenton reagent passes through Fe under acidic conditions
2+Excite, the OH that hydrogen peroxide is produced has high oxidisability, its oxidizing electrode current potential is 2.80eV, is only second to F in common oxygenant.
Reaction process is as follows:
Fe
2++H
2O
2→Fe
3++HO·+HO
-
Fe
3++H
2O
2→Fe
2++HOO·+H
+
Fe
2++HO·→Fe
3++HO
-
HOO·+Fe
3+→+Fe
2++O
2+H
+
HO·+H
2O
2→HOO·+H
2O
Fe
2++HOO·→HO
2 -+Fe
3+
Wherein, the speed of entire reaction has been controlled in the reaction of generation OH.OH is consumed gradually by reaction or with the organism reaction.
2, the coagulation mechanism of Fenton oxidation style
Fenton reagent is brought into play its oxygenizement under acidic conditions, also complexing, precipitin reaction are taking place simultaneously, and the special pH that is done when for maintenance effluent quality neutrality improves process and will more help the generation of Fenton coagulating.
〔Fe(H
2O)
6〕
3++H
2O→〔Fe(H
2O)
5OH〕
2++H
3O
+
〔Fe(H
2O)
5OH〕
2++H
2O→〔Fe(H
2O)
4(OH)
2〕+H
3O
+
When the pH value was 3～7, above-mentioned complex compound became:
2〔Fe(H
2O)
5OH〕
2+→〔Fe
2(H
2O)
8(OH)
2〕
4++2H
2O
〔Fe
2(H
2O)
8(OH)
3〕
3++H
2O→〔Fe
2(H
2O)
7(OH)
3〕
3++H
3O
+
〔Fe
2(H
2O)
7(OH)
3〕
3++〔Fe(H
2O)
5(OH)
2〕
2+→〔Fe
3(H
2O)
10(OH)
4〕
5++2H
2O
It is to add Fe earlier that the Fenton common law is disposed of sewage
2+, add acid then and transfer pH to specifying acidic value, enter reactor and add H again
2O
2, add behind the oxidation certain hour about adjusting PH with base to 7, flocculation sediment then, supernatant liquor separates.This method is 80～85% to the COD clearance, is 70～75% to the clearance of colourity, awaits further raising.
Summary of the invention
Purpose of the present invention is exactly the defective that exists at prior art, and a kind of Fenton two-stage method oxidation processing technique for paper-making pulping waste water is provided.Its target is can bring up to 90～95% of novel process, increase rate about 10% by common-law 80～85% to the COD clearance; Clearance to colourity can bring up to 98～99%, increase rate about 25% by common-law 70～75%.And do not increase cost of sewage disposal, opposite processing costs has decline slightly.
Know-why of the present invention
1, at the characteristic of paper-making effluent, its principal pollutant are hydrotropic lignins, lignins a large amount of in pulping process are dissolved in the water, the COD that has promptly increased water has also increased the colourity of water, characteristics of the present invention are at paper-making effluent pollutent feature, made full use of the physicochemical property of lignin, utilized of the change of A medicament, reached the purpose of further oxidation removal pollutent the lignin survival.
2, after the oxidizing reaction of Fenton finishes, what rely on to a great extent is that coagulation mechanism is separated out pollutent and become mud and water sepn from water, thereby reaches the purpose of removing dirt.The reaction conditions of the present invention and Fenton adapts, and has utilized the acidic conditions of oxidizing reaction necessity, has promoted the A medicament to play a role, and impels the lignin pollutent in the sewage to obtain the maximum efficient of removing.
3, after mud-water separation, add a part of A medicament again and can improve water quality, final drainage index is further revised.
The technical scheme of Ti Chuing is therefrom: comprise adding Fe in the pulping sewage earlier
2+, add acid then and transfer pH to 4-5, enter reactor and add H again
2O
2, add basic agent after oxidation 15-20 minute and transfer pH, flocculation sediment then, supernatant liquor separates, described Fe
2+Adopt ferrous sulfate, ferrous sulfate and H
2O
2Add-on and waste water in the proportioning of COD be 0.6: 1: 2.25, described basic agent is that metal catalyst and alkali are formed, adding at twice after the oxidation and behind the primary sedimentation, final adjustment pH value is that 7 described metal catalysts are the titanium metal catalyzer, and described acid comprises hydrochloric acid, sulfuric acid, nitric acid.
Difference of the present invention is: find an oxidizing reaction to close on the optimum separating point that finishes the back mud-water separation, add the alkali electroless medicament respectively before and after this separation point.The effect that adds the alkali electroless medicament before the separation point is to improve oxidation and flocculating effect, keeps mud-water separation more thorough, and the effect that adds the alkali electroless medicament behind the separation point is further to improve water quality.
Effect of the present invention: can bring up to 90～95% of novel process, increase rate about 10% by common-law 80～85% to the COD clearance; Can bring up to 98～99% by common-law 70～75% to the clearance of colourity, increase rate about 25%, and do not increase cost of sewage disposal, opposite processing costs has decline slightly.
Embodiment
Embodiment 1: according to pulp-making waste-water COD content, press ferrous sulfate and H
2O
2With the proportioning of COD in the waste water is to prepare ferrous sulfate and H at 0.6: 1: 2.25
2O
2Amount.Add ferrous sulfate in the pulping sewage earlier, add hydrochloric acid then and transfer pH, enter reactor and add H again to 4-5
2O
2, add titanium metal catalyzer and sodium hydroxide first after oxidation 15-20 minute, behind the flocculation sediment, add titanium metal catalyzer and sodium hydroxide once more then, finally adjusting the pH value is 7, and supernatant liquor separates, and clear water reaches emission standard.
Embodiment 2: according to pulp-making waste-water COD content, press ferrous sulfate and H
2O
2With the proportioning of COD in the waste water is to prepare ferrous sulfate and H at 0.6: 1: 2.25
2O
2Amount.Add ferrous sulfate in the pulping sewage earlier, add sulfuric acid (perhaps carbonic acid) then and transfer pH, enter reactor and add H again to 4-5
2O
2, add titanium metal catalyzer and potassium hydroxide first after oxidation 15-20 minute, behind the flocculation sediment, add titanium metal catalyzer and potassium hydroxide once more then, finally adjusting the pH value is 7, and supernatant liquor separates, and clear water reaches emission standard.
Carried out the comparison of common law and novel process according to the foregoing description, utilized two of its biological treatment water water sample that settles out, carry out sewage disposal under the situation in same medicine amount and reaction times, operation result is as follows:
| Project | COD(mg/L)? | Colourity (doubly) |
| Former water | 627? | 400? |
| Common Fenton method | 102? | 103? |
| Common law clearance % | 83.73? | 74.25? |
| Novel process of the present invention | 37? | 4? |
| Clearance % of the present invention | 94.10? | 99.00? |
Claims (1)
1. a Fenton two-stage method oxidation processing technique for paper-making pulping waste water comprises adding Fe in the pulping sewage earlier
2+, add acid for adjusting pH then to 4-5, enter reactor and add H again
2O
2, adding the basic agent adjust pH after oxidation 15-20 minute, flocculation sediment adds basic agent once more then, and supernatant liquor separates, and it is characterized in that: described Fe
2+Adopt ferrous sulfate, ferrous sulfate and H
2O
2Add-on and waste water in the proportioning 0.6: 1: 2.25 of COD, described basic agent is that titanium metal catalyzer and alkali are formed, and is adding at twice after the oxidation and behind the primary sedimentation, finally adjusting the pH value is 7, described acid comprises hydrochloric acid, sulfuric acid or nitric acid.
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|---|---|---|---|
| CN2007101148877A CN101186402B (en) | 2007-11-27 | 2007-11-27 | Fenton two-stage method oxidation processing technique for paper-making and pulping waste water |
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|---|---|---|---|
| CN2007101148877A CN101186402B (en) | 2007-11-27 | 2007-11-27 | Fenton two-stage method oxidation processing technique for paper-making and pulping waste water |
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| CN101186402A CN101186402A (en) | 2008-05-28 |
| CN101186402B true CN101186402B (en) | 2011-06-01 |
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| CN2007101148877A Expired - Fee Related CN101186402B (en) | 2007-11-27 | 2007-11-27 | Fenton two-stage method oxidation processing technique for paper-making and pulping waste water |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103818994A (en) * | 2014-02-26 | 2014-05-28 | 郑州大学 | Dosing method for ozone oxidation decolorant used for papermaking pulping waste water |
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| CN102050541B (en) * | 2009-10-27 | 2012-07-18 | 中国石油化工股份有限公司 | Treatment method for wastewater from stripping tower |
| CN102206011B (en) * | 2010-03-31 | 2012-11-14 | 中国石油天然气股份有限公司 | Coagulation-oxidation combined type method for processing sewage |
| CN102060395B (en) * | 2010-10-28 | 2013-03-13 | 广东工业大学 | Method for treating complex chemical wastewater by combination of Fenton and starch-based flocculant |
| CN102086053B (en) * | 2010-12-29 | 2012-05-30 | 山东太阳纸业股份有限公司 | Method for preparing flocculant from chemically and physically treated sludge of papermaking waste water |
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| CN104261589A (en) * | 2014-09-29 | 2015-01-07 | 天津大学 | Separated-point inflow type Fenton reagent oxidation treatment device and method for treating wastewater |
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| CN105000718B (en) * | 2015-08-11 | 2017-01-18 | 湛江晨鸣浆纸有限公司 | Pulp paper wastewater treatment process |
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| ES2932649T3 (en) * | 2017-06-29 | 2023-01-23 | Kemira Oyj | Composition, its use and method of removing and preventing moisture resistant resins from contaminating papermaking equipment |
| CN107746085A (en) * | 2017-12-05 | 2018-03-02 | 广东省造纸研究所 | A kind of paper-making waste water treating agent and its method for handling paper waste |
| CN109354289A (en) * | 2018-11-19 | 2019-02-19 | 深圳市三利谱光电科技股份有限公司 | A kind of processing method of dyestuff system polaroid waste water |
| CN112759105A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Method for selectively removing thiocyanate in nitrile-containing wastewater |
| CN114477524A (en) * | 2022-01-11 | 2022-05-13 | 云南云铜锌业股份有限公司 | Method for removing COD (chemical oxygen demand) in flue gas wastewater of zinc leaching residue rotary kiln by ozone pretreatment |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999021801A1 (en) * | 1997-10-29 | 1999-05-06 | Prox T.E.C. Poprad, S.R.O. | Method for water purification based on the fenton reaction |
| CN1355143A (en) * | 2000-11-28 | 2002-06-26 | 中国科学院生态环境研究中心 | Process and equipment for treating sewage in oil field |
| CN1724420A (en) * | 2005-06-14 | 2006-01-25 | 华南理工大学 | Process for combined water treatment of chemical oxidizing-biological biological filtering tank |
| CN101041475A (en) * | 2007-03-09 | 2007-09-26 | 华南理工大学 | Fenton and air-float integral water treating method |
-
2007
- 2007-11-27 CN CN2007101148877A patent/CN101186402B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999021801A1 (en) * | 1997-10-29 | 1999-05-06 | Prox T.E.C. Poprad, S.R.O. | Method for water purification based on the fenton reaction |
| CN1355143A (en) * | 2000-11-28 | 2002-06-26 | 中国科学院生态环境研究中心 | Process and equipment for treating sewage in oil field |
| CN1724420A (en) * | 2005-06-14 | 2006-01-25 | 华南理工大学 | Process for combined water treatment of chemical oxidizing-biological biological filtering tank |
| CN101041475A (en) * | 2007-03-09 | 2007-09-26 | 华南理工大学 | Fenton and air-float integral water treating method |
Non-Patent Citations (2)
| Title |
|---|
| 刘晓静,文一波.Fenton试剂法深度处理造纸废水的实验研究.中国资源综合利用25 4.2007,25(4),11-13. * |
| 苑宝玲,王洪杰.水处理新技术原理与应用 1.化学工业出版社,环境·能源出版中心,2006,16. * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103818994A (en) * | 2014-02-26 | 2014-05-28 | 郑州大学 | Dosing method for ozone oxidation decolorant used for papermaking pulping waste water |
| CN103818994B (en) * | 2014-02-26 | 2016-02-17 | 郑州大学 | Throwing method joined by a kind of paper-making pulping waste water ozone oxidation discoloring agent |
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