CN101659484B - Catalytic oxidation method capable of recycling waste residues - Google Patents

Catalytic oxidation method capable of recycling waste residues Download PDF

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Publication number
CN101659484B
CN101659484B CN2008101194460A CN200810119446A CN101659484B CN 101659484 B CN101659484 B CN 101659484B CN 2008101194460 A CN2008101194460 A CN 2008101194460A CN 200810119446 A CN200810119446 A CN 200810119446A CN 101659484 B CN101659484 B CN 101659484B
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waste water
value
oxidation
catalytic oxidation
waste
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CN101659484A (en
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高峰
马欣
桑军强
李本高
张莉
张利强
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The invention discloses a catalytic oxidation method capable of recycling waste residues, which comprises (1) delivering wastewater to be treated into an oxidation reactor, adding an acid to adjust the pH value of the wastewater and adding an oxidizer and ferrous iron ions (Fe<2+>) serving as a catalyst to perform catalytic oxidation reaction; (2) adding an alkali into the wastewater obtained after the completion of the reaction to adjust the pH value of the wastewater, and delivering the wastewater to a settling basin for flocculating setting; (3) after the completion of the settling, discharging supernatant, delivering the settled waste residues into a reduction reactor, adding an acid into the waste residues to adjust the pH value of the waste residues, dissolving the waste residues to form solution containing ferric ion (Fe<3+>), and adding a reducer to reduce the Fe<3+> into Fe<2+> at the same time; and (4) circulating the reduced solution containing the Fe<2+> to an oxidation reactor to use the solution as a catalyst to perform the catalytic oxidation reaction. Compared with the conventional catalytic oxidation, the method reduces the discharge of waste iron residues, reduces the waste iron residue treatment cost, protects environment, reduces the usage amount of the catalyst in a catalytic oxidation process and saves resources.

Description

A kind of catalysed oxidation processes of waste residue recycle
Technical field
The present invention relates to a kind of treatment by catalytic oxidation that is used for sewage disposal, the method for the waste residue cycling and reutilization that produces in especially a kind of waste water treating process by catalytic oxidation.
Background technology
For a long time, low B/C is a difficult point in the water technology than the processing of organic waste water always in the environment, also is the important difficult problem of puzzlement countries in the world environment circle.Such waste water since B/C than low, biodegradability is poor, be difficult to directly adopt biochemical method to handle, substantially there is not effect by the processing of ordinary methods such as common filtration and flocculation, and charcoal absorption even depth treatment technology cost is too high, membrane separation technique is because also there is certain difficulty in practical problemss such as investment costliness and film pollution on using.
Be that the high-level oxidation technology of representative is handled low B/C and obtained significant progress than the research of organic waste water in recent years with the catalyzed oxidation.Because it is simple to operate that the catalyzed oxidation technology has, react characteristics such as quick, thereby obtained extensive studies.But in actual applications, catalyzed oxidation adopts Fe 2+Ion is made catalyzer, Fe in the reaction process 2+Ion is oxidized to Fe 3+Generated ferric hydroxide precipitate after the generation, because catalytic oxidation treatment waste water is especially handled in the high-concentration hardly-degradable waste water process Fe 2+The ion large usage quantity, thereby the ironic hydroxide waste residue that produces is more, and these waste residues are difficult to handle, this just makes the industrialized application of catalyzed oxidation be subjected to bigger restriction, thereby be necessary that the employing method reduces the waste residue amount that produces in the waste water treating process by catalytic oxidation, makes the catalyzed oxidation technology be more widely used industrial.
At present, document both domestic and external mainly concentrates on the improvement raising of catalysis technique of catalyzed oxidation technology and catalyzed oxidation and other treatment technology couplings and handles the waste water aspect for the report that reduces treatment by catalytic oxidation, for example:
A.CN1724420A proposes the method for a kind of chemical oxidation-BAF associating water treatment, and the COD that this method adopts Fenton reagent-biological aerated filter process to handle chemical plant secondary biochemical treatment wastewater effluent can reduce to 30mg/L.
B.CN16366893A proposes a kind of using up and helps Fenton's reaction, flocculation and microbiological deterioration coupling to handle the method for waste water, and its COD clearance can reach 98.9%.
C.CN1235668C has proposed the catalytic oxidation method of Scale inhibitors in a kind of reverse osmosis concentrated liquid, adopt this method can destroy the Scale inhibitors of reverse osmosis concentrated liquid, by coagulation the scaling salt class in the solution is separated out again, thereby concentrated solution can be utilized again as water inlet.
Summary of the invention
The present invention proposes a kind of method by catalytic oxidation treatment waste water, this method can make the waste residue cyclically utilizing of generation, thereby reduces the waste residue amount that produces in the catalytic oxidation process, and the catalyzed oxidation technology is used more widely industrial obtaining.
Method provided by the invention comprises:
(1) pending waste water enters in the oxidation reactor, adds acid for adjusting pH value, adds oxygenant and catalyzer ferrous ion [Fe 2+] carry out catalytic oxidation;
(2) waste water after reaction finishes adds alkali and regulates the pH value, enters and carries out flocculating settling in the settling bowl;
(3) sedimentation finishes, and directly discharges after supernatant liquor is discharged or is for further processing; The all or part of waste residue that settles down enters in the reduction reactor, adds acid for adjusting pH value in reduction reactor, and waste residue is dissolved as ferric ion [Fe 3+] solution, add reductive agent simultaneously and make Fe 3+Be reduced to Fe 2+
(4) Fe after will reducing 2+Solution circulated is carried out catalytic oxidation as catalyzer to oxidation reactor.
Said oxygenant can be a kind of in hydrogen peroxide, clorox, potassium hypochlorite, the ozone, preferred hydrogen peroxide.
Said catalyzer is a ferrous ion, can come from ferrous sulfate, iron protochloride, the Iron nitrate one or more, and preferably sulfuric acid is ferrous.
Said reductive agent can be a kind of in iron filings, sodium bisulfite, S-WAT, the V-Brite B.
The acid that the present invention adds can be a kind of in sulfuric acid, hydrochloric acid, the nitric acid, preferably sulfuric acid.
The alkali that adds among the present invention can be a kind of in sodium hydroxide, potassium hydroxide, sodium bicarbonate, the yellow soda ash, preferred sodium hydroxide.
In oxidation reactor, the pH value of regulating waste water is 1-6, preferred 2-5.The ratio of the organic mass concentration in oxygenant and the waste water is 5:1-1:100, preferred 2:1-1:20.Oxygenant and Fe 2+Mol ratio be 10:1-1:3, preferred 5:1-1:2.Residence time 30-120 minute.
In the settling bowl, the pH value of regulating waste water is 5-9, preferred 6-8.The residence time is 0.5-5 hour.
In reduction reactor, the pH value of regulating waste water is 0-4, preferred 0.5-2.Reductive agent and Fe 3+Mol ratio 1:10-2:1, preferred 1:1, the residence time in the reduction pond is 10-120 minutes.
Compare with the conventional catalyst oxidation style, the present invention has following advantage: 1, reduced the quantity discharged of scrap iron slag, reduced the cost of handling the scrap iron slag, protected environment simultaneously.2, reduce the usage quantity of catalyzer in the catalytic oxidation process, saved resource.
Description of drawings
Fig. 1 is a detailed process of the present invention.Pending waste water enters in the oxidation reactor, adds the pH value that waste water is regulated in acid, adds oxygenant and Fe simultaneously 2+Carry out catalytic oxidation.Enter after the waste water adding alkali adjusting pH value after reaction finishes and carry out flocculating settling in the settling bowl.After sedimentation finishes, directly discharge after supernatant liquor is discharged or be for further processing; And all or part of waste residue that settles down enters in the reduction reactor, adds acid for adjusting pH value in reduction reactor waste residue is dissolved as Fe 3+Solution adds reductive agent simultaneously and makes Fe 3+Be reduced to Fe 2+, with the Fe after the reduction 2+The solution reuse is carried out catalytic oxidation as catalyzer to oxidation reactor.
Embodiment
The present invention is further detailed explanation below in conjunction with embodiment, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1
Handle not standard discharge waste water of certain refinery, adopt H 2O 2Be oxygenant, Fe 2SO 4Be catalyzer, iron filings are reductive agent, and used soda acid is dense H 2SO 4And NaOH.Operational condition is defined as: H 2O 2The COD mass concentration ratio 1:3 of/waste water, H 2O 2With Fe 2+Molar concentration rate is 1:2, reductive agent and Fe 3+Mol ratio be 1:1; Oxidizing reaction pond pH is 3, and reduction reaction pond pH is 1, and settling bowl pH is 6.5, and 30 minutes oxidizing reaction pond residence time, the settling bowl residence time is 1 hour, and the reduction pond residence time is 20 minutes; Reductive agent and Fe 3+Molar concentration rate is 1:1.The data that adopt treatment by catalytic oxidation of the present invention and conventional catalyst oxidation treatment method to handle waste water relatively see Table 1.The result of table 1 shows employing method processing of the present invention waste water, and waste residue and catalyzer usage quantity obviously reduce.
Table 1 is handled not standard discharge waste water of refinery
Treatment process Waste sludge discharge amount (kg/t waste water) Catalyst amounts (kg/t waste water)
The conventional catalyst oxidation style 18 0.8
Embodiment 1 10 0.4
(waste residue weight is by 98% water content meter)
Embodiment 2
Handle certain chemical fibre factory's waste water, adopt H 2O 2Be oxygenant, Fe 2SO 4Be catalyzer, sodium bisulfite is a reductive agent, and used soda acid is dense H 2SO 4And NaOH.Operational condition is defined as: H 2O 2The COD mass concentration ratio 1:10 of/waste water, H 2O 2With Fe 2+Molar concentration rate is 1:1, reductive agent and Fe 3+Mol ratio be 1:1; Oxidizing reaction pond pH is 5, and settling bowl pH is 6.5, and reduction reaction pond pH is 1.5; 30 minutes oxidizing reaction pond residence time, the settling bowl residence time is 1 hour, and the reduction pond residence time is 30 minutes.The data that adopt treatment by catalytic oxidation of the present invention and conventional catalyst oxidation treatment method to handle waste water relatively see Table 2.The result of table 2 shows employing method processing of the present invention waste water, and waste residue and catalyzer usage quantity significantly reduce.
Table 2 is handled chemical fibre factory's waste water
Treatment process Waste sludge discharge amount (kg/t waste water) Catalyst amounts (kg/t waste water)
The conventional catalyst method for oxidation 50 2.5
Embodiment 2 10 0.5
(waste residue weight is by 98% water content meter)
Embodiment 3
Handle certain pharmaceutical factory's waste water, the employing clorox is an oxygenant, Fe 2SO 4Be catalyzer, sodium hyposulfate is a reductive agent, and used soda acid is dense H 2SO 4And NaOH.Operational condition is defined as: H 2O 2The COD mass concentration ratio 1:5 of/waste water, oxygenant and Fe 2+Molar concentration rate is 1:3; Oxidizing reaction pond pH is 3, and settling bowl pH is 6.5, and reduction reaction pond pH is 1.2; 30 minutes oxidizing reaction pond residence time, the settling bowl residence time is 1 hour, and the reduction pond residence time is 30 minutes.The data that adopt treatment by catalytic oxidation of the present invention and conventional catalyst oxidation treatment method to handle waste water relatively see Table 2.The result of table 3 shows employing method processing of the present invention waste water, and waste residue and catalyzer usage quantity significantly reduce.
Two kinds of treatment by catalytic oxidation processing plants of table 3 reverse osmosis concentrated water
Treatment process Waste sludge discharge amount (kg/t waste water) Catalyst amounts (kg/t waste water)
The conventional catalyst method for oxidation 30 2
Embodiment 3 6 0.3
(waste residue weight is by 98% water content meter)

Claims (6)

1. the catalysed oxidation processes of a waste residue recycle comprises:
(1) pending waste water enters in the oxidation reactor, adds acid for adjusting pH value, adds oxygenant and catalyzer ferrous ion and carries out catalytic oxidation;
(2) waste water after reaction finishes adds alkali and regulates the pH value, enters and carries out flocculating settling in the settling bowl;
(3) sedimentation finishes, and supernatant liquor is discharged, and the waste residue that settles down enters in the reduction reactor, adds acid for adjusting pH value, and waste residue is dissolved as ferric ion [Fe 3+] solution, add reductive agent simultaneously and make Fe 3+Be reduced to Fe 2+, said reductive agent is a kind of in iron filings, sodium bisulfite, S-WAT, the V-Brite B, in the reduction reactor, the pH value of regulating waste water is 0-4, reductive agent and Fe 3+Mol ratio 1: 10-2: 1;
(4) Fe after will reducing 2+Solution circulated is carried out catalytic oxidation as catalyzer to oxidation reactor.
2. in accordance with the method for claim 1, it is characterized in that said oxygenant is a kind of in hydrogen peroxide, clorox, potassium hypochlorite and the ozone.
3. in accordance with the method for claim 1, it is characterized in that in oxidation reactor, the pH value of regulating waste water is 1-6.
4. in accordance with the method for claim 1, it is characterized in that the ratio of the organic mass concentration in oxygenant and the waste water is 5: 1-1: 100.
5. in accordance with the method for claim 1, it is characterized in that the mol ratio of oxygenant and Fe2+ is 10: 1-1: 3.
6. in accordance with the method for claim 1, it is characterized in that in the settling bowl, the pH value of regulating waste water is 5-9.
CN2008101194460A 2008-08-29 2008-08-29 Catalytic oxidation method capable of recycling waste residues Active CN101659484B (en)

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CN102275955B (en) * 2011-05-17 2013-04-24 湖南丽臣实业股份有限公司 Method for preparing mirabilite by using sulfonated end gas absorption solution, and apparatus thereof
CN102794098A (en) * 2012-09-12 2012-11-28 河南绿典环保节能科技有限公司 Flue gas wet-type oxidation denitration and resource utilization method
CN103496819A (en) * 2013-09-18 2014-01-08 苏州市阳澄湖现代农业产业园特种水产养殖有限公司 Method for sterilization treatment on aquaculture wastewater
CN103936135B (en) * 2014-05-07 2015-10-28 东华大学 A kind of method of marmatite catalysis hydrogen peroxide oxidation process trade effluent
CN105858978A (en) * 2016-06-17 2016-08-17 东莞道汇环保科技有限公司 Method for treating wastewater with Fenton reagent and wastewater treatment system
CN107311291A (en) * 2017-03-16 2017-11-03 安徽同新源科技有限公司 The method of sulfite oxidation degraded organic pollutants is combined using heterogeneous iron-based material under aeration condition
CN107082482A (en) * 2017-04-18 2017-08-22 东南大学 A kind of synergy of Fenton systems and discharge-reducing method
JP2019171367A (en) * 2018-03-26 2019-10-10 三菱ケミカルアクア・ソリューションズ株式会社 Method for treating waste liquid containing acidic aggregate and water treatment apparatus
CN109467215A (en) * 2018-11-28 2019-03-15 南京环保产业创新中心有限公司 Integrate the iron full price state application integration wastewater treatment method of catalysis, oxidation, reduction and coagulation
CN109694160A (en) * 2019-01-11 2019-04-30 浙江奇彩环境科技股份有限公司 A kind of minimizing technology of waste water foul odour

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