CN102225802A - Method for inhibiting generation of dinitrobenzene compounds during processing aromatic hydrocarbon nitrified wastewater by using zero-valent irons - Google Patents
Method for inhibiting generation of dinitrobenzene compounds during processing aromatic hydrocarbon nitrified wastewater by using zero-valent irons Download PDFInfo
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- CN102225802A CN102225802A CN 201110090536 CN201110090536A CN102225802A CN 102225802 A CN102225802 A CN 102225802A CN 201110090536 CN201110090536 CN 201110090536 CN 201110090536 A CN201110090536 A CN 201110090536A CN 102225802 A CN102225802 A CN 102225802A
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Abstract
The invention discloses a method for inhibiting generation of dinitrobenzene compounds during processing aromatic hydrocarbon nitrified wastewater by using zero-valent irons. According to the present invention, a method for oxidation treatment of the aromatic hydrocarbon nitrified wastewater is improved. The method provided by the present invention comprises the following steps: (1) a pretreatment reduction reaction for the zero-valent irons, wherein the nitrified wastewater is introduced in a zero-valent iron reactor, and is subjected to a reduction reaction with the zero-valent irons in the reactor; (2) a oxidizing reaction, wherein the reduced waste water is introduced in a oxidation tank, followed by adding a oxidizing agent and carrying out a oxidizing reaction. The method is applicable for processing the nitrified wastewater in the industry of weaving, printing and dyeing, explosives, tanning and the like. According to the present invention, investment cost and operation cost can be reduced, toxicity of the oxidized discharge water is reduced, and biodegradability of the oxidized discharge water is improved.
Description
Technical field
The present invention relates to a kind of method of wastewater from chemical industry oxide treatment, more particularly, it relates to a kind of employing Zero-valent Iron pre-treatment reduction reaction, is used for suppressing the method that aromatic nitration wastewater oxidation treating processes produces the dinitrobenzene compounds.
Background technology
Nitrobenzene compounds is widely used in industries such as weaving, printing and dyeing, explosive and process hides as a class important chemical material, yet can produce a large amount of nitrobenzene wastewaters in its production process.Nitrobenzene has characteristics such as high stability, strong toxicity and potential carinogenicity, and is very big to ecotope and HUMAN HEALTH influence.Have the nitryl group of haling electronics on the nitrobenzene compounds phenyl ring, this makes the phenyl ring stabilizer pole that becomes.In addition, nitrobenzene compounds also has stronger toxic action to microorganism.Traditional chemical oxidation style and biological treatment are difficult to handle effectively this type of highly toxic nitration waste water.Therefore, seek a kind of cost-effective treatment technology and cause domestic and international numerous investigators' concern.
High-level oxidation technology is a kind of important process technology of organic wastewater with difficult degradation thereby, and pollution substance is poisoned in can the oxidative degradation water body multiple difficult degradation, thereby reduces the toxicity of waste water and improve the biodegradability of waste water.Common high-level oxidation technology comprises Fenton oxidation style, class Fenton facture, photochemistry and photocatalytic oxidation, electrochemical process, ozone oxidation method and ultrasonic oxidation method etc.Advanced oxidation processes has confirmed it is a kind of the effective of nitration waste water and essential treatment technology handled.Advantages such as wherein traditional Fenton oxidation style is compared with other advanced oxidation processes, and, reaction simple to operate because of it is quick gain great popularity.
Engineering practice and achievement in research show that aromatic nitration waste water significantly produces the bigger dinitrobenzene by product of murder by poisoning in oxidation processes regular meeting.The researchist has done it and has furtherd investigate (2008 the 72nd phase 952-958 pages or leaves and 2010 the 80th phase 340-345 pages or leaves of being published in international well-known periodical " Chemosphere "), when find adopting oxidation technology treatment of Nitrobenzene class waste water such as Fenton, class Fenton and light Fenton even can form productive rate up to 6% dinitrobenzene compounds.Result of study points out that also the toxicity of dinitrobenzene is 30 times (being published in 2007 the 68th phase 695-702 pages or leaves of international well-known periodical " Chemosphere ") of former nitrobenzene class pollutant approximately.Poison bigger and the secondary pollutant of difficult degradation more exactly because oxide treatment has significantly produced, often effect is undesirable to make conventional oxidation technical finesse nitration waste water, wastewater biodegradability improves limited after the oxide treatment, microorganism is still had stronger toxic action, serious harm and increased the weight of the burden of follow-up biochemical system.
How to reduce in the oxide treatment and to poison dinitrobenzene compound output and become an important topic.Engineering technical personnel have carried out correlative study, show that high dosage oxygenant (as hydrogen peroxide) or the lasting strong irradiation of ultraviolet help to reduce the output of dinitrobenzene compounds, this may be because the enhanced oxidation capacity can further be degraded due to the dinitrobenzene compounds.Although above-mentioned reinforcement oxide treatment technology has good treatment effect, investment and running cost have but been increased greatly, as problems such as the consumed cost of higher oxygenant, higher ultraviolet equipment cost and high power consumption running costs, these reasons limit its small-scale engineering that only is fit to nitration waste water and handle just.Therefore, the dinitrobenzene compounds produces in the nitration waste water oxide treatment to suppress to develop a kind of cost-effective method, and is significant to the widespread use that promotes oxidation technology.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of Zero-valent Iron to suppress the method that the dinitrobenzene compounds produces in the aromatic nitration wastewater treatment, improved the method that the aromatic nitration wastewater oxidation is handled, can reduce investment and running cost by present method, reduce the toxicity of oxidation water outlet, and improve the biodegradability of oxidation water outlet.
The present invention is achieved by following technical proposals.
Zero-valent Iron suppresses the method that the dinitrobenzene compounds produces in the aromatic nitration wastewater treatment, comprises the following steps:
(1) Zero-valent Iron pre-treatment reduction reaction: nitration waste water is fed zero-valent iron reactor, with the Zero-valent Iron generation reduction reaction in the reactor;
(2) oxidizing reaction: the waste water after reduction, enter oxidation trough, add oxygenant, carry out oxidizing reaction and handle.
In the described Zero-valent Iron pre-treatment reduction reaction, adjust water inlet acidity, Zero-valent Iron consumption and hydraulic detention time, make that nitrobenzene reduction turnover ratio is greater than 40% in the waste water, residue nitrobenzene concentration is less than 80mg/L in the waste water.After the described Zero-valent Iron pre-treatment reduction reaction, add ferrously, adjusting dissolved iron concentration and nitrobenzene concentration ratio is more than 2.0.Described zero-valent iron reactor adopts stirring-type, fluidized-bed or fixed bed operation scheme.When adopting the reactor of stirring-type and fluidized-bed,, utilize the conservation of electrons principle to calculate the equivalent dosage of Zero-valent Iron according to needs reductive nitrobenzene content in the waste water.When adopting the fixed bed zero-valent iron reactor,, utilize the reaction kinetics principle to calculate required hydraulic detention time according to needs reductive nitrobenzene content in the waste water.
The invention has the beneficial effects as follows:
(1) compare with traditional Fenton oxidation, during aromatic nitration wastewater oxidation of the present invention was handled, dinitrobenzene compounds generation reduced, and had significantly reduced the toxicity of oxidation water outlet.
(2) compare with traditional Fenton oxidation, after aromatic nitration wastewater oxidation of the present invention is handled, but oxidation water outlet qualified discharge behind simple biochemistry, the biodegradability of oxidation water outlet significantly improves.
(3) investment and running cost are low.The running cost that the existing high dosage oxygenant of aromatic nitration wastewater oxidation technology based on the Zero-valent Iron pretreatment process of the present invention is strengthened oxidation technology reduces by 50%～60%, the cost of strengthening the oxidation technology processing than ultraviolet descends about 70%, compare Zero-valent Iron and reduce preconditioning technique fully and reduced the expense of iron loss consumption and sludge disposal, this method can make processing cost descend about 45%.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1
The oil of mirbane factory effluent (COD 2000 mg/L～3000mg/L, nitrobenzene concentration 100mg/L, pH=2.1).Selecting nitrobenzene reduction turnover ratio is 40% o'clock, and residue nitrobenzene concentration is 60mg/L in the processed waste water, satisfy nitrobenzene reduzate production rate simultaneously and be not less than 40%, and reduction back residue nitrobenzene concentration is not higher than 80mg/L.According to required reductive nitrobenzene amount, utilize the conservation of electrons principle to calculate the Zero-valent Iron consumption, enter 0.1%(w/w is housed) carry out mechanical stirring in the stirring reactor of Zero-valent Iron, hydraulic detention time is 1h.The dissolved iron concentration that the reaction back produces is 140mg/L, and this moment, dissolved iron concentration was 2.3 with the nitro phenenyl concentration ratio, need not to add ferrous.After waste water after the pre-treatment is adjusted to pH and is 3, enter oxidation trough, abundant reaction 2h in the system that adds 0.5% (w/w) hydrogen peroxide solution.Compare with no pre-treatment control group, the output of dinitrobenzene compounds is reduced to 0.5mg/L from 6mg/L, waste water BOD in the pretreated oxidation water outlet of regulation and control reduction Zero-valent Iron
5/ COD is increased to 0.41, waste water photogenic bacterium EC from 0.23
50Also be increased to 84% from 43%.
From the economy angle analysis, for reaching the same treatment effect, the intensifying technology running cost of high dosage oxygenant is 3～4 times of this method.Ultraviolet intensifying technology cost (comprise investment and working cost) even up to more than 4 times of this method.The preconditioning technique total cost (comprising iron loss cost and sludge disposal cost) of reducing fully also is 2～3 times of its cost.
Embodiment 2
The nitrotoluene factory effluent (COD～7000mg/L, nitrobenzene concentration 300mg/L, pH=4.0).Selecting nitrobenzene reduction turnover ratio is 73.4% o'clock, and residue nitrobenzene concentration is 80mg/L in the processed waste water, satisfy nitrobenzene reduzate production rate simultaneously and be not less than 40%, and reduction back residue nitrobenzene concentration is not higher than 80mg/L.According to required reductive nitrobenzene amount, utilize the reaction kinetics principle to calculate hydraulic detention time, enter the Solid Bed of loading the plane iron flower, the control hydraulic detention time is 0.5h.The dissolved iron concentration that reaction produces is 86mg/L, and need add the ferrous solution concentration of iron that makes in the waste water is 147mg/L, and this moment, dissolved iron concentration and nitrobenzene concentration ratio were 2.0.Oxidation step is with embodiment 1.Compare with no pre-treatment control group, the output of dinitrobenzene compounds is reduced to from 12mg/L and is lower than 0.9mg/L, waste water BOD in the pretreated oxidation water outlet of regulation and control reduction Zero-valent Iron
5/ COD is increased to 0.38, waste water photogenic bacterium EC from 0.16
50Also be increased to 81% from 37%.
From the economy angle analysis, for reaching the same treatment effect, the intensifying technology running cost of high dosage oxygenant is about 3 times of this method.Ultraviolet intensifying technology cost (comprise investment and working cost) even up to 3～4 times of this method.The preconditioning technique total cost (comprising iron loss cost and sludge disposal cost) of reducing fully also is 2 times of its cost approximately.
Embodiment 3
The oil of mirbane factory effluent (COD～4500mg/L, nitrobenzene concentration 150mg/L, pH=3.0).Selecting nitrobenzene reduction turnover ratio is 50% o'clock, and residue nitrobenzene concentration is 75mg/L in the processed waste water, satisfy nitrobenzene reduzate production rate simultaneously and be not less than 40%, and reduction back residue nitrobenzene concentration is not higher than 80mg/L.Enter 0.2%(w/w be housed) fully react in the Zero-valent Iron fluidized-bed reactor, hydraulic detention time is 1h.The dissolved iron concentration that reaction produces is 120mg/L, and adding the ferrous solution concentration of iron that makes is 180mg/L, and this moment, dissolved iron concentration and nitrobenzene concentration ratio were 2.4.Oxidation step is with embodiment 1.Compare with no pre-treatment control group, the output of dinitrobenzene compounds is reduced to from 10mg/L and is lower than 0.6mg/L, waste water BOD in the pretreated oxidation water outlet of regulation and control reduction Zero-valent Iron
5/ COD is increased to 0.45, waste water photogenic bacterium EC from 0.20
50Also be increased to 90% from 40%.
From the economy angle analysis, for reaching the same treatment effect, the intensifying technology running cost of high dosage oxygenant is 2～2.5 times of this method, promptly the invention enables cost to reduce by 50%～60%.Ultraviolet intensifying technology cost (comprise investment and working cost) even up to 3 times of this method promptly the invention enables cost to reduce about 67%.The preconditioning technique total cost (comprising iron loss cost and sludge disposal cost) of reducing fully also is 1.8 times of its cost approximately, promptly the invention enables cost to reduce by 45%.
Claims (6)
1. a Zero-valent Iron suppresses the method that the dinitrobenzene compounds produces in the aromatic nitration wastewater treatment, the steps include:
(1) Zero-valent Iron pre-treatment reduction reaction: nitration waste water is fed zero-valent iron reactor, with the Zero-valent Iron generation reduction reaction in the reactor;
(2) oxidizing reaction: the waste water after reduction, enter oxidation trough, add oxygenant, carry out oxidizing reaction and handle.
2. Zero-valent Iron according to claim 1 suppresses the method that the dinitrobenzene compounds produces in the aromatic nitration wastewater treatment, it is characterized in that, in the described Zero-valent Iron pre-treatment reduction reaction, adjust water inlet acidity, Zero-valent Iron consumption and hydraulic detention time, make in the waste water nitrobenzene reduction turnover ratio greater than 40%, residue nitrobenzene concentration is less than 80mg/L in the waste water.
3. Zero-valent Iron according to claim 2 suppresses the method that the dinitrobenzene compounds produces in the aromatic nitration wastewater treatment, it is characterized in that, after the described Zero-valent Iron pre-treatment reduction reaction, add ferrously, adjusting dissolved iron concentration and nitrobenzene concentration ratio is more than 2.0.
4. Zero-valent Iron according to claim 3 suppresses the method that the dinitrobenzene compounds produces in the aromatic nitration wastewater treatment, it is characterized in that, described zero-valent iron reactor adopts stirring-type, fluidized-bed or fixed bed operation scheme.
5. suppress the method that the dinitrobenzene compounds produces in the aromatic nitration wastewater treatment according to the Zero-valent Iron described in the claim 4, it is characterized in that, when adopting the reactor of stirring-type or fluidized-bed, according to needs reductive nitrobenzene content in the waste water, utilize the conservation of electrons principle to calculate the equivalent dosage of Zero-valent Iron.
6. Zero-valent Iron according to claim 4 suppresses the method that the dinitrobenzene compounds produces in the aromatic nitration wastewater treatment, it is characterized in that, when adopting the fixed bed zero-valent iron reactor, according to needs reductive nitrobenzene content in the waste water, utilize the reaction kinetics principle to calculate required hydraulic detention time.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583690A (en) * | 2012-03-02 | 2012-07-18 | 中国海洋大学 | Method for processing nitrobenzene organic pollutants in wastewater |
| CN104190437A (en) * | 2014-07-29 | 2014-12-10 | 中国万宝工程公司 | Preparation method and application of light metal ceramic catalyst for degrading DBP (double-base propellant) wastewater |
| CN104591426A (en) * | 2014-12-15 | 2015-05-06 | 南京理工大学 | Zero-valent iron reduction-Fenton oxidation integrated reaction device and method for treating nitroaromatic compound wastewater by using zero-valent iron reduction-Fenton oxidation integrated reaction device |
| CN104944637A (en) * | 2015-06-09 | 2015-09-30 | 复旦大学 | Method for treating nitrobenzene waste liquid through iron scrap reduction by Fenton method |
| CN109455796A (en) * | 2018-12-29 | 2019-03-12 | 青岛科技大学 | A kind of technique for treating industrial wastewater of zeroth order internal electrolysis of iron coupling internal circulating fluidized bed Fenton |
| CN114163036A (en) * | 2021-12-10 | 2022-03-11 | 南京环保产业创新中心有限公司 | Method for treating semi-coke wastewater by pre-oxidation oil removal dephenolization-electro-Fenton technology |
Citations (1)
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|---|---|---|---|---|
| CN101531430A (en) * | 2009-04-22 | 2009-09-16 | 南京大学 | Method for releasing biological toxicity of mixed acid nitrified wastewater |
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2011
- 2011-04-12 CN CN 201110090536 patent/CN102225802A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531430A (en) * | 2009-04-22 | 2009-09-16 | 南京大学 | Method for releasing biological toxicity of mixed acid nitrified wastewater |
Non-Patent Citations (1)
| Title |
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| 《持久性有机污染物论坛2010暨第五届持久性有机污染物全国学术研讨会论文集》 20101231 姜笔存等 全混式零价铁与芬顿组合工艺处理硝化废水研究 第155-156页 1-6 , * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583690A (en) * | 2012-03-02 | 2012-07-18 | 中国海洋大学 | Method for processing nitrobenzene organic pollutants in wastewater |
| CN104190437A (en) * | 2014-07-29 | 2014-12-10 | 中国万宝工程公司 | Preparation method and application of light metal ceramic catalyst for degrading DBP (double-base propellant) wastewater |
| CN104190437B (en) * | 2014-07-29 | 2016-03-30 | 中国万宝工程公司 | A kind of preparation method of light-weight metal ceramic catalyst of DBP waste water of degrading and application |
| CN104591426A (en) * | 2014-12-15 | 2015-05-06 | 南京理工大学 | Zero-valent iron reduction-Fenton oxidation integrated reaction device and method for treating nitroaromatic compound wastewater by using zero-valent iron reduction-Fenton oxidation integrated reaction device |
| CN104944637A (en) * | 2015-06-09 | 2015-09-30 | 复旦大学 | Method for treating nitrobenzene waste liquid through iron scrap reduction by Fenton method |
| CN109455796A (en) * | 2018-12-29 | 2019-03-12 | 青岛科技大学 | A kind of technique for treating industrial wastewater of zeroth order internal electrolysis of iron coupling internal circulating fluidized bed Fenton |
| CN109455796B (en) * | 2018-12-29 | 2021-12-14 | 青岛科技大学 | Industrial wastewater treatment process of zero-valent iron internal electrolysis coupling internal circulating fluidized bed Fenton |
| CN114163036A (en) * | 2021-12-10 | 2022-03-11 | 南京环保产业创新中心有限公司 | Method for treating semi-coke wastewater by pre-oxidation oil removal dephenolization-electro-Fenton technology |
| CN114163036B (en) * | 2021-12-10 | 2023-12-05 | 南京环保产业创新中心有限公司 | Method for treating semi-coke wastewater by preoxidation degreasing and dephenolization-electro-Fenton technology |
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Application publication date: 20111026 |