CN101406838A - Method for preparing active carbon supported ferriferous oxide catalyst and wastewater treatment system thereof - Google Patents

Method for preparing active carbon supported ferriferous oxide catalyst and wastewater treatment system thereof Download PDF

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Publication number
CN101406838A
CN101406838A CNA2008101977507A CN200810197750A CN101406838A CN 101406838 A CN101406838 A CN 101406838A CN A2008101977507 A CNA2008101977507 A CN A2008101977507A CN 200810197750 A CN200810197750 A CN 200810197750A CN 101406838 A CN101406838 A CN 101406838A
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active carbon
wastewater treatment
ferriferous oxide
oxide catalyst
carbon supported
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CN101406838B (en
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张晖
高洪
张道斌
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Wuhan University WHU
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Wuhan University WHU
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Abstract

The invention discloses a method for preparing an activated carbon supported iron oxide catalyst, as well as a wastewater treatment system thereof, which relates to a wastewater treatment technique, in particular to a method for treating refractory toxic organic pollutants in wastewater. The activated carbon supported iron oxide catalyst is a catalyst which is low in price and can be reclaimed. The catalyst can be combined with other techniques so as to be applied to wastewater treatment under mild conditions, wherein the catalyst is combined with ozone so as to form a catalytic ozonation technique and is combined with hydrogen peroxide so as to form a heterogeneous phase Fenton technique; the heterogeneous phase Fenton technique is combined with ultrasound so as to form an ultrasonic synergistic heterogeneous phase Fenton technique; the techniques have good effect of removing refractory wastewater; and a solid phase catalyst is easy to separate, can not introduce new impurities, and allow effluent to be easy to reach the standard. The method has the advantages of simple technological process, low cost and good prospects in actual application.

Description

The preparation method of active carbon supported ferriferous oxide catalyst and wastewater treatment system thereof
Technical field
The present invention relates to a kind of wastewater processing technology, relate in particular to a kind of preparation method and wastewater treatment system thereof of active carbon supported ferriferous oxide catalyst, specifically, relate to a kind of catalyst of handling the difficult degradation toxic organic pollutant in the waste water.
Background technology
Toxic organic pollutant in the waste water is owing to the stability of its chemical constitution, and toxicity is big, the intractability height; It is used the conventional treatment technology,, be difficult to the treatment effect that reaches satisfied, still lack cost-effective practical technique so far as the method for physico-chemical process, chemical method and biochemical process and combination thereof.
The high-level oxidation technology of using heterogeneous catalysis is to utilize the organic pollution materials that generates in the catalytic reaction in the highly active hydroxyl oxidize decomposition water body, impels most of hardly degraded organic substance oxidations or coupling.
The method of using the heterogeneous catalysis dye wastewater treatment using at present mainly contains catalytic wet air oxidation, photocatalytic oxidation etc.Catalytic wet air oxidation is a kind of high-level oxidation technology of handling high concentration hard-degraded organic waste water that eighties of last century grows up the eighties.Catalytic wet air oxidation is because reaction condition comparatively harsh (HTHP), the noble metal of its use since expensive price limit its application; And photocatalytic oxidation has also limited its range of application owing to used semi-conducting material catalyst, the development of the catalytic activity of its visible light and efficiency light reactor to await further to improve.
Summary of the invention:
Purpose of the present invention just is to overcome the shortcoming and defect that prior art exists, and a kind of preparation method and wastewater treatment system thereof of active carbon supported ferriferous oxide catalyst is provided.
This active carbon supported ferriferous oxide catalyst is a kind of cheap, and callable catalyst, this catalyst can combine with other technologies under relatively mild condition and be applied to wastewater treatment, form multiple new wastewater treatment system.
The object of the present invention is achieved like this:
1, the preparation method of active carbon supported ferriferous oxide catalyst
The preparation method of active carbon supported ferriferous oxide catalyst mainly may further comprise the steps:
(following all be weight percentage)
1. after active carbon being flooded 24h with 10% sodium hydroxide solution, filter, deionized water is washed till neutrality;
2. with 1. processed active carbon of step, behind 10% salpeter solution dipping 24h, filter, deionized water is washed till neutrality; Put into baking oven, 90~100 ℃ of oven dry, stand-by;
3. with step 2. processed active carbon add and to contain in the solution of iron ion, at 20~30 ℃, in atmosphere of inert gases, pH is adjusted to 3~7;
4. in the atmosphere that contains 30~80% oxygen concentrations, at 30~50 ℃, stir, heat 3. solution of above-mentioned steps, obtain the ferriferous oxide precipitation;
5. with the 4. ferriferous oxide precipitation of gained of step, at 70~90 ℃, water bath with thermostatic control aging 48 hours down;
6. again in the precipitation of vacuum drying gained below 100 ℃, promptly obtain a kind of active carbon supported ferriferous oxide catalyst.
By the catalyst of this method preparation, ferriferous oxide weight percent content scope is 0.5~5.0%, and active carbon weight percent content scope is 95.0~99.5%.
2, the application of active carbon supported ferriferous oxide catalyst in wastewater treatment
1) heterogeneous Fenton wastewater treatment system
A certain amount of active carbon supported ferriferous oxide catalyst and hydrogen peroxide are added to (hydrogen peroxide can add disposable or continuously) in the waste water simultaneously, implement simultaneously to stir, promptly be built into heterogeneous Fenton wastewater treatment system.
2) the heterogeneous Fenton wastewater treatment system of supersonic synergic
In above-mentioned heterogeneous Fenton wastewater treatment system, increase ultrasonic radiation, promptly be built into the heterogeneous Fenton wastewater treatment system of supersonic synergic.
3) heterogeneous catalysis ozonisation wastewater treatment system
A certain amount of active carbon supported ferriferous oxide catalyst is added in the waste water, behind the feeding ozone gas, promptly is built into heterogeneous catalysis ozonisation wastewater treatment system.
Wherein: Fenton is a name, can be translated into " Fenton ".
The present invention has following advantage and good effect:
1, this active carbon supported ferriferous oxide catalyst can combine with ozone respectively and constitute the catalytic ozonation technology, combine the heterogeneous Fenton technology of formation with hydrogen peroxide, the latter constitutes the heterogeneous Fenton technology of supersonic synergic with combination of ultrasound again, these technology have good effect of removing to used water difficult to degradate, and solid-phase catalyst is easy to separate, can not introduce new impurity, water outlet is up to standard easily;
2, technological process is simple, and expense is low, has the prospect of good practice.
The specific embodiment
Application in wastewater treatment describes in detail to this catalyst below in conjunction with embodiment:
1, embodiment one heterogeneous Fenton wastewater treatment system
In the present embodiment, choosing basic-dyeable fibre crystal violet is the target persistent organic pollutants, the simulation organic wastewater with difficult degradation thereby.The content of crystal violet is 200mg/L.Catalyst (the ferriferous oxide weight percent content is 3%) and the hydrogen peroxide of 2.5g/L are added in the waste water, after handling 50 minutes under the room temperature, can reach 56.4% percent of decolourization.
1) operating condition:
Dyes concentration: 200mg/L; Catalyst amounts: 2.5g/L;
Hydrogen peroxide dosage: 0.18mmol/L; PH=3; Room temperature.
2) two, experimental result:
Time (minute) 0 5 10 20 30 50
Percent of decolourization (%) 0 21.7 30.2 45.2 54.2 56.4
2, the heterogeneous Fenton wastewater treatment system of embodiment two supersonic synergics
In the present embodiment, choosing basic-dyeable fibre crystal violet is the target persistent organic pollutants, the simulation organic wastewater with difficult degradation thereby, and the content of crystal violet is 200mg/L.Catalyst (the ferriferous oxide weight percent content is 3%) and the hydrogen peroxide of 2.5g/L are added in the waste water, after handling 50 minutes under the room temperature, can reach 87.8% percent of decolourization.Comparative example one knows that the percent of decolourization of heterogeneous Fenton system only is 56.4% under the similarity condition, and separately the percent of decolourization of ultrasonic radiation is almost 0, shows that ultrasonic and heterogeneous Fenton technology combines and has cooperative effect.Detail operations condition and result are as follows:
1) operating condition
Dyes concentration: 200mg/L; Catalyst amounts: 2.5g/L;
Hydrogen peroxide dosage: 0.18mmol/L; PH=3; Ultrasonic power density 201W/L; Room temperature.
2) experimental result
Time (minute) 0 5 10 20 30 50
Percent of decolourization (%) 0 34.4 53.4 67.5 79.1 87.8
3, embodiment three heterogeneous catalysis ozonisation wastewater treatment systems
In the present embodiment, choose basic-dyeable fibre crystal violet and be target persistent organic pollutants simulation organic wastewater with difficult degradation thereby, the content of crystal violet is 400mg/L.The catalyst (the ferriferous oxide weight percent content is 3%) of 2.5g/L is added in the waste water, feed ozone, handle and to reach 96.8% percent of decolourization after 30 minutes, and the independent ozone under the similarity condition (not adding catalyst) processing percent of decolourization only is 84.1%, shows the decolorizing effect that can significantly strengthen ozone that adds of this catalyst.Detail operations condition and result are as follows:
1) operating condition
Dyes concentration: 400mg/L; Gas flow: 300mL/min;
Ozone concentration: 14.8mg/L; PH=7; Room temperature.
2) experimental result:
Time (minute) 0 5 10 15 20 25 30
The percent of decolourization (%) of independent ozonisation 0 44.9 65.8 75.6 81.5 83.82 84.2
The percent of decolourization of heterogeneous catalysis ozonisation (%) 0 58.1 84.7 93.1 95.7 96.4 96.8

Claims (4)

1, a kind of preparation method of active carbon supported ferriferous oxide catalyst is characterized in that mainly may further comprise the steps:
1. after active carbon being flooded 24h with 10% sodium hydroxide solution, filter, deionized water is washed till neutrality;
2. with 1. processed active carbon of step, behind 10% salpeter solution dipping 24h, filter, deionized water is washed till neutrality; Put into baking oven, 90~100 ℃ of oven dry, stand-by;
3. with step 2. processed active carbon add and to contain in the solution of iron ion, at 20~30 ℃, in atmosphere of inert gases, pH is adjusted to 3~7;
4. in the atmosphere that contains 30~80% oxygen concentrations, at 30~50 ℃, stir, heat 3. solution of above-mentioned steps, obtain the ferriferous oxide precipitation;
5. with the 4. ferriferous oxide precipitation of gained of step, at 70~90 ℃, water bath with thermostatic control aging 48 hours down;
6. again in the precipitation of vacuum drying gained below 100 ℃, promptly obtain a kind of active carbon supported ferriferous oxide catalyst;
Above-mentioned percentage all is weight percentage.
2, the application of a kind of active carbon supported ferriferous oxide catalyst in wastewater treatment is characterized in that:
A certain amount of active carbon supported ferriferous oxide catalyst and hydrogen peroxide are added in the waste water simultaneously, implement simultaneously to stir, promptly be built into heterogeneous Fenton wastewater treatment system;
Fenton is a name, can be translated into " Fenton ".
3, the application of a kind of active carbon supported ferriferous oxide catalyst in wastewater treatment is characterized in that:
In heterogeneous Fenton wastewater treatment system, increase ultrasonic radiation, promptly be built into the heterogeneous Fenton wastewater treatment system of supersonic synergic.
4, the application of a kind of active carbon supported ferriferous oxide catalyst in wastewater treatment is characterized in that:
A certain amount of active carbon supported ferriferous oxide catalyst is added in the waste water, behind the feeding ozone gas, promptly is built into heterogeneous catalysis ozonisation wastewater treatment system.
CN2008101977507A 2008-11-20 2008-11-20 Method for preparing active carbon supported ferriferous oxide catalyst and wastewater treatment system thereof Expired - Fee Related CN101406838B (en)

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CN102059132A (en) * 2010-12-02 2011-05-18 华东理工大学 Load type solid catalyst for heterogeneous phase Fenton system and application thereof in water treatment
CN102218321A (en) * 2011-05-06 2011-10-19 重庆理工大学 Method for preparing heterogeneous phase Fenton catalyst used for methyl orange wastewater treatment
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CN102765799A (en) * 2012-07-10 2012-11-07 广州市环境保护工程设计院有限公司 Method of chain scission for high concentration persistent organic pollutants in wastewater
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CN105330088A (en) * 2014-08-06 2016-02-17 中国石油化工股份有限公司 Ethylene spent lye treatment method
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CN106622239A (en) * 2016-12-13 2017-05-10 中国科学院青岛生物能源与过程研究所 Lignin-based heterogeneous fenton catalyst and preparation method thereof
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