CN103991943A - Method for inhibiting generation of bromate through catalytic ozonation - Google Patents
Method for inhibiting generation of bromate through catalytic ozonation Download PDFInfo
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- CN103991943A CN103991943A CN201410210644.3A CN201410210644A CN103991943A CN 103991943 A CN103991943 A CN 103991943A CN 201410210644 A CN201410210644 A CN 201410210644A CN 103991943 A CN103991943 A CN 103991943A
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- bromate
- catalytic ozonation
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- graphene composite
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Abstract
The invention relates to a method for inhibiting generation of bromate through catalytic ozonation, belonging to the technical field of drinking water purification. The method comprises the following steps: forming a catalytic ozonation system from composite graphene active carbon as a catalyst to quickly generate a large quantity of hydroxyl radicals so as to quickly degrade organic matters and inhibit generation of bromate. The method has the characteristics that a novel carbon material, namely composite graphene active carbon can be used for performing the catalytic ozonation, the effect of inhibiting generation of bromate is remarkable, and the effect of removing other organic matters from water is good in comparison with that of independent ozone; the method is simple and convenient to operate, efficient and environment-friendly, and can be used for purifying drinking water.
Description
Technical field
The present invention relates to a kind of catalytic ozonation and suppress the method that bromate generates, belong to drink water purifying technical field.
Background technology
Along with industrial fast development, water environment pollution problem is also on the rise, and meanwhile the safety problem of tap water also becomes the focus that people pay close attention to.Ozone (O
3) as a kind of strong oxidizer, organism and inorganics in energy the efficient oxidation water, be often applied to water purification from the beginning.But in ozone oxidation process, be difficult to thoroughly remove TOC in water and COD even can produce some to the detoxicated product of harm as bromate.Bromate (BrO
3 -) there is carinogenicity and genetoxic, be mainly because brominated water source produces in ozone oxidation process.Environmental Protection Agency, the World Health Organization and international cancer research association all classify bromate may have to the mankind material (Group2B) of potential carcinogenic risk as.In the sterilization rules of Environmental Protection Agency's issue, stipulate that bromate maximum acceptable concentration (MCL) value is 10 μ g/L, long-term goal controlling valu is decided to be to zero simultaneously.In China < < drinking water sanitary standard GB5749-2006 > >, also the content of regulation bromate is no more than 10 μ g/L.
Catalytic ozonation technology is a kind of novel will be difficult to by the ozone method of the oxidation operation of oxidation or degraded separately at normal temperatures and pressures, utilize a large amount of strong oxidizing property free radicals (hydroxyl radical free radical) of fast decoupled ozone generation in reaction process thus come organism in oxygenolysis water to reach purification of water quality, block the approach that bromide anion is bromate by ozone oxidation simultaneously, thereby suppress the generation of bromate.
The research that current use carbon material catalytic ozonation is controlled bromate generation is very few, and the inhibiting rate that the independent catalytic ozonation of gac generates bromate is lower than 40%.Graphene, as new carbon, has many advantages: simple two-dirnentional structure is conducive to experimental analysis; Specific surface area is large, and adsorption site is many, and the Graphene composite activated carbon use rate of recovery and repeat usage is high.Using Graphene modified activated carbon as catalyzer, form catalytic ozonation system with ozone coupling, in the time of degradation of organic substances, suppress the generation of bromate, there is far-reaching Research Significance and application prospect widely.
Summary of the invention
The object of the present invention is to provide a kind of new catalytic ozonation process to suppress the method that bromate generates, solve prior art in the deficiency existing aspect inhibition bromate, can reach the object of purifying drinking water simultaneously.
In catalytic ozonation process provided by the invention, suppress the method that bromate generates, to make catalyzer with new carbon Graphene composite activated carbon, form catalytic ozonation system, rapid, high volume produces hydroxyl radical free radical, in the organic while of fast degradation because making the ozone can be by a large amount of conversions, thereby greatly suppressed Br
-approach through ozone oxidation generates bromate.
The present invention adopts hydrothermal method, take polyvinyl alcohol as tackiness agent, and it is 2%-10% that Graphene accounts for matrix material mass percent, within the scope of 170 ℃-180 ℃, by Graphene and Mixture of Activated Carbon reacting by heating, is prepared into Graphene composite reactive Carbon Materials.
In containing bromide anion and organic mixing solutions, add ozone 1-3mg/L (or 0.05-0.2L/min); Graphene composite activated carbon 50-100mg/L, reacts it, finally, in this catalytic ozonation system, has also effectively suppressed the generation of bromate in degradation of organic substances.
The present invention finds that, when pH is 4-8.8 scope, the inhibition that bromate is generated does not change with pH value in exploring Graphene composite activated carbon catalytic ozonation inhibition bromate process.
In catalytic ozonation process provided by the invention, suppress the method that bromate generates, initiative employing new carbon Graphene composite activated carbon as catalyzer, not only to suppressing the unusual effect that has of bromate, and compare with independent ozone, present method also has better degraded removal effect to other organism in water.This is a kind of easy and simple to handle, and the method that in the catalytic ozonation process of efficient quick, bromate generates, can be widely used in drinking water disinfection.
Accompanying drawing explanation
Fig. 1 is the chart that Graphene composite activated carbon Catalytic Ozonation oxalic acid suppresses bromate simultaneously.
Fig. 2 is the charts of different Graphene composite activated carbon dosages on the impact of bromate inhibition.
Fig. 3 is the chart of catalytic ozonation to bromate inhibition under condition of different pH.
Embodiment
A. prepare Graphene composite reactive Pd/carbon catalyst: adopt hydrothermal method, take polyvinyl alcohol as tackiness agent, take Graphene and gac as raw material, cooperatively interact, wherein the shared mass percent of Graphene is 2%-10%, at 170-180 ℃, by Graphene and Mixture of Activated Carbon reacting by heating, finally make Graphene composite reactive Pd/carbon catalyst;
B. in containing bromide anion and organic mixing solutions, add ozone 1-3mg/L (or 0.05-0.2L/min); Graphene composite reactive Pd/carbon catalyst 50-100mg/L, controls pH value in 4-8.8 scopes, and it is reacted, and finally, in this catalytic ozonation system, has also effectively suppressed the generation of bromate in degradation of organic substances.
relevant every test of the present invention
Test example 1
Utilize the generation of Graphene composite activated carbon catalytic ozonation inhibition bromate with oxalic acid, to be degraded to the organic experiment of example explanation Graphene composite activated carbon Catalytic Ozonation carries out simultaneously according to the following steps: use head space bottle, ozone passes into continuously, flow is 0.05L/min, Graphene modified activated carbon dosage is 100mg/L, bromide anion starting point concentration is 0.5mg/L, oxalic acid starting point concentration is 10mg/L, and regulating pH is 4, and experiment total time is 30min.Experimental result is shown in Fig. 1.
Test example 2
Different Graphene modified activated carbon dosages carry out according to the following steps on the experiment of bromate inhibition impact: adjusting pH is 6.98, Br
-starting point concentration is 0.5mg/L, and ozone concn is 3mg/L, and Graphene composite activated carbon dosage is respectively 0,5,10,25,50,100,200mg/L, and experiment total time is 30min.Experimental result is shown in Fig. 2.
Test example 3
The experiment that under condition of different pH, catalytic ozonation generates control effect to bromate is carried out according to the following steps: regulate pH to be respectively 5.3,6.98,8.8, Br
-starting point concentration is 0.5mg/L, and ozone concn is 3mg/L, and Graphene composite activated carbon dosage is 50mg/L, and experiment total time is 30min.Experimental result is shown in Fig. 3.
each tests the interpretation of result of gained accompanying drawing
1, accompanying drawing 1 interpretation of result
In accompanying drawing 1, catalytic ozonation system G/GAC+O
3the effect of (Graphene composite activated carbon and ozone mixed system) degraded oxalic acid is best, O
3(ozone) group is taken second place, and G/GAC (Graphene composite activated carbon) group is the poorest, in degradation of organic substances, and contrast ozone group, catalytic ozonation group bromate growing amount obviously reduces.More than illustrate that take the catalytic ozonation system that G/GAC (Graphene composite activated carbon) is that catalyzer forms can effectively suppress the generation of bromate in degradation of organic substances.
2, accompanying drawing 2 interpretations of result
From accompanying drawing 2, can find out the increase along with Graphene composite activated carbon dosage, BrO
3 -growing amount constantly reduces, the control effect generating from bromate, when the dosage of Graphene composite activated carbon is 50-100mg/L, than independent ozonize, be that Graphene composite activated carbon dosage is while being 0mg/L, it is best that the inhibiting rate that bromate generates has reached, therefore Graphene composite activated carbon catalytic ozonation is remarkable to the inhibition of bromate, in conjunction with practical situation and economic benefit, can determine optimum dosage.
3, accompanying drawing 3 interpretations of result
From accompanying drawing 3, can find out, pH is raised at 8.8 o'clock by 5.3, although bromate concentration increases, the effect that catalytic ozonation suppresses bromate is still very remarkable.Illustrate that the effect that Graphene catalytic ozonation system control bromate generates is not affected by pH, this technique is used potential of hydrogen scope wide.
Claims (1)
1. in catalytic ozonation process, suppress the method that bromate generates, it is characterized in that having following process and step:
A. prepare Graphene composite reactive Pd/carbon catalyst: adopt hydrothermal method, take polyvinyl alcohol as tackiness agent, take Graphene and gac as raw material, cooperatively interact, wherein the shared mass percent of Graphene is 2%-10%, at 170-180 ℃, by Graphene and Mixture of Activated Carbon reacting by heating, finally make Graphene composite reactive Pd/carbon catalyst;
B. in containing bromide anion and organic mixing solutions, add ozone 1-3mg/L (or 0.05-0.2L/min); Graphene composite reactive Pd/carbon catalyst 50-100mg/L, controls pH value in 4-8.8 scopes, and it is reacted, and finally, in this catalytic ozonation system, has also effectively suppressed the generation of bromate in degradation of organic substances.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115180739A (en) * | 2022-07-18 | 2022-10-14 | 威海智洁环保技术有限公司 | Method for removing 2-methylisoborneol and geosmin in drinking water |
Citations (6)
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| JPH1085764A (en) * | 1996-09-12 | 1998-04-07 | Japan Organo Co Ltd | Method for treating water containing bromic acid by active carbon |
| JP2000288562A (en) * | 1999-04-01 | 2000-10-17 | Kubota Corp | Ozone treatment method and apparatus |
| US6602426B2 (en) * | 2001-10-01 | 2003-08-05 | Black & Veatch Holding Company | Water treatment using ozone and having a reduced likelihood of bromate formation from bromides found in the water |
| CN101327985A (en) * | 2008-07-31 | 2008-12-24 | 哈尔滨工业大学 | Method for removing organic pollutant in water by catalysis ozonation |
| CN102020372A (en) * | 2009-09-11 | 2011-04-20 | 董旭 | Ozone water purifying method capable of reducing and eliminating bromates |
| CN102513088A (en) * | 2011-12-09 | 2012-06-27 | 西南交通大学 | Preparation method of compound catalyst for controlling generation of bromate in process of using ozone |
-
2014
- 2014-05-19 CN CN201410210644.3A patent/CN103991943B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1085764A (en) * | 1996-09-12 | 1998-04-07 | Japan Organo Co Ltd | Method for treating water containing bromic acid by active carbon |
| JP2000288562A (en) * | 1999-04-01 | 2000-10-17 | Kubota Corp | Ozone treatment method and apparatus |
| US6602426B2 (en) * | 2001-10-01 | 2003-08-05 | Black & Veatch Holding Company | Water treatment using ozone and having a reduced likelihood of bromate formation from bromides found in the water |
| CN101327985A (en) * | 2008-07-31 | 2008-12-24 | 哈尔滨工业大学 | Method for removing organic pollutant in water by catalysis ozonation |
| CN102020372A (en) * | 2009-09-11 | 2011-04-20 | 董旭 | Ozone water purifying method capable of reducing and eliminating bromates |
| CN102513088A (en) * | 2011-12-09 | 2012-06-27 | 西南交通大学 | Preparation method of compound catalyst for controlling generation of bromate in process of using ozone |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115180739A (en) * | 2022-07-18 | 2022-10-14 | 威海智洁环保技术有限公司 | Method for removing 2-methylisoborneol and geosmin in drinking water |
| CN115180739B (en) * | 2022-07-18 | 2023-06-13 | 威海智洁环保技术有限公司 | Method for removing 2-methyl isoborneol and skatole in drinking water |
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