CN102616916B - Method for controlling formation quantity of bromate in ozone oxidized water treatment process by TiO2 - Google Patents
Method for controlling formation quantity of bromate in ozone oxidized water treatment process by TiO2 Download PDFInfo
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- CN102616916B CN102616916B CN201210121989.2A CN201210121989A CN102616916B CN 102616916 B CN102616916 B CN 102616916B CN 201210121989 A CN201210121989 A CN 201210121989A CN 102616916 B CN102616916 B CN 102616916B
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Abstract
The invention relates to a method for controlling the formation quantity of bromate in an ozone oxidation process of drinking water by introducing a nano TiO2 catalyst, which avoids negative effects brought to the safety and the reliability of the drinking water of the traditional method for controlling the bromate by adding chemical drugs. According to the method, settled water treated by a conventional method is directly filled into a nano TiO2 catalyst bed for ozone contact and catalytic ozone oxidation, or after the settled water is subjected to ozone contact and catalytic ozone oxidation in a primary nano TiO2 catalyst bed, water still containing ozone is filled into a secondary nano TiO2 catalyst bed for carrying out a catalytic reaction, wherein the contact oxidation time is 10-20min. The method has the advantages that the nano TiO2 has obvious efficiency of reducing the formation quantity of the bromate in the ozone oxidation process and also has obvious control efficiency to the formation quantity of the bromate in the ozone oxidation process of water with high bromide ion concentration, the formation potential to trihalomethane and the reduction efficiency to DOC of individual ozone oxidation can be improved, and other toxic and side effects cannot be caused to the quality of the drinking water.
Description
Technical field
The present invention relates to a kind of method that suppresses bromate growing amount in the ozone oxidation process, be specifically related to a kind of use Nano titanium dioxide (TiO
2) method of bromate growing amount while as catalyzer, controlling ozone oxidation bromine ion-containing water.
Background technology
In recent years, along with day by day increasing the weight of of pollution of waterhead and improving constantly of water quality standard for drinking water, much earth's surface water factory all starts to adopt ozone oxidation as pre-treatment or advanced treatment process gradually.In the production of some drink waters, mineral water, ozone usually also be absolutely necessary advanced treatment or sterilization process.But if, while in water, having bromide anion, ozone oxidation can cause the generation of bromate, bromate has potential carcinogenic effect, by the deciding grade and level of international cancer research institution, has been 2B level potential carcinogen.At present, bromate is based in the advanced treatment process of ozone oxidation, a kind of oxidized byproduct that people are the most responsive.Each developed country's water quality standard for drinking water all maximum permissible concentration of regulation bromate is 10 μ g/L.Generally contain bromide anion in the surface water of compare Chang， coastland, China shoreline, and in the water source of some natural mineral waters, the content of bromide anion is also higher.Current, the problem of bromate has caused the Chinese government and the whole people's great attention.In the water quality standard for drinking water that China is new and new " natural mineral water " national standard, all stipulate, the content of bromate must not surpass 0.01mg/L.Bromate just is difficult to be removed once forming.The problem of bromate has in fact become the restraining factors of ozone application maximum in drinking water treatment.
In actual production, usually and gac or the coupling of biologic active carbon filtration technique, granular carbon absorbing and reducing method is the method for more removal bromate of studying both at home and abroad to ozone.But charcoal absorption reduction method loading capacity is limited, it is saturated easily to adsorb and absorbing and reducing usefulness can change into biological activated carbon and greatly reduce with gac.The charcoal absorption reduction method can not fundamentally solve the problem of bromate, and this just need to set about from the ozone oxidation process, fundamentally suppresses the growing amount of bromate.
In recent years, the researchist has carried out more research to the method that suppresses bromate growing amount in the ozone oxidation process both at home and abroad, mainly comprises: add ammoniacal liquor or chlorine ammonia (Cl
2and NH
3add in proportion), add hydrogen peroxide, acid adding or pass into CO
2reduce pH, add free-radical scavengers or HOBr scavenging agent etc.Wherein, the effect that the method for ammonification (chlorine ammonia) and reduction pH value is controlled bromate output is the most obvious, can reduce the growing amount of the bromate of 50% left and right, and its control principle has all related to BrO
3 -very important intermediate product HOBr/OBr in generative process
-conversion.The method of ammonification (chlorine ammonia) can cause the formation of more nitrogenous disinfection byproducts, and current research finds that nitrogenous disinfection byproducts is stronger than the toxicity of carbon containing disinfection byproduct (DBP).In addition, the bromine ammonia formed after ammonification can consume ozone and ozone decomposed produces
.oH, and then the ability of inhibition ozone oxidation organic pollutant.Simultaneously, the prechlorination in chlorination ammonia can bring the risk that very high chloro disinfection byproduct (DBP) exceeds standard.And the method that reduces the pH value can increase the generation gesture of total organic bromine (TOBr), and both inconvenience was also uneconomical to add the water treatment mode of acid for adjusting pH value, and what in actual production, adopt passes into CO
2also there is the problem that cost is higher in the method that reduces the pH value.On the whole, these suppress the method that in the ozone oxidation process, bromate forms, and all will in water, introduce other chemical agents.The negative effect that the method for existing introducing chemical agent control bromate is brought to the drinking water safety reliability may be not second to bromate itself, these methods tool in actual production has a serious limitation, and brings risk all can to a great extent the safe reliability of tap water.
Summary of the invention
The growing amount of bromate in order efficiently to suppress ozone oxidation bromine ion-containing water the time, and synchronously improve ozone oxidation and control Chlorination Disinfection By-products, reduce organic usefulness, solve the existing negative effect that the bromate method brings to the drinking water safety reliability (generate nitrogenous disinfection byproducts that toxicity is higher, increase total organic bromine generate gesture etc.) of controlling simultaneously.The invention provides a kind of method of controlling bromate growing amount in the brominated tap water process of ozone oxidation by introducing the nano-metal-oxide catalyzer.The method does not add other chemical agents in water, can not bring the negative effect of existing control method of bromate to tap water.Concrete steps of the present invention are: earth's surface water factory through coagulation, precipitation after heavy after conventional processing water directly enter the nano-metal-oxide catalytic bed and carry out O3 catalytic oxidation, the catalyzer fixed in position is in catalytic bed, ozone dosage is 0.4-3.5mgO
3/ (mg DOC), after heavy, water directly completes and the contacting and O3 catalytic oxidation of ozone in catalytic bed simultaneously, the catalytic oxidation time is 10-20min, and water outlet enters after sand filter/activated carbon filter further filters rear chlorination (chloramines) sterilization and sends into the user.
Different from aforesaid method is heavy after water enter the catalytic ozonation bed and carry out ozone oxidation reaction 5-15min, the water that out still contains ozone from one-level catalytic ozonation bed enters in the second catalyst bed that inside is filled with the load-type nanometer metal oxide catalyst again, and the time of controlling second stage catalyzed oxidation is 5-10min.Other steps are identical with aforesaid method with processing condition.
Nano-metal-oxide catalyzer of the present invention is to prepare the powder titanium dioxide at 300～500 ℃ of sintering by sol-gel method; Or load to activated alumina, zeolite or other mesopore materials by sol-gel, roasting method, the loading nano-titania of 300～500 ℃ of sintering that obtain.
Research through the contriver shows, nano titanium oxide has the usefulness that in obvious inhibition ozone oxidation process, bromate generates, in the situation that in water, bromide ion concentration is 0.5-1.0mg/L, the bromate that can reduce during nano titanium oxide throwing amount 200mg/L more than 70% generates; Under low bromide ion concentration (0.1-0.25mg/L), during nano titanium oxide throwing amount 200mg/L, the reduction amplitude of bromate growing amount can reach more than 90%, and after catalyzed oxidation the growing amount of bromate all below 10 μ g/L.In addition, research proved titanium dioxide to human body without any toxicity, can not accumulate at human body, be a kind of inert substance that can not endanger the human body generation, therefore can not exist as existing and add the negative effect that chemical agent suppresses bromate growing amount method in water.In addition, the nano titanium oxide O3 catalytic oxidation can also further improve ozone to organic degradation efficiency in water, DOC than the raising of independent ozone oxidation 20% left and right; And can synchronization control the haloform Chlorination Disinfection By-products, the haloform total amount than the reduction of independent ozone oxidation 20%-30%.When carrying out the drinking water deep processing by the method, in conjunction with follow-up gac filter bed, can further remove the small organic molecule in water outlet and a small amount of bromate of generation after catalyzed oxidation, greatly reduce water outlet DOC and bromate, ensure safe reliability and the high-quality water quality of tap water.
This invention is applicable to take the city tap-water factory advanced treatment that surface water is water source, and high-end residential community, large stadium prepare high-quality tap water.
The accompanying drawing explanation
The schema that Fig. 1 is the invention process method one correspondence.
Fig. 2 is the schema that the invention process method two is corresponding.
The schema that Fig. 3 is the invention process method three correspondences, Fig. 3 (a) is the schema that single-stage catalytic bed ozone gas, bromine ion-containing water synchronously enter from the bottom ejector; Fig. 3 (b) is that two-stage catalytic bed ozone gas, bromine ion-containing water synchronously enter the schema of catalytic bed reaction from the bottom ejector.
Fig. 4 is initial bromide ion concentration while being 1mg/L, nano-TiO
2the generation situation of bromate in the O3 catalytic oxidation process, wherein 1,2 represent respectively independent O
3oxidation and CeO
2/ O
3the growing amount of bromate in oxidising process.
Fig. 5 is initial bromide ion concentration while being 0.2mg/L, nano-TiO
2the generation situation of bromate in the O3 catalytic oxidation process, wherein 1,2 represent respectively independent O
3oxidation and CeO
2/ O
3the growing amount of bromate in oxidising process.
In figure, 1. bromine ion-containing water 2. ozone gas 3. one-level O3 catalytic oxidation post 4. sand filtrations/activated carbon column 5. ozone tail gas breaking plant 6. residual ozone tail gas pipeline 7. secondary O3 catalytic oxidation posts
Embodiment
Embodiment one: water after heavy after conventional treatment process coagulation, precipitation process, the catalytic bed that enters inner filling load-type nanometer metal oxide compound is carried out O3 catalytic oxidation, ozone enters from the catalytic bed bottom, after heavy, from catalytic bed, the position near top enters water, and ozone dosage is: 0.4-3.5mgO
3/ mgDOC, the catalytic Contact time is: 10-20min; Water outlet enters after sand filtration/activated carbon filter further filters rear chlorination (chloramines) sterilization and sends into the user.Idiographic flow is shown in accompanying drawing 1.
Embodiment two: different from above-mentioned implementation method one is, heavy rear water enters one-level catalytic ozonation bed and carries out ozone oxidation reaction 5-15min, the water that out still contains ozone from the catalytic ozonation bed enters in the second catalyst bed that inside is filled with the load-type nanometer metal oxide catalyst again, and the time of controlling second stage catalyzed oxidation is 5-10min.Other steps are identical with aforesaid method with processing condition.Idiographic flow is shown in accompanying drawing 2.
Embodiment three: different from above-mentioned implementation method one, two is, when the catalytic bed that after heavy, water enters inner filling load-type nanometer metal oxide compound is carried out O3 catalytic oxidation, after heavy, water is from entering under catalytic bed (or catalyzing tank) bottom or bottom feed-water end by ejector enters (particular location as shown in Figure 3), ozone from the catalytic bed bottom sides enter by air distribution plate or ejector with heavy water contact fast, and carrying out O3 catalytic oxidation by catalyzer at once, other embodiments are corresponding identical with implementation method one, two respectively with processing condition.
Claims (5)
1. a method that suppresses bromine ion-containing drinking water bromate growing amount in the ozone oxidation process by nanocatalyst, the method is specific as follows: the nano titanic oxide catalyst filling catalytic bed jointly made by sol-gel method and roasting method is for ozone oxidation, heavy rear water after earth's surface water factory conventional processing directly enters the nano titanium oxide catalytic bed and carries out O3 catalytic oxidation, the catalyzer fixed in position is in catalytic bed, after heavy, water directly completes and the contacting and O3 catalytic oxidation of ozone in catalytic bed simultaneously, water outlet enters sand filtration or activated carbon filter and further filters after 20-30min and send into the user after chlorination, the method adopts nm-class catalyst to suppress the growing amount of bromate in the ozone oxidation process, and can reduce the bromate growing amount more than 90% under the low bromide ion concentration of 0.1-0.25mg/L, in the high bromide ion concentration scope of 0.5-1.0mg/L, the growing amount of bromate also can reduce more than 70%, the ozone dosage of described O3 catalytic oxidation is 0.4-3.5mgO
3/ mg DOC, after heavy, water directly completes and the contacting and the O3 catalytic oxidation reaction of ozone in catalytic bed simultaneously, after heavy, water enters after the one-level catalytic bed carries out ozone contact and catalytic oxidation, the water that out still contains ozone from the one-level catalytic bed enters in the secondary catalytic bed again and carries out the secondary catalytic oxidation, the catalytic oxidation time of the one-level catalytic bed of this reactive system is controlled as 5-15min, and the residence time of controlling the secondary catalyzed oxidation is 5-10min, the reaction total time of controlling catalyzed oxidation is 10-20min.
2. a kind of method that suppresses bromine ion-containing drinking water bromate growing amount in the ozone oxidation process by nanocatalyst according to claim 1, is characterized in that the nanocatalyst loaded in catalytic bed is load type nano titanium dioxide catalyst.
3. a kind of method that suppresses bromine ion-containing drinking water bromate growing amount in the ozone oxidation process by nanocatalyst according to claim 2, the preparation method who it is characterized in that load type nano titanium dioxide catalyst is as follows: the dilute nitric acid solution impregnated carrier of first using pH=1-3, clean carrier with ultrapure water after 8-24h, until water outlet pH is constant several times continuously, dry afterwards, put into the beaker bottom for preparing titanium dioxide by sol-gel method, be sequentially added into afterwards volume ratio 3-5: 1: 0.08-0.12: the ethanol of 0.6-0.9, butyl (tetra) titanate, hydrochloric acid, water carries out sol-gel method and prepares titanium dioxide, the jelly made is respectively at 300-500 ℃ of lower roasting 2-5h, sinter load type nano titanium dioxide catalyst into, described load type nano titanium dioxide catalyst carrier used is activated alumina, zeolite, supersiliceous zeolite or haydite.
4. a kind of method that suppresses bromine ion-containing drinking water bromate growing amount in the ozone oxidation process by nanocatalyst according to claim 3, the particle diameter that it is characterized in that carrier is 1-4mm.
5. a kind of method that suppresses bromine ion-containing drinking water bromate growing amount in the ozone oxidation process by nanocatalyst according to claim 1, the loadings that it is characterized in that catalyzer in catalytic bed was determined by the empty bed residence time of its design: the loaded catalyst of one-level catalytic bed is by empty bed residence time 5-15min filling, and the loaded catalyst of secondary catalytic bed is by empty bed residence time 5-10min filling.
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| CN103663669B (en) * | 2012-09-07 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of method and apparatus improving ozone oxidation efficiency |
| CN103663613A (en) * | 2013-12-05 | 2014-03-26 | 乐山市洁宇纳米应用技术研究所 | Bromate treating method |
| CN106608672B (en) * | 2015-10-22 | 2020-09-01 | 南开大学 | Method for controlling trichloronitromethane generation potential by catalytic ozonation |
| CN105236691A (en) * | 2015-11-10 | 2016-01-13 | 山东建筑大学 | Production process for controlling generation of ozonized bromate |
| CN108671920A (en) * | 2018-05-30 | 2018-10-19 | 淮海工学院 | Mesoporous γ-Fe-Ti-Al2O3Catalyst and preparation method thereof and purposes |
Citations (3)
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|---|---|---|---|---|
| CN1695796A (en) * | 2005-03-11 | 2005-11-16 | 哈尔滨工业大学 | Preparation for catalyst of Nano titanium dioxide, and method for treating ozonized water of catalysis |
| JP2007083207A (en) * | 2005-09-26 | 2007-04-05 | Fuji Electric Systems Co Ltd | Accelerated oxidation water treatment method and apparatus |
| CN101050036A (en) * | 2007-05-21 | 2007-10-10 | 哈尔滨工业大学 | Method for controlling generation quantity of bromic acid radicle in treating procedure for oxidizing drinking water by ozone |
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| CN1695796A (en) * | 2005-03-11 | 2005-11-16 | 哈尔滨工业大学 | Preparation for catalyst of Nano titanium dioxide, and method for treating ozonized water of catalysis |
| JP2007083207A (en) * | 2005-09-26 | 2007-04-05 | Fuji Electric Systems Co Ltd | Accelerated oxidation water treatment method and apparatus |
| CN101050036A (en) * | 2007-05-21 | 2007-10-10 | 哈尔滨工业大学 | Method for controlling generation quantity of bromic acid radicle in treating procedure for oxidizing drinking water by ozone |
Non-Patent Citations (4)
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| 纳米级TiO2/粉煤灰/UV催化臭氧化处理水中苯胺的研究;杨监峰;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑 》;20120315(第03期);第29-30页 * |
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