CN101402047B - Ozone decomposition catalyst and method of producing the same - Google Patents
Ozone decomposition catalyst and method of producing the same Download PDFInfo
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- CN101402047B CN101402047B CN2008100797757A CN200810079775A CN101402047B CN 101402047 B CN101402047 B CN 101402047B CN 2008100797757 A CN2008100797757 A CN 2008100797757A CN 200810079775 A CN200810079775 A CN 200810079775A CN 101402047 B CN101402047 B CN 101402047B
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Abstract
The invention relates to a catalyst for ozone decomposition and a method for preparing the same. The catalyst uses activated carbon particles or activated carbon fiber as a carrier, and uses manganese, nickel, silver, and cerium as active components of the catalyst. The method for preparing the catalyst comprises the following steps: A. mixing the same volume of a manganese nitrate solution, a nickel nitrate solution, a silver nitrate solution and a cerium nitrate solution to prepare an active component solution; B. selecting the activated carbon particles or the activated carbon fiber as thecatalyst carrier, immersing the carrier in the prepared active component solution, and then taking out the carrier for washing and drying; C. taking out the carrier and immersing the carrier in a sodium carbonate solution; and D. taking out the carrier for washing, drying, and baking to obtain a finished product of the catalyst. The method for preparing the catalyst has the advantages of simple process, high ozone decomposition efficiency, low cost, stable performance, long service life, and wide application prospect.
Description
Relate to the field
The present invention relates to a kind of ozone decomposition catalyst and preparation method thereof.
Background technology
Ozone is strong oxidizer, also be wide spectrum disinfective agent, can be widely used in various water treatments, health care, food fresh keeping and remove hard-degraded substance etc., but because the utilization rate of ozone is lower, in actual use, tend to produce a large amount of residue ozones.If these residual ozone directly are discharged in the atmosphere, certainly will cause environmental pollution.In addition, also will directly influence surrounding air, when ozone concentration surpasses 0.06mgm from the ozone of generations such as cabin, duplicator and electrion
-3The time will produce certain harm to human body.Therefore, before ozone is discharged, handle, be translated into very necessity of innocuous substance.
At present, being used for the catalyst activity component that ozone decomposes mainly contains following several: the compound of noble metal, transition metal oxide, manganese.The agent of noble metal ozone catalytic mainly is to contain platinum, palladium, the catalyst of compositions such as rhodium, as publication number is CN1316300, name is called the application for a patent for invention of " a kind of ozone (O3) reducing catalyst and manufacture method thereof ", a kind of support type ozone reduction catalyst is disclosed, with ferric nitrate, nickel nitrate, silver nitrate, palladium nitrate is in deionized water, make in the column-shaped active carbon of immersion as carrier, according to this patent application document record, this catalyst at normal temperatures and pressures 10-1 second just effectively decomposition-reduction ozone (O3) be oxygen (O2), the 100g catalyst life reaches 1500 ~ 2000h, reaches ozone tail gas discharge index 0.04ppm/m2; Publication number is CN1785511, name is called the application for a patent for invention of " Ru/Al2O3 catalytic ozone oxidation catalyst and microwave synthesis method thereof ", disclosing a kind of carrier is Al2O3, active component is the RuO2 catalytic ozone oxidation catalyst, according to this patent application document record, this catalyst all has good effect of removing for materials such as incretion interferent, aldehydes matter, little molecule acids under condition of neutral pH; Publication number is CN1990102, name is called the application for a patent for invention of " the Au/TiO2 catalyst that ozone is eliminated in photocatalysis ", disclosing a kind of is active component with Au, TiO2 is the catalyst of active carrier, according to this patent application document record, this catalyst catalytic performance is good, be used for photocatalysis and eliminate ozone, required carrier is simple, catalyst consumption is less, be particularly suitable for the elimination of ozone in the indoor air-purification device, and preparation technology is simple, cost also reduces greatly, is suitable for suitability for industrialized production.The technical scheme that these patent applications propose has all been used the noble metal composition, this type of catalyst decomposability is better, but its cost height, and steam can strong inhibition ozone decomposable process when existing, necessary thermal regeneration after use a period of time, its use is subjected to bigger restriction.Also has a kind of catalyst of transition metal oxide, this is a kind of relatively inexpensive ozone decomposition catalyst, as K.Kodama (Chinese translation: the Kodak horse) in the patent of its application, exactly transition metal oxide CoOx and NiOx are loaded to the catalyst that obtains on the silica gel, this type of catalyst to deodorization, decolouring, sterilization, decomposing organic matter after the decomposition of residual ozone effective especially, but its decomposition efficiency is lower, service life is short, and must there be certain water vapour environment when using, environment for use is had relatively high expectations, be difficult to promote the use of.Oyama) etc. in addition, the compound catalyst of manganese also is the more a kind of catalyst of research, Oyama (Chinese translation: at Al
2O
3Drawn MnO in the ozone disaggregate approach work of carrier
2Active best conclusion, the work of most researchers after this all are to contain MnO
2For carrying out modification on the catalyst on basis, but make with this ozone catalytic exist preparation technology complicated, and the shortcoming that is restricted of application conditions still can not be satisfied the demand.
Summary of the invention
Purpose of the present invention is exactly the deficiency that exists at prior art, proposes a kind of ozone decomposition catalyst and preparation method thereof, and its technology is simple, catalyst ozone decomposition efficiency height, and stable performance, cost is low, long service life.
The present invention relates to a kind of ozone decomposition catalyst, carrier is activated carbon granule or NACF, it is characterized in that: the oxide of manganese, manganese or carbonate are main active component, and the oxide of nickel, silver and cerium or carbonate are for helping active component; Described three kinds to help the percentage by weight of active component nickel, silver, cerium be 2 ~ 7: 1 ~ 4: 1 ~ 6, and described main active component is 3 ~ 20: 5 ~ 17 with helping the percentage by weight of active component.
Ozone decomposition catalyst of the present invention is prepared with the dipper precipitation method, and the preparation method comprises the following steps: A, preparation active component solution: with concentration is 0.40 ~ 0.60molL
-1Manganese nitrate solution, 0.08 ~ 0.12molL
-1Nickel nitrate solution, 0.08 ~ 0.12molL
-1The solution and the 0.04 ~ 0.06molL of silver nitrate
-1Cerous nitrate solution be mixed and made into active component solution with equal volume; B, the active processing: select for use activated carbon granule or NACF as catalyst carrier, immersed the above-mentioned active component solution that is made into 15 ~ 30 hours, take out washing, 80 ℃ are carried out drying in baking oven; C, will immerse 0.50 ~ 0.80molL through the above-mentioned active catalyst carrier of handling
-1Sodium carbonate liquor 15 ~ 30 hours; D, will be dry through the catalyst carrier washing that above-mentioned sodium carbonate liquor immerses, under 100 ~ 300 ℃ of conditions, baking was burnt 6 ~ 10 hours, made the catalyst finished product.
Preparation technology of the present invention is simpler, and the catalyst that makes has characteristics such as ozone decomposition efficiency height, stable performance, cost are low, long service life, at air speed 20000h
-1, the ozone initial concentration is under the situation of 200ppm, reacts after 2000 hours, catalyst decomposes efficient is still up to more than 90%.
The specific embodiment
Embodiment 1
The concentration of preparation manganese nitrate, nickel nitrate, silver nitrate and cerous nitrate is respectively 0.40molL
-1, 0.08molL
-1, 0.08molL
-1, 0.04molL
-1Solution, it is mixed with equal volume, the carrier active carbon particle is immersed wherein, take out distilled water washing, drying behind the 15h; Again with carrier impregnation in 0.05molL
-1Sodium carbonate liquor in, take out distilled water washing behind the 15h, dry, burn 6h in 100 ℃ of bakings then, make that main active component is 12: 7 with helping the percentage by weight of active component in the ozone decomposition catalyst, wherein three kinds to help the percentage by weight of active component nickel, silver, cerium be 4: 1: 2.
Embodiment 2
The concentration of preparation manganese nitrate, nickel nitrate, silver nitrate and cerous nitrate is respectively 0.50molL
-1, 0.10molL
-1, 0.10molL
-1, 0.05molL
-1Solution, it is mixed with equal volume, the carrier active carbon particle is immersed wherein, take out distilled water washing, drying behind the 24h; Again with carrier impregnation in 0.60molL
-1Sodium carbonate liquor in, take out distilled water washing behind the 24h, dry, burn 8h in 200 ℃ of bakings then, make that main active component is 13: 10 with helping the percentage by weight of active component in the ozone decomposition catalyst, wherein three kinds to help the percentage by weight of active component nickel, silver, cerium be 5: 3: 2.
Embodiment 3
The concentration of preparation manganese nitrate, nickel nitrate, silver nitrate, cerous nitrate is respectively 0.60molL
-1, 0.12molL
-1, 0.12molL
-1, 0.06molL
-1Solution, it is mixed with equal volume, the carrier active carbon particle is immersed wherein, take out distilled water washing, drying behind the 30h; Again with carrier impregnation in 0.8molL
-1Sodium carbonate liquor in, take out distilled water washing behind the 30h, dry, burn 10h in 300 ℃ of bakings then, make that main active component is 17: 11 with helping the percentage by weight of active component in the ozone decomposition catalyst, wherein three kinds to help the percentage by weight of active component nickel, silver, cerium be 5: 3: 3.
Embodiment 4
The concentration of preparation manganese nitrate, nickel nitrate, silver nitrate, cerous nitrate is respectively 0.40molL
-1, 0.09molL
-1, 0.08molL
-1, 0.04molL
-1Solution, it is mixed with equal volume, the carrier active carbon fiber is immersed wherein, take out distilled water washing, drying behind the 15h; Again with carrier impregnation in 0.05molL
-1Sodium carbonate liquor in, take out distilled water washing behind the 15h, dry, burn 6h in 100 ℃ of bakings then, make that main active component is 13: 8 with helping the percentage by weight of active component in the ozone decomposition catalyst, wherein three kinds to help the percentage by weight of active component nickel, silver, cerium be 4: 1: 3.
Embodiment 5
The concentration of preparation manganese nitrate, nickel nitrate, silver nitrate, cerous nitrate is respectively 0.50molL
-1, 0.09molL
-1, 0.09molL
-1, 0.05molL
-1Solution, it is mixed with equal volume, the carrier active carbon fiber is immersed wherein, take out distilled water washing, drying behind the 15h; Again with carrier impregnation in 0.06molL
-1Sodium carbonate liquor in, take out distilled water washing behind the 15h, dry, burn 6h in 100 ℃ of bakings then, make that main active component is 15: 11 with helping the percentage by weight of active component in the ozone decomposition catalyst, wherein three kinds to help the percentage by weight of active component nickel, silver, cerium be 6: 2: 3.
Embodiment 6
The concentration of preparation manganese nitrate, nickel nitrate, silver nitrate, cerous nitrate is respectively 0.60molL
-1, 0.09molL
-1, 0.12molL
-1, 0.06molL
-1Solution, it is mixed with equal volume, the carrier active carbon fiber is immersed wherein, take out distilled water washing, drying behind the 15h; Again with carrier impregnation in 0.06molL
-1Sodium carbonate liquor in, take out distilled water washing behind the 15h, dry, burn 6h in 100 ℃ of bakings then, make that main active component is 17: 10 with helping the percentage by weight of active component in the ozone decomposition catalyst, wherein three kinds to help the percentage by weight of active component nickel, silver, cerium be 5: 2: 3.
Claims (3)
1. ozone decomposition catalyst, carrier is activated carbon granule or NACF, it is characterized in that: the oxide of manganese or carbonate are main active component, and the oxide of nickel, silver and cerium or carbonate are for helping active component; Described three kinds to help the weight ratio of active component nickel, silver, cerium be 2~7: 1~4: 1~6, and described main active component is 3~20: 5~17 with helping the weight ratio of active component.
2. ozone decomposition catalyst according to claim 1 is characterized in that: described main active component is 5~12: 7~13 with helping the active component weight ratio.
3. the preparation method of an ozone decomposition catalyst is prepared with the dipper precipitation method, and comprise the following steps: A, preparation active component solution: with concentration is 0.40~0.60molL
-1Manganese nitrate solution, 0.08~0.12molL
-1Nickel nitrate solution, 0.08~0.12molL
-1The solution and the 0.04~0.06molL of silver nitrate
-1Cerous nitrate solution be mixed and made into active component solution with equal volume; B, the active processing: select for use activated carbon granule or NACF as catalyst carrier, immersed the above-mentioned active component solution that is made into 15~30 hours, take out washing, 80 ℃ are carried out drying in baking oven; C, will immerse 0.50~0.80molL through the above-mentioned active catalyst carrier of handling
-1Sodium carbonate liquor 15~30 hours; D, will be dry through the catalyst carrier washing that above-mentioned sodium carbonate liquor immerses, under 100~300 ℃ of conditions, baking was burnt 6~10 hours, made the catalyst finished product.
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Families Citing this family (12)
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CN101757933B (en) * | 2010-02-01 | 2013-01-02 | 苏州亚都环保科技有限公司 | Ozonolysis catalyst and preparation method thereof |
CN102078753A (en) * | 2010-12-31 | 2011-06-01 | 华东理工大学 | Cellular activated carbon-based denitration catalyst as well as preparation and application thereof |
CN102258997B (en) * | 2011-05-19 | 2012-12-12 | 哈尔滨工业大学 | Manganese-loaded multiphase catalyst, and water treatment method for producing high-activity quinquevalent manganese by catalyzing ozone through same |
CN102513106B (en) * | 2011-11-23 | 2013-06-19 | 苏州工业园区安泽汶环保技术有限公司 | Room-temperature efficient ozone decomposition catalyst and preparation method thereof |
CN102583894A (en) * | 2012-02-24 | 2012-07-18 | 浙江省农业科学院 | Method for treating landfill leachate tail water through magnetic carbon catalyzed ozonation |
CN104549275B (en) * | 2013-10-12 | 2018-06-15 | 王颖华 | Transient metal doped solid catalyst, preparation method and the method for handling water |
CN104001502B (en) * | 2014-05-29 | 2016-03-16 | 中国科学院生态环境研究中心 | Cerium Mn catalyst, the preparation method and its usage of ozone decomposition under a kind of room temperature high humility |
CN106423060A (en) * | 2016-10-13 | 2017-02-22 | 天津城建大学 | Preparation method of modified activated carbon for adsorbing dye |
CN108212153B (en) * | 2018-02-06 | 2021-06-22 | 华东师范大学 | Self-supporting noble metal modified manganese-based composite oxide catalyst and preparation method and application thereof |
CN110665539A (en) * | 2019-09-25 | 2020-01-10 | 西南石油大学 | Formula and process of manganese silicate-based ozone removal material |
CN111437818B (en) * | 2020-04-28 | 2023-06-02 | 盐城师范学院 | Novel heterogeneous ozone catalyst for treating wastewater and preparation method thereof |
CN115138372A (en) * | 2022-07-22 | 2022-10-04 | 山东亮剑环保新材料有限公司 | Preparation method of supported activated carbon catalyst for ozonolysis |
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