CN103028413A - Chromium-doped catalyst for catalytic oxidation of nitric oxide at normal temperature and pressure, as well as preparation method and application thereof - Google Patents
Chromium-doped catalyst for catalytic oxidation of nitric oxide at normal temperature and pressure, as well as preparation method and application thereof Download PDFInfo
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- CN103028413A CN103028413A CN2012105361929A CN201210536192A CN103028413A CN 103028413 A CN103028413 A CN 103028413A CN 2012105361929 A CN2012105361929 A CN 2012105361929A CN 201210536192 A CN201210536192 A CN 201210536192A CN 103028413 A CN103028413 A CN 103028413A
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Abstract
The invention relates to a chromium-doped catalyst for catalytic oxidation of nitric oxide at a normal temperature and pressure, as well as a preparation method and an application thereof. The chromium-doped catalyst is prepared by using a deposition precipitation method. The preparation method comprises the following steps: weighing a chromium precursor; dissolving the chromium precursor in deionized water; adding one or a combination of nitrate, chloride and hydrogen chloride, wherein the doping content is from 0.5% to 100%; stirring the mixture at the normal temperature to 100 DEG C; adding a precipitator; after regulating the pH value as 3 to 10, stirring for 5 to 8 hours and carrying out a filtering and washing operation; drying for 12 hours at the temperature of 60 to 150 DEG C; and calcining for 2 to 6 hours at the temperature of 100 to 700 DEG C, thereby obtaining the chromium-doped catalyst for the catalytic oxidation of nitric oxide at the normal temperature and pressure. When the chromium-doped catalyst is applied to a catalytic oxidation reaction of the nitric oxide (NO), the nitric oxide (NO) can be converted into nitrogen dioxide (NO2) through the catalytic oxidation at the normal temperature and pressure, so that a higher conversion rate is obtained; and the high activity and high stability of the chromium-doped catalyst are maintained for a long time. The chromium-doped catalyst provided by the invention has the advantages of easiness in raw material obtainment and simplicity in preparation, thereby having a very good application prospect.
Description
Technical field
The present invention relates to a kind of mix chrome catalysts and preparation and application, particularly relate to and a kind ofly mix chrome catalysts and preparation and application for the nitric oxide normal temperature and pressure catalytic oxidation.NO catalytic oxidation mainly in the environment is applicable to the elimination of air pollutants, has application prospect in depollution of environment field.
Background technology
Along with the fast development of Urbanization in China, Urban vehicles poputation is also constantly soaring.The environmental pollution that thereupon causes is also day by day serious, and national motor vehicle emission pollutant was 5143.3 ten thousand tons in 2009, and wherein carbon monoxide is 4018.8 ten thousand tons, 482.2 ten thousand tons in hydrocarbon, 583.3 ten thousand tons of nitrogen oxide, 59.0 ten thousand tons of particles.As seen nitrogen oxide (NOx) is exactly one of major pollutants wherein.
The NOx end treatment technology of scale of input chemical industry journey application mainly is selective catalytic reduction (Topics in Catalysis, Volume 11-12, Numbers 1-4,2000,111-122 at present; A kind of method that removes NO in the flue gas, number of patent application: 201110039827.X), the vehicle tail gas triple effect catalysis method (the China YouSe Acta Metallurgica Sinica, 2004,14:347-353), absorption method (Fuel, Vol. 76, No. 6, pp. 543-548,1997; Applied Catalysis B:Environmental 125 (2012) 398 – 408; Chemical Engineering Journal 116 (2006) 25 – 37), absorption process (Chemical Engineering Journal, 192 (2012) 99 – 104; Fuel 96 (2012) 440 – 445; Catalysis Today, June 2012, doi:10.1016/j.cattod.2012.05.050; Catalysis Today 126 (2007) 400 – 405).Elimination factor can reach more than 80%, the NOx concentration in the dusty gas can be dropped to 100-200 ppm from about 1000 ppm, and but, it can't be applied to low temperature (≤200 ℃) or the low concentration (≤200ppm) purification of NOx.Even the method by absorption, because among the NOx of motor vehicle emission, be NO more than 90%, and NO is supercritical fluid more than normal temperature, its physisorption is very weak, therefore, the NOx clean-up effect is still relatively poor, and absorption do not change the existence of NO, with it from adsorbent behind the desorption, or to face the governing problem of NO, can not thoroughly solve the NOx pollution problem.And simple by the absorption process of acid-base neutralization reaction, and pollutant NOx can be converted into commercial product, turn waste into wealth, have application prospect.The use prerequisite of this method is, is NO with the NO partial oxidation
2, obtain NO
2Accounting heavily is the NOx gas of 50-60%, so just is conducive to absorb efficiently.NO catalytic oxidation temperature is usually 200 at present
oMore than the C, normal temperature almost can't make its conversion.The long NO catalytic oxidation material that uses is NACF, but efficient is lower.Therefore in the present invention, we have developed the chromium catalysis material that a kind of transition metal, alkali metal or alkali earth metal mix, and have realized the efficiently catalyzing and oxidizing of NO normal temperature and pressure, there is no at present report.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of for the chromium-doped catalyst of nitric oxide room-temperature catalytic oxidation and preparation and application.
A kind of preparation method for the chromium-doped catalyst of nitric oxide normal temperature and pressure catalytic oxidation, it is characterized in that, the preparation of employing deposition-precipitation method, taking by weighing chromium precursor 10.0 grams is dissolved in 100 ml deionized water, add nitrate, chloride, a kind of or its combination in the hydroxide, doping is 0.5～100%, in normal temperature～100 ℃ stirring, add precipitating reagent, after adjusting PH is 3～10, stirred 5～8 hours, filter washing, 60～150 ℃ of dryings 12 hours, calcined 2～6 hours for 100～700 ℃, obtain to be used for the chromium-doped catalyst of nitric oxide normal temperature and pressure catalytic oxidation.
Described chromium precursor is a kind of or its combination in chromic nitrate, the chromium chloride.
Described precipitating reagent is carbonic hydroammonium, urea, NaOH, potassium hydroxide, ammoniacal liquor, a kind of or its combination in the sodium carbonate.
Described nitrate is cerous nitrate, ferric nitrate, manganese nitrate, zinc nitrate, nitric acid molybdenum, nitric acid tungsten, cobalt nitrate, a kind of or its combination in the nickel nitrate, described chloride is cerium chloride, iron chloride, manganese chloride, zinc chloride, molybdenum chloride, tungsten chloride, cobalt chloride, a kind of or its combination in the nickel chloride, described hydroxide is NaOH, a kind of or its combination in the potassium hydroxide.
A kind ofly be used for the chromium-doped catalyst of nitric oxide normal temperature and pressure catalytic oxidation by what method of the present invention prepared.
Of the present invention for the application of the chromium-doped catalyst of nitric oxide normal temperature and pressure catalytic oxidation as nitric oxide catalytic oxidation catalyst.
Reaction atmosphere when described catalyst is used is 5-100 ppm NO, and all the other are air.
Reactivity is estimated: take by weighing the above-mentioned catalyst that obtains of 1.0 g and begin to pass into reaction gas in environment temperature, carry out active testing, total flow is 〉=720 ml/min (STP).
Described catalyst is used for the NO catalytic oxidation, can and can keep long-time stability at normal temperature adsoption catalysis oxidation NO.25 ℃ can make the NO efficient oxidation, and conversion ratio reaches 70%, and conversion ratio still remains on more than 50% within 1000 minutes that investigate.
Catalyst of the present invention has the high and long-time stable characteristics of reactivity, can greatly catalytic oxidation NO, make it Efficient Conversion.This has not only realized room-temperature catalytic oxidation NO reaction, it is carried out normal temperature eliminate, and can keep for a long time higher conversion ratio, and is stable.Catalyst raw material of the present invention is easy to get, and technique is simple, has good application prospect.
Description of drawings
Fig. 1 is the active result of the NO catalytic oxidation of the embodiment of the invention 1,2,3,4 Kaolinite Preparation of Catalysts.
Fig. 2 is the active result of the NO catalytic oxidation of the embodiment of the invention 5,6 Kaolinite Preparation of Catalysts.
The specific embodiment
Following instance is used for illustrating in greater detail the present invention, but the present invention is not limited to this.
Embodiment 1
:
The deposition sedimentation method prepares a kind of chrome catalysts of element doping, taking by weighing chromic nitrate 10.0 g is dissolved in the 100 ml deionized waters, whipping temp is environment temperature, adds ferric nitrate, adds precipitating reagent ammoniacal liquor and regulates PH=8-9, stir 6 h, filter washing, 100 ℃ of drying 12 h, 300 ℃ of calcining 4 h obtain catalyst.Doping is 5%.
Take by weighing the above-mentioned catalyst that obtains of 1.0 g and begin to pass into reaction gas at normal temperature, carry out active testing, gas composition is 15 ppm NO, and all the other are air, and total flow is 〉=720 ml/min (STP).
Embodiment 2:
Compare with embodiment 1, different is to add cerous nitrate, and the unclassified stores consumption is identical with embodiment 1 with operating condition.
Embodiment 3:
Compare with embodiment 1, different is to add copper nitrate, and the unclassified stores consumption is identical with embodiment 1 with operating condition
Embodiment 4:
Compare with embodiment 1, different is that precipitating reagent is cobalt nitrate, and the unclassified stores consumption is identical with embodiment 1 with operating condition.
Embodiment 5:
The deposition sedimentation method prepares the chrome catalysts of multi-element doping, taking by weighing chromic nitrate 10.0 g is dissolved in the 100 ml deionized waters, whipping temp is environment temperature, adds ferric nitrate and cerous nitrate, adds precipitating reagent ammoniacal liquor and regulates PH=8-9, stir 6 h, filter washing, 100 ℃ of drying 12 h, 300 ℃ of calcining 4 h obtain catalyst.Doping is 5%, Fe:Ce=1:1.
Take by weighing the above-mentioned catalyst that obtains of 1.0 g and begin to pass into reaction gas at normal temperature, carry out active testing, gas composition is 15 ppm NO, and all the other are air, and total flow is 〉=720 ml/min (STP).
Embodiment 6:
Compare with embodiment 5, different is, and what to add is ferric nitrate and cobalt nitrate, and the unclassified stores consumption is identical with embodiment 5 with operating condition.
Above embodiment 1,2,3,4 the results are shown in Fig. 1, as can see from Figure 1, doped chemical is different, will affect the activity of catalytic oxidation NO of the chrome catalysts of doping, Fe mix shown active preferably.The catalytic oxidation NO conversion ratio of the chrome catalysts that the deposition-precipitation method preparation is mixed is 70%, conversion ratio still remains on more than 50% within 1000 minutes of investigating, catalyst of the present invention has improved the active and stable of normal temperature and pressure catalytic oxidation NO, amplification production for rear catalyst provides extraordinary actual application prospect.
Above embodiment 5,6 the results are shown in Fig. 2, as can see from Figure 2, the codope element is different, and the activity of the catalytic oxidation NO of the chrome catalysts of codope is had slight impact, Fe Ce codope has shown active preferably.The catalytic oxidation NO conversion ratio that deposition-precipitation method prepares the chrome catalysts of codope is 55%, conversion ratio still remains on more than 30% within 1000 minutes of investigating, catalyst of the present invention has improved the active and stable of normal temperature and pressure catalytic oxidation NO, amplification production for rear catalyst provides extraordinary actual application prospect.
Claims (6)
1. preparation method who is used for the chromium-doped catalyst of nitric oxide normal temperature and pressure catalytic oxidation, it is characterized in that, the preparation of employing deposition-precipitation method, taking by weighing chromium precursor 10.0 grams is dissolved in 100 ml deionized water, add nitrate, chloride, a kind of or its combination in the hydroxide, doping is 0.5～100%, in normal temperature～100 ℃ stirring, add precipitating reagent, after adjusting PH is 3～10, stirred 5～8 hours, filter washing, 60～150 ℃ of dryings 12 hours, calcined 2～6 hours for 100～700 ℃, obtain to be used for the chromium-doped catalyst of nitric oxide normal temperature and pressure catalytic oxidation.
2. described preparation method for the chromium-doped catalyst of nitric oxide normal temperature and pressure catalytic oxidation according to claim 1 is characterized in that described chromium precursor is a kind of or its combination in chromic nitrate, the chromium chloride.
3. described preparation method for the chromium-doped catalyst of nitric oxide normal temperature and pressure catalytic oxidation according to claim 1 is characterized in that described precipitating reagent is carbonic hydroammonium, urea, NaOH, potassium hydroxide, ammoniacal liquor, a kind of or its combination in the sodium carbonate.
4. described preparation method for the chromium-doped catalyst of nitric oxide normal temperature and pressure catalytic oxidation according to claim 1 is characterized in that described nitrate is cerous nitrate, ferric nitrate, manganese nitrate, zinc nitrate, nitric acid molybdenum, nitric acid tungsten, cobalt nitrate, a kind of or its combination in the nickel nitrate, described chloride is cerium chloride, iron chloride, manganese chloride, zinc chloride, molybdenum chloride, tungsten chloride, cobalt chloride, a kind of or its combination in the nickel chloride, described hydroxide is NaOH, a kind of or its combination in the potassium hydroxide.
5. one kind is used for the chromium-doped catalyst of nitric oxide normal temperature and pressure catalytic oxidation by what the described method of claim 1～4 any one prepared.
6. the requirement 5 of having the right is described for the application of the chromium-doped catalyst of nitric oxide normal temperature and pressure catalytic oxidation as nitric oxide catalytic oxidation catalyst.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103357370A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Nitric oxide oxidation catalyst with dual functions and preparation method thereof |
| CN103394344A (en) * | 2013-07-15 | 2013-11-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Chrome oxide manganese-supported catalyst, and preparation and application thereof |
| CN104801314A (en) * | 2015-04-22 | 2015-07-29 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of iron, cerium and manganese catalyst for eliminating low-concentration nitric oxide at normal temperature |
| CN104984659A (en) * | 2015-06-24 | 2015-10-21 | 方耀 | Coal-fired flue gas denitrification method |
| CN109666463A (en) * | 2017-10-14 | 2019-04-23 | 新沂市中诺新材料科技有限公司 | A kind of preparation method of oil base drilling fluid thickening extracting and cutting agent |
| CN110833831A (en) * | 2019-11-07 | 2020-02-25 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of chromium-cobalt-based nitric oxide normal-temperature normal-pressure catalyst, product and application thereof |
| CN110833832A (en) * | 2019-11-07 | 2020-02-25 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of ferrochromium-based catalyst for normal-temperature normal-pressure efficient treatment of nitric oxide, product and application thereof |
| CN111185154A (en) * | 2020-03-05 | 2020-05-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Integral chromium-manganese-nitrogen monoxide purifying catalyst and preparation method and application thereof |
| CN111774068A (en) * | 2020-07-08 | 2020-10-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of integral manganese oxide nitric oxide purification catalyst, product and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103357370A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Nitric oxide oxidation catalyst with dual functions and preparation method thereof |
| CN103357370B (en) * | 2013-06-28 | 2015-07-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Nitric oxide oxidation catalyst with dual functions and preparation method thereof |
| CN103394344A (en) * | 2013-07-15 | 2013-11-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Chrome oxide manganese-supported catalyst, and preparation and application thereof |
| CN104801314A (en) * | 2015-04-22 | 2015-07-29 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of iron, cerium and manganese catalyst for eliminating low-concentration nitric oxide at normal temperature |
| CN104984659A (en) * | 2015-06-24 | 2015-10-21 | 方耀 | Coal-fired flue gas denitrification method |
| CN109666463A (en) * | 2017-10-14 | 2019-04-23 | 新沂市中诺新材料科技有限公司 | A kind of preparation method of oil base drilling fluid thickening extracting and cutting agent |
| CN110833831A (en) * | 2019-11-07 | 2020-02-25 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of chromium-cobalt-based nitric oxide normal-temperature normal-pressure catalyst, product and application thereof |
| CN110833832A (en) * | 2019-11-07 | 2020-02-25 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of ferrochromium-based catalyst for normal-temperature normal-pressure efficient treatment of nitric oxide, product and application thereof |
| CN110833832B (en) * | 2019-11-07 | 2022-07-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of ferrochromium-based catalyst for normal-temperature normal-pressure efficient treatment of nitric oxide, product and application thereof |
| CN111185154A (en) * | 2020-03-05 | 2020-05-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Integral chromium-manganese-nitrogen monoxide purifying catalyst and preparation method and application thereof |
| CN111185154B (en) * | 2020-03-05 | 2022-04-05 | 上海纳米技术及应用国家工程研究中心有限公司 | Integral chromium-manganese-nitrogen monoxide purifying catalyst and preparation method and application thereof |
| CN111774068A (en) * | 2020-07-08 | 2020-10-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of integral manganese oxide nitric oxide purification catalyst, product and application thereof |
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