CN103028413B - 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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- CN103028413B CN103028413B CN201210536192.9A CN201210536192A CN103028413B CN 103028413 B CN103028413 B CN 103028413B CN 201210536192 A CN201210536192 A CN 201210536192A CN 103028413 B CN103028413 B CN 103028413B
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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 one and mix chrome catalysts and Synthesis and applications, particularly relate to one and mix chrome catalysts and Synthesis and applications for nitric oxide normal temperature and pressure catalytic oxidation.Mainly for the NO catalytic oxidation in environment, be applicable to the elimination of air pollutants, in depollution of environment field, there is application prospect.
Background technology
Along with the fast development of Urbanization in China, Urban vehicles poputation is also constantly soaring.The environmental pollution thereupon caused is also day by day serious, national motor vehicle emission pollutant 5143.3 ten thousand tons, wherein carbon monoxide 4018.8 ten thousand tons in 2009,482.2 ten thousand tons, hydrocarbon, nitrogen oxide 583.3 ten thousand tons, particle 59.0 ten thousand tons.Visible nitrogen oxide (NOx) is exactly wherein one of major pollutants.
NOx end-of-pipe control technology mainly selective catalytic reduction (Topics in Catalysis, Volume 11-12, Numbers 1-4,2000, the 111-122 of current scale of input engineer applied; Remove a method of NO in flue gas, number of patent application: 201110039827.X), vehicle tail gas triple effect catalysis method (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 dusty gas can be dropped to 100-200 ppm from about 1000 ppm, and but, it cannot be applied to the purification of low temperature (≤200 DEG C) or low concentration (≤200ppm) NOx.Even if by the method for absorption, due in the NOx of motor vehicle emission, more than 90% is NO, and NO is supercritical fluid more than normal temperature, and its physisorption is very weak, therefore, NOx clean-up effect is still poor, and absorption does not change the existence of NO, by it from adsorbent after desorption, or the governing problem of NO to be faced, can not thoroughly solve NOx pollution problem.And the absorption process of being reacted by acid-base neutralization is simple, 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 by NO partial oxidation
2, obtain NO
2accounting is heavily the NOx gas of 50-60%, is so just conducive to absorbing efficiently.Current NO catalytic oxidation temperature is usually 200
omore than C, normal temperature almost cannot make it transform.The NO catalytic oxidation material of longer use is NACF, but efficiency is lower.Therefore in the present invention, we have developed the chromium catalysis material of a kind of transition metal, alkali metal or alkali earth metal doping, achieve the efficiently catalyzing and oxidizing of NO normal temperature and pressure, there is no report at present.
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 Synthesis and applications.
A kind of preparation method for the chromium-doped catalyst of nitric oxide normal temperature and pressure catalytic oxidation, it is characterized in that, prepared by employing deposition-precipitation method, taking chromium precursor 10.0 grams is dissolved in 100 ml deionized water, add nitrate, chloride, one in hydroxide or its combination, doping is 0.5 ~ 100%, DEG C stirring in normal temperature ~ 100, add precipitating reagent, PH is regulated to be after 3 ~ 10, stir 5 ~ 8 hours, filter, washing, 60 ~ 150 DEG C of dryings 12 hours, calcine 2 ~ 6 hours for 100 ~ 700 DEG C, obtain and be used for the chromium-doped catalyst of nitric oxide normal temperature and pressure catalytic oxidation.
Described chromium precursor is one in chromic nitrate, chromium chloride or its combination.
Described precipitating reagent is carbonic hydroammonium, urea, NaOH, potassium hydroxide, ammoniacal liquor, the one in sodium carbonate or its combination.
Described nitrate is cerous nitrate, ferric nitrate, manganese nitrate, zinc nitrate, nitric acid molybdenum, nitric acid tungsten, cobalt nitrate, the one in nickel nitrate or its combination, described chloride is cerium chloride, iron chloride, manganese chloride, zinc chloride, molybdenum chloride, tungsten chloride, cobalt chloride, one in nickel chloride or its combination, described hydroxide is NaOH, the one in potassium hydroxide or its combination.
A kind of by method of the present invention prepare for the chromium-doped catalyst of nitric oxide normal temperature and pressure catalytic oxidation.
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 during described catalyst application is 5-100 ppm NO, and all the other are air.
Reactivity is evaluated: take above-mentioned the obtained catalyst of 1.0 g and start to pass into reaction gas in environment temperature, carry out active testing, total flow is >=720 ml/min (STP).
Described catalyst is used for NO catalytic oxidation, also can keep long-time stability at normal temperature adsoption catalysis oxidation NO.25 DEG C can make NO efficient oxidation, and conversion ratio reaches 70%, and within 1000 minutes that investigate, conversion ratio still remains on more than 50%.
Catalyst of the present invention has the feature of the high and long-time stable of reactivity, can greatly catalytic oxidation NO, makes it Efficient Conversion.This not only achieves room-temperature catalytic oxidation NO and reacts, and carries out normal temperature elimination to it, and can keep higher conversion ratio for a long time, stable.Catalyst raw material of the present invention is easy to get, and technique is simple, has good application prospect.
Accompanying drawing explanation
Fig. 1 is the NO catalytic oxidation Activity Results of the embodiment of the present invention 1,2,3,4 Kaolinite Preparation of Catalyst.
Fig. 2 is the NO catalytic oxidation Activity Results of the embodiment of the present invention 5,6 Kaolinite Preparation of Catalyst.
Detailed description of the invention
Following instance is used for illustrating in greater detail the present invention, but the present invention is not limited to this.
Embodiment 1
:
Deposition sedimentation method prepares a kind of chrome catalysts of element doping, taking chromic nitrate 10.0 g is dissolved in 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 DEG C of drying 12 h, 300 DEG C of calcining 4 h, obtain catalyst.Doping is 5%.
Take above-mentioned the obtained catalyst of 1.0 g to start 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:
Compared with embodiment 1, unlike adding cerous nitrate, unclassified stores consumption is identical with embodiment 1 with operating condition.
Embodiment 3:
Compared with embodiment 1, unlike adding copper nitrate, unclassified stores consumption is identical with embodiment 1 with operating condition
Embodiment 4:
Compared with embodiment 1, be cobalt nitrate unlike precipitating reagent, unclassified stores consumption is identical with embodiment 1 with operating condition.
Embodiment 5:
Deposition sedimentation method prepares the chrome catalysts of multi-element doping, taking chromic nitrate 10.0 g is dissolved in 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 DEG C of drying 12 h, 300 DEG C of calcining 4 h, obtain catalyst.Doping is 5%, Fe:Ce=1:1.
Take above-mentioned the obtained catalyst of 1.0 g to start 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:
Compared with embodiment 5, be ferric nitrate and cobalt nitrate unlike what add, unclassified stores consumption is identical with embodiment 5 with operating condition.
The result of above embodiment 1,2,3,4 is shown in Fig. 1, and as can see from Figure 1, doped chemical is different, will affect the activity of the catalytic oxidation NO of the chrome catalysts of doping, and Fe doping shows good activity.The catalytic oxidation NO conversion ratio of the chrome catalysts of deposition-precipitation method preparation doping is 70%, within investigated 1000 minutes, conversion ratio still remains on more than 50%, catalyst of the present invention improves activity and the stability of normal temperature and pressure catalytic oxidation NO, for producing with the amplification of rear catalyst, provide extraordinary actual application prospect.
The result of above embodiment 5,6 is shown in Fig. 2, and as can see from Figure 2, codope element is different, and have slight impact to the activity of the catalytic oxidation NO of the chrome catalysts of codope, Fe Ce codope shows good activity.The catalytic oxidation NO conversion ratio that deposition-precipitation method prepares the chrome catalysts of codope is 55%, within investigated 1000 minutes, conversion ratio still remains on more than 30%, catalyst of the present invention improves activity and the stability of normal temperature and pressure catalytic oxidation NO, for producing with the amplification of rear catalyst, provide extraordinary actual application prospect.
Claims (3)
1. the preparation method for the chromium-doped catalyst of nitric oxide normal temperature and pressure catalytic oxidation, it is characterized in that, prepared by employing deposition-precipitation method, taking chromium presoma 10.0 grams is dissolved in 100 ml deionized water, add nitrate, one in chloride or its combination, doping is 0.5 ~ 5%, DEG C stirring in normal temperature ~ 100, add precipitating reagent, pH is regulated to be after 3 ~ 10, stir 5 ~ 8 hours, filter, washing, 60 ~ 150 DEG C of dryings 12 hours, calcine 2 ~ 6 hours for 100 ~ 700 DEG C, obtain and be used for the chromium-doped catalyst of nitric oxide normal temperature and pressure catalytic oxidation,
Described chromium presoma is one in chromic nitrate, chromium chloride or its combination;
Described precipitating reagent is carbonic hydroammonium, urea, NaOH, potassium hydroxide, ammoniacal liquor, the one in sodium carbonate or its combination;
Described nitrate is cerous nitrate, ferric nitrate, manganese nitrate, zinc nitrate, nitric acid molybdenum, nitric acid tungsten, cobalt nitrate, the one in nickel nitrate or its combination, described chloride is cerium chloride, iron chloride, manganese chloride, zinc chloride, molybdenum chloride, tungsten chloride, cobalt chloride, the one in nickel chloride or its combination.
2. one kind by method according to claim 1 prepare for the chromium-doped catalyst of nitric oxide normal temperature and pressure catalytic oxidation.
3. described in claim 2 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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| CN201210536192.9A CN103028413B (en) | 2012-12-13 | 2012-12-13 | Chromium-doped catalyst for catalytic oxidation of nitric oxide at normal temperature and pressure, as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN103394344B (en) * | 2013-07-15 | 2015-07-08 | 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 |
| CN104801314B (en) * | 2015-04-22 | 2017-03-29 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of low concentration nitric oxide room temperature eliminates the preparation of ferrum cerium Mn catalyst |
| 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 |
| 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 |
| CN110833831B (en) * | 2019-11-07 | 2022-11-01 | 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 |
| 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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| CN102423628A (en) * | 2010-08-10 | 2012-04-25 | 通用汽车环球科技运作有限责任公司 | Base metal oxides oxidation catalyst |
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