CN103801286B - A kind of loaded chromium oxide catalyst and preparation thereof and application - Google Patents
A kind of loaded chromium oxide catalyst and preparation thereof and application Download PDFInfo
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- CN103801286B CN103801286B CN201210455792.2A CN201210455792A CN103801286B CN 103801286 B CN103801286 B CN 103801286B CN 201210455792 A CN201210455792 A CN 201210455792A CN 103801286 B CN103801286 B CN 103801286B
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Abstract
The present invention relates to a kind of loaded chromium oxide catalyst and preparation thereof and application. A kind of loaded chromium oxide catalyst, with the one in aluminium oxide, silicon oxide, manganese oxide, titanium oxide or its be combined as carrier, one in chromic nitrate, Chlorizate chromium or its combination are as chromium source, adopt deposition-precipitation method or the loaded chrome catalysts being active component with chromium that infusion process prepares. It is applied in the normal temperature and pressure catalytic oxidation reaction of NO, it is possible to be NO at normal temperature and pressure catalytic oxidation NO2, it is thus achieved that high conversion ratio, and high activity and high stability can be kept for a long time. Catalyst raw material of the present invention is easy to get, and technique is simple, has fabulous application prospect.
Description
Technical field
The present invention relates to a kind of catalyst and preparation thereof and application, more particularly to a kind of loaded chromium oxide catalyst and preparation thereof and application, it is possible at ambient temperature catalytic oxidation NO, it is thus achieved that high conversion ratio, and can remain stable for for a long time.
Background technology
Along with the fast development of Urbanization in China, Urban vehicles poputation is also constantly soaring. The environmental pollution caused therewith is also day by day serious, national motor vehicle emission pollutant 5143.3 ten thousand tons in 2009, wherein carbon monoxide 4018.8 ten thousand tons, Hydrocarbon 482.2 ten thousand tons, nitrogen oxides 583.3 ten thousand tons, particulate matter 59.0 ten thousand tons. Visible nitrogen oxides (NOx) is exactly wherein one of major pollutants.
The NOx end-of-pipe control technology of scale of input engineer applied is mainly selective catalytic reduction, vehicle tail gas triple effect catalysis method (China YouSe Acta Metallurgica Sinica, 2004,14:347-353), absorption method (Fuel at present; Vol.76; No.6, pp.543-548,1997; AppliedCatalysisB:Environmental125 (2012) 398 408; ChemicalEngineeringJournal116 (2006) 25 37), absorption process (ChemicalEngineeringJournal, 192 (2012) 99 104; Fuel96 (2012) 440 445; CatalysisToday, June2012, doi:10.1016/j.cattod.2012.05.050; CatalysisToday126 (2007) 400 405). NOx concentration in dusty gas, up to more than 80%, can be dropped to 100-200ppm from about 1000ppm by elimination factor, 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 adsorbed, due in the NOx of motor vehicle emission, more than 90% is NO, and NO is supercritical fluid more than room temperature, and its physisorption is very weak, therefore, NOx clean-up effect is still poor, and adsorbs and do not change the existence of NO, by it from adsorbent after desorption, or to face the governing problem of NO, can not thoroughly solve NOx pollution problem. And the absorption process reacted by acid-base neutralization is simple, and pollutant NOx can be converted into commercial product, turn waste into wealth, great application prospect. The use premise of this method is, is NO by NO partial oxidation2, obtain NO2Accounting is heavily the NOx gas of 50-60%, is so just conducive to absorbing efficiently. Current NO catalytic oxidation temperature is generally 200oMore than C, room temperature almost cannot make it convert. The NO catalytic oxidation material of longer use is NACF, but inefficient. Therefore in the present invention, we have developed a kind of loaded containing chromium catalysis material, not only achieve the efficiently catalyzing and oxidizing of NO normal temperature and pressure, and longer stability can be kept, be report at present in the supported catalyst for NO catalytic oxidation active in the good catalysis material of stability.
Summary of the invention
In order to overcome the deficiencies in the prior art, the present invention provides a kind of loaded chromium oxide catalyst and preparation thereof and application.
A kind of loaded chromium oxide catalyst, it is characterized in that, with the one in aluminium oxide, silicon oxide, manganese oxide, titanium oxide or its be combined as carrier, one in chromic nitrate, Chlorizate chromium or its combination are as chromium source, adopt deposition-precipitation method or the loaded chrome catalysts being active component with chromium that infusion process prepares.
The preparation method of a kind of loaded chromium oxide catalyst, it is characterised in that described loaded chrome catalysts adopts deposition-precipitation method, or infusion process preparation obtains, particularly as follows:
(1) deposition-precipitation method: weigh chromium precursor 10.0 grams and be dissolved in 100 ml deionized water, add support powder, stir in room temperature～100 DEG C, add precipitant, regulating PH is after 3～9, stir 5～8 hours, filter, washing, 60～150 DEG C dry 12 hours, calcining 2～6 hours for 100～700 DEG C, obtain the loaded chromium oxide catalyst of normal temperature and pressure catalytic oxidation, theoretical loading is the 1～300% of carrier;
(2) infusion process: weigh chromium precursor, wiring solution-forming, add oxide support powder, theoretical loading is the 1～300% of carrier, stirring, stands 12～72 hours, and 100 DEG C dry 12～72 hours, calcine 2～6 hours at 100～700 DEG C, obtain the loaded chromium oxide catalyst of normal temperature and pressure catalytic oxidation.
Described chromium precursor is the one in chromic nitrate, Chlorizate chromium or its combination.
Described precipitant is ammonium hydrogen carbonate (NH4HCO3), carbamide, sodium hydroxide, potassium hydroxide, ammonia, sodium carbonate (Na2CO3) in one or its combination.
Described support powder is that aluminium oxide, silicon oxide, manganese oxide, titanium oxide etc. are single-phase or one in mixed phase oxide or its combination.
A kind of loaded chromium oxide catalyst is in the nitric oxide production application of ambient temperature catalytic oxidation.
The reaction atmosphere during application of described catalyst is 5-100ppmNO, and all the other are air.
Reactivity is evaluated: weighing catalyst above-mentioned obtained for 1.0g and start to pass into reaction gas in ambient temperature, carry out active testing, total flow is >=720ml/min (STP).
Described catalyst is used for NO catalytic oxidation, can aoxidize NO can remaining stable over property in room temperature adsoption catalysis.20oC can make NO efficient oxidation, and conversion ratio reaches 80%, and within 400 minutes investigated, conversion ratio stills remain in more than 50%.
Catalyst of the present invention has the high feature with long-time stable of reactivity, it is possible to catalytic oxidation NO greatly, so as to Efficient Conversion. This not only achieves room-temperature catalytic oxidation NO reaction, and it is carried out room temperature elimination, 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 that the embodiment of the present invention 1,2,3,4,5 prepares 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 loaded chromium oxide catalyst, weighs chromic nitrate 10.0g and is dissolved in 100ml deionized water, and whipping temp is ambient temperature, adds alumina support powder, after adding precipitant ammonia 14ml, stirs 6h, filters, washing, and 100oC dries 12h, and 300oC calcines 4h, it is thus achieved that catalyst.
Weighing catalyst above-mentioned obtained for 1.0g to start to pass into reaction gas at room temperature, carry out active testing, gas group becomes 15ppmNO, and all the other are air, and total flow is >=720ml/min (STP).
Embodiment 2:
Compared with embodiment 1, the difference is that support powder is silicon oxide, unclassified stores consumption is identical with embodiment 1 with operating condition.
Embodiment 3:
Compared with embodiment 1, the difference is that support powder is manganese oxide, unclassified stores consumption is identical with embodiment 1 with operating condition
Embodiment 4:
Compared with embodiment 1, the difference is that precipitant is titanium oxide, unclassified stores consumption is identical with embodiment 1 with operating condition.
Embodiment 5:
Infusion process prepares loaded chromium oxide catalyst, weighs 10g chromic nitrate, is dissolved in 5g deionized water, adds 3g alumina support powder, stirs, and room temperature stands 12h, and 100oC dries 12h, and 300oC calcines 4h, it is thus achieved that catalyst.
Weighing catalyst above-mentioned obtained for 1.0g to start to pass into reaction gas at room temperature, carry out active testing, gas group becomes 15ppmNO, and all the other are air, and total flow is >=720ml/min (STP).
The result of above example 1,2,3,4,5 is shown in Fig. 1, it will be noted from fig. 1 that carrier is different, it will affect the activity of the catalytic oxidation NO of loaded chromium oxide catalyst, aluminium oxide has gone out good activity as carriers display, and deposition-precipitation method is better than infusion process. It is 80% that aluminium oxide prepared by deposition-precipitation method supports the catalytic oxidation NO conversion ratio of chrome catalysts, within 400 minutes investigated, conversion ratio is still maintained at more than 50%, catalyst of the present invention improves activity and the stability of normal temperature and pressure catalytic oxidation NO, produce for the amplification with rear catalyst, it is provided that extraordinary actual application prospect.
Claims (1)
1. the preparation method of a loaded chromium oxide catalyst, described catalyst with the one in aluminium oxide, silicon oxide, manganese oxide, titanium oxide or its be combined as carrier, one in chromic nitrate, Chlorizate chromium or its combination are as chromium source, adopt deposition-precipitation method, or infusion process prepares the loaded chrome catalysts being active component with chromium; It is characterized in that, described loaded chrome catalysts adopts deposition-precipitation method, or infusion process preparation obtains, particularly as follows:
(1) deposition-precipitation method: weigh chromium precursor 10.0 grams and be dissolved in 100 ml deionized water, add support powder, stir in room temperature～100 DEG C, add precipitant, regulating pH is after 3～9, stir 5～8 hours, filter, washing, 60～150 DEG C dry 12 hours, calcining 2～6 hours for 100～700 DEG C, obtain the loaded chromium oxide catalyst of normal temperature and pressure catalytic oxidation, theoretical loading is the 1～300% of carrier;
(2) infusion process: weigh chromium precursor, wiring solution-forming, add oxide support powder, theoretical loading is the 1～300% of carrier, stirring, stands 12～72 hours, and 100 DEG C dry 12～72 hours, calcine 2～6 hours at 100～700 DEG C, obtain the loaded chromium oxide catalyst of normal temperature and pressure catalytic oxidation;
Described chromium precursor is the one in chromic nitrate, Chlorizate chromium or its combination;
Described precipitant is ammonium hydrogen carbonate NH4HCO3, carbamide, sodium hydroxide, potassium hydroxide, ammonia, sodium carbonate Na2CO3In one or its combination;
Described support powder is that aluminium oxide, silicon oxide, manganese oxide, titanium oxide be single-phase or one in mixed phase oxide or its combination.
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| CN110508309B (en) * | 2019-08-15 | 2022-02-11 | 江苏理工学院 | Carbon nitride supported chromium oxide catalyst and preparation method and application thereof |
| CN111662215A (en) * | 2020-07-27 | 2020-09-15 | 重庆化工职业学院 | Process for preparing carbamates |
| CN113289616A (en) * | 2021-06-17 | 2021-08-24 | 南京工业大学 | Catalyst for NO oxidation and preparation method thereof |
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| CN102716737A (en) * | 2012-03-26 | 2012-10-10 | 南京理工大学 | Preparation of catalyst with carrier of ceria-zirconia solid solution and application of catalyst in NOx removal |
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| CN102716737A (en) * | 2012-03-26 | 2012-10-10 | 南京理工大学 | Preparation of catalyst with carrier of ceria-zirconia solid solution and application of catalyst in NOx removal |
Non-Patent Citations (2)
| Title |
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| Control of NOx emissions from diesel engine by selective catalytic reduction(SCR) with urea;Joon Hyun Baik等;《Topics in Catalysis》;20040731;第30/31卷(第1-4期);第37-41页 * |
| Selective Catalytic Reduction of NO on Cr-Mn Mixed Oxide at Low Temperature;CHEN Zhihang等;《Advanced Materials Research》;20110512;第233-235卷;第1564-1567页 * |
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