CN103357397B - Cerium-oxide-accelerated chrome-oxide-supported manganese catalyst, and preparation and application thereof - Google Patents
Cerium-oxide-accelerated chrome-oxide-supported manganese catalyst, and preparation and application thereof Download PDFInfo
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- CN103357397B CN103357397B CN201310267806.2A CN201310267806A CN103357397B CN 103357397 B CN103357397 B CN 103357397B CN 201310267806 A CN201310267806 A CN 201310267806A CN 103357397 B CN103357397 B CN 103357397B
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Abstract
The invention relates to a cerium-oxide-accelerated chrome-oxide-supported manganese catalyst, and preparation and application thereof. According to the catalyst, a precipitation process is utilized to prepare the chrome oxide support, an impregnation process is utilized to prepare the cerium-oxide-accelerated chrome oxide support, and a deposition precipitation process is utilized to prepare the cerium-oxide-accelerated chrome-oxide-supported manganese catalyst; when the catalyst is used in normal-temperature normal-pressure catalytic oxidation reaction of NO, NO can be catalytically oxidated into NO2 under the condition of normal temperature and pressure; and thus, the catalyst can obtain very high conversion rate, and can remain high activity and high stability for a long time. The catalyst provided by the invention has the advantages of accessible raw materials and simple technique, and has wide application prospects.
Description
Technical field
The chromium oxide that the present invention relates to the promotion of a kind of cerium oxide supports Mn catalyst and Synthesis and applications thereof, mainly for the NO catalytic oxidation in environment, is applicable to the elimination of air pollutants, has application prospect in depollution of environment field.
Background technology
Along with urbanization process is fast-developing, tunnel, parking lot, the hemi-closure spaces such as colliery get more and more. in these hemi-closure spaces, because gravity-flow ventilation is restricted, the tail gas of vehicular emission cannot be discharged in time, pollutant is caused to be accumulated, air pollution is serious, nitrogen oxide (NOx) is one of main pollutant, the annual discharge capacity from national motor vehicle is up to 583.3 ten thousand tons, more than 90% is nitric oxide (NO). the most frequently used NOx Treatment process is selective catalytic reduction (SCR), but the method needs to have higher reaction temperature (being generally 200-400 DEG C), the normal temperature that cannot be applicable to NOx in hemi-closure space is eliminated. adopt gas phase selective catalytic oxidation, namely be first NO by NO catalytic oxidation
2, then carry out absorption elimination with alkali lye, be a kind of effective method.
That the current report of the catalysis material for NO room-temperature catalytic oxidation is maximum is NACF (ACF), the NACF of alkali lye coating or doping vario-property or active carbon (AC) etc., such catalysis material has larger specific area, more pore structure and surface functional group, react mainly through reoxidizing NO absorption, but the NO produced
2be easy to be adsorbed on carbon surface, along with NO
2increase, Adsorption reduces, activity decrease, cannot meet actual application demand, is therefore badly in need of developing that a kind of activity is high, the room-temperature catalytic oxidation NO catalyst of good stability, has efficient stable, for the purification of hemi-closure space internal contamination thing.
Have document to show, catalyst of transition metal oxide has good catalytic oxidation activity. and Xu Li jasmine detailed examination Mn, Ce, Co, Fe tetra-kinds of transition metal oxides, find at 250-350
oin C temperature range, NO catalytic oxidation activity order is MnOx > CoOx > CuOx > FeOx, when temperature is lower than 200
oduring C, the very low. Tang Xiaolong of the catalytic oxidation activity of these four kinds of catalyst etc. have investigated a series of catalyst of transition metal oxide, find 200 DEG C time, Mn, Cr and Co 3 kinds of metal oxides have good NO catalytic oxidation activity, conversion ratio is even higher than 50%. Luwen's matter and Teng Tang Shang Zhi etc., study preparation parameter (the Cu/Mn ratio of copper-manganese catalyst in great detail, sintering temperature and time etc.) impact on NO catalytic oxidation performance, find that copper-manganese catalyst has good NO catalytic oxidation performance in room temperature, as Cu:Mn=1:6, NO conversion ratio can reach 100%.Research finds, at 300 DEG C, compared to CuO, ZnO and V
2o
5catalyst, Cr
2o
3show good NO catalytic oxidation activity. separately have report cerium oxide to have stronger storage and release oxygen performance, impact is related to the carrying out of oxygen reaction, detailed have studied cerium oxide to TiO
2the Cr-Ce catalyst supported, for the impact of NO catalytic oxidation, has investigated Cr/Ce mol ratio, activity component load quantity, kind of carrier, the impact of the factors such as sintering temperature, finds that Cr/Ce mol ratio is 2:1, Cr
2o
3and CeO
2total load amount is 30% of vehicle weight, the amorphous Cr-Ce/TiO that 350 DEG C of roastings obtain
2catalyst has best conversion ratio 80.7%. to sum up at 330 DEG C, visible chromium, manganese, and cerium has NO catalytic oxidation activity respectively, but nobody reports that the chromium oxide of cerium oxide promotion supports Mn catalyst and has NO catalytic oxidation performance at normal temperatures.
Summary of the invention
In order to overcome the deficiencies in the prior art, the chromium oxide that the invention provides the promotion of a kind of cerium oxide supports Mn catalyst and Synthesis and applications.
The chromium oxide that a kind of cerium oxide promotes supports the preparation method of Mn catalyst, it is characterized in that, the precipitation method prepare chromium oxide carrier, and infusion process prepares the chromium oxide carrier that cerium oxide promotes, then the chromium oxide adopting deposition-precipitation method to obtain cerium oxide promotion supports Mn catalyst; Wherein chromium source, cerium source and manganese source are nitrate.
Described chromium oxide carrier adopts precipitation method preparation to obtain, and is specially:
Chromic nitrate 10.0 grams is dissolved in 100 ml deionized water, in stirring at normal temperature, adds precipitating reagent ammoniacal liquor, regulates after PH=8, stirs 5-8 hour, filters, washing, and 60-150 DEG C of drying 12 hours, 100-700 DEG C of calcining 2-6 hour, obtains chromium oxide carrier.
Described employing infusion process prepares the chromium oxide carrier that cerium oxide promotes, is specially:
Take 3.0 grams of deionized waters, add cerous nitrate, then add 5.0 grams, the chromium oxide carrier of above-mentioned acquisition, stir, room temperature leaves standstill 12 hours, and put into 60-150 DEG C of oven drying 12 hours, at 200-700 DEG C of roasting 2-6 hour, the theoretical loading of cerium is 10% of carrier.
The chromium oxide that described employing deposition-precipitation method prepares cerium oxide promotion supports Mn catalyst, is specially:
Take 100 ml deionized water, add manganese nitrate, 5.0 grams, the chromium oxide carrier that the cerium oxide adding above-mentioned acquisition again promotes, 60 DEG C of stirrings, dropwise add precipitating reagent ammoniacal liquor, regulate PH=7-9, stir 5 hours, rear filtration washing, put into 60-150 DEG C of oven drying 12 hours, at 100-700 DEG C of roasting 2-6 hour, the theoretical loading of manganese is the 10-50% of carrier.
The chromium oxide that cerium oxide promotes supports a Mn catalyst, and it is characterized in that, according to above-mentioned arbitrary claim, method prepares.
The chromium oxide that cerium oxide promotes supports Mn catalyst for nitric oxide catalytic oxidation, in the nitric oxide production application of normal temperature and pressure efficiently catalyzing and oxidizing.
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 1.0g 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, can obtain good NO catalytic oxidation activity at room-temperature catalytic oxidation NO.25 DEG C can make NO efficient oxidation, and conversion ratio reaches 85%.
The chromium oxide that the invention provides the promotion of a kind of cerium oxide for NO room-temperature catalytic oxidation supports Mn catalyst and Synthesis and applications thereof.Raw material adopts nitrate (chromic nitrate, manganese nitrate, cerous nitrate etc.) as precursor, the precipitation method are adopted to prepare chromium oxide carrier, rear employing infusion process prepares the chromium oxide carrier that cerium oxide promotes, the chromium oxide adopting deposition-precipitation method to prepare cerium oxide promotion again supports Mn catalyst, and it is active that this catalyst has good NO catalytic oxidation at normal temperatures and pressures.
Catalyst of the present invention adopts cerium oxide as promoter, and improve and store oxygen performance, accelerating oxidation chromium supports Mn catalyst at room-temperature catalytic oxidation NO, can have the advantages that reactivity is high.This achieve room-temperature catalytic oxidation NO to react, can eliminate NO at normal temperature.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 and embodiment 2 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:
Intermediate processing prepares chromium oxide carrier, and take chromic nitrate 10.0g and be dissolved in 100ml deionized water, whipping temp is environment temperature, adds precipitating reagent ammoniacal liquor and regulates PH=8, stir 5h, filter, washing, 100 DEG C of dry 12h, 400 DEG C of calcining 4h, obtain chromium oxide carrier.
Adopt infusion process to prepare the chromium oxide carrier of cerium oxide promotion, be specially:
Infusion process:
Take 3.0g deionized water, add cerous nitrate, then add the chromium oxide carrier 5.0g of above-mentioned acquisition, stir, room temperature leaves standstill 12h, puts into 100
oc oven drying 12h is 10% of carrier at the theoretical loading of 400 DEG C of roasting 4h. ceriums.
The chromium oxide adopting deposition-precipitation method to prepare cerium oxide promotion supports Mn catalyst, is specially:
Deposition-precipitation method:
Take 100ml deionized water, add manganese nitrate, the chromium oxide carrier 5.0g that the cerium oxide adding above-mentioned acquisition again promotes, 60 DEG C of stirrings, dropwise add precipitating reagent ammoniacal liquor, regulate PH=8, stir 5h, rear filtration washing, puts into 100 DEG C of oven drying 12h, is 30% of carrier at the theoretical loading of 300 DEG C of roasting 4h. manganese.
Take above-mentioned the obtained catalyst of 1.0g 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, the theoretical loading unlike manganese is 50%, and unclassified stores consumption is identical with embodiment 1 with operating condition.
Embodiment 3:
Compared with embodiment 1, the theoretical loading unlike manganese is 80%, and unclassified stores consumption is identical with embodiment 1 with operating condition.
The result of above embodiment 1,2,3 is shown in Fig. 1, as can see from Figure 1, adopt the chromium oxide that cerium oxide is prepared as promoter, support manganese, NO catalytic oxidation maximum conversion reaches 100%, support 50-80% manganese, NO catalytic oxidation conversion ratio is almost identical, and catalyst of the present invention utilizes cerium oxide to store oxygen performance, improves the activity that chromium oxide supports Mn catalyst normal temperature and pressure catalytic oxidation NO, for producing with the amplification of rear catalyst, provide extraordinary actual application prospect.
Claims (3)
1. the chromium oxide of a cerium oxide promotion supports the preparation method of Mn catalyst, it is characterized in that, the precipitation method prepare chromium oxide carrier, and infusion process prepares the chromium oxide carrier that cerium oxide promotes, then the chromium oxide adopting deposition-precipitation method to obtain cerium oxide promotion supports Mn catalyst; Wherein chromium source, cerium source and manganese source are nitrate;
Described chromium oxide carrier adopts precipitation method preparation to obtain, and is specially:
Chromic nitrate 10.0 grams is dissolved in 100 ml deionized water, in stirring at normal temperature, adds precipitating reagent ammoniacal liquor, regulates after PH=8, stirs 5-8 hour, filters, washing, 60-150 DEG C of drying 12 hours, and 100-700 DEG C of calcining 2-6 hour, obtains chromium oxide carrier;
Described employing infusion process prepares the chromium oxide carrier that cerium oxide promotes, is specially:
Take 3.0 grams of deionized waters, add cerous nitrate, then add 5.0 grams, the chromium oxide carrier of above-mentioned acquisition, stir, room temperature leaves standstill 12 hours, and put into 60-150 DEG C of oven drying 12 hours, at 200-700 DEG C of roasting 2-6 hour, the theoretical loading of cerium is 10% of carrier;
The chromium oxide that described employing deposition-precipitation method prepares cerium oxide promotion supports Mn catalyst, is specially:
Take 100 ml deionized water, add manganese nitrate, 5.0 grams, the chromium oxide carrier that the cerium oxide adding above-mentioned acquisition again promotes, 60 DEG C of stirrings, dropwise add precipitating reagent ammoniacal liquor, regulate PH=7-9, stir 5 hours, rear filtration washing, put into 60-150 DEG C of oven drying 12 hours, at 100-700 DEG C of roasting 2-6 hour, the theoretical loading of manganese is the 10-50% of carrier.
2. the chromium oxide that cerium oxide promotes supports a Mn catalyst, and it is characterized in that, method prepares according to claim 1.
3. the chromium oxide that cerium oxide promotes according to claim 2 supports Mn catalyst for nitric oxide catalytic oxidation, in the nitric oxide production application of normal temperature and pressure efficiently catalyzing and oxidizing.
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