CN103657632B - A kind of base extraction monoblock type chromium oxide catalyst and preparation method and application - Google Patents
A kind of base extraction monoblock type chromium oxide catalyst and preparation method and application Download PDFInfo
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- CN103657632B CN103657632B CN201310613496.5A CN201310613496A CN103657632B CN 103657632 B CN103657632 B CN 103657632B CN 201310613496 A CN201310613496 A CN 201310613496A CN 103657632 B CN103657632 B CN 103657632B
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Abstract
The present invention relates to a kind of base extraction monoblock type chromium oxide catalyst and preparation method and application, this catalyst adopts infusion process to be impregnated on inert carrier cordierite honeycomb ceramic by active component chromium, the specific area of integral catalyzer increases by the mode by base extraction after drying and roasting, change the chemical state of active component, add active sites, NO catalytic oxidation activity and long-time stability under raising normal temperature and pressure.Present invention process is simple, and raw material is easy to get, and achieves through engineering approaches application.
Description
Technical field
The present invention relates to the application of a kind of base extraction legal system for monoblock type chromium oxide catalyst, 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 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, and more than 90% is nitric oxide (NO). and integral catalyzer is the key realizing through engineering approaches NO purification.
The preparation method of integral catalyzer is generally divided into three kinds: 1) by the catalyst for preparing directly through extruded (USP 4912077); 2) on monolithic substrate (as molecular sieve, active carbon, aluminium oxide) through active constituent loading, obtain integral catalyzer after activation process, (USP 4631268,4657880); 3) through active constituent loading after applying active coating on chemically inert monoblock type material, activation process obtains integral catalyzer, as cordierite honeycomb ceramic, and honeycomb coal smoke carbon carrier etc.; Also can directly the catalysis material prepared be coated on monolithic substrate, then after activation process obtained (Catal Today 77 (2003): 419).Usually it is low to there is load capacity in the catalyst adopting above several method to prepare, and active component embeds, the problems such as specific area is low, thus makes the catalytic efficiency of integral catalyzer low.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of monoblock type chromium oxide catalyst and preparation method and application.
A preparation method for base extraction monoblock type chromium oxide catalyst, is characterized in that, comprise the following steps:
(1) there is the integral catalyzer preparation of chromium oxide coating: adopt infusion process preparation to have the integral catalyzer of chromium oxide coating;
Taking chromium precursor 100.0 grams is dissolved in 200 ml deionized water, in stirring at normal temperature, after being uniformly dissolved, pour on cordierite honeycomb ceramic carrier, repeatedly after dipping, 100 DEG C of dryings, 300 DEG C of roastings 4 hours, obtain the integral catalyzer with chromium oxide coating;
(2) base extraction legal system is for monoblock type chromium oxide catalyst:
Adopt the mode of excessive dipping, the integral catalyzer with chromium oxide coating of above-mentioned preparation is soaked in alkali lye, alkali lye PH=8-10, soak after 1-12 hour, put into 60-100 DEG C of oven drying after 12 hours, put into Muffle furnace 200-400 DEG C of roasting 2-6 hour, obtain alkali lye surface treatment monoblock type chromium oxide catalyst.
Described chromium precursor is chrome cake acid, or chromium chloride, and described alkali lye is ammoniacal liquor, potassium hydroxide, NaOH, the one in carbonic hydroammonium or its combination.
The monoblock type chromium oxide catalyst that a kind of preparation method of base extraction monoblock type chromium oxide catalyst prepares.
Base extraction monoblock type chromium oxide catalyst is used for nitric oxide catalytic oxidation, can maintain long-time stability at normal temperature and pressure efficiently catalyzing and oxidizing nitric oxide.
Reaction atmosphere during described catalyst application is 5-100 ppm NO, and all the other are air.
Reactivity is evaluated: the integral catalyzer of above-mentioned obtained 10*10*10cm is passed into reaction gas at ambient temperature, carries 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 and stability at room-temperature catalytic oxidation NO.Environment temperature can make NO efficient oxidation, and conversion ratio reaches more than 50%, and can keep the stability of more than 24h.
A kind of base extraction method is the object of the present invention is to provide to prepare monoblock type chromium oxide catalyst for NO room-temperature catalytic oxidation.Raw material adopts nitrate or chloride (chromic nitrate or chromium chloride etc.) as precursor, infusion process is adopted to be impregnated on inert carrier cordierite honeycomb ceramic by active component chromium, the specific area of integral catalyzer increases by the mode by base extraction after drying and roasting, change the chemical state of active component, NO catalytic oxidation activity and long-time stability under raising normal temperature and pressure.
Catalyst of the present invention adopts base extraction legal system to get everything ready the integral catalyzer of chromium oxide coating, increase the specific area of integral catalyzer, change the crystalline structure on surface, add active sites, improve and store NO performance, promote that monoblock type chromium oxide catalyst at room-temperature catalytic oxidation NO, can not only have the feature that reactivity is high, and long-time stability improves.This achieve room-temperature catalytic oxidation NO to react, can eliminate NO at normal temperature, achieve through engineering approaches application.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, embodiment 2, embodiment 3 and comparing embodiment 1 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.
realexecute example 1:
Infusion process preparation has the integral catalyzer of chromium oxide coating:
Taking chromic nitrate 100.0g is dissolved in 200ml deionized water, in stirring at normal temperature, after being uniformly dissolved, pours on cordierite honeycomb ceramic carrier, and repeatedly after dipping, 100 DEG C of dryings, 300 DEG C of roasting 4 h, obtain the integral catalyzer with chromium oxide coating.
Base extraction legal system is for monoblock type chromium oxide catalyst:
Adopt the mode of excessive dipping, the integral catalyzer with chromium oxide coating of above-mentioned preparation is soaked in alkali lye, in ammoniacal liquor, PH=8-10, after soaking 2h, puts into 100
oafter C oven drying 12 h, put into Muffle furnace 300 DEG C of roasting 4h, obtain catalyst.
The 10*10*10cm integral catalyzer of above-mentioned preparation is placed in reactor, and normal temperature passes into reaction gas, carries out active testing, and 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, be ammonium bicarbonate soln unlike alkali lye, unclassified stores consumption is identical with embodiment 1 with operating condition.
Embodiment 3:
Compared with embodiment 1, be KOH mixed solution unlike alkali lye, unclassified stores consumption is identical with embodiment 1 with operating condition.
Comparing embodiment 1:
Compared with embodiment 1, will without base extraction, the integral catalyzer with chromium oxide coating is directly used in the test of NO catalytic oxidation, and unclassified stores consumption is identical with embodiment 1 with operating condition.
Above embodiment 1, embodiment 2, the result of embodiment 3 and comparing embodiment 1 is shown in Fig. 1, as can see from Figure 1, adopt the monoblock type chromium oxide catalyst that base extraction legal system is standby, NO catalytic oxidation has higher conversion and reaches 80%, and stability maintenance is at more than 24h, catalyst of the present invention adopts base extraction legal system to get everything ready the integral catalyzer of chromium oxide coating, increase the specific area of integral catalyzer, change the crystalline structure on surface, add active sites, improve and store NO performance, promote that monoblock type chromium oxide catalyst can at room-temperature catalytic oxidation NO, not only there is the feature that reactivity is high, and long-time stability improves.This achieve room-temperature catalytic oxidation NO to react, can eliminate NO at normal temperature, achieve through engineering approaches application.
Claims (3)
1. a preparation method for base extraction monoblock type chromium oxide catalyst, is characterized in that, comprises the following steps:
(1) there is the integral catalyzer preparation of chromium oxide coating: adopt infusion process preparation to have the integral catalyzer of chromium oxide coating;
Taking chromium precursor 100.0 grams is dissolved in 200 ml deionized water, in stirring at normal temperature, after being uniformly dissolved, pour on cordierite honeycomb ceramic carrier, repeatedly after dipping, 100 DEG C of dryings, 300 DEG C of roastings 4 hours, obtain the integral catalyzer with chromium oxide coating;
(2) base extraction legal system is for monoblock type chromium oxide catalyst:
Adopt the mode of excessive dipping, the integral catalyzer with chromium oxide coating of above-mentioned preparation is soaked in alkali lye, alkali lye pH=8-10, soak after 1-12 hour, put into 60-100 DEG C of oven drying after 12 hours, put into Muffle furnace 200-400 DEG C of roasting 2-6 hour, obtain alkali lye surface treatment monoblock type chromium oxide catalyst;
Described chromium precursor is chrome cake acid, or chromium chloride, and described alkali lye is ammoniacal liquor, potassium hydroxide, NaOH, the one in carbonic hydroammonium or its combination.
2. the monoblock type chromium oxide catalyst for preparing of a kind of preparation method of base extraction monoblock type chromium oxide catalyst according to claim 1.
3. base extraction monoblock type chromium oxide catalyst described in claim 2 is used for a nitric oxide catalytic oxidation, can maintain long-time stability at normal temperature and pressure efficiently catalyzing and oxidizing nitric oxide.
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| CN103990448A (en) * | 2014-05-16 | 2014-08-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Monolithic chromium oxide catalyst as well as preparation method and application thereof |
| CN104014327B (en) * | 2014-05-28 | 2016-02-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Chromium oxide cellular integrated Catalysts and its preparation method and application |
| CN106076112B (en) * | 2016-06-03 | 2018-12-11 | 阳煤集团深州化工有限公司 | It is a kind of to remove N simultaneously2O and NOxMethod |
| CN107552047A (en) * | 2017-08-01 | 2018-01-09 | 上海纳米技术及应用国家工程研究中心有限公司 | Rare earth doped perovskite catalyst preparation methods of monoblock type Pd and products thereof and application |
| CN109364686A (en) * | 2018-12-19 | 2019-02-22 | 江苏瑞丰科技实业有限公司 | A kind of efficient deodorizing oxygen material |
| 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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| CN102000600B (en) * | 2010-11-17 | 2012-05-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Integral normal-temperature micro nitrogen oxide purification material and preparation method thereof |
| CN101983766B (en) * | 2010-11-29 | 2012-11-21 | 华东理工大学 | Integral catalyst for NOx selective catalytic reduction and preparation method thereof |
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