CN102319573B - Simple and convenient preparation method of copper-manganese compound oxide monolithic catalyst - Google Patents
Simple and convenient preparation method of copper-manganese compound oxide monolithic catalyst Download PDFInfo
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- CN102319573B CN102319573B CN 201110195027 CN201110195027A CN102319573B CN 102319573 B CN102319573 B CN 102319573B CN 201110195027 CN201110195027 CN 201110195027 CN 201110195027 A CN201110195027 A CN 201110195027A CN 102319573 B CN102319573 B CN 102319573B
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- monolithic catalyst
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- compound oxide
- manganese compound
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Abstract
The invention discloses a simple and convenient preparation method of a copper-manganese compound oxide monolithic catalyst, belonging to the technical field of catalytic technologies. The preparation method comprises the following steps of: mixing pseudoboehmite, urea, a surfactant, metal nitrate and deionized water; adjusting the pH value to 1.5-3 with nitric acid; stirring to obtain integral sol slurry which has high flowability, is uniform and stable and contains active metal salts; soaking a dichroite honeycomb carrier which is pretreated by acid etching into the slurry for 1-3 minutes; drying at 80-150 DEG C for 0.5-3 hours; and baking at 400-800 DEG C for 2-10 hours to obtain the monolithic catalyst. When used for catalyzing combustion and purification of xylene organic waste gases, the prepared monolithic catalyst has high catalytic activity. Meanwhile, the preparation method of the monolithic catalyst has the advantages of simple and convenient process, firm adhesion of active matters, low cost, contribution to industrial mass production, wide application prospect, and the like.
Description
Technical field
The present invention relates to a kind of easy integral catalyzer preparation method, specifically a kind of simple and convenient process for preparing of the copper-manganese compound oxide monolithic catalyst that purifies for organic waste gas catalytic combustion.
Background technology
Integral catalyzer is the integrated catalyst that many narrow parallel channels proper alignment are arranged, and usually is comprised of integral carrier, coating and active component three parts.Integral carrier is the basic framework of catalyst, common honeycomb ceramic carrier and metallic carrier two classes; Coating is used for increasing the specific area of catalyst, can also strengthen the adhesion property of load active component on integral carrier simultaneously, and itself also has certain catalytic activity some coating; Active component is the key component of integral catalyzer, can provide reaction required catalytic active site.Owing to have the advantages such as bed pressure drop is low, catalytic efficiency is high, enlarge-effect is little, integral catalyzer has been widely used in many chemical fields in recent years, such as heterogeneous reaction of vehicle exhaust and industrial organic exhaust gas catalytic combustion, natural gas catalytic combustion, NOx SCR and some organic syntheses etc., become in the current heterogeneous catalysis field one of the most potential research direction.
Catalytic combustion is a kind of organic waste-gas purification treatment technology of practical simplicity, and this technology is that organic molecule is converted into harmless carbon dioxide and water at catalyst surface effect generation deep oxidation.Catalytically-active materials adopts noble metal, nonmetal oxide or the mixture of the two mostly.CN101138728B relates to metallic oxide mixture catalyzer of a kind of cleaning organic waste gas and preparation method thereof such as patent.This catalyst is strengthened pretreated cordierite honeycomb ceramic as carrier take nitric acid, on carrier once the active oxidation aluminized coating of property cerium-carrying lanthanum Zr mixed oxide modification with contain the active component of Multimetal oxide mixture, prepared catalyst has the advantages such as the high and initiation temperature of catalytic combustion efficient is low to organic exhaust gas such as benzene,toluene,xylene and polycyclic aromatic hydrocarbons.
Along with the extensive use of integral catalyzer in fields such as organic waste gas catalytic combustion purifications, its demand is increasing, therefore is badly in need of solving the easy production problem of large-scale.Two-step method is adopted in the preparation of relevant integral catalyzer at present usually, namely applies first one deck γ-Al on honeycomb ceramic carrier
2O
3The isoreactivity coating, and then by impregnating process supported copper manganese isoreactivity component.This preparation process is more loaded down with trivial details, develop for this reason a kind of not only had high activity but also integral catalyzer easy and simple to handle significant.
Summary of the invention
Technical problem:The object of the invention is to for deficiencies such as present integral catalyzer preparation process are complicated, active material adhesion stability on integral carrier is lower, a kind of simple and convenient process for preparing of the copper-manganese compound oxide monolithic catalyst that purifies for organic waste gas catalytic combustion is provided.
Technical scheme:The preparation method of easy copper-manganese compound oxide monolithic catalyst of the present invention is: boehmite, urea, surfactant, metal nitrate and deionized water are mixed, wherein calculate by weight:
Boehmite 15～30 wt%
Urea 6～36 wt%
Surfactant 1～15 wt%
Copper nitrate 1.8～5.8 wt%
Manganese nitrate 2.0～6.5 wt%
Deionized water 30～60 wt%,
Be 1.5～3 with the nitre acid for adjusting pH value, stirring make have good fluidity, uniform and stable, the integrated colloidal sol slurries that contain active metal salt, then the pretreated cordierite honeycomb carrier of acid etching is soaked wherein 1～3 min, behind 80～150 ℃ of drying 0.5～3 h, 400～800 ℃ of roasting 2～10 h, make integral catalyzer again.
Described surfactant is one or more among cationic CTAB, anionic SDBS, nonionic Tween20 or the nonionic Tween80.
Beneficial effect:Integral catalyzer preparation method's of the present invention preparation technology is simple, and prepared organic waste gas catalytic combustion catalyst has the advantages such as function admirable, mechanical stability be high, cheap.
The specific embodiment
It is matrix that the prepared integral catalyzer of the present invention adopts cordierite honeycomb ceramic carrier, is coated with γ-Al at its duct inner surface
2O
3Coating and Cu-Mn complex oxide active component.Alumina load amount (with respect to the initial mass of ceramic monolith) is 15.1 ~ 23.5 wt%, and copper manganese mol ratio is 1:1 in the Cu-Mn complex oxide active component, and copper Mn oxide load capacity (with respect to the initial mass of ceramic monolith) is 2.05 ~ 3.20 wt%.
Integral catalyzer preparation method of the present invention is: first boehmite is mixed with into the integrated aluminium colloidal sol that contains active metal salt with metal nitrate etc., then adopts one-step method that it is coated on cordierite carrier, detailed process is as follows:
Boehmite powder, urea, surfactant, copper nitrate crystal, manganese nitrate solution (mass fraction is 50%) and deionized water are mixed, regulate acidity with nitric acid, vigorous stirring, make have good fluidity, uniform and stable, the integrated aluminium colloidal sol slurries that contain active metal salt; Then the pretreated honeycomb ceramic carrier of acid etching is immersed in slurries and takes out after a period of time, namely make integral catalyzer through processing such as air purge, drying and roastings.Surfactant is one or more among cationic CTAB, anionic SDBS, nonionic Tween20 or the nonionic Tween80.Slurry pH value is 1.5 ~ 3, and each constituent content (calculating by weight) is: boehmite 15～30 wt%, urea 6～36 wt%, surfactant 1～15 wt%, copper nitrate 1.8～5.8 wt%, manganese nitrate 2.0～6.5 wt%, water 30～60 wt%.The time that honeycomb ceramic carrier is immersed in the slurries is 1 ~ 3 min, and time of repose is 12 ~ 48 h; Baking temperature is 80 ~ 150 ℃, drying time 0.5 ~ 3 h; 400 ~ 800 ℃ of sintering temperatures, roasting time 2 ~ 10 h.
Below in conjunction with embodiment, specify the simple and convenient process for preparing of integral catalyzer, describe simultaneously the catalytic performance test result of prepared catalyst, but the present invention is not limited to these embodiment.
Embodiment 1
(1) preparation of slurries
Take by weighing 5 g boehmite powders, 2.5 g urea, 1.2476 g manganese nitrate solutions (mass fraction is 50%), 0.8434 g Cu (NO
3)
23H
2O, 1 ml CTAB and 1 ml Tween80 and add 12.5 ml deionized waters in the beaker of 80 ml, be placed on the magnetic stirring apparatus, with nitre acid for adjusting pH value to 2, vigorous stirring 1 h.Leave standstill 15 min, form have high solids content, good fluidity, uniform and stable, the aluminium colloidal sol slurries that contain active metal salt.
(2) coating of carrier
Cordierite honeycomb ceramic carrier (forms Mg
2Al
4Si
5O
18, specification is: f 8 ' 24 mm, square opening, hole density 400 cpsi, wall thickness 0.21 mm) in 50% acetum, soak 1 h, 600 ℃ of lower roasting 2 h after, immerse them in above-mentioned slurries and constantly stir and slowly take out after keeping 2 min.By air stream blow off in the duct and outer wall on unnecessary liquid, upset 1 h leaves standstill 12 h, then 110 ℃ of drying 1 h under room temperature, in 500 ℃ of roasting 2 h, namely make the integral catalyzer of alumina load amount 15.1 wt% and copper Mn oxide load capacity 2.05 wt% again.
(3) catalytic performance test
Evaluation response is to carry out in the normal pressure quartz tube reactor, take ortho-xylene as model organic exhaust gas thing.One road air (78.84 ml/min) passes into the bubbler that ortho-xylene is housed, and then with after another road air (121.16 ml/min) mixes, enters reactor.Bubbler temperature is controlled at 0 ℃, and the total flow of air is 200 ml/min, and corresponding overall reactor is amassed air speed (GHSV) and is about 10000 h
-1(with respect to whole integral catalyzer volume), the ortho-xylene volume fraction is about 1000 ppm in the reaction gas, tail gas gas-chromatography on-line analysis.The result shows that prepared integral catalyzer is 333 ℃ to the initiation temperature of ortho-xylene, and conversion temperature is 357 ℃ fully.
Embodiment 2
(1) preparation of slurries
Take by weighing manganese nitrate solution (mass fraction is 50%), the 0.8439 g Cu (NO of 5 g boehmites, 3 g urea, 1.2482 g
3)
23H
2O, 1.5 ml CTAB and 2 ml Tween80 and add 10 ml deionized waters in the beaker of 80 ml, be placed on the magnetic stirring apparatus, with nitre acid for adjusting pH value to 1.5, vigorous stirring 1 h.Leave standstill 15 min, form have high solids content, good fluidity, uniform and stable, the aluminium colloidal sol slurries that contain active metal salt.
(2) coating of carrier
The pretreated carrier cordierite ceramic of acid etching immersed in the above-mentioned slurries and constantly stir and slowly take out after keeping 1 min.By air stream blow off in the duct and outer wall on unnecessary liquid, upset 1 h leaves standstill 18 h, then 120 ℃ of drying 1 h under room temperature, 500 ℃ of roasting 3 h more namely make the integral catalyzer of alumina load amount 19.3 wt% and copper Mn oxide load capacity 2.63 wt%.
(3) catalytic performance test
By the evaluation method of implementing 1, this copper-manganese compound oxide monolithic catalyst is 321 ℃ to the initiation temperature of ortho-xylene, and conversion temperature is 338 ℃ fully.
Embodiment 3
(1) preparation of slurries
Take by weighing manganese nitrate solution (mass fraction is 50%), the 0.8430 g Cu (NO of 5 g boehmites, 2.5 g urea, 1.2475 g
3)
23H
2O, 2 ml SDBS and 2 ml Tween20 and add 10 ml deionized waters in the beaker of 80 ml, be placed on the magnetic stirring apparatus, with nitre acid for adjusting pH value to 1.5, vigorous stirring 1 h.Leave standstill 15 min, form have high solids content, good fluidity, uniform and stable, the aluminium colloidal sol slurries that contain active metal salt.
(2) coating of carrier
The pretreated carrier cordierite ceramic of acid etching immersed in the above-mentioned slurries and constantly stir and slowly take out after keeping 2 min.By air stream blow off in the duct and outer wall on unnecessary liquid, upset 1 h leaves standstill 24 h, then 150 ℃ of drying 2 h under room temperature, 500 ℃ of roasting 3 h more namely make the integral catalyzer of alumina load amount 19.9 wt% and copper Mn oxide load capacity 2.70 wt%.
(3) catalytic performance test
By the evaluation method of implementing 1, this copper-manganese compound oxide monolithic catalyst is 330 ℃ to the initiation temperature of ortho-xylene, and conversion temperature is 348 ℃ fully.
From the above embodiments, can find out when the prepared integral catalyzer of the present invention is used for xylene organic waste gas catalytic combustion purified treatment, under lower temperature, to have good catalytic activity.Simultaneously, integral catalyzer preparation technology of the present invention is simple.Because adopting base metal copper Mn oxide is main active component, causes the Catalyst Production cost greatly to reduce, be easy to promote, have broad application prospects, be conducive to suitability for industrialized production.
Claims (2)
1. the preparation method of an easy copper-manganese compound oxide monolithic catalyst is characterized in that: boehmite, urea, surfactant, metal nitrate and deionized water are mixed, wherein calculate by weight:
Boehmite 15～30 wt%
Urea 6～36 wt%
Surfactant 1～15 wt%
Copper nitrate 1.8～5.8 wt%
Manganese nitrate 2.0～6.5 wt%
Deionized water 30～60 wt%,
Be 1.5～3 with the nitre acid for adjusting pH value, stirring make have good fluidity, uniform and stable, the integrated colloidal sol slurries that contain active metal salt, then the pretreated cordierite honeycomb carrier of acid etching is soaked wherein 1～3 min, behind 80～150 ℃ of drying 0.5～3 h, 400～800 ℃ of roasting 2～10 h, make integral catalyzer again.
2. the preparation method of a kind of easy copper-manganese compound oxide monolithic catalyst according to claim 1 is characterized in that described surfactant is one or more among cationic CTAB, anionic SDBS, nonionic Tween20 or the nonionic Tween80.
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| CN 201110195027 CN102319573B (en) | 2011-07-13 | 2011-07-13 | Simple and convenient preparation method of copper-manganese compound oxide monolithic catalyst |
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| CN104445356B (en) * | 2014-10-30 | 2016-06-29 | 东南大学 | The preparation method of copper-containing metal composite oxides catalysis material |
| CN106378145B (en) * | 2016-11-18 | 2019-06-11 | 济南大学 | A kind of gaseous state hydrogen peroxide catalyst and its application |
| CN111744498B (en) * | 2020-05-25 | 2021-05-25 | 广州广钢气体能源股份有限公司 | Manganese-copper composite oxide catalyst and preparation method and application thereof |
| CN112569960A (en) * | 2020-12-17 | 2021-03-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of weak crystallization monolithic manganese oxide catalyst and product thereof |
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| CN101138728B (en) * | 2007-10-19 | 2010-06-23 | 华南理工大学 | Metallic oxide mixture catalyzer for purifying organic waste gas and method of preparing the same |
| CN101474566B (en) * | 2009-01-05 | 2012-02-01 | 东南大学 | Integral catalyst for catalytic combustion of toluol exhaust gas and preparation method thereof |
| CN101982239B (en) * | 2010-09-30 | 2012-05-30 | 南京工业大学 | Preparation method of composite metal oxide catalyst for catalytic combustion |
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