CN101590412A - Loaded catalyst of a kind of low temperature elimination CO and its production and use - Google Patents
Loaded catalyst of a kind of low temperature elimination CO and its production and use Download PDFInfo
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- CN101590412A CN101590412A CNA2009101002573A CN200910100257A CN101590412A CN 101590412 A CN101590412 A CN 101590412A CN A2009101002573 A CNA2009101002573 A CN A2009101002573A CN 200910100257 A CN200910100257 A CN 200910100257A CN 101590412 A CN101590412 A CN 101590412A
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- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The present invention relates to loaded catalyst of a kind of low temperature elimination CO and its production and use, this catalyst is with α-MnO
2Be carrier, CuO is an active component, and the compound of K is an auxiliary agent, and CuO and K's is compound loaded at α-MnO
2On, the quality of CuO is α-MnO
21%～25% of quality, the amount of substance of K ion are α-MnO
210%～14% of amount of substance.This Preparation of catalysts method is with Cu salt, K salt and α-MnO
2Carrier evenly mixes in deionized water; Remove moisture content then; Dry this mixture; Roasting obtains catalyst of the present invention.Catalyst of the present invention can be eliminated CO under cryogenic conditions, and transforms the efficient height of CO at low temperatures, and catalyst amount is few.This Preparation of catalysts method is simple, and cost is low, and feasible degree is high.
Description
Technical field
The present invention relates to a kind of catalytic oxidation that is used for and eliminate loaded catalyst of atmosphere poisonous fume and its production and use, particularly loaded catalyst of a kind of low temperature elimination CO and its production and use.
Background technology
CO is a kind of inflammable, explosive, harmful gas pollutant.The CO oxidation reaction also is to eliminate especially one of the important reaction of purifying vehicle exhaust of air pollution.The catalyst activity component that traditional catalytic oxidation is eliminated CO mostly is a precious metals pt, Pd, and Rh etc. load on them on the metal oxide carrier.Though noble metal catalyst has very high catalytic activity to CO, noble metal catalyst exists easily poisons and expensive weak point, so people more and more pay close attention to dynamical non-precious metal catalyst, particularly catalyst of transition metal oxide.
The Cu base oxide catalyst is widely used in the research of CO catalytic oxidation under low temperature because cheap and catalytic performance is excellent.With the Cu base oxide catalyst of different carriers preparation, mutually far short of what is expected to the activity of CO oxidation, so the selection of carrier and method for preparing catalyst are very big to the performance impact of catalyst.Copper cerium, copper-aluminium catalyst and the Cu-Zr catalyst of CO eliminated in more being used to of research at present, all will be to the complete conversion temperature of CO more than 100 ℃, and also these catalyst at room temperature do not have activity substantially, are subjected to bigger restriction in actual applications.Therefore, it is catalyst based that necessity is developed the Cu with low temperature high activity, is applied to low-temperature oxidation and eliminates the CO field.
α-MnO
2Be a kind of nano material that is similar to the zeolite-type molecular sieves tunnel structure, its crystal structure is by the octahedra MnO on 2 * 2 common limits
6Chain constitutes, and interchain is by octahedra MnO
6The oxygen atom on summit links to each other and constitutes approximately
One-dimensional channels.Because α-MnO
2Structure be similar to zeolite molecular sieve, so be called the OMS-2 molecular sieve usually again.Because α-MnO
2Manganese ion (Mn with mixed valence
2+, Mn
3+And Mn
4+), a large amount of interlayer and pore passage structures that open wide are arranged, so α-MnO again
2Be applied in fields such as catalysis and electrode material as a kind of novel material.
Summary of the invention
The objective of the invention is the higher shortcoming of non-precious metal catalyst serviceability temperature, loaded catalyst of a kind of low temperature elimination CO and its production and use is provided at the existing CO of being used for elimination.
For realizing this goal of the invention, the technical solution used in the present invention is
The loaded catalyst of a kind of low temperature elimination CO is characterized in that: this catalyst is with α-MnO
2Be carrier, CuO is an active component, and the compound of K is an auxiliary agent, and CuO and K's is compound loaded at α-MnO
2On, the quality of CuO is α-MnO
21%～25% of quality, the amount of substance of K ion are α-MnO
210%～14% of amount of substance.
The compound of described K is K
2O or K salt and K
2The mixture of O.
The preparation method of the loaded catalyst of a kind of low temperature elimination CO is characterized in that: with Cu salt, K salt and α-MnO
2Carrier evenly mixes in deionized water; Remove moisture content then; Dry this mixture; Roasting obtains catalyst of the present invention.
Specifically comprise the steps:
(1) quality by CuO in the catalyst accounts for 1%～25% of catalyst gross mass, and the amount of K ionic species accounts for α-MnO
210%～14% of amount of substance takes by weighing Cu salt, K salt and α-MnO respectively
2
(2) with the Cu salt, K salt and the α-MnO that weigh up
2In deionized water, evenly mix, obtain suspension;
(3) above-mentioned suspension is removed moisture content under 60～120 ℃, dried 5～12 hours down for 40～120 ℃;
(4) with 300～500 ℃ of roastings of dried solid 2～10 hours, obtain finished catalyst.
Described mantoquita can be Cu (NO
3)
23H
2O, Cu (CH
3OO)
2H
2O, CuSO
45H
2O.
Described K salt is selected from KNO
3, CH
3OOK, K
2C
2O
4In a kind of.
The amount of water can be for 10～30 times of the gross mass of mixture, so that evenly disperse Cu salt, K salt and α-MnO
2Carrier.
The roasting of step (4) can be at N
2Or O
2Or carry out under the air atmosphere, but be not limited thereto.
If in the above-mentioned preparation process K salt decompose fully in the catalyst for K
2If O is incomplete decomposing then be K salt and K
2The mixture of O.
Raw material α-MnO that this catalyst of above-mentioned preparation is used
2Be that known substance can directly be buied from the market, also can be by document: R.N.DeGuzman, Y.F.Shen, E.J.Neth, S.L.Suib, C.L.O ' Young, S.T.Levine, J.M.Newsam, Chem.Mater.6 (1994) 815 described method preparations, its preparation process is:
(1) with MnSO
4H
2O is dissolved in the salpeter solution of pH=1, adds KMnO under stirring
4
(2) 100 ℃ of above-mentioned suspensions stir 24h down, then suspension are filtered, and constantly wash with distilled water, until filtrate pH=6.5-7.O, put into 120 ℃ in baking oven drier 12 hours down, promptly make α-MnO
2
The application of the catalyst of technique scheme in low temperature elimination CO.
α-MnO
2Having good oxygen storage capacity, oxidation-reduction quality and heat endurance, is a kind of oxidation catalyst carrier of excellent performance.The particularly short grained nanometer CuO of CuO is because the nano effect of its special electronic structure and granule CuO makes it have remarkable absorption and activation CO ability.Therefore, make CuO embed α-MnO by improving the preparation method with nano shape
2The surface, reinforced nano CuO and Mn
4+The coelectron effect, make the CO catalytic oxidation temperature reduce.K in the while catalyst
+Reduction plays a role to the CO catalytic oxidation temperature.Compared with prior art, the present invention has following advantage:
(1) compare with existing non-precious metal catalyst, catalyst of the present invention is easy to use, can eliminate CO under cryogenic conditions.
(2) compare with existing non-precious metal catalyst, catalyst of the present invention transforms the efficient height of CO at low temperatures, and catalyst amount is few.
(3) to compare the preparation method simple for this catalyst and the noble metal catalyst of present use, and cost is low, and feasible degree is high.
Description of drawings
Fig. 1 is the XRD figure spectrum of the catalyst of the present invention of different CuO content.Zero expression α-MnO among Fig. 1
2The XRD characteristic diffraction peak; ● the XRD characteristic diffraction peak of expression CuO; A, B, C, D, E curve are respectively α-MnO
2, embodiment 1, embodiment 2, embodiment 3, embodiment 4 catalyst the XRD analysis result;
Fig. 2 is the H of the catalyst of the present invention of different CuO content
2-TPR collection of illustrative plates.A, b, c, d curve are respectively the H of the catalyst of embodiment 1, embodiment 2, embodiment 3, embodiment 4 among Fig. 2
2-TPR analysis result;
The specific embodiment
The present invention may implement in many different modes, should not be construed as the scope that is restricted to the embodiment of mentioning herein:
Preparation α-MnO
2
Take by weighing 11.33g MnSO
4H
2O is dissolved in the salpeter solution of 40mL pH=1, takes by weighing 7.57gKMnO
4, the deionized water dissolving of adding 120mL; Again with KMnO
4Drips of solution is added to acid MnSO
4In the solution, the suspension that obtains was stirred 24 hours down at 100 ℃, then, precipitation is leached and wash repeatedly,, the solid after the washing is put into 120 ℃ of bakings of baking oven 12 hours, promptly make α-MnO to filtrate pH=6.5-7.0 with deionized water
2
Embodiment 1
Take by weighing 0.036g Cu (NO
3)
23H
2O, 0.126g KNO
3, 1.2g α-MnO
2Join in the 15mL deionized water, remove deionized water in 60 ℃, product is put into 40 ℃ of bakings of baking oven 12 hours, 300 ℃ of roastings 10 hours under air atmosphere then make catalyst, and the amount of K ionic species accounts for α-MnO in this catalyst
2Amount of substance 10%, the quality of CuO accounts for α-MnO
21% of quality.
Embodiment 2
Take by weighing 0.191g Cu (NO
3)
23H
2O, 0.138g KNO
3, 1.2g α-MnO
2Join in the 20mL deionized water, remove deionized water in 120 ℃, product is put into 80 ℃ of bakings of baking oven 10 hours, the following 400 ℃ of roastings of air atmosphere are 6 hours then, make catalyst, and the amount of K ionic species accounts for α-MnO in this catalyst
2Amount of substance 11%, the quality of CuO accounts for α-MnO
25.13% of quality.
Embodiment 3
Take by weighing 0.403g Cu (NO
3)
23H
2O, 0.151g KNO
3, 1.2g α-MnO
2Join in the 25mL deionized water, remove deionized water in 120 ℃, product is put into 100 ℃ of bakings of baking oven 8 hours, the following 500 ℃ of roastings of air atmosphere are 4 hours then, make catalyst, and the amount of K ionic species accounts for α-MnO in this catalyst
2Amount of substance 12%, the quality of CuO accounts for α-MnO
210.26% of quality.
Embodiment 4
Take by weighing 0.640g Cu (NO
3)
23H
2O, 0.163g KNO
3, 1.2g α-MnO
2Join in the 25mL deionized water, remove deionized water in 120 ℃, product is put into 120 ℃ of bakings of baking oven 5 hours, the following 500 ℃ of roastings of air atmosphere are 2 hours then, make catalyst, and the amount of K ionic species accounts for α-MnO in this catalyst
2Amount of substance 13%, the quality of CuO accounts for α-MnO
215.38% of quality.
Embodiment 5
Take by weighing 0.906g Cu (NO
3)
23H
2O, 0.176g KNO
3, 1.2g α-MnO
2Join in the 25mL deionized water, remove deionized water in 120 ℃, product is put into 120 ℃ of bakings of baking oven 6 hours, the following 500 ℃ of roastings of air atmosphere are 2 hours then, make catalyst, and K ionic species amount accounts for α-MnO in this catalyst
2Amount of substance 14%, the quality of CuO accounts for α-MnO
225% of quality.
Embodiment 6
According to the method identical with embodiment 4, different is, with 0.529g Cu (CH
3OO)
2H
2O replaced C u (NO
3)
23H
2O.
Embodiment 7
According to the method identical with embodiment 4, different is to use 0.011g CH
3OOK replaces KNO
3
Embodiment 8
According to the method identical with embodiment 4, different is to use N
2Roasting replaces air roasting.
Embodiment 9
According to the method identical with embodiment 4, different is not add K salt.
Prepared catalyst carries out the XRD sign in the foregoing description 1～4
Carry out on the X ' of PANalytical company Pert PRO MPD type X-ray diffractometer, LASER Light Source is a Cu K alpha ray, tube voltage 40kV, tube current 40mA, the sweep limits of catalyst conventional structure analysis is 10～90 °, and scanning step is 0.03 °, time of staying 8s.The XRD figure spectrum is seen Fig. 1, and as can be seen from Figure 1, catalyst of the present invention has only the characteristic peak that just occurs CuO when CuO content is 10%; These declaratives CuO is that the form with high dispersive exists.
Catalyst prepared in the foregoing description 1～4 carries out H
2-TPR characterizes
The redox property H of catalyst
2-TPR characterizes.Reducing gases consists of H
25%, N
2Balance, gas flow rate are 30mL/min, and the catalyst loading amount is 15mg.H
2-N
2Gaseous mixture uses after first deoxidation is dewatered again, with 10 ℃ of min
-1Heating rate rise to 700 ℃ from room temperature, detect H by the thermal conductance detection cell
2Consumption.H
2-TPR collection of illustrative plates is seen Fig. 2, and as can be seen from Figure 2, an ownership all appears in catalyst of the present invention about 180 ℃ be granule CuO and α-MnO
2The peak of reduction, this is that other similar catalysts institutes does not have, this also illustrates owing to granule CuO and α-MnO
2Interaction make that the required oxygen species of catalytic reaction become more active in the catalyst.
Application examples
With the application of catalyst prepared in the above embodiment of the present invention 1～9 in eliminating CO, be reflected at fixed bed and carry out, control CO concentration is 1vol%.Catalyst amount is 200mg, and reaction condition is: O
2=1vol%, N
2As balance gas, the volume ratio total flow is 40ml/min.The results are shown in Table 1, the data from table 1 as can be known, catalyst of the present invention have a higher CO oxidation activity.The CO conversion ratio is that 90% reaction temperature all is lower than 100 ℃, and oxidation still has 50% conversion ratio to embodiment 6 catalyst to CO under 28 ℃.
The CO oxidation activity of table 1 catalyst
Annotate: T
20, T
50, T
90Be respectively that the CO conversion ratio is the reaction temperature of 20%, 50% and 90% correspondence
Claims (7)
1, the loaded catalyst of a kind of low temperature elimination CO is characterized in that: this catalyst is with α-MnO
2Be carrier, CuO is an active component, and the compound of K is an auxiliary agent, and CuO and K's is compound loaded at α-MnO
2On, the quality of CuO is α-MnO
21%～25% of quality, the amount of substance of K ion are α-MnO
210%～14% of amount of substance.
2, the loaded catalyst of low temperature elimination CO according to claim 1 is characterized in that: the compound of described K is K
2O or K salt and K
2The mixture of O.
3, the preparation method of the loaded catalyst of a kind of low temperature elimination CO is characterized in that: comprise the steps:
(1) quality by CuO in the catalyst is α-MnO
21%～25% of quality, the amount of K ionic species are α-MnO
210%～14% of amount of substance takes by weighing Cu salt, K salt and α-MnO respectively
2
(1) with the Cu salt, K salt and the α-MnO that weigh up
2In deionized water, evenly mix, obtain suspension;
(2) above-mentioned suspension is removed moisture content under 60～120 ℃, dried 5～12 hours down for 40～120 ℃;
(3) with 300～500 ℃ of roastings of dried solid 2～10 hours, obtain finished catalyst.
4, preparation method according to claim 3 is characterized in that: described Cu salt is selected from Cu (NO
3)
23H
2O, Cu (CH
3OO)
2H
2O, CuSO
45H
2A kind of among the O.
5, preparation method according to claim 3 is characterized in that: described K salt is selected from KNO
3, CH
3OOK, K
2C
2O
4In a kind of.
6, preparation method according to claim 3 is characterized in that: the roasting of step (4) is at N
2Or O
2Or carry out under the air atmosphere.
7, the application of the described catalyst of claim 1 in low temperature elimination CO.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101002573A CN101590412B (en) | 2009-07-02 | 2009-07-02 | Supported catalyst for eliminating CO at low temperature, preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101002573A CN101590412B (en) | 2009-07-02 | 2009-07-02 | Supported catalyst for eliminating CO at low temperature, preparation method and application thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101590412A true CN101590412A (en) | 2009-12-02 |
| CN101590412B CN101590412B (en) | 2011-06-29 |
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109579032A (en) * | 2018-12-13 | 2019-04-05 | 重庆工商大学 | A kind of method of the copper-based catalyst CO completely burned of bi-component |
| CN111744498A (en) * | 2020-05-25 | 2020-10-09 | 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 |
| CN114669191A (en) * | 2022-03-31 | 2022-06-28 | 中国科学院生态环境研究中心 | Manganese copper ore material and application thereof in removing carbon monoxide at room temperature |
| CN114832832A (en) * | 2022-06-06 | 2022-08-02 | 武汉理工大学 | Copper doped alpha-MnO 2 -110 catalyst, preparation method and application thereof |
-
2009
- 2009-07-02 CN CN2009101002573A patent/CN101590412B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109579032A (en) * | 2018-12-13 | 2019-04-05 | 重庆工商大学 | A kind of method of the copper-based catalyst CO completely burned of bi-component |
| CN111744498A (en) * | 2020-05-25 | 2020-10-09 | 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 |
| CN114669191A (en) * | 2022-03-31 | 2022-06-28 | 中国科学院生态环境研究中心 | Manganese copper ore material and application thereof in removing carbon monoxide at room temperature |
| CN114832832A (en) * | 2022-06-06 | 2022-08-02 | 武汉理工大学 | Copper doped alpha-MnO 2 -110 catalyst, preparation method and application thereof |
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| Publication number | Publication date |
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| CN101590412B (en) | 2011-06-29 |
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Application publication date: 20091202 Assignee: Jinhua Lun Catalyst Technology Co., Ltd. Assignor: Zhejiang Normal University Contract record no.: 2014330000186 Denomination of invention: Supported catalyst for eliminating CO at low temperature, preparation method and application thereof Granted publication date: 20110629 License type: Exclusive License Record date: 20140522 |
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