CN105289639B - A kind of lanthanum-carried Mn-powder ore type oxidation of nitric oxide catalyst of cobalt and preparation method - Google Patents
A kind of lanthanum-carried Mn-powder ore type oxidation of nitric oxide catalyst of cobalt and preparation method Download PDFInfo
- Publication number
- CN105289639B CN105289639B CN201510671623.6A CN201510671623A CN105289639B CN 105289639 B CN105289639 B CN 105289639B CN 201510671623 A CN201510671623 A CN 201510671623A CN 105289639 B CN105289639 B CN 105289639B
- Authority
- CN
- China
- Prior art keywords
- cobalt
- catalyst
- lanthanum
- nitrate
- mno
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a kind of lanthanum-carried Mn-powder ore type oxidation of nitric oxide catalyst of cobalt and preparation method, molecular formula is xCo/La1‑yCeyMnO3；2.5%≤x≤20%, x is mass fraction；0.1≤y≤0.3, y is molal quantity.Catalyst is used as active component and carrier using rare earth metal cerium doped lanthanum Mn-powder ore, and another active component cobalt is added, the conversion ratio of nitric oxide catalysis oxidation can reach more than 85%, and it is simple to prepare the technique used in catalyst, cost is relatively low, easily realizes industrialized production.
Description
Technical field
The present invention relates to a kind of preparation of the lanthanum-carried Mn-powder ore type catalyst of cobalt and in nitric oxide catalysis oxidation
Using there is application prospect in depollution of environment field.
Background technology
Nitric oxide（NO）Catalysis oxidation is nitrogen dioxide（NO2）, NO2It is anti-in catalysis as a kind of important intermediate product
Very crucial effect is played in answering.First, NO is oxidized to NO2It is nitrogen oxides storage reduction（NSR）The first step of technology is closed
Key reacts, and NO oxidations will be that the storage of nitrogen oxides and sequential reduction provide strong support.Secondly, at 200-300 DEG C
In temperature range, SCR（SCR）The reaction rate of technology is with NO in atmosphere2The increase of concentration and increase, adjust
Save NO in aerobic atmosphere2Content to SCR react it is particularly important.Finally, NO2As a kind of strong oxidizer, its presence can be effective
The initial temperature of soot oxidizing fire is reduced, the efficiency of carbon-smoke combustion conversion can be significantly improved.As can be seen here, NO oxidations are whole
Played a crucial role during individual removal of nitrogen oxide and subsequent reactions are played a driving role, therefore, research NO oxidation reactions are to whole
Individual exhaust gas aftertreatment system is all significant.
At present, loaded noble metal catalyst, metal oxide are mainly included applied to the NO all kinds of catalyst aoxidized
Catalyst etc..Noble metal catalyst is using Pt bases catalyst as representative, with high NO oxidation activities, when Pt is supported on different loads
When on body, NO catalysis oxidations are NO2Activity show larger difference.SiO is respectively adopted in Xue etc.2、γ-Al2O3And ZrO2Make
It is used for supporting Pt for carrier, finds the oxidation reaction for NO, the activity order of three kinds of Pt base catalyst is Pt/SiO2> Pt/γ-Al2O3> Pt/ZrO2。
Although noble metal catalyst activity is very high, its is expensive, and metal oxide catalyst overcomes well
This shortcoming, while having preferable catalytic oxidation activity again.The research such as Machida, Tikhomirov finds that Mn-Ce is combined
Oxide catalyst has preferable low temperature NO oxidation susceptibilities, and at 150 DEG C, conversion ratio is more than 60%, and Ce presence can be carried
High Mn dispersiveness.The research such as Lopez-Suarez finds SrTiCuO3Perovskite catalyst has preferable NO oxidation susceptibilities.
Ueda etc. has found (La0.7Ba0.3)(Fe0.776Nb0.194Pd0.03)O3Perovskite catalyst NO conversion rates of oxidation at 250 DEG C are
47%。
Usual perovskite only participates in NO oxidation as catalyst, and both using perovskite as active component in the present invention,
Again as carrier loaded another active component cobalt, the cerium dopping lanthanum Mn-powder ore catalyst of cobalt load is prepared, with general calcium
Titanium ore is compared, and largely improves oxidation susceptibility of the catalyst to NO, and compared with conventional precious metal catalyst, valency
Lattice are cheap, Stability Analysis of Structures, with good catalytic activity and high-temperature thermodynamics stability, the features such as service life is long, in tail gas
Catalytic purification field has good development prospect.
The content of the invention
The invention aims to overcome the deficiencies in the prior art, there is provided a kind of lanthanum-carried oxidation of Mn-powder ore type one of cobalt
The preparation method of nitrogen oxidation catalyst.
A kind of preparation method of the lanthanum-carried Mn-powder ore type oxidation of nitric oxide catalyst of cobalt, it is characterised in that catalyst
Molecular formula be xCo/La1-yCeyMnO3；2.5%≤x≤20%, x is mass fraction；0.1≤y≤0.3, y is molal quantity, including
Following steps：
The first step, the presoma containing lanthanum, cerium, manganese is mixed by catalyst molecule formula atomic ratio, deionized water is dissolved in
In, stirring to abundant dissolving；
Citric acid, in 70-90 DEG C of water-bath, be added in mixing salt solution by second step while stirring, and citric acid rubs
Your number is 1.0-1.2 times of metal total mole number；
3rd step, by resulting solution, heating stirring, will up to the thick colloid of moisture evaporation generation in 70-90 DEG C of water-bath
The colloid of gained is put into 80-120 DEG C of baking oven and dried 8-24 hours, takes out finely ground, is calcined 4-6 hours, obtains at 650-750 DEG C
La1-yCeyMnO3Black powder；
4th step, weighs a certain amount of cobalt precursor and is dissolved in deionized water, obtains cobalt liquor, then weigh the acquisition of the 3rd step
Black powder, be put into cobalt liquor, stand 8-12 hour, drying 8-24 hours is put into 60-80 DEG C of baking oven, then in 400-
600 DEG C are calcined 4-6 hours, obtain xCo/La1-yCeyMnO3Catalyst.
Described lanthanum presoma is lanthanum nitrate or lanthanum chloride；Described cerium precursor is cerous nitrate or ammonium ceric nitrate；It is described
Manganese presoma be manganese nitrate or manganese acetate；Described cobalt precursor is cobalt nitrate or cobalt chloride.
A kind of lanthanum-carried Mn-powder ore type catalyst of cobalt prepared by above-mentioned any one methods described.
The lanthanum-carried Mn-powder ore type catalyst of cobalt prepared by any one above-mentioned method is catalyzed oxygen in nitric oxide
Change the application in reaction, specific reaction condition is as follows：30-400 DEG C of reaction temperature, total gas flow rate 420mL/min, reaction gas group
As 200ppmNO, 5%O2And Balance Air N2。
In the present invention, catalyst is added another using rare earth metal cerium doped lanthanum Mn-powder ore as active component and carrier
One active component cobalt, the conversion ratio of nitric oxide catalysis oxidation can reach more than 85%.The technique prepared used in catalyst is simple,
Cost is relatively low, easily realizes industrialized production.
Brief description of the drawings
Fig. 1 is catalyst 10%Co/La described in the embodiment of the present invention 10.7Ce0.3MnO3X-ray diffractogram.
Embodiment
It is described in detail with reference to specific embodiment：The present embodiment is carried out lower premised on technical solution of the present invention
Implement, give detailed embodiment and specific operation process, but protection scope of the present invention is not limited to following embodiments.
Embodiment 1：
It will be placed in containing 2.27 grams of lanthanum nitrates, 1.30 grams of cerous nitrates, 3.57 grams of 50wt% manganese nitrates in deionized water, fully
80 DEG C are warming up to after dissolving, 4.62 grams of citric acids are added while stirring, continues to stir up to the thick colloid of moisture evaporation generation,
The colloid of gained is put into 110 DEG C of baking ovens and dried 12 hours, takes out finely ground, is calcined 5 hours, obtains at 700 DEG C
La0.7Ce0.3MnO3Black powder.Weigh 0.247 gram of cobalt nitrate to be dissolved in 1.50 ml deionized waters, then weigh 0.500 gram
Black powder is put into cobalt liquor, stands 10 hours, is put into 70 DEG C of baking ovens and is dried 12 hours, then small in 500 DEG C of roastings 5
When, understood through X-ray powder diffraction, the powder is 10%Co/La0.7Ce0.3MnO3Catalyst, as shown in Figure 1.
Embodiment 2：
Compared with Example 1 compared with, unlike the quality of cobalt nitrate be 0.123 gram, unclassified stores consumption and operating condition
It is same as Example 1, obtain 5%Co/La0.7Ce0.3MnO3Catalyst.
Embodiment 3：
Compared with Example 1 compared with, unlike the quality of cobalt nitrate be 0.494 gram, unclassified stores consumption and operating condition
It is same as Example 1, obtain 2.5%Co/La0.7Ce0.3MnO3Catalyst.
Embodiment 4：
Compared with Example 1 compared with, unlike the quality of cobalt nitrate be 0.494 gram, unclassified stores consumption and operating condition
It is same as Example 1, obtain 20%Co/La0.7Ce0.3MnO3Catalyst.
Embodiment 5：
Compared with Example 1 compared with, unlike the quality of lanthanum nitrate be 2.92 grams, the quality of cerous nitrate is 0.431 gram,
Unclassified stores consumption and operating condition are same as Example 1, obtain 10%Co/La0.9Ce0.1MnO3Catalyst.
Embodiment 6：
Compared with Example 1 compared with, unlike the quality of lanthanum nitrate be 2.60 grams, the quality of cerous nitrate is 0.870 gram,
Unclassified stores consumption and operating condition are same as Example 1, obtain 10%Co/La0.8Ce0.2MnO3Catalyst.
Test case：
Fresh obtained catalyst is respectively taken to be attached separately in crystal reaction tube.Test temperature is from 30-400 DEG C, in 100-400
Between DEG C, a test point is taken every 25 DEG C, is respectively kept for 10 minutes in each test point.The highest NO conversion rates of oxidation of catalyst
As shown in table 1.
The catalytic activity of the lanthanum-carried cerium Mn-powder ore catalyst of the cobalt of table 1
Claims (2)
1. a kind of preparation method of the lanthanum-carried Mn-powder ore type oxidation of nitric oxide catalyst of cobalt, it is characterised in that catalyst
Molecular formula is xCo/La1-yCeyMnO3；2.5%≤x≤20%, x is mass fraction；0.1≤y≤0.3, y is molal quantity, including such as
Lower step：
The first step, the presoma containing lanthanum, cerium, manganese is mixed by catalyst molecule formula atomic ratio, is dissolved in deionized water, stirs
Mix to abundant dissolving；
Citric acid, in 70-90 DEG C of water-bath, is added in mixing salt solution by second step while stirring, the molal quantity of citric acid
It is 1.0-1.2 times of metal total mole number；
3rd step, by resulting solution, heating stirring is up to the thick colloid of moisture evaporation generation in 70-90 DEG C of water-bath, by gained
Colloid be put into 80-120 DEG C of baking oven dry 8-24 hour, take out it is finely ground, 650-750 DEG C roasting 4-6 hours, obtain La1- yCeyMnO3Black powder；
4th step, weighs a certain amount of cobalt precursor and is dissolved in deionized water, obtains cobalt liquor, then weigh the black of the 3rd step acquisition
Color powder, is put into cobalt liquor, stands 8-12 hours, is put into 60-80 DEG C of baking oven and dries 8-24 hours, then in 400-600
DEG C roasting 4-6 hours, obtain xCo/La1-yCeyMnO3Catalyst；
Described lanthanum presoma is lanthanum nitrate or lanthanum chloride；Described cerium precursor is cerous nitrate or ammonium ceric nitrate；Described manganese
Presoma is manganese nitrate or manganese acetate；Described cobalt precursor is cobalt nitrate or cobalt chloride.
2. a kind of lanthanum-carried Mn-powder ore type catalyst of cobalt prepared by claim 1 methods described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510671623.6A CN105289639B (en) | 2015-10-16 | 2015-10-16 | A kind of lanthanum-carried Mn-powder ore type oxidation of nitric oxide catalyst of cobalt and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510671623.6A CN105289639B (en) | 2015-10-16 | 2015-10-16 | A kind of lanthanum-carried Mn-powder ore type oxidation of nitric oxide catalyst of cobalt and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105289639A CN105289639A (en) | 2016-02-03 |
| CN105289639B true CN105289639B (en) | 2017-08-11 |
Family
ID=55187858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510671623.6A Active CN105289639B (en) | 2015-10-16 | 2015-10-16 | A kind of lanthanum-carried Mn-powder ore type oxidation of nitric oxide catalyst of cobalt and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105289639B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106475105B (en) * | 2016-08-26 | 2019-02-05 | 西安交通大学 | A kind of double-perovskite type O composite metallic oxide catalyst and the preparation method and application thereof |
| CN107456977B (en) * | 2017-08-25 | 2019-10-01 | 中石化炼化工程（集团）股份有限公司 | Denitration reaction carbon monoxide-olefin polymeric and preparation method thereof and non-fully regeneration catalyzing cracking regenerating unit denitration method for flue gas |
| CN107570145A (en) * | 2017-10-24 | 2018-01-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Tin dope cerium zirconium compound oxide Supported Manganese denitrating catalyst preparation method and products thereof and application |
| CN108745368A (en) * | 2018-05-15 | 2018-11-06 | 昆明理工大学 | A kind of double-perovskite catalyst and the preparation method and application thereof |
| CN108745364A (en) * | 2018-05-15 | 2018-11-06 | 昆明理工大学 | A kind of preparation method of perovskite catalyst for catalytic oxidation NO |
| CN113145126B (en) * | 2021-03-11 | 2023-03-24 | 中国科学院城市环境研究所 | Composite catalyst and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034789C (en) * | 1992-01-24 | 1997-05-07 | 北京大学 | Metal composite oxide three-element purifying catalyst |
| CN1973962A (en) * | 2005-11-28 | 2007-06-06 | 中国科学院生态环境研究中心 | RE perovskite type catalyst for oxidizing NO |
| CN101385975A (en) * | 2007-09-14 | 2009-03-18 | 湖南中烟工业有限责任公司 | Composite metal oxides and preparation method and use thereof |
| CN101791550B (en) * | 2010-03-23 | 2012-03-21 | 昆明理工大学 | Catalyst for removing NO through efficient catalysis-oxidation under the condition of plasma |
-
2015
- 2015-10-16 CN CN201510671623.6A patent/CN105289639B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105289639A (en) | 2016-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105289639B (en) | A kind of lanthanum-carried Mn-powder ore type oxidation of nitric oxide catalyst of cobalt and preparation method | |
| CN104353455B (en) | Different crystalline phase zirconia catalyst of gold load and its preparation method and application | |
| CN108722431B (en) | A-site doped double perovskite catalyst and preparation method and application thereof | |
| CN107456964A (en) | For the extra specific surface area perovskite type composite oxide catalyst of hydrocarbon low-temperature oxidation and its preparation | |
| CN105289641B (en) | A kind of cobalt cerium-carrying manganese oxide catalyst and preparation method thereof | |
| CN107511147A (en) | A kind of high stability catalyst for catalytic oxidation and preparation method | |
| CN102580623B (en) | For the nitric oxide production method and system in oxidizing gas logistics | |
| JP4090547B2 (en) | Exhaust gas purification catalyst | |
| CN102989448A (en) | Preparation method and application of lanthanum-manganese perovskite type NOx removing catalyst | |
| JP2006346603A (en) | Catalyst composition | |
| CN101745405A (en) | Perovskite type composite oxide catalyst for purifying tail gas of internal combustion engine | |
| CN102600832A (en) | Combined catalyst for improving denitration performance and application thereof | |
| CN111672519A (en) | Noble metal-rare earth perovskite type integral three-way catalyst and preparation method thereof | |
| CN110773150B (en) | Composite oxide, preparation thereof and application of composite oxide as carbon particle combustion catalyst | |
| CN104959150B (en) | Preferential oxidation CO Au/CuO/CeO2‑TiO2Catalyst and preparation method | |
| CN101433837B (en) | SCR catalyst with wide active temperature windows as well as preparation method and use thereof | |
| CN101678276B (en) | Oxygen storage/release material and exhaust gas purifying catalyst comprising the same | |
| CN106732536A (en) | A kind of CeO2@MnOx low-temperature SCR catalyst for denitrating flue gas and preparation method and application | |
| JP2006346602A (en) | Catalyst composition | |
| CN102744064B (en) | Catalyst and its preparation for nitrogen oxide in automobile exhaust processing | |
| CN112958075A (en) | Ce-doped sodium-manganese composite oxide catalyst and preparation method and application thereof | |
| CN112642450A (en) | Preparation method of phosphorus-doped carbon aerogel supported manganese cerium catalyst | |
| CN106693954B (en) | A kind of manganese oxide load cerium oxide catalyst and preparation and application | |
| CN103212419A (en) | Preparation method and application of catalyst for treating acrylonitrile contained waste gas | |
| CN103599789A (en) | Perovskite-type catalyst for selective catalytic reduction of nitrogen oxides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |