CN107570145A - Tin dope cerium zirconium compound oxide Supported Manganese denitrating catalyst preparation method and products thereof and application - Google Patents
Tin dope cerium zirconium compound oxide Supported Manganese denitrating catalyst preparation method and products thereof and application Download PDFInfo
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- CN107570145A CN107570145A CN201710999457.1A CN201710999457A CN107570145A CN 107570145 A CN107570145 A CN 107570145A CN 201710999457 A CN201710999457 A CN 201710999457A CN 107570145 A CN107570145 A CN 107570145A
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Abstract
The invention discloses a kind of tin dope cerium zirconium compound oxide Supported Manganese denitrating catalyst and its preparation method and application, by cerium, zirconium and tin presoma are added in deionized water, add citric acid while stirring, move in 70 90 DEG C of water-baths, be stirred continuously until that moisture evaporation produces thick colloid；Colloid is put into 80 120 DEG C of baking ovens, until foaming is complete, is ground into 40 60 mesh powders；Powder is calcined 46 hours at 400 600 DEG C, obtains yellow CeyZr1‑ySnzOnPowder；Manganese presoma is dissolved in deionized water, and is added dropwise to the Ce that 1.0 grams of steps 4 obtainyZr1‑ ySnzOnIn powder, dipping was put into 60 100 DEG C of baking ovens and dried 24 hours, be then calcined 35 hours at 300 500 DEG C, obtain xMn/Ce after 18 hoursyZr1‑ySnzOnCatalyst.For nitric oxide production SCR, the features such as conversion of nitric oxide gas rate can reach more than 90% at 150 DEG C, and the raw material of preparation is easy to get, and technique is simple, and cost is low.
Description
Technical field
The present invention relates to a kind of tin dope cerium zirconium compound oxide Supported Manganese denitrating catalyst preparation method and products thereof and
Using its product is applied to environmental contaminants NO SCR, has application prospect in depollution of environment field.
Background technology
NOx is major pollutants common in air, as primary pollution, any animals and plants can be caused a variety of direct
Harm, and NO can also be acted on by photochemical oxidation and is converted into NO2, nitric acid and nitrous acid are then formed, is the main of acid rain
Contributor.And NOx-SCR technologies are most widely used, the most ripe in the world and maximally effective gas denitrifying technologies, the technology
Middle use is most wide and efficiency highest catalyst is MoO3Or WO3The V of auxiliary2O5/TiO2Catalyst, reaction temperature window are generally
300-400 DEG C, in order to avoid Repeat-heating flue gas, it is necessary to after economizer, before desulfurization, dust arrester, thus produce
The a series of problem such as raw burn knot, poisoning, the service life of catalyst is reduced, based on above reason, people are by NOx-SCR skills
The research emphasis of art is placed on exploitation with high activity, the non-V of lower temperature2O5Catalyst, so as to which NOx-SCR reactors is straight
Connect and be configured at after dedusting and desulfurizer, reduce the harm of dust and sulphur to catalyst.
For middle low temperature NOx-SCR catalyst, active component is concentrated mainly on the research of manganese base, and cerium-zirconium composite oxide
Thing carrier has excellent oxygen storage capacity and redox ability, and in denitrating flue gas field by extensive concern, therefore, cerium zirconium is answered
It is very significant to close oxide serial carrier load manganese-based catalyst and carry out research in SCR denitration system.In general, cerium zirconium
The preparation of composite oxides is what is realized by adding the process such as precipitating reagent, regulation pH value, such as Chinese invention patent
CN105983403A discloses the application of a kind of cerium zirconium compound oxide, its preparation method and catalyst, from hydroxide etc.
As precipitating reagent, regulation pH value is in 7-13, and the precipitation to obtaining is aged, separation, and washing etc., above-mentioned technical process is more
Complexity, it is cumbersome.Chinese patent CN106745295A discloses a kind of purifying vehicle exhaust hydrogen-storing material, is made from absolute ethyl alcohol
For solvent, soluble cerium salt, soluble zirconates, soluble ferric iron salt and citric acid are formed into vitreosol, concentrated nitric acid is added and is formed
Yellow gel, then foam, grind, roasting etc., concentrated nitric acid has been used in preparation process, has caused the process dangerous index to carry significantly
Height is higher by the use of ethanol as solvent cost.
The content of the invention
It is complicated for catalyst preparation process in current technology, the problems such as hazard index height, present invention aims at：
A kind of tin dope cerium zirconium compound oxide Supported Manganese denitrating catalyst preparation method is provided.
Tin dope cerium zirconium compound oxide Supported Manganese denitration is made it is still another object of the present invention to provide the above method to urge
Agent product.
A further object of the present invention is to provide answering for above-mentioned tin dope cerium zirconium compound oxide Supported Manganese denitrating catalyst
With.
The object of the invention is achieved through the following technical solutions：A kind of tin dope cerium zirconium compound oxide Supported Manganese denitration catalyst
The preparation method of agent, the composition of catalyst is xMn/CeyZr1-ySnzOn, wherein, 2.5%≤x≤15%, x are mass fraction；0.1<
y<1, y is molal quantity；0≤z≤0.03, z are molal quantity；Preparation process need not add precipitating reagent, it is not necessary to adjust pH value, be not required to
Alcohol solvent is added, only using deionized water as exclusive solvents, is comprised the following steps that：
Step 1, cerium, zirconium and tin presoma are added in deionized water, are stirred at room temperature to being completely dissolved, add lemon while stirring
Lemon acid, continue to stir 1-3 hours, wherein, the molal quantity of citric acid is 1.0-1.2 times of metal total mole number；
Step 2, the solution of step 1 is moved in 70-90 DEG C of water-bath, is stirred continuously until that moisture evaporation produces thick colloid；
Step 3, the colloid of step 2 is put into 80-120 DEG C of baking oven, until foaming is complete, is ground into the powder of 40-60 mesh
End；
Step 4, the powder of step 3 is calcined 4-6 hours at 400-600 DEG C, obtains yellow CeyZr1-ySnzOnPowder；
Step 5, manganese presoma is dissolved in deionized water, and is added dropwise to the Ce that 1.0 grams of steps 4 obtainyZr1-ySnzOn
In powder, dipping was put into 60-100 DEG C of baking oven and dried 24 hours, be then calcined 3-5 hours at 300-500 DEG C after 18 hours,
Obtain xMn/CeyZr1-ySnzOnCatalyst.
Tin dope cerium zirconium compound oxide Supported Manganese denitrating catalyst preparation method of the present invention, using deionized water as only
One solvent, by stirring, foam, roasting, impregnating process can obtain tin dope cerium zirconium compound oxide Supported Manganese denitration and urge
Agent.Building-up process is simple, and raw material is easy to get, lower-cost technology of preparing, and the technology has to NOx-SCR denitrations preferably should
With.
On the basis of such scheme, described cerium precursor is cerous nitrate, one kind in ammonium ceric nitrate.
Described tin presoma is stannic chloride pentahydrate.
Described zirconium precursor body is zirconyl nitrate, one kind in zirconyl chloride.
Described manganese presoma is one kind in manganese nitrate or manganese acetate.
The present invention provides one kind and the load of tin dope cerium zirconium compound oxide is prepared by above-mentioned any one methods described
Manganese denitrating catalyst.
The present invention also provides a kind of tin dope cerium zirconium compound oxide Supported Manganese denitrating catalyst in NH3In-SCR reactions
Using specific reaction condition is as follows：25-300 DEG C of reaction temperature, the mL/min of total gas flow rate 500, reaction gas composition is 100-
500 ppm nitric oxides, 100-500 ppm ammonias, 3-10% oxygen, remaining is nitrogen.
The present invention has advantages below：
（1）Prepare the raw material used in catalyst be easy to get, only with conventional soluble salt, only with deionized water as unique molten
Agent.
（2）PH value need not be adjusted by soda acid etc. in preparation process, reduce danger, technique is relatively simple.
Brief description of the drawings
Fig. 1 is the NH of catalyst described in the embodiment of the present invention 1 ~ 53- SCR reactivity figures.Wherein circle is embodiment
1, equilateral triangle is embodiment 2, and del is embodiment 3, and pentagon is embodiment 4, and square is embodiment 5.
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
3.91 grams of cerous nitrates, 4.86 grams of zirconyl nitrates are weighed, 0.35 gram of butter of tin is added in 200 ml deionized waters, room
Temperature stirring adds 6.55 grams of citric acids while stirring to being completely dissolved, and continues stirring 1 hour, solution then is moved into 80 DEG C of water
In bath, it is stirred continuously until that moisture evaporation produces thick colloid, then colloid is put into 110 DEG C of baking ovens, until having foamed
Entirely, 40-60 mesh powders are ground into, then powder is calcined 4 hours at 500 DEG C, obtains yellow Ce0.3Zr0.7Sn0.03On
Powder.
0.2 gram of manganese acetate is dissolved in 0.8 ml deionized water, and is added dropwise to 0.5 gram of Ce0.3Zr0.7Sn0.03On
In powder, dipping was put into 80 DEG C of baking ovens and dried 24 hours, be then calcined 4 hours at 400 DEG C, obtain 10%Mn/ after 18 hours
Ce0.3Zr0.7Sn0.03OnCatalyst.
Embodiment 2
Compared with Example 1 compared with, unlike the quality of cerous nitrate be 6.51 grams, the quality of zirconyl nitrate is 3.47 grams, other
Operating condition is same as Example 1, obtains 10%Mn/Ce0.5Zr0.5Sn0.03OnCatalyst.
Embodiment 3
Compared with Example 1 compared with, unlike the quality of cerous nitrate be 9.12 grams, the quality of zirconyl nitrate is 2.08 grams, other
Operating condition is same as Example 1, obtains 10%Mn/Ce0.7Zr0.3Sn0.03OnCatalyst.
Embodiment 4
Compared with Example 1 compared with the difference is that the quality of cerous nitrate is 6.51 grams, nitric acid quality is that the quality of oxygen zirconium is 3.47
Gram, the quality of manganese acetate is 0.3 gram, and other operating conditions are same as Example 1, obtain 15%Mn/Ce0.5Zr0.5Sn0.03OnCatalysis
Agent.
Embodiment 5
Compared with Example 1 compared with the difference is that the quality of cerous nitrate is 6.51 grams, nitric acid quality is that the quality of oxygen zirconium is 3.47
Gram, the quality of butter of tin is 0 gram, and other operating conditions are same as Example 1, obtain 10%Mn/Ce0.5Zr0.5Sn0OnCatalysis
Agent.
Test case
Fresh obtained catalyst is respectively taken to be attached separately in crystal reaction tube.Test temperature takes one from 25-300 DEG C, every 25 DEG C
Individual test point, respectively kept for 10 minutes in each test point.Nitric oxide production conversion ratio is as shown in figure 1, it can be seen that work as
The mol ratio of cerium and zirconium is 1:When 1, obtained catalyst activity is optimal, at 150 DEG C, you can reaches more than 90%.
Claims (7)
1. a kind of preparation method of tin dope cerium zirconium compound oxide Supported Manganese denitrating catalyst, it is characterised in that catalyst
Form as xMn/CeyZr1-ySnzOn；2.5%≤x≤15%, x are mass fraction；0.1<y<1, y is molal quantity；0≤z≤0.03, z
For molal quantity；Preparation process need not add precipitating reagent, it is not necessary to adjust pH value, it is not necessary to alcohol solvent be added, only with deionization
Water comprises the following steps that as exclusive solvents：
Step 1, cerium, zirconium and tin presoma are added in deionized water, are stirred at room temperature to being completely dissolved, add lemon while stirring
Lemon acid, continue to stir 1-3 hours, wherein, the molal quantity of citric acid is 1.0-1.2 times of metal total mole number；
Step 2, the solution of step 1 is moved in 70-90 DEG C of water-bath, is stirred continuously until that moisture evaporation produces thick colloid；
Step 3, the colloid of step 2 is put into 80-120 DEG C of baking oven, until foaming is complete, is ground into the powder of 40-60 mesh
End；
Step 4, the powder of step 3 is calcined 4-6 hours at 400-600 DEG C, obtains yellow CeyZr1-ySnzOnPowder；
Step 5, manganese presoma is dissolved in deionized water, and is added dropwise to the Ce that 1.0 grams of steps 4 obtainyZr1-ySnzOn
In powder, dipping was put into 60-100 DEG C of baking oven and dried 24 hours, be then calcined 3-5 hours at 300-500 DEG C after 18 hours,
Obtain xMn/CeyZr1-ySnzOnCatalyst.
2. a kind of preparation method of tin dope cerium zirconium compound oxide Supported Manganese denitrating catalyst according to claim 1,
Characterized in that, described cerium precursor is cerous nitrate, one kind in ammonium ceric nitrate.
3. a kind of preparation method of tin dope cerium zirconium compound oxide Supported Manganese denitrating catalyst according to claim 1,
Characterized in that, described tin presoma is stannic chloride pentahydrate.
4. a kind of preparation method of tin dope cerium zirconium compound oxide Supported Manganese denitrating catalyst according to claim 1,
Characterized in that, described zirconium precursor body is zirconyl nitrate, one kind in zirconyl chloride.
5. a kind of preparation method of tin dope cerium zirconium compound oxide Supported Manganese denitrating catalyst according to claim 1,
Characterized in that, described manganese presoma is one kind in manganese nitrate or manganese acetate.
6. tin dope cerium zirconium compound oxide Supported Manganese denitration is prepared by claim 1-5 any one methods describeds in one kind
Catalyst.
7. tin dope cerium zirconium compound oxide Supported Manganese denitrating catalyst is in NH according to claim 63Answering in-SCR reactions
With, it is characterised in that specific reaction condition is as follows：25-300 DEG C of reaction temperature, the mL/min of total gas flow rate 500, reaction gas group
As 100-500 ppm nitric oxides, 100-500 ppm ammonias, 3-10% oxygen, remaining is nitrogen.
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| CN108704650A (en) * | 2018-06-22 | 2018-10-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of low temperature porous composite oxide denitrating catalyst and products thereof and application |
| CN110975920A (en) * | 2019-12-25 | 2020-04-10 | 福州大学 | Preparation method of nitrogen-doped grid macromolecule in-situ growth denitration sulfur-resistant catalyst |
| CN111729669A (en) * | 2020-06-28 | 2020-10-02 | 云南中烟工业有限责任公司 | Metal-loaded cerium-zirconium solid solution material, preparation method thereof and application of metal-loaded cerium-zirconium solid solution material in catalytic synthesis of carvone |
| CN112439408A (en) * | 2019-09-04 | 2021-03-05 | 有研稀土新材料股份有限公司 | Rare earth manganese-loaded cerium-zirconium composite compound, preparation method and catalyst |
| CN112439407A (en) * | 2019-09-04 | 2021-03-05 | 有研稀土新材料股份有限公司 | Core-shell structure rare earth manganese/cerium zirconium composite compound, preparation method and catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108704650A (en) * | 2018-06-22 | 2018-10-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of low temperature porous composite oxide denitrating catalyst and products thereof and application |
| CN112439408A (en) * | 2019-09-04 | 2021-03-05 | 有研稀土新材料股份有限公司 | Rare earth manganese-loaded cerium-zirconium composite compound, preparation method and catalyst |
| CN112439407A (en) * | 2019-09-04 | 2021-03-05 | 有研稀土新材料股份有限公司 | Core-shell structure rare earth manganese/cerium zirconium composite compound, preparation method and catalyst |
| CN112439407B (en) * | 2019-09-04 | 2022-05-10 | 有研稀土新材料股份有限公司 | Core-shell structure rare earth manganese/cerium zirconium composite compound, preparation method and catalyst |
| CN110975920A (en) * | 2019-12-25 | 2020-04-10 | 福州大学 | Preparation method of nitrogen-doped grid macromolecule in-situ growth denitration sulfur-resistant catalyst |
| CN110975920B (en) * | 2019-12-25 | 2021-04-27 | 福州大学 | Preparation method of nitrogen-doped grid macromolecule in-situ growth denitration sulfur-resistant catalyst |
| WO2021128814A1 (en) * | 2019-12-25 | 2021-07-01 | 福州大学 | Method for preparing denitration anti-sulfur catalyst grown in situ on nitrogen-doped grid macromolecules |
| CN111729669A (en) * | 2020-06-28 | 2020-10-02 | 云南中烟工业有限责任公司 | Metal-loaded cerium-zirconium solid solution material, preparation method thereof and application of metal-loaded cerium-zirconium solid solution material in catalytic synthesis of carvone |
| CN111729669B (en) * | 2020-06-28 | 2022-10-18 | 云南中烟工业有限责任公司 | Metal-loaded cerium-zirconium solid solution material, preparation method thereof and application of metal-loaded cerium-zirconium solid solution material in catalytic synthesis of carvone |
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