CN103990451A - Simple preparation method of efficient cerium tungsten oxide catalyst - Google Patents
Simple preparation method of efficient cerium tungsten oxide catalyst Download PDFInfo
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- CN103990451A CN103990451A CN201410232031.XA CN201410232031A CN103990451A CN 103990451 A CN103990451 A CN 103990451A CN 201410232031 A CN201410232031 A CN 201410232031A CN 103990451 A CN103990451 A CN 103990451A
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- oxide catalyst
- tungsten oxide
- cerium
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Abstract
The invention discloses a preparation method of a cerium tungsten oxide catalyst, and the cerium tungsten oxide catalyst is used in a occasion that ammonia is used for selectively catalyzing and reducing nitrous oxides. The preparation method comprises the following steps of mixing a cerium source and tungstate solids, grinding to obtain ground solids, and directly calcining the ground solids, so as to obtain the cerium tungsten oxide catalyst. According to the preparation method, non-toxic and innocuous raw materials are adopted, a simple and easy method is adopted to prepare the cerium based oxide catalyst with the excellent catalytic performance, and the catalyst is suitable for being used in nitrogen oxide catalyzing and purifying devices by taking diesel exhaust as moving sources and coal-fired power plant smoke as stationary sources represented.
Description
Technical field
The present invention discloses a kind of method for preparing catalyst, and particularly a kind of preparation method of the cerium tungsten oxide catalyst for catalytic cleaning nitrogen oxide, belongs to field of material preparation.
Background technology
Nitrogen oxide (NO
x, mainly refer to NO and NO
2) be a kind of important atmosphere pollution, can produce directly harm to health especially respiratory system, and can cause the important environmental problems such as acid rain, photochemical fog and gray haze.Research shows, China NO
xdischarge capacity rapid development, 2010 annual emissions have reached 26.1Mt, and steam power plant, industry and traffic are main NO
xemission source.According to prediction, if China can not effectively carry out power plant's denitration, the NO of following 5 to 10 years
xdischarge capacity will increase sharply, and if can not effectively control the NO of heavy-duty diesel vehicle
xdischarge will cause in future very serious consequence for a long time.Therefore, effectively control NO
xdischarge is the Major Strategic Demand of China.
NH
3selective Catalytic Reduction of NO
x(NH
3-SCR) be a kind of moving source NO that the stationary source denitrating flue gas that coal-burning power plant is representative and the diesel vehicle of take are representative that is widely used in take
xthe technology of emission control.The NH of industrial applications
3-SCR catalyst is mainly with V
2o
5as active component, with WO
3as catalyst aid, with TiO
2as carrier, the V of preparation
2o
5-WO
3/ TiO
2catalyst.Because the active component vanadium in this catalyst is poisonous, and this catalyst has poor heat stability, high temperature N
2o growing amount greatly, is easily oxidized SO
2for SO
3etc. problem, although China also allows production and the use of catalytic component based on vanadium at present, along with the raising of environmental protection requirement and the progress of technology, eliminate catalytic component based on vanadium is also matter of time comprehensively.Therefore, be necessary very much to carry out non-vanadium base NH
3the developmental research of-SCR catalyst.
At present, in world wide in, heavy rare earth consumption constantly increases, and the high abundance LREEs such as Ce overstock in a large number.Therefore, Ce element utilizes the exploitation of approach to have very important significance to efficient, the rationally utilization of rare earth resources.Existing patent (publication number CN102000560B) discloses a kind ofly take urea as precipitating reagent, and the cerium tungsten oxide catalyst that adopts sluggish precipitation to prepare has excellent NH
3-SCR catalytic performance, but its preparation process relative complex, key reaction is carried out in liquid phase, and need to use excessive precipitating reagent, in preparation process, can produce waste water, precipitating reagent decomposes can produce waste gas, and in solution, remaining precipitating reagent also will produce and pollute and waste.
Summary of the invention
For the deficiency existing in existing cerium tungsten oxide catalyst preparation process, the present invention provides a kind of preparation method of extremely easy cerium tungsten oxide catalyst first.
A simple method for preparing for efficient cerium tungsten oxide catalyst, adopts solid grinding method, comprises the steps:
(1) hybrid solid of preparation cerium source and tungstates grinds under normal temperature condition;
(2) gained solid content is directly carried out to roasting, obtain described cerium tungsten oxide catalyst.
In step (1), described cerium source is selected from least one in cerous nitrate, ammonium ceric nitrate, cerous chlorate or cerous sulfate.
In step (1), described tungstates is selected from least one in ammonium tungstate or ammonium paratungstate.
In step (1), described cerium source and the mol ratio of tungstates are 0.2～2.0, preferably 0.5～2.0.
In step (1), the described mixed grinding time is 0.5～1h.
In step (2), described roasting is carried out in air atmosphere, and described sintering temperature is 400～800 ℃, preferably 400～600 ℃.
In step (2), described roasting time is 1～24h, preferably 4～6h.
Compared with prior art, tool of the present invention has the following advantages:
(1) described preparation method is extremely easy, and operating procedure is few, lasts shortly, and cost is low, and green, environmental protection;
(2) the cerium tungsten oxide catalyst that uses the method to prepare still can show excellent catalytic performance under high-speed environment, is a kind of SCR catalyst very efficiently;
(3) the cerium tungsten oxide catalyst that uses the method to prepare has very excellent N
2generate selective;
(4) the cerium tungsten oxide catalyst that uses the method to prepare has extraordinary anti-poisoning capability and thermal stability.
The specific embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
According to Ce/W mol ratio, be 1.0, add ammonium tungstate solid and cerous nitrate solid in mortar, mixed grinding 0.5h, then directly makes powder catalyst by gained solid content through Muffle furnace roasting 5h in 500 ℃ of air continuously, is called catalyst A.
Embodiment 2
Other condition is as constant in embodiment 1, and changing Ce/W mol ratio is 2.0, obtains catalyst B.
Embodiment 3
Other condition is as constant in embodiment 1, and changing Ce/W mol ratio is 0.5, obtains catalyst C.
Embodiment 4
According to Ce/W mol ratio, be 1.0, add ammonium tungstate solid and cerous nitrate solid in mortar, mixed grinding 5h, then directly makes powder catalyst by gained solid content through Muffle furnace roasting 10h in 500 ℃ of air continuously, is called catalyst D.
Embodiment 5
According to Ce/W mol ratio, be 1.0, add ammonium tungstate solid and cerous nitrate solid in mortar, mixed grinding 0.5h, then directly makes powder catalyst by gained solid content through Muffle furnace roasting 1h in 700 ℃ of air continuously, is called catalyst E.
Comparative example 1
Take a certain amount of ammonium tungstate solid, cerous nitrate solid, be placed in respectively agate mortar and grind to form pressed powder, by its through Muffle furnace in 500 ℃ of air respectively roasting 5h make WO
3, CeO
2, according to Ce/W mol ratio, be then 1.0, by WO
3, CeO
2continuously grinding 0.5h after mixing, is called catalyst F.
Comparative example 2
Other condition is as constant in comparative example 1, and changing Ce/W mol ratio is 2.0, obtains catalyst G.
Application examples 1
The sample A, the B that make, C, F, G are carried out to compressing tablet, grind, sieve, get 40～60 order particles and on fixed bed reactors, carry out NH
3selective Catalytic Reduction of NO
x(NH
3-SCR) investigation of reactivity.
The use amount of catalyst is 0.12mL, the consisting of of reaction mixture gas: [NO]=[NH
3]=500ppm, [O
2]=5%, N
2make Balance Air, total gas flow rate is 400mL/min, and air speed is 200,000h
-1, 150～450 ℃ of reaction temperatures.NO and NH
3and accessory substance N
2o, NO
2all utilize Nicolet Antaris IGS infrared gas analyser to measure.NO
xconversion ratio and N
2o generates concentration respectively as shown in Table 1 and Table 2.
The NO of the different samples of table 1
xconversion ratio
The N of the different samples of table 2
2o generates concentration
As shown in Table 1, under same reaction conditions, the NH of catalyst A and B in the present invention
3-SCR activity is apparently higher than adopting cerium tungsten catalyst F and the G grinding again after the independent roasting in Yu Wu source, cerium source, and the catalyst that adopts method provided by the invention to prepare has very excellent NO
xremoval efficiency.
As shown in Table 2, under same reaction conditions, the N of catalyst A and B in the present invention
2o generates concentration and is starkly lower than cerium tungsten catalyst F and the G grinding again after the employing independent roasting in Yu Wu source, cerium source, and the catalyst that adopts method provided by the invention to prepare has very excellent N
2selectively.
In addition, comparing result also shows, in baking mixed Kaolinite Preparation of Catalyst process, can make cerium and tungsten mutually combine, rather than simple physical mixed, therefore can be at NH
3in-SCR reaction, produce synergy, make it have more excellent activity.
Application examples 2
The sample A making is carried out to compressing tablet, grinds, sieves, get 40～60 order particles and on fixed bed reactors, carry out the NH under different air speed conditions
3-SCR reactivity is investigated.
Consisting of of reaction mixture gas: [NO]=[NH
3]=500ppm, [O
2]=5%, N
2make Balance Air, total gas flow rate is 400mL/min, and the use amount of catalyst is 0.24mL, 0.12mL, 0.06mL, and corresponding reaction velocity is respectively 100,000h
-1, 200,000h
-1, 400,000h
-1, 150～450 ℃ of reaction temperatures.NO and NH
3and accessory substance N
2o, NO
2all utilize Nicolet Antaris IGS infrared gas analyser to measure.NO
xconversion ratio is as shown in table 3.
The NO of catalyst sample A under table 3 differential responses air speed condition
xconversion ratio
As shown in Table 3, catalyst A provided by the invention can efficiently be removed NO under high-speed environment
xeven, at 400,000h
-1high-speed condition under, still can in 250～350 ℃ of temperature ranges, realize more than 80% NO
xconversion ratio.Meanwhile, there is extraordinary N
2generate selectively high-temperature stability and water resistant sulfur resistance.
During actual use, catalyst is placed in to exhaust pipe way, in the upstream of catalyst, spraying into reducing agent and tail gas mixes, reducing agent adopts ammonia or urea (can obtain ammonia after hydrolysis), reducing agent consumption is 0.8～1.2 times of nitrogen oxide in tail gas, can be by NO in very wide temperature window under excess oxygen
xbe reduced to N
2and H
2o possesses very high N simultaneously
2generate selective and anti-sulphur water repelling property.
Described tail gas is preferably moving source gas containing nitrogen oxide, for example exhaust gas from diesel vehicle, or stationary source gas containing nitrogen oxide, for example coal-fired plant flue gas.Described gas is preferably exhaust gas from diesel vehicle, i.e. the present invention is specially adapted to the catalytic purification of nitrogen oxide in exhaust gas from diesel vehicle.
Claims (7)
1. a simple method for preparing for efficient cerium tungsten oxide catalyst, adopts solid grinding method, it is characterized in that, comprises the steps:
(1) hybrid solid of preparation cerium source and tungstates grinds under normal temperature condition;
(2) gained solid content is directly carried out to roasting, obtain described cerium tungsten oxide catalyst.
2. the simple method for preparing of efficient cerium tungsten oxide catalyst according to claim 1, is characterized in that, the cerium source described in step (1) is selected from least one in cerous nitrate, ammonium ceric nitrate, cerous chlorate or cerous sulfate.
3. the simple method for preparing of efficient cerium tungsten oxide catalyst according to claim 1, is characterized in that, the tungstates described in step (1) is selected from least one in ammonium tungstate or ammonium paratungstate.
4. according to the simple method for preparing of the arbitrary described efficient cerium tungsten oxide catalyst of claim 1-3, it is characterized in that, the mol ratio of the cerium source described in step (1) and tungstates is 0.5～2.0.
5. the simple method for preparing of efficient cerium tungsten oxide catalyst according to claim 1, is characterized in that, the milling time in step (1) is 0.5～1h.
6. the simple method for preparing of efficient cerium tungsten oxide catalyst according to claim 1, is characterized in that, the roasting in step (2) is carried out in air atmosphere, and described sintering temperature is 400～600 ℃.
7. the simple method for preparing of efficient cerium tungsten oxide catalyst according to claim 1, is characterized in that, the roasting time in step (2) is 4～6h.
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|---|---|---|---|
| CN201410232031.XA CN103990451A (en) | 2014-05-28 | 2014-05-28 | Simple preparation method of efficient cerium tungsten oxide catalyst |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107497429A (en) * | 2017-10-09 | 2017-12-22 | 福州大学 | A kind of preparation method and application of Ag doping tungsten oxide photcatalyst |
| CN107583945A (en) * | 2017-10-31 | 2018-01-16 | 爱土工程环境科技有限公司 | A kind of method of organic polluted soil production fired brick |
| CN110918084A (en) * | 2019-12-13 | 2020-03-27 | 中国科学院城市环境研究所 | Composite oxide catalyst and preparation method and application thereof |
| CN112110490A (en) * | 2020-10-09 | 2020-12-22 | 东北大学 | Preparation method of cerium tungstate and prepared cerium tungstate |
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| EP0785246B1 (en) * | 1991-09-03 | 2001-03-28 | STEAG encotec GmbH | Method for operating a coal-fired power plant |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107497429A (en) * | 2017-10-09 | 2017-12-22 | 福州大学 | A kind of preparation method and application of Ag doping tungsten oxide photcatalyst |
| CN107497429B (en) * | 2017-10-09 | 2019-10-15 | 福州大学 | A kind of preparation method and application of Ag doping tungsten oxide photcatalyst |
| CN107583945A (en) * | 2017-10-31 | 2018-01-16 | 爱土工程环境科技有限公司 | A kind of method of organic polluted soil production fired brick |
| CN107583945B (en) * | 2017-10-31 | 2021-05-28 | 爱土工程环境科技有限公司 | Method for producing sintered bricks from organic contaminated soil |
| CN110918084A (en) * | 2019-12-13 | 2020-03-27 | 中国科学院城市环境研究所 | Composite oxide catalyst and preparation method and application thereof |
| CN112110490A (en) * | 2020-10-09 | 2020-12-22 | 东北大学 | Preparation method of cerium tungstate and prepared cerium tungstate |
| CN112110490B (en) * | 2020-10-09 | 2021-07-16 | 东北大学 | Preparation method of cerium tungstate and prepared cerium tungstate |
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Application publication date: 20140820 |