CN102974363A - Silicon controlled rectifier (SCR) smoke denitration catalyst and preparation method thereof - Google Patents
Silicon controlled rectifier (SCR) smoke denitration catalyst and preparation method thereof Download PDFInfo
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- CN102974363A CN102974363A CN2012105255949A CN201210525594A CN102974363A CN 102974363 A CN102974363 A CN 102974363A CN 2012105255949 A CN2012105255949 A CN 2012105255949A CN 201210525594 A CN201210525594 A CN 201210525594A CN 102974363 A CN102974363 A CN 102974363A
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Abstract
The invention discloses a silicon controlled rectifier (SCR) smoke denitration catalyst and a preparation method thereof. The catalyst comprises a carrier, a catalytic active component and a cocatalyst and is characterized in that the carrier is cordierite honeycomb-shaped ceramic coated with an Al2O3 film; the active component is copper oxide; and the cocatalyst is one of oxides of manganese, lanthanum and cerium. The preparation method of the catalyst is simple; raw materials are low in cost and easily available and cannot cause secondary pollution to the environment; and in a temperature range of 250 to 400 DEG C, the SCR denitration activity is not less than 85 percent.
Description
Technical field
The invention belongs to catalyst field, relate in particular to a kind of SCR catalyst for denitrating flue gas and preparation method thereof.
Background technology
Nitrogen oxide mainly is to come from mankind's activity to cause to the pollution sources of environment structure harm, the whole world year exhaust emission amount be about 86*10
6Ton, mainly from the discharging of industry and communications and transportation fuel combustion, the discharging that also has part to produce and use the industrial department of nitric acid from nitric plant, sulfuric acid plant, nitrogen fertilizer plant, dyestuff factory, explosive factory etc. is one of primary pollution source that causes atmosphere pollution for it.Along with China's process of industrialization is constantly accelerated, NO
xPollution is on the rise.In " fossil-fuel power plant atmospheric pollutant emission standard " (the GB 13223-2011) (replacing GB13223-2003) that promulgates in July, 2011, adjusted the Air Pollutant Emission concentration limit, stipulated that from 1 day January in 2012, newly-built thermal power generation boiler and gas turbine group were carried out 100 mg/m
3Emission limits of nitrogen oxides.Simultaneously, China will strengthen the energy-saving and emission-reduction dynamics during " 12 ", increase denitration (NO
xRemove) this restrictive unalterable quota.
SCR (SCR) denitration is the most widely technology of present domestic and international application because efficient is high, technology maturation.But its used catalyst is the V-Ti system of severe toxicity, simultaneously because anatase TiO
2Transformation of crystal and V easily occur
2O
5The high in cost of production reason makes V
2O
5/ TiO
2The application of catalyst is restricted.Therefore, develop the cheapness of domestic autonomous innovation, nontoxic, abandoning property SCR catalyst for denitrating flue gas tool is of great significance.
Existing about CuO-Al
2O
3The SCR catalyst for denitrating flue gas of system all is CuO to be loaded on scribble Al
2O
3The honeycomb-like cordierite carrier on make honeycomb-like cordierite base CuO-Al
2O
3Catalyst.Wherein, Al
2O
3The preparation method who films and coating effect are one of factors that affects the catalyst denitration activity.
Summary of the invention
For solving above technical problem, the purpose of this invention is to provide that a kind of denitration efficiency is high, with low cost, technique is simple, environmental protection and can not cause SCR catalyst for denitrating flue gas of secondary pollution and preparation method thereof.
Above-mentioned purpose of the present invention is achieved by the following technical solution:
A kind of SCR catalyst for denitrating flue gas comprises carrier, catalytic active component and co-catalyst, it is characterized in that: carrier is coating Al
2O
3The cordierite honeycomb of film pottery, active component is cupric oxide, co-catalyst is a kind of in the oxide of manganese, lanthanum or cerium.
In the present invention, selectable Al
2O
3Include but not limited to α-Al
2O
3, β-Al
2O
3, γ-Al
2O
3, optimum is γ-Al
2O
3, its quality percentage composition is 1 ~ 20%, is preferably 3 ~ 10%; Cupric oxide quality percentage composition is 1 ~ 15%, more preferably 2 ~ 10 %; The quality percentage composition of the oxide of manganese, lanthanum or cerium is 1 ~ 10%, more preferably 1-5%.
Another purpose among the present invention provides a kind of preparation method of above-mentioned SCR catalyst for denitrating flue gas, may further comprise the steps:
(1) γ-Al
2O
3The preparation of film immersion liquid: aluminium salt is dissolved in is configured to solution A in the distilled water;
(2) γ-Al
2O
3The load of film: the cordierite honeycomb carrier impregnation is in A solution, dry, be put in roasting in the Muffle furnace after dipping finishes, namely make the carrier B of filming;
(3) preparation of activity component impregnation liquid: mantoquita is dissolved in is configured to solution in the distilled water, and add a kind of stable metal salting liquid C that is mixed with of manganese, lanthanum or cerium salt;
(4) load of active component: the carrier B of will filming impregnated in the C solution, and is dry, be put in roasting in the Muffle furnace after dipping finishes, and namely makes the described catalyst of catalyst.
In the present invention, the described aluminium salt of step 1 is preferably those at the salt that high temperature (for example in the Muffle furnace after the roasting) decomposes, and includes but not limited to nitrate, is preferably the hydrate of aluminum nitrate, for example Al (NO
3)
39H
2O; Al (NO
3)
39H
2The consumption of O is controlled in the scope of every 250ml solution 110.0-368.0 g, such as 120.3 g, 220.7 g, 354.7 g etc.
Further, in step 2, the consumption of cordierite honeycomb carrier is 50.0-100.0 g, is preferably 50.0-80.0 g.
In the present invention, the described mantoquita of step 3 and manganese, lanthanum, cerium salt are preferably those at the salt that high temperature (for example in the Muffle furnace after the roasting) decomposes, and include but not limited to nitrate; Mantoquita is preferably Cu (NO
3)
23H
2O, its consumption are controlled in the scope of every 250ml solution 60.0-250.0 g, for example 60.8 g, 151.9g or 243.1g; Manganese, lanthanum, cerium salt are preferably Mn (NO
3)
2, La (NO
3)
36H
2O, Ce (NO
3)
36H
2Its consumption of O is 0.1-0.5 g/cm
3
As preferably, the temperature of roasting is 300 ° of C ~ 600 ° C in step of the present invention (2) and (4), time 1 ~ 4 h, and drying mode can be nature and dries in the shade, times 24 ~ 48 h; In addition, the drying mode in the step (2) also can be the air dry oven drying, temperature 60 C ~ 120 ℃, 8 ~ 24 h.
Described SCR catalyst for denitrating flue gas of the present invention is at work generally in the following way: catalyst is heated to 250 ℃ ~ 400 ℃, passes into and contain NO
xPending flue gas, denitration efficiency 〉=85%.
The present invention can reach following technique effect: the prepared method for preparing catalyst of the present invention is simple, raw material is cheap and easy to get and environment is not produced secondary pollution, in 250 ℃ ~ 400 ℃ temperature ranges, can reach 〉=85% SCR denitration activity.
Description of drawings
Fig. 1 is the catalyst activity system safety testing device figure among the present invention.
The specific embodiment
The present invention is described in further detail below in conjunction with the specific embodiment.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Embodiment 1
(1) with 220.7 g Al (NO
3)
39H
2O is dissolved in the distilled water until then fully dissolving places 250 mL volumetric flasks to add water to scale, namely is configured to γ-Al
2O
3Film immersion liquid;
(2) with 100.0 g cordierite honeycomb carrier impregnation in the coating liquid that step (1) configures, dry, be put in roasting in the Muffle furnace after dipping finishes, 300 ℃ ~ 600 ℃ of temperature, 1 ~ 4 h namely makes and is coated with membrane carrier;
(3) with 60.8 g Cu (NO
3)
23H
2O and 50.5 g Mn (NO
3)
2Solution is dissolved in the distilled water until then fully dissolving places 250 mL volumetric flasks to add water to scale, namely is made into the Cu-Mn dipping solution;
What (4) step (2) is made films carrier impregnation in the Cu-Mn dipping solution that step (3) prepares, and takes out nature and dries in the shade behind 48 h, through 500 ℃ of roasting 3 h of Muffle furnace, namely gets the catalyst finished product.
The activity test method of catalyst
Catalyst is packed in the reaction tube, and temperature is carried out programme-control by tube type resistance furnace.The mist simulated flue gas is provided by corresponding steel cylinder.The shared ratio (volume fraction) of corresponding mist is: n
NO=1000 ppm, n
NH3=1200 ppm, O
2%=1%, residual gas adopts N
2Gas is as Balance Air, and the gaseous state air speed is 5000h
-1Analyze exit gas NO content and calculate denitration efficiency X:
| Reaction temperature/° C | 250 | 300 | 350 | 400 |
| n The NO outlet/ppm | 150 | 132 | 90 | 61 |
| X/% | 85.0 | 86.8 | 91.0 | 93.9 |
From above-mentioned checking example, can find out, SCR catalyst for denitrating flue gas of the present invention, under 250 ℃ ~ 400 ℃ flue-gas temperature condition, denitration efficiency 〉=85.1%.
Embodiment 2
(1) with 120.3 g Al (NO
3)
39H
2O is dissolved in the distilled water until then fully dissolving places 250 mL volumetric flasks to add water to scale, namely is configured to γ-Al
2O
3Film immersion liquid;
(2) with 50.0 g cordierite honeycomb carrier impregnation in the coating liquid that step (1) configures, dry, be put in roasting in the Muffle furnace after dipping finishes, 300 ℃ ~ 600 ℃ of temperature, 1 ~ 4 h namely makes and is coated with membrane carrier;
(3) with 151.9g Cu (NO
3)
23H
2O and 40.2 g La (NO
3)
36H
2O solution is dissolved in the distilled water until then fully dissolving places 250 mL volumetric flasks to add water to scale, namely is made into the Cu-La dipping solution;
What (4) step (2) is made films carrier impregnation in the Cu-La dipping solution that step (3) prepares, and takes out nature and dries in the shade behind 48 h, through 500 ℃ of roasting 3 h of Muffle furnace, namely gets the catalyst finished product.
The activity test method of catalyst is with embodiment 1, and the active result who records is that when 300 ℃ flue-gas temperature scope, the denitration efficiency of catalyst reaches 85.5%.
| Reaction temperature/° C | 300 |
| n The NO outlet/ppm | 145 |
| X/% | 85.5 |
Embodiment 3
(1) with 354.7 g Al (NO
3)
39H
2O is dissolved in the distilled water until then fully dissolving places 250 mL volumetric flasks to add water to scale, namely is configured to γ-Al
2O
3Film immersion liquid;
(2) with 80.0 g cordierite honeycomb carrier impregnation in the coating liquid that step (1) configures, dry, be put in roasting in the Muffle furnace after dipping finishes, 300 ℃ ~ 600 ℃ of temperature, 1 ~ 4 h namely makes and is coated with membrane carrier;
(3) with 243.1g Cu (NO
3)
23H
2O and 38.9 g Ce (NO
3)
36H
2O solution is dissolved in the distilled water until then fully dissolving places 250 mL volumetric flasks to add water to scale, namely is made into the Cu-Ce dipping solution;
What (4) step (2) is made films carrier impregnation in the Cu-Ce dipping solution that step (3) prepares, and takes out nature and dries in the shade behind 48 h, through 500 ℃ of roasting 3 h of Muffle furnace, namely gets the catalyst finished product.
The activity test method of catalyst is with embodiment 1.The active result who records is that when 300 ℃ flue-gas temperature scope, the denitration efficiency of catalyst reaches more than 86.2%.
| Reaction temperature/° C | 300 |
| n The NO outlet/ppm | 138 |
| X/% | 86.2 |
The above embodiment is the preferred embodiment that proves absolutely that the present invention lifts, and protection scope of the present invention is not limited to this.Being equal to that those skilled in the art do on basis of the present invention substitutes or conversion, all within protection scope of the present invention.
Claims (10)
1. a SCR catalyst for denitrating flue gas comprises carrier, catalytic active component and co-catalyst, it is characterized in that: carrier is coating Al
2O
3The cordierite honeycomb of film pottery, active component is cupric oxide, co-catalyst is a kind of in the oxide of manganese, lanthanum or cerium.
2. SCR catalyst for denitrating flue gas as claimed in claim 1, wherein said Al
2O
3Be α-Al
2O
3, β-Al
2O
3Or γ-Al
2O
3, preferred γ-Al
2O
3
3. SCR catalyst for denitrating flue gas as claimed in claim 1 or 2, wherein said Al
2O
3The quality percentage composition be 1 ~ 20%, be preferably 3 ~ 10%; Cupric oxide quality percentage composition is 1 ~ 15%, is preferably 2 ~ 10 %; The quality percentage composition of the oxide of manganese, lanthanum or cerium is 1 ~ 10%, more preferably 1-5%.
4. one kind prepares each said SCR catalyst for denitrating flue gas method such as claim 1-3, may further comprise the steps:
(1) γ-Al
2O
3The preparation of film immersion liquid: aluminium salt is dissolved in is configured to solution A in the distilled water;
(2) γ-Al
2O
3The load of film: the cordierite honeycomb carrier impregnation is in A solution, dry, be put in roasting in the Muffle furnace after dipping finishes, namely make the carrier B of filming;
(3) preparation of activity component impregnation liquid: mantoquita is dissolved in is configured to solution in the distilled water, and add a kind of stable metal salting liquid C that is mixed with of manganese, lanthanum or cerium salt;
(4) load of active component: the carrier B of will filming impregnated in the C solution, and is dry, be put in roasting in the Muffle furnace after dipping finishes, and namely makes described catalyst.
5. method as claimed in claim 4, wherein the described aluminium salt of step (1) is nitrate, is preferably Al (NO
3)
39H
2O; Its consumption is controlled in the scope of every 250ml solution 110.0-368.0 g.
6. such as claim 4 or 5 described methods, wherein the consumption of cordierite honeycomb carrier is 50.0-100.0 g in the step (2), is preferably 50.0-80.0 g.
7. such as each described method of claim 4-6, wherein the described mantoquita of step (3) is Cu (NO
3)
23H
2O, its consumption are controlled in the scope of every 250ml solution 60.0-250.0 g; Manganese, lanthanum or cerium salt is Mn (NO respectively
3)
2, La (NO
3)
36H
2O or Ce (NO
3)
36H
2O, its consumption are 0.1-0.5 g/cm
3
8. such as each described method of claim 4-6, wherein the temperature of roasting is 300 ℃ ~ 600 ℃ in step (2) and (4), and time 1 ~ 4 h, drying mode are that nature dries in the shade, times 24 ~ 48 h.
9. such as each described method of claim 4-6, wherein the drying mode in the step (2) is that air dry oven is dry, temperature 60 C ~ 120 ℃, 8 ~ 24 h.
As claim 1-3 as described in each SCR catalyst for denitrating flue gas contain NO in processing
xFlue gas in application, comprise the SCR catalyst for denitrating flue gas is heated to 250 ° of C ~ 400 ° C, pass into and contain NO
xPending flue gas.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (6)
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|---|---|---|---|---|
| CN104056667A (en) * | 2014-07-04 | 2014-09-24 | 萍乡市和鑫环保填料设备有限责任公司 | Ceramic honeycomb catalyst for high-temperature waste gas denitrification and preparation method thereof |
| CN104676695A (en) * | 2015-02-11 | 2015-06-03 | 深圳市飚火节能环保科技有限公司 | Intelligent environment-friendly cooking fume purifier |
| CN105597777A (en) * | 2015-12-24 | 2016-05-25 | 浙江大学 | Ordered mesoporous carbon loading Cu-Mn bi-metal denitration catalyst and preparation method thereof |
| CN107754810A (en) * | 2017-11-10 | 2018-03-06 | 西南化工研究设计院有限公司 | A kind of wide temperature smoke denitrating catalyst of non-vanadium base monolithic, preparation method and application |
| CN108543535A (en) * | 2018-05-14 | 2018-09-18 | 王研 | The method of catalyst and coal combustion high-temperature flue gas denitration |
| CN115155610A (en) * | 2022-07-12 | 2022-10-11 | 中晶环境科技股份有限公司 | Catalyst, preparation method and application thereof, and flue gas treatment method |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104056667A (en) * | 2014-07-04 | 2014-09-24 | 萍乡市和鑫环保填料设备有限责任公司 | Ceramic honeycomb catalyst for high-temperature waste gas denitrification and preparation method thereof |
| CN104056667B (en) * | 2014-07-04 | 2016-06-01 | 萍乡市和鑫环保填料设备有限责任公司 | A kind of ceramic honeycomb Catalysts and its preparation method for high-temp waste gas denitration |
| CN104676695A (en) * | 2015-02-11 | 2015-06-03 | 深圳市飚火节能环保科技有限公司 | Intelligent environment-friendly cooking fume purifier |
| CN104676695B (en) * | 2015-02-11 | 2017-10-20 | 深圳市飚火节能环保科技有限公司 | A kind of intelligent environment protection oil fume purifier |
| CN105597777A (en) * | 2015-12-24 | 2016-05-25 | 浙江大学 | Ordered mesoporous carbon loading Cu-Mn bi-metal denitration catalyst and preparation method thereof |
| CN107754810A (en) * | 2017-11-10 | 2018-03-06 | 西南化工研究设计院有限公司 | A kind of wide temperature smoke denitrating catalyst of non-vanadium base monolithic, preparation method and application |
| CN108543535A (en) * | 2018-05-14 | 2018-09-18 | 王研 | The method of catalyst and coal combustion high-temperature flue gas denitration |
| CN108543535B (en) * | 2018-05-14 | 2021-09-07 | 王研 | Catalyst and method for denitration of coal combustion high-temperature flue gas |
| CN115155610A (en) * | 2022-07-12 | 2022-10-11 | 中晶环境科技股份有限公司 | Catalyst, preparation method and application thereof, and flue gas treatment method |
| CN115155610B (en) * | 2022-07-12 | 2024-04-26 | 中晶环境科技股份有限公司 | Catalyst, preparation method and application thereof, and flue gas treatment method |
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Application publication date: 20130320 |