CN102513121A - SCR (Styrene-Chloroprene Rubber) smoke denitration catalyst and preparation method thereof - Google Patents
SCR (Styrene-Chloroprene Rubber) smoke denitration catalyst and preparation method thereof Download PDFInfo
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- CN102513121A CN102513121A CN2011104203603A CN201110420360A CN102513121A CN 102513121 A CN102513121 A CN 102513121A CN 2011104203603 A CN2011104203603 A CN 2011104203603A CN 201110420360 A CN201110420360 A CN 201110420360A CN 102513121 A CN102513121 A CN 102513121A
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- flue gas
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Abstract
The invention belongs to the field of catalysts and particularly relates to an SCR (Styrene-Chloroprene Rubber) smoke denitration catalyst and a preparation method thereof. The SCR smoke denitration catalyst comprises a carrier, a catalytic activity component and a catalyst promoter. According to the catalyst, spherical gamma-Al2O3 is used as the carrier, copper oxide is used as the catalytic activity component, and appropriate amounts of chromium, lanthanum and cerium are respectively added to be used as the catalyst promoter, wherein the content of the copper oxide of the catalytic activity component is 10-20% and the content of the chromium, the lanthanum and the cerium of the catalyst promoter is 1-10%. The preparation method provided by the invention comprises the following step of soaking the carrier gamma-Al2O3 into a composite solution of a copper salt and a catalyst promote metal salt to prepare a catalytic activity component coating. The SCR smoke denitration catalyst provided by the invention has the characteristics of low price, no toxin, disposability, simple preparation method, and better denitration activity at a room temperature in a range of 250-400 DEG C.
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 " thermal power plant's atmosphere pollutants emission standards " (GB 13223-2011) (replacing GB 13223-2003) of promulgation in July in this year; Adjusted the Air Pollutant Emission concentration limit; Stipulated that newly-built thermal power generation boiler and gas turbine group were carried out 100 mg/m from January 1st, 2012
3The discharged nitrous oxides limit value.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 a present domestic and international application technology the most widely because of efficient is high, technology maturation.But its used catalyst is the V-Ti system of severe toxicity, simultaneously because anatase TiO
2Being prone to take place crystal formation transforms and V
2O
5Reasons such as cost height make V
2O
5/ TiO
2Application of Catalyst is restricted.Therefore, develop the cheapness of domestic autonomous innovation, nontoxic, abandoning property SCR catalyst for denitrating flue gas has crucial meaning.
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 process honeycomb-like cordierite base CuO-Al
2O
3Catalyst.Wherein, Al
2O
3Preparation method who films and coating effect are one of factors that influences 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, technology is simple, environmental protection and can not cause SCR catalyst for denitrating flue gas of secondary pollution and preparation method thereof.
A kind of SCR catalyst for denitrating flue gas of the present invention comprises carrier, catalytic active component and co-catalyst, it is characterized in that: carrier is ball-type γ-Al
2O
3, active component is a cupric oxide, co-catalyst is a kind of in chromium, lanthanum or the ce metal oxide.
Wherein cupric oxide content is 10 ~ 20 % (annotate: said content all is the quality percentage composition), and the content of chromium, lanthanum or ce metal oxide is 1 ~ 10 %.
The preparation method of the SCR catalyst for denitrating flue gas among the present invention may further comprise the steps:
(1) preparation of activity component impregnation liquid: the 184-354.3g/L mantoquita is dissolved in the distilled water until dissolving fully, and adds a kind of preparation stable metal salting liquid A of 39-319g/L chromium, lanthanum, cerium salt;
(2) load of active component: with 60-200g/L γ-Al
2O
3Carrier impregnation is in A solution, and is dry, be put in roasting in the Muffle furnace after dipping finishes, 300 ° of C ~ 600 ° C of temperature, and 1 ~ 4 h promptly makes catalyst semi-finished product B;
(3) secondary load of active component:, promptly make the catalyst finished product with catalyst semi-finished product B repeating step (2).
Mantoquita and chromium, lanthanum, cerium salt can be the nitrate of copper, chromium, lanthanum or cerium.
Drying mode in the step (2) can be nature and dries in the shade, 24 ~ 48 h.
Drying mode in the step (2) can be the air dry oven drying, 60 ° of C ~ 120 ° C of temperature, 8 ~ 24 h;
The SCR catalyst for denitrating flue gas is heated to 250 ° of C ~ 400 ° C, and feeding contains 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, low in raw material cost is easy to get and environment is not produced secondary pollution, in ° C temperature range of 250 ° of C ~ 400, can reach >=85% SCR denitration activity.
The specific embodiment
Below in conjunction with specific embodiment the present invention is described further so that those skilled in the art the present invention may be better understood and can implement, but the embodiment that lifts not conduct to qualification of the present invention.
Embodiment 1
With 276.4 g Cu (NO
3)
23H
2O and 143.6 g Cr (NO
3)
29H
2O is dissolved in the distilled water until dissolving fully, places 500 mL volumetric flasks to add water to scale then, promptly is made into the Cu-Cr dipping solution.
With 100 g γ-Al
2O
3Carrier impregnation is taken out nature and is dried in the shade behind 48 h in the Cu-Cr dipping solution that step (1) prepares, and through 500 ° of C roasting 3 h of Muffle furnace, promptly gets the catalyst semi-finished product.
With dipping in the catalyst semi-finished product repeating step (2) of step (2) preparation, dry, calcination steps 1 time, promptly accomplish Preparation of catalysts.
The activity of such catalysts method of testing
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 gas, and the gaseous state air speed is 5000h
-1Analyze gas NO content and calculate denitration efficiency X:
| Reaction temperature/° C | 250 | 300 | 350 | 400 |
| n The NO outlet/ppm | 149 | 130 | 91 | 62 |
| X/% | 85.1 | 87.0 | 90.9 | 93.8 |
From above-mentioned checking example, can find out, SCR catalyst for denitrating flue gas of the present invention, under the flue-gas temperature condition of 250 ° of C ~ 400 ° C, denitration efficiency >=85.1%.
Embodiment 2
With 243.2 g Cu (NO
3)
23H
2O and 77.6 g La (NO
3)
36H
2O is dissolved in the distilled water until dissolving fully, places 500 mL volumetric flasks to add water to scale then, promptly is made into the Cu-La dipping solution.
With 60 g γ-Al
2O
3Carrier impregnation is taken out and is placed air dry oven in the Cu-La dipping solution that step (1) prepares, and behind dry 24 h of 110 ° of C, through 300 ° of C roastings of Muffle furnace 4h, promptly gets the catalyst semi-finished product.
With dipping in the catalyst semi-finished product repeating step (2) of step (2) preparation, dry, calcination steps 1 time, promptly accomplish Preparation of catalysts.
The activity of such catalysts method of testing is with embodiment 1, and the active result who records is that when the flue-gas temperature scope of 300 ° of C, the denitration efficiency of catalyst reaches 85.6%.
| Reaction temperature/° C | 300 |
| n The NO outlet/ppm | 144 |
| X/% | 85.6 |
Embodiment 3
With 184.3 g Cu (NO
3)
23H
2O and 39.0 g Ce (NO
3)
36H
2O is dissolved in the distilled water until dissolving fully, places 500 mL volumetric flasks to add water to scale then, promptly is made into the Cu-Ce dipping solution.
With 100 g γ-Al
2O
3Carrier impregnation is taken out nature and is dried in the shade behind the 24h in the Cu-Ce dipping solution that step (1) prepares, and through 600 ° of C roastings of Muffle furnace 1h, promptly gets the catalyst semi-finished product.
With dipping in the catalyst semi-finished product repeating step (2) of step (2) preparation, dry, calcination steps 1 time, promptly accomplish Preparation of catalysts.
The activity of such catalysts method of testing is with embodiment 1.The active result who records is that when the flue-gas temperature scope of 300 ° of C, the denitration efficiency of catalyst reaches more than 86.1%.
| Reaction temperature/° C | 300 |
| n The NO outlet/ppm | 139 |
| X/% | 86.1 |
Embodiment 4
With 354.3 g Cu (NO
3)
23H
2O and 319.1 g Ce (NO
3)
36H
2O is dissolved in the distilled water until dissolving fully, places 500 mL volumetric flasks to add water to scale then, promptly is made into the Cu-Ce dipping solution.
With 200 g γ-Al
2O
3Carrier impregnation is taken out nature and is dried in the shade behind the 24h in the Cu-Ce dipping solution that step (1) prepares, and through 600 ° of C roastings of Muffle furnace 1h, promptly gets the catalyst semi-finished product.
With dipping in the catalyst semi-finished product repeating step (2) of step (2) preparation, dry, calcination steps 1 time, promptly accomplish Preparation of catalysts.
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 thereto.Being equal to that the technical staff in present technique field is done on basis of the present invention substitutes or conversion, all within protection scope of the present invention.
Claims (8)
1. a SCR catalyst for denitrating flue gas comprises carrier, catalytic active component and co-catalyst, it is characterized in that: carrier is ball-type γ-Al
2O
3, active component is a cupric oxide, co-catalyst is a kind of in chromium, lanthanum or the ce metal oxide.
2. a kind of SCR catalyst for denitrating flue gas according to claim 1 is characterized in that: cupric oxide content is 10 ~ 20 % in the above-mentioned catalyst.
3. a kind of SCR catalyst for denitrating flue gas according to claim 1 is characterized in that: the content of chromium, lanthanum or ce metal oxide is 1 ~ 10 % in the above-mentioned catalyst.
4. the preparation method of a SCR catalyst for denitrating flue gas as claimed in claim 1 is characterized in that: may further comprise the steps:
(1) preparation of activity component impregnation liquid: the 184-354.3g/L mantoquita is dissolved in the distilled water until dissolving fully, and adds a kind of preparation stable metal salting liquid A of 39-319g/L chromium, lanthanum, cerium salt;
(2) load of active component: with 60-200g/L γ-Al
2O
3Carrier impregnation is in A solution, and is dry, be put in roasting in the Muffle furnace after dipping finishes, 300 ° of C ~ 600 ° C of temperature, and 1 ~ 4 h promptly makes catalyst semi-finished product B;
(3) secondary load of active component:, promptly make the catalyst finished product with catalyst semi-finished product B repeating step (2).
5. preparation method according to claim 4 is characterized in that: mantoquita and chromium, lanthanum, cerium salt can be the nitrate of copper, chromium, lanthanum or cerium.
6. preparation method according to claim 4 is characterized in that: the drying mode in the step (2) can be nature and dries in the shade, 24 ~ 48 h.
7. preparation method according to claim 4 is characterized in that: the drying mode in the step (2) can be the air dry oven drying, 60 ° of C ~ 120 ° C of temperature, 8 ~ 24 h.
8. each described catalyst application in the SCR denitrating flue gas of claim 1 ~ 7 is characterized in that: the SCR catalyst for denitrating flue gas is heated to 250 ° of C ~ 400 ° C, and feeding contains NO
xPending flue gas, denitration efficiency>=85%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104203603A CN102513121A (en) | 2011-12-15 | 2011-12-15 | SCR (Styrene-Chloroprene Rubber) smoke denitration catalyst and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104203603A CN102513121A (en) | 2011-12-15 | 2011-12-15 | SCR (Styrene-Chloroprene Rubber) smoke denitration catalyst and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974363A (en) * | 2012-12-10 | 2013-03-20 | 西南化工研究设计院有限公司 | Silicon controlled rectifier (SCR) smoke denitration catalyst and preparation method thereof |
| CN103464156A (en) * | 2013-09-10 | 2013-12-25 | 太原理工大学 | Denitrification catalyst and preparation method thereof |
| CN105797577A (en) * | 2016-04-27 | 2016-07-27 | 华北电力大学 | Process and catalyst for catalytically reducing NOX by using methane |
| CN109201067A (en) * | 2018-11-23 | 2019-01-15 | 中石化炼化工程（集团）股份有限公司 | Denitrating catalyst and preparation method thereof and the method for reducing circulating fluidized bed boiler discharged nitrous oxides |
| CN111558372A (en) * | 2020-04-27 | 2020-08-21 | 生态环境部华南环境科学研究所 | Medium-low temperature supported nano copper oxide particle catalyst and preparation method and application thereof |
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|---|---|---|---|---|
| CN101181684A (en) * | 2007-12-06 | 2008-05-21 | 上海大学 | Absorption catalyst for desulfurization of smoke gas and preparation method thereof |
| CN101920213A (en) * | 2010-07-23 | 2010-12-22 | 中环（中国）工程有限公司 | Low temperature SCR denitration catalyst taking organic metal framework as carrier and preparation method thereof |
| CN102049266A (en) * | 2010-12-03 | 2011-05-11 | 上海大学 | SO2 poisoning resisting flue gas denitration catalyst and preparation method thereof |
-
2011
- 2011-12-15 CN CN2011104203603A patent/CN102513121A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101181684A (en) * | 2007-12-06 | 2008-05-21 | 上海大学 | Absorption catalyst for desulfurization of smoke gas and preparation method thereof |
| CN101920213A (en) * | 2010-07-23 | 2010-12-22 | 中环（中国）工程有限公司 | Low temperature SCR denitration catalyst taking organic metal framework as carrier and preparation method thereof |
| CN102049266A (en) * | 2010-12-03 | 2011-05-11 | 上海大学 | SO2 poisoning resisting flue gas denitration catalyst and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974363A (en) * | 2012-12-10 | 2013-03-20 | 西南化工研究设计院有限公司 | Silicon controlled rectifier (SCR) smoke denitration catalyst and preparation method thereof |
| CN103464156A (en) * | 2013-09-10 | 2013-12-25 | 太原理工大学 | Denitrification catalyst and preparation method thereof |
| CN105797577A (en) * | 2016-04-27 | 2016-07-27 | 华北电力大学 | Process and catalyst for catalytically reducing NOX by using methane |
| CN105797577B (en) * | 2016-04-27 | 2019-03-01 | 华北电力大学 | A kind of methyl hydride catalyzed reduction NOxTechnique and catalyst |
| CN109201067A (en) * | 2018-11-23 | 2019-01-15 | 中石化炼化工程（集团）股份有限公司 | Denitrating catalyst and preparation method thereof and the method for reducing circulating fluidized bed boiler discharged nitrous oxides |
| CN109201067B (en) * | 2018-11-23 | 2021-08-31 | 中石化炼化工程（集团）股份有限公司 | Denitration catalyst, preparation method thereof and method for reducing emission of nitrogen oxides of circulating fluidized bed boiler |
| CN111558372A (en) * | 2020-04-27 | 2020-08-21 | 生态环境部华南环境科学研究所 | Medium-low temperature supported nano copper oxide particle catalyst and preparation method and application thereof |
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Application publication date: 20120627 |