CN105214650A - Containing the low temperature SCR denitration catalyst and preparation method thereof of zirconium manganese oxide - Google Patents
Containing the low temperature SCR denitration catalyst and preparation method thereof of zirconium manganese oxide Download PDFInfo
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- CN105214650A CN105214650A CN201510601967.XA CN201510601967A CN105214650A CN 105214650 A CN105214650 A CN 105214650A CN 201510601967 A CN201510601967 A CN 201510601967A CN 105214650 A CN105214650 A CN 105214650A
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Abstract
The invention discloses a kind of low temperature SCR denitration catalyst containing zirconium manganese oxide and preparation method thereof, this catalyst is prepared from by following raw material: attapulgite, hydrochloric acid, Citric Acid Mono, 50% manganese nitrate solution, five water zirconium nitrates, glacial acetic acid, preparation is through comprising following step: 1, attapulgite is purified through ultrasonic wave process and acid treatment; 2,2mol/l citric acid solution 500ml is configured; Manganese nitrate and zirconium nitrate to be dissolved in and to add attapulgite after in 2mol/L citric acid solution and stir and form colloidal sol by 3; 4, in Muffle furnace, required catalyst is namely obtained after calcining again after the colloidal sol formed ageing under uniform temperature being formed gel.This catalyst can be used for the conversion of nitrogen oxide in catalysis coal-burning power plant flue gas, and production cost is low, simple to operate, and effect is high, has larger using value and market prospects.
Description
Technical field
The present invention relates to the technical field of Air Pollutants removal of nitrogen oxide, particularly relate to a kind of preparation method of low-temperature SCR catalyst for denitrating flue gas, be applicable to the coal-burning boiler low-temperature flue gas process such as thermal power plant, cement plant.
Background technology
Nitrogen oxide (NO
x) be one of main chief culprit causing air environmental pollution, there is very strong toxicity, be discharged in air and can cause very large harm to health, living environment and ecologic stability.Acid rain, photochemical fog, gray haze can be caused and great harm is caused to human health and animal and plant growth, wherein the flue gas of discharged from coal-fired boiler is that NO_x in Air Environment mainly must one of be originated, account for 46%, therefore the control of exhaustion of nitrogen oxides from coal-fired boiler is seemed particularly important, existing denitration technology mainly contains selective catalytic reduction, non-selective catalytic reduction, plasma method, absorption method etc.Wherein, SCR (SCR) method is current most widely used the most effective general denitration technology, mainly by reducing agent NH
3mix with flue gas in injection of flue gas, under catalyst action, NH
3at a certain temperature selectively with NO
xthere is redox reaction and generate N
2and H
2o, thus the object reaching clean discharge.
Conventional SCR denitration mainly experienced by noble metal catalyst, zeolite molecular sieve catalyst and present widely used metal oxide catalyst according to development course, and metal oxide is generally with Detitanium-ore-type TiO
2for carrier, with V
2o
5, V
2o
5-WO
3, V
2o
5-MoO
3or V
2o
5-WO
3-MoO
3be active catalyst component Deng metal oxide, active temperature windows is between 300-400 DEG C.In conjunction with China's coal-burning boiler present situation, flue gas at the same time after deduster and desulfurization temperature can decline to a great extent, so normally cannot meet the optimum activity temperature window scope of conventional commercial catalysts, extra installation steam heater and heat exchanger is needed to carry out height flue-gas temperature, waste mass energy, directly causes SCR technique input cost significantly to increase, and is unfavorable for the feasibility of industry, in addition, catalyst activity is also subject to steam, SO
2deng impact, therefore the unaffected SCR catalyst developed under low temperature environment obviously has realistic meaning.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of this invention is to provide a kind of preparation method of low temperature SCR denitration catalyst, low temperature SCR denitration catalyst prepared by the method has good low-temperature denitration performance, and preparation cost is relatively cheap.
A kind of zirconium manganese oxide of the present invention and attapulgite clay compounded low temperature SCR denitration catalyst, carrier material is attapulgite, and active component is Mn oxide, and Supplementary active compounds is Zirconium oxide
Present invention also offers described zirconium manganese oxide and attapulgite clay compounded denitrating catalyst preparation method, comprise the following steps:
Step 1, be distributed in 200ml deionized water by under 20g attapulgite Ultrasonic Conditions, add the hydrochloric acid solution 20ml that mass fraction is 37% more wherein, after uniform temperature water-bath back flow reaction, filtration washing is extremely neutral and dry, obtains the attapulgite after purifying for subsequent use;
Step 2, take 210.14g Citric Acid Mono [C
6h
8o
7h
2o] put into 200ml beaker, add after 100ml deionized water and stirring is dissolved and be transferred in 500ml volumetric flask, then adding deionized water, to be configured to 2mol/L citric acid solution 500ml for subsequent use;
Step 3, take a certain amount of manganese nitrate [50%Mn (NO
3)
2] and cerous nitrate [Ce (NO
3)
45H
2o] join in 100ml beaker, add 2mol/L citric acid solution 50ml wherein, stir and make it dissolve, then add the attapulgite 2g after purification, continue to stir until present colloidal sol shape again after stirring added appropriate glacial acetic acid after one hour;
Step 4, the gel of above-mentioned formation is put into incubator, after uniform temperature ageing 24h, colloidal sol becomes gel, is moved in Muffle furnace by gel and calcines, and carries out the obtained zirconium manganese oxide of grinding screening and attapulgite clay compounded low temperature SCR denitration catalyst to the solid after calcining.
As preferred preparation method, the back flow reaction described in step 1 is reflux 12 hours in 60 DEG C of water-baths.
As preferred preparation method, the manganese nitrate consumption described in step 3 to be 2.27g mass fraction be 50% manganese nitrate solution.
As preferred preparation method, the zirconium nitrate consumption described in step 3 is the mol ratio of element manganese and zirconium is 20 ~ 6:1.
As preferred preparation method, the glacial acetic acid consumption described in step 3 is 8ml.
As preferred preparation method, the uniform temperature described in step 4 is 60 DEG C.
As preferred preparation method, the calcining heat described in step 4 is 300 DEG C, and heating rate is 10-15 DEG C/min, and calcination time is 6 hours.
The present invention selects attapulgite to replace Detitanium-ore-type TiO
2as catalyst carrier, Mn oxide is as active catalytic components, and Zirconium oxide is as auxiliary activity catalyst component.Attapulgite has large specific area and pore volume, can provide sufficient active component attachment site, and plays abundance, cheap and easy to get, environment friendly and pollution-free; Manganese has multiple variable valence, can meet the gain and loss of electronics in low-temperature denitration reaction, thus low-temperature denitration reaction can be completed, and the auxiliary catalysis of Zirconium oxide can improve the quantity of reaction site, thus the performance of catalyst in low temperature.
Advantage of the present invention is:
(1) the present invention selects attapulgite to replace Detitanium-ore-type TiO
2as catalyst carrier, it has large specific area and pore volume, can provide sufficient attachment site catalysis to active catalytic components; Select Mn oxide as active catalytic components, mainly because element manganese has multiple variable valence, the gain and loss of electronics in low-temperature denitration reaction can be met, thus make catalysis low-temperature denitration react feasible, select the auxiliary catalysis of Zirconium oxide can improve the quantity of reaction site, thus improve the performance of catalyst in low temperature;
(2) adopt hydrochloric acid purification attapulgite original soil that the soluble metallic salt in attapulgite can be made to dissolve, increased surface area and the pore volume of attapulgite further, for active component provides more active attachment site;
(3) attapulgite is rich in minerals, cheap and easy to get, asepsis environment-protecting, the nitrate compound of active presoma component manganese zirconium is easy to get, and manganese nitrate is the presoma of major constituent, and zirconium nitrate is the presoma of Supplementary active compounds, citric acid solution is solvent, be conducive to forming colloidal sol, safe preparation process is simple to operation, and raw material availability is high;
(4) catalyst that prepared by the present invention is applied to the district's denitration of boiler fired coal flue gas low-temperature, do not need to make large change to China's existing device, the interval catalyst of the pyroreaction easily problem such as the interval catalyst performance difference of poisoning and low-temp reaction can be avoided again, reduce production cost, improve transformation efficiency;
(5) catalyst provided by the present invention is by SO
2affect minimum, at logical SO
2condition under still there is fabulous activity.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in more detail, but embodiments of the present invention are not limited only to this.
All first, purification processes is carried out to attapulgite in following enforcement, through following treatment step: be distributed in 200ml deionized water by under 20g attapulgite Ultrasonic Conditions, add the hydrochloric acid solution 20ml that mass fraction is 37% more wherein, after uniform temperature water-bath back flow reaction, filtration washing is extremely neutral and dry, obtains the attapulgite after purifying for subsequent use.
Embodiment 1
(1) to feed intake configuration mixed solution according to following parameter:
2mol/L citric acid solution is 20ml
50% manganese nitrate solution is 1.7086g
Five water cerous nitrate quality are 0.1172g
(2) by the mixed solution stirring and dissolving of gained, the attapulgite 2g after adding purification, continues to stir;
(3) in mixture, add 10ml glacial acetic acid continue to stir, to forming colloidal sol shape;
(4) colloidal sol of formation is put into insulating box, constant temperature 60 DEG C of ageings 24 hours, become gel;
(5) being transferred to by gel in Muffle furnace is that 10-15 DEG C/min is warming up to 300 DEG C with speed, and keeps 6 hours, and cooling, grinding obtain low-temperature SCR catalyst.
Embodiment 2
(1) to feed intake configuration mixed solution according to following parameter:
2mol/L citric acid solution is 20ml
50% manganese nitrate solution is 1.7086g
Five water cerous nitrate quality are 0.1302g
(2) by the mixed solution stirring and dissolving of gained, the attapulgite 2g after adding purification, continues to stir;
(3) in mixture, add 10ml glacial acetic acid continue to stir, to forming colloidal sol shape;
(4) colloidal sol of formation is put into insulating box, constant temperature 60 DEG C of ageings 24 hours, become gel;
(5) being transferred to by gel in Muffle furnace is that 10-15 DEG C/min is warming up to 300 DEG C with speed, and keeps 6 hours, and cooling, grinding obtain low-temperature SCR catalyst.
Embodiment 3
(1) to feed intake configuration mixed solution according to following parameter:
2mol/L citric acid solution is 20ml
50% manganese nitrate solution is 1.7086g
Five water cerous nitrate quality are 0.1465g
(2) by the mixed solution stirring and dissolving of gained, the attapulgite 2g after adding purification, continues to stir;
(3) in mixture, add 10ml glacial acetic acid continue to stir, to forming colloidal sol shape;
(4) colloidal sol of formation is put into insulating box, constant temperature 60 DEG C of ageings 24 hours, become gel;
(5) being transferred to by gel in Muffle furnace is that 10-15 DEG C/min is warming up to 300 DEG C with speed, and keeps 6 hours, and cooling, grinding obtain low-temperature SCR catalyst.
Embodiment 4
(1) to feed intake configuration mixed solution according to following parameter:
2mol/L citric acid solution is 20ml
50% manganese nitrate solution is 1.7086g
Five water cerous nitrate quality are 0.1675g
(2) by the mixed solution stirring and dissolving of gained, the attapulgite 2g after adding purification, continues to stir;
(3) in mixture, add 10ml glacial acetic acid continue to stir, to forming colloidal sol shape;
(4) colloidal sol of formation is put into insulating box, constant temperature 60 DEG C of ageings 24 hours, become gel;
(5) being transferred to by gel in Muffle furnace is that 10-15 DEG C/min is warming up to 300 DEG C with speed, and keeps 6 hours, and cooling, grinding obtain low-temperature SCR catalyst.
Embodiment 5
(1) to feed intake configuration mixed solution according to following parameter:
2mol/L citric acid solution is 20ml
50% manganese nitrate solution is 1.7086g
Five water cerous nitrate quality are 0.1954g
(2) by the mixed solution stirring and dissolving of gained, the attapulgite 2g after adding purification, continues to stir;
(3) in mixture, add 10ml glacial acetic acid continue to stir, to forming colloidal sol shape;
(4) colloidal sol of formation is put into insulating box, constant temperature 60 DEG C of ageings 24 hours, become gel;
(5) being transferred to by gel in Muffle furnace is that 10-15 DEG C/min is warming up to 300 DEG C with speed, and keeps 6 hours, and cooling, grinding obtain low-temperature SCR catalyst.
Embodiment 6
(1) to feed intake configuration mixed solution according to following parameter:
2mol/L citric acid solution is 20ml
50% manganese nitrate solution is 1.7086g
Five water cerous nitrate quality are 0.2344g
(2) by the mixed solution stirring and dissolving of gained, the attapulgite 2g after adding purification, continues to stir;
(3) in mixture, add 10ml glacial acetic acid continue to stir, to forming colloidal sol shape;
(4) colloidal sol of formation is put into insulating box, constant temperature 60 DEG C of ageings 24 hours, become gel;
(5) being transferred to by gel in Muffle furnace is that 10-15 DEG C/min is warming up to 300 DEG C with speed, and keeps 6 hours, and cooling, grinding obtain low-temperature SCR catalyst.
Embodiment 7
(1) to feed intake configuration mixed solution according to following parameter:
2mol/L citric acid solution is 20ml
50% manganese nitrate solution is 1.7086g
Five water cerous nitrate quality are 0.2930g
(2) by the mixed solution stirring and dissolving of gained, the attapulgite 2g after adding purification, continues to stir;
(3) in mixture, add 10ml glacial acetic acid continue to stir, to forming colloidal sol shape;
(4) colloidal sol of formation is put into insulating box, constant temperature 60 DEG C of ageings 24 hours, become gel;
(5) being transferred to by gel in Muffle furnace is that 10-15 DEG C/min is warming up to 300 DEG C with speed, and keeps 6 hours, and cooling, grinding obtain low-temperature SCR catalyst.
Embodiment 8
(1) to feed intake configuration mixed solution according to following parameter:
2mol/L citric acid solution is 20ml
50% manganese nitrate solution is 1.7086g
Five water cerous nitrate quality are 0.3907g
(2) by the mixed solution stirring and dissolving of gained, the attapulgite 2g after adding purification, continues to stir;
(3) in mixture, add 10ml glacial acetic acid continue to stir, to forming colloidal sol shape;
(4) colloidal sol of formation is put into insulating box, constant temperature 60 DEG C of ageings 24 hours, become gel;
(5) being transferred to by gel in Muffle furnace is that 10-15 DEG C/min is warming up to 300 DEG C with speed, and keeps 6 hours, and cooling, grinding obtain low-temperature SCR catalyst.
Invention adopts fixed bed reactors to carry out the selective catalyst reduction of nitrogen oxides performance test of catalyst, take the quartz ampoule (internal diameter is 11mm) that about 0.3g catalyst is placed in fixed bed reactors, the catalytic performance of the low-temperature catalytic activity window between investigating 100 ~ 240 DEG C.In experiment, the total flow of simulated flue gas is 800-1000ml/min, and air speed is 35000-45000h
-1(air speed is the index of reacting gas reactant in the catalyst bed interlayer time of staying, and air speed is higher, and the activity of catalyst is higher, and the disposal ability of device is stronger), simulated flue gas is by 3%O
2, 600ppmNO, 600ppmNH
3, 100-300ppmSO
2(research SO
2pass into during catalyst efficiency impact experiment) and Balance Air N
2composition, all gas flow is regulated by mass flow controller.During kinetics experiment, selected analog gas total flow is 1000ml/min, and the loading of catalyst is 25mg, selects the quartz sand suitable with catalyst particle size as filler, ensures that bed height is with the same before.
Adopt coal-fired flue-gas analyzer to carry out reactor and import and export NO, NO
2the measurement of concentration, denitration efficiency computing formula is as follows:
As fully visible, NO
xremoval efficiency, up to 98%, leads to SO
2rear NO
xremoval efficiency is still up to 95%.
Claims (8)
1., containing a low temperature SCR denitration catalyst for zirconium manganese oxide, it is characterized in that: described catalyst carrier material is attapulgite, active component is Mn oxide, and Supplementary active compounds is Zirconium oxide.
2. the low temperature SCR denitration catalyst containing zirconium manganese oxide according to claim 1, is characterized in that, comprise the steps:
Step 1, be distributed in 200ml deionized water by under 20g attapulgite Ultrasonic Conditions, add the hydrochloric acid solution 20ml that mass fraction is 37% more wherein, after uniform temperature water-bath back flow reaction, filtration washing is extremely neutral and dry, obtains the attapulgite after purifying for subsequent use;
Step 2, take 210.14g Citric Acid Mono [C
6h
8o
7h
2o] put into 200ml beaker, add after 100ml deionized water and stirring is dissolved and be transferred in 500ml volumetric flask, then adding deionized water, to be configured to 2mol/L citric acid solution 500ml for subsequent use;
Step 3, take a certain amount of manganese nitrate [50%Mn (NO
3)
2] and cerous nitrate [Ce (NO
3)
45H
2o] join in 100ml beaker, add 2mol/L citric acid solution 50ml wherein, stir and make it dissolve, then add the attapulgite 2g after purification, continue to stir until present colloidal sol shape again after stirring added appropriate glacial acetic acid after one hour;
Step 4, the gel of above-mentioned formation is put into incubator, after uniform temperature ageing 24h, colloidal sol becomes gel, is moved in Muffle furnace by gel and calcines, and carries out the obtained zirconium manganese oxide of grinding screening and attapulgite clay compounded low temperature SCR denitration catalyst to the solid after calcining.
3. the low temperature SCR denitration catalyst containing zirconium manganese oxide according to claim 2, is characterized in that: the back flow reaction described in step 1 is reflux 12 hours in 60 DEG C of water-baths.
4. the low temperature SCR denitration catalyst containing zirconium manganese oxide according to claim 2, is characterized in that: the manganese nitrate consumption described in step 3 to be 2.27g mass fraction be 50% manganese nitrate solution.
5. the low temperature SCR denitration catalyst containing zirconium manganese oxide according to claim 2, is characterized in that: the zirconium nitrate consumption described in step 3 is the mol ratio of element manganese and zirconium is 20 ~ 6:1.
6. the low temperature SCR denitration catalyst containing zirconium manganese oxide according to claim 2, is characterized in that: the glacial acetic acid consumption described in step 3 is 8ml.
7. the low temperature SCR denitration catalyst containing zirconium manganese oxide according to claim 2, is characterized in that: the uniform temperature described in step 4 is 60 DEG C.
8. the low temperature SCR denitration catalyst containing zirconium manganese oxide according to claim 2, it is characterized in that: the calcining heat described in step 4 is 300 DEG C, heating rate is 10-15 DEG C/min, and calcination time is 6 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107694575A (en) * | 2017-09-15 | 2018-02-16 | 大唐南京环保科技有限责任公司 | A kind of complex carrier SCR denitration and preparation method |
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| CN103464177A (en) * | 2013-09-24 | 2013-12-25 | 盐城工学院 | Fluorine-doped ceria and attapulgite SCR denitration catalyst and preparation method thereof |
-
2015
- 2015-09-21 CN CN201510601967.XA patent/CN105214650A/en active Pending
Patent Citations (2)
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| CN102114424B (en) * | 2010-12-29 | 2012-10-24 | 国电科学技术研究院 | Low-temperature smoke denitration SCR (silicon controlled rectifier) catalyst and preparation method |
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Non-Patent Citations (2)
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107694575A (en) * | 2017-09-15 | 2018-02-16 | 大唐南京环保科技有限责任公司 | A kind of complex carrier SCR denitration and preparation method |
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Application publication date: 20160106 |