CN103831096B - A kind of MnOOH nanometer rods denitrating catalyst and preparation method thereof - Google Patents
A kind of MnOOH nanometer rods denitrating catalyst and preparation method thereof Download PDFInfo
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- CN103831096B CN103831096B CN201410092029.7A CN201410092029A CN103831096B CN 103831096 B CN103831096 B CN 103831096B CN 201410092029 A CN201410092029 A CN 201410092029A CN 103831096 B CN103831096 B CN 103831096B
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- nanometer rods
- mnooh
- mnooh nanometer
- catalyst
- denitrating catalyst
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Abstract
The present invention discloses a kind of MnOOH nanometer rods denitrating catalyst and preparation method thereof, and this catalyst comprises MnOOH nanometer rods and CeO attached thereto
2.Preparation method is: potassium permanganate and DMF are carried out solvent thermal reaction 2h ~ 4h at 100 ~ 200 DEG C and obtains MnOOH nanometer rods; Absolute ethyl alcohol and nano Ce O
2particle joins in reacted solution, and ultrasonic wave stirs 3h-5h, makes nano Ce O
2the abundant load of particle is in MnOOH nanometer rods; Then carry out Separation of Solid and Liquid to the product after dipping, washing, drying obtain MnOOH-CeO
2composite catalyst.This preparation method's process is simple, and easy and simple to handle, be convenient to suitability for industrialized production, this catalyst does not have toxicity, and security is high, decreases the harm that the catalyst after use causes environment.
Description
Technical field
The present invention relates to flue gas demercuration technical field, for coal-burning power plant's denitrating catalyst, be specifically related to a kind of MnOOH nanometer rods denitrating catalyst.
Background technology
Nitrogen oxide (NOx) emission control of coal fired power plant is the major tasks in country " 12 " period energy-conserving and environment-protective field, and " fossil-fuel power plant atmospheric pollutant emission standard " (GB13223-2011) of up-to-date promulgation has formulated control criterion (100mg/m the strictest in world wide especially to NOx emission concentration
3).Along with the appearance of these national policies, how effectively the discharge of control NOx has become one of important topic urgently to be resolved hurrily in current power field of Environment Protection.
At present, SCR denitration demercuration technology is adopted in the denitrating flue gas knot group about 90% built or plan to build.Catalyst is the core of SCR technology, and existing commercial catalyst is generally V
2o
5-WO
3/ TiO
2.
The SCR that the SCR that SCR demercuration technology can be divided into high ash to arrange according to position difference, low ash are arranged and the SCR that end is arranged.But due to the restriction of demercuration temperature, most factory faces adopt high ash to arrange.In China, because the shortage that clean coal technology uses, after coal combustion, fly ash content is very high.Directly cause catalysis to block passivation serious, catalyst is shorter than abroad service life, and power plant's denitration cost significantly increases.Simultaneously due to V
2o
5itself belongs to extremely toxic substance, the V after using
2o
5very large destruction is caused to environment.
Summary of the invention
For the problems referred to above that prior art exists, an object of the present invention is the deficiency existed for present demercuration technical field, provide a kind of high security, low stain, catalytic performance excellent and the MnOOH nanometer rods denitrating catalyst of product low cost.
Another object is to provide a kind of method preparing above-mentioned MnOOH nanometer rods denitrating catalyst.
For achieving the above object, the present invention adopts following technical scheme: a kind of MnOOH nanometer rods denitrating catalyst, comprises MnOOH nanometer rods and CeO attached thereto
2, wherein MnOOH nanometer rods is carrier and active material, CeO
2it is active material.
As optimization, described MnOOH nanometer rods and CeO
2mol ratio be 5.93 ~ 1.98:1.Inventor is through many experiments and data analysis, find when the mol ratio of two kinds of active materials controls in above-mentioned scope, catalyst denitration rate obtained under this proportioning is the most desirable, and the productive rate of catalyst is also higher, thus significantly reduces the generation cost of catalyst.
Described MnOOH nanorod diameter is 8nm ~ 12nm, and length is 50nm ~ 500nm.Reach the requirement of experiment to specific surface area of catalyst, prolong smoke, in the time of staying of catalytic inner, is convenient to the activation of catalyst and reuses.
Prepare a method for above-mentioned MnOOH nanometer rods denitrating catalyst, comprise the following steps:
1) by potassium permanganate and N, dinethylformamide carries out solvent thermal reaction 2h ~ 4h at the temperature of 100 DEG C ~ 200 DEG C, obtain MnOOH nanometer rods, wherein potassium permanganate and N, dinethylformamide reacts according to the w/v of 1g: 20 ~ 100ml, namely the quality of potassium permanganate and the volume ratio of DMF are 1g:20 ~ 100ml;
2) by absolute ethyl alcohol and nano Ce O
2particle joins in the reacted solution of step 1), and ultrasonic wave stirs 3h ~ 5h, makes nano Ce O
2fully be carried in MnOOH nanometer rods, wherein MnOOH nanometer rods and CeO
2mol ratio be: 5.93 ~ 1.98:1;
3) step is by 2) in reacted product carry out Separation of Solid and Liquid, then successively with distilled water, acetone washing be separated after solid, finally at the temperature of 30 DEG C ~ 100 DEG C, dry 1h ~ 3h obtains MnOOH nanometer rods denitrating catalyst.
As optimization, described step 1) is carried out in autoclave.Under the reaction of this enclosed system, effectively reduce air and the oxidation of required presoma disturb, and course of reaction relatively simple, be easy to control.Control the growth of crystal by solvent DMF, the MnOOH nanorod shape finally formed is controlled.
The mode of centrifugation is adopted to carry out Separation of Solid and Liquid in described step 3).The mode of centrifugation effectively can improve the speed of separation, thus obtained highly purified composite catalyst.
Relative to prior art, tool of the present invention has the following advantages:
1, this is a breakthrough in denitration technology field, proposes first with MnOOH to be carrier.According to up-to-date experimental result, MnOOH nanometer rods inherently has good denitration rate, and under typical simulation flue gas condition, at 350 DEG C, denitration rate is stabilized in about 70%.The present invention with MnOOH nanometer rods for carrier, carrying active substance CeO
2the active sites of the two can be allowed mutually to superpose, reach desirable denitration rate.MnOOH nanometer rods is as a kind of low temperature without harm or normal-temperature catalyst simultaneously, has extremely strong researching value.
2, relative to traditional vanadium titanium tungsten catalyst, MnOOH nanometer rods denitrating catalyst and MnOOH-CeO
2composite catalyst does not have toxicity, and therefore security is high, the more important thing is, decreases the harm that the catalyst after use causes environment.
3, due to special confinement effect and quantum effect, the growth of active nanoparticles suffers restraints, and its size diminishes, and contributes to generating more Donna rice grain defect and Lacking oxygen, and its catalytic activity strengthens, and the selective of reaction also effectively strengthens, therefore, once CeO
2enter in MnOOH nanometer rods, its catalytic activity and selectively all will effectively to strengthen.
4, with traditional commercial V
2o
5-WO
3/ TiO
2graininess denitrating catalyst is compared, and solid-state noxious material completely cuts off outside tube wall by MnOOH nanometer rods provided by the invention, makes it contact to be positioned at the active nano CeO of pipe interior
2particle, avoids the toxic action of poisonous substance to active nanoparticles.
5, MnOOH nanometer rods denitrating catalyst preparation method provided by the invention is simple, easy and simple to handle, be convenient to suitability for industrialized production, the catalyst simultaneously prepared has good denitration rate, the requirement of denitrating flue gas can be met, be conducive to promoting China's denitrating catalyst industrialization process, have a good application prospect.
Accompanying drawing explanation
Fig. 1 is the FB(flow block) of MnOOH nanometer rods denitrating catalyst preparation method.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
embodiment 1:
Get 1g potassium permanganate and 20mlN, dinethylformamide puts into autoclave, carries out solvent thermal reaction 2h, obtain MnOOH nanometer rods at the temperature of 100 DEG C.Get 1gCeO
2particle and 5ml absolute ethyl alcohol join in reacted solution, and ultrasonic wave stirs 3h, makes CeO
2in sufficient load and MnOOH nanometer rods.Then adopt the mode of centrifugation that reacted product is carried out Separation of Solid and Liquid, wash with distilled water, acetone successively the solid after being separated, finally at the temperature of 30 DEG C, dry 1h obtains MnOOH nanometer rods denitrating catalyst and MnOOH-CeO
2composite catalyst.The end product of grinding gained, gets 0.2g and carries out denitration experiment.
Obtained 0.2g catalyst is put into quartz tube reactor, carries out denitration experiment.Smoke reaction condition is: total gas flow rate is 1L/min, C
o2=4%, C
cO2=12%, N
2=50ml, NH
3=50ml, NH
3/ NO=1:1, N
2as balanced gas, air speed is 60000h
-1.In 350 ~ 400 DEG C, reaction temperature interval, denitration rate is stabilized in more than 86%.
embodiment 2:
Get 1g potassium permanganate and 50mlN, dinethylformamide puts into autoclave, carries out solvent thermal reaction 2h, obtain MnOOH nanometer rods at the temperature of 150 DEG C.Get 0.5gCeO
2particle and 2ml absolute ethyl alcohol join in reacted solution, and ultrasonic wave stirs 3.5h, makes CeO
2in sufficient load and MnOOH nanometer rods.Then adopt the mode of centrifugation that reacted product is carried out Separation of Solid and Liquid, wash with distilled water, acetone successively the solid after being separated, finally at the temperature of 60 DEG C, dry 2h obtains MnOOH nanometer rods denitrating catalyst and MnOOH-CeO
2composite catalyst.The end product of grinding gained, gets 0.2g and carries out denitration experiment.
Obtained 0.2g catalyst is put into quartz tube reactor, carries out denitration experiment.Smoke reaction condition is: total gas flow rate is 1L/min, C
o2=4%, C
cO2=12%, N
2=50ml, NH
3=50ml, NH
3/ NO=1:1, N
2as balanced gas, air speed is 60000h
-1.In 350 ~ 400 DEG C, reaction temperature interval, denitration rate is stabilized in more than 85%.
embodiment 3:
Get 1g potassium permanganate and 75mlN, dinethylformamide, put into autoclave, at the temperature of 175 DEG C, carry out solvent thermal reaction 4h, obtain MnOOH nanometer rods.Get 0.25gCeO
2particle and 1ml absolute ethyl alcohol join in reacted solution, and ultrasonic wave stirs 4h, makes CeO
2in sufficient load and MnOOH nanometer rods.Then adopt the mode of centrifugation that reacted product is carried out Separation of Solid and Liquid, wash with distilled water, acetone successively the solid after being separated, finally at the temperature of 80 DEG C, dry 2.5h obtains MnOOH nanometer rods denitrating catalyst and MnOOH-CeO
2composite catalyst.The end product of grinding gained, gets 0.2g and carries out denitration experiment.
Obtained 0.2g catalyst is put into quartz tube reactor, carries out denitration experiment.Smoke reaction condition is: total gas flow rate is 1L/min, C
o2=4%, C
cO2=12%, N
2=50ml, NH
3=50ml, NH
3/ NO=1:1, N
2as balanced gas, air speed is 60000h
-1.In 350 ~ 400 DEG C, reaction temperature interval, denitration rate is stabilized in more than 88%.
embodiment 4:
Get 1g potassium permanganate and 100mlN, dinethylformamide, put into autoclave, at the temperature of 200 DEG C, carry out solvent thermal reaction 4h, obtain MnOOH nanometer rods.Get 0.1gCeO
2particle and 0.5ml absolute ethyl alcohol join in reacted solution, and ultrasonic wave stirs 5h, makes CeO
2in sufficient load and MnOOH nanometer rods.Then adopt the mode of centrifugation that reacted product is carried out Separation of Solid and Liquid, wash with distilled water, acetone successively the solid after being separated, finally at the temperature of 100 DEG C, dry 3h obtains MnOOH nanometer rods denitrating catalyst and MnOOH-CeO
2composite catalyst.The end product of grinding gained, gets 0.2g and carries out denitration experiment.
Obtained 0.2g catalyst is put into quartz tube reactor, carries out denitration experiment.Smoke reaction condition is: total gas flow rate is 1L/min, C
o2=4%, C
cO2=12%, N
2=50ml, NH
3=50ml, NH
3/ NO=1:1, N
2as balanced gas, air speed is 60000h
-1.In 350 ~ 400 DEG C, reaction temperature interval, denitration rate is stabilized in more than 85%.
What finally illustrate is, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (5)
1. prepare a method for MnOOH nanometer rods denitrating catalyst, it is characterized in that, described MnOOH nanometer rods denitrating catalyst comprises MnOOH nanometer rods and CeO attached thereto
2;
Preparation process comprises:
1) potassium permanganate and DMF are carried out solvent thermal reaction 2h ~ 4h at the temperature of 100 DEG C ~ 200 DEG C, obtain MnOOH nanometer rods, wherein potassium permanganate and DMF react according to the w/v of 1g:20 ~ 100ml;
2) by absolute ethyl alcohol and nano Ce O
2particle joins in the reacted solution of step 1), and ultrasonic wave stirs 3h ~ 5h, makes nano Ce O
2fully be carried in MnOOH nanometer rods, wherein MnOOH nanometer rods and CeO
2mol ratio be: 5.93 ~ 1.98:1;
3) by step 2) in reacted product carry out Separation of Solid and Liquid, then successively with distilled water, acetone washing be separated after solid, finally at the temperature of 30 DEG C ~ 100 DEG C, dry 1h ~ 3h obtains MnOOH nanometer rods denitrating catalyst.
2. prepare the method for MnOOH nanometer rods denitrating catalyst as claimed in claim 1, it is characterized in that: described step 1) is carried out in autoclave.
3. prepare the method for MnOOH nanometer rods denitrating catalyst as claimed in claim 1, it is characterized in that: in described step 3), adopt the mode of centrifugation to carry out Separation of Solid and Liquid.
4. prepare the method for MnOOH nanometer rods denitrating catalyst as claimed in claim 1, it is characterized in that: described MnOOH nanometer rods and CeO
2mol ratio be 5.93 ~ 1.98:1.
5. prepare the method for MnOOH nanometer rods denitrating catalyst as claimed in claim 1, it is characterized in that: described MnOOH nanorod diameter is 8nm ~ 12nm, length is 50nm ~ 500nm.
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| CN104383920B (en) * | 2014-11-18 | 2016-07-06 | 安徽师范大学 | The preparation method of a kind of MnOOH/Ag nano composite material and application thereof |
| CN112516997B (en) * | 2020-11-30 | 2023-04-18 | 南京邮电大学 | CeO 2 /MnO 2 Method for preparing nano-rod |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101011659A (en) * | 2007-02-07 | 2007-08-08 | 南开大学 | Catalyst for SCR denitration in boiler low-temperature fume and preparation method thereof |
| CN102219263A (en) * | 2011-05-20 | 2011-10-19 | 浙江大学 | Method for preparing Gamma-MnOOH nanometer rod |
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|---|---|---|---|---|
| JP2003080033A (en) * | 2001-09-07 | 2003-03-18 | Mitsubishi Heavy Ind Ltd | Method for denitrifying exhaust gas and system therefor |
| JP4508584B2 (en) * | 2003-09-05 | 2010-07-21 | 三菱重工業株式会社 | Denitration catalyst for high temperature exhaust gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101011659A (en) * | 2007-02-07 | 2007-08-08 | 南开大学 | Catalyst for SCR denitration in boiler low-temperature fume and preparation method thereof |
| CN102219263A (en) * | 2011-05-20 | 2011-10-19 | 浙江大学 | Method for preparing Gamma-MnOOH nanometer rod |
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Granted publication date: 20151230 Termination date: 20180313 |