CN108636401B - Novel Mn and Ce co-doped ZrO2Aerogel low-temperature denitration catalyst - Google Patents
Novel Mn and Ce co-doped ZrO2Aerogel low-temperature denitration catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 15
- 239000004964 aerogel Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011572 manganese Substances 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000005520 cutting process Methods 0.000 claims abstract description 6
- 239000000701 coagulant Substances 0.000 claims abstract description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 5
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 claims description 4
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 9
- 235000019441 ethanol Nutrition 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 229910000420 cerium oxide Inorganic materials 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract description 2
- 229910002651 NO3 Inorganic materials 0.000 abstract 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 15
- 239000000499 gel Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910001960 metal nitrate Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000004967 Metal oxide aerogel Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000352 supercritical drying Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Abstract
The invention discloses a novel Mn and Ce co-doped ZrO2An aerogel low-temperature denitration catalyst. The catalyst takes zirconia as a carrier, 5-20% of cerium oxide as a catalytic assistant and 5-20% of manganese oxide as an active component, is a low-temperature denitration catalyst with mesopores and micropores coexisting and an aerogel structure, and has a specific surface area of 350-500 m2·g‑1The pore size distribution is 1-50 nm. Mn, Ce codoped ZrO2The low-temperature denitration catalyst for the aerogel takes nitrate as a raw material, the nitrate is dissolved in an alcohol aqueous solution according to a certain proportion, a coagulant and a drying control agent are added, the mixture is uniformly stirred, and then the mixture is subjected to water bath at a certain temperature to form gel; and cutting the gel into blocks, placing the blocks in absolute ethyl alcohol to obtain alcohol gel, and drying the alcohol gel in an oven to constant weight to obtain the catalyst. The novel Mn and Ce co-doped ZrO2The aerogel low-temperature denitration catalyst has the advantages of low cost, high denitration efficiency, strong sulfur resistance and the like, and instruments and equipment required by preparation are simple, so that the industrial production is easy to realize.
Description
Technical Field
The invention belongs to the field of catalytic technology and environmental protection, and particularly relates to a novel Mn and Ce co-doped ZrO2An aerogel low-temperature denitration catalyst.
Technical Field
In recent years, nitrogen oxides have been reported to be one of the important causes of haze weather. Causing great harm to the ecological environment and human health. The emission of nitrogen oxides in China has become the world first by 2012, and reaches 2194 ten thousand t. It is expected that the emission of nitrogen oxides will reach 3000 kilotons by 2020. The emission reduction of nitrogen oxides is urgently controlled, and the nitrogen oxides are an important task for controlling air pollution in the coming years. Currently, the industrialized denitration technology is mainly adopted by NH3Is a selective catalytic reduction (NH) of a reducing agent3SCR) denitration technology, the catalyst being the core of this technology. The catalyst which has been commercialized is V2O5-WO3/TiO2The high-temperature SCR denitration catalyst is mainly high in working temperature and easy to be influenced by the external environment, so that the efficiency of the catalyst is reduced, and the service life of the catalyst is shortened. Therefore, research into low-temperature, high-efficiency NH3SCR denitration catalysts become hot spots. Currently, NH with manganese and cerium as main active components3SCR catalyst, because of their special electronic arrangement and their synergistic effect, the series of catalysts shows good low-temperature catalytic performance. NH with manganese and cerium as main active components3The SCR catalyst mainly adopts a sol impregnation method to load an active component on a carrier, and the problems of unstable load, low specific surface area of the active component, unfavorable influence of a pore structure on gas adsorption and mass transfer process in catalytic reaction and the like exist, so that the catalytic activity of the catalyst is limited to be improvedHigh and reduced service life.
The aerogel is also called xerogel, and when the gel is dried, the pore structure is retained to the maximum extent, and a solid substance with extremely low density is generated. In the last 30 s of the century, aerogels were first prepared synthetically by Kistler. The aerogel has the characteristics of high specific area, high porosity, pore size distribution with different sizes and the like, and is widely applied to the fields of catalysts, catalyst carriers, heat insulation materials, filtering materials, acoustic impedance coupling materials and the like.
The method for preparing the metal oxide aerogel generally uses metal alkoxide as a raw material, prepares metal alkoxide gel by a sol-gel method, and finally prepares the metal oxide aerogel by a supercritical drying method. However, the above-mentioned preparation method has disadvantages of expensive price of metal alkoxide, difficult storage, complicated operation of supercritical drying method, and the like, and has a certain risk. In recent years, ZrO is prepared by taking metal nitrate as a raw material and propylene oxide as a network inducer in a normal pressure drying mode2、Al2O3And the like. The normal pressure drying method simplifies the preparation process of the aerogel, reduces the preparation cost and greatly promotes the industrial application of the aerogel. The present invention is directed to the current NH3The problems of lower specific surface area, non-ideal pore structure and the like of the SCR catalyst are solved by providing the Mn and Ce co-doped ZrO with high specific surface area and high porosity2The aerogel low-temperature denitration catalyst can provide a large number of active sites for catalytic reaction, improves the adsorption performance of reaction gas, and provides favorable guarantee for the activity of the catalyst. The catalyst is prepared by using cheap metal nitrate as a raw material and adopting an improved simple normal-pressure drying method, so that the preparation cost of the catalyst is reduced, and the catalyst has an industrial prospect.
Disclosure of Invention
The invention aims to disclose a novel Mn and Ce co-doped ZrO with low cost, high efficiency and good sulfur resistance, and is suitable for flue gas of industrial enterprises2The aerogel low-temperature denitration catalyst is a mesoporous and microporous low-temperature denitration catalyst with an aerogel structureA catalyst. The specific surface area of the low-temperature denitration catalyst with the aerogel structure is 350-500 m2·g-1The pore size distribution is 1-50 nm. The aerogel structure low-temperature denitration catalyst takes zirconia as a carrier, 5-20% of cerium oxide as a catalytic assistant and 5-20% of manganese oxide as an active component. The preparation method of the aerogel structure low-temperature denitration catalyst comprises the following steps:
(1) preparing a certain proportion of alcohol-water solution and placing the alcohol-water solution in a reaction container;
(2) adding soluble zirconyl nitrate, manganese nitrate tetrahydrate and cerium nitrate into a reaction vessel according to a ratio, and stirring for 40-60 min until the soluble zirconyl nitrate, the manganese nitrate tetrahydrate and the cerium nitrate are fully dissolved;
(3) adding a certain amount of propylene oxide as a gel coagulant, adding a proper amount of formamide as a chemical drying control additive, and stirring for 20-30 min;
(4) putting the solution in a water bath kettle at the temperature of 60-80 ℃ for 1-3 h;
(5) cutting the obtained gel into blocks, and soaking in absolute ethyl alcohol for 20-50 h;
(6) drying the obtained alcohol gel in an oven at the temperature of 40-60 ℃ to constant weight to obtain the novel Mn and Ce co-doped ZrO2An aerogel low-temperature denitration catalyst.
The invention has the advantages and beneficial effects that:
(1) the invention firstly proposes that Mn and Ce are codoped with ZrO2The aerogel is used as a low-temperature denitration catalyst, the catalyst has an aerogel pore structure, the specific surface area is high, and the pore structure is favorable for the adsorption of the catalyst on gas and the mass transfer process in the catalytic reaction.
(2) The catalyst disclosed by the invention is ZrO2The aerogel is used as a catalyst carrier, the doped Ce is used as a catalytic assistant, and the Mn is used as an active component, so that the low-temperature denitration efficiency is high, the sulfur resistance is good, and the service life of the catalyst is long.
(3) The catalyst disclosed by the invention is prepared by taking cheap metal nitrate as a raw material and adopting an improved normal-pressure drying method, and has the characteristics of low cost, simple operation steps and easiness in industrial production.
Drawings
FIG. 1 shows the catalyst obtained in example 1N of A2Adsorption-desorption isotherms and pore size distribution of catalyst a.
Figure 2 is the XRD diffraction pattern of catalyst a of example 1 after calcination at 500 ℃.
FIG. 3 is a scanning electron micrograph of catalyst A of example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention:
example 1:
50ml of an alcohol-water solution having an alcohol-water ratio of 3 was weighed and placed in a beaker, and 0.0135mol of Zr (NO) was added3)4·5H2O with 0.0015mol of Ce (NO)3)3·6H2Dissolving O in the above solution, and stirring for 30min to obtain clear solution. To the above solution was added 12ml of propylene oxide followed by 0.9ml of formamide and stirring was continued for 30 min. The sample was then gelled and aged for 2.5h in a water bath environment at 70 ℃. Cutting the formed alcohol hydrogel into blocks, soaking the blocks in a water bath environment at 60 ℃ for 48 hours by using absolute ethyl alcohol, and finally blowing and drying the soaked gel in an oven at 40 ℃ to obtain the blocky aerogel denitration catalyst A with the specific surface area of 442.16m2·g-1. When the denitration reaction temperature is 150 ℃, the denitration efficiency of the catalyst A reaches 85%.
Example 2:
50ml of an aqueous alcohol solution having an alcohol-water ratio of 2.5 was measured and placed in a beaker, and 0.012mol of Zr (NO) was added3)4·5H2O, 0.0015mol of Mn (NO)3)2·4H2O with 0.0015mol of Ce (NO)3)3·6H2And O, dissolving in the solution, and stirring for 30min to obtain a clear solution. To the above solution was added 10.6ml of propylene oxide followed by 0.6ml of formamide and stirring was continued for 30 min. The sample was then subjected to a gelation and aging process in a water bath environment at 65 ℃ for 3 hours. Cutting the formed alcohol hydrogel into blocks, soaking the blocks in a water bath environment at 60 ℃ for 35 hours by using absolute ethyl alcohol, and finally blowing and drying the soaked gel in an oven at 50 ℃ to obtain a blocky aerogel denitration catalyst B with the specific surface area of 402.31m2·g-1. When the denitration reaction temperature is 150 ℃, the denitration efficiency of the catalyst B reaches 90%.
Example 3:
50ml of an alcohol-water solution having an alcohol-water ratio of 2.8 was measured and placed in a beaker, and 0.0115mol of Zr (NO)3)4·5H2O, 0.002mol of Mn (NO)3)2·4H2O with 0.0015mol of Ce (NO)3)3·6H2And O, dissolving in the solution, and stirring for 30min to obtain a clear solution. To the above solution was added 12.0ml of propylene oxide followed by 1.0ml of formamide and stirring was continued for 30 min. The sample was then subjected to a gelation and aging process in a 70 ℃ water bath environment for 3 hours. Cutting the formed alcohol hydrogel into blocks, soaking the blocks in a water bath environment at 60 ℃ for 40 h by using absolute ethyl alcohol, replacing the absolute ethyl alcohol once in the process, and finally blowing and drying the soaked gel at 55 ℃ in an oven to obtain a blocky aerogel denitration catalyst B, wherein the specific surface area of the blocky aerogel denitration catalyst B reaches 402.31m2·g-1. When the denitration reaction temperature is 150 ℃, the denitration efficiency of the catalyst B reaches 95%.
Denitration test conditions:
denitration activity test reaction condition: catalyst space velocity (NO) ═ NH3)＝0.05％，(O2) 5 percent, the space velocity ratio is 30000/h, and nitrogen with the purity of 99.99 percent is adopted as the balance gas.
The denitration activity of the catalyst is characterized by the conversion rate, and the conversion rate eta is calculated according to the following formula:
η＝(NOx inlet－NOx outlet)/NOx inlet×100％
In the formula: NOx inletIs the inlet NO of the reactorxConcentration of NOx outletIs export NOxAnd (4) concentration.
NOx＝NO+NO2。
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (2)
1. Mn and Ce co-doped ZrO2The aerogel low-temperature denitration catalyst is characterized by being a low-temperature denitration catalyst with mesopores and micropores and an aerogel structure, and ZrO is used as the catalyst2The aerogel is used as a catalyst carrier, 5-20% of doped Ce is used as a catalytic assistant, and 5-20% of doped Mn is used as an active component; the preparation method of the catalyst comprises the following steps:
(1) preparing a certain proportion of alcohol-water solution and placing the alcohol-water solution in a reaction container;
(2) adding soluble zirconyl nitrate, manganese nitrate tetrahydrate and cerium nitrate into a reaction vessel according to a ratio, and stirring for 40-60 min until the soluble zirconyl nitrate, the manganese nitrate tetrahydrate and the cerium nitrate are fully dissolved;
(3) adding a certain amount of propylene oxide as a gel coagulant, adding a proper amount of formamide as a chemical drying control additive, and stirring for 20-30 min;
(4) putting the solution in a water bath kettle at the temperature of 60-80 ℃ for 1-3 h;
(5) cutting the obtained gel into blocks, and soaking in absolute ethyl alcohol for 20-50 h;
(6) drying the obtained alcogel in an oven at the temperature of 40-60 ℃ to constant weight to obtain Mn and Ce co-doped ZrO2An aerogel low-temperature denitration catalyst.
2. A Mn, Ce co-doped ZrO according to claim 12The aerogel low-temperature denitration catalyst is characterized in that the proportion of an alcohol-water solution is 1-3.
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| CN201810394288.3A CN108636401B (en) | 2018-04-27 | 2018-04-27 | Novel Mn and Ce co-doped ZrO2Aerogel low-temperature denitration catalyst |
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| CN201810394288.3A CN108636401B (en) | 2018-04-27 | 2018-04-27 | Novel Mn and Ce co-doped ZrO2Aerogel low-temperature denitration catalyst |
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| CN108636401B true CN108636401B (en) | 2020-12-11 |
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| CN111346678A (en) * | 2020-03-30 | 2020-06-30 | 安徽元琛环保科技股份有限公司 | Preparation method of denitration catalyst with aerogel as carrier and prepared catalyst |
| CN114870849A (en) * | 2022-03-31 | 2022-08-09 | 南京工业大学 | Composite oxide aerogel catalytic material and preparation method and application thereof |
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