CN100528345C - Denitration catalyst, and preparation method - Google Patents
Denitration catalyst, and preparation method Download PDFInfo
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- CN100528345C CN100528345C CNB2006100281918A CN200610028191A CN100528345C CN 100528345 C CN100528345 C CN 100528345C CN B2006100281918 A CNB2006100281918 A CN B2006100281918A CN 200610028191 A CN200610028191 A CN 200610028191A CN 100528345 C CN100528345 C CN 100528345C
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Abstract
A denitrating catalyst for the reduction reaction of Nox/NH3 gas mixture to generate N2 and H2O is proportionally prepared from bentone, TiO2, Fe2O3, CuO and H2O. Its preparing process is also disclosed. It has high thermal stability and high resistance to steam.
Description
Technical field
The present invention relates to a kind of denitrating catalyst, and utilize multivariant oxide and bentonite to prepare the method for this denitrating catalyst.
Background technology
The coal in China consumption is big, and the environmental pollution of Yin Faing is particularly serious thus, removes SO
2Outside flue dust, the NOx nitrogen oxide also is main polluter.The present situation of China coal fired power plant NOx discharged nitrous oxides is, nineteen ninety-five discharge capacity be 2,650,000 tons, 2000 is 4,690,000 tons, 2002 is 5,200,000 tons, expects 2010 and will reach 5,500,000 tons, the NOx nitrogen oxide becomes the topmost pollutant effulent of thermal power generation.Nitrogen oxide belongs to toxic and harmful, and human body directly sucks, and can damage nervous centralis and lung tissue, and the NOx in the atmosphere also can generate the bigger photochemical fog of toxicity under certain condition, causes the withered and crowd's death of plant.In addition, nitrogen oxide still is one of main source of acid rain, can cause serious destruction to environment.At present, the most promising NOx control technology is SCR (SCR) NOx control technology, and the key of SCR is to obtain high performance catalyst.
At present, industrial SCR catalyst mainly is V
2O
5/ TiO
2Perhaps V
2O
5-WO
3/ TiO
2Verified these two kinds of catalyst have higher durability and good reactivity, but to sulphur and water vapour sensitivity, and the catalyst murder by poisoning that can be worn and torn, block and be subjected to materials such as arsenic, alkali metal by dust in flue gas, inactivation is comparatively serious, and use cost is high.Therefore, the denitrating catalyst of developing a kind of cheapness is the problem that Selective Catalytic Reduction of NO x control technology presses for solution.
Summary of the invention
First technical problem to be solved by this invention provides a kind of denitrating catalyst that can remove the flue gas NOx pollutant; Second technical problem to be solved by this invention provides a kind of method for preparing above-mentioned denitrating catalyst; The present invention can be widely used in electric power and relevant enterprise flue gas selectivity catalytic denitration (SCR) equal energy source environment-protecting industrial field.
The technical solution used in the present invention: a kind of denitrating catalyst, form by following component: the TiO of the bentonite of 30～70 parts by weight, 5～20 parts by weight
2, 5～10 parts by weight Fe
2O
3, the CuO of 5～15 parts by weight, the moisture content of 3～6 parts by weight.
A kind of method for preparing denitrating catalyst comprises the following steps:
A. be 5～20: 1～5 according to mol ratio: 2～15 prepare absolute ethyl alcohol, butyl titanate and nitric acid, concentration of nitric acid is 0.5～1mol/L, earlier butyl titanate is added in the absolute ethyl alcohol, fully stir and make it to generate yellow solution, then yellow solution is dripped in the described nitric acid, vigorous stirring generates transparent solution, after this be the pH value that the NaOH solution of 0.51mol/L is regulated this clear solution with concentration again, make it to reach 2, fully stir simultaneously, it is stand-by to generate new clear solution;
B. get the bentonite of purification, water fully soaks into, to wherein adding softex kw, wherein said bentonitic molal quantity is 5～20 times of butyl titanate molal quantity, the molal quantity of softex kw is 3～10 times of bentonite molal quantity, the abundant stirring reaction of warp 12～24 hours, adding molal quantity again is the lauryl amine of 5～10 times of bentonite molal quantitys, through abundant stirring reaction after 12～24 hours, it is mixed with new clear solution that step a makes, 60～80 ℃ of vigorous stirring reactions 2～6 hours, adding molal quantity then is the ferric nitrate and the copper nitrate of 0.2～1.0 times of butyl titanate molal quantity, the mol ratio of ferric nitrate and copper nitrate is 0.5～1.5, and last and excess of ammonia water reacts Separation of Solid and Liquid, washing;
C. the mixture that step b is made is dried under 60～100 ℃ of temperature, 400 ℃ roasting temperatures 2～4 hours, promptly makes described denitrating catalyst.
Beneficial effect of the present invention: the present invention is based on natural montmorillonite nanometer layer structure and come compound multivariant oxide, make the catalyst porous and reach cheap large-scale industrial and use.The present invention will be through the combination of oxides Fe that verifies repeatedly
2O
3-TiO
2-CuO, stage by stage carry out the catalyst that reaction in-situ is made high specific surface area, made full use of Fe
2O
3-TiO
2Synergy between-CuO and the bentonite structure, catalyst surface is formed fully expose, be easy to approaching catalytic reaction activity center, catalyst is when having higher stability, bring into play the synergy at surperficial multicomponent reactive center, reached the purpose of the high efficiency NOx of removing environmental contaminants.Work as NOx/NH
3Mixture enter into the pore structure of catalyst surface prosperity, with catalyst generation reduction reaction, generate N
2And H
2Behind the O, product gas also easier can escape out, helps denitration reaction.The used primary raw material of the present invention is cheapness and abundant mineral and compound, and preparation process is simple, controlled, does not relate to complex apparatus and operation, and cost is very low.Catalyst of the present invention carries out compoundization and porous with multivariant oxide and bentonite, has not only significantly improved its heat endurance, has water-fast preferably steam performance, and environmental friendliness.
The specific embodiment
Below by embodiment the present invention is described in further detail, a kind of denitrating catalyst is made up of following component: the TiO of the bentonite of 30～70 parts by weight, 5～20 parts by weight
2, 5～10 parts by weight Fe
2O
3, the CuO of 5～15 parts by weight, the moisture content of 3～6 parts by weight.The method for preparing above-mentioned denitrating catalyst, comprise the following steps: that a. is 5～20: 1～5 according to mol ratio: 2～15 prepare absolute ethyl alcohol, butyl titanate and nitric acid, concentration of nitric acid is 0.5～1mol/L, earlier butyl titanate is added in the absolute ethyl alcohol, fully stir and make it to generate yellow solution, yellow solution is dripped in the described nitric acid then, vigorous stirring generates transparent solution, after this be the pH value that the NaOH solution of 0.51mol/L is regulated this clear solution with concentration again, make it to reach 2, fully stir simultaneously, it is stand-by to generate new clear solution; B. get the bentonite of purification, water fully soaks into, to wherein adding softex kw, wherein said bentonitic molal quantity is 5～20 times of butyl titanate molal quantity, the molal quantity of softex kw is 3～10 times of bentonite molal quantity, the abundant stirring reaction of warp 12～24 hours, adding molal quantity again is the lauryl amine of 5～10 times of bentonite molal quantitys, through abundant stirring reaction after 12～24 hours, it is mixed with new clear solution that step a makes, 60～80 ℃ of vigorous stirring reactions 2～6 hours, adding molal quantity then is the ferric nitrate and the copper nitrate of 0.2～1.0 times of butyl titanate molal quantity, the mol ratio of ferric nitrate and copper nitrate is 0.5～1.5, and last and excess of ammonia water reacts Separation of Solid and Liquid, washing; C. the mixture that step b is made is dried under 60～100 ℃ of temperature, 400 ℃ roasting temperatures 2～4 hours, promptly makes described denitrating catalyst.
The invention provides the method that a kind of ternary oxide combination and bentonite prepare novel denitrating catalyst in proportion, be mainly used in the improvement of environmental contaminants.Catalyst of the present invention is converted into N with NOx
2After the discharging, environment and ecological protection have been realized.Catalyst of the present invention is easy to regeneration and uses, even long-term storage or directly abandon secondary pollution can not take place yet.Adopt Japanese D/Max of science one 2500VB2+/PC X-ray diffractometer to analyze the pore structure of (XRD) research catalyst of the present invention, the structure sheaf spacing can be asked for by Bragg formula λ=2dsin θ; Adopt JEM one 2000EX type transmission electron microscope that catalyst of the present invention is carried out particle diameter and morphology analysis thereof; Adopt U.S. ASAP 2405 absorption instrument (BET method) to measure the specific area of catalyst.The test condition of catalyst denitration performance is: internal diameter 10mm fixed bed reactors, inlet mist are that to contain mol ratio be 1 NOx/NH in carrier gas with nitrogen
3, add 1% water vapour, temperature is 350 ℃, to in fixed bed reactors, establish the steel wire of 1～2 layer of aperture during the catalyst filling less than agent kind particle diameter, online face laying depth is that 200mm, granularity are the porcelain ball of about 10mm, and catalyst agent bed should load smooth even as far as possible, atmospheric operation.
Embodiment one
Measure mol ratio and be 5: 2: 3 absolute ethyl alcohol, butyl titanate, concentration is the nitric acid of 1mol/L, earlier butyl titanate is added in the absolute ethyl alcohol, makes it to form yellow solution, then this drips of solution is added in the above-mentioned nitric acid through fully stirring, generate transparent solution through vigorous stirring, after this regulate making the pH value reach 2 again with the NaOH solution of concentration 0.5mol/L, fully stir simultaneously, clear solution is stand-by until generating.Get the bentonite of purification, its amount is 8 times of the butyl titanate molal quantity, and water fully soaks into, adding molal quantity again is the softex kw of 10 times of bentonites, the abundant stirring reaction of warp 12 hours, adding molal quantity again is the lauryl amine of 10 times of bentonites, continue reaction after 24 hours, it is mixed with the above-mentioned clear solution that makes, and 80 ℃ of vigorous stirring reactions 2 hours, adding molal quantity then was 0.5 times magnesium nitrate and copper nitrate of butyl titanate, the mol ratio of ferric nitrate and copper nitrate is 0.5, after reacting by excess of ammonia water, with its Separation of Solid and Liquid, washing, then this mixture is dried under 80 ℃ temperature, 400 ℃ roasting temperature 2 hours, promptly make described catalyst subsequently, its composition is the bentonite of 61wt%; The TiO of 20wt%
2The Fe of 10wt%
2O
3The CuO of 5wt%; Total water content of 4wt%.The interlamellar spacing of XRD determining is 3.05nm, and tem analysis oxide particle particle diameter is between 20～50nm, and the specific area that BET measures is 265m
2/ g, the removal efficiency of NOx are 85%.
Embodiment two
Measure mol ratio and be 15: 5: 3 absolute ethyl alcohol, butyl titanate, concentration is the nitric acid of 1mol/L, earlier butyl titanate is added in the absolute ethyl alcohol, makes it to form yellow solution, then this drips of solution is added in the above-mentioned nitric acid through fully stirring, generate transparent solution through vigorous stirring, after this regulate making the pH value reach 2 again with the NaOH solution of concentration 0.5mol/L, fully stir simultaneously, clear solution is stand-by until generating.Get the bentonite of purification, its amount is 20 times of the butyl titanate molal quantity, and fully soak into the water of same quality, adding molal quantity again is the softex kw of 5 times of bentonites, the abundant stirring reaction of warp 12 hours, adding molal quantity again is the lauryl amine of 5 times of bentonites, continue reaction after 12 hours, it is mixed with the above-mentioned clear solution that makes, and 60 ℃ of vigorous stirring reactions 2 hours, adding molal quantity then was 1.0 times magnesium nitrate and copper nitrate of butyl titanate, the mol ratio of ferric nitrate and copper nitrate is 1, after reacting by excess of ammonia water, with its Separation of Solid and Liquid, washing, then this mixture is dried under 60 ℃ temperature, 400 ℃ roasting temperature 2 hours, promptly make described catalyst subsequently, its composition is the bentonite of 66wt%; The TiO of 15wt%
2The Fe of 8wt%
2O
3The CuO of 8wt%; Total water content of 3wt%.The interlamellar spacing of XRD determining is 2.89nm, and tem analysis oxide particle particle diameter is between 15～50nm, and the specific area that BET measures is 208m
2/ g, the removal efficiency of NOx are 81%.
Embodiment three
Measure mol ratio and be 12: 3: 5 absolute ethyl alcohol, butyl titanate, concentration is the nitric acid of 1mol/L, earlier butyl titanate is added in the absolute ethyl alcohol, makes it to form yellow solution, then this drips of solution is added in the above-mentioned nitric acid through fully stirring, generate transparent solution through vigorous stirring, after this regulate making the pH value reach 2 again with the NaOH solution of concentration 0.5mol/L, fully stir simultaneously, clear solution is stand-by until generating.Get the bentonite of purification, its amount is 15 times of the butyl titanate molal quantity, and fully soak into the water of same quality, adding molal quantity again is the softex kw of 5 times of bentonites, the abundant stirring reaction of warp 24 hours, adding molal quantity again is the lauryl amine of 10 times of bentonites, continue reaction after 12 hours, it is mixed with the above-mentioned clear solution that makes, and 80 ℃ of vigorous stirring reactions 6 hours, adding molal quantity then was 1.0 times magnesium nitrate and copper nitrate of butyl titanate, the mol ratio of ferric nitrate and copper nitrate is 1.5, after reacting by excess of ammonia water, with its Separation of Solid and Liquid, washing, then this mixture is dried under 100 ℃ temperature, 400 ℃ roasting temperature 2 hours, promptly make described catalyst subsequently, its composition is the bentonite of 75wt%; The TiO of 10wt%
2The Fe of 5wt%
2O
3The CuO of 5wt%; Total water content of 5wt%.The interlamellar spacing of XRD determining is 3.08nm, and tem analysis oxide particle particle diameter is between 15～50nm, and the specific area that BET measures is 289m
2/ g, the removal efficiency of NOx are 88%.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (1)
1. a denitrating catalyst is made up of following component: the TiO of the bentonite of 30～70 parts by weight, 5～20 parts by weight
2, 5～10 parts by weight Fe
2O
3, the CuO of 5～15 parts by weight, the moisture content of 3～6 parts by weight; Prepare the method for described denitrating catalyst, comprise the following steps:
A. be 5～20: 1～5 according to mol ratio: 2～15 prepare absolute ethyl alcohol, butyl titanate and nitric acid, concentration of nitric acid is 0.5～1mol/L, earlier butyl titanate is added in the absolute ethyl alcohol, fully stir and make it to generate yellow solution, then yellow solution is added drop-wise in the described nitric acid, vigorous stirring generates transparent solution, after this be the pH value that the NaOH solution of 0.51mol/L is regulated this clear solution with concentration again, make it to reach 2, fully stir simultaneously, it is stand-by to generate new clear solution;
B. get the bentonite of purification, water fully soaks into, to wherein adding softex kw, wherein said bentonitic molal quantity is 5～20 times of butyl titanate molal quantity, the molal quantity of softex kw is 3～10 times of bentonite molal quantity, the abundant stirring reaction of warp 12～24 hours, adding molal quantity again is the lauryl amine of 5～10 times of bentonite molal quantitys, through abundant stirring reaction after 12～24 hours, it is mixed with new clear solution that step a makes, 60～80 ℃ of vigorous stirring reactions 2～6 hours, adding molal quantity then is the ferric nitrate and the copper nitrate of 0.2～1.0 times of butyl titanate molal quantity, the mol ratio of ferric nitrate and copper nitrate is 0.5～1.5, and last and excess of ammonia water reacts Separation of Solid and Liquid, washing;
C. the mixture that step b is made is dried under 60～100 ℃ of temperature, 400 ℃ roasting temperatures 2～4 hours, promptly makes described denitrating catalyst.
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| CN103194292A (en) * | 2013-04-25 | 2013-07-10 | 兰州熙瑞化工科技有限公司 | Boiler coal combustion-improving desulfurizing and denitrifying agent composition and preparation method thereof |
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| CN101380578B (en) * | 2007-09-06 | 2011-07-20 | 中国科学院生态环境研究中心 | Ferrotitanium composite oxides catalyst for ammonia selective reduction nitric oxides |
| CN101554589B (en) * | 2008-08-19 | 2012-01-11 | 北京银飞思达科技有限公司 | Copper and iron modified titanium dioxide pillared bentonite catalyst and preparation method thereof |
| CN103706369A (en) * | 2014-01-02 | 2014-04-09 | 张继惟 | Toxic-free perovskite-type catalyst capable of being molded rapidly |
| CN104128188A (en) * | 2014-08-15 | 2014-11-05 | 安徽省元琛环保科技有限公司 | Denitration catalyst used in waste incineration power plant and preparation method thereof |
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| CN109529917B (en) * | 2016-11-03 | 2020-01-24 | 内蒙古黄河工贸集团千里山煤焦化有限责任公司 | Preparation method of TiO2, CuO/ZSM-5 molecular sieve catalyst |
| CN109589986B (en) * | 2018-12-20 | 2022-01-11 | 中国科学院青岛生物能源与过程研究所 | Montmorillonite and titanium dioxide composite carrier loaded active ingredient catalyst, preparation and application |
| CN113385030A (en) * | 2021-06-05 | 2021-09-14 | 北京工业大学 | Method for preparing cement kiln flue gas denitration material by using silicate minerals and application |
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2006
- 2006-06-27 CN CNB2006100281918A patent/CN100528345C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| Cation exchanged and impregnated Ti-pillaredclays forselective catalytic reduction of NOx by propylene. J. L. Valverde et al.Applied Catalysis B: Environmental,Vol.43 No.1. 2003 |
| Cation exchanged and impregnated Ti-pillaredclays forselective catalytic reduction of NOx by propylene. J. L. Valverde et al.Applied Catalysis B: Environmental,Vol.43 No.1. 2003 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103194292A (en) * | 2013-04-25 | 2013-07-10 | 兰州熙瑞化工科技有限公司 | Boiler coal combustion-improving desulfurizing and denitrifying agent composition and preparation method thereof |
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