CN101554587B - Low-temperature ammonia selective oxidation catalyst - Google Patents
Low-temperature ammonia selective oxidation catalyst Download PDFInfo
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- CN101554587B CN101554587B CN2008101038706A CN200810103870A CN101554587B CN 101554587 B CN101554587 B CN 101554587B CN 2008101038706 A CN2008101038706 A CN 2008101038706A CN 200810103870 A CN200810103870 A CN 200810103870A CN 101554587 B CN101554587 B CN 101554587B
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Abstract
The invention provides a low-temperature ammonia selective oxidation catalyst which is used for eliminating ammonia gas pollution generated in the field of industry, agriculture, traffic, architecture, and the like, and selectively catalyzing and oxidizing the ammonia into pollution-free nitrogen and water under lower temperature. The oxidation catalyst can completely convert the ammonia under thetemperature above 160 DEG C, and has the nitrogen selectivity of nearly 80 percent, good low-temperature oxidbillity, high catalytic efficiency and high stability. The oxidation catalyst contains por ous inorganic oxide carrier, silver as an active component and cerium as an accessory ingredient, wherein the porous inorganic oxide carrier can be silicon dioxide, aluminium oxide, zirconia, lanthana, zinc oxide or titanium dioxide or the mixture of more than one of the oxide; the active component is formed by loading silver which a metal element with the weight conversion value of 1-15 percent on the inorganic oxide carrier; and the accessory ingredient is formed by simultaneously loading cerium and silver with the metal element weight conversion value of 5-50 percent on the inorganic oxide carrier.
Description
Technical field
The present invention relates to a kind ofly be used for eliminating the ammonia that processes such as industry, agricultural, traffic and building produce and pollute, ammine selective catalytic oxidation is become the catalyst of free of contamination nitrogen G﹠W.This oxidation catalyst conversion ratio to ammonia more than 160 ℃ the time reaches 100%, and the nitrogen selectivity can effectively reduce the energy consumption of eliminating in the ammonia pollution course near 80%.
Technical background
The source that ammonia pollutes is more extensive, comprises industrial source (ammonia of the exhaust emissions in the liquefied ammonia production process, ammonia selective reducing nitrogen oxide reaction is revealed); Agricultural, animal husbandry source; And the indoor ammonia that the concrete admixture that adds in the building industry construction, wooden boards, house decorative material, humans and animals metabolin etc. cause pollutes or the like.The ammonia of indoor low concentration will produce harm to the health of human body, positions such as the eyes of stimulation human body, schneiderian membrance.And ammonia can produce NO, N after oxidized
2O, NO
2Deng pollutant, cause forming acid rain, cause atmosphere pollution and greenhouse effects.The purification techniques that the research ammonia pollutes has generally caused people's attention.
The technology of eliminating the ammonia pollution at present mainly contains: adsorbents adsorb, absorption, drip washing, high-temp combustion incineration, catalytic decomposition and selective catalytic oxidation ammonia generate the nitrogen G﹠W.The operation of adsorbents adsorb, absorption process is fairly simple, but adsorbent need regularly replace, and easily produces secondary pollution.The purification efficiency of drip washing technology is then lower.High-temp combustion incinerates Technology Need at high-temp combustion, and energy consumption is higher and easily generate pollutant such as nitrogen oxide.The catalytic decomposition technology is difficult for producing secondary pollution, but the temperature window that catalytic decomposition needs is higher, and energy consumption is also higher.The ammine selective catalytic oxidation technology is to utilize catalyst that ammine selective catalytic oxidation is become free of contamination nitrogen G﹠W.Catalyst system commonly used at present mainly contains following three major types: noble metal catalyst, metal oxide catalyst and ion exchanged zeolite type catalyst.The temperature window of noble metal catalyst is lower, but preparation cost is higher and selectivity is bad, easily produces N
2The O accessory substance.Metal oxide catalyst is relative better with ion exchanged zeolite type selection of catalysts, but temperature window is higher.Therefore, cheap, the low-temperature catalyzed efficient height of development cost, ammoxidation catalyst that selectivity is good are very important.
Summary of the invention
The invention provides a kind of ammine selective oxidation catalyst that low temperature active is good, selectivity is high that pollutes at the ammonia of eliminating sources such as industry, agricultural, traffic and building industry, realize low temperature, low energy consumption, efficiently handle ammonia pollution, ammine selective catalytic oxidation is become free of contamination nitrogen G﹠W.The catalyst that is provided reaches 100% in temperature more than 160 ℃ to the conversion ratio of ammonia, and the nitrogen selectivity is near 80%, and is all better than the low temperature active of catalyst such as the noble metal platinum of bibliographical information, iridium, reaches the purpose that can eliminate ammonia at a lower temperature fully.
Catalyst of the present invention is made up of active component silver, adjuvant component cerium and porous inorganic oxide carrier three parts.This catalyst uses silver to be active component, and silver components is 1-15% by the load capacity that the metal element wt converts on carrier, and its active specy is simple substance silver, silver oxide, silver sulfate, silver orthophosphate, silver chlorate one or more a mixture wherein; Add the adjuvant component cerium and can promote to improve low temperature active, cerium component and the silver components of the 5-50% that converts by the metal element wt load on the inorganic oxide carrier simultaneously; Inorganic oxide is silica, alundum (Al, zirconia, lanthana, zinc oxide, titanium dioxide one or more hopcalites wherein.
Catalyst of the present invention adopts infusion process or the precipitation method or sol-gel process preparation.According to the present invention, silver components can be by the aqueous solution with the soluble compound of finite concentration silver, loads on the aforesaid inorganic oxide carrier simultaneously or with any sequencing with the aqueous solution of the soluble compound of finite concentration cerium.For example, select infusion process for use, the inorganic oxide powder carrier is slowly poured in the aqueous solution of certain density silver nitrate and cerous nitrate under constantly stirring, stirred 1-5 hour, 80-120 ℃ of drying, under air or nitrogen or the hydrogen condition, in Muffle furnace 400-1000 ℃ roasting 3-72 hour.
Preparation process of the present invention is simple, and is easy to operate.Compare with existing ammoxidation catalyst, the present invention has following advantage:
(1) catalyst of the present invention selects for use silver to be active component, cheap being easy to get such as the relative noble metal platinum of preparation raw material, iridium, and the preparation method is simple.
(2) catalyst of the present invention reaches 100% in temperature more than 160 ℃ to the conversion ratio of ammonia, and the nitrogen selectivity is near 80%, and is better than the low temperature active of catalyst such as noble metal platinum, iridium.
(3) catalyst of the present invention is carried on active component silver on the carrier surface jointly with the adjuvant component cerium, and the interpolation of cerium has improved the low-temperature oxidation activity of catalyst, is better than separately silver being carried on the low temperature active of the catalyst on the inorganic oxide carrier.
(4) catalyst of the present invention is under excess oxygen, and the 160 ℃ of conversion ratios that can realize ammonia are near 100%, and the activity under this temperature keeps stable.
The specific embodiment
In order to be illustrated more clearly in the present invention, enumerate following examples, but it there is not any restriction to the scope of application of the present invention.
[embodiment 1]
Get 100 gram γ-alundum (Al powder carriers (specific area: 250 meters squared per gram), under constantly stirring, slowly pour in 500 milliliters of aqueous solution that dissolved 15.75 gram silver nitrates and 30.97 gram cerous nitrates.Stir after 1 hour, use the Rotary Evaporators evaporating water, 120 ℃ of oven dry are spent the night.Catalyst after the oven dry in air atmosphere, with the programming rate of 10 ℃ of per minutes, is warmed up to 600 ℃ from room temperature, 600 ℃ of roastings 3 hours.Sieving is that 20～40 order particles are standby, promptly makes the catalyst of embodiment 1.Preparing chemical composition is 10%Ag/10%Ce/Al
2O
3Oxidation catalyst.
[embodiment 2]
Get 100 gram γ-alundum (Al powder carriers (specific area: 250 meters squared per gram), under constantly stirring, slowly pour in 500 milliliters of aqueous solution that dissolve 15.75 gram silver nitrates.Stir after 1 hour, use the Rotary Evaporators evaporating water, 120 ℃ of oven dry are spent the night.Catalyst after the oven dry in air atmosphere, with the programming rate of 10 ℃ of per minutes, is warmed up to 600 ℃ from room temperature, 600 ℃ of roastings 3 hours.Sieving is that 20～40 order particles are standby, promptly makes the catalyst of embodiment 2.Preparing chemical composition is 10%Ag/Al
2O
3Oxidation catalyst.
[embodiment 3]
The catalyst that takes by weighing 0.2 gram embodiment 1 is positioned in the tubular fixed-bed reactor and reacts.
Reacting gas pollutes waste gas for the industrial ammonia of simulation.Gas composition: the mist total flow is 200 milliliters of per minutes, wherein, oxygen 10%, ammonia 500ppm, nitrogen are balanced gas.Reaction velocity (GHSV) is 20,000/ hours to catalyst.The reaction temperature interval is from room temperature to 220 ℃.Ammonia and production concentration utilize the infrared-gas pond to measure.
Reaction result shows: the conversion ratio of ammonia surpasses 80% in the time of 100 ℃; In the time of 120 ℃, the conversion ratio of ammonia is near 100%; More than 160 ℃ during temperature the conversion ratio to ammonia reach 100%.
Table one 10%Ag/10%Ce/Al
2O
3The catalyst activity evaluation result
[Comparative Examples 1]
The catalyst that takes by weighing 0.2 gram embodiment 2 is positioned in the tubular fixed-bed reactor and reacts.
Reacting gas pollutes waste gas for the industrial ammonia of simulation.Gas composition: the mist total flow is 200 milliliters of per minutes, wherein, oxygen 10%, ammonia 500ppm, nitrogen are balanced gas.Reaction velocity (GHSV) is 20,000/ hours to catalyst.The reaction temperature interval is from room temperature to 220 ℃.Ammonia and production concentration utilize the infrared-gas pond to measure.
Reaction result shows: the ammonia conversion ratio is lower than 25% in the time of 100 ℃, and is poorer than the catalyst low-temperature activity of embodiment 1; The conversion ratio of ammonia reaches 100% in the time of 160 ℃, and the selectivity of nitrogen is lower.
Table two 10%Ag/Al
2O
3The catalyst activity evaluation result
[embodiment 4]
Get 100 gram γ-alundum (Al powder carriers (specific area: 250 meters squared per gram), under constantly stirring, slowly pour in 500 milliliters of aqueous solution that dissolved 15.75 gram silver nitrates and 46.455 gram cerous nitrates.Stir after 1 hour, use the Rotary Evaporators evaporating water, 120 ℃ of oven dry are spent the night.Catalyst after the oven dry in air atmosphere, with the programming rate of 10 ℃ of per minutes, is warmed up to 600 ℃ from room temperature, 600 ℃ of roastings 3 hours.Sieving is that 20～40 order particles are standby, promptly makes the catalyst of embodiment 4.Preparing chemical composition is 10%Ag/15%Ce/Al
2O
3Oxidation catalyst.
[embodiment 5]
Get 100 gram γ-alundum (Al powder carriers (specific area: 250 meters squared per gram), under constantly stirring, slowly pour in 500 milliliters of aqueous solution that dissolved 15.75 gram silver nitrates and 61.94 gram cerous nitrates.Stir after 1 hour, use the Rotary Evaporators evaporating water, 120 ℃ of oven dry are spent the night.Catalyst after the oven dry in air atmosphere, with the programming rate of 10 ℃ of per minutes, is warmed up to 600 ℃ from room temperature, 600 ℃ of roastings 3 hours.Sieving is that 20～40 order particles are standby, promptly makes the catalyst of embodiment 5.Preparing chemical composition is 10%Ag/20%Ce/Al
2O
3Oxidation catalyst.
[embodiment 6]
The catalyst that takes by weighing 0.2 gram embodiment 4 is positioned in the tubular fixed-bed reactor and reacts.
Reacting gas pollutes waste gas for the industrial ammonia of simulation.Gas composition: the mist total flow is 200 milliliters of per minutes, wherein, oxygen 10%, ammonia 500ppm, nitrogen are balanced gas.Reaction velocity (GHSV) is 20,000/ hours to catalyst.The reaction temperature interval is from room temperature to 220 ℃.Ammonia and production concentration utilize the infrared-gas pond to measure.
Reaction result shows: the conversion ratio of ammonia surpasses 60% in the time of 120 ℃; More than 160 ℃ the time, the conversion ratio of ammonia reaches 100%, increases than selection of catalysts in the Comparative Examples 1.
Table three 10%Ag/15%Ce/Al
2O
3The catalyst activity evaluation result
[embodiment 7]
The catalyst that takes by weighing 0.2 gram embodiment 5 is positioned in the tubular fixed-bed reactor and reacts.
Reacting gas pollutes waste gas for the industrial ammonia of simulation.Gas composition: the mist total flow is 200 milliliters of per minutes, wherein, oxygen 10%, ammonia 500ppm, nitrogen are balanced gas.Reaction velocity (GHSV) is 20,000/ hours to catalyst.The reaction temperature interval is from room temperature to 220 ℃.Ammonia and production concentration utilize the infrared-gas pond to measure.
Reaction result shows: the conversion ratio of ammonia surpasses 94% in the time of 160 ℃; More than 200 ℃ the time, the conversion ratio of ammonia reaches 100%, and the selectivity of nitrogen surpasses 80%, and is more obvious than selection of catalysts raising in the Comparative Examples 1.
Table four 10%Ag/20%Ce/Al
2O
3The catalyst activity evaluation result
Claims (1)
1. a catalyst is used for eliminating the ammonia pollution that industry, agricultural, traffic and architectural process produce, with the ammonia selective catalytic oxidation is the application of nitrogen G﹠W, it is characterized in that this catalyst is loaded on the inorganic oxide carrier by active component silver and adjuvant component cerium to constitute; The silver that active component is counted 1-15% by metallic element weight scaled value is carried on the inorganic oxide carrier, and active specy is simple substance silver, silver oxide, silver sulfate, silver orthophosphate, silver chlorate one or more a mixture wherein; The cerium that adjuvant component is counted 5-50% by metallic element weight scaled value is carried on the inorganic oxide carrier, and auxiliary agent is made of cerium oxide; Inorganic oxide is silica, alundum (Al, zirconia, lanthana, zinc oxide, titanium dioxide one or more hopcalites wherein.
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| CN2008101038706A CN101554587B (en) | 2008-04-11 | 2008-04-11 | Low-temperature ammonia selective oxidation catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921432B (en) * | 2012-10-09 | 2014-07-30 | 常州大学 | Method for preparing catalyst used in promotion of conversion of ammonia nitrogen in oil refining waste water |
| TWI543813B (en) * | 2013-04-12 | 2016-08-01 | 財團法人工業技術研究院 | Catalyst for oxidizing ammonia and method for removing ammonia |
| CN105032410B (en) * | 2015-06-03 | 2017-08-11 | 中国科学院生态环境研究中心 | A kind of Ag/Al2O3Catalyst, preparation method and its usage |
| CN105502468B (en) * | 2015-12-22 | 2017-06-16 | 天津大学 | A kind of ceric oxide nanorod and its preparation method and application |
| CN107213897A (en) * | 2016-03-22 | 2017-09-29 | 重庆理工大学 | A kind of Ag-La-Ti catalyst and preparation method for the NO that degrades |
| CN108568312B (en) * | 2017-03-07 | 2021-03-09 | 中国科学院青岛生物能源与过程研究所 | High-stability hollow molecular sieve, selective catalyst prepared by using hollow molecular sieve and application |
| CN108543416B (en) * | 2018-03-05 | 2021-05-04 | 攀枝花市蓝鼎环保科技有限公司 | Treatment system for coking flue gas mixed with raw coke oven gas and construction process thereof |
| CN108854518B (en) * | 2018-06-22 | 2021-01-26 | 中国科学院生态环境研究中心 | Method for photo-catalytic oxidation of ammonia gas |
| CN109261150A (en) * | 2018-09-26 | 2019-01-25 | 中国科学院生态环境研究中心 | A kind of low-temperature ammonia selective oxidation catalyst and preparation method thereof, purposes and application method |
| CN111068512B (en) * | 2019-12-26 | 2021-06-18 | 南京工大环境科技有限公司 | Integrated catalytic conversion system and method for reducing exhaust ammonia emission |
| CN112316975A (en) * | 2020-09-14 | 2021-02-05 | 昆明理工大学 | High-water-resistance supported ammonia oxidation catalyst and preparation method and application thereof |
| CN113019411B (en) * | 2021-02-04 | 2023-05-16 | 上海大学 | Boron nitride supported platinum-based catalyst for low-temperature selective catalytic oxidation of ammonia, preparation method and application thereof |
| CN114146705A (en) * | 2021-12-03 | 2022-03-08 | 中汽研（天津）汽车工程研究院有限公司 | High water resistance nano-carrier low-temperature ammonia catalytic oxidation catalyst |
| CN116272984B (en) * | 2023-03-01 | 2024-09-27 | 陕西延长石油（集团）有限责任公司 | Catalyst for preparing gamma-butyrolactone by catalyzing 1, 4-butanediol to dehydrogenate, and preparation method and application thereof |
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2008
- 2008-04-11 CN CN2008101038706A patent/CN101554587B/en active Active
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| 罗孟飞等.Ag-Ce/γ-Al2O3催化剂上CO的氧化.《催化学报》.1995,第16卷(第4期),328-331. * |
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