CN101979140A - Metal loaded catalyst used for selective catalytic oxidation of ammonia, preparation method and application thereof - Google Patents
Metal loaded catalyst used for selective catalytic oxidation of ammonia, preparation method and application thereof Download PDFInfo
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- CN101979140A CN101979140A CN2010105119644A CN201010511964A CN101979140A CN 101979140 A CN101979140 A CN 101979140A CN 2010105119644 A CN2010105119644 A CN 2010105119644A CN 201010511964 A CN201010511964 A CN 201010511964A CN 101979140 A CN101979140 A CN 101979140A
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Abstract
The invention provides a catalyst for removing ammonia pollution, a preparation method and application thereof, and belongs to the technical field of air pollution control. In the catalyst, active metal components are loaded on a porous inorganic carrier by a volume dipping method. The porous inorganic carrier of the catalyst is a mixture of one or more of silicon dioxide, aluminum oxide, titanium dioxide, ceric oxide and ferric oxide; and the active ingredient is the mixture of one or more of copper component and manganese component; and the load of the active metals is computed according to the weight of metallic elements and is 2 to 20 percent. The catalyst is also characterized in that: the catalyst can effectively remove ammonia pollution; and at the temperature of between 250 and 350 DEG C, ammonia conversion can reach above 98 percent, and ammonia selectivity is almost 90 percent. A product obtained after catalytic oxidation is harmless nitrogen and water without secondary pollution, and can be widely used for treating the ammonia produced in the process of industry, agriculture, aquaculture, architecture and the like.
Description
Technical field
The present invention relates to the air contaminant treatment technical field, relate to a kind of method for preparing catalyst, specially refer to a kind of load type metal catalyst, preparation method and application thereof that ammonia pollutes of eliminating.
Background technology
Ammonia is a kind of important pollutant, and its source is very extensive.Industrial source has, and the ammonia of the ammonia emission of the exhaust emissions in the liquefied ammonia production process, chemical fertilizer production process and leakage, ammonia selective reducing nitrogen oxide reaction is revealed; Animal metabolism also is the important source that ammonia pollutes in chemical fertilizer decomposition in the agricultural and the animal husbandry; Concrete admixture, house decorative material and furniture etc. can cause that also indoor ammonia pollutes in the building industry simultaneously.Ammonia has very big harm to human body and ecological environment, and it can benumb people's respiratory tract cilium and infringement mucosal epithelium tissue, makes pathogenic microorganism be easy to invade, and lowers the resistance of human body to disease; After sucking lung, easily combine, destroy the fortune oxygen function of blood with hemoglobin.Ammonia can promote acid rain to form its oxidation product NO, N in atmosphere
2O, NO
2Deng being the important pollutant that causes acid rain also; Ammonia enters in the water body can cause body eutrophication.So the purification techniques that ammonia pollutes has caused people's extensive concern.
The technology of eliminating the ammonia pollution at present mainly contains: adsorbents adsorb, absorption, high temperature incineration, catalytic decomposition and selective catalytic oxidation ammonia.Adsorbents adsorb, absorption process adsorbent need regularly replace, and easily cause secondary pollution; The high temperature incineration reaction temperature is higher, the generation nitrogen oxide causes secondary pollution; The catalytic decomposing method reaction temperature is higher, and energy consumption is bigger.In the ammonia catalytic oxidation technical research at present, obtained the low-temperature ammonia selective oxidation catalyst Ag/Al of national inventing patent (patent No. CN 101554587A)
2O
3, the selectivity that ammonia is converted into nitrogen lower (less than 60%).
Summary of the invention
The present invention utilizes the catalytic oxidation can be with NH under certain condition
3Be converted into the characteristic of nontoxic nitrogen G﹠W, provide and to have eliminated load type metal catalyst, preparation method and the application thereof that ammonia pollutes.
Catalyst of the present invention is made up of porous inorganic oxide carrier and active metal component two parts.Porous inorganic oxide carrier can be one or more hopcalites in the materials such as silica, alundum (Al, titanium dioxide, ceria, di-iron trioxide, zirconium dioxide.Active metal component is one or both hopcalites in cupric oxide, meta-aluminic acid copper, manganese dioxide, the manganese sesquioxide managnic oxide.
The preparation process of above-mentioned load type metal catalyst was divided into for two steps, i.e. the preparation of inorganic oxide carrier, the load of active metal component.
The preparation of inorganic oxide is to adopt the peroxidating under strong alkaline condition of soluble metal salting liquid to obtain, and obtains as nitrate or carbonate peroxidating under strong alkaline condition of metal.Al for example
2O
3Preparation, be to certain density Al (NO
3)
3Drip NaOH to pH=10 in the solution, aging 1 hour, filter, dry 12 hours, calcine and promptly got required Al in 6 hours
2O
3Carrier.
Active constituent loading adopts the incipient impregnation method.The active component presoma is a kind of in copper, the manganese soluble compound, the perhaps mixture formed of two kinds of soluble compounds of copper and manganese, active specy is cupric oxide, meta-aluminic acid copper, manganese dioxide, manganese sesquioxide managnic oxide one or more a mixture wherein, and load capacity is 2-10wt%.
Concrete steps are as follows:
(1) with the active component presoma aqueous solution of making soluble in water, and with the inorganic oxide carrier incipient impregnation wherein.
(2) sample that above-mentioned (1) is obtained stirs dry 5-12h at normal temperatures.
(3) sample that above-mentioned (2) are obtained keeps 12-24h under 80-150 ℃.
(4) sample that above-mentioned (3) are obtained keeps 2-4h under 400-800 ℃.
The load type metal catalyst that the present invention selects for use, its structure, stable performance can be handled the ammonia that produces from industry, agricultural, aquaculture etc.This catalyst application conditions is: catalyst temperature is remained on 250-350 ℃, and ammonia concentration is 500-5000ppm in the pending mixed airflow, and oxygen concentration is 2-20%.
Preparation process of the present invention is simple, and is easy to operate.Compare with existing ammoxidation catalyst, the present invention has following advantage:
Cheap being easy to get of Preparation of Catalyst raw material of the present invention, the preparation method is simple.
Catalyst degradable ammonia concentration scope of the present invention is wider, from 500-5000ppm.
Service condition of the present invention is simple, and temperature maintenance gets final product at 250-350 ℃.
Service condition of the present invention is simple, oxygen concentration oxygen deprivation oxygen enrichment all can, concentration is 2-20%.
The conversion ratio height of catalyst ammonia of the present invention, the ammonia selectivity is good, and product is harmless, non-secondary pollution.
Description of drawings
Fig. 1 is Cu/Al
2O
3Reactivity figure.
Fig. 2 is Mn/Al
2O
3Reactivity figure.
Among the figure :-■-NH
3Conversion ratio;--N
2Selectivity
The specific embodiment
In order to be illustrated more clearly in the present invention, enumerate embodiment, but it there is not any restriction to scope of the present invention.
Embodiment 1
In 100 gram γ-alundum (Al powder carriers (specific area: 152.7 meters squared per gram), in constantly stirring, slowly pour in 180 milliliters of aqueous solution that are dissolved with 38.02 gram copper nitrates.Stirred 10 hours, following dry 12 hours at 100 ℃ afterwards.Catalyst after the oven dry with the programming rate of 10 ℃ of per minutes, was warming up to 600 ℃ from room temperature under air atmosphere, 600 ℃ of following roastings 3 hours.The chemical constituent for preparing is 10%Cu/Al
2O
3Catalyst.
Embodiment 2
According to the preparation method of the present invention of embodiment 1, replace copper nitrate aqueous solution with 180 milliliters of aqueous solution that are dissolved with 21.1 milliliter of 50% manganese nitrate, the chemical constituent for preparing is 10%Mn/Al
2O
3Catalyst.
Embodiment 3
The catalyst that takes by weighing 0.2 gram embodiment 1 is positioned in the U type fixed bed reactors and reacts.
Reacting gas pollutes waste gas for the industrial ammonia of simulation.Gas composition: oxygen 10%, ammonia 1000ppm, helium are balanced gas.Reaction velocity (GHSV) is 50,000h
-1The reaction temperature interval is 150 ℃ to 350 ℃.
Reaction result shows: the conversion ratio of ammonia surpasses 98% in the time of 300 ℃, and in the time of 350 ℃, the conversion ratio of ammonia reaches 100%.Catalytic activity is seen Fig. 1.
Embodiment 4
According to the experimental technique among the embodiment 3, the catalyst that takes by weighing 0.2 gram embodiment 2 replaces catalyst among the embodiment 3.
The result of catalytic reaction shows: the conversion ratio of ammonia surpasses 94% in the time of 250 ℃, and in the time of 300 ℃, the conversion ratio of ammonia reaches 100%.Catalytic activity is seen Fig. 2.
Claims (3)
1. the metal load type catalyst of a selective catalytic oxidation ammonia is characterized in that, catalyst of the present invention is made up of porous inorganic oxide carrier and active metal component two parts; Porous inorganic oxide carrier is one or more hopcalites in silica, alundum (Al, titanium dioxide, ceria, di-iron trioxide, the zirconium dioxide; Active metal component is one or both hopcalites in cupric oxide, meta-aluminic acid copper, manganese dioxide, the manganese sesquioxide managnic oxide.
2. the preparation method of the described metal load type catalyst of claim 1 is characterized in that,
Preparation process was divided into for two steps, i.e. the preparation of inorganic oxide carrier, the load of active metal component;
The preparation of inorganic oxide is to adopt the peroxidating under strong alkaline condition of soluble metal salting liquid to obtain;
Active constituent loading adopts the incipient impregnation method; The active component presoma is a kind of in copper, the manganese soluble compound, the perhaps mixture formed of two kinds of soluble compounds of copper and manganese, active specy is cupric oxide, meta-aluminic acid copper, manganese dioxide, manganese sesquioxide managnic oxide one or more a mixture wherein, and load capacity is 2-10wt%;
Concrete steps are as follows:
(1) with the active component presoma aqueous solution of making soluble in water, and with the inorganic oxide carrier incipient impregnation wherein;
(2) sample that above-mentioned (1) is obtained stirs dry 5-12h at normal temperatures;
(3) sample that above-mentioned (2) are obtained keeps 12-24h under 80-150 ℃;
(4) sample that above-mentioned (3) are obtained keeps 2-4h under 400-800 ℃;
3. the application of the described metal load type catalyst of claim 1 is characterized in that,
Catalyst temperature is remained on 250-350 ℃, and ammonia concentration is 500-5000ppm in the pending mixed airflow, and oxygen concentration is 2-20%.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921432A (en) * | 2012-10-09 | 2013-02-13 | 常州大学 | Method for preparing catalyst used in promotion of conversion of ammonia nitrogen in oil refining waste water |
| CN103521227A (en) * | 2013-10-12 | 2014-01-22 | 昆明理工大学 | Preparation method of catalyst for catalytic oxidation of ammonia (NH3) |
| CN103752168A (en) * | 2014-01-10 | 2014-04-30 | 大连理工大学 | Application method for MIL-100(Fe) catalyst in NH3-SCR (Selective Catalytic Reduction) reaction |
| CN103958033A (en) * | 2011-09-30 | 2014-07-30 | 皮雷利&C.环境有限责任公司 | Post-treatment system of an exhaust gas, catalyst useful for said system and processes for their preparation |
| CN105249564A (en) * | 2015-11-13 | 2016-01-20 | 无锡桥阳机械制造有限公司 | Mask for preventing and treating haze |
| CN106362582A (en) * | 2015-07-24 | 2017-02-01 | 中船重工海博威（江苏）科技发展有限公司 | Method and apparatus for catalytic oxidation treatment of ammonia-containing exhaust gas |
| CN109053012A (en) * | 2018-08-28 | 2018-12-21 | 江苏恒大高性能材料有限公司 | A kind of preparation method of corrosion resistance mineral additive |
| CN109046378A (en) * | 2018-09-29 | 2018-12-21 | 浙江树人学院 | A kind of catalyst and preparation method thereof for ammonia of degrading |
| CN109513447A (en) * | 2018-08-01 | 2019-03-26 | 沈炳龙 | A kind of removal of carbon monoxide catalyst and preparation method thereof |
| WO2019114261A1 (en) * | 2017-12-12 | 2019-06-20 | 清华大学 | Copper-based supported ammoxidation catalyst and preparation method therefor |
| CN109926048A (en) * | 2019-04-09 | 2019-06-25 | 大连理工大学 | A kind of one pack system double activated position Cu2O-CuO nanometers of mixed phase structure copper oxide catalysts, preparation method and application |
| 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 |
| CN112774665A (en) * | 2021-01-29 | 2021-05-11 | 华中科技大学 | Mullite catalyst for improving ammonia selectivity and preparation method and application thereof |
| CN113019411A (en) * | 2021-02-04 | 2021-06-25 | 上海大学 | Boron nitride supported platinum-based catalyst for low-temperature selective catalytic oxidation of ammonia, and preparation method and application thereof |
| CN114797893A (en) * | 2022-04-25 | 2022-07-29 | 昆明理工大学 | Ammonia oxidation catalyst and preparation method and application thereof |
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| CN1413765A (en) * | 2001-10-22 | 2003-04-30 | 中国石油化工股份有限公司 | Catalyst of ammonia selective reducing nitrogen oxide |
| CN101365535A (en) * | 2005-12-08 | 2009-02-11 | 香港科技大学 | Low temperature ammonia remediation catalysts |
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Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103958033A (en) * | 2011-09-30 | 2014-07-30 | 皮雷利&C.环境有限责任公司 | Post-treatment system of an exhaust gas, catalyst useful for said system and processes for their preparation |
| CN103958033B (en) * | 2011-09-30 | 2016-06-15 | 皮雷利&C.环境有限责任公司 | Exhausted gas post-processing system, Catalysts and its preparation method for described system |
| 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 |
| CN102921432A (en) * | 2012-10-09 | 2013-02-13 | 常州大学 | Method for preparing catalyst used in promotion of conversion of ammonia nitrogen in oil refining waste water |
| CN103521227A (en) * | 2013-10-12 | 2014-01-22 | 昆明理工大学 | Preparation method of catalyst for catalytic oxidation of ammonia (NH3) |
| CN103521227B (en) * | 2013-10-12 | 2015-03-11 | 昆明理工大学 | Preparation method of catalyst for catalytic oxidation of ammonia (NH3) |
| CN103752168A (en) * | 2014-01-10 | 2014-04-30 | 大连理工大学 | Application method for MIL-100(Fe) catalyst in NH3-SCR (Selective Catalytic Reduction) reaction |
| CN106362582A (en) * | 2015-07-24 | 2017-02-01 | 中船重工海博威（江苏）科技发展有限公司 | Method and apparatus for catalytic oxidation treatment of ammonia-containing exhaust gas |
| CN105249564A (en) * | 2015-11-13 | 2016-01-20 | 无锡桥阳机械制造有限公司 | Mask for preventing and treating haze |
| WO2019114261A1 (en) * | 2017-12-12 | 2019-06-20 | 清华大学 | Copper-based supported ammoxidation catalyst and preparation method therefor |
| CN109513447B (en) * | 2018-08-01 | 2021-10-22 | 沈炳龙 | Catalyst for removing carbon monoxide and preparation method thereof |
| CN109513447A (en) * | 2018-08-01 | 2019-03-26 | 沈炳龙 | A kind of removal of carbon monoxide catalyst and preparation method thereof |
| CN109053012A (en) * | 2018-08-28 | 2018-12-21 | 江苏恒大高性能材料有限公司 | A kind of preparation method of corrosion resistance mineral additive |
| CN109046378A (en) * | 2018-09-29 | 2018-12-21 | 浙江树人学院 | A kind of catalyst and preparation method thereof for ammonia of degrading |
| CN109926048B (en) * | 2019-04-09 | 2021-08-20 | 大连理工大学 | Single-component double-active-site Cu2O-CuO nano mixed phase structure copper oxide catalyst, preparation method and application |
| CN109926048A (en) * | 2019-04-09 | 2019-06-25 | 大连理工大学 | A kind of one pack system double activated position Cu2O-CuO nanometers of mixed phase structure copper oxide catalysts, preparation method and application |
| 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 |
| CN112774665A (en) * | 2021-01-29 | 2021-05-11 | 华中科技大学 | Mullite catalyst for improving ammonia selectivity and preparation method and application thereof |
| CN113019411A (en) * | 2021-02-04 | 2021-06-25 | 上海大学 | Boron nitride supported platinum-based catalyst for low-temperature selective catalytic oxidation of ammonia, and preparation method and application thereof |
| CN114797893A (en) * | 2022-04-25 | 2022-07-29 | 昆明理工大学 | Ammonia oxidation catalyst and preparation method and application thereof |
| CN114797893B (en) * | 2022-04-25 | 2023-08-11 | 昆明理工大学 | Ammonia oxidation catalyst, preparation method and application thereof |
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Application publication date: 20110223 |