CN109012173A - A method of processing nitrogen oxides - Google Patents
A method of processing nitrogen oxides Download PDFInfo
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- CN109012173A CN109012173A CN201810852433.8A CN201810852433A CN109012173A CN 109012173 A CN109012173 A CN 109012173A CN 201810852433 A CN201810852433 A CN 201810852433A CN 109012173 A CN109012173 A CN 109012173A
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- nitrogen oxides
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Abstract
The present invention provides a kind of methods for handling nitrogen oxides, including contacting the gas comprising nitrogen oxides to react generation nitric acid with absorbing liquid, wherein the absorbing liquid is the aqueous solution comprising oxidant and nano ceric oxide.The method of processing nitrogen oxides of the invention is catalyzed by using nano ceric oxide, it can be nitric acid by the conversion of nitrogen oxides generated in production process, its catalytic conversion efficiency can reach 99% or more, the concentration of nitric acid of generation can achieve 40%, and tail gas reaches the requirement (being less than 240mg/L) of national emission standard.
Description
The application be submit on August 17th, 2015 application No. is 201510502201.6 Chinese invention patent Shens of the same name
Divisional application please.
Technical field
The present invention relates to a kind of processing nitrogen oxides methods.
Background technique
Nitrogen oxides (NOx) is a kind of gas that toxicity is very big, is directly discharged in atmosphere, is formed striking without improvement
Brown (red) yellow smog, NOx difficulty in numerous waste gas pollution control and treatments is maximum, is one of the arch-criminal for polluting atmosphere.If cannot have
Effect control, it is not only very harmful to the health of operator and plant environment, but also flutter with the wind diffusion couple nearby residents
Life causes public hazards with ecological environment.Scholarly forecast, if do not tightened control, nitrogen oxides will become the main of In The Atmosphere Over China pollution
Pollutant.
The method of purified treatment NOx is mainly the following at present.
Selective catalytic reduction (SCR method): under an oxygen-containing atmosphere, the catalysis that reducing agent is preferentially reacted with NO in exhaust gas
Journey is known as selective catalytic reduction.With NH3Make reducing agent, V2O5-TiO2Stationary source (such as thermal power plant) is eliminated for catalyst
The technique of the NO of discharge comparative maturity and the currently the only practical approach that NO can be removed under oxidizing atmosphere.But due to
NH3The control error of amount and caused by the reasons such as secondary pollution so that common removal efficiency only up to 65%~80%.
Non-catalytic selective reduction method (SNCR method): this method principle is with SCR method, due to not having catalyst, needed for reaction
Temperature is higher (900~1200 DEG C), therefore need to control reaction temperature, in case ammonia is oxidized to nitrogen oxides.The method purifying rate
It is 50%.
Liquid absorption method: NOx is sour gas, and the NOx in exhaust gas can be purified by alkaline solution absorption.Common absorbent
Have: water, dilute HNO3、NaOH、Ca(OH)2、NH4OH、Mg(OH)2Deng.To improve the absorption efficiency of NOx, and oxidative absorption can be used
Method absorbs reduction method and Absorption via Chemical Complexation etc..The method on experimental provision to the removal efficiency of NO up to 90%, but in commercial plant
On be extremely difficult to such removal efficiency.Peter, Harris et al. have reached 10%~60% NO removal efficiency in pilot-scale.
Technical process is simple, and investment is less, many for the absorbent of application, and can be recycled in exhaust gas in the form of nitrate
NOx, but removal efficiency is low, and energy consumption is high, and the solution after absorbing exhaust gas is difficult to handle, and be easy to cause secondary pollution.In addition, absorbing
Agent, oxidant, reducing agent and complex compound it is costly, the higher exhaust gas containing NOx concentration should not be used.
Nitric acid uses and production unit, can generate a large amount of nitrous oxides exhaust gas, the row of these exhaust gas in process of production
It puts, not only there is greatly harm to the mankind and ecological environment, but also cause the waste of resource.Therefore from the economy effect of enterprise
Benefit and social benefit are set out, and the optimal path for handling nitrous oxides exhaust gas is exactly recycling treatment, 100% can be converted into nitre
Acid is adequately recycled, and the pollution problem of nitrogen oxides is on the one hand solved, and on the other hand increases the economic effect of enterprise
Benefit.
Therefore, this field needs a kind of method of economic, efficient processing nitrogen oxides.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of methods for handling nitrogen oxides, including make comprising nitrogen
The gas of oxide is contacted with absorbing liquid to react generation nitric acid, wherein the absorbing liquid is to include oxidant and nanometer titanium dioxide
The aqueous solution of cerium.According to the preferred embodiment of the present invention, the oxidant is hydrogen peroxide.
According to the preferred embodiment of the present invention, the particle size of the nano ceric oxide is 3-20 nanometers, preferably 4-
It is 10 nanometers, 4-6 nanometers more preferable.
According to the preferred embodiment of the present invention, the nano ceric oxide is ball shaped nano ceria.
According to the preferred embodiment of the present invention, concentration of the oxidant in absorbing liquid is 5-30wt%.
According to the preferred embodiment of the present invention, concentration of the nano ceric oxide in absorbing liquid is 0.01-
1wt%, preferably 0.05-0.5wt%, more preferable 0.05-0.15wt%.
According to the preferred embodiment of the present invention, the reaction is at 0-65 DEG C, and preferably 15-50 DEG C, more preferable 15-35 DEG C
At a temperature of carry out.
According to the preferred embodiment of the present invention, NO in the gas comprising nitrogen oxides2Molar ratio with NO is 00:
10-95:5, preferably 0:100-55:45.
According to the preferred embodiment of the present invention, the contact is achieved in that the gas of nitrogen-containing oxide
Body is passed into absorbing liquid bottom with the rate of 1000-12000mg/min, wherein the liquid level of the absorbing liquid and the receiving suction
The diameter ratio for receiving the container of liquid is 1:3-1:10.Preferably, connect gas sufficiently with absorbing liquid in the way of dispersion pipeline
Touching.According to the preferred embodiment of the present invention, the time of the contact is 0.5-15s, preferably 5-12s, more preferable 7-10s.
In a specific embodiment, oxides of nitrogen gas of the invention such as uses nitre from the use process of nitric acid
The production process of acid production nitrate (such as silver nitrate, copper nitrate, cobalt nitrate).
The method of processing nitrogen oxides of the invention is catalyzed by using nano ceric oxide, can will be generated in production process
Conversion of nitrogen oxides be nitric acid, catalytic conversion efficiency can reach 99% or more, and the concentration of nitric acid of generation can achieve 40%,
Tail gas reaches the requirement (being less than 240mg/L) of national emission standard.Also, the method for processing nitrogen oxides of the invention is suitble to use
In the nitric oxide of any ratio and the nitrogen oxides of nitrogen dioxide.The NO that cannot be effectively treated is absorbed especially for lye to account for
The situation of 60% or more nitrogen oxides total amount uses method of the invention that can urge by the conversion of nitrogen oxides of generation for nitric acid
Changing transformation efficiency can reach 99% or more.
Specific embodiment
The present invention will be further described combined with specific embodiments below, but the present invention is not limited in following embodiments.
The nano ceric oxide of 4nm used in embodiment and 6nm all in accordance with document J.Phys.Chem.C 2011,115,
Method disclosed in 1740-1745 is prepared；Cerium oxide powder used in comparative example 3 (particle size is micron order) purchase
From lark prestige Science and Technology Ltd..
If other substances are common commercially available without specified otherwise.
Embodiment 1:
Copper powder 1Kg is weighed, is added in reaction kettle, is slowly added to 60% concentrated nitric acid 2.5L, nitric acid is anti-with copper powder rapidly
It answers, generates a large amount of rufous nitrogen oxides (NO, NO immediately2), reaction time 30min.Using level Four series connection absorption process to production
Raw nitrogen oxides is absorbed.The hydrogenperoxide steam generator 20L that mass concentration is 10% is respectively added in absorption tower, 10g ball is added
Shape nano ceric oxide (its particle size is 4nm), the diameter ratio on liquid level and absorption tower are 1:5.With 10000mg/min
Rate the nitrogen oxides of generation is passed through absorbing liquid bottom.Method using dispersion pipeline keeps nitrogen oxides abundant with absorbing liquid
Contact, and reaction is carried out at 15 DEG C by thermostatically-controlled equipment.Nitrous oxides concentration after the process in tail gas is
96.5mg/m3, meet the environmental requirement of country.By repeatedly reacting, after absorbing repeatedly, concentration of nitric acid is finally reached in absorption tower
40%.
Cu+4HNO3(dense) → Cu (NO3)2+2NO2↑+2H2O (1)
3Cu+8HNO3(dilute) → 3Cu (NO3)2+2NO↑+4H2O (2)
Embodiment 2:
Silver powder 1Kg is weighed, is added in reaction kettle, is slowly added to 60% concentrated nitric acid 1.5L, nitric acid is anti-with silver powder rapidly
It answers, generates a large amount of rufous nitrogen oxides (NO, NO immediately2), reaction time 30min.Mass concentration is respectively added in absorption tower
It for 10% hydrogenperoxide steam generator 20L, is added 15g ball shaped nano ceria (its particle size is 6nm), liquid level and suction
The diameter ratio for receiving tower is 1:5.The nitrogen oxides of generation is passed through absorbing liquid bottom with the rate of 5000mg/min, utilizes dispersion
The method of pipeline comes into full contact with nitrogen oxides with absorbing liquid, and carries out reaction at 25 DEG C by thermostatically-controlled equipment.Through this
Nitrous oxides concentration 87.9mg/m after process in tail gas3, meet the environmental requirement of country.By repeatedly reacting, repeatedly
After absorption, concentration of nitric acid is finally reached 40% in absorption tower.
Ag+2HNO3(dense) → AgNO3+NO2↑+H2O (1)
3Ag+4HNO3(dilute) → 3AgNO3+NO↑+2H2O (2)
Embodiment 3:
Cobalt powder 1Kg is weighed, is added in reaction kettle, is slowly added to 60% concentrated nitric acid 3L, nitric acid is reacted with cobalt powder rapidly,
A large amount of rufous nitrogen oxides (NO, NO are generated immediately2), reaction time 30min.Using level Four series connection absorption process to generation
Nitrogen oxides is handled.The hydrogenperoxide steam generator 20L that mass concentration is 10% is respectively added in absorption tower in level Four series connection, adds simultaneously
Enter 10g ball shaped nano ceria (its particle size is 4nm), the diameter ratio on liquid level and absorption tower is 1:5.With
The nitrogen oxides of generation is passed through absorbing liquid bottom by the rate of 8000mg/min, using dispersion pipeline method make nitrogen oxides with
Absorbing liquid comes into full contact with, and carries out reaction at 35 DEG C by thermostatically-controlled equipment.Nitrogen oxygen after the process in tail gas
Compound concentration is 103.4mg/m3, meet the environmental requirement of country.By repeatedly reacting, after absorbing repeatedly, nitric acid in absorption tower
Concentration is finally reached 40%.
Co+4HNO3(dense) → Cu (NO3)2+2NO2↑+2H2O (1)
3Co+8HNO3(dilute) → 3Cu (NO3)2+2NO↑+4H2O (2)
Comparative example 1
Silver powder 1Kg is weighed, is added in reaction kettle, is slowly added to 60% concentrated nitric acid 1.5L, nitric acid is anti-with silver powder rapidly
It answers, generates a large amount of rufous nitrogen oxides (NO, NO immediately2), reaction time 30min.Using level Four series connection absorption process to life
The nitrogen oxides of production is absorbed.10% hydrogenperoxide steam generator 20L is respectively added in level Four series connection absorption tower.Liquid level and suction
The diameter ratio for receiving tower is 1:5.The nitrogen oxides of generation is passed through absorbing liquid bottom with the rate of 2000mg/min, utilizes dispersion
The method of pipeline comes into full contact with nitrogen oxides with absorbing liquid, and carries out reaction at 25 DEG C by thermostatically-controlled equipment.Through
Nitrous oxides concentration after the process in tail gas is 856.5mg/m3, tail gas do not meet country environmental requirement, Bu Nengda
Mark discharge.
Ag+2HNO3(dense) → AgNO3+NO2↑+H2O (1)
3Ag+4HNO3(dilute) → 3AgNO3+NO↑+2H2O (2)
Comparative example 2
Silver powder 1Kg is weighed, is added in reaction kettle, is slowly added to 60% concentrated nitric acid 1.5L, nitric acid is anti-with silver powder rapidly
It answers, generates a large amount of rufous nitrogen oxides (NO, NO immediately2), reaction time 30min.Using level Four series connection absorption process to production
Raw nitrogen oxides is absorbed.Respectively be added 20% sodium hydroxide solution 20L in absorption tower, liquid level and absorption tower it is straight
The ratio between diameter is 1:5.The nitrogen oxides of generation is passed through absorbing liquid bottom with the rate of 2000mg/min, utilizes the side of dispersion pipeline
Method comes into full contact with nitrogen oxides with absorbing liquid, and carries out reaction at 25 DEG C by thermostatically-controlled equipment.At the technique
Nitrous oxides concentration after reason in tail gas is 1235.7mg/m3, tail gas do not meet country environmental requirement, be unable to qualified discharge.
Comparative example 3
Silver powder 1Kg is weighed, is added in reaction kettle, is slowly added to 60% concentrated nitric acid 3L, nitric acid is reacted with silver powder rapidly,
A large amount of rufous nitrogen oxides (NO, NO are generated immediately2), reaction time 30min.Using level Four series connection absorption process to generation
Nitrogen oxides is handled.The hydrogenperoxide steam generator 20L that mass concentration is 10% is respectively added in absorption tower in level Four series connection, adds simultaneously
Enter 10g cerium oxide powder, the diameter ratio on liquid level and absorption tower is 1:5.With the rate of 2000mg/min by generation
Nitrogen oxides is passed through absorbing liquid bottom, and the method using dispersion pipeline comes into full contact with nitrogen oxides with absorbing liquid, and passes through perseverance
Temperature control device carries out reaction at 35 DEG C.Nitrous oxides concentration after the process in tail gas is 1023.4mg/m3, tail
Gas does not meet the environmental requirement of country, is unable to qualified discharge.
The method of processing nitrogen oxides of the invention can make 99% or more nitrogen oxidation by nano ceric oxide catalysis
Object is converted into nitric acid, and tail gas completely can be with qualified discharge.
Claims (10)
1. a kind of method for handling nitrogen oxides, including contacting the gas comprising nitrogen oxides to react generation nitre with absorbing liquid
Acid, wherein the absorbing liquid is the aqueous solution comprising oxidant and nano ceric oxide.
2. the method for processing nitrogen oxides according to claim 1, which is characterized in that the partial size of the nano ceric oxide
Size is 3-20 nanometers, preferably 4-10 nanometers, 4-6 nanometers more preferable.
3. the method for processing nitrogen oxides according to claim 1 or 2, which is characterized in that the nano ceric oxide is
Ball shaped nano ceria.
4. the method for processing nitrogen oxides according to any one of claim 1-3, which is characterized in that the oxidant exists
Concentration in absorbing liquid is 5-30wt%.
5. the method for nitrogen oxides is handled described in any one of -4 according to claim 1, which is characterized in that the nano-silica
Changing concentration of the cerium in absorbing liquid is 0.01-1wt%, preferably 0.05-0.5wt%, more preferable 0.05-0.15wt%.
6. the method for processing nitrogen oxides according to any one of claims 1-5, which is characterized in that the reaction is in 0-
It is carried out at a temperature of 65 DEG C, preferably 15-35 DEG C.
7. it is according to claim 1 to 6 processing nitrogen oxides method, which is characterized in that the contact when
Between be 0.5-15s, preferably 5-12s.
8. the method for nitrogen oxides is handled described in any one of -7 according to claim 1, which is characterized in that described includes nitrogen oxygen
NO in the gas of compound2Molar ratio with NO is 0:100-45:55.
9. it is according to claim 1 to 8 processing nitrogen oxides method, which is characterized in that it is described contact be with
As under type is realized: the gas comprising nitrogen oxides is passed into absorbing liquid bottom with the rate of 1000-12000mg/min,
Wherein the diameter ratio of the container of the liquid level of the absorbing liquid and the receiving absorbing liquid is 1:3-1:10.
10. the method for processing nitrogen oxides according to claim 1 to 9, which is characterized in that described includes nitrogen
The nitrogen oxides that the gas of oxide generates in nitric acid use process.
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| CN201810852433.8A CN109012173A (en) | 2015-08-17 | 2015-08-17 | A method of processing nitrogen oxides |
| CN201510502201.6A CN105126584A (en) | 2015-08-17 | 2015-08-17 | Method for treating nitrogen oxides |
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| CN108176193B (en) * | 2017-12-26 | 2020-12-04 | 西北大学 | Nano fluid absorbent for wet flue gas denitration |
| CN108295858B (en) * | 2017-12-29 | 2019-07-23 | 兰州大学 | Magnetic nanometer composite material and its preparation method and application |
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| CN102688680A (en) * | 2012-06-19 | 2012-09-26 | 国电科学技术研究院 | Method for removing sulfur and nitrogen in coal-fired power plant by combining seawater |
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| FR2693125B1 (en) * | 1992-07-03 | 1994-09-02 | Socrematic | Process for the treatment of waste gases containing sulfur dioxide and nitrogen oxides. |
| DE19533715A1 (en) * | 1995-09-12 | 1997-03-13 | Basf Ag | Process for removing nitrogen oxides from a gas stream containing them |
| CA2238304C (en) * | 1995-12-01 | 2002-03-12 | Drinkard Metalox, Inc. | Nitric acid production and recycle |
| DE102011011881A1 (en) * | 2011-02-21 | 2012-08-23 | Thyssenkrupp Uhde Gmbh | Process for removing N2O and NOX from nitric acid production process |
| CN104086464B (en) * | 2014-06-13 | 2016-03-23 | 通辽市龙盛化工有限公司 | A kind of method that H acid denitration exhaust-gas resource utilizes |
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| CN102688680A (en) * | 2012-06-19 | 2012-09-26 | 国电科学技术研究院 | Method for removing sulfur and nitrogen in coal-fired power plant by combining seawater |
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| 中国科协学会学术部: "《稀土资源绿色高效高值化利用》", 31 October 2013 * |
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| CN114368774A (en) * | 2021-12-20 | 2022-04-19 | 兰州大学 | Preparation method of porous cerium oxide and method for treating nitrogen oxide |
| CN114368774B (en) * | 2021-12-20 | 2024-02-13 | 兰州大学 | Preparation method of porous cerium oxide and method for treating nitrogen oxides |
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