CN105536503A - Method for removing nitric oxide from airflow - Google Patents
Method for removing nitric oxide from airflow Download PDFInfo
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- CN105536503A CN105536503A CN201610021238.1A CN201610021238A CN105536503A CN 105536503 A CN105536503 A CN 105536503A CN 201610021238 A CN201610021238 A CN 201610021238A CN 105536503 A CN105536503 A CN 105536503A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
- B01D53/82—Solid phase processes with stationary reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
- B01D53/565—Nitrogen oxides by treating the gases with solids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
- B01D53/83—Solid phase processes with moving reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The invention relates to a method for removing a nitric oxide from airflow, and belongs to the technical field of air pollution control and environment protection. The method comprises the treatment processes that treated gas is guided into a gas-solid reaction tower, meanwhile, aluminum chloride solid particles are guided into the gas-solid reaction tower, the nitric oxide in the airflow is subjected to a gas-solid adsorption chemical reaction with aluminum chloride in the gas-solid reaction tower to be absorbed and removed, and therefore the gas purification purpose is achieved. The invention further discloses a special device. The method has the advantages that the investment cost and operation cost are low, by-products can be recycled, operation is easy, the treatment efficiency is high, and the handling capacity is large.
Description
Technical field
The present invention relates to a kind of method removing nitrogen oxide from air-flow, belong to Air Pollution Control and relevant environment resist technology field.
Background technology
Nitrogen oxide (the NO that mankind's activity produces
x) mainly comprise NO and NO
2, what wherein produced by fuel combustion accounts for more than 90%, is secondly nitric acid production, the nitration reaction of chemical pharmaceutical, the industrial process such as metal surface and semiconductor processes.NOx has intoxicating effect to people, and a large amount of discharged nitrous oxides still causes the one of the main reasons of atmospheric photochemistry mist and acid rain.Atmospheric environment sulfur dioxide pollution owner will result from fossil fuel combustion process.China Environmental State Bulletin statistics shows that the contribution of nitrogen oxide in China's Urban Acid Rain is in continuous increase, and the Acid Rain Pollution character in some places has started by sulfuric acid type to the ever-increasing compound conversion of nitrate ion (national environmental protection portion: China Environmental State Bulletin in 2010).In recent years, country has newly formulated some laws, regulation, and the nitrogen oxide of the nitrogen oxide particularly combustion process such as thermoelectricity discharge has been made to stricter control and reduced discharging regulation.
Usually, the nitrous oxides concentration in the flue gas that thermal power plant etc. produce with combustion of fossil fuel is about hundreds of to several thousand ppm, and wherein more than 90% is nitric oxide.Current selective catalysis conversion method (SCR) is one of Main Means administering flue gas NOx at present, but catalyst requires strict to service condition, need ammonia as reducing agent, very large, particularly very high to the operating cost of the thermal power plant taking coal as fuel to the aging effects of catalyst containing sulfide and dust etc. in air-flow; Wet method adopts various liquid to absorb NOx, be the main method of discharged at lower temperature source process, mainly contain oxidative absorption method and reducing absorping method two kinds, wherein, oxidizing process adopts hydrogen peroxide, clorox and potassium permanganate etc. as oxidative absorption agent, carries out absorption process; Reducing process adopts sodium sulfite, vulcanized sodium and urea etc. as reducing agent, carries out absorption process.But to containing the more nitrogen oxide of nitric oxide, because nitric oxide solubility is in the solution very little, absorption efficiency is lower, and medicament is more expensive, runs cost of use high.Therefore, research and development improve the purification techniques of Novel flue gas nitrogen oxide, are urgent problems in this skilled industry application.
The object of this invention is to provide a kind of method, nitrogen oxide in air-flow is removed at a lower temperature, thus reaches the object of gas purification.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method removing nitrogen oxide from air-flow, and it has simple to operate, reliable, and treatment effeciency is high.
Another technical problem to be solved by this invention is to provide and uses the cost of investment of said method low, and operating cost is cheap, the special purpose device that treating capacity is large.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of method removing nitrogen oxide from air-flow, processed gas is it is characterized in that to import gas-solid reaction tower, import aluminum chloride solids particle to gas-solid reaction tower simultaneously, nitrogen oxide in air-flow is absorbed at gas-solid reaction tower and aluminium chloride generation gas-solid adsorption chemical reaction, generate solid product, thus reaching gas purification object, a small amount of hydrogen chloride gas that course of reaction produces can be removed after solid or liquid-absorbant absorb.
Nitrogen oxide of the present invention comprises nitric oxide and nitrogen dioxide, mainly containing nitric oxide.In described technical scheme, the solid product of the generation gas-solid adsorption chemical reaction of nitrogen oxide and aluminium chloride is complex compound and the related salts of aluminium chloride and nitrogen oxide.
Air-flow of the present invention is mainly thermal power generation, smelts the flue gas containing nitrogen oxide waiting and produce with combustion of fossil fuel, may also be the relevant gas flow that other industrial process produce.The concentration of general nitrogen oxides in effluent at 1% (volume content) below, during for nitrous oxides concentration in other industrial gas higher than 1% (volume content), is also suitable for method of the present invention.The gas-solid contact reactors such as fixed bed, moving bed, ebullated bed, fluid bed and recirculating fluidized bed that gas-solid reaction tower of the present invention can adopt chemical engineering unit operation conventional, the various ways such as following current, adverse current and cross-flow can be adopted, specifically can referring to chemical reaction relevant device handbook, effect is about the same.For recirculating fluidized bed reaction system, the side lower part of described gas-solid reaction tower is provided with the gas feed connecting air-flow, middle part is provided with aluminium chloride particle and adds entrance, feed postition can adopt the mode such as power feed or strength charging), air distributor is provided with above the lower gas import of tower body, make the abundant hybrid reaction of gas-solid in tower, the top of tower body is provided with tube connector, described air-flow is connected with gas-solid separator by tube connector, after gas-solid separator gas solid separation, air-flow is discharged from the top of gas-solid separator, solid particle is discharged from gas-solid separator bottom, wherein partial particulate can return in tower and participate in reaction, also can not return, the ratio (scope can be 0-100%) that specifically material can be regulated to return in tower participate in reaction according to the extent of reaction.
Range of reaction temperature in gas-solid reaction tower of the present invention under normal pressure is generally 20 DEG C-180 DEG C, and preferential temperature range is 50 DEG C-120 DEG C, can be lower under negative pressure.Course of reaction gas-solid contact time is generally 0.1s-100s, is preferentially taken as 1s-10s.The stoichiometric proportion of aluminium chloride and nitrogen oxide gas-solid adsorption chemical reaction is about 1: 1 to 1: 3, actual mechanical process, and the dosage of aluminium chloride can require according to reaction tower form, gas flow temperature, duration of the reaction and conversion ratio etc. and determine.For recirculating fluidized bed gas-solid reaction tower, the mol ratio of aluminium chloride and nitrogen oxide or sulfur dioxide is generally 0.5-100, the larger reaction effect of mol ratio is better, but operating cost rises, preferentially be taken as 5-30, for fixed bed, moving bed, ebullated bed and fluid bed, without particular requirement, optionally add.Described aluminum chloride solids particle, is generally Powdered, and can adopt industrialization commercial pellet powder, its particle diameter is generally 0.01mm-1mm, and particle diameter is less as well.Also the granular fillers such as a quartz sand, pottery or zeolite can be adopted to mix rear importing gas-solid reaction tower by a certain percentage with aluminum chloride powder, to improve gas-solid mixing effect and gas-contact area, reduction flow resistance in reaction tower, improve the utilization rate of reaction efficiency and material, general ratio is 99% (volume ratio) to the maximum, specifically can determine according to reaction tower form and operating parameter, general employing fluid bed reacting tower, the ratio of filler can be lower, fixed bed reaction tower can be high.After particle diameter as mixed 50% (volume ratio) in fixed bed gas-solid reaction tower is about the quartz sand of 2mm-5mm, reaction efficiency more than 20% can be improved.The removal impact of oxygen content change in air-flow on nitrogen oxide is little.
The solid product obtained after reaction can discharge absorbed nitrogen oxide by modes such as heating, more than 150 DEG C are generally under heating-up temperature normal pressure, be preferably 180 DEG C-350 DEG C, after also solid product can being dissolved in clear water equal solvent, release absorbed oxides of nitrogen gas.Recyclable nitric acid, further also recyclable aluminium oxide byproduct after process.Solid product also can be used to regeneration aluminium chloride Posterior circle and uses.
Compared with prior art, the invention has the advantages that: adopt aluminium chloride at a certain temperature with the nitrogen oxide generation gas-solid adsorption chemical reaction in air-flow, nitrogen oxide in air-flow is removed, thus reach gas purification object, nitric acid recyclable after solid product process or aluminium oxide byproduct, also renewable aluminium chloride, there is cost of investment and operating cost is low, simple to operate, treatment effeciency is high, the large feature for the treatment of capacity, be applicable to promoting the use of.
Accompanying drawing explanation
Fig. 1 is embodiment of the present invention recirculating fluidized bed gas-solid reaction used tower apparatus structural representation, wherein: 1 gas feed; 2 gas distributors; 3 solid particles add entrance; 4 gas-solid reaction tower tower bodies; 5 tube connectors; 6 gas vents; 7 gas-solid separators; 8 solid particle return ports; 9 solid particle outlets; 10 access holes; Solid particle outlet at the bottom of 11 towers.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in further detail.
A kind of device removing the method for nitrogen oxide from air-flow as shown in Figure 1.The side lower part of the gas-solid reaction tower tower body (4) of described device is provided with the gas feed (1) connecting air-flow, the lower stream of airflow entrance top of tower body is provided with air distributor (2) and makes the abundant hybrid reaction of gas-solid in tower, middle part is provided with solid particle and adds entrance (3), the top of tower body is provided with tube connector (5) and is connected with gas-solid separator (7), the top of gas-solid separator is provided with gas vent (6), the bottom of gas-solid separator is provided with solid particle outlet (9), and have solid particle return port (8) to be communicated with tower body, tower body middle and lower part and bottom are also respectively arranged with solid particle outlet (11) at the bottom of access hole (10) and tower.
Processing technological flow is that pending air-flow enters gas-solid reaction tower tower body (4) by gas feed (1), through gas distributor (2) with added after aluminium chloride particle that entrance (3) adds mixes by solid particle, there is Chemisorption, air-flow after purification enters gas-solid separator (7) from the tube connector (5) on tower top and carries out gas solid separation, air-flow is discharged from gas vent (6), fraction solids particle returns in gas-solid reaction tower tower body (4) by solid particle return port (8) and continues to participate in reaction, remainder is discharged by solid particle outlet (9), tower bottom is also provided with solid particle outlet (11) at the bottom of tower and discharges unnecessary solid particle simultaneously.
Embodiment 1: a kind of recirculating fluidized bed gas-solid reaction tower apparatus removing the method for nitrogen oxide from air-flow as shown in Figure 1.Described recirculating fluidized bed gas-solid reaction tower tower diameter is Φ 60mm, and tower height is 2500mm, and composition of tower shell material is 316L stainless steel.In air-flow, the concentration of nitrogen oxide (nitric oxide is about 90%) is 500ppm, and oxygen is 8% (volume), and moisture is 10% (volume), and all the other are nitrogen.Aluminium chloride is commercially available technical grade powdery granule, and average grain diameter is about 0.1mm, and reaction temperature is respectively 20 DEG C, 50 DEG C, 90 DEG C, 120 DEG C and 180 DEG C, and in reaction tower, gas-solid time of contact is about 4-6s.Nitrogen oxide and aluminium chloride mol ratio are about 1: 5.After gas-solid separator (employing cyclone separator) obtains reacting, solid particle does not return in tower.Experimental result is as shown in table 1.
Table 1
Embodiment 2: nitrogen oxide and aluminium chloride mol ratio are about 1: 15.Other conditions are with embodiment 1.Experimental result is as shown in table 2.
Table 2
Embodiment 3: adopt aluminium chloride particle as reactant, the particle diameter mixing 20% (volume) in material is about the quartz sand of 1mm-3mm, and nitrogen oxide and aluminium chloride mol ratio are about 1: 15.Reaction temperature is respectively 50 DEG C, 90 DEG C and 120 DEG C.Other conditions are with embodiment 1.Experimental result is as shown in table 3.
Table 3
Should be noted that above embodiment only for illustration of technical scheme of the present invention, protection scope of the present invention is not limited thereto.For a person skilled in the art; within the spirit and principles in the present invention all; technical scheme described in each embodiment is modified; or any equivalent replacement, amendment, changes and improvements etc. are carried out to portion of techniques feature wherein, all should be included within protection scope of the present invention.
Claims (7)
1. from air-flow, remove the method for nitrogen oxide for one kind, processed gas is it is characterized in that to import gas-solid reaction tower, import aluminum chloride solids particle to gas-solid reaction tower simultaneously, nitrogen oxide in air-flow generates solid product with aluminium chloride generation gas-solid adsorption chemical reaction in gas-solid reaction tower, thus reaches gas purification object.
2. method according to claim 1, is characterized in that described gas-solid reaction tower adopts the one of fixed bed, moving bed, ebullated bed, fluid bed or recirculating fluidized bed reaction tower.
3. method according to claim 1 and 2, is characterized in that the range of reaction temperature in described gas-solid reaction tower is 20 DEG C-180 DEG C.
4. method according to claim 2, is characterized in that in described gas-solid reaction tower, gas-solid time of contact is 0.1s-100s.
5. method according to claim 2, its feature adopts the mixing match of quartz sand, pottery or zeolite granular filler and aluminium chloride particle powder in described gas-solid reaction tower, and the volume accounting of described filler is 0-99%.
6. method according to claim 1, is characterized in that described solid product, by discharging absorbed nitrogen oxide after heating, is more than 150 DEG C under heating-up temperature normal pressure.
7. the special purpose device of a method according to claim 1, it is characterized in that the side lower part of described gas-solid reaction tower is provided with the gas feed connecting air-flow, middle part is provided with described aluminum chloride solids particle and adds entrance, air distributor is provided with above lower gas import in tower body, the top of tower body is provided with tube connector, described tube connector is connected with gas-solid separator, gas vent is arranged at the top of described gas-solid separator, bottom is provided with the rear solid particle outlet of reaction and solid particle return port, described solid particle return port is communicated with gas-solid reaction tower tower body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610021238.1A CN105536503A (en) | 2016-01-06 | 2016-01-06 | Method for removing nitric oxide from airflow |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610021238.1A CN105536503A (en) | 2016-01-06 | 2016-01-06 | Method for removing nitric oxide from airflow |
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| CN105536503A true CN105536503A (en) | 2016-05-04 |
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| CN201610021238.1A Withdrawn CN105536503A (en) | 2016-01-06 | 2016-01-06 | Method for removing nitric oxide from airflow |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105944554A (en) * | 2016-06-08 | 2016-09-21 | 黄立维 | Method and device for removing harmful gas |
| WO2017000879A1 (en) * | 2015-07-02 | 2017-01-05 | 黄立维 | Method and apparatus for removing nitrogen oxides from air flow |
| CN106753566A (en) * | 2016-11-23 | 2017-05-31 | 广东东燃热能科技有限公司 | A kind of low NO of biomass boilerXCombustion method |
| CN110283203A (en) * | 2018-03-19 | 2019-09-27 | 浙江新安化工集团股份有限公司 | It is a kind of using methyl chloride aluminum for the system and preparation method of methylisothiouronium methylphosphite ester |
| CN110283196A (en) * | 2018-03-19 | 2019-09-27 | 浙江新安化工集团股份有限公司 | A kind of system and method preparing methyl dichloro phosphorus |
| CN110283202A (en) * | 2018-03-19 | 2019-09-27 | 浙江新安化工集团股份有限公司 | It is a kind of using methyl chloride aluminum for the system and preparation method of methylisothiouronium methylphosphite ester |
| CN110283205A (en) * | 2018-03-19 | 2019-09-27 | 浙江新安化工集团股份有限公司 | A kind of system and method preparing methylisothiouronium methylphosphite ester |
| CN110283195A (en) * | 2018-03-19 | 2019-09-27 | 浙江新安化工集团股份有限公司 | A kind of system and preparation method thereof preparing methyl chloride aluminium |
| CN112844002A (en) * | 2021-02-03 | 2021-05-28 | 江西新金叶实业有限公司 | Dense-phase semi-dry flue gas desulfurization device and method thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EA036691B1 (en) * | 2015-07-02 | 2020-12-08 | Ливэй Хуан | Method and apparatus for removing nitrogen oxides from gas streams |
| WO2017000879A1 (en) * | 2015-07-02 | 2017-01-05 | 黄立维 | Method and apparatus for removing nitrogen oxides from air flow |
| US10406479B2 (en) | 2015-07-02 | 2019-09-10 | Liwei Huang | Method and apparatus for removing nitrogen oxides from gas streams |
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| CN106753566A (en) * | 2016-11-23 | 2017-05-31 | 广东东燃热能科技有限公司 | A kind of low NO of biomass boilerXCombustion method |
| CN110283203A (en) * | 2018-03-19 | 2019-09-27 | 浙江新安化工集团股份有限公司 | It is a kind of using methyl chloride aluminum for the system and preparation method of methylisothiouronium methylphosphite ester |
| CN110283196A (en) * | 2018-03-19 | 2019-09-27 | 浙江新安化工集团股份有限公司 | A kind of system and method preparing methyl dichloro phosphorus |
| CN110283202A (en) * | 2018-03-19 | 2019-09-27 | 浙江新安化工集团股份有限公司 | It is a kind of using methyl chloride aluminum for the system and preparation method of methylisothiouronium methylphosphite ester |
| CN110283205A (en) * | 2018-03-19 | 2019-09-27 | 浙江新安化工集团股份有限公司 | A kind of system and method preparing methylisothiouronium methylphosphite ester |
| CN110283195A (en) * | 2018-03-19 | 2019-09-27 | 浙江新安化工集团股份有限公司 | A kind of system and preparation method thereof preparing methyl chloride aluminium |
| CN110283196B (en) * | 2018-03-19 | 2023-07-25 | 浙江新安化工集团股份有限公司 | System and method for preparing methyl phosphorus dichloride |
| CN110283195B (en) * | 2018-03-19 | 2023-09-01 | 浙江新安化工集团股份有限公司 | System for preparing methyl aluminum chloride and preparation method thereof |
| CN112844002A (en) * | 2021-02-03 | 2021-05-28 | 江西新金叶实业有限公司 | Dense-phase semi-dry flue gas desulfurization device and method thereof |
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Application publication date: 20160504 |