CN105536500A - Method for removing nitrogen oxide in airflow - Google Patents
Method for removing nitrogen oxide in airflow Download PDFInfo
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- CN105536500A CN105536500A CN201610021088.4A CN201610021088A CN105536500A CN 105536500 A CN105536500 A CN 105536500A CN 201610021088 A CN201610021088 A CN 201610021088A CN 105536500 A CN105536500 A CN 105536500A
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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
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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
- B01D53/46—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
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- 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 provides a method for removing nitrogen oxide in airflow and belongs to the technical fields of atmosphere pollution control and environment protection. The treatment process in the method includes the steps that treated gas is introduced into a gas-solid reaction tower, meanwhile polyferric chloride or polyaluminum chloride solid particles are introduced into the gas-solid reaction tower, at a certain temperature, nitrogen oxide in gas and polyferric chloride or polyaluminum chloride have a gas and solid chemical reaction in the gas-solid reaction tower so that the nitrogen oxide can be absorbed and removed, and the aim of purifying the gas is achieved. The invention further provides a special device which has the advantages that investment cost and operation cost are low, use is safe, by-products can be recycled, operation is easy, treatment efficiency is high, and the treatment amount is large.
Description
Technical field
The present invention relates to a kind of method of the nitrogen oxide removed in 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.NO
xhave intoxicating effect to people, a large amount of discharged nitrous oxides still causes the one of the main reasons of atmospheric photochemistry mist and acid rain.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) administers flue gas NO at present
xone of Main Means, but catalyst requires strict to service condition, reaction temperature is higher, needs 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 NO
xabsorbing, is the main method of the emission source process such as chemical engineering industry, mainly contains oxidative absorption method and reducing absorping method two kinds, and 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 wet method is to containing the more nitrogen oxide of nitric oxide, and 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, researching and developing the purification techniques of new nitrogen oxide, is urgent problem 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 of the nitrogen oxide removed in 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 of the nitrogen oxide removed in air-flow, processed gas is it is characterized in that to import gas-solid reaction tower, import poly-ferric chloride or PAFC solid particle to gas-solid reaction tower simultaneously, in gas-solid reaction tower, poly-ferric chloride or PAFC activated at a certain temperature and occur decompose and with the nitrogen oxide generation gas solid chemical reaction in air-flow, nitrogen oxide in air-flow is absorbed to generate solid product, thus reach gas purification object, a small amount of hydrogen chloride gas that course of reaction produces can be absorbed by solid or liquid-absorbant and be removed.
Nitrogen oxide of the present invention comprises nitric oxide and nitrogen dioxide, mainly containing nitric oxide.In described technical scheme, the solid product of nitrogen oxide and poly-ferric chloride or PAFC generation gas solid chemical reaction is relevant complex compound and salt.
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 poly-ferric chloride or PAFC solid particle adds entrance, feed postition can adopt the mode such as power feed or strength charging), gas distributor is provided with above the lower stream of airflow 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-120 DEG C, and preferential temperature range is 40 DEG C-70 DEG C, can be lower under negative pressure.At ambient pressure, course of reaction first poly-ferric chloride or PAFC is heated to more than 70 DEG C, be generally 70 DEG C-180 DEG C, wherein, the heating-up temperature of poly-ferric chloride is lower, is generally 70 DEG C-150 DEG C, the heating-up temperature of PAFC can be higher, be generally 75 DEG C-180 DEG C, make poly-ferric chloride or PAFC be activated and decomposition reaction occurs, then with nitrogen oxide generation gas solid chemical reaction.Poly-ferric chloride or PAFC can be heated in gas-solid reaction tower, also first reaction tower can be imported after poly-ferric chloride or PAFC heating material, gaseous state iron chloride will be produced when poly-ferric chloride or PAFC are heated to more than about 120 DEG C at ambient pressure, when PAFC is heated to more than 180 DEG C, will gaseous aluminum chloride be produced.The general effect of poly-ferric chloride that adopts when lower temperature is better compared with PAFC.Course of reaction gas-solid contact time is generally 0.1s-100s, is preferentially taken as 1s-10s.The mass ratio of poly-ferric chloride or PAFC and nitrogen oxide gas solid chemical reaction is about 3: 1 to 6: 1, actual mechanical process, the dosage of poly-ferric chloride or PAFC can require according to reaction tower form, gas temperature, duration of the reaction and conversion ratio etc. and determine.For recirculating fluidized bed gas-solid reaction tower, the mass ratio of poly-ferric chloride or PAFC and nitrogen oxide is generally 0.5-100, the larger reaction effect of mass 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 poly-ferric chloride or PAFC solid particle, be 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 poly-ferric chloride or aluminium polychloride iron 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 80 DEG C are generally under heating-up temperature normal pressure, be preferably 100 DEG C-350 DEG C, after also solid product can being dissolved in clear water, acetone and ethanol equal solvent, release absorbed oxides of nitrogen gas.Recyclable nitric acid, further also recyclable iron oxide and aluminium oxide byproduct after process.Solid product also can be used to regeneration poly-ferric chloride or PAFC Posterior circle uses.
Compared with prior art, the invention has the advantages that: adopt poly-ferric chloride or PAFC at a certain temperature with the nitrogen oxide generation gas solid chemical reaction in air-flow, nitrogen oxide in air-flow is removed, thus reach gas purification object, byproducts such as nitric acid recyclable after solid product process, iron oxide and aluminium oxide, also renewable poly-ferric chloride or PAFC, there is cost of investment and operating cost is low, use safety, simple to operate, treatment effeciency is high, the large feature for the treatment of capacity, is 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 in air-flow the method removing nitrogen oxide 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 gas entrance top of tower body is provided with gas 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 poly-ferric chloride that entrance (3) adds or PAFC particle mix by solid particle, there is gas solid chemical reaction, purified gas 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 of method of the nitrogen oxide removed in 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.Poly-ferric chloride is adopted to be commercially available technical grade powdery granule, average grain diameter is about 0.1mm, poly-ferric chloride imports gas-solid reaction tower after being heated separately 70 DEG C, 90 DEG C and 120 DEG C of reaction temperatures, enter tower air-flow gas temperature and be respectively 20 DEG C, 40 DEG C, 55 DEG C and 70 DEG C, in reaction tower, gas-solid time of contact is about 4-6s.Nitrogen oxide and poly-ferric chloride mass ratio are about 1: 10.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: employing poly-ferric chloride is reactant, commercially available technical grade powdery granule, average grain diameter is about 0.1mm, PAFC imports gas-solid reaction tower after being heated separately 80 DEG C, 120 DEG C and 150 DEG C of reaction temperatures, enter tower air-flow gas temperature and be respectively 90 DEG C and 120 DEG C, other conditions are with embodiment 1.Experimental result is as shown in table 2.
Table 2
Embodiment 3: poly-ferric chloride imports gas-solid reaction tower at normal temperatures, in tower, gas temperature is for being respectively 80 DEG C, 95 DEG C and 120 DEG C, and nitrogen oxide and poly-ferric chloride mass ratio are about 1: 15.Other conditions are with embodiment 1.Experimental result is as shown in table 3.
Table 3
Embodiment 4: adopt poly-ferric chloride particle as reactant, the particle diameter mixing 20% (volume) in material is about the quartz sand of 1mm-3mm.Other conditions are with embodiment 3.Experimental result is as shown in table 4.
Table 4
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 (8)
1. remove the method for the nitrogen oxide in air-flow for one kind, processed gas is it is characterized in that to import gas-solid reaction tower, import poly-ferric chloride or PAFC solid particle to gas-solid reaction tower simultaneously, described poly-ferric chloride or PAFC activated at a certain temperature and occur decompose and with the nitrogen oxide generation gas solid chemical reaction in gas, nitrogen oxide in air-flow is absorbed, generate solid product, thus reach 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-120 DEG C.
4. method according to claim 1 and 2, is characterized in that first described poly-ferric chloride or PAFC are heated to more than 70 DEG C at ambient pressure, and poly-ferric chloride or PAFC are activated.
5. method according to claim 2, is characterized in that in described gas-solid reaction tower, gas-solid time of contact is 0.1s-100s.
6. method according to claim 2, its feature adopts quartz sand, pottery or zeolite granular filler and poly-ferric chloride or PAFC particle powder mixing match in described gas-solid reaction tower, and described packing volume accounting is 0-99%.
7. method according to claim 1, is characterized in that described solid product, by discharging absorbed nitrogen oxide after heating, is more than 80 DEG C under heating-up temperature normal pressure.
8. 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 poly-ferric chloride or PAFC solid particle adds entrance, gas 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.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610021088.4A CN105536500A (en) | 2016-01-06 | 2016-01-06 | Method for removing nitrogen oxide in airflow |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610021088.4A CN105536500A (en) | 2016-01-06 | 2016-01-06 | Method for removing nitrogen oxide in airflow |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106000079A (en) * | 2015-07-02 | 2016-10-12 | 黄立维 | Method and device for removing nitrogen oxides from airflow |
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| US3750372A (en) * | 1971-04-01 | 1973-08-07 | Vulcan Materials Co | Prevention of air pollution by using solid adsorbents to remove particulates of less than 0.5 microns in size from flue gases |
| CN102895865A (en) * | 2011-07-25 | 2013-01-30 | 琳德股份公司 | Method for removing contaminant in gas stream |
| CN104470622A (en) * | 2012-04-30 | 2015-03-25 | 琳德股份公司 | Methods for removing contaminants from exhaust gases |
| CN105032163A (en) * | 2015-07-02 | 2015-11-11 | 黄立维 | Method and apparatus for removing nitrogen oxide and sulfur dioxide from air flow |
-
2016
- 2016-01-06 CN CN201610021088.4A patent/CN105536500A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3750372A (en) * | 1971-04-01 | 1973-08-07 | Vulcan Materials Co | Prevention of air pollution by using solid adsorbents to remove particulates of less than 0.5 microns in size from flue gases |
| CN102895865A (en) * | 2011-07-25 | 2013-01-30 | 琳德股份公司 | Method for removing contaminant in gas stream |
| CN104470622A (en) * | 2012-04-30 | 2015-03-25 | 琳德股份公司 | Methods for removing contaminants from exhaust gases |
| CN105032163A (en) * | 2015-07-02 | 2015-11-11 | 黄立维 | Method and apparatus for removing nitrogen oxide and sulfur dioxide from air flow |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106000079A (en) * | 2015-07-02 | 2016-10-12 | 黄立维 | Method and device for removing nitrogen oxides from airflow |
| 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 |
| EA036691B1 (en) * | 2015-07-02 | 2020-12-08 | Ливэй Хуан | Method and apparatus for removing nitrogen oxides from gas streams |
| CN106000079B (en) * | 2015-07-02 | 2021-05-14 | 黄立维 | Method for removing nitric oxide from gas flow |
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