CN105582868B - The processing method of industrial waste gas - Google Patents
The processing method of industrial waste gas Download PDFInfo
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- CN105582868B CN105582868B CN201510301807.3A CN201510301807A CN105582868B CN 105582868 B CN105582868 B CN 105582868B CN 201510301807 A CN201510301807 A CN 201510301807A CN 105582868 B CN105582868 B CN 105582868B
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Abstract
The invention discloses a kind of processing method of industrial waste gas, choose that Native Oxide miberal powder is matrix and to be ground into powdery particulate matter standby, a certain proportion of technical grade TiO is added in powdered granule thing2、Fe2O3、K2O, MnO, oxidant is obtained；The processing method of industrial waste gas is contacted to flue gas conditioning processing, oxidant first in first-stage reactor by Geldart-D particle into first-stage reactor, and with flue gas；Mixed flue gas and oxidant, which enter in second reactor, fully to be reacted, and the sulfur dioxide and nitrogen oxides that produce in instantaneous oxidation flue gas of hydroxyl radical free radical, remove sulfur dioxide in flue gas, nitrogen oxides in oxidant；Subsequently into the third-stage reactor of processing unit, oxidant is reclaimed, controls smog discharge temperature and water capacity.Treatment method raw material sources are extensive, adapt to industrial applications；Energy consumption and reaction temperature are low, improve treatment effect.
Description
Technical field
The present invention relates to a kind of processing method of industrial waste gas.
Background technology
With industrial development, the discharge of industrial waste gas is all the more serious, causes more ground haze weather to take place frequently, and influence
Scope has a strong impact on environment, jeopardizes the health of people in trend is constantly expanded；Industrial waste gas is fuel combustion and production work
The caused various general names containing contaminant gases for being discharged into air during skill, including sulfur dioxide, carbon disulfide, vulcanization
Hydrogen, fluoride, nitrogen oxides, chlorine, hydrogen chloride, carbon monoxide, sulfuric acid（Mist）Lead mercury, beryllide, flue dust and industrial dust
Deng, wherein, especially pollution of the sulfur dioxide and nitrogen oxides in fuel combustion discharge flue gas to environment is even more serious, mainly relates to
And the enterprise such as coal-burning power plant, steel, cement, coking, glass.
Desulphurization and denitration technology is related generally to currently for the widely used industrial waste gas Treatment process of smoke pollution.Wherein
The principle of desulfurization technology is to neutralize the sulfur dioxide in flue gas using the material of one or more of alkalescence, reaches and reduces in flue gas
The purpose of sulfur dioxide concentration, its technique can be divided into wet method, dry method and half-dried again（It is semi-moist）Method, in these techniques, wet method efficiency
Height, but generally existing seriously corroded, operation and maintenance cost are high and easily cause secondary pollution problems；Dry method and semidry method are present
Desulfuration efficiency is low, and reaction speed is compared with the problems such as slow, equipment is huge.And the main selective catalysis reduction of denitration technology（SCR）With
Non-selective catalytic reduction（SNCR）, wherein SCR operating costs are expensive, and one time construction cost is also very high, and enterprise can not bear at all
Load, and the efficiency of SNCR denitration is very low, often can not meet emission request.
Hydroxyl radical free radical (.OH) is a kind of important active oxygen, has the extremely strong electronic capability that obtains, that is, energy of oxidation
Power, oxidizing potential 2.8v, it is the oxidant that fluorine is only second in nature, and one of offensive most strong chemical substance, easy oxygen
Change various organic matters and inorganic matter, oxidation efficiency is high, and reaction speed is fast.
Chinese patent CN202087222U discloses a kind of oxygen active particles and hydroxyl free based device is formed in gas, but
It is that the technology needs to carry out in specific device, and provides high-frequency and high-voltage power supply, severe reaction conditions, the effect in practical application
Fruit is also without the verification experimental verification of correlation, plant-scale application foundation shortcoming, especially apply processing huge discharge, complicated component,
Do not studied accordingly also in the exhaust-gas treatment of the Industrial Stoves of working condition change greatly.
In summary, the preparation method of the existing hydroxyl radical free radical (OH) applied to exhaust-gas treatment is although possible in theory,
But all without the checking for carrying out commercial Application, if disclosure satisfy that industrialized application is not understood also, existing preparation in addition
Also there is the difficult points such as device is complicated, operating condition is harsh in the method for hydroxyl radical free radical (OH), cause it to fail to be applied to work
In industry；Meanwhile traditional industrial waste gas desulphurization and denitration technology high energy consumption, investment is big, secondary pollution is also very serious.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of processing method of industrial waste gas, treatment method is simple,
Convenient, raw material sources are extensive, adapt to industrial applications；The equipment dynamic energy consumption that it is related to is low, and reaction temperature is low, effectively removes useless
The secondary pollution such as the pollutant in flue gas, no waste water and waste residue, improves treatment effect.
In order to solve the above technical problems, the production method of hydroxyl radical free radical of the present invention, it is matrix to choose Native Oxide miberal powder,
It is standby to be ground into powdered granule thing of the granularity more than 250 mesh, 5 are added into the powdered granule thing ground:3:3:9 work
Industry level TiO2、Fe2O3、K2O, MnO, obtain oxidant, in the oxidant aoxidize miberal powder matrix quality account for gross mass 47~
65%, the TiO of addition2、Fe2O3、K2O, mass fraction of the gross mass of tetra- kinds of metal oxides of MnO in oxidant is maintained at gold
The total mass fraction of category oxide is maintained at 30~45%, and the moisture of oxidant is less than 8%, oxidant is produced hydroxyl with smoke reaction
Base free radical.
Further, the oxidation miberal powder is zinc oxide miberal powder.
Further, the moisture of the oxidant is controlled 2~8%.
A kind of processing method of industrial waste gas comprises the following steps：
Step 1: flue gas enters processing unit by flue, first-stage reactor is first passed around in processing unit and carries out cigarette
Gas it is quenched, flue gas is uniformly distributed in first-stage reactor, and uniform decrease in temperature, to 80~160 DEG C, flue gas flow rate control exists
20~50m/s；
Step 2: above-mentioned oxidant is contacted into first-stage reactor, and with flue gas by Geldart-D particle, oxygen
The supply of agent is depending on sulfur dioxide in flue gas and the total amount of nitrogen oxides, sulfur dioxide and nitrogen oxides per ton, oxygen
The supply of agent is 0.1~0.5 ton；
Fully reacted Step 3: mixed flue gas and oxidant enter in the second reactor of processing unit, this
When oxidant in metal oxide and flue gas carry out fluidization and contact, occur a variety of free radical chain reactionses, hydroxyl in oxidant
The sulfur dioxide and nitrogen oxides that produce in instantaneous oxidation flue gas of base free radical, and moisture with oxidant surface, in flue gas
Vapor combine generation acid, or directly is combined with the metal oxide in oxidant generate salt, oxidant and flue gas are two
In residence time in stage reactor, the metal oxide in the final oxidized agent of acid absorbs generation salt, completes dioxy in flue gas
Change the removal of sulphur, nitrogen oxides；
Step 4: the flue gas entrainment oxidant after sulfur dioxide, nitrogen oxides is removed in second reactor enters processing
In the third-stage reactor of device, oxidant in the presence of third-stage reactor, catch second reactor escape or with oneself
The sulfur dioxide and nitrogen oxides reacted by base, continue to play the function of second reactor, improve the efficiency of desulfurization and denitration, warp
The mixed flue gas for crossing reaction carries out gas solid separation in the rear end of third-stage reactor, reclaims oxidant, while by the flue gas after purification
Air is discharged into through chimney, smog discharge temperature is at 70~80 DEG C, and water capacity is suitable with the water capacity of before processing in flue gas.
Further, nebulized in first-stage reactor using industry water through high pressure atomizing nozzle and spray to flue gas implementation uniformly drop
Temperature.
Because the processing method of industrial waste gas of the present invention employs above-mentioned technical proposal, i.e. this method chooses natural oxidation ore
Powder is matrix and to be ground into powdery particulate matter standby, and a certain proportion of technical grade TiO is added in powdered granule thing2、Fe2O3、K2O、
MnO, oxidant is obtained, the total mass fraction of metal oxide is maintained at 30 ~ 45%, moisture less than 8% in the oxidant；Industry Waste
The processing method of gas first processing unit first-stage reactor to flue gas conditioning, make flue gas even distribution in first-stage reactor, and
And uniform decrease in temperature, coutroi velocity；Oxidant is contacted into first-stage reactor, and with flue gas by Geldart-D particle, oxygen
The supply of agent is depending on sulfur dioxide in flue gas and the total amount of nitrogen oxides；At mixed flue gas and oxidant enter
Manage and fully reacted in the second reactor of device, the dioxy produced in instantaneous oxidation flue gas of hydroxyl radical free radical in oxidant
Change sulphur and nitrogen oxides, remove sulfur dioxide in flue gas, nitrogen oxides；Subsequently into the third-stage reactor of processing unit, return
Oxidant is received, while smog discharge temperature, at 70~80 DEG C, water capacity is suitable with the water capacity of before processing in flue gas.This generation side
Simply, conveniently, raw material sources are extensive for method, adapt to industrial applications；The equipment dynamic energy consumption that treatment method is related to is low, reaction temperature
Spend it is low, effectively remove flue gas in the secondary pollution such as pollutant, no waste water and waste residue, improve treatment effect.
Embodiment
The production method of hydroxyl radical free radical of the present invention, it is matrix to choose Native Oxide miberal powder, is ground into granularity 250
Powdered granule thing more than mesh is standby, and 5 are added into the powdered granule thing ground:3:3:9 technical grade TiO2、Fe2O3、K2O、
MnO, oxidant is obtained, the quality that miberal powder matrix is aoxidized in the oxidant accounts for the 47~65% of gross mass, the TiO of addition2、Fe2O3、
K2O, mass fraction of the gross mass of tetra- kinds of metal oxides of MnO in oxidant is maintained at the total mass fraction of metal oxide
30~45% are maintained at, the moisture of oxidant is less than 8%, oxidant is produced hydroxyl radical free radical with smoke reaction.
Preferably, the oxidation miberal powder is zinc oxide miberal powder.Zinc oxide ore powder raw material wide material sources, adapting to industrialization should
With, and reduce cost.
Preferably, the moisture of the oxidant is controlled 2~8%.
A kind of processing method of industrial waste gas comprises the following steps：
Step 1: flue gas enters processing unit by flue, first-stage reactor is first passed around in processing unit and carries out cigarette
Gas it is quenched, flue gas is uniformly distributed in first-stage reactor, and uniform decrease in temperature, to 80~160 DEG C, flue gas flow rate control exists
20~50m/s；
Step 2: above-mentioned oxidant is contacted into first-stage reactor, and with flue gas by Geldart-D particle, oxygen
The supply of agent is depending on sulfur dioxide in flue gas and the total amount of nitrogen oxides, sulfur dioxide and nitrogen oxides per ton, oxygen
The supply of agent is 0.1~0.5 ton；
Fully reacted Step 3: mixed flue gas and oxidant enter in the second reactor of processing unit, this
When oxidant in metal oxide and flue gas carry out fluidization and contact, occur a variety of free radical chain reactionses, hydroxyl in oxidant
The sulfur dioxide and nitrogen oxides that produce in instantaneous oxidation flue gas of base free radical, and moisture with oxidant surface, in flue gas
Vapor combine generation acid, or directly is combined with the metal oxide in oxidant generate salt, oxidant and flue gas are two
In residence time in stage reactor, the metal oxide in the final oxidized agent of acid absorbs generation salt, completes dioxy in flue gas
Change the removal of sulphur, nitrogen oxides；
Step 4: the flue gas entrainment oxidant after sulfur dioxide, nitrogen oxides is removed in second reactor enters processing
In the third-stage reactor of device, oxidant in the presence of third-stage reactor, catch second reactor escape or with oneself
The sulfur dioxide and nitrogen oxides reacted by base, continue to play the function of second reactor, improve the efficiency of desulfurization and denitration, warp
The mixed flue gas for crossing reaction carries out gas solid separation in the rear end of third-stage reactor, reclaims oxidant, while by the flue gas after purification
Air is discharged into through chimney, smog discharge temperature is at 70~80 DEG C, and water capacity is suitable with the water capacity of before processing in flue gas.
Preferably, nebulized in first-stage reactor using industry water through high pressure atomizing nozzle and spray to flue gas implementation uniformly drop
Temperature.The drop sprayed using high pressure atomizing nozzle uniformly, nebulize, the uniform decrease in temperature of flue gas can be achieved, and in reactor
It will not condense.
The generation for the hydroxyl radical free radical (OH) that the present invention is directed in the existing processing applied to industrial waste gas, application aspect are deposited
Difficult point, propose the generation of hydroxyl radical free radical (OH) and technique for applying in a kind of gaseous environment.Hydroxyl radical free radical (OH) should
For the processing of industrial waste gas, the extremely strong hydroxyl radical free radical of oxidisability (OH) meeting rapid oxidation has the titanium dioxide of reproducibility
Sulphur, nitrogen oxides, any one in sulfur trioxide, nitrogen dioxide, metal oxide, alkaline matter, water is generated, will be quickly
It is changed into acid or sulfuric acid/nitrate, greatly accelerates sulfur dioxide, the speed that nitrogen oxides removes from flue gas, and not
With selectivity, as long as in the system can for having hydroxyl radical free radical (OH) while removing sulfur dioxide and nitrogen oxides, therefore
One device can completes desulphurization and denitration, solves the problems, such as that conventional desulphurization and denitration device needs to build respectively.Using hydroxyl
Base free radical (OH) be applied to industrial waste gas processing reaction condition is gentle, the scope of application is wide, reaction temperature is 80 ~ 160 DEG C,
Pollutant removing rate is influenceed small by initial sulfur dioxide, nitrous oxides concentration and smoke components.
Concrete application example 1：The desulphurization denitration processing of certain factory 75t/h fluid bed exhaust-heat boiler flue gas：
Exhaust-heat boiler flue gas amount is 160000 m3/ h, 160 DEG C of exhaust gas temperature, SO is contained in flue gas2Measure 5000 mg/m3, contain
NOXMeasure 300 mg/m3.Transformed on flue between the existing sack cleaner outlet of plant area and chimney, will by new flue
Flue gas introduces processing unit（Wherein containing first-stage reactor, second reactor）, flue gas is anti-in first-stage reactor and second reactor
Three-level intensified response and retracting device should be entered afterwards, after treated by the present method, survey the SO of smoke evacuation2Concentration<100mg/Nm3, NOX
Concentration<100mg/Nm3。
Concrete application example 2：The denitration process of certain glass factory 500t/d glass furnace flue gases：
Glass furnace exhaust gas volumn is 70000 m3/ h, 160 DEG C of exhaust gas temperature, flue gas contain SO2Measure 600 mg/m3, containing NOXAmount
1000 mg/m3, original flue gas desulfurization device can reach 50 using wet-type magnesia desulfurizer, desulfurized effect
mg/Nm3Emission request, denitrating technique need it is newly-built.Required to retain present wet desulphurization device according to owner, only increase is de-
Nitre device.The horizontal flue that original desulfurizing tower is exported between chimney is transformed in process implementing, made using this method
Flue gas carries out reaction with oxidant in first-stage reactor, second reactor and completes denitration, enters back into third-stage reactor afterwards and returns
Oxidant dust is received, an oxidant part for recovery is recycled into system, part recycling, surveys the nitrogen oxygen of exhanst gas outlet
Compound concentration<100mg/Nm3。
The present invention demonstrates good to the removal effect of sulfur dioxide, nitrogen oxides by concrete application example, and locates
Equipment dynamic energy consumption that reason process is related to is small, reaction temperature is low, the raw material sources of oxidant are extensive, the letter of practical application technique
It is single；The secondary pollutions such as no waste water and waste residue treated by the present method, and greatly reduce the corrosion of chimney.
Claims (2)
1. a kind of processing method of industrial waste gas, it is characterised in that this method comprises the following steps：
Step 1: flue gas enters processing unit by flue, first-stage reactor is first passed around in processing unit and carries out flue gas
It is quenched, flue gas is uniformly distributed in first-stage reactor, and uniform decrease in temperature is to 80~160 DEG C, flue gas flow rate control 20~
50m/s；
Step 2: it is matrix to choose Native Oxide miberal powder, it is standby to be ground into powdered granule thing of the granularity more than 250 mesh,
5 are added into the powdered granule thing ground:3:3:9 technical grade TiO2、Fe2O3、K2O, MnO, oxidant is obtained, the oxidant
The quality of middle oxidation miberal powder matrix accounts for the 47~65% of gross mass, the TiO of addition2、Fe2O3、K2O, MnO tetra- kinds of metal oxides
Mass fraction of the gross mass in oxidant is maintained at 30~45%, and the moisture of oxidant is less than 8%, and the oxidation miberal powder is oxidation
Zinc ore powder, oxidant are contacted by Geldart-D particle into first-stage reactor, and with flue gas, the supply of oxidant according to
Depending on sulfur dioxide in flue gas and the total amount of nitrogen oxides, sulfur dioxide and nitrogen oxides per ton, the supply of oxidant is 0.1
~0.5 ton；
Fully reacted Step 3: mixed flue gas and oxidant enter in the second reactor of processing unit, now oxygen
Metal oxide in agent carries out fluidization with flue gas and contacted, and occurs a variety of free radical chain reactionses, in oxidant hydroxyl from
By the sulfur dioxide and nitrogen oxides that produce in instantaneous oxidation flue gas of base, and moisture with oxidant surface, the water in flue gas
Steam combines generation acid, or generation salt is directly combined with the metal oxide in oxidant, and oxidant and flue gas are anti-in two level
To answer in the residence time in device, the metal oxide in sour final oxidized agent, which absorbs, generates salt, completion sulfur dioxide in flue gas,
The removal of nitrogen oxides；
Step 4: the flue gas entrainment oxidant after sulfur dioxide, nitrogen oxides is removed in second reactor enters processing unit
Third-stage reactor in, oxidant in the presence of third-stage reactor, catch second reactor escape or without and free radical
The sulfur dioxide and nitrogen oxides of reaction, continue to play the function of second reactor, the efficiency of desulfurization and denitration is improved, by anti-
The mixed flue gas answered carries out gas solid separation in the rear end of third-stage reactor, reclaims oxidant, while by the flue gas after purification through cigarette
Chimney is discharged into air, and smog discharge temperature is at 70~80 DEG C, and water capacity is suitable with the water capacity of before processing in flue gas.
2. the processing method of industrial waste gas according to claim 1, it is characterised in that：Industry water is used in first-stage reactor
Nebulized through high pressure atomizing nozzle and spray to flue gas implementation uniform decrease in temperature.
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| JP3642270B2 (en) * | 2000-09-12 | 2005-04-27 | 日産自動車株式会社 | Fuel reformer |
| CN202096874U (en) * | 2011-02-25 | 2012-01-04 | 东南大学 | Flue gas purification device based on advanced oxidization combined with wet washing |
| CN102755820A (en) * | 2012-08-09 | 2012-10-31 | 大恩(天津)环境技术研发有限公司 | Synchronous deep purification technology for various pollutants in industrial flue gas |
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Effective date of registration: 20200407 Address after: 201913 room 21767, building 3, 1800 Panyuan Road, Changxing Town, Chongming District, Shanghai Patentee after: SHANGHAI GUOHUI ENVIRONMENTAL PROTECTION TECHNOLOGY GROUP Co.,Ltd. Address before: 201103, room 528, 1001 Xu Hong Road, Shanghai, Minhang District Patentee before: SHANGHAI HAOSHEN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. |