CN105582868A - Method for generating hydroxyl free radicals and method for treating industrial waste gas - Google Patents
Method for generating hydroxyl free radicals and method for treating industrial waste gas Download PDFInfo
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Abstract
The invention discloses a method for generating hydroxyl free radicals and a method for treating industrial waste gas. The method for generating the hydroxyl free radicals includes the steps that natural oxidized ore powder is selected to serve as a matrix, and is ground into powdery particulate matter ready for use, industrial-grade TiO2, industrial-grade Fe2O3, industrial-grade K2O and industrial-grade MnO which are in a certain proportion are added into the powdery particulate matter, and an oxidizing agent is obtained. The method for treating the industrial waste gas includes the steps that smoke is subjected to thermal refining in a first reactor, and the oxidizing agent is delivered into the first reactor through pneumatic force, and is in contact with the smoke; the smoke and the oxidizing agent which are mixed enter a second reactor to be fully reacted, sulfur dioxide and nitric oxide in the smoke are instantaneously oxidized when the hydroxyl free radicals are generated in the oxidizing agent, and the sulfur dioxide and the nitric oxide in the smoke are removed; the product enters a third reactor of a treating device, the oxidizing agent is recycled, and the exhausting temperature and the moisture content of the smoke are controlled. The generating method is wide in raw material source and suitable for industrial application; the treating method is low in energy consumption and reaction temperature, and the treating effect is improved.
Description
Technical field
The present invention relates to a kind of processing method of production method and industrial waste gas of hydroxyl radical free radical.
Background technology
Along with industrial development, the discharge of industrial waste gas is all the more serious, causes many ground haze weather to take place frequently, and coverage is continuous expansion trend, has a strong impact on environment, jeopardizes the healthy of people; Industrial waste gas is the various general names that contain contaminant gases that enter air that produce in fuel combustion and production process, comprise sulfur dioxide, carbon disulfide, hydrogen sulfide, fluoride, nitrogen oxide, chlorine, hydrogen chloride, carbon monoxide, the plumbous mercury of sulfuric acid (mist), beryllide, flue dust and industrial dust etc., wherein, especially sulfur dioxide and the nitrogen oxide in fuel combustion discharge flue gas is even more serious to the pollution of environment, relates generally to the enterprises such as coal-burning power plant, iron and steel, cement, coking, glass.
The industrial waste gas improvement technology extensively adopting for smoke pollution at present relates generally to desulphurization and denitration technology. Wherein the principle of desulfur technology is the sulfur dioxide during one or more alkaline materials of employing come and in flue gas, reach the object that reduces sulfur dioxide in flue gas concentration, its technique can be divided into again wet method, dry method and half-dried (half is wet) method, in these techniques, wet method efficiency is high, but ubiquity seriously corroded, operation and maintenance cost are high and easily cause secondary pollution problems; The problems such as dry method and semidry method exist desulfuration efficiency low, and reaction speed is slow, equipment is huge. And denitration technology mainly contains SCR (SCR) and non-selective catalytic reduction (SNCR), wherein SCR operating cost costliness, one time construction cost is also very high, and enterprise cannot bear at all, 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, there is the extremely strong electronic capability that obtains, namely oxidability, oxidizing potential 2.8v, being the oxidant that occurring in nature is only second to fluorine, is also one of chemical substance that offensiveness is the strongest, oxidizable 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 in gas, has formed hydroxyl free based device, but this Technology Need carries out in specific device, and provide high-frequency and high-voltage power supply, severe reaction conditions, also not relevant verification experimental verification of effect in practical application, plant-scale application foundation shortcoming, is especially applied in and processes also not corresponding research in the exhaust-gas treatment that large discharge capacity, complicated component, working condition change Industrial Stoves greatly.
In sum, the existing hydroxyl radical free radical (OH) that is applied to exhaust-gas treatment although preparation method's possible in theory, but all do not carry out the checking of commercial Application, whether can meet industrialized application also not known, in addition also there is the difficult points such as device complexity, operating condition be harsh in the existing method of preparing hydroxyl radical free radical (OH), causes it to fail to be applied in industry; Meanwhile, traditional industrial waste gas desulphurization and denitration technology energy consumption is high, investment is large, secondary pollution is also very serious.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of processing method of production method and industrial waste gas of hydroxyl radical free radical, and this production method is simple, convenient, and raw material sources are extensive, adapt to industrial applications; The equipment dynamic energy consumption that this processing method relates to is low, and reaction temperature is low, effectively removes the pollutant in useless flue gas, without the secondary pollution such as waste water and waste residue, has improved treatment effect.
For solving the problems of the technologies described above, the production method of hydroxyl radical free radical of the present invention, choosing natural oxidation ore powder is matrix, is ground into the powdered granule thing of granularity more than 250 orders for subsequent use, to the technical grade TiO that adds 5:3:3:9 in the powdered granule thing grinding2、Fe2O3、K2O, MnO, obtain oxidant, and the quality that is oxidized breeze matrix in this oxidant accounts for 47～65% of gross mass, the TiO of interpolation2、Fe2O3、K2The gross mass mark that the mass fraction of the gross mass of O, tetra-kinds of metal oxides of MnO in oxidant remains on metal oxide remains on 30～45%, and the moisture of oxidant is less than 8%, makes oxidant and smoke reaction produce hydroxyl radical free radical.
Further, described oxidation breeze is zinc oxide breeze.
Further, the moisture of described oxidant is controlled at 2～8%.
A kind of processing method of industrial waste gas comprises the steps:
Step 1, flue gas enter treating apparatus by flue, in treating apparatus, first carry out the modified of flue gas through A reactor, and flue gas is uniformly distributed in A reactor, and uniform decrease in temperature to 80～160 DEG C, and flue gas flow rate is controlled at 20～50m/s;
Step 2, above-mentioned oxidant is delivered in A reactor by pneumatic transporting, and contact with flue gas, the supply of oxidant is determined according to the total amount of sulfur dioxide in flue gas and nitrogen oxide, sulfur dioxide per ton and nitrogen oxide, and the supply of oxidant is 0.1～0.5 ton;
Step 3, mixed flue gas and oxidant enter in the second reactor for the treatment of apparatus and fully react, now the metal oxide in oxidant carries out fluidization with flue gas and contacts, there is multiple free radical chain reactions, sulfur dioxide and nitrogen oxide in oxidant in the generation moment of hydroxyl radical free radical oxidation flue gas, and with the moisture on oxidant surface, steam in flue gas is in conjunction with generating acid, or directly the metal oxide in oxidant is combined and is generated salt, in oxidant and the flue gas time of staying in second reactor, metal oxide in sour final oxidized dose absorbs and generates salt, complete sulfur dioxide in flue gas, the removal of nitrogen oxide,
Step 4, in second reactor, remove sulfur dioxide, flue gas entrain oxygen agent after nitrogen oxide enters in the three reactor for the treatment of apparatus, oxidant is under the effect of three reactor, catch second reactor escape or not with sulfur dioxide and the nitrogen oxide of radical reaction, continue the function of performance second reactor, improve the efficiency of desulfurization and denitration, mixed flue gas through reaction carries out gas solid separation in the rear end of three reactor, reclaim oxidant, flue gas after purifying is entered to atmosphere through chimney simultaneously, smog discharge temperature is at 70～80 DEG C, in flue gas, water capacity is suitable with water capacity before treatment.
Further, in A reactor, adopt industry water to nebulize and spray to flue gas enforcement uniform decrease in temperature through high-pressure atomization nozzle.
Because the production method of hydroxyl radical free radical of the present invention and the processing method of industrial waste gas have adopted technique scheme, it is the production method of hydroxyl radical free radical, choose natural oxidation ore powder and be matrix and grind to form powdery particle for subsequent use, in powdered granule thing, add a certain proportion of technical grade TiO2、Fe2O3、K2O, MnO, obtain oxidant, and in this oxidant, the gross mass mark of metal oxide remains on 30 ~ 45%, moisture is less than 8%. The processing method of industrial waste gas first at the A reactor for the treatment of apparatus to flue gas conditioning, make flue gas even distribution in A reactor, and uniform decrease in temperature, coutroi velocity; Oxidant is delivered in A reactor by pneumatic transporting, and contacted with flue gas, the supply of oxidant is determined according to the total amount of sulfur dioxide in flue gas and nitrogen oxide; Mixed flue gas and oxidant enter in the second reactor for the treatment of apparatus and fully react, and sulfur dioxide and nitrogen oxide in oxidant in the generation moment of hydroxyl radical free radical oxidation flue gas, remove sulfur dioxide in flue gas, nitrogen oxide; Then enter in the three reactor for the treatment of apparatus, reclaim oxidant, smog discharge temperature is at 70～80 DEG C simultaneously, and in flue gas, water capacity is suitable with water capacity before treatment. This production method is simple, convenient, and raw material sources are extensive, adapts to industrial applications; The equipment dynamic energy consumption that this processing method relates to is low, and reaction temperature is low, effectively removes the pollutant in useless flue gas, without the secondary pollution such as waste water and waste residue, has improved treatment effect.
Detailed description of the invention
The production method of hydroxyl radical free radical of the present invention, choosing natural oxidation ore powder is matrix, is ground into the powdered granule thing of granularity more than 250 orders for subsequent use, to the technical grade TiO that adds 5:3:3:9 in the powdered granule thing grinding2、Fe2O3、K2O, MnO, obtain oxidant, and the quality that is oxidized breeze matrix in this oxidant accounts for 47～65% of gross mass, the TiO of interpolation2、Fe2O3、K2The gross mass mark that the mass fraction of the gross mass of O, tetra-kinds of metal oxides of MnO in oxidant remains on metal oxide remains on 30～45%, and the moisture of oxidant is less than 8%, makes oxidant and smoke reaction produce hydroxyl radical free radical.
Preferably, described oxidation breeze is zinc oxide breeze. Zinc oxide ore powder raw material wide material sources, adapt to industrial applications, and reduce costs.
Preferably, the moisture of described oxidant is controlled at 2～8%.
A kind of processing method of industrial waste gas comprises the steps:
Step 1, flue gas enter treating apparatus by flue, in treating apparatus, first carry out the modified of flue gas through A reactor, and flue gas is uniformly distributed in A reactor, and uniform decrease in temperature to 80～160 DEG C, and flue gas flow rate is controlled at 20～50m/s;
Step 2, above-mentioned oxidant is delivered in A reactor by pneumatic transporting, and contact with flue gas, the supply of oxidant is determined according to the total amount of sulfur dioxide in flue gas and nitrogen oxide, sulfur dioxide per ton and nitrogen oxide, and the supply of oxidant is 0.1～0.5 ton;
Step 3, mixed flue gas and oxidant enter in the second reactor for the treatment of apparatus and fully react, now the metal oxide in oxidant carries out fluidization with flue gas and contacts, there is multiple free radical chain reactions, sulfur dioxide and nitrogen oxide in oxidant in the generation moment of hydroxyl radical free radical oxidation flue gas, and with the moisture on oxidant surface, steam in flue gas is in conjunction with generating acid, or directly the metal oxide in oxidant is combined and is generated salt, in oxidant and the flue gas time of staying in second reactor, metal oxide in sour final oxidized dose absorbs and generates salt, complete sulfur dioxide in flue gas, the removal of nitrogen oxide,
Step 4, in second reactor, remove sulfur dioxide, flue gas entrain oxygen agent after nitrogen oxide enters in the three reactor for the treatment of apparatus, oxidant is under the effect of three reactor, catch second reactor escape or not with sulfur dioxide and the nitrogen oxide of radical reaction, continue the function of performance second reactor, improve the efficiency of desulfurization and denitration, mixed flue gas through reaction carries out gas solid separation in the rear end of three reactor, reclaim oxidant, flue gas after purifying is entered to atmosphere through chimney simultaneously, smog discharge temperature is at 70～80 DEG C, in flue gas, water capacity is suitable with water capacity before treatment.
Preferably, in A reactor, adopt industry water to nebulize and spray to flue gas enforcement uniform decrease in temperature through high-pressure atomization nozzle. Adopt the drop of high-pressure atomization nozzle ejection even, nebulize, can realize the uniform decrease in temperature of flue gas, and also can dewfall in reactor.
The present invention is directed to the existing generation of the hydroxyl radical free radical (OH) in industrial waste gas processing, the difficult point that application aspect exists of being applied to, propose generation and the technique for applying of hydroxyl radical free radical in a kind of gaseous environment (OH). hydroxyl radical free radical (OH) is applied in the processing of industrial waste gas, the extremely strong hydroxyl radical free radical (OH) of oxidisability can be oxidized rapidly the sulfur dioxide with reproducibility, nitrogen oxide, generate sulfur trioxide, nitrogen dioxide, metal oxide, alkaline matter, any one in water, will change very soon acid or sulfuric acid/nitrate into, greatly accelerate sulfur dioxide, the speed that nitrogen oxide is removed from flue gas, and do not have selective, as long as just can remove sulfur dioxide and nitrogen oxide in the system that has hydroxyl radical free radical (OH) simultaneously, therefore a device just can complete desulfurization, denitration, solve desulfurization in the past, the problem that denitrification apparatus need to be built respectively. adopt hydroxyl radical free radical (OH) to be applied to reaction condition gentleness, the scope of application of industrial waste gas processing wide, reaction temperature is 80 ~ 160 DEG C, and it is little that pollutant removing rate is affected by initial sulfur dioxide, nitrous oxides concentration and smoke components.
Concrete application example 1: the desulphurization denitration processing of certain 75t/h of factory fluid bed exhaust-heat boiler flue gas:
Exhaust-heat boiler flue gas amount is 160000m3/ h, 160 DEG C of exhaust gas temperatures, contain SO in flue gas2Amount 5000mg/m3, containing NOXAmount 300mg/m3. On the flue between the existing sack cleaner outlet of plant area and chimney, transform, by new flue, flue gas is introduced to treating apparatus (wherein containing A reactor, second reactor), flue gas enters three grades of intensified responses and retracting device after A reactor and second reactor reaction, after this method is processed, the SO of actual measurement smoke evacuation2Concentration < 100mg/Nm3，NOXConcentration < 100mg/Nm3。
Concrete application example 2: the denitration processing of certain 500t/d of glass factory glass furnace flue gas:
Glass furnace exhaust gas volumn is 70000m3/ h, 160 DEG C of exhaust gas temperatures, flue gas is containing SO2Amount 600mg/m3, containing NOXAmount 1000mg/m3, what original flue gas desulfur device adopted is wet-type magnesia desulfurizer, desulfurized effect can reach 50mg/Nm3Emission request, denitrating technique need newly-built. Require to retain present wet desulphurization device according to owner, only increase denitrification apparatus. The horizontal flue in process implementing, original desulfurizing tower being exported between chimney is transformed, adopt this method to make flue gas react denitration with oxidant in A reactor, second reactor, enter again afterwards three reactor and reclaim oxidant dust, the oxidant part circulation of reclaiming enters system, a part is recycled, the nitrous oxides concentration < 100mg/Nm of actual measurement exhanst gas outlet3。
The present invention is by concrete application example, verified the removal effect of sulfur dioxide, nitrogen oxide well, and the equipment dynamic energy consumption that processing procedure relates to is little, reaction temperature is low, the raw material sources of oxidant are extensive, and practical application technique is simple; Process without the secondary pollution such as waste water and waste residue through this method, and greatly reduced the corrosion of chimney.
Claims (5)
1. a production method for hydroxyl radical free radical, is characterized in that: choosing natural oxidation ore powder is matrix, is ground into the powdered granule thing of granularity more than 250 orders for subsequent use, to the technical grade TiO that adds 5:3:3:9 in the powdered granule thing grinding2、Fe2O3、K2O, MnO, obtain oxidant, and the quality that is oxidized breeze matrix in this oxidant accounts for 47～65% of gross mass, the TiO of interpolation2、Fe2O3、K2The mass fraction of the gross mass of O, tetra-kinds of metal oxides of MnO in oxidant remains on 30～45%, and the moisture of oxidant is less than 8%, makes oxidant and smoke reaction produce hydroxyl radical free radical.
2. the production method of hydroxyl radical free radical according to claim 1, is characterized in that: described oxidation breeze is zinc oxide breeze.
3. the production method of hydroxyl radical free radical according to claim 1, is characterized in that: the moisture of described oxidant is controlled at 2～8%.
4. a processing method for industrial waste gas, is characterized in that this method comprises the steps:
Step 1, flue gas enter treating apparatus by flue, in treating apparatus, first carry out the modified of flue gas through A reactor, and flue gas is uniformly distributed in A reactor, and uniform decrease in temperature to 80～160 DEG C, and flue gas flow rate is controlled at 20～50m/s;
Step 2, the oxidant that claims 1 to 3 any one is obtained are delivered in A reactor by pneumatic transporting, and contact with flue gas, the supply of oxidant is determined according to the total amount of sulfur dioxide in flue gas and nitrogen oxide, sulfur dioxide per ton and nitrogen oxide, the supply of oxidant is 0.1～0.5 ton;
Step 3, mixed flue gas and oxidant enter in the second reactor for the treatment of apparatus and fully react, now the metal oxide in oxidant carries out fluidization with flue gas and contacts, there is multiple free radical chain reactions, sulfur dioxide and nitrogen oxide in oxidant in the generation moment of hydroxyl radical free radical oxidation flue gas, and with the moisture on oxidant surface, steam in flue gas is in conjunction with generating acid, or directly the metal oxide in oxidant is combined and is generated salt, in oxidant and the flue gas time of staying in second reactor, metal oxide in sour final oxidized dose absorbs and generates salt, complete sulfur dioxide in flue gas, the removal of nitrogen oxide,
Step 4, in second reactor, remove sulfur dioxide, flue gas entrain oxygen agent after nitrogen oxide enters in the three reactor for the treatment of apparatus, oxidant is under the effect of three reactor, catch second reactor escape or not with sulfur dioxide and the nitrogen oxide of radical reaction, continue the function of performance second reactor, improve the efficiency of desulfurization and denitration, mixed flue gas through reaction carries out gas solid separation in the rear end of three reactor, reclaim oxidant, flue gas after purifying is entered to atmosphere through chimney simultaneously, smog discharge temperature is at 70～80 DEG C, in flue gas, water capacity is suitable with water capacity before treatment.
5. the processing method of industrial waste gas according to claim 4, is characterized in that: in A reactor, adopt industry water to nebulize and spray to flue gas enforcement uniform decrease in temperature through high-pressure atomization nozzle.
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| US6991663B2 (en) * | 2000-09-12 | 2006-01-31 | Nissan Motor Co., Ltd. | Hydrogen-rich gas supply device for fuel cell |
| 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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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6991663B2 (en) * | 2000-09-12 | 2006-01-31 | Nissan Motor Co., Ltd. | Hydrogen-rich gas supply device for fuel cell |
| 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 |
Non-Patent Citations (1)
| Title |
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| 常文贵: "高级氧化技术中羟基自由基产生的机理", 《安庆师范学院学报》 * |
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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. |