CN105771577A - Device and method for preparing chlorine dioxide and using chlorine dioxide for flue-gas denitration - Google Patents
Device and method for preparing chlorine dioxide and using chlorine dioxide for flue-gas denitration Download PDFInfo
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Abstract
The invention belongs to the technical field of environmental-pollution treatment and particularly relates to a device and method for preparing chlorine dioxide and using chlorine dioxide for flue-gas denitration. The device comprises a Y-shaped three-way pipeline, wherein an included angle between two V-shaped pipelines is 55-65 degrees; the two V-shaped pipelines are used as two feeding pipelines, and the third pipeline is used as a mixing-reaction generator; a distributing and spraying device is arranged at the outlet end of the pipeline and comprises a safety valve and a plurality of parallel spraying heads; the spraying heads can go deep into a flue-gas pipeline directly; and a mixture containing chlorine dioxide and flue gas are uniformly mixed to generate denitration reaction. The device and the method have the advantages that the mixture containing chlorine dioxide generated from reaction can enter the flue-gas denitration process in an ordered and controllable manner, the reaction between misted chlorine dioxide and flue gas can be fuller and the discharging amount of chlorine dioxide can be adjusted by the distributing and spraying device according to the flue-gas condition.
Description
Technical field
The invention belongs to technical field of environment pollution control, particularly to a kind of apparatus and method prepared chlorine dioxide and use it for denitrating flue gas.
Background technology
For preventing from producing too much NOx contaminated environment after burning in boiler, it is necessary to flue gas is carried out denitration process.Reduction denitration and oxidation and denitration can be divided into according to denitration principle difference.
Wherein reduction denitration includes SNCR denitration method (SNCR) and selective-catalytic-reduction denitrified method (SCR).Described non-selective reductant denitration method (SNCR) is that one does not use catalyst, reduces the method for NOx in 850～1100 DEG C of temperature ranges, and most-often used medicine is ammonia and carbamide；In general, SNCR denitration efficiency to Large-sized Coal-fired Power group up to 25%～40%, to small unit up to 80%；Owing to this method is affected very big by boiler structure size, the supplementary process means being used as low-NO_x combustion technology more；Its construction costs is low, it is simple and easy to arrange, floor space is little, is suitable for modernizing and expanding the existing factory, new factory can according to boiler design with the use of；But the temperature window of SNCR technological requirement is little, such as spray unreasonable boiler and the follow-up equipment of damaging of ammonia, there is the problems such as efficiency is low in SNCR denitration simultaneously.Described selective catalytic reduction (SCR) is to utilize reducing agent (NH3, carbamide) and under metallic catalyst effect, optionally react generation N with NOx2And H2O, rather than by O2Oxidation, therefore it is called that " selectivity " reduces；SCR technique popular in the world is broadly divided into ammonia process SCR and urea method SCR two kinds, and this both of which is the restoring function utilizing ammonia to NOx, under the effect of catalyst, NOx (mainly NO) is reduced to the N on the few of impact of air2And water, reducing agent is NH3；The catalyst used in SCR is mostly with TiO2For carrier, with V2O5Or V2O5-WO3Or V2O5-MoO3For active component, being applied to the SCR catalyst in denitrating flue gas and can be divided into high temperature catalyst (345 DEG C～590 DEG C), middle temperature catalyst (260 DEG C～380 DEG C) and low temperature catalyst (80 DEG C～300 DEG C), the suitable reaction temperature of different catalyst is different；If reaction temperature is on the low side, the activity of catalyst can reduce, and causes that denitration efficiency declines, and if catalyst continue operation at low temperatures and can make catalyst generation permanent damage；If reaction temperature is too high, NH3Being oxidized easily, NOx generation amount increases, and also can cause the phase transformation of catalyst material, makes the activity degeneration of catalyst；Domestic and international SCR system adopts high temperature, reaction temperature interval to be 315 DEG C～400 DEG C mostly；This method denitration efficiency is high, and relative low price is widely used in domestic and international project, becomes the mainstream technology of generating plant flue gas denitration；But SCR technique is currently mainly applied on the big boiler controller system such as power plant, boiler working condition is stable, and Industrial Boiler is less due to boiler load, operating mode is unstable, easily cause the problems such as SCR catalyst blocking, poisoning, inactivation, process will largely effect on denitration efficiency not in time, make flue gas can not qualified discharge, even affect the stable operation of whole SCR system.
The method that current oxidation and denitration is applied is mainly Ozonation denitration.Mainly by the strong oxidizing property of ozone, it is high-valence state nitrogen oxides by the lower valency nitrogen oxides in flue gas, then by nox adsorption in scrubbing tower, reaches the purpose of elimination.But owing to the current ozone generating apparatus ozoniferous efficiency of product is low so that it is application is limited, and the denitration being only applicable to low discharge flue gas is administered.
As far back as 1811, American scientist H.Davery utilized KClO3Aqueous solution and hydrochloric acid reaction, synthesize first and have collected chlorine dioxide.Owing to the volumetric concentration in chlorine dioxide air just has explosivity more than 10%, there is the irritant gas similar to chlorine, have rank smell.Limit its popularization and application.Until the thirties in 20th century, ClO2Just it is able to safe and economically large-scale production, starts industrialized extensive use.Nineteen forty-four, chlorine dioxide is used for processing the drinking water in New York, United States Niagara Falls city as disinfectant first, is generalized to rapidly the whole world afterwards.China's application Chloride Dioxide Disinfection Technology starts from the eighties.1987, health supervision department of Guangdong Province ratified it and may be used for food sterilization, fresh-keeping and food apparatus, equipment disinfection.Nineteen ninety Shanghai sanitation approved by management its may be used for water process, food processing and aquaculture, deodorization etc..China's Ministry of Public Health also clearly proposed before 2000, progressively substitutes chlorine with chlorine dioxide and carries out the sterilization of drinking water.Owing to high concentration of chlorine dioxide is dangerous big, transport difficult, can only in situ preparation, onsite application.But its application of success is only limitted to process association area at water, but current used chlorine dioxide production equipment is due to low conversion rate, and response speed is slow, is not suitable with the fluctuation of flue gas, limits its successful Application.
Summary of the invention
For prior art Problems existing, the present invention provides a kind of apparatus and method prepared chlorine dioxide and use it for denitrating flue gas, purpose is to prepare chlorine dioxide rapidly, efficiently, and is directly used in denitrating flue gas, lays good basis for flue gas subsequent treatment.
Realize preparing chlorine dioxide and using it for the device of denitrating flue gas and include a Y-type three way type pipeline of the object of the invention, angle between the pipeline that two of which is V-shaped is 55 ° ~ 65 °, as two feed pipes, and non-return valve is installed on pipeline, remaining Article 3 pipeline is as hybrid reaction generator, the port of export at pipeline is provided with Pressure gauge and distribution spray device, wherein said distribution spray device includes the spray head of relief valve and several parallel connections, and spray head can directly be deep in flue.
Wherein, the described Article 3 duct length as hybrid reaction generator is 950 ~ 1200mm.
Adopt and above-mentioned prepare chlorine dioxide and use it for the device of denitrating flue gas and be prepared chlorine dioxide and use it for the method for denitrating flue gas and carry out according to following steps:
(1) with mass concentration for 15 ~ 18% sodium chlorate solutions and technical hydrochloric acid that mass concentration is 31% for raw material, raw material is previously heated to 55 ~ 70 DEG C, then dosing pump is adopted, according to volume ratio technical hydrochloric acid: sodium chlorate solution=1:(1 ~ 1.2) ratio sodium chlorate solution and technical hydrochloric acid are respectively fed in the v-shaped tube that two angles are 55 ° ~ 65 ° of three-way pipeline, Article 3 pipeline carries out hybrid reaction；
(2) obtain containing strong oxidizer ClO after hybrid reaction occurring pipeline2Mixture, by gas-liquid mixture being dispersed into fine mist after the distribution spray device uniform distribution of pipe outlet, namely and ClO the spray head of distribution spray device is directly deep in flue, and by it with flue gas Homogeneous phase mixing, the lower valency nitrogen oxides (NO) in flue gas2Redox reaction occurs, and lower valency nitrogen oxides (NO) is oxidized to the nitrogen oxides (NO of high-valence state2), oxidation afterproduct alkali liquor absorbs.
Compared with prior art, the feature of the present invention and providing the benefit that:
In prior art, chlorine dioxide uses the maximum limiting factor received to be exactly its unstable and uncontrollability.nullCompared with prior art，The present invention prepares chlorine dioxide and uses it for the device of denitrating flue gas by arranging a three-way pipeline，Using in three-way pipeline as pipeline reactor，Length is 950 ~ 1200mm，Angle is that the pipeline of 55 ° ~ 65 ° is as two feed pipes，When the angle of feed pipe is 55 ° ~ 65 °，The flow of raw material、Pressure can obtain optimal control results，Oxidation reaction is made promptly to occur in pipeline reactor，Whole process only has tens seconds the soonest，And by arranging distribution spray device at the pipeline reactor port of export，The mixture containing chlorine dioxide that reaction produces can be made controllably to enter into denitrating flue gas flow process in order，It is provided with on two feed pipes when non-return valve is prevented from feeding process dosing pump termination of pumping simultaneously and recharges，Pressure gauge and relief valve on pipeline also are able to prevent pipeline pressure excessive，Convenient control in time adjusts fill process.
Fine mist containing strong oxidizer ClO2Mixture and flue gas Homogeneous phase mixing after, namely and ClO the lower valency nitrogen oxides (NO) in flue gas2Redox reaction occurs, and lower valency nitrogen oxides (NO) is oxidized to the nitrogen oxides (NO of high-valence state2), oxidation afterproduct alkali liquor absorbs, and the chlorine dioxide of fine mist and the reaction of flue gas are more abundant, and can pass through the distribution spray device load according to flue gas condition adjustment chlorine dioxide, and the reaction that Chlorine Dioxide Oxidation agent specifically occurs is:
2NaClO3+4HCl→2NaCl+2ClO2+Cl2+2H2O
Cl2+NO+H2O→NO2+2HCl
2ClO2+5NO+H2O→5NO2+2HCl
2NaOH+3NO2→2NaNO3+NO+H2O
2NaOH+NO2+NO→2NaNO2+H2O
HCl+NaOH→NaCl+H2O
If containing SO in flue gas2, then in flue gas, there is following reaction:
SO2+H2O→H2SO3
NO+NO2+H2O→HNO2
H2SO3+HNO2→N2+H2SO4
In this process, desulphurization denitration carries out simultaneously, it is possible to reduce flue gas subsequent treatment burden.
Accompanying drawing explanation
Fig. 1 is preparing chlorine dioxide and using it for the device schematic diagram of denitrating flue gas of the present invention；
Wherein: 1: three-way pipeline；2: non-return valve；3: distribution spray device；4: spray head；5: Pressure gauge；6: relief valve.
Detailed description of the invention
The preparing chlorine dioxide and use it for the device of denitrating flue gas as shown in Figure 1 of the embodiment of the present invention, including a Y-type three way type pipeline 1, angle between the pipeline that two of which is V-shaped is 55 ° ~ 65 °, as two feed pipes, and non-return valve 2 is installed on pipeline, remaining Article 3 pipeline is as hybrid reaction generator, the port of export at pipeline is provided with Pressure gauge 5 and distribution spray device 3, wherein said distribution spray device 3 includes the spray head 4 of relief valve 6 and several parallel connections, and spray head 4 can directly be deep in flue.
Embodiment 1
The present embodiment adopts preparing chlorine dioxide and using it for the device of denitrating flue gas and prepare chlorine dioxide and use it for the method for denitrating flue gas and carry out according to following steps shown in Fig. 1:
(1) with mass concentration for 15% sodium chlorate solution and technical hydrochloric acid that mass concentration is 31% for raw material, raw material is previously heated to 55 DEG C, then dosing pump is adopted, according to volume ratio technical hydrochloric acid: sodium chlorate solution and technical hydrochloric acid are respectively fed in the v-shaped tube that two angles are 55 ° of three-way pipeline by the ratio of sodium chlorate solution=1:1.2, carry out hybrid reaction in Article 3 pipeline；
(2) obtain containing strong oxidizer ClO after hybrid reaction occurring pipeline2Mixture, by gas-liquid mixture is dispersed into after the distribution spray device uniform distribution of pipe outlet fine mist, the spray head of distribution spray device is directly deep in flue, and certain chemical plant boiler is with water-coal-slurry for fuel, tonnage is 75t/h, flue gas flow 70000m3/ h, flue-gas temperature about 55 DEG C, nitrogen oxides in effluent mean concentration is 450mg/Nm3Namely and ClO, by it with flue gas Homogeneous phase mixing, the lower valency nitrogen oxides (NO) in flue gas2Redox reaction occurs, and lower valency nitrogen oxides (NO) is oxidized to the nitrogen oxides (NO of high-valence state2), oxidation afterproduct alkali liquor absorbs, and the concentration of flue outlet place nitrogen oxides reaches 65mg/Nm after testing3, reach the country GB13223-2011 discharge standard (100mg/Nm specified3).
Embodiment 2
The present embodiment adopts preparing chlorine dioxide and using it for the device of denitrating flue gas and prepare chlorine dioxide and use it for the method for denitrating flue gas and carry out according to following steps shown in Fig. 1:
(1) with mass concentration for 16% sodium chlorate solution and technical hydrochloric acid that mass concentration is 31% for raw material, raw material is previously heated to 68 DEG C, then dosing pump is adopted, according to volume ratio technical hydrochloric acid: sodium chlorate solution and technical hydrochloric acid are respectively fed in the v-shaped tube that two angles are 65 ° of three-way pipeline by the ratio of sodium chlorate solution=1:1.1, carry out hybrid reaction in Article 3 pipeline；
(2) obtain containing strong oxidizer ClO after hybrid reaction occurring pipeline2Mixture, by gas-liquid mixture is dispersed into after the distribution spray device uniform distribution of pipe outlet fine mist, the spray head of distribution spray device is directly deep in flue, and certain chemical plant boiler is with water-coal-slurry for fuel, tonnage is 75t/h, flue gas flow 70000m3/ h, flue-gas temperature about 55 DEG C, nitrogen oxides in effluent mean concentration is 450mg/Nm3Namely and ClO, by it with flue gas Homogeneous phase mixing, the lower valency nitrogen oxides (NO) in flue gas2Redox reaction occurs, and lower valency nitrogen oxides (NO) is oxidized to the nitrogen oxides (NO of high-valence state2), oxidation afterproduct alkali liquor absorbs, and the concentration of flue outlet place nitrogen oxides reaches 45mg/Nm after testing3, reach the country GB13223-2011 discharge standard (100mg/Nm specified3).
Embodiment 3
The present embodiment adopts preparing chlorine dioxide and using it for the device of denitrating flue gas and prepare chlorine dioxide and use it for the method for denitrating flue gas and carry out according to following steps shown in Fig. 1:
(1) with mass concentration for 17% sodium chlorate solution and technical hydrochloric acid that mass concentration is 31% for raw material, raw material is previously heated to 65 DEG C, then dosing pump is adopted, according to volume ratio technical hydrochloric acid: sodium chlorate solution and technical hydrochloric acid are respectively fed in the v-shaped tube that two angles are 60 ° of three-way pipeline by the ratio of sodium chlorate solution=1:1, carry out hybrid reaction in Article 3 pipeline；
(2) obtain containing strong oxidizer ClO after hybrid reaction occurring pipeline2Mixture, by gas-liquid mixture is dispersed into after the distribution spray device uniform distribution of pipe outlet fine mist, the spray head of distribution spray device is directly deep in flue, and certain chemical plant boiler is with water-coal-slurry for fuel, tonnage is 75t/h, flue gas flow 70000m3/ h, flue-gas temperature about 55 DEG C, nitrogen oxides in effluent mean concentration is 450mg/Nm3Namely and ClO, by it with flue gas Homogeneous phase mixing, the lower valency nitrogen oxides (NO) in flue gas2Redox reaction occurs, and lower valency nitrogen oxides (NO) is oxidized to the nitrogen oxides (NO of high-valence state2), oxidation afterproduct alkali liquor absorbs, and the concentration of flue outlet place nitrogen oxides reaches 28mg/Nm after testing3, reach the country GB13223-2011 discharge standard (100mg/Nm specified3).
Embodiment 4
The present embodiment adopts preparing chlorine dioxide and using it for the device of denitrating flue gas and prepare chlorine dioxide and use it for the method for denitrating flue gas and carry out according to following steps shown in Fig. 1:
(1) with mass concentration for 18% sodium chlorate solution and technical hydrochloric acid that mass concentration is 31% for raw material, raw material is previously heated to 55 DEG C, then dosing pump is adopted, according to volume ratio technical hydrochloric acid: sodium chlorate solution and technical hydrochloric acid are respectively fed in the v-shaped tube that two angles are 55 ° of three-way pipeline by the ratio of sodium chlorate solution=1:1.2, carry out hybrid reaction in Article 3 pipeline；
(2) obtain containing strong oxidizer ClO after hybrid reaction occurring pipeline2Mixture, by gas-liquid mixture is dispersed into after the distribution spray device uniform distribution of pipe outlet fine mist, the spray head of distribution spray device is directly deep in flue, and certain boiler of power plant is with coal for fuel, tonnage is 130t/h, flue gas flow 140000m3/ h, flue-gas temperature about 50 DEG C, nitrogen oxides in effluent mean concentration is 400mg/Nm3Namely and ClO, by it with flue gas Homogeneous phase mixing, the lower valency nitrogen oxides (NO) in flue gas2Redox reaction occurs, and lower valency nitrogen oxides (NO) is oxidized to the nitrogen oxides (NO of high-valence state2), oxidation afterproduct alkali liquor absorbs, and the concentration of flue outlet place nitrogen oxides reaches 70mg/Nm after testing3, reach the country GB13223-2011 discharge standard (100mg/Nm specified3).
Embodiment 5
The present embodiment adopts preparing chlorine dioxide and using it for the device of denitrating flue gas and prepare chlorine dioxide and use it for the method for denitrating flue gas and carry out according to following steps shown in Fig. 1:
(1) with mass concentration for 18% sodium chlorate solution and technical hydrochloric acid that mass concentration is 31% for raw material, raw material is previously heated to 60 DEG C, then dosing pump is adopted, according to volume ratio technical hydrochloric acid: sodium chlorate solution and technical hydrochloric acid are respectively fed in the v-shaped tube that two angles are 65 ° of three-way pipeline by the ratio of sodium chlorate solution=1:1.1, carry out hybrid reaction in Article 3 pipeline；
(2) obtain containing strong oxidizer ClO after hybrid reaction occurring pipeline2Mixture, by gas-liquid mixture is dispersed into after the distribution spray device uniform distribution of pipe outlet fine mist, the spray head of distribution spray device is directly deep in flue, and certain boiler of power plant is with coal for fuel, tonnage is 130t/h, flue gas flow 140000m3/ h, flue-gas temperature about 50 DEG C, nitrogen oxides in effluent mean concentration is 400mg/Nm3Namely and ClO, by it with flue gas Homogeneous phase mixing, the lower valency nitrogen oxides (NO) in flue gas2Redox reaction occurs, and lower valency nitrogen oxides (NO) is oxidized to the nitrogen oxides (NO of high-valence state2), oxidation afterproduct alkali liquor absorbs, and the concentration of flue outlet place nitrogen oxides reaches 48mg/Nm after testing3, reach the country GB13223-2011 discharge standard (100mg/Nm specified3).
Embodiment 6
The present embodiment adopts preparing chlorine dioxide and using it for the device of denitrating flue gas and prepare chlorine dioxide and use it for the method for denitrating flue gas and carry out according to following steps shown in Fig. 1:
(1) with mass concentration for 15% sodium chlorate solution and technical hydrochloric acid that mass concentration is 31% for raw material, raw material is previously heated to 70 DEG C, then dosing pump is adopted, according to volume ratio technical hydrochloric acid: sodium chlorate solution and technical hydrochloric acid are respectively fed in the v-shaped tube that two angles are 60 ° of three-way pipeline by the ratio of sodium chlorate solution=1:1, carry out hybrid reaction in Article 3 pipeline；
(2) obtain containing strong oxidizer ClO after hybrid reaction occurring pipeline2Mixture, by gas-liquid mixture is dispersed into after the distribution spray device uniform distribution of pipe outlet fine mist, the spray head of distribution spray device is directly deep in flue, and certain boiler of power plant is with coal for fuel, tonnage is 130t/h, flue gas flow 140000m3/ h, flue-gas temperature about 50 DEG C, nitrogen oxides in effluent mean concentration is 400mg/Nm3Namely and ClO, by it with flue gas Homogeneous phase mixing, the lower valency nitrogen oxides (NO) in flue gas2Redox reaction occurs, and lower valency nitrogen oxides (NO) is oxidized to the nitrogen oxides (NO of high-valence state2), oxidation afterproduct alkali liquor absorbs, and the concentration of flue outlet place nitrogen oxides reaches 15mg/Nm after testing3, reach the country GB13223-2011 discharge standard (100mg/Nm specified3).
Claims (4)
1. prepare chlorine dioxide and use it for the device of denitrating flue gas for one kind, it is characterized in that device includes a Y-type three way type pipeline, angle between the pipeline that two of which is V-shaped is 55 ° ~ 65 °, as two feed pipes, and non-return valve is installed on pipeline, remaining Article 3 pipeline is as hybrid reaction generator, the port of export at pipeline is provided with Pressure gauge and distribution spray device, wherein said distribution spray device includes the spray head of relief valve and several parallel connections, and spray head can directly be deep in flue.
2. a kind of device prepared chlorine dioxide and use it for denitrating flue gas according to claim 1, it is characterised in that the described Article 3 duct length as hybrid reaction generator is 950 ~ 1200mm.
3. adopt to prepare chlorine dioxide as claimed in claim 1 and use it for the device of denitrating flue gas and be prepared chlorine dioxide the method using it for denitrating flue gas, it is characterised in that carry out according to following steps:
(1) with sodium chlorate solution and technical hydrochloric acid for raw material, raw material is previously heated to 55 ~ 70 DEG C, then dosing pump is adopted, according to volume ratio sodium chlorate solution: technical hydrochloric acid=1:(1 ~ 1.2) ratio sodium chlorate solution and technical hydrochloric acid are respectively fed in the v-shaped tube that two angles are 55 ° ~ 65 ° of three-way pipeline, Article 3 pipeline carries out hybrid reaction；
(2) obtain containing strong oxidizer ClO after hybrid reaction occurring pipeline2Mixture, by gas-liquid mixture being dispersed into fine mist after the distribution spray device uniform distribution of pipe outlet, the spray head of distribution spray device is directly deep in flue, and by itself and flue gas Homogeneous phase mixing, the lower valency nitrogen oxides in flue gas is and ClO2Redox reaction occurs, and lower valency nitrogen oxides is oxidized to the nitrogen oxides of high-valence state, and oxidation afterproduct alkali liquor absorbs.
4. according to claim 3 a kind of prepare chlorine dioxide the method using it for denitrating flue gas, it is characterised in that described sodium chlorate solution's mass concentration is 15 ~ 18%, and technical hydrochloric acid mass concentration is 31%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN111228993A (en) * | 2020-03-11 | 2020-06-05 | 山东师范大学 | Method and system for flue gas denitration by using chlorine dioxide and spray tower |
| CN111229006A (en) * | 2020-03-11 | 2020-06-05 | 山东师范大学 | Method for denitration by using chlorine dioxide-containing liquid |
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| CN106975337A (en) * | 2017-04-28 | 2017-07-25 | 包训祥 | Chlorine dioxide gaseous oxidation denitration integrated device and its technique |
| CN111228993A (en) * | 2020-03-11 | 2020-06-05 | 山东师范大学 | Method and system for flue gas denitration by using chlorine dioxide and spray tower |
| CN111229006A (en) * | 2020-03-11 | 2020-06-05 | 山东师范大学 | Method for denitration by using chlorine dioxide-containing liquid |
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