CN105561769A - Denitration device achieving denitration by using salt reinforcing hydrogen peroxide solution to oxidize NO and denitration method - Google Patents
Denitration device achieving denitration by using salt reinforcing hydrogen peroxide solution to oxidize NO and denitration method Download PDFInfo
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- CN105561769A CN105561769A CN201410552782.XA CN201410552782A CN105561769A CN 105561769 A CN105561769 A CN 105561769A CN 201410552782 A CN201410552782 A CN 201410552782A CN 105561769 A CN105561769 A CN 105561769A
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Abstract
The invention relates to a denitration device achieving denitration by using salt reinforcing hydrogen peroxide solution to oxidize NO and a denitration method. The device comprises a bubbling reactor provided with a heat exchanger inside, wherein a smoke inlet pipeline on the upper portion of the bubbling reactor enters the bubbling reactor to be communicated with a gas distributor, and a smoke outlet pipeline at one end of the upper portion of the bubbling reactor is communicated with an external chimney; a bottom absorbent outlet pipeline is communicated with an absorbent recovery treatment device, a cyclone separator and a mother liquor tank in sequence, and an H2O2 solution tank, a salt solution tank and an outlet pipeline of the mother liquor tank are communicated and then gathered at the position of an absorbent inlet pipeline in the middle of the bubbling reactor to be communicated with the bubbling reactor. According to the denitration method, nitric oxide in smoke is absorbed by an absorbent in the bubbling reactor, the absorbent is an H2O2 and salt mixed solution, the concentration of H2O2 in the absorbent is 0.05-0.5 mol/L, the concentration of salt in the absorbent is 0.5-5 mol/L, and salt is one of sodium chloride, calcium chloride, magnesium chloride and sodium bicarbonate. The nitric oxide removing efficiency is 50% or above.
Description
Technical field
The present invention relates to air contaminant treatment field, particularly a kind of denitrification apparatus based on salt strengthening hydrogen peroxide solution oxidation NO and method.
Background technology
NO
xit is the one of the main reasons causing the environmental problem such as acid rain and photochemical fog.Along with the development of China's industry, and affect by the energy resource structure based on coal, China's nitrogen oxides pollution situation is serious, prevention and control situation is severe.According to statistics, electric power and thermoelectricity industry discharged nitrous oxides account for 66.7% of Industrial Nitrogen emissions of oxides.Along with the raising day by day of environmental requirement, newly-built coal-burning power plant of China has all installed denitrification apparatus additional, implements stricter NO in " 12 " period simultaneously
xdischarge standard, to control the day by day serious NO of China
xpollute.
At present, for NO
xremoving sulfuldioxide be mainly divided into two classes: one be burning in remove, namely adopt low NO
xcombustion technology, reduces the NO that in burner hearth, coal combustion generates
xamount; Another kind removes after burning, namely from flue gas, removes NO
x, typical selective catalytic reduction method and SNCR method.For low NO
xcombustion technology, general denitration efficiency is low, and may cause stove internal corrosion, slagging scorification, even reduces efficiency of combustion.For selective catalytic reduction and SNCR method, although there is higher removal efficiency, occupation area of equipment can be made large, investment and operating cost high, even also can cause secondary pollution.
Chinese patent CN102553416 discloses a kind of method of power-plant flue gas denitration and absorbent used thereof.The method is characterized in that and utilize absorption tower, adopt by H
2o
2the modified Fenton reaction formed with ferric sulfate and EDTA be the aqueous solution of additive as absorbent, control temperature is under the condition of 30-80 DEG C, NO is oxidized in absorption tower and then is absorbed by absorbent thus complete denitration.But the method is in advance by H
2o
2with Fe
2(SO
4)
3solution mixes, and the time that free radical is generated to reaction is long, H
2o
2consumption is comparatively large, and cost is higher.
Chinese patent CN103007753 discloses a kind of heterogeneous Fenton reagent and its preparation method and application.The method is characterized in that described heterogeneous Fenton reagent is by H
2o
2the aqueous solution and Al
2o
3the pH of load Fe catalyst composition is the mixed solution of 5 ~ 6.Method of denitration is add heterogeneous Fenton reagent in the bubble tower of routine, and the NO in flue gas is oxidized to HNO
3.But absorption reagent first passes in absorption tower by the method, then carry out denitration, H by forming bubbling in flue gas injection to absorbent
2o
2consumption is large, and cost is high, also needs flue gas to carry out pressurized jet simultaneously, and energy consumption is higher.
There is no a kind of method of denitration being applicable to the high efficiency, low cost of middle-size and small-size power plant at present, therefore, find a kind of Low investment cost, efficient convenient denitration technology is still the task of top priority.
The present invention will propose a kind of salt strengthening H
2o
2the denitrification apparatus of solution oxide NO and method.Adopt the H of low concentration
2o
2the aqueous solution just can obtain high removal of nitrogen oxide efficiency, have construction and operating cost low, the advantage of secondary pollution can not be caused.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, provide a kind of salt to strengthen H
2o
2the denitrification apparatus of solution oxide NO and method.
The present invention is realized by following technical scheme:
A kind of salt strengthening H
2o
2the denitrification apparatus of solution oxide NO, it is characterized in that, described device comprises: a bubbling reactor 1, center, top has a gas approach pipeline 2 to enter in bubbling reactor 1 to be connected with gas distributor 12, be provided with heat exchanger 14 in bubbling reactor 1, bubbling reactor 1 upper one end arranges an exhanst gas outlet pipeline 3 and passes into outside chimney 11; Be provided with absorbent inlet pipeline 4 in the middle part of bubbling reactor 1, the absorbent outlet conduit 5 bottom bubbling reactor 1 is connected with absorbent recycling and processing device, cyclone separator, mother liquor tank 8 successively, H
2o
2the outlet conduit of solution tank 9, salting liquid groove 10 and mother liquor tank 8 is connected and is collected to absorbent inlet pipeline 4 and is communicated with bubbling reactor 1.
Described gas distributor 12 is the gas distributor of cone shape, and opening angle is 100 ° ~ 150 °; Its cone bottom surface radius is 60% ~ 90% of bubbling reactor cross sectional radius, and its cone upper bottom surface radius is 1/3 of bottom surface radius; Gas distributor surface is evenly equipped with aperture, and aperture is 1 ~ 2mm, and porosity is 5% ~ 10%; Bottom 10 ~ the 20cm of bottom surface distance bubbling reactor.
Described bubbling reactor 1 is provided with a demister 13, is positioned at the below of bubbling reactor 1 top exhanst gas outlet.
The present invention also proposes a kind of salt strengthening H
2o
2the method of denitration of solution oxide NO: it is characterized in that, described method comprises the steps:
1) flue gas pretreatment: flue gas first through dust arrester dedusting, and by flue gas cool-down to 40-60 DEG C;
2) absorbent is configured: at H
2o
2the H that concentration is 1mol/L is added in solution tank
2o
2solution, adds the salting liquid that concentration is 5mol/L, H in salting liquid groove
2o
2solution and salting liquid are mixed with absorbent after entering pipeline mixing, wherein, and H in absorbent
2o
2concentration be 0.05 ~ 0.5mol/L, the concentration of salt is 0.5 ~ 5mol/L, and the pH value controlling absorbent is 6.5; Wherein, described salt is the one in sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium acid carbonate;
3) denitrating flue gas:
Through step 2) absorbent for preparing enters bubbling reactor by absorbent inlet pipeline, and the volume controlling the absorbent entered is the 60%-70% of bubbling reactor total measurement (volume);
Through step 1) the gas approach pipeline of pretreated flue gas through bubbling reactor top send in reactor, the control of flue gas flow is by the volume of bubbling reactor inner absorbent divided by the residence Time Calculation gained of flue gas at bubbling reactor, and the described time of staying is 1 ~ 5 minute;
The flue gas entered will be distributed in absorbent by gas distributor equably, contact with each other and will react, complete removal of nitrogen oxide with absorbent, and wherein, absorbent temperature controls at 40 ~ 60 DEG C;
4) in flue gas, drop removes:
Step 3) in flue gas after denitration flow through the demister on bubbling reactor top, remove drop entrained in flue gas, droplets fall back is in bubbling reactor, and the clean flue gas of gained flows out from the exhanst gas outlet pipeline at bubbling reactor top, enters smoke stack emission;
5) absorbent regeneration
The absorbent participating in reaction enters absorbent recycling and processing device, react with the ammoniacal liquor added and generate ammonium nitrate solution, carry out stirring and indirectly cooling with water, ammonium nitrate crystal is separated out in feeding cyclone separator and is separated, absorbent removes solid particle by cyclone separator and enters mother liquor tank; Absorbent in mother liquor tank and H
2o
2the H of solution tank
2o
2after the salting liquid mixing of solution and salting liquid groove, enter bubbling reactor by absorbent inlet duct, realize recycling of absorbent.
The salt such as NaCl are dissolved in H by the present invention
2o
2in the aqueous solution, improve the surface tension coefficient of solution on the one hand, reduce the diameter of the bubble containing NO, improve the contact area of gas liquid reaction; On the other hand, NaCl etc. improves NO at H adding of salt
2o
2solubility in the aqueous solution.The acting in conjunction of above two aspects, significantly can improve H
2o
2the efficiency of solution oxide NO.
H
2o
2as follows with the reaction equation of NO, the mainly NO of the anion in denitration waste liquid
3 -.
Beneficial effect
Invention adopts and the salt such as NaCl is dissolved in H
2o
2form absorbent in the aqueous solution, salt significantly can improve H
2o
2the efficiency of solution oxide NO.In bubbling reactor, gas residence time is 1-5 minute, NO concentration when being 100-500ppm, and the removal efficiency of nitrogen oxide is more than 50%.Because of H
2o
2become water after oxidation NO, can not cause secondary pollution, be environmental protection method of denitration.It is high that the present invention has removal efficiency, investment and operating cost low, simply, stable, absorbent utilization rate is high, and product easily processes, and is convenient to the features such as popularization for equipment.The present invention is applicable to the occasion that small power plant, cement plant, small-sized petrochemical plant etc. produce a small amount of discharged nitrous oxides, has good application prospect.
Accompanying drawing explanation
Fig. 1: process chart of the present invention;
Wherein, 1, bubbling reactor; 2, gas approach pipeline; 3, exhanst gas outlet pipeline; 4, absorbent inlet pipeline; 5, absorbent outlet conduit; 6, absorbent recycling and processing device; 7, cyclone separator; 8, mother liquor tank; 9, H
2o
2solution tank; 10, salting liquid groove; 11, chimney.
Fig. 2: bubbling reactor structure chart
Wherein, 2, gas approach pipeline; 3, exhanst gas outlet pipeline; 4, absorbent inlet pipeline; 5, absorbent outlet conduit; 12, gas distributor; 13, demister; 14, heat exchanger.
Detailed description of the invention
Below by embodiment, the present invention is further elaborated:
Embodiment 1:
Total measurement (volume) in cylinder bubbling reactor is 5m
3, internal diameter is 1.6 meters.The gas distributor opening angle of the bubbling reactor female cone bodily form is 120 °, and its cone bottom surface radius is 1.2 meters, and upper bottom surface radius is 0.4 meter.The gas distributor of cone shape is evenly equipped with aperture, and aperture is 1.5mm, and the gas distributor porosity of cone shape is 8%.The bottom 15cm of cone bottom surface distance bubbling reactor.
3.5m is injected by bubbling reactor
3absorbent, absorbent used is H
2o
2with the mixed solution of salt, described salt is sodium chloride; H in absorbent
2o
2concentration be 0.2mol/L, the concentration of sodium chloride is 1mol/L.The temperature being controlled bubbler inner absorbent by heat exchanger is 50 DEG C.Flue gas draws gas for adding side line by blower fan from coal-burning power plant's flue, and gas flow is 420m
3/ h, wherein NO concentration is 120ppm.Gas is entered by bubbling reactor gas approach, by the gas distributor bubbling of the bubbling reactor female cone bodily form in reactor.Nitrogen oxide in absorbent chemical absorbing gas, in bubbling reactor smoke outlet gas, NO concentration is 50ppm.
Bubbler inner absorbent is with 0.2m
3the flow of/h flows out to absorbent recycling and processing device by the absorbent outlet bottom bubbling reactor, adds ammoniacal liquor and absorbent and reacts and generate ammonium nitrate solution, carry out stirring and indirectly cooling with water, ammonium nitrate crystal is separated out; The solid particle that then absorbent is removed in absorbent by cyclone separator enters mother liquor tank; Absorbent in mother liquor tank and H
2o
2the H of solution tank
2o
2after the salting liquid mixing of solution and salting liquid groove, enter bubbling reactor by the absorbent entrance of bubbling reactor, realize recycling of absorbent.H
2o
2the concentration of solution is 1mol/L; The concentration value of described salting liquid is 5mol/L.Control H
2o
2the flow of concentrated solution and salting liquid, makes to enter H in the absorbent of bubbler absorbent inlet duct
2o
2concentration be 0.2mol/L, the concentration of sodium chloride is 1mol/L.
Whole system stable operation 72 hours, bubbling reactor smoke outlet NO concentration remains on 50ppm.
Embodiment 2:
Total measurement (volume) in cylinder bubbling reactor is 5m
3, internal diameter is 1.6 meters.The gas distributor opening angle of the bubbling reactor female cone bodily form is 120 °, and its cone bottom surface radius is 1.2 meters, and upper bottom surface radius is 0.4 meter.The gas distributor of cone shape is evenly equipped with aperture, and aperture is 1.5mm, and the gas distributor porosity of cone shape is 8%.The bottom 15cm of cone bottom surface distance bubbling reactor.
3.5m is injected by bubbling reactor
3absorbent, absorbent used is H
2o
2with the mixed solution of salt, described salt is magnesium chloride; H in absorbent
2o
2concentration is 0.1mol/L, and the concentration of magnesium chloride is 2mol/L.The temperature being controlled bubbler inner absorbent by heat exchanger is 50 DEG C.Flue gas draws gas for adding side line by blower fan from coal-burning power plant's flue, and gas flow is 420m
3/ h, wherein NO concentration is 126ppm.Gas is entered by bubbling reactor gas approach, by the gas distributor bubbling of the bubbling reactor female cone bodily form in reactor.Nitrogen oxide in absorbent chemical absorbing gas, in bubbling reactor smoke outlet gas, NO concentration is 45ppm.
Bubbler inner absorbent is with 0.2m
3the flow of/h flows out to absorbent recycling and processing device by the absorbent outlet bottom bubbler, adds ammoniacal liquor and absorbent and reacts and generate ammonium nitrate solution, carry out stirring and indirectly cooling with water, ammonium nitrate crystal is separated out; The solid particle that then absorbent is removed in absorbent by cyclone separator enters mother liquor tank; Absorbent in mother liquor tank and H
2o
2h in solution tank
2o
2after the middle salting liquid mixing of solution and salting liquid groove, enter bubbling reactor by the absorbent entrance of bubbling reactor, realize recycling of absorbent.H
2o
2the concentration of solution is 1mol/L; The concentration value of described salting liquid is 5mol/L.Control H
2o
2concentrated solution and the dense molten flow of salt, make to enter H in the absorbent of bubbler absorbent inlet duct
2o
2concentration be 0.1mol/L, the concentration of magnesium chloride is 2mol/L.
Whole system stable operation 72 hours, bubbling reactor smoke outlet NO concentration remains on 45ppm.
Claims (4)
1. a salt strengthening H
2o
2the denitrification apparatus of solution oxide NO, it is characterized in that, described device comprises: a bubbling reactor 1, center, top has a gas approach pipeline 2 to enter in bubbling reactor 1 to be connected with gas distributor 12, be provided with heat exchanger 14 in bubbling reactor 1, bubbling reactor 1 upper one end arranges an exhanst gas outlet pipeline 3 and passes into outside chimney 11; Be provided with absorbent inlet pipeline 4 in the middle part of bubbling reactor 1, the absorbent outlet conduit 5 bottom bubbling reactor 1 is connected with absorbent recycling and processing device 6, cyclone separator 7, mother liquor tank 8 successively, H
2o
2the outlet conduit of solution tank 9, salting liquid groove 10 and mother liquor tank 8 is connected and is collected to absorbent inlet pipeline 4 and is communicated with bubbling reactor 1.
2. salt strengthening H as claimed in claim 1
2o
2the denitrification apparatus of solution oxide NO, is characterized in that, described gas distributor 12 is the gas distributor of cone shape, and opening angle is 100 ° ~ 150 °; Its cone bottom surface radius is 60% ~ 90% of bubbling reactor cross sectional radius, and its cone upper bottom surface radius is 1/3 of bottom surface radius; Gas distributor surface is evenly equipped with aperture, and aperture is 1 ~ 2mm, and porosity is 5% ~ 10%; Bottom 10 ~ the 20cm of bottom surface distance bubbling reactor.
3. salt strengthening H as claimed in claim 1
2o
2the denitrification apparatus of solution oxide NO, is characterized in that, described bubbling reactor 1 is provided with a demister 13, is positioned at the below of bubbling reactor 1 top exhanst gas outlet.
4. adopt a method of denitration for out of stock device as claimed in claim 1, rise and be characterised in that, described method comprises the steps:
1) flue gas pretreatment: flue gas first through dust arrester dedusting, and by flue gas cool-down to 40-60 DEG C;
2) absorbent is configured: at H
2o
2the H that concentration is 1mol/L is added in solution tank
2o
2solution, adds the salting liquid that concentration is 5mol/L, H in salting liquid groove
2o
2solution and salting liquid are mixed with absorbent after entering pipeline mixing, wherein, and H in absorbent
2o
2concentration be 0.05 ~ 0.5mol/L, the concentration of salt is 0.5 ~ 5mol/L, and the pH value controlling absorbent is 6.5; Wherein, described salt is the one in sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium acid carbonate;
3) denitrating flue gas:
Through step 2) absorbent for preparing enters bubbling reactor by absorbent inlet pipeline, and the volume controlling the absorbent entered is the 60%-70% of bubbling reactor total measurement (volume);
Through step 1) the gas approach pipeline of pretreated flue gas through bubbling reactor top send in reactor, the control of flue gas flow is by the volume of bubbling reactor inner absorbent divided by the residence Time Calculation gained of flue gas at bubbling reactor, and the described time of staying is 1 ~ 5 minute;
The flue gas entered is distributed in absorbent equably by gas distributor, contacts with each other and reacts, complete removal of nitrogen oxide with absorbent, and wherein, absorbent temperature controls at 40 ~ 60 DEG C;
4) in flue gas, drop removes:
Step 3) in flue gas after denitration flow through the demister on bubbling reactor top, remove drop entrained in flue gas, droplets fall back is in bubbling reactor, and the clean flue gas of gained flows out from the exhanst gas outlet pipeline at bubbling reactor top, enters smoke stack emission;
5) absorbent regeneration
The absorbent participating in reaction enters absorbent recycling and processing device, react with the ammoniacal liquor added and generate ammonium nitrate solution, carry out stirring and indirectly cooling with water, ammonium nitrate crystal is separated out in feeding cyclone separator and is separated, absorbent removes solid particle by cyclone separator and enters mother liquor tank; Absorbent in mother liquor tank and H
2o
2the H of solution tank
2o
2after the salting liquid mixing of solution and salting liquid groove, enter bubbling reactor by absorbent inlet duct, realize recycling of absorbent.
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|---|---|---|---|
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|---|---|---|---|
| CN201410552782.XA CN105561769B (en) | 2014-10-17 | 2014-10-17 | Salt strengthens the denitrification apparatus and method of hydrogen peroxide solution oxidation NO |
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| CN105561769B CN105561769B (en) | 2019-05-21 |
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Cited By (5)
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|---|---|---|---|---|
| CN106310880A (en) * | 2016-10-25 | 2017-01-11 | 华东理工大学 | Device and method for removing NO |
| CN106377987A (en) * | 2016-08-31 | 2017-02-08 | 上海甘澍环境科技有限公司 | Flue gas wet-process denitration device and flue gas wet-process denitration method |
| CN107497273A (en) * | 2017-09-25 | 2017-12-22 | 济南大学 | A kind of preparation method and application of environment protection, low cost smoke denitrifier |
| CN108159807A (en) * | 2017-12-29 | 2018-06-15 | 南京理工大学 | A kind of dust removal method and device that nanometer grit is captured using moist steam condensation phenomenon |
| CN111905548A (en) * | 2019-05-07 | 2020-11-10 | 山东师范大学 | Method for low-temperature denitration of flue gas by using aqueous hydrogen peroxide solution |
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| CN107497273A (en) * | 2017-09-25 | 2017-12-22 | 济南大学 | A kind of preparation method and application of environment protection, low cost smoke denitrifier |
| CN108159807A (en) * | 2017-12-29 | 2018-06-15 | 南京理工大学 | A kind of dust removal method and device that nanometer grit is captured using moist steam condensation phenomenon |
| CN111905548A (en) * | 2019-05-07 | 2020-11-10 | 山东师范大学 | Method for low-temperature denitration of flue gas by using aqueous hydrogen peroxide solution |
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|---|---|
| CN105561769B (en) | 2019-05-21 |
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