CN109224820A - A kind of ozone oxidation and denitration method of boiler flue gas - Google Patents

A kind of ozone oxidation and denitration method of boiler flue gas Download PDF

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Publication number
CN109224820A
CN109224820A CN201811338782.4A CN201811338782A CN109224820A CN 109224820 A CN109224820 A CN 109224820A CN 201811338782 A CN201811338782 A CN 201811338782A CN 109224820 A CN109224820 A CN 109224820A
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China
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denitration
ozone
boiler flue
flue gas
flue
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CN201811338782.4A
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郑永耀
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Friend Chemical (yangzhou) Co Ltd
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Friend Chemical (yangzhou) Co Ltd
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Priority to CN201811338782.4A priority Critical patent/CN109224820A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/54Nitrogen compounds
    • B01D53/56Nitrogen oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/76Gas phase processes, e.g. by using aerosols
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77Liquid phase processes
    • B01D53/78Liquid phase processes with gas-liquid contact

Abstract

The invention belongs to environmental protection technical fields; more particularly to a kind of ozone oxidation and denitration method of boiler flue gas; the following steps are included: spraying into oxygen to boiler flue first; when boiler flue temperature drops to 200-250 DEG C; then ozone is sprayed into boiler flue, the nitric oxide in ozone and flue occurs oxidation reaction and obtains NO2, NO3With N2O5Mixed gas;Mixed gas is sent into denitration absorption tower from the bottom on denitration absorption tower, then absorbing liquid is added into the tower reactor on denitration absorption tower, absorbing liquid is squeezed into using circulating pump the top on denitration absorption tower, carry out Sprayer Circulation absorption, denitration is carried out to mixed gas;Flue gas after denitration is discharged through chimney.Denitrification rate is high, greatly reduces atmosphere pollution, realizes the harmless treatment of flue gas, fully meets existing discharge standard.

Description

A kind of ozone oxidation and denitration method of boiler flue gas
Technical field
The invention belongs to environmental protection technical field more particularly to a kind of ozone oxidation and denitration method of boiler flue gas.
Background technique
The selective catalytic reduction technique of the main method of denitrating flue gas (SCR), selective non-catalytic reduction technology (SNCR), wet process complex absorption techniques, oxidation-absorption technology etc..SCR is most common method of denitration, although the technology Denitration efficiency is high, but infrastructure investment, operating cost are expensive.In addition, the bad adaptability of the technology centering, sulphur coal, in flue gas Sulphur component can reduce catalyst life, and the coal sulfur content that is produced from China is generally higher.Therefore, come from the current national conditions in China It sees, SCR technology is difficult to widely popularize at home.
For the feasible gas denitrifying technology of exploiting economy, various oxidation-absorption denitration technologies are put forward one after another.They are Using gas phase or liquid-phase oxidation by flue gas nitrogen oxide NOxThe middle lesser nitric oxide NO of solubility is oxidized to nitrogen dioxide NO2, dinitrogen pentoxide N2O5Deng then being absorbed again with alkalinity, the absorbing liquid of oxidisability or reproducibility.With SCR technology phase Than, the investment of oxidation-absorption denitration technology, operating cost are lower, and denitration efficiency is high, and it is preferable to the adaptability of coal, it can apply In the boiler of various scales.
It is de- that the Chinese invention patent specification of Publication No. CN1768902 individually discloses a kind of boiler smoke ozone oxidation Nitre method.It absorbs the nitrogen oxides by aoxidizing to a certain degree using lye as absorbent, and main thought is to utilize ozone O3, nitric oxide is when being partly or entirely oxidized to nitrogen dioxide by liquid phase strong oxidizer or catalysis oxidation means, absorbent is to NO The low efficiency of absorption and the higher, complex process in the presence of investment operating cost, therefore apply and be still subject to certain restrictions, do not meet reality Demand.
Summary of the invention
It is an object of the invention to overcome the absorbent in denitration technology to provide one kind to the defect of the NO low efficiency absorbed Ozone oxidation and denitration method of boiler flue gas.
A kind of ozone oxidation and denitration method of boiler flue gas, comprising the following steps:
(1) oxygen is sprayed into boiler flue first, when the flue-gas temperature in boiler flue drops to 200-250 DEG C, so Backward boiler flue sprays into ozone, and the nitric oxide in ozone and flue occurs oxidation reaction and obtains NO2, NO3With N2O5Mixing Gas;Oxygen O is sprayed into boiler flue2, on the one hand can cool down boiler flue, the oxidation in another aspect dilution tunnel Nitrogen, reduces nitric oxide concentration, and oxygen mixes with ozone, is conducive to nitrogen oxides and sufficiently reacts with ozone, be conducive to efficient oxygen Change the nitric oxide in flue, improves denitrification rate, advantageously reduce atmosphere pollution;
(2) mixed gas is sent into denitration absorption tower from the bottom on denitration absorption tower, into the tower reactor on denitration absorption tower Absorbing liquid is added, absorbing liquid is squeezed into using circulating pump the top on denitration absorption tower, Sprayer Circulation absorption is carried out, to mixed gas Carry out denitration process;
(3) flue gas after denitration is discharged through chimney;
Preferably, the volume ratio of the oxygen and ozone is 1:20-50.
Preferably, the reaction time of the oxidation reaction is 0.2-0.6s.The reaction time of oxidation reaction is short, greatly improves Out of stock efficiency.
Preferably, the mole of the ozone is 0.5-2.5 times of nitric oxide mole.
Preferably, the absorbing liquid and mixed gas volume ratio are 1:500-1000.
Preferably, the preparation method of the absorbing liquid includes the following steps: that magnesium sulfite is added in deionized water, sulfurous It is added potassium permanganate after the dissolution completely of sour magnesium, after ultrasonic 20-30min, stands after 10-20min to obtain absorbing liquid.
Preferably, the weight fraction ratio of the magnesium sulfite and potassium permanganate is 1:1-1.3.It is added in absorbent-water Magnesium sulfite, potassium permanganate act on magnesium sulfite, potassium permanganate and ozone cooperative, efficiently aoxidize the NO in flue gas.
Preferably, the temperature of deionized water is 80-100 DEG C.
Preferably, potassium permanganate and the weight fraction ratio of deionized water are 1:100-500.
The beneficial effect of the present invention compared with the existing technology is:
1, magnesium sulfite and potassium permanganate is added in the present invention in absorbent (i.e. deionized water), makes magnesium sulfite and Gao Meng Sour potassium and ozone cooperative act on, and efficiently aoxidize the NO in flue gas, and high-efficient, the denitration of 90% or more acquisition is absorbed to NO Rate.
2, the oxygen of penetrating first O of the invention2, on the one hand can cool down boiler flue, in another aspect dilution tunnel Nitric oxide, reduces nitric oxide concentration, and oxygen mixes with ozone, is conducive to nitrogen oxides and sufficiently reacts with ozone, be conducive to Nitric oxide in efficient oxidation flue improves denitrification rate, greatly reduces atmosphere pollution.
3, the method for denitration time of the invention is short, and method of denitration is simple, investment is low, operating cost is low, contains suitable for processing The flue gas of nitrogen oxides realizes the harmless treatment of flue gas, fully meets existing discharge standard.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below.
Ozone oxidation and denitration method of boiler flue gas of the invention, comprising the following steps:
(1) oxygen is sprayed into boiler flue first, when the flue-gas temperature in boiler flue drops to 200-250 DEG C, so Backward boiler flue sprays into ozone, and oxidation reaction 0.2-0.6s occurs for the nitric oxide in ozone and flue, obtains NO2, NO3With N2O5Mixed gas, the volume ratio of oxygen and ozone is 1:20-50, and the mole of ozone is the 0.5- of nitric oxide mole 2.5 again;
(2) mixed gas is sent into denitration absorption tower from the bottom on denitration absorption tower, into the tower reactor on denitration absorption tower Absorbing liquid is added, absorbing liquid is squeezed into using circulating pump the top on denitration absorption tower, Sprayer Circulation absorption is carried out, to mixed gas Denitration process is carried out, absorbing liquid and mixed gas volume ratio are 1:500-1000;
(3) flue gas after denitration is discharged through chimney.
The preparation method of absorbing liquid includes the following steps: that magnesium sulfite, sulfurous are added in 80-100 DEG C of deionized water It is added potassium permanganate after the dissolution completely of sour magnesium, after ultrasonic 20-30min, stands after 10-20min to obtain absorbing liquid.Magnesium sulfite and height The weight fraction ratio of potassium manganate is 1:1-1.3.Potassium permanganate and the weight fraction ratio of deionized water are 1:100-500.
Embodiment 1
Using ozone oxidation and denitration method of boiler flue gas of the invention, in 5m3It is simulated on the experimental simulation device of/h scale Denitrating flue gas process.Exhaust gas volumn 5m3/ h, flue gas composition are as follows: O2For 5%, NO 200ppm, remaining is N2, in boiler flue Flue-gas temperature is 200 DEG C, 1 atmospheric pressure of pressure.Oxidation reaction 0.2s occurs for the nitric oxide in ozone and flue, oxygen with it is smelly The volume ratio of oxygen is 1:20, and the mole of ozone is 0.5 times of nitric oxide mole, absorbing liquid and mixed gas volume ratio It is: 1:500.The weight fraction ratio of 100 DEG C of the temperature of deionized water, magnesium sulfite and potassium permanganate is 1:1.3, potassium permanganate with The weight fraction ratio of deionized water is 1:100, and final denitrification rate is 92%.
Embodiment 2
Using ozone oxidation and denitration method of boiler flue gas of the invention, in 5m3It is simulated on the experimental simulation device of/h scale Denitrating flue gas process.Exhaust gas volumn 5m3/ h, flue gas composition are as follows: O2For 5%, NO 200ppm, remaining is N2, in boiler flue Flue-gas temperature is 220 DEG C, 1 atmospheric pressure of pressure.Oxidation reaction 0.4s occurs for the nitric oxide in ozone and flue, oxygen with it is smelly The volume ratio of oxygen is 1:35, and the mole of ozone is 1.5 times of nitric oxide mole, absorbing liquid and mixed gas volume ratio It is: 1:800.The weight fraction ratio of 90 DEG C of the temperature of deionized water, magnesium sulfite and potassium permanganate is 1:1.2, potassium permanganate with The weight fraction ratio of deionized water is 1:300, and final denitrification rate is 94%.
Embodiment 3
Using ozone oxidation and denitration method of boiler flue gas of the invention, in 5m3It is simulated on the experimental simulation device of/h scale Denitrating flue gas process.Exhaust gas volumn 5m3/ h, flue gas composition are as follows: O2For 5%, NO 200ppm, remaining is N2, in boiler flue Flue-gas temperature is 250 DEG C, 1 atmospheric pressure of pressure.Oxidation reaction 0.6s occurs for the nitric oxide in ozone and flue, oxygen with it is smelly The volume ratio of oxygen is 1:50, and the mole of ozone is 2.5 times of nitric oxide mole, absorbing liquid and mixed gas volume ratio It is: 1:1000.The weight fraction ratio of 80 DEG C of the temperature of deionized water, magnesium sulfite and potassium permanganate is 1:1, potassium permanganate with go The weight fraction ratio of ionized water is 1:500, and final denitrification rate is 95%.
Comparative example 1
The ozone oxidation and denitration method of boiler flue gas of comparative example 1, comprising the following steps:
(1) first to boiler flue spray into oxygen, when the flue-gas temperature in boiler flue drops to 200 DEG C, then to Boiler flue sprays into ozone, and oxidation reaction 0.2s occurs for the nitric oxide in ozone and flue, obtains NO2, NO3With N2O5It is mixed Gas is closed, ozone and nitric oxide production molal weight ratio are 0.5, and the volume ratio of oxygen and ozone is 1:20;
(2) mixed gas is sent into denitration absorption tower from the bottom on denitration absorption tower, then to the tower on denitration absorption tower Absorbing liquid is added in kettle, absorbing liquid is squeezed into using circulating pump the top on denitration absorption tower, Sprayer Circulation absorption is carried out, to mixing Gas carries out denitration;Absorbing liquid is with mixed gas volume ratio: 1:500.Absorbing liquid is deionized water;
(3) flue gas after denitration is discharged through chimney.
Using above-mentioned method for oxidizing and denitrating ozone, in 5m3Denitrating flue gas process is simulated on the experimental simulation device of/h scale. Exhaust gas volumn 5m3/ h, flue gas composition are as follows: O2For 5%, NO 200ppm, remaining is N2, 200 DEG C of flue-gas temperature, 1 atmosphere of pressure Pressure.The volume ratio of nitric oxide generation oxidation reaction 0.2s in ozone and flue, oxygen and ozone is 1:20, ozone and an oxygen The molal weight ratio for changing nitrogen is 0.5, and absorbing liquid (deionized water) is with mixed gas volume ratio: 1:500, final denitrification rate are 43%.From this comparative example 1 as can be seen that denitrification rate is low when absorbing liquid is deionized water.By embodiment 1 and 1 phase of comparison Than, it can be seen that when magnesium sulfite and potassium permanganate are added in absorbent (deionized water), make magnesium sulfite and potassium permanganate It is acted on ozone cooperative, efficiently aoxidizes the NO in flue gas, greatly improve denitrification rate, obtain 90% or more denitrification rate.
Comparative example 2
The ozone oxidation and denitration method of boiler flue gas of comparative example 2, comprising the following steps:
(1) first when the flue-gas temperature in boiler flue is 200 DEG C, then to boiler flue spray into ozone, ozone with Oxidation reaction 0.2s occurs for the nitric oxide in flue, obtains NO2, NO3With N2O5Mixed gas, ozone with it is nitric oxide production Molal weight ratio is 0.5, and the volume ratio of oxygen and ozone is 1:20;
(2) mixed gas is sent into denitration absorption tower from the bottom on denitration absorption tower, then to the tower on denitration absorption tower Absorbing liquid is added in kettle, absorbing liquid is squeezed into using circulating pump the top on denitration absorption tower, Sprayer Circulation absorption is carried out, to mixing Gas carries out denitration;Absorbing liquid is with mixed gas volume ratio: 1:500.Absorbing liquid is deionized water;
(3) flue gas after denitration is discharged through chimney.
The preparation method of absorbing liquid includes the following steps: that magnesium sulfite, magnesium sulfite are added in 100 DEG C of deionized water Potassium permanganate is added after dissolution completely, after ultrasonic 30min, stands after 20min to obtain absorbing liquid.The weight of magnesium sulfite and potassium permanganate Measuring portion rate is 1:1.3.Potassium permanganate and the weight fraction ratio of deionized water are 1:100.
Using above-mentioned method for oxidizing and denitrating ozone, in 5m3Denitrating flue gas process is simulated on the experimental simulation device of/h scale. Exhaust gas volumn 5m3/ h, flue gas composition are as follows: O2For 5%, NO 200ppm, remaining is N2, the flue-gas temperature in boiler flue is 200 DEG C, 1 atmospheric pressure of pressure.Oxidation reaction 0.2s occurs for the nitric oxide in ozone and flue, and the volume ratio of oxygen and ozone is 1:20, ozone and nitric oxide production molal weight ratio are 0.5, and absorbing liquid is with mixed gas volume ratio: 1:500, deionized water 100 DEG C of temperature, the weight fraction ratio of magnesium sulfite and potassium permanganate is 1:1.3, the parts by weight of potassium permanganate and deionized water Number ratio is 1:100, and final denitrification rate is 49%.Find out from comparative example 2, when starting not spray into oxygen O2When, denitrification rate is low.Through Embodiment 1 is crossed compared with comparison 2, it can be seen that oxygen O is sprayed into when beginning2, on the one hand can cool down boiler flue, on the other hand Nitric oxide in dilution tunnel reduces nitric oxide concentration, and oxygen is mixed with ozone, and the volume ratio of oxygen and ozone is 1: 20-50 is conducive to nitrogen oxides and sufficiently reacts with ozone, be conducive to the nitric oxide in efficient oxidation flue, greatly improves de- Nitre rate.
The above is only section Examples of the invention, not do limitation in any form to the present invention, it is all according to According to any simple modification that technical spirit of the invention makees above-described embodiment, equivalent variations and modification belong to the present invention In technical proposal scope.

Claims (9)

1. a kind of ozone oxidation and denitration method of boiler flue gas, which comprises the following steps:
(1) first to boiler flue spray into oxygen, when the flue-gas temperature in boiler flue drops to 200-250 DEG C, then to Boiler flue sprays into ozone, and the nitric oxide in ozone and flue occurs oxidation reaction and obtains NO2, NO3With N2O5Gaseous mixture Body;
(2) mixed gas is sent into denitration absorption tower from the bottom on denitration absorption tower, is added into the tower reactor on denitration absorption tower Absorbing liquid squeezes into absorbing liquid using circulating pump on the top on denitration absorption tower, carries out Sprayer Circulation absorption, carries out to mixed gas Denitration process;
(3) flue gas after denitration is discharged through chimney.
2. ozone oxidation and denitration method of boiler flue gas according to claim 1, it is characterised in that: the oxygen and ozone Volume ratio is 1:20-50.
3. ozone oxidation and denitration method of boiler flue gas according to claim 2, it is characterised in that: the oxidation reaction it is anti- It is 0.2-0.6s between seasonable.
4. ozone oxidation and denitration method of boiler flue gas according to claim 1, it is characterised in that: the mole of the ozone It is 0.5-2.5 times of nitric oxide mole.
5. ozone oxidation and denitration method of boiler flue gas according to claim 1, it is characterised in that: the absorbing liquid with mix The volume ratio of gas is 1:500-1000.
6. ozone oxidation and denitration method of boiler flue gas according to claim 1-5, it is characterised in that: the absorption The preparation method of liquid includes the following steps: that magnesium sulfite is added in deionized water, and Gao Meng is added after magnesium sulfite dissolution completely Sour potassium after ultrasonic 20-30min, stands after 10-20min to obtain absorbing liquid.
7. ozone oxidation and denitration method of boiler flue gas according to claim 6, it is characterised in that: the magnesium sulfite and height The weight fraction ratio of potassium manganate is 1:1-1.3.
8. ozone oxidation and denitration method of boiler flue gas according to claim 6, it is characterised in that: the temperature of deionized water is 80-100℃。
9. ozone oxidation and denitration method of boiler flue gas according to claim 6, it is characterised in that: potassium permanganate and deionization The weight fraction ratio of water is 1:100-500.
CN201811338782.4A 2018-11-12 2018-11-12 A kind of ozone oxidation and denitration method of boiler flue gas Pending CN109224820A (en)

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