CN115105934A - Oxidation chamber and denitration oxidant for glass melting furnace flue gas denitration equipment - Google Patents
Oxidation chamber and denitration oxidant for glass melting furnace flue gas denitration equipment Download PDFInfo
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- CN115105934A CN115105934A CN202210710675.XA CN202210710675A CN115105934A CN 115105934 A CN115105934 A CN 115105934A CN 202210710675 A CN202210710675 A CN 202210710675A CN 115105934 A CN115105934 A CN 115105934A
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- 239000003546 flue gas Substances 0.000 title claims abstract description 146
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 80
- 230000003647 oxidation Effects 0.000 title claims abstract description 79
- 239000007800 oxidant agent Substances 0.000 title claims abstract description 67
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 65
- 239000011521 glass Substances 0.000 title claims abstract description 45
- 238000002844 melting Methods 0.000 title claims abstract description 38
- 230000008018 melting Effects 0.000 title claims abstract description 38
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims abstract description 78
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000000034 method Methods 0.000 claims abstract description 50
- 239000011259 mixed solution Substances 0.000 claims abstract description 43
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 39
- 239000011148 porous material Substances 0.000 claims description 67
- 239000007789 gas Substances 0.000 claims description 14
- 239000000428 dust Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000006477 desulfuration reaction Methods 0.000 claims description 8
- 230000023556 desulfurization Effects 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000011494 foam glass Substances 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 230000004308 accommodation Effects 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 6
- 230000007774 longterm Effects 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 description 63
- 239000012670 alkaline solution Substances 0.000 description 37
- 239000000446 fuel Substances 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 27
- 238000004519 manufacturing process Methods 0.000 description 24
- 239000000779 smoke Substances 0.000 description 23
- 239000005329 float glass Substances 0.000 description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000011575 calcium Substances 0.000 description 11
- 239000002006 petroleum coke Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 10
- 239000003513 alkali Substances 0.000 description 9
- 239000000295 fuel oil Substances 0.000 description 9
- 239000003345 natural gas Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003034 coal gas Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
- B01D53/565—Nitrogen oxides by treating the gases with solids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
- B01D53/82—Solid phase processes with stationary reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/104—Ozone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0241—Other waste gases from glass manufacture plants
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses an oxidation chamber and a denitration oxidant used in denitration equipment for glass melting furnace flue gas, wherein the denitration oxidant comprises a mixed solution composed of a main oxidant ozone, an auxiliary oxidant sodium hypochlorite and peroxyacetic acid. The denitration oxidant disclosed by the invention is wide in source and low in cost, and can ensure long-term high efficiency of denitration in the using process; the one-time investment of denitration is reduced, no catalyst is needed, and the denitration operation cost is greatly reduced. The oxidation chamber occupies small area, is convenient to maintain and has low cost.
Description
The application is a divisional application of an invention patent application with the application number of 201610450414.3, which is filed in 2016 for 6, 21 days and is named as ' denitration oxidant and denitration device and denitration method for glass melting furnace flue gas ' by the national intellectual property office of the people's republic of China.
Technical Field
The invention relates to the technical field of glass melting furnace flue gas treatment, in particular to an oxidation chamber and a denitration oxidant for glass melting furnace flue gas denitration equipment.
Background
At present, the number of glass production lines in China is large, and as long as 2016 (4) months, the number of glass production lines is 400, and nearly 3000 glass production lines for daily use, bottle glass, glass fiber and other special glass are produced. According to statistics, the glass production lines mainly use petroleum coke powder, heavy oil, natural gas, coal gas and coal powder as fuels, wherein 55% of the petroleum coke powder is used as the fuel, 25% of the petroleum coke powder is used as the fuel, and the rest 20% of the petroleum coke powder, the heavy oil and the coal gas are used as the fuels. According to the relevant data and combining the on-site monitoring data, the content of pollutants in the flue gas of the glass melting furnace adopting different fuels is different, which is shown in table 1.
TABLE 1 content of pollutants in flue gases of glass melting furnaces using different fuels
Fuel | Dust concentration (mg/m) 3 ) | SO 2 Concentration (mg/m) 3 ) | NO X Concentration (mg/m) 3 ) |
Petroleum coke powder | 200~1200 | 200~6500 | 1800~3300 |
Heavy oil | 150~900 | 1500~4000 | 1850~3000 |
Natural gas | 80~280 | 100~500 | 1800~2500 |
Coal gas | 120~400 | 350~4500 | 1850~2900 |
Pulverized coal | 300~1500 | 500~5500 | 2000~3450 |
As can be seen from the data in Table 1, NO in the glass melting furnace flue gas is comparable to pollutants such as sulfur dioxide and dust x Has a high content of (A), wherein NO is the main component and accounts for NO x More than 95% of the total content, and the balance of NO 2 。NO x Not only is one of the main substances for forming acid rain, but also can form photochemical smog in the atmosphere to destroy the ozone layer, so the emission concentration is the environmental protection regulationOne of the control indexes of the flue gas emission of glass production factories. No is required in the emission standard of atmospheric pollutants for the plate glass industry (GB26453-2011) which must be executed by the existing plate glass production enterprises x The discharge content is not higher than 700mg/Nm 3 . Therefore, the flue gas generated by the glass melting furnace must be subjected to denitration treatment to make NO in the flue gas x The content is in accordance with the regulation and then can be discharged into the atmosphere, namely the flue gas is emptied.
Existing denitration methods are classified into oxidation methods and reduction methods. The oxidation method mainly uses ozone as an oxidant to react NO x Oxidizing to achieve the aim of denitration, but the denitration efficiency of the oxidation method is low and is generally below 60 percent, and NO in the flue gas of the glass melting furnace x The content of NO in the flue gas after denitration by the method is too high x The content cannot meet the emission requirement. Patent application with publication number CN104190223A discloses a liquid-phase oxidation flue gas desulfurization and denitration absorption process and device. In the process, NO in the flue gas is mixed with the flue gas in a slurry spraying mode x The reaction adopts one-step oxidation denitration, and because the contact time of slurry and flue gas is short and the reaction is insufficient, the denitration efficiency is low, and the method is not suitable for high-content NO generated by a glass melting furnace x Flue gas; in addition, the application of sodium hydroxide as the alkali absorption liquid has high cost, and the generated sodium nitrite and sodium nitrate become new problems to be solved.
In view of the defects of the oxidation denitration, the main denitration technology of the glass melting furnace flue gas at present is the reduction denitration, and is divided into selective catalytic reduction denitration (SCR) and selective non-catalytic reduction denitration (SNCR).
The denitration reaction temperature of the selective catalytic reduction denitration SCR is 250-450 ℃, and the denitration rate can reach 70-90%. The technology is mature and reliable, is widely applied in the world, particularly developed countries at present, but the process equipment investment is large, the flue gas needs to be preheated, the catalyst is expensive, the service life is short, and the problems of ammonia leakage, easy corrosion of equipment and the like exist at the same time.
The denitration reaction temperature of the selective non-catalytic reduction denitration SNCR is 870-1200 ℃, and the denitration rate is less than 50%. The technology also has the defects of large investment of process equipment, need of preheating treatment of flue gas, easy corrosion of equipment and the like, and has low denitration rate, high ammonia escape rate, incapability of meeting the treatment requirement and capability of meeting the emission requirement only by using the technology together with other methods.
At present, the denitration mode of the glass melting furnace flue gas basically adopts a reduction method, but NO in the glass melting furnace flue gas x High content (generally 1800 mg/Nm) 3 -3400mg/Nm 3 High up to 4000mg/Nm 3 Above), low denitration efficiency, NO after denitration x The concentration of the nitrogen-containing gas is difficult to reach the national standard emission standard, and the glass melting furnace flue gas controls NO x The difficulty is high, the cost is high, and the problem to be solved in the field is needed.
Disclosure of Invention
The invention aims to solve the technical defects in the prior art, and provides an oxidation chamber for glass melting furnace flue gas denitration equipment.
The lower space of the accommodating space is provided with a plate-shaped porous stopper distributed with a plurality of through holes, and the porous stopper is arranged on the inner wall of the lower part of the accommodating space; the material can be selected from polytetrafluoroethylene, and the aperture is 8-25 mm.
The upper space of the accommodating space is provided with a porous material layer, and the porous material layer is arranged on the inner wall of the upper part of the accommodating space; the porous material constituting the porous material layer may be selected from one or a mixture of several of porous ceramics, open-cell foam glass, and porous carbon materials, and the pore diameter of the porous material is 2-37 μm, and is preferably porous material with open pores.
The main oxidant is ozone, and the auxiliary oxidant is a mixed solution composed of sodium hypochlorite and peroxyacetic acid.
The mass percentage of the peroxyacetic acid and the mass percentage of the sodium hypochlorite in the mixed solution are respectively 5-22 wt% and 3-16 wt%.
The molar ratio of ozone to sodium hypochlorite to peroxyacetic acid is (20-50): (0.67-2.96): (0.39-2.1); preferably (30-40): (1-2.5): (0.5-1.5), most preferably 35: 2: 1.
in a second aspect, the denitration oxidant contained in the oxidation chamber provided by the invention comprises a main oxidant and an auxiliary oxidant respectively contained, wherein the main oxidant is ozone, and the auxiliary oxidant is a mixed solution composed of sodium hypochlorite and peroxyacetic acid.
The mass percentage of the peroxyacetic acid and the sodium hypochlorite in the mixed solution is respectively 5-22 wt% and 3-16 wt%.
The molar ratio of ozone to sodium hypochlorite to peroxyacetic acid is (20-50): (0.67-2.96): (0.39-2.1); preferably (30-40): (1-2.5): (0.5-1.5), most preferably 35: 2: 1.
in a third aspect, the invention provides a denitration method for glass melting furnace flue gas, which comprises the steps of introducing the glass melting furnace flue gas subjected to dust removal and desulfurization into an oxidation chamber by using the oxidation chamber and the denitration oxidant, and oxidizing NO in the glass melting furnace flue gas into NO by using the denitration oxidant 2 To remove NO in the flue gas;
preferably, the method comprises the following steps:
1) sending the glass melting furnace flue gas subjected to dust removal and desulfurization into an oxidation chamber through a flue gas conveying opening;
2) firstly, the flue gas of the glass melting furnace is contacted with an auxiliary oxidant in an oxidation chamber for primary oxidation to obtain primary oxidation flue gas; the residence time of the glass melting furnace flue gas in the auxiliary oxidant is 0.5-2 min;
3) continuously rising the primary oxidation flue gas obtained in the step 2), contacting with ozone, carrying out secondary oxidation to obtain secondary oxidation flue gas, and discharging the secondary oxidation flue gas from a flue gas outlet; the residence time of the secondary oxidation flue gas in the ozone is 2-10 min.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention adopts an oxidation method for denitration, and NO in the flue gas is oxidized into NO by using the oxidant of the invention 2 Can effectively remove NO in the smoke x The denitration oxidant can be used for enabling NO in the glass melting furnace flue gas x The concentration is reduced by more than 90 percent, and the national standard emission standard is reached; and the secondary pollution is small, and the operation, the popularization and the application are easy.
2) The denitration oxidant can ensure long-term high efficiency of denitration in the using process; the one-time investment of denitration is reduced, no catalyst is needed, and the denitration operation cost is greatly reduced.
3) The oxidation chamber has the advantages of small occupied area, convenient maintenance and low cost.
Drawings
FIG. 1 is a schematic view showing the structure of an oxidation chamber in a denitration apparatus according to the present invention;
FIG. 2 is an enlarged view of a part A of the barrier layer in the denitration apparatus according to the present invention.
Detailed Description
The invention provides an oxidation chamber used in denitration equipment for glass melting furnace flue gas and a denitration oxidant contained in the oxidation chamber, which are specially used for high NO generated by a glass melting furnace x The content of the flue gas is oxidized by adopting a two-step method to oxidize NO in the flue gas x : firstly, oxidizing by using an aqueous solution containing peroxyacetic acid and sodium hypochlorite, and secondly, oxidizing by using ozone to ensure NO x Wherein the NO is totally oxidized to NO 2 Thus facilitating the absorption of alkaline solution; in addition, the mixed solution formed by peroxyacetic acid and sodium hypochlorite is adopted, so that the retention time of the flue gas in the mixed solution is long, the oxidation reaction time is long, the reaction is sufficient, and the denitration efficiency is high; the alkaline solution used in the invention is calcium hydroxide aqueous solution, and NO is absorbed by the alkaline solution 2 Formation of calcium nitrate Ca (NO) 3 ) 2 And calcium nitrite Ca (NO) 2 ) 2 The method can be applied to the preparation of cement hardening accelerator and antifreezing rust inhibitor, does not generate new pollution, changes waste into valuable, and is beneficial to the comprehensive utilization of waste.
Because of the technical composition of desulfurization and dust removal of the glass melting furnaceLow cost of cooking, investment and operation, and the purpose of removing NO as much as possible in the flue gas treatment process x The flue gas for denitration is subjected to dust removal and desulfurization, and then NO in the flue gas is oxidized into NO by adopting an oxidation method 2 Then absorbing NO with alkaline solution 2 Thereby effectively removing NO in the smoke x . If dust removal desulfurization and denitration are accomplished simultaneously, cause denitration equipment to block up easily, the oxidant also can be SO simultaneously 2 Is oxidized to SO 3 The consumption of the oxidant is increased, and the denitration efficiency cannot be guaranteed.
The present invention will be described more specifically and further illustrated with reference to specific examples, which are by no means intended to limit the scope of the present invention.
In the oxidation denitration process, two steps of oxidation are adopted, wherein the first step adopts a liquid oxidant which is a mixed solution formed by sodium hypochlorite and peroxyacetic acid, and the second step adopts a gas oxidant which is ozone. In the two-step oxidation, ozone is mainly oxidized and mixed solution is secondarily oxidized, namely, the ozone is used as a main oxidant, the mixed solution formed by sodium hypochlorite and peroxyacetic acid is used as an auxiliary oxidant, and NO in the flue gas is completely oxidized into NO 2 . The molar ratio of ozone, sodium hypochlorite and peroxyacetic acid in the oxidant is (20-50): (0.67-2.96): (0.39-2.1); preferably (30-40): (1-2.5): (0.5-1.5), most preferably 35: 2: 1. the ratio of the initial state of each component of the oxidant is that in the actual use process, the ozone is continuously introduced, the content of the ozone in the oxidation chamber is always kept to be 1.5-6mol/L, the oxidant in the mixed solution is slowly consumed, and NO is colorless gas, so that NO is slowly consumed 2 Is reddish brown gas, and can judge whether to add liquid oxidant by observing the gas color depth in the ozone space, and the color depth indicates NO 2 The gas is much, the oxidation effect is good, NO liquid oxidant is needed to be added, and the light color indicates that NO is oxidized into NO 2 The addition of liquid oxidizing agent is not sufficiently required.
The invention provides a glass melting furnace flue gas denitration device by utilizing the oxidant, which comprises an oxidation chamber I and an alkali liquor absorption chamber II which are sequentially connected as shown in figure 1, wherein a flue gas outlet 18 of the oxidation chamber I is connected with a flue gas inlet 19 of the alkali liquor absorption chamber II through a flue gas channel 11.
The oxidation chamber I is a holding space with good air tightness, the bottom of the oxidation chamber I is provided with a flue gas conveying port 1, the top of the oxidation chamber I is provided with a flue gas outlet 18, the lower part of the oxidation chamber I is provided with oxidant discharge ports 9 (the number of the oxidant discharge ports is not limited), and the upper part of the oxidation chamber I is provided with a solution adding port 10 for adding auxiliary oxidant. A mixed solution 8 composed of sodium hypochlorite and peroxyacetic acid is contained in the lower space of the oxidation chamber I and used as an auxiliary oxidant, the accommodating space of the oxidation chamber I is divided into an upper space and a lower space, the concentration of the peroxyacetic acid in the whole mixed solution is 5-22 wt%, the concentration of the sodium hypochlorite is 3-16 wt%, and a porous barrier 2 is arranged below a liquid surface line 3 of the mixed solution 8 and used for prolonging the detention time of the flue gas in the mixed solution so as to fully oxidize NO in the mixed solution; the porous stopper 2 can be made of polytetrafluoroethylene, and is processed into a plate shape, and then a through hole is processed on the polytetrafluoroethylene plate, wherein the aperture of the through hole is adjusted according to the type of fuel and the amount of flue gas, and is generally 8-25 mm. The oxidizer discharge port 9 is also provided below the liquid line 3 of the mixed solution 8.
An ozone generator 4 is provided outside the oxidation chamber I, and the generated ozone enters a space 7 (i.e., an upper space) between the upper part of the liquid surface line 3 of the mixed solution 8 and the top of the oxidation chamber I through an ozone inlet 5. The upper part of the space 7 is provided with a porous material layer 6, the porous material layer 6 is made of porous material distributed with pores, the porous material can be one or a mixture of more of porous ceramics, open-cell foam glass and porous carbon material, open-cell pores are generally selected, the pore diameter can be adjusted according to the type of fuel and the smoke gas amount, and the pore diameter is generally 2-37 mu m; the porous material layer is used for prolonging the residence time of the smoke in the ozone atmosphere, so that NO in the smoke is completely oxidized into NO 2 The residence time can be controlled by the pore size of the porous material, and is available from Zhejiang Zhensheng adiabatic science and technology, Inc.
The alkali liquor absorption chamber II is also a holding space with good air tightness, the bottom is provided with a flue gas inlet 19 connected with a flue gas outlet 18 of the oxidation chamber I, the top is provided with a denitration flue gas outlet 16, the lower part is provided with alkali liquor discharge ports 13 (one or more), and the upper part is provided withA lye addition port 15. Alkaline solution 14 is contained in the alkaline solution absorption chamber II and used for absorbing NO in the flue gas 2 The alkaline solution 14 may be selected from Ca (OH) 2 Aqueous solution of alkaline substances such as NaOH and KOH, wherein the alkaline substances can be one or a mixture of more than one, and the mass percentage of the alkaline substances is 10-30 wt%; the alkaline solution is preferably Ca (OH) 2 Preferably Ca (OH) 2 A saturated aqueous solution of (a). The alkaline solution 14 is provided with a barrier layer 12, the barrier layer is obliquely arranged at the lower part of the alkaline solution absorption chamber II, the inclination angle is 10-25 degrees, the barrier layer is completely immersed in the alkaline solution, the barrier layer 12 is also of a porous plate-shaped structure and is provided with a plurality of small holes 17 (see figure 2) for prolonging the retention time of the smoke in the alkaline solution and increasing NO in the smoke 2 Reaction time with alkaline solution to make NO in it 2 Is fully absorbed; the barrier layer 12 is made of polytetrafluoroethylene into a plate shape, and then through holes are processed on the polytetrafluoroethylene plate, wherein the aperture of each through hole is adjusted according to the type of fuel and the amount of flue gas, and is generally 2-12 mm. The lye discharge opening 13 is arranged below the level line of the alkaline solution 14.
In addition, an air pump can be added into the denitration equipment to ensure the flow rate of the flue gas in the denitration equipment. The oxidation chamber, the alkali liquor absorption chamber, the flue gas channel and other special instructions for removing are all welded by 022Cr17Ni12Mo2 stainless steel.
On the basis, the invention also provides a method for denitrating the flue gas of the glass melting furnace by using the equipment, which comprises the following specific operations:
1) the glass melting furnace flue gas after dust removal and desulfurization is sent into an oxidation chamber I through a flue gas conveying port 1;
2) firstly, contacting the flue gas with an auxiliary oxidant, namely a mixed solution containing sodium hypochlorite and peroxyacetic acid, in an oxidation chamber I, and carrying out primary oxidation to obtain primary oxidation flue gas; in this process, NO is oxidized to NO 2 ,NO 2 The generated nitric acid can ionize hydrogen ions to enable hypochlorite to play a better oxidation role, and the generated NO can overflow the mixed solution along with the smoke, so the smoke can be partially oxidized; by controlling a plurality ofThe aperture in the hole stopper 2 ensures that the residence time of the flue gas in the mixed solution is 0.5-2 min;
the chemical reactions taking place are formula 1 and formula 2 (small amount of NO) 2 The reaction of formula 2 occurs):
2NO+CH 3 COOOH+NaClO→2NO 2 +NaCl+CH 3 COOH formula 1
3NO 2 +H 2 O→2HNO 3 + NO formula 2
3) Continuously rising the primary oxidation flue gas obtained in the step 2), fully contacting NO with ozone, carrying out secondary oxidation, and reacting to obtain NO 2 Removing NO in the flue gas to obtain secondary oxidation flue gas, and discharging the secondary oxidation flue gas from a flue gas outlet 18; the retention time of the flue gas in the ozone is controlled to be 2-10 min by controlling the pore diameter in the porous material layer 6;
the chemical reaction that takes place is formula 3:
3NO+O 3 →3NO 2 formula 3
4) The secondary oxidation flue gas obtained in the step 3) enters an alkali liquor absorption chamber II from a flue gas inlet 19 through a flue gas channel 11 and is fully contacted with an alkaline solution 14, wherein NO is contained in the secondary oxidation flue gas 2 Is absorbed by the alkaline solution to generate nitrite and nitrate, so as to obtain denitrated flue gas, and the denitrated flue gas is discharged into the atmosphere from a denitrated flue gas outlet 16; the residence time of the smoke in the alkaline solution is 10s-3min by controlling the aperture in the barrier layer 12. The alkaline solution is Ca (OH) 2 The water solution needs to be supplemented periodically, and the supplementing speed is 20-300kg/h of hydrated lime; ca (NO) in alkaline solution 2 ) 2 And Ca (NO) 3 ) 2 The obtained Ca (NO) is discharged through an alkali liquor discharge port 13 periodically 2 ) 2 And Ca (NO) 3 ) 2 Can be applied to the preparation of cement hardening accelerator and antifreezing rust inhibitor without generating new pollution.
The chemical reaction that takes place is formula 4:
4NO 2 +2Ca(OH) 2 →Ca(NO 2 ) 2 +Ca(NO 3 ) 2 +2H 2 o formula 4
Example 1:
taking 600 tons/day float glass production line as an example, the fuel: the smoke gas amount per hour of the petroleum coke powder is 85000Nm 3 NO in flue gas x The content is 2750mg/Nm 3 . The concentrations of sodium hypochlorite and peracetic acid were 3 wt% and 5 wt%, respectively, the concentration of ozone was 3mol/l, the pore diameters of the porous barrier 2, the porous material layer 6, and the barrier layer 12 were 8mm, 2 μm, and 2mm, respectively, the inclination angle of the barrier layer 12 was 10 °, and the residence times of the reaction in the mixed solution, ozone, and alkaline solution were 2min, 10min, and 3min, respectively. By the denitration device and the denitration method, NO in the flue gas exhausted into the atmosphere x The content is 638mg/Nm 3 And reaches the national standard of discharge.
Example 2:
taking a 600 ton/day float glass production line as an example, the fuel: the smoke gas amount per hour of the petroleum coke powder is 85000Nm 3 NO in flue gas x The content is 2750mg/Nm 3 . The concentrations of sodium hypochlorite and peracetic acid were 16 wt% and 22 wt%, respectively, the concentration of ozone was 2mol/l, the pore diameters of the porous barrier 2, the porous material layer 6, and the barrier layer 12 were 25mm, 37 μm, and 12mm, respectively, the inclination angle of the barrier layer 12 was 25 °, and the residence times of the reaction in the mixed solution, ozone, and alkaline solution were 0.5min, 2min, and 10s, respectively. By the denitration device and the denitration method, NO in the flue gas exhausted into the atmosphere x The content is 626mg/Nm 3 And reaches the national standard of discharge.
Example 3:
taking a 600 ton/day float glass production line as an example, the fuel: the smoke gas amount per hour of the petroleum coke powder is 85000Nm 3 NO in flue gas x The content is 2750mg/Nm 3 . The concentrations of sodium hypochlorite and peracetic acid were 7 wt% and 15 wt%, respectively, the concentration of ozone was 4mol/l, the pore diameters of the porous barrier 2, the porous material layer 6, and the barrier layer 12 were 19mm, 22 μm, and 8mm, respectively, the inclination angle of the barrier layer 12 was 15 °, and the residence times of the reaction in the mixed solution, ozone, and alkaline solution were 1min, 5min, and 1min, respectively. By the denitration device and the denitration method, NO in the flue gas exhausted into the atmosphere x The content is 435mg/Nm 3 To reach the national standardAnd (4) emission standard.
Example 4:
taking a 600 ton/day float glass production line as an example, the fuel: the smoke amount per hour of the petroleum coke powder is 85000Nm 3 NO in flue gas x The content is 2750mg/Nm 3 . The concentrations of sodium hypochlorite and peracetic acid were 9 wt% and 14 wt%, respectively, the concentration of ozone was 5mol/l, the pore diameters of the porous barrier 2, the porous material layer 6, and the barrier layer 12 were 17mm, 19 μm, and 7mm, respectively, the inclination angle of the barrier layer 12 was 17 °, and the residence times of the reaction in the mixed solution, ozone, and alkaline solution were 1min, 6min, and 1.5min, respectively. By the denitration device and the denitration method, NO in the flue gas exhausted into the atmosphere x The content is 395mg/Nm 3 And reaches the national standard of discharge.
Comparative example 1:
taking a 600 ton/day float glass production line as an example, the fuel: the smoke gas amount per hour of the petroleum coke powder is 85000Nm 3 NO in flue gas x The content is 2750mg/Nm 3 . The concentrations of sodium hypochlorite and peracetic acid were 20 wt% and 3 wt%, respectively, the concentration of ozone was 1.5mol/l, the pore diameters of the porous barrier 2, the porous material layer 6, and the barrier layer 12 were 20mm, 30 μm, and 10mm, respectively, the inclination angle of the barrier layer 12 was 20 °, and the residence times of the reaction in the mixed solution, ozone, and alkaline solution were 1min, 6min, and 1min, respectively. The NO in the flue gas exhausted into the atmosphere by the denitration device and the denitration method of the invention x The content is 876mg/Nm 3 And can not reach the national standard of discharge.
Comparative example 2:
taking a 600 ton/day float glass production line as an example, the fuel: the smoke gas amount per hour of the petroleum coke powder is 85000Nm 3 NO in flue gas x The content is 2750mg/Nm 3 . The concentrations of sodium hypochlorite and peracetic acid were 3 wt% and 13 wt%, respectively, the concentration of ozone was 6mol/l, the pore diameters of the porous barrier 2, the porous material layer 6, and the barrier layer 12 were 16mm, 10 μm, and 10mm, respectively, the inclination angle of the barrier layer 12 was 15 °, and the residence times of the reaction in the mixed solution, ozone, and alkaline solution were 1min, 8min, and 2.5min, respectively. By the denitration device and the denitration method, NO in the flue gas exhausted into the atmosphere x The content is 793mg/Nm 3 And can not reach the national standard of discharge.
Example 5:
taking a float glass production line of 900 tons/day as an example, the fuel: heavy oil, with a flue gas content of 110000 Nm/h 3 NO in flue gas x The content is 2560mg/Nm 3 . The concentrations of sodium hypochlorite and peracetic acid are 3 wt% and 5 wt%, respectively, the concentration of ozone is 3.5mol/l, the pore diameters of the porous barrier 2, the porous material layer 6 and the barrier layer 12 are 18mm, 12 μm and 8mm, respectively, the inclination angle of the barrier layer 12 is 15 °, and the residence time of the reaction in the mixed solution, ozone and alkaline solution is 1min, 8min and 2min, respectively. The NO in the flue gas exhausted into the atmosphere by the denitration device and the denitration method of the invention x The content is 577mg/Nm 3 And reaches the national standard of discharge.
Example 6:
taking 900 tons/day float glass production line as an example, the fuel: heavy oil with a flue gas content of 110000 Nm/hour 3 NO in flue gas x The content is 2560mg/Nm 3 . The concentrations of sodium hypochlorite and peracetic acid were 16 wt% and 22 wt%, respectively, the concentration of ozone was 2.5mol/l, the pore diameters of the porous barrier 2, the porous material layer 6, and the barrier layer 12 were 15mm, 22 μm, and 8mm, respectively, the inclination angle of the barrier layer 12 was 15 °, and the residence times of the reaction in the mixed solution, ozone, and alkaline solution were 1min, 8min, and 2min, respectively. By the denitration device and the denitration method, NO in the flue gas exhausted into the atmosphere x The content is 511mg/Nm 3 And reaches the national standard of discharge.
Example 7:
taking a float glass production line of 900 tons/day as an example, the fuel: heavy oil with a flue gas content of 110000 Nm/hour 3 NO in flue gas x The content is 2560mg/Nm 3 . The concentrations of sodium hypochlorite and peracetic acid were 7 wt% and 15 wt%, respectively, the concentration of ozone was 4.5mol/l, the pore diameters of the porous barrier 2, the porous material layer 6, and the barrier layer 12 were 8mm, 28 μm, and 8mm, respectively, the inclination angle of the barrier layer 12 was 19 °, and the residence times of the reaction in the mixed solution, ozone, and alkaline solution were 2min, 5min, and 1min, respectively. Smoke discharged into the atmosphere by the denitration device and method of the inventionNO in gas x The content is 399mg/Nm 3 And reaches the national standard of discharge.
Example 8:
taking a float glass production line of 900 tons/day as an example, the fuel: heavy oil with a flue gas content of 110000 Nm/hour 3 NO in flue gas x The content is 2560mg/Nm 3 . The concentrations of sodium hypochlorite and peracetic acid were 9 wt% and 14 wt%, respectively, the concentration of ozone was 3mol/l, the pore diameters of the porous barrier 2, the porous material layer 6, and the barrier layer 12 were 25mm, 19 μm, and 7mm, respectively, the inclination angle of the barrier layer 12 was 17 °, and the residence times of the reaction in the mixed solution, ozone, and alkaline solution were 0.5min, 6min, and 1.5min, respectively. By the denitration device and the denitration method, NO in the flue gas exhausted into the atmosphere x The content is 355mg/Nm 3 And reaches the national standard of discharge.
Comparative example 3:
taking a float glass production line of 900 tons/day as an example, the fuel: heavy oil with a flue gas content of 110000 Nm/hour 3 NO in flue gas x The content is 2560mg/Nm 3 . The concentrations of sodium hypochlorite and peracetic acid were 10 wt% and 20 wt%, respectively, the concentration of ozone was 4mol/l, the pore diameters of the porous barrier 2, the porous material layer 6, and the barrier layer 12 were 30mm, 30 μm, and 10mm, respectively, the inclination angle of the barrier layer 12 was 20 °, and the residence times of the reaction in the mixed solution, ozone, and alkaline solution were 10s, 5min, and 30s, respectively. By the denitration device and the denitration method, NO in the flue gas exhausted into the atmosphere x The content is 833mg/Nm 3 And can not reach the national standard of discharge.
Comparative example 4:
taking a float glass production line of 900 tons/day as an example, the fuel: heavy oil with a flue gas content of 110000 Nm/hour 3 NO in flue gas x The content is 2560mg/Nm 3 . The concentrations of sodium hypochlorite and peracetic acid were 13 wt% and 13 wt%, respectively, the concentration of ozone was 4mol/l, the pore diameters of the porous barrier 2, the porous material layer 6, and the barrier layer 12 were 16mm, 40 μm, and 11mm, respectively, the inclination angle of the barrier layer 12 was 15 °, and the residence times of the reaction in the mixed solution, ozone, and alkaline solution were 1min, and 2min, respectively. The denitration equipment and the method of the inventionMethod, NO in flue gases discharged to the atmosphere x The content is 866mg/Nm 3 And can not reach the national standard of discharge.
Example 9:
taking a float glass production line of 150 tons/day as an example, the fuel: natural gas. The smoke amount per hour is 36000Nm 3 NO in flue gas x The content is 2250mg/Nm 3 . The concentrations of sodium hypochlorite and peracetic acid were 15 wt% and 13 wt%, respectively, the concentration of ozone was 4.5mol/l, the pore diameters of the porous barrier 2, the porous material layer 6, and the barrier layer 12 were 15mm, 2 μm, and 11mm, respectively, the inclination angle of the barrier layer 12 was 13 °, and the residence times of the reaction in the mixed solution, ozone, and alkaline solution were 1.5min, 10min, and 2.5min, respectively. By the denitration device and the denitration method, NO in the flue gas exhausted into the atmosphere x The content is 550mg/Nm 3 And reaches the national standard of discharge.
Example 10:
taking a float glass production line of 150 tons/day as an example, the fuel: natural gas. The smoke amount per hour is 36000Nm 3 NO in flue gas x The content is 2250mg/Nm 3 . The concentrations of sodium hypochlorite and peracetic acid were 15 wt% and 12 wt%, respectively, the concentration of ozone was 2.5mol/l, the pore diameters of the porous barrier 2, the porous material layer 6, and the barrier layer 12 were 18mm, 37 μm, and 9mm, respectively, the inclination angle of the barrier layer 12 was 12 °, and the residence times of the reaction in the mixed solution, ozone, and alkaline solution were 1min, 2min, and 1.5min, respectively. By the denitration device and the denitration method, NO in the flue gas exhausted into the atmosphere x The content is 515mg/Nm 3 And reaches the national standard of discharge.
Example 11:
taking a float glass production line of 150 tons/day as an example, the fuel: natural gas. The smoke amount per hour is 36000Nm 3 NO in flue gas x The content is 2250mg/Nm 3 . The concentrations of sodium hypochlorite and peracetic acid were 7 wt% and 15 wt%, respectively, the concentration of ozone was 4.6mol/l, the pore diameters of the porous barrier 2, the porous material layer 6, and the barrier layer 12 were 12mm, 22 μm, and 2mm, respectively, the inclination angle of the barrier layer 12 was 10 °, and the residence time of the reaction in the mixed solution, ozone, and alkaline solution was 1min, 5min, and 3min, respectivelyAnd (5) min. By the denitration device and the denitration method, NO in the flue gas exhausted into the atmosphere x The content is 232mg/Nm 3 And reaches the national standard of discharge.
Example 12:
taking a float glass production line of 150 tons/day as an example, the fuel: natural gas. The smoke amount per hour is 36000Nm 3 NO in flue gas x The content is 2250mg/Nm 3 . The concentrations of sodium hypochlorite and peracetic acid were 9 wt% and 14 wt%, respectively, the concentration of ozone was 4.9mol/l, the pore diameters of the porous barrier 2, the porous material layer 6, and the barrier layer 12 were 17mm, 19 μm, and 12mm, respectively, the inclination angle of the barrier layer 12 was 25 °, and the residence times of the reaction in the mixed solution, ozone, and alkaline solution were 1min, 6min, and 10s, respectively. By the denitration device and the denitration method, NO in the flue gas exhausted into the atmosphere x The content is 285mg/Nm 3 And reaches the national standard of discharge.
Comparative example 5:
taking a float glass production line of 150 tons/day as an example, the fuel: natural gas. The smoke amount per hour is 36000Nm 3 NO in flue gas x The content is 2250mg/Nm 3 . The concentrations of sodium hypochlorite and peracetic acid were 10 wt% and 20 wt%, respectively, the concentration of ozone was 4.6mol/l, the pore diameters of the porous barrier 2, the porous material layer 6, and the barrier layer 12 were 20mm, 30 μm, and 20mm, respectively, the inclination angle of the barrier layer 12 was 5 °, and the residence times of the reaction in the mixed solution, ozone, and alkaline solution were 1.5min, 4min, and 5s, respectively. By the denitration device and the denitration method, NO in the flue gas exhausted into the atmosphere x The content is 790mg/Nm 3 And can not reach the national standard of discharge.
Comparative example 6:
taking a float glass production line of 150 tons/day as an example, the fuel: natural gas. The smoke amount per hour is 36000Nm 3 NO in flue gas x The content is 2250mg/Nm 3 . The concentrations of sodium hypochlorite and peracetic acid were 1 wt% and 25 wt%, respectively, the concentration of ozone was 4.9mol/l, the pore diameters of the porous barrier 2, the porous material layer 6, and the barrier layer 12 were 6mm, 50 μm, and 15mm, respectively, the inclination angle of the barrier layer 12 was 5 °, and the reaction retention in the mixed solution, ozone, and alkaline solution was observedThe time is 3min, 1min and 5s respectively. By the denitration device and the denitration method, NO in the flue gas exhausted into the atmosphere x The content is 788mg/Nm 3 And can not reach the national standard of discharge.
From the above examples, it can be seen that the denitration device and the denitration method of the present invention for treating flue gas of a glass melting furnace have lower investment and operation costs than those of the reduction method (the reduction method uses platinum as a catalyst, the catalyst has large one-time investment, and the catalyst is easy to be poisoned, the raw materials of the present invention are easy to obtain, and the investment and operation costs are low).
Meanwhile, when the denitration equipment disclosed by the invention is used for denitration of flue gas generated by different fuel types or flue gas with different flue gas amounts, the pore diameters of the oxidation chamber porous stopper 2, the porous material layer 6 and the alkali liquor absorption chamber barrier layer 12 are adjusted, the equipment does not need to be replaced, and the application range is wide.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The utility model provides an oxidation chamber for glass melting furnace flue gas denitration equipment which characterized in that, the oxidation chamber is equipped with an airtight accommodation space that is used for holding the denitration oxidant, the denitration oxidant is including the main oxidant and the auxiliary oxidant that hold respectively, and the lower part space of accommodation space is used for holding liquid auxiliary oxidant, and the upper portion space is used for holding gaseous state main oxidant, and the bottom is equipped with the flue gas delivery port, and the top is equipped with the exhanst gas outlet, and the lower part is equipped with the oxidant discharge port that is used for discharging auxiliary oxidant, and upper portion is equipped with the solution that main oxidant entry and auxiliary oxidant adds the mouth.
2. The oxidation chamber as claimed in claim 1, wherein the lower space of the accommodating space is provided with a plate-shaped porous stopper distributed with a plurality of through holes, and the porous stopper is mounted on the inner wall of the lower part of the accommodating space; the material can be selected from polytetrafluoroethylene, and the aperture is 8-25 mm.
3. The oxidation chamber as claimed in claim 1 or 2, wherein the upper space of the accommodating space is provided with a porous material layer, and the porous material layer is mounted on an inner wall of the upper part of the accommodating space; the porous material constituting the porous material layer may be selected from one or a mixture of several of porous ceramics, open-cell foam glass, and porous carbon materials, and the pore diameter of the porous material is 2-37 μm, and is preferably porous material with open pores.
4. The oxidation chamber as set forth in any one of claims 1 to 3 wherein the primary oxidant is ozone and the secondary oxidant is a mixed solution of sodium hypochlorite and peracetic acid.
5. The oxidation chamber as claimed in claim 4, wherein the mass percentages of peroxyacetic acid and sodium hypochlorite in the mixed solution are 5-22 wt% and 3-16 wt%, respectively.
6. The oxidation chamber of claim 4 or 5, wherein the molar ratio of ozone to sodium hypochlorite to peroxyacetic acid is (20-50): (0.67-2.96): (0.39-2.1); preferably (30-40): (1-2.5): (0.5-1.5), most preferably 35: 2: 1.
7. the denitration oxidizer contained in the oxidation chamber as set forth in any one of claims 1 to 3, which comprises a primary oxidizer and a secondary oxidizer separately contained, wherein the primary oxidizer is ozone, and the secondary oxidizer is a mixed solution of sodium hypochlorite and peracetic acid.
8. The denitration oxidant of claim 7, wherein the mass percentages of the peroxyacetic acid and the sodium hypochlorite in the mixed solution are respectively 5-22 wt% and 3-16 wt%.
9. The denitration oxidant according to claim 7 or 8, wherein the molar ratio of ozone, sodium hypochlorite and peroxyacetic acid is (20-50): (0.67-2.96): (0.39-2.1); preferably (30-40): (1-2.5): (0.5-1.5), most preferably 35: 2: 1.
10. a method for denitrating flue gas of a glass melting furnace, which comprises the steps of introducing the dedusted and desulfurized flue gas of the glass melting furnace into an oxidation chamber by using the oxidation chamber of any one of claims 1 to 6 and the denitration oxidant of any one of claims 7 to 9, and oxidizing NO in the flue gas of the glass melting furnace into NO by using the denitration oxidant 2 To remove NO in the flue gas;
preferably, the method comprises the following steps:
1) sending the glass melting furnace flue gas subjected to dust removal and desulfurization into an oxidation chamber through a flue gas conveying opening;
2) firstly, the flue gas of the glass melting furnace is contacted with an auxiliary oxidant in an oxidation chamber for primary oxidation to obtain primary oxidation flue gas; the residence time of the glass melting furnace flue gas in the auxiliary oxidant is 0.5-2 min;
3) continuously rising the primary oxidation flue gas obtained in the step 2), contacting with ozone, carrying out secondary oxidation to obtain secondary oxidation flue gas, and discharging the secondary oxidation flue gas from a flue gas outlet; the residence time of the secondary oxidation flue gas in the ozone is 2-10 min.
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