CN106955589B - Boiler flue gas simultaneous desulfurization and denitrification device - Google Patents
Boiler flue gas simultaneous desulfurization and denitrification device Download PDFInfo
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- CN106955589B CN106955589B CN201710234117.XA CN201710234117A CN106955589B CN 106955589 B CN106955589 B CN 106955589B CN 201710234117 A CN201710234117 A CN 201710234117A CN 106955589 B CN106955589 B CN 106955589B
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- 239000003546 flue gas Substances 0.000 title claims abstract description 74
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 72
- 230000023556 desulfurization Effects 0.000 title claims abstract description 72
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000007788 liquid Substances 0.000 claims abstract description 49
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 45
- 239000007921 spray Substances 0.000 claims abstract description 36
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- 238000003860 storage Methods 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011941 photocatalyst Substances 0.000 claims abstract description 15
- 230000009471 action Effects 0.000 claims abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
- 230000001699 photocatalysis Effects 0.000 claims abstract description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 7
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 6
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007146 photocatalysis Methods 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 230000005284 excitation Effects 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 26
- 230000003647 oxidation Effects 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 229910052602 gypsum Inorganic materials 0.000 description 8
- 239000010440 gypsum Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000618 nitrogen fertilizer Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000009982 effect on human Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- -1 phosphotungstic acid modified carbon Chemical class 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Images
Classifications
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- 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
- B01D53/86—Catalytic processes
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/106—Peroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- 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
- B01D2258/0283—Flue gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/804—UV light
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (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)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a device for simultaneously desulfurizing and denitrating boiler flue gas, which comprises one or more serially connected desulfurizing and denitrating tower bodies and an external hydrogen peroxide storage tank, wherein the tower bodies are sequentially provided with a desulfurizing and denitrating tower body from top to bottomThe desulfurization and denitrification module consists of a spray pipe, an ultraviolet lamp, a regular nano photocatalyst plate and a sieve plate; the spray pipe is connected to the hydrogen peroxide storage tank through a hydrogen peroxide circulating pump; a flue gas inlet is formed in the side face of the bottom of the tower body, and a liquid seal tank is vertically arranged at the bottom end of the tower body; boiler flue gas enters the tower body from a flue gas inlet, and SO is generated under the action of the desulfurization and denitrification module and hydrogen peroxide3And NO2Respectively oxidizing and absorbing into sulfuric acid and nitric acid, removing, allowing the liquid after photocatalytic hydrogen peroxide oxidation reaction to pass through a sieve plate, then entering a liquid seal tank and finally converging into a storage tank, and discharging the treated clean flue gas through a flue gas outlet at the top end of the tower body. The invention can lead SO in the coal-fired boiler to be converted into the SO2And NO is totally oxidized to SO3And NO2The desulfurization rate and the denitration rate can respectively reach more than 99 percent and 90 percent.
Description
Technical Field
The invention relates to a device for simultaneously desulfurizing and denitrating boiler flue gas, in particular to a device for desulfurizing and denitrating boiler flue gas by using oxidation reaction, and belongs to the field of industrial waste gas treatment.
Background
The flue gas of the coal-fired boiler contains a large amount of atmospheric pollutants, mainly SO2、NOx. Wherein, SO2And NOxNot only has the damage effect on human bodies and plants, especially crops and economic crops, but also can form acid rain, optical smoke, haze and the like, and can destroy the ozone layer and the like. The estimated NOx emission in 2020 and 2030 years in China reaches 2900 and 4000 ten thousand tons respectively. In 2011, China revises the emission standard of atmospheric pollutants of thermal power plants (GB 13223-; the national institute and related departments in 2012 have exported the twelve and five plans of energy conservation and emission reduction and the environmental protectionTwelve and five plans, and twelve and five plans for preventing and treating air pollution in key areas. The environmental protection standard faced by thermal power enterprises is getting tighter and tighter, and the emission standard requires NO of the existing thermal power generation boiler and gas turbine set from 1 month and 1 day of 2012xThe discharge will be performed at 100 mg/m3The concentration limit of (2). Meanwhile, the national environmental pollution treatment investment in 2012 is 8253.6 billion yuan, which accounts for 1.59 percent of the total domestic production value and 2.20 percent of the fixed capital investment of society, and is increased by 37.0 percent compared with the last year. Visible, NOXThe development of control technology and the treatment of atmospheric pollutants have become one of the important issues for a long time now and in the future.
At present, the wet limestone-gypsum method and the MgO method are most applied to the industry in China for desulfurization. Although the lime-gypsum method has mature industrial application and high desulfurization efficiency, plays a certain role in reducing the pollution of SO2 in the flue gas, the following defects exist:
1) the method has the problems of waste water post-treatment, complex operation, huge equipment, large energy consumption and high cost, the temperature of the washed flue gas is low, the discharge of the purified flue gas is not facilitated, the highest desulfurization rate is 95 percent, the increasingly strict discharge requirement is difficult to achieve, and if the desulfurization rate of more than 99 percent is required to be achieved, double towers are connected in series, so that huge investment and operation cost are caused;
2) per 1 ton SO treated2About 0.7 ton of CO is emitted2If the method is adopted for desulfurization, the emission of CO is increased every year2Billions of tons far exceeding the natural photosynthesis and seawater absorption capabilities, and China will produce about 4600 million yuan of CO according to Paris' agreement and future carbon customs and carbon finance2Emission reduction technology market;
3) the high water consumption of the technology also causes great difficulty in the technical popularization and application of the water-deficient areas in the middle and the west of China, and the areas are the most areas of coal-fired power plants in China;
4) in the method, 1 ton of SO is removed2About 2.7 tons of gypsum is discharged, the performance of the by-product gypsum cannot be compared with that of mineral gypsum due to loose texture, so that the desulfurized gypsum is discarded, a large amount of land is occupied, and the desulfurized gypsum can release toxic substances after being stacked for a long timeSecondary pollution is caused due to the quality, and the post-treatment cost is very high;
5) china is a country with great demand for sulfur, sulfuric acid and ammonium sulfate, but valuable sulfur resources in the flue gas are not recycled and productively utilized;
6) denitration can not be carried out, and denitration equipment needs to be redesigned and installed, so that the occupied area is large, the process is complex, and the operating cost is high.
The MgO method has high desulfurization efficiency, does not have the technical problems of scaling and the like, but has not been used on a 200MW coal-fired power plant boiler to date.
Ammonia (water) method desulfurization technology: ammonia is more alkaline than calcium-and magnesium-based absorbents relative to lime-gypsum calcium-based and MgO desulfurization processes. Ammonia absorption of SO in flue gas2The method is a gas-liquid or gas-gas reaction, has high reaction speed and complete reaction, high utilization rate of the absorbent and can achieve high desulfurization efficiency. The flue gas desulfurization technology does not produce any secondary pollution, neither waste water nor new waste gas, nor waste residue, and the desulfurization byproduct ammonium sulfate of ammonia is a common chemical fertilizer, so that the desulfurization byproduct ammonium sulfate can be left in a product and provided for use in a nitrogen fertilizer mode, so that the practical value of the product is higher, and the sales income of the byproduct can be greatly reduced. The system is simple and the equipment volume is small. The disadvantages are that: when the temperature of the flue gas is high and the dust content in the flue gas is high, ammonia is easy to volatilize, the operation and control are difficult, the consumption of the ammonia water absorbent is large, and simultaneously, the SO in the flue gas is caused2The method has no enrichment and concentration, the obtained ammonium sulfate solution is very thin, the process needs oxygen introduction for oxidation, and the absorption and crystallization need great energy consumption.
Similarly, flue gas denitration technologies mature and applied in the current coal-fired power plants mainly comprise an SCR selective catalyst reduction method, an SNCR selective non-catalytic reduction method, an electron beam irradiation method and a simultaneous desulfurization and denitration method. The SCR selective catalytic reduction method is the most applied and mature flue gas denitration technology in the world at present. The SCR selective catalytic reduction method is to use NH under the action of a catalyst3As a reducing agent, the catalyst reacts selectively with NOx in the smoke and generates nontoxic and pollution-free N2And H2And O. The method was first initiated by Engelhard company discovered that it applied for a related patent in 1957. Then Japan successfully achieved V, which is now widely used, under the pressure of its government environmental policy2O5/TiO2Catalysts, and were successfully put into commercial use in fuel and coal fired boilers in 1977 and 1979, respectively. However, the conventional SCR still has the following disadvantages: (1) the catalyst is easily poisoned by the abrasion of dust and the corrosion of alkali/alkaline earth metal for a long time; (2) the high reaction temperature of the catalyst requires a large catalyst device arrangement space to be reserved between the economizer and the air preheater; (3) the traditional SCR catalytic method has inevitable heat loss, which causes energy waste; (4) consumption of NH due to SCR technology3And the problems of storage, leakage, transportation and the like of the liquid ammonia cause the defects of high operating cost and large equipment investment.
Unlike SCR, SCO is a selective catalytic oxidation process that converts NO in flue gas to NO under oxygen-rich conditions2And absorbing NO by ammonia water combined with wet desulphurization process2Then ammonium nitrate with high added value is generated. Compared with the common high-temperature SCR technology, the method has the advantages of low energy consumption, convenient system arrangement, long service life of the catalyst, low operation cost and the like, has industrial application prospect, and is a hot spot of the current domestic and foreign flue gas denitration technology research. At present, the research on the catalyst of the selective catalytic oxidation SCO method mainly focuses on carbon materials, molecular sieves and metal oxides. The activated semicoke is a porous carbon material prepared from coal serving as a raw material, and the activated semicoke is a denitration catalyst with the greatest prospect due to the advantages of wide source, low price, easiness in regeneration and the like. Li Chunhu et al have applied for a number of Chinese patents in this field, such as "A SHAPED HALF-JIAO2NO adsorption catalyst and its preparation method (application No. 200810139810. X), & A preparation method of semi-coke flue gas denitrifier for low-temperature catalytic oxidation (application No. 201010204883. X), etc. And guides the completion of several research papers, such as research on the use of active semicoke for desulfurization and denitrification of flue gas (Master thesis, 2009), 'research on the removal of NO from flue gas by low-temperature catalytic oxidation of active semicoke (doctor thesis, 2010)' improvement of water resistance of flue gas oxidation and denitrification by phosphotungstic acid modified carbon materialStudy (master graduate thesis, 2013). Meanwhile, the Lichunhu technology combines an inexpensive and easily available activated carbocoal catalytic oxidation denitration technology with a power plant ultra-clean flue gas microalgae cultivation technology, effectively utilizes waste gas and waste heat, and can produce high-added-value nitrogenous fertilizer and biodiesel. However, the active semicoke is used for NO and H in the process of flue gas oxidation denitration2The competitive adsorption of O is easy to cause the water poisoning phenomenon of the catalyst, so that the denitration activity is obviously reduced.
The photocatalysis being by H2O and O2Active free radicals are generated on the surface of the photocatalyst, and the strong oxidizing property of the active free radicals can rapidly react SO2And oxidation of NO to readily water soluble SO3And NO2Especially under the action of an Ultraviolet (UV) lamp, the amount of superoxide radical, hydroxyl radical, ultrasonic wave, active ultraviolet body and ozone generated on the surface of the nano photocatalyst is dozens of times of that of the photocatalyst under a common UV lamp.
Disclosure of Invention
The invention aims to provide a catalyst based on an ultraviolet lamp, a nano photocatalyst and H, which has a simple structure and a good flue gas treatment effect2O2Boiler flue gas desulfurization denitration device simultaneously of oxidation synergism.
In order to achieve the purpose, the invention adopts the following specific technical scheme:
a boiler flue gas simultaneous desulfurization and denitrification device is characterized by comprising one or more desulfurization and denitrification tower bodies connected in series and an external hydrogen peroxide storage tank, wherein a desulfurization and denitrification module consisting of a spray pipe, an ultraviolet lamp, a regular nano photocatalyst plate and a sieve plate is sequentially arranged in each tower body from top to bottom; the spray pipe is connected to the hydrogen peroxide storage tank through a hydrogen peroxide circulating pump; a flue gas inlet is formed in the side face of the bottom of the tower body, and a liquid seal tank is vertically arranged at the bottom end of the tower body; boiler flue gas enters the tower body from a flue gas inlet and moves in the tower body from bottom to top, and SO in the flue gas is converted into superoxide radical, ozone and hydroxyl radical by ultraviolet discharge release molecular free radical and photocatalysis under the action of the desulfurization and denitrification module2And oxidation of NO to readily water soluble SO3And NO2And is sprayed from top to bottom through a spray pipeHydrogen peroxide of different concentrations to react SO3And NO2Respectively oxidized and absorbed into sulfuric acid and nitric acid, and then removed, when high-concentration hydrogen peroxide (5-30% by mass) is adopted, SO can be simultaneously removed by one tower2And complete oxidation of NO to readily water-soluble SO3And NO2However, when low-concentration hydrogen peroxide (0-5% by mass) is adopted, SO is in the first tower2Complete oxidation to readily water-soluble SO3With only a small amount of NO being oxidized to NO2And in the second column, the NO is completely oxidized to readily water-soluble NO2(ii) a Liquid after the photocatalytic hydrogen peroxide oxidation reaction enters the liquid seal tank through the sieve plate and finally converges to the storage tank, and the treated clean flue gas is discharged through a flue gas outlet at the top end of the tower body.
Furthermore, the desulfurization module is one or more groups, and at the moment, the second group or the nth group of spray pipes except the first group are connected with the liquid seal tank through a liquid circulating pump to absorb liquid in the liquid seal tank for spraying.
Further, a pH meter, a liquid level meter and an acid concentration tester are also arranged in the liquid seal tank at the bottom of the tower.
Further, an ultraviolet lamp is further arranged in the liquid seal tank and used for further purifying the sulfite and the nitrite which are not oxidized in the spray liquid.
Furthermore, a demister is arranged above the spray pipe in the tower body and used for defoaming the treated flue gas to ensure that the clean flue gas smoothly passes through the gas outlet.
Furthermore, the main body of the ultraviolet lamp is a quartz lamp tube, magnets with high Gauss density are symmetrically arranged on the quartz lamp tube, and a light excitation coating is coated inside and outside the quartz lamp tube and is positioned around the magnets.
Furthermore, the excitation coating is nano TiO2And a rare earth luminophor.
Further, the regular nano photocatalyst is nano TiO2。
The invention has the advantages that: desulfurization and desulfurization are simultaneously carried out by combining an ultraviolet lamp, a nano regular photocatalyst and hydrogen peroxideThe nitre and ultraviolet lamp have triple functions, provide light source for photocatalyst, and can ionize gas molecules to release molecular free radicals and ozone, H2O2Is green oxidant, under the action of ultraviolet lamp, H2O2Has higher oxidation speed to SO2And more complete oxidation of NO. The boiler flue gas is purified under multiple actions, SO that SO in the flue gas can be rapidly purified2And oxidation of NO to readily water soluble SO3And NO2And then sulfuric acid and nitric acid are by-produced, so that the desulfurization rate and the denitration rate of the boiler flue gas can reach more than 99%.
Drawings
Fig. 1 is a schematic view of the general structure of the present invention.
Wherein, 1, a desulfurizing tower; 2. a denitration tower; 3-1, a desulfurization tower ultraviolet lamp; 3-2, ultraviolet lamps of a denitration tower; 4-1, regulating the nanometer photocatalyst plate by the desulfurizing tower; 4-2, regulating the nano photocatalyst plate by the denitration tower; 5-1, a desulfurizing tower sieve plate; 5-2, a sieve plate of the denitration tower; 6-1, a sulfuric acid storage tank; 6-2. a nitric acid storage tank; 7-1, a spray pipe of the desulfurizing tower; 7-2, a spraying pipe of the denitration tower; 8-1, a foam remover of the desulfurizing tower; 8-2, a demister of the denitration tower; 9-1, liquid sealing the desulfurizing tower; 9-2, liquid sealing the denitration tower; 10-1, a flue gas inlet of a desulfurizing tower; 10-2, a flue gas inlet of the denitration tower; 11. a hydrogen peroxide storage tank; 12-1, a hydrogen peroxide circulating pump of the desulfurizing tower; 12-2, a hydrogen peroxide circulating pump of the denitration tower; 12-3, a desulfurizing tower liquid circulating pump; 12-4, a liquid circulating pump of the denitration tower; 13-1, a flue gas outlet of the desulfurizing tower; 13-2, a clean flue gas outlet; 14-1, a second spray pipe of the desulfurizing tower; 14-2, a second spraying pipe of the denitration tower.
Detailed Description
The invention is further illustrated by the following specific embodiments in conjunction with the accompanying drawings.
In the embodiment, two tower bodies are connected in series, and low-concentration (2.0 wt%) hydrogen peroxide is adopted to perform desulfurization and denitrification in the two towers respectively, namely, the first tower is mainly used for desulfurization, and the second tower is mainly used for denitrification; two groups of desulfurization and denitrification modules are arranged in each tower body.
As shown in figure 1, the device comprises a desulfurization tower 1, a denitration tower 2 and an external hydrogen peroxide storage tank 11 which are connected in series, wherein the desulfurization tower 1 is internally provided with the hydrogen peroxide storage tank from top to bottomThe desulfurization module is sequentially provided with a desulfurization tower spray pipe 7-1, a desulfurization tower ultraviolet lamp 3-1, a desulfurization tower regular nano photocatalyst plate 4-1 and a desulfurization tower sieve plate 5-1, wherein the desulfurization tower spray pipe 7-1 is connected to a hydrogen peroxide storage tank 11 through a desulfurization tower hydrogen peroxide circulating pump 12-1, and the two groups of desulfurization modules are arranged; a desulfurizing tower liquid seal tank 9-1 is vertically arranged at the bottom end of the desulfurizing tower 1, and the desulfurizing tower liquid seal tank 9-1 is connected with a desulfurizing tower second spray pipe 14-1 through a desulfurizing tower liquid circulating pump 12-3 to absorb liquid therein for spraying; a desulfurizing tower flue gas inlet 10-1 is arranged on one side of the bottom of the desulfurizing tower 1, boiler flue gas enters the desulfurizing tower 1 from the inlet and moves from bottom to top in the desulfurizing tower 1, and ozone is released by an ultraviolet lamp and photocatalysis is carried out to generate superoxide radical and hydroxyl radical to remove SO in the flue gas under the action of a desulfurizing module2Oxidation to SO3(in this case only a small amount of NO is oxidized to NO2) Absorbing and removing the 2.0wt% hydrogen peroxide spray liquid from top to bottom through a spray pipe 7-1 of the desulfurizing tower to obtain sulfuric acid, passing through a sieve plate 5-1 of the desulfurizing tower, entering a liquid seal tank 9-1 of the desulfurizing tower, and finally converging the sulfuric acid into a sulfuric acid storage tank 6-1; the flue gas after desulfurization is discharged through a flue gas outlet 13-1 of the desulfurization tower at the top end of the desulfurization tower 1 and then enters a denitration tower 2 through a flue gas inlet 10-2 of the denitration tower; a denitration module consisting of a denitration tower spray pipe 7-2, a denitration tower ultraviolet lamp 3-2, a denitration tower regular nano photocatalyst plate 4-2 and a denitration tower sieve plate 5-2 is also sequentially arranged in the denitration tower 2 from top to bottom, the denitration tower spray pipe 7-2 is connected to the hydrogen peroxide storage tank 11 through a denitration tower hydrogen peroxide circulating pump 12-2, the denitration modules are also two groups, a denitration tower liquid seal tank 9-2 is vertically arranged at the bottom end of the denitration tower 2, and the denitration tower liquid seal tank 9-2 is connected with a denitration tower second spray pipe 14-2 through a denitration tower liquid circulating pump 12-4 to absorb liquid therein for spraying; the flue gas entering the denitration tower 2 from the flue gas inlet 10-2 of the denitration tower moves from bottom to top in the denitration tower 2, and under the action of the denitration module, ozone is released by the ultraviolet lamp and the ultraviolet lamp is used for generating superoxide radical and hydroxyl radical through photocatalysis to further oxidize NO in the flue gas into NO2Absorbing and removing the hydrogen peroxide spray liquid from top to bottom by the spray pipe 7-2 of the denitration tower to form nitric acid, passing through the sieve plate 5-2 of the denitration tower, and then entering the denitration tower for denitrationThe tower liquid is sealed in the tank 9-2 and finally collected into the nitric acid storage tank 6-2; and the flue gas after desulfurization and denitrification treatment is discharged through a clean flue gas outlet 13-2 at the top end of the denitrification tower 2.
Ultraviolet lamps are further arranged in the liquid seal tank 9-1 of the desulfurization tower and the liquid seal tank 9-2 of the denitration tower and are used for further purifying sulfite and nitrite which are not oxidized in the spray liquid.
And a desulfurizing tower demister 8-1 and a denitrifying tower demister 8-2 are respectively arranged above the spray pipes in the desulfurizing tower and the denitrifying tower and used for defoaming the treated gas so as to enable the clean gas to smoothly pass through a flue gas outlet.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and do not limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope.
Claims (7)
1. A boiler flue gas simultaneous desulfurization and denitrification device is characterized by comprising a desulfurization tower, a denitrification tower and an external hydrogen peroxide storage tank which are connected in series, wherein desulfurization modules consisting of a desulfurization tower spray pipe, a desulfurization tower ultraviolet lamp, a desulfurization tower regular nano photocatalyst plate and a desulfurization tower sieve plate are sequentially arranged in the desulfurization tower from top to bottom, and the two groups of desulfurization modules are arranged; the spray pipes of the desulfurization tower in the first group of desulfurization modules are connected to the hydrogen peroxide storage tank through a hydrogen peroxide circulating pump of the desulfurization tower; the bottom end of the desulfurizing tower is vertically provided with a desulfurizing tower liquid seal tank which is connected with a desulfurizing tower spray pipe in the second group of desulfurizing modules through a desulfurizing tower liquid circulating pump to absorb liquid therein for spraying; one side of the bottom of the desulfurizing tower is provided with a desulfurizing tower flue gas inlet, boiler flue gas enters the desulfurizing tower from the desulfurizing tower flue gas inlet and moves from bottom to top in the desulfurizing tower, and ozone and photocatalysis generated by an ultraviolet lamp are released under the action of a desulfurizing module to generate superoxide radical and hydroxyl radical to remove SO in the flue gas2Oxidation to SO3Absorbing and removing the 2.0wt% hydrogen peroxide spray liquid sprayed from top to bottom through a spray pipe of the desulfurizing tower to obtain sulfuric acid, passing through a sieve plate of the desulfurizing tower, entering a liquid sealing tank of the desulfurizing tower and finally converging the sulfuric acid storage tank; to pass throughThe flue gas after desulfurization treatment is discharged through a flue gas outlet of the desulfurization tower at the top end of the desulfurization tower and then enters the denitration tower through a flue gas inlet of the denitration tower; denitration modules consisting of denitration tower spray pipes, denitration tower ultraviolet lamps, denitration tower regular nano photocatalyst plates and denitration tower sieve plates are also sequentially arranged in the denitration tower from top to bottom, and the number of the denitration modules is also two; the denitration tower spray pipes in the first group of denitration modules are connected to the hydrogen peroxide storage tank through the denitration tower hydrogen peroxide circulating pump, the bottom end of the denitration tower is vertically provided with a denitration tower liquid seal tank, and the denitration tower liquid seal tank is connected with the denitration tower spray pipes in the second group of denitration modules through the denitration tower liquid circulating pump to absorb liquid in the denitration tower spray pipes for spraying; the flue gas entering the denitration tower from the flue gas inlet of the denitration tower moves from bottom to top in the denitration tower, and under the action of the denitration module, ozone is released by the ultraviolet lamp and the ultraviolet lamp catalyzes the flue gas to generate superoxide radical and hydroxyl radical to further oxidize NO in the flue gas into NO2Hydrogen peroxide spray liquid sprayed from top to bottom through a spray pipe of the denitration tower absorbs and removes the hydrogen peroxide spray liquid to become nitric acid, and the nitric acid enters a liquid seal tank of the denitration tower after passing through a sieve plate of the denitration tower and finally converges to a nitric acid storage tank; and the flue gas after desulfurization and denitrification treatment is discharged through a clean flue gas outlet at the top end of the denitrification tower.
2. The desulfurization and denitrification apparatus according to claim 1, wherein a pH meter, a liquid level meter and an acid concentration meter are respectively provided in the desulfurization tower liquid seal tank and the denitrification tower liquid seal tank.
3. The desulfurization and denitrification apparatus according to claim 1, wherein ultraviolet lamps are further provided in the liquid-sealed tank of the desulfurization tower and the liquid-sealed tank of the denitrification tower, respectively.
4. The desulfurization and denitrification apparatus according to claim 1, wherein a demister is provided above each of the desulfurization tower spray pipe and the denitrification spray pipe.
5. The desulfurization and denitrification apparatus according to claim 1 or 3, wherein the ultraviolet lamp has a quartz tube, and the quartz tube is symmetrically provided with high-Gauss-density magnets.
6. The desulfurization and denitrification apparatus as claimed in claim 5, wherein a light excitation coating is further coated on the inside and outside of the quartz lamp tube.
7. The desulfurization and denitrification apparatus as claimed in claim 6, wherein the excitation coating is nano TiO2And a rare earth luminophor.
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| CN109046017A (en) * | 2018-09-17 | 2018-12-21 | 中国海洋大学 | A kind of integrated apparatus and technique of flue gas selective photocatalysis desulphurization denitration |
| CN109266418A (en) * | 2018-09-30 | 2019-01-25 | 青岛大学 | A method of arsenic in coal being leached under ultraviolet light using flue gas |
| CN109224654A (en) * | 2018-11-03 | 2019-01-18 | 郭绍华 | System for cleaning fume |
| CN109821413A (en) * | 2019-04-02 | 2019-05-31 | 宋铭宇 | A kind of flue gas ammonia method desulfurizing denitration minimum discharge integrated tower |
| CN112495446A (en) * | 2020-12-17 | 2021-03-16 | 南京永能新材料有限公司 | Cement denitration catalyst and preparation method and application thereof |
| CN116510492A (en) * | 2023-06-12 | 2023-08-01 | 山东正赢电力工程有限公司 | Green's flue gas desulfurization denitration system |
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| CN203862132U (en) * | 2014-01-26 | 2014-10-08 | 北京诺曼斯佰环保科技有限公司 | Wet flue gas desulfurization tower and deep flue gas purification system |
| CN104801178B (en) * | 2015-04-21 | 2019-12-31 | 南京朗洁环保科技有限公司 | Method for simultaneously desulfurizing, denitrifying and removing mercury by combining radical pre-oxidation with wet absorption |
| CN104815538B (en) * | 2015-04-21 | 2019-12-31 | 南京朗洁环保科技有限公司 | Up-down opposite spraying fluidized bed desulfurization and denitrification method for photolysis of peroxide |
| WO2016192755A1 (en) * | 2015-05-29 | 2016-12-08 | Sánchez Luis Domínguez | Titanium dioxide-catalysed oxidation method and use thereof |
| CN105327614B (en) * | 2015-11-06 | 2017-09-29 | 河北工业大学 | SO in joint removing coal-fired flue-gas2、NOXWith the method for Hg pollutants |
| CN205216581U (en) * | 2015-12-21 | 2016-05-11 | 河南弘康环保科技有限公司 | Can realize device of flue gas desulfurization denitration simultaneously |
| CN206069448U (en) * | 2016-10-17 | 2017-04-05 | 青岛海科绿邦环保科技有限公司 | A kind of industrial waste water disposal device |
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