CN110711488A - Flue gas desulfurization, denitration and demercuration integrated method - Google Patents
Flue gas desulfurization, denitration and demercuration integrated method Download PDFInfo
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- CN110711488A CN110711488A CN201911028431.8A CN201911028431A CN110711488A CN 110711488 A CN110711488 A CN 110711488A CN 201911028431 A CN201911028431 A CN 201911028431A CN 110711488 A CN110711488 A CN 110711488A
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- flue gas
- desulfurization
- denitration
- integrated method
- demercuration
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- 239000003546 flue gas Substances 0.000 title claims abstract description 102
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 34
- 230000023556 desulfurization Effects 0.000 title claims abstract description 34
- 238000001914 filtration Methods 0.000 claims abstract description 46
- 230000000694 effects Effects 0.000 claims abstract description 33
- 238000000746 purification Methods 0.000 claims abstract description 27
- 239000012784 inorganic fiber Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 25
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 13
- 229910052745 lead Inorganic materials 0.000 claims abstract description 8
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 claims abstract description 6
- 229910052924 anglesite Inorganic materials 0.000 claims abstract description 5
- 239000000779 smoke Substances 0.000 claims description 34
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 14
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000011069 regeneration method Methods 0.000 claims description 8
- 238000006703 hydration reaction Methods 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 230000036571 hydration Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 239000003054 catalyst Substances 0.000 abstract description 2
- 230000010354 integration Effects 0.000 abstract 1
- 230000001131 transforming effect Effects 0.000 abstract 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 30
- 239000000835 fiber Substances 0.000 description 19
- 230000008569 process Effects 0.000 description 17
- 239000007789 gas Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 238000001514 detection method Methods 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 239000003245 coal Substances 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 229910052815 sulfur oxide Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000011575 calcium Substances 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- B01D53/74—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
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
-
- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
-
- 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
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
-
- 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
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Treating Waste Gases (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a flue gas desulfurization, denitration and demercuration integrated method, which weaves modified high-activity inorganic fiber into a flue gas filtering material, installs the flue gas filtering material in modular flue gas purification equipment to form a flue gas filtering module, SO that the flue gas is limited to pass through the flue gas filtering material in the flue gas filtering module, thereby NO and SO in the flue gas are treated2Can be stably removed from the flue gas, and Hg and Pb in the flue gas can also be removed as HgSO4And PbSO4The form of the catalyst is stable, the module can realize random serial and parallel use, and the reaction condition is stableSurely, small, so abandoned the huge reaction tower of traditional SOx/NOx control equipment, because module itself is filtering material, purifying effect is good, so can abandon traditional chimney again, also can use the desulfurization mode of traditional fluidized bed to simplify into desulfurization, denitration, demercuration, deleading integration equipment through transforming.
Description
Technical Field
The invention relates to the new technical field of environmental protection, in particular to a method for integrating flue gas desulfurization, denitration and demercuration.
Background
According to the data of the reserves in 2018, domestic coal can be combusted for 500 years according to the usage amount in 2010, and the coal producing area in southwest takes high-sulfur coal as the main material, and sulfur dioxide and nitrogen oxide generated by coal combustion are the main pollutants causing air pollution at present and are the main reasons for generating acid rain; is the main reason that PM10 and PM2.5 exceed standards. In 2011, the total emission of sulfur dioxide reaches 2217.9 ten thousand tons, the total emission of nitrogen oxides reaches 2404.3 ten thousand tons, and 90 percent of SO270 percent of NOx is derived from the combustion of coal, while 70 percent of the energy structure in China is coal, the emission of NOx is still the main cause of the standard exceeding of PM2.5 in natural gas power generation, and SO in heavy oil combustion2And NOx emissions are also so severe that state-related policy regulations. The use of heavy oil is strictly prohibited for ships in the fifty nautical mile offshore. Therefore, it is necessary to develop a high-efficiency and low-cost deep purification technology for sulfur dioxide and nitrogen oxides. The existing desulfurization technologies comprise a wet method, a semi-dry method and a dry method, and an active coke method. The limestone-gypsum wet flue gas desulfurization engineering is representative, and the engineering application exceeding nine percent is a wet desulfurization technology. The disadvantages of large and high reaction tower bodies exist in the operating wet desulphurization engineering, and are all for increasing SO2And Ca (OH)2The collision probability of the droplets and the reaction time, which increases the construction costs. The tower body is huge and needs more Ca (OH)2The slurry has the defects of complex wet process technology, huge equipment, high investment, high operation cost and high energy consumption, and also has the problems of corrosion and scaling of the equipment, blockage and secondary pollution (calcium escape) to the atmosphere, thus causing the situation of low standard reaching rate and low operation input rate of the prior desulfurization. The semi-dry desulfurization technique is also based on limestone (Ca (OH)2) Systematic or magnesium desulfurization (Mg (OH)2) Although the method has the advantages of little investment and low energy consumption for the wet method, the method is characterized in thatOnly the improvement of the wet desulphurization process is limited by the reaction mechanism, and the problems of low desulphurization efficiency and poor effect still exist. Dry desulfurization is a more advanced desulfurization process with higher desulfurization efficiency at present, but active coke is adopted to adsorb SO at present2Adsorbed SO2And V2O5Advanced oxidation reaction is carried out to remove SO2By oxidation to SO3And SO2Is easy to absorb moisture to generate H2SO4The reaction mechanism is extremely fast, the sulfur removal efficiency is high, but the active coke is expensive and large in volume, and the reaction tower occupies a larger area than a wet method, so that the defects of extremely high construction cost and large cost investment for purchasing the active coke at one time exist, and the operation cost is high. The denitration efficiency of the SCR method can reach about 90 percent in engineering, but the SCR method has the problems of high catalyst cost, high consumption, high energy consumption and NH, and the reaction temperature reaches 300-450 DEG C3Serious problem of slip, NH although NOx is removed3The pollution is not negligible, and the SCNR method is low in denitration efficiency and higher in operation temperature (800-. Because the wet method and the dry method have essential differences in process and the denitration can not be used in the same environment, generally, the flue gas desulfurization process is connected with the SCR flue gas denitration process in series, because the SCR method must be operated at the temperature of 300 plus-450 ℃, the SNCR rule is operated at the temperature of 800 plus-900 ℃, the denitration must be carried out after the desulfurization due to the process stability, the flue gas must be heated to the temperature of 300 plus-450 ℃ or even 800 plus-900 ℃ again for denitration, the process is more complicated and the energy consumption is higher, and therefore the existing desulfurization and denitration process needs to be greatly renovated. The activated carbon fiber has the defects that the activated carbon fiber has extremely high cost and must be replaced regularly, the dust content of flue gas entering a reactor is required to be low, and otherwise, the activated carbon fiber is easy to pollute, wear and block an activated carbon pore channel to reduce the performance of the activated carbon fiber. SO (SO)2And NOx must be carried out in two reactors in the activated carbon fiber desulfurization and denitrification technology, which also causes the defects of complicated equipment and high investment cost. The synchronous desulfurization and denitrification method of the pyrolusite essentially belongs to wet removal, and SO2And NOx break through MnO in gas-liquid interface and pyrolusite2Take place inverselyThe gas-liquid mass transfer efficiency is low, and the good flue gas dispersion effect is ensured to ensure the removal effect, so that the requirements on a reaction device are extremely high, the reaction tower is huge, the metal mixture is expensive, the regeneration cost is high, the flue gas pressure loss in the reaction device is large, and the difficulty is higher particularly in large-scale engineering application. The invention relates to a method for simultaneously desulfurizing and denitrating flue gas by inquiring the invention patent number CN103301749B (published Japanese 20151202), which is used for desulfurizing and denitrating the flue gas containing SO after the state is adjusted2After the flue gas of NO and the micro-material of transition metal oxide or the micro-material of the mixture containing transition metal compound are fully mixed, contacted and reacted, SO2Is catalytically oxidized into SO3Catalytic oxidation of NO to NO2In which most of the SO3With NO2Directly carrying out hydration reaction with water, and finally existing on the surface of the particles in the form of sulfate and nitrate to remove the SO which is not participated in the hydration reaction in the smoke3With NO2The waste water is purified by absorption of alkali liquor, and discharged reactor micro-materials are recycled after being recovered, so that the method can realize desulfurization and denitrification simultaneously. The invention has the greatest advantages of realizing synchronous desulfurization and denitrification and high removal efficiency, but the flue gas can enter the reaction tower for reaction only after the flue gas is fully adjusted, the reaction tower must be filled with metal oxide particles and the particles are required to keep certain density and concentration, if the concentration in the reaction tower is changed, the flue gas directly penetrates through the gaps of the powder particle rate to cause short circuit escape, and the biggest engineering application difficulty of the invention is that the concentration of the particles in the large reaction tower is uncontrollable, the gas flow field in the reaction tower is extremely complex, the flue gas emission is uncontrollable escape, secondary pollution is caused, the regeneration process of the transition metal oxide is complicated, and the risk of secondary pollution is caused, so the verification in the experiment is feasible, but no method is used for realizing large-scale engineering application.
Disclosure of Invention
The invention aims to provide a method for integrating flue gas desulfurization, denitration and demercuration, so as to solve the problems in the background technology.
In order to solve the above technical problems, the present invention providesThe technical scheme is as follows: weaving the modified high-activity inorganic fiber into a flue gas filtering material, and installing the flue gas filtering material in a modularized flue gas purifying device, thereby forming a flue gas filtering module, limiting the flue gas, and enabling the limited flue gas to pass through the flue gas filtering material in the flue gas filtering module, SO that SO in the flue gas2After NO collides with transition metal oxide crystals in the modified high-activity inorganic fibers, the NO undergoes a violent catalytic oxidation reaction at a low temperature to react SO in the flue gas2Rapid catalytic oxidation to SO3The NO in the flue gas is quickly catalyzed and oxidized into NO2Simultaneously with H in the flue gas2O hydration to H2SO4And HNO3Then adsorbed by the modified high-activity inorganic fiber, and meanwhile, Hg and Pb in the smoke and H adsorbed on the surface of the modified high-activity inorganic fiber are adsorbed when the Hg and Pb in the smoke pass through the smoke filtering module2SO4The solution reacts rapidly to generate HgSO4And PbSO4And is adsorbed by the modified high-activity inorganic fiber, and finally the sulfur, the nitrate, the mercury and the lead in the flue gas are removed.
The modified high-activity inorganic fiber is a high-temperature-resistant inorganic fiber prepared from a metal oxide and a transition metal oxide with a brand-new formula, and a tunnel-type structure is formed on the surface of the high-activity inorganic fiber and a transition metal oxide crystal grain formed on the surface of the high-activity inorganic fiber after modification.
The flue gas filtering module can select the combination of series connection, parallel connection or series-parallel connection modes according to the concentration and the quantity of the flue gas.
And substances adsorbed on the surface of the smoke filtering module can be directly washed and activated by water after being saturated and then can be continuously used.
When the activity of the modified high-activity inorganic fiber in the flue gas filtering module is declined, the flue gas filtering module can be detached, and the flue gas filtering module is soaked in water, dehydrated, activated and dried, and recycled by 4 steps to realize regeneration.
The filtering pore of the smoke filtering material is 1-4 microns.
The smoke filtering module can stably work at the smoke temperature of 50-350 ℃.
The minimum single volume of the smoke filtering module is 0.06m3。
The metal oxide comprises one or a mixture of several of silicon dioxide, aluminum oxide, calcium oxide and magnesium oxide.
The transition metal oxide comprises one or a mixture of more of manganese dioxide, vanadium pentoxide, titanium dioxide, iron oxide, copper oxide, nickel oxide and zinc oxide.
Compared with the prior art, the invention has the following beneficial effects: the integrated method for desulfurization, denitration, demercuration and deleading comprises the steps of weaving modified inorganic fibers with high-activity structures into a flue gas filtering material, arranging the filtering material in a modular reactor, and allowing the flue gas to be limited and to pass through a multi-pore tunnel filtering material, SO that SO is filtered2Is catalytically oxidized into SO3Catalytic oxidation of NO to NO2In which most of the SO3With NO2Directly carrying out hydration reaction with water, finally existing on the surface of particles in the form of sulfate and nitrate, and removing Hg and Pb in the flue gas in the form of HgSO4And PbSO4The form of the fiber is stable and removed, the series connection and parallel connection use of any module can be realized by controlling the air pressure of the smoke emission, the huge reaction tower of the traditional desulfurization and denitration equipment is abandoned due to stable reaction conditions and small volume, the desulfurization mode of the traditional fluidized bed can be also used and simplified into the desulfurization, denitration and demercuration integrated equipment through transformation, the module is a filter material, the purification effect is good, the traditional chimney can be abandoned, the fiber has the characteristics of low manufacturing cost, stable chemical property and high temperature resistance, the flue gas purification cost can be further reduced, the flue gas purification module can realize on-line regeneration and off-line regeneration, the regeneration process is simple, the module can be detached to enter the activation process for activation regeneration only through simple washing process for cleaning and removing the fiber surface attachments when the activity of the surface structure material is declined, the flue gas purification module can be used in series and parallel connection and is suitable for various SO2And NOXThe module can be used in series when the concentration is high, and the flue gas quantity can be increasedThe combined use greatly facilitates the factory production of the modules, and the efficiency effect difference caused by the field construction difference can not occur, so that the large-scale engineering application is facilitated.
Detailed Description
The embodiments of the present invention will now be described in detail, with the understanding that the present disclosure is to be considered as a exemplification of the invention and is not intended to limit the invention to the specific embodiments illustrated. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
1) continuous fibers with the diameter of 6 microns of monofilament fibers are selected and modified to be woven into a column type filter with the thickness of 10mm, the filtering precision of 1um, the diameter of 160mm and the height of 30 mm.
2) The smoke purification module is made into a sandwich structure by using a lining mode and an outer protecting net mode, the size of the smoke purification module is phi 180H 3000mm, a specially designed standard connecting flange is attached to the smoke purification module, and the smoke purification module is connected with a smoke temporary storage device.
3) Prepared SO2The concentration is 5000mg/m3NO concentration 1000mg/m3Experiment gas injection flue gas generation device with temperature of 180 ℃ and SO monitoring2Concentration and NO concentration.
4) The fan connected with the outlet of the module is opened, and the fan extracts SO in the flue gas generation device through the flue gas purification module2、NOXMixture with air, discharged to contain SO2The exhaust gas concentration is detected in synchronization with the NO detection sensor in the pipe.
5) Monitoring SO in the tail gas duct2The concentration is reduced to 2mg/m3,NOXThe concentration is reduced to 35mg/m3。
Example 2:
1) the modified continuous fiber with the diameter of 15 microns monofilament fiber is woven into a column type filter with the thickness of 10mm, the filtration precision of 4um, the diameter of 160mm and the height of 3000 mm.
2) And reinforcing the column filter by using the inner and outer protective nets to form a standard flue gas purification module with phi 180 x 3000 mm.
3) Prepared SO2The concentration is 5000mg/m3. NO concentration of 1000mg/m3The experimental flue gas with the temperature of 180 ℃ is introduced into the flue gas temporary storage device, the device is connected with the inlet of the standard flue gas purification module, and the concentration of the inlet of the purification module is monitored.
3) Opening the fan at the outlet of the module to extract SO2In mixture with NO, simultaneous detection of SO at the outlet2And NOx concentration.
4) Detected SO in house tubes2Concentration of<2mg/m3,NOx<5mg/m3。
Example 3:
1) the continuous fiber with the diameter of 6 microns monofilament fiber is modified and woven into a column type filter with the thickness of 10mm, the filtering precision of 1um, the diameter of 160mm and the height of 30 mm.
2) The smoke purification module is made into a sandwich structure by using a lining mode and an outer protecting net mode, the size of the smoke purification module is phi 180H 3000mm, a specially designed standard connecting flange is attached to the smoke purification module, and the smoke purification module is connected with a smoke temporary storage device.
3) Prepared SO2The concentration is 5000mg/m3. NO concentration of 1000mg/m3The temperature is 180 ℃, and the mixed gas with mercury vapor is 10mg/m3And detecting the concentration of SOx, NOx and Hg.
4) The fan connected with the outlet of the module is opened, and the fan extracts SO in the flue gas generating device through the flue gas purification module2NOx and mercury vapor to a gas mixture containing SO2The exhaust gas concentration is detected in the same frequency as that in the pipeline of the NO detection sensor.
5) Detection of SOx concentration in monitored house air pipe<2mg/m3Concentration of NOx<5mg/m3The Hg concentration was not detected.
Example 4:
1) the modified continuous fiber with the diameter of 15 microns monofilament fiber is woven into a column type filter with the thickness of 10mm, the filtration precision of 4um, the diameter of 160mm and the height of 3000 mm.
2) The column filter is reinforced by using the inner and outer protective nets to form a standard flue gas purification module with phi 180 x 3000 mm.
3) Prepared SO2The concentration is 5000mg/m3. NO concentration of 1000mg/m3The temperature is 180 ℃, and the mixed gas with mercury vapor is 10mg/m3And introducing a smoke temporary storage device, and connecting the device with an inlet of the standard smoke purification module. The SOx concentration, NOx concentration, Hg concentration are detected.
4) Opening the fan at the outlet of the module to extract SO2In mixture with NO, simultaneous detection of SO at the outlet2And NOx, Hg concentration.
5) Detected SO in house tubes2Concentration of<2mg/m3，NOx<5mg/m3The Hg concentration was not detected.
Example 5:
1) the modified fiber with the monofilament diameter of 6um is chopped into chopped strands with the diameter of 6um and the length of less than 5mm, the chopped strands are made into a filter felt through a sintering process, and a column-shaped filter with the thickness of 10mm, the diameter of 160mm and the length of 3000mm is sewn by the filter felt.
2) Prepared SO2The concentration is 5000mg/m3. NO concentration of 1000mg/m3The experimental flue gas with the humidity of 180 ℃ is introduced into the flue gas temporary storage device, the device is connected with the inlet of the standard flue gas purification module, and the concentration of the inlet of the purification module is monitored.
3) Opening the fan at the outlet of the module to extract SO2In mixture with NO, simultaneous detection of SO at the outlet2And NOx concentration.
4) Detected SO in house tubes2Concentration of<2mg/m3,NOx<5mg/m3。
Example 6:
1) the modified fiber with the monofilament diameter of 6um is chopped into chopped strands with the diameter of 6um and the length of less than 5mm, the chopped strands are made into a filter felt through a sintering process, and a column-shaped filter with the thickness of 10mm, the diameter of 160mm and the length of 3000mm is sewn by the filter felt.
2) Prepared SO2NO, mixed gas of 10mg/m with mercury-containing vapor3And detecting the concentration of SOx, NOx and Hg.
3) Fan for opening outlet connection of moduleThe fan extracts SO in the smoke generating device through the smoke purifying module2NOx and mercury vapor to a gas mixture containing SO2The exhaust gas concentration is detected in synchronization with the NO detection sensor in the pipe.
4) Detection of SOx concentration in monitored house air pipe<2mg/m3Concentration of NOx<5mg/m3The Hg concentration was not detected.
Example 7:
1) the modified fiber with the monofilament diameter of 15um is chopped into chopped strands with the diameter of 15um and the length of less than 5mm, the chopped strands are made into a filter felt through a sintering process, and a column-shaped filter with the thickness of 10mm, the diameter of 160mm and the length of 3000mm is sewn by the filter felt.
2) Prepared SO2The concentration is 5000mg/m3. NO concentration of 1000mg/m3The experimental flue gas with the humidity of 180 ℃ is introduced into the flue gas temporary storage device, the device is connected with the inlet of the standard flue gas purification module, and the concentration of the inlet of the purification module is monitored.
3) Opening the fan at the outlet of the module to extract SO2In mixture with NO, simultaneous detection of SO at the outlet2And NOx concentration.
4) Detected SO in house tubes2Concentration of<2mg/m3,NOx<5mg/m3。
Example 8:
1) the modified fiber with unit diameter of 15um is chopped into chopped strands with diameter of 15um and length of less than 5mm, the chopped strands are made into a filter felt through a sintering process, and the filter felt is sewn into a column filter with thickness of 10mm, diameter of 160mm and length of 3000 mm.
2) Prepared SO2NO, mixed gas of 10mg/m with mercury-containing vapor3And detecting the concentration of SOx, NOx and Hg.
3) The fan connected with the outlet of the module is opened, and the fan extracts SO in the flue gas generating device through the flue gas purification module2NOx and mercury vapor to a gas mixture containing SO2The exhaust gas concentration is detected in the same frequency as that in the pipeline of the NO detection sensor.
4) Monitored room atmosphereDetection of SOx concentration in a tube<2mg/m3Concentration of NOx<5mg/m3The Hg concentration was not detected.
Based on the above, the invention has the advantages that the high-activity inorganic fiber and the pore tunnel type structure formed on the surface of the transition metal oxide crystal grain formed on the modified surface of the high-activity inorganic fiber are utilized, the modified high-activity inorganic fiber is woven into the smoke filtering material, the filtering material is arranged in the modularized reactor, smoke is limited to pass through the filtering material with multiple pore tunnels, the transition metal oxide crystal of the structure generated after the modification in the filtering material has a very large specific surface area, SO that SO in the smoke has a very large specific surface area2NO must pass through and collide with it. The transition metal oxide in the fiber formula and the transition metal oxide in the modified formula are subjected to violent catalytic oxidation reaction at low temperature to react SO in the flue gas2Rapid catalytic oxidation to SO3The NO in the flue gas is quickly catalyzed and oxidized into NO2Oxidized SO3Has strong hygroscopicity; the coal contains H generated by burning H (hydrogen) element2O and SO3Hydration to H2SO4，NO2Is also reacted with H2O hydration to HNO3Because the channel tunnel structure on the surface of the active fiber can quickly adsorb the generated H2SO4With HNO3Thereby mixing NO and SO in the flue gas2Stably removing the mercury (Hg) and Pb from the flue gas, wherein the Hg in the flue gas is adsorbed on the surfaces of the fibers2SO4The solution reacts rapidly to generate HgSO4。HgSO4Adsorbing the Hg and Pb in the flue gas as HgSO by adsorbing the Hg and Pb on the surface of the active fiber4And PbSO4The form of (A) is stably removed.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The integrated method for desulfurization, denitration and demercuration of flue gas is characterized in that modified high-activity inorganic fibers are woven into a flue gas filtering material, the flue gas filtering material is installed in a modularized flue gas purification device, SO that a flue gas filtering module is formed, the flue gas is limited and must pass through the flue gas filtering material in the flue gas filtering module, and SO in the flue gas is enabled to be contained2After NO collides with transition metal oxide crystals in the modified high-activity inorganic fibers, the NO undergoes a violent catalytic oxidation reaction at a low temperature to react SO in the flue gas2Rapid catalytic oxidation to SO3The NO in the flue gas is quickly catalyzed and oxidized into NO2Simultaneously with H in the flue gas2O hydration to H2SO4And HNO3Then adsorbed by the modified high-activity inorganic fiber, and meanwhile, Hg and Pb in the smoke and H adsorbed on the surface of the modified high-activity inorganic fiber are adsorbed when the Hg and Pb in the smoke pass through the smoke filtering module2SO4The solution reacts rapidly to generate HgSO4And PbSO4And is adsorbed by the modified high-activity inorganic fiber, and finally the sulfur, the nitrate, the mercury and the lead in the flue gas are removed.
2. The integrated method of claim 1, wherein the modified high-activity inorganic fiber is a high-temperature-resistant inorganic fiber made of a metal oxide and a transition metal oxide with a brand-new formula, and a tunnel-type structure is formed on the surface of a transition metal oxide crystal grain formed on the surface of the high-activity inorganic fiber and the modified surface of the high-activity inorganic fiber.
3. The integrated method for desulfurization, denitrification and demercuration of flue gas as claimed in claim 1, wherein the flue gas filtering modules are selected from a group consisting of series connection, parallel connection and series-parallel connection according to the concentration and quantity of flue gas.
4. The integrated method for flue gas desulfurization, denitration and demercuration as claimed in claim 1, wherein the substances adsorbed on the surface of the flue gas filtering module can be directly washed and activated with water after being saturated and then can be used continuously.
5. The integrated method for flue gas desulfurization, denitration and demercuration as claimed in claim 1, wherein when the activity of the modified high-activity inorganic fiber in the flue gas filtering module is degraded, the flue gas filtering module can be detached, and the modified high-activity inorganic fiber is soaked in water, dehydrated, activated, dried, recycled and reused in 4 steps to realize regeneration and utilization.
6. The integrated method for flue gas desulfurization, denitration and demercuration as claimed in claim 1, wherein: the filtering pore of the smoke filtering material is 1-4 microns.
7. The integrated method for flue gas desulfurization, denitration and demercuration as claimed in claim 1, wherein: the smoke filtering module can stably work at the smoke temperature of 50-350 ℃.
8. The integrated method for flue gas desulfurization, denitration and demercuration as claimed in claim 1, wherein: the minimum single volume of the smoke filtering module is 0.06m3。
9. The integrated method of claim 2, wherein the metal oxide comprises one or more of silicon dioxide, aluminum oxide, calcium oxide and magnesium oxide.
10. The integrated method of claim 2, wherein the transition metal oxide comprises one or more of manganese dioxide, vanadium pentoxide, titanium dioxide, iron oxide, copper oxide, nickel oxide and zinc oxide.
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