CN109529621B - Semi-dry desulfurization, denitrification and demercuration device and method based on catalytic oxidation and deep condensation - Google Patents
Semi-dry desulfurization, denitrification and demercuration device and method based on catalytic oxidation and deep condensation Download PDFInfo
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- CN109529621B CN109529621B CN201910028989.XA CN201910028989A CN109529621B CN 109529621 B CN109529621 B CN 109529621B CN 201910028989 A CN201910028989 A CN 201910028989A CN 109529621 B CN109529621 B CN 109529621B
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- 230000023556 desulfurization Effects 0.000 title claims abstract description 32
- 230000003647 oxidation Effects 0.000 title claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 29
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 117
- 239000003546 flue gas Substances 0.000 claims abstract description 117
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 21
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- 239000000463 material Substances 0.000 claims description 7
- 239000012263 liquid product Substances 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- FKBGOUXGDAMMHP-UHFFFAOYSA-N [V+5].[O-2].[Mn+2] Chemical compound [V+5].[O-2].[Mn+2] FKBGOUXGDAMMHP-UHFFFAOYSA-N 0.000 claims description 3
- LQWKWJWJCDXKLK-UHFFFAOYSA-N cerium(3+) manganese(2+) oxygen(2-) Chemical compound [O--].[Mn++].[Ce+3] LQWKWJWJCDXKLK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001338 liquidmetal Inorganic materials 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- IXZOTKANSDQAHZ-UHFFFAOYSA-N manganese(ii) titanate Chemical group [O-2].[O-2].[O-2].[Ti+4].[Mn+2] IXZOTKANSDQAHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
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- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000010962 carbon steel Substances 0.000 claims description 2
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- 230000008859 change Effects 0.000 claims description 2
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- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 229910001039 duplex stainless steel Inorganic materials 0.000 claims description 2
- 239000002320 enamel (paints) Substances 0.000 claims description 2
- 229920002313 fluoropolymer Polymers 0.000 claims description 2
- 239000002918 waste heat Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 1
- CDEIGFNQWMSEKG-UHFFFAOYSA-M chloro-[4-[(2-hydroxynaphthalen-1-yl)diazenyl]phenyl]mercury Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C([Hg]Cl)C=C1 CDEIGFNQWMSEKG-UHFFFAOYSA-M 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 238000001556 precipitation Methods 0.000 abstract description 4
- 238000002485 combustion reaction Methods 0.000 abstract description 2
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- 239000002803 fossil fuel Substances 0.000 abstract description 2
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- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 8
- 229910052753 mercury Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
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- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- WYCDUUBJSAUXFS-UHFFFAOYSA-N [Mn].[Ce] Chemical group [Mn].[Ce] WYCDUUBJSAUXFS-UHFFFAOYSA-N 0.000 description 1
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- MECMQNITHCOSAF-UHFFFAOYSA-N manganese titanium Chemical group [Ti].[Mn] MECMQNITHCOSAF-UHFFFAOYSA-N 0.000 description 1
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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
- B01D53/90—Injecting reactants
-
- 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
- B01D53/002—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 condensation
-
- 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
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
-
- 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
- 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
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/104—Ozone
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/106—Peroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/2073—Manganese
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- 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
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- 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
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- 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
Abstract
The invention discloses a semi-dry desulfurization, denitrification and demercuration device and method based on catalytic oxidation and deep condensation, wherein the basic flow is NO in flue gas after dust removal X ，SO 2 And Hg via O 3 /H 2 O 2 Combined with a catalyst to produce NO 3 ‑ 、SO 4 2‑ And Hg of 2+ Then realizing the deep removal of the pollutant components in the flue gas in a multistage condensation mode; the purified flue gas is discharged into the environment after being treated by defogging and reheating processes; the humidity of the flue gas is controlled in a certain range through a humidity regulating device to ensure the activity of the catalyst, and the oxidized product after deep condensation is subjected to subsequent processes such as precipitation, concentration, enrichment and the like to realize the recycling of pollutants, so that the recycled working medium after the deep condensation process is used for carrying out reheat treatment on the purified flue gas to realize the whitening of the flue gas; the invention can not only deeply remove NO after fossil fuel combustion X ，SO 2 And Hg, can also realize the resource utilization of the treated pollutants, and achieve the purpose of eliminating 'smoke plume', and finally realize the ultra-clean emission of the smoke.
Description
Technical Field
The invention belongs to the technical field of nitrogen, sulfur oxide and heavy metal mercury environmental pollution treatment, and particularly relates to a semi-dry desulfurization, denitrification and mercury removal device and method based on catalytic oxidation and deep condensation.
Background
Atmospheric pollution is a serious problem that endangers human living environment, SO discharged by coal-fired power plants 2 、NO X And Hg of 0 Significant harm to human health and ecological environment; wherein SO2 is the main cause of acid rain, NOx can generate photochemical smog, destroy ozone layer and generate greenhouse effect, and elemental mercury (Hg) 0 ) Strong toxicity, stable form and difficult biodegradation. The most mature methods for three pollutant removal at present are wet desulfurization, SCR denitration and activated carbon injection mercury removal technologies respectively. However, the method for removing a single contaminant using a single apparatus has major problems: (1) the synergistic effect between the devices is not fully considered; (2) Under the condition of achieving the same efficiency, the system investment and the operation cost are larger; (3) it is difficult to meet the requirement of "ultra clean emissions". Therefore, to economically and efficiently remove the pollutants in the flue gas of the coal-fired power plant, the synergistic effect among the pollutant removing devices of the flue gas must be fully utilized from the perspective of the whole flue gas treatment system. In the existing integrated removal process, the traditional wet flue gas pollutant integrated removal technology has the problems of high investment and operation cost, large occupied area, large water consumption, easiness in secondary pollution generation, oxidant leakage and the like although the traditional wet flue gas pollutant integrated removal technology has higher removal efficiency, and the flue gas whitening device is additionally arranged to prevent the phenomenon of 'smoke plume', so that the initial investment cost of a power plant is increased. The traditional integrated removal technology for the dry flue gas pollutants overcomes the technical problems of low removal efficiency, incapability of comprehensively utilizing byproducts, expensive adsorption, reduced adsorption performance and the like of the wet flue gas pollutants, and brings certain difficulty to popularization and application of the integrated removal technology. The semi-dry integrated desulfurization, denitration and demercuration technology has the advantages of high reaction speed and high removal efficiency of the wet integrated pollutant removal technology, and has the advantages of no sewage and waste acid discharge by a dry method and easy treatment of products after pollutant removal, so that the semi-dry integrated desulfurization, denitration and demercuration technology is widely paid attention to.
Disclosure of Invention
In order to overcome the problems of the prior art, the object of the present inventionThe device and the method for semi-dry desulfurization, denitrification and demercuration based on catalytic oxidation and deep condensation are provided, the temperature range almost accords with the smoke exhaust level of all power plants, and NO in the smoke after dust removal can be removed x 、SO 2 And heavy metal mercury and the like are subjected to deep oxidation and removal, ultra-clean discharge is realized, the collected waste liquid can be recycled, and a traditional smoke abatement feather device is omitted.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
semi-dry desulfurization denitration demercuration device based on catalytic oxidation and degree of depth condensation, including reaction tower 2, its characterized in that: the middle part of the reaction tower 2 is provided with a multistage condensation heat exchanger 9, and condensate on the surface of the multistage condensation heat exchanger directly falls into a condensate recovery device 19 to enter subsequent treatment; the top of the reaction tower 2 is provided with a flue gas inlet communicated with the dust remover 1, and the flue gas treated by the dust remover 1 is sent into the reaction tower 2 through the flue gas inlet; a grating 7 and a catalyst unit 8 are arranged between a flue gas inlet at the top and a condensing heat exchanger 9 in sequence, the grating 7 is communicated with a humidifying device 3 through a first upper opening 18 at one side of the upper part of the reaction tower 2, the grating 7 is communicated with an oxidant preparation and storage device 4 through a second upper opening 17 at the other side of the upper part of the reaction tower 2, a flow meter 5 and a conveying pump 6 are arranged on a pipeline communicated with the oxidant preparation and storage device 4, and when the flue gas humidity is low, the humidifying device 3 sends water into the grating 7 through the first upper opening 18 of the reaction tower to increase the flue gas humidity; the oxidant prepared in the oxidant preparation and storage device 4 is fed into the grid 7 from the second upper opening 17 of the reaction tower to be mixed with the flue gas sequentially through the flowmeter 5 and the delivery pump 6; the bottom of the reaction tower 2 is provided with a condensate recovery device 19, and the condensate recovery device 19 is directly communicated with the acid liquid separation treatment device 10 through a pipeline; a demister 11 and a multi-stage flue gas reheater 12 are sequentially arranged in a flue gas pipeline at the bottom of the reaction tower 2, condensate obtained by the demister 11 is also sent into an acid liquid separation treatment device 10 for treatment, and a flue gas outlet of the final-stage flue gas reheater is communicated with a chimney 16 through a pipeline and an induced draft fan 15; the number of the multi-stage flue gas reheaters 12 is the same as that of the multi-stage condensation heat exchangers 9, and the inlet and outlet of each stage of condensation heat exchanger are respectively communicated with the inlet and outlet of the corresponding flue gas reheater to provide heat for the corresponding flue gas reheater.
The heat exchange element of the multistage condensation heat exchanger 9 adopts a tubular or tube plate type heat exchanger, the heat exchange element adopts 2205/2507 duplex stainless steel material or fluoroplastic, or polytetrafluoroethylene, enamel coating and Cr are laid on the outer side of the heat exchange element 2 O 3 Or TiO 2 The corrosion-resistant material can prevent the outer surface of the multistage condensing heat exchanger 9 from being corroded by condensed acid liquor, and the inner side material of the heat exchange element adopts carbon steel with strong heat conductivity coefficient to enhance heat exchange.
The multistage condensation heat exchanger 9 is used for ensuring complete condensation of oxidation products in the flue gas, the first stage condensation heat exchanger is mainly used for recovering sensible heat of the flue gas, the subsequent stages condensation heat exchangers are respectively used for condensing and recovering different gaseous acid vapors with acid dew points reduced in sequence, and the temperature level of the flue gas is 25-35 ℃ after the flue gas passes through the multistage condensation heat exchanger.
The multistage condensation heat exchanger 9 takes cooling water as a first stage condensation working medium, is convenient to obtain and has lower cost; the subsequent condensation working medium of each stage uses liquid metal, ammonia water or lithium bromide phase change medium, and the temperature is reduced step by step for condensation so as to ensure the sufficient condensation of gaseous acid vapor in the flue gas.
The oxidant used in the oxidant preparation and storage device 4 is ozone or hydrogen peroxide vapor, wherein the molar ratio of the oxidant to pollutants in the flue gas is 0.8-1.1: 1.
the catalyst in the catalyst unit 8 is selected from alpha-MnO 2 The composite transition metal oxide is an active ingredient, and the loading concentration of the composite transition metal oxide is 10-20%.
The composite transition metal oxide is manganese titanium oxide, manganese cerium oxide or manganese vanadium oxide.
The oxidant preparation and storage device 4, the mixing area of the oxidant and the flue gas in the reaction tower 2 and the connecting pipeline between the oxidant preparation and storage device and the mixing area are coated with polytetrafluoroethylene or ceramic inert materials for preventing ineffective decomposition of the oxidant and equipment corrosion.
The catalyst unit 8 is honeycomb-shaped.
Said catalyst-basedThe method for desulfurizing, denitrating and demercurating by using semi-dry desulfurizing, denitrating and demercurating device with chemical oxidation and deep condensation includes such steps as precisely metering oxidant in oxidant preparing and storing device 4 by flowmeter 5, feeding the oxidant into grille 7 from the second upper opening 17 of reaction tower by conveying pump 6, mixing with flue gas treated by dust collector 1, reacting the mixed gas with catalyst unit 8 at 110-160 deg.C, and removing NO in flue gas X 、SO 2 And Hg of 0 Conversion to HNO by catalytic oxidation 3 、H 2 SO 4 HgO; in order to ensure the catalytic activity of the catalyst, the humidity of the flue gas before entering the catalyst unit 8 is controlled within a range of 10-15% by the humidifying device 3; the oxidation products in the flue gas are converted into liquid products by steam through deep condensation after passing through the multistage condensation heat exchanger 9, and then the acid products in the flue gas are completely condensed and removed through the demister 11; the condensed products in the multistage condensing heat exchanger 9 and the demister 11 are sent into an acid liquid separation treatment device 10 to be subjected to sedimentation, concentration and enrichment treatment, so as to be recycled; the purified flue gas is heated by a multi-stage flue gas reheater 12 and then is conveyed by a draught fan 15 and discharged into the atmosphere by a chimney 16; the multistage flue gas reheater 12 heats purified flue gas to 45 ℃ by using the recovered waste heat in the deep condensation process, thereby achieving the purpose of eliminating 'smoke plume'.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts a semi-dry process of catalytic oxidation and deep condensation, and utilizes the property that the acid dew points of different acids are different to enable gaseous acid vapor generated by catalytic oxidation to be deeply condensed and recovered on the surfaces of all stages of condensation heat exchangers, thereby achieving the purpose of removing flue gas pollutants. The process route can deeply remove nitrogen, sulfur oxide and mercury after the combustion of fossil fuel, and realize ultra-clean emission.
2. The sensible heat of the flue gas and the latent heat of the gaseous acid vapor recovered when the multistage condensing heat exchanger condenses the gaseous acid vapor are used for a flue gas reheating system, so that the flue gas is reheated to 45 ℃, the flue gas discharging standard of related industries is met, the energy is optimally utilized in a heat complementation mode, and the aim of eliminating 'smoke plume' is fulfilled.
3. In the invention, the condensate product recovered by the multistage condensing heat exchanger and the demister is finally sent into an acid liquid separation treatment device to be separated and recovered by processes such as precipitation, concentration, enrichment and the like, so that the recycling of pollutants is realized.
4. The catalyst used in the invention is alpha-MnO 2 Composite transition metal oxides such as manganese titanium oxide, manganese cerium oxide or manganese vanadium oxide as active ingredients. alpha-MnO 2 alpha-MnO in a composite transition metal oxide as an active ingredient 2 The loading concentration of (2) is 10-20%. The oxidant and the catalyst used in the invention have the advantages of low catalytic temperature level, high pollutant removal efficiency, reasonable process design, environmental protection, no toxicity, low manufacturing cost and stable product quality.
Drawings
FIG. 1 is a schematic diagram of a semi-dry desulfurization, denitrification and demercuration device and method based on catalytic oxidation and deep condensation.
In the figure: 1-a dust remover; 2-a reaction tower; 3-a humidity control device; 4-oxidant preparation and storage device; 5-a flow meter; 6-a delivery pump; 7-grating; an 8-catalyst unit; 9-a multistage condensing heat exchanger; 10-an acid liquor separation treatment device; 11-a demister; 12-a multi-stage flue gas reheater; 13-a first condensing working medium pump; 14-a second condensing working medium pump; 15-induced draft fan; 16-chimney; 17-a second upper opening of the reaction column; 18-a first upper opening of the reaction column; 19-condensate recovery apparatus.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
As shown in fig. 1, the semi-dry desulfurization, denitrification and demercuration device based on catalytic oxidation and deep condensation comprises a reaction tower 2, and is characterized in that: the middle part of the reaction tower 2 is provided with a multistage condensation heat exchanger 9, and condensate on the surface of the multistage condensation heat exchanger directly falls into a condensate recovery device 19 to enter subsequent treatment; the top of the reaction tower 2 is provided with a flue gas inlet communicated with the dust remover 1, and the flue gas treated by the dust remover 1 is sent into the reaction tower 2 through the flue gas inlet; a grating 7 and a catalyst unit 8 are arranged between a flue gas inlet at the top and a condensing heat exchanger 9 in sequence, the grating 7 is communicated with a humidifying device 3 through a first upper opening 18 at one side of the upper part of the reaction tower 2, the grating 7 is communicated with an oxidant preparation and storage device 4 through a second upper opening 17 at the other side of the upper part of the reaction tower 2, a flow meter 5 and a conveying pump 6 are arranged on a pipeline communicated with the oxidant preparation and storage device 4, and when the flue gas humidity is low, the humidifying device 3 sends water into the grating 7 through the first upper opening 18 of the reaction tower to increase the flue gas humidity; the oxidant prepared in the oxidant preparation and storage device 4 is fed into the grid 7 from the second upper opening 17 of the reaction tower to be mixed with the flue gas sequentially through the flowmeter 5 and the delivery pump 6; the bottom of the reaction tower 2 is provided with a condensate recovery device 19, and the condensate recovery device 19 is directly communicated with the acid liquid separation treatment device 10 through a pipeline; a demister 11 and a multi-stage flue gas reheater 12 are sequentially arranged in a flue gas pipeline at the bottom of the reaction tower 2, condensate obtained by the demister 11 is also sent into an acid liquid separation treatment device 10 for treatment, and a flue gas outlet of the final-stage flue gas reheater is communicated with a chimney 16 through a pipeline and an induced draft fan 15; the number of the multi-stage flue gas reheaters 12 is the same as that of the multi-stage condensation heat exchangers 9, and the inlet and outlet of each stage of condensation heat exchanger are respectively communicated with the inlet and outlet of the corresponding flue gas reheater to provide heat for the corresponding flue gas reheater.
The method for desulfurizing, denitrifying and demercurating based on the semi-dry desulfurization, denitrification and demercuration device of catalytic oxidation and deep condensation comprises the following steps:
the oxidant in the oxidant preparation and storage device 4 is accurately metered by the flowmeter 5, is sent into the grating 7 from the second upper opening 17 of the reaction tower through the delivery pump 6, is mixed with the flue gas treated by the dust remover 1, and the mixed gas is reacted by the catalyst unit 8, wherein the reaction temperature is 110-160 ℃, and NO in the flue gas X 、SO 2 And Hg of 0 Conversion to HNO by catalytic oxidation 3 、H 2 SO 4 HgO; in order to ensure the catalytic activity of the catalyst, the humidity of the flue gas before entering the catalyst unit 8 is controlled within a range of 10-15% by the humidifying device 3; oxidation product in flue gas after passing through multistage condensing heat exchanger 9The substances are converted into liquid products from steam in a deep condensation mode, and then the liquid products are completely condensed and removed from the flue gas through a demister 11; the condensed products in the multistage condensing heat exchanger 9 and the demister 11 are sent into an acid liquid separation treatment device 10 to be subjected to sedimentation, concentration and enrichment treatment, so as to be recycled; the purified flue gas is heated by a multi-stage flue gas reheater 12, and then is conveyed by a draught fan 15 and discharged into the atmosphere through a chimney 16.
Example 1:
the oxidant in the oxidant preparation and storage device 4 is accurately metered by the flowmeter 5, enters the reaction tower 2 through the delivery pump 6, the oxidant is mixed with the flue gas treated by the dust remover 1 after passing through the grid 7, the mixed gas reacts through the (honeycomb) catalyst unit 8, and NO in the flue gas X 、SO 2 And Hg of 0 The concentrations are 300mg/m respectively 3 Concentration is 2000mg/m 3 And Hg concentration 20g/m 3 The flue gas inlet temperature is 140 ℃, the mole ratio of oxidant to pollutant is 0.9:1, and the catalyst is manganese cerium composite oxide, wherein alpha-MnO 2 Is 15%; in order to ensure the catalytic activity of the catalyst, the humidity of the flue gas before entering the catalyst unit 8 is controlled to 12% by the humidifying device 3; the oxidation products in the flue gas are converted into liquid products by steam through deep condensation after passing through the multistage condensation heat exchanger 9, and then the acid products in the flue gas are completely condensed and removed through the demister 11; the condensation products in the multistage condensation heat exchanger 9 and the demister 11 are recycled through processes of precipitation, concentration, enrichment and the like, wherein the condensation working medium is respectively water and liquid metal Ga 68 In 20 Sn 12 The method comprises the steps of carrying out a first treatment on the surface of the The purified flue gas is heated by a multi-stage flue gas reheater 12, and then is conveyed by a draught fan 15 and discharged into the atmosphere through a chimney 16. The desulfurization efficiency of the process is 99.2%, the denitration efficiency is 95.8% and the mercury removal efficiency is 100% by detecting the pollutant concentration before and after the treatment process.
Example 2:
the oxidant in the oxidant preparation and storage device 4 is accurately metered by the flowmeter 5, enters the reaction tower 2 through the delivery pump 6, and is treated by the dust remover 1 after passing through the grid 7Mixing the obtained flue gas, reacting the mixed gas with (honeycomb) catalyst unit 8, and collecting NO in the flue gas X 、SO 2 And Hg of 0 The concentrations are respectively 350mg/m 3 Concentration 1900mg/m 3 And Hg concentration 20g/m 3 The flue gas inlet temperature is 130 ℃, the mole ratio of the oxidant to the pollutant is 1:1, and the catalyst is manganese-titanium composite oxide, wherein alpha-MnO 2 Is 15%; in order to ensure the catalytic activity of the catalyst, the humidity of the flue gas before entering the catalyst unit 8 is controlled to 10% by the humidifying device 3; the oxidation products in the flue gas are converted into liquid products by steam through deep condensation after passing through the multistage condensation heat exchanger 9, and then the acid products in the flue gas are completely condensed and removed through the demister 11; the condensed products in the multistage condensing heat exchanger 9 and the demister 11 are recycled through technologies such as precipitation, concentration and enrichment, wherein the condensed working medium is respectively selected from water and lithium bromide; the purified flue gas is heated by a multi-stage flue gas reheater 12, and then is conveyed by a draught fan 15 and discharged into the atmosphere through a chimney 16. The desulfurization efficiency of the process is 98.2%, the denitration efficiency is 93.2% and the mercury removal efficiency is 100% by detecting the pollutant concentration before and after the treatment process.
Claims (9)
1. The method for carrying out desulfurization, denitrification and demercuration by using the semi-dry desulfurization, denitrification and demercuration device based on catalytic oxidation and deep condensation comprises a reaction tower (2), and is characterized in that: the oxidant in the oxidant preparation and storage device (4) is accurately metered by a flowmeter (5), is sent into a grid (7) from a second upper opening (17) of the reaction tower through a delivery pump (6), is mixed with the flue gas treated by the dust remover (1), the mixed gas is reacted by a catalyst unit (8), the reaction temperature is 110-160 ℃, and NOX, SO2 and Hg0 in the flue gas are converted into HNO3, H2SO4 and HgO through a catalytic oxidation process; in order to ensure the catalytic activity of the catalyst, the humidity of the flue gas before entering the catalyst unit (8) is controlled to be within a range of 10-15% by a humidifying device (3); the oxidation products in the flue gas are converted into liquid products by steam through deep condensation after passing through the multistage condensation heat exchanger (9), and then the acid products in the flue gas are completely condensed and removed through the demister (11); the condensed products in the multistage condensing heat exchanger (9) and the demister (11) are sent into an acid liquid separation treatment device (10) to be subjected to sedimentation, concentration and enrichment treatment, so that recycling is realized; the purified flue gas is heated by a multi-stage flue gas reheater (12), and then is conveyed by a draught fan (15) and discharged into the atmosphere by a chimney (16); the multistage flue gas reheater (12) is used for heating purified flue gas to 45 ℃ by recycling waste heat in the deep condensation process, so that the aim of eliminating 'smoke plume' is fulfilled;
a multistage condensation heat exchanger (9) is arranged in the middle of the reaction tower (2), and condensate on the surface of the multistage condensation heat exchanger directly falls into a condensate recovery device (19) to enter subsequent treatment; a flue gas inlet communicated with the dust remover (1) is arranged at the top of the reaction tower (2), and the flue gas treated by the dust remover (1) is sent into the reaction tower (2) through the flue gas inlet; a grid (7) and a catalyst unit (8) are arranged between a flue gas inlet at the top and a condensing heat exchanger (9) in sequence, the grid (7) is communicated with a humidifying device (3) through a first upper opening (18) at one side of the upper part of a reaction tower (2), the grid (7) is communicated with an oxidant preparation and storage device (4) through a second upper opening (17) at the other side of the upper part of the reaction tower (2), a flow meter (5) and a conveying pump (6) are arranged on a pipeline communicated with the oxidant preparation and storage device (4), and when the flue gas humidity is low, the humidifying device (3) sends water into the grid (7) through the first upper opening (18) of the reaction tower to increase the flue gas humidity; the oxidant prepared in the oxidant preparation and storage device (4) is fed into the grid (7) from the second upper opening (17) of the reaction tower to be mixed with the flue gas sequentially through the flowmeter (5) and the delivery pump (6); the bottom of the reaction tower (2) is provided with a condensate recovery device (19), and the condensate recovery device (19) is directly communicated with the acid liquid separation treatment device (10) through a pipeline; a demister (11) and a multi-stage flue gas reheater (12) are sequentially arranged in a flue gas pipeline at the bottom of the reaction tower (2), condensate obtained by the demister (11) is also sent into an acid liquid separation treatment device (10) for treatment, and a flue gas outlet of the final-stage flue gas reheater is communicated with a chimney (16) through a pipeline and an induced draft fan (15); the number of the multi-stage flue gas reheaters (12) is the same as that of the multi-stage condensation heat exchangers (9), and the inlet and outlet of each stage of condensation heat exchanger are respectively communicated with the inlet and outlet of the corresponding flue gas reheater to provide heat for the corresponding flue gas reheater.
2. The method for desulfurization, denitrification and demercuration by using the semi-dry desulfurization, denitrification and demercuration device based on catalytic oxidation and deep condensation according to claim 1, which is characterized in that: the heat exchange element of the multistage condensation heat exchanger (9) adopts a tubular or tube plate type heat exchanger, the heat exchange element adopts 2205/2507 duplex stainless steel material or fluoroplastic, or polytetrafluoroethylene, enamel coating, cr2O3 or TiO2 corrosion-resistant material is laid on the outer side of the heat exchange element, the outer surface of the multistage condensation heat exchanger (9) is prevented from being corroded by condensed acid liquor, and the inner side of the heat exchange element adopts carbon steel with strong heat conductivity coefficient, so that heat exchange is enhanced.
3. The method for desulfurization, denitrification and demercuration by using the semi-dry desulfurization, denitrification and demercuration device based on catalytic oxidation and deep condensation according to claim 1, which is characterized in that: the multistage condensation heat exchanger (9) is used for ensuring complete condensation of oxidation products in the flue gas, the first stage condensation heat exchanger is mainly used for recovering sensible heat of the flue gas, the subsequent stages of condensation heat exchangers are respectively used for condensing and recovering different gaseous acid vapors with acid dew points reduced in sequence, and the temperature level of the flue gas is 25-35 ℃ after the flue gas passes through the multistage condensation heat exchanger.
4. The method for desulfurization, denitrification and demercuration by using the semi-dry desulfurization, denitrification and demercuration device based on catalytic oxidation and deep condensation according to claim 1, which is characterized in that: the multistage condensation heat exchanger (9) takes cooling water as a first stage condensation working medium, is convenient to obtain and has lower cost; the subsequent condensation working medium of each stage uses liquid metal, ammonia water or lithium bromide phase change medium, and the temperature is reduced step by step for condensation so as to ensure the sufficient condensation of gaseous acid vapor in the flue gas.
5. The method for desulfurization, denitrification and demercuration by using the semi-dry desulfurization, denitrification and demercuration device based on catalytic oxidation and deep condensation according to claim 1, which is characterized in that: the oxidant used in the oxidant preparation and storage device (4) is ozone or hydrogen peroxide vapor, wherein the mole ratio of the oxidant to pollutants in the flue gas is (0.8-1.1): 1.
6. the method for desulfurization, denitrification and demercuration by using the semi-dry desulfurization, denitrification and demercuration device based on catalytic oxidation and deep condensation according to claim 1, which is characterized in that: the catalyst in the catalyst unit (8) is selected from composite transition metal oxide with alpha-MnO 2 as an active component, and the loading concentration of the composite transition metal oxide is 10-20%.
7. The method for desulfurization, denitrification and demercuration based on the semi-dry desulfurization, denitrification and demercuration device of catalytic oxidation and deep condensation of claim 6, which is characterized in that: the composite transition metal oxide is manganese titanium oxide, manganese cerium oxide or manganese vanadium oxide.
8. The method for desulfurization, denitrification and demercuration by using the semi-dry desulfurization, denitrification and demercuration device based on catalytic oxidation and deep condensation according to claim 1, which is characterized in that: the oxidant preparation and storage device (4), the mixing area of the oxidant and the flue gas in the reaction tower (2) and the connecting pipeline between the oxidant preparation and storage device and the mixing area are coated with polytetrafluoroethylene or ceramic inert materials for preventing ineffective decomposition of the oxidant and equipment corrosion.
9. The method for desulfurization, denitrification and demercuration by using the semi-dry desulfurization, denitrification and demercuration device based on catalytic oxidation and deep condensation according to claim 1, which is characterized in that: the catalyst unit (8) is honeycomb-shaped.
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