CN107497298B - Low-temperature multi-pollutant comprehensive purification system and method for flue gas dry ammonia process of coal-fired power plant - Google Patents
Low-temperature multi-pollutant comprehensive purification system and method for flue gas dry ammonia process of coal-fired power plant Download PDFInfo
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- CN107497298B CN107497298B CN201710976801.5A CN201710976801A CN107497298B CN 107497298 B CN107497298 B CN 107497298B CN 201710976801 A CN201710976801 A CN 201710976801A CN 107497298 B CN107497298 B CN 107497298B
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 176
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000003546 flue gas Substances 0.000 title claims abstract description 109
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 17
- 230000008569 process Effects 0.000 title claims description 9
- 238000000746 purification Methods 0.000 title claims description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 161
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 111
- 230000023556 desulfurization Effects 0.000 claims abstract description 111
- 238000006243 chemical reaction Methods 0.000 claims abstract description 88
- 238000011069 regeneration method Methods 0.000 claims abstract description 46
- 230000008929 regeneration Effects 0.000 claims abstract description 45
- 238000005507 spraying Methods 0.000 claims abstract description 45
- 239000002131 composite material Substances 0.000 claims abstract description 13
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 32
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 25
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000003860 storage Methods 0.000 claims description 11
- 239000000428 dust Substances 0.000 claims description 10
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 238000006479 redox reaction Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003139 buffering effect Effects 0.000 claims 3
- 238000004064 recycling Methods 0.000 claims 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 12
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 12
- 235000011130 ammonium sulphate Nutrition 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 7
- 229910052878 cordierite Inorganic materials 0.000 description 6
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 239000000779 smoke Substances 0.000 description 5
- 230000001502 supplementing effect Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000012719 wet electrostatic precipitator Substances 0.000 description 2
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009423 ventilation Methods 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
- B01D53/90—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
- B01D53/34—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
- B01D53/88—Handling or mounting catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- 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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- 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)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a system and a method for comprehensively purifying low-temperature multi-pollutants by a dry ammonia method of flue gas of a coal-fired power plant, wherein the system comprises a secondary composite reactor, an ammonia spraying device, a catalyst conveying device, a regeneration tower and a catalyst return conveying device; the secondary composite reactor comprises a desulfurization reaction cavity and a denitration reaction cavity; the desulfurization reaction cavity is provided with a catalyst inlet, a catalyst outlet, a flue gas inlet and an ammonia gas inlet; an ammonia gas inlet and a clean flue gas outlet are arranged in the denitration reaction cavity; the ammonia spraying device comprises a first ammonia spraying pipe and a second ammonia spraying pipe, the first ammonia spraying pipe is communicated with an ammonia inlet of the desulfurization reaction cavity, and the second ammonia spraying pipe is communicated with an ammonia inlet of the denitration reaction cavity; the inlet of the regeneration tower is arranged at the discharge end of the catalyst conveying device; the outlet of the regeneration tower is arranged above the catalyst return conveying device, and the discharge end of the catalyst return conveying device is communicated with the catalyst inlet of the desulfurization reaction cavity. The system and the method can realize higher desulfurization and denitrification performance.
Description
Technical Field
The invention belongs to the field of air pollution control, and relates to a system and a method for comprehensively purifying low-temperature multi-pollutants by a dry ammonia method of flue gas of a coal-fired power plant.
Background
The proportion of coal to primary energy production and consumption in China is always above 70%, and NOx and SO are produced in the combustion process 2 、SO 3 Etc. are the main pollutants in the flue gas. Strictly controlling NOx and SO of coal-fired power plant 2 、SO 3 The emission of the atmospheric pollutants is not only the national demand of social and economic development, but also the green, harmonious and sustainable industry demand of the electric power industry.
The emission standard of atmospheric pollutants in thermal power plants (GB 13223-2011) prescribes smoke dust and SO in the flue gas of the coal-fired power plants 2 NOx emissionsConcentration limits of 30mg/Nm respectively 3 、100mg/Nm 3 、100mg/Nm 3 The office of the national environmental protection department issues a comprehensive implementation of the working scheme for ultra-low emission and energy-saving transformation of coal-fired power plants on the 12 th month 11 2015, and all coal-fired power plants with transformation conditions nationwide are required to strive for realizing ultra-low emission before 2020, namely smoke dust and SO in flue gas 2 The NOx emission concentration limits were 10mg/Nm, respectively 3 、35mg/Nm 3 、50mg/Nm 3 And stricter environmental protection emission requirements are provided for coal-fired power plants. In recent years, the technology of ultralow emission reformation of a coal-fired thermal power unit is basically based on the original technology of treatment of single pollutants, namely, the emission of various pollutants such as sulfur dioxide, nitrogen oxides, smoke dust and the like generated by a coal-fired power station is mainly controlled by adopting a terminal treatment method, namely, denitration, dust removal and desulfurization facilities are arranged at the tail part of combustion equipment in series, the reformation and synergy are carried out on the basis of the series facilities along with the gradual strict environmental protection requirement, the system is increasingly complex, the flue resistance is increased along with the increase of the ventilation energy consumption of the flue, in addition, the equipment investment, the occupied area and the operation cost are also greatly increased along with the increase of the flue, and the complexity of the system also causes the operation of environmental protection equipment to influence the operation of other equipment (such as the ammonia escape caused by an SCR system can increase the blocking risk of downstream equipment such as an economizer) to increasingly present inconveniently. Therefore, the research and development of the emerging comprehensive control technology for various pollutants of the coal-fired power plant is not only the requirement of resource-saving and environment-friendly social construction, but also the requirement of green harmony sustainable development of the power industry.
Patent 201310415859.4 proposes a low-temperature SCR catalyst capable of adsorbing and removing sulfur dioxide in flue gas and catalytically removing nitrogen oxides in flue gas, and patent 201420240959.8 proposes a reactor which can be applied to industrial practice, but because the catalytic activity of the catalyst is low, the reactor bed is dense, a certain thickness is required, the pressure loss of the system is increased, and the application range of the method is limited. The patent 201010606894 and 201010611242.6 propose a preparation method of a low-temperature SCR catalyst with higher activity, and the patent 201110434570.8 further proposes a honeycomb low-temperature SCR catalyst prepared industrially, but the catalyst is deactivated faster when the sulfur dioxide concentration is higher, so that the application and popularization of the catalyst under the flue gas condition of a thermal power plant are limited.
The application scheme is provided, which is an urgent problem to be solved at present, and has relatively low flue gas pressure loss and high comprehensive removal capability of sulfur dioxide and nitrogen oxides.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a system and a method for comprehensively purifying low-temperature multi-pollutants in a dry ammonia method by using flue gas of a coal-fired power plant SO as to effectively control NOx and SO in the flue gas 2 、SO 3 And the like.
The above purpose is achieved by the following technical scheme:
the low-temperature multi-pollutant comprehensive purification system for the flue gas dry ammonia method of the coal-fired power plant comprises a secondary composite reactor, an ammonia spraying device, a catalyst conveying device, a regeneration tower and a catalyst return conveying device;
the secondary composite reactor comprises a desulfurization reaction cavity and a denitration reaction cavity which are vertically arranged side by side, and the tops of the desulfurization reaction cavity and the denitration reaction cavity are communicated; the inner wall of the desulfurization reaction cavity is provided with a guide plate which is arranged obliquely downwards, one side of the upper part is provided with a catalyst inlet, the bottom is provided with a catalyst outlet, the catalyst outlet is provided with a vibrating screen, a discharge hole of the vibrating screen is arranged above the catalyst conveying device, and one side of the lower part is provided with a flue gas inlet and an ammonia gas inlet; a bracket or a sieve plate for placing an SCR denitration catalyst is arranged in the denitration reaction cavity, an ammonia gas inlet is formed in one side of the upper part, and a clean flue gas outlet is formed in one side of the lower part; the flue gas purifying and guiding unit comprises a guiding nozzle arranged on the side wall of the desulfurization reaction cavity and communicated with the desulfurization reaction cavity, a guiding pipeline for connecting the guiding nozzle and a flue gas purifying outlet and a guiding fan arranged on the guiding pipeline; the clean flue gas flow guiding unit guides the clean flue gas with lower temperature to the desulfurization reaction cavity, can obviously improve the condensation adsorption quantity and adsorption efficiency of ammonium sulfate and ammonium bisulfate on the surface of the desulfurization catalyst, and effectively improves the flue gas desulfurization effect on the premise of a certain dosage of the desulfurization catalyst.
The ammonia spraying device comprises a first ammonia spraying pipe and a second ammonia spraying pipe, one ends of the first ammonia spraying pipe and the second ammonia spraying pipe are communicated with an ammonia air mixed gas source through ammonia spraying pipelines, the other end of the first ammonia spraying pipe is communicated with an ammonia inlet of the desulfurization reaction cavity, and the other end of the second ammonia spraying pipe is communicated with an ammonia inlet of the denitration reaction cavity;
the regeneration tower is a desulfurization catalyst regeneration tower, and an inlet of the regeneration tower is arranged at the discharge end of the catalyst conveying device; the outlet of the regeneration tower is arranged above the catalyst return conveying device, and the discharge end of the catalyst return conveying device is communicated with the catalyst inlet of the desulfurization reaction cavity;
and a new catalyst feeding device is also arranged, and the outlet of the new catalyst feeding device is communicated with the catalyst conveying device.
The granular desulfurization catalyst and gas in the desulfurization reaction cavity are in split-flow staggered movement, SO that gas-solid contact is improved, and simultaneously, the sprayed ammonia gas and SO are sprayed 2 Ammonium sulfate and ammonium bisulfate are easy to generate in the temperature range of 100-150 ℃, and under the guidance of flue gas sprayed by a flow guide nozzle with relatively low temperature, the ammonium sulfate and the ammonium bisulfate are rapidly coagulated and adsorbed on the surface of a desulfurization catalyst, SO that SO in the flue gas is efficiently removed 2 The method comprises the steps of carrying out a first treatment on the surface of the A low-temperature SCR catalyst is arranged in the denitration reaction cavity, and the low-temperature SCR catalyst is fully utilized to treat low SO 2 And NOx in the flue gas is efficiently removed under the concentration condition.
The desulfurization catalyst can be prepared by coating adsorption materials such as phenolic resin, furan, polyvinyl alcohol and the like on the surface of porous materials such as molecular sieve, mesoporous silicon, cordierite and the like, heating to 700 ℃ in a carbon dioxide protection gas environment and maintaining at 900 ℃ for about 8 hours for activation, or can be prepared by adopting the catalyst described in patent 201310415859.4, wherein when the molecular sieve, mesoporous silicon, cordierite and the like are adopted, the desulfurization reaction cavity only removes sulfur dioxide in flue gas, and when the molecular sieve, the mesoporous silicon, the cordierite and the like are adopted, part of nitrogen oxides are also removed when the sulfur dioxide in the flue gas is removed. The denitration catalyst can be prepared into a honeycomb or granular SCR catalyst according to the preparation method of low-temperature SCR catalysts of patent 201110434570.8 and the like.
Preferably, a buffer storage bin is further arranged between the catalyst return conveying device and the catalyst inlet of the desulfurization reaction cavity, the discharge end of the catalyst return conveying device is arranged above the buffer storage bin, and the discharge end of the buffer storage bin is communicated with the catalyst inlet of the desulfurization reaction cavity.
Preferably, the ammonia spraying pipeline is provided with an ammonia preheater.
Preferably, the upper part of the regeneration tower is provided with a high-temperature steam inlet and a high-temperature steam outlet, the lower part of the regeneration tower is provided with a cooling air inlet and a cooling air outlet, and a nitrogen inlet and a concentrated gas outlet are communicated. The regeneration tower is divided into a high-temperature heating section and a cooling section, the adsorbent loaded with ammonium sulfate and ammonium bisulfate in the high-temperature heating section is heated to 400-500 ℃ under the action of high-temperature steam introduced into a heat exchange tube to volatilize and decompose the ammonium sulfate and the ammonium bisulfate (test data show that NH begins to be released at about 400℃) 3 、SO 2 High NH speed at about 500 DEG C 3 、SO 2 Release of (c) a release of (c); after cooling in the cooling section, the cooling leaves the regeneration tower.
Preferably, the outlet of the regeneration tower is provided with a vibrating screen, and the discharge port of the vibrating screen is arranged above the catalyst return conveying device.
A method for comprehensively purifying low-temperature multi-pollutants by using the system for dry ammonia method of flue gas of a coal-fired power plant comprises the following steps:
(1) The tail flue gas of the coal-fired power plant boiler enters the secondary composite reactor after being treated by a dust remover, the temperature of the flue gas is 100-150 ℃, and the sulfur dioxide content is 1000-2500 mg/Nm 3 Sulfur trioxide content of 1-25 mg/Nm 3 The content of nitrogen oxide is 200-1500 mg/Nm 3 ；
(2) The granular desulfurization catalyst slides downwards along the guide plate from top to bottom in the desulfurization reaction cavity, the flue gas to be treated enters from a flue gas inlet of the desulfurization reaction cavity, meanwhile, the first ammonia spraying pipe sprays ammonia gas, the flue gas is mixed with the ammonia gas, the mixed gas is fully contacted with the desulfurization catalyst, and the flue gas is SO (sulfur dioxide) in the moving process 2 With NH in a mixed gas 3 Is adsorbed on the surface of the desulfurization catalyst; the mixed flue gas enters a denitration reaction cavity and is mixed with ammonia gas sprayed by a second ammonia spraying pipe, the mixed flue gas is fully contacted with a low-temperature SCR catalyst in the denitration reaction cavity, and the flue gasNOx and injected NH 3 Under the catalysis of SCR catalyst, oxidation-reduction reaction is carried out to generate N 2 、H 2 The harmless products of O are discharged through a clean flue gas outlet;
(3) Discharging the adsorption saturated desulfurization catalyst from a catalyst outlet at the bottom of the desulfurization reaction cavity, feeding the desulfurization catalyst into a regeneration tower through a vibrating screen and a catalyst conveying device, maintaining the temperature of the regeneration tower between 300 and 600 ℃, and decomposing ammonium salt adsorbed by the desulfurization catalyst into SO under the protection of nitrogen purging 2 、NH 3 And mixing the concentrated gas, and feeding the concentrated gas into a byproduct recovery system for recovery.
(4) The regenerated desulfurization catalyst is sieved by a vibration sieve to remove powder generated by collision extrusion in the desulfurization process, and the powder is returned to a catalyst inlet of a desulfurization reaction cavity by a catalyst return conveying device.
And supplementing a certain amount of new catalyst into the desulfurization reaction cavity before entering the desulfurization reaction cavity, wherein the supplementing amount is 0.005% -10% of the regeneration amount.
The invention has the beneficial effects that:
the system and the method can realize higher desulfurization and denitrification performance, the sulfur dioxide removal rate is more than 99 percent, the nitrogen oxide removal rate is 70-95 percent, the sulfur trioxide removal rate is more than 90 percent, and the system and the method are suitable for not only new boilers but also the reconstruction of old boilers and have low space requirements on power plants. The system operation stability and the adaptability are improved through the continuous regeneration mode of the desulfurization catalyst, meanwhile, part of ammonium sulfate can be recovered, the method is more economical than other desulfurization and denitration methods at present, and smoke dust in the flue gas is removed by matching a wet electrostatic precipitator at the tail part, so that the flue gas can reach ultralow emission marking, the method is suitable for the current national conditions of China, and the method has wide application prospect.
Drawings
FIG. 1 is a block diagram of a system of the present invention;
in the figure, a 1-two-stage composite reactor (a left side cavity is a desulfurization reaction cavity, a right side cavity is a denitration reaction cavity), a 2-first ammonia injection pipe and a 2' -second ammonia injection pipe; 3-catalyst conveying device, 4-regeneration tower, 5-catalyst return conveying device, 6-buffer storage bin, 7-vibrating screen, 8-new catalyst feeding device, 9-ammonia preheater, 10-concentrated gas exhaust fan and 11-diversion fan.
Detailed Description
The technical scheme of the invention is specifically described below with reference to the accompanying drawings and embodiments.
Example 1:
the system for comprehensively purifying the low-temperature multi-pollutants by using the flue gas dry ammonia method of the coal-fired power plant as shown in fig. 1 comprises a secondary composite reactor 1, an ammonia spraying device, a catalyst conveying device 3, a regeneration tower 4 and a catalyst return conveying device 5;
the secondary composite reactor comprises a desulfurization reaction cavity and a denitration reaction cavity which are vertically arranged side by side, and the tops of the desulfurization reaction cavity and the denitration reaction cavity are communicated; the inner wall of the desulfurization reaction cavity is provided with a guide plate which is obliquely arranged downwards, one side of the upper part is provided with a catalyst inlet, the bottom is provided with a catalyst outlet, the catalyst outlet is provided with a vibrating screen 7, a discharge hole of the vibrating screen is arranged above the catalyst conveying device 3, and one side of the lower part is provided with a flue gas inlet and an ammonia gas inlet; a sieve plate for placing an SCR denitration catalyst is arranged in the denitration reaction cavity, an ammonia gas inlet is formed in one side of the upper part, and a clean flue gas outlet is formed in one side of the lower part; the flue gas purifying and guiding unit comprises a guiding nozzle arranged on the side wall of the desulfurization reaction cavity and communicated with the desulfurization reaction cavity, a guiding pipeline for connecting the guiding nozzle and a flue gas purifying outlet, and a guiding fan 11 arranged on the guiding pipeline;
the ammonia spraying device comprises a first ammonia spraying pipe 2 and a second ammonia spraying pipe 2', one ends of the first ammonia spraying pipe 2 and the second ammonia spraying pipe 2' are communicated with an ammonia air mixing air source through an ammonia spraying pipeline, the other end of the first ammonia spraying pipe 2 is communicated with an ammonia inlet of a desulfurization reaction cavity, the other end of the second ammonia spraying pipe 2' is communicated with an ammonia inlet of a denitration reaction cavity, and an ammonia preheater 9 is arranged on the ammonia spraying pipeline;
the regeneration tower 4 is a desulfurization catalyst regeneration tower, and an inlet of the regeneration tower 4 is arranged at the discharge end of the catalyst conveying device 3; the outlet of the regeneration tower 4 is provided with a vibrating screen, a discharge port of the vibrating screen is arranged above the catalyst return conveying device 5, a buffer storage bin 6 is arranged between the catalyst return conveying device 5 and the catalyst inlet of the desulfurization reaction cavity, a discharge end of the catalyst return conveying device 5 is arranged above the buffer storage bin 6, and a discharge end of the buffer storage bin 6 is communicated with the catalyst inlet of the desulfurization reaction cavity.
The upper part of the regeneration tower is provided with a high-temperature steam inlet and a high-temperature steam outlet, the lower part of the regeneration tower is provided with a cooling air inlet and a cooling air outlet, and the regeneration tower is also communicated with a nitrogen inlet and a concentrated gas outlet. The regeneration tower is divided into a high-temperature heating section and a cooling section, the adsorbent loaded with ammonium sulfate and ammonium bisulfate in the high-temperature heating section is heated to 400-500 ℃ under the action of high-temperature steam introduced into a heat exchange tube to volatilize and decompose the ammonium sulfate and the ammonium bisulfate (test data show that the high-speed NH is achieved at about 500℃) 3 、SO 2 Release of (c) a release of (c); after cooling in the cooling section, the cooling leaves the regeneration tower.
A new catalyst feeding device 8 is also arranged, and the outlet of the new catalyst feeding device 8 is communicated with the catalyst conveying device 3.
The granular desulfurization catalyst and gas in the desulfurization reaction cavity are in split-flow staggered movement, SO that gas-solid contact is improved, and simultaneously, the sprayed ammonia gas and SO are sprayed 2 Ammonium sulfate and ammonium bisulfate are easy to generate in the temperature range of 100-150 ℃, and under the guidance of flue gas sprayed by a flow guide nozzle with relatively low temperature, the ammonium sulfate and the ammonium bisulfate are rapidly coagulated and adsorbed on the surface of a desulfurization catalyst, SO that SO in the flue gas is efficiently removed 2 The method comprises the steps of carrying out a first treatment on the surface of the A low-temperature SCR catalyst is arranged in the denitration reaction cavity, and the low-temperature SCR catalyst is fully utilized to treat low SO 2 And NOx in the flue gas is efficiently removed under the concentration condition.
The desulfurization catalyst can be prepared by coating adsorption materials such as phenolic resin, furan, polyvinyl alcohol and the like on the surfaces of molecular sieve, mesoporous silicon and cordierite, heating to 700 ℃ in a carbon dioxide protection environment and keeping at 900 ℃ for about 8 hours for activation, or can be prepared by adopting the catalyst of patent 201310415859.4, wherein when the molecular sieve, mesoporous silicon and cordierite are adopted, the desulfurization reaction cavity only removes sulfur dioxide in flue gas, and when the molecular sieve, the mesoporous silicon and cordierite are adopted, the desulfurization reaction cavity also removes part of nitrogen oxides when the sulfur dioxide in the flue gas is removed. The denitration catalyst can be prepared into a honeycomb SCR catalyst according to the preparation method of low-temperature SCR catalysts of patent 201110434570.8 and the like.
A method for comprehensively purifying low-temperature multi-pollutants by using the system for dry ammonia method of flue gas of a coal-fired power plant comprises the following steps:
(1) The tail flue gas of the coal-fired power plant boiler enters the secondary composite reactor after being treated by a dust remover, the temperature of the flue gas is 100-150 ℃, and the sulfur dioxide content is 1000-2500 mg/Nm 3 Sulfur trioxide content of 1-25 mg/Nm 3 The content of nitrogen oxide is 200-1500 mg/Nm 3 ；
(2) The granular desulfurization catalyst slides downwards along the guide plate from top to bottom in the desulfurization reaction cavity, the flue gas to be treated enters from a flue gas inlet of the desulfurization reaction cavity, meanwhile, the first ammonia spraying pipe sprays ammonia gas, the flue gas is mixed with the ammonia gas, the mixed gas is fully contacted with the desulfurization catalyst, and the flue gas is SO (sulfur dioxide) in the moving process 2 With NH in a mixed gas 3 Is adsorbed on the surface of the desulfurization catalyst; the mixed flue gas enters a denitration reaction cavity and is mixed with ammonia gas sprayed by a second ammonia spraying pipe, the mixed flue gas is fully contacted with a low-temperature SCR catalyst in the denitration reaction cavity, and NOx in the flue gas is fully contacted with injected NH 3 Under the catalysis of SCR catalyst, oxidation-reduction reaction is carried out to generate N 2 、H 2 The harmless products of O are discharged through a clean flue gas outlet;
(3) Discharging the adsorption saturated desulfurization catalyst from a catalyst outlet at the bottom of the desulfurization reaction cavity, feeding the desulfurization catalyst into a regeneration tower through a vibrating screen and a catalyst conveying device, maintaining the temperature of the regeneration tower between 300 and 600 ℃, and decomposing ammonium salt adsorbed by the desulfurization catalyst into SO under the protection of nitrogen purging 2 、NH 3 And mixing the concentrated gas, and feeding the concentrated gas into a byproduct recovery system for recovery.
(4) The regenerated desulfurization catalyst is sieved by a vibration sieve to remove powder generated by collision extrusion in the desulfurization process, and the powder is returned to a catalyst inlet of a desulfurization reaction cavity by a catalyst return conveying device.
And supplementing a certain amount of new catalyst into the desulfurization reaction cavity before entering the desulfurization reaction cavity, wherein the supplementing amount is 0.005% -10% of the regeneration amount.
Example 2:
120 ten thousand m of flue gas discharged by a boiler of a certain power station 3 And/h, the concentration of sulfur dioxide in the flue gas is 1500mg/Nm 3 Sulfur trioxide content of 15 mg-Nm 3 Nitrogen oxide concentration of 450mg/Nm 3 Total mercury concentration of 25ug/Nm 3 . The designed section of the reactor is 7.5 m multiplied by 5m, the height is 20 m, the granular desulfurization catalyst is prepared according to the method of patent 201310415859.4, the grain diameter is 2.5-10 mm, the circulating total amount is 300 tons, and the honeycomb SCR catalyst adopts the catalyst described in patent 201110434570.8. The specific flow is as follows:
the flue gas from the outlet of the dust remover enters a secondary composite reactor 1, the circulating volume of the granular desulfurization catalyst is about 300 tons, the temperature of the honeycomb SCR catalyst flue gas is 120 ℃, the flue gas is mixed and contacted with ammonia gas from an ammonia preheater 9 through a first ammonia spraying pipe 2, the flue gas enters a desulfurization reaction cavity together, a flow guiding nozzle is arranged in the desulfurization reaction cavity, a certain amount of flue gas is extracted from a clean flue gas outlet, the flue gas is sprayed in the middle part of the desulfurization reaction cavity, the mixing of the flue gas and catalyst particles is guided, and the temperature of the flow guiding flue gas is 1-10 ℃ lower than that of the flue gas due to certain heat loss of a flow guiding flue gas pipeline, SO that SO in the flue gas is reduced by 1-10 DEG C 2 And SO 3 The catalyst is quickly reacted with ammonia gas and oxygen and water in the flue gas under the guidance of guide gas to generate strong-viscosity and adsorptivity ammonium bisulfate, the strong-viscosity and adsorptivity ammonium bisulfate is adsorbed on the surface of a desulfurization catalyst, the catalyst adsorbed with the ammonium bisulfate is discharged from the bottom of a desulfurization reaction cavity and is sent into a regeneration tower 4 by a catalyst conveying device 3 through a vibrating screen 7, and under the heating action of high-temperature steam and under the protection of the introduced nitrogen, ammonium salt is decomposed into SO (sulfur-oxygen) 2 、NH 3 Etc. by the vacuum provided by the concentrate exhaust fan 10 to extract high concentration SO 2 、NH 3 The gas can be used for recovering ammonium sulfate. The regenerated desulfurization catalyst is discharged from the lower part of the regeneration tower 4 after passing through the cooling section, a powdery catalyst discharge system is selected through a vibrating screen 7', the rest catalyst is fed into a buffer storage bin 6 by a catalyst return conveying device 5, the catalyst is buffered and then is fed into a desulfurization reaction cavity, and meanwhile, a certain amount of new adsorbent is supplemented by a new catalyst feeding device 8, and the supplementing amount is 0.05% of the regeneration amount. SO removal 2 And SO 3 The flue gas enters a denitration reaction cavity after passing through a second ammonia spraying pipe 2'; because the flue gas is subjected to primary purification, most of SO in the flue gas 2 And SO 3 The gas which is removed and mixed with the ammonia is justUnder the optimal operation condition of the low-temperature SCR catalyst, NOx and NH are in the denitration reaction cavity 3 Reacting to form N 2 And H 2 The O, low temperature SCR catalyst is honeycomb or plate-shaped, and is divided into two stages, the catalyst efficiently catalyzes and removes NOx in the flue gas, and can adsorb a small amount of residual SO in the flue gas 2 And the denitration efficiency of the system is improved. Operation of the system SO 2 The removal efficiency reaches 98 percent, SO 3 The removal efficiency reaches 95%, the denitration efficiency reaches 90%, and the mercury removal efficiency reaches 85.4%.
In summary, the system and the method can realize higher desulfurization and denitrification performance, are suitable for not only new boilers but also old boilers, and have low space requirements on power plants. The system operation stability and the adaptability are improved through the continuous regeneration mode of the desulfurization catalyst, meanwhile, part of ammonium sulfate can be recovered, the method is more economical than other desulfurization and denitration methods at present, and smoke dust in the flue gas is removed by matching a wet electrostatic precipitator at the tail part, so that the flue gas can reach ultralow emission marking, the method is suitable for the current national conditions of China, and the method has wide application prospect.
The above-described embodiments are only for illustrating the gist of the present invention, but are not intended to limit the scope of the present invention. It will be understood by those skilled in the art that various modifications and equivalent substitutions may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (6)
1. A coal-fired power plant flue gas dry ammonia low temperature multi-pollutant comprehensive purification system is characterized in that: comprises a secondary composite reactor, an ammonia spraying device, a catalyst conveying device, a regeneration tower and a catalyst return conveying device;
the secondary composite reactor comprises a desulfurization reaction cavity and a denitration reaction cavity which are vertically arranged side by side, and the tops of the desulfurization reaction cavity and the denitration reaction cavity are communicated; the inner wall of the desulfurization reaction cavity is provided with a guide plate which is arranged obliquely downwards, one side of the upper part is provided with a catalyst inlet, the bottom is provided with a catalyst outlet, the catalyst outlet is provided with a vibrating screen, a discharge hole of the vibrating screen is arranged above the catalyst conveying device, and one side of the lower part is provided with a flue gas inlet and an ammonia gas inlet; an SCR denitration catalyst is arranged in the denitration reaction cavity, an ammonia gas inlet is formed in one side of the upper part, and a clean flue gas outlet is formed in one side of the lower part; the flue gas purifying and guiding unit comprises a guiding nozzle arranged on the side wall of the desulfurization reaction cavity and communicated with the desulfurization reaction cavity, a guiding pipeline for connecting the guiding nozzle and a flue gas purifying outlet and a guiding fan arranged on the guiding pipeline;
the ammonia spraying device comprises a first ammonia spraying pipe and a second ammonia spraying pipe, one ends of the first ammonia spraying pipe and the second ammonia spraying pipe are communicated with an ammonia air mixed gas source through ammonia spraying pipelines, the other end of the first ammonia spraying pipe is communicated with an ammonia inlet of the desulfurization reaction cavity, and the other end of the second ammonia spraying pipe is communicated with an ammonia inlet of the denitration reaction cavity;
the regeneration tower is a desulfurization catalyst regeneration tower, and an inlet of the regeneration tower is arranged at the discharge end of the catalyst conveying device; the outlet of the regeneration tower is arranged above the catalyst return conveying device, and the discharge end of the catalyst return conveying device is communicated with the catalyst inlet of the desulfurization reaction cavity;
the catalyst conveying device is provided with a catalyst conveying device, and the outlet of the catalyst conveying device is communicated with the catalyst conveying device;
the flue gas is mixed and contacted with ammonia gas from an ammonia gas preheater through a first ammonia spraying pipe, the mixed and contacted flue gas enters a desulfurization reaction cavity, a guide nozzle is arranged in the desulfurization reaction cavity, a certain amount of flue gas is extracted from a clean flue gas outlet and sprayed in the middle of the desulfurization reaction cavity, the flue gas is guided to be mixed with catalyst particles, and because a guide flue gas pipeline is subjected to certain heat loss, the temperature of the guide flue gas is 1-10 ℃ lower than that of the flue gas, and SO in the flue gas is reduced 2 And SO 3 The catalyst reacts with ammonia gas and oxygen and water in the flue gas rapidly under the guidance of the guide gas to generate strong-viscosity and absorptive ammonium bisulfate, the strong-viscosity and absorptive ammonium bisulfate is adsorbed on the surface of a desulfurization catalyst, and the catalyst adsorbed with the ammonium bisulfate is discharged from the bottom of the desulfurization reaction cavity.
2. The system according to claim 1, wherein: and a buffering storage bin is further arranged between the catalyst return conveying device and the catalyst inlet of the desulfurization reaction cavity, the discharge end of the catalyst return conveying device is arranged above the buffering storage bin, and the discharge end of the buffering storage bin is communicated with the catalyst inlet of the desulfurization reaction cavity.
3. The system according to claim 1, wherein: the ammonia spraying pipeline is provided with an ammonia preheater.
4. The system according to claim 1, wherein: the upper part of the regeneration tower is provided with a high-temperature steam inlet and a high-temperature steam outlet, the lower part of the regeneration tower is provided with a cooling air inlet and a cooling air outlet, and the regeneration tower is also communicated with a nitrogen inlet and a concentrated gas outlet.
5. The system according to claim 1, wherein: and a vibrating screen is arranged at the outlet of the regeneration tower, and a discharge hole of the vibrating screen is arranged above the catalyst return conveying device.
6. A method for comprehensively purifying low-temperature multi-pollutants by using the system of any one of claims 1-5 in a dry ammonia process for flue gas of a coal-fired power plant, which is characterized by comprising the following steps:
(1) The tail flue gas of the coal-fired power plant boiler enters the secondary composite reactor after being treated by a dust remover, the temperature of the flue gas is 100-150 ℃, and the sulfur dioxide content is 1000-2500 mg/Nm 3 The sulfur trioxide content is 1-25 mg/Nm 3 The content of nitrogen oxides is 200-1500 mg/Nm 3 ；
(2) The granular desulfurization catalyst slides downwards along the guide plate from top to bottom in the desulfurization reaction cavity, the flue gas to be treated enters from a flue gas inlet of the desulfurization reaction cavity, meanwhile, the first ammonia spraying pipe sprays ammonia gas, the flue gas is mixed with the ammonia gas, the mixed gas is fully contacted with the desulfurization catalyst, and the flue gas is SO (sulfur dioxide) in the moving process 2 With NH in a mixed gas 3 Is adsorbed on the surface of the desulfurization catalyst; the mixed flue gas enters a denitration reaction cavity and is mixed with ammonia gas sprayed by a second ammonia spraying pipe, the mixed flue gas is fully contacted with a low-temperature SCR catalyst in the denitration reaction cavity, and NOx in the flue gas is fully contacted with the ammonia gasInjected NH 3 Under the catalysis of SCR catalyst, oxidation-reduction reaction is carried out to generate N 2 、H 2 The harmless products of O are discharged through a clean flue gas outlet;
(3) Discharging the adsorption saturated desulfurization catalyst from a catalyst outlet at the bottom of the desulfurization reaction cavity, feeding the desulfurization catalyst into a regeneration tower through a vibrating screen and a catalyst conveying device, maintaining the temperature of the regeneration tower between 300 and 600 ℃, and decomposing ammonium salt adsorbed by the desulfurization catalyst into SO under the protection of nitrogen purging 2 、NH 3 Mixing the concentrated gas, and recycling the concentrated gas in a byproduct recycling system;
(4) The regenerated desulfurization catalyst is sieved by a vibration sieve to remove powder generated by collision extrusion in the desulfurization process, and the powder is returned to a catalyst inlet of a desulfurization reaction cavity by a catalyst return conveying device.
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| CN102423616A (en) * | 2011-08-30 | 2012-04-25 | 湖南麓南脱硫脱硝科技有限公司 | Flue gas purification device for middle and small coal-fired boiler |
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