CN107261789A - The ammonia method desulfurizing system and method for a kind of high-sulfur flue gas - Google Patents

The ammonia method desulfurizing system and method for a kind of high-sulfur flue gas Download PDF

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CN107261789A
CN107261789A CN201710451972.6A CN201710451972A CN107261789A CN 107261789 A CN107261789 A CN 107261789A CN 201710451972 A CN201710451972 A CN 201710451972A CN 107261789 A CN107261789 A CN 107261789A
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auxiliary
main
flue gas
absorbing liquid
slurries
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CN107261789B (en
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肖文德
李学刚
娄爱娟
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SHENCHUAN ENVIRONMENT PROTECTION SCIENCE AND TECHNOLOGY Co Ltd SHANGHAI
Shanghai Jiaotong University
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SHENCHUAN ENVIRONMENT PROTECTION SCIENCE AND TECHNOLOGY Co Ltd SHANGHAI
Shanghai Jiaotong University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75—Multi-step processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
    • 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
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/24—Sulfates of ammonium
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Inorganic Chemistry (AREA)
  • Treating Waste Gases (AREA)

Abstract

The present invention relates to a kind of ammonia method desulfurizing system of high-sulfur flue gas and method, using ammonia, technique water and air as raw material, it is characterised in that including three circulatory systems：First circulatory system is cooling condensing crystallizing system (100), oxidative system (200) is absorbed based on second circulatory system, oxidative system (300) is absorbed supplemented by 3rd circulatory system, high-sulfur flue gas sequentially enters the cooling condensing crystallizing system (100), main absorption oxidative system (200) and auxiliary absorption oxidative system (300), process water sequentially enters the auxiliary absorption oxidative system (300), main absorption oxidative system (200) and cooling condensing crystallizing system (100), ammonia and air enter the main absorption oxidative system (200) and auxiliary absorption oxidative system (300) simultaneously.Raw material high-sulfur flue gas is pre-washed by cooling, main desulfurization and auxiliary desulfurization.Compared with prior art, the present invention have the advantages that the flue gas of resistance to high-sulfur, desulfuration efficiency are high, the escaping of ammonia discharged fume and Aerosol Pollution is few, stable and reliable operation.

Description

The ammonia method desulfurizing system and method for a kind of high-sulfur flue gas
Technical field
The invention belongs to chemical industry and environmental technology field, more particularly, to a kind of ammonia method desulfurizing system of high-sulfur flue gas and Method.
Background technology
Power plant or thermal power plant boiler, and steel works sintering machine, or the flue gas that other equipment for using sulfurous fuels are produced In all contain sulfur dioxide, according to the size of sulfur content in fuel, SO in flue gas2Content is in 300-15000mg/Nm3, it is generally less than 2000 claim to turn into middle sulphur flue gas between low-sulfur flue gas, 2000-4000, and 4000 referred above to high-sulfur flue gas.
Flue gas desulfurization is that a key of field of Environment Protection is also widely used technology.But, flue gas desulfurization device is not only It is an environmental protecting device, can also look at as a process units.Using different desulfurization materials, such as lime stone, magnesia And ammonia, gypsum, magnesium sulfate and ammonium sulfate can be respectively obtained, be all can as merchandise sales chemicals.Gypsum can make water The slow setting additive of mud, consumption can be high to 5%, and market consumption is very big, and magnesium sulfate can be as fertiliser containing magnesium, and ammonium sulfate is inherently Chemical fertilizer, also can as composite fertilizer formula, market consumption is very big.Therefore, sulfur content is higher, and desulfurizer can all the more be seen As a process units.
As process units, the higher the better for the value of product.In described flue gas desulfurization technique, in China, due to China Population, grain and chemical fertilizer big country, with abundant ammonia resource, development and promote ammonia-process desulfurization technique have obvious environment, Economy and social effect.But, due to the volatile feature of ammonia, existing ammonia-process desulfurization technique is primarily suitable for low-sulfur flue gas, For middle sulphur, especially high-sulfur flue gas, easily there is the escaping of ammonia and aerosol, and desulfuration efficiency is low and ammonia raw material availability Low the problem of, cause ammonia-process desulfurization technique to be difficult to large-scale promotion application, be especially difficult to enter large-scale thermal power field.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of achievable high-sulfur cigarette The ammonia method desulfurizing system and method for the high-sulfur flue gas that the high-efficiency desulfurization of gas and SO2 recycling are reclaimed.
The purpose of the present invention can be achieved through the following technical solutions：A kind of ammonia method desulfurizing system of high-sulfur flue gas, with Ammonia, technique water and air are raw material, it is characterised in that including three circulatory systems：First circulatory system is cooling concentration knot Crystallographic system is united, and absorbs oxidative system based on second circulatory system, and oxidative system, high-sulfur cigarette are absorbed supplemented by the 3rd circulatory system Gas sequentially enters the cooling condensing crystallizing system, main absorption oxidative system and auxiliary absorption oxidative system, and process water is sequentially entered The auxiliary absorption oxidative system, main absorption oxidative system and cooling condensing crystallizing system, ammonia and air enter the main suction simultaneously Receive oxidative system and auxiliary absorption oxidative system.
Described main absorption oxidative system is included inside columnar main absorber portion and main oxidation panel, the main absorber portion Include and include primary air aerator inside main absorbing liquid spraying layer, the main oxidation panel, the outside of the main oxidation panel and The outside of the main absorber portion is connected by main absorbing liquid circulating line with main absorbing liquid circulating pump, and the main oxidation panel connects It is connected to the input pipe that raw material ammonia is also associated with air inlet duct, the main oxidation panel or the main absorbing liquid circulating line；
The auxiliary absorption oxidative system includes wrapping inside columnar auxiliary absorber portion and auxiliary oxidation panel, the auxiliary absorber portion Included and included auxiliary air aeration device inside auxiliary absorbing liquid spraying layer, the auxiliary oxidation panel, the auxiliary outside for stating oxidation panel and The outside of the auxiliary absorber portion is connected by auxiliary absorbing liquid circulating line with auxiliary absorbing liquid circulating pump, and the auxiliary oxidation panel connects It is connected to the input pipe that raw material ammonia is also associated with air inlet duct, the auxiliary oxidation panel or the auxiliary absorbing liquid circulating line；
The cooling condensing crystallizing system includes the cooling enriching section and crystallizing pond section of cylinder type, the cooling enriching section Inside include slurries spraying layer, the crystallizing pond intersegmental part includes agitator, crystallizing pond section outside and cool it is dense The outside of contracting section is connected by serum recycle pipeline with slurry circulating pump, in the cooling enriching section and crystallizing pond section Between be provided with high-sulfur flue gas import.
In the cooling enriching section, demister is additionally provided with, flushing is provided with above or below the demister Spraying component, and the rinse spray component is connected by liquid line by flushing pump with the main oxidation panel.
Demister is provided with above the main absorbing liquid spraying layer, is set above the auxiliary absorbing liquid spraying layer It is equipped with demister.
Also include sulphur ammonium extract the circulatory system, the sulphur ammonium extraction system include the dense device of slurries, centrifuge, drying machine and Packing machine, the crystallizing pond section is connected by the circulating pump that discharges with the dense device of slurries of the sulphur ammonium extraction system, and the slurries are dense The magma mouthful of close device is connected with the centrifuge, and the solid outlet of the centrifuge is connected with the drying machine, the drying The solid outlet of machine is connected with the packing machine, and the clear liquid mouthful of the dense device of slurries and the mother liquor of the centrifuge discharge Mouth is connected with crystallizing pond section.
Also include electrostatic precipitator, the electrostatic precipitator includes electric discharge cathode line and gather dust anode tube, the anode tube of gathering dust It is made of the fiberglass added with carbon fiber, the electrostatic precipitator is connected between the auxiliary absorption oxidative system and chimney.
A kind of ammonia method desulfurizing method that high-sulfur flue gas is carried out using any of the above-described system, it is characterised in that including with Lower step：
(1) flue gas cool-down is pre-washed：High-sulfur flue gas enters the gas approach of cooling condensing crystallizing system, flows up, with The sulphur ammonium slurry liquid contacts that slurries spraying layer is sprayed, mass-and heat-transfer, the reduction of high-sulfur flue-gas temperature and humidity increase, and high-sulfur Dirt and highly acid gas in flue gas, which are washed, enters slurries；
(2) sulphur ammonium is crystallized：The sulphur ammonium slurries, by the slurry circulating pump, flow through the slurry in crystallizing pond section Liquid circulating line, circulation conveying is to the slurries spraying layer, and the atomizer by slurries spraying layer is changed into drop, to flow down Dynamic, with high warm flue gas counter current contacting, heat and mass, slurries are concentrated, and ammonium sulfate concentrations therein is exceeded solubility, are entered And crystallize and separate out crystal ammonium sulphate, the slurries containing sulphur ammonium solid are obtained, sulphur ammonium Han Liang≤50%, pH≤4.5 of the slurries；
(3) the main desulfurization of flue gas：The flue gas obtained from step (1) leaves the cooling enriching section and enters the main absorption oxygen The main absorber portion of change system, is flowed up, the drop counter current contacting sprayed with the main absorbing liquid spraying layer, and mass transfer is inhaled Receive SO2, obtain ammonium sulfurous and enter absorbing liquid；The absorbing liquid is back to the main oxidation panel, is blasted by the primary air aerator Air oxidation be ammonium sulfate, while adding desulfurization material ammonia, maintain the pH value of absorbing liquid, then circulate through the main absorbing liquid Pipeline is by the main absorbing liquid circulating pump circulation conveying to the main absorbing liquid spraying layer, continuous desulfurization, in the absorbing liquid Sulphur ammonium content is between 15-45%, pH≤6.0, and the main desulfuration efficiency for absorbing oxidative system is more than 90%；
(4) the auxiliary desulfurization of flue gas：The flue gas obtained from step (3) leaves the main absorber portion and enters the auxiliary absorption oxidation The auxiliary absorber portion of system, is flowed up, the drop counter current contacting sprayed with the auxiliary absorbing liquid spraying layer, and mass transfer absorbs SO2, obtain ammonium sulfurous and enter absorbing liquid；The absorbing liquid is back to the auxiliary oxidation panel, is blasted by the auxiliary air aeration device Air oxidation is ammonium sulfate, while adding desulfurization material ammonia, maintains the pH value of absorbing liquid, then through the auxiliary absorbing liquid circulation pipe The auxiliary absorbing liquid circulating pump circulation conveying is route to the auxiliary absorbing liquid spraying layer, continuous desulfurization, sulphur ammonium in the absorbing liquid Han Liang≤10%, pH≤5.5；After the auxiliary absorption oxidative system, the SO in flue gas2Han Liang≤100mg/Nm3, dust content ≦30mg/Nm3；
(5) water balance is controlled：Control the crystallizing pond section, the liquid level maintenance of the main oxidation panel and the auxiliary oxidation panel The water balance of the high-sulfur flue gas ammonia method desulfurizing system；The liquid level of the crystallizing pond section passes through the liquid by the main oxidation panel The Flow-rate adjustment of body pipeline and the ammonium sulfate solution of flushing pump conveying is controlled；The liquid level of the main oxidation panel is by described auxiliary Oxidation panel is transported to the Flow-rate adjustment of the main ammonium sulfate solution for absorbing oxidative system to control；The liquid level of the auxiliary oxidation panel By the Flow-rate adjustment for the process water for being added to the auxiliary oxidation panel is controlled；
(6) sulphur ammonium is extracted：The slurries containing sulphur ammonium solid obtained from step (2) are pumped into by the discharging circulation The sulphur ammonium extracts the circulatory system, sequentially passes through the dense device of the slurries, centrifuge, drying machine and packing machine, obtains sulphur ammonium production Product；The clear liquid of the dense device of slurries and the mother liquor reflux of the centrifuge are to crystallizing pond section, then condensing crystallizing.
Also include the ultra-clean dust removal step of flue gas, the flue gas after desulfurization obtained from step (4) enters the electrostatic precipitator, warp It is too high to press electric treatment, the ultra-fine acid mist particle in flue gas is removed, makes Han Chen Liang≤10mg/Nm in purifying smoke3, then pass through By the smoke stack emission.
The pH value of the crystallizing pond section, main oxidation panel and the ammonium sulfate solution in auxiliary oxidation panel is respectively in 3.5-4.5,5.2- Between 6.0 and 4.0-6.0.
The purifying smoke is via the smoke stack emission, SO2Han Liang≤35mg/Nm3, dirt Han Liang≤5mg/Nm3。
Compared with prior art, the beneficial effects of the invention are as follows high-sulfur flue gas sequentially passes through cooling condensing crystallizing, main suction Receive oxidation and auxiliary absorb aoxidizes these three circulatory systems, realize SO2Efficient removal and reduce the escaping of ammonia and smoke evacuation gas it is molten Glue stain, and system run all right is reliable.
Brief description of the drawings
Fig. 1 is the first process flow diagram of the invention；
Fig. 2 is second of process flow diagram of the invention；
Fig. 3 is the third process flow diagram of the invention；
Fig. 4 is the 4th kind of process flow diagram of the invention.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
One thermal power plant, two 300MW units, coal-fired sulfur content 2%, every flue gas flow is 1,200,000 Nm3/ Hr, amount of sulfur contenting in smoke is 4800mg/Nm3, 130 DEG C of flue-gas temperature, desulphurization system is the line of a stove one, using height as shown in Figure 1 Sulphur flue gas ammonia method desulfurizing system, using ammonia as desulfurizing agent, is aided with technique water and air, including three circulatory systems：First circulation System is cooling condensing crystallizing system 100, absorbs oxidative system 200 based on second circulatory system, the 3rd circulatory system is Auxiliary absorption oxidative system 300, three circulatory systems are independently set；
Wherein：Main absorption oxidative system 200 includes columnar main absorber portion 210 and main oxidation panel 220, main absorber portion Include inside 210 and include primary air aerator 221, main oxidation panel inside main absorbing liquid spraying layer 211, main oxidation panel 220 220 outside and the outside of the main absorber portion 210 pass through main absorbing liquid circulating line 240 and the main phase of absorbing liquid circulating pump 250 Connection, main oxidation panel 220 is connected with the input pipe that raw material ammonia is also associated with air inlet duct, main oxidation panel 220；Inhaled main The top for receiving the main absorbing liquid spraying layer 211 inside section 210 is provided with demister, is sprayed to eliminate main absorbing liquid spraying layer 211 Drench the mist produced.
Auxiliary absorption oxidative system 300 is included in columnar auxiliary absorber portion 310 and auxiliary oxidation panel 320, auxiliary absorber portion 310 Portion, which includes, includes auxiliary air aeration device 321 inside auxiliary absorbing liquid spraying layer 311, auxiliary oxidation panel 220, auxiliary oxidation panel 320 It is outside to be connected with the outside of auxiliary absorber portion 310 by auxiliary absorbing liquid circulating line 340 with auxiliary absorbing liquid circulating pump 350, auxiliary oxygen Change section 320 and be connected with the input pipe that raw material ammonia is also associated with air inlet duct, auxiliary oxidation panel 320；In auxiliary absorber portion 310 The top of the auxiliary absorbing liquid spraying layer 311 in portion is also equipped with demister, is produced to eliminate the auxiliary spray of absorbing liquid spraying layer 311 Mist.
The condensing crystallizing system 100 that cools includes the cooling enriching section 110 and crystallizing pond section 120 of cylinder type, and cool enriching section 110 inside, which includes, to be included inside slurries spraying layer 111, crystallizing pond section 120 outside agitator 121, crystallizing pond section 120 Portion is connected with the outside of cooling enriching section 110 by serum recycle pipeline 140 with slurry circulating pump 150, in cooling enriching section The import 130 of high-sulfur flue gas is provided between 110 and crystallizing pond section 120.In cooling enriching section 110, demister is additionally provided with, Rinse spray component is provided with above demister, and the liquid of rinse spray component comes from main oxidation panel.
The system also includes sulphur ammonium and extracts the circulatory system 600, and sulphur ammonium extraction system 600 includes the dense device of slurries, centrifugation Machine, drying machine and packing machine, crystallizing pond section 120 pass through circulating pump 610 and the dense device of slurries of sulphur ammonium extraction system 600 of discharging It is connected, the magma mouthful of the dense device of slurries is connected with centrifuge, and the solid outlet of centrifuge is connected with drying machine, drying machine Solid outlet is connected with packing machine, the clear liquid mouthful of the dense device of slurries and the mother liquor discharging opening of centrifuge and crystallizing pond 120 phases of section Even.
The system also includes electrostatic precipitator 400, and electrostatic precipitator 400 includes electric discharge cathode line and gather dust anode tube, anode The effective fiberglass added with carbon fiber is made, electrostatic precipitator 400 be connected to it is auxiliary absorption oxidative system 300 and chimney 500 it Between.
High-sulfur flue gas sequentially enters cooling condensing crystallizing system 100, main absorption oxidative system 200 and auxiliary absorb and aoxidizes system System 300, process water sequentially enters the auxiliary absorption oxidative system 300, main absorption oxidative system 200 and cooling condensing crystallizing system System 100, ammonia and air enter the main absorption oxidative system 200 and auxiliary absorption oxidative system 300 simultaneously；Make high-sulfur flue gas successively By the condensing crystallizing that cools, main absorption oxidation and auxiliary absorb aoxidize these three circulatory systems, realize SO2Efficient removal and subtract The Aerosol Pollution of the escaping of ammonia and smoke evacuation is lacked, concrete application said system carries out high-sulfur flue gas ammonia method desulfurizing, including following step Suddenly：
(1) flue gas cool-down is pre-washed：Raw material high-sulfur flue gas enters the gas approach of the cooling condensing crystallizing system 100 130, flow up, the sulphur ammonium slurry liquid contacts sprayed with the slurries spraying layer 111, mass-and heat-transfer, flue-gas temperature reduction And humidity increases, and the dirt and highly acid gas in flue gas are washed and enter slurries；
(2) sulphur ammonium is crystallized：The crystallizing pond section 120 has sulphur ammonium slurries, and the sulphur ammonium slurries derive from slurries spraying layer 111 Spray and sulphur ammonium slurries are obtained after liquid is contacted with high-sulfur flue gas adverse current flow to crystallizing pond section 120, and from main oxidation panel 220 after liquid line 21 and the top rinse spray component 113 of the input cooling condensing crystallizing of flushing pump 22 system 100 by leaving Fluid, the fluid through the demisting of demister 112, and with import 130 flow into high-sulfur flue gas adverse current contact, obtain sulphur ammonium slurries Crystallizing pond section 120 is flow to, the sulphur ammonium slurries of the crystallizing pond section 120 pass through the slurry circulating pump 150, flow through the slurries Circulating line 140, circulation conveying to the slurries spraying layer 111, the atomizer by the slurries spraying layer 111 is changed into Drop, is flowed downward, with high warm flue gas counter current contacting, and heat and mass, slurries are concentrated, and surpasses ammonium sulfate concentrations therein Solubility is crossed, and then crystallizes precipitation crystal ammonium sulphate, the slurries containing ammonium sulfate solids, the ammonium sulphate content of the slurries are obtained It is 4.5 for 50%, pH；
(3) the main desulfurization of flue gas：The flue gas obtained from step (1) leaves the cooling enriching section 110 and enters the main absorption The main absorber portion 210 of oxidative system 200, is flowed up, the absorbing liquid liquid sprayed with the main absorbing liquid spraying layer 211 Counter current contacting is dripped, mass transfer absorbs SO2, obtain ammonium sulfurous and enter absorbing liquid；The absorbing liquid is back to the main oxidation panel 220, quilt The air oxidation that the primary air aerator 221 is blasted is ammonium sulfate, while adding desulfurization material ammonia, maintains the pH of absorbing liquid Value, then through the main absorbing liquid circulation line 240 by the main circulation conveying of absorbing liquid circulating pump 250 to the main absorbing liquid Sulphur ammonium content in spraying layer 211, continuous desulfurization, the absorbing liquid is that 20%, pH is 5.5, the main absorption oxidative system Desulfuration efficiency is 91%；
(4) the auxiliary desulfurization of flue gas：The flue gas obtained from step (3) leaves the main absorber portion 210 and enters the auxiliary absorption oxygen The auxiliary absorber portion 310 of change system 300, is flowed up, the absorbing liquid drop sprayed with the auxiliary absorbing liquid spraying layer 311 Counter current contacting, mass transfer absorbs SO2, obtain ammonium sulfurous and enter absorbing liquid；The absorbing liquid is back to the auxiliary oxidation panel 320, by institute It is ammonium sulfate to state the air oxidation that auxiliary air aeration device 321 blasts, while adding desulfurization material ammonia, maintains the pH value of absorbing liquid, Sprayed again through the auxiliary absorbing liquid circulation line 340 by the auxiliary circulation conveying of absorbing liquid circulating pump 350 to the auxiliary absorbing liquid Sulphur ammonium content is that 9%, pH is 5.0 in layer 311, continuous desulfurization, the absorbing liquid；By the auxiliary absorption oxidative system 300 Afterwards, the SO in flue gas2Content is in 33.6mg/Nm3Hereinafter, dust content is in 25mg/Nm3Below；
(5) water balance is controlled：The crystallizing pond section 120 is controlled, the main oxidation panel 220 and the auxiliary oxidation panel 320 Liquid level maintains the water balance of the high-sulfur flue gas ammonia method desulfurizing system；The liquid level of the crystallizing pond section 120 is by the main oxidation panel 220 control by the Flow-rate adjustment of the liquid line 21 and the ammonium sulfate solutions of the conveying of the flushing pump 22；The main oxidation The liquid level of section 220 is transported to the Flow-rate adjustment of the main ammonium sulfate solution for absorbing oxidative system 200 by the auxiliary oxidation panel 320 To control；The liquid level of the auxiliary oxidation panel 320 is controlled by the Flow-rate adjustment for being added to the process water of the auxiliary oxidation panel 320；
(6) sulphur ammonium is extracted：The sulphur ammonium slurries containing ammonium sulfate solids obtained from step (2) are circulated by the discharging Pump 610 is sent to the sulphur ammonium and extracts the circulatory system 600, sequentially passes through the dense device of the slurries, centrifuge, drying machine and packaging Machine, obtains ammonium sulfate products；The clear liquid of the dense device of slurries and the mother liquor reflux of the centrifuge to crystallizing pond section 120, Condensing crystallizing again.
The sulfur method also includes the ultra-clean dust removal step of flue gas, and the flue gas after desulfurization obtained from step (4) enters the electricity Demister 400, is handled by electrion, is removed the ultra-fine acid mist particle in flue gas, is down to the dustiness in purifying smoke 4.3mg/Nm3Hereinafter, then via the chimney 500 discharge.
Using the high-sulfur flue gas ammonia method desulfurizing system and method for the present invention, it is possible to achieve the exiting flue gas SO of chimney 5002Content 33.6mg/Nm3, dustiness 4.3mg/Nm3Emissions object, its yield be 23.83 tons/hr of sulphur ammonium, whole year by 6000 hours send out Electricity, annual sulphur ammonium yield is 14.3 ten thousand tons.
Embodiment 2
One thermal power plant, two 600MW units, coal-fired sulfur content 3.5%, every flue gas flow is 2,250,000 Nm3/ Hr, amount of sulfur contenting in smoke is 9200mg/Nm3, and 135 DEG C of flue-gas temperature, desulphurization system is the line of a stove one, using height as shown in Figure 2 Sulphur flue gas ammonia method desulfurizing system, using ammonia as desulfurizing agent, is aided with water and air, including three circulatory systems：First circulatory system For cooling condensing crystallizing system 100, oxidative system 200 is absorbed based on second circulatory system, inhaled supplemented by the 3rd circulatory system Receive oxidative system 300.As different from Example 1, the columnar main suction of the main absorption oxidative system 200 in the present embodiment Receive section 210 and share a tower, and the main columnar main absorber portion for absorbing oxidative system 200 with cooling condensing crystallizing system 100 210 cooling condensing crystallizing system 100 top, between have blast cap divides.
Wherein, main absorption oxidative system 200 includes columnar main absorber portion 210 and main oxidation panel 220, main absorber portion Include inside 210 and include primary air aerator 221, main oxidation panel inside main absorbing liquid spraying layer 211, main oxidation panel 220 220 outside and the outside of the main absorber portion 210 pass through main absorbing liquid circulating line 240 and the main phase of absorbing liquid circulating pump 250 Connection, main oxidation panel 220 is connected with the input that raw material ammonia is also associated with air inlet duct, main absorbing liquid circulating line 240 Pipe；The top of main absorbing liquid spraying layer 211 inside main absorber portion 210 is provided with demister, inside auxiliary absorber portion 310 The top of auxiliary absorbing liquid spraying layer 311 be provided with demister.
Auxiliary absorption oxidative system 300 is included in columnar auxiliary absorber portion 310 and auxiliary oxidation panel 320, auxiliary absorber portion 310 Portion, which includes, includes auxiliary air aeration device 321 inside auxiliary absorbing liquid spraying layer 311, auxiliary oxidation panel 220, auxiliary oxidation panel 320 It is outside to be connected with the outside of auxiliary absorber portion 310 by auxiliary absorbing liquid circulating line 340 with auxiliary absorbing liquid circulating pump 350, auxiliary oxygen Change section 320 and be connected with the input pipe that raw material ammonia is also associated with air inlet duct, auxiliary absorbing liquid circulating line 340；
The condensing crystallizing system 100 that cools includes the cooling enriching section 110 and crystallizing pond section 120 of cylinder type, and cool enriching section 110 inside, which includes, to be included inside slurries spraying layer 111, crystallizing pond section 120 outside agitator 121, crystallizing pond section 120 Portion is connected with the outside of cooling enriching section 110 by serum recycle pipeline 140 with slurry circulating pump 150, in cooling enriching section It is the import 130 of the high-sulfur flue gas between 110 and crystallizing pond section 120.In cooling enriching section 110, demisting is additionally provided with Device, is provided with rinse spray component above demister, and required rinse spray liquid comes from main oxidation panel 220.
The system also includes sulphur ammonium and extracts the circulatory system 600, and sulphur ammonium extraction system 600 includes the dense device of slurries, centrifugation Machine, drying machine and packing machine, crystallizing pond section 120 pass through circulating pump 610 and the dense device of slurries of sulphur ammonium extraction system 600 of discharging It is connected, the magma mouthful of the dense device of slurries is connected with centrifuge, and the solid outlet of centrifuge is connected with drying machine, drying machine Solid outlet is connected with packing machine, the mother liquor discharging opening of the clear liquid of the dense device of slurries mouthful and centrifuge and crystallizing pond section 12) phase Even.
The system also includes electrostatic precipitator 400, and electrostatic precipitator 400 includes electric discharge cathode line and gather dust anode tube, anode The effective fiberglass added with carbon fiber is made, electrostatic precipitator 400 be connected to it is auxiliary absorption oxidative system 300 and chimney 500 it Between.
High-sulfur flue gas sequentially enters cooling condensing crystallizing system 100, main absorption oxidative system 200 and auxiliary absorb and aoxidizes system System 300, process water sequentially enters the auxiliary absorption oxidative system 300, main absorption oxidative system 200 and cooling condensing crystallizing system System 100, ammonia and air enter the main absorption oxidative system 200 and auxiliary absorption oxidative system 300 simultaneously；Make high-sulfur flue gas according to Secondary to pass through cooling condensing crystallizing, these three circulatory systems of main absorption oxidation and auxiliary absorption oxidation realize SO2Efficient removal and The Aerosol Pollution of the escaping of ammonia and smoke evacuation is reduced, concrete application said system carries out high-sulfur flue gas ammonia method desulfurizing, including following Step：
(1) flue gas cool-down is pre-washed：Raw material high-sulfur flue gas enters the gas approach of the cooling condensing crystallizing system 100 130, flow up, the sulphur ammonium slurry liquid contacts sprayed with the slurries spraying layer 111, mass-and heat-transfer, flue-gas temperature reduction And humidity increases, and the dirt and highly acid gas in flue gas are washed and enter slurries；
(2) sulphur ammonium is crystallized：The sulphur ammonium slurries, by the slurry circulating pump 150, are flowed through in crystallizing pond section 120 The serum recycle pipeline 140, circulation conveying to the slurries spraying layer 111, by the atomization of the slurries spraying layer 111 Nozzle is changed into drop, flows downward, with high warm flue gas counter current contacting, and heat and mass, the slurries are concentrated, and are made therein Ammonium sulfate concentrations exceed solubility, and then crystallize precipitation crystal ammonium sulphate, obtain the slurries containing sulphur ammonium solid, the slurries Sulphur ammonium content for 50%, pH be 4.5；
(3) the main desulfurization of flue gas：The flue gas obtained from step (1) leaves the cooling enriching section 110 and enters the main absorption The main absorber portion 210 of oxidative system 200, is flowed up, the drop adverse current sprayed with the main absorbing liquid spraying layer 211 Contact, mass transfer absorbs SO2, obtain ammonium sulfurous and enter absorbing liquid；The absorbing liquid is back to the main oxidation panel 220, by the master The air oxidation that air aeration device 221 is blasted is ammonium sulfate, while adding desulfurization material ammonia, maintains the pH value of absorbing liquid, then pass through The main absorbing liquid circulation line 240 is by the main circulation conveying of absorbing liquid circulating pump 250 to the main absorbing liquid spraying layer 211, continuous desulfurization, sulphur ammonium content in the absorbing liquid is 5.0 for 30%, pH, the main desulfurization effect for absorbing oxidative system Rate is 90%；
(4) the auxiliary desulfurization of flue gas：The flue gas obtained from step (3) leaves the main absorber portion 210 and enters the auxiliary absorption oxygen The auxiliary absorber portion 310 of change system 300, is flowed up, and the drop adverse current sprayed with the auxiliary absorbing liquid spraying layer 311 connects Touch, mass transfer absorbs SO2, obtain ammonium sulfurous and enter absorbing liquid；The absorbing liquid is back to the auxiliary oxidation panel 320, by described auxiliary The air oxidation that air aeration device 321 is blasted is ammonium sulfate, while adding desulfurization material ammonia, maintains the pH value of absorbing liquid, then pass through The auxiliary absorbing liquid circulation line 340 is by the auxiliary circulation conveying of absorbing liquid circulating pump 350 to the auxiliary absorbing liquid spraying layer 311, continuous desulfurization, sulphur ammonium content is that 8%, pH is 5.5 in the absorbing liquid；After the auxiliary absorption oxidative system 300, SO in flue gas2Content is in 46mg/Nm3Hereinafter, dust content is in 20mg/Nm3Below；
(5) water balance is controlled：The crystallizing pond section 120 is controlled, the main oxidation panel 220 and the auxiliary oxidation panel 320 Liquid level maintains the water balance of the high-sulfur flue gas ammonia method desulfurizing system；The liquid level of the crystallizing pond section 120 is by the main oxidation panel 220 control by the Flow-rate adjustment of the liquid line 21 and the ammonium sulfate solutions of the conveying of the flushing pump 22；The main oxidation The liquid level of section 220 is transported to the Flow-rate adjustment of the main ammonium sulfate solution for absorbing oxidative system 200 by the auxiliary oxidation panel 320 To control；The liquid level of the auxiliary oxidation panel 320 is controlled by the Flow-rate adjustment for being added to the process water of the auxiliary oxidation panel 320；
(6) sulphur ammonium is extracted：The sulphur ammonium slurries containing sulphur ammonium solid obtained from step (2) pass through the slurry feeding pump It is sent to the sulphur ammonium and extracts the circulatory system 600, sequentially passes through the dense device of the slurries, centrifuge, drying machine and packing machine, obtain To ammonium sulfate products；The clear liquid of the dense device of slurries and the mother liquor reflux of the centrifuge are then dense to crystallizing pond section 120 Sheepshank is brilliant.
The sulfur method also includes the ultra-clean dust removal step of flue gas, and the flue gas after desulfurization obtained from step (4) enters the electricity Demister 400, is handled by electrion, is removed the ultra-fine acid mist particle in flue gas, is down to the dustiness in purifying smoke 8.1mg/Nm3Hereinafter, then via the chimney 500 discharge.
Using the high-sulfur flue gas ammonia method desulfurizing system and method for the present invention, it is possible to achieve the exiting flue gas SO of chimney 5002Content 46mg/Nm3, dustiness 8.1mg/Nm3Emissions object, its yield be 85.82 tons/hr of sulphur ammonium, whole year by 6000 hours generate electricity, Annual sulphur ammonium yield is 51.49 ten thousand tons.
Embodiment 3
, there are 4 260 tons of water-tube boilers one coal plant, and 3 open 1 quilt, coal-fired sulfur content 5.0%, every flue gas flow For 330,000 Nm3/hr, amount of sulfur contenting in smoke is 12600mg/Nm3, and 145 DEG C of flue-gas temperature, desulphurization system is the line of three stove one, using such as High-sulfur flue gas ammonia method desulfurizing system shown in Fig. 3, using ammonia as desulfurizing agent, is aided with water and air, including three circulatory systems：The One circulatory system is cooling condensing crystallizing system 100, absorbs oxidative system 200 based on second circulatory system, the 3rd is followed Oxidative system 300 is absorbed supplemented by loop system.From unlike embodiment 1 or 2, the auxiliary absorption oxidative system 300 in the present embodiment Columnar auxiliary absorber portion 310, the main columnar main absorber portion 210 for absorbing oxidative system 200 and cooling condensing crystallizing system System 100 shares a tower, and the auxiliary columnar auxiliary absorber portion 310 for absorbing oxidative system 300 is in main absorption oxidative system 200 Columnar main absorber portion 210 top, the columnar main absorber portion 210 of main absorption oxidative system 200 concentrates in cooling The top of crystal system 100, between have blast cap dividing plate separation.
Main absorption oxidative system 200 is included in columnar main absorber portion 210 and main oxidation panel 220, main absorber portion 210 Portion, which includes, includes primary air aerator 221 inside main absorbing liquid spraying layer 211, main oxidation panel 220, main oxidation panel 220 The outside outside with the main absorber portion 210 is connected by main absorbing liquid circulating line 240 with main absorbing liquid circulating pump 250, Main oxidation panel 220 is connected with the input pipe that raw material ammonia is also associated with air inlet duct, main oxidation panel 220；
Auxiliary absorption oxidative system 300 is included in columnar auxiliary absorber portion 310 and auxiliary oxidation panel 320, auxiliary absorber portion 310 Portion, which includes, includes auxiliary air aeration device 321 inside auxiliary absorbing liquid spraying layer 311, auxiliary oxidation panel 220, auxiliary oxidation panel 320 It is outside to be connected with the outside of auxiliary absorber portion 310 by auxiliary absorbing liquid circulating line 340 with auxiliary absorbing liquid circulating pump 350, auxiliary oxygen Change section 320 and be connected with the input pipe that raw material ammonia is also associated with air inlet duct, auxiliary oxidation panel 320；
The condensing crystallizing system 100 that cools includes the cooling enriching section 110 and crystallizing pond section 120 of cylinder type, and cool enriching section 110 inside, which includes, to be included inside slurries spraying layer 111, crystallizing pond section 120 outside agitator 121, crystallizing pond section 120 Portion is connected with the outside of cooling enriching section 110 by serum recycle pipeline 140 with slurry circulating pump 150, in cooling enriching section It is the import 130 of the high-sulfur flue gas between 110 and crystallizing pond section 120.
The system also includes sulphur ammonium and extracts the circulatory system 600, and sulphur ammonium extraction system 600 includes the dense device of slurries, centrifugation Machine, drying machine and packing machine, crystallizing pond section 120 pass through circulating pump 610 and the dense device of slurries of sulphur ammonium extraction system 600 of discharging It is connected, the magma mouthful of the dense device of slurries is connected with centrifuge, and the solid outlet of centrifuge is connected with drying machine, drying machine Solid outlet is connected with packing machine, the clear liquid mouthful of the dense device of slurries and the mother liquor discharging opening of centrifuge and crystallizing pond 120 phases of section Even.
The system also includes electrostatic precipitator 400, and electrostatic precipitator 400 includes electric discharge cathode line and gather dust anode tube, anode The effective fiberglass added with carbon fiber is made, electrostatic precipitator 400 be connected to it is auxiliary absorption oxidative system 300 and chimney 500 it Between.
High-sulfur flue gas sequentially enters cooling condensing crystallizing system 100, main absorption oxidative system 200 and auxiliary absorb and aoxidizes system System 300, process water sequentially enters the auxiliary absorption oxidative system 300, main absorption oxidative system 200 and cooling condensing crystallizing system System 100, ammonia and air enter the main absorption oxidative system 200 and auxiliary absorption oxidative system 300 simultaneously；Make high-sulfur flue gas according to Secondary to pass through cooling condensing crystallizing, these three circulatory systems of main absorption oxidation and auxiliary absorption oxidation realize SO2Efficient removal and The Aerosol Pollution of the escaping of ammonia and smoke evacuation is reduced, concrete application said system carries out high-sulfur flue gas ammonia method desulfurizing, including following Step：
(1) flue gas cool-down is pre-washed：Raw material high-sulfur flue gas enters the gas approach of the cooling condensing crystallizing system 100 130, flow up, the sulphur ammonium slurry liquid contacts sprayed with the slurries spraying layer 111, mass-and heat-transfer, flue-gas temperature reduction And humidity increases, and the dirt and highly acid gas in flue gas are washed and enter slurries；
(2) sulphur ammonium is crystallized：The sulphur ammonium slurries, by the slurry circulating pump 150, are flowed through in crystallizing pond section 120 The serum recycle pipeline 140, circulation conveying to the slurries spraying layer 111, by the atomizer of the spraying layer 110 It is changed into drop, flows downward, with high warm flue gas counter current contacting, heat and mass, the slurries is concentrated, and make sulfuric acid therein Ammonium concentration exceedes solubility, and then crystallizes precipitation crystal ammonium sulphate, obtains the slurries containing sulphur ammonium solid, the sulphur of the slurries Ammonium content is that 50%, pH is 4.5；
(3) the main desulfurization of flue gas：The flue gas obtained from step (1) leaves the cooling enriching section 110 and enters the main absorption The main absorber portion 210 of oxidative system 200, is flowed up, the drop adverse current sprayed with the main absorbing liquid spraying layer 211 Contact, mass transfer absorbs SO2, obtain ammonium sulfurous and enter absorbing liquid；The absorbing liquid is back to the main oxidation panel 220, described The air oxidation that primary air aerator 221 is blasted is ammonium sulfate, while adding desulfurization material ammonia, maintains the pH value of absorbing liquid, then Through the main absorbing liquid circulation line 240 by the main circulation conveying of absorbing liquid circulating pump 250 to the main absorbing liquid spraying layer 211, continuous desulfurization, sulphur ammonium content in the absorbing liquid is 5.0 for 30%, pH, the main desulfurization effect for absorbing oxidative system Rate is 90%；
(4) the auxiliary desulfurization of flue gas：The flue gas obtained from step (3) leaves the main absorber portion 210 and enters the auxiliary absorption oxygen The auxiliary absorber portion 310 of change system 300, is flowed up, and the drop adverse current sprayed with the auxiliary absorbing liquid spraying layer 311 connects Touch, mass transfer absorbs SO2, obtain ammonium sulfurous and enter absorbing liquid；The absorbing liquid is back to the auxiliary oxidation panel 320, by described auxiliary The air oxidation that air aeration device 321 is blasted is ammonium sulfate, while adding desulfurization material ammonia, maintains the pH value of absorbing liquid, then pass through The auxiliary absorbing liquid circulation line 330 is by the auxiliary circulation conveying of absorbing liquid circulating pump 340 to the auxiliary absorbing liquid spraying layer 311, continuous desulfurization, sulphur ammonium content is that 8%, pH is 5.5 in the absorbing liquid；After the auxiliary absorption oxidative system 300, SO in flue gas2Content is in 63mg/Nm3Hereinafter, dust content is in 30mg/Nm3Below；
(5) water balance is controlled：The crystallizing pond section 120 is controlled, the main oxidation panel 220 and the auxiliary oxidation panel 320 Liquid level maintains the water balance of the high-sulfur flue gas ammonia method desulfurizing system；The liquid level of the crystallizing pond section 120 is by the main oxidation panel 220 control by the Flow-rate adjustment of the liquid line 21 and the ammonium sulfate solutions of the conveying of the flushing pump 22；The main oxidation The liquid level of section 220 is transported to the Flow-rate adjustment of the main ammonium sulfate solution for absorbing oxidative system 200 by the auxiliary oxidation panel 320 To control；The liquid level of the auxiliary oxidation panel 320 is controlled by the Flow-rate adjustment for being added to the process water of the auxiliary oxidation panel 320；
(6) sulphur ammonium is extracted：The sulphur ammonium slurries containing sulphur ammonium solid obtained from step (2) pass through the slurry feeding pump It is sent to the sulphur ammonium and extracts the circulatory system 600, sequentially passes through the dense device of the slurries, centrifuge, drying machine and packing machine, obtain To ammonium sulfate products；The clear liquid of the dense device of slurries and the mother liquor reflux of the centrifuge are then dense to crystallizing pond section 120 Sheepshank is brilliant.
The sulfur method also includes the ultra-clean dust removal step of flue gas, and the flue gas after desulfurization obtained from step (4) enters the electricity Demister 400, is handled by electrion, is removed the ultra-fine acid mist particle in flue gas, is down to the dustiness in purifying smoke 15.8mg/Nm3Hereinafter, then via the chimney 500 discharge.
Using the high-sulfur flue gas ammonia method desulfurizing system and method for the present invention, it is possible to achieve exiting flue gas SO2Content 63mg/ Nm3, dustiness 15.8mg/Nm3Emissions object, its yield be 25.86 tons/hr of sulphur ammonium, whole year operation by 8400 hours calculate, Annual sulphur ammonium yield is 21.72 ten thousand tons.
Embodiment 4
, there is 1 360m in one steel plant2Sintering machine, flue gas flow is 1,200,000 Nm3/ hr, amount of sulfur contenting in smoke is 5500mg/ Nm3, 150 DEG C of flue-gas temperature, using high-sulfur flue gas ammonia method desulfurizing system as shown in Figure 4, using ammonia as desulfurizing agent, be aided with water and Air, including three circulatory systems：First circulatory system is cooling condensing crystallizing system 100, based on second circulatory system Oxidative system 200 is absorbed, oxidative system 300 is absorbed supplemented by the 3rd circulatory system.From unlike embodiment 1 or 2 or 3, this The columnar auxiliary absorber portion 310 of auxiliary absorption oxidative system 300 in embodiment shares one with main absorption oxidative system 200 Tower, and the auxiliary columnar auxiliary absorber portion 310 for absorbing oxidative system 300 is in the top of main absorption oxidative system 200, Zhi Jianyou Blast cap dividing plate separates.
Main absorption oxidative system 200 is included in columnar main absorber portion 210 and main oxidation panel 220, main absorber portion 210 Portion, which includes, includes primary air aerator 221 inside main absorbing liquid spraying layer 211, main oxidation panel 220, main oxidation panel 220 The outside outside with the main absorber portion 210 is connected by absorbing liquid circulating line 240 with main absorbing liquid circulating pump 250, main Oxidation panel 220 is connected with the input pipe that raw material ammonia is also associated with air inlet duct, main oxidation panel 220；
Auxiliary absorption oxidative system 300 is included in columnar auxiliary absorber portion 310 and auxiliary oxidation panel 320, auxiliary absorber portion 310 Portion, which includes, includes auxiliary air aeration device 321 inside auxiliary absorbing liquid spraying layer 311, auxiliary oxidation panel 220, auxiliary oxidation panel 320 It is outside to be connected with the outside of auxiliary absorber portion 310 by auxiliary absorbing liquid circulating line 340 with auxiliary absorbing liquid circulating pump 350, auxiliary oxygen Change section 320 and be connected with the input pipe that raw material ammonia is also associated with air inlet duct, auxiliary oxidation panel 320；
The condensing crystallizing system 100 that cools includes the cooling enriching section 110 and crystallizing pond section 120 of cylinder type, and cool enriching section 110 inside, which includes, to be included inside slurries spraying layer 111, crystallizing pond section 120 outside agitator 121, crystallizing pond section 120 Portion is connected with the outside of cooling enriching section 110 by serum recycle pipeline 140 with slurry circulating pump 150, in cooling enriching section It is the import 130 of the high-sulfur flue gas between 110 and crystallizing pond section 120.
The system also includes sulphur ammonium and extracts the circulatory system 600, and sulphur ammonium extraction system 600 includes the dense device of slurries, centrifugation Machine, drying machine and packing machine, crystallizing pond section 120 pass through circulating pump 610 and the dense device of slurries of sulphur ammonium extraction system 600 of discharging It is connected, the magma mouthful of the dense device of slurries is connected with centrifuge, and the solid outlet of centrifuge is connected with drying machine, drying machine Solid outlet is connected with packing machine, the clear liquid mouthful of the dense device of slurries and the mother liquor discharging opening of centrifuge and crystallizing pond 120 phases of section Even.
The system also includes electrostatic precipitator 400, and electrostatic precipitator 400 includes electric discharge cathode line and gather dust anode tube, anode The effective fiberglass added with carbon fiber is made, electrostatic precipitator 400 be connected to it is auxiliary absorption oxidative system 300 and chimney 500 it Between.
High-sulfur flue gas sequentially enters cooling condensing crystallizing system 100, main absorption oxidative system 200 and auxiliary absorb and aoxidizes system System 300, process water sequentially enters the auxiliary absorption oxidative system 300, main absorption oxidative system 200 and cooling condensing crystallizing system System 100, ammonia and air enter the main absorption oxidative system 200 and auxiliary absorption oxidative system 300 simultaneously；Make high-sulfur flue gas according to Secondary to pass through cooling condensing crystallizing, these three circulatory systems of main absorption oxidation and auxiliary absorption oxidation realize SO2Efficient removal and The Aerosol Pollution of the escaping of ammonia and smoke evacuation is reduced, concrete application said system carries out high-sulfur flue gas ammonia method desulfurizing, including following Step：
(1) flue gas cool-down is pre-washed：Raw material high-sulfur flue gas enters the gas approach of the cooling condensing crystallizing system 100 130, flow up, the sulphur ammonium slurry liquid contacts sprayed with the slurries spraying layer 111, mass-and heat-transfer, flue-gas temperature reduction And humidity increases, and the dirt and highly acid gas in flue gas are washed and enter slurries；
(2) sulphur ammonium is crystallized：The sulphur ammonium slurries, by the slurry circulating pump 150, are flowed through in crystallizing pond section 120 The serum recycle pipeline 140, circulation conveying to the slurries spraying layer 111, by the atomizer of the spraying layer 110 It is changed into drop, flows downward, with high warm flue gas counter current contacting, heat and mass, the slurries is concentrated, and make sulfuric acid therein Ammonium concentration exceedes solubility, and then crystallizes precipitation crystal ammonium sulphate, obtains the slurries containing sulphur ammonium solid, the sulphur of the slurries Ammonium content is that 50%, pH is 4.5；
(3) the main desulfurization of flue gas：The flue gas obtained from step (1) leaves the cooling enriching section 110 and enters the main absorption The main absorber portion 210 of oxidative system 200, is flowed up, the drop adverse current sprayed with the main absorbing liquid spraying layer 211 Contact, mass transfer absorbs SO2, obtain ammonium sulfurous and enter absorbing liquid；The absorbing liquid is back to the main oxidation panel 220, described The air oxidation that primary air aerator 221 is blasted is ammonium sulfate, while adding desulfurization material ammonia, maintains the pH value of absorbing liquid, then Through the main absorbing liquid circulation line 240 by the main circulation conveying of absorbing liquid circulating pump 250 to the main absorbing liquid spraying layer 211, continuous desulfurization, sulphur ammonium content in the absorbing liquid is 5.0 for 30%, pH, the main desulfurization effect for absorbing oxidative system Rate is 90%；
(4) the auxiliary desulfurization of flue gas：The flue gas obtained from step (3) leaves the main absorber portion 210 and enters the auxiliary absorption oxygen The auxiliary absorber portion 310 of change system 300, is flowed up, and the drop adverse current sprayed with the auxiliary absorbing liquid spraying layer 311 connects Touch, mass transfer absorbs SO2, obtain ammonium sulfurous and enter absorbing liquid；The absorbing liquid is back to the auxiliary oxidation panel 320, by described auxiliary The air oxidation that air aeration device 321 is blasted is ammonium sulfate, while adding desulfurization material ammonia, maintains the pH value of absorbing liquid, then pass through The auxiliary absorbing liquid circulation line 330 is by the auxiliary circulation conveying of absorbing liquid circulating pump 340 to the auxiliary absorbing liquid spraying layer 311, continuous desulfurization, sulphur ammonium content is that 8%, pH is 5.5 in the absorbing liquid；After the auxiliary absorption oxidative system 300, SO in flue gas2Content is in 27.5mg/Nm3Hereinafter, dust content is in 20mg/Nm3Below；
(5) water balance is controlled：The crystallizing pond section 120 is controlled, the main oxidation panel 220 and the auxiliary oxidation panel 320 Liquid level maintains the water balance of the high-sulfur flue gas ammonia method desulfurizing system；The liquid level of the crystallizing pond section 120 is by the main oxidation panel 220 control by the Flow-rate adjustment of the liquid line 21 and the ammonium sulfate solutions of the conveying of the flushing pump 22；The main oxidation The liquid level of section 220 is transported to the Flow-rate adjustment of the main ammonium sulfate solution for absorbing oxidative system 200 by the auxiliary oxidation panel 320 To control；The liquid level of the auxiliary oxidation panel 320 is controlled by the Flow-rate adjustment for being added to the process water of the auxiliary oxidation panel 320；
(6) sulphur ammonium is extracted：The sulphur ammonium slurries containing sulphur ammonium solid obtained from step (2) pass through the slurry feeding pump It is sent to the sulphur ammonium and extracts the circulatory system 600, sequentially passes through the dense device of the slurries, centrifuge, drying machine and packing machine, obtain To ammonium sulfate products；The clear liquid of the dense device of slurries and the mother liquor reflux of the centrifuge are then dense to crystallizing pond section 120 Sheepshank is brilliant.
The sulfur method also includes the ultra-clean dust removal step of flue gas, and the flue gas after desulfurization obtained from step (4) enters the electricity Demister 400, is handled by electrion, is removed the ultra-fine acid mist particle in flue gas, is down to the dustiness in purifying smoke 3.8mg/Nm3Hereinafter, then via the chimney 500 discharge.
Using the high-sulfur flue gas ammonia method desulfurizing system and method for the present invention, it is possible to achieve exiting flue gas SO2Content 27.5mg/Nm3, dustiness 3.8mg/Nm3Emissions object, its yield is 13.68 tons/hr of sulphur ammonium, and whole year, operation was by 8400 small When calculate, annual sulphur ammonium yield be 11.49 ten thousand tons.
Embodiment 5
One carbon element factory, 200,000 tons/year of carbons of production capacity, uses high sulfur petroleum coke for raw material, and flue gas flow is 500,000 Nm3/ hr, amount of sulfur contenting in smoke is 8000mg/Nm3, 160 DEG C of flue-gas temperature, using high-sulfur flue gas ammonia method desulfurizing system as shown in Figure 1 System, using ammonia as desulfurizing agent, is aided with water and air, including three circulatory systems：First circulatory system is cooling condensing crystallizing system System 100, absorbs oxidative system 200 based on second circulatory system, and oxidative system 300, three are absorbed supplemented by the 3rd circulatory system The individual circulatory system is independently set.
Main absorption oxidative system 200 is included in columnar main absorber portion 210 and main oxidation panel 220, main absorber portion 210 Portion, which includes, includes primary air aerator 221 inside main absorbing liquid spraying layer 211, main oxidation panel 220, main oxidation panel 220 The outside outside with the main absorber portion 210 is connected by absorbing liquid circulating line 240 with main absorbing liquid circulating pump 250, main Oxidation panel 220 is connected with the input pipe that raw material ammonia is also associated with air inlet duct, main oxidation panel 220；
Auxiliary absorption oxidative system 300 is included in columnar auxiliary absorber portion 310 and auxiliary oxidation panel 320, auxiliary absorber portion 310 Portion, which includes, includes auxiliary air aeration device 321 inside auxiliary absorbing liquid spraying layer 311, auxiliary oxidation panel 220, auxiliary oxidation panel 320 It is outside to be connected with the outside of auxiliary absorber portion 310 by auxiliary absorbing liquid circulating line 340 with auxiliary absorbing liquid circulating pump 350, auxiliary oxygen Change section 320 and be connected with the input pipe that raw material ammonia is also associated with air inlet duct, auxiliary oxidation panel 320；
The condensing crystallizing system 100 that cools includes the cooling enriching section 110 and crystallizing pond section 120 of cylinder type, and cool enriching section 110 inside, which includes, to be included inside slurries spraying layer 111, crystallizing pond section 120 outside agitator 121, crystallizing pond section 120 Portion is connected with the outside of cooling enriching section 110 by serum recycle pipeline 140 with slurry circulating pump 150, in cooling enriching section It is the import 130 of the high-sulfur flue gas between 110 and crystallizing pond section 120.
The system also includes sulphur ammonium and extracts the circulatory system 600, and sulphur ammonium extraction system 600 includes the dense device of slurries, centrifugation Machine, drying machine and packing machine, crystallizing pond section 120 pass through circulating pump 610 and the dense device of slurries of sulphur ammonium extraction system 600 of discharging It is connected, the magma mouthful of the dense device of slurries is connected with centrifuge, and the solid outlet of centrifuge is connected with drying machine, drying machine Solid outlet is connected with packing machine, the clear liquid mouthful of the dense device of slurries and the mother liquor discharging opening of centrifuge and crystallizing pond 120 phases of section Even.
The system also includes electrostatic precipitator 400, and electrostatic precipitator 400 includes electric discharge cathode line and gather dust anode tube, anode The effective fiberglass added with carbon fiber is made, electrostatic precipitator 400 be connected to it is auxiliary absorption oxidative system 300 and chimney 500 it Between.
High-sulfur flue gas sequentially enters cooling condensing crystallizing system 100, main absorption oxidative system 200 and auxiliary absorb and aoxidizes system System 300, process water sequentially enters the auxiliary absorption oxidative system 300, main absorption oxidative system 200 and cooling condensing crystallizing system System 100, ammonia and air enter the main absorption oxidative system 200 and auxiliary absorption oxidative system 300 simultaneously；Make high-sulfur flue gas according to Secondary to pass through cooling condensing crystallizing, these three circulatory systems of main absorption oxidation and auxiliary absorption oxidation realize SO2Efficient removal and The Aerosol Pollution of the escaping of ammonia and smoke evacuation is reduced, concrete application said system carries out high-sulfur flue gas ammonia method desulfurizing, including following Step：
(1) flue gas cool-down is pre-washed：Raw material high-sulfur flue gas enters the gas approach of the cooling condensing crystallizing system 100 130, flow up, the sulphur ammonium slurry liquid contacts sprayed with the slurries spraying layer 111, mass-and heat-transfer, flue-gas temperature reduction And humidity increases, and the dirt and highly acid gas in flue gas are washed and enter slurries；
(2) sulphur ammonium is crystallized：The sulphur ammonium slurries, by the slurry circulating pump 150, are flowed through in crystallizing pond section 120 The serum recycle pipeline 140, circulation conveying to the slurries spraying layer 111, by the atomizer of the spraying layer 110 It is changed into drop, flows downward, with high warm flue gas counter current contacting, heat and mass, the slurries is concentrated, and make sulfuric acid therein Ammonium concentration exceedes solubility, and then crystallizes precipitation crystal ammonium sulphate, obtains the slurries containing sulphur ammonium solid, the sulphur of the slurries Ammonium content is that 60%, pH is 4.0；
(3) the main desulfurization of flue gas：The flue gas obtained from step (1) leaves the cooling enriching section 110 and enters the main absorption The main absorber portion 210 of oxidative system 200, is flowed up, the drop adverse current sprayed with the main absorbing liquid spraying layer 211 Contact, mass transfer absorbs SO2, obtain ammonium sulfurous and enter absorbing liquid；The absorbing liquid is back to the main oxidation panel 220, described The air oxidation that primary air aerator 221 is blasted is ammonium sulfate, while adding desulfurization material ammonia, maintains the pH value of absorbing liquid, then Through the main absorbing liquid circulation line 240 by the main circulation conveying of absorbing liquid circulating pump 250 to the main absorbing liquid spraying layer 211, continuous desulfurization, sulphur ammonium content in the absorbing liquid is 5.0 for 30%, pH, the main desulfurization effect for absorbing oxidative system Rate is 94%；
(4) the auxiliary desulfurization of flue gas：The flue gas obtained from step (3) leaves the main absorber portion 210 and enters the auxiliary absorption oxygen The auxiliary absorber portion 310 of change system 300, is flowed up, and the drop adverse current sprayed with the auxiliary absorbing liquid spraying layer 311 connects Touch, mass transfer absorbs SO2, obtain ammonium sulfurous and enter absorbing liquid；The absorbing liquid is back to the auxiliary oxidation panel 320, by described auxiliary The air oxidation that air aeration device 321 is blasted is ammonium sulfate, while adding desulfurization material ammonia, maintains the pH value of absorbing liquid, then pass through The auxiliary absorbing liquid circulation line 330 is by the auxiliary circulation conveying of absorbing liquid circulating pump 340 to the auxiliary absorbing liquid spraying layer 311, continuous desulfurization, sulphur ammonium content is that 8%, pH is 4.0 in the absorbing liquid；After the auxiliary absorption oxidative system 300, SO in flue gas2Content is in 40.0mg/Nm3Hereinafter, dust content is in 20mg/Nm3Below；
(5) water balance is controlled：The crystallizing pond section 120 is controlled, the main oxidation panel 220 and the auxiliary oxidation panel 320 Liquid level maintains the water balance of the high-sulfur flue gas ammonia method desulfurizing system；The liquid level of the crystallizing pond section 120 is by the main oxidation panel 220 control by the Flow-rate adjustment of the liquid line 21 and the ammonium sulfate solutions of the conveying of the flushing pump 22；The main oxidation The liquid level of section 220 is transported to the Flow-rate adjustment of the main ammonium sulfate solution for absorbing oxidative system 200 by the auxiliary oxidation panel 320 To control；The liquid level of the auxiliary oxidation panel 320 is controlled by the Flow-rate adjustment for being added to the process water of the auxiliary oxidation panel 320；
(6) sulphur ammonium is extracted：The sulphur ammonium slurries containing sulphur ammonium solid obtained from step (2) pass through the slurry feeding pump It is sent to the sulphur ammonium and extracts the circulatory system 600, sequentially passes through the dense device of the slurries, centrifuge, drying machine and packing machine, obtain To ammonium sulfate products；The clear liquid of the dense device of slurries and the mother liquor reflux of the centrifuge are then dense to crystallizing pond section 120 Sheepshank is brilliant.
The sulfur method also includes the ultra-clean dust removal step of flue gas, and the flue gas after desulfurization obtained from step 4 is removed into the electricity Day with fog 400, is handled by electrion, is removed the ultra-fine acid mist particle in flue gas, is down to the dustiness in purifying smoke 8.5mg/Nm3Hereinafter, then via the chimney 500 discharge.
Using the system and method for the present invention, it is possible to achieve exiting flue gas SO2Content 40.0mg/Nm3, dustiness 8.5mg/ Nm3Emissions object, its yield is 8.29 tons/hr of sulphur ammonium, and whole year operation was calculated by 8400 hours, and annual sulphur ammonium yield is 6.965 ten thousand tons.
Preferred embodiment of the invention described in detail above.It should be appreciated that one of ordinary skill in the art without Need creative work just can make many modifications and variations according to the design of the present invention.Therefore, all technologies in the art Personnel can be obtained by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea Technical scheme, all should be in the protection domain being defined in the patent claims.

Claims (10)

1. a kind of ammonia method desulfurizing system of high-sulfur flue gas, using ammonia, technique water and air as raw material, it is characterised in that including three The circulatory system：First circulatory system is cooling condensing crystallizing system (100), and oxidative system is absorbed based on second circulatory system (200) oxidative system (300), is absorbed supplemented by the 3rd circulatory system, high-sulfur flue gas sequentially enters the cooling condensing crystallizing system System (100), main absorption oxidative system (200) and auxiliary absorption oxidative system (300), process water sequentially enter auxiliary absorb and aoxidized System (300), main absorption oxidative system (200) and cooling condensing crystallizing system (100), ammonia and air enter the main suction simultaneously Receive oxidative system (200) and auxiliary absorption oxidative system (300).
2. a kind of ammonia method desulfurizing system of high-sulfur flue gas according to claim 1, it is characterised in that described main absorption oxygen Change system (200) includes including inside columnar main absorber portion (210) and main oxidation panel (220), the main absorber portion (210) Have and include primary air aerator (221), the main oxidation inside main absorbing liquid spraying layer (211), the main oxidation panel (220) The section outside of (220) and the outside of the main absorber portion (210) are circulated by main absorbing liquid circulating line (240) and main absorbing liquid Pump (250) is connected, and the main oxidation panel (220) is connected with air inlet duct, the main oxidation panel (220) or the main absorption The input pipe of raw material ammonia is also associated with liquid circulating line (240)；
The auxiliary absorption oxidative system (300) includes columnar auxiliary absorber portion (310) and auxiliary oxidation panel (320), the auxiliary suction Receive and include auxiliary absorbing liquid spraying layer (311) inside section (310), include auxiliary air aeration inside the auxiliary oxidation panel (320) The outside of device (321), the auxiliary outside for stating oxidation panel (320) and the auxiliary absorber portion (310) passes through auxiliary absorbing liquid circulation pipe Road (340) is connected with auxiliary absorbing liquid circulating pump (350), and the auxiliary oxidation panel (320) is connected with air inlet duct, the auxiliary oxygen Change the input pipe that raw material ammonia is also associated with section (320) or the auxiliary absorbing liquid circulating line (340)；
The cooling condensing crystallizing system (100) includes the cooling enriching section (110) and crystallizing pond section (120) of cylinder type, described The inside of cooling enriching section (110) includes and includes agitator inside slurries spraying layer (111), the crystallizing pond section (120) (121), serum recycle pipeline (140) and slurries are passed through in the outside of the outside of crystallizing pond section (120) and cooling enriching section (110) Circulating pump (150) is connected, and high-sulfur flue gas is provided between the cooling enriching section (110) and crystallizing pond section (120) Import (130).
3. the ammonia method desulfurizing system of a kind of high-sulfur flue gas according to claim 2, it is characterised in that in the cooling concentration In section (110), demister is additionally provided with, rinse spray component, and the punching are provided with above or below the demister Washing and spraying component is connected by liquid line by flushing pump with the main oxidation panel (220).
4. the ammonia method desulfurizing system of a kind of high-sulfur flue gas according to claim 2, it is characterised in that in the main absorbing liquid Spraying layer is provided with demister above (211), and demister is provided with above the auxiliary absorbing liquid spraying layer (311).
5. the ammonia method desulfurizing system of a kind of high-sulfur flue gas according to claim 2, it is characterised in that also extracted including sulphur ammonium The circulatory system (600), the sulphur ammonium extraction system (600) includes the dense device of slurries, centrifuge, drying machine and packing machine, the knot Brilliant pond section (120) is connected by the circulating pump that discharges (610) with the dense device of slurries of the sulphur ammonium extraction system (600), the slurries The magma mouthful of dense device is connected with the centrifuge, and the solid outlet of the centrifuge is connected with the drying machine, described dry The solid outlet of dry machine is connected with the packing machine, and the clear liquid mouthful of the dense device of slurries and the mother liquor of the centrifuge discharge Mouth is connected with crystallizing pond section (120).
6. the ammonia method desulfurizing system of a kind of high-sulfur flue gas according to claim 2, it is characterised in that also including electrostatic precipitator (400), the electrostatic precipitator (400) includes electric discharge cathode line and anode tube of gathering dust, and the anode tube of gathering dust uses fine added with carbon The fiberglass of dimension is made, and the electrostatic precipitator (400) is connected between the auxiliary absorption oxidative system (300) and chimney (500).
7. any system carries out the ammonia method desulfurizing method of high-sulfur flue gas in a kind of use claim 1~6, its feature exists In comprising the following steps：
(1) flue gas cool-down is pre-washed：High-sulfur flue gas enters the gas approach (130) of cooling condensing crystallizing system (100), to upstream It is dynamic, the sulphur ammonium slurry liquid contacts sprayed with slurries spraying layer (111), mass-and heat-transfer, high-sulfur flue-gas temperature is reduced and humidity increases Plus, and dirt and highly acid gas in high-sulfur flue gas are washed enters slurries；
(2) sulphur ammonium is crystallized：The sulphur ammonium slurries by the slurry circulating pump (150), are flowed through in crystallizing pond section (120) The serum recycle pipeline (140), circulation conveying is to the slurries spraying layer (111), by the atomization of slurries spraying layer (111) Nozzle is changed into drop, flows downward, with high warm flue gas counter current contacting, and heat and mass, slurries are concentrated, and make ammonium sulfate therein Concentration exceedes solubility, and then crystallizes precipitation crystal ammonium sulphate, obtains the slurries containing sulphur ammonium solid, the sulphur ammonium content of the slurries ≤ 50%, pH≤4.5；
(3) the main desulfurization of flue gas：The flue gas obtained from step (1) leaves the cooling enriching section (110) and enters the main absorption oxygen The main absorber portion (210) of change system (200), is flowed up, and the drop sprayed with the main absorbing liquid spraying layer (211) is inverse Stream contact, mass transfer absorbs SO2, obtain ammonium sulfurous and enter absorbing liquid；The absorbing liquid is back to the main oxidation panel (220), by institute It is ammonium sulfate to state the air oxidation that primary air aerator (221) blasts, while adding desulfurization material ammonia, maintains the pH of absorbing liquid Value, then through the main absorbing liquid circulating line (240) by main absorbing liquid circulating pump (250) circulation conveying to the main absorption Sulphur ammonium content in liquid spraying layer (211), continuous desulfurization, the absorbing liquid is between 15-45%, pH≤6.0, the main absorption The desulfuration efficiency of oxidative system is more than 90%；
(4) the auxiliary desulfurization of flue gas：The flue gas obtained from step (3) leaves the main absorber portion (210) and enters the auxiliary absorption oxidation The auxiliary absorber portion (310) of system (300), is flowed up, the drop adverse current sprayed with the auxiliary absorbing liquid spraying layer (311) Contact, mass transfer absorbs SO2, obtain ammonium sulfurous and enter absorbing liquid；The absorbing liquid is back to the auxiliary oxidation panel (320), described The air oxidation that auxiliary air aeration device (321) blasts is ammonium sulfate, while adding desulfurization material ammonia, maintains the pH value of absorbing liquid, Again through the auxiliary absorbing liquid circulation line (340) by auxiliary absorbing liquid circulating pump (350) circulation conveying to the auxiliary absorbing liquid Sulphur ammonium Han Liang≤10%, pH≤5.5 in spraying layer (311), continuous desulfurization, the absorbing liquid；System is aoxidized by auxiliary absorb After system (300), the SO in flue gas2Han Liang≤100mg/Nm3, dirt Han Liang≤30mg/Nm3；
(5) water balance is controlled：Control the crystallizing pond section (120), the main oxidation panel (220) and the auxiliary oxidation panel (320) Liquid level maintain the water balance of the high-sulfur flue gas ammonia method desulfurizing system；The liquid level of the crystallizing pond section (120) is by the main oxygen Change section (220) by the Flow-rate adjustment of the liquid line (21) and the ammonium sulfate solution of the flushing pump (22) conveying to control； The liquid level of the main oxidation panel (220) is transported to the main sulphur ammonium for absorbing oxidative system (200) by the auxiliary oxidation panel (320) The Flow-rate adjustment of solution is controlled；The liquid level of the auxiliary oxidation panel (320) is by being added to the process water of the auxiliary oxidation panel (320) Flow-rate adjustment control；
(6) sulphur ammonium is extracted：The slurries containing sulphur ammonium solid obtained from step (2) are sent to by the discharging circulating pump (610) The sulphur ammonium extracts the circulatory system (600), sequentially passes through the dense device of the slurries, centrifuge, drying machine and packing machine, obtains sulphur Ammonium product；The clear liquid of the dense device of slurries and the mother liquor reflux of the centrifuge are to crystallizing pond section (120), then concentrate knot It is brilliant.
8. the ammonia method desulfurizing method of high-sulfur flue gas according to claim 7, it is characterised in that also including the ultra-clean dedusting of flue gas Step, the flue gas after desulfurization obtained from step (4) enters the electrostatic precipitator (400), is handled by electrion, removes flue gas In ultra-fine acid mist particle, make Han Chen Liang≤10mg/Nm in purifying smoke3, then via the chimney (500) discharge.
9. the ammonia method desulfurizing method of high-sulfur flue gas according to claim 7, it is characterised in that the crystallizing pond section (120), The pH value of main oxidation panel (220) and the ammonium sulfate solution in auxiliary oxidation panel (320) is respectively in 3.5-4.5,5.2-6.0 and 4.0-6.0 Between.
10. the ammonia method desulfurizing method of high-sulfur flue gas according to claim 8, it is characterised in that the purifying smoke via Chimney (500) discharge, SO2Han Liang≤35mg/Nm3, dirt Han Liang≤5mg/Nm3。
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