CN106422693A - Method and device of removing SO2 in flue gas by acid-ammonia method - Google Patents
Method and device of removing SO2 in flue gas by acid-ammonia method Download PDFInfo
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- CN106422693A CN106422693A CN201610988474.0A CN201610988474A CN106422693A CN 106422693 A CN106422693 A CN 106422693A CN 201610988474 A CN201610988474 A CN 201610988474A CN 106422693 A CN106422693 A CN 106422693A
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- flue gas
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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
- B01D53/46—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
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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
- B01D53/73—After-treatment of removed components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
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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
- B01D53/96—Regeneration, reactivation or recycling of reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/608—Sulfates
Abstract
The invention discloses a method and device of removing SO2 in flue gas by an acid-ammonia method. The reaction device comprises an air blower used for blowing the flue gas, sulfuric acid reaction equipment connected with the air blower, neutralization reaction equipment, ammonium sulfate crystallization treatment equipment and water recycle recovery equipment; and the sulfuric acid reaction equipment and the neutralization reaction equipment, the neutralization reaction equipment and the ammonium sulfate crystallization treatment equipment, the ammonium sulfate crystallization treatment equipment and the water recycle recovery equipment as well as the water recycle recovery equipment and the sulfuric acid reaction equipment are respectively connected to each other through a pipeline and a pump. The device is not limited by flue gas operation conditions, can be used when the temperature of the flue gas is within 100 DEG C, and can be used under any condition without being limited by the amount of the flue gas and the concentration of the SO2; and the SO2 in the flue gas and oxygen in the flue gas are at a high oxidation speed under the action of a catalyst, the SO2 and O2 synchronously produce sulfuric acid in an aqueous solution without a specially arranged oxidizing reaction device, and thus a process is simpler than an ammonia-ammonium sulfate method.
Description
Technical field
The invention belongs to industrial treatment SO2SO in a kind of technical field, more particularly to acid-ammonia process removing flue gas2Method and
Device.
Background technology
Fume desulphurization method is mutually classified by the thing of desulfurizing agent.It is broadly divided into dry desulfurization with two class of wet desulphurization.Dry method
Desulfurization：Using the SO in solid phase absorbents, adsorbent or catalyst removal flue gas2.Advantage is that no spent acid, the process of waste water set
Apply, in SO2The relatively low occasion of concentration can be used；Have the disadvantage that desulfuration efficiency is relatively low and unstable, equipment is huge；Adsorbent is used
Time is not long, needs periodic replacement, changes adsorbent high labor intensive, to cause dust secondary pollution；Most of adsorbent is not
Can regenerate, cause operating cost height.
Wet desulphurization：Typically SO is removed as absorbent using alkaline solution or slurry solution2.Advantage be desulfuration efficiency relatively
High and stable, equipment is simple, processing ease, and operating cost is relatively low.As different by-products can be produced using different absorbent
Thing, the process to by-product can be divided into the method for abandoning and two kinds of absorption method.The method of abandoning is that the by-product for producing desulfurization makees waste throwing
Abandon.Abandon method to process simply, processing cost is low, but substantial amounts of place of banking up need to be taken, also have secondary pollution, the sulfur of preciousness unavoidably
Resource is also wasted therewith.Reclaiming rule need to increase substantial amounts of investment and operating cost, but the utilization of resources is abundant, secondary pollution
Few.
Current flue gas desulfurization process kind more than 200 both at home and abroad, only more than ten planting with industrial application value.Most
Conventional is wet desulphurization, and most common method is limestone/lime method, ammonia process, sodium method, Dual alkali etc., in wet desulphurization skill
In art, the current technology of limestone/lime method is the most ripe, technique desulfuration efficiency height (desulfurization degree more than 90%), the absorbent valency
Honest and clean and originate wide, but the method system complex, investment and energy consumption are big, and production waste residue using value is little, easily causes secondary pollution.
Ammonia process (also referred to as ammonia-ammonium sulfate method) ammonia is a kind of alkaline absorbent, and its alkalescence is better than calcium-base absorbing agent, absorbs cigarette with ammonia
SO in gas2Response speed is fast, absorption efficiency height, and absorption equipment can be substantially reduced.SO is reclaimed in ammonia-ammonium sulfate method desulfurization2It is divided into four
Individual key step：Absorb, regenerate, oxidation and sulphur ammonium are produced.Ammonia-ammonium sulfate method by-product can be used as fertilizer, as ammonia is volatility
Material, unavoidably will be taken away by flue gas, in desulfurization with ammonia loss by volatilization, be limited by flue gas operating condition, flue gas temperature
Degree is higher, and loss is bigger, and exhaust gas volumn is bigger, SO2Concentration is lower, by flue gas take away more, lose bigger, lose bigger operation
Cost is just high, and ammonia process is using limited；The product major part that ammonia-ammonium sulfate method is obtained is ammonium sulfite, to need to use at relatively high temperatures
Air oxygen is melted into sulphur ammonium, and sulfite oxidation speed is very slow, needs larger oxidation furnaces.Other sodium methods or Dual alkali cost are same
Sample height, by-product utilization is worth also less, and enterprise is economically under great stress.Currently, country to air quality more and more
Pay attention to, more and more big to the environmental protection pressure of enterprise, pressure is also power, sight should be placed on as environmentalist
In innovation, should have an economic benefit in environmental improvement Shang Shi enterprise, and while carry out recycling.
Content of the invention
For the deficiencies in the prior art, the present invention provides SO in a kind of acid-ammonia process removing flue gas2Method and device.This
Invention adds catalyst, using liquid catalytic, by the SO in flue gas with water cheap and easy to get as solvent2Dilute sulfur is synchronously generated
Acid, then uses in ammonia and generates sulphur ammonium, and flue gas is purified, and realizes recycling.
Technical scheme is as follows：SO in a kind of acid-ammonia process removing flue gas2Device, the reaction unit includes
Send the aerator of flue gas H connected with aerator for drum2SO4Consersion unit, neutralization reaction equipment, ammonium sulfate crystallization is processed and is set
Standby, water circulation reclaimer, the H2SO4Between consersion unit and neutralization reaction equipment, neutralization reaction equipment and ammonium sulfate crystallization
Between processing equipment, between ammonium sulfate crystallization processing equipment and water circulation reclaimer, water circulation reclaimer and H2SO4Reaction
All connected by pipeline and pump between equipment.
Further, the H2SO4Consersion unit includes foam reactant tower, H2SO4Storage tank, catalyst dissolution groove, wherein,
Catalyst dissolution groove is by pipeline and pump and H2SO4Storage tank connects, H2SO4Storage tank is with foam reactant tower by circulating pump and circulation
Pipeline connects；
The neutralization reaction equipment includes ammonia basin, neutralization reaction groove, neutralization reaction liquid storage tank, screw pump, pressure filter
With ammonium sulfate storage tank, wherein, neutralization reaction groove top and H2SO4Storage tank, ammonia basin are connected by pipeline and pump respectively, in
It is connected with neutralization reaction liquid storage tank with reaction tank bottom, neutralization reaction liquid storage tank is connected with pressure filter by screw pump；Pressure filter
Connect with ammonium sulfate storage tank；
The ammonium sulfate crystallization processing equipment includes vaporizer connected with ammonium sulfate storage tank, connected with vaporizer
Crystallization tank, centrifuge connected with crystallization tank, mother liquor tank connected with centrifuge and drying machine, mother liquor tank also with vaporizer phase
Even；
The water circulation reclaimer includes condenser connected with vaporizer, condensed fluid storage tank connected with condenser,
The condensed fluid storage tank and H2SO4Storage tank connects.
The foam reactant tower is connected using multistage foam reactant tower, is provided with Sptting plate in the reaction tower, reaction
Plate is provided with multiple apertures, and afterbody foam reactant tower inner top is provided with demister.
The foam reactant tower is substituted using pipeline reactor, is provided with atomizer in the pipeline reactor.
The flue gas prepares H2SO4Consersion unit include pipeline reactor and catalyst dissolution groove, the bottom of pipeline reactor
Portion is connected with the front portion of neutralization reaction equipment, is provided with atomizer, atomizer and neutralization reaction equipment in pipeline reactor
Rear portion connection, be provided with limestone desulfurization oxidant layer or ammonia desulfurization oxidant layer between the front portion of neutralization reaction equipment and rear portion, described in
It is connected with catalyst dissolution groove with the rear portion of consersion unit.
The present invention also provides SO in a kind of acid-ammonia process removing flue gas2Method, methods described using said apparatus realize,
Specifically include following steps：
Step (1) manganese sulfate solution enters H by catalyst dissolution groove in the way of Deca2SO4In storage tank, then by circulating pump
It is sent to H2SO4Consersion unit top, flue gas is sent into H by aerator pressurization2SO4The bottom of consersion unit, flue gas with top-down
Manganese sulfate solution contact preparation obtains H2SO4, H2SO4H is flowed into manganese sulfate solution2SO4In storage tank, then H2SO4Molten with manganese sulfate
Liquid is re-circulated into H2SO4Consersion unit top；
Step (2) H2SO4With the H in manganese sulfate solution2SO4After concentration reaches setting, it is continually introduced into neutralization by pump
In reactive tank, H2SO4The ammonia reaction that sends with liquid ammonia storage tank in neutralization reaction groove with manganese sulfate, obtains suspension, suspension
It is sent in pressure filter with filter pump and is filtered, filtrate enters in ammonium sulfate storage tank and stores, the manganous hydroxide being filtrated to get
Solid is recycled in catalyst dissolution groove and dissolves；The manganous hydroxide solid for obtaining is also containing other metal ions such as hydrated ferric oxide .s
Hydroxide, hybrid solid is recycled in catalyst dissolution groove, and manganous hydroxide, hydrated ferric oxide. etc. can be in manganese sulfate solutions
Dissolving is reclaimed, and continues cycling through catalytic reaction, even if solid can not be completely dissolved, with the process for preparing sulphuric acid, hydroxide
Manganese, hydrated ferric oxide. can also be completely dissolved.
Step (3) ammonium sulfate enters evaporation in vaporizer by pump and obtains ammonium sulfate supersaturated solution, ammonium sulfate mistake
Saturated solution crystallisation by cooling in crystallization tank, and using the isolated ammonium sulfate solids of centrifuge and mother solution, disposing mother liquor is to mother
Liquid bath, then continuation evaporation in vaporizer is pumped into, ammonium sulfate solids are entered in drying machine and are dry；The water vapour of evaporator evaporation is entered
Condenser is condensed, and is stored in condensate storage tank, then pumps into H2SO4Recycle in storage tank.
Concentration during step (1) the manganese sulfate solution catalytic reaction is 0.5～1%, it is also possible on the basis of this concentration
It is adjusted.
Step (2) H2SO4With H in manganese sulfate solution2SO4After concentration reaches 20～25%, solution is continuously led to neutralization
In reactive tank, if H in solution2SO4When concentration is more than 25%, it is unfavorable for that manganese sulfate is catalyzed, reduces catalytic efficiency.
Step (2) H2SO4, manganese sulfate and ammonia react to pH8～9 after stopped reaction.
Step (3) ammonium sulfate evaporating temperature reaches 110～120 DEG C, the satisfactory sulphuric acid of the gravity after evaporation
Ammonium supersaturated solution, is then placed in crystallization tank crystallisation by cooling, when temperature drop is to 35～40 DEG C, carries out centrifugal drying,
After drying, solid ammonium sulfate water content reaches less than 1.5%.
The present invention adopts acid-ammonia process of desulfurization, is that China's flue gas pollutant control proposes a feasible way, and acid-ammonia process takes off
Except SO in flue gas2The technological principle for obtaining sulphur ammonium is as follows：
1. catalysis oxidation produces dilute sulfuric acid
Catalyst sulfuric acid manganese is added in water, and manganese sulfate solution absorbs SO2Using foaming tower or atomization conduit reactor, flue gas
Contact with manganese sulfate solution, the SO in flue gas2With O2Under the catalysis of manganese sulfate, carry out catalytic oxidation and synchronously generate dilute sulfur
Acid, reacts as follows：
2. in ammonia and generate sulphur ammonium
The dilute sulfuric acid of generation is reacted with ammonia and generates sulphur ammonium, and neutralization reaction is carried out in averager, and neutralization reaction is as follows：
2NH3+H2SO4==(NH4)2SO4
The ammonium sulfate solution of generation is concentrated, crystallization, the operation such as separate, dry and obtain ammonium sulfate products.
Using above-mentioned principle, the present invention devises the device of acid-ammonia process of desulfurization, and flue gas enters foam reactant tower from bottom to top
In, contact with top-down catalyst solution and sulphuric acid is obtained, after sulfuric acid concentration reaches setting, be pumped in neutralization reaction groove
Reacted with ammonia, obtained ammonium sulfate suspension solution；Pumping in pressure filter through filter pump (screw pump) carries out solid-liquid separation,
Obtain manganous hydroxide solid and ammonium sulfate；Manganous hydroxide is reclaimed and obtains manganese sulfate catalyst recycling, ammonium sulfate
Crystallize through evaporator evaporation and in crystallization tank, separate through centrifuge, ammonium sulfate solids and mother solution is obtained, receive after drying
Collection；Mother solution returns evaporator evaporation, crystallization, centrifugation；In addition the vapor of evaporator evaporation is collected after condenser condensation
In the sink, it is recovered in sulfuric acid tank or catalyst dissolution groove and recycles.
SO is reclaimed in traditional ammonia-ammonium sulfate method desulfurization2It is divided into four key steps：Absorb, regenerate, oxidation and sulphur ammonium are produced,
As ammonia is volatile material, unavoidably to be taken away by flue gas, in desulfurization with ammonia loss by volatilization, by flue gas operating condition
Restriction, flue-gas temperature is higher, loses bigger, and exhaust gas volumn is bigger, SO2Concentration is lower, by flue gas take away more, loss is got over
Greatly, bigger operating cost is lost just high, ammonia process is used and is limited；The product that ammonia-ammonium sulfate method is obtained is most of for ammonium sulfite, needs
Sulphur ammonium is melted into air oxygen under higher temperature (700～800 DEG C), sulfite oxidation speed is very slow, needs larger oxidation
Equipment.
The present invention need not carry out being catalyzed the reaction that ammonium sulfite and air oxygen are melted into ammonium sulfate, therefore apparatus of the present invention are used
Do not limited by flue gas operating condition, equipment cost is saved, energy consumption is reduced, shortened the time cost of flue gas desulfurization, while
Improve SO2Removal efficiency, improve production capacity；The ammonium sulfate purity that the present invention is prepared is higher, can make as chemical fertilizer
With, it is to avoid calcium method absorbs stockyard, the secondary pollution problems for causing, and generally speaking, the process equipment that the present invention is provided is simple,
Cost and operating cost are low, and suitable China's major part medium-sized and small enterprises are used.
Compared with prior art, the invention has the advantages that：
(1) apparatus of the present invention are not using being limited by flue gas operating condition, and flue-gas temperature can be all used within 100 DEG C,
Flue gas size, SO2Concentration level is unrestricted, any under the conditions of can all use；
(2) SO in flue gas2With oxygen in flue gas in the presence of catalyst, oxidation rate quickly, SO2With O2Water-soluble
Dilute sulfuric acid is synchronously generated in liquid, it is not necessary to this step of ad hoc oxidation reaction, technique is simpler compared with ammonia-ammonium sulfate method；
(3) quickly, equipment is little for catalysis oxidation speed, and investment is relatively saved；
(4) desulfuration efficiency height, gas cleaning degree height, easy qualified discharge；
(5) no solidss are discharged, and without the need for stockyard, will not also produce secondary pollution；
(6) no ammonia loss, sulphur ammonium yield height, operating cost is low, and there is preferable economic benefit in enterprise.
Description of the drawings
SO in the removing flue gas that Fig. 1 is provided for the present invention2Device structural representation；
In figure labelling：1- pressurization blower, 2- first order foaming tower, 3- second level foaming tower, 4- the first sulphuric acid storage tank, 5-
First circulation pump, 6- the second sulphuric acid storage tank, 7- second circulation pump, 8- catalyst dissolution groove, 9- sulfuric acid pump, 10- ammonia basin, 11-
Neutralization reaction groove, 12- neutralization reaction liquid storage tank, 13- screw pump, 14- pressure filter, 15- ammonium sulfate storage tank；16- ammonium sulfate
Pump；17- vaporizer, 18- crystallization tank, 19- centrifuge, 20- ammonium sulfate liquor groove, 21- mother solution pump, 22- drying machine, 23- is condensed
Device, 24- condensate storage tank, 25- demister, 26- Sptting plate.
Specific embodiment
With specific embodiment, technical scheme is described in further details below in conjunction with the accompanying drawings, but the present invention is simultaneously
It is not limited to technical scheme below.
Embodiment 1
SO in a kind of acid-ammonia process removing flue gas2Device, the reaction unit include for drum send flue gas aerator,
H connected with aerator2SO4Consersion unit, neutralization reaction equipment, ammonium sulfate crystallization processing equipment, water circulation reclaimer, institute
State H2SO4Between consersion unit and neutralization reaction equipment, between neutralization reaction equipment and ammonium sulfate crystallization processing equipment, ammonium sulfate
Between crystallization treatment equipment and water circulation reclaimer, water circulation reclaimer and H2SO4Between consersion unit all by pipeline and
Pump connects.
The H2SO4Consersion unit includes the first foam reactant tower 2 and the second foam reactant tower 3 that connects, and the first sulphuric acid is store
Groove 4, first circulation pump 5, the second sulphuric acid storage tank 6, second circulation pump 7, catalyst dissolution groove 8, wherein, catalyst dissolution groove 8 leads to
Piping and pump are connected with the second sulphuric acid storage tank 6, and the second sulphuric acid storage tank 6 is connected to the second bubble by second circulation pump 7 and pipeline
3 top of foam reaction tower, 3 bottom of the second foam reactant tower is connected with the second sulphuric acid storage tank 6 also by pipeline；First sulphuric acid storage tank 4
The top of the first foam reactant tower 2 is connected to by first circulation pump 5 and pipeline, 2 bottom of the first foam reactant tower is also by pipe
Road is connected with the first sulphuric acid storage tank 4, and the first sulphuric acid storage tank 4 and the second sulphuric acid storage tank 6 are connected by pipeline.
The neutralization reaction equipment includes ammonia basin 10, neutralization reaction groove 11, neutralization reaction liquid storage tank 12, screw pump
13, pressure filter 14 and ammonium sulfate storage tank 15, wherein, 10 points of 11 top of neutralization reaction groove and two sulphuric acid storage tanks, ammonia basin
Not Tong Guo pipeline and pump connection, 11 bottom of neutralization reaction groove is connected with neutralization reaction liquid storage tank 12, and neutralization reaction liquid storage tank 12 leads to
Cross screw pump 13 to be connected with pressure filter 14；Pressure filter 14 and ammonium sulfate storage tank 15 connect；
The ammonium sulfate crystallization processing equipment includes and 15 connected vaporizer 17 of ammonium sulfate storage tank, with vaporizer 17
Connected crystallization tank 18, and 18 connected centrifuge 19 of crystallization tank, and 19 connected mother liquor tank 20 of centrifuge and drying machine 21, female
Liquid bath 20 is also connected with vaporizer 21, and the ammonium sulfate liquor in mother liquor tank is pumped in vaporizer 17 by mother solution pump 20, ammonium sulfate
Solution in solution storage tank 15 is pumped in vaporizer by ammonium sulfate pump 16.
The water circulation reclaimer includes and 18 connected condenser 23 of vaporizer, condensed fluid connected with condenser 23
Storage tank 24, the condensed fluid storage tank 24 is connected with sulphuric acid storage tank.
Sptting plate 26 is provided with the foam reactant tower, and Sptting plate 26 is provided with multiple apertures, second level foam reactant tower
Inner top is provided with demister 25.
Embodiment 2
The device for being provided using embodiment 1 carries out the SO in removing flue gas2；Anode calcines exhaust gas volumn：60000Nm3/ h, SO2
Concentration：3000mg/Nm3, being pressurizeed by pressurization blower 1, flue gas enters the bubble of the foaming tower 2, second level series connection of first order series connection
Foam tower 3, the tower diameter of two reaction towers is 3m, contacts with the top-down dilute acid soln containing catalyst, sloughs sulfuric acid tail gas
In SO2, the flue gas after purification is through the removing droplet of demister in tower 25, and the purifying smoke after demisting is vented by chimney.
Manganese sulfate is added after being dissolved by catalyst dissolution groove 8 in the way of Deca in second diluted acid storage tank 6, is followed by second
Ring pump 7 is sent to two grades of 3 tops of foaming tower, and manganese sulfate solution flows downward out absorption SO from the aperture of Sptting plate2, absorb SO2After obtain
Diluted acid (sulphuric acid) is entered in the second diluted acid storage tank 6, subsequently in the first diluted acid storage tank 4, then is sent to two grades with first circulation pump 5
First grade desulfurizing is carried out in foaming tower 2, and desulfurization absorbing liquid is returned 4 in the first diluted acid storage tank.
First diluted acid storage tank, 4 dilute acid concentration is sent in neutralization reaction groove 11 after reaching flue gas, and reactive tank is passed through by ammonia storage tank
10 gas ammonias that sends are neutralized, and the metal precipitates for producing after reaction are entered in neutralization reaction liquid storage tank 12, then use filter pump
13 are sent in pressure filter 14 and are filtered, and filtrate enters in dilute sulphur ammonium (dilute sulfuric acid ammonium) storage tank 15 and keeps in.
Dilute sulphur ammonium is sent in vaporizer 17 after effusion meter with dilute sulphur ammonium pump 16, here steam heating evaporation, solution ratio
The satisfactory ammonium sulfate liquor of weight, is put in crystallization tank 18, is passed through recirculated water and is cooled down, while blender stirring is started, when
When temperature drop is to 35～40 DEG C, centrifuge dehydration is carried out with centrifuge 19, mother solution is flowed in mother liquor tank 20, is returned with mother solution pump 21
Vaporizer re-evaporation.Sulphur ammonium after separating dries required product in drying machine 22.
The indirect steam that vaporizer 17 is steamed enters condensate cooler 23 and is cooled down with cooling water, condenses the condensation of gained
Condensed water in water and evaporator heater is entered in condensate storage tank 24 together, is returned in the second dilute acid bath 6 and is recycled.
The process parameter control of the present embodiment is as follows：
(1) during the catalysis of catalyst sulfuric acid manganese concentration control in the range of 0.5～1%：
(2) the dilute sulfuric acid concentration control after catalysis oxidation in solution is in the range of 20～25%, and the dilute sulfuric acid for being produced is continuous
Draw；
(3) dilute sulfuric acid with during ammonia neutralization reaction, control ph 8～9, make manganese and precipitation of iron ions, it is ensured that sulphur ammonium quality；
(4) after ammonium sulfate solution evaporation, solution temperature reaches 110～120 DEG C or so, the satisfactory ammonium sulfate liquor of gravity,
Crystallization tank crystallisation by cooling is put into, when temperature drop is to 35～40 DEG C, centrifugal drying is carried out, after drying, solid ammonium sulfate is aqueous
Amount reaches less than 1.5%.
Flue gas is through process, SO2Removal efficiency be more than 85%, compared with prior art, energy consumption save more than 15%, throw
Money operating cost reduces by more than 20%.
Embodiment 3
On the basis of embodiment 1, two-stage tandem foam reactant tower is changed to one-level foam reactant tower, aluminium cell flue gas
Amount：108000Nm3/ h, SO2Concentration：400mg/Nm3, because of SO2Concentration is relatively low, using first grade desulfurizing flow process.By pressurization blower 1
Pressurization, enters first order foaming tower 2, and tower diameter is 3.8m, to contact with the top-down dilute acid soln containing catalyst, slough sulfur
SO in sour tail gas2, the flue gas after purification is through demister removing droplet in tower, and the purifying smoke after demisting is vented by chimney, work
Skill parameter is with embodiment 2.Flue gas is through process, SO2Removal efficiency be more than 85%, compared with prior art, energy consumption saving
More than 30%, investment operating cost reduces by more than 20%.
Claims (9)
1. a kind of acid-ammonia process removes SO in flue gas2Device, it is characterised in that the reaction unit include for drum send flue gas
Aerator H connected with aerator2SO4Consersion unit, neutralization reaction equipment, ammonium sulfate crystallization processing equipment, water circulation is reclaimed
Equipment, the H2SO4Between consersion unit and neutralization reaction equipment, between neutralization reaction equipment and ammonium sulfate crystallization processing equipment,
Between ammonium sulfate crystallization processing equipment and water circulation reclaimer and water circulation reclaimer and H2SO4Between consersion unit all
Connected by pipeline and pump.
2. acid as claimed in claim 1-ammonia process removes SO in flue gas2Device, it is characterised in that the H2SO4Consersion unit
Including foam reactant tower, H2SO4Storage tank, catalyst dissolution groove, wherein, catalyst dissolution groove is by pipeline and pump and H2SO4Storage tank
Connection, H2SO4Storage tank is connected by circulating pump and circulating line with foam reactant tower；
The neutralization reaction equipment includes ammonia basin, neutralization reaction groove, neutralization reaction liquid storage tank, screw pump, pressure filter and sulfur
Acid ammonium solution storage tank, wherein, neutralization reaction groove top and H2SO4Storage tank, ammonia basin are connected by pipeline and pump respectively, and neutralization is anti-
Trench bottom is answered to be connected with neutralization reaction liquid storage tank, neutralization reaction liquid storage tank is connected with pressure filter by screw pump；Pressure filter and sulfur
Acid ammonium solution storage tank connects；
The ammonium sulfate crystallization processing equipment includes vaporizer connected with ammonium sulfate storage tank, crystallization connected with vaporizer
Groove, centrifuge connected with crystallization tank, mother liquor tank connected with centrifuge and drying machine, mother liquor tank is also connected with vaporizer；
The water circulation reclaimer includes condenser connected with vaporizer, and condensed fluid storage tank connected with condenser is described
Condensed fluid storage tank and H2SO4Storage tank connects.
3. acid as claimed in claim 2-ammonia process removes SO in flue gas2Device, it is characterised in that the foam reactant tower is adopted
Connected with multistage foam reactant tower, Sptting plate in the reaction tower, is provided with, Sptting plate is provided with multiple apertures, afterbody
Foam reactant tower inner top is provided with demister.
4. acid as claimed in claim 2-ammonia process removes SO in flue gas2Device, it is characterised in that the foam reactant tower is adopted
Substituted with pipeline reactor, in the pipeline reactor, be provided with atomizer.
5. a kind of acid-ammonia process removes SO in flue gas2Method, it is characterised in that the method comprising the steps of：
Step (1) manganese sulfate solution enters H by catalyst dissolution groove in the way of Deca2SO4In storage tank, then it is sent to by circulating pump
H2SO4Consersion unit top, flue gas is sent into H by aerator pressurization2SO4The bottom of consersion unit, flue gas and top-down sulphuric acid
Manganese solution contact preparation obtains H2SO4, H2SO4H is flowed into manganese sulfate solution2SO4In storage tank, then H2SO4With manganese sulfate solution again
It is recycled into H2SO4Consersion unit top；
Step (2) H2SO4With the H in manganese sulfate solution2SO4After concentration reaches setting, it is continually introduced into neutralization reaction by pump
In groove, H2SO4The ammonia reaction that sends with liquid ammonia storage tank in neutralization reaction groove with manganese sulfate, obtains suspension, and suspension is used
Filter pump is sent in pressure filter and is filtered, and filtrate enters in ammonium sulfate storage tank and stores, the manganous hydroxide solid being filtrated to get
It is recycled in catalyst dissolution groove and dissolves；
Step (3) ammonium sulfate enters evaporation in vaporizer by pump and obtains ammonium sulfate supersaturated solution, ammonium sulfate supersaturation
Solution crystallisation by cooling in crystallization tank, and using the isolated ammonium sulfate solids of centrifuge and mother solution, disposing mother liquor to mother liquor tank,
Pumped in vaporizer again and continue evaporation, ammonium sulfate solids are entered in drying machine and dry；The water vapour of evaporator evaporation enters condensation
Device is condensed, and is stored in condensate storage tank, then pumps into H2SO4Recycle in storage tank.
6. acid as claimed in claim 5-ammonia process removes SO in flue gas2Method, it is characterised in that step (1) manganese sulfate
Concentration during solution catalyzing reaction is 0.5～1%.
7. acid as claimed in claim 5-ammonia process removes SO in flue gas2Method, it is characterised in that step (2) H2SO4And sulfur
H in sour manganese solution2SO4After concentration reaches 20～25%, solution is continuously led in neutralization reaction groove.
8. acid-ammonia process as claimed in claim 5 removes SO in flue gas2Method, it is characterised in that step (2) H2SO4, sulphuric acid
Manganese react to pH8～9 with ammonia after stopped reaction.
9. acid as claimed in claim 5-ammonia process removes SO in flue gas2Method, it is characterised in that step (3) ammonium sulfate
Evaporating temperature reaches 110～120 DEG C, and it is cold that the satisfactory ammonium sulfate supersaturated solution of the gravity after evaporation places into crystallization tank
But crystallize, the centrifugal drying when temperature drop is to 35～40 DEG C, after drying, ammonium sulfate water content is less than 1.5%.
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| CN116081646A (en) * | 2022-11-21 | 2023-05-09 | 昆明理工大学 | Method for efficiently treating ammonia desulfurization mother liquor through multistage oxidation |
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| CN101143291A (en) * | 2006-09-13 | 2008-03-19 | 史选增 | Low-consumption high-quality ammonium sulfate fertilizer recovery wet ammonia process desulfurizing technology |
| CN104258710A (en) * | 2014-09-28 | 2015-01-07 | 西安华陆环保设备有限公司 | Method for removing SO2 from exhaust gas by liquid-phase catalytic oxidation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101143291A (en) * | 2006-09-13 | 2008-03-19 | 史选增 | Low-consumption high-quality ammonium sulfate fertilizer recovery wet ammonia process desulfurizing technology |
| CN104258710A (en) * | 2014-09-28 | 2015-01-07 | 西安华陆环保设备有限公司 | Method for removing SO2 from exhaust gas by liquid-phase catalytic oxidation |
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| CN116081646A (en) * | 2022-11-21 | 2023-05-09 | 昆明理工大学 | Method for efficiently treating ammonia desulfurization mother liquor through multistage oxidation |
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