CN108310938A - By dechlorination to control the method and system of desulfurization wastewater discharge - Google Patents
By dechlorination to control the method and system of desulfurization wastewater discharge Download PDFInfo
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- CN108310938A CN108310938A CN201810354239.7A CN201810354239A CN108310938A CN 108310938 A CN108310938 A CN 108310938A CN 201810354239 A CN201810354239 A CN 201810354239A CN 108310938 A CN108310938 A CN 108310938A
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
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- B01D53/34—Chemical or biological purification of waste gases
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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Abstract
It is provided by the invention by dechlorination to control the method and system of desulfurization wastewater discharge, method is：Before carrying out wet desulphurization, to deduster before flue in spray alkaline absorbent, with reacted with the gaseous chlorine in flue gas generate particle containing chlorine；Flue gas before carrying out wet desulphurization, still provides for the injection of alkaline absorbent and collects the particle containing chlorine of formation after deduster dedusting；Wherein, the emitted dose of alkaline absorbent is determined according to the content of gaseous chlorine, gaseous chlorine removal efficiency in exhaust gas volumn, flue gas.This programme is before carrying out wet desulphurization, the gaseous chlorine in flue gas is removed by acid-base neutralization reaction, and the alkaline absorbent amount of injection by chlorine for the purpose of approaching and be totally removed, the particle containing chlorine generated after reaction is removed by deduster, into without outside waste discharge, fully realizing active desulfurization wastewater zero-emission.And this programme is " two-stage dechlorination ", can meet the content's index regulation about chlorine so that complete dechlorination disclosure satisfy that practical application in industry.
Description
Technical field
The present invention relates to flue gases purification fields, and in particular to it is a kind of by dechlorination with control desulfurization wastewater discharge side
Method and system.
Background technology
Chlorinity is different with coal in coal in China, and according to existing analysis, the average content of chlorine is more than in anthracite
Chlorine average content is in 180mg/kg or so in 200mg/kg, bituminous coal and lignite.Chlorine is in coal mostly with alkali metal chloride, nothing
The forms such as machine chloride are present in the lattice of coal.Combustion mechanism research shows that chlorine element in combustion mainly with HCl shapes
Formula is discharged into flue gas, while having a small amount of Cl2With particulate form chlorine.
In coal unit, particulate form chlorine is removed by dry collector, and removal efficiency is 90% or more；And gaseous chlorine (HCl and
Cl2) the then cooperation-removal in Limestone-gypsum Wet Flue Gas Desulfurization Process, i.e., in the absorption tower of wet desulfurization system while desulfurization
Also gaseous chlorine is removed, arresting efficiency is 93% or more.
Limestone-gypsum method flue gas desulfurization technique (WFGD) is at present in the SO that China is most widely used, technology is most ripe2
Removing sulfuldioxide accounts for about and has installed the 90% of flue gas desulfurization (FGD) unit capacity, this technique has desulfuration efficiency high, reliable for operation
Property it is high, absorbent utilization rate is high, adapts to large sized unit and high concentration SO2The features such as flue gas condition.
However, following defects can be led to by removing chlorine while wet desulphurization：
In above-mentioned technical process, the chlorine element in coal-fired flue-gas, lime stone and process water can be dissolved in desulfurization slurry,
So that chlorine ion concentration gradually rises in desulfurization slurry.Gaseous chlorine wherein in coal-fired flue-gas is the master of chlorion in desulfurization slurry
Want source.When chlorine ion concentration is excessively high in desulfurization slurry, the corrosion of equipment and pipeline can be caused, and then influence the fortune on absorption tower
Row and service life；SO can also be inhibited2Physical and chemical reaction process between desulfurization slurry, influences SO2It absorbs, reduces de-
Sulphur efficiency；Simultaneously as the presence of chlorion can inhibit the dissolving of absorbent, and then make the consumption of desulfurization absorbent with chlorination
The increase of object concentration and increase, remaining absorbent also increases with it in gypsum slurries, and desulfuration efficiency is made to reduce, and increases follow-up
Gypsum dehydration is difficult, influences gypsum qualitt.
Therefore, in order to ensure system stabilization safe operation and keep higher desulfuration efficiency, wet method is de- for current coal-burning power plant
A certain amount of desulfurization slurry must be periodically discharged in sulphur system, general to maintain desulfurization slurry to reduce desulfurization slurry chlorion degree of enrichment
Chlorine ion concentration is in 10000mg/L~20000mg/L or so in liquid.
But said program still has defect, because the desulfurization slurry being periodically discharged is unable to direct emission, needs to carry out
Wastewater treatment.There is existing wet desulphurization waste water high salt content, suspension content height, hardness height to cause easy fouling, corrosivity strong
And water quality it is different with operating mode at any time and the characteristics of change.Traditional wastewater treatment is divided into wastewater treatment based on chemical means
With Treatment of Sludge two parts, direct emission after being handled by dosing coagulating sedimentation.Traditional chemical precipitation method is to make at present
With most wide method for treating desulfurized wastewater, have easy to operate, operating cost is low, the advantages that capable of making desulfurization wastewater qualified discharge,
But there is dosages greatly, sludge yield is big, water outlet salt content is high, low to the removal efficiency such as chlorion salt and selenium, mercury etc. to lack
Point, direct emission can cause secondary pollution, the problems such as causing the salinization of soil in soil, surface water salt content to increase, and seriously affect
The surface water quality of adjacent domain.Meanwhile this method equipment is more, construction investment is costly.
Domestic desulfurization wastewater zero-discharge technology currently in use is mainly made of 3 parts at present：Wastewater Pretreatment softens, is dense
Reduction and curing process.Wherein, pretreatment softening is by changes such as feeding lime-sodium carbonate, sodium hydroxide-sodium carbonate
Medicament is learned to go the calcium and magnesium hardness in water removal；Concentration decrement the purpose is to reduce wastewater flow rate, reduce subsequent evaporation curing system
Investment and operating cost, including the concentration of hot method and film concentration.Hot method concentration mainly uses multiple-effect evaporation (MED) or mechanical vapour
Waste water concentrating is to close to solute saturated mode after recompressing (MVR) technique and pre-processing, in addition, reverse osmosis, electrodialysis, positive infiltration etc.
Embrane method Decrement Technique has also been employed for wastewater reduction operation；Curing process is that the waste water after being concentrated to softening is evaporated knot
The evaporation of brilliant or fume afterheat, makes the moisture in waste water vaporize, the outer row of salinity solidification crystallization, final to realize desulfurization wastewater zero-emission.
As it can be seen that in order to realize that the zero-emission of desulfurization wastewater, this field have been devoted to change desulfuration waste water treatment process
Into nevertheless, waste water treatment process is required for taking time and effort, and a large amount of equipment increases production cost.
Therefore, desulfurization wastewater zero-emission how is realized as possible, and can simplify equipment, reduces cost, is art technology
Personnel's technical problem urgently to be resolved hurrily.
Invention content
In order to solve the above technical problems, this programme provide it is a kind of by dechlorination with control desulfurization wastewater discharge method and
System can simplify equipment, reduce cost under the premise of realizing desulfurization wastewater zero-emission as possible.
Method provided by the invention by dechlorination to control desulfurization wastewater discharge,
Before carrying out wet desulphurization, to deduster before flue in spray alkaline absorbent, with the gas in flue gas
The reaction of state chlorine generates particle containing chlorine；
Flue gas before carrying out wet desulphurization, still provides for the injection of alkaline absorbent and continues to collect after deduster dedusting
The particle containing chlorine formed；
Wherein, the emitted dose of above-mentioned alkaline absorbent is removed according to the content of gaseous chlorine, gaseous chlorine in exhaust gas volumn, flue gas
Efficiency determines.
Optionally, the injection of alkaline absorbent is carried out at least at following one：
Flue, front flue of dust collector before flue, air preheater before SCR reactors.
Optionally, chlorinity limit value is set, according to the chlorinity limit value, the alkalinity before controlling the deduster absorbs
Agent emitted dose makes chlorinity in the particulate matter of the deduster collection be not higher than chlorinity limit value.
Optionally, alkaline absorbent is sprayed in the form of powder or droplet into flue gas, powder diameter ranging from 1~100 μ
The particle size range of m, droplet are 1~500 μm.
Optionally, the alkaline absorbent is Ca agent, Mg agent or Na agent；
The alkaline absorbent is controlled according to following ratios：
Ca2+With the molar equivalent ratio ranging from 0.1~3 of Cl-；
Mg2+With the molar equivalent ratio ranging from 0.1~3 of Cl-；
Na+With the molar equivalent ratio ranging from 0.1~4 of Cl-.
Optionally, residence time of the alkaline absorbent in flue gas is 0.2~10 second, and/or the injection position chosen
The flue-gas temperature for setting place is 90~410 DEG C.
Optionally, molar equivalent ratio, the chlorine of alkaline absorbent type, grain size, temperature, alkaline absorbent and gaseous chlorine are established
The correspondence of five parameters of removal efficiency；
When injection, according to the temperature at the type of alkaline absorbent, eject position, alkaline absorbent grain size is chosen, to protect
Card is under the molar equivalent ratio of isodose, chlorine removal efficiency highest.
System provided by the invention by dechlorination to control desulfurization wastewater discharge, including：
Injection apparatus, the flue between flue and deduster and absorption tower before deduster, is used for flue
Middle injection alkaline absorbent, alkaline absorbent can be reacted with the gaseous chlorine in flue gas generates particle containing chlorine；Wherein, the injection
Device sprays the emitted dose of alkaline absorbent, is determined according to the content of gaseous chlorine, gaseous chlorine removal efficiency in exhaust gas volumn, flue gas；
Further include grain catcher, the grain catcher is between the deduster and the absorption tower, for receiving
Collection corresponding position injection apparatus sprays alkaline absorbent and reacts the particle containing chlorine generated with the gaseous chlorine in flue gas.
Optionally, further include metering feeding device, the metering feeding device contains according to gaseous chlorine in exhaust gas volumn, flue gas
Amount and gaseous chlorine removal efficiency determine the amount of the alkaline absorbent provided to the injection apparatus.
Optionally, the downstream of boiler is sequentially equipped with SCR reactors, air preheater, deduster, before the deduster
Flue include it is following at least one：
Flue, the front flue of dust collector before flue, air preheater before SCR reactors.
Optionally, the grain catcher is electric precipitator or bag dust collector.
This programme is mainly before carrying out wet desulphurization, i.e., middle a certain amount of alkalinity of injection in flue before deduster
Absorbent removes the gaseous chlorine in flue gas by acid-base neutralization reaction, and the alkaline absorbent amount sprayed is chlorine to be totally removed
Or for the purpose of being almost totally removed, the particle containing chlorine generated after reaction is removed by deduster, prevents the gaseous chlorine in flue gas in advance
Into in the absorption tower of wet desulfurization system.When chlorine ion concentration reduction in the slurries on absorption tower, the corrosion feelings of equipment and pipeline
Condition is alleviated, and the operation on absorption tower and service life increase, and desulfuration efficiency also can be improved, and gypsum qualitt correspondingly improves.
Accordingly, due in flue gas gaseous chlorine be removed, chlorion is eliminated or only has a small amount of chlorion in desulfurization slurry
(being discharged eventually by gypsum) is not required into active desulfurization wastewater zero-emission without outside waste discharge, is fully realized
It considers further that how to optimize wastewater treatment realizes zero-emission, but greatly extends the discharge period, it might even be possible to not arrange almost.Cause
This, the program not only solves the problem of discharge of wastewater causes water resource waste in wet desulfurization system, meanwhile, it is big without input
Amount fund buys desulfurization wastewater processing equipment and builds corresponding establishment, saves substantial contribution.Moreover, this method and simple system,
Operation facility, equipment investment is low, and operation is convenient, can be widely applied to wet fuel gas desulfurizing technology.
In addition, this programme sprays alkaline absorbent in the flue before deduster, and after deduster dedusting also into
The removing of chlorine of row realizes " two-stage dechlorination ", and the collection of the particle containing chlorine is carried out after firsts and seconds dechlorination.This
Sample, one side two-stage dechlorination are conducive to chlorine and remove more thorough, and it is possible to after controlling level-one dechlorination and two level dechlorination, receive
The content of the particle containing chlorine of collection, to meet the content's index regulation about chlorine so that complete dechlorination disclosure satisfy that actual industrial is answered
With.
Description of the drawings
Fig. 1 is a kind of structural schematic diagram of wet desulfurization system provided by the present invention；
It is 343 DEG C that Fig. 2, which is in test temperature, selects trona (NaHCO3) it is used as alkaline absorbent, and with dry powder shape
When formula is sprayed, chlorion removal efficiency and Na+:The contrast curve of Cl-molar ratio, grain size；
It is 343 DEG C that Fig. 3, which is in test temperature, selects grain size to make alkaline absorbent for 25 μm of trona, and with dry powder shape
In flue before formula penetrating air preheater, HCl concentration sprays into the change curve of time with absorbent；
It is 163 DEG C that Fig. 4, which is in test temperature, selects trona (NaHCO3) it is used as alkaline absorbent, and with dry powder shape
When formula is sprayed, chlorion removal efficiency and Na+:The contrast curve of Cl-molar ratio, grain size；
Fig. 5 is the structural schematic diagram of another wet desulfurization system provided by the present invention.
The reference numerals are as follows in Fig. 1-5：
10- boilers；20- economizers；30-SCR reactors；40- air preheaters；50- dedusters；
60- air-introduced machines；The absorption towers 70-；70a- exhaust outlets；80- injection apparatus；90- grain catchers.
Specific implementation mode
It is below in conjunction with the accompanying drawings and specific real in order to make those skilled in the art more fully understand technical scheme of the present invention
Applying example, the present invention is described in further detail.
Referring to FIG. 1, Fig. 1 is a kind of structural schematic diagram of wet desulfurization system provided by the present invention.
The flue gas flowed out from boiler 10, generally can be followed by economizer 20, SCR reactors 30, in order to utilize heat, also
Air preheater 40 is further set, the flue gas of discharge and the air for entering boiler 10 exchange heat in air preheater 40, to
Enter the air of boiler 10 using flue-gas temperature heating.Deduster 50 is also set up in 40 downstream of air preheater, deduster 50 exists
Both it is not limited in the present embodiment, can be electric precipitator (being illustrated as electric precipitator) or bag dust collector, can also be
Combination or compound.Absorption tower 70 is set in the downstream of deduster 50, to carry out wet desulphurization, purified flue gas is from absorption tower
70 exhaust outlet 70a discharges.In Fig. 1, it is additionally provided with air-introduced machine 60 between deduster 50 and absorption tower 70, is provided for flow of flue gas
Power enters convenient for flue gas in absorption tower 70.
The present embodiment provides a kind of systems by dechlorination to control desulfurization wastewater discharge, as shown in Figure 1, the system includes
Injection apparatus 80, injection apparatus 80 can spray alkaline absorbent into flue.Alkaline absorbent for example can be sodium base, magnesium-based,
One kind in calcium base or two kinds two or more configure.
Alkaline absorbent can be sprayed in dry powder form, can also be to be sprayed in the form of solution, suspension, lotion
It injects into flue, solution, suspension, lotion droplet rapid evaporation in flue, the alkaline absorbent fine grained after droplet evaporation
Object reacts in flue gas with gaseous chlorine, and configuration solution, suspension, lotion, concentration can control within the scope of 1-500g/L.Alkalinity absorbs
When dry powder is selected as in agent, powder diameter may range from 1~100 μm, in the range to ensure gas-solid reaction efficiency；Alkalinity absorbs
When agent is sprayed with solution, suspension, lotion droplet shape, mist droplet particle size may range from 1~500 μm.For ease of in difference
At a temperature of fully react, need according to different temperatures provide reaction needed for time, in the present solution, alkaline absorbent is in flue gas
Residence time be 0.2~10 second, can be far from deduster 50 such as when injection apparatus 80 is set in the preceding flue of deduster 50
Certain distance, to guarantee to there is time enough to be reacted.
The system can also include specifically conveying equipment and metering feeding device, and conveying equipment is for conveying alkaline absorbent
To injection apparatus 80, metering feeding device controls the emitted dose of injection apparatus 80 according to required alkaline absorbent amount.Injection dress
Injection stream etc. can be adjusted according to demand by setting 80, to ensure that alkaline absorbent is uniformly mixed with flue gas.
Here the alkaline absorbent amount needed for is determined according to the content of gaseous chlorine in exhaust gas volumn, flue gas.It can be from this programme
Operation principle understand, principle be exactly using acid-base neutralization reaction generate salt, by flue gas gaseous state chlorine body carrying chlorion
Removing, such as injection alkaline absorbent NaHCO3、Ca(OH)2、Mg(OH)2The reaction of Shi Fasheng：
3NaHCO3+SO2+ gaseous chlorine → Na2SO3+NaCl+2H2O+3CO2
3/2Ca(OH)2+SO2+ gaseous chlorine → CaSO3+1/2CaCl2+2H2O
3/2Mg(OH)2+SO2+ gaseous chlorine → MgSO3+1/2MgCl2+2H2O
Therefore, exhaust gas volumn and the content of gaseous chlorine can be monitored, you can the amount for knowing the gaseous chlorine that needs neutralize, according to anti-
Formula, and reaction efficiency when injection are answered, the emitted dose of required alkaline propellant can be calculated.
This programme removes chlorine before wet desulphurization, is as follows：
It is equipped with alkaline absorbent；
According to exhaust gas volumn, the online monitoring data of gaseous state chlorinity and gaseous chlorine removal efficiency, determine that required alkalinity is inhaled
Alkaline absorbent is delivered to injection dress by the emitted dose for receiving agent by conveying equipment by measuring feeding device feed via pipeline
Set 80；
It in duct sorbent injection alkaline absorbent, is sprayed by injection apparatus 80, injection apparatus 80 can be according to coverage rate, spray
Radion diameter etc. is because usually controlling, such as when the alkaline absorbent of injection is dry powder, i.e., powdered, then can control compressed air and
Flow ensures that alkaline absorbent is uniformly mixed with flue gas, improves reaction efficiency, particle containing chlorine is generated after reaction；
The particle containing chlorine is collected before wet desulphurization.For example, in Fig. 1, the particle containing chlorine ultimately generated can be absorbed
The deduster 50 of tower upstream is collected.
Due to generation particle containing chlorine needs be collected, deduster 50 be wet desulfurization system before flue gas emission
In cleaner inherently, so injection apparatus 80 may be provided in before the deduster 50 of wet desulfurization system.Such as Fig. 1 institutes
Show, injection apparatus 80 is arranged in the flue before deduster 50 at three altogether, the preceding flue of SCR reactors 30 is located at first, i.e.,
The flue of upstream, it is specific between SCR reactors 30 and economizer 20；It is located at the preceding flue of air preheater 40 at second,
That is the flue of upstream, it is specific between air preheater 40 and SCR reactors 30；It is located at the preceding cigarette of deduster 50 at third
Road, the i.e. flue of upstream, it is specific between deduster 50 and air preheater 40.It is appreciated that being at least arranged at one at three
The purpose that can reach removing chlorine is respectively provided at three certainly, and the removal effect of chlorine can be more preferable.Injection reaction generates above three
Particle containing chlorine collected by deduster 50.
With continued reference to FIG. 2, Fig. 2 is to select trona (NaHCO3) it is used as alkaline absorbent, and spray in dry powder form
When penetrating, chlorion removal efficiency and Na+:The contrast curve of Cl-molar ratio, grain size.In Fig. 2, alkaline absorbent is in air
It is sprayed in flue before preheater 40, test temperature is 343 DEG C, selects 20 μm, 25 μm, 35 μm, 45 μm of dry powder injections
Grain size compares different Na+:The removing effect of chlorion under Cl-molar ratio (ratio of reaction alkaline absorbed dose of radiation and gaseous state chlorine dose)
Rate.Generally speaking, with Na+:Cl-molar ratio increases, and HCl removal efficiencies increase, that is, increasing alkaline absorbent emitted dose can carry
The removal efficiency of high chlorine；Moreover, when it is 45 μm to select grain size, preferable removal efficiency can be reached with smaller molar ratio.
By experiment, when with Ca2+:Cl—And Mg2+:Cl—When as parameter, two kinds of chemical molar equivalent ratios can be 0.1~3
It is chosen in range；With Na+:Cl—When as parameter, Na+:Cl—Chemical molar equivalent ratio can be selected between 0.1~4
It takes., it should be understood that in practical boiler fired coal exhaust process, actual condition belong to the process of dynamic change, such as exhaust gas volumn, smoke temperature with
And coal-fired coal quality etc., the molar equivalent ratio of alkaline absorbent and chlorine delimited through overtesting into line range here, is convenient for basis
Actual condition and dechlorination effect feedback carry out the adjustment of alkaline absorbent emitted dose in the range, choose and are most suitable for current work
The molar equivalent ratio of condition.
With continued reference to FIG. 3, Fig. 3 is that the trona that grain size is 25 μm is selected to make alkaline absorbent, and spray in dry powder form
Enter in the flue before air preheater 40, HCl concentration sprays into the change curve of time with absorbent.Test temperature is 343
DEG C, it can be seen that the HCl concentration after alkaline absorbent penetrating 2min in flue gas drastically declines, 20ppmv is dropped to from 76ppmv,
As time increases, HCl concentration constantly declines in flue gas, and ultimate density is down to 0.
Please see that Fig. 4, Fig. 4 are to select trona (NaHCO again3) it is used as alkaline absorbent, and when spraying in dry powder form,
Chlorion removal efficiency and Na+:The contrast curve of Cl-molar ratio, grain size.In Fig. 4, alkaline absorbent is in deduster 50
It is sprayed in flue before, test temperature is 163 DEG C, selects 20 μm, 25 μm, 35 μm of dry powder injection grain sizes, comparison different
Na+:The removal efficiency of chlorion under Cl-molar ratio.As seen from the figure, with Na+:Cl-molar ratio rises, and HCl removal efficiencies carry
Height, grain size can reach preferable removal efficiency when being 25 μm with smaller molar ratio.
Comparison diagram 2,4 is it is found that injection apparatus 80 for different location, due to the difference of test temperature, particle size and
Molar ratio, the relationship of chlorine removal efficiency simultaneously differ, such as in Fig. 2, under 343 DEG C of test temperatures, bigger grain size, more favorably
In reaching preferable removal efficiency under smaller molar ratio；And under 163 DEG C of test temperatures, but for the 25 of centre position size
μm grain size, is more advantageous under smaller molar ratio and reaches preferable removal efficiency.
Therefore, can establish alkaline absorbent type, grain size, temperature, alkaline absorbent and gaseous chlorine molar equivalent ratio,
The correspondence of five parameters of chlorine removal efficiency.When injection, can according to the temperature at the type of alkaline absorbent, eject position,
Choose alkaline absorbent grain size, to ensure under the molar equivalent ratio of isodose, chlorine removal efficiency highest.Cigarette at eject position
Temperature degree is generally between 90~410 DEG C, for example, general in 30 entrance of SCR reactors and 40 inlet position of air preheater
Between 300~410 DEG C, and 50 inlet temperature of deduster is generally at 90~170 DEG C.
It, can root i.e. in the present solution, due to having further contemplated grain size than, the influence of temperature, molar ratio to removal efficiency
According to different eject positions, highest removal efficiency is realized with minimum cost, to have scientific and reasonable guidance to make to spraying
With economy can be improved.
This programme is mainly before carrying out wet desulphurization, i.e., middle a certain amount of alkali of injection into flue before deduster 50
Property absorbent, the gaseous chlorine in flue gas is removed by acid-base neutralization reaction, and the alkaline absorbent amount sprayed is with all de- by chlorine
For the purpose of removing or being almost totally removed, the particle containing chlorine generated after reaction is removed by deduster 50, prevents the gas in flue gas in advance
State chlorine enters in the absorption tower 70 of wet desulfurization system.When chlorine ion concentration reduction, equipment and pipeline in the slurries on absorption tower 70
Corrosion condition alleviate, the operation on absorption tower 70 and service life increase, and desulfuration efficiency also can be improved, and gypsum qualitt correspondingly becomes
It is good.
Accordingly, due in flue gas gaseous chlorine be removed, chlorion is eliminated or only has a small amount of chlorion in desulfurization slurry
(being discharged by gypsum) no longer examines into active desulfurization wastewater zero-emission without outside waste discharge, is fully realized
How worry, which optimizes wastewater treatment, is realized zero-emission, but greatly the extension discharge period, (Examples below discharged for several times 1 hour
It is extended for discharging 1 time for 16 hours), it might even be possible to it does not arrange almost.Therefore, the program not only solves water in wet desulfurization system and provides
The problem of source wastes, meanwhile, without putting into substantial contribution purchase desulfurization wastewater processing equipment and building corresponding establishment, save a large amount of
Fund.Moreover, this method and simple system, operation facility, equipment investment is low, and operation is convenient, can be widely applied to wet method
Flue gas desulfurization technique.
More specifically four embodiments will be hereafter enumerated, dechlorination is carried out for a specific 360MW coal unit
Experiment.
Embodiment 1
It selects trona to do alkaline absorbent, sprays in dry powder form.Storage device is arranged at this time, storage device includes storage
Tank, storage tank are equipped with feed inlet and exhaust outlet, and the two can be set to the top of storage tank.Powder can pass through gas by external mobile storage tank vehicle
Pump is squeezed into storage tank, and filter, such as bag filter can be installed at the top vent of storage tank, to filter gas containing powder,
Discharge gas is avoided to carry dust polluting environment while keeping pressure of storage tank to stablize.
On-line detector can be arranged, the content of gaseous chlorine can be measured by on-line detector, and flue gas flow can be by flue gas flow
Meter detection obtains, then combines the content of exhaust gas volumn and gaseous chlorine that can calculate required alkaline absorbent emitted dose, then should
Data are exported to metering feeding device, and metering feeding device has function of weighing, can by after required alkaline dry powder accurate weighing,
It is sent into conveying equipment, conveying equipment front half section conveying high-pressure air source can be used by alkaline dry powder after being connect with metering feeding device
High-pressure air source is through pipeline to injection apparatus 80.Injection apparatus 80 can adjust injection flow velocity according to demand, can also adjust pressure
Contracting air and powder proportions ensure that powder is uniformly mixed with flue gas.More than, detection calculates and to metering feeding device, conveying
The control of equipment, all can by controller control and monitor, to realize on the spot, remote control, and can with DCS (power plant point
Cloth control system) communication robust is reliable.
Specifically, injection flow control is 150g/h, and spray site is selected in before air preheater 40 at flue, powder diameter choosing
With 45 μm, 343 DEG C of smoke temperature, Na+/ Cl-chemistry molar equivalent is than selecting 0.81.
Carry out calculating analysis for this 360MW coal units, flue gas composition is as shown in table 1 below, the chlorine through following formula from
Quantum balancing formula (1) can calculate the wastewater flow rate of unit：
QPCP+QFCm-QF’Cn=QWCW+QgCg (1)
In formula：Qp is industrial water, m3/h；QFFor 70 import flue gas flow (6%O of absorption tower2, butt, mark condition), m3/h；
QF’For 70 exiting flue gas flow (6%O of absorption tower2, butt, mark condition), m3/h；QWFor wastewater discharge, m3/h；QgIt is produced for gypsum
Amount, kg/h；CPFor chlorine ion concentration in industry water, kg/m3；CmFor chlorine ion concentration in 70 import flue gas of absorption tower, kg/m3；Cn
For chlorine ion concentration (generally taking 0) in 70 exiting flue gas of absorption tower, kg/m3；CWFor chlorine ion concentration in waste water, mg/L；CgFor stone
Chlorine ions percentage in cream, generally 0.01% (using no free water gypsum as benchmark)；
It can be calculated through table 1, generator set desulfurization wastewater flow rate is 5.11m before non-dechlorination3/h.After chlorine removing in flue gas, due to
Chlorine ion concentration declines to a great extent in flue gas so that desulfurization wastewater amount declines therewith.Assuming that setting Na+/Cl—Molar equivalent ratio is
0.81, HCl removal efficiency is 99.9% (can refer to Fig. 2), is calculated through chloride equilibrium, desulfurization wastewater will decline to a great extent after dechlorination
To 0.32m3/ h, then desulfurization wastewater discharge in 16 hours is primary, realizes the emission reduction of desulfurization wastewater, reduces wastewater treatment running cost
With.When not carrying out prior dechlorination, may be drained for several times generally in 1 hour.
Certain the 1 × 360MW unit limestone-gypsum method flue gas desulfurization project discharge of wastewater result of calculation of table 1
Embodiment 2
Specific method and system and embodiment 1 are essentially identical, except that the eject position of alkaline absorbent is selected in and removes
Before dirt device 50, the removal efficiency of gaseous chlorine is up to 98% (as shown in Figure 4) at this time.
Embodiment 3
Specific method and system embodiment 1 are essentially identical, are a difference in that and change alkaline absorbent injection grain size into 35 μm,
Gaseous chlorine removal efficiency is up to 99.8%.
Embodiment 4
Specific method and system embodiment 1 are essentially identical, are a difference in that alkaline absorbent being substituted for Ca (OH)2, gas
State chlorine removal efficiency is up to 95%.
Above example mainly for injection apparatus 80 individually the flue before the deduster 50 or air preheater 40 it
Preceding flue all has very high removal efficiency, almost eliminates into the flue gas before sulfur removal technology after spraying alkaline absorbent
In gaseous chlorine.Obviously, when the two before SCR reactors, before air preheater 40, before deduster 50 or both arrangement above
When injection apparatus 80, removal efficiency can be promoted further, can be according to the feedback of the removal efficiency of chlorine, at selection one or many places
Injection apparatus 80 is set, to take into account efficiency and cost.
With continued reference to FIG. 5, Fig. 5 is the structural schematic diagram of another wet desulfurization system provided by the present invention.
The system and wet desulfurization system structure described in Fig. 1 are essentially identical, differ only in, in Fig. 5 embodiments, no longer
Air-introduced machine 60 is set, but another cleaner, i.e. grain catcher 90 are set between deduster 50 and absorption tower 70, and
Injection apparatus 80 is set simultaneously at this, which can be electric precipitator or bag dust collector.
That is, in this embodiment, flue gas before carrying out wet desulphurization, can still carry out after 50 dedusting of the deduster
The injection of alkaline absorbent simultaneously continues the absorbent granules containing chlorine that removing is formed by grain catcher 90, is equivalent to form " two
Grade dechlorination ", deduster 50 is primary dust removing equipment, and grain catcher 90 is two-stage dust removal equipment.Level-one dechlorination is in deduster
Injection apparatus 80 is set before 50, and the particle containing chlorine generated is collected by deduster 50；Two level dechlorination be after deduster 50,
Injection apparatus 80 is set before absorption tower 70, and the particle containing chlorine generated is collected by corresponding grain catcher 90.
As previously mentioned, injection apparatus 80 is arranged only in previous place's flue of deduster 50, sprayed according to alkaline absorbent
The control of the parameters such as amount, the removal efficiency of chlorine can reach 98%, 99% or more, substantially eliminate chlorine, and two are arranged at this time
Grade dechlorination, it is clear that the removal efficiency of chlorine can be further increased so that chlorine removes more thorough, total alkalinity of two-stage dechlorination
Sorbent injection amount is still and is determined according to the removal efficiency of the content of chlorine, exhaust gas volumn and gaseous chlorine at different levels；Also,
Due to caning be controlled in the emitted dose of two-stage dechlorination process neutral and alkali adsorbent, after level-one dechlorination and two level dechlorination can be controlled, receive
The content of the particle containing chlorine of collection, to meet the content's index regulation about chlorine so that complete dechlorination disclosure satisfy that actual industrial is answered
With.
Specifically, chlorinity limit value can be set, according to chlorinity in the chlorinity limit value and flue gas, controls dedusting
Alkaline absorbent emitted dose before device 50, so that chlorinity is not higher than chlorinity limit value in the particulate matter that deduster 50 is collected,
Chlorinity limit value can be determined according to dust purposes.This is primarily due to deduster 50 in addition to collecting particle containing chlorine, substantially
Function is the particle collected in flue gas, obtains flyash, flyash collecting amount is larger, can industrially there is application, is applying
When according to the difference of purposes, can generally set the index limitation of chlorinity, for example, flyash the industries such as building materials using when just have
Certain chlorinity index limitation, here can be by controlling emitted dose, it is ensured that the chlorinity of flyash will not be exceeded, without secondary
Processing, such as can be used as cement matrix；It is more than after chlorinity limit value controls, it is desirable to reduce remove if chlorinity is higher
Alkaline absorbent straying quatity before dirt device 50, corresponding its are discharged chlorine in flue gas and may handle not enough thoroughly, at this point, two level dechlorination
It plays a role, can remove remaining chlorine, the grain catcher 90 when two level dechlorination only will produce a small amount of flyash, accordingly
This part ash chlorinity may be higher, can only carry out landfill disposal or be used as roadbed.
The embodiment, compared to Fig. 1 schemes, it is clear that the process that can preferably control dechlorination, before meeting abundant dechlorination
It puts, and the flyash chlorine for not interfering with collection is exceeded.It is found that when chlorinity is relatively low, in the flyash that deduster 50 is collected
Chlorinity may not be more than chlorinity limit value, and the secondary granule trap 90 in 50 downstream of deduster can not also be opened at this time,
Correspondingly, injection apparatus 80 herein can not also be opened, and unlatching joint dechlorination dedusting is also possible of course simultaneously, Ke Yijian
It cares for dechlorination effect and economy is selected.The mould to sum up, embodiment can be put into operation by coordination level-one, secondary smoke dechlorination
Formula and corresponding alkaline absorbent straying quatity, it is ensured that flyash chlorinty meets the index of different usages, realizes full coal
It plants, the coal-fired flue-gas dechlorination combined desulfurization wastewater zero discharge that full working scope and flyash chlorinity are up to standard.
It the above is only the preferred embodiment of the present invention, it is noted that those skilled in the art are come
It says, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should be regarded as
Protection scope of the present invention.
Claims (11)
1. the method by dechlorination to control desulfurization wastewater discharge, which is characterized in that
Before carrying out wet desulphurization, to deduster before flue in spray alkaline absorbent, with the gaseous chlorine in flue gas
Reaction generates particle containing chlorine；
Flue gas is after deduster dedusting, before carrying out wet desulphurization, still provides for the injection of alkaline absorbent and continue to collect to be formed
Particle containing chlorine；
Wherein, the emitted dose of above-mentioned alkaline absorbent, according to the content of gaseous chlorine, gaseous chlorine removal efficiency in exhaust gas volumn, flue gas
It determines.
2. the method by dechlorination to control desulfurization wastewater discharge as described in claim 1, which is characterized in that at least following
The injection of alkaline absorbent is carried out at one：
Flue, front flue of dust collector before flue, air preheater before SCR reactors.
3. the method by dechlorination to control desulfurization wastewater discharge as described in claim 1, which is characterized in that setting chlorinity
Limit value controls the alkaline absorbent emitted dose before the deduster according to the chlorinity limit value, and the deduster is made to collect
Particulate matter in chlorinity be not higher than chlorinity limit value.
4. the method as described in any one of claims 1-3 by dechlorination to control desulfurization wastewater discharge, which is characterized in that alkali
Property absorbent is sprayed in the form of powder or droplet into flue gas, ranging from 1~100 μm of powder diameter, the particle size range of droplet
It is 1~500 μm.
5. the method as described in any one of claims 1-3 by dechlorination to control desulfurization wastewater discharge, which is characterized in that institute
It is Ca agent, Mg agent or Na agent to state alkaline absorbent；
The alkaline absorbent is controlled according to following ratios：
Ca2+With the molar equivalent ratio ranging from 0.1~3 of Cl-；
Mg2+With the molar equivalent ratio ranging from 0.1~3 of Cl-；
Na+With the molar equivalent ratio ranging from 0.1~4 of Cl-.
6. the method as described in any one of claims 1-3 by dechlorination to control desulfurization wastewater discharge, which is characterized in that institute
It is 0.2~10 second to state residence time of the alkaline absorbent in flue gas, and/or the flue-gas temperature at the eject position chosen is 90
~410 DEG C.
7. the method as described in any one of claims 1-3 by dechlorination to control desulfurization wastewater discharge, which is characterized in that build
Vertical alkaline absorbent type, five parameters of molar equivalent ratio, chlorine removal efficiency of grain size, temperature, alkaline absorbent and gaseous chlorine
Correspondence；
When injection, according to the temperature at the type of alkaline absorbent, eject position, alkaline absorbent grain size is chosen, to ensure
Under the molar equivalent ratio of isodose, chlorine removal efficiency highest.
8. the system by dechlorination to control desulfurization wastewater discharge, which is characterized in that including：
Injection apparatus, the flue between flue and deduster and absorption tower before deduster, for being sprayed into flue
Alkaline absorbent is penetrated, alkaline absorbent can be reacted with the gaseous chlorine in flue gas generates particle containing chlorine；Wherein, the injection apparatus
The emitted dose for spraying alkaline absorbent is determined according to the content of gaseous chlorine, gaseous chlorine removal efficiency in exhaust gas volumn, flue gas；
Further include grain catcher, the grain catcher is between the deduster and the absorption tower, for collecting phase
It answers injection apparatus injection alkaline absorbent at position and reacts the particle containing chlorine generated with the gaseous chlorine in flue gas.
9. the system by dechlorination to control desulfurization wastewater discharge as claimed in claim 8, which is characterized in that further include metering
Feeding device, the metering feeding device are determined according to the content of gaseous chlorine in exhaust gas volumn, flue gas and gaseous chlorine removal efficiency
The amount of the alkaline absorbent provided to the injection apparatus.
10. the system by dechlorination to control desulfurization wastewater discharge as claimed in claim 8, which is characterized in that under boiler
Trip is sequentially equipped with SCR reactors, air preheater, deduster, the flue before the deduster include it is following at least one：
Flue, the front flue of dust collector before flue, air preheater before SCR reactors.
11. the system by dechlorination to control desulfurization wastewater discharge as claimed in claim 8, which is characterized in that the particle
Trap is electric precipitator or bag dust collector.
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