CN109342284A - A detection system and detection method for harmful substances in flue gas - Google Patents
A detection system and detection method for harmful substances in flue gas Download PDFInfo
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- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
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- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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Abstract
本发明公开了一种用于烟气中有害物质的检测系统及检测方法，该检测系统包括烟气采样单元、空气吹扫单元、三氧化硫检测单元、可凝结颗粒物捕集单元、汞检测单元、第一自动采样仪、第二自动采样仪和数控装置；烟气采样单元、三氧化硫检测单元、可凝结颗粒物补集单元、汞检测单元和第一自动采样仪依次连通，空气吹扫单元与烟气采样单元的烟气出口连通，第二自动采样仪通过第一干燥瓶与可凝结颗粒物检测单元的烟气出口连通；数控装置分别与烟气采样单元、空气吹扫单元、三氧化硫检测单元、可凝结颗粒物捕集单元、汞检测单元、第一自动采样仪和第二自动采样仪电连接。上述检测系统操作便捷、适用性强，应用范围广，可对烟气中多种有害物质进行检测。
The invention discloses a detection system and a detection method for harmful substances in flue gas. The detection system includes a flue gas sampling unit, an air purging unit, a sulfur trioxide detection unit, a condensable particulate matter capture unit, and a mercury detection unit. , the first automatic sampler, the second automatic sampler and the numerical control device; the flue gas sampling unit, the sulfur trioxide detection unit, the condensable particulate matter collection unit, the mercury detection unit and the first automatic sampler are connected in sequence, and the air purge unit It is communicated with the flue gas outlet of the flue gas sampling unit, and the second automatic sampler is communicated with the flue gas outlet of the condensable particulate matter detection unit through the first drying bottle; the numerical control device is respectively connected with the flue gas sampling unit, the air purging unit, the sulfur trioxide The detection unit, the condensable particulate matter capture unit, the mercury detection unit, the first automatic sampler and the second automatic sampler are electrically connected. The above detection system is convenient to operate, has strong applicability, and has a wide range of applications, and can detect a variety of harmful substances in flue gas.
Description
Technical field
The present invention relates to flue gas emission control technology field more particularly to a kind of detection systems for harmful substances from flue gases
System.The invention further relates to a kind of detection methods for harmful substances from flue gases.
Background technique
Current China achieves larger achievement on traditional coal smoke type contamination control, with typical coal-burning power plant's pollutant
For control means, realized by the gas pollution controls facility such as SCR denitration, electrostatic or bag-type dusting and wet desulphurization to combustion
NOx, flue dust and SO in flue-gas2Minimum discharge.However, being effectively controlled in above-mentioned three kinds traditional coal-fired flue-gas pollutants
In the case where, air heavily contaminated phenomenon still protrudes in region, restricts the sustainable development of social economy, threatens public's body strong
Health.Therefore outside above-mentioned three kinds of pollutants, coal fire discharged condensable particulate matter, heavy metal Hg, SO3The pollution of equal initiations is increasingly
It is taken seriously, becomes new research hotspot.
Coal fire discharged particulate matter can be divided into directly discharge in solid form may filter that particulate matter (filterable
Particulate matter, FPM) and condensable particulate matter (Condensable Particulate Matter, CPM).Root
According to the definition of US Gov Env Protection Agency (EPA), CPM refers to be existed in a gaseous form in flue, is emitted into atmosphere immediately
Condense the substance of the solid-state or liquid particles object that are formed.From the perspective of morphology, CPM is mainly agglomerated by gaseous material, partial size one
As less than 1 μm, belong to fine particle, be present in surrounding air in the form of an aerosol.It is various due to being usually enriched on CPM
The pollutants such as heavy metal (such as Se, As, Pb, Cr) and PAHs (polycyclic aromatic hydrocarbon), mostly carcinogen and genotoxicity paramorphogen
Matter, it is very harmful.
Analysis according to Louis A.Corio team of the U.S. to the 18 granular material discharged results of coal-fired flue-gas in the U.S., flue gas
It is that account for total particle object amount average value be 51% to 49%, FPM that CPM, which accounts for total particle object amount average value, in particulate matter.This means that coal-fired
CPM discharge amount is in phase same level, and its portion in the total emission volumn of PM10 and PM2.5 with FPM substantially in flue gas
It is bigger, it can not be ignored.However, conventional particle detection method is only applicable to the trapping of FPM at present, coal-burning particle cannot be represented
The true emission behaviour of object.It can be seen that accurate detection CPM discharge amount calculates particulate matter of the coal-fired source to environmental emission to complete,
Realize that particulate matter emission reduction has great significance to real.
Coal fire discharged SO3It is mainly derived from two aspects: being on the one hand in coal-fired process about 0.5~1.5% sulfur meeting
It is oxidized to SO3, be on the other hand during SCR denitration, under the effect of the catalyst in flue gas about 1~2% or so SO2
It is converted into SO3.SO for the medium-high sulfur coal that burns, in the flue gas of the exit SCR3Concentration is up to 100~200mg/m3。SO3With
The ammonium hydrogen sulfate (ABS) generated after the reaction of SCR process escape ammonia not only influences the catalytic activity of catalyst itself, and is easily adhered
On subsequent air preheater heat-transfer surface, cause the corrosion and blocking of equipment.In addition, dischargeing the SO of atmosphere from chimney entrance3
By complicated physics chemical action, environmental pollution phenomenons such as " blue smokes " are formed.
Mercury in coal-fired flue-gas is mainly with gaseous state nonvalent mercury (Hg0), gaseous state divalent ion mercury (Hg2+) and particle mercury
(Hgp) etc. three kinds of forms exist, wherein nonvalent mercury (Hg0) account for about the 30%~80% of flue gas total mercury content.Nonvalent mercury (Hg0) no
It is dissolved in water, and volatility is extremely strong, existing dedusting or desulphurization plant are difficult to capture, and almost all is discharged into the atmosphere；Bivalent mercury
(Hg2+) soluble easily in water, it is also easily adsorbed by the particulate matter in flue gas, so existing dedusting and desulphurization plant are to bivalent mercury (Hg2+)
There is certain removal efficiency；Particle mercury (Hgp) then easily trapped by cleaner.Therefore, it is discharged into atmosphere in coal-fired flue-gas
Mercury mainly by nonvalent mercury (Hg0) and a small amount of bivalent mercury (Hg2+) composition.
Currently, most domestic coal-fired flue-gas is to realize pollutant removing by pollutant minimum discharge technology, due to
It is low etc. by flue gas presentation high humility, low temperature, the pollutant concentration discharged after wet desulphurization wherein the characteristics of wet desulfurizing process
Feature, horizontal to pollutant monitoring more stringent requirements are proposed, moreover, the existing coal-fired flue-gas contamination detection method in China is big
More are detected to Single Pollution object and (there is no related specifications standard to CPM detection method in particulate matter), to different pollutants
Detection method between to interfere with each other consideration insufficient.Therefore, coal-fired flue-gas condensable particle can be detected simultaneously by developing one kind
The system and method for object, sulfur trioxide and heavy metal Hg seem very necessary and urgently.
Summary of the invention
The purpose of the present invention is to solve at least one above-mentioned problem, which is by the following technical programs
It realizes.
The present invention provides a kind of detection systems for harmful substances from flue gases, including flue gas sampling unit, air to blow
Sweep unit, sulfur trioxide detection unit, condensable particle collection unit, mercury detection unit, the first automatic sampling instrument, second certainly
Dynamic sampling instrument and numerical control device；
The flue gas sampling unit, the sulfur trioxide detection unit, the condensable particulate matter supplementary set unit, the mercury
Detection unit and first automatic sampling instrument are sequentially communicated, the flue gas of the air purge unit and the flue gas sampling unit
Outlet, second automatic sampling instrument pass through the exhanst gas outlet of the first drying bottle and the condensable particulate matter detection unit
Connection；
The numerical control device is detected with the flue gas sampling unit, the air purge unit, the sulfur trioxide respectively
Unit, the condensable particle collection unit, the mercury detection unit, first automatic sampling instrument and described second are automatically
Sampling instrument electrical connection.
Preferably, the flue gas sampling unit includes gas sampling gun, sampling gun sealing flange, S type Pitot tube and built-in
The sampling end of the hot filtration apparatus of quartz filter, the gas sampling gun is arranged in flue, and the S type Pitot tube is arranged in institute
It states on sampling end, the gas sampling gun is affixed by the outer wall of the sampling gun sealing flange and the flue, the heating
The exhanst gas outlet of the gas sampling gun is arranged in filter, and the exhanst gas outlet of the hot filtration apparatus is connected by the first heat tracing pipe
It is connected to the first triple valve, first triple valve is connected to the sulfur trioxide detection unit and air purge unit respectively；
The gas sampling gun includes quartz glass tube and stainless steel tube, and the quartz glass tube is sleeved on the stainless steel
In pipe.
Preferably, the air purge unit includes the air compressor machine, air filter and air heater being sequentially communicated, institute
It states air heater to be connected to by the first compressed air hose with first triple valve, the air heater passes through the second compression
Air hose is connected to the gas inlet of the sulfur trioxide detection unit, is provided with the first valve on second compressed air hose.
Preferably, the sulfur trioxide detection unit includes the first flue gas condenser, absorbs liquid case, absorbing liquid pump, centre
Case, flush box, flush water pump, buffering liquid case, buffer solution pump, developer solution liquid case, developer solution liquid pump, delivery pump and luminosity
Meter；
First flue gas condenser includes the first serpentine condenser and the second serpentine condenser, the first snakelike condensation
One end connection of pipe has the second heat tracing pipe of the second valve, and one end connection of second serpentine condenser has the of third valve
Three heat tracing pipes, second heat tracing pipe and the third heat tracing pipe are parallel in the one outlet of first triple valve, described
The other end of first serpentine condenser is provided with the 4th valve, and the other end of second serpentine condenser is provided with the 5th valve, institute
It states the 4th valve and the 5th valve is respectively connected to the arrival end of the 4th heat tracing pipe with the 6th valve, the condensable particulate matter is caught
The gas inlet of collection unit is connected to the 4th heat tracing pipe, and communicating position is located at the front end of the 6th valve；
The absorption liquid case by the absorbing liquid pump respectively with the entrance of first serpentine condenser, second snake
The entrance of shape condenser pipe is connected to first valve, and the communicating position of the absorbing liquid pump and first serpentine condenser is arranged
There is the 7th valve, the absorbing liquid pump and the communicating position of second serpentine condenser are provided with the 8th valve；
The intermediate box respectively with first serpentine condenser outlet and the second serpentine condenser outlet, institute
The communicating position for stating intermediate box and first serpentine condenser is provided with the 9th valve, and the intermediate box is snakelike cold with described second
The communicating position of solidifying pipe is provided with the tenth valve；
The photometer includes light source, PH electrode, absorption cell and detector, and the absorption cell is transparent configuration, the light
Source and the detector are split in the two sides of the absorption cell, and the PH electrode is arranged in the absorption cell, the intermediate box
It being connected to by the delivery pump with the absorption cell, the flush box is connected to by the flush water pump with the absorption cell,
The buffering liquid case is connected to by the buffer solution pump with the absorption cell, and the developer solution liquid case passes through the developer solution
Liquid pump is connected to the absorption cell.
Preferably, the condensable particle collection unit includes the second flue gas condenser, deionization water tank, deionized water
Pump hits bottle, the filter of built-in filter membrane, the second drying bottle, nitrogen cylinder, n-hexane case and n-hexane pump；
Second flue gas condenser is built-in with third serpentine condenser, and the third serpentine condenser passes through the 11st valve
Be connected to the 4th heat tracing pipe, and communicating position is located at the front end of the 6th valve, the nitrogen cylinder by the 12nd valve with
The entrance of the third serpentine condenser is connected to, and the n-hexane case passes through n-hexane pump and the third serpentine condenser
Entrance connection, the communicating position of n-hexane pump and the third serpentine condenser is provided with the 13rd valve, it is described go from
Sub- water tank is connected to by the deionization water pump with the entrance of the third serpentine condenser, the deionization water pump and described the
The communicating position of three serpentine condensers is provided with the 14th valve, and the outlet of the third serpentine condenser is sequentially communicated the shock
The outlet of bottle, the filter and second drying bottle, second drying bottle is dry by the 5th heat tracing pipe and described first
Dry bottle is connected to, and is provided with the 15th valve on the 5th heat tracing pipe, and the rear end of the 6th valve is connected to the 5th heat tracing pipe,
The communicating position of 6th valve and the 5th heat tracing pipe is located at the rear end of the 15th valve, and first drying bottle goes out
Mouth is connected to by the 6th heat tracing pipe with second automatic sampling instrument.
Preferably, the mercury detection unit includes the second triple valve, third triple valve, total mercury reforming unit, nonvalent mercury turn
Makeup is set, third drying bottle and mercury analyzer, second triple valve are connected to the 5th heat tracing pipe, the total mercury conversion dress
The entrance set is connected to by the 7th heat tracing pipe with second triple valve, and the entrance of the zero frame mercury reforming unit passes through the 8th companion
Heat pipe is connected to second triple valve, and the outlet of the total mercury reforming unit and the outlet of the zero frame mercury reforming unit are distinguished
It being connected to the third triple valve, the third triple valve is connected to by the 9th heat tracing pipe with the entrance of the third drying bottle,
The outlet of the third drying bottle is connected to by the tenth heat tracing pipe with the analyzer, and the analyzer passes through the 11st heat tracing pipe
It is connected to first automatic sampling instrument.
Preferably, the mercury analyzer mainly includes mercury lamp, heater, measuring chamber, mercury detector, and the one of the measuring chamber
The outlet at end and the third drying bottle, the other end of the measuring chamber is connected to first automatic sampling instrument, described
Mercury lamp and the mercury detector are separately positioned on the two sides when measurement, and the heater is arranged close to the measuring chamber.
The present invention provides a kind of detection method for harmful substances from flue gases, and the detection method by using as described above
Implement in the detection system of harmful substances from flue gases, which comprises the steps of:
S1: each unit equipment is connected as required, starts numerical control device, the temperature of gas sampling gun is set in
200~240 DEG C, the temperature of hot filtration apparatus is set in 200~240 DEG C, by the first heat tracing pipe, the second heat tracing pipe and third companion
The temperature of heat pipe is set in 200~240 DEG C, by the 4th heat tracing pipe, the 5th heat tracing pipe, the 7th heat tracing pipe, the 8th heat tracing pipe and
The temperature of nine heat tracing pipes is set in 110~120 DEG C, and the temperature of the 6th heat tracing pipe, the tenth heat tracing pipe and the 11st heat tracing pipe is set
40~50 DEG C are scheduled on, the first flue gas condenser temperature is set in 60~80 DEG C, the second flue gas condenser temperature is set in 30
DEG C hereinafter, when temperature reach control require after start to sample；
S2: opening the first automatic sampling instrument and the second automatic sampling instrument, controls sampling flow by numerical control device, first certainly
Dynamic sampling instrument, which generates negative pressure with the second automatic sampling instrument, makes flue gas to be measured is continuous, constant speed enters there is the flue gas of S type Pitot tube to adopt
Sample rifle, hot filtration apparatus are mounted in flue gas sampling gun back end, remove by hot filtration apparatus and may filter that the flue gas of particulate matter by the
One heat tracing pipe, the first triple valve, the second heat tracing pipe or third heat tracing pipe enter the first flue gas condenser, at this point, the first triple valve
It is remained turned-off with the compressed air line of air purge unit；
S3: after flue gas enters the first flue gas condenser, be parallel in the first flue gas condenser the first serpentine condenser and
Second serpentine condenser, two groups of serpentine condensers replace switch operating, when sulfur trioxide in one group of serpentine condenser condensation flue gas
When for sulfuric acid droplets, condensed sulfuric acid droplets are sent into luminosity after intermediate box mixes with absorbing liquid in another group of serpentine condenser
Meter carries out chromogenic reaction in photometer and color developing agent, detects the content of sulfur trioxide in reaction solution, use flushing water after detection
It is switched to another group of serpentine condenser after flushing and continues to test next group, such cycle operation；
S4: the flue gas of sulfur trioxide has been condensed according to requiring to be passed through condensable particle collection unit by the 4th heat tracing pipe
Or next component detection unit is passed through by the 5th heat tracing pipe, it is passed sequentially through when flue gas enters condensable particle collection unit
Third serpentine condenser, shock bottle and filter, the particulate matter of flue gas condensable at this time are caught through condensation, collision and membrane filtration
Collection takes out filter membrane from filter after trapping, is stored in special container, while being sent into first into third serpentine condenser
Deionized water makes inorganic component and deionized water in condensate liquid be mixed to form inorganic phase in hitting bottle, then with nitrogen to pipe
In road residual liquid and hit bottle in inorganic phase purged, purging finish after be sent into third serpentine condenser just oneself
Alkane makes organic component and n-hexane in condensate liquid be mixed to form organic phase in hitting bottle, and inorganic phase, organic phase are together with filter membrane
Laboratory to be returned carries out condensable particulate matter off-line analysis；
S5: flue gas a part by S4 step is arranged from system after recording sampling volume by the second automatic sampling instrument
Out, another part enters mercury detection unit, into mercury detection unit after flue gas divide two-way: be total mercury reforming unit all the way, be used for
Bivalent mercury in flue gas is completely converted into nonvalent mercury；Another way is nonvalent mercury reforming unit, for absorbing bivalent mercury in flue gas, only
Retain nonvalent mercury, mercury analyzer is entered by the flue gas of reforming unit after drying, utilizes atomic absorption spectrum in mercury analyzer
Method detects the nonvalent mercury concentration in flue gas, and mercury detection unit realizes different price by the control of the second triple valve and third triple valve
The measurement request of state mercury, the difference of two-way mercury concentration are mercuric concentration in flue gas, and the flue gas after detecting mercury is automatic by first
Sampling instrument is discharged from system.
Preferably, the nonvalent mercury reforming unit includes be sequentially connected in series 5~15% KC1 solution wash bottle and 5~15%
The first NaOH solution wash bottle, the KC1 solution wash bottle is connected to the 8th heat tracing pipe, the first NaOH solution wash bottle with
The third triple valve connection；
The total mercury reforming unit includes be sequentially connected in series 5~15% the second NaOH solution wash bottle and 5~15%
SnCl2Solution wash bottle, the second NaOH solution wash bottle are connected to the 7th heat tracing pipe, the SnCl2Solution wash bottle with it is described
The connection of third triple valve.
Preferably, absorbing liquid is 5% aqueous isopropanol in the sulfur trioxide detection unit, and buffer is that dilute NaOH is molten
Liquid, chromogenic reagent solution 1,3-N, N '-is bis--and the dimethyl sulfoxide of [4- (4 '-nitrophenylazo) phenyl] different side's acid diamides is molten
Liquid.
Compared with prior art, the detection system and detection method provided by the present invention for harmful substances from flue gases has
It has the advantage that
1. the present invention is according to sampling and the testing principle of flue gas condensable particulate matter, sulfur trioxide and mercury, organic coupling three
The sample detecting unit of person, it is reasonable in design, it is easy to operate, it is easy to accomplish sample detecting while three of the above component, it can
It is widely used in the monitoring system of atmosphere multiple pollutant.
2. flue gas pipeline is all made of heat tracing pipe between each detection unit of the present invention, and different zones heat tracing pipe controls not equality of temperature
Degree, avoids flue gas from condensing on the flue gas pipeline outside each detection unit while energy consumption is effectively reduced, guarantee have in flue gas
Effect ingredient is all detected, and error is reduced, and by air purge unit, is carried out regular blowback cleaning to systematic pipeline, protected
Card system is continuous, continual sample detecting.
3. passing through three oxidations in two groups of serpentine condensers condensation flue gases in parallel in sulfur trioxide detection unit of the present invention
Sulphur, two groups of serpentine condensers work alternatively, and continuous, uninterrupted detection may be implemented, meanwhile, with a kind of azo dyes (BNBPS)
Color developing agent of the DMSO solution as sulfate ion, using SO in direct spectrophotometry measurement condensate liquid4 2-Concentration, directly
Measure SO3Content is removed the disturbing factors such as cumbersome precipitation and separation from compared with existing barium salt-indirect spectrophotometric methods, is mentioned
The precision of high detection.
4. mercury detection unit of the present invention is equipped in parallel nonvalent mercury reforming unit and total mercury reforming unit, and on demand can be with
When switching, it can be achieved that flue gas nonvalent mercury and total mercury while, is detected, and mercuric content is equal to total mercury and subtracts nonvalent mercury, i.e.,
On-line checking while flue gas different valence state mercury may be implemented.
5. flue gas of the present invention uses isokinetic sampling, the detection of flue gas condensable particulate matter caused by avoiding because of various speed sampling
Error, and condensable particle collection unit is arranged in parallel by-pass line, when condensable particle collection finishes progress offline
When analysis, flue gas directly arrives next detection unit without influencing subsequent detection by bypass.
Detailed description of the invention
By reading the following detailed description of the preferred embodiment, various other advantages and benefits are common for this field
Technical staff will become clear.The drawings are only for the purpose of illustrating a preferred embodiment, and is not considered as to the present invention
Limitation.And throughout the drawings, the same reference numbers will be used to refer to the same parts.In the accompanying drawings:
Fig. 1 is the structural block diagram of the detection system provided by the present invention for harmful substances from flue gases；
Fig. 2 is the flow chart of the detection method provided by the present invention for harmful substances from flue gases.
Appended drawing reference
001 is the first valve, and 002 is the second valve, and 003 is third valve, and 004 is the 4th valve, and 005 is the 5th valve, and 006 is the 6th
Valve, 007 is the 7th valve, and 008 is the 8th valve, and 009 is the 9th valve, and 010 is the tenth valve, and 011 is the 11st valve, and 012 is the 12nd
Valve, 013 is the 13rd valve, and 014 is the 14th valve, and 015 is the 15th valve；
100 be the first heat tracing pipe, and 101 be the second heat tracing pipe, and 102 be third heat tracing pipe, and 103 be the 4th heat tracing pipe, and 104 are
5th heat tracing pipe, 105 be the 6th heat tracing pipe, and 106 be the 7th heat tracing pipe, and 107 be the 8th heat tracing pipe, and 108 be the 9th heat tracing pipe,
109 be the tenth heat tracing pipe；
1 is flue gas sampling unit, and 11 be gas sampling gun, and 12 be S type Pitot tube, and 13 be sampling gun sealing flange, and 14 are
Hot filtration apparatus, 15 be the first triple valve；
2 be air purge unit, and 21 be air compressor machine, and 22 be air filter, and 23 be air heater；
3 be sulfur trioxide detection unit, and 301 be the first flue gas condenser, and 3011 be the first serpentine condenser, and 3012 be the
Two serpentine condensers, 302 be absorbing liquid pump, and 303 is absorb liquid case, and 304 be intermediate box, and 305 be delivery pump, and 306 be buffer
Pump, 307 be flush water pump, and 308 be flush box, and 309 is buffer liquid case, and 310 be developer solution liquid case, and 311 be developer solution
Liquid pump, 312 be photometer, and 3121 be detector, and 3122 be PH electrode, and 3123 be absorption cell, and 3124 be light source；
4 be condensable particle collection unit, and 41 be nitrogen cylinder, and 42 be the second flue gas condenser, and 421 is snakelike cold for third
Solidifying pipe, 43 be deionization water pump, and 44 be deionization water tank, and 45 be n-hexane case, and 46 pump for n-hexane, and 47 is hit bottle, and 48 are
Filter, 49 be the second drying bottle；
5 be mercury detection unit, and 51 be the second triple valve, and 52 be nonvalent mercury reforming unit, and 53 be total mercury reforming unit, and 54 are
Third triple valve, 55 be mercury analyzer, and 551 be mercury lamp, and 552 be heater, and 553 be measuring chamber, and 554 be mercury detector, and 56 are
Third drying bottle；
6 be the first automatic sampling instrument；
7 be the second automatic sampling instrument；
8 be the first drying bottle；
9 be numerical control device.
Specific embodiment
The illustrative embodiments of the disclosure are more fully described below with reference to accompanying drawings.Although showing this public affairs in attached drawing
The illustrative embodiments opened, it being understood, however, that may be realized in various forms the disclosure without the reality that should be illustrated here
The mode of applying is limited.It is to be able to thoroughly understand the disclosure on the contrary, providing these embodiments, and can be by this public affairs
The range opened is fully disclosed to those skilled in the art.
Fig. 1 and Fig. 2 are please referred to, Fig. 1 is the structure of the detection system provided by the present invention for harmful substances from flue gases
Block diagram；Fig. 2 is the flow chart of the detection method provided by the present invention for harmful substances from flue gases.
In a specific embodiment, the detection system for harmful substances from flue gases provided by the present invention, specifically
Sample detecting while applied to flue gas condensable particulate matter, sulfur trioxide and mercury, including flue gas sampling unit 1, air purging
Unit 2, sulfur trioxide detection unit 3, condensable particle collection unit 4, mercury detection unit 5, the first automatic sampling instrument 6,
Two automatic sampling instruments 7 and numerical control device 9；Flue gas sampling unit 1, sulfur trioxide detection unit 3, condensable particulate matter supplementary set list
Member, mercury detection unit 5 and the first automatic sampling instrument 6 are sequentially communicated, and air purge unit 2 and the flue gas of flue gas sampling unit 1 go out
Mouth connection, the second automatic sampling instrument 7 are connected to by the first drying bottle 8 with the exhanst gas outlet of condensable particulate matter detection unit；Number
Control device 9 respectively with flue gas sampling unit 1, air purge unit 2, sulfur trioxide detection unit 3, condensable particle collection list
Member 4, mercury detection unit 5, the first automatic sampling instrument 6 and the electrical connection of the second automatic sampling instrument 7.Gas sampling gun 11 passes through sampling gun
Sealing flange 13 and the outer wall of flue are affixed, and the inside of flue, gas sampling gun 11 is arranged in the collection terminal of gas sampling gun 11
For the stainless steel tube for embedding quartz glass tube, stainless steel tube installs thermocouple additional, and also arrangement makes flue gas on 11 inner wall of gas sampling gun
Sampling gun 11 maintains 200~240 DEG C of heating layer, and thermocouple is connect with heating layer with numerical control device 9, when thermocouple is transmitted to numerical control
Numerical control device 9 feeds back to heating layer heating signal when the surveyed flue-gas temperature of device 9 is lower, guarantees the temperature of gas sampling gun 11
200~240 DEG C are maintained, measurement error caused by preventing flue gas from condensing in sampling gun.
Flue gas sampling realized by the negative pressure that the first automatic sampling instrument 6 and the second automatic sampling instrument 7 provide, flue gas sampling
11 leading portion of rifle, which is also matched, is set with S type Pitot tube 12, for measuring flue gas total pressure and static pressure difference and pressure signal being transmitted to number in real time
Device 9 is controlled, the second automatic sampling instrument 7 is fed back to after pressure signal is converted into flow signal by numerical control device 9, second adopts automatically
Sample instrument 7 adjusts flue gas sampling flow according to flow signal in real time, guarantees that flue gas flow rate is consistent with flue gas sampling flow velocity in flue, i.e.,
Isokinetic sampling.
Hot filtration apparatus 14 is arranged in the rear end of gas sampling gun 11, may filter that particulate matter in flue gas for filtering, heating
Filter 14 includes quartz filter (replaceable), filter membrane support component, heating device and thermocouple, and passes through thermocouple, numerical control
Temperature signal transmitting between device 9 and heating device is with feedback to maintain 14 temperature of hot filtration apparatus at 200~240 DEG C.
First triple valve 15 is arranged in the exhanst gas outlet of hot filtration apparatus 14, and the exit end of the first triple valve 15 passes through the
Two heat tracing pipes 101 and third heat tracing pipe 102 are connect with sulfur trioxide detection unit 3, and the other end passes through compressed air hose and air
Purge unit 2 connects, and wherein air purge unit 2 includes air compressor machine 21, air filter 22 and air heater 23, air compressor machine
21 compressed airs provided heat after air filter 22 removes the impurity such as particle, greasy dirt, the moisture in air through air
Device 23 purges after being heated to 40~50 DEG C for system pipeline, guarantees continuous, the uninterrupted operation of system.
100 to the 11st heat tracing pipe of the first heat tracing pipe is interior outer double-layer structure in Fig. 1, and internal layer is polytetrafluoroethylene (PTFE)
(PTFE) it manages, in polyfluortetraethylene pipe external sheath heater strip and heat preservation outer layer, and passes through numerical control device 9, heater strip and heat preservation
Temperature signal transmitting between outer layer is with feedback to maintain heat tracing inner tube smoke required temperature.
The flue gas acquired through flue gas sampling unit 1 passes through the second heat tracing pipe 101 first or third heat tracing pipe 102 enters three oxygen
Change the first flue gas condenser 301 of sulphur detection unit 3, the temperature of the first flue gas condenser 301 is controlled by numerical control device 9
System.First serpentine condenser 3011 and the second snakelike condensation in parallel are set in first flue gas condenser 301 of present embodiment
Pipe 3012, the entrance of two serpentine condensers pass through threeway and corresponding valve and the second heat tracing pipe 101 or third heat tracing pipe respectively
102, air purge unit 2 is connected with liquid case 303 is absorbed, and the outlet of two serpentine condensers is connected by threeway with corresponding valve
Intermediate box 304 and the 4th heat tracing pipe 103.
It for the first serpentine condenser 3011, is connected to by the first valve 001 with air purge unit 2, by the second valve 002 and
The connection of two heat tracing pipes 101, is connected to absorbing liquid pump 302 by the 7th valve 007, is connected to by the 4th valve 004 with the 4th heat tracing pipe 103,
It is connected to by the 9th valve 009 with intermediate box 304；For the second serpentine condenser 3012, by the first valve 001 and air purge unit 2
Connection, is connected to third heat tracing pipe 102 by third valve 003, is connected to by the 8th valve 008 with absorbing liquid pump 302, by the 5th valve 005
It is connected to the 4th heat tracing pipe 103, is connected to by the tenth valve 010 with intermediate box 304.
It absorbs liquid case 303 and absorbing liquid pump 302 is set, for absorbing liquid pump 302 to be entered two serpentine condensers, intermediate box
Delivery pump 305, the absorption for the mixed liquor of intermediate box 304 being pumped into photometer 312 are set between 304 and photometer 312
Pond 3123.
Sulfur trioxide detection unit 3 further includes flush box 308 and flush water pump 307, by pipeline and intermediate box 304 with
Absorption cell 3123 in photometer 312 connects, the flushing for intermediate box 304 and absorption cell 3123.Likewise, buffering liquid case
309 are connected with buffer solution pump 306, developer solution liquid case 310 and developer solution liquid pump 311 by corresponding pipeline and absorption cell 3123
It connects, be respectively used to absorb the pH control of mixed liquor in absorption cell 3123 and absorb the colour developing of mixed liquor.The one of absorption cell 3123
Light source 3124 is arranged in side, is received through the light in reactive absorption pond 3123 by the detector 3121 and is converted to SO4 2-Concentration signal passes
To numerical control device 9.PH electrode 3122 is also installed in absorption cell 3123, PH electrode 3122 passes 3123 solution ph signal of absorption cell
To with numerical control device 9, numerical control device 9 according to pH value control buffer solution pump 306 operation, guarantee absorb liquor pH be maintained at
Testing requirements.Intermediate box 304 and absorption cell 3123 are arranged discharge pipe and are used for drain.
The flue gas for having detected sulfur trioxide through sulfur trioxide detection unit 3 enters condensable particle with the 4th heat tracing pipe 103
Object capture unit 4.Due to carrying out off-line analysis after flue gas condensable particle collection in present embodiment, with condensable
Bypass, threeway, the 11st valve 011, the 6th valve 006 and the 15th valve 015 is arranged in parallel in particle collection unit 4, can coagulate every time
Flue gas is bypassed to next detection unit after knot particle collection, to not influence continuous, the uninterrupted fortune of system
Row.The temperature of second flue gas condenser 42 is controlled by numerical control device 9 in condensable particle collection unit 4.Second cigarette
Third serpentine condenser 421 is set in gas condenser 42, by the 11st valve 011, the 12nd valve 012, the 13rd valve 013 and the tenth
Four valves 014 control 421 entrance of third serpentine condenser and the 4th heat tracing pipe 103, nitrogen cylinder 41, deionization water tank 44, between
Connection.The outlet of third serpentine condenser 421, which is set gradually, hits bottle 47, filter 48, the second drying bottle 49.Filter 48 includes
Quartz filter (replaceable), filter membrane support component and temperature sensor, temperature sensor are connect with numerical control device 9, detection and control
Flue-gas temperature is not more than 30 DEG C at filter 48 processed.Deionization is set between deionization water tank 44 and third serpentine condenser 421
Water pump 43, for the deionization water pump 43 of deionization water tank 44 to be entered third serpentine condenser 421.N-hexane case 45 and third snake
N-hexane is set between shape condenser pipe 421 and pumps 46, for the n-hexane pump 46 of n-hexane case 45 to be entered third serpentine condenser
421。
Third drying is passed sequentially through with 104 a part of the 5th heat tracing pipe by the flue gas of condensable particle collection unit 4
It is discharged from system after bottle 56 and the second automatic sampling instrument 7, another part enters mercury detection unit 5.First adopts sampling instrument automatically
With flow, temperature, pressure instrumentation are set in the second automatic sampling instrument 7, and relevant parameter is passed in numerical control device 9 and is carried out
Sampling volume analysis.
Flue gas into mercury detection unit 5 divides two-way, controls flue gas by the second triple valve of import 51 and third triple valve 54
Into total mercury reforming unit 53 or nonvalent mercury reforming unit 52.The outlet of third triple valve 54 passes through the 9th heat tracing pipe 108 successively
It is connect with third drying bottle 56, mercury analyzer 55, the first automatic sampling instrument 6.The side setting of measuring chamber 553 in mercury analyzer 55
Mercury lamp 551, the light issued by mercury lamp 551 are irradiated to mercury detector 554, mercury detector after measuring chamber 553 is absorbed by mercury atom
554 optical signals are converted to mercury concentration signal and pass to numerical control device 9.Furthermore, heater 552 is set in mercury analyzer 55, is kept
The stabilization of optical unit temperature avoids baseline drift caused by temperature.
In present embodiment numerical control device 9 detect, show, record, feed back and control the temperature of above-mentioned each unit, pressure,
The signals such as flow, pH, concentration.The mixed liquor SO wherein detected according to photometer 3124 2-Concentration signal and the second automatic sampling instrument 7
Sampling volume signal calculate sulfur trioxide in flue gas concentration；According to the mercury concentration signal and the of mercury analyzer 55 (506) detection
Two triple valves 51 connect signal with third triple valve 54 and show flue gas total mercury concentration and nonvalent mercury concentration, and it is dense to calculate bivalent mercury
Degree.In addition, numerical control device 9 records the sampling volume of the second automatic sampling instrument 7 during flue gas condensable particle collection, and it is offline
The condensable particulate matter weight analyzed calculates the concentration of flue gas condensable particulate matter together.
Please continue to refer to Fig. 1 and Fig. 2, the present invention provides the detection method for harmful substances from flue gases, the detection sides
Method is implemented by being used for the detection system of harmful substances from flue gases as described above, which comprises the steps of:
S1: each unit equipment is connected as required, starts numerical control device 9, and the temperature of gas sampling gun 11 is set
At 200~240 DEG C, the temperature of hot filtration apparatus 14 is set in 200~240 DEG C, by the first heat tracing pipe 100, the second heat tracing pipe
101 and the temperature of third heat tracing pipe 102 be set in 200~240 DEG C, by the 4th heat tracing pipe 103, the 5th heat tracing pipe 104, the 7th companion
The temperature of heat pipe 106, the 8th heat tracing pipe 107 and the 9th heat tracing pipe 108 is set in 110~120 DEG C, by the 6th heat tracing pipe 105,
The temperature of ten heat tracing pipes 109 and the 11st heat tracing pipe is set in 40~50 DEG C, and 301 temperature of the first flue gas condenser is set in 60
~80 DEG C, 42 temperature of the second flue gas condenser is set in 30 DEG C hereinafter, starting to sample when temperature reaches after control requires；
S2: the first triple valve 15 is transferred to flue gas sampling unit 1 and is connect with the second heat tracing pipe 101 or third heat tracing pipe 102, opens
The first automatic sampling instrument 6 and the second automatic sampling instrument 7 are opened, sampling flow, the first automatic sampling instrument 6 are controlled by numerical control device 9
Generating negative pressure with the second automatic sampling instrument 7 makes that flue gas to be measured is continuous, constant speed enters the gas sampling gun with S type Pitot tube 12
11, hot filtration apparatus 14 is mounted in 11 rear end of gas sampling gun, removes by hot filtration apparatus 14 and may filter that the flue gas of particulate matter is logical
It crosses the first heat tracing pipe 100, the first triple valve 15, the second heat tracing pipe 101 or third heat tracing pipe 102 and enters the first flue gas condenser
301, at this point, the first triple valve 15 and the compressed air line of air purge unit 2 remain turned-off；
S3: after flue gas enters the first flue gas condenser 301, it is snakelike cold that first is parallel in the first flue gas condenser 301
Solidifying pipe 3011 and the second serpentine condenser 3012, two groups of serpentine condensers replace switch operating, when one group of serpentine condenser condenses
When sulfur trioxide is sulfuric acid droplets in flue gas, condensed sulfuric acid droplets and absorbing liquid are in intermediate box in another group of serpentine condenser
It is sent into photometer 312 after 304 mixing, chromogenic reaction is carried out in photometer 312 and color developing agent, detects sulfur trioxide in reaction solution
Content is switched to another group of serpentine condenser and continues to test next group after being rinsed after detection with flushing water, such circulation industrial
Make.Specifically, third valve 003, the first valve 001, the 7th valve 007, the 8th valve 008, the tenth valve 010 remain turned-off, Open valve
Second valve 002 makes flue gas by the first serpentine condenser 3011, and sulfur trioxide is condensed into sulfuric acid droplets in flue gas, when flue gas condensing
Between according to using flow control in 5~10min.After first serpentine condenser 3011 samples, the second valve of valve 002 is closed,
Open valve third valve 003 switches to the second serpentine condenser 3012, continues to condense the sulfur trioxide in flue gas.It opens at this time
5% aqueous isopropanol of absorption liquid case 303 is pumped into first by absorbing liquid pump 302 by the 7th valve 007 of valve and the 9th valve 009
It is different in 30~60s, 5% to be pumped into time control in 30~50mL for serpentine condenser 3011, the 5% aqueous isopropanol control being pumped into
Propyl alcohol and sulfuric acid droplets mixed liquor pass through the 9th valve 009 feeding intermediate box 304.Absorbing liquid pump 302 is closed after sending, and is beaten simultaneously
The first valve 001 is opened, using the compressed air of air purge unit 2 is blown into the residual liquid in the first serpentine condenser 3011
Between case 304, purge time control in 30~60s.Valve the first valve 001, the second valve 002, the 9th valve are closed after purging
009, open delivery pump 305, the absorption cell 3123 mixed liquor of intermediate box 304 being delivered on a small quantity in photometer 312.It closes defeated
Developer solution liquid pump 311 is opened after sending pump 305, color developing agent a certain amount of in developer solution liquid case 310 is pumped into absorption cell 3123,
And then buffer solution pump 306 is opened, dilute NaOH solution in buffering liquid case 309 is pumped into absorption cell 3123, adjusts absorption cell 3123
Mixed liquor pH value be 4.5~7.5.Buffer solution pump 306 and developer solution liquid pump 311 are closed after adjusting pH, at this time light source 3124
The light that wavelength is 630-650nm is issued, after the absorption of absorption cell 3123, the light of transmission is received by detector 3121 and by SO4 2-It is dense
Degree signal feeds back to numerical control device 9.Obtain SO4 2-After concentration signal, the mixed liquor in intermediate box 304 and absorption cell 3123 is discharged,
Flush water pump 307 is opened simultaneously, the deionization water pump 43 of flush box 308 is entered intermediate box 304 and absorption cell 3123, rinses phase
It closes container and closes flush water pump 307 after waste liquid is discharged, first group of measurement terminates at this time.
After next group is measured as the sampling of the second serpentine condenser 3012, valve third valve 003, Open valve are closed
Second valve 002 switches to the first serpentine condenser 3011 and is sampled, the measurement of sulfuric acid droplets in the second serpentine condenser 3012
Method is identical as the first serpentine condenser 3011, only correspond to valve by the 7th valve 007, the 9th valve 009 become the 8th valve 008,
Tenth valve 010.
S4: the flue gas of sulfur trioxide has been condensed according to requiring to be passed through condensable particle collection by the 4th heat tracing pipe 103
Unit 4 is passed through next component detection unit by the 5th heat tracing pipe 104, when flue gas enters condensable particle collection unit 4
When pass sequentially through third serpentine condenser 421, hit bottle 47 and filter 48, the particulate matter of flue gas condensable at this time and condensed, touched
Hit with membrane filtration and be captured, after trapping from filter 48 take out filter membrane, be stored in special container, at the same first to
It is sent into deionized water in third serpentine condenser 421, mixes inorganic component in condensate liquid in hitting bottle 47 with deionized water
Inorganic phase is formed, then inorganic phase in residual liquid in pipeline and shock bottle 47 is purged with nitrogen, after purging
It is sent into n-hexane into third serpentine condenser 421, organic component and n-hexane in condensate liquid is made to mix shape in hitting bottle 47
At organic phase, inorganic phase, organic phase the progress condensable particulate matter off-line analysis in laboratory to be returned together with filter membrane.
Specifically, when flue gas needs to be passed through condensable particle collection unit 4,11 valve the 011, the tenth of the opening valve family status
Five valves 015 close the 12nd valve 012 of valve, the 14th valve 014, the 6th valve 006, the 13rd valve 013.Flue gas passes sequentially through
Third serpentine condenser 421 in two flue gas condensers 42 hits bottle 47 and filter 48, at this time condensable particulate matter in flue gas
Through condensation, collision, membrane filtration and be captured, trapped the flue gas of condensable particulate matter by the second drying bottle 49 and removed flue gas
Lead to next detection unit with the 5th heat tracing pipe 104 after middle moisture.Each condensable particle collection time is not less than
60min closes the 11st valve 011 of valve, the 15th valve 015, six valve 006 of the opening valve family status, from three oxidations after trapping
The flue gas of sulphur detection unit 3 is directly entered next detection unit through bypass.Quartz filter is taken out from filter 48 first later,
It is stored in special container, and new quartz filter is installed to filter 48.It is then turned on the 14th valve 014 of valve, simultaneously
It opens deionization water pump 43 (404), deionization water pump 43 in deionization water tank 44 is entered third serpentine condenser 421, is pumped into
Deionized water control is pumped into time control in 30~60s, deionized water and condensable particulate matter condensate liquid in 50~100mL
Inorganic component is sent by pipeline hits the formation inorganic phase of bottle 47.Deionization water pump 43 closes the 14th valve of valve after sending
014, the 12nd valve 012 is opened simultaneously, to third serpentine condenser 421 and is hit inorganic in bottle 47 using the nitrogen of nitrogen cylinder 41
It is mutually purged, purge time is controlled in 5~10min, the SO that may be dissolved in inorganic phase2Stripping is gone out, and SO is reduced2To can
Condense the influence of particulate matter test result.The 12nd valve 012 of valve is closed after purging, opens the 13rd valve 013 of valve, together
N-hexane pump 46 in n-hexane case 45 is entered third serpentine condenser 421, the n-hexane control being pumped by Shi Kaiqi n-hexane pump 46
In 50~100mL, it is pumped into time control organic component in 30~60s, n-hexane and condensable particulate matter condensate liquid and passes through pipe
Road, which is sent into, hits the formation organic phase of bottle 47.Primary trapping process terminates at this time, and the shock bottle 47 more renewed does condensable next time
Particle collection is spare.In shock bottle 47 inorganic phase and organic phase and quartz filter take back together laboratory carry out can coagulate
Tie particulate matter off-line analysis.Condensable aerosol sample in laboratory analyzes the EPA Method according to Environmental Protection Agency (EPA)
202 standards execute.
S5: flue gas a part by S4 step is arranged from system after recording sampling volume by the second automatic sampling instrument 7
Out, the sampling volume information of the second automatic sampling instrument 7 passes to numerical control device 9, and another part enters mercury detection unit 5, into mercury
Flue gas divides two-way after detection unit 5: being total mercury reforming unit 53 all the way, for bivalent mercury in flue gas to be completely converted into zeroth order
Mercury；Another way is nonvalent mercury reforming unit 52, for absorbing bivalent mercury in flue gas, only retains nonvalent mercury, passes through reforming unit
Flue gas enters mercury analyzer 55 after drying, dense using the nonvalent mercury in atomic absorption spectrography (AAS) detection flue gas in mercury analyzer 55
Degree, mercury detection unit 5 realize the measurement request of different valence state mercury by the control of the second triple valve 51 and third triple valve 54, two
The difference of road mercury concentration is mercuric concentration in flue gas, and the flue gas after detecting mercury is arranged from system by the first automatic sampling instrument 6
Out.Specifically, when the second triple valve 51 is transferred to 53 channel of total mercury reforming unit with third triple valve 54 simultaneously, flue gas is passed sequentially through
10% the first NaOH solution wash bottle and 10% SnCl2Solution wash bottle, the bivalent mercury in flue gas are completely converted into nonvalent mercury, so
By mercury analyzer 55 is entered after the drying of the second drying bottle 49, mercury lamp 551 issues the light that wavelength is 253nm at this time, in measuring chamber
553 by after mercury in flue gas Atomic absorption, and the light of transmission is received by mercury detector 554 and mercury concentration signal is transmitted to numerical control device 9.
What is measured at this time is total mercury concentration in flue gas.When the second triple valve 51 is transferred to nonvalent mercury reforming unit with third triple valve 54 simultaneously
52 channels, flue gas pass sequentially through 10% KC1 solution wash bottle and 10% the second NaOH solution wash bottle, and mercury analyzer 55 is surveyed at this time
Amount is nonvalent mercury concentration in flue gas.The difference of two-way gas mercury concentration is mercuric concentration in flue gas.Cigarette after detecting mercury
Gas is discharged from system after recording sampling volume by the first automatic sampling instrument 6.
Compared with prior art, the detection system and detection method provided by the present invention for harmful substances from flue gases has
It has the advantage that
1. the present invention is according to sampling and the testing principle of flue gas condensable particulate matter, sulfur trioxide and mercury, organic coupling three
The sample detecting unit of person, it is reasonable in design, it is easy to operate, it is easy to accomplish sample detecting while three of the above component, it can
It is widely used in the monitoring system of atmosphere multiple pollutant.
2. flue gas pipeline is all made of heat tracing pipe between each detection unit of the present invention, and different zones heat tracing pipe controls not equality of temperature
Degree, avoids flue gas from condensing on the flue gas pipeline outside each detection unit while energy consumption is effectively reduced, guarantee have in flue gas
Effect ingredient is all detected, and error is reduced, and by air purge unit, is carried out regular blowback cleaning to systematic pipeline, protected
Card system is continuous, continual sample detecting.
3. passing through three oxidations in two groups of serpentine condensers condensation flue gases in parallel in sulfur trioxide detection unit of the present invention
Sulphur, two groups of serpentine condensers work alternatively, and continuous, uninterrupted detection may be implemented, meanwhile, with a kind of azo dyes (BNBPS)
Color developing agent of the DMSO solution as sulfate ion, using SO in direct spectrophotometry measurement condensate liquid4 2-Concentration, directly
Measure SO3Content is removed the disturbing factors such as cumbersome precipitation and separation from compared with existing barium salt-indirect spectrophotometric methods, is mentioned
The precision of high detection.
4. mercury detection unit of the present invention is equipped in parallel nonvalent mercury reforming unit and total mercury reforming unit, and on demand can be with
When switching, it can be achieved that flue gas nonvalent mercury and total mercury while, is detected, and mercuric content is equal to total mercury and subtracts nonvalent mercury, i.e.,
On-line checking while flue gas different valence state mercury may be implemented.
5. flue gas of the present invention uses isokinetic sampling, the detection of flue gas condensable particulate matter caused by avoiding because of various speed sampling
Error, and condensable particle collection unit is arranged in parallel by-pass line, when condensable particle collection finishes progress offline
When analysis, flue gas directly arrives next detection unit without influencing subsequent detection by bypass.
It should be understood that although multiple element, portion can be described using term first, second, third, etc. in the text
Part, region, layer and/or section, still, these component, assembly units, region, layer and/or section should not be limited by these terms.
These terms can only be used to a component, assembly unit, region, layer or section and another component, assembly unit, region, layer or section
It distinguishes.Unless context is it is manifestly intended that otherwise the term and other numerical terms of such as " first ", " second " etc exist
Sequence or order is not implied that when using in text.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention answers the protection model with claim
Subject to enclosing.
Claims (10)
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| CN111426646A (en) * | 2020-05-25 | 2020-07-17 | 中煤科工集团重庆研究院有限公司 | Pretreatment method for detecting sulfur trioxide in discharged flue gas |
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