CN108535154B - Equipment and method for detecting secondary pollutants in flue gas - Google Patents
Equipment and method for detecting secondary pollutants in flue gas Download PDFInfo
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- CN108535154B CN108535154B CN201810078136.2A CN201810078136A CN108535154B CN 108535154 B CN108535154 B CN 108535154B CN 201810078136 A CN201810078136 A CN 201810078136A CN 108535154 B CN108535154 B CN 108535154B
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003546 flue gas Substances 0.000 title claims abstract description 74
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 20
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title abstract description 23
- 238000001514 detection method Methods 0.000 claims abstract description 89
- 238000010438 heat treatment Methods 0.000 claims abstract description 55
- 239000002245 particle Substances 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 19
- 239000013618 particulate matter Substances 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 14
- 239000011163 secondary particle Substances 0.000 claims abstract description 14
- 239000011164 primary particle Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000002848 electrochemical method Methods 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- 238000004611 spectroscopical analysis Methods 0.000 claims description 3
- 239000000779 smoke Substances 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011882 ultra-fine particle Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- LVGQIQHJMRUCRM-UHFFFAOYSA-L calcium bisulfite Chemical compound [Ca+2].OS([O-])=O.OS([O-])=O LVGQIQHJMRUCRM-UHFFFAOYSA-L 0.000 description 1
- 235000010260 calcium hydrogen sulphite Nutrition 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 238000000738 capillary electrophoresis-mass spectrometry Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
- G01N15/06—Investigating concentration of particle suspensions
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
- G01N15/06—Investigating concentration of particle suspensions
- G01N15/075—Investigating concentration of particle suspensions by optical means
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
- G01N2015/0042—Investigating dispersion of solids
- G01N2015/0046—Investigating dispersion of solids in gas, e.g. smoke
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Abstract
The invention provides a detection device and a method for secondary pollutants in flue gas, wherein the detection device comprises: the system comprises a heating system, two industrial particle concentration detection systems and two flue gas detection systems, wherein the two industrial particle concentration detection systems and the two flue gas detection systems are arranged at an inlet and an outlet of the heating system; the flue gas detection system is used for detecting the concentration of various gases in the flue gas. The detection method comprises the following steps: introducing the flue gas carrying the droplets containing the dissolved substances into a heating system, simultaneously detecting the concentration of original particulate matters and the concentration of gas in the flue gas at the inlet of the heating system, and obtaining the concentration values of the substances in a standard state; starting a heating system to completely dry fog drops in the flue gas entering the heating system, detecting the total concentration and gas concentration of secondary particles and primary particles at an outlet of the heating system, and obtaining concentration values of the substances in standard states; and subtracting the concentration of the original particulate matter at the inlet from the total concentration of the particulate matter at the outlet in the standard state to obtain a secondary particulate matter value.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a device and a method for detecting secondary pollutants in flue gas.
Background
The generation of secondary particles after the smoke carries droplets containing dissolved substances into the atmosphere is identified as an important cause of atmospheric pollution and is the main cause of haze. However, secondary particles are generated after entering the atmosphere, and are affected by many factors such as temperature, humidity, wind direction, and diffusion conditions, and the generation time and the generation position are uncertain, so that detection is difficult. In addition, the data detected by the existing detection instrument are only detected aiming at gaseous pollutants and particulate matters, and the droplets containing the dissolved substances cannot be detected, so that the monitoring of the droplets containing the dissolved substances is out of control. For example, the detection data of the wet calcium desulphurization process on sulfur is biased, the existing equipment can only detect gaseous sulfur, while the existing wet desulphurization process can only detect the gaseous sulfur, the water vapor of the discharged flue gas is in a saturated state, and only if the temperature is reduced, fog drops can be separated out, and the fog drops and gaseous SO2Infinite specific contact surface area, SO2Water which is easily separated out is adsorbed and dissolved, and the detection equipment cannot detect the SO2The desulphurization solution contains a large amount of calcium hydrogen sulfite if escaping to the atmosphereCan be decomposed into calcium sulfite and SO after medium water loss2This sulfur is also undetectable, resulting in inaccurate detection data. And a great amount of dissolved salts and alkali are contained in the desulfurization liquid carried by the flue gas, and because the solution is transparent, the existing detection equipment can only detect solid particulate matters, liquid solutes cannot be detected, and just secondary ultrafine dust generated after the substances enter the atmosphere is ultrafine particulate matters which cause haze, namely PM 2.5. Therefore, it brings great difficulty to the administrative law enforcement monitoring.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a device and a method for detecting secondary pollutants in flue gas. The technical scheme of the invention is as follows:
in a first aspect, the present invention provides a flue gas secondary pollutant detection device, including: the system comprises a heating system, two industrial particle concentration detection systems and two flue gas detection systems, wherein the two industrial particle concentration detection systems and the two flue gas detection systems are arranged at an inlet and an outlet of the heating system; the flue gas detection system is used for detecting the concentration of various gases in the flue gas, and adopts a spectroscopic method and an electrochemical method; the industrial particle concentration detection system and the flue gas detection system are both provided with a temperature sensor and a pressure sensor.
Further, the heating system is embodied as a non-closed tube fitted with a heating device.
In a second aspect, the invention provides a method for detecting secondary pollutants in flue gas, which comprises the following steps:
(1) introducing the flue gas carrying the droplets containing the dissolved substances into a heating system through a pump air blower, and simultaneously detecting the concentration of original particulate matters and SO in the flue gas at the inlet of the heating system through an industrial particle concentration detection system and a flue gas detection system2Concentration, and obtaining concentration values of the substances in standard states;
(2) starting the heating system to completely dry the fog drops in the smoke entering the heating system, and simultaneously passing through the industrial particle concentration detection system and the smokeThe gas detection system detects the total concentration of secondary particles and primary particles at the outlet of the heating system and SO2Concentration, and obtaining concentration values of the substances in standard states;
(3) subtracting the concentration of the original particulate matter at the inlet from the total concentration of the particulate matter at the outlet of the heating system in the standard state, wherein the concentration difference of the two is the value of the secondary particulate matter; and heating the SO at the outlet of the system in a standard state2Concentration and inlet SO2The concentration is subtracted, and the difference of the concentration value of the two is the acid gas SO dissolved by the water mist2And SO decomposed by salt2A contaminant value.
The amount of the dissolved substances carried by the smoke is reflected by the value of the secondary particles, namely the capacity of generating the secondary particles after the smoke enters the atmosphere. The important point for treating the haze is to control the emission value of the smoke. SO at inlet and outlet2The difference is the water mist dissolved acid gas and the pollutant SO decomposed by salt2I.e., pseudo-removal of contaminants, because these contaminants are released as the droplets enter the atmosphere, the original detection method is not detectable, thus resulting in actual emissions being greater than the detection data. This is why our flue gas is already ultra-clean and will corrode the stack seriously.
Because the wet flue gas contains free water drops, the wet flue gas can dilute pollutants after being gasified, the national regulation of the emission standard of free water is less than 75 mg/cubic meter, at present, the emission of a lot of flue gas can be about 200-300 mg/cubic meter, the density of air is 1100000 mg/cubic meter, namely the proportion of the gasified free water is less than one thousandth, the influence on the counting value of the pollutants is small within the error of a plurality of detection instruments, and therefore the gasified free water is ignored and is only considered together when equipment is corrected.
The invention has the beneficial effects that: the detection system of the invention introduces the flue gas into the heating system for complete drying, and H in the fog drops at the moment2SO3Release SO due to water loss2And Ca (HSO)3)2Is decomposed into SO2、H2O and CaSO3Other solutes may be dehydrated and separated outSolid particles are formed, and some substances contain different crystal water along with different temperatures and humidity and all the crystal water is lost along with the temperature rise to a certain height. Thus, SO can be thoroughly solved in the detection process2The gas escapes during detection, and the original purpose of the gas is restored by heating and warming, so that the emission value of the gas is more accurate; through heating and temperature rising, make the desulfurization liquid class solute of escaping separate out before the detection, the particulate matter that can only generate after originally entering the atmosphere, generate before entering the atmosphere, consequently, be convenient for detect, but the particle size distribution that detects this moment can be inclined to the particle size increase, because it generates after the diffusion when the atmosphere generates, therefore the particulate matter of actual generation can be more tiny, atmospheric temperature can be than the temperature when detecting low, consequently, can contain more crystal water, the particulate matter of actual production can be greater than the testing data, but they are directly proportional, so the testing data can reflect the clean degree of flue gas. Can meet the requirements of tax collection and law enforcement. This equipment is taken off and is secretly a main haze source, and the demonstration of datamation haze cause provides the theoretical foundation for haze treatment, lets the science treat the haze and becomes the reality. The harm caused by blind haze treatment to the society is avoided, and people can distinguish haze in the early days and keep away from the haze damage in the early days. The monitoring leak is blocked, the loss caused by inaccurate detection data to the country is avoided, and the monitoring means for controlling the ultrafine particles is perfected.
The device can also be used for on-line monitoring of the flue gas, and an industrial particle concentration detection system and a flue gas detection system at an inlet can be omitted during on-line detection.
Drawings
Fig. 1 is a schematic structural diagram of the secondary particle detection equipment of the present invention, wherein 1 is a pump gas engine, 2 is a flue gas detection system, 3 is an industrial particle concentration detection system, and 4 is a heating system.
Detailed Description
The model of the industrial particle concentration detection system adopted by the embodiment of the invention is CCZ 1000.
The model of the smoke detection system adopted by the embodiment of the invention is ZYF-CEMS.
The present invention will now be described in further detail with reference to the following figures and specific examples, which are intended to be illustrative, but not limiting, of the invention.
The specific embodiment of the present invention provides a detection apparatus for secondary pollutants in flue gas, as shown in fig. 1, including: the system comprises a heating system, two industrial particle concentration detection systems and two flue gas detection systems, wherein the two industrial particle concentration detection systems and the two flue gas detection systems are arranged at an inlet and an outlet of the heating system; the heating system is specifically a non-closed pipe barrel provided with heating equipment; the industrial particle concentration detection system is used for detecting the concentration of particulate matters in the flue gas, and adopts a laser diffuse scattering refocusing principle; the flue gas detection system is used for detecting the concentration of various gases in the flue gas, and adopts a spectroscopic method and an electrochemical method; the industrial particle concentration detection system and the flue gas detection system are both provided with a temperature sensor and a pressure sensor.
Example 1
Through the above devices, the present embodiment provides a method for detecting secondary pollutants in flue gas, which performs a detection experiment on 75 tons of boiler flue gas dual alkali method equipment in a chemical plant at shenyang, and specifically includes the following steps:
(1) introducing the flue gas carrying the droplets containing the dissolved substances into a heating system through a pump air blower, and simultaneously detecting the concentration of original particulate matters and SO in the flue gas at the inlet of the heating system through an industrial particle concentration detection system and a flue gas detection system2、SO3、NO、NO2And O2Concentration, the detection result is: raw particulate matter, 19 mg/cubic meter; SO (SO)233 mg/cubic meter; SO (SO)33 mg/cubic meter; NO, 44 mg/cubic meter; NO 24 mg/cubic meter;
(2) starting the heating system to completely dry the flue gas entering the heating system, and simultaneously detecting the total concentration of secondary particles and primary particles and SO at the outlet of the heating system through the industrial particle concentration detection system and the flue gas detection system2、SO3、NO、NO2And O2Concentration, the detection result is: total particulates, 35 mg/cubic meter; SO (SO)239 mg/cubic meter; SO (SO)35 mg/cubic meter; NO, 44 mg/cubic meter; NO 24 mg/cubic meter;
as can be seen from the above test data, the secondary particles were 16 mg/m, SO2、SO3、NO2All increased and NO was unchanged. Meanwhile, the original online detection equipment is not suitable for the current wet desulphurization process.
Example 2
Through the above devices, the embodiment provides a method for detecting secondary pollutants in flue gas, and a detection comparison experiment is performed on 40-ton boiler magnesium oxide wet desulphurization equipment of a heating company in Shenyang. The method specifically comprises the following steps:
(1) introducing the flue gas carrying the droplets containing the dissolved substances into a heating system through a pump air blower, and simultaneously detecting the concentration of original particulate matters and SO in the flue gas at the inlet of the heating system through an industrial particle concentration detection system and a flue gas detection system2、SO3、NO、NO2And O2Concentration, the detection result is: raw particulate matter, 45 mg/cubic meter; SO (SO)298 mg/cubic meter; SO (SO)35 mg/cubic meter; NO, 215 mg/cubic meter; NO211 mg/cubic meter;
(2) starting the heating system to completely dry the flue gas entering the heating system, and simultaneously detecting the total concentration of secondary particles and primary particles and SO at the outlet of the heating system through the industrial particle concentration detection system and the flue gas detection system2、SO3、NO、NO2And O2Concentration, the detection result is: total particulates, 56 mg/cubic meter; SO (SO)2105 mg/cubic meter; SO (SO)37 mg/cubic meter; NO, 215 mg/cubic meter; NO213 mg/cubic meter;
as can be seen from the above test data, the secondary particles were 11 mg/m, SO2、SO3、NO2There is an increase.
Example 3
Through the above-mentioned equipment, this embodiment provides a detection method of flue gas secondary pollutant, does the experiment on 120 tons of heating boiler lime gypsum method desulfurization flue gas of a certain heating company of shenyang, specifically includes the following steps:
(1) introducing the flue gas carrying the droplets containing the dissolved substances into a heating system through a pump air blower, and simultaneously detecting the concentration of original particulate matters and SO in the flue gas at the inlet of the heating system through an industrial particle concentration detection system and a flue gas detection system2、SO3、NO、NO2And O2Concentration, the detection result is: raw particulate matter, 36 mg/cubic meter; SO (SO)274 mg/cubic meter; SO (SO)34 mg/cubic meter; NO, 244 mg/cubic meter; NO212 mg/cubic meter;
(2) starting the heating system to completely dry the flue gas entering the heating system, and simultaneously detecting the total concentration of secondary particles and primary particles and SO at the outlet of the heating system through the industrial particle concentration detection system and the flue gas detection system2、SO3、NO、NO2And O2Concentration, the detection result is: total particulates, 42 mg/cubic meter; SO (SO)285 mg/cubic meter; SO (SO)33 mg/cubic meter; NO, 244 mg/cubic meter; NO214 mg/cubic meter;
the experiment shows that the original detection equipment is not suitable for the prior desulfurization process. The secondary particles increased by 6 mg/cubic meter and the gaseous pollutants increased.
Through the results of the above examples, it can be found that secondary dust is generated after the flue gas is heated and the secondary dust generated by the double alkali method and the magnesium oxide method is higher than that generated by the limestone-gypsum method, SO method and magnesium oxide method2、SO3、NO2Almost all three pollutants are increased after being heated and heated, and SO of limestone-gypsum method2The increase is more, and the NO of the desulfurization processes is hardly changed.
Through the above several examples, it can be proved that the tail gas of wet desulphurization is a manufacturing source of ultrafine particles, and is the main culprit of haze.
Although embodiments of the present invention have been shown and described above, it should be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that changes, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (3)
1. The utility model provides a detection equipment of flue gas secondary pollutant which characterized in that includes: the system comprises a heating system, two industrial particle concentration detection systems and two flue gas detection systems, wherein the two industrial particle concentration detection systems and the two flue gas detection systems are arranged at an inlet and an outlet of the heating system; the flue gas detection system is used for detecting the concentration of various gases in the flue gas, and adopts a spectroscopic method and an electrochemical method; the industrial particle concentration detection system and the flue gas detection system are both provided with a temperature sensor and a pressure sensor.
2. The detection device for secondary pollutants in flue gas as claimed in claim 1, wherein the heating system is a non-closed tube provided with a heating device.
3. A detection method of secondary pollutants in flue gas adopts the detection equipment of claim 1, and is characterized by comprising the following steps:
(1) introducing the flue gas carrying the droplets containing the dissolved substances into a heating system through a pump air blower, and simultaneously detecting the concentration of original particulate matters and SO in the flue gas at the inlet of the heating system through an industrial particle concentration detection system and a flue gas detection system2Concentration, and obtaining concentration values of the substances in standard states;
(2) starting the heating system to completely dry the fog drops in the flue gas entering the heating system, and simultaneously detecting the total concentration of secondary particles and primary particles and SO at the outlet of the heating system through the industrial particle concentration detection system and the flue gas detection system2Concentration, and obtaining concentration values of the substances in standard states;
(3) subtracting the concentration of the original particulate matter at the inlet from the total concentration of the particulate matter at the outlet of the heating system in the standard state, wherein the concentration difference of the two is the value of the secondary particulate matter; and heating the sample in the state of the standardSO at system outlet2Concentration and inlet SO2The concentration is subtracted, and the difference of the concentration values of the two is the SO dissolved by the water mist2And SO decomposed by salt2Concentration values.
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| CN110779843B (en) * | 2019-09-30 | 2022-06-07 | 成都市环境保护科学研究院 | Typing analytic system of atmosphere secondary particle pollution process |
| CN112986086B (en) * | 2021-04-16 | 2021-07-27 | 北京英视睿达科技有限公司 | Primary emission monitoring method and device for fine particles, storage medium and equipment |
| CN113624652A (en) * | 2021-08-16 | 2021-11-09 | 济宁华源热电有限公司 | Boiler flue gas monitoring device |
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