CN103245545A - Pre-treatment and analysis device and method for online monitoring on H2SO4 acid mist in wet flue gas - Google Patents

Pre-treatment and analysis device and method for online monitoring on H2SO4 acid mist in wet flue gas Download PDF

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CN103245545A
CN103245545A CN2013101991632A CN201310199163A CN103245545A CN 103245545 A CN103245545 A CN 103245545A CN 2013101991632 A CN2013101991632 A CN 2013101991632A CN 201310199163 A CN201310199163 A CN 201310199163A CN 103245545 A CN103245545 A CN 103245545A
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acid mist
flue gas
converter
gas
mist converter
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CN103245545B (en
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瞿赞
晏乃强
裴冰
徐浩淼
潘杰
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Shanghai Jiaotong University
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Abstract

The invention relates to a pre-treatment and analysis device and method for online monitoring on H2SO4 acid mist in wet flue gas. The monitoring method mainly comprises the following steps of: pumping coal-fired flue gas from a flue by virtue of a sampling gun, and maintaining temperature of the sampled flue-gas to be 150-250 DEG C by utilizing a heat tracing pipeline; then introducing flue gas into a specific H2SO4 acid mist transforming device filled with phosphorus pentoxide as a transforming agent, transforming H2SO4 acid mist into SO3 easy for online measurement by utilizing dehydration property of phosphorus pentoxide at the temperature of 200-300 DEG C, and adsorbing and drying moisture in the flue gas; carrying out continuous monitoring on SO3 in the dry flue gas by virtue of an instrument which can continuously monitor in real time; and then respectively sequentially passing the exhaust gas through a gas flowmeter and a sampling pump and finally discharging into the atmosphere. Compared with the prior art, the pre-treatment and analysis device and method for online monitoring on H2SO4 acid mist in wet flue gas can eliminate interference of moisture, acid mist and SO2 in the flue gas, and SO3 gas in exhaust gas of the flue gas can be accurately monitored.

Description

H in the wet flue gas 2SO 4The pre-treatment of acid mist on-line monitoring and analytical equipment and method
Technical field
The invention belongs to field of environment protection, relate to H in a kind of wet flue gas 2SO 4The pre-treatment of acid mist on-line monitoring and analytical approach utilize this Apparatus and method for can get rid of the interference of moisture and other components in the flue gas, accurately the SO3 gas in the flue gas are detected.
Background technology
Oxysulfide major part in the coal-fired flue-gas is SO 2, it is SO that sub-fraction is wherein also arranged 3Along with SCR (Selective Catalytic Reduction) technology begins to be applied in China, the active component in the SCR catalyzer can catalysis be accelerated SO 2Oxidation reaction, and promote SO 3Generation, cause SO in the coal-fired flue-gas thus 3And sulfuric acid mist (SO 3/ H 2SO 4) concentration significantly increases.
SO 3Be a kind of material of very easily moisture absorption, studies show that when temperature surpasses 200 ℃, and the moisture in the flue gas is when surpassing 8% left and right sides, 99% SO 3All will be converted into sulfuric acid mist; And when flue-gas temperature was lower than the dewpoint temperature of sulfuric acid vapor, sulfuric acid mist can condensation form sulfuric acid droplets, and wherein the sulfuric acid droplets of 0.5-3.0 μ m can form the sulfuric acid gasoloid.As PM 2.5Presoma sulfuric acid gasoloid again can be to PM 2.5Discharging cause material impact.Simultaneously, sulfuric acid mist also may stick to the upstream device of boiler or SCR system, as the surface of equipment such as air preheater, electrostatic precipitator, can cause serious corrosion to these equipment during long-time running.Therefore, SO in monitoring and the analysis flue gas 3/ H 2SO 4Concentration, for regulation and control boiler operatiopn condition, it is most important to reduce the sulfuric acid aerosol discharge.Yet, still do not have the SO that obtains extensive approval at present 3/ H 2SO 4Monitoring method.The flue gas analyzer that is widely used in fume component analysis is not analyzed SO yet 3This function of content, this mainly is because SO 3Chemical property is active, H 2SO 4The gasoloid adsorbability is strong, and they are very easily adsorbed by various material walls, and surveying instrument and sample devices are caused corrosion, makes instrumental calibration and quantitative measurement have great difficulty.Secondly, the SO that has high concentration in the flue gas 2, measure the SO in the flue gas 3The method of content generally is to be translated into SO 4 2-Behind the sample solution, by analyzing SO 4 2-SO is measured in the content brief introduction 3Content.Yet this detection method is easy to be subjected to SO 2Interference because SO 2In absorption liquid, can generate SO 3 2-, and SO 3 2-Can be oxidized to SO 4 2-, this will cause flue gas SO 3Concentration monitoring causes error.The 3rd, the SO in the flue gas 3Concentration is very low, and less error at measurment can be brought bigger relative error.Chinese patent application 2O0610095389.8 has proposed SO in a kind of flue gas 3Content detecting method and device wherein utilize the spiral collection tube to gather the SO in the flue gas 3, and after handling, obtain SO 4 2-Sample solution is by SO in the analytic sample 4 2-The cubage flue gas in SO 3Concentration.This method is for the SO that gathers the droplet shape 3Relatively effectively, but for the SO of gaseous state 3Just can not effectively collect, and adopt this device also the water vapor in the flue gas may to be collected in the lump, so just may be with the SO in the flue gas 2Also absorb, and resultant interference is to SO 3The detection of content.Chinese patent application 200910211691.9 proposed to utilize a kind of for detection of, measure and control flue gas in the method and apparatus of sulfuric anhydride and other condensable material.This method is utilized the electric signal difference that the dew point of different material is different and produce when condensing in device, the condensables in the flue gas is monitored.But this method is difficult to H 2SO 4Acid mist with absorbed SO 2The water vapor of gas is distinguished.Therefore, currently demand seeking SO in the new flue gas urgently 3The monitoring method of content.In addition, existing aqueous isopropanol absorbs in conjunction with SO in the thoron colour developing titration measuring flue gas 3Also there is SO 2Disturb excessively, be difficult to realize the problem of continuous real-time monitoring.
In addition, for the flue gas of wet desulphurization or dedusting, wherein SO 3Substantially all be converted into acid mist, and these acid mists are difficult to effectively be removed, can form gasoloid or PM along with fume emission enter atmosphere 2.5Material.But, because moisture is higher in this class wet flue gas, sulfuric acid mist directly to be measured comparatively difficult, not only error is bigger for above-mentioned several measuring methods, samples simultaneously and analyzes the requirement that is difficult to satisfy the flue gas continuous real-time monitoring.Therefore, if can utilize suitable method with the moisture removal in the flue gas, simultaneously sulfuric acid mist is converted into SO 3, then can utilize infrared or the laser measuring technique method to the SO in the flue gas 3Carry out measuring in real time fast.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of doctor solution cost that can significantly reduce in order to overcome the defective that above-mentioned prior art exists, and reduces waste water generation, H in the wet flue gas efficiently 2SO 4The pre-treatment of acid mist on-line monitoring and analytical equipment and method.
Purpose of the present invention can be achieved through the following technical solutions: H in a kind of wet flue gas 2SO 4The pre-treatment of acid mist on-line monitoring and analytical equipment is characterized in that, comprise flue gas sampling rifle, H 2SO 4Acid mist converter, special SO 3Checkout equipment and the control system of bleeding, described flue gas sampling rifle outlet is by gas connection pipe road and H 2SO 4Acid mist converter entrance is connected H 2SO 4The outlet of acid mist converter and special SO 3The detecting device entrance connects by gas piping, and special SO 3The detecting device outlet is connected by gas piping with the entrance of the control system of bleeding.The present invention provides power by the control system of bleeding, and extracts quantitative flue gas by the flue gas sampling rifle from flue; Flue gas is by special H 2SO 4Behind the acid mist transforming agent, H wherein 2SO 4Will be converted into SO 3Gas, the moisture in the flue gas also can be absorbed simultaneously; Next Gan Zao flue gas will be by special SO 3Detecting device detects, and flue gas finally enters atmosphere by the control system outlet of bleeding.Utilize said method and equipment, can get rid of moisture in the flue gas, acid mist and SO 2Interference, to the SO in the flue tail gas 3Gas is accurately monitored.
Described flue gas sampling rifle is that liner quartz glass outside is coating the heat tracing pipe composition, utilize heat tracing pipe that the flue gas sampling rifle is carried out heated at constant temperature, be used for guaranteeing that the flue gas of gathering maintains the 150-250 degree, avoid flue gas and in sampling process, cause the error of measurement because cooling is condensate in the sampling rifle, and prevent H 2SO 4The sampling rifle corrosion that acid mist condenses and causes.
Described H 2SO 4The acid mist converter is by H 2SO 4Acid mist converter entrance, H 2SO 4Acid mist converter main body, H 2SO 4Acid mist transforming agent, H 2SO 4The capping of acid mist converter, H 2SO 4Acid mist converter heating jacket and H 2SO 4The outlet of acid mist converter is formed; Described H 2SO 4The acid mist transforming agent places H 2SO 4In the acid mist converter main body, described H 2SO 4Acid mist converter heating jacket is set in H 2SO 4On the acid mist converter main body, described H 2SO 4The capping of acid mist converter is arranged on H 2SO 4Described H is sealed at acid mist converter main body top 2SO 4Acid mist converter entrance places H 2SO 4Acid mist converter main body one side bottom, described H 2SO 4The outlet of acid mist converter places H 2SO 4Acid mist converter main body opposite side top.
Described H 2SO 4Acid mist converter main material is corrosion resistant stainless steel or enamel material; Described H 2SO 4The acid mist transforming agent is the phosphorus pentoxide particle, and particle diameter is the 0.5-2.0 millimeter, and use amount is 10-100g; During sampling with H 2SO 4Acid mist converter heating jacket is connected power supply, keeps H 2SO 4Acid mist converter body temperature is at the 200-300 degree.
Described special SO 3Checkout equipment is: the infrared flue gas analyzer of FTIR or laser enhancing analyser, and can be directly to the SO in the flue gas 3Carry out real-time analysis, and overcome SO 2Interference.
The described control system of bleeding is made up of the control system entrance of bleeding, gas meter, the control system of bleeding outlet and vacuum sampling pump, and the vacuum sampling pump is used for extracting flue gas from flue; The gas collecting flow controls to 0.5-1.0L/min by gas meter.
The described device of a kind of employing is to H in the wet flue gas 2SO 4The pre-treatment of acid mist on-line monitoring and analytical approach is characterized in that, this method may further comprise the steps:
1) gas connection pipe road and H are passed through in the outlet of flue gas sampling rifle 2SO 4Acid mist converter entrance is connected H 2SO 4The outlet of acid mist converter and special SO 3The detecting device entrance connects by gas piping, and special SO 3The detecting device outlet is connected by gas piping with the entrance of the control system of bleeding, thus with flue gas sampling rifle, H 2SO 4Acid mist converter, special SO 3Checkout equipment and the control system of bleeding are connected in turn;
2) heat tracing pipe of flue gas sampling rifle is connected power supply, make temperature maintenance in the flue gas sampling rifle at the 150-250 degree;
3) with H 2SO 4Acid mist converter heating jacket is connected power supply, keeps H 2SO 4Temperature maintenance in the acid mist converter is at the 200-300 degree;
4) the flue gas sampling rifle is stretched in the flue, open the vacuum sampling pump in the control system of bleeding simultaneously, and adjustments of gas flowmeter collection flow, it is stabilized between the 0.5-1.0L/min;
5) to special SO 3The checkout equipment reading carries out record, records once second every 5-30, recorded altogether 10 minutes, at last with recorded sum up average, get final product SO in the flue gas 3Mean concentration.
Compared with prior art, the inventive method and equipment are primarily aimed at the SO in the flue gas 3Sample and detect, even SO 3In flue gas, meet water and formed H 2SO 4Acid mist still can be by method and apparatus of the present invention to the SO in the flue gas 3Monitor.This method sampling operation is simple and convenient, avoided moisture and SO in the flue gas simultaneously 2The interference of gas etc. can be to the SO in the flue gas 3Concentration is accurately monitored.
Description of drawings
The equipment synoptic diagram that Fig. 1 adopts for the present invention.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
Embodiment 1
As shown in Figure 1, device therefor of the present invention is by flue gas sampling rifle, H 2SO 4Acid mist converter, special SO 3Checkout equipment 11 and control system 14 grades of bleeding are partly formed.Wherein, flue gas sampling rifle liner is that quartz glass 1 outside is coating heat tracing pipe 2, utilize 2 pairs of flue gas sampling rifles of heat tracing pipe to carry out heated at constant temperature, be used for guaranteeing that the flue gas of gathering maintains the 150-250 degree, avoid flue gas and in sampling process, cause the error of measurement because cooling is condensate in the sampling rifle, and prevent H 2SO 4The sampling rifle corrosion that acid mist condenses and causes.
Described H 2SO 4The acid mist converter is by H 2SO 4Acid mist converter entrance 4, H 2SO 4Acid mist converter main body 5, H 2SO 4Acid mist transforming agent 6, H 2SO 4Acid mist converter capping 7, H 2SO 4Acid mist converter heating jacket 8 and H 2SO 4Acid mist converter outlet 9 is formed; Described H 2SO 4Acid mist transforming agent 6 places H 2SO 4In the acid mist converter main body 5, described H 2SO 4Acid mist converter heating jacket 8 is set in H 2SO 4On the acid mist converter main body 5, described H 2SO 4Acid mist converter capping 7 is arranged on H 2SO 4Described H is sealed at acid mist converter main body 5 tops 2SO 4Acid mist converter entrance 4 places H 2SO 4Acid mist converter main body 5 one side bottoms, described H 2SO 4Acid mist converter outlet 9 places H 2SO 4Acid mist converter main body 5 opposite side tops.
Described H 2SO 4Acid mist converter main body 5 materials are corrosion resistant stainless steel or enamel material; Described H 2SO 4Acid mist transforming agent 6 is the phosphorus pentoxide particle, and particle diameter is the 0.5-2.0 millimeter, and use amount is 10-100g; During sampling with H 2SO 4Acid mist converter heating jacket 8 is connected power supply, keeps H 2SO 4Acid mist converter main body 5 temperature are at the 200-300 degree.
Described special SO 3Checkout equipment 11 is: the infrared flue gas analyzer of FTIR or laser enhancing analyser, and can be directly to the SO in the flue gas 3Carry out real-time analysis, and overcome SO 2Interference.
The described control system 14 of bleeding is made up of the control system entrance 13 of bleeding, gas meter 15, the control system of bleeding outlet 16 and vacuum sampling pump 17, and vacuum sampling pump 17 is used for extracting flue gas from flue; The gas collecting flow controls to 0.5-1.0L/min by gas meter.
The outlet 3 of flue gas sampling rifle is by gas connection pipe road 20 and H 2SO 4Acid mist converter entrance 4 is connected.H 2SO 4Acid mist converter outlet 9 and special SO 3 Checkout equipment entrance 10 connects by gas piping 19, and special SO 3 Checkout equipment outlet 12 is connected by gas piping 18 with the entrance 13 of the control system of bleeding.The inventive method provides power by the control system of bleeding, and extracts quantitative flue gas by the flue gas sampling rifle from flue; Flue gas is by special H 2SO 4Behind the acid mist transforming agent 6, H wherein 2SO 4Will be converted into SO 3Gas, and the moisture in the flue gas also can be absorbed; Next Gan Zao flue gas will be by special SO 3Checkout equipment 11 detects, and flue gas finally enters atmosphere by the control system outlet 16 of bleeding.
Flue gas SO of the present invention 3And H 2SO 4The acid mist monitoring method specifically may further comprise the steps:
1) gas connection pipe road 20 and H are passed through in flue gas sampling rifle outlet 3 2SO 4Acid mist converter entrance 4 is connected.H 2SO 4Acid mist converter outlet 9 and special SO 3 Checkout equipment entrance 10 connects by gas piping 19, and special SO 3 Checkout equipment outlet 12 is connected by gas piping 18 with the entrance 13 of the control system of bleeding.Thus with flue gas sampling rifle 1, H 2SO 4Acid mist converter main body 5, special SO 3Checkout equipment 11 and control system 14 grades of bleeding partly are connected in turn.
2) heat tracing pipe 2 of flue gas sampling rifle is connected power supplys, make temperature maintenance in the flue gas sampling rifle at the 110-140 degree.
3) with H 2SO 4Acid mist converter heating jacket 8 is connected power supply, keeps H 2SO 4Temperature maintenance in the acid mist converter main body 5 is at the 200-300 degree.
4) the flue gas sampling rifle is stretched in the flue, open the vacuum sampling pump 17 in the control system 14 of bleeding simultaneously, and adjustments of gas flowmeter 15 collection flows, it is stabilized between the 0.5-1.0L/min.
5) to special SO 3Checkout equipment 11 readings carry out record, every 30 seconds records once, record altogether 10 minutes, at last will be recorded sum up on average, get final product SO in the flue gas 3Mean concentration.
Embodiment 2
Certain coal-fired plant flue gas SO 3Detection: at first utilize the gas connection pipe road successively with flue gas sampling rifle, H 2SO 4Acid mist converter main body 5, special SO 3Checkout equipment 11 and control system 14 grades of bleeding partly couple together.
2) heat tracing pipe 2 of flue gas sampling rifle is connected power supply, the temperature control in the flue gas sampling rifle is spent 120.
3) with H 2SO 4Acid mist converter heating jacket 8 is connected power supply, keeps H 2SO 4Temperature control in the acid mist converter main body 5 is at 250 degree.
4) flue gas sampling rifle 1 is stretched in the flue, open the vacuum sampling pump 17 in the control system 14 of bleeding simultaneously, and adjustments of gas flowmeter 15 collection flows, it is stabilized between the 0.5L/min.
5) to special SO 3Checkout equipment 11 readings carry out record, every 30 seconds records once, record altogether 10 minutes, obtain detecting data and are respectively: 10.1ppm, 11.2ppm, 10.8ppm, 9.2ppm, 10.9ppm, 10.0ppm, 9.8ppm, 9.7ppm, 10.6ppm, 10.7ppm, 10.3ppm, 9.7ppm, 10.1ppm, 10.0ppm, 11.0ppm, 9.5ppm, 9.8ppm, 9.3ppm, 10.0ppm 10.8ppm sums up SO in average, final the flue gas with recorded at last 3Mean concentration be 10.2 (± 1.0) ppm.

Claims (7)

1. H in the wet flue gas 2SO 4The pre-treatment of acid mist on-line monitoring and analytical equipment is characterized in that, comprise flue gas sampling rifle, H 2SO 4Acid mist converter, special SO 3Checkout equipment (11) and the control system of bleeding (14), described flue gas sampling rifle outlet (3) is by gas connection pipe road (20) and H 2SO 4Acid mist converter entrance (4) is connected H 2SO 4Acid mist converter outlet (9) and special SO 3Checkout equipment entrance (10) connects by gas piping (19), and special SO 3Checkout equipment outlet (12) is connected by gas piping (18) with the entrance (13) of the control system of bleeding.
2. H in a kind of wet flue gas according to claim 1 2SO 4The pre-treatment of acid mist on-line monitoring and analytical equipment, it is characterized in that, described flue gas sampling rifle is that liner quartz glass (1) outside is coating heat tracing pipe (2) composition, utilizes heat tracing pipe (2) that the flue gas sampling rifle is carried out heated at constant temperature, is used for guaranteeing that the flue gas of gathering maintains the 150-250 degree.
3. H in a kind of wet flue gas according to claim 1 2SO 4The pre-treatment of acid mist on-line monitoring and analytical equipment is characterized in that, described H 2SO 4The acid mist converter is by H 2SO 4Acid mist converter entrance (4), H 2SO 4Acid mist converter main body (5), H 2SO 4Acid mist transforming agent (6), H 2SO 4Acid mist converter capping (7), H 2SO 4Acid mist converter heating jacket (8) and H 2SO 4Acid mist converter outlet (9) is formed; Described H 2SO 4Acid mist transforming agent (6) places H 2SO 4In the acid mist converter main body (5), described H 2SO 4Acid mist converter heating jacket (8) is set in H 2SO 4On the acid mist converter main body (5), described H 2SO 4Acid mist converter capping (7) is arranged on H 2SO 4Described H is sealed at acid mist converter main body (5) top 2SO 4Acid mist converter entrance (4) places H 2SO 4Acid mist converter main body (5) one side bottoms, described H 2SO 4Acid mist converter outlet (9) places H 2SO 4Acid mist converter main body (5) opposite side top.
4. H in a kind of wet flue gas according to claim 3 2SO 4The pre-treatment of acid mist on-line monitoring and analytical equipment is characterized in that, described H 2SO 4Acid mist converter main body (5) material is corrosion resistant stainless steel or enamel material; Described H 2SO 4Acid mist transforming agent (6) is the phosphorus pentoxide particle, and particle diameter is the 0.5-2.0 millimeter, and use amount is 10-100g; During sampling with H 2SO 4Acid mist converter heating jacket (8) is connected power supply, keeps H 2SO 4Acid mist converter main body (5) temperature is at the 200-300 degree.
5. H in a kind of wet flue gas according to claim 1 2SO 4The pre-treatment of acid mist on-line monitoring and analytical equipment is characterized in that, described special SO 3Checkout equipment (11) is: the infrared flue gas analyzer of FTIR or laser enhancing analyser.
6. H in a kind of wet flue gas according to claim 1 2SO 4The pre-treatment of acid mist on-line monitoring and analytical equipment, it is characterized in that, the described control system of bleeding (14) is made up of the control system entrance (13) of bleeding, gas meter (15), the control system of bleeding outlet (16) and vacuum sampling pump (17), and vacuum sampling pump (17) is used for extracting flue gas from flue; The gas collecting flow controls to 0.5-1.0L/min by gas meter (15).
7. one kind is adopted among the claim 1-6 arbitrary described device to H in the wet flue gas 2SO 4The pre-treatment of acid mist on-line monitoring and analytical approach is characterized in that, this method may further comprise the steps:
1) gas connection pipe road (20) and H are passed through in flue gas sampling rifle outlet (3) 2SO 4Acid mist converter entrance (4) is connected H 2SO 4Acid mist converter outlet (9) and special SO 3Checkout equipment entrance (10) connects by gas piping (19), and special SO 3Checkout equipment outlet (12) is connected by gas piping (18) with the entrance (13) of the control system of bleeding, thus with flue gas sampling rifle (1), H 2SO 4Acid mist converter, special SO 3Checkout equipment (11) and the control system of bleeding (14) are connected in turn;
2) heat tracing pipe (2) of flue gas sampling rifle (1) is connected power supply, make temperature maintenance in the flue gas sampling rifle at the 150-250 degree;
3) with H 28O 4Acid mist converter heating jacket (8) is connected power supply, keeps H 2SO 4Temperature maintenance in the acid mist converter is at the 200-300 degree;
4) flue gas sampling rifle (1) is stretched in the flue, open the vacuum sampling pump (17) in the control system (14) of bleeding simultaneously, and adjustments of gas flowmeter (15) collection flow, it is stabilized between the 0.5-1.0L/min;
5) to special SO 3Checkout equipment (11) reading carries out record, records once second every 5-30, recorded altogether 10 minutes, at last with recorded sum up average, get final product SO in the flue gas 3Mean concentration.
CN201310199163.2A 2013-05-24 2013-05-24 H in wet flue gas 2sO 4the pre-treatment of acid mist on-line monitoring and analytical equipment and method Active CN103245545B (en)

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CN113720738A (en) * 2021-09-03 2021-11-30 上海交通大学 Optimized calibration method for aerosol mass concentration

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CN109406435A (en) * 2018-12-14 2019-03-01 安徽皖仪科技股份有限公司 The continuous on-line monitoring system of flue gas
CN113720738A (en) * 2021-09-03 2021-11-30 上海交通大学 Optimized calibration method for aerosol mass concentration

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