WO2012043411A1 - ガス分析装置、水銀除去システム、ガス分析方法及び排ガス中の水銀除去方法 - Google Patents
ガス分析装置、水銀除去システム、ガス分析方法及び排ガス中の水銀除去方法 Download PDFInfo
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- WO2012043411A1 WO2012043411A1 PCT/JP2011/071710 JP2011071710W WO2012043411A1 WO 2012043411 A1 WO2012043411 A1 WO 2012043411A1 JP 2011071710 W JP2011071710 W JP 2011071710W WO 2012043411 A1 WO2012043411 A1 WO 2012043411A1
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- Prior art keywords
- exhaust gas
- gas
- ammonium chloride
- concentration
- heat
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- 238000004868 gas analysis Methods 0.000 title claims abstract description 17
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims description 49
- 229910052753 mercury Inorganic materials 0.000 title claims description 45
- 238000000034 method Methods 0.000 title claims description 30
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 154
- 239000000428 dust Substances 0.000 claims abstract description 24
- 238000005259 measurement Methods 0.000 claims abstract description 20
- 230000001678 irradiating effect Effects 0.000 claims abstract 2
- 239000007789 gas Substances 0.000 claims description 317
- 235000019270 ammonium chloride Nutrition 0.000 claims description 75
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 72
- 238000006477 desulfuration reaction Methods 0.000 claims description 38
- 230000023556 desulfurization Effects 0.000 claims description 38
- 230000002829 reductive effect Effects 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 31
- 238000011084 recovery Methods 0.000 claims description 31
- 239000007921 spray Substances 0.000 claims description 31
- 238000000605 extraction Methods 0.000 claims description 19
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000011144 upstream manufacturing Methods 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 8
- 238000003303 reheating Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 2
- 239000000779 smoke Substances 0.000 abstract 2
- 239000000460 chlorine Substances 0.000 description 151
- 239000010440 gypsum Substances 0.000 description 23
- 229910052602 gypsum Inorganic materials 0.000 description 23
- 239000002002 slurry Substances 0.000 description 22
- 238000006722 reduction reaction Methods 0.000 description 19
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 18
- 235000011941 Tilia x europaea Nutrition 0.000 description 18
- 239000004571 lime Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229910052815 sulfur oxide Inorganic materials 0.000 description 12
- 238000010586 diagram Methods 0.000 description 11
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 239000002250 absorbent Substances 0.000 description 6
- 230000002745 absorbent Effects 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000033116 oxidation-reduction process Effects 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- -1 chlorine ions Chemical class 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 4
- 229940008718 metallic mercury Drugs 0.000 description 4
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 229910000474 mercury oxide Inorganic materials 0.000 description 3
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000004071 soot Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 239000012717 electrostatic precipitator Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004094 preconcentration Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/30—Controlling by gas-analysis apparatus
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/2202—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling
-
- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/07—Investigating materials by wave or particle radiation secondary emission
- G01N2223/076—X-ray fluorescence
Definitions
- the present invention relates to a gas analyzer, a mercury removal system, a gas analysis method, and a mercury removal method in exhaust gas for measuring the concentration of ammonium chloride supplied in the exhaust gas of a boiler.
- a flue gas treatment apparatus includes a denitration apparatus that reduces NOx and a wet desulfurization apparatus that uses an alkaline absorbent as an SOx absorbent, and supplies ammonia (NH 3 ) in the flue on the upstream side of the denitration apparatus.
- nitrogen monoxide (NO) is reduced by the denitration catalyst of the denitration device to remove NOx, and the wet desulfurization device absorbs SOx in the alkali absorption liquid and is contained in the exhaust gas.
- the harmful components to be treated are treated (for example, see Patent Document 1). 4NO + 4NH 3 + O 2 ⁇ 4N 2 + 6H 2 O (1)
- NH 3 is supplied in the upstream process of the denitration device, but NH 3 is also used for neutralization of SO 3 , so it is necessary to adjust the supply amount of NH 3 as well. there were.
- the exhaust gas generated when burning coal-fired exhaust gas or heavy oil may contain metal mercury (Hg 0 ) in addition to soot, SOx, NOx.
- metal mercury Hg 0
- various devices and methods for treating metallic mercury (Hg 0 ) have been devised in combination with a denitration device that reduces NOx and a wet desulfurization device that absorbs SOx.
- NH 3 undergoes a reduction reaction with NOx in the exhaust gas as shown in the above formula (1) on the denitration catalyst packed in the reduction denitrification apparatus, and HCl is in the exhaust gas as shown in the following formula (4).
- the oxidation reaction proceeds with Hg 0 .
- NH 3 is reduced and denitrated on the denitration catalyst, and metal mercury (Hg 0 ) is oxidized to form water-soluble mercury chloride (HgCl 2 ), and then HgCl 2 is treated with water by a wet desulfurization device installed on the downstream side.
- SOx contained in the exhaust gas is absorbed and removed.
- the present invention was made in view of the above, Cl contained in the exhaust gas - to provide a concentration gas analyzer capable of measuring, mercury removal system, the mercury removal method of the gas analysis method and the exhaust gas For the purpose.
- the first invention of the present invention for solving the above-mentioned problems is an exhaust gas extraction pipe for extracting the exhaust gas discharged from the boiler and supplying ammonium chloride from the flue, and the exhaust gas provided and extracted in the exhaust gas extraction pipe Dust removing means for removing dust contained therein, precipitation means provided in the exhaust gas extraction pipe for precipitating ammonium chloride contained in the exhaust gas, and X-ray or laser on the ammonium chloride deposited by the precipitation means And a measuring means for detecting ammonium chloride contained in the exhaust gas by detecting fluorescent X-rays generated by light irradiation.
- the second invention is the gas analyzer according to the first aspect, wherein the exhaust gas further contains sulfurous acid, the precipitation means precipitates sulfurous acid, and the measurement means measures sulfurous acid.
- a third invention is a mercury removal system that removes mercury contained in exhaust gas discharged from a boiler, ammonium chloride supply means for spraying a solution containing ammonium chloride into the flue of the boiler, and in the exhaust gas Reduction denitration device having a denitration catalyst that reduces nitrogen oxides of ammonia with ammonia and oxidizes mercury in the presence of hydrogen chloride, and wet desulfurization device that removes mercury oxidized in the reduction denitration device using an alkaline absorbent And ammonium chloride concentration measuring means for analyzing the concentration of the ammonium chloride contained in the exhaust gas, provided on either or both of the upstream side and the downstream side of the reduction denitration device, and the ammonium chloride concentration
- the gas analyzer according to claim 1 is used as a measurement means, and the measurement was performed by the ammonium chloride concentration measurement means.
- a heat exchanger provided between the reductive denitration device and the wet desulfurization device, for exchanging heat with the exhaust gas passing through the reductive denitration device and recovering heat.
- the mercury removal system is characterized in that the gas temperature of the exhaust gas passing through the heat exchanger is controlled based on the relationship between the ammonium chloride concentration and the gas temperature determined in advance.
- a heat exchanger provided between the reductive denitration device and the wet desulfurization device, for exchanging heat with the exhaust gas passing through the reductive denitration device and recovering heat.
- the gas analyzer of the second invention is used, and either the relationship between the ammonium chloride concentration and the gas temperature determined in advance or the relationship between the sulfurous acid concentration and the gas temperature or
- the mercury removal system is characterized in that the gas temperature of the exhaust gas passing through the heat exchanger is controlled based on both.
- the exhaust gas discharged from the boiler and supplied with ammonium chloride is extracted from the flue, the dust contained in the exhaust gas is removed, and the ammonium chloride contained in the exhaust gas is precipitated, and then precipitated.
- the ammonium chloride contained in the analysis gas is measured after the ammonium chloride is contained in the analysis gas and the analysis gas is extracted.
- a seventh invention is a gas analysis method according to the sixth invention, wherein the exhaust gas further contains sulfurous acid, sulfurous acid is precipitated in addition to ammonium chloride, and the precipitated sulfurous acid is measured.
- An eighth invention is a mercury removal method for removing mercury contained in exhaust gas discharged from a boiler, wherein an ammonium chloride supply step of spraying a solution containing ammonium chloride into the flue of the boiler, and in the exhaust gas Reduction denitration step having a denitration catalyst that oxidizes mercury in the presence of hydrogen chloride and oxidizing the mercury in the presence of hydrogen chloride, and a wet desulfurization step of removing mercury oxidized in the reduction denitration step using an alkali absorbent And an ammonium chloride concentration measurement step for analyzing the concentration of the ammonium chloride contained in the exhaust gas at either or both of the upstream side and the downstream side of the reduction denitration device, and the ammonium chloride concentration measurement step,
- the ammonium chloride contained in the exhaust gas by the ammonium chloride concentration measurement step using the gas analysis method of the sixth invention Determine the concentration of bromide, a mercury removal method in an exhaust gas to control the spray amount of a solution containing the ammonium
- a heat recovery step of exchanging heat between the exhaust gas and a heat medium circulating in a heat exchanger between the reductive denitration step and the wet desulfurization step, and the wet type The gas analysis method according to claim 6, further comprising: a reheating step of reheating the purified gas by exchanging heat between the purified gas discharged from the desulfurization apparatus and the heat medium, and the ammonium chloride concentration measuring step. Is used to control the gas temperature of the exhaust gas that exchanges heat with the heat medium in the heat recovery step based on the relationship between the ammonium chloride concentration determined in advance and the gas temperature.
- a heat recovery step of exchanging heat between the exhaust gas and a heat medium circulating in a heat exchanger between the reductive denitration step and the wet desulfurization step, and the wet type And a reheating step of reheating the purified gas by exchanging heat between the purified gas discharged from the desulfurization apparatus and the heating medium.
- the gas analysis method according to the seventh aspect of the invention is used.
- the exhaust gas used to exchange heat with the heat medium in the heat recovery step based on one or both of the relationship between ammonium chloride concentration and gas temperature obtained in advance and the relationship between sulfurous acid concentration and gas temperature. This is a method for removing mercury in exhaust gas to control the temperature.
- the precipitated ammonium chloride is analyzed, and the Cl ⁇ concentration contained in the exhaust gas is measured, whereby the ammonium chloride contained in the exhaust gas is measured.
- the concentration can be determined.
- FIG. 1 is a schematic view showing a gas analyzer according to the first embodiment of the present invention.
- FIG. 2 is a diagram simply showing the configuration of the roll filter.
- FIG. 3 is a schematic diagram showing an Hg removal system according to the second embodiment of the present invention.
- FIG. 4 is a diagram simply showing the configuration of the spray nozzle.
- FIG. 5 is a diagram showing a configuration of an Hg removal system according to the third embodiment of the present invention.
- FIG. 6 is a diagram simply showing the configuration of the heat exchanger.
- FIG. 1 is a schematic diagram showing a gas analyzer according to the first embodiment of the present invention
- FIG. 1 is a schematic diagram showing a gas analyzer according to the first embodiment of the present invention
- the gas analyzer 10 has an exhaust gas 11A from a flue 12 to which an exhaust gas 11 containing both ammonium chloride (NH 4 Cl) and sulfurous acid (SO 3 ) is supplied.
- an exhaust gas 11 containing both ammonium chloride (NH 4 Cl) and sulfurous acid (SO 3 ) is supplied.
- a roll filter (precipitation means) 15 for depositing both NH 4 Cl and SO 3 contained therein, and a sample 16 containing both NH 4 Cl and SO 3 deposited by the roll filter 15 are irradiated with X-rays 17.
- a measuring device (measuring means) 19 for detecting both fluorescent X-rays 18 generated from the sample 16 and measuring both NH 4 Cl and SO 3 contained in the exhaust gas 11A.
- the exhaust gas 11 is gas discharged from the boiler, and the exhaust gas 11 contains SO 3 . Since the NH 4 Cl solution is supplied into the exhaust gas 11 in the flue 12, the exhaust gas 11 contains NH 4 Cl.
- the gas component to be measured in the exhaust gas 11 includes both NH 4 Cl and SO 3 , but this embodiment is not limited to this, and the exhaust gas 11 includes at least NH 4 Cl. Any gas can be used.
- gas components contained in the exhaust gas 11, in addition to NH 4 Cl and SO 3 for example, nitrogen monoxide (NO), carbon monoxide (CO), water (H 2 O), nitrogen dioxide (NO 2 ), Methane (CH 4 ), ammonia, benzene and the like may be contained.
- the exhaust gas extraction pipe 13 is connected to the flue 12, and a part of the exhaust gas 11 flowing through the flue 12 is extracted from the exhaust gas extraction pipe 13.
- the exhaust gas extraction pipe 13 is provided with a control valve V11 to adjust the flow rate of the exhaust gas 11 extracted from the flue 12 to the exhaust gas extraction pipe 13. Since the exhaust gas 11 can be continuously extracted from the exhaust gas extraction pipe 13, the gas component in the exhaust gas 11 can be measured semi-continuously.
- the exhaust gas 11 ⁇ / b> A extracted to the exhaust gas extraction pipe 13 is fed to the collector 14 through the exhaust gas extraction pipe 13.
- the collector 14 removes the dust contained in the exhaust gas 11A.
- a cyclone dust collector is used as the collector 14, but the present embodiment is not particularly limited to this.
- the collector 14 After the dust contained in the exhaust gas 11 ⁇ / b> A is removed by the collector 14, the exhaust gas 11 ⁇ / b> A is fed to the roll filter 15. Moreover, the collector 14 has the dust conveyance pipe
- the roll filter 15 includes a pair of rollers 22, a conveyor belt 23, a filter 24, and an exhaust gas supply pipe 25. In the roll filter 15, when the pair of rollers 22 rotate, the conveying belt 23 also rotates, and the filter 24 moves.
- the measuring device 19 analyzes the concentration of each of NH 4 Cl and SO 3 contained in the exhaust gas 11A. Examples of the measuring device 19 include a fluorescent X-ray analyzer.
- the measurement device 19 includes an X-ray irradiation device 26 that irradiates the sample 16 with the X-rays 17 and a detector 27 that detects the fluorescent X-rays 18 generated from the sample 16.
- the measuring device 19 is provided with an opening 19 a on the wall surface side where the filter 24 is provided, and the X-ray 17 is irradiated from the X-ray irradiation device 26 to the filter 24.
- the exhaust gas 11A fed from the exhaust gas extraction pipe 13 to the exhaust gas feed pipe 25 is fed to the filter 24, and when passing through the filter 24, NH 4 Cl and SO 3 contained in the exhaust gas 11A are adsorbed by the filter 24.
- the sample 16 a containing both NH 4 Cl and SO 3 is deposited on the filter 24.
- the sample 16a deposited on the roll filter 15 is transported to the measuring device 19 as the filter 24 moves.
- the X-ray 17 is irradiated from the X-ray irradiation device 26 to the sample 16b moved to the vicinity of the opening 19a in the measurement device 19.
- NH 4 Cl and SO 3 contained in the sample 16 b are excited by irradiation with the X-rays 17.
- Fluorescent X-rays 18 are generated from the excited NH 4 Cl and SO 3 .
- the generated fluorescent X-ray 18 is detected by a detector 27 and analyzed. Detector 27, based on the NH 4 Cl, the energy of the fluorescent X-ray 18 emitted when the X-ray 17 to the SO 3 is irradiated sample 16b, NH 4 Cl contained in the exhaust gas 11A, analyzing the SO 3 To do.
- the measuring device 19 is not limited to the fluorescent X-ray analyzer, and other analyzers may be used as long as they can analyze NH 4 Cl and SO 3 contained in the exhaust gas 11A. .
- the exhaust gas supply pipe 25 that flows the exhaust gas 11A aggregates moisture contained in the exhaust gas 11A and measures It is preferable that a heater is provided on the outer periphery of the exhaust gas supply pipe 25 so that the analysis accuracy in the apparatus 19 does not deteriorate.
- the gas analyzer 10 after the NH 4 Cl contained in the exhaust gas 11 is deposited, by analyzing the fluorescent X-rays 18 generated from the deposited NH 4 Cl and SO 3 , The concentrations of ammonium ions (NH 4 + ), chlorine ions (Cl ⁇ ), and SO 3 contained in the exhaust gas 11 can be analyzed stably and simultaneously. For this reason, the concentration of NH 4 Cl and SO 3 contained in the exhaust gas 11 can be measured stably and simultaneously. Therefore, solution of NH 4 Cl when oxidizing the Hg, even when supplied in addition to solution of NH 4 Cl in NH 3 gas or NH 3 water to flue 12, supplied to the flue 12 contained in the exhaust gas 11 The concentration of can be determined appropriately.
- a solution containing NH 4 Cl is used for the exhaust gas 11.
- the present embodiment is not limited to this, and oxidizes Hg when vaporized. Any auxiliary can be used as long as it produces an oxidizing gas used in the process and a reducing gas used to reduce NOx.
- a solution containing NH 4 Cl is used, HCl gas is used as the oxidizing gas, and NH 3 gas is used as the reducing gas.
- a solution containing ammonium halide such as ammonium bromide (NH 4 Br) or ammonium iodide (NH 4 I) may be used.
- FIG. 3 is a schematic diagram showing an Hg removal system according to the second embodiment of the present invention. Since the Hg removal system according to this embodiment uses the gas analyzer 10 according to the first embodiment shown in FIGS. 1 and 2 as the NH 4 Cl measuring device (NH 4 Cl measuring means), NH 4 Cl Description of the measuring device is omitted.
- the Hg removal system 30 ⁇ / b> A is an Hg removal system that removes Hg contained in the exhaust gas 11 discharged from the boiler 31, and is disposed in the flue 12 downstream of the boiler 31.
- NH 4 Cl solution supply means 32 for spraying the NH 4 Cl solution 41
- a reduction denitration apparatus having a NOx removal catalyst for reducing NOx in the exhaust gas 11 with NH 3 gas and oxidizing Hg 0 in the presence of HCl gas ( Reductive denitration means) 33, an air heater (AH) 34 for exchanging heat from the denitrated exhaust gas 11, a dust collector (ESP: Electrostatic Precipitator) 35 for removing dust in the denitrated exhaust gas 11, and a reductive denitration device 33
- a wet desulfurization device 37 that removes the oxidized Hg using a lime gypsum slurry (alkali absorbing solution) 36, and a reductive denitration device 33 upstream and downstream, Those having a
- the exhaust gas 11 discharged from the boiler 31, solution of NH 4 Cl 41 is supplied from the solution of NH 4 Cl supply unit 32.
- the NH 4 Cl solution supply means 32 is a spray nozzle 42 for oxidizing Hg 0 contained in the exhaust gas 11, and an ammonium chloride (NH 4 Cl) solution that supplies the NH 4 Cl solution 41 to the spray nozzle 42 in a liquid state. It has a supply pipe 43 and an air supply pipe 45 that supplies air 44 for compressing and spraying the NH 4 Cl solution 41 into the flue 12 to the spray nozzle 42.
- the spray nozzle 42 is a two-fluid nozzle that is provided by being inserted into the flue 12 and injects the NH 4 Cl solution 41 and the air 44 into the flue 12 at the same time.
- FIG. 4 is a diagram simply showing the configuration of the spray nozzle.
- the spray nozzle 42 is formed of a double pipe 48 including an inner pipe 46 and an outer pipe 47 and a nozzle head 49 provided at the tip of the double pipe 48.
- the inner tube 46 is a tube used for feeding the NH 4 Cl solution 41.
- the outer tube 47 is a tube that is provided so as to cover the outer periphery of the inner tube 46 and is used to feed the air 44 into the space with the inner tube 46.
- the spray nozzle 42 sprays the NH 4 Cl solution 41 from the nozzle head 49 into the flue 12 (see FIG. 3) and jets air 44 into the flue 12.
- solution of NH 4 Cl 41 is fed to the spray nozzle 42 through a solution of NH 4 Cl supply tube 43 from the solution of NH 4 Cl tank 51.
- the flow rate of the NH 4 Cl solution 41 supplied from the NH 4 Cl solution supply pipe 43 is adjusted by the control valve V21.
- the NH 4 Cl solution 41 is adjusted to a predetermined concentration in the NH 4 Cl solution tank 51.
- the NH 4 Cl solution 41 can be generated by dissolving ammonium chloride (NH 4 Cl) powder in water. NH 4 Cl powder, it is possible to adjust the solution of NH 4 Cl 41 with a predetermined concentration by adjusting the supply amount of each of the water.
- the NH 4 Cl solution 41 may be generated by mixing an HCl solution and an NH 3 solution at a predetermined concentration ratio.
- the air 44 is supplied from the air supply unit 52 to the spray nozzle 42 via the air supply pipe 45 and is used as compression air when the NH 4 Cl solution 41 is sprayed from the nozzle head 49.
- a solution of NH 4 Cl 41 ejected from the nozzle head 49 can be sprayed as fine droplets into the flue 12.
- the flow rate of the air 44 supplied from the air supply pipe 45 is adjusted by the control valve V22.
- the droplets of the NH 4 Cl solution 41 sprayed from the nozzle head 49 into the flue 12 are evaporated and vaporized by the high-temperature atmosphere temperature of the exhaust gas 11 to form fine NH 4 Cl solid particles.
- it is decomposed into HCl and NH 3 and sublimated. Therefore, the NH 4 Cl solution 41 sprayed from the spray nozzle 42 is decomposed to generate HCl and NH 3 , and NH 3 gas and HCl gas can be supplied into the flue 12.
- the size of the droplets of the NH 4 Cl solution 41 sprayed from the nozzle holes of the nozzle head 49 can be adjusted by the flow rate of the air 44 supplied from the air supply pipe 45.
- the flow rate of the air 44 ejected from the nozzle head 49 is preferably set to, for example, an air / water ratio of 100 to 10,000 (volume ratio). This is because the NH 4 Cl solution 41 ejected from the nozzle head 49 is sprayed into the flue 12 as fine droplets.
- the air 44 serves to cool the NH 4 Cl solution 41.
- the heat of the exhaust gas 11 inside can be suppressed from being transferred to the NH 4 Cl solution 41 by the air 44. Since the NH 4 Cl solution 41 can be prevented from being heated by the heat of the exhaust gas 11, the liquid state can be maintained until immediately before the NH 4 Cl solution 41 is jetted.
- the exhaust gas 11 contains HCl gas and NH 3 gas generated from droplets of the NH 4 Cl solution 41 sprayed into the flue 12 from the NH 4 Cl solution supply means 32 and then reduced.
- the denitration device 33 is fed.
- NH 3 gas generated by decomposition of NH 4 Cl is used for NOx reductive denitration
- HCl gas is used for Hg oxidation to remove NOx and Hg from the exhaust gas 11.
- the reductive denitration device 33 includes one denitration catalyst layer 53.
- the present embodiment is not limited to this, and the reductive denitration device 33 appropriately determines the number of denitration catalyst layers 53 according to the denitration performance. Can be changed.
- the exhaust gas 11 is supplied to the wet desulfurization device 37 through the air heater 34 and the dust collector (ESP) 35 after reduction of NOx in the exhaust gas 11 and oxidation of Hg in the reduction denitration device 33.
- ESP dust collector
- the exhaust gas 11 is fed from the bottom wall surface in the apparatus main body 55, and the lime gypsum slurry 36 used as the alkali absorbent is supplied into the apparatus main body 55 through the absorption liquid supply line 54. It is made to jet from 56 toward the tower top side.
- the exhaust gas 11 rising from the bottom side in the apparatus main body 55 and the lime gypsum slurry 36 jetted from the nozzle 56 are brought into gas-liquid contact with each other, and HgCl 2 and sulfur oxide (SOx) in the exhaust gas 11 are brought into contact with each other.
- the exhaust gas 11 purified by the lime gypsum slurry 36 is discharged from the tower top side as the purified gas 57 and is discharged from the chimney 58 to the outside of the system.
- the lime gypsum slurry 36 used for the desulfurization of the exhaust gas 11 includes lime slurry CaCO 3 in which limestone powder is dissolved in water, gypsum slurry CaSO 4 in which lime and SOx in the exhaust gas 11 are reacted and further oxidized, and water. Produced by mixing.
- As the lime gypsum slurry 36 for example, a pumped liquid stored in the tower bottom 59 of the apparatus main body 55 of the wet desulfurization apparatus 37 is used. In the apparatus main body 55, SOx in the exhaust gas 11 reacts with the lime-gypsum slurry 36 as shown in the following formula (8).
- the lime-gypsum slurry 36 that has absorbed SOx in the exhaust gas 11 is mixed with water 61 supplied into the apparatus main body 55 and oxidized by air 62 supplied to the tower bottom 59 of the apparatus main body 55.
- the lime gypsum slurry 36 that has flowed down inside the apparatus main body 55 causes a reaction such as the following formula (9) with water 61 and air 62.
- the lime gypsum slurry 36 used for the desulfurization stored in the tower bottom 59 of the wet desulfurization apparatus 37 is oxidized, extracted from the tower bottom 59 and fed to the dehydrator 63, and then mercury chloride (HgCl). It is discharged out of the system as a dehydrated cake (gypsum) 64 containing.
- a dehydrated cake gypsum
- the dehydrator 63 for example, a belt filter or the like is used.
- the dehydrated filtrate (dehydrated filtrate) is subjected to wastewater treatment such as removal of suspensions in the dehydrated filtrate, heavy metals, and pH adjustment of the dehydrated filtrate. A part of this drained filtrate is returned to the wet desulfurization apparatus 37, and the other part of the dehydrated filtrate is treated as waste water.
- Lime gypsum slurry 36 is used as the alkali absorbing liquid, but other solutions can be used as the alkali absorbing liquid as long as it can absorb HgCl 2 in the exhaust gas 11.
- the lime gypsum slurry 36 is not limited to the method of jetting from the nozzle 56 toward the tower top side, and may be caused to flow down from the nozzle 56 so as to face the exhaust gas 11, for example.
- the NH 4 Cl measuring device 38-1 is provided on the upstream side of the reducing denitration device 33, and the NH 4 Cl measuring device 38-2 is provided on the downstream side of the reducing denitration device 33.
- the NH 4 Cl measuring devices 38-1 and 38-2 use the gas analyzer 10 according to the first embodiment shown in FIGS. Therefore, the NH 4 Cl measuring devices 38-1 and 38-2 can analyze the concentration of NH 4 Cl supplied from the spray nozzle 42 in the exhaust gas 11. Further, when the boiler 31 is, for example, a coal fired boiler 31, SO 3 is also contained in the exhaust gas 11, but the NH 4 Cl measuring devices 38-1 and 38-2 are SO 3 contained in the exhaust gas 11. The concentration of can also be measured. Therefore, the NH 4 Cl measuring devices 38-1 and 38-2 can simultaneously measure the concentrations of NH 4 Cl and SO 3 contained in the exhaust gas 11.
- Controller 70 a map showing the previously obtained NH 4 Cl concentration and NH 4 relationship between the gas temperature of Cl to precipitate, and a map showing the relationship between the gas temperature concentration and SO 3 in the SO 3 is deposited Record it.
- Controller 70 a map showing the previously obtained NH 4 Cl concentration and NH 4 relationship between the gas temperature of Cl to precipitate, and a map showing the relationship between the gas temperature concentration and SO 3 in the SO 3 is deposited Record it.
- the higher the NH 4 Cl concentration the higher the gas temperature at which NH 4 Cl precipitates, and the higher the SO 3 concentration, the higher the gas temperature at which SO 3 precipitates.
- NH 4 By Cl concentration and NH 4 concentration and SO 3 maps and SO 3 showing the relationship between the gas temperature Cl is precipitated obtained in advance a map representing the relationship between the gas temperature to precipitate, NH 4 Cl
- the gas temperature can be adjusted so that NH 4 Cl and SO 3 do not precipitate according to the concentration of SO 3 or the concentration of SO 3 .
- Controller 70 previously obtained of NH 4 Cl concentration and NH 4 Cl is precipitated from the measurement result of the concentration of NH 4 Cl contained in the exhaust gas 11 measured in NH 4 Cl measuring device 38-1, 38-2 to on the basis of a map showing the relationship between the gas temperature Cl contained in the exhaust gas 11 - analyzing the concentration of, it is possible to determine the concentration of NH 4 Cl contained in the exhaust gas 11.
- the control device 70 can control the spray amount of the NH 4 Cl solution, so that the NH 4 Cl solution sprayed from the spray nozzle 42 can be appropriately controlled. The amount of spray can be set.
- the NH 4 Cl measuring devices 38-1 and 38-2 can measure the concentration of SO 3 in addition to the concentration of NH 4 Cl contained in the exhaust gas 11, the NH 4 Cl measuring device 38-1, 38-2 transmits the concentration of SO 3 contained in the exhaust gas 11 to the control device 70.
- the control device 70 determines the SO 3 concentration obtained in advance from the measurement result of the concentration of SO 3 contained in the exhaust gas 11 measured by the NH 4 Cl measuring devices 38-1 and 38-2 and the gas temperature at which SO 3 is deposited. on the basis of a map showing the relationship between the by analyzing the concentration of SO 3 contained in the exhaust gas 11, it is possible to determine the concentration of SO 3 contained in the flue gas 11.
- the control device 70 can control the spray amount of the NH 4 Cl solution, so that the NH 4 Cl solution sprayed from the spray nozzle 42 can be appropriately sprayed. It can be an amount.
- the concentrations of NH 4 + , Cl ⁇ and SO 3 contained in the exhaust gas 11 can be stably and simultaneously analyzed.
- the concentrations of NH 4 Cl and SO 3 contained in the exhaust gas 11 can be measured stably and simultaneously. Therefore, since the NH 4 Cl solution 41 can be sprayed in an appropriate amount from the spray nozzle 42 into the flue 12, it is possible to stably maintain the Hg removal performance and the NOx reduction performance in the reductive denitration device 33. it can.
- a flow meter 71 for measuring the flow rate of the exhaust gas 11 is provided on the upstream side of the spray nozzle 42.
- the flow rate of the exhaust gas 11 is measured by the flow meter 71.
- the flow rate value of the exhaust gas 11 measured by the flow meter 71 is sent to the control device 70, and the flow rate, angle, initial velocity, etc. of the NH 4 Cl solution 41 injected from the nozzle head 49 based on the flow rate value of the exhaust gas 11 are determined. Can be adjusted.
- a NOx concentration meter 72 is provided on the outlet side of the reductive denitration device 33.
- the value of the NOx concentration in the exhaust gas 11 measured by the NOx concentration meter 72 is transmitted to the control device 70.
- the control device 70 can confirm the NOx reduction ratio in the reductive denitration device 33 from the value of the NOx concentration in the exhaust gas 11 measured by the NOx concentration meter 72. Therefore, the NH 4 Cl concentration and supply amount of the NH 4 Cl solution 41 sprayed from the spray nozzle 42 are adjusted from the value of the NOx concentration in the exhaust gas 11 measured by the NOx concentration meter 72 and supplied separately into the exhaust gas 11.
- the amount of NH 3 water supplied can be adjusted, and the mixing ratio of NH 3 can be adjusted. Thereby, NOx of the exhaust gas 11 can be reduced in the reduction denitration apparatus 33, and the reduction denitration apparatus 33 can satisfy a predetermined denitration performance.
- the flue 12 is provided with Hg concentration meters 73-1 to 73-3 for measuring the Hg content in the exhaust gas 11 discharged from the boiler 31.
- the Hg concentration meter 73-1 is provided in the flue 12 between the boiler 31 and the nozzle head 49, and the Hg concentration meter 73-2 is provided between the reductive denitration device 33 and the air heater 34.
- 73-3 is provided on the downstream side of the wet desulfurization apparatus 37.
- the value of the Hg concentration in the exhaust gas 11 measured by the Hg concentration meters 73-1 to 73-3 is transmitted to the control device 70.
- the control device 70 can confirm the content of Hg contained in the exhaust gas 11 from the value of the Hg concentration in the exhaust gas 11 measured by the Hg concentration meters 73-1 to 73-3.
- the Hg densitometers 73-1 to 73-3 are composed of metallic mercury Hg 0 , mercury oxide Hg 2+ , and total mercury (amount of mercury including metallic mercury Hg 0 and mercury oxide Hg 2+ ). And can be arbitrarily measured. By grasping the ratio of mercury oxide Hg 2+ to the total mercury with the Hg concentration meters 73-2 and 73-3, the mercury oxidation rate of Hg contained in the exhaust gas 11 can be obtained.
- the nozzle head 49 By controlling the NH 4 Cl concentration and supply flow rate of the NH 4 Cl solution 41 from the Hg concentration value and mercury oxidation rate in the exhaust gas 11 measured by the Hg concentration meters 73-1 to 73-3, the nozzle head 49 The NH 4 Cl concentration and supply flow rate of the sprayed NH 4 Cl solution 41 can satisfy the predetermined denitration performance and maintain the Hg oxidation performance.
- An oxidation-reduction potential measurement controller (ORP controller) 74 that measures the oxidation-reduction potential of the lime gypsum slurry 36 is provided at the tower bottom 59 of the wet desulfurization apparatus 37.
- This ORP controller 74 measures the value of the oxidation-reduction potential of the lime gypsum slurry 36.
- the supply amount of the air 62 supplied to the tower bottom 59 of the wet desulfurization apparatus 37 is adjusted based on the measured oxidation-reduction potential value. By adjusting the supply amount of the air 62 supplied to the tower bottom 59, the oxidized Hg collected in the lime gypsum slurry 36 stored in the tower bottom 59 of the wet desulfurization apparatus 37 is reduced. And can be prevented from being diffused from the chimney 58.
- the oxidation-reduction potential of the lime gypsum slurry 36 in the wet desulfurization device 37 is preferably in the range of, for example, 0 mV or more and +600 mV or less in order to prevent re-scattering of Hg from the lime gypsum slurry 36. This is because if the oxidation-reduction potential is within the above range, Hg collected as HgCl 2 in the lime-gypsum slurry 36 is a stable region, and re-scattering into the atmosphere can be prevented.
- a solution containing NH 4 Cl is used to oxidize Hg and reduce NOx, but the present embodiment is not limited to this.
- a solution containing ammonium halide such as NH 4 Br or NH 4 I may be used.
- FIG. 5 is a diagram showing the configuration of the Hg removal system according to the third embodiment of the present invention
- FIG. 6 is a diagram simply showing the configuration of the heat exchanger.
- symbol is attached
- the Hg removal system 30 ⁇ / b> B heats the exhaust gas 11 that has passed through the reductive denitration device 33 between the air heater 34 and the dust collector 35 to recover heat.
- An exchanger 80 is provided.
- the heat exchanger 80 includes a heat recovery unit 81 and a reheater 82.
- the heat recovery unit 81 is provided between the air heater 34 and the dust collector 35 and exchanges heat between the exhaust gas 11 discharged from the boiler 31 and the heat medium 83 circulating in the heat exchanger 80.
- the gas temperature of the exhaust gas 11 discharged from the boiler 31 is in the range of, for example, 130 ° C. to 150 ° C.
- the gas temperature of the exhaust gas 11 is in the range of 80 ° C.
- the reheater 82 is provided on the downstream side of the wet desulfurization device 37, exchanges heat between the purified gas 57 discharged from the wet desulfurization device 37 and the heat medium 83, and reheats the purified gas 57.
- the heat exchanger 80 has a heat medium circulation passage 84 through which the heat medium 83 circulates between the heat recovery unit 81 and the reheater 82.
- the heat medium 83 circulates between the heat recovery device 81 and the reheater 82 via the heat medium circulation passage 84.
- a plurality of fin tubes 85 are provided on the surface of the heat medium circulation passage 84 provided in each of the heat recovery device 81 and the reheater 82.
- a heat exchanging portion 86 is provided in the heat medium circulation passage 84, and the medium temperature of the heat medium 83 can be adjusted by exchanging the heat medium 83 with the steam 87.
- the controller 70 determines the concentration of NH 4 Cl determined in advance.
- the heat exchange section 86 generates heat based on one or both of a map showing the relationship between the gas temperature at which NH 4 Cl is deposited and a map showing the relationship between the SO 3 concentration and the gas temperature at which SO 3 is deposited. By exchanging the heat of the medium 83 with the steam 87, the medium temperature of the heat medium 83 is raised.
- the SO 3 can be inhibited from precipitating on the fin tube 85 of the heat recovery unit 81 Can do. Thereby, corrosion of the fin tube 85 of the heat recovery device 81 can be suppressed.
- the heat recovery amount recovered by the heat recovery device 81 by the heat recovery device 81 decreases, so that the outlet gas temperature of the heat recovery device 81 maintains a high state. Since the heat medium 83 flowing into the reheater 82 has a small amount of heat, the temperature of the purified gas 57 entering the reheater 82 cannot be increased. Therefore, in order to increase the temperature of the purified gas 57 that has passed through the reheater 82, the amount of addition of the steam 87 is increased, and the amount of heat of the heat medium 83 flowing into the reheater 82 is increased. The temperature of the purified gas 57 passing through 82 can be raised.
- the heat recovery amount recovered by the heat medium 83 by the heat recovery device 81 is increased.
- the outlet gas temperature of the exhaust gas 11 exiting from the heat recovery device 81 is lowered, and the temperature of the heat medium 83 flowing into the reheater 82 is raised, so that the temperature of the purified gas 57 entering the reheater 82 is raised. be able to.
- the supply amount of the steam 87 supplied for heat exchange with the heat medium 83 can be reduced.
- the heat medium 83 is supplied from the heat medium tank 88 to the heat medium circulation passage 84.
- the heat medium 83 is circulated in the heat medium circulation passage 84 by the heat medium feed pump 89. Further, the supply amount of the steam 87 is adjusted by the control valve V31 according to the gas temperature of the purified gas 57, and sent to the reheater 82 by the control valve V32 according to the gas temperature of the exhaust gas 11 discharged from the heat recovery device 81.
- the supplied heat medium 83 is supplied to the heat recovery unit 81, and the supply amount of the heat medium 83 supplied to the reheater 82 is adjusted.
- the NH 4 Cl measuring device 38-1 and 38-2 to measure the NH 4 Cl concentration and SO 3 concentration contained in the exhaust gas 11, pre-concentration of the obtained NH 4 Cl and NH 4 Cl is precipitated Gas a map showing the relationship between the temperature, increasing the medium temperature of the heat medium 83 based on either one or both of the map showing the relationship between the gas temperature concentration and SO 3 in the SO 3 is deposited, the heat recovery unit The gas temperature of the exhaust gas 11 on the outlet side 81 is set to be equal to or higher than the gas temperature at which NH 4 Cl and SO 3 are deposited.
- the heat exchanger 80 is provided between the air heater 34 and the dust collector 35, but the present embodiment is not limited to this, and the reductive denitration device 33, the wet desulfurization device 37, and the like. Between.
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Abstract
Description
4NO+4NH3+O2→4N2+6H2O・・・(1)
NH3+SO3+H2O=NH4HSO4・・・(2)
2NH3+SO3+H2O=(NH4)2SO4・・・(3)
Hg0+1/2O2+2HCl→HgCl2+H2O・・・(4)
[第1の実施形態]
本発明による第1の実施形態に係るガス分析装置について、図面を参照して説明する。図1は、本発明の第1の実施形態に係るガス分析装置を示す概略図であり、図2は、ロールフィルタの構成を簡略に示す図である。図1、2に示すように、本実施形態に係るガス分析装置10は、塩化アンモニウム(NH4Cl)、亜硫酸(SO3)の両方を含む排ガス11が送給される煙道12から排ガス11Aを抜出す排ガス抜出し管13と、排ガス抜出し管13に設けられ、抜き出した排ガス11A中に含まれる煤塵を除去する捕集器(煤塵除去手段)14と、排ガス抜出し管13に設けられ、排ガス11A中に含まれるNH4Cl、SO3の両方を析出させるロールフィルタ(析出手段)15と、ロールフィルタ15で析出されたNH4Cl、SO3の両方を含む試料16にX線17を照射させて試料16から発生する蛍光X線18を検出して排ガス11A中に含まれるNH4Cl、SO3の両方を測定する測定装置(測定手段)19とを含むものである。
本発明による第2の実施形態に係るHg除去システムについて、図面を参照して説明する。図3は、本発明の第2の実施形態に係るHg除去システムを示す概略図である。本実施形態に係るHg除去システムは、NH4Cl測定装置(NH4Cl測定手段)として、図1、2に示す第1の実施形態に係るガス分析装置10を用いているため、NH4Cl測定装置の説明は省略する。
NH4Cl→NH3+HCl・・・(5)
4NO+4NH3+O2→4N2+6H2O・・・(6)
Hg+1/2O2+2HCl→HgCl2+H2O・・・(7)
CaCO3+SO2+0.5H2O→CaSO3・0.5H2O+CO2・・・(8)
CaSO3・0.5H2O+0.5O2+1.5H2O→CaSO4・2H2O・・・(9)
NH4Cl測定装置38-1は、還元脱硝装置33の前流側に設けられ、NH4Cl測定装置38-2は、還元脱硝装置33の後流側に設けられている。NH4Cl測定装置38-1、38-2は、上述の通り、図1、2に示す第1の実施形態に係るガス分析装置10を用いている。よって、NH4Cl測定装置38-1、38-2は、排ガス11中に噴霧ノズル42から供給されたNH4Clの濃度を分析することができる。また、ボイラ31が、例えば石炭焚きボイラ31の場合、排ガス11中にはSO3も含まれているが、NH4Cl測定装置38-1、38-2は、排ガス11中に含まれるSO3の濃度も測定することができる。従って、NH4Cl測定装置38-1、38-2は、排ガス11中に含まれるNH4ClおよびSO3の濃度を同時に測定することができる。
本発明による第3の実施形態に係る噴霧装置を適用したHg除去システムについて、図面を参照して説明する。図5は、本発明の第3の実施形態に係るHg除去システムの構成を示す図であり、図6は、熱交換器の構成を簡略に示す図である。なお、本発明の第2の実施形態に係るHg除去システムの構成と重複する部材については、同一符号を付してその説明は省略する。
11、11A 排ガス
12 煙道
13 排ガス抜出し管
14 捕集器(煤塵除去手段)
15 ロールフィルタ(析出手段)
16、16a、16b 試料
17 X線
18 蛍光X線
19 測定装置(測定手段)
19a 開口部
21 煤塵搬送管
22 ローラ
23 搬送用ベルト
24 フィルタ
25 排ガス送給管
26 X線照射装置
27 検出器
30A、30B Hg除去システム
31 ボイラ
32 NH4Cl溶液供給手段
33 還元脱硝装置(還元脱硝手段)
34 エアヒータ(AH)
35 集塵器(ESP)
36 石灰石膏スラリー(アルカリ吸収液)
37 湿式脱硫装置
38-1、38-2 NH4Cl測定装置(NH4Cl測定手段)
41 NH4Cl溶液
42 噴霧ノズル
43 塩化アンモニウム(NH4Cl)溶液供給管
44 空気
45 空気供給管
46 内管
47 外管
48 二重管
49 ノズルヘッド
51 塩化アンモニウム(NH4Cl)溶液タンク
52 空気供給部
53 脱硝触媒層
54 吸収液送給ライン
55 装置本体
56 ノズル
57 浄化ガス
58 煙突
59 塔底部
61 水
62 空気
63 脱水器
64 脱水ケーキ(石膏)
70 制御装置
71 流量計
72 NOx濃度計
73-1~73-3 水銀(Hg)濃度計
74 酸化還元電位測定制御装置(ORPコントローラ)
80 熱交換器
81 熱回収器
82 再加熱器
83 熱媒体
84 熱媒体循環通路
85 フィンチューブ
86 熱交換部
87 スチーム
88 熱媒体タンク
V11、V21、V22、V31、V32 調節弁
Claims (10)
- ボイラから排出され、塩化アンモニウムを供給した排ガスを煙道から抜出す排ガス抜出し管と、
前記排ガス抜出し管に設けられ、抜出した排ガス中に含まれる煤塵を除去する煤塵除去手段と、
前記排ガス抜出し管に設けられ、前記排ガス中に含まれる塩化アンモニウムを析出させる析出手段と、
前記析出手段で析出された塩化アンモニウムにX線またはレーザ光を照射させて発生する蛍光X線を検出して、排ガス中に含まれる塩化アンモニウムを測定する測定手段と、
を含むことを特徴とするガス分析装置。 - 請求項1において、
前記排ガスが、更に亜硫酸を含み、前記析出手段が亜硫酸を析出させると共に、前記測定手段が亜硫酸を測定するガス分析装置。 - ボイラから排出される排ガス中に含まれる水銀を除去する水銀除去システムであり、
前記ボイラの煙道内に、塩化アンモニウムを含む溶液を噴霧する塩化アンモニウム供給手段と、
前記排ガス中の窒素酸化物をアンモニアで還元すると共に、塩化水素共存下で水銀を酸化する脱硝触媒を有する還元脱硝装置と、
該還元脱硝装置において酸化された水銀をアルカリ吸収液を用いて除去する湿式脱硫装置と、
前記還元脱硝装置の上流側と下流側の何れか一方又は両方に設けられ、前記排ガス中に含まれる前記塩化アンモニウムの濃度を分析する塩化アンモニウム濃度測定手段とを有し、
前記塩化アンモニウム濃度測定手段として、請求項1に記載のガス分析装置が用いられ、
前記塩化アンモニウム濃度測定手段により求められた前記塩化アンモニウムの濃度に応じて前記塩化アンモニウムを含む溶液の噴霧量を制御することを特徴とする水銀除去システム。 - 請求項3において、
前記還元脱硝装置と前記湿式脱硫装置との間に設けられ、前記還元脱硝装置を通過した排ガスと熱交換して熱回収する熱交換器とを有し、
予め求めた塩化アンモニウム濃度とガス温度との関係に基づいて前記熱交換器を通過する排ガスのガス温度を制御することを特徴とする水銀除去システム。 - 請求項3において、
前記還元脱硝装置と前記湿式脱硫装置との間に設けられ、前記還元脱硝装置を通過した排ガスと熱交換して熱回収する熱交換器とを有し、
前記塩化アンモニウム濃度測定手段として、請求項2に記載のガス分析装置が用いられ、
予め求めた塩化アンモニウム濃度とガス温度との関係と、亜硫酸濃度とガス温度との関係との何れか一方又は両方に基づいて前記熱交換器を通過する排ガスのガス温度を制御することを特徴とする水銀除去システム。 - ボイラから排出され、塩化アンモニウムを供給した排ガスを煙道から抜出し、前記排ガス中に含まれる煤塵を除去し、前記排ガス中に含まれる塩化アンモニウムを析出させた後、析出された塩化アンモニウムを分析用ガス中に含有させ、前記分析用ガスを抜き出した後、前記分析用ガス中に含まれる前記塩化アンモニウムを測定することを特徴とするガス分析方法。
- 請求項6において、
前記排ガスが、更に亜硫酸を含み、塩化アンモニウムの他に亜硫酸を析出させ、析出した亜硫酸を測定するガス分析方法。 - ボイラから排出される排ガス中に含まれる水銀を除去する水銀除去方法であり、
前記ボイラの煙道内に、塩化アンモニウムを含む溶液を噴霧する塩化アンモニウム供給工程と、
前記排ガス中の窒素酸化物をアンモニアで還元すると共に、塩化水素共存下で水銀を酸化する脱硝触媒を有する還元脱硝工程と、
該還元脱硝工程において酸化された水銀をアルカリ吸収液を用いて除去する湿式脱硫工程と、
前記還元脱硝装置の上流側と下流側の何れか一方又は両方で、前記排ガス中に含まれる前記塩化アンモニウムの濃度を分析する塩化アンモニウム濃度測定工程を含み、
前記塩化アンモニウム濃度測定工程では、請求項6に記載のガス分析方法を用い、
前記塩化アンモニウム濃度測定工程により前記排ガス中に含まれる前記塩化アンモニウムの濃度を求め、求められた前記塩化アンモニウムの濃度に応じて前記塩化アンモニウムを含む溶液の噴霧量を制御する排ガス中の水銀除去方法。 - 請求項8において、
前記還元脱硝工程と前記湿式脱硫工程との間に、前記排ガスと熱交換器内を循環する熱媒体とを熱交換する熱回収工程と、
前記湿式脱硫装置から排出される浄化ガスと前記熱媒体とを熱交換して、前記浄化ガスを再加熱する再加熱工程とを含み、
前記塩化アンモニウム濃度測定工程では、請求項6に記載のガス分析方法を用い、
予め求めた塩化アンモニウム濃度とガス温度との関係に基づいて前記熱回収工程で前記熱媒体と熱交換する前記排ガスのガス温度を制御する排ガス中の水銀除去方法。 - 請求項8において、
前記還元脱硝工程と前記湿式脱硫工程との間に、前記排ガスと熱交換器内を循環する熱媒体とを熱交換する熱回収工程と、
前記湿式脱硫装置から排出される浄化ガスと前記熱媒体とを熱交換して、前記浄化ガスを再加熱する再加熱工程とを含み、
前記塩化アンモニウム濃度測定工程では、請求項7に記載のガス分析方法を用い、
予め求めた塩化アンモニウム濃度とガス温度との関係と、亜硫酸濃度とガス温度との関係との何れか一方又は両方に基づいて前記熱回収工程で前記熱媒体と熱交換する前記排ガスのガス温度を制御する排ガス中の水銀除去方法。
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