GB2498272A - Exhaust gas treatment device - Google Patents
Exhaust gas treatment device Download PDFInfo
- Publication number
- GB2498272A GB2498272A GB1303447.5A GB201303447A GB2498272A GB 2498272 A GB2498272 A GB 2498272A GB 201303447 A GB201303447 A GB 201303447A GB 2498272 A GB2498272 A GB 2498272A
- Authority
- GB
- United Kingdom
- Prior art keywords
- exhaust gas
- mercury
- oxides
- desulphuration
- sea water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000011282 treatment Methods 0.000 title description 25
- 239000007789 gas Substances 0.000 abstract description 94
- 239000013535 sea water Substances 0.000 abstract description 54
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 53
- 229910052753 mercury Inorganic materials 0.000 abstract description 53
- 229910000474 mercury oxide Inorganic materials 0.000 abstract description 50
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical class [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 abstract description 50
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 230000002378 acidificating effect Effects 0.000 abstract description 24
- 239000003054 catalyst Substances 0.000 abstract description 22
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 21
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 abstract description 19
- 239000003245 coal Substances 0.000 abstract description 13
- 238000002485 combustion reaction Methods 0.000 abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 10
- HHIQWSQEUZDONT-UHFFFAOYSA-N tungsten Chemical compound [W].[W].[W] HHIQWSQEUZDONT-UHFFFAOYSA-N 0.000 description 10
- 229910052721 tungsten Inorganic materials 0.000 description 9
- 239000010937 tungsten Substances 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000013618 particulate matter Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000013056 hazardous product Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- SHZVCTRRRIRFOC-UHFFFAOYSA-N mercury(1+) Chemical compound [Hg+] SHZVCTRRRIRFOC-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- LKJMGLFKGKSOCH-UHFFFAOYSA-N titanium Chemical compound [Ti].[Ti].[Ti] LKJMGLFKGKSOCH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
-
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
-
- 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
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
-
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
-
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
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- 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
- B01D2251/2062—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/10—Inorganic absorbents
- B01D2252/103—Water
- B01D2252/1035—Sea water
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20776—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
- B01D2257/2045—Hydrochloric acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Combustion & Propulsion (AREA)
- Treating Waste Gases (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
Abstract
A denitrification device (7) which adds a reducing agent to acidic exhaust gas which includes mercury, produced by combustion of coal, and reduces nitrogen oxides in the acidic exhaust gas in the presence of a catalyst, and a desulphuration device (13) which removes sulphur oxides in the acidic exhaust gas discharged from the denitrification device (7), by absorption in sea water, are provided/ and by setting the temperature of the acidic exhaust gas on the inlet side of the denitrification device (7) to a temperature such that reactions producing mercury oxides are suppressed in the denitrification device (7) and the concentration of mercury oxides on the inlet side of the desulphuration device (13) is no more than a set value, the mercury concentration in sea water released from the desulphuration device (13) is kept no higher than the permitted value.
Description
Description
Title of Invention: EXHAUST GAS TREATMENT DEVICE
Technical Field
[000lJ The present invention relates to an exhaust gas treatment device, and particularly relates to a technology for removing sulphur oxides in an acidic exhaust gas containing mercury, which is generated by the combustion of coal, by making sea water absorb the sulphur oxides.
Background Art
[0002J For instance, in Patent Literature 1, an exhaust gas treatment device is proposed that teads an acidic exhaust gas containing nitrogen oxides and sulphur oxides generated by the combustion of coal into a denitrification device, which reduces the nitrogen oxides with a reducing agent such as ammonium in the presence of a catalyst, and removes the sulphur oxides in the acidic exhaust gas discharged from the denitrification device by making an absorbing liquid such as a calcium-based absorbing liguid absorb the sulphur oxides. In addition, in the same Patent Literature 1, it is described that mercury contained in the acidic exhaust gas reacts with halogen such as chlorine contained in the same exhaust gas due to the catalyst of the denitrification device and is converted into mercury oxides, and these mercury oxides are removed by being absorbed into the absorbing liquid of the desuiphuration device. Thus, in the same Patent Literature 1, the mercury is removed by promoted reactions that produce the mercury oxides in the denitrification device.
[0003J On the other hand, in Patent Literature 2, it is proposed to use sea water as the absorbing liquid of the desulphuration device in order to inexpensively remove sulphur, in the case where a desuiphuration device is constructed near the sea. The same Patent Literature 2 proposes a process of spraying the sea water into the exhaust gas containing the sulphur oxides to make the sea water absorb the sulphur oxides, then subjecting the resultant sea water to neutralization treatment with the use of calcium carbonate, and returning the neutralized sea water to the sea.
Citation List Patent Literature [0004J Patent Literature 1: JP-A-2009-226238 Patent Literature 2: JP-A-8-206447
Summary of Invention
Technical Problem [0005] However, when the sea water described in Patent Literature 2 is used as the absorbing liquid of the desulphuration device of Patent Literature 1, mercury oxides may be dissolved into the sea water, and accordingly the mercury, which is a hazardous material, cannot be removed only by the neutralization treatment to which the sea water is subjected before being released to the sea. Because of this, the sea water to be released to the sea must be subjected to waste water treatment for removing the mercury from the sea water, and accordingly there is no advantage of using the sea water as the absorbing liguid of the desulphuration device.
[00061 An object of the present invention is to use sea water as an absorbing liquid of a desulphuration device, and is also to reduce the concentration of mercury in sea water to be discharged from the desulphuraticn device to a permitted value or lower without providing particuler waste water treatment.
Solution to Problem [00071 In order to solve the above described problems, the present invention provides an exhaust gas treatment device that includes: a denitrification device that adds a reducing agent to an acidic exhaust gas containing mercury, which is generated by the combustion of coal, and reduces nitrogen oxides in the acidic exhaust gas in the presence of a catalyst; and a desulphuration device that removes sulphur oxides in the acidic exhaust gas discharged from the denitrification device by making sea water absorb sulphur oxides, wherein a temperature of the acidic exhaust gas on an inlet side of the denitrification device is set to a temperature at which reactions of producing mercury oxides in the denitrification device are suppressed so as to control a concentration of mercury oxides on an inlet side of the desulphuration device to a set value or lower.
[0008J Thereby, the exhaust gas treatment device can adjust the reactions of producing the mercury oxides by a temperature at the inlet side of the denitrification device, accordingly can control the concentration of the mercury oxides in the acidic exhaust gas to be led into the desuiphuration device, decreases the mercury oxides to be absorbed by the sea water, which is the absorbing liquid of the desuiphuration device, and can control the concentration of mercury in the sea water to be discharged from the desulphuration device to the sea at the permitted value or lower. For this reason, it is not necessary to perform the waste water treatment for removing mercury from the sea water to be released from the desuiphuration device to the sea. Incidentally, the set value for the concentration of the mercury oxides at the inlet side of the desulphuration device is appropriately selected according to the permitted value for the concentration of mercury in the sea water to be released from the desulphuration device.
[00091 In addition, the temperature of the acidic exhaust gas at the inlet side of the denitrification device can be set to such a temperature that the concentration of mercury in the sea water released from the desulphuration device reaches at the set value or lower, Specifically, the permitted value for the concentration of mercury in the sea water as the absorbing liguid, which is discharged from the desulphuration device or is circulated to the desulphuration device, Is set so that the concentration of mercury in the sea water to be released from the desulphuration device to the sea reaches a permitted value (regulation value) or lower, the concentration of mercury in the sea water as the absorbing liguid is detected, and the temperature of the acidic exhaust gas at the inlet side of the denitrification device is set so that the detected value satisfies the permitted value.
[00l0J In addition, it is preferable to provide a mercury adsorption device for adsorbing and removing mercury in the acidic exhaust gas, on the downstream side of the desulphuration device. Then, the provided mercury adsorption device can reduce the concentration of mercury in the exhaust gas to be released from the exhaust gas treatment device.
[O0l1J Incidentally, the temperature of the acidic exhaust gas at the inlet side of the denitrification device can be appropriately set according to the permitted value for the concentration of mercury in the sea water to be released from the desulphuration device, and can be set so as to reach 400°C or hHgher, for instance, under 1001 load. Specifically, it is preferable to set the temperature of the acidic exhaust gas at the inlet side of the denitrification device to a high temperature, because the reactions of producing the mercury oxides in the denitrification device are suppressed at the high temperature. In this case, if the temperature of the acidic exhaust gas at the inlet side of the denitrification device has been set to an excessively high value, NOx removal efficiency may be lowered, and the set temperature may exceed a heat resistant temperature of a catalyst or the like. For this reason, it is preferable to set the temperature of the acidic exhaust gas at the inlet side of the denitrification device to 45000 or lower, for instance.
[0012] In addition, the inventors of the present invention have found cut that the reactions of producing the mercury oxides in the denitrification device can be suppressed by setting the temperature of the acidic exhaust gas at the inlet side cf the denitrification device to 400°C or higher and also by using a catalyst formed from titanium to which tungsten is added, in the denitrification device. The reactions of producing the mercury oxides in the denitrification device can be further suppressed by using the catalyst particularly having a ratio of titanium/tungsten = 60/1 to 50/40.
[0013] In addition, it is preferable to wash coal with water to reduce the chlorine content ccntained therein and then combust the coal, because the reactions of producing the mercury oxides in the denitrification device are promoted when the chlorine concentration in the acidic exhaust gas is high. Thereby, the chlorine concentration in the acidic exhaust gas to be led into the denitrification device can be reduced, and accordingly the reactions of producing the mercury oxides can be suppressed.
Advantageous Effect of Invention [0014] The exhaust gas treatment device according to the present invention uses sea water as an absorbing liquid of a desulphuration device, and also can control the concentration of mercury in the sea water to be released from the desulphuration device to a permitted value or lower, without providing particuler waste water treatment.
Brief Description of Drawing
[0015] [Figure 1] Figure 1 is a block diagram of an exhaust gas treatment device of one embodiment according to the present invention.
Description of Embodiment
[0016J (Embodiment) The present invention will be described below with reference to an embodiment. As is illustrated in Figure 1, an exhaust gas treatment device 1 of the present embodiment is connected to a boiler 3 for combusting coal, for instance, and is structured so as to subject an exhaust gas exhausted from the boiler 3, for instance, an exhaust gas that contains an acidic component such as nitrogen oxides, sutphur oxides and mercury, to cleaning treatment.
[0017J In the exhaust gas treatment device 1, a denitrification device 7 is provided, which denitrifies the exhaust gas, for instance, with a selective catalytic reduction process. The denitrification device 7 is structured so as to add a reducing agent 5, for instance, ammonium, to the exhaust gas, and reduce the nitrogen oxides in the exhaust gas in the presence of a catalyst.
On the outlet side of the denitrification device 7, an air preheater 9 is provided, which heats air to be used for the combustion of the boiler 3, for instance, with the exhaust gas. On the outlet side of the air preheater 9, dust-collecting equipment 11 is provided, which collects particulate matter such as fly ash in the exhaust gas and removes the particulate matter from the exhaust gas. On the outlet side of the dust-collecting equipment 11, a wet desulphuration device 13 is provided, which removes the sulphur oxides from the exhaust gas by making sea water absorb the sulphur oxides.
[0018] The desulphuration device 13 is structured so as to spray, for instance, the sea water pumped up by a pump or the like to the exhaust gas. Thereby, the desulphuration device 13 can remove the sulphur oxides in the exhaust gas by making sea water absorb the sulphur oxides. The desulphuration device 13 is provided, for instance, a with a not-shown purification device which is structured so as to remove the sulphur oxides absorbed in the sea -10 -water, and release the sea water from which the sulphur oxides have been removed, to the sea. Incidentally, the desulphuration device 13 can be appropriately selected from a circulation type desulphuration device that the sea water for an absorbing liquid therein and then releases the used sea water to the sea, a one-through type that the sea water for an absorbing liguid that has been passed through once therein without circulating, and the like.
[0019] On the outlet side of the desulphuration device 13, a mercury adsorption device 15 is provided, which adsorbs and removes the mercury in the exhaust gas. The mercury adsorption device 15 provides, for instance, an adsorption tower 17 therein that is filled with activated carbon that can adsorb mercury, and a regeneration tower 19 therein that removes the mercury adsorbed by the activated carbon and regenerates the activated carbon.
Thereby, the mercury adsorption device 15 is structured so as to be capable of using the activated carbon ciroulated therein, and removing the mercury from the exhaust gas, as is illustrated by a dotted line in Figure 1. On the outlet side of the mercury adsorption device 15, a chimney is provided, which is structured so as to release the purified exhaust gas to the air.
[0020J -11 -Next, a characteristic structure of the exhaust gas treatment device of the present embodiment will be described below. The temperature of the exhaust gas at the inlet side of the denitrification device 7 is set to such a temperature that a detected value or a designed value of the concentration of the mercury oxides at the inlet side of the desulphuration device 13 reaches a set value or less. The temperature of the exhaust gas at the inlet side of the denitrification device 7 can be set, for instance, by an appropriate adjustment for a heat transfer area of a coal economizer or the like in the boiler 3 or for the guantity of supplied water flowing in the boiler 3. Thereby, the temperature of the exhaust gas at the inlet side of the denitrification device 7 is set to a temperature, for instance, of 400°C or higher, at which the reactions of producing the mercury oxides in the denitrificatiori device 7 are suppressed. In addition, the set value of the concentration of the mercury oxides is appropriately set according to a regulation defining an allowable limit for the concentration of mercury in the sea water to be released from the desulphuration device 13. Specifically, the concentration of mercury in the sea water to be released from the desulphuration device has a correlation with the concentration of the mercury oxides at the inlet side of the desulphuration device 13, and the concentration of the mercury oxides at the inlet side of the desulphuration device 13 can be -12 -adjusted by the temperature of the exhaust gas at the inlet side of the denitrification device 7. Accordingly, the temperature of the exhaust gas at the inlet side of the denitrification device 7 is set so that the concentration of the mercury oxides at the inlet side of the desulphuration device 13 reaches a set value or lower.
[0021J The operation of the exhaust gas treatment device 1 that is structured in this way will be described below.
The nitrogen oxides in the exhaust gas discharged from the boiler 3 are denitrified by the denitrification device 7. The denitrified exhaust gas is led into the air preheater 9, and its temperature is lowered by heat exchange between the exhaust gas and air to be used for the combustion of the boiler 3. The particulate matter such as ash content and an unburned carbon in the exhaust gas of which the temperature has been lowered is removed from the exhaust gas by the dust-collecting equipment 11.
The sea water is sprayed to the exhaust gas discharged from the dust-collecting equipment 11, in the desulphuration device 13, and the sulphur oxides in the exhaust gas is absorbed by the sea water. Thus, the exhaust gas is desulphurized. The sea water absorbed the sulphur oxides is treated, for instance, by purification treatments for removing the sulphur oxides, and then purified sea water is released to the sea.
[0022J -13 -The exhaust gas discharged from the desulphuratiori device 13 is led into the adsorption tower 17 of the mercury adsorption device 15. Thereby, metal mercury in the exhaust gas is adsorbed by an adsorbent such as activated carbon, and is removed from the exhaust gas.
The exhaust gas from which the mercury has been removed is heated by a reheater, for instance, and is then released to the atmosphere from a chimney 21.
[0023J Next, a characteristic effect of the present embodiment will be described below. Generally, in the presence of a catalyst in the denitrification device 7, reactions occur, which are a so-called denitrification reaction, expressed by the following (Formula 1), a reaction of producing sulfur trioxide by the oxidization of sulfur dioxide expressed by (Formula 2), and a reaction of producing mercury oxides by the oxidization of metal mercury expressed by (Formula 3) 4N0 + 4NH3 + 0, > 4N2 -I-6F120... (Formula 1) 2302 + 02 -* 2303. . . (Formula 2) 2Hg + 4H01 + 02 -* 2HgCl2 + 2H20. . . (Formula 3) Due to the reaction of (Formula 3) , metal mercury (Hg) that is difficult to dissolve in water is converted into mercury oxide (EigCl2) that is easily dissolvable in water. Because of this, the mercury oxide dissolves into the sea water, which is the absorbing liquid of the desulphuration device 13 that is arranged in the -14 -downstream of the denitrification device 7, and mercury may be mixed into the sea water to be discharged from the desulphuration device 13. Then, the temperature of the exhaust gas at the inlet side of the denitrification device 7 is set to a temperature at which the reactions of producing the mercury oxides are suppressed so that the concentration of the mercury oxides at the inlet side of the desulphuration device 13 reaches a set value or lower. Thereby, the mercury oxides to be absorbed in the sea water of the desulphuration device 13 can be decreased, and the concentration of mercury in the sea water to be released from the desulphuration device can be controlled to the permitted value or lower. As a result, the exhaust gas treatment device does not need to provide a treatment facility therein for removing the mercury from the sea water.
[0024J In addition, the exhaust gas treatment device detects the concentration of the mercury oxides in the sea water, which is the absorbing liquid of the desuiphuration device 13, and sets the temperature of the exhaust gas at the inlet side of the denitrification device 7 at a temperature at which the reactions of producing the mercury oxides are suppressed so that the detected value reaches a set value or less, Specifically, the permitted value is set for the concentration of mercury in the sea water, which is the absorbing liquid -15 -to be discharged from the desuiphuration device 13 or is circulated to the desulphuration device 13, and the temperature of the exhaust gas at the inlet side of the denitrification device 7 can be set so that the concentration of mercury in the sea water, which is the absorbing liquid, reaches the permitted value or lower.
Thereby, the concentration of mercury in the sea water to be released from the desulphuration device 13 to the sea can be set to the set value or lower, and accordingly the exhaust gas treatment device does not need to provide a treatment facility for removing the mercury therein.
[0025] In addition, the reactions of producing the mercury oxides are suppressed in a high temperature atmosphere, according to an example that will be described later, and accordingly the temperature of the exhaust gas at the inlet side of the denitrification device 7 is preferably set to, for instance, 400°C or higher under 100-load.
Tncidentally, if the temperature of the exhaust gas at the inlet side of the denitrification device 7 has been set to an excessively high value, NOx removal efficiency may be lowered, and the temperature may exceed a heat resistant temperature of a catalyst or the like.
Accordingly, the temperature of the exhaust gas at the inlet side of the denitrification device 7 is preferably set to, for instance, 450°C or lower.
-26 -
Examples
[0026] Here, a relationship between a temperature of an exhaust gas at the inlet side of a denitrification device 7 and a production rate of mercury cxides (oxidation rate of mercury) will be described below with reference to an example. Example 1 is an example in which NCx removal efficiency in the denitrification device 7 that employed titanium oxide as a catalyst, was set to 90%, and the temperature of the exhaust gas at the inlet side of the denitrification device 7 was set to 400°C. Comparative Example 1 is an example in which the temperature of the exhaust gas at the inlet side of the denitrification device 7 was set to 350°C, on conditions of Example 1.
Comparative Example 2 is an example in which the temperature of the exhaust gas at the inlet side of the denitrification device 7 was set to 380°C. Tn these Example 1 and Comparative Examples 1 and 2, production rates of mercury oxides were measured. The results are shown in Table 1. In addition, other measurement conditions are just as shown in Table 1.
[0027]
[Table 1]
-17 -Comparative Comparative
Example 1
Example 1 Example 2
Concentration of NOx at inlet of 300 300 300 denitrification device (ppm) ___________ ____________ ____________ Temperature of 400 350 380 exhaust gas ( C) NOx removal 90 90 90 efficiency (I) Concentration cf ammonia having leaked 2 2 2 from denitrification device (ppm) __________ ____________ ____________ Catalyst amount (m) 1065 1065 1100 Oxidation rate of 12 67 36 mercury () [0028] According to this Table 1, Example 1 in which the temperature of the exhaust gas at the inlet side of the denitrification device 7 was set to 400°C could suppress the production of the mercury oxides approximately 82% more than Comparative Example 1 in which the temperature was set to 350°C, and could suppress the production of the mercury oxides approximately 67% more than Comparative Example 2 in which the temperature was set to 380°C. In other words, it is understood that the reactions of producing the mercury oxides have a correlation with the temperature, and that the reactions of producing the mercury oxides can be suppressed when the temperature becomes high. Accordingly, the reactions of producing the mercury oxides can be adjusted by the -18 -temperature of the exhaust gas at the inlet side of the denitrificatlon device 7 and the concentration of the mercury oxides in the exhaust gas to be led into a desulphuration device 13 can be controlled. Accordingly, the mercury oxides to be absorbed by the sea water in the desulphuration device 13 can be decreased and the concentration of mercury in the sea water to be released can be controlled to the permitted value or lower.
[0029J Next, an example was determined to be Example 2, which employed a catalyst obtained by adding tungsten to the titanium oxide as a co-catalyst, in place of the catalyst of Example 1 in which the temperature of the exhaust gas at the inlet side of the denitrification device 7 was set to 40000. In addition, an example was determined to be Example 3, in which the coal of Example 2 was subjected to washing treatment and then the washed coal was combusted. In addition, an example was determined to be Example 4, in which the amount nf the catalyst in Example 3 was reduced and NOx removal efficiency was set to 80%. The production rates of mercury oxides (oxidation rate of mercury) in Examples 2 to 4 were measured. The results are shown in Table 2.
Other measurement conditions are the same as those in
Example 1.
[00301
[Table 2]
-19 - _________________________ Example 2 Example 3 Example 4 Titanium Titanium Titanium Catalyst composition oxide oxide oxide _________________________ Tungsten Tungsten Tungsten Wash with Wash with Not water water Pretreatment for coal oonducted before before combustion combustion Concentration of NOx at inlet of 300 300 300 denitrification device (ppm) ____________ ____________ ____________ Temperature of exhaust 400 400 400 gas ( C) NOx removal efficiency 90 90 80 Concentration of ammonia having leaked 2 2 2 from denitrification device (ppm) ____________ ___________ ___________ Catalyst aitiourit (m:) 910 910 740 Oxidation rate of 10 5 4 mercury (i) [0031J According to the Examples 2 to 4, it is understood that the reactions of producing the mercury oxides can be further suppressed in comparison with those in Example 1.
Tn other words, the reactions of producing the mercury oxides can be further suppressed by a method of setting the temperature of the exhaust gas at the inlet side of the denitrification device 7 to 400°C and forming the catalyst from titanium oxide to which tungsten (W) was added. Incidentally, a ratio of the tungsten, which is the co-catalyst, can be appropriately selected according -20 -to the NOx removal efficiency to be required, the temperature of the exhaust gas, the amount of the exhaust gas and the like. However, when the amount of the tungsten to be added is too small, an effect of suppressing the productinn of the mercury oxides is lowered and a deterioration speed of the catalyst increases. On the other hand, because the tungsten is expensive, the excessive use of the tungsten remarkably increases the price of the catalyst. Accordingly, it is preferable to control the amount of the tungsten to be added in a range of Ti/W = 60/1 to 50/40.
[0032] In addition, because the metal mercury reacts with the hydrogen chloride to produce the mercury oxides, the coal can be cornbusted after having been subjected to the washing treatment to decrease its chlorine content contained in the coal, as is illustrated in Example 3.
Thereby, the chlorine content in the exhaust gas to be discharged from the boiler 3 can be decreased, and the production of the mercury oxides can be suppressed. In addition, when the required NOx removal efficiency is, for instance, 80% as is illustrated in Example 4, the reactions of producing the mercury oxides due to the catalyst can be suppressed by a method of reducing the amount of the catalyst provided in the denitrification device 7. Accordingly, in Examples 2 to 4 as well, the reactions of producing the mercury oxides in the -21 -desuiphuration device 13 can be suppressed, the concentration of the mercury oxides in the exhaust gas to be led into the desulphuration device 13 can be decreased, accordingly the mercury oxides to be absorbed by the sea water of the desuiphuration device 13 can be decreased, and the concentration of mercury in the sea water to be released can be controlled to the permitted value or lower.
Reference Signs List [0033] 1 Exhaust gas treatment device Reducing agent 7 Denitrification device 13 Desulphuration device Mercury adsorption device
Applications Claiming Priority (2)
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| JP2010192295A JP5709438B2 (en) | 2010-08-30 | 2010-08-30 | Exhaust gas treatment equipment |
| PCT/JP2011/004794 WO2012029279A1 (en) | 2010-08-30 | 2011-08-29 | Exhaust gas treatment device |
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| GB2498272A true GB2498272A (en) | 2013-07-10 |
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| CN (1) | CN103079692A (en) |
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| EP2724772A1 (en) * | 2012-10-26 | 2014-04-30 | Alstom Technology Ltd | Arrangement of a flue gas treatment system and a combustion device |
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| JP5991664B2 (en) * | 2012-05-25 | 2016-09-14 | 三菱重工環境・化学エンジニアリング株式会社 | Flue gas desulfurization system |
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| JP2005066505A (en) * | 2003-08-26 | 2005-03-17 | Mitsubishi Heavy Ind Ltd | Exhaust gas treatment equipment and treatment method |
| JP2006205128A (en) * | 2005-01-31 | 2006-08-10 | Babcock Hitachi Kk | Removal apparatus of trace harmful substance in exhaust gas and its operation method |
| JP2007021442A (en) * | 2005-07-20 | 2007-02-01 | Mitsubishi Heavy Ind Ltd | Method and facilities for treating exhaust gas |
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| JP3498402B2 (en) * | 1995-02-06 | 2004-02-16 | 石川島播磨重工業株式会社 | Desulfurization equipment |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005066505A (en) * | 2003-08-26 | 2005-03-17 | Mitsubishi Heavy Ind Ltd | Exhaust gas treatment equipment and treatment method |
| JP2006205128A (en) * | 2005-01-31 | 2006-08-10 | Babcock Hitachi Kk | Removal apparatus of trace harmful substance in exhaust gas and its operation method |
| JP2007021442A (en) * | 2005-07-20 | 2007-02-01 | Mitsubishi Heavy Ind Ltd | Method and facilities for treating exhaust gas |
| JP2009226238A (en) * | 2008-03-19 | 2009-10-08 | Babcock Hitachi Kk | Method of treating exhaust gas and catalyst |
| JP2009226254A (en) * | 2008-03-19 | 2009-10-08 | Chiyoda Kako Kensetsu Kk | Mercury adsorbent and method of treating gas using the same |
| WO2010013729A1 (en) * | 2008-07-29 | 2010-02-04 | バブコック日立株式会社 | Method for purifying exhaust gas containing mercury metal, oxidation catalyst for mercury metal in exhaust gas and method for producing the same |
| JP2009208078A (en) * | 2009-06-16 | 2009-09-17 | Mitsubishi Heavy Ind Ltd | Method for treating mercury in tail gas, and treatment system for tail gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2724772A1 (en) * | 2012-10-26 | 2014-04-30 | Alstom Technology Ltd | Arrangement of a flue gas treatment system and a combustion device |
| US10518212B2 (en) | 2012-10-26 | 2019-12-31 | General Electric Technology Gmbh | Method of treating a carbon dioxide rich flue gas and a flue gas treatment system |
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| JP2012045521A (en) | 2012-03-08 |
| JP5709438B2 (en) | 2015-04-30 |
| GB2498272B (en) | 2018-05-30 |
| WO2012029279A1 (en) | 2012-03-08 |
| GB201303447D0 (en) | 2013-04-10 |
| CN103079692A (en) | 2013-05-01 |
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