WO2009107729A1 - 排ガス処理触媒 - Google Patents
排ガス処理触媒 Download PDFInfo
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- WO2009107729A1 WO2009107729A1 PCT/JP2009/053573 JP2009053573W WO2009107729A1 WO 2009107729 A1 WO2009107729 A1 WO 2009107729A1 JP 2009053573 W JP2009053573 W JP 2009053573W WO 2009107729 A1 WO2009107729 A1 WO 2009107729A1
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- Prior art keywords
- exhaust gas
- mercury
- gas treatment
- catalyst
- tio
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 239000007789 gas Substances 0.000 claims abstract description 57
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 21
- 230000003647 oxidation Effects 0.000 abstract description 16
- 238000007254 oxidation reaction Methods 0.000 abstract description 16
- 239000012320 chlorinating reagent Substances 0.000 abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 8
- 230000002829 reductive effect Effects 0.000 abstract description 4
- 239000004480 active ingredient Substances 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract 2
- 239000011574 phosphorus Substances 0.000 abstract 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract 1
- 239000011733 molybdenum Substances 0.000 abstract 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract 1
- 239000010937 tungsten Substances 0.000 abstract 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 12
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 9
- 238000006477 desulfuration reaction Methods 0.000 description 9
- 230000023556 desulfurization Effects 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229940008718 metallic mercury Drugs 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000013056 hazardous product Substances 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940100892 mercury compound Drugs 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
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- 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
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
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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
- B01D53/74—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
- B01D53/8628—Processes characterised by a specific catalyst
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- 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
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
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- 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
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
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- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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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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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24149—Honeycomb-like
Definitions
- the present invention relates to an exhaust gas treatment catalyst having mercury oxidation performance as well as denitration performance.
- Mercury present in the flue gas contains metallic mercury that is insoluble in water and mercury chloride that is soluble in water, and is difficult to dissolve in water when mercury is in the form of metallic mercury.
- the mercury removal rate by the wet desulfurization apparatus is low.
- mercury can be removed because HgCl or HgCl 2 of the exhaust gas dissolves in water by gas-liquid contact with a wet desulfurization apparatus. That is, if metal mercury can be converted to mercury chloride in the presence of a catalyst such as a denitration catalyst, mercury can be removed by a downstream desulfurization apparatus.
- the flow path from the boiler 10 to the reduction denitration unit 60 is supplied with NH 3 supplied from the NH 3 tank 30 from NH 3 feed point 20 and the mercury-chlorinating agent tank 40 is injected into the exhaust gas HCl
- An HCl injection point 21 for injecting a mercury chlorinating agent such as the above into the exhaust gas is provided.
- the exhaust gas from the boiler 10 is introduced into the reducing denitration device 60.
- the exhaust gas into which NH 3 and HCl have been injected undergoes a reaction between NH 3 and NO x in the reductive denitration device 60, and at the same time, metal Hg is oxidized to HgCl 2 in the presence of HCl.
- the wet desulfurization apparatus 100 removes HgCl 2 simultaneously with the removal of SO 2 in the exhaust gas.
- excess HCl is contained in the exhaust gas exiting the reducing denitration device 60, but it is absorbed by the alkaline aqueous solution such as lime milk by the desulfurization device 100, so that it is not discharged from the chimney.
- the above method proposes a system that sprays a chlorinating agent such as HCl in the upstream of the denitration catalyst, oxidizes (chlorinates) mercury on the catalyst, and removes mercury in the downstream wet-type desulfurization equipment (for example, see Patent Document 1). Japanese Patent Laid-Open No. 10-230137
- an object of the present invention is to provide an exhaust gas treatment catalyst capable of reducing the amount of highly corrosive mercury chlorinating agent while maintaining high mercury oxidation efficiency in exhaust gas treatment.
- an exhaust gas treatment catalyst is an exhaust gas treatment catalyst that catalytically removes nitrogen oxides in exhaust gas using ammonia as a reducing agent and oxidizes mercury using halogen as an oxidizing agent.
- the carrier comprises at least one oxide selected from the group consisting of V, W and Mo as an active component, and is composed of Bi and P and a compound containing Bi and / or P. At least one selected from the group is supported as a promoter component.
- a compound containing chlorine (Cl) such as NH 4 Cl in addition to HCl, or a compound containing bromine (Br) is suitable.
- the said promoter component can be implemented as the following forms.
- A In the case of Bi alone.
- B In the case of only P alone.
- C In the case of including both Bi and P alone.
- D In the case of a compound of Bi and P.
- E In the case of a compound containing Bi.
- F In the case of a compound containing P.
- G In the case of a compound containing Bi and P.
- the promoter component is composed of P or a compound containing P.
- the exhaust gas treatment catalyst according to the present invention comprises Bi or a compound containing Bi.
- an exhaust gas treatment catalyst capable of reducing the amount of highly corrosive mercury chlorinating agent while maintaining high mercury oxidation efficiency in exhaust gas treatment.
- FIG. It is a conceptual diagram explaining arrangement
- FIG. It is a conceptual diagram explaining the conventional waste gas treatment method.
- the support for the exhaust gas treatment catalyst according to the present invention is made of TiO 2 .
- at least one selected from the group consisting of TiO 2 , SiO 2 , ZrO 2 , Al 2 O 3 and their composite oxides, and zeolite can be used as the catalyst carrier.
- the exhaust gas treatment catalyst according to the present invention carries at least one oxide selected from the group consisting of V, W and Mo as an active component on such a carrier.
- the exhaust gas treatment catalyst according to the present invention is supported on a carrier using as a promoter component at least one selected from the group consisting of Bi and P and a compound containing Bi and / or P.
- the cocatalyst component is preferably present in the form of an oxide, complex oxide or heteropolyacid. Since the compound containing Bi or P takes the form of a compound having a different oxidation number, the oxidation of mercury can be promoted by the effect of the redox cycle. Bi functions as a promoter because it can form a complex oxide with Mo. On the other hand, P can be combined with Mo or W to form a heteropolyacid having a very strong oxidizing power. Both Bi and P do not exist separately, but function as promoters because they are elements capable of forming a compound.
- the ratio of the promoter component to the active component is as follows.
- the number of V atoms contained: the number of Mo atoms: the number of P atoms 32: 12: It is preferably 1 to 10: 12: 1.
- the number of V atoms contained: the number of Mo atoms: the number of Bi atoms 1: 3: 0.1
- the ratio is ⁇ 1: 10: 1.5. In the above case, it is preferable to carry 0.1 to 2% by mass of the active ingredient per 100 g of the carrier.
- the exhaust gas treatment catalyst according to the present invention is generally produced as follows. (1) For example, a catalyst paste containing a carrier component and an active component is formed into a honeycomb shape and fired. (2) The honeycomb is impregnated with a promoter component and fired.
- an aqueous solution of ammonium metavanadate in an amount of 0.5% by mass in terms of V 2 O 5 and an aqueous solution of ammonium molybdate in an amount of 7% by mass in terms of MoO 3 were mixed thoroughly, dried, and dried at 450 ° C.
- a powder (A) composed of titanium oxide [TiO 2 ] -vanadium oxide [V 2 O 5 ] -molybdenum oxide [MoO 3 ] was obtained.
- Table 2 shows the test results. As understood from the results in Table 2, it can be seen that 79.8% of mercury is oxidized after the third stage by using the exhaust gas treatment catalyst 1 according to the present invention.
- powder (A) 25 g of carboxymethyl cellulose and 12.5 g of polyethylene oxide were placed in a kneader, moderate water was added and kneaded for 30 minutes, extruded into a 30 mm 2 honeycomb shape, dried and fired at 500 ° C. for 5 hours. .
- Example 1 Mercury oxidation performance test
- the honeycomb-shaped exhaust gas treatment catalyst 2 prepared as described above was installed in three stages as shown in FIG.
- the mercury oxidation performance was tested.
- a sample exhaust gas having the same O 2 to NO x properties as in Table 1 was flowed under the conditions in Table 3, and the mercury oxidation performance of the exhaust gas treatment catalyst 2 was tested.
- Table 4 shows the test results. As is understood from the results in Table 4, it can be seen that 89.1% of mercury is oxidized after the third stage by using the exhaust gas treatment catalyst 2 according to the present invention.
- an aqueous solution of ammonium metavanadate in an amount of 0.5% by mass in terms of V 2 O 5 and an aqueous solution of ammonium molybdate in an amount of 7% by mass in terms of MoO 3 were mixed, dried, and dried at 450 ° C.
- a powder (A) composed of titanium oxide [TiO 2 ] -vanadium oxide [V 2 O 5 ] -molybdenum oxide [MoO 3 ] was obtained.
- Table 5 shows the test results. As is understood from the results in Table 5, it can be seen that 79.5% of mercury is oxidized after the third stage by using the comparative exhaust gas treatment catalyst according to the present invention.
- Example 1 As understood from the results of Example 1, Example 2, and Comparative Example, by using the exhaust gas treatment catalyst according to the present invention, addition of highly corrosive mercury chlorinating agent while maintaining high mercury oxidation efficiency The amount can be reduced.
- addition of a new mercury oxidizer by HCl, HBr spraying device or NH 4 Cl supply device for oxidizing mercury may be extremely small. Therefore, flue corrosion due to highly corrosive HCl can be reduced.
- coal-derived HCl contains several tens of ppm in the exhaust gas, it is not necessary to install an HCl spray device. In that case, it is possible to greatly reduce the equipment cost required for the safety management measures of HCl which requires careful handling. Therefore, the exhaust gas treatment catalyst according to the present invention can be used in the exhaust gas treatment method described with reference to FIG.
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Abstract
Description
(a)Biの単体のみの場合。
(b)Pの単体のみの場合。
(c)Biの単体とPの単体の両方を含む場合。
(d)BiとPの化合物の場合。
(e)Biを含む化合物の場合。
(f)Pを含む化合物の場合。
(g)BiとPを含む化合物の場合。
本発明に係る排ガス処理触媒は、さらに他の実施の形態で、上記助触媒成分がBi又はBiを含む化合物から成る。
10 ボイラ
20 NH3供給箇所
21 HCl注入箇所
30 NH3タンク
40 水銀塩素化剤タンク
60 還元脱硝装置
70 エアヒータ
80 熱交換器
90 集塵器
100 脱硫装置
例えば、Vの酸化物を活性成分とし、Pを含むヘテロポリ酸(モリブドリン酸)を助触媒成分とした場合、含有されるVの原子数:Moの原子数:Pの原子数=32:12:1~10:12:1とすることが好適である。
また、例えば、Vの酸化物を活性成分とし、Biを含む化合物を助触媒成分とした場合、含有されるVの原子数:Moの原子数:Biの原子数=1:3:0.1~1:10:1.5とすることが好適である。
上記の場合、担体100g当たり0.1~2質量%の活性成分を担持することが好適である。
(1)例えば、担体成分及び活性成分を含む触媒ペーストをハニカム状に成型し、焼成する。
(2)助触媒成分をハニカムに含浸し、焼成する。
TiO2―V2O5系脱硝触媒(TiO2:V2O5=95.5:0.5(質量比))を以下のように調製した。
メタチタン酸スラリー(TiO2含量30質量%)3600gにNH3含量25%のアンモニア水を加えpHを6.5に調節し、2時間湿式で混練後乾燥し、さらに550℃で5時間焼成して、酸化チタン粉末を得た。この粉末にメタバナジン酸アンモンの水溶液をV2O5換算で0.5質量%、モリブデン酸アンモニウムの水溶液をMoO3換算で7質量%となるよう添加し、充分混合した後乾燥し450℃で4時間焼成して、酸化チタン[TiO2]―酸化バナジウム[V2O5]―酸化モリブデン[MoO3]からなる粉末(A)を得た。粉末(A)1000gにカルボキシメチルセルロース25g、ポリエチレンオキサイド12.5gをニーダーに入れ、適度の水を加えて30分混練し、30mm2のハニカム形状に押出し成型し、乾燥後500℃で5時間焼成した。さらに、硝酸ビスマスの水溶液を調整し、Bi2O3換算で1.5質量%となるようにハニカムに含浸し、500℃で3時間焼成して、Bi2O3(1.5)-MoO3(7)-V2O5/TiO2触媒を調製した。
以上のようにして調製したハニカム状の排ガス処理触媒1を4穴×7穴の500mm長さになるように図1に示すように3段に設置し、水銀酸化性能について試験を行った。
以下の表1に示すO2~NOxの性状を持つサンプル排ガスを、同表1の条件で流し、排ガス処理触媒1の水銀酸化性能を試験した。なお、表中の記号の意味は、以下の通りである。
Ugs:空塔速度
AV:接ガス面積基準の処理ガス量
サンプル排ガスの抽出位置を図1中のS1~S2とした。
TiO2―V2O5系脱硝触媒(TiO2:V2O5=95.5:0.5(質量比))を以下のように調製した。
メタチタン酸スラリー(TiO2含量30質量%)3600gにNH3含量25%のアンモニア水を加えpHを6.5に調節し、2時間湿式で混練後乾燥し、さらに550℃で5時間焼成して、酸化チタン粉末を得た。この粉末にメタバナジン酸アンモンの水溶液をV2O5換算で0.5質量%となる様添加し、充分混合した後乾燥し450℃で4時間焼成して、酸化チタン[TiO2]―酸化バナジウム[V2O5]からなる粉末(A)を得た。粉末(A)1000gにカルボキシメチルセルロース25g、ポリエチレンオキサイド12.5gをニーダーに入れ、適度の水を加えて30分混練し、30mm2のハニカム形状に押出し成型し、乾燥後500℃で5時間焼成した。さらに、リンモリブデン酸の水溶液を調整し、MoO3換算で7質量%となるようにハニカムに含浸し、500℃で3時間焼成して、P-MoO3(7)-V2O5(0.5)/TiO2触媒を調製した。
以上のようにして調製したハニカム状の排ガス処理触媒2を4穴×7穴の500mm長さになるように、実施例1の場合と同様に、図1に示すように3段に設置し、水銀酸化性能について試験を行った。
表1と同じO2~NOxの性状を持つサンプル排ガスを、表3の条件で流し、排ガス処理触媒2の水銀酸化性能を試験した。
TiO2―V2O5系脱硝触媒(TiO2:V2O5=95.5:0.5(質量比))を以下のように調製した。
メタチタン酸スラリー(TiO2含量30質量%)3600gにNH3含量25%のアンモニア水を加えpHを6.5に調節し、2時間湿式で混練後乾燥し、さらに550℃で5時間焼成して、酸化チタン粉末を得た。この粉末にメタバナジン酸アンモンの水溶液をV2O5換算で0.5質量%、モリブデン酸アンモニウムの水溶液をMoO3換算で7質量%となる様添加し、充分混合した後乾燥し450℃で4時間焼成して、酸化チタン[TiO2]―酸化バナジウム[V2O5]―酸化モリブデン[MoO3]からなる粉末(A)を得た。粉末(A)1000gにカルボキシメチルセルロース25g、ポリエチレンオキサイド12.5gをニーダーに入れ、適度の水を加えて30分混練し、30mm2のハニカム形状に押出し成型し、乾燥後500℃で5時間焼成して、比較例のMoO3(7)-V2O5/TiO2触媒を調製した。
以上のようにして調製したハニカム状の比較用排ガス処理触媒を4穴×7穴の500mm長さになるように、実施例1の場合と同様に、図1に示すように3段に設置し、水銀酸化性能について試験を行った。
表1と同じO2~NOxの性状を持つサンプル排ガスを流し、比較用排ガス処理触媒の水銀酸化性能を試験した。
本発明に係る排ガス処理触媒を用いる場合には、水銀を酸化するためのHCl、HBr噴霧装置やNH4Cl供給装置による新たな水銀酸化剤の添加は極微量でよい。そのため、腐食性の高いHClによる煙道腐食を減殺することができる。
また、石炭由来のHClが排ガス中に数十ppm含まれる場合は、HCl噴霧装置の設置は不要である。その場合、取扱い上注意要するHClの安全管理対策にかかる設備コストを大幅に低減できる。
したがって、本発明に係る排ガス処理触媒は、図2について説明した排ガス処理方法に用いることができる。
Claims (3)
- アンモニアを還元剤として接触的に排ガス中の窒素酸化物を除去するとともに、ハロゲンを酸化剤として水銀を酸化する排ガス処理触媒において、TiO2を担体として、該担体上にV,W及びMoからなる群より選ばれる少なくとも1種類の酸化物を活性成分として担持し、かつBi及びP、並びにBi及び/又はPを含む化合物からなる群から選ばれる少なくとも1種類を助触媒成分として担持して成る排ガス処理触媒。
- 上記助触媒成分がP又はPを含む化合物から成る請求項1の排ガス処理触媒。
- 上記助触媒成分がBi又はBiを含む化合物から成る請求項1の排ガス処理触媒。
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US12/670,420 US8410013B2 (en) | 2008-02-27 | 2009-02-26 | Catalyst for treating exhaust gas |
KR1020107003692A KR101195633B1 (ko) | 2008-02-27 | 2009-02-26 | 배기가스 처리 촉매 |
EP09714242.6A EP2248583B1 (en) | 2008-02-27 | 2009-02-26 | USE OF A CATALYST CONTAINING V2O5, MoO3 AND P ON TiO2-SUPPORT FOR EXHAUST GAS TREATMENT |
CA2694632A CA2694632C (en) | 2008-02-27 | 2009-02-26 | Catalyst for treating exhaust gas |
BRPI0903918-0A BRPI0903918A2 (pt) | 2008-02-27 | 2009-02-26 | Catalisador para tratar gás de exaustão |
CN200980100196.9A CN102083529B (zh) | 2008-02-27 | 2009-02-26 | 废气处理催化剂 |
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JP2008045818A JP5386096B2 (ja) | 2008-02-27 | 2008-02-27 | 排ガス処理触媒 |
JP2008-045818 | 2008-02-27 |
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EP (1) | EP2248583B1 (ja) |
JP (1) | JP5386096B2 (ja) |
KR (1) | KR101195633B1 (ja) |
CN (1) | CN102083529B (ja) |
BR (1) | BRPI0903918A2 (ja) |
CA (1) | CA2694632C (ja) |
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CN102218266A (zh) * | 2010-04-15 | 2011-10-19 | 中国科学院城市环境研究所 | 一种用于催化氧化燃煤烟气中单质汞的方法 |
US9802180B2 (en) * | 2013-12-11 | 2017-10-31 | Zhejiang University | Catalyst for synergistic control of oxynitride and mercury and method for preparing the same |
JP6697287B2 (ja) * | 2016-03-02 | 2020-05-20 | 三菱日立パワーシステムズ株式会社 | 金属水銀の酸化反応および窒素酸化物の還元反応用触媒、ならびに排ガスの浄化方法 |
GB201715663D0 (en) * | 2017-03-31 | 2017-11-08 | Johnson Matthey Plc | A Catalyst for treating an exhaust gas, an exhaust system and a method |
CN111760595A (zh) * | 2020-07-08 | 2020-10-13 | 河南城建学院 | 一种用于低温脱硝除Hg0的杂多酸/CeO2基催化剂及其制备方法和应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS56168835A (en) * | 1980-05-31 | 1981-12-25 | Mitsubishi Petrochem Co Ltd | Denitrating catalyst and denitrating method |
JPS59213442A (ja) * | 1983-05-17 | 1984-12-03 | Mitsubishi Petrochem Co Ltd | 脱硝触媒の調製方法 |
JP2007167698A (ja) * | 2005-12-19 | 2007-07-05 | Mitsubishi Heavy Ind Ltd | 排ガス処理装置および排ガス処理方法 |
JP2009006226A (ja) * | 2007-06-27 | 2009-01-15 | Babcock Hitachi Kk | 触媒の再生方法 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4085122A (en) | 1975-01-10 | 1978-04-18 | Lonza, Ltd. | Production of maleic anhydride using a mixed-oxide oxidation catalyst containing vanadium and pentavalent phosphorus |
CH598863A5 (ja) | 1975-01-10 | 1978-05-12 | Lonza Ag | |
DE2925682A1 (de) | 1979-06-26 | 1981-01-29 | Basf Ag | Vanadinpentoxid, titandioxid, phosphor, rubidium und/oder caesium und ggf. zirkondioxid enthaltender traegerkatalysator |
US4537874A (en) * | 1982-10-22 | 1985-08-27 | Nippon Shokubai Kagaku Kogyo Co Ltd | Catalyst for production of unsaturated aldehydes |
JP3935547B2 (ja) | 1997-02-19 | 2007-06-27 | 三菱重工業株式会社 | 排ガス処理方法及び排ガス処理装置 |
DE19707943C2 (de) | 1997-02-27 | 1999-07-08 | Basf Ag | Verfahren zur Herstellung von Phthalsäureanhydrid und Katalysator hierfür |
JP2005342711A (ja) * | 2004-05-07 | 2005-12-15 | Mitsubishi Chemical Engineering Corp | ディーゼルエンジン排ガスの脱硝方法 |
US8242049B2 (en) * | 2005-12-08 | 2012-08-14 | The Hong Kong University Of Science And Technology | Low temperature ammonia remediation catalysts |
KR101450360B1 (ko) | 2007-01-30 | 2014-10-14 | 바브콕-히다찌 가부시끼가이샤 | 배기 가스 정화용 촉매 및 그의 제조방법 |
US8470728B2 (en) * | 2007-09-07 | 2013-06-25 | Babcock Hitachi Kabushiki Kaisha | Exhaust gas purifying catalyst |
US20110250114A1 (en) * | 2010-04-13 | 2011-10-13 | Millennium Inorganic Chemicals, Inc. | Vanadia-Based DeNOx Catalysts and Catalyst Supports |
-
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- 2009-02-26 US US12/670,420 patent/US8410013B2/en active Active
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- 2009-02-26 BR BRPI0903918-0A patent/BRPI0903918A2/pt not_active Application Discontinuation
- 2009-02-26 EP EP09714242.6A patent/EP2248583B1/en active Active
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- 2009-02-26 RU RU2010106052/04A patent/RU2429908C1/ru active
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS56168835A (en) * | 1980-05-31 | 1981-12-25 | Mitsubishi Petrochem Co Ltd | Denitrating catalyst and denitrating method |
JPS59213442A (ja) * | 1983-05-17 | 1984-12-03 | Mitsubishi Petrochem Co Ltd | 脱硝触媒の調製方法 |
JP2007167698A (ja) * | 2005-12-19 | 2007-07-05 | Mitsubishi Heavy Ind Ltd | 排ガス処理装置および排ガス処理方法 |
JP2009006226A (ja) * | 2007-06-27 | 2009-01-15 | Babcock Hitachi Kk | 触媒の再生方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2248583A4 * |
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BRPI0903918A2 (pt) | 2015-06-30 |
CN102083529B (zh) | 2014-12-10 |
JP2009202084A (ja) | 2009-09-10 |
EP2248583A1 (en) | 2010-11-10 |
KR101195633B1 (ko) | 2012-10-30 |
EP2248583B1 (en) | 2019-04-03 |
CA2694632C (en) | 2012-10-16 |
EP2248583A4 (en) | 2011-09-14 |
US8410013B2 (en) | 2013-04-02 |
RU2429908C1 (ru) | 2011-09-27 |
US20100210455A1 (en) | 2010-08-19 |
CN102083529A (zh) | 2011-06-01 |
CA2694632A1 (en) | 2009-09-03 |
JP5386096B2 (ja) | 2014-01-15 |
KR20100034046A (ko) | 2010-03-31 |
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