US20110116999A1 - Exhaust gas purification catalyst on which influence of iron compound has been suppressed - Google Patents
Exhaust gas purification catalyst on which influence of iron compound has been suppressed Download PDFInfo
- Publication number
- US20110116999A1 US20110116999A1 US12/934,301 US93430109A US2011116999A1 US 20110116999 A1 US20110116999 A1 US 20110116999A1 US 93430109 A US93430109 A US 93430109A US 2011116999 A1 US2011116999 A1 US 2011116999A1
- Authority
- US
- United States
- Prior art keywords
- catalyst
- moles
- exhaust gas
- active component
- phosphoric acid
- 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.)
- Abandoned
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 238000000746 purification Methods 0.000 title claims abstract description 17
- 150000002506 iron compounds Chemical class 0.000 title 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 28
- -1 phosphoric acid compound Chemical class 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010937 tungsten Substances 0.000 claims abstract description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000002956 ash Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 235000002918 Fraxinus excelsior Nutrition 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 description 33
- 238000007254 oxidation reaction Methods 0.000 description 33
- 239000000463 material Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 239000010965 430 stainless steel Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 6
- 229940010552 ammonium molybdate Drugs 0.000 description 6
- 235000018660 ammonium molybdate Nutrition 0.000 description 6
- 239000011609 ammonium molybdate Substances 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 101100352919 Caenorhabditis elegans ppm-2 gene Proteins 0.000 description 1
- 101000993059 Homo sapiens Hereditary hemochromatosis protein Proteins 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229940008718 metallic mercury Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
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- 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
- 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
-
- 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
- B01D53/74—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
-
- 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
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
-
- 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
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- B01J23/28—Molybdenum
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
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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
- B01D2255/20723—Vanadium
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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
- B01D2255/20769—Molybdenum
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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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- B01J35/58—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
Definitions
- the present invention relates to an exhaust gas purification catalyst, and more particularly to, a catalyst used for oxidizing elemental mercury (Hg) as well as reducing nitrogen oxides (NOx) contained in coal combustion exhaust gas by ammonia, which can maintain to a very low level an activity of oxidizing SO 2 contained in the exhaust gas to SO 3 for a long period of time by suppressing an increase in the activity of oxidizing SO 2 with the lapse of time by an increase in Fe compound, and a method of producing the same.
- Hg oxidizing elemental mercury
- NOx nitrogen oxides
- the denitration catalyst for ammonia catalytic reduction containing titanium oxide as a main component has high activity and favorable durability, it is generally used worldwide for the treatment of exhaust gas such as gas released from a boiler and constitutes the mainstream denitration catalyst (Patent Document 1).
- Patent Document 1 Japanese Patent Application Laid-Open (JP-A) No. 50-128681
- Patent Document 2 JP-A No. 2-184342
- Patent Document 3 JP-A No. 09-220468
- SO 2 oxidation active site of a denitration catalyst there are SO 2 oxidation active site that is intrinsic to the catalyst component and SO 2 oxidation active site that is newly formed by adhesion of a Fe component contained in combustion ash to the catalyst or by migration of a Fe component accompanied with corrosion of a substrate to the catalyst, when a metal substrate is used for the catalyst.
- SO 2 oxidation active site that is intrinsic to the catalyst component
- SO 2 oxidation active site that is newly formed by adhesion of a Fe component contained in combustion ash to the catalyst or by migration of a Fe component accompanied with corrosion of a substrate to the catalyst, when a metal substrate is used for the catalyst.
- a dramatic increase in SO 2 oxidizing activity is caused when the degree of forming SO 2 active site in the catalyst is huge.
- Fe 2 O 3 is contained at high concentration of 20 to 30% by weight in combustion ash of high S coals that are produced in the United States, etc., for the treatment of combustion exhaust gas of such high S coals, it is necessary to suppress an increase in SO 2 oxidizing activity caused by adhesion of Fe 2 O 3 to the catalyst.
- SO 2 oxidation rate of the catalyst component itself can be suppressed to a low level, and therefore sufficiently low initial SO 2 oxidation rate is obtained for the catalyst.
- sufficient consideration regarding the suppression of an increase in SO 2 oxidation rate of the catalyst that is caused by an increase in a Fe component in the latter case was not made, and therefore the SO 2 oxidation rate of the catalyst with the lapse of time is still big and improvements are needed in several aspects.
- An object of the present invention is to provide, considering the problems of the conventional technology above, an exhaust gas purification catalyst that can suppress an increase in SO 2 oxidation with an increase in a Fe component in the denitration catalyst with the lapse of time attributable to internal and external causes and, even in exhaust gases of fuels having a high Fe content such as high S coals, can realize operation at a low SO 2 oxidation rate for a long period of time, and a method of producing the same.
- An exhaust gas purification catalyst containing titanium oxide as a main component and an oxide of one element or two or more elements selected from the group consisting of tungsten (W), molybdenum (Mo), and vanadium (V) as an active component, in which the catalyst contains phosphoric acid or a water soluble phosphoric acid compound so that the atomic ratio of phosphorus (P) to a catalytically active component represented by the following formula is more than 0 and 1.0 or less;
- P/catalytically active component (atomic ratio) number of moles of P/(number of moles of W+number of moles of Mo+number of moles of V).
- a method of producing an exhaust gas purification catalyst including: adding an oxide or an oxo-acid salt of one element or two or more elements selected from the group consisting of tungsten (W), molybdenum (Mo), and vanadium (V) to titanium oxide; adding water; and kneading followed by drying and calcination, wherein phosphoric acid or a water soluble phosphoric acid compound is added to the oxide or the oxo-acid salt thereof for a reaction so that the atomic ratio of P to a catalytically active component represented by the following formula is more than 0 and 1.0 or less;
- a method of producing an exhaust gas purification catalyst including: adding an oxide or an oxo-acid salt of one element or two or more elements selected from the group consisting of tungsten (W), molybdenum (Mo), and vanadium (V) to titanium oxide; adding water; kneading followed by drying and calcination; and immersing the resultant in a solution that is prepared separately in advance by adding phosphoric acid or a water soluble phosphoric acid compound to an oxide or an oxo-acid salt of one element or two or more elements selected from the group consisting of tungsten (W), molybdenum (Mo), and vanadium (V) to be reacted so that the atomic ratio of P to a catalytically active component represented by the following formula is more than 0 and 1.0 or less;
- the atomic ratio of P to a catalytically active component in the catalyst to be within the range described above, formation of SO 2 oxidation active site in the catalyst that is caused by the adhesion of a Fe component comprised in ash from gas to be treated is suppressed, and therefore SO 2 oxidation rate can be maintained at a low level for a long period of time.
- formation of SO 2 active site caused by corrosion product containing a Fe component, that is generated when the catalyst is used in harsh condition is prevented so that even for the catalyst using a metal substrate as a carrier the SO 2 oxidation rate can be maintained at a low level for a long period of time.
- the catalyst of the invention has not only high denitrating performance and Hg oxidizing performance but also low SO 2 oxidation rate, when it is used for denitration of exhaust gas from a high S coal boiler used in the United States, etc., generation of SO 3 can be suppressed to a low level. Furthermore, since it is difficult for SO 2 oxidation rate to increase even when the Fe component contained in ash or the like migrates into the catalyst, problems such as generation of purple smoke due to SO 3 resulting from oxidation of SO 2 can be avoided when it is applied for exhaust gas of high S coals containing a great amount of a Fe component.
- Fe component such as iron oxide or the like adheres on the surface of a catalyst or corrosion of a metal substrate occurs at the interface between the metal substrate and the catalyst component, but no increase in SO 2 oxidation rate occurs during this step.
- the Fe component in the catalyst is sulphated by SOx present in exhaust gas.
- the sulphate is dissolved in water which is absorbed when operation of a combustion furnace is on hold, and as a result, it migrates as a Fe ion to the inside of the catalyst.
- the migrated Fe ion is adsorbed onto titanium oxide to form SO 2 oxidation active site.
- part of the catalytically active component is present as a complex resulting from a qualitative reaction with phosphoric acid/phosphoric acid compound, and it is believed that Fe ion and the complex of phosphoric acid and the active component undergo the reaction as follows.
- the Fe ion forms insoluble iron phosphate by which absorption onto TiO 2 is inhibited, and therefore an increase in SO 2 oxidation rate is prevented.
- WO 3 , MoO 3 and V 2 O 5 are also formed as an active component along with the generation of FePO 4 . As such, it is also expected to obtain the effect of maintaining the denitration activity or Hg oxidation activity at a high level.
- the catalyst of the invention it is important to have the atomic ratio of P to a catalytically active component in the catalyst to be more than 0 and 1.0 or less.
- P reacts with the catalytically active component to lower the denitration activity, there is a tendency that denitration activity is reduced by excessive P.
- the atomic ratio of P to a catalytically active component is more than 0 and 0.5 or less.
- any one of the oxides, salts or the like of the corresponding component may be used.
- the P compound needs to react with a Mo compound or a W compound and a V compound
- soluble salts of the corresponding compound for example, oxo acid or ammonium salts of the corresponding element and mixing them with titanium oxide in the presence of water
- Phosphoric acid/phosphoric acid compound i.e., P compound
- P compound may be directly added during the process of producing the catalyst as described above.
- a method in which a compound obtained by reacting in advance phosphoric acid/P compound (i.e., complex) or a solution containing the compound is added during a process of kneading raw materials for producing the catalyst, aside from the W, Mo, and V compounds that are added as an active component, or it is immersed after producing the catalyst or the like may be adopted.
- the latter method is preferable in that the influence of P on catalytic activity can be easily controlled.
- the water soluble phosphoric acid compound include ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
- a reducing agent like ammonia is injected and reacted by contact with the catalyst according to the method known per se in the art.
- Titanium oxide (specific surface area: 290 m 2 /g, manufactured by Ishihara Sangyo K.K.) (900 g), ammonium molybdate (107 g), ammonium metavanadate (28.3 g), 85% phosphoric acid (68.3 g), silica sol (trade name: OS SOL, manufactured by Nissan Chemical Industries, Ltd.) (404 g), and water (50 g) were placed in a kneader, and then kneaded for 60 minutes.
- silica-alumina ceramic fiber manufactured by Toshiba Fine Flex K.K.
- 151 g silica-alumina ceramic fiber
- the mixture was kneaded for 30 minutes, to thereby yield a catalyst paste having a water content of 27% by weight.
- the paste obtained was applied onto a base material (thickness: 0.7 mm) produced by subjecting a SUS 430 stainless steel plate (thickness: 0.2 mm) to a metal-lath processing; the base material was sandwiched between two polyethylene sheets; and the thus-sandwiched base material was passed through a pair of pressure rollers so that the meshes of the metal lath base were filled with the paste.
- the paste-filled base material was air-dried, and then calcined at 500° C. for two hours, to thereby obtain a catalyst of the invention.
- Composition of the catalyst of this invention was found to have a Ti/Mo/V (atomic proportions) of 93/5/2, and a P/(Mo+V) (atomic ratio) of 0.5.
- the catalyst of the invention was obtained in the same manner as Example 1, except that ammonium molybdate used in Example 1 was replaced by an equimolar amount of ammonium metatungstate, to thereby obtain a catalyst of the invention.
- Composition of the catalyst of this invention was found to have a Ti/WN (atomic proportions) of 93/5/2, and a P/(Mo+V) (atomic ratio) of 0.5.
- the catalyst was prepared in the same manner as Example 1 and Example 2, except that no phosphoric acid was added.
- Titanium oxide (specific surface area: 290 m 2 /g, manufactured by Ishihara Sangyo K.K.) (900 g), ammonium molybdate (113 g), ammonium metavanadate (105 g), 85% phosphoric acid (18 g (Example 3), 53 g (Example 4), 88 g (Example 5), 124 g (Example 6) and 177 g (Example 7)) and silica sol (trade name: OS SOL, manufactured by Nissan Chemical Industries, Ltd.) (404 g) were placed in a kneader, and then kneaded for 60 minutes.
- OS SOL silica sol
- silica-alumina ceramic fiber manufactured by Toshiba Fine Flex K.K.
- 151 g silica-alumina ceramic fiber
- the mixture was kneaded for 30 minutes, to thereby obtain a catalyst paste having a water content of 27% by weight.
- the obtained paste was applied onto a base material (thickness: 0.7 mm) produced by subjecting a SUS 430 stainless steel plate (thickness: 0.2 mm) to a metal-lath processing; the base material was sandwiched between two polyethylene sheets; and the thus-sandwiched base material was passed through a pair of pressure rollers so that the meshes provided in the metal lath base were filled with the paste.
- the paste-filled base material was air-dried, and then calcined at 500° C. for two hours, to thereby obtain a catalyst of the invention.
- Composition of the catalyst of this invention was found to have a Ti/MoN (atomic proportions) of 88/5/7 and a P/(Mo+V) (atomic ratio) of 0.1, 0.3, 0.5, 0.7 and 1.0 for Example 3 to 7, respectively.
- the catalyst was prepared in the same manner as Example 3, except that no phosphoric acid/phosphoric acid compound was added.
- Titanium oxide (specific surface area: 290 m 2 /g, manufactured by Ishihara Sangyo K.K.) (900 g), ammonium molybdate (113 g), ammonium metavanadate (42.9 g), ammonium dihydrogen phosphate (110 g), silica sol (trade name: OS SOL, manufactured by Nissan Chemical Industries, Ltd.) (404 g) and water (50 g) were placed in a kneader, and then kneaded for 60 minutes.
- silica-alumina ceramic fiber manufactured by Toshiba Fine Flex K.K.
- 151 g silica-alumina ceramic fiber
- the mixture was kneaded for 30 minutes, to thereby obtain a catalyst paste having a water content of 27% by weight.
- the obtained paste was applied onto a base material (thickness: 0.7 mm) produced by subjecting a SUS 430 stainless steel plate (thickness: 0.2 mm) to a metal-lath processing; the base material was sandwiched between two polyethylene sheets; and the thus-sandwiched base material was passed through a pair of pressure rollers so that the meshes provided in the metal lath base were filled with the paste.
- the paste-filled base material was air-dried, and then calcined at 500° C. for two hours, to thereby obtain a catalyst of the invention.
- Composition of the catalyst of this invention was found to have a Ti/MoN (atomic proportions) of 93/5/3 and a P/(Mo+V) (atomic ratio) of 0.4.
- Titanium oxide (specific surface area: 290 m 2 /g, manufactured by Ishihara Sangyo K.K.) (900 g), molybdenum trioxide (88 g), ammonium metavanadate (42.9 g), ammonium dihydrogen phosphate (110 g), silica sol (trade name: OS SOL, manufactured by Nissan Chemical Industries, Ltd.) (404 g) and water (50 g) were placed in a kneader, and then kneaded for 60 minutes.
- silica-alumina ceramic fiber manufactured by Toshiba Fine Flex K.K.
- 151 g silica-alumina ceramic fiber
- the mixture was kneaded for 30 minutes, to thereby obtain a catalyst paste having a water content of 27%.
- the obtained paste was applied onto a base material (thickness: 0.7 mm) produced by subjecting a SUS 430 stainless steel plate (thickness: 0.2 mm) to a metal-lath processing; the base material was sandwiched between two polyethylene sheets; and the thus-sandwiched base material was passed through a pair of pressure rollers so that the meshes provided in the metal lath base were filled with the paste.
- the paste-filled base material was air-dried, and then calcined at 500° C. for two hours, to thereby obtain a catalyst of the invention.
- Composition of the catalyst of this invention was found to have a Ti/MoN (atomic proportions) of 93/5/3 and a P/(Mo +V) (atomic ratio) of 0.4.
- the catalyst was prepared in the same manner as Examples 8 and Examples 9, except that no ammonium dihydrogen phosphate was added.
- Ammonium metavanadate (42.9 g) was dispersed in water (100 ml) and added with 85% phosphoric acid (45 g). According to the reaction between them, a red slurry-like product was obtained.
- titanium oxide (specific surface area: 290 m 2 /g, manufactured by Ishihara Sangyo K.K.) (900 g), ammonium molybdate (117 g), ammonium metavanadate (103 g), and silica sol (trade name: OS SOL, manufactured by Nissan Chemical Industries, Ltd.) (404 g) were placed in a kneader, and then kneaded for 30 minutes to obtain a past. To the paste, the red slurry obtained from the above was added and kneaded further for 30 minutes.
- silica-alumina ceramic fiber manufactured by Toshiba Fine Flex K.K.
- 151 g silica-alumina ceramic fiber
- the obtained paste was applied onto a base material (thickness: 0.7 mm) produced by subjecting a SUS 430 stainless steel plate (thickness: 0.2 mm) to a metal-lath processing; the base material was sandwiched between two polyethylene sheets; and the thus-sandwiched base material was passed through a pair of pressure rollers so that the meshes provided in the metal lath base were filled with the paste, to thereby obtain a catalyst of the invention.
- Composition of the catalyst of this invention was found to have a Ti/Mo/V (atomic proportions) of 85/5/10 and a P/(Mo+V) (atomic ratio) of 0.2.
- Titanium oxide (specific surface area: 290 m 2 /g, manufactured by Ishihara Sangyo K.K.) (900 g), ammonium metavanadate (105 g), and silica sol (trade name: OS SOL, manufactured by Chemical Industries, Ltd.) (404 g) were placed in a kneader, and then kneaded for 60 minutes. Thereafter, while silica-alumina ceramic fiber (manufactured by Toshiba Fine Flex K.K.) (151 g) was gradually added to the mixture, the mixture was kneaded for 30 minutes, to thereby obtain a catalyst paste having a water content of 27% by weight.
- silica-alumina ceramic fiber manufactured by Toshiba Fine Flex K.K.
- the obtained paste was applied onto a base material (thickness: 0.7 mm) produced by subjecting a SUS 430 stainless steel plate (thickness: 0.2 mm) to a metal-lath processing; the base material was sandwiched between two polyethylene sheets; and the thus-sandwiched base material was passed through a pair of pressure rollers so that the meshes provided in the metal lath base were filled with the paste.
- the resulting catalyst was air-dried, and then calcined at 500° C. for two hours, to thereby obtain a catalyst of the invention.
- ammonium molybdate (112 g) was dispersed in water (200 ml) and added with 85% phosphoric acid (89 g) to obtain a solution in which the two components are reacted with each other.
- the catalyst obtained from the above was immersed, the liquid was removed, and then the catalyst was air-dried at room temperature or calcined at 350° C. for one hour, to thereby obtain a catalyst of the invention.
- Composition of the catalyst of this invention was found to have a Ti/Mo/V (atomic proportions) of 88/5/7 and a P/(Mo+V) (atomic ratio) of 0.5.
- Each of the catalysts prepared in Examples 1 to 11 and Comparative examples 1 to 5 was cut into test pieces, each having a rectangular shape with a size of 100 mm ⁇ 20 mm.
- the test pieces of each catalyst were brought into contact with the gas under the condition shown in Table 1 to measure the denitrating performance and the Hg oxidation rate of the catalyst. Furthermore, they were brought into contact with the gas under the condition shown in Table 2 to measure the SO 2 oxidizing performance of each catalyst, and the initial activity was also determined.
- combustion ash of bituminous coal known as high S coals was pulverized with a ball mill until 200 mesh pass ratio is at least 95% to prepare simulated ash.
- This simulated ash was applied to a vat, added with the catalyst of Examples 1 to 11 and Comparative examples 1 to 5, and added further with the simulated ash to have thickness of about 1 mm.
- the vessel was placed in a calcination furnace in which atmosphere is adjusted to have SO 2 of 500 ppm, humidity of 10% and air for the remainder, and the vessel was kept at 400° C. for 50 hours. After that, the vessel was kept for 100 hours under the condition including the temperature of 35° C.
- the Fe components included in the ash were forced to move into the catalyst.
- the Fe 2 O 3 concentration on the surface of the catalyst was increased about 2.6% by weight on average.
- the Fe 2 O 3 was increased up to 0.38% by weight on average compared to the whole components of the catalyst.
- the catalyst of the invention has higher denitration rate and Hg oxidation rate with much lower SO 2 oxidation rate compared to the catalyst of the Comparative examples.
- the SO 2 oxidation rate has dramatically increased with the catalyst of the Comparative examples, while the increase in the SO 2 oxidation rate was minor for the catalyst of the present invention.
- the catalyst of the invention is resistant to the adhesion of a Fe component.
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- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
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JP2008-078280 | 2008-03-25 | ||
JP2008078280 | 2008-03-25 | ||
PCT/JP2009/055903 WO2009119639A1 (ja) | 2008-03-25 | 2009-03-25 | 鉄化合物の影響を抑制した排ガス浄化触媒 |
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US13/888,700 Division US9186657B2 (en) | 2008-03-25 | 2013-05-07 | Exhaust gas purification catalyst suppressing influence of iron compound |
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US12/934,301 Abandoned US20110116999A1 (en) | 2008-03-25 | 2009-03-25 | Exhaust gas purification catalyst on which influence of iron compound has been suppressed |
US13/888,700 Active US9186657B2 (en) | 2008-03-25 | 2013-05-07 | Exhaust gas purification catalyst suppressing influence of iron compound |
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EP (1) | EP2269732B1 (ja) |
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US20180280943A1 (en) * | 2017-03-31 | 2018-10-04 | Johnson Matthey Public Limited Company | Catalyst for treating an exhaust gas, an exhaust system and a method |
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JP5596992B2 (ja) * | 2010-02-09 | 2014-10-01 | バブコック日立株式会社 | バイオマス燃焼排ガス用脱硝触媒及び脱硝方法 |
US20110250114A1 (en) * | 2010-04-13 | 2011-10-13 | Millennium Inorganic Chemicals, Inc. | Vanadia-Based DeNOx Catalysts and Catalyst Supports |
JP5604235B2 (ja) * | 2010-09-07 | 2014-10-08 | バブコック日立株式会社 | 排ガス脱硝触媒およびその製造方法 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20180280943A1 (en) * | 2017-03-31 | 2018-10-04 | Johnson Matthey Public Limited Company | Catalyst for treating an exhaust gas, an exhaust system and a method |
US10882031B2 (en) * | 2017-03-31 | 2021-01-05 | Johnson Matthey Public Limited Company | Catalyst for treating an exhaust gas, an exhaust system and a method |
Also Published As
Publication number | Publication date |
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US20130251612A1 (en) | 2013-09-26 |
EP2269732A1 (en) | 2011-01-05 |
TW200948462A (en) | 2009-12-01 |
EP2269732B1 (en) | 2020-07-01 |
CA2719289C (en) | 2015-06-23 |
WO2009119639A1 (ja) | 2009-10-01 |
TWI465285B (zh) | 2014-12-21 |
CA2719289A1 (en) | 2009-10-01 |
EP2269732A4 (en) | 2013-01-02 |
JP5360834B2 (ja) | 2013-12-04 |
KR20100135829A (ko) | 2010-12-27 |
US9186657B2 (en) | 2015-11-17 |
KR101606218B1 (ko) | 2016-03-24 |
JPWO2009119639A1 (ja) | 2011-07-28 |
CN102015104A (zh) | 2011-04-13 |
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