WO2022157971A1 - 脱硝触媒及びその製造方法 - Google Patents
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- WO2022157971A1 WO2022157971A1 PCT/JP2021/002436 JP2021002436W WO2022157971A1 WO 2022157971 A1 WO2022157971 A1 WO 2022157971A1 JP 2021002436 W JP2021002436 W JP 2021002436W WO 2022157971 A1 WO2022157971 A1 WO 2022157971A1
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- denitration catalyst
- denitration
- metal
- catalyst
- vanadium oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 110
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000002184 metal Substances 0.000 claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 27
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims description 26
- 238000010521 absorption reaction Methods 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 238000000740 diffuse reflectance ultraviolet--visible spectrum Methods 0.000 claims description 8
- 229910014486 Na0.33V2O5 Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 8
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 5
- 229910021529 ammonia Inorganic materials 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 150000001340 alkali metals Chemical class 0.000 abstract description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 2
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 40
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 32
- 239000000203 mixture Substances 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010304 firing Methods 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 6
- 238000004455 differential thermal analysis Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000012018 catalyst precursor Substances 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 239000013522 chelant Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- YMNMFUIJDSASQW-UHFFFAOYSA-N distrontium;oxygen(2-);vanadium Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[V].[V].[Sr+2].[Sr+2] YMNMFUIJDSASQW-UHFFFAOYSA-N 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- OGRLITDAVSILTM-UHFFFAOYSA-N lead(2+);oxido(dioxo)vanadium Chemical compound [Pb+2].[O-][V](=O)=O.[O-][V](=O)=O OGRLITDAVSILTM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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
- 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
- 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
-
- B01J35/613—
-
- 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
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J37/08—Heat treatment
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/202—Alkali metals
- B01D2255/2022—Potassium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2255/2027—Sodium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2255/2045—Calcium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2255/20723—Vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- 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
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Definitions
- the present invention relates to a denitration catalyst and a method for producing the same.
- Nitrogen oxides are one of the pollutants emitted into the atmosphere by combustion of fuel. be done. Nitrogen oxides cause acid rain, ozone depletion, photochemical smog, etc., and seriously affect the environment and the human body.
- a selective catalytic reduction reaction (NH 3 -SCR) using ammonia (NH 3 ) as a reducing agent is known as a technique for removing the above nitrogen oxides.
- a catalyst used for selective catalytic reduction reaction a catalyst in which titanium oxide is used as a carrier and vanadium oxide is supported is widely used. Titanium oxide is considered to be the best carrier because of its low activity against sulfur oxides and its high stability.
- vanadium oxide plays a major role in NH 3 -SCR, it oxidizes SO 2 to SO 3 , so vanadium oxide could not be supported in the catalyst in an amount of about 1 wt % or more.
- the catalyst in which vanadium oxide is supported on a titanium oxide carrier hardly reacts at low temperatures, it has to be used at a high temperature of 350-400°C.
- the present inventors found a denitration catalyst containing 43 wt % or more of vanadium pentoxide, having a BET specific surface area of 30 m 2 /g or more, and used for denitration at 200° C. or lower (Patent Document 2).
- the denitration catalyst described in Patent Document 2 can obtain a favorable denitration rate at 200° C. or less, but the conditions under which the denitration catalyst is actually used are often accompanied by water vapor, and the denitration rate in the presence of water vapor is still low. There was room for improvement.
- the inventors of the present invention have attempted to further improve the denitration catalyst disclosed in Patent Document 2, and as a result of intensive studies, have found a denitration catalyst that provides a favorable denitration rate, particularly at 200°C or less and in the presence of steam.
- the purpose of the present invention is to provide a denitration catalyst that exhibits an excellent denitration rate at low temperatures and in the presence of water vapor during a selective catalytic reduction reaction using ammonia as a reducing agent.
- the present invention is a denitration catalyst containing vanadium oxide as a main component and a second metal, wherein the second metal M is selected from the group consisting of Li, Na, K, Mg and Ca. is at least one denitrification catalyst.
- the vanadium oxide is V 2 O 5
- the second metal is at least one of Li, Na, and K
- the second metal has a molar ratio to the V 2 O 5 is 0.16 to 0.66, the denitration catalyst according to (1).
- the ratio of the absorption intensity at 700 nm to the absorption intensity at 400 nm (400 nm:700 nm), normalized by the absorption intensity at 400 nm in the diffuse reflection UV-Vis spectrum, is 1:0.45 to 1:0.88.
- the denitration catalyst according to any one of (1) to (3).
- the present invention can provide a denitration catalyst that exhibits an excellent denitration rate at low temperatures and in the presence of water vapor during a selective catalytic reduction reaction using ammonia as a reducing agent.
- 4 is a graph showing denitration rates of denitration catalysts containing each metal element as a second metal. It is a graph which shows the relationship between the denitration rate and denitration temperature of each denitration catalyst. 4 is a graph showing the relationship between the composition ratio of a denitration catalyst and the denitration rate. 4 is an XRD chart showing the relationship between the composition ratio of the denitration catalyst and the crystal phase. 4 is a graph showing the relationship between the composition ratio of a denitration catalyst and the BET specific surface area. 4 is a graph showing the relationship between the sintering temperature of a denitration catalyst and the denitration rate. 4 is an XRD chart showing the relationship between the sintering temperature of the denitration catalyst and the crystal phase.
- 4 is a graph showing TG-DTA measurement results of a denitration catalyst.
- 4 is a graph showing the relationship between the sintering temperature of the denitration catalyst and the diffuse reflectance UV-Vis spectrum.
- 10 is a graph showing the relationship between the absorption intensity ratio (400 nm:700 nm) normalized from FIG. 9 and the denitrification rate.
- the denitration catalyst according to the present embodiment contains vanadium oxide as a main component and a second metal.
- the second metal is at least one selected from the group consisting of Li, Na, K, Mg and Ca.
- the denitration catalyst according to the present embodiment exhibits a high denitration rate even in a low-temperature environment and in the presence of water vapor compared to conventionally used denitration catalysts.
- the denitrification rate may be expressed as the NO conversion rate.
- the NO conversion rate is shown by the following formula (1).
- NO conversion rate (%) (NO concentration before denitration reaction - NO concentration after denitration reaction) / (NO concentration before denitration reaction) x 100 (1)
- vanadium oxide examples of vanadium oxide used in the denitration catalyst according to the present embodiment include vanadium oxide (II) (VO), vanadium trioxide (III) (V 2 O 3 ), vanadium tetroxide (IV) (V 2 O 4 ), and vanadium (V) pentoxide (V 2 O 5 ).
- the vanadium oxide is preferably vanadium pentoxide.
- the V atom of vanadium pentoxide may have a valence of pentavalent, tetravalent, trivalent, or divalent during the denitration reaction.
- the content of vanadium oxide in the denitration catalyst is preferably 50 wt% or more in terms of vanadium pentoxide, more preferably 60 wt% or more.
- the second metal used in the denitration catalyst according to this embodiment is at least one selected from the group consisting of Li, Na, K, Mg, and Ca.
- the second metal in the denitration catalyst containing vanadium oxide as a main component it is possible to exhibit a high denitration rate even in a low-temperature environment and in the presence of water vapor, compared to conventional denitration catalysts.
- the second metal has a molar ratio to vanadium (V) pentoxide (V 2 O 5 ) when vanadium (V) pentoxide (V 2 O 5 ) is used as the vanadium oxide is 0.16 to 0.66. and more preferably 0.33 to 0.66.
- the reason why the molar ratio of the second metal to vanadium pentoxide (V 2 O 5 ) is preferably 0.16 to 0.66 is that the above molar ratio allows the second metal and vanadium pentoxide (V) (V 2 O 5 ) form a specific crystal phase, and this crystal phase is considered to contribute to a high denitrification rate especially at low temperatures and in the presence of water vapor.
- the crystal phase formed by Na as the second metal and vanadium pentoxide (V) (V 2 O 5 ) preferably includes a Na 0.33 V 2 O 5 crystal phase.
- the Na 0.33 V 2 O 5 crystal phase is a monoclinic crystal structure assigned to C2/m.
- Another crystal phase formed by Na and vanadium pentoxide (V) (V 2 O 5 ) is Na 1.2 V 3 having a monoclinic crystal structure assigned to P2 1 /m. O8 crystalline phase.
- the denitration catalyst according to the present embodiment can be obtained, for example, by calcining a precursor containing vanadium oxide and a second metal.
- the firing temperature is preferably 260 to 400.degree. C., more preferably 300 to 400.degree.
- the denitration catalyst By setting the denitration catalyst to a baking temperature of 260° C. or higher, it is believed that the precursor containing vanadium oxide and the second metal is decomposed to form the Na 0.33 V 2 O 5 crystal phase. In addition, as the denitration catalyst sintering temperature rises, O is desorbed from V 2 O 5 and the ratio of V 4+ in the denitration catalyst increases. Since the denitrification reaction proceeds in the oxidation-reduction cycle of V5 + and V4+, it is considered that there exists a preferable ratio of V5 + and V4+ . By setting the calcination temperature of the denitration catalyst to 400° C. or lower, it is presumed that the ratio of V 5+ and V 4+ becomes a preferable ratio.
- the proportion of V 5+ and V 4+ present in the denitration catalyst can be estimated from the diffuse reflectance UV-Vis spectrum which can be measured by known methods.
- the absorption intensity at 400 nm of the diffuse reflectance UV-Vis spectrum corresponds to the amount of V 5+ in the denitration catalyst.
- the absorption intensity at 700 nm of the diffuse reflectance UV-Vis spectrum corresponds to the amount of V 4+ in the denitration catalyst.
- the ratio of the absorption intensity at 400 nm to the absorption intensity at 700 nm (400 nm:700 nm), normalized by the absorption intensity at 400 nm in the diffuse reflectance UV-Vis spectrum, gives the preferred ratio of V 5+ and V 4+ in the denitration catalyst.
- the absorption intensity ratio (400 nm:700 nm) is preferably 1:0.45 to 1:0.88.
- the denitration catalyst according to the present embodiment may contain other substances as long as the effects of the present invention are not impaired.
- the denitration catalyst according to the present embodiment preferably further contains carbon in addition to the above. It is thought that the inclusion of carbon as an impurity in the denitration catalyst causes strain in the lines and planes in the crystal lattice in the crystal structure of vanadium oxide described above, thereby exhibiting a high denitration rate in a low-temperature environment.
- the content of carbon in the denitration catalyst is preferably 0.05 wt % or more and 3.21 wt % or less. More preferably, the carbon content is 0.07 wt % or more and 3.21 wt % or less.
- the carbon content is 0.11 wt % or more and 3.21 wt % or less. More preferably, the carbon content is 0.12 wt % or more and 3.21 wt % or less. More preferably, the carbon content is 0.14 wt % or more and 3.21 wt % or less. More preferably, the carbon content is 0.16 wt % or more and 3.21 wt % or less. More preferably, the carbon content is 0.17 wt % or more and 3.21 wt % or less. More preferably, the carbon content is 0.70 wt % or more and 3.21 wt % or less.
- the denitration catalyst according to the present embodiment is preferably used for denitration reactions at 350° C. or lower. Moreover, it is preferable because a high denitration rate can be obtained even in the denitration reaction at a reaction temperature of 300° C. or less. In the denitration reaction at a reaction temperature of 200° C. or less, oxidation of SO 2 to SO 3 does not occur, which is preferable.
- the reaction temperature is more preferably 100 to 250°C, even more preferably 160 to 200°C.
- the reaction temperature may be 80-150°C.
- the denitration catalyst containing only vanadium (V) pentoxide (V 2 O 5 ) as the denitration catalyst undergoes changes such as a decrease in the specific surface area when the reaction temperature is 300° C. or higher.
- the reaction temperature cannot be higher than 300°C.
- the denitration catalyst according to the present embodiment having the second metal can maintain a high denitration rate even when the reaction temperature is 300° C. or higher.
- the denitration catalyst according to this embodiment can be produced, for example, as follows. First, a precursor containing each component contained in the denitration catalyst is prepared.
- the vanadium oxide contained in the denitration catalyst is contained in the precursor as, for example, an aqueous solution of vanadate. Examples of the vanadate include ammonium metavanadate, magnesium vanadate, strontium vanadate, barium vanadate, zinc vanadate, lead vanadate, and lithium vanadate.
- the second metal in the denitration catalyst can be obtained by mixing nitrates, chlorides, sulfates, chelate complexes, hydrates, ammonium compounds, phosphate compounds, etc. of each metal with the aqueous solution of vanadic acid. contained in Examples of chelate complexes include complexes of oxalic acid, citric acid, and the like.
- a denitration catalyst precursor powder is obtained by a calcination step of calcining the precursor powder at a predetermined temperature and time.
- the firing temperature in the firing step is preferably 260 to 400°C, more preferably 300 to 400°C, as described above.
- the present invention is not limited to the above embodiments, and includes modifications, improvements, etc. within the scope of achieving the object of the present invention.
- Example 1 Ammonium vanadate (NH 4 VO 3 ) and oxalic acid ((COOH) 2 ) were dissolved in pure water to synthesize a precursor complex solution. To this precursor complex solution, a nitrate salt of Na, which is the second metal, was added in an amount that gave a compositional formula of Na 0.66 V 2 O 5 and mixed to obtain a precursor solution of a denitration catalyst. The denitrification catalyst of Example 1 was obtained by evaporating the precursor solution to dryness and calcining it twice for 4 hours at a temperature of 300° C. in the atmosphere. DeNOx catalysts were also prepared in the same procedure as above for examples containing other metals as the second metal, examples with different composition ratios of Na, and comparative examples with no addition of the second metal.
- FIG. 1 shows a denitration catalyst according to each example, which uses vanadium pentoxide (V) (V 2 O 5 ) as the main component and Li, Na, K, Mg, or Ca as the second metal
- V vanadium pentoxide
- 5 is a graph comparing the denitration rate of denitration catalysts (none) according to comparative examples using only vanadium pentoxide (V 2 O 5 ).
- the vertical axis in FIG. 1 indicates the NO conversion rate.
- a denitration catalyst using an alkali metal such as Li, Na, or K as the second metal was used in an amount such that the composition formula, where M is the second metal, is M 0.66 V 2 O 5 .
- the denitration catalyst using Mg or Ca, which is an alkaline earth metal, as the second metal was used in an amount that gives M 0.33 V 2 O 5 in the composition formula where M is the second metal.
- the amount of catalyst was 0.375 g and the reaction temperature was 150°C.
- the reaction gas was NO (250 ppm), NH 3 (250 ppm), 4% by volume O 2 , Ar gas, and the gas flow rate was 250 ml/min ⁇ 1 .
- a reaction gas containing 10% by volume of H 2 O was used with respect to the reaction gas of "Dry".
- the denitrification catalysts according to the respective examples containing vanadium oxide as the main component and using Li, Na, K, Mg, or Ca as the second metal are comparative examples containing only vanadium oxide. It is clear that the NO conversion rate is particularly high in the presence of steam compared to such denitration catalysts.
- FIG. 2 is a graph showing the relationship between the reaction temperature and the denitration rate (NO conversion rate) of denitration catalysts according to examples and comparative examples containing vanadium pentoxide (V) (V 2 O 5 ) as a main component.
- V vanadium pentoxide
- VW/TiO 2 is a comparative example simulating an industrial catalyst and has a composition of 1 wt % V 2 O 5 , 5 wt % WO 3 /TiO 2 .
- Na—V” and “Mg—V” have the same composition as in FIG.
- the denitration catalyst containing vanadium oxide as the main component and using Na or Mg as the second metal is superior to the denitration catalyst according to the comparative example, especially at low temperatures of 120° C. or less. It is clear that it shows high NO conversion.
- the comparative examples containing only vanadium pentoxide (V) (V 2 O 5 ) it was impossible to raise the reaction temperature to 300°C or higher, but the denitration catalysts according to the examples raised the reaction temperature to 300°C. It was confirmed that a high NO conversion rate of 80% or more is exhibited even at temperatures above 350°C.
- FIG. 3 is a graph showing the relationship between the composition of the denitration catalyst and the NO conversion rate when vanadium pentoxide (V) (V 2 O 5 ) is used as the vanadium oxide and Na is used as the second metal.
- the horizontal axis in FIG. 3 indicates the molar ratio of Na to vanadium pentoxide, and the vertical axis in FIG. 3 indicates the NO conversion rate.
- the "Dry” and “Wet" conditions in FIG. 3 are the same as the conditions in FIG. As shown in FIG. 3, when the molar ratio of Na to vanadium (V) pentoxide (V 2 O 5 ) is within the range of 0.16 to 0.66, a high NO conversion rate can be obtained. it is obvious.
- FIG. 4 is a graph showing XRD charts when using Na as the second metal and changing the molar ratio of Na to vanadium pentoxide (V 2 O 5 ).
- V 2 O 5 vanadium pentoxide
- the peaks observed when the composition of the denitration catalyst is V 2 O 5 , Na 0.33 V 2 O 5 and Na 1.00 V 2 O 5 are V 2 O 5 (1), Na 0.33 V 2 O 5 (2), and Na 1.2 V 3 O 8 (3) peaks attributed to single-phase crystal phases.
- the composition of the denitration catalyst was Na 0.16 V 2 O 5 , both peaks attributed to the crystal phases (1) and (2) were observed.
- FIG. 5 is a graph showing the relationship between the specific surface area and composition of the denitration catalyst.
- the vertical axis of FIG. 5 indicates the BET specific surface area ( m 2 /g) of the denitration catalyst, and the horizontal axis of FIG.
- the composition of the denitration catalyst in the case of using Na as is shown. It is clear from FIG. 5 that the specific surface area of the denitration catalyst decreases as the ratio of Na increases. On the other hand, when comparing the results of FIGS. 5 and 3 , the relationship between the specific surface area and the NO conversion rate is , is clearly not proportional. Therefore, it is clear that the inclusion of the Na 0.33 V 2 O 5 crystal phase (2) contributes to a higher denitration rate than simply having a large specific surface area.
- FIG. 6 is a graph showing the relationship between the sintering temperature of the denitration catalyst and the NO conversion rate.
- the vertical axis in FIG. 6 indicates the NO conversion rate, and the horizontal axis in FIG. 6 indicates the calcination temperature (° C.) of the denitration catalyst. From FIG. 6, it is clear that a high NO conversion rate of the denitration catalyst can be obtained by setting the sintering temperature of the denitration catalyst to 300 to 400.degree.
- FIG. 7 is a graph showing XRD charts when the sintering temperature of the denitration catalyst is changed.
- a denitration catalyst having a composition of Na 0.33 V 2 O 5 was used. From the results of FIG. 7, a peak attributed to the Na 0.33 V 2 O 5 crystal phase of (2) above was observed at any firing temperature. Therefore, it is clear that the difference in NO conversion due to the difference in calcination temperature is not due to the type of crystal phase.
- FIG. 8 is a chart showing the results of weight change due to heating of a denitration catalyst precursor having a composition of Na 0.33 V 2 O 5 measured by TG-DTA (simultaneous thermogravimetry and differential thermal analysis).
- the solid line indicates the TG (thermogravimetric analysis) curve
- the dashed line indicates the DTA (differential thermal analysis) curve.
- the left vertical axis in FIG. 8 indicates the weight ratio (%) with respect to the initial weight corresponding to the TG curve
- the right vertical axis indicates the temperature difference ( ⁇ V) from the reference material corresponding to the DTA curve.
- the horizontal axis of FIG. 8 indicates temperature (° C.). From the results of the TG curve in FIG.
- FIG. 9 shows the diffuse reflectance UV-Vis spectrum of the denitration catalyst precursor with a composition of Na 0.33 V 2 O 5 at calcination temperatures of 300° C., 400° C., 500° C., and 600° C., respectively. It is a graph normalized by absorption intensity at a wavelength of 400 nm.
- the vertical axis in FIG. 9 indicates the KM function used for quantitative analysis, and the horizontal axis indicates wavelength (nm).
- the diffuse reflectance UV-Vis spectrum was measured with an ultraviolet-visible-near-infrared spectrophotometer (UV-3100PC, manufactured by Shimadzu Corporation).
- the relative intensity ratio of the absorption intensity at 700 nm to the absorption intensity at 400 nm (400 nm:700 nm) calculated from FIG. Similarly, when the firing temperature is 400 ° C., (400 nm:700 nm) is 1:0.88, and when the firing temperature is 500 ° C., (400 nm:700 nm) is 1:1.35. (400 nm:700 nm) was 1:1.69 when the temperature was 600.degree.
- FIG. 10 is a graph comparing the results of FIG. 9 and the results of FIG.
- the vertical axis in FIG. 10 indicates the NO conversion rate (%), and the horizontal axis indicates the relative intensity ratio of absorption intensity at 700 nm to absorption intensity at wavelength 400 nm (700 nm/400 nm). From the results of FIG. 10, it is clear that the preferred ratio (400 nm:700 nm) is 1:0.45 to 1:0.88.
Abstract
Description
本実施形態に係る脱硝触媒は、酸化バナジウムを主成分として、第2の金属を含有する。上記第2の金属は、Li、Na、K、Mg、及びCaからなる群から選ばれる少なくとも一つである。本実施形態に係る脱硝触媒は、従来用いられている脱硝触媒と比較して、低温環境下かつ水蒸気存在下でも高い脱硝率を発揮する。
NO転化率(%)=(脱硝反応前のNO濃度-脱硝反応後のNO濃度)/(脱硝反応前のNO濃度)×100 (1)
本実施形態に係る脱硝触媒に用いられる酸化バナジウムとしては、例えば、酸化バナジウム(II)(VO)、三酸化バナジウム(III)(V2O3)、四酸化バナジウム(IV)(V2O4)、及び五酸化バナジウム(V)(V2O5)が挙げられる。酸化バナジウムとしては、五酸化バナジウムであることが好ましい。五酸化バナジウムのV原子は、脱硝反応中、5価、4価、3価、又は2価の価数を有してもよい。
本実施形態に係る脱硝触媒に用いられる第2の金属は、Li、Na、K、Mg、及びCaからなる群から選ばれる少なくとも一つである。酸化バナジウムを主成分とする脱硝触媒に上記第2の金属が含まれることにより、従来の脱硝触媒と比較して、低温環境下かつ水蒸気存在下でも高い脱硝率を発揮できる。
第2の金属は、酸化バナジウムとして五酸化バナジウム(V)(V2O5)を用いた場合の五酸化バナジウム(V)(V2O5)に対するモル比が、0.16~0.66であることが好ましく、0.33~0.66であることがより好ましい。第2の金属の五酸化バナジウム(V)(V2O5)に対するモル比が、0.16~0.66であることが好ましい理由としては、上記モル比とすることにより、第2の金属と五酸化バナジウム(V)(V2O5)とが特定の結晶相を形成し、この結晶相が特に低温かつ水蒸気存在下における高い脱硝率に寄与するものと考えられる。
第2の金属としてのNaと、五酸化バナジウム(V)(V2O5)とが形成する結晶相としては、Na0.33V2O5結晶相を含むことが好ましい。Na0.33V2O5結晶相は、C2/mに帰属される単斜晶型の結晶構造である。他にNaと、五酸化バナジウム(V)(V2O5)とが形成する結晶相としては、P21/mに帰属される単斜晶型の結晶構造を有する、Na1.2V3O8結晶相が挙げられる。
脱硝触媒は、その比表面積が大きいほど反応サイトが増大し、高い脱硝率が得られることが期待される。しかし、本実施形態に係る脱硝触媒は、比表面積が単に大きいというだけでなく、脱硝触媒が上記好ましい結晶相を含むことがより重要である。
本実施形態に係る脱硝触媒は、詳細は後述するが、例えば、酸化バナジウムと第2の金属とを含む前駆体を焼成することで得られる。上記焼成時の温度は、260~400℃であることが好ましく、300~400℃とすることがより好ましい。
脱硝触媒中に存在するV5+とV4+の割合は、公知の方法により測定できる拡散反射UV-Visスペクトルにより推定できる。拡散反射UV-Visスペクトルの400nmにおける吸収強度は、脱硝触媒中のV5+の量に相当する。同様に、拡散反射UV-Visスペクトルの700nmにおける吸収強度は、脱硝触媒中のV4+の量に相当する。従って、拡散反射UV-Visスペクトルの400nmの吸収強度で規格化される、400nmにおける吸収強度と700nmにおける吸収強度との比(400nm:700nm)により、脱硝触媒中の好ましいV5+とV4+の割合を示すことができる。上記吸収強度の比(400nm:700nm)は、1:0.45~1:0.88であることが好ましい。
本実施形態に係る脱硝触媒は、本発明の効果を阻害しない範囲で、他の物質を含有していてもよい。例えば、本実施形態に係る脱硝触媒は、上記以外に更に炭素を含有することが好ましい。脱硝触媒が不純物として炭素を含むことで、上述した酸化バナジウムの結晶構造において結晶格子中の線や面にひずみが生じることにより、低温環境下における高い脱硝率を発揮できると考えられる。炭素の含有量は、脱硝触媒中において0.05wt%以上3.21wt%以下であることが好ましい。上記炭素の含有量は、0.07wt%以上3.21wt%以下であることがより好ましい。上記炭素の含有量は、0.11wt%以上3.21wt%以下であることがより好ましい。上記炭素の含有量は、0.12wt%以上3.21wt%以下であることがより好ましい。上記炭素の含有量は、0.14wt%以上3.21wt%以下であることがより好ましい。上記炭素の含有量は、0.16wt%以上3.21wt%以下であることがより好ましい。上記炭素の含有量は、0.17wt%以上3.21wt%以下であることがより好ましい。上記炭素の含有量は、0.70wt%以上3.21wt%以下であることがより好ましい。
本実施形態に係る脱硝触媒は、例えば、以下のようにして製造できる。まず、脱硝触媒に含まれる各成分を含有する前駆体を調製する。脱硝触媒に含まれる酸化バナジウムは、例えば、バナジン酸塩の水溶液として前駆体中に含有される。上記バナジン酸塩としては、例えば、メタバナジン酸アンモニウム、バナジン酸マグネシウム、バナジン酸ストロンチウム、バナジン酸バリウム、バナジン酸亜鉛、バナジン酸鉛、バナジン酸リチウム等を用いてもよい。
(実施例1)
バナジン酸アンモニウム(NH4VO3)とシュウ酸((COOH)2)とを純水に溶解させ、前駆体錯体溶液を合成した。この前駆体錯体溶液に対し、第2の金属であるNaの硝酸塩を、組成式でNa0.66V2O5となる量添加して混合し、脱硝触媒の前駆体溶液を得た。上記前駆体溶液を蒸発乾固させ、大気中で300℃の温度で4時間、2回焼成することにより、実施例1の脱硝触媒を得た。第2の金属として、他の金属を含む実施例、Naの組成比を変更した実施例及び、第2の金属を添加しない比較例についても上記と同様の手順で脱硝触媒を調製した。
図1は、五酸化バナジウム(V)(V2O5)を主成分とし、第2の金属として、Li、Na、K、Mg、又はCaをそれぞれ用いた各実施例に係る脱硝触媒と、五酸化バナジウム(V)(V2O5)のみを用いた比較例に係る脱硝触媒(none)の脱硝率を比較するグラフである。図1の縦軸はNO転化率を示す。第2の金属として、アルカリ金属であるLi、Na又はKを用いた脱硝触媒は、第2の金属をMとした場合における組成式でM0.66V2O5となる量用いた。第2の金属として、アルカリ土類金属であるMg、又はCaを用いた脱硝触媒は、第2の金属をMとした場合における組成式でM0.33V2O5となる量用いた。触媒量は0.375gとし、反応温度を150℃とした。反応ガスとして、図1における「Dry」の場合、NO(250ppm)、NH3(250ppm)、4体積%O2、Arガス中とし、ガス流量を250ml/min-1とした。図1における「Wet」の場合、「Dry」の反応ガスに対して更に10体積%のH2Oを含む反応ガスとした。
図2は、五酸化バナジウム(V)(V2O5)を主成分とする実施例及び比較例に係る脱硝触媒の、反応温度と脱硝率(NO転化率)との関係を示すグラフである。図2中、「VO」は、五酸化バナジウム(V)(V2O5)のみを含有する比較例を示す。「V-W/TiO2」は、工業触媒を模した比較例であり、1wt%V2O5、5wt% WO3/TiO2の組成を有する。「Na-V」及び「Mg-V」は、五酸化バナジウム(V)(V2O5)を主成分とし、それぞれ第2の金属としてNa及びMgを含有する、図1と同様の組成を有する実施例に係る脱硝触媒を示す。図2中の「Dry」及び「Wet」の反応ガス条件は図1と同一であり、反応温度を変更したこと以外は、図1と同じ条件でNO転化率を測定した。
図3は、酸化バナジウムとして五酸化バナジウム(V)(V2O5)を用い、第2の金属としてNaを用いた場合における脱硝触媒の組成とNO転化率との関係を示すグラフである。図3における横軸は、五酸化バナジウムに対するNaのモル比を示し、図3における縦軸は、NO転化率を示す。図3における「Dry」及び「Wet」の条件は、図1における条件と同一である。図3に示すように、五酸化バナジウム(V)(V2O5)に対するNaのモル比が、0.16~0.66の範囲内であることで、高いNO転化率が得られることが明らかである。
図4は、第2の金属としてNaを用い、Naの五酸化バナジウム(V)(V2O5)に対するモル比を変化させた場合におけるXRDチャートを示すグラフである。図3に示すように、脱硝触媒の組成をそれぞれV2O5、Na0.33V2O5、Na1.00V2O5、とした場合に観察されるピークはそれぞれV2O5(1)、Na0.33V2O5(2)、Na1.2V3O8(3)の単相の結晶相に帰属するピークである。一方、脱硝触媒の組成をNa0.16V2O5とした場合は上記(1)と(2)の結晶相に帰属するピークがいずれも観察された。また、脱硝触媒の組成をNa0.46V2O5又はNa0.66V2O5とした場合は上記(2)と(3)の結晶相に帰属するピークがいずれも観察された。従って、図3の結果と併せて考察すると、上記(2)のNa0.33V2O5結晶相が脱硝触媒に含まれることによって、高い脱硝率が得られているものと推察される。
図5は、脱硝触媒の比表面積と組成との関係を示すグラフである。図5の縦軸は脱硝触媒のBET比表面積(m2/g)を示し、図5の横軸は、酸化バナジウムとして五酸化バナジウム(V)(V2O5)を用い、第2の金属としてNaを用いた場合における脱硝触媒の組成を示す。図5から、Naの割合を増大させると共に脱硝触媒の比表面積が低下することが明らかである。一方で、図5と図3の結果を照合すると、比表面積とNO転化率の関係は、特にNaの五酸化バナジウム(V)(V2O5)に対する割合が0.66以下である場合において、比例関係にないことが明らかである。従って、脱硝触媒が、単に大きな比表面積を有することよりも、(2)のNa0.33V2O5結晶相を含むことが、高い脱硝率により寄与することが明らかである。
図6は、脱硝触媒の焼成温度とNO転化率との関係を示すグラフである。図6の縦軸はNO転化率を示し、図6の横軸は脱硝触媒の焼成温度(℃)を示す。図6から、脱硝触媒の焼成温度を300~400℃とすることで、脱硝触媒の高いNO転化率が得られることが明らかである。
Claims (5)
- 酸化バナジウムを主成分とし、第2の金属を含有する脱硝触媒であって、
前記第2の金属Mが、Li、Na、K、Mg、及びCaからなる群より選ばれる少なくとも1種である、脱硝触媒。 - 前記酸化バナジウムは、V2O5であり、前記第2の金属は、Li、Na、Kのうち少なくとも何れかであり、
前記第2の金属は、前記V2O5に対するモル比が0.16~0.66である、請求項1に記載の脱硝触媒。 - Na0.33V2O5結晶相を含む、請求項1又は2に記載の脱硝触媒。
- 拡散反射UV-Visスペクトルにおける400nmの吸収強度で規格化される、400nmの吸収強度に対する700nmの吸収強度の比(400nm:700nm)が、1:0.45~1:0.88である、請求項1~3いずれかに記載の脱硝触媒。
- 請求項1~4いずれかに記載の脱硝触媒の製造方法であって、
前記酸化バナジウム及び前記第2の金属を含む前駆体を260~400℃で焼成する焼成工程を含む、脱硝触媒の製造方法。
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