WO2020179076A1 - Catalyseur de dénitration et son procédé de fabrication - Google Patents

Catalyseur de dénitration et son procédé de fabrication Download PDF

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WO2020179076A1
WO2020179076A1 PCT/JP2019/009201 JP2019009201W WO2020179076A1 WO 2020179076 A1 WO2020179076 A1 WO 2020179076A1 JP 2019009201 W JP2019009201 W JP 2019009201W WO 2020179076 A1 WO2020179076 A1 WO 2020179076A1
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Prior art keywords
denitration catalyst
metal
vanadium
catalyst
denitration
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PCT/JP2019/009201
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English (en)
Japanese (ja)
Inventor
英嗣 清永
吉田　和広
啓一郎 盛田
徹 村山
春田　正毅
慎一 秦
雄介 猪股
Original Assignee
中国電力株式会社
公立大学法人首都大学東京
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Application filed by 中国電力株式会社, 公立大学法人首都大学東京 filed Critical 中国電力株式会社
Priority to JP2019538453A priority Critical patent/JP7388653B2/ja
Priority to PCT/JP2019/009201 priority patent/WO2020179076A1/fr
Priority to CN202080019195.8A priority patent/CN113874109A/zh
Priority to EP20767017.5A priority patent/EP3936706A4/fr
Priority to SG11202109733U priority patent/SG11202109733UA/en
Priority to PCT/JP2020/009542 priority patent/WO2020179891A1/fr
Priority to JP2020549726A priority patent/JP7429012B2/ja
Priority to US17/436,958 priority patent/US20220168712A1/en
Priority to CN202080019137.5A priority patent/CN113631804A/zh
Priority to EP20766854.2A priority patent/EP3936230A4/fr
Priority to PCT/JP2020/009543 priority patent/WO2020179892A1/fr
Priority to JP2020549727A priority patent/JP7445925B2/ja
Priority to US17/436,965 priority patent/US20220170403A1/en
Priority to SG11202109743T priority patent/SG11202109743TA/en
Publication of WO2020179076A1 publication Critical patent/WO2020179076A1/fr

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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
    • 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
    • B01D53/90—Injecting reactants
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • 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

Definitions

  • the present invention relates to a denitration catalyst and a method for producing the same. More specifically, the present invention relates to a denitration catalyst used for purifying exhaust gas generated by combustion of fuel, and a method for producing the same.
  • Nitrogen oxides cause acid rain, ozone layer depletion, photochemical smog, etc., and have a serious impact on the environment and the human body, so their treatment has become an important issue.
  • a selective catalytic reduction reaction (NH 3 —SCR) using ammonia (NH 3 ) as a reducing agent is known.
  • a catalyst used for the selective catalytic reduction reaction a catalyst using titanium oxide as a carrier and supporting vanadium oxide is widely used. Titanium oxide is considered to be the best carrier because of its low activity against sulfur oxides and high stability.
  • vanadium oxide plays a major role in NH 3 —SCR, it oxidizes SO 2 to SO 3, and therefore vanadium oxide could not be supported by about 1 wt% or more.
  • the catalyst in which vanadium oxide is supported on the titanium oxide carrier hardly reacts at a low temperature, so that the catalyst must be used at a high temperature of 350 to 400°C.
  • An object of the present invention is to provide a catalyst having better denitration efficiency at a low temperature as compared with the prior art in 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, wherein the content of the oxide of the second metal is 1 wt% or more and 40 wt% or less, and the second metal is Co, W, Mo, It relates to a denitration catalyst which is at least one metal element selected from the group consisting of Nb, Ce, Sn, Ni and Fe.
  • the denitration catalyst is preferably used for denitration at 300°C or lower.
  • the denitration catalyst further contains carbon.
  • the carbon content is preferably 0.05 wt% or more.
  • the method for producing a denitration catalyst according to the present invention preferably has a step of firing a mixture of vanadate, a chelate compound, and the compound of the second metal.
  • the mixture further contains ethylene glycol.
  • the firing step is preferably a step of firing at a temperature of 270° C. or lower.
  • the denitration catalyst according to the present invention has even better denitration efficiency at low temperatures than in the prior art during a selective catalytic reduction reaction using ammonia as a reducing agent.
  • the denitration catalyst of the present invention is a denitration catalyst containing vanadium oxide as a main component, wherein the content of the oxide of the second metal is 1 wt% or more and 40 wt% or less, and the second metal is Co or W. , Mo, Nb, Ce, Sn, Ni, and Fe, at least one metal element selected from the group.
  • a denitration catalyst can exhibit a higher denitration effect even in a low temperature environment as compared with a denitration catalyst such as a vanadium / titanium catalyst conventionally used.
  • the denitration catalyst of the present invention contains vanadium oxide as a main component.
  • This vanadium oxide is vanadium (II) oxide (VO), vanadium (III) trioxide (V 2 O 3 ), vanadium tetraoxide (IV) (V 2 O 4 ), vanadium pentoxide (V) (V 2 O). 5 ) is included, and the V element of vanadium pentoxide (V 2 O 5 ) may take a pentavalent, tetravalent, trivalent or divalent form during the denitration reaction.
  • This vanadium oxide is the main component of the denitration catalyst of the present invention, and may contain other substances within the range that does not impair the effects of the present invention.
  • vanadium pentoxide conversion it is preferable that the content is 50 wt% or more. More preferably, vanadium oxide is present in the denitration catalyst of the present invention in an amount of 60 wt% or more in terms of vanadium pentoxide.
  • the denitration catalyst of the present invention has a second metal oxide content of 1 wt% or more and 40 wt% or less, but it has been conventionally used by including such a second metal oxide.
  • a higher denitration effect can be exhibited even in a low temperature environment.
  • impurities enter into the denitration catalyst of the present invention an amorphous part is generated in the denitration catalyst, so that the crystal structure is not continuous, and the lines and planes in the crystal lattice are distorted, thereby exhibiting a high denitration effect.
  • the higher the amount of the oxide of the second metal as the impurity the higher the denitration effect will be exhibited.
  • the coexistence of water is present.
  • the NO conversion rate was 79% to 100%, and when it was in the presence of water, the NO conversion rate was 38% to 90%.
  • a selective catalytic reduction reaction at a reaction temperature of 200° C. or less using a denitration catalyst having a cobalt oxide content of 0 wt% as the oxide of the second metal 76% NO was obtained in the absence of water.
  • the conversion rate and the NO conversion rate of 32% were only shown in the presence of water.
  • the denitration catalyst of the present invention has the second metal oxide content of 1 wt% or more and 40 wt% or less, but it is preferably 3 wt% or more and 38 wt% or less. Further, the content of the oxide of the second metal is more preferably 3 wt% or more and 10 wt% or less. Further, the content of the oxide of the second metal is more preferably 5 wt% or more and 10 wt% or less. Further, the content of the oxide of the second metal is more preferably 5 wt% or more and 8 wt% or less. The oxide content of the second metal is more preferably 6 wt% or more and 8 wt% or less. Further, the content of the oxide of the second metal is more preferably 6 wt% or more and 7 wt% or less.
  • the second metal is at least one metal element selected from the group consisting of Co, W, Mo, Nb, Ce, Sn, Ni and Fe.
  • the crystal structure of vanadium oxide is disturbed, and Lewis acidity can be enhanced.
  • Co, Mo, Ce, Sn, Ni, and Fe it accelerates the redox cycle of V 2 O 5 .
  • Co is known to have a strong oxidizing power.
  • W, Mo, and Nb functions as a solid acid and provides an adsorption site for ammonia, so that ammonia can efficiently contact and react with NO.
  • the selective catalytic reduction reaction at a reaction temperature of 200° C. or less using a denitration catalyst having a molybdenum oxide content of 5.4 wt% as the second metal oxide The NO conversion rate of 97% was shown without coexistence, and the NO conversion rate of 62% was shown without water coexistence.
  • the selective catalytic reduction reaction at a reaction temperature of 200 ° C. or lower using a denitration catalyst having a niobium pentoxide content of 5.0 wt% as the oxide of the second metal the water content is reduced.
  • the NO conversion rate of 96.7% was shown when not coexisting, and the NO conversion rate was 61.7% when not coexisting with water.
  • the NO conversion rate of 89.8% was shown when not coexisting, and the NO conversion rate was 52.9% when not coexisting with water.
  • in the embodiment of the present invention in the selective catalytic reduction reaction at a reaction temperature of 200° C.
  • the denitration catalyst of the present invention is preferably used for denitration at 300°C or lower. This is because the denitration catalyst of the present invention has a firing temperature of 300°C.
  • the denitration catalyst of the present invention exerted a high denitration effect in the selective catalytic reduction reaction at a reaction temperature of 200° C. or lower, so that the denitration catalyst of the present invention It can be used for denitration. Since oxidation of SO 2 to SO 3 does not occur at 200° C. or lower, as was found in Patent Document 2 described above, during selective catalytic reduction reaction at 200° C. or lower, SO 2 is converted to SO 3 Not accompanied by oxidation.
  • the denitration catalyst of the present invention is preferably used for denitration at 300° C. or lower, but may be preferably used for denitration at 200° C. or lower, more preferably, the reaction temperature is It may be used for denitration at 100 to 200°C. More preferably, it may be used for denitration at a reaction temperature of 160-200 ° C. Alternatively, it may be used for denitration with a reaction temperature of 80-150 ° C.
  • the denitration catalyst of the present invention preferably further contains carbon.
  • the carbon content is preferably 0.05 wt% or more.
  • the carbon content may be 0.07 wt% or more. More preferably, the carbon content may be 0.11 wt% or more. More preferably, the carbon content may be 0.12 wt% or more. More preferably, the carbon content may be 0.14 wt% or more. More preferably, the carbon content may be 0.16 wt% or more. More preferably, the carbon content may be 0.17 wt% or more. More preferably, the carbon content may be 0.70 wt% or more.
  • a denitration catalyst containing vanadium oxide as a main component wherein the content of the oxide of the second metal is 1 wt% or more and 40 wt% or less, and the second metal is Co, W, Mo, Nb,
  • a method for producing a denitration catalyst that is at least one metal element selected from the group consisting of Ce, Sn, Ni, and Fe will be described.
  • the above method for producing a denitration catalyst includes a step of calcining a mixture of vanadate, a chelate compound, and a compound of a second metal.
  • vanadate for example, ammonium vanadate, magnesium vanadate, strontium vanadate, barium vanadate, zinc vanadate, lead vanadate, lithium vanadate, etc. may be used.
  • the chelate compound include those having a plurality of carboxyl groups such as oxalic acid and citric acid, those having a plurality of amino groups such as acetylacetonate and ethylenediamine, and those having a plurality of hydroxyl groups such as ethylene glycol. Etc. may be used.
  • the compound of the second metal may be a chelate complex, a hydrate, an ammonium compound or a phosphoric acid compound.
  • the chelate complex may be, for example, a complex such as oxalic acid or citric acid.
  • the hydrate for example, (NH 4) may be 10 W 12 O 41 ⁇ 5H 2 O and H 3 PW 12 O 40 ⁇ nH 2 O.
  • the ammonium compound for example, (NH 4) may be 10 W 12 O 41 ⁇ 5H 2 O.
  • Examples of the phosphoric acid compound may be, for example, H 3 PW 12 O 40 ⁇ nH 2 O.
  • the above mixture further contains ethylene glycol.
  • the denitration catalyst produced by these methods can exhibit a high denitration effect even in a low temperature environment as compared with denitration catalysts such as vanadium/titanium catalysts that have been conventionally used.
  • denitration catalysts such as vanadium/titanium catalysts that have been conventionally used.
  • the denitration catalyst prepared by the method of calcining a mixture of ammonium vanadate, oxalic acid, and an oxalic acid complex of a second metal has a denitration rate of 74.5 to 100% in the absence of water.
  • the NO conversion was 33.9 to 90% in the presence of water.
  • the denitration catalyst produced by the method in which the above mixture further contains ethylene glycol has a NO conversion rate of 100% in the absence of water and an NO conversion rate of 89% in the presence of water. Indicated.
  • a denitration catalyst manufactured by a method not including such a step for example, ammonium vanadate and oxalic acid are mixed, but a method of firing without mixing the oxide of the second metal is used.
  • the denitration catalyst thus obtained showed a NO conversion of 76% in the absence of water and a NO conversion of 32% in the presence of water.
  • the above-mentioned firing is preferably performed at a temperature of 270° C. or lower.
  • the structure of the vanadium pentoxide crystal contained in the denitration catalyst is locally disordered by firing at a temperature of 270° C. or lower, which is lower than the normal 300° C., Although a high denitration effect can be exerted, it is speculated that a high denitration effect is exerted particularly by the appearance of sites lacking oxygen atoms in the crystal structure of vanadium pentoxide. Note that the “site devoid of oxygen atoms” is also referred to as “oxygen defect site”.
  • the denitration catalyst prepared in this manner is a denitration catalyst containing vanadium oxide as a main component, wherein the content of the oxide of the second metal is 1 wt% or more and 40 wt% or less, and the second metal Is at least one metal element selected from the group consisting of Co, W, Mo, Nb, Ce, Sn, Ni, and Fe.
  • the denitration catalyst containing vanadium as a main component, wherein the content of the oxide of the second metal is 1 wt% or more and 40 wt% or less, It is assumed that the second metal is at least one metal element selected from the group consisting of Co, W, Mo, Nb, Ce, Sn, Ni and Fe.
  • the denitration catalyst in the case of a selective catalytic reduction reaction using ammonia as a reducing agent at a reaction temperature of 200 ° C. or lower, the effect that the denitration efficiency at a low temperature is higher can be exhibited as compared with the prior art. Further, this denitration catalyst easily adsorbs NO and can exhibit a higher NO conversion rate.
  • the denitration catalyst according to the above embodiment is preferably used for denitration at 300°C or lower.
  • a high denitration effect is brought about without oxidizing SO 2 .
  • the denitration catalyst according to the above embodiment preferably further contains carbon.
  • the denitration catalyst according to the above-described embodiment can exhibit a NO conversion rate of 100% or more under the condition that it does not coexist with water.
  • the carbon content is preferably 0.05 wt% or more.
  • the denitration catalyst according to the above-described embodiment can exhibit a NO conversion rate of 100% or more under the condition that it does not coexist with water.
  • the method for producing a denitration catalyst according to the above embodiment preferably includes a step of calcining a mixture of vanadate, a chelate compound, and the compound of the second metal.
  • the denitration catalyst according to the above embodiment contains the second metal, and the denitration effect in the selective catalytic reduction reaction at a reaction temperature of 200° C. or less using the denitration catalyst according to the above embodiment is improved.
  • the above mixture preferably further contains ethylene glycol.
  • the denitration catalyst according to the above embodiment contains carbon and the second metal, and the denitration effect in the selective catalytic reduction reaction at the reaction temperature of 200° C. or less using the denitration catalyst according to the above embodiment is improved. To do.
  • the firing step in the above manufacturing method is preferably a firing step at a temperature of 270° C. or lower.
  • Example 1 4.96 g (42.4 mmol) of ammonium vanadate (NH 4 VO 3 ) and 11.5 g (127.6 mmol) of oxalic acid ((COOH) 2 ) were dissolved in pure water to synthesize a precursor complex.
  • a oxalic acid complex of cobalt (Co) which is a second metal, is added so that cobalt (Co) is 3.5 mol% in terms of metal atom, that is, Co 3 O in terms of metal oxide. 4 was added so as to be 3.1 wt %.
  • the resulting vanadium - 4 hours at a temperature of 300 ° C. by an electric furnace heterogeneous metal complex mixture, by firing twice, to obtain a denitration catalyst of vanadium pentoxide containing cobalt (Co) (V 2 O 5 ) ..
  • Example 2 4.96 g (42.4 mmol) of ammonium vanadate (NH 4 VO 3 ) and 11.5 g (127.6 mmol) of oxalic acid ((COOH) 2 ) were dissolved in pure water to synthesize a precursor complex.
  • the oxalic acid complex of tungsten (W) which is the second metal, is added so that the tungsten (W) is 3.5 mol% in terms of metal atom, that is, WO 3 is converted into metal oxide. It was added so as to be 8.4 wt%.
  • the resulting vanadium - 4 hours at a temperature of 300 ° C. by an electric furnace heterogeneous metal complex mixture, by firing twice, to obtain a denitration catalyst of vanadium pentoxide containing tungsten (W) (V 2 O 5 ) ..
  • Example 3 4.96 g (42.4 mmol) of ammonium vanadate (NH 4 VO 3 ) and 11.5 g (127.6 mmol) of oxalic acid ((COOH) 2 ) were dissolved in pure water to synthesize a precursor complex.
  • the oxalic acid complex of molybdenum (Mo) which is the second metal, has molybdenum (Mo) of 3.5 mol% in terms of metal atoms, that is, MoO 3 in terms of metal oxides. It was added so as to be 5.4 wt%.
  • the resulting vanadium - 4 hours at a temperature of 300 ° C. by an electric furnace heterogeneous metal complex mixture, by firing twice, to obtain a denitration catalyst of vanadium pentoxide containing molybdenum (Mo) (V 2 O 5 ) ..
  • Example 4 4.96 g (42.4 mmol) of ammonium vanadate (NH 4 VO 3 ) and 11.5 g (127.6 mmol) of oxalic acid ((COOH) 2 ) were dissolved in pure water to synthesize a precursor complex.
  • the obtained vanadium-different metal complex mixture was baked twice in an electric furnace at a temperature of 300° C. for 4 hours to obtain a vanadium pentoxide (V 2 O 5 ) denitration catalyst containing niobium (Nb). ..
  • Example 5 4.96 g (42.4 mmol) of ammonium vanadate (NH 4 VO 3 ) and 11.5 g (127.6 mmol) of oxalic acid ((COOH) 2 ) were dissolved in pure water to synthesize a precursor complex. With respect to this precursor complex, an oxalic acid complex of cesium (Ce), which is the second metal, was added so that cesium (Ce) would be 3.5 mol% in terms of metal atom, that is, CeO 2 in terms of metal oxide. It was added so as to be 6.4 wt%. The vanadium-dissimilar metal complex mixture thus obtained was calcined twice in an electric furnace at a temperature of 300° C. for 4 hours to obtain a vanadium pentoxide (V 2 O 5 ) denitration catalyst containing cesium (Ce). ..
  • V 2 O 5 vanadium pentoxide
  • Example 6 4.96 g (42.4 mmol) of ammonium vanadate (NH 4 VO 3 ) and 11.5 g (127.6 mmol) of oxalic acid ((COOH) 2 ) were dissolved in pure water to synthesize a precursor complex.
  • the oxalic acid complex of the second metal tin (Sn) is added to the precursor complex so that tin (Sn) is 3.5 mol% in terms of metal atom, that is, SnO 2 is in terms of metal oxide. It was added so as to be 5.6 wt%.
  • the resulting vanadium - 4 hours at a temperature of 300 ° C. by an electric furnace heterogeneous metal complex mixture, by firing twice, to obtain a denitration catalyst of vanadium pentoxide containing tin (Sn) (V 2 O 5 ) ..
  • Example 7 4.96 g (42.4 mmol) of ammonium vanadate (NH 4 VO 3 ) and 11.5 g (127.6 mmol) of oxalic acid ((COOH) 2 ) were dissolved in pure water to synthesize a precursor complex.
  • 0.113 g of nickel (Ni) as a second metal as nickel carbonate and 3.5 mol% of nickel (Ni) in terms of metal atoms, that is, NiO in terms of metal oxides. was added so as to be 2.9 wt %.
  • the vanadium-different metal complex mixture thus obtained was calcined twice in an electric furnace at a temperature of 300° C. for 4 hours to obtain a vanadium pentoxide (V 2 O 5 ) denitration catalyst containing nickel (Ni). ..
  • Example 8 4.96 g (42.4 mmol) of ammonium vanadate (NH 4 VO 3 ) and 11.5 g (127.6 mmol) of oxalic acid ((COOH) 2 ) were dissolved in pure water to synthesize a precursor complex.
  • the oxalic acid complex of iron (Fe) which is the second metal, is added so that iron (Fe) is 3.5 mol% in terms of metal atom, that is, Fe 2 O in terms of metal oxide. 3 was added so as to be 3.1 wt %.
  • the resulting vanadium - 4 hours at a temperature of 300 ° C. by an electric furnace heterogeneous metal complex mixture, by firing twice, to obtain a denitration catalyst of vanadium pentoxide containing iron (Fe) (V 2 O 5 ) ..
  • NO conversion rate was calculated by the following formula (1). Note that NO in is the NO concentration at the reaction tube inlet, and NO out is the NO concentration at the reaction tube outlet.
  • Table 2 shows the NO conversion rates of each vanadium pentoxide catalyst in both the case where water does not coexist and the case where water coexists.
  • FIG. 1 is a graph of this Table 2.
  • the denitration catalyst of the example In both the case where water did not coexist and the case where water coexisted, the denitration catalyst of the example generally showed a higher NO conversion rate than the denitration catalyst of the comparative example.
  • the denitration catalyst obtained by adding cobalt, tungsten, molybdenum, and niobium to ammonium vanadate and firing showed a high NO conversion rate.
  • Example 3 adding molybdenum
  • Example 1 adding cobalt
  • Example 1 (adding cobalt) showed the highest NO conversion rate, so the amount of cobalt added was changed. As a result, vanadium catalysts according to the following examples were produced.
  • Example 9 Ammonium vanadate (NH 4 VO 3 ) and oxalic acid ((COOH) 2 ) were dissolved in pure water to synthesize a precursor complex. An oxalic acid complex of the second metal, cobalt (Co), was added to this precursor complex such that Co 3 O 4 was 1 wt% in terms of metal oxide. The resulting vanadium - 4 hours at a temperature of 300 ° C. The cobalt complex mixture by an electric furnace and fired twice to obtain a denitration catalyst of vanadium pentoxide containing cobalt (Co) (V 2 O 5 ).
  • Co vanadium pentoxide containing cobalt
  • Example 10 Ammonium vanadate (NH 4 VO 3 ) and oxalic acid ((COOH) 2 ) were dissolved in pure water to synthesize a precursor complex. An oxalic acid complex of cobalt (Co), which is the second metal, was added to this precursor complex such that Co 3 O 4 was 3 wt% in terms of metal oxide. The resulting vanadium - 4 hours at a temperature of 300 ° C. The cobalt complex mixture by an electric furnace and fired twice to obtain a denitration catalyst of vanadium pentoxide containing cobalt (Co) (V 2 O 5 ).
  • Co cobalt
  • Example 11 Ammonium vanadate (NH 4 VO 3 ) and oxalic acid ((COOH) 2 ) were dissolved in pure water to synthesize a precursor complex. An oxalic acid complex of cobalt (Co), which is the second metal, was added to this precursor complex such that Co 3 O 4 was 5 wt% in terms of metal oxide. The resulting vanadium - 4 hours at a temperature of 300 ° C. The cobalt complex mixture by an electric furnace and fired twice to obtain a denitration catalyst of vanadium pentoxide containing cobalt (Co) (V 2 O 5 ).
  • Co cobalt
  • Example 12 Ammonium vanadate (NH 4 VO 3 ) and oxalic acid ((COOH) 2 ) were dissolved in pure water to synthesize a precursor complex. To this precursor complex, an oxalic acid complex of the second metal, cobalt (Co), was added so that Co 3 O 4 was 6 wt% in terms of metal oxide. The resulting vanadium - 4 hours at a temperature of 300 ° C. The cobalt complex mixture by an electric furnace and fired twice to obtain a denitration catalyst of vanadium pentoxide containing cobalt (Co) (V 2 O 5 ).
  • Co vanadium pentoxide containing cobalt
  • Example 13 Ammonium vanadate (NH 4 VO 3 ) and oxalic acid ((COOH) 2 ) were dissolved in pure water to synthesize a precursor complex. An oxalic acid complex of the second metal, cobalt (Co), was added to this precursor complex such that Co 3 O 4 was 7 wt% in terms of metal oxide. The resulting vanadium - 4 hours at a temperature of 300 ° C. The cobalt complex mixture by an electric furnace and fired twice to obtain a denitration catalyst of vanadium pentoxide containing cobalt (Co) (V 2 O 5 ).
  • Co cobalt
  • Example 14 Ammonium vanadate (NH 4 VO 3 ) and oxalic acid ((COOH) 2 ) were dissolved in pure water to synthesize a precursor complex. An oxalic acid complex of the second metal, cobalt (Co), was added to this precursor complex so that Co 3 O 4 was 8 wt% in terms of metal oxide. The resulting vanadium - 4 hours at a temperature of 300 ° C. The cobalt complex mixture by an electric furnace and fired twice to obtain a denitration catalyst of vanadium pentoxide containing cobalt (Co) (V 2 O 5 ).
  • Co cobalt
  • Example 15 Ammonium vanadate (NH 4 VO 3 ) and oxalic acid ((COOH) 2 ) were dissolved in pure water to synthesize a precursor complex.
  • a oxalic acid complex which is a precursor of cobalt (Co), which is a second metal, was added so that Co 3 O 4 was 10 wt% in terms of metal oxide.
  • the cobalt complex mixture by an electric furnace and fired twice to obtain a denitration catalyst of vanadium pentoxide containing cobalt (Co) (V 2 O 5 ).
  • Table 3 shows the charged amount of the precursor in Example 9 to Example 15 when cobalt was introduced.
  • the NH 3 —SCR reaction was carried out at a reaction temperature of 150° C. using a fixed bed flow type catalytic reactor.
  • NO was analyzed by Jasco FT-IR-4700. Further, the NO conversion rate was calculated by the above equation (1).
  • Table 4 shows the NO conversion of each vanadium oxide catalyst both in the absence of water and in the presence of water.
  • FIG. 2 is a graph of this Table 4.
  • the denitration catalysts of the examples all showed higher NO conversion than the denitration catalysts of the comparative examples both in the absence of water and in the presence of water. Particularly, in the case where water does not coexist, Example 12 (6 wt%) and Example 13 (7 wt%) show the highest NO conversion, and in the case where water coexists, Example 14 (8 wt%). The highest NO conversion was shown.
  • Powder X-ray diffraction> (Diffraction method) The powder X-ray diffraction was measured by Rigaku smart lab using Cu-K ⁇ .
  • FIG. 3 shows powder XRD of Example 9 (1 wt %), Example 10 (3 wt %), Example 12 (6 wt %), Example 15 (10 wt %), and Comparative Example 1 (None: 0 wt %).
  • X-Ray Diffraction pattern is shown. It was shown that V 2 O 5, which is a stable phase, is present as a main component, and that when the addition rate of Co is increased, a Co 3 O 4 phase also appears.
  • Raman spectra were measured by Raman spectroscopy to analyze the crystal structure of each vanadium pentoxide catalyst. More specifically, a small amount of each catalyst sample was placed on a slide glass, and the Raman spectrum was measured by a Raman spectroscope. A NRS-4100 Raman spectrophotometer manufactured by JASCO Corporation was used as a measuring instrument.
  • FIG. 4 shows the Raman spectrum of each catalyst. It was shown that when the amount of Co added was increased, the crystal structure of V 2 O 5 collapsed and the pattern strength weakened.
  • Example 9 ⁇ 2.2.4 X-ray photoelectron spectrum (XPS) measurement> (Measuring method) To analyze the electronic state of Example 9 (1 wt%), Example 10 (3 wt%), Example 12 (6 wt%), Example 15 (10 wt%), and Comparative Example 1 (None: 0 wt%). , X-ray photoelectron spectrum (XPS: X-Ray Photoelectron Spectrom) was measured. More specifically, powder samples of the catalysts of Examples and Comparative Examples were fixed to a sample holder using a carbon tape, and X-ray photoelectron spectra were measured. As a measuring device, a JPS-9010MX photoelectron spectrometer manufactured by JEOL Ltd. was used.
  • FIG. 5A shows an XPS spectrum in the V2p region.
  • FIG. 5B shows an XPS spectrum in the Co2p region. It was shown that increasing the added amount of Co increased the V 4+ and Co 2+ components.
  • Example 2 in the case where water coexists, Example 2 (adding tungsten) showed the second highest NO conversion rate, so the amount of tungsten added was changed.
  • a vanadium catalyst according to each of the following examples was produced. It should be noted that not only the amount of tungsten added is changed, but also when K 2 WO 4 is used as the precursor and when H 3 PW 12 O 40 ⁇ nH 2 O is used as a precursor, tungsten is used as described later. The amount added was changed.
  • Example 16 To a mixture of ammonium vanadate (NH 4 VO 3 ), 43.9 mmol of K 2 WO 4 and 20 ml of pure water, 11.9 g (131.7 mmol) of oxalic acid ((COOH) 2 ) was added, and the mixture was cooled to room temperature. After stirring for 10 minutes at 70° C. for 12 hours. By firing this precursor sample at 300° C. for 4 hours, a denitration catalyst of vanadium pentoxide (V 2 O 5 ) containing tungsten (W) was obtained. The amount of ammonium vanadate as a raw material was adjusted so that the total weight ratio of WO 3 in the produced denitration catalyst was 4.9 wt%.
  • V 2 O 5 vanadium pentoxide
  • Example 17 To a mixture of ammonium vanadate (NH 4 VO 3 ), 43.9 mmol of K 2 WO 4 and 20 ml of pure water, 11.9 g (131.7 mmol) of oxalic acid ((COOH) 2 ) was added, and the mixture was cooled to room temperature. After stirring for 10 minutes at 70° C. for 12 hours. By firing this precursor sample at 300° C. for 4 hours, a denitration catalyst of vanadium pentoxide (V 2 O 5 ) containing tungsten (W) was obtained. The amount of ammonium vanadate as a raw material was adjusted so that the total weight ratio of WO 3 in the produced denitration catalyst was 11.8 wt %.
  • V 2 O 5 vanadium pentoxide
  • Example 18 11.9 g (131.7 mmol) of oxalic acid was added to a mixture of ammonium vanadate (NH 4 VO 3 ), 43.9 mmol of K 2 WO 4 and 20 ml of pure water, and the mixture was stirred at room temperature for 10 minutes. , 70 ° C. for 12 hours. By firing this precursor sample at 300° C. for 4 hours, a denitration catalyst of vanadium pentoxide (V 2 O 5 ) containing tungsten (W) was obtained. The amount of ammonium vanadate as a raw material was adjusted so that the total weight ratio of WO 3 in the produced denitration catalyst was 22.1 wt%.
  • V 2 O 5 vanadium pentoxide
  • Table 5 shows the amount of the precursor charged at the time of introducing tungsten in Examples 16 to 18 and Comparative Example 2.
  • Example 19 Ammonium vanadate (NH 4 VO 3), and H 3 PW 12 O 40 ⁇ nH 2 O, a mixture of pure water 20 ml, oxalic acid ((COOH) 2) a 11.9g (131.7mmol) was added The mixture was stirred at room temperature for 10 minutes and then at 70° C. for 12 hours. By firing this precursor sample at 300° C. for 4 hours, a denitration catalyst of vanadium pentoxide (V 2 O 5 ) containing tungsten (W) was obtained. Incidentally, the total weight ratio of WO 3 in the denitration catalyst to be generated, so that the 38.4Wt%, and adjust the amount of ammonium vanadate and H 3 PW 12 O 40 ⁇ nH 2 O as raw materials.
  • V 2 O 5 vanadium pentoxide
  • W tungsten
  • Table 6 shows the amount of precursor charged at the time of introducing tungsten in Example 19 and Comparative Examples 3 to 6. ⁇ 3.2 Evaluation> ⁇ 3.2.1 Outline> Under the conditions shown in Table 1 above, the NH 3- SCR reaction was carried out at a reaction temperature of approximately 150 ° C. using a fixed bed flow type catalytic reaction apparatus. Of the gas that passed through the catalyst layer, NO was analyzed by Jasco FT-IR-4700. Further, the NO conversion rate was calculated by the above equation (1).
  • Table 7 shows the NO conversion rates of each vanadium pentoxide catalyst in both the case where water does not coexist and the case where water coexists.
  • FIG. 6 is a graph of Table 7.
  • Comparative Example 1 having a tungsten content of 0 wt% and Comparative Examples 2-5 and 7 having a tungsten content of 39 wt% to 100 wt% both in the case where water does not coexist and in the case where water coexists.
  • the addition amount of tungsten between 10 and 38 wt% is effective.
  • FIG. 7 shows Example 16 (4.9 wt %), Example 17 (11.8 wt %), Example 18 (22.1 wt %), Comparative Example 1 (0 wt %), and Comparative Example 2 (100 wt %).
  • 3 shows a powder XRD pattern.
  • FIG. 8 shows the percentage (%) of the tungsten element when the horizontal axis represents mol% of K 2 WO 4 .
  • Table 8 shows the NO conversion rates of each vanadium pentoxide catalyst in both the case where water does not coexist and the case where water coexists.
  • FIG. 9 is a graph of this Table 6.
  • Powder X-ray diffraction and elemental analysis> Measured method
  • a measurement was performed using Cu—K ⁇ by Rigaku smart lab.
  • elemental analysis by SEM-EDS was performed.
  • FIG. 10 shows Example 19 (38.4 wt %), Comparative Example 4 (61.7 wt %), Comparative Example 5 (77.3 wt %), Comparative Example 6 (84.4 wt %), Comparative Example 7 (100 wt %).
  • FIG. 11 shows the proportion (%) of the tungsten element when the horizontal axis is mol% of H 3 PW 12 O 40 ⁇ nH 2 O.
  • Table 9 shows the NO conversion rates of each vanadium pentoxide catalyst in both the case where water does not coexist and the case where water coexists.
  • FIG. 12 is a graph of this Table 9.
  • Example 4 shows the second highest NO conversion rate, and water coexists.
  • the vanadium catalyst according to each of the following examples was produced by changing the addition amount of niobium.
  • Example 20 Ammonium vanadate (NH 4 VO 3 ) and oxalic acid ((COOH) 2 ) were dissolved in pure water to synthesize a precursor complex.
  • a oxalic acid complex of niobium (Nb) was added so that Nb 2 O 5 was 1.8 wt% in terms of metal oxide.
  • the obtained vanadium-niobium complex mixture was calcined twice at a temperature of 300° C. for 4 hours in an electric furnace to obtain a denitration catalyst of vanadium pentoxide (V 2 O 5 ) containing niobium (Nb).
  • Example 21 Ammonium vanadate (NH 4 VO 3 ) and oxalic acid ((COOH) 2 ) were dissolved in pure water to synthesize a precursor complex.
  • a oxalic acid complex of niobium (Nb) was added so that Nb 2 O 5 was 5.2 wt% in terms of metal oxide.
  • the obtained vanadium-niobium complex mixture was calcined twice at a temperature of 300° C. for 4 hours in an electric furnace to obtain a denitration catalyst of vanadium pentoxide (V 2 O 5 ) containing niobium (Nb).
  • Example 22 Ammonium vanadate (NH 4 VO 3 ) and oxalic acid ((COOH) 2 ) were dissolved in pure water to synthesize a precursor complex.
  • a oxalic acid complex of niobium (Nb) which is a second metal, was added so that Nb 2 O 5 was 8.5 wt% in terms of metal oxide.
  • the cobalt complex mixture by an electric furnace and fired twice to obtain a denitration catalyst of vanadium pentoxide containing cobalt (Co) (V 2 O 5 ).
  • Example 23 Ammonium vanadate (NH 4 VO 3 ) and oxalic acid ((COOH) 2 ) were dissolved in pure water to synthesize a precursor complex.
  • a oxalic acid complex of niobium (Nb) which is a second metal, was added so that Nb 2 O 5 was 11.7 wt% in terms of metal oxide.
  • Example 24 Ammonium vanadate (NH 4 VO 3 ) and oxalic acid ((COOH) 2 ) were dissolved in pure water to synthesize a precursor complex.
  • a oxalic acid complex of niobium (Nb) which is a second metal, was added so that Nb 2 O 5 was 16.2 wt% in terms of metal oxide.
  • Table 10 shows the amount of the precursor charged at the time of introducing niobium in Examples 20 to 24.
  • ⁇ 4.2 Evaluation> ⁇ 4.2.1 NO conversion> (Measuring method) Under the conditions shown in Table 1 above, the NH 3- SCR reaction was carried out at a reaction temperature of 150 ° C. using a fixed-bed flow catalytic reactor. Of the gas that passed through the catalyst layer, NO was analyzed by Jasco FT-IR-4700. Further, the NO conversion rate was calculated by the above equation (1).
  • Table 11 shows the NO conversion of each vanadium oxide catalyst both in the absence of water and in the presence of water.
  • FIG. 13 is a graph of this table 11.
  • the denitration catalysts of the examples all showed higher NO conversion than the denitration catalysts of the comparative examples both in the absence of water and in the presence of water.
  • Example 22 9 wt%) showed the highest NO conversion
  • Example 21 5 wt%) showed the highest NO conversion. ..
  • Example 25 Ammonium vanadate (NH 4 VO 3 ) and oxalic acid were dissolved in pure water to synthesize a precursor complex. To this precursor complex, ethylene glycol and an oxalic acid complex which is a precursor of cobalt (Co) which is the second metal were added so that Co 3 O 4 was 6 wt% in terms of metal oxide. The obtained catalyst skeleton was fired in an electric furnace at a temperature of 270° C. for 2 hours to obtain a vanadium oxide denitration catalyst containing carbon and cobalt (Co). In addition, Table 12 below shows the charged amount of the precursor when cobalt was introduced in Example 25.
  • each vanadium pentoxide catalyst When measuring the carbon content of each vanadium pentoxide catalyst, the carbon content was quantified by elemental analysis of C (carbon), H (hydrogen), and N (nitrogen). More specifically, each denitration catalyst is completely combusted and decomposed in a high-temperature reaction tube inside the CE-440F manufactured by Starbucks Analytical Co., and C, H, and N, which are main constituent elements, are CO 2 , H 2 O, After conversion to N 2 , these three components were sequentially quantified by three thermal conductivity detectors, and the contents of C, H, and N in the constituent elements were measured.
  • Table 13 shows the NO conversion rates of the vanadium pentoxide catalysts of Comparative Example 1, Example 12, and Example 25 in both the case where water does not coexist and the case where water coexists.
  • FIG. 14 is a graph of this table 13.
  • the denitration catalyst of Example 25 showed the highest NO conversion rate in both the case where water did not coexist and the case where water coexisted.

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Abstract

La présente invention concerne un catalyseur dans lequel, dans une réaction de réduction catalytique sélective dans laquelle de l'ammoniac est utilisé comme agent réducteur, l'efficacité de dénitration à basses températures est meilleure que l'état de la technique. Ce catalyseur de dénitration a un oxyde de vanadium en tant que composant principal, dans lequel : la teneur d'un oxyde d'un second métal est de 1 à 40 % en poids inclus; et le second métal étant au moins un élément métallique choisi dans le groupe constitué par Co, W, Mo, Nb, Ce, Sn, Ni, et Fe.
PCT/JP2019/009201 2019-03-07 2019-03-07 Catalyseur de dénitration et son procédé de fabrication WO2020179076A1 (fr)

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JP2019538453A JP7388653B2 (ja) 2019-03-07 2019-03-07 脱硝触媒、及びその製造方法
PCT/JP2019/009201 WO2020179076A1 (fr) 2019-03-07 2019-03-07 Catalyseur de dénitration et son procédé de fabrication
CN202080019195.8A CN113874109A (zh) 2019-03-07 2020-03-05 脱硝催化剂及其制造方法
EP20767017.5A EP3936706A4 (fr) 2019-03-07 2020-03-05 Système de combustion
SG11202109733U SG11202109733UA (en) 2019-03-07 2020-03-05 Denitration catalyst and method for manufacturing same
PCT/JP2020/009542 WO2020179891A1 (fr) 2019-03-07 2020-03-05 Catalyseur de dénitration et son procédé de fabrication
JP2020549726A JP7429012B2 (ja) 2019-03-07 2020-03-05 脱硝触媒、及びその製造方法
US17/436,958 US20220168712A1 (en) 2019-03-07 2020-03-05 Denitration catalyst and method for manufacturing same
CN202080019137.5A CN113631804A (zh) 2019-03-07 2020-03-05 燃烧***
EP20766854.2A EP3936230A4 (fr) 2019-03-07 2020-03-05 Catalyseur de dénitration et son procédé de fabrication
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2020179891A1 (fr) * 2019-03-07 2020-09-10
CN113926466A (zh) * 2021-11-23 2022-01-14 商河县格尔环保科技服务中心 一种脱硝催化剂及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5055577A (fr) * 1973-09-18 1975-05-15
JPH01258746A (ja) * 1988-04-08 1989-10-16 Mitsubishi Heavy Ind Ltd 触媒フイルター及びその製造方法
JP2001509432A (ja) * 1997-07-10 2001-07-24 エス ケー コーポレイション 窒素酸化物の除去のための選択的触媒還元及びその触媒体
JP2003053147A (ja) * 2001-08-22 2003-02-25 Nkk Corp 有機塩素化合物、窒素酸化物の除去方法
JP6093101B1 (ja) * 2016-09-12 2017-03-08 中国電力株式会社 脱硝触媒、及びその製造方法
CN107349935A (zh) * 2017-08-31 2017-11-17 复旦大学 一种低温脱硝催化剂及其制备方法和应用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103623814B (zh) * 2012-08-27 2016-08-17 中国科学院生态环境研究中心 一种用于氨选择性催化还原氮氧化物的锰钒复合氧化物催化剂
WO2020179891A1 (fr) * 2019-03-07 2020-09-10 中国電力株式会社 Catalyseur de dénitration et son procédé de fabrication

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5055577A (fr) * 1973-09-18 1975-05-15
JPH01258746A (ja) * 1988-04-08 1989-10-16 Mitsubishi Heavy Ind Ltd 触媒フイルター及びその製造方法
JP2001509432A (ja) * 1997-07-10 2001-07-24 エス ケー コーポレイション 窒素酸化物の除去のための選択的触媒還元及びその触媒体
JP2003053147A (ja) * 2001-08-22 2003-02-25 Nkk Corp 有機塩素化合物、窒素酸化物の除去方法
JP6093101B1 (ja) * 2016-09-12 2017-03-08 中国電力株式会社 脱硝触媒、及びその製造方法
CN107349935A (zh) * 2017-08-31 2017-11-17 复旦大学 一种低温脱硝催化剂及其制备方法和应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
INGLOT, A. ET AL.: "Phases in vanadium pentoxide- tungsten trioxide catalysts", JOURNAL OF THE CHEMICAL SOCIETY FARADAY TRANSACTIONS, vol. 91, 7 January 1995 (1995-01-07), pages 145 - 148, XP000485492, DOI: 10.1039/ft9959100145 *
NAJBAR, M. ET AL.: "Low-temperature reactivity of the surface species of vanadia-tungsta catalyst", SOLID STATE IONICS, vol. 141, no. 142, 1 May 2001 (2001-05-01), pages 499 - 506, XP085645831, DOI: 10.1016/S0167-2738(01)00780-9 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2020179891A1 (fr) * 2019-03-07 2020-09-10
JP7429012B2 (ja) 2019-03-07 2024-02-07 中国電力株式会社 脱硝触媒、及びその製造方法
CN113926466A (zh) * 2021-11-23 2022-01-14 商河县格尔环保科技服务中心 一种脱硝催化剂及其制备方法

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