WO2020059760A1 - Structure de catalyseur pour la purifier les gaz d'échappement - Google Patents

Structure de catalyseur pour la purifier les gaz d'échappement Download PDF

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Publication number
WO2020059760A1
WO2020059760A1 PCT/JP2019/036597 JP2019036597W WO2020059760A1 WO 2020059760 A1 WO2020059760 A1 WO 2020059760A1 JP 2019036597 W JP2019036597 W JP 2019036597W WO 2020059760 A1 WO2020059760 A1 WO 2020059760A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
plate
exhaust gas
flat
purifying
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Application number
PCT/JP2019/036597
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English (en)
Japanese (ja)
Inventor
啓一郎 甲斐
今田　尚美
清司 池本
加藤　泰良
Original Assignee
三菱日立パワーシステムズ株式会社
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Application filed by 三菱日立パワーシステムズ株式会社 filed Critical 三菱日立パワーシステムズ株式会社
Publication of WO2020059760A1 publication Critical patent/WO2020059760A1/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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths

Definitions

  • the present invention relates to an exhaust gas purifying plate catalyst element and an exhaust gas purifying catalyst unit. More specifically, the present invention relates to an exhaust gas purifying catalytic element having a low pressure loss and a high denitration efficiency, and an exhaust gas purifying catalytic unit obtained by stacking the elements so that a gas flow path is secured.
  • Nitrogen oxides in gas discharged from furnaces such as boilers in thermal power plants and various factories are decomposed in the presence of a denitration catalyst to purify exhaust gas.
  • Various denitration catalyst structures have been proposed to decompose nitrogen oxides in exhaust gas with high efficiency.
  • Patent Literature 1 discloses a flue gas denitration device used in a facility that generates exhaust gas containing sulfur oxides by combustion.
  • a flue gas denitration device at least one catalyst layer among a plurality of catalyst layers installed in a gas flow direction is used.
  • a catalyst structure obtained by laminating a plurality of catalyst elements having ridges formed of band-shaped protrusions and plate portions alternately at predetermined intervals, so that the ridges of adjacent catalyst elements are orthogonal to each other. has been disclosed.
  • Patent Literature 2 is a catalyst structure formed by stacking a large number of flat catalyst elements in which spacers formed of peaks and valleys are formed linearly at regular intervals in a gas flow direction on a flat plate, Concave portions are formed at predetermined intervals in the mountain-like portion and the valley-like portion, and a bar-shaped gas agitator is arranged in the concave portion so as to be located at the center of a flow path formed between the spacers.
  • An exhaust gas purifying catalyst structure is disclosed.
  • Patent Literature 3 is an exhaust gas purifying catalyst structure disposed in a frame adapted to an exhaust gas channel, and the catalyst structure is formed by alternately bending plate-shaped catalysts at predetermined intervals in opposite directions. Exhaust gas consisting of a stack of protruding parts or a plate-shaped catalyst having many peaks and valleys, and a gas dispersion made of a metal, ceramic or glass mesh having many holes penetrating on both sides. A purification catalyst structure is disclosed.
  • Patent Literature 4 discloses that a flat catalyst element including a flat portion, which is a main component, and a linear spacer portion including a ridge and a ridge, is provided with a gas flow path along the longitudinal direction of the spacer portion.
  • An exhaust gas purifying catalyst structure formed by stacking as described above, wherein the flat portion is a leg plate erected on the flat portion at a height lower than the height of the spacer portion based on the flat portion, and an upper side of the leg plate.
  • a catalyst structure for purifying exhaust gas which has at least one baffle portion composed of a top plate installed substantially parallel to a flat portion and capable of disturbing the gas flowing through the gas flow passage at the baffle portion. I have.
  • An object of the present invention is to provide a plate catalyst element for purifying exhaust gas having a low pressure loss and high denitration efficiency, and a catalyst unit for purifying exhaust gas obtained by stacking the elements so that a gas flow path is secured. It is.
  • a plate-shaped catalyst in which flat portions and spacer portions formed of ridges are alternately arranged, and a height level lower than the height of the ridges based on the flat portions and not parallel to the ridges
  • An exhaust gas purifying plate-shaped catalytic element having a band-shaped baffle portion extending in a direction above a flat portion.
  • the baffle portion is formed of a band member having a portion bent so as to be able to receive the ridges present in the plate-shaped catalyst.
  • An exhaust gas purifying catalyst unit obtained by stacking at least two plate-like exhaust gas purifying catalyst elements according to any one of the above [1] to [3] so as to secure a gas flow path. .
  • the exhaust gas purifying plate catalyst element and exhaust gas purifying catalyst unit of the present invention have low pressure loss, hardly accumulate dust, and can efficiently disturb the gas flow, and as a result, denitration per catalyst weight High rate.
  • the exhaust gas purifying plate catalyst element and the exhaust gas purifying catalyst unit of the present invention have higher denitration performance with the same amount of catalyst than conventional products, so that the amount of catalyst used can be significantly reduced.
  • since the installation conditions of the baffle unit can be arbitrarily changed according to the exhaust gas treatment conditions of the actual machine, it is possible to deal with a wide range of exhaust gas.
  • the exhaust gas purifying plate catalyst element and the exhaust gas purifying catalyst unit of the present invention can be preferably used particularly for treating a gas containing a relatively large amount of dust discharged from a coal-fired boiler.
  • FIG. 2 is a perspective view showing an example of a plate catalyst element for exhaust gas purification of the present invention.
  • FIG. 2 is a perspective view showing a baffle section 4 constituting the exhaust gas-purifying plate-like catalyst element shown in FIG. 1.
  • FIG. 2 is a perspective view showing a plate catalyst 1 constituting the exhaust gas purifying plate catalyst element shown in FIG. 1.
  • FIG. 2 is a perspective view for explaining a positional relationship of superposition of the exhaust-gas-purifying plate-like catalyst elements shown in FIG. 1.
  • FIG. 2 is a cross-sectional view showing a state in which the exhaust-gas-purifying plate-like catalyst elements shown in FIG. 1 are overlaid.
  • It is a perspective view showing an example of the catalyst unit for exhaust gas purification of the present invention. It is a conceptual diagram which shows the state of the gas flow between the superposed plate catalyst elements for exhaust gas purification.
  • the exhaust gas purifying plate catalyst element of the present invention has a plate catalyst 1 and a baffle portion 4. As shown in FIG. 3, the plate-shaped catalyst 1 has spacers 2 and flat portions 3 arranged alternately.
  • the flat portion 3 and the spacer portion 2 carry a catalyst.
  • the catalyst is not particularly limited as long as it is used for the denitration reaction.
  • a catalyst containing a catalyst component containing an element such as Ti, Mo, W, or V a catalyst containing a zeolite or an aluminosilicate which may support a noble metal element such as Cu or a base metal element such as Fe;
  • a mixed catalyst of a catalyst containing a catalyst component containing an element such as Ti and the above-mentioned catalyst containing zeolite or aluminosilicate can be used.
  • the base material on which the catalyst is supported examples include planar materials such as a metal flat plate, a woven wire mesh, a punching metal, an expanded metal (also called lath metal, metal lath), a wire mesh, a glass woven fabric, and a glass nonwoven fabric.
  • Stainless steel is preferably used for the substrate.
  • the flat base material can easily form the flat portion and the spacer portion by die bending (press bending) or the like.
  • the thickness of the planar substrate supporting the catalyst is not particularly limited, but is preferably 0.1 mm to 0.3 mm.
  • a paste-like composition containing a catalyst component (hereinafter, referred to as a catalyst paste) is placed on one surface of a flat lath metal base material, pressed with a roll or the like, then dried and dried.
  • a method comprising firing according to a method, applying a catalyst paste to one surface of a flat substrate made of glass fiber woven fabric, placing another flat substrate made of glass fiber woven fabric on the application surface, Lay the catalyst paste between the two substrates, apply the catalyst paste on both sides of the superposed substrate as needed, and crush it strongly with a roll etc. to immerse the catalyst paste into the substrate Then, it can be carried out by a method including drying and, if necessary, baking.
  • the catalyst layers are laminated on both sides of the flat substrate. It is preferable that the spaces between the meshes of the base material are also filled with the catalyst paste.
  • the thickness of the substrate on which the catalyst is supported is not particularly limited, but is preferably 0.2 to 2 mm.
  • the spacer portion serves as a spacer for securing a space in which gas can pass between the elements when a plurality of the exhaust-gas-purifying plate-like catalyst elements are stacked, that is, a gas flow path.
  • the spacer portion is formed of a ridge on which the catalyst is supported.
  • the cross-sectional shape of the ridge is not particularly limited. For example, a spacer portion having a mountain-shaped cross section made of an upwardly protruding ridge, a spacer portion 2 having a cross-sectional waveform formed of an upwardly protruding ridge and a downwardly protruding ridge, and the like can be given.
  • the spacer portion 2 can be formed by bending a planar base material.
  • the interval between the ridges is preferably 20 to 200 mm.
  • the width of one ridge is preferably 10 to 20 mm.
  • the total width of the downwardly projecting ridges and the upwardly projecting ridges is preferably 20 to 40 mm.
  • the height of the ridge with respect to the flat portion is preferably 4 to 10 mm.
  • the baffle part 4 is made of a band member.
  • the band member is stretched above the flat portion in a direction not parallel to the ridge, preferably at a right angle, at a height level lower than the height of the ridge relative to the flat portion.
  • the height level of the baffle portion is preferably 2/5 to 3/5 of the height of the ridge based on the flat portion.
  • the thickness of the baffle part is preferably 0.2 to 2 mm.
  • the surface of the baffle part 4 is arranged substantially parallel to the flat part, so that the area against which the gas flow collides can be reduced to the thickness of the band member.
  • the baffle portion may be formed of a band member having a portion bent so as to be able to receive a ridge existing in the exhaust-gas-purifying plate-like catalyst element.
  • the shape of the bent portion is not particularly limited as long as it can accept the ridge.
  • the bent portion 5 capable of receiving the upward ridge is bent in the same shape as the top shape of the upward ridge, and the bent portion 5 capable of receiving the downward ridge.
  • the portion 6 is bent into a rectangle with a width larger than the width of the ridge.
  • the width of the bent portion 6 in FIG. 2 is preferably 10 to 20 mm.
  • the length of the flat portion 7 of the baffle portion 4 can be appropriately selected according to the width of the gas flow path formed when the exhaust-gas-purifying plate-like catalyst elements are overlapped.
  • the band member can be formed of a flat plate such as a metal flat plate, a woven wire mesh, a punching metal, an expanded metal (also called a lath metal, a metal lath), a wire mesh, a glass woven fabric, or a glass nonwoven fabric.
  • a catalyst may be supported on the band member.
  • the catalyst to be supported may be the same as that described as the catalyst to be supported on the flat portion or the spacer portion.
  • the baffle portion is preferably made of a stainless steel plate or a member having a catalyst supported thereon, or a stainless steel expanded metal or a member having a catalyst supported thereon.
  • the band width D of the baffle part is preferably 10 to 30 mm.
  • the first baffle part is preferably installed at a distance of 100 to 300 mm, more preferably 150 to 200 mm away from the front edge of the plate catalyst element for exhaust gas purification, and the second baffle part is placed at a distance from the first baffle part. , Preferably 30 to 200 mm away behind. Further, the third and subsequent baffles may be provided at intervals of preferably 30 to 200 mm.
  • the baffle part in one exhaust gas purifying plate catalyst element is overlapped, the baffle part in the adjacent exhaust gas purifying plate catalyst element is located at the same position as viewed from the normal direction of the flat part. It may be installed or may be installed at a different position.
  • the spacer portion and the baffle portion of the exhaust-gas-purifying plate catalyst element are not particularly limited in the forming method, and can be formed, for example, as follows.
  • the plate-like catalyst 1 having a spacer portion having a corrugated cross section can be formed by press-bending a flat sheet-like base material on which a catalyst paste is carried.
  • a band member having a bent portion can be formed by press-bending a flat band-shaped base material on which the catalyst paste is carried so as to be able to receive the ridges of the spacer portion.
  • the exhaust gas purifying plate catalyst element of the present invention can be obtained.
  • the plate catalyst element for purifying exhaust gas obtained by such a method or the like can be appropriately cut into a size that can be accommodated in the frame 10.
  • the exhaust gas purifying catalyst unit of the present invention is formed by stacking at least two plate-like exhaust gas purifying catalytic elements of the present invention so as to secure a gas flow path.
  • the superposed exhaust-gas-purifying plate-like catalyst elements can be accommodated in the frame body 10 so as not to collapse.
  • the method of stacking the exhaust gas purifying plate catalyst elements is not particularly limited as long as a space through which gas can pass can be secured between the exhaust gas purifying plate catalyst elements.
  • the spacer portions having cross-sectional waveforms may be overlapped so as to be parallel to each other, may be overlapped so as to be perpendicular to each other, or may be overlapped so as to have an intermediate angle between parallel and right angles.
  • the stacking may be performed so that the spacers do not fit each other, that is, the stacking may be performed so that the spacer in one exhaust gas-purifying plate catalyst element is in contact with the flat portion in the adjacent exhaust gas-purifying plate catalyst element. It is preferable from the viewpoint of obtaining a high aperture ratio and a high denitration efficiency.
  • the number of sheets to be overlapped can be appropriately set in accordance with the size of the frame and the size of the plate catalyst element for exhaust gas purification. Usually, about 20 to 40 plate catalyst elements for exhaust gas purification are stacked.
  • the frame is not particularly limited as long as it has a structure capable of guiding gas between the stacked exhaust-gas-purifying plate catalyst elements.
  • the frame 10 may be a rectangular tube formed of four metal flat plates.
  • Example 1 10 kg of titanium oxide, 2 kg of ammonium molybdate tetrahydrate, 1 kg of ammonium metavanadate and 1 kg of oxalic acid were mixed, and kneaded with a kneader for 1 hour while adding water to form a paste. To this, 2 kg of silica-alumina-based inorganic fibers were added and kneaded for another 30 minutes to obtain a catalyst paste having a water content of about 30%. Using a pair of rolling rollers, the catalyst paste was pressed against the gaps between the laths and the surface of a long 500 mm wide SUS430 stainless steel expanded metal and 0.7 mm thick. A plate catalyst was obtained.
  • a band member made of a SUS430 stainless steel plate having a thickness of 1 mm, a length of 500 mm, and a width (D) of 10 mm was subjected to mold bending using a press machine to form a bent portion 6.
  • the two band members are oriented in a direction substantially perpendicular to the ridge so that the bent portion 6 is located substantially at the center of the flat portion of the plate catalyst 1 and at a position 200 mm and 400 mm away from the front edge of the plate catalyst 1.
  • the baffle part 4 was stretched over the flat part at a height level of 3.5 mm with respect to the flat part.
  • the plate-like catalyst elements a were overlapped as shown in FIG. This was air-dried for 24 hours and then calcined in air at 500 ° C. for 2 hours to obtain a catalyst unit A.
  • Example 2 A plate-like catalyst element b and a catalyst unit B were obtained in the same manner as in Example 1 except that the thickness of the SUS430 stainless steel plate band member was changed to 0.5 mm.
  • Example 3 A plate-like catalyst element c and a catalyst unit C were obtained in the same manner as in Example 1, except that the thickness of the band member made of SUS430 stainless steel plate was changed to 2 mm.
  • Example 4 A plate-like catalyst element d and a catalyst unit D were obtained in the same manner as in Example 1 except that the width (D) of the SUS430 stainless steel plate band member was changed to 20 mm.
  • Example 5 A plate-like catalyst element e and a catalyst unit E were obtained in the same manner as in Example 1 except that the band member made of SUS430 stainless steel plate was changed to a band member made of SUS430 stainless steel expanded metal.
  • Example 6 The catalyst paste obtained in Example 1 was pressed against a band member made of SUS430 stainless steel expanded metal with a roller to obtain a band member (thickness 0.7 mm) supporting the catalyst.
  • a plate-like catalyst element f and a catalyst unit F were obtained in the same manner as in Example 1, except that the band member made of a SUS430 stainless steel plate was changed to a band member carrying a catalyst.
  • Comparative Example 1 A catalyst unit G was obtained in the same manner as in Example 1, except that the plate catalyst 1 obtained in Example 1 was used instead of the plate catalyst element.
  • the catalyst units A to G were subjected to a denitration reaction under the conditions shown in Table 1, and the reaction rate ratio and pressure loss were measured.
  • Table 2 shows the results.
  • the catalyst units A to F obtained by stacking the plate-like catalyst elements a to f of the present invention have higher denitration performance than the catalyst unit G.
  • the denitration performance is higher as the thickness and width (D) of the baffle portion are larger. It can be seen that the greater the thickness or width (D) of the baffle, the higher the pressure loss, but the smaller the increase. If a baffle section supporting a catalyst is provided, the denitration efficiency is further improved.
  • the catalyst unit of the present invention has a low pressure loss and is unlikely to accumulate dust even if the exhaust gas contains dust. It is suitable for purifying exhaust gas containing a large amount of dust discharged from a coal-fired boiler or the like, and can greatly reduce the environmental load as compared with a conventional catalyst unit.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Biomedical Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Catalysts (AREA)

Abstract

Cette unité de catalyseur pour purifier un gaz d'échappement comprend : un catalyseur en forme de plaque ayant des parties plates et des parties d'espacement avec des crêtes, les parties plates et les parties d'espacement étant disposées en alternance; et des éléments de catalyseur en forme de plaque pour purifier un gaz d'échappement, ayant des parties de déflecteur en forme de courroie qui s'étendent sur les parties plates dans une direction non parallèle aux crêtes, à une hauteur qui est inférieure à la hauteur des crêtes par rapport à la partie plate. Au moins deux des éléments de catalyseur en forme de plaque se chevauchent de façon à fixer des chemins d'écoulement de gaz.
PCT/JP2019/036597 2018-09-20 2019-09-18 Structure de catalyseur pour la purifier les gaz d'échappement WO2020059760A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018176029A JP7195094B2 (ja) 2018-09-20 2018-09-20 排ガス浄化用触媒構造体
JP2018-176029 2018-09-20

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WO2020059760A1 true WO2020059760A1 (fr) 2020-03-26

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CN111569643A (zh) * 2020-04-29 2020-08-25 江苏卓高环保科技有限公司 一种净化pm2.5甲醛的复合净化材料及其制备的空气净化器

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6187274B1 (en) * 1995-12-13 2001-02-13 Sandvik Ab Turbulence inducer in a catalytic converter channel
US6589910B1 (en) * 1999-05-14 2003-07-08 Helmut Swars Catalytic converter substrate
JP2006015344A (ja) * 1994-11-15 2006-01-19 Babcock Hitachi Kk 触媒構造体と被処理ガス浄化装置
JP2008280864A (ja) * 2007-05-08 2008-11-20 Nichidai Filter Corp 排ガスフィルタ装置
JP2013107046A (ja) * 2011-11-22 2013-06-06 Babcock Hitachi Kk 排ガス浄化用触媒構造体及びその製造法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006015344A (ja) * 1994-11-15 2006-01-19 Babcock Hitachi Kk 触媒構造体と被処理ガス浄化装置
US6187274B1 (en) * 1995-12-13 2001-02-13 Sandvik Ab Turbulence inducer in a catalytic converter channel
US6589910B1 (en) * 1999-05-14 2003-07-08 Helmut Swars Catalytic converter substrate
JP2008280864A (ja) * 2007-05-08 2008-11-20 Nichidai Filter Corp 排ガスフィルタ装置
JP2013107046A (ja) * 2011-11-22 2013-06-06 Babcock Hitachi Kk 排ガス浄化用触媒構造体及びその製造法

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