WO2017169450A1 - 排ガス浄化触媒 - Google Patents

排ガス浄化触媒 Download PDF

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Publication number
WO2017169450A1
WO2017169450A1 PCT/JP2017/007597 JP2017007597W WO2017169450A1 WO 2017169450 A1 WO2017169450 A1 WO 2017169450A1 JP 2017007597 W JP2017007597 W JP 2017007597W WO 2017169450 A1 WO2017169450 A1 WO 2017169450A1
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Prior art keywords
exhaust gas
catalyst
carrier
zeolite
denitration
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/007597
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English (en)
French (fr)
Japanese (ja)
Inventor
諭史 吉田
日数谷　進
恵美 庄野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kanadevia Corp
Original Assignee
Hitachi Zosen Corp
Hitachi Shipbuilding and Engineering Co Ltd
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Filing date
Publication date
Application filed by Hitachi Zosen Corp, Hitachi Shipbuilding and Engineering Co Ltd filed Critical Hitachi Zosen Corp
Priority to KR1020187025652A priority Critical patent/KR20180132623A/ko
Priority to CN201780021500.5A priority patent/CN109070067A/zh
Priority to US16/089,886 priority patent/US20190083964A1/en
Priority to EP17773995.0A priority patent/EP3437736A4/en
Publication of WO2017169450A1 publication Critical patent/WO2017169450A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • B01J29/69—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by 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
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9427—Processes characterised by a specific catalyst for removing nitrous oxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion
    • F01N3/206—Adding periodically or continuously substances to exhaust gases for promoting purification, e.g. catalytic material in liquid form, NOx reducing agents
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion
    • F01N3/206—Adding periodically or continuously substances to exhaust gases for promoting purification, e.g. catalytic material in liquid form, NOx reducing agents
    • F01N3/2066—Selective catalytic reduction [SCR]
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2825—Ceramics
    • F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/209—Other metals
    • B01D2255/2096—Bismuth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • 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 [3D] monoliths
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2330/00—Structure of catalyst support or particle filter
    • F01N2330/06—Ceramic, e.g. monoliths
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2370/00—Selection of materials for exhaust purification
    • F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
    • F01N2370/04—Zeolitic material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
    • F01N2510/063—Surface coverings for exhaust purification, e.g. catalytic reaction zeolites
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2590/00—Exhaust or silencing apparatus adapted to particular use, e.g. for military applications, airplanes, submarines
    • F01N2590/02—Exhaust or silencing apparatus adapted to particular use, e.g. for military applications, airplanes, submarines for marine vessels or naval applications
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/03—Adding substances to exhaust gases the substance being hydrocarbons, e.g. engine fuel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention removes nitrogen oxide (NOx) in combustion exhaust gas discharged from a diesel engine for ships, which generates combustion exhaust gas having a high sulfur oxide content and a relatively low temperature among internal combustion engines.
  • the present invention relates to an exhaust gas purifying catalyst.
  • ammonia selective catalytic reduction uses a denitration catalyst mainly composed of vanadium or titania as a catalyst, and uses ammonia as a reducing agent.
  • C heavy oil has a high content of sulfur compounds in addition to nitrogen compounds. Therefore, when it is burned, the combustion exhaust gas produces sulfur oxides together with nitrogen oxides that cannot be ignored. Become.
  • an alcohol such as ethanol is used as a reducing agent, and a denitration catalyst in which a specific metal is supported on ⁇ zeolite is used.
  • Patent Document 2 describes a denitration method using alcohol such as methanol as a reducing agent and using proton type ⁇ zeolite as a denitration catalyst.
  • alcohol such as methanol
  • Patent Document 2 describes a denitration method using proton type ⁇ zeolite as a denitration catalyst.
  • JP 2004-358454 A JP 2006-220107 A
  • a denitration catalyst layer is disposed in each of the exhaust gas treatment channels branched into two systems in order to solve the problem of deterioration of the catalyst over time as in Patent Document 1, and one exhaust gas
  • the denitration catalyst layer of the one exhaust gas treatment channel is heated at 350 to 800 ° C. on the spot while the treatment channel is closed to stop the supply of exhaust gas and the exhaust gas treatment is continued in the other exhaust gas treatment channel.
  • the reduced denitration performance is recovered, and this operation is repeated two times alternately.
  • the object of the present invention is to solve the above-mentioned problems of the prior art, using nitrogen oxide in a relatively low temperature exhaust gas discharged from a marine diesel engine or the like, using a reducing agent in a smaller amount than before,
  • An object of the present invention is to provide an exhaust gas purifying catalyst that can be efficiently removed.
  • the present inventors have determined the peak area (A) of the Al—OH spectrum measured with a Fourier transform infrared spectrometer (FT-IR) as the weight of the measurement carrier ( The inventors have found that a zeolite-supported catalyst having a value (S) divided by W) of 1500 to 3500 has a higher denitration performance than a conventionally known catalyst, and has completed the present invention.
  • A peak area
  • FT-IR Fourier transform infrared spectrometer
  • the present invention is used in a combustion exhaust gas purification method that reduces and removes nitrogen oxides in combustion exhaust gas to nitrogen, and alcohol is added to the combustion exhaust gas as a reducing agent for reducing the nitrogen oxides.
  • the exhaust gas purification catalyst comprises a carrier and a denitration catalyst metal supported on the carrier, and the carrier is an Al--particle measured by a Fourier transform infrared spectrometer (FT-IR).
  • FT-IR Fourier transform infrared spectrometer
  • the zeolite is characterized in that the value (S) obtained by dividing the peak area (A) of the OH spectrum by the measurement carrier weight (W) is 1500 to 3500.
  • the zeolite has a FER type structure.
  • the denitration catalyst metal is Bi.
  • the exhaust gas treatment catalyst according to the present invention has a value (S) of 1500, which is obtained by dividing the peak area (A) of the Al—OH spectrum measured by a Fourier transform infrared spectrometer (FT-IR) by the measured carrier weight (W).
  • S the value of 1500, which is obtained by dividing the peak area (A) of the Al—OH spectrum measured by a Fourier transform infrared spectrometer (FT-IR) by the measured carrier weight (W).
  • FT-IR Fourier transform infrared spectrometer
  • FIG. 1 shows an example of an exhaust gas purification apparatus (1) to which an exhaust gas purification catalyst according to the present invention is applied, (a) a perspective view and (b) a front view showing a honeycomb structure. It is a perspective view which shows the modification of an exhaust gas treatment catalyst structure, and shows what consists of a small piece of a corrugated sheet-like base material. It is a flow sheet which shows the outline
  • FT-IR Fourier transform infrared spectrometer
  • the exhaust gas purification catalyst according to the present invention is used in a combustion exhaust gas purification method for removing nitrogen oxides in combustion exhaust gas by reducing them to nitrogen.
  • the alcohol as the reducing agent to be added is not particularly limited as long as it has a reducing power at the temperature at the time of the reduction treatment of the combustion exhaust gas. Since there is a problem of lowering, it is preferable to use methanol, ethanol, or the like, which is an alcohol having a small carbon number.
  • the present invention is an exhaust gas purifying catalyst capable of improving the denitration performance in a low alcohol concentration range, and the concentration of alcohol as a reducing agent added is preferably 1000 to 7000 ppm, and more preferably 1000 to 6000 ppm.
  • the exhaust gas purifying catalyst according to the present invention is assumed to be applied when the temperature of combustion exhaust gas of marine diesel, oil-fired boiler, gas turbine, etc. is relatively low. More specifically, the present invention The exhaust gas purification catalyst according to is used for reducing and removing nitrogen oxides in combustion exhaust gas at a temperature in the range of 180 to 400 ° C., preferably 200 to 300 ° C., to nitrogen.
  • the exhaust gas purification catalyst according to the present invention comprises a carrier and a denitration catalyst metal supported on the carrier.
  • the carrier used for the catalyst of the present invention is a value obtained by dividing the peak area (A) of the Al—OH spectrum measured by a Fourier transform infrared spectrometer (FT-IR) by the measured carrier weight (W) (S). Zeolite having a value in the range of 1500 to 3500, preferably 1530 to 3260 (hereinafter referred to as “value (S)” for simplicity) is used.
  • the peak area (A) of the Al—OH spectrum is obtained by integrating the peaks of the Al—OH spectrum measured with a Fourier transform infrared spectrometer (FT-IR).
  • the peak area (A) indicates a portion surrounded by a straight line obtained by cutting both ends of the peak with a straight line.
  • FT-IR Fourier transform infrared spectrometer
  • Al—OH in the zeolite is generated by cutting a part of “—O—Al—O—” in the basic skeleton.
  • the measurement carrier weight (W) is the weight of a measurement sample measured with a Fourier transform infrared spectrometer (FT-IR). For example, a pellet formed by putting only sample powder into a mold and pressurizing it into a pellet It is determined by measuring the weight of the form carrier.
  • FT-IR Fourier transform infrared spectrometer
  • the amount of Al—OH in the zeolite skeleton becomes an appropriate amount, and the rate (selectivity) of reaching the catalyst metal of alcohol as a reducing agent is improved.
  • the denitration rate is improved.
  • a zeolite having a value (S) smaller than 1500 the acid point is decreased and the alcohol selectivity of the reducing agent is improved.
  • the denitration rate is lowered because the reactivity itself is lowered.
  • a zeolite having a value (S) larger than 3500 is used, the acid point (number) becomes excessive, and alcohol is wasted, so that the denitration rate is considered to decrease.
  • the zeolite is calcined and heated (eg, It is preferable to remove moisture contained in the zeolite surface by performing vacuum heating.
  • FT-IR Fourier transform infrared spectrometer
  • the value (S) is used in order to correct the influence of the thickness of the measurement carrier (pellet) that differs between samples measured by a Fourier transform infrared spectrometer (FT-IR).
  • FT-IR Fourier transform infrared spectrometer
  • the zeolite used as the carrier is not particularly limited as long as it has the above range of values (S) and can exhibit denitration performance.
  • a zeolite having a structure with strong acid strength such as MOR type zeolite
  • a large amount of reducing agent is required.
  • a zeolite having a weak acid strength such as ⁇ -type zeolite and Y-type zeolite is less reactive with the reducing agent, so that it is relatively more acidic than the MOR type.
  • MFI-type zeolite having a structure with weak strength and stronger acid strength than ⁇ -type zeolite and Y-type zeolite is preferable.
  • the zeolite used for the catalyst carrier according to the present invention has a characteristic that the value (S) is in the range of 1500 to 3500.
  • a zeolite having such a characteristic is a Fourier transform infrared spectrometer ( By subjecting the zeolite to calcination in an inert gas atmosphere such as nitrogen until the appropriate amount of Al—OH in the zeolite framework, represented by the value (S) obtained by measurement by FT-IR), is obtained. can get.
  • the firing conditions at that time are specifically, pulverized zeolite powder, charged in a reactor, and then fired at a predetermined temperature and time in an inert atmosphere. For example, it is preferable to perform calcination for about 12 to 36 hours at 500 to 800 ° C. with a commercially available zeolite.
  • the denitration catalyst metal supported on the carrier is not particularly limited as long as it can exhibit the denitration performance, and examples thereof include at least one selected from Co, Bi, Ag, and Pb. Of these, Bi is a particularly preferred metal.
  • the exhaust gas purifying catalyst according to the present invention is prepared by supporting the catalyst metal on the carrier.
  • the catalyst metal precursor compound for example, inorganic acid salts (for example, nitrates and chlorides) and organic acid salts (for example, acetates) can be used.
  • the catalyst metal is supported on a specific zeolite as a support by ion exchange.
  • a catalyst metal is dissolved in a predetermined solvent, and zeolite particles having the above characteristics are added to the slurry. And stirring the slurry in a heated state, and then cooling to room temperature.
  • the solvent used for such catalyst preparation is a solvent that uniformly dissolves the catalyst metal.
  • ethylene glycol, acetic acid, dilute nitric acid, 2-methoxyethanol and the like are preferable solvents.
  • this compound is hardly soluble in water, so it is suspended in water but the catalyst metal is supported on zeolite. Is possible.
  • the exhaust gas purifying catalyst according to the present invention may have any form as long as it can contact nitrogen oxide in combustion exhaust gas and reduce it to nitrogen, for example, granular, pellet-like, honeycomb-like, wave-like small
  • the shape include a piece shape and a plate shape, but can be arbitrarily selected depending on the reactor to be applied and gas flow conditions.
  • FIG. 1 shows an example of an exhaust gas purifying apparatus (1) to which an exhaust gas purifying catalyst according to the present invention is applied.
  • Corrugated base materials (2) and flat base materials (3) are alternately laminated.
  • the casing (4) is filled to form a honeycomb shape.
  • the honeycomb (honeycomb) -like structure generally means a structure composed of a plurality of through holes (cells) partitioned by partition walls and through which exhaust gas can flow and the partition walls.
  • the cross-sectional shape is not particularly limited, and examples thereof include a circular shape, an arc shape, a square shape, a rectangular shape, and a hexagonal shape.
  • the corrugated base material (2) and the flat base material (3) are alternately laminated and bonded to each other to form an integral structure, whereby the honeycomb structure is formed.
  • the corrugated base material (2) and the flat base material (3) may be laminated without being alternately bonded, and the above FIG.
  • the corrugated base material (2) and the flat base material (3) may be fixed so as not to be separated from each other by filling the casing (4).
  • a corrugated base material (2) and a flat base material (3) are laminated and a casing (4) that surrounds and fixes the periphery of the base material. Form a honeycomb structure.
  • the honeycomb structure as shown in FIG. 1 has a structure in which the base material is formed depending on the passage of use time during the operation of filling the casing (4) when the catalyst is supported on each base material constituting the base material or the base material before molding. This is advantageous in that it can be easily operated with separate substrate units as compared with those integrated by bonding to each other, for example, when replacing or activating the catalyst. In this respect, FIG. The configuration shown is preferred.
  • the casing (4) maintains a state in which the corrugated base material (2) and the flat base material (3) are alternately laminated and processed. What is necessary is just to open both ends in order to ventilate the target flue gas, and the cross-sectional structure may have any shape, but the above-mentioned base materials can be filled easily without any gaps. In view of this, it is preferable to have a square or rectangular cross-sectional structure, that is, a rectangular tube shape.
  • the casing (4) having each cylindrical shape as described above may have an integral type or a two-body type formed by combining two bodies.
  • the corrugated plate-like and flat plate-like substrates (2) and (3) are pushed from either open end in a state where they are laminated together. To fill the casing (4).
  • the casing (4) has a two-body type, one structure in which the corrugated and flat base materials (2) and (3) are laminated on the honeycomb structure becomes the casing (4). Since it is only necessary to connect the other structure to this after placing it on the bottom surface portion, the operation of filling each base material in the casing (4) becomes easier.
  • an inorganic fiber blanket is laid on the inner surface of the casing (4).
  • vibration countermeasures can be taken by the frictional force generated by the flat or corrugated base material and the inorganic fiber blanket on the inner surface of the casing (4).
  • the base material may be of any material as long as it can be formed into a corrugated plate shape or the like, but preferred examples include glass paper or ceramic paper in consideration of ease of forming.
  • glass paper commercially available non-woven glass paper can be used.
  • general glass paper also has a surface that is difficult to mold as it is because it contains an organic binder, but this process can be achieved by adding a process for supporting an inorganic binder to the molding process. Can cover the disadvantages of the points.
  • the thickness of the glass paper is preferably from 0.3 to 1.5 mm, more preferably from 0.5 to 1.2 mm, from the viewpoint that it can be easily molded and has the necessary strength. It is.
  • an inorganic binder is supported along with such an exhaust gas purification catalyst.
  • This inorganic binder functions to support the exhaust gas purification catalyst on the glass paper, and is used to maintain the shape of the glass paper and impart curability.
  • the inorganic binder can be exemplified as a preferable one composed of at least one selected from zirconia, alumina, silica, silica alumina, and titania.
  • the inorganic binder may be zirconia or alumina. preferable.
  • silica sol is used as a starting material.
  • an acidic type neutral or basic type can be used
  • the weight ratio of zeolite, water, and silica sol as an inorganic binder is, for example, 100: 75: 46, and is adjusted to a slurry by mixing and stirring them.
  • the dipping method is a method in which glass paper as a base material is immersed in the slurry for a predetermined time, and then the glass paper is pulled up, dried and fired sequentially.
  • the above slurry is applied to glass paper.
  • any conventionally known method may be used, and examples thereof include a so-called soaking method, a brush coating method, a spray coating method, and a dropping coating method.
  • firing is performed.
  • FIG. 1 As an example of a structure to which the exhaust gas treatment catalyst according to the present invention is applied, a honeycomb structure composed of a combination of two kinds of substrates carrying the exhaust gas treatment catalyst according to the present invention as described above is shown in FIG. Thus, it may consist of a small piece of such a corrugated base material.
  • the width dimension per concave groove (indicated by A) and the number of repetitions in the width direction (indicated by n) ), Height dimension (indicated by B) and depth (indicated by C) all have small values.
  • the width dimension (A) is, for example, 2.0 to 100 mm.
  • the height dimension (B) is, for example, 1.0 to 50 mm.
  • the depth dimension (C) is, for example, 3.0 to 200 mm.
  • the number of repetitions (n) in the width direction is, for example, 1 to 10 times.
  • the exhaust gas treatment catalyst according to the present invention is characterized in that a carrier having specific properties with respect to Al—OH is used.
  • a carrier having specific properties with respect to Al—OH is used as the carrier of the exhaust gas treatment catalyst of Examples 1 to 4 below.
  • the peak area (A) of the Al—OH spectrum derived from the FER type zeolite and measured by a Fourier transform infrared spectrometer (FT-IR) is A zeolite having a value (S) of 1500 to 3500 divided by the measurement carrier weight (W) was used.
  • the zeolite after the above treatment is molded into pellets using a predetermined jig, and this is used as a sample.
  • vacuum heating at 450 ° C. for 3 hours, moisture contained on the zeolite surface is removed, and FT-IR measurement is performed. Provided.
  • FT-IR measurement was performed in the range of 1000 to 4000 cm ⁇ 1 by the transmission method, and a peak in the range of 3500 to 3700 cm ⁇ 1 was used as the peak of Al—OH.
  • the carrier of the exhaust gas treatment catalyst of Comparative Example 1 had a value (S) of 1242 and a value smaller than 1500 according to the above FT-IR measurement.
  • Bismuth nitrate hexahydrate 1.45 g was added to 40 g of ion-exchanged water to form a suspension, and the suspension was heated to 80 ° C. Ion exchange was performed by immersing 10 g of the zeolite in the suspension kept at this temperature for 15 hours. After the ion exchange, it was taken out from the aqueous solution, washed with 440 mL of ion exchange water, and then dried at 80 ° C. for 12 hours to obtain the desired catalyst.
  • Example 2 A catalyst using a FER type zeolite (manufactured by Tosoh Corporation) having a value (S) of 1766 as a carrier was prepared. The preparation procedure was the same as in Example 1 except that the zeolite was changed.
  • Example 3 A catalyst using a FER type zeolite (manufactured by Tosoh Corporation) having a value (S) of 2323 as a carrier was prepared. The procedure for this was the same as in Example 1 except that the zeolite was changed.
  • Example 4 A catalyst using a FER type zeolite (manufactured by Tosoh Corp.) having a value (S) of 3265 as a carrier was prepared. The procedure for this was the same as in Example 1 except that the zeolite was changed.
  • Example 1 A catalyst using a FER type zeolite (manufactured by Tosoh Corporation) having a value (S) of 1242 as a carrier was prepared. The procedure for this was the same as in Example 1 except that the zeolite was changed.
  • Catalyst performance test Catalyst performance tests were performed on the catalysts of Examples 1 to 4 and Comparative Example 1 described above. Each of the catalysts of Examples 1 to 4 and Comparative Example 1 was subjected to press molding, and then the molded product was pulverized and sized to a mesh size of 26 to 16.
  • Fig. 3 shows the outline of the test equipment used for the catalyst performance test.
  • the granular catalyst obtained as described above was charged into a denitration reactor (11).
  • the denitration reactor (11) filled with the catalyst is introduced with a test gas shown in detail in Table 1 below from the upper part, and treated with an exhaust gas treatment catalyst from the lower part. The finished gas is discharged.
  • the test gas introduced into the denitration reactor (11) is prepared by mixing air, N 2 gas and NO gas in nitrogen.
  • Each line for supplying these gases is provided with a valve, and the flow rate and mixing ratio of each gas are adjusted by adjusting the opening degree.
  • the mixed gas is introduced into the upper part of the evaporator (12).
  • the evaporator (12) is supplied with water containing a predetermined amount of reducing agent via a separate path. That is, in the water tank (14), water containing methanol as a reducing agent at a predetermined concentration is pumped up by the pump (13) and supplied to the upper part of the evaporator (12).
  • the mixed gas and methanol-containing water are heated in the evaporator (12) and water and methanol are vaporized and supplied to the denitration reactor (11).
  • the treated gas discharged from the denitration reactor (11) was subjected to gas analysis.
  • test conditions When performing a test using the test apparatus shown in FIG. 3, the test conditions are summarized in Table 1 below.
  • “Balance” in Table 1 represents that N 2 is added so that the total gas composition is 100%.
  • the space velocity (SV) is the volume of gas to be treated (m 3 / h) flowing into the denitration reactor (11) by the volume occupied by the denitration reactor (11) where the catalyst is installed ( It is a value obtained by dividing by m 3 ), and if the value is large, the efficiency in contact with the catalyst is good.
  • the gas analysis at the outlet of the reactor measured the outlet NOx concentration using a nitrogen oxide (NOx) meter. From the measured value with the NOx meter, the NOx removal rate, which is the NOx removal performance of the catalyst, was calculated by the following mathematical formula (1).
  • Denitration rate (%) (NOxin ⁇ NOxout) / NOxin ⁇ 100 (1)
  • FER type zeolite having an appropriate value (S) was used, but the zeolite was calcined in an inert gas atmosphere such as nitrogen until the appropriate amount of Al—OH in the zeolite framework was obtained. It can also be obtained by performing processing.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Toxicology (AREA)
  • Analytical Chemistry (AREA)
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  • Biomedical Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Exhaust Gas After Treatment (AREA)
PCT/JP2017/007597 2016-03-31 2017-02-28 排ガス浄化触媒 Ceased WO2017169450A1 (ja)

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US16/089,886 US20190083964A1 (en) 2016-03-31 2017-02-28 Exhaust gas purification catalyst
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WO2015147257A1 (ja) * 2014-03-27 2015-10-01 日立造船株式会社 ハニカム構造体、およびこれを用いた排ガス浄化用触媒、並びに排ガス浄化用触媒の製造方法

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WO2015147257A1 (ja) * 2014-03-27 2015-10-01 日立造船株式会社 ハニカム構造体、およびこれを用いた排ガス浄化用触媒、並びに排ガス浄化用触媒の製造方法

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EP3437736A1 (en) 2019-02-06
CN109070067A (zh) 2018-12-21
EP3437736A4 (en) 2019-11-20

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