WO2018154872A1 - Device for purifying exhaust gas with heat recovery function - Google Patents

Device for purifying exhaust gas with heat recovery function Download PDF

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Publication number
WO2018154872A1
WO2018154872A1 PCT/JP2017/040797 JP2017040797W WO2018154872A1 WO 2018154872 A1 WO2018154872 A1 WO 2018154872A1 JP 2017040797 W JP2017040797 W JP 2017040797W WO 2018154872 A1 WO2018154872 A1 WO 2018154872A1
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Prior art keywords
exhaust gas
methane
heat
gas
heat recovery
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PCT/JP2017/040797
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French (fr)
Japanese (ja)
Inventor
寛子 中野
保城 五味
金澤　一弘
正浩 白木
智史 森本
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東京瓦斯株式会社
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Publication of WO2018154872A1 publication Critical patent/WO2018154872A1/en

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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
    • B01D53/92—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
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • F01N3/24—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
    • 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
    • F01N5/00—Exhaust or silencing apparatus combined or associated with devices profiting by exhaust energy
    • F01N5/02—Exhaust or silencing apparatus combined or associated with devices profiting by exhaust energy the devices using heat
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • 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

  • This disclosure relates to an exhaust gas purification apparatus with heat recovery.
  • unburned methane is contained in the exhaust gas of the gas consuming apparatus that consumes fuel gas containing methane as a fuel component.
  • Japanese Patent Application Laid-Open No. 2012-180765 discloses a technique for improving thermal efficiency by adsorbing unburned methane on an adsorbent, desorbing it, and recirculating it to a gas engine.
  • a control device for switching between adsorption of the methane to the catalyst and desorption from the catalyst is required.
  • a circulation passage and a control valve are required for circulating the desorbed methane to the intake passage of the gas engine.
  • exhaust gas cooling means for cooling the exhaust gas to a temperature suitable for methane adsorption is required.
  • ancillary equipment such as emission gas heating means for heating the exhaust gas to a temperature suitable for methane desorption is required. This complicates the mechanism of the gas engine. There is also a concern that heat loss may occur due to temperature rise / fall.
  • the present disclosure aims to provide an exhaust gas purification apparatus with heat recovery that can effectively use methane in exhaust gas without using incidental facilities.
  • the exhaust gas purifying apparatus with heat recovery is a catalyst capable of oxidizing the methane contained in the exhaust gas having a temperature of 350 ° C. or higher and lower than 500 ° C. when the exhaust gas discharged from the gas consuming device is introduced And a heat exchanger for exchanging heat between the exhaust gas after methane oxidation discharged from the oxidation processor and the fluid recirculated from the heat utilization unit.
  • unreacted methane contained in the exhaust gas discharged from the gas consuming apparatus is oxidized by the catalyst of the oxidation processor.
  • This catalyst can oxidize methane at an exhaust gas temperature of 350 ° C. or higher and lower than 500 ° C.
  • the catalyst contains platinum in the configuration of the first aspect.
  • the catalyst for oxidizing methane contains platinum.
  • the catalyst containing platinum can oxidize methane when the temperature of the exhaust gas is 350 ° C. or more and less than 500 ° C.
  • methane in the exhaust gas can be effectively used without using incidental equipment.
  • the gas utilization device 10 is an electric and heat cogeneration system that includes a power generation unit 12, an exhaust heat recovery unit 14, and an exhaust heat utilization unit 16. is there.
  • the power generation unit 12 includes a gas engine 20 that burns city gas mainly composed of methane (CH 4 ) and converts it into power, and a generator 22 that is driven by the gas engine 20.
  • the gas engine 20 is an example of a gas consumption device according to the present disclosure.
  • the gas consuming device may be an internal combustion engine such as a gas turbine, a GHP (gas heat pump air conditioner), a fuel cell, a boiler, an industrial furnace, a burner, or the like.
  • the exhaust heat recovery unit 14 as an example of the exhaust gas purifying apparatus with heat recovery in the present disclosure includes an oxidation processor 30 into which exhaust gas discharged from the gas engine 20 is introduced, and exhaust gas discharged from the oxidation processor 30 (that is, Exhaust gas after oxidation of methane (exhaust gas after methane oxidation in the present disclosure) and a heat exchanger 40 for exchanging heat between the fluid flowing through the flow path 16A are provided.
  • the exhaust heat utilization unit 16 is a heat utilization device such as an air conditioner or a water heater, and uses the heat extracted from the fluid flowing through the distribution channel 16A.
  • a heat medium that transfers heat such as water, oil, water vapor, or a mixture of water and water vapor, can be appropriately selected.
  • the oxidation processor 30 is a device that oxidizes and processes methane contained in the exhaust gas discharged from the gas engine 20, and a catalyst 32 is accommodated therein.
  • the catalyst 32 is configured by supporting platinum (Pt) on porous zirconia (ZrO 2 ), and is formed by applying to a honeycomb-shaped substrate. Stainless steel or cordierite is used for this substrate.
  • the burning city gas mainly composed of methane (CH 4) gas engine 20.
  • CH 4 methane
  • the unburned methane is contained in the exhaust gas after combustion, since methane is a stable compound, it is difficult to oxidize in the exhaust heat recovery unit 14 when the temperature of the exhaust gas is 500 ° C. or lower (for example, 400 ° C.). .
  • an exhaust gas heating means for heating the exhaust gas to a temperature suitable for methane oxidation is required, and heating equipment and energy are required.
  • the “catalyst mounted in the conventional exhaust heat recovery unit” is an oxidation catalyst for the purpose of removing hydrocarbons (NMHC) and carbon monoxide excluding methane, and is 500 ° C. or lower (eg, 400 ° C., for example). ) That cannot oxidize methane at the exhaust gas temperature.
  • methane is adsorbed by an adsorbent and may be recycled to the gas engine.
  • an adsorbent or the like is necessary.
  • a control device is required to switch between adsorption of methane to the catalyst and desorption from the catalyst.
  • a circulation passage and a control valve for circulating the desorbed methane to the intake passage of the gas engine are necessary.
  • an exhaust gas cooling means for cooling to a temperature suitable for methane adsorption is required.
  • ancillary facilities such as emission gas heating means for heating to a temperature suitable for methane desorption are necessary.
  • a catalyst 32 configured by supporting platinum on zirconia is used.
  • the catalyst 32 can oxidize methane in a temperature range of 350 ° C. or higher and lower than 500 ° C.
  • the methane contained in waste gas can be oxidized at low temperature.
  • the gas utilization device 10 when the concentration of unburned methane contained in the exhaust gas discharged from the gas engine 20 increases by 0.2%, the exhaust gas temperature increases by about 50 ° C. due to the oxidation reaction of methane. By recovering this reaction heat with the heat exchanger 40, the amount of recovered heat of exhaust heat increases by about 20%.
  • the gas utilization device 10 methane is oxidized in a temperature range of 350 ° C. or higher and lower than 500 ° C. For this reason, the density
  • the catalyst 32 is configured by supporting platinum on zirconia, but the embodiment of the present disclosure is not limited thereto.
  • a configuration in which platinum, iridium, and rhenium (Re) are supported on zirconia for example, described in JP2012-96221, paragraph [0021], etc. The same applies to the following examples).
  • a configuration in which platinum and ruthenium (Ru) are supported on zirconia Japanese Patent Laid-Open No. 2007-90331, paragraph [0020]
  • a structure in which platinum, ruthenium, and chlorine (Cl) are supported on zirconia Japanese Patent Laid-Open No.
  • the substance used as a carrier is not limited to zirconia, and titanium oxide (TiO 2 ), tin oxide (SnO 2 ), silicoaluminophosphate ((Si x Al y P z ) O 2 ) or alumina (Al 2 ). O 3 ) or the like can be used.
  • titanium oxide is used as a carrier
  • a structure in which platinum, iridium, rhenium, and zirconium are supported Japanese Patent Laid-Open No. 2014-140807, paragraph [0021]
  • a structure in which platinum, iridium, and tantalum (Ta) are supported Japanese Patent Laid-Open No. 2013-215718, paragraph [0020]
  • a structure in which platinum, iridium, and rhenium are supported Japanese Patent Laid-Open No. 2012-196664, paragraph [0021] may be used.
  • tin oxide When tin oxide is used as a carrier, for example, a structure in which platinum is supported (Japanese Patent Laid-Open No. 2004-351236, paragraph [0010]) may be used. Alternatively, platinum may be supported, and iridium may be supported as a co-catalyst (Japanese Patent Laid-Open No. 2006-272079, paragraph [0011]). Alternatively, a structure in which iridium and tantalum are supported (Japanese Patent Laid-Open No. 2013-215718, paragraph [0020]) may be employed. Alternatively, a structure in which platinum, iridium, and rhenium are supported (Japanese Patent Laid-Open No. 2012-196664, paragraph [0021]) can be employed.
  • silicoaluminophosphate is used as a carrier
  • a configuration in which palladium and platinum are supported may be employed.
  • palladium and platinum may be supported, and lanthanum (La) or cerium (Ce) may be supported (Japanese Patent Laid-Open No. 11-76829, paragraph [0025]).
  • lanthanum (La) or cerium (Ce) may be supported (Japanese Patent Laid-Open No. 10-337476, paragraphs [0013], [0014]) can be used.
  • methane can be oxidized in a temperature range of 350 ° C. to 500 ° C.
  • the order in which each substance is supported on the support (simultaneous support or sequential support), the amount or mass ratio of the supported catalyst, the firing temperature, and the like are determined. It is appropriately selected according to the methane oxidation temperature, the durability of the catalyst, and the like.
  • the exhaust gas discharged from the gas engine 20 is assumed to flow directly into the oxidation processor 30, but the embodiment of the present disclosure is not limited thereto.
  • a desulfurizer may be disposed between the gas engine 20 and the oxidation processor 30.
  • the desulfurizer is a device that hydrodesulfurizes or adsorptive desulfurizes sulfur compounds contained in the exhaust gas discharged from the gas engine 20. By providing this desulfurizer, the sulfidation of the catalyst 32 is suppressed, and the methane oxidizing action is suppressed from decreasing.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
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  • Combustion & Propulsion (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Toxicology (AREA)
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  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
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  • Chimneys And Flues (AREA)
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Abstract

A device for purifying exhaust gas with a heat recovery function and equipped with: an oxidation treatment device into which exhaust gas discharged from a gas-consuming device is introduced, and which houses a catalyst capable of oxidizing methane contained in the exhaust gas, which is at a temperature of at least 350°C but less than 500°C; and a heat exchanger for carrying out an exchange of heat between a fluid circulated from a heat utilization unit and the methane-oxidized exhaust gas discharged from the oxidation treatment device.

Description

熱回収を伴う排ガス浄化装置Exhaust gas purification equipment with heat recovery
　本開示は熱回収を伴う排ガス浄化装置に関する。 This disclosure relates to an exhaust gas purification apparatus with heat recovery.
　燃料成分としてメタンを含む燃料ガスを消費するガス消費装置の排ガス中には、未燃のメタンが含まれる場合がある。特開２０１２－１８０７６５号公報には、この未燃のメタンを吸着剤に吸着した後脱着し、ガスエンジンへ再循環することにより熱効率を向上させる技術が開示されている。 In some cases, unburned methane is contained in the exhaust gas of the gas consuming apparatus that consumes fuel gas containing methane as a fuel component. Japanese Patent Application Laid-Open No. 2012-180765 discloses a technique for improving thermal efficiency by adsorbing unburned methane on an adsorbent, desorbing it, and recirculating it to a gas engine.
　しかし、吸着剤に吸着されたメタンを脱着しガスエンジンへ再循環させる場合、メタンの触媒への吸着及び触媒からの脱着を切り換えるための制御装置が必要になる。また、脱着されたメタンをガスエンジンの吸気通路に循環させるための循環通路や制御弁が必要になる。また、排ガスをメタン吸着に適する温度に冷却するための排ガス冷却手段が必要になる。さらに、排ガスをメタン脱離に適した温度に加熱するための放出ガス加熱手段等の付帯設備が必要になる。このためガスエンジンの機構が複雑になる。また、温度の昇温降温に伴う熱ロスが生じる懸念もある。 However, when the methane adsorbed by the adsorbent is desorbed and recirculated to the gas engine, a control device for switching between adsorption of the methane to the catalyst and desorption from the catalyst is required. In addition, a circulation passage and a control valve are required for circulating the desorbed methane to the intake passage of the gas engine. Further, exhaust gas cooling means for cooling the exhaust gas to a temperature suitable for methane adsorption is required. Furthermore, ancillary equipment such as emission gas heating means for heating the exhaust gas to a temperature suitable for methane desorption is required. This complicates the mechanism of the gas engine. There is also a concern that heat loss may occur due to temperature rise / fall.
　本開示は上記事実を考慮して、付帯設備を用いなくても排ガス中のメタンを有効に利用できる熱回収を伴う排ガス浄化装置を提供することを目的とする。 In view of the above facts, the present disclosure aims to provide an exhaust gas purification apparatus with heat recovery that can effectively use methane in exhaust gas without using incidental facilities.
　本開示の第一態様に係る熱回収を伴う排ガス浄化装置は、ガス消費装置から排出された排ガスが導入され、温度が３５０℃以上かつ５００℃未満の前記排ガスに含まれる前記メタンを酸化できる触媒が収納された酸化処理器と、前記酸化処理器から排出されたメタン酸化後排ガスと熱利用部から還流された流体とを熱交換させる熱交換器と、を備えている。 The exhaust gas purifying apparatus with heat recovery according to the first aspect of the present disclosure is a catalyst capable of oxidizing the methane contained in the exhaust gas having a temperature of 350 ° C. or higher and lower than 500 ° C. when the exhaust gas discharged from the gas consuming device is introduced And a heat exchanger for exchanging heat between the exhaust gas after methane oxidation discharged from the oxidation processor and the fluid recirculated from the heat utilization unit.
　本開示の第一態様に係る熱回収を伴う排ガス浄化装置では、ガス消費装置から排出された排ガスに含まれる未反応のメタンが、酸化処理器の触媒により酸化処理される。この触媒は、排ガスの温度が３５０℃以上かつ５００℃未満でメタンを酸化できる。 In the exhaust gas purification apparatus with heat recovery according to the first aspect of the present disclosure, unreacted methane contained in the exhaust gas discharged from the gas consuming apparatus is oxidized by the catalyst of the oxidation processor. This catalyst can oxidize methane at an exhaust gas temperature of 350 ° C. or higher and lower than 500 ° C.
　メタンの酸化反応は発熱反応であるため、低温の排ガスに含まれるメタンを酸化することによりメタン酸化後排ガスは昇温される。このため、熱交換器において熱利用部から還流された流体が熱交換される熱量が多くなる。これにより、吸着剤を用いなくても排ガス中のメタンを熱エネルギーとして回収し、有効に利用することができる。 Since the oxidation reaction of methane is an exothermic reaction, the exhaust gas after methane oxidation is heated by oxidizing methane contained in the low temperature exhaust gas. For this reason, in the heat exchanger, the amount of heat by which the fluid recirculated from the heat utilization unit is heat-exchanged increases. Thereby, even if it does not use an adsorbent, the methane in exhaust gas can be collect | recovered as thermal energy, and can be utilized effectively.
　本開示の第二態様に係る熱回収を伴う排ガス浄化装置では、第一態様の構成において、前記触媒は白金を含有している。 In the exhaust gas purification apparatus with heat recovery according to the second aspect of the present disclosure, the catalyst contains platinum in the configuration of the first aspect.
　本開示の第二態様に係る熱回収を伴う排ガス浄化装置では、メタンを酸化処理する触媒が、白金を含有している。白金を含有する触媒は、排ガスの温度が３５０℃以上かつ５００℃未満でメタンを酸化できる。 In the exhaust gas purification apparatus with heat recovery according to the second aspect of the present disclosure, the catalyst for oxidizing methane contains platinum. The catalyst containing platinum can oxidize methane when the temperature of the exhaust gas is 350 ° C. or more and less than 500 ° C.
　本開示に係る熱回収を伴う排ガス浄化装置によれば、付帯設備を用いなくても排ガス中のメタンを有効に利用することができる。 According to the exhaust gas purification apparatus with heat recovery according to the present disclosure, methane in the exhaust gas can be effectively used without using incidental equipment.
本開示の実施形態に係るガス利用装置を示す全体構成図である。It is a whole lineblock diagram showing the gas utilization device concerning the embodiment of this indication.
（ガス利用装置）
　図１に示すように、本実施形態に係るガス利用装置１０は、発電部１２と、排熱回収部１４と、排熱利用部１６とを備えて構成された電気と熱のコジェネレーションシステムである。 (Gas utilization equipment)
As shown in FIG. 1, the gas utilization device 10 according to the present embodiment is an electric and heat cogeneration system that includes a power generation unit 12, an exhaust heat recovery unit 14, and an exhaust heat utilization unit 16. is there.
　発電部１２は、メタン（ＣＨ４）を主成分とする都市ガスを燃焼して動力に変換するガスエンジン２０と、ガスエンジン２０によって駆動される発電機２２とを備えている。なお、ガスエンジン２０は本開示におけるガス消費装置の一例である。このガス消費装置は、ガスエンジン２０の他、例えばガスタービン等の内燃機関や、ＧＨＰ（ガスヒートポンプエアコン）、燃料電池、ボイラ、工業炉、バーナーなどとすることができる。 The power generation unit 12 includes a gas engine 20 that burns city gas mainly composed of methane (CH 4 ) and converts it into power, and a generator 22 that is driven by the gas engine 20. The gas engine 20 is an example of a gas consumption device according to the present disclosure. In addition to the gas engine 20, the gas consuming device may be an internal combustion engine such as a gas turbine, a GHP (gas heat pump air conditioner), a fuel cell, a boiler, an industrial furnace, a burner, or the like.
　本開示における熱回収を伴う排ガス浄化装置の一例としての排熱回収部１４は、ガスエンジン２０から排出された排ガスが導入される酸化処理器３０と、酸化処理器３０から排出された排ガス（すなわち、メタンが酸化処理された後の排ガス。本開示におけるメタン酸化後排ガス）と流通経路１６Ａを流れる流体とを熱交換させる熱交換器４０と、を備えている。 The exhaust heat recovery unit 14 as an example of the exhaust gas purifying apparatus with heat recovery in the present disclosure includes an oxidation processor 30 into which exhaust gas discharged from the gas engine 20 is introduced, and exhaust gas discharged from the oxidation processor 30 (that is, Exhaust gas after oxidation of methane (exhaust gas after methane oxidation in the present disclosure) and a heat exchanger 40 for exchanging heat between the fluid flowing through the flow path 16A are provided.
　排熱利用部１６は、空調機や給湯器等の熱利用機器であり、流通経路１６Ａを流れる流体から温熱を取り出して利用する。流通経路１６Ａに流す流体は、水、油、水蒸気、又は水と水蒸気の混合体など熱を伝える熱媒を適宜選択することができる。 The exhaust heat utilization unit 16 is a heat utilization device such as an air conditioner or a water heater, and uses the heat extracted from the fluid flowing through the distribution channel 16A. As the fluid flowing through the flow path 16A, a heat medium that transfers heat, such as water, oil, water vapor, or a mixture of water and water vapor, can be appropriately selected.
（酸化処理器）
　酸化処理器３０は、ガスエンジン２０から排出された排ガスに含まれるメタンを酸化して処理する装置であり、内部に触媒３２が収納されている。触媒３２は、白金（Ｐｔ）を、多孔質のジルコニア（ＺｒＯ２）に担持させて構成されており、ハニカム形状の基材に塗布して形成されている。この基材にはステンレスやコージェライトが使用される。 (Oxidation processor)
The oxidation processor 30 is a device that oxidizes and processes methane contained in the exhaust gas discharged from the gas engine 20, and a catalyst 32 is accommodated therein. The catalyst 32 is configured by supporting platinum (Pt) on porous zirconia (ZrO 2 ), and is formed by applying to a honeycomb-shaped substrate. Stainless steel or cordierite is used for this substrate.
（作用及び効果）
　本実施形態に係るガス利用装置１０では、ガスエンジン２０でメタン（ＣＨ４）を主成分とする都市ガスを燃焼している。燃焼後の排ガスには未燃のメタンが含まれるが、メタンは安定な化合物であるため、排ガスの温度が５００℃以下（例えば４００℃）の場合、排熱回収部１４において酸化することが難しい。 (Function and effect)
In gas utilization device 10 according to this embodiment, the burning city gas mainly composed of methane (CH 4) gas engine 20. Although the unburned methane is contained in the exhaust gas after combustion, since methane is a stable compound, it is difficult to oxidize in the exhaust heat recovery unit 14 when the temperature of the exhaust gas is 500 ° C. or lower (for example, 400 ° C.). .
　従来の排熱回収部に搭載されている触媒を用いる場合、排ガスをメタン酸化に適した温度に加熱するための排ガス加熱手段が必要となり、加熱のための設備やエネルギーが必要である。なお、「従来の排熱回収部に搭載されている触媒」とは、メタンを除く炭化水素（ＮＭＨＣ）及び一酸化炭素の除去を目的とした酸化触媒であり、かつ５００℃以下（例えば４００℃）の排ガス温度ではメタンを酸化できないものを指す。 When using a catalyst mounted on a conventional exhaust heat recovery unit, an exhaust gas heating means for heating the exhaust gas to a temperature suitable for methane oxidation is required, and heating equipment and energy are required. The “catalyst mounted in the conventional exhaust heat recovery unit” is an oxidation catalyst for the purpose of removing hydrocarbons (NMHC) and carbon monoxide excluding methane, and is 500 ° C. or lower (eg, 400 ° C., for example). ) That cannot oxidize methane at the exhaust gas temperature.
　また、従来は、未燃のメタンを再利用するために、メタンを吸着剤に吸着させてガスエンジンへ再循環することがある。この場合、吸着剤などが必要である。さらに、メタンの触媒への吸着及び触媒からの脱着を切り換えるための制御装置が必要である。また、脱着されたメタンをガスエンジンの吸気通路に循環させるための循環通路や制御弁が必要である。また、メタン吸着に適する温度に冷却するための排ガス冷却手段が必要である。さらに、メタン脱離に適した温度に加熱するための放出ガス加熱手段等などの付帯設備が必要である。 Also, conventionally, in order to reuse unburned methane, methane is adsorbed by an adsorbent and may be recycled to the gas engine. In this case, an adsorbent or the like is necessary. Furthermore, a control device is required to switch between adsorption of methane to the catalyst and desorption from the catalyst. In addition, a circulation passage and a control valve for circulating the desorbed methane to the intake passage of the gas engine are necessary. Further, an exhaust gas cooling means for cooling to a temperature suitable for methane adsorption is required. Furthermore, ancillary facilities such as emission gas heating means for heating to a temperature suitable for methane desorption are necessary.
　これに対して、本実施形態に係るガス利用装置１０では、白金をジルコニアに担持させて構成された触媒３２を用いている。触媒３２は、３５０℃以上５００℃未満という温度域においてメタンを酸化することができる。これにより、従来の排熱回収部に搭載されている触媒を用いる場合と比較して低温で排ガスに含まれるメタンを酸化処理することができる。 On the other hand, in the gas utilization apparatus 10 according to the present embodiment, a catalyst 32 configured by supporting platinum on zirconia is used. The catalyst 32 can oxidize methane in a temperature range of 350 ° C. or higher and lower than 500 ° C. Thereby, compared with the case where the catalyst mounted in the conventional waste heat recovery part is used, the methane contained in waste gas can be oxidized at low temperature.
　メタンの酸化反応は発熱反応であるため、低温の排ガスに含まれるメタンを酸化することによりメタン酸化後排ガスは昇温される。このため、熱交換器４０において、排熱利用部１６から還流された流体が熱交換できる熱量が多くなる。これにより、排ガス中のメタンを熱エネルギーとして有効利用することができる。 Since the oxidation reaction of methane is an exothermic reaction, the exhaust gas after methane oxidation is heated by oxidizing methane contained in the low temperature exhaust gas. For this reason, in the heat exchanger 40, the amount of heat that the fluid recirculated from the exhaust heat utilization unit 16 can exchange heat increases. Thereby, methane in exhaust gas can be effectively used as thermal energy.
　例えばガス利用装置１０によれば、ガスエンジン２０から排出された排ガスに含まれる未燃メタンの濃度が０．２％高くなると、メタンの酸化反応により、排ガス温度は５０℃程度高くなる。この反応熱を熱交換器４０で回収することにより、排熱の回収熱量は２０％程度増加する。 For example, according to the gas utilization device 10, when the concentration of unburned methane contained in the exhaust gas discharged from the gas engine 20 increases by 0.2%, the exhaust gas temperature increases by about 50 ° C. due to the oxidation reaction of methane. By recovering this reaction heat with the heat exchanger 40, the amount of recovered heat of exhaust heat increases by about 20%.
　また、ガス利用装置１０では、３５０℃以上５００℃未満という温度域においてメタンが酸化される。このため、酸化処理器３０から排出されるメタン酸化後排ガスにおける未燃メタンの濃度は、従来の排熱回収部に搭載されている触媒を用いる場合と比較して低くなる。これにより、外部へ放出されるメタンの量を削減できる。したがって、ガス利用装置１０は吸着剤や付帯設備を必要としない。 In the gas utilization device 10, methane is oxidized in a temperature range of 350 ° C. or higher and lower than 500 ° C. For this reason, the density | concentration of unburned methane in the waste gas after methane oxidation discharged | emitted from the oxidation processor 30 becomes low compared with the case where the catalyst mounted in the conventional waste heat recovery part is used. Thereby, the amount of methane released to the outside can be reduced. Therefore, the gas utilization apparatus 10 does not require an adsorbent or incidental equipment.
　なお、本実施形態において触媒３２はジルコニアに白金を担持させて構成したが、本開示の実施形態はこれに限らない。例えば、ジルコニアに白金、イリジウム及びレニウム（Ｒｅ）を担持させた構成（一例として、特開２０１２－９６２２１、段落［００２１］等に記載されている。以下に示す例についても同様である。）としてもよい。また、ジルコニアに白金及びルテニウム（Ｒｕ）を担持させた構成（特開２００７－９０３３１、段落［００２０］）としてもよい。また、ジルコニアに白金、ルテニウム及び塩素（Ｃｌ）を担持させた構成（特開２０１３－１６９４８０、段落［００１２］）としてもよい。また、ジルコニアに次の（ａ）、（ｂ）及び（ｃ）を担持させた構成（特開２０１４－１５５９１９、段落［００２４］）等とすることができる。
　（ａ）タングステン
　（ｂ）白金
　（ｃ）イリジウム及びルテニウムから選ばれる少なくとも一種 In the present embodiment, the catalyst 32 is configured by supporting platinum on zirconia, but the embodiment of the present disclosure is not limited thereto. For example, a configuration in which platinum, iridium, and rhenium (Re) are supported on zirconia (for example, described in JP2012-96221, paragraph [0021], etc. The same applies to the following examples). Also good. Alternatively, a configuration in which platinum and ruthenium (Ru) are supported on zirconia (Japanese Patent Laid-Open No. 2007-90331, paragraph [0020]) may be employed. Further, a structure in which platinum, ruthenium, and chlorine (Cl) are supported on zirconia (Japanese Patent Laid-Open No. 2013-169480, paragraph [0012]) may be employed. Further, a configuration in which the following (a), (b), and (c) are supported on zirconia (Japanese Patent Laid-Open No. 2014-155919, paragraph [0024]) can be employed.
(A) Tungsten (b) Platinum (c) At least one selected from iridium and ruthenium
　また、担体とする物質はジルコニアに限定されるものではなく、酸化チタン（ＴｉＯ２）、酸化スズ（ＳｎＯ２）、シリコアルミノホスフェート（（ＳｉｘＡｌｙＰｚ）Ｏ２）又はアルミナ（Ａｌ２Ｏ３）等を用いることができる。 Moreover, the substance used as a carrier is not limited to zirconia, and titanium oxide (TiO 2 ), tin oxide (SnO 2 ), silicoaluminophosphate ((Si x Al y P z ) O 2 ) or alumina (Al 2 ). O 3 ) or the like can be used.
　酸化チタンを担体とした場合は、例えば白金、イリジウム、レニウム及びジルコニウムを担持させた構成（特開２０１４－１４０８０７、段落［００２１］）としてもよい。また、白金、イリジウム及びタンタル（Ｔa）を担持させた構成（特開２０１３－２１５７１８、段落［００２０］）としてもよい。また、白金、イリジウム及びレニウムを担持させた構成（特開２０１２－１９６６６４、段落［００２１］）等としてもよい。 When titanium oxide is used as a carrier, for example, a structure in which platinum, iridium, rhenium, and zirconium are supported (Japanese Patent Laid-Open No. 2014-140807, paragraph [0021]) may be employed. Alternatively, a structure in which platinum, iridium, and tantalum (Ta) are supported (Japanese Patent Laid-Open No. 2013-215718, paragraph [0020]) may be employed. Alternatively, a structure in which platinum, iridium, and rhenium are supported (Japanese Patent Laid-Open No. 2012-196664, paragraph [0021]) may be used.
　酸化スズを担体とした場合は、例えば白金を担持させた構成（特開２００４－３５１２３６、段落［００１０］）としてもよい。また、白金を担持させ、さらに助触媒としてイリジウムを担持させた構成（特開２００６－２７２０７９、段落［００１１］）としてもよい。また、イリジウム及びタンタルを担持させた構成（特開２０１３－２１５７１８、段落［００２０］）としてもよい。また、白金、イリジウム及びレニウムを担持させた構成（特開２０１２－１９６６６４、段落［００２１］）等とすることができる。 When tin oxide is used as a carrier, for example, a structure in which platinum is supported (Japanese Patent Laid-Open No. 2004-351236, paragraph [0010]) may be used. Alternatively, platinum may be supported, and iridium may be supported as a co-catalyst (Japanese Patent Laid-Open No. 2006-272079, paragraph [0011]). Alternatively, a structure in which iridium and tantalum are supported (Japanese Patent Laid-Open No. 2013-215718, paragraph [0020]) may be employed. Alternatively, a structure in which platinum, iridium, and rhenium are supported (Japanese Patent Laid-Open No. 2012-196664, paragraph [0021]) can be employed.
　シリコアルミノホスフェートを担体とした場合は、パラジウム及び白金を担持させた構成としてもよい。また、パラジウム及び白金を担持させ、さらにランタン（Ｌａ）又はセリウム（Ｃｅ）を担持させた構成（特開平１１－７６８２９、段落［００２５］）としてもよい。また、(特開平１０－３３７４７６、段落［００１３］、［００１４］)等とすることができる。 In the case where silicoaluminophosphate is used as a carrier, a configuration in which palladium and platinum are supported may be employed. Alternatively, palladium and platinum may be supported, and lanthanum (La) or cerium (Ce) may be supported (Japanese Patent Laid-Open No. 11-76829, paragraph [0025]). Also, (Japanese Patent Laid-Open No. 10-337476, paragraphs [0013], [0014]) can be used.
　アルミナを担体とした場合は、白金及びパラジウムを担持させた構成（特開２００１－１２９４００、段落［００１６］）等とすることができる。 When alumina is used as a carrier, a structure in which platinum and palladium are supported (Japanese Patent Laid-Open No. 2001-129400, paragraph [0016]) can be used.
　これらのような触媒を用いても、３５０℃～５００℃という温度域においてメタンを酸化することができる。なお、これらの物質を用いて触媒を形成するにあたり、担体に対して各物質を担持させる順序（同時担持又は逐次担持）、担持させる触媒の物質量又は質量の割合、焼成温度等は、求められるメタン酸化温度、触媒の耐久性などに応じて適宜選択される。 Even if such a catalyst is used, methane can be oxidized in a temperature range of 350 ° C. to 500 ° C. In forming a catalyst using these substances, the order in which each substance is supported on the support (simultaneous support or sequential support), the amount or mass ratio of the supported catalyst, the firing temperature, and the like are determined. It is appropriately selected according to the methane oxidation temperature, the durability of the catalyst, and the like.
　また、本実施形態においては、ガスエンジン２０から排出された排ガスが酸化処理器３０に直接流入するものとしたが、本開示の実施形態はこれに限らない。例えばガスエンジン２０と酸化処理器３０との間に、脱硫器を配置してもよい。脱硫器は、ガスエンジン２０から排出された排ガス中に含まれる硫黄化合物を水素化脱硫又は吸着脱硫する装置である。この脱硫器を設けることで触媒３２の硫化が抑制され、メタンの酸化作用が低下することが抑制される。 Further, in the present embodiment, the exhaust gas discharged from the gas engine 20 is assumed to flow directly into the oxidation processor 30, but the embodiment of the present disclosure is not limited thereto. For example, a desulfurizer may be disposed between the gas engine 20 and the oxidation processor 30. The desulfurizer is a device that hydrodesulfurizes or adsorptive desulfurizes sulfur compounds contained in the exhaust gas discharged from the gas engine 20. By providing this desulfurizer, the sulfidation of the catalyst 32 is suppressed, and the methane oxidizing action is suppressed from decreasing.
　２０１７年２月２２日に出願された日本国特許出願２０１７－０３０９４７号の開示は、その全体が参照により本明細書に取り込まれる。本明細書に記載されたすべての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。 The entire disclosure of Japanese Patent Application No. 2017-030947 filed on Feb. 22, 2017 is incorporated herein by reference. All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually described to be incorporated by reference, Incorporated herein by reference.

Claims (2)

  1. 　ガス消費装置から排出された排ガスが導入され、温度が３５０℃以上かつ５００℃未満の前記排ガスに含まれるメタンを酸化できる触媒が収納された酸化処理器と、
    　前記酸化処理器から排出されたメタン酸化後排ガスと熱利用部から還流された流体とを熱交換させる熱交換器と、
    　を備えた熱回収を伴う排ガス浄化装置。     An oxidation treatment device in which exhaust gas discharged from the gas consuming apparatus is introduced and a catalyst capable of oxidizing methane contained in the exhaust gas having a temperature of 350 ° C. or higher and lower than 500 ° C. is stored;
    A heat exchanger for exchanging heat between the exhaust gas after methane oxidation discharged from the oxidation processor and the fluid recirculated from the heat utilization unit;
    An exhaust gas purification device with heat recovery.
  2. 　前記触媒は白金を含有する、請求項１に記載の熱回収を伴う排ガス浄化装置。 The exhaust gas purifier with heat recovery according to claim 1, wherein the catalyst contains platinum.
PCT/JP2017/040797 2017-02-22 2017-11-13 Device for purifying exhaust gas with heat recovery function WO2018154872A1 (en)

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JP2001193562A (en) * 2000-01-11 2001-07-17 Osaka Gas Co Ltd Gas engine power generating device
JP2003247420A (en) * 2002-02-21 2003-09-05 Osaka Gas Co Ltd Unfired heat recovery method and unfired heat device of gas fired prime mover
JP2016150296A (en) * 2015-02-17 2016-08-22 三井造船株式会社 Method for producing catalyst, and catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001193562A (en) * 2000-01-11 2001-07-17 Osaka Gas Co Ltd Gas engine power generating device
JP2003247420A (en) * 2002-02-21 2003-09-05 Osaka Gas Co Ltd Unfired heat recovery method and unfired heat device of gas fired prime mover
JP2016150296A (en) * 2015-02-17 2016-08-22 三井造船株式会社 Method for producing catalyst, and catalyst

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