JP2018135809A - Exhaust gas purification device with heart recovery - Google Patents
Exhaust gas purification device with heart recovery Download PDFInfo
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- JP2018135809A JP2018135809A JP2017030947A JP2017030947A JP2018135809A JP 2018135809 A JP2018135809 A JP 2018135809A JP 2017030947 A JP2017030947 A JP 2017030947A JP 2017030947 A JP2017030947 A JP 2017030947A JP 2018135809 A JP2018135809 A JP 2018135809A
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- 238000011084 recovery Methods 0.000 title claims abstract description 23
- 238000000746 purification Methods 0.000 title claims abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 22
- 239000012530 fluid Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 41
- 229910052697 platinum Inorganic materials 0.000 claims description 20
- 239000007789 gas Substances 0.000 description 75
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 16
- 229910052741 iridium Inorganic materials 0.000 description 8
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000003795 desorption Methods 0.000 description 4
- 229910052702 rhenium Inorganic materials 0.000 description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 230000003134 recirculating effect Effects 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Analytical Chemistry (AREA)
- Biomedical Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Toxicology (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Exhaust Gas After Treatment (AREA)
- Chimneys And Flues (AREA)
- Incineration Of Waste (AREA)
Abstract
Description
本発明は熱回収を伴う排ガス浄化装置に関する。 The present invention 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。特許文献１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 a gas consuming apparatus that consumes fuel gas containing methane as a fuel component. Patent Document 1 discloses a technique for improving thermal efficiency by adsorbing this 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、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、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、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り、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 desorbing methane adsorbed by the adsorbent and recirculating it to the gas engine, a control device for switching between adsorption to and desorption of methane from the catalyst, circulates the desorbed methane to the intake passage of the gas engine. Attached equipment such as a circulation passage and control valve for cooling, an exhaust gas cooling means for cooling to a temperature suitable for methane adsorption, and a discharge gas heating means for heating to a temperature suitable for methane desorption are required. The mechanism becomes complicated. There is also a concern that heat loss may occur due to temperature rise / fall.
本発明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, an object of the present invention is to provide an exhaust gas purification apparatus with heat recovery that can effectively use methane in exhaust gas without using incidental equipment.
請求項１の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 claim 1 is an oxidation treatment apparatus in which exhaust gas discharged from a gas consuming apparatus is introduced and a catalyst capable of oxidizing the methane contained in the exhaust gas having a temperature of 350 ° C. or higher is housed. 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.
請求項１の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 claim 1, 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 adsorption agent, methane in exhaust gas can be collected as thermal energy, and can be used effectively.
請求項２の熱回収を伴う排ガス浄化装置では、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 claim 2, the catalyst contains platinum.
請求項２の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 claim 2, 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.
本発明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利用できる。 According to the exhaust gas purification apparatus with heat recovery according to the present invention, methane in exhaust gas can be effectively used without using incidental equipment.
（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は本発明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 consuming device in the present invention. 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.
本発明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（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 invention includes an oxidation processor 30 into which exhaust gas exhausted from the gas engine 20 is introduced, and exhaust gas (methane that is exhausted from the oxidation processor 30). A heat exchanger 40 for exchanging heat between the exhaust gas after oxidation) and the fluid flowing through the flow passage 16A.
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 hot water heater, and uses the heat extracted from the fluid flowing through the distribution path 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）、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 less (for example, 400 ° C.). ) That cannot oxidize methane at the exhaust gas temperature.
あるいは、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、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、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、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。 Or in order to recycle unburned methane, when adsorbing methane on an adsorbent and recirculating it to a gas engine, an adsorbent or the like is required. Furthermore, a control device for switching between adsorption and desorption of methane on the catalyst, a circulation path and control valve for circulating the desorbed methane to the intake passage of the gas engine, and cooling to a temperature suitable for methane adsorption Attached facilities such as an exhaust gas cooling means and a discharge 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に用いている白金をジルコニアに担持させて構成された触媒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, the catalyst 32 configured by supporting platinum used in the gas utilization apparatus 10 according to the present embodiment on zirconia 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％多くなると、メタンの酸化反応により、排ガス温度は５０℃程度増加する。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、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とにより、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メタン濃度は、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減される。これにより、外部へ放出されるメタンの量を削減できる。このため、吸着剤や付帯設備を必要としない。 Further, when methane is oxidized in a temperature range of 350 ° C. or higher and lower than 500 ° C., the methane concentration in the exhaust gas after methane oxidation discharged from the oxidation processor 30 is determined by the catalyst mounted in the conventional exhaust heat recovery unit. It is reduced compared with the case of using. Thereby, the amount of methane released to the outside can be reduced. For this reason, an adsorbent and incidental equipment are not required.
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、本発明の実施形態はこれに限らない。例えば、ジルコニアに白金、イリジウムおよびレニウム（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。）、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］）、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］）、ジルコニアにタングステン（Ｗ）、白金、イリジウム及びルテニウムの少なくとも一種を担持させた構成（特開２０１４−１５５９１９、段落［００２４］）等とすることができる。 In the present embodiment, the catalyst 32 is configured by supporting platinum on zirconia, but the embodiment of the present invention is not limited thereto. For example, a structure in which platinum, iridium, and rhenium (Re) are supported on zirconia (as an example, it is described in JP 2012-96221 A, paragraph [0021], etc.). A structure in which platinum and ruthenium (Ru) are supported on zirconia (JP 2007-90331, paragraph [0020]), and a structure in which platinum, ruthenium and chlorine (Cl) are supported on zirconia (JP 2013-169480, paragraph [ 0012]), a structure in which at least one of tungsten (W), platinum, iridium, and ruthenium is supported on zirconia (Japanese Patent Laid-Open No. 2014-155919, paragraph [0024]).
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）、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, but is made of titanium oxide (TiO 2 ), tin oxide (SnO 2 ), silicoaluminophosphate ((Si x Al y P z ) O 2 ), 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］）、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］）、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。 In the case of using titanium oxide as a carrier, for example, a configuration in which platinum, iridium, rhenium and zirconium are supported (Japanese Patent Laid-Open No. 2014-140807, paragraph [0021]), a configuration in which platinum, iridium and tantalum (Ta) are supported (special features). Open 2013-215718, paragraph [0020]), a structure in which platinum, iridium, and rhenium are supported (Japanese Patent Laid-Open No. 2012-196664, paragraph [0021]).
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］）、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］）、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］）、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]), a structure in which platinum is supported and iridium is further supported as a promoter (Japanese Patent Laid-Open No. 2006-272079). , Paragraph [0011]), a structure supporting iridium and tantalum (JP 2013-215718, paragraph [0020]), a structure supporting platinum, iridium and rhenium (JP 2012-196664, paragraph [0021]). Etc.
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、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］）、(特開平１０−３３７４７６、段落［００１３］、［００１４］)等とすることができる。 When silicoaluminophosphate is used as a carrier, a structure in which palladium and platinum are supported, a structure in which palladium and platinum are supported, and further lanthanum (La) or cerium (Ce) is supported (Japanese Patent Laid-Open No. 11-76829, paragraph [ [0025]), (Japanese Patent Laid-Open No. 10-337476, paragraphs [0013], [0014]).
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 employed.
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 substances, the firing temperature, etc. It is appropriately selected according to the 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、本発明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。 Moreover, in this embodiment, although the exhaust gas discharged | emitted from the gas engine 20 shall flow directly into the oxidation processor 30, embodiment of this invention is not restricted to this. 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.
１４ 排熱回収部（熱回収を伴う排ガス浄化装置）
２０ ガスエンジン（ガス消費装置）
３０ 酸化処理器
３２ 触媒
４０ 熱交換器
14 Waste heat recovery unit (exhaust gas purification device with heat recovery)
20 Gas engine (gas consuming equipment)
30 Oxidizer 32 Catalyst 40 Heat exchanger
Claims (2)
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 containing a catalyst capable of oxidizing methane contained in the exhaust gas having a temperature of 350 ° C. or higher and lower than 500 ° C.
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.
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| PCT/JP2017/040797 WO2018154872A1 (en) | 2017-02-22 | 2017-11-13 | Device for purifying exhaust gas with heat recovery function |
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| JP2021134773A (en) * | 2020-02-28 | 2021-09-13 | 三菱重工マリンマシナリ株式会社 | Methane slip suppression system, and vessel and offshore floating facility comprising the same |
Citations (3)
| 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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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2021134773A (en) * | 2020-02-28 | 2021-09-13 | 三菱重工マリンマシナリ株式会社 | Methane slip suppression system, and vessel and offshore floating facility comprising the same |
| JP7341084B2 (en) | 2020-02-28 | 2023-09-08 | 三菱重工マリンマシナリ株式会社 | Methane slip suppression system and ships and offshore floating facilities equipped with the methane slip suppression system |
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