JP5159800B2 - 内燃機関用水素供給装置および内燃機関の運転方法 - Google Patents
内燃機関用水素供給装置および内燃機関の運転方法 Download PDFInfo
- Publication number
- JP5159800B2 JP5159800B2 JP2009553329A JP2009553329A JP5159800B2 JP 5159800 B2 JP5159800 B2 JP 5159800B2 JP 2009553329 A JP2009553329 A JP 2009553329A JP 2009553329 A JP2009553329 A JP 2009553329A JP 5159800 B2 JP5159800 B2 JP 5159800B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- dehydrogenation
- internal combustion
- combustion engine
- hydrogen supply
- 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.)
- Active
Links
- 239000001257 hydrogen Substances 0.000 title claims description 151
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 151
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 141
- 238000002485 combustion reaction Methods 0.000 title claims description 62
- 238000000034 method Methods 0.000 title claims description 8
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 101
- 239000003054 catalyst Substances 0.000 claims description 44
- 239000000446 fuel Substances 0.000 claims description 36
- 238000007254 oxidation reaction Methods 0.000 claims description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 22
- 238000003860 storage Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229930195733 hydrocarbon Natural products 0.000 claims description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 11
- 239000001569 carbon dioxide Substances 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000010953 base metal Substances 0.000 claims description 4
- 238000005485 electric heating Methods 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000002048 anodisation reaction Methods 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 15
- 239000003502 gasoline Substances 0.000 description 14
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 10
- 239000002918 waste heat Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 150000004678 hydrides Chemical class 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003584 silencer Effects 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- NHCREQREVZBOCH-UHFFFAOYSA-N 1-methyl-1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalene Chemical compound C1CCCC2C(C)CCCC21 NHCREQREVZBOCH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 239000002828 fuel tank Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
- F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
-
- 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
- F01N3/103—Oxidation catalysts for HC and CO only
-
- 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 ; Methods of operation or control of catalytic converters
- F01N3/2053—By-passing catalytic reactors, e.g. to prevent overheating
-
- 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 ; Methods of operation or control of catalytic converters
- 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
- F01N3/24—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
- F01N3/30—Arrangements for supply of additional air
-
- 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
- F01N3/36—Arrangements for supply of additional fuel
-
- 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
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02D—CONTROLLING COMBUSTION ENGINES
- F02D19/00—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures
- F02D19/06—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed
- F02D19/0639—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed characterised by the type of fuels
- F02D19/0642—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed characterised by the type of fuels at least one fuel being gaseous, the other fuels being gaseous or liquid at standard conditions
- F02D19/0644—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed characterised by the type of fuels at least one fuel being gaseous, the other fuels being gaseous or liquid at standard conditions the gaseous fuel being hydrogen, ammonia or carbon monoxide
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02D—CONTROLLING COMBUSTION ENGINES
- F02D19/00—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures
- F02D19/06—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed
- F02D19/0663—Details on the fuel supply system, e.g. tanks, valves, pipes, pumps, rails, injectors or mixers
- F02D19/0668—Treating or cleaning means; Fuel filters
- F02D19/0671—Means to generate or modify a fuel, e.g. reformers, electrolytic cells or membranes
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02D—CONTROLLING COMBUSTION ENGINES
- F02D19/00—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures
- F02D19/06—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed
- F02D19/0663—Details on the fuel supply system, e.g. tanks, valves, pipes, pumps, rails, injectors or mixers
- F02D19/0684—High pressure fuel injection systems; Details on pumps, rails or the arrangement of valves in the fuel supply and return systems
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02D—CONTROLLING COMBUSTION ENGINES
- F02D19/00—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures
- F02D19/06—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed
- F02D19/0663—Details on the fuel supply system, e.g. tanks, valves, pipes, pumps, rails, injectors or mixers
- F02D19/0686—Injectors
- F02D19/0692—Arrangement of multiple injectors per combustion chamber
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M21/00—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form
- F02M21/02—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form for gaseous fuels
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M25/00—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture
- F02M25/10—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture adding acetylene, non-waterborne hydrogen, non-airborne oxygen, or ozone
- F02M25/12—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture adding acetylene, non-waterborne hydrogen, non-airborne oxygen, or ozone the apparatus having means for generating such gases
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M27/00—Apparatus for treating combustion-air, fuel, or fuel-air mixture, by catalysts, electric means, magnetism, rays, sound waves, or the like
- F02M27/02—Apparatus for treating combustion-air, fuel, or fuel-air mixture, by catalysts, electric means, magnetism, rays, sound waves, or the like by catalysts
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M33/00—Other apparatus for treating combustion-air, fuel or fuel-air mixture
-
- 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
- F01N2610/04—Adding substances to exhaust gases the substance being hydrogen
-
- 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
-
- 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
- Y02T10/30—Use of alternative fuels, e.g. biofuels
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Exhaust Gas After Treatment (AREA)
- Catalysts (AREA)
Description
ところが、脱水素反応触媒はハニカム担体に担持されたものであって、内燃機関の排気管を取り巻いて形成されたハニカム担体には、排気の有する熱エネルギーが排気管を熱伝達して利用されるものの、熱伝達速度が遅く、加速時には水素発生量が充分に追従しないという問題があった。
基材金属自体への通電加熱によって脱水素触媒を加熱する通電加熱手段を有する前記の内燃機関用水素供給装置である。
脱水素反応器には、温度センサ、水素供給体噴射ノズルとともに、水素反応部の加熱用の脱水素生成物供給ノズルおよび空気供給管が設けられた前記の内燃機関用水素供給装置である。
また、脱水素反応器に接続する排気管には、排気管を分岐する分岐部が設けられ、分岐部には水素発生部の温度によって流量が調整される排気流量調整弁が設けられた前記の内燃機関用水素供給装置である。
発生した水素を排気浄化触媒コンバータに供給する水素供給手段を設けた前記の内燃機関用水素供給装置である。
脱水素反応器の水素反応部の温度が所定の温度以下の場合に、脱水素生成物供給ノズルから脱水素生成物と、空気供給管から供給される空気によって脱水素生成物の燃焼させて、水素反応部を所定の温度に加熱した後に水素供給体噴射ノズルから水素供給体を噴射して脱水素反応を行う前記の内燃機関の運転方法である。
図1は、本発明の水素供給装置を備えた内燃機関の全体構成を説明する図である。
内燃機関1には、空気清浄器3で清浄化された空気が空気流量計5を通じて供給され、また、燃料タンク7に貯蔵されたガソリン等の炭化水素が供給ポンプ9によってガソリンインジェクタ11から供給噴射されて吸気系からシリンダ内に供給され、点火プラグ13によって点火されて内燃機関の運転が行われる。
燃焼後の排気は、排気管15によって排気浄化触媒コンバータ17に送られて浄化された後に脱水素反応器19に供給される。
生成した水素と脱水素生成物の混合物は、混合物排出管25を通じて水素分離装置26に送られて水素と、脱水素生成物が分離される。水素は圧縮ポンプ27によって圧縮されて水素貯槽29に貯蔵される。また、トルエン等の脱水素生成物は水素貯蔵体として再度使用するために水素貯蔵体貯槽31に貯蔵される。
また、水素貯槽29に貯蔵された水素は、水素インジェクタ45から吸気系に供給されて内燃機関の燃料とされる。
また、水素貯槽29に貯蔵された水素は、水素インジェクタ45Aによって排気触媒コンバータ17へ供給すると、リーンバーン状態で発生量が増加した窒素酸化物の濃度を低下させることができる。
また、以上の説明では、水素はシリンダの外部において吸気系の空気に混合されることを説明したが、水素は加圧されて貯蔵された水素貯槽からシリンダ内に直接供給することもできる。
内燃機関1の始動時に、ステップS21により運転条件を検知し、ステップS22で必要水素量が計算される。次にステップS23で脱水素反応器19の脱水素反応部の脱水素触媒温度が検知されステップS24により噴射すべき水素供給体量が算出され水素供給体が算出量に応じて噴射される。
このとき脱水素反応器の脱水素触媒の温度がステップS25により300℃以下と判断された場合は、ステップS26で脱水素触媒温度を上昇させるために水素貯蔵体貯槽31に貯留された脱水素生成物である水素貯蔵体を水素貯蔵体供給管37を通じて供給する供給ポンプ38、インジェクタ40、水素貯蔵体を燃焼させるための空気供給手段35を駆動させることにより温度を上昇させる。
また、本発明の脱水素反応器においては、加熱用電気ヒータを装着して通電加熱したり、あるいは脱水素反応器の脱水素反応部の基材金属に直接通電して加熱しても良い。
図3(A)は、平面図、図3(B)は、A−A’線で切断した断面図、図3(C)は、B−B’線で切断した断面図、図3(D)は、図3(C)で示した一つの反応管の拡大図である。
脱水素反応器19は、内部にステンレス鋼等の耐熱性金属材料からなる筐体61の内に、脱水素反応部63、酸化反応部65を両面に形成した少なくとも1個の反応管62を有している。
反応管62は、ステンレス鋼、ニッケル合金等の金属基材67の両面に、クラッド、無電解めっき等の方法によってアルミニウム層69が積層されたものであって、アルミニウム層の表面は、アルマイト処理を行った後に、更に熱水処理等の方法によって多孔質なアルミナ層を形成されている。そして、多孔質アルミナ層上には、脱水素触媒71および酸化触媒73が担持されている。
脱水素触媒、酸化触媒は、白金、パラジウム、ロジウム、レニウム、ルテニウムから選ばれる少なくとも一種の元素を含む化合物の溶液を塗布した後に焼成することによって製造することができる。
また、耐熱性の金属材料に通電手段を接続して自動車に搭載した電池等の電源から通電し、耐熱性の金属材料自体を加熱することによって脱水素触媒を所定の温度としても良い。
図3に示した脱水素反応器では、管状の反応器を例に挙げて説明したが、連続した波板上の部材の両面にそれぞれ、脱水素触媒層、酸化触媒層を設けたものであっても良い。
実施例1および比較例1
1Lエンジンを搭載した自動車に図3に示すフィン型白金担持アルマイト触媒管状リアクタを有する水素発生装置を搭載し、触媒の温度をエンジン排気による加熱で300℃−350℃の間に保持して、有機ハイドライドとしてメチルシクロヘキサンを触媒に噴射して水素を発生させた。
発生した水素を10−50L/分の供給速度で水素インジェクタからエンジンに導入した。ガソリンに水素を添加したガソリン−水素混焼システムと、従来のガソリンのみを用いたガソリン燃焼システムについて排出二酸化炭素濃度と燃料消費率をシャーシダイナモにおいて測定して、その結果をエンジン回転数(rpm)、空気/燃料比とともに表1に示す。
実施例については試験1−1〜1−4に示し、比較例については、比1−1〜1−2に示す。
なお、試験1−1,1−2,1−4,1−5では、ガソリン供給量:3.1L/h
試験1−3では、ガソリン供給量:4.2L/h
比較1−1,1−2では、ガソリン供給量:6.1L/h
の条件で運転した。またいずれも、アクセル開度30%でエンジンを稼働した。
水素を排気浄化触媒コンバータに供給した点を除き実施例1と同様にエンジンを運転した場合の排気中の窒素酸化物濃度の変化を、試験2−1〜2-4および比較2−1〜2−4として表2に示す。
なお、試験2−1、2−2、2−4、及び比較2−1〜2−4では、
ガソリン供給量:3.1L/h
試験2−3、及び比較2−3では、
ガソリン供給量:4.2L/h で運転した。またいずれも、アクセル開度30%でエンジンを稼働した。
Claims (9)
- 水素供給体および炭化水素系燃料の少なくともいずれか一方を燃料源とし、水素供給体から水素を生成する脱水素反応器を備え、脱水素反応器は一方の面に脱水素触媒を担持した水素発生部を有し、他方の面には内燃機関からの排気が通過するとともに水素供給体から生成した脱水素生成物を酸化して発熱させる酸化触媒を担持した酸化反応部を有し、発生した水素と脱水素生成物とを分離する水素分離手段、分離された水素を貯蔵する貯蔵手段および脱水素生成物を貯蔵する手段、および発生した水素を燃料源に添加供給する手段とを備えたことを特徴とする内燃機関用水素供給装置。
- 脱水素反応器の脱水素触媒および酸化触媒は、基材金属に積層したアルミニウム層のアルマイト化の後に形成された多孔質アルミナ層の表面に担持されたものであることを特徴とする請求項1記載の内燃機関用水素供給装置。
- 基材金属自体への通電加熱によって脱水素触媒を加熱する通電加熱手段を有することを特徴とする請求項2記載の内燃機関用水素供給装置。
- 脱水素反応器には、温度センサ、水素供給体噴射ノズルとともに、水素反応部の加熱用の脱水素生成物供給ノズルおよび空気供給管が設けられていることを特徴とする請求項1ないし3のいずれか1項記載の内燃機関用水素供給装置。
- 脱水素反応器に接続する排気管には、排気管を分岐する分岐部が設けられ、分岐部には水素発生部の温度によって流量が調整される排気流量調整弁が設けられたことを特徴とする請求項1ないし4のいずれか1項記載の内燃機関用水素供給装置。
- 発生した水素を排気浄化触媒コンバータに供給する水素供給手段を設けたことを特徴とする請求項1ないし5のいずれか1項記載の内燃機関用水素供給装置。
- 水素供給体および炭化水素系燃料の少なくともいずれか一方を燃料源とし、水素供給体から水素を生成する脱水素反応器を備え、脱水素反応器は一方の面に脱水素触媒を担持した水素発生部を有し、他方の面には内燃機関からの排気が通過するとともに、水素供給体から生成した脱水素生成物を酸化して発熱させる酸化触媒を担持した酸化反応部を有し、発生した水素と脱水素生成物とを分離する水素分離手段、分離された水素を貯蔵する貯蔵手段および脱水素生成物を貯蔵する手段、および発生した水素を燃料源に添加供給する手段を備え、内燃機関の排気管から大気に放出される二酸化炭素濃度の量を濃度センサによって測定し、二酸化炭素の測定値が所定値以下となるように炭化水素燃料に対する水素の混合比率を制御することを特徴とする内燃機関の運転方法。
- 脱水素反応器を構成する部材への通電加熱によって脱水素触媒を加熱することを特徴とする請求項7記載の内燃機関の運転方法。
- 脱水素反応器の水素反応部の温度が所定の温度以下の場合に、脱水素生成物供給ノズルから脱水素生成物と、空気供給管から供給される空気によって脱水素生成物の燃焼させて、水素反応部を所定の温度に加熱した後に水素供給体噴射ノズルから水素供給体を噴射して脱水素反応を行うことを特徴とする請求項7または8のいずれか1項に記載の内燃機関の運転方法。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009553329A JP5159800B2 (ja) | 2008-02-13 | 2008-07-04 | 内燃機関用水素供給装置および内燃機関の運転方法 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008032353 | 2008-02-13 | ||
JP2008032353 | 2008-02-13 | ||
JP2009553329A JP5159800B2 (ja) | 2008-02-13 | 2008-07-04 | 内燃機関用水素供給装置および内燃機関の運転方法 |
PCT/JP2008/062196 WO2009101715A1 (ja) | 2008-02-13 | 2008-07-04 | 内燃機関用水素供給装置および内燃機関の運転方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPWO2009101715A1 JPWO2009101715A1 (ja) | 2011-06-02 |
JP5159800B2 true JP5159800B2 (ja) | 2013-03-13 |
Family
ID=40956759
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2009553329A Active JP5159800B2 (ja) | 2008-02-13 | 2008-07-04 | 内燃機関用水素供給装置および内燃機関の運転方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20110036310A1 (ja) |
JP (1) | JP5159800B2 (ja) |
CN (1) | CN102007286B (ja) |
GB (1) | GB2469977B (ja) |
WO (1) | WO2009101715A1 (ja) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102010003382B4 (de) * | 2010-03-29 | 2014-07-17 | Faktorplus Green Technology Gmbh | Verfahren zum Emissionsmindern von Verbrennungskraftmaschinen und Verbrennungskraftmaschine |
DE102010042678B4 (de) * | 2010-10-20 | 2015-05-13 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Vorrichtung und Verfahren zur Erzeugung von mechanischer und elektrischer Energie aus einem Brennstoff |
CN101982653B (zh) * | 2010-10-22 | 2012-07-25 | 北京工业大学 | 一种重整气制备、存储装置及其控制方法 |
US9932912B2 (en) * | 2011-03-04 | 2018-04-03 | General Electric Company | Methods and systems for emissions control in a dual fuel engine |
JP2013087820A (ja) * | 2011-10-14 | 2013-05-13 | Jx Nippon Oil & Energy Corp | 水素ステーション |
CN102518531B (zh) * | 2011-12-05 | 2016-01-06 | 北京理工大学 | 一种进气道喷射氢内燃机的燃料供应装置及其控制方法 |
DE102016011208A1 (de) * | 2016-09-16 | 2018-03-22 | Friedrich-Alexander-Universität Erlangen-Nürnberg | Verfahren und Vorrichtung zur Verminderung des Stickoxidausstoßes von Verbrennungsmotoren |
EP3607179A4 (en) * | 2017-04-04 | 2020-10-21 | BASF Corporation | HYDROGEN REDUCING AGENTS FOR CATALYTIC POLLUTION REDUCTION |
CN109850846B (zh) * | 2019-01-29 | 2022-06-07 | 武汉船用电力推进装置研究所(中国船舶重工集团公司第七一二研究所) | 一种自热式有机液体脱氢供氢系统及其应用 |
JP2021160960A (ja) * | 2020-03-31 | 2021-10-11 | Eneos株式会社 | 水素供給システム |
CN113548643B (zh) * | 2021-07-16 | 2024-03-01 | 陕西氢易能源科技有限公司 | 一种集成高温热泵的有机液体供氢系统 |
US20230358186A1 (en) * | 2022-05-05 | 2023-11-09 | Caterpillar Inc. | Dual fuel engine operating strategy for optimized hydrogen and hydrocarbon fueling |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003184667A (ja) * | 2001-12-19 | 2003-07-03 | Honda Motor Co Ltd | 内燃機関を搭載し,且つ燃料の改質・供給機能を有する車両 |
JP2005147124A (ja) * | 2003-10-21 | 2005-06-09 | Toyota Motor Corp | 水素利用内燃機関 |
JP2006257906A (ja) * | 2005-03-15 | 2006-09-28 | Toyota Motor Corp | 水素利用内燃機関 |
JP2007138799A (ja) * | 2005-11-17 | 2007-06-07 | Toyota Motor Corp | 水素利用内燃機関 |
JP2007239671A (ja) * | 2006-03-10 | 2007-09-20 | Hitachi Ltd | エンジンシステム |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5253148A (en) * | 1975-10-28 | 1977-04-28 | Nissan Motor Co Ltd | Air/fuel ratio controller |
SE514089C2 (sv) * | 1999-04-16 | 2000-12-18 | Volvo Lastvagnar Ab | Tryckluftssystem i ett fordon, innefattande en oxidationskatalysator för rening av tryckluften |
JP3998432B2 (ja) * | 2001-04-05 | 2007-10-24 | 三菱ふそうトラック・バス株式会社 | 蓄圧式燃料噴射装置 |
US7482303B2 (en) * | 2001-10-10 | 2009-01-27 | Dominique Bosteels | Catalytic burning reaction |
US6827047B2 (en) * | 2001-12-19 | 2004-12-07 | Honda Giken Kogyo Kabushiki Kaisha | Vehicle provided with internal combustion engine and fuel reforming/supplying functions |
CA2422188A1 (en) * | 2002-10-02 | 2004-04-02 | Westport Research Inc. | Bypass controlled regeneration of nox adsorbers |
KR101052385B1 (ko) * | 2002-10-18 | 2011-07-28 | 몬산토 테크놀로지 엘엘씨 | 알코올 개질용 금속 지지 구리 촉매의 용도 |
CN100427741C (zh) * | 2003-10-21 | 2008-10-22 | 丰田自动车株式会社 | 氢利用内燃机 |
US7951349B2 (en) * | 2006-05-08 | 2011-05-31 | The California Institute Of Technology | Method and system for storing and generating hydrogen |
-
2008
- 2008-07-04 CN CN2008801286244A patent/CN102007286B/zh active Active
- 2008-07-04 WO PCT/JP2008/062196 patent/WO2009101715A1/ja active Application Filing
- 2008-07-04 US US12/867,678 patent/US20110036310A1/en not_active Abandoned
- 2008-07-04 JP JP2009553329A patent/JP5159800B2/ja active Active
- 2008-07-04 GB GB1014737.9A patent/GB2469977B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003184667A (ja) * | 2001-12-19 | 2003-07-03 | Honda Motor Co Ltd | 内燃機関を搭載し,且つ燃料の改質・供給機能を有する車両 |
JP2005147124A (ja) * | 2003-10-21 | 2005-06-09 | Toyota Motor Corp | 水素利用内燃機関 |
JP2006257906A (ja) * | 2005-03-15 | 2006-09-28 | Toyota Motor Corp | 水素利用内燃機関 |
JP2007138799A (ja) * | 2005-11-17 | 2007-06-07 | Toyota Motor Corp | 水素利用内燃機関 |
JP2007239671A (ja) * | 2006-03-10 | 2007-09-20 | Hitachi Ltd | エンジンシステム |
Also Published As
Publication number | Publication date |
---|---|
GB201014737D0 (en) | 2010-10-20 |
CN102007286A (zh) | 2011-04-06 |
JPWO2009101715A1 (ja) | 2011-06-02 |
WO2009101715A1 (ja) | 2009-08-20 |
GB2469977B (en) | 2012-05-23 |
US20110036310A1 (en) | 2011-02-17 |
GB2469977A (en) | 2010-11-03 |
CN102007286B (zh) | 2013-03-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5159800B2 (ja) | 内燃機関用水素供給装置および内燃機関の運転方法 | |
JP4039383B2 (ja) | 水素利用内燃機関 | |
JP6263256B2 (ja) | フレックス燃料水素発生器 | |
US8061120B2 (en) | Catalytic EGR oxidizer for IC engines and gas turbines | |
US8561578B2 (en) | Hydrogen generator and internal combustion engine provided with hydrogen generator | |
JP6233035B2 (ja) | 内燃機関 | |
WO2020246302A1 (ja) | アンモニア燃焼システム | |
Woo et al. | On-board LPG reforming system for an LPG· hydrogen mixed combustion engine | |
US7700070B2 (en) | Process and apparatus for catalytic conversion of hydrocarbons for generating a gas rich in hydrogen | |
JP2011162372A (ja) | 水素製造システム | |
JP2013130179A (ja) | 内燃機関の制御装置 | |
KR101866886B1 (ko) | 연료 개질기 | |
RU2488013C2 (ru) | Способ работы двигателя внутреннего сгорания | |
KR101866899B1 (ko) | 연료 개질기 | |
JP2004189585A (ja) | 水素ガス生成装置 | |
CN108060955B (zh) | 废热重组产氢装置 | |
JP2004251196A (ja) | 改質ガス製造装置、これを用いた改質ガス製造方法及び排気浄化システム | |
US9162203B1 (en) | Hydrogen generator | |
TWI609130B (zh) | Waste heat recombination hydrogen production device | |
JP2006052688A (ja) | 内燃機関用燃料の供給方法および内燃機関用燃料供給装置 | |
Marsh et al. | SULEV emission technologies for a five cylinder N/A engine | |
US10337465B2 (en) | Device for producing hydrogen by reforming reaction and waste heat | |
Sendilvelan et al. | Pollution studies on gasoline engine with electrically heated catalyst | |
JP2014156823A (ja) | 燃料改質装置 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20110701 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120608 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120731 |
|
A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20120731 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20120731 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120924 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20121130 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20121211 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 5159800 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20151221 Year of fee payment: 3 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |