JP2007246737A - Unleaded high-octane number gasoline - Google Patents
Unleaded high-octane number gasoline Download PDFInfo
- Publication number
- JP2007246737A JP2007246737A JP2006073663A JP2006073663A JP2007246737A JP 2007246737 A JP2007246737 A JP 2007246737A JP 2006073663 A JP2006073663 A JP 2006073663A JP 2006073663 A JP2006073663 A JP 2006073663A JP 2007246737 A JP2007246737 A JP 2007246737A
- Authority
- JP
- Japan
- Prior art keywords
- gasoline
- content
- less
- volume
- octane
- 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.)
- Granted
Links
- 239000003502 gasoline Substances 0.000 title claims abstract description 82
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 32
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 27
- 125000003118 aryl group Chemical group 0.000 claims abstract description 24
- 238000004821 distillation Methods 0.000 claims abstract description 16
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001336 alkenes Chemical class 0.000 claims abstract description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- 239000011593 sulfur Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 30
- 235000014676 Phragmites communis Nutrition 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 16
- 238000002156 mixing Methods 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 7
- 230000001133 acceleration Effects 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 238000004523 catalytic cracking Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 230000003749 cleanliness Effects 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000001273 butane Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000001833 catalytic reforming Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- -1 alkaline earth metal salts Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000002816 fuel additive Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003556 thioamides Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Liquid Carbonaceous Fuels (AREA)
Abstract
Description
本発明は、エタノールおよびエチル・ターシャリー・ブチル・エーテルを配合したガソリンに関し、詳しくは特定された蒸留性状及び特定された成分組成を有し、自動車用燃料として環境に配慮し、かつ始動性、運転性、及び吸気バルブの清浄性に優れた無鉛高オクタン価ガソリンに関する。 The present invention relates to a gasoline blended with ethanol and ethyl tertiary butyl ether, and in particular, has a specified distillation property and a specified component composition, is environmentally friendly as a fuel for automobiles, and has a startability. The present invention relates to unleaded high octane gasoline with excellent operability and cleanliness of intake valves.
近年、ガソリンエンジン用燃料油としては、高オクタン価で運転性能に優れると共に、環境性能にも優れるものが要望されるようになってきた。
一般に、高オクタン価ガソリンとして、重質で芳香族分含有量の多い高オクタン価基材を配合し、特定の蒸留性状及び成分組成を有するものが知られている(例えば、特許文献1参照)。
In recent years, fuel oils for gasoline engines have been demanded that have a high octane number and excellent driving performance as well as excellent environmental performance.
In general, as a high-octane gasoline, a high octane number base material having a heavy and high aromatic content and a specific distillation property and component composition are known (see, for example, Patent Document 1).
この高オクタン価ガソリンの場合、重質で芳香族分含有量が多い高オクタン価基材を配合するために、高沸点留分のオクタン価は向上するが、ガソリンの重質化、エンジン内のデポジットの生成、特に吸気バルブへのデポジットの付着、及び運転性への影響等が懸念される。
このような、ガソリンの重質化、吸気バルブへのデポジットの付着を改善するには、軽質・高オクタン価基材を配合することが重要であると考えられる。
In the case of this high-octane gasoline, the octane number of the high-boiling fraction is improved because a high-octane base material with a heavy aromatic content is added. However, the gasoline becomes heavier and produces deposits in the engine. In particular, there are concerns about deposits on the intake valves and influence on drivability.
In order to improve the heaviness of gasoline and the adhesion of deposits to the intake valve, it is considered important to add a light and high octane base material.
また、自動車排出ガス中の一酸化炭素(CO)、全炭化水素(THC)等の低減には、含酸素化合物であるメチルターシャリーブチルエーテル(MTBE)を配合したガソリンが知られている(例えば、特許文献2参照)。
しかしながら、MTBEの環境面への影響が懸念され、現在は日本国内でのMTBEを配合したガソリンの生産・販売が自制されている。MTBEはオクタン価が高い基材であるために、MTBEの配合を中止する場合には、それに代わる高いオクタン価基材が必要とされている。その中で、ガソリンのオクタン価低下を補い、また環境負荷が低いと考えられる、MTBE以外の含酸素有機化合物が新しいガソリン基材として注目されている。中でも、エタノールは、オクタン価も高く、芳香族分やオレフィン分を含まず、バイオマスとして考える場合には再生可能燃料としてとらえることができるといった利点を有している(例えば、非特許文献1参照)。
In addition, gasoline that contains methyl tertiary butyl ether (MTBE), which is an oxygen-containing compound, is known for reducing carbon monoxide (CO), total hydrocarbons (THC), and the like in automobile exhaust gases (for example, Patent Document 2).
However, there is concern about the environmental impact of MTBE, and now production and sales of gasoline containing MTBE are restrained in Japan. Since MTBE is a base material having a high octane number, when the mixing of MTBE is stopped, a high octane number base material is required instead. Among them, oxygen-containing organic compounds other than MTBE, which compensate for the decrease in octane number of gasoline and are considered to have a low environmental load, are attracting attention as new gasoline base materials. Among these, ethanol has a high octane number, does not contain aromatics and olefins, and has an advantage that it can be regarded as a renewable fuel when considered as biomass (see, for example, Non-Patent Document 1).
一方、CO2削減の観点から、バイオマス由来のエタノールあるいはそれから派生するETBEをガソリンへ混合する議論がされている。しかしながら、CO2削減量を多くするために、エタノールをよりガソリンに配合しようとすると、炭化水素とエタノールの共沸現象が顕著になり、蒸留曲線がいびつになることで運転性などが悪化する場合があることが知られている。これを回避するために、エタノールをイソブチレンと反応させて得られるETBEをガソリンへ配合することが考えられるが、バイオマス混合によるCO2削減の観点から見ると、多量のETBEをガソリンへ配合する必要が生じ、ガソリン生産の経済性が劣ることになる。 On the other hand, from the viewpoint of CO 2 reduction, there is a discussion of mixing ethanol derived from biomass or ETBE derived therefrom with gasoline. However, if ethanol is added to gasoline in order to increase CO 2 reduction, the azeotropic phenomenon of hydrocarbon and ethanol becomes prominent, and the operability and the like deteriorate due to the distorted distillation curve. It is known that there is. In order to avoid this, it is conceivable to blend ETBE obtained by reacting ethanol with isobutylene into gasoline, but from the viewpoint of CO 2 reduction by biomass mixing, it is necessary to blend a large amount of ETBE into gasoline. This will make the economy of gasoline production inferior.
エタノールとETBEをガソリンに配合したものとしては、エタノールを1〜10容量%、エチル・ターシャリー・ブチル・エーテルを1〜20容量%、炭素数4の炭化水素を5.5容量%以上含有したものや、エタノールを1〜3容量% 、エチル・ターシャリー・ブチル・エーテルを0〜20容量%含有するガソリン組成物が挙げられる(例えば、特許文献3、特許文献4)。 As a blend of ethanol and ETBE in gasoline, it contained 1 to 10% by volume of ethanol, 1 to 20% by volume of ethyl tertiary butyl ether, and 5.5% by volume or more of hydrocarbons having 4 carbon atoms. And gasoline compositions containing 1 to 3% by volume of ethanol and 0 to 20% by volume of ethyl tertiary butyl ether (for example, Patent Document 3 and Patent Document 4).
特許文献3は、エタノールの蒸気圧が従来の石油のみから製造されるガソリンよりも高いことから、エタノールを添加した場合でも、軽質な炭化水素の含有量を減らすことのないことを課題としており、特許文献4は、エタノールの水分の影響について検討し、比較的低濃度のエタノールを添加した場合でも相分離が起こりにくいガソリンの提供を課題としている。しかし、いずれもエタノールとETBEを配合したガソリンによる自動車の始動性や加速性については更なる改善が必要である。 Patent Document 3 has a problem that the content of light hydrocarbons is not reduced even when ethanol is added because the vapor pressure of ethanol is higher than that of gasoline produced only from conventional petroleum. Patent Document 4 examines the influence of the water content of ethanol, and has a problem of providing gasoline that hardly causes phase separation even when a relatively low concentration of ethanol is added. However, in any case, further improvement is required in terms of startability and acceleration of a vehicle using gasoline containing ethanol and ETBE.
本発明は、大気環境に配慮し、自動車の始動性や加速性及びIVD生成が抑制されて吸気バルブの清浄性にも優れたエタノールおよびエチル・ターシャリー・ブチル・エーテル配合無鉛高オクタン価ガソリンを提供することを目的とするものである。 The present invention provides an unleaded high-octane gasoline containing ethanol and ethyl tertiary butyl ether that is superior in intake valve cleanliness, with consideration given to the atmospheric environment, suppression of vehicle startability, acceleration, and IVD generation, and excellent intake valve cleanliness. It is intended to do.
本発明者らは、上記目的を達成するために鋭意研究を重ねた結果、軽質な高オクタン価基材であるエタノール(EtOH)とエチル・ターシャリー・ブチル・エーテル(ETBE)を選定し、EtOHとETBEの特定量と特定の成分組成及び特定の蒸留性状を有するようにガソリンを構成することにより、燃料油中の芳香族分含有量を抑えつつ、吸気バルブの清浄性を改善し、かつ、優れた諸性能を有するガソリンが得られ、上記目的を達成し得ることを見出し、本発明を完成するに至った。
即ち、本発明は、エタノール(EtOH)を0.5〜10.0容量%、エチルターシャリーブチルエーテル(ETBE)を0.5〜15.0容量%含み、かつ、以下の性状を満足することを特徴とする無鉛高オクタン価ガソリンを提供する。
(1)リサーチ法オクタン価(RON)が97〜105
(2)モーター法オクタン価(MON)が84〜92
(3)リード蒸気圧(RVP)が45〜93kPa
(4)50%留出温度(T50)が75〜110℃
(5)芳香族分含有量が45容量%以下
(6)オレフィン分含有量が25容量%以下
(7)ベンゼン含有量が1容量%以下
(8)硫黄分含有量が10質量ppm以下
(9)60℃における気液比(V/L)が30〜70
(10)下記式(1)で表される多環芳香族指数が6以下
Y=(0.002×3R-A)+(0.01×4R-A)+(0.07×5R-A)+(0.2×6R+-A)・・・・(1)
(式中、3R-Aは3環芳香族分量を表し、4R-Aは4環芳香族分量を表し、5R-Aは5環芳香族分量を表し、6R+-Aは6環以上の芳香族分量を表す。なお、該多環芳香族分量はいずれもガソリン中の含有量で質量ppmを示す。)
As a result of intensive research to achieve the above object, the present inventors selected ethanol (EtOH) and ethyl tertiary butyl ether (ETBE), which are light high octane number base materials, and EtOH and By configuring gasoline so that it has a specific amount of ETBE, a specific component composition and a specific distillation property, it improves the cleanliness of the intake valve while suppressing the aromatic content in the fuel oil, and is excellent It was found that gasoline having various performances was obtained, and that the above-mentioned object could be achieved, and the present invention was completed.
That is, the present invention contains 0.5 to 10.0% by volume of ethanol (EtOH), 0.5 to 15.0% by volume of ethyl tertiary butyl ether (ETBE), and satisfies the following properties. Providing unleaded high-octane gasoline.
(1) Research octane number (RON) is 97-105
(2) Motor method octane number (MON) is 84 ~ 92
(3) Reed vapor pressure (RVP) 45 ~ 93kPa
(4) 50% distillation temperature (T50) is 75-110 ° C
(5) Aromatic content 45% or less (6) Olefin content 25% or less (7) Benzene content 1% or less (8) Sulfur content 10 mass ppm or less (9 ) Gas-liquid ratio (V / L) at 60 ℃ is 30 ~ 70
(10) Polycyclic aromatic index represented by the following formula (1) is 6 or less
Y = (0.002 × 3R-A) + (0.01 × 4R-A) + (0.07 × 5R-A) + (0.2 × 6R + -A) ... (1)
(In the formula, 3R-A represents a 3-ring aromatic content, 4R-A represents a 4-ring aromatic content, 5R-A represents a 5-ring aromatic content, and 6R + -A represents an aromatic having 6 or more rings. (The amount of polycyclic aromatics is the content in gasoline and indicates ppm by mass.)
本発明の無鉛高オクタン価ガソリンは、エタノールとエチルターシャリーブチルエーテルを特定量配合し、自動車のガソリンエンジンに用いられ、大気環境の保全性に優れ、始動性や運転性にも優れたものであり、実用性能を維持しつつ大気環境の保全が図られるものである。また、多環芳香族分を環数の多いものほど含有量を順次低く制限して、エンジン内のデポジットの生成の抑制、特に吸気バルブへのデポジットの付着の抑制や、排出ガス中の有害成分量の一層の低減を図っている。 The lead-free high-octane gasoline of the present invention contains a specific amount of ethanol and ethyl tertiary butyl ether, is used in automobile gasoline engines, has excellent air environment conservation, and excellent startability and drivability. It is intended to preserve the atmospheric environment while maintaining practical performance. In addition, the higher the number of polycyclic aromatic components, the lower the content, and the lower the content, the less the formation of deposits in the engine, in particular, the prevention of deposit adhesion to the intake valve, and the harmful components in exhaust gas. The amount is further reduced.
以下、本発明の内容を更に詳しく説明する。
本発明の無鉛高オクタン価ガソリンに用いられるエタノール(EtOH)は、純度が92.0容量%以上であって、好ましくは95.0容量%以上、更に好ましくは99.5容量%以上である。
エタノールの製造方法は特に限定されるものではなく、一般的に製造される全てのエタノールが使用可能である。
エタノールの含有量は、エタノール配合ガソリン全量に対し0.5容量%以上10.0容量%以下の範囲にあり、好ましくは1.0容量%以上7.0容量%以下である。0.5容量%以上であれば、エタノール配合によるオクタン価向上の利点が得られ、10.0容量%以下とすることで他のガソリン基材との共沸現象により蒸発特性が著しく変化することがなく、ガソリン自動車の適正な運転性が確保できる。
Hereinafter, the contents of the present invention will be described in more detail.
Ethanol (EtOH) used in the lead-free high-octane gasoline of the present invention has a purity of 92.0% by volume or more, preferably 95.0% by volume or more, more preferably 99.5% by volume or more.
The method for producing ethanol is not particularly limited, and all generally produced ethanol can be used.
The ethanol content is in the range of 0.5% by volume or more and 10.0% by volume or less, preferably 1.0% by volume or more and 7.0% by volume or less, with respect to the total amount of ethanol-blended gasoline. If it is 0.5% by volume or more, the advantage of improving the octane number by blending with ethanol is obtained, and if it is 10.0% by volume or less, the evaporation characteristics may change significantly due to the azeotropic phenomenon with other gasoline base materials. Therefore, it is possible to ensure proper driving performance of gasoline cars.
本発明の無鉛高オクタン価ガソリンに用いられるエチルターシャリーブチルエーテル(ETBE)は、公知の製造法から得られるもの全て使用可能であり、その製造方法は特に限定されるものではない。本発明の無鉛高オクタン価ガソリンにおけるETBEの配合量は0.5〜15.0容量%、好ましくは1.0〜10.0容量%である。ETBEの配合量が上記範囲内であれば、発熱量の低下による燃費への悪影響の懸念なく、排出ガス中のCO、THC等の低減などを図ることができる。 Any ethyl tertiary butyl ether (ETBE) used in the unleaded high octane gasoline of the present invention can be obtained from a known production method, and the production method is not particularly limited. The blending amount of ETBE in the unleaded high octane gasoline of the present invention is 0.5 to 15.0% by volume, preferably 1.0 to 10.0% by volume. If the blending amount of ETBE is within the above range, it is possible to reduce CO, THC, etc. in the exhaust gas without fear of an adverse effect on fuel consumption due to a decrease in calorific value.
本発明の無鉛高オクタン価ガソリンの(a)リサーチ法オクタン価(RON)は、97〜105、好ましくは97〜102、(b)モーター法オクタン価(MON)は、84〜92、好ましくは84〜90であり、RONが97以上ならば、高い運転性能を維持することが可能となり、MONが84以上であれば高速走行時のアンチノック性の低下を防止することができる。なお、このRON及びMONは、JIS K 2280に準拠して測定した値である。 The lead-free high-octane gasoline of the present invention has a (a) research method octane number (RON) of 97 to 105, preferably 97 to 102, and (b) a motor method octane number (MON) of 84 to 92, preferably 84 to 90. If RON is 97 or higher, it is possible to maintain high driving performance, and if MON is 84 or higher, it is possible to prevent a decrease in anti-knock performance during high-speed driving. Note that RON and MON are values measured in accordance with JIS K 2280.
また、本発明の無鉛高オクタン価ガソリンのリード蒸気圧(RVP)は、45〜93kPa、好ましくは50〜90kPaである。RVPを93kPa以下にすることによって蒸発ガスの量を少なくすることができ、45kPa以上とすることで低温始動性、暖気性の低下を防ぐことができる。なお、このリード蒸気圧(RVP)は、JIS K 2258に準拠して測定した値である。 The lead vapor pressure (RVP) of the unleaded high octane gasoline of the present invention is 45 to 93 kPa, preferably 50 to 90 kPa. By setting the RVP to 93 kPa or less, the amount of evaporative gas can be reduced, and by setting it to 45 kPa or more, it is possible to prevent the low temperature startability and warming performance from being deteriorated. This Reid vapor pressure (RVP) is a value measured according to JIS K 2258.
本発明の無鉛高オクタン価ガソリンの蒸留性状は、50%留出温度(T50)が、75〜110℃、好ましくは75〜105℃であり、T50が上記範囲内であれば、始動性、運転性、加速性に不具合が生じる場合を防ぐことができる。なお、これらの蒸留性状はJIS K 2254に準拠して測定した値である。 The distillation properties of the lead-free high-octane gasoline of the present invention have a 50% distillation temperature (T50) of 75 to 110 ° C., preferably 75 to 105 ° C. If T50 is within the above range, startability and operability. , It is possible to prevent a case where a problem occurs in acceleration. These distillation properties are values measured in accordance with JIS K 2254.
本発明の無鉛高オクタン価ガソリンの芳香族分含有量は、45容量%以下、好ましくは5〜45容量%である。この芳香族分含有量が45容量%以内であれば、排出ガス中の有害成分の増加を防ぐことができる。なお、この芳香族分含有量は、石油学会法JPI-5S-33-90(ガスクロマトグラフ法)に準拠して測定した値である。 The aromatic content of the unleaded high octane gasoline of the present invention is 45% by volume or less, preferably 5 to 45% by volume. When the aromatic content is within 45% by volume, an increase in harmful components in the exhaust gas can be prevented. The aromatic content is a value measured in accordance with the Petroleum Institute Method JPI-5S-33-90 (gas chromatographic method).
本発明の無鉛高オクタン価ガソリンのオレフィン分含有量は、25容量%以下、好ましくは5〜25容量%である。このオレフィン分含有量が25容量%以内であれば、酸化安定性の低下を防ぐことができる。なお、このオレフィン分含有量は、石油学会法JPI-5S-33-90(ガスクロマトグラフ法)に準拠して測定した値である。 The olefin content of the unleaded high octane gasoline of the present invention is 25% by volume or less, preferably 5 to 25% by volume. When the olefin content is within 25% by volume, a decrease in oxidation stability can be prevented. The olefin content is a value measured in accordance with the Petroleum Institute method JPI-5S-33-90 (gas chromatographic method).
本発明の無鉛高オクタン価ガソリンのベンゼン含有量は、1容量%以下、好ましくは0.8容量%以下である。このベンゼン含有量が1容量%以内であれば、大気中のベンゼン濃度の増加を防止し、環境汚染を低減できる可能性がある。なお、このベンゼン含有量は、石油学会法JPI-5S-33-90(ガスクロマトグラフ法)に準拠して測定した値である。 The lead-free high octane gasoline of the present invention has a benzene content of 1% by volume or less, preferably 0.8% by volume or less. If the benzene content is within 1% by volume, there is a possibility that the increase in benzene concentration in the atmosphere can be prevented and environmental pollution can be reduced. The benzene content is a value measured according to the Petroleum Institute method JPI-5S-33-90 (gas chromatographic method).
本発明の無鉛高オクタン価ガソリンの硫黄分含有量は、10質量ppm以下、好ましくは8質量ppm以下である。この硫黄分含有量が10質量ppm以内であれば、排出ガス浄化触媒の能力低下を防止し、排出ガス中のNOx、CO、THCの濃度上昇を防止できる可能性がある。なお、この硫黄分含有量は、JIS K 2541に準拠して測定した値である。 The lead content of the lead-free high octane gasoline of the present invention is 10 ppm by mass or less, preferably 8 ppm by mass or less. If the sulfur content is within 10 ppm by mass, there is a possibility that the exhaust gas purification catalyst capacity can be prevented from being lowered and the concentration of NOx, CO and THC in the exhaust gas can be prevented from increasing. The sulfur content is a value measured according to JIS K 2541.
本発明の無鉛高オクタン価ガソリンの60℃における気液比(V/L)は、30〜70、好ましくは30〜60である。このV/Lが30以上とすることで、良好な始動性を確保することができる。また、V/Lを70以下とすることで、加速性、運転性の不具合が低減できる可能性がある。なお、このV/Lは、ASTM D 2533-93aに準拠して測定した値である。 The gas-liquid ratio (V / L) at 60 ° C. of the unleaded high octane gasoline of the present invention is 30 to 70, preferably 30 to 60. When this V / L is 30 or more, good startability can be ensured. In addition, by setting V / L to 70 or less, there is a possibility that defects in acceleration and drivability can be reduced. The V / L is a value measured according to ASTM D 2533-93a.
本発明の無鉛高オクタン価ガソリンにおいて、炭素数9以上の芳香族分と全芳香族分の比(以下、(C9+A)/TAともいう。)は0.80以下、好ましくは0.10〜0.80である。炭素数9以上の芳香族分と全芳香族分の比が0.80以下ならば、プラグの対くすぶり性の低下を防止できる可能性があるので好ましい。なお、この芳香族分含有量は、石油学会法JPI-5S-33-90(ガスクロマトグラフ法)に準拠して測定した値である。 In the lead-free high-octane gasoline of the present invention, the ratio of aromatics having 9 or more carbon atoms to the total aromatics (hereinafter also referred to as (C9 + A) / TA) is 0.80 or less, preferably 0.10 to 0.00. 80. It is preferable that the ratio of the aromatic component having 9 or more carbon atoms and the total aromatic component is 0.80 or less because it is possible to prevent the smoldering property of the plug from being lowered. The aromatic content is a value measured in accordance with the Petroleum Institute Method JPI-5S-33-90 (gas chromatographic method).
そして、本発明の無鉛高オクタン価ガソリンは、式(1)で表される多環芳香族分指数Yが6以下、好ましくは5.5以下、更に好ましくは5以下である。
Y=(0.002×3R-A)+(0.01×4R-A)+(0.07×5R-A)+(0.2×6R+-A)・・・・(1)
〔式中、3R-Aは3環芳香族分量、4R-Aは4環芳香族分量、5R-Aは5環芳香族分量、6R+-Aは6環以上の芳香族分量(何れもガソリン中の含有量で質量ppm)を示す〕
ここで、多環芳香族指数Yは、多環芳香族分の含有量とエンジン内のデポジット量の関係から求められる実験式であり、3環、4環、5環、6環以上と多環になるほど高い値を示す。これは、排出ガス中の有害成分の増加、及びエンジン内のデポジットの生成が多環ほど高くなることを示している。
該指数Yが6以下であれば、排出ガス中の有害成分の増加、及びエンジン内のデポジットの生成の増加を防ぐことができる。なお、これら多環芳香族分含有量は、以下に示すガスクロマトグラフ法により環数別の定量を行った値であり、定量法は環数別の代表的な標準試料による絶対検量線法とした。すなわち、カラムには長さ30m、内径0.25mmであるジメチルシリコンのキャピラリーカラムを用い、検出器は水素イオン化検出器(FID)、キャリアガスは流量1.3ml/minのヘリウム、スプリットレス注入、注入口温度300℃、検出器温度350℃の条件において、カラム温度を初期温度50℃より終期温度350℃まで昇温させて測定した値である。
The lead-free high octane gasoline of the present invention has a polycyclic aromatic content index Y represented by the formula (1) of 6 or less, preferably 5.5 or less, more preferably 5 or less.
Y = (0.002 × 3R-A) + (0.01 × 4R-A) + (0.07 × 5R-A) + (0.2 × 6R + -A) ... (1)
[In the formula, 3R-A is a 3-ring aromatic content, 4R-A is a 4-ring aromatic content, 5R-A is a 5-ring aromatic content, 6R + -A is an aromatic content of 6 or more rings (both in gasoline) (Ppm by mass)
Here, the polycyclic aromatic index Y is an empirical formula obtained from the relationship between the content of polycyclic aromatics and the amount of deposits in the engine, and is composed of three rings, four rings, five rings, six rings or more. The higher the value is. This indicates that the increase in harmful components in the exhaust gas and the generation of deposits in the engine become higher as the polycycle increases.
If the index Y is 6 or less, it is possible to prevent an increase in harmful components in the exhaust gas and an increase in the generation of deposits in the engine. The polycyclic aromatic content is a value determined by the number of rings by the gas chromatographic method shown below, and the quantitative method is an absolute calibration curve method using typical standard samples by number of rings. . That is, a dimethyl silicon capillary column with a length of 30 m and an inner diameter of 0.25 mm is used as the column, the detector is a hydrogen ionization detector (FID), the carrier gas is helium at a flow rate of 1.3 ml / min, splitless injection, inlet temperature This is a value measured by raising the column temperature from the initial temperature of 50 ° C. to the final temperature of 350 ° C. under the conditions of 300 ° C. and detector temperature of 350 ° C.
上記のような性状を有する無鉛高オクタン価ガソリンを製造するためのEtOHおよびETBE以外の基材については、特に制限はないが、例えば、下記のような各種留分を基材として用いることができる。
(イ)重質の直留ナフサなどを接触改質法(プラットフォーミング法、マグナフォーミング法、アロマイジング法、レニフォーミング法、フードリフォーミング法、ウルトラフォーミング法、パワーフォーミング法等)により、水素気流中で高温・加圧下で触媒(例えば、アルミナ担体に白金やロジウムと塩素とを担持したもの等)と接触処理して得られた改質ガソリンからベンゼン留分を蒸留により取り除いた脱ベンゼン接触改質ガソリン。
(ロ)上記接触改質法により接触処理して得られた改質ガソリンを蒸留により、軽質留分、ベンゼン留分、重質留分に分けた内の軽質留分(脱ベンゼン軽質接触改質ガソリン)及び重質留分(脱ベンゼン重質接触改質ガソリン)。
(ハ)灯・軽油から常圧残油に至る石油留分、好ましくは重質軽油や減圧軽油を、従来から知られている接触分解法、特に流動接触分解法(UOP法、シェル二段式法、フレキシ
クラッキング法、ウルトラオルソフロー法、テキサコ法、ガルフ法、ウルトラキャットクラッキング法、RCC法、HOC法等)により、固体酸触媒(例えば、シリカ・アルミナにゼオライトを配合したもの等)で分解して得られた接触分解ガソリンを蒸留して得られる軽質接触分解ガソリン。
(ニ)イソブタンと低級オレフィン(ブテン、プロピレン等)を原料として、酸触媒(硫酸、フッ化水素、塩化アルミニウム等)の存在下で反応させて得られるアルキレート。
(ホ)原油や粗油等の常圧蒸留時、改質ガソリン製造時、あるいは分解ガソリン製造時等に蒸留して得られるブタン、ブテン類を主成分としたC4留分。
(ヘ)直鎖の低級パラフィン系炭化水素の異性化によって得られるアイソメレート、あるいはアイソメレートを精密蒸留して得られるイソペンタン、接触改質ガソリンから得られるトルエン、キシレン、あるいは炭素数9以上の芳香族を主体とする成分等。
The base material other than EtOH and ETBE for producing unleaded high octane gasoline having the above-described properties is not particularly limited. For example, the following various fractions can be used as the base material.
(B) Hydrogen stream by contact reforming method (Platforming method, Magnaforming method, Aromaizing method, Reforming method, Food reforming method, Ultraforming method, Powerforming method, etc.) for heavy straight-run naphtha, etc. In which the benzene fraction is removed by distillation from a reformed gasoline obtained by contact treatment with a catalyst (for example, platinum, rhodium and chlorine supported on an alumina carrier) at high temperature and pressure. Quality gasoline.
(B) The reformed gasoline obtained by contact treatment by the above catalytic reforming method is separated into light fraction, benzene fraction, and heavy fraction by distillation. Gasoline) and heavy fractions (debenzene heavy catalytic reforming gasoline).
(C) Petroleum fraction ranging from kerosene / light oil to atmospheric residual oil, preferably heavy gas oil or vacuum gas oil, is conventionally known catalytic cracking method, especially fluid catalytic cracking method (UOP method, shell two-stage type) Decomposition with a solid acid catalyst (eg, silica / alumina blended with zeolite) by the method, flexi cracking method, ultra ortho flow method, texaco method, Gulf method, ultra cat cracking method, RCC method, HOC method Light catalytic cracking gasoline obtained by distilling the catalytic cracking gasoline obtained in this way.
(D) An alkylate obtained by reacting isobutane and a lower olefin (butene, propylene, etc.) in the presence of an acid catalyst (sulfuric acid, hydrogen fluoride, aluminum chloride, etc.).
(E) C4 fractions mainly composed of butane and butenes obtained by distillation during the atmospheric distillation of crude oil or crude oil, during the production of reformed gasoline, or during the production of cracked gasoline.
(F) Isomerate obtained by isomerization of straight-chain lower paraffin hydrocarbons, or isopentane obtained by precision distillation of isomerate, toluene, xylene obtained from catalytically reformed gasoline, or fragrance having 9 or more carbon atoms Ingredients mainly composed of tribes.
上記のような各種留分を、前記各性状を満たすように、該各種留分の性状等に応じて配合量を適宜選択して、EtOH+ETBEと共に適宜配合することにより本発明の無鉛高オクタン価ガソリンを製造することができる。例えば、(I)EtOHを0.5〜10.0容量%、(II)ETBEを0.5〜15.0容量%、(III)RONが100以上、MONが88以上、RVPが30kPa以上、沸点範囲が30〜200℃の脱ベンゼン接触改質ガソリンを2〜50容量%、又は(IV)RONが78以上、MONが70以上、RVPが85kPa以上、沸点範囲が26〜80℃の脱ベンゼン軽質接触改質ガソリンを2〜15容量%、RONが101以上、MONが89以上、RVPが3kPa以上、沸点範囲が90〜200℃の脱ベンゼン重質接触改質ガソリンを2〜50容量%、及び(V)RONが93以上、MONが81以上、RVPが90kPa以上、沸点範囲が25〜110℃の軽質接触分解ガソリンを10〜50容量%、前記各性状を満たすように配合して本発明の無鉛高オクタン価ガソリンを製造することができる。また、上記のような各基材の配合物に、更に(VI)RONが93以上、MONが90以上、RVPが40kPa以上、沸点範囲が30〜210℃、C8留分が65容量%以上のアルキレートを5〜30容量%、又はブタン、ブテン類を主成分としたC4留分を1〜10容量%、前記各性状を満たすように配合して本発明の無鉛高オクタン価ガソリンを製造することもできる。 The unleaded high-octane gasoline of the present invention can be obtained by appropriately blending the various fractions as described above according to the properties of the various fractions so as to satisfy the properties and appropriately blending with EtOH + ETBE. Can be manufactured. For example, (I) EtOH is 0.5-10.0% by volume, (II) ETBE is 0.5-15.0% by volume, (III) RON is 100 or more, MON is 88 or more, RVP is 30kPa or more, and the boiling point range is 30 to 200 ° C. 2 to 50% by volume of debenzene-catalyzed reformed gasoline, or (IV) 2 or more of debenzene light-catalyzed reformed gasoline with RON of 78 or more, MON of 70 or more, RVP of 85 kPa or more, and boiling point range of 26-80 ° C 15% by volume, RON is 101 or more, MON is 89 or more, RVP is 3kPa or more, 2-50% by volume of debenzene heavy catalytic reforming gasoline with a boiling range of 90-200 ° C, and (V) RON is 93 or more , MON is 81 or more, RVP is 90 kPa or more, and light catalytic cracking gasoline having a boiling point range of 25 to 110 ° C. is blended so as to satisfy the above properties, and the unleaded high octane gasoline of the present invention is produced. be able to. In addition, the composition of each substrate as described above has (VI) RON of 93 or more, MON of 90 or more, RVP of 40 kPa or more, boiling range of 30 to 210 ° C., and C8 fraction of 65% by volume or more. The lead-free high-octane gasoline of the present invention is produced by blending 5 to 30% by volume of alkylate or 1 to 10% by volume of C4 fraction mainly composed of butane and butenes so as to satisfy the above properties. You can also.
さらに、本発明の無鉛高オクタン価ガソリンには、必要に応じて、各種の添加剤を適宜配合することが出来る。このような添加剤としては、フェノール系、アミン系等の酸化防止剤、チオアミド化合物等の金属不活性剤、有機リン系化合物等の表面着火防止剤、コハク酸イミド、ポリアルキルアミン、ポリエーテルアミン、ポリイソブチレンアミン等の清浄分散剤、多価アルコール及びそのエーテル等の氷結防止剤、有機酸のアルカリ金属やアルカリ土類金属塩、高級アルコールの硫酸エステル等の助燃剤、アニオン系界面活性剤、カチオン系界面活性剤、両性界面活性剤等の帯電防止剤、アルケニル琥珀酸エステル等の錆止め剤、及びアゾ染料等の着色剤等、公知の燃料添加剤が挙げられる。これらを1種または数種組み合わせて添加することが出来る。これら燃料添加剤の添加量は任意であるが、通常、その合計添加量が0.1質量%以下とすることが好ましい。 Furthermore, various additives can be appropriately blended in the lead-free high octane gasoline of the present invention as necessary. Such additives include phenolic and amine antioxidants, metal deactivators such as thioamide compounds, surface ignition inhibitors such as organophosphorus compounds, succinimides, polyalkylamines, polyetheramines. Detergents such as polyisobutylene amine, anti-freezing agents such as polyhydric alcohols and ethers thereof, organic metal alkali metal and alkaline earth metal salts, auxiliary alcohols such as higher alcohol sulfates, anionic surfactants, Known fuel additives include antistatic agents such as cationic surfactants and amphoteric surfactants, rust inhibitors such as alkenyl succinates, and colorants such as azo dyes. These can be added singly or in combination. The addition amount of these fuel additives is arbitrary, but usually the total addition amount is preferably 0.1% by mass or less.
以下に本発明の内容を実施例及び比較例により具体的に説明するが、本発明はこれらによって制限されるものではない。 The content of the present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
実施例1,2
接触分解装置、接触改質装置又は常圧蒸留装置から生成するC4留分(ブタン、ブテン類)、表2に示す性状の脱ベンゼン接触改質ガソリン、脱ベンゼン軽質接触改質ガソリン、脱ベンゼン重質接触改質ガソリン、軽質接触分解ガソリン、アルキレート、及びETBE、EtOHを表3に示す配合比で配合することにより、表3に記載する性状のガソリンを得た。
Examples 1 and 2
C4 fraction (butane, butenes) produced from catalytic cracking equipment, catalytic reforming equipment or atmospheric distillation equipment, debenzene catalyzed reformed gasoline, debenzene light catalytic reformed gasoline, debenzene heavy weight with properties shown in Table 2 Gasoline reforming gasoline, light catalytic cracking gasoline, alkylate, ETBE, and EtOH were blended at the blending ratios shown in Table 3 to obtain gasoline having the properties shown in Table 3.
比較例1〜3
実施例1、2に記載のC4留分(ブタン、ブテン類)、脱ベンゼン接触改質ガソリン、脱ベンゼン軽質接触改質ガソリン、脱ベンゼン重質接触改質ガソリン、軽質接触分解ガソリン、及びアルキレートを表3に示す配合比で配合することにより、表3に記載する性状のガソリンを得た。
Comparative Examples 1-3
C4 fraction (butane, butenes) described in Examples 1 and 2, debenzene catalytic reformed gasoline, debenzene light catalytic reformed gasoline, debenzene heavy catalytic reformed gasoline, light catalytic cracked gasoline, and alkylate Were blended at the blending ratios shown in Table 3 to obtain gasoline having the properties shown in Table 3.
上記実施例と比較例で得られたガソリンを用いて、以下に述べる各種の性能評価試験を行った。 Various performance evaluation tests described below were performed using the gasoline obtained in the above Examples and Comparative Examples.
始動性、運転性、及びデメリット点数評価を、排気量2L、直接噴射方式(DI)、オートマチックトランスミッション(AT)の車両を用い、試験温度20℃、湿度50%の条件で行った。
また、吸気バルブデポジット(IVD)試験を、排気量1.5L、マルチポイントインジェクション(MPI)方式の車両を用い、シャシーダイナモにおいて、60−100km/hの加減速×1,500サイクル(8,000km走行)の条件で行った。
これらの評価ないし試験方法を以下に記し、結果を表3に示す。
Startability, drivability, and demerit scores were evaluated using a 2L displacement, direct injection (DI), automatic transmission (AT) vehicle at a test temperature of 20 ° C and humidity of 50%.
In addition, the intake valve deposit (IVD) test was performed using a 1.5-liter, multi-point injection (MPI) type vehicle, and a chassis dynamo with 60-100 km / h acceleration / deceleration x 1,500 cycles (8,000 km travel). I went there.
These evaluations and test methods are described below, and the results are shown in Table 3.
(始動性)
クランキング開始から完爆までの時間(エンジンが自力で回転が続けられるようになるまでの時間)で評価した。
(加速性)
エンジン始動後、10秒間アイドリングを行い、アクセル開度50%で車速が40km/hに到達するまでの時間で評価した。
(デメリット点数)
CRC(Coordinating Research Council)Report No.483評価方法に準拠して評価した。
評価方法としては、発生した現象の程度によって与えられるデメリット点数(Σ=デメリット評点×不具合の係数)により判断した。
なお、アイドル時及び走行中ストールは演算せず、それぞれの係数を加算した。点数が小さい方が性能が優れていることを示す。
(Startability)
The time from cranking start to complete explosion (time until the engine can continue to rotate by itself) was evaluated.
(Acceleration)
The engine was idled for 10 seconds after the engine was started, and the time until the vehicle speed reached 40 km / h with an accelerator opening of 50% was evaluated.
(Demerit points)
Evaluation was performed according to the CRC (Coordinating Research Council) Report No. 483 evaluation method.
The evaluation method was determined by the demerit score given by the degree of the phenomenon that occurred (Σ = demerit score × defect coefficient).
Note that stalls during idling and running were not calculated, and the respective coefficients were added. The smaller the score, the better the performance.
(IVD試験)
運転前後の吸気バルブ重量を秤量することにより得られる、吸気バルブに付着したデポジット(IVD)重量及びIVD評点(Rating:CRC No.16)により評価した。なお、このRating値は、数値が大きい方が、IVD量が少ないことを示す。
(IVD test)
Evaluation was made based on the weight of the deposit (IVD) adhering to the intake valve and the IVD rating (Rating: CRC No. 16) obtained by weighing the intake valve weight before and after operation. The rating value indicates that the larger the numerical value, the smaller the IVD amount.
(プラグのくすぶり性試験)
総排気量2L、MPI方式、オートマチックトランスミッション(AT)の車両を用い、−10℃の試験温度条件で、1サイクル約30分(エンジン始動⇒10−20km/hの加減速を10回繰り返し⇒28分間冷却)の繰返し試験を行い、そのプラグの絶縁抵抗を測定することによりプラグの汚損度を測定した。なお、プラグのくすぶりは、プラグの絶縁抵抗値が100MΩ以下で発生したと判定した。
(Plug smoldering test)
Using a vehicle with a total displacement of 2L, MPI method, automatic transmission (AT), and a test temperature condition of -10 ° C, about 30 minutes per cycle (engine start ⇒ 10-20 km / h acceleration / deceleration repeated 10 times ⇒ 28 The degree of fouling of the plug was measured by measuring the insulation resistance of the plug. It was determined that plug smoldering occurred when the plug insulation resistance value was 100 MΩ or less.
以上の結果から、本発明の無鉛高オクタン価ガソリンは、エタノールとエチルターシャリーブチルエーテルを特定量配合し、始動性や運転性能及び吸気バルブの清浄性に優れ、実用性能を維持しつつ大気環境の保全が図れるものであることは明らかである。 Based on the above results, the lead-free high-octane gasoline of the present invention contains a specific amount of ethanol and ethyl tertiary butyl ether, is excellent in startability, operating performance, cleanliness of the intake valve, and preserves the atmospheric environment while maintaining practical performance It is clear that can be achieved.
Claims (1)
(1)リサーチ法オクタン価(RON)が97〜105
(2)モーター法オクタン価(MON)が84〜92
(3)リード蒸気圧(RVP)が45〜93kPa
(4)50%留出温度(T50)が75〜110℃
(5)芳香族分含有量が45容量%以下
(6)オレフィン分含有量が25容量%以下
(7)ベンゼン含有量が1容量%以下
(8)硫黄分含有量が10質量ppm以下
(9)60℃における気液比(V/L)が30〜70
(10)下記式(1)で表される多環芳香族指数が6以下
Y=(0.002×3R-A)+(0.01×4R-A)+(0.07×5R-A)+(0.2×6R+-A)・・・・(1)
(式中、3R-Aは3環芳香族分量を表し、4R-Aは4環芳香族分量を表し、5R-Aは5環芳香族分量を表し、6R+-Aは6環以上の芳香族分量を表す。なお、該芳香族分量はいずれもガソリン中の含有量で質量ppmを示す。) Lead-free high octane number characterized by containing 0.5-10.0% by volume of ethanol (EtOH) and 0.5-15.0% by volume of ethyl tertiary butyl ether (ETBE) and satisfying the following properties: gasoline.
(1) Research octane number (RON) is 97-105
(2) Motor method octane number (MON) is 84 ~ 92
(3) Reed vapor pressure (RVP) 45 ~ 93kPa
(4) 50% distillation temperature (T50) is 75-110 ° C
(5) Aromatic content 45% or less (6) Olefin content 25% or less (7) Benzene content 1% or less (8) Sulfur content 10 mass ppm or less (9 ) Gas-liquid ratio (V / L) at 60 ℃ is 30 ~ 70
(10) Polycyclic aromatic index represented by the following formula (1) is 6 or less
Y = (0.002 × 3R-A) + (0.01 × 4R-A) + (0.07 × 5R-A) + (0.2 × 6R + -A) ... (1)
(In the formula, 3R-A represents a 3-ring aromatic content, 4R-A represents a 4-ring aromatic content, 5R-A represents a 5-ring aromatic content, and 6R + -A represents an aromatic having 6 or more rings. (The amount of aromatics is the content in gasoline and indicates ppm by mass.)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006073663A JP4913430B2 (en) | 2006-03-17 | 2006-03-17 | Unleaded high octane gasoline |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006073663A JP4913430B2 (en) | 2006-03-17 | 2006-03-17 | Unleaded high octane gasoline |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2007246737A true JP2007246737A (en) | 2007-09-27 |
JP4913430B2 JP4913430B2 (en) | 2012-04-11 |
Family
ID=38591372
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2006073663A Active JP4913430B2 (en) | 2006-03-17 | 2006-03-17 | Unleaded high octane gasoline |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4913430B2 (en) |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6284181A (en) * | 1985-07-31 | 1987-04-17 | エクソン・リサ−チ・アンド・エンジニアリング・カンパニ− | Enhancement of octane value by conversion of condensed polycyclic aromatics or hydroaromatics to low-molecular compound |
JPS6284182A (en) * | 1985-07-31 | 1987-04-17 | エクソン・リサ−チ・アンド・エンジニアリング・カンパニ− | Removal of polycyclic aromatic hydrocarbon compound from liquid hydrocarbon mixture |
JPH07207286A (en) * | 1993-11-30 | 1995-08-08 | Idemitsu Kosan Co Ltd | Fuel oil for gasoline engine |
JP2000073073A (en) * | 1998-08-30 | 2000-03-07 | Nippon Mitsubishi Oil Corp | Unleaded gasoline |
JP2004244532A (en) * | 2003-02-14 | 2004-09-02 | Nippon Oil Corp | Gasoline |
JP2005013306A (en) * | 2003-06-24 | 2005-01-20 | Aruze Corp | Slot machine |
WO2005042672A1 (en) * | 2003-11-04 | 2005-05-12 | Shell Internationale Research Maatschappij B.V. | Process for upgrading a liquid hydrocarbon stream with a non-porous or nano-filtration membrane |
JP2005187706A (en) * | 2003-12-26 | 2005-07-14 | Japan Energy Corp | Ethanol-containing gasoline and method for manufacturing the same |
JP2005213332A (en) * | 2004-01-28 | 2005-08-11 | Japan Energy Corp | Gasoline composition |
-
2006
- 2006-03-17 JP JP2006073663A patent/JP4913430B2/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6284181A (en) * | 1985-07-31 | 1987-04-17 | エクソン・リサ−チ・アンド・エンジニアリング・カンパニ− | Enhancement of octane value by conversion of condensed polycyclic aromatics or hydroaromatics to low-molecular compound |
JPS6284182A (en) * | 1985-07-31 | 1987-04-17 | エクソン・リサ−チ・アンド・エンジニアリング・カンパニ− | Removal of polycyclic aromatic hydrocarbon compound from liquid hydrocarbon mixture |
JPH07207286A (en) * | 1993-11-30 | 1995-08-08 | Idemitsu Kosan Co Ltd | Fuel oil for gasoline engine |
JP2000073073A (en) * | 1998-08-30 | 2000-03-07 | Nippon Mitsubishi Oil Corp | Unleaded gasoline |
JP2004244532A (en) * | 2003-02-14 | 2004-09-02 | Nippon Oil Corp | Gasoline |
JP2005013306A (en) * | 2003-06-24 | 2005-01-20 | Aruze Corp | Slot machine |
WO2005042672A1 (en) * | 2003-11-04 | 2005-05-12 | Shell Internationale Research Maatschappij B.V. | Process for upgrading a liquid hydrocarbon stream with a non-porous or nano-filtration membrane |
JP2005187706A (en) * | 2003-12-26 | 2005-07-14 | Japan Energy Corp | Ethanol-containing gasoline and method for manufacturing the same |
JP2005213332A (en) * | 2004-01-28 | 2005-08-11 | Japan Energy Corp | Gasoline composition |
Also Published As
Publication number | Publication date |
---|---|
JP4913430B2 (en) | 2012-04-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2006213897A (en) | Lead-free high-octane gasoline | |
JP4913448B2 (en) | Unleaded high octane gasoline | |
JP4913441B2 (en) | Unleaded gasoline | |
JP4913440B2 (en) | Unleaded gasoline | |
JP4881638B2 (en) | Unleaded high octane gasoline and method for producing the same | |
JP4913430B2 (en) | Unleaded high octane gasoline | |
JP4913433B2 (en) | Unleaded high octane gasoline | |
JP4913432B2 (en) | Unleaded high octane gasoline | |
JP4913431B2 (en) | Unleaded high octane gasoline | |
JP4913438B2 (en) | Unleaded gasoline | |
JP4913439B2 (en) | Unleaded gasoline | |
JP4913445B2 (en) | Unleaded high octane gasoline | |
JP4913449B2 (en) | Unleaded gasoline | |
JP4913452B2 (en) | Unleaded gasoline | |
JP4804972B2 (en) | Unleaded gasoline and method for producing the same | |
JP4804971B2 (en) | Unleaded gasoline and method for producing the same | |
JP4913451B2 (en) | Unleaded gasoline | |
JP4913447B2 (en) | Unleaded high octane gasoline | |
JP4913429B2 (en) | Unleaded high octane gasoline | |
JP4913446B2 (en) | Unleaded high octane gasoline | |
JP4913450B2 (en) | Unleaded gasoline | |
JP4804973B2 (en) | Unleaded gasoline and method for producing the same | |
JP4913437B2 (en) | Unleaded gasoline | |
JP2007246736A (en) | Unleaded high-octane number gasoline | |
JP2007246756A (en) | Unleaded high octane number gasoline |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20071129 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20081121 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110425 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110510 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110708 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20110830 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20111129 |
|
A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20111207 |
|
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: 20120110 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120119 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 4913430 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: 20150127 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 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |