JP4633352B2 - Fuel composition for diesel engines - Google Patents
Fuel composition for diesel engines Download PDFInfo
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- JP4633352B2 JP4633352B2 JP2003395049A JP2003395049A JP4633352B2 JP 4633352 B2 JP4633352 B2 JP 4633352B2 JP 2003395049 A JP2003395049 A JP 2003395049A JP 2003395049 A JP2003395049 A JP 2003395049A JP 4633352 B2 JP4633352 B2 JP 4633352B2
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- 239000000446 fuel Substances 0.000 title claims description 26
- 239000000203 mixture Substances 0.000 title claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 125000002619 bicyclic group Chemical group 0.000 claims 1
- 239000003205 fragrance Substances 0.000 claims 1
- 239000003921 oil Substances 0.000 description 35
- 235000019198 oils Nutrition 0.000 description 35
- 229920001971 elastomer Polymers 0.000 description 13
- 239000005060 rubber Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000010779 crude oil Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 230000002522 swelling effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000002816 fuel additive Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- -1 fatty acid ester Chemical class 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
本発明は、環境への影響を低減するために硫黄化合物、芳香族炭化水素化合物などの含有量を低減した場合においても、従来のディーゼル自動車などに適合するゴム膨潤性を有するディーゼルエンジン用燃料組成物に関する。 The present invention provides a fuel composition for a diesel engine having rubber swellability suitable for a conventional diesel vehicle even when the content of a sulfur compound, an aromatic hydrocarbon compound or the like is reduced in order to reduce the influence on the environment. Related to things.
近年、自動車の排出ガス規制強化により、ディーゼルエンジンを用いた自動車(ディーゼル自動車)から排出されるNOxやPMを低減するために都市部を中心として排ガス浄化装置の装着が義務付けられている。一方、ディーゼル燃料の硫黄分は排ガス浄化装置に及ぼす悪影響が大きいことから、これを低減することが必要である。 In recent years, due to stricter exhaust gas regulations for automobiles, in order to reduce NOx and PM emitted from automobiles using diesel engines (diesel automobiles), it is mandatory to install exhaust gas purification devices mainly in urban areas. On the other hand, since the sulfur content of diesel fuel has a large adverse effect on the exhaust gas purification device, it is necessary to reduce this.
また、排ガス浄化装置の装着が義務付けされていない地域においてはPMの原因物質を低減する必要があるが、このPMの原因物質のひとつとして二環以上の多環芳香族炭化水素化合物(以下、単に「多環芳香族」ともいう)が挙げられている。 In areas where exhaust gas purification equipment is not required, it is necessary to reduce PM causative substances. As one of the causative substances of PM, two or more polycyclic aromatic hydrocarbon compounds (hereinafter simply referred to as PM) Also referred to as “polycyclic aromatic”.
このような要望に対応するために、ディーゼルエンジン用燃料の硫黄分の低減と、芳香族分、特に二環以上の多環芳香族含有量の低減が求められている。このために、ディーゼルエンジン用燃料の原料となる石油由来の軽油留分を水素化脱硫することが一般に行われる。硫黄分を10質量ppm以下とするようなレベルまで水素化脱硫を行なった場合には、同時に芳香族化合物の分解などが起こるため、軽油留分中の芳香族含有量が低下することとなる。 In order to meet such a demand, reduction of the sulfur content of the fuel for diesel engines and reduction of the aromatic content, particularly the polycyclic aromatic content of two or more rings are required. For this purpose, hydrodesulfurization of petroleum-derived light oil fraction, which is a raw material for diesel engine fuel, is generally performed. When hydrodesulfurization is performed to such a level that the sulfur content is 10 mass ppm or less, aromatic compounds are decomposed at the same time, so that the aromatic content in the light oil fraction decreases.
しかし、芳香族分が低下すると、ディーゼル燃料のゴム膨潤性が著しく低下する。従来のディーゼル自動車などのディーゼルエンジン機関では、その燃料系に合成ゴムなどを用い、ディーゼルエンジン用燃料によりゴム膨潤が起こることを前提に設計されている。このため、ディーゼル燃料のゴム膨潤性が低下した場合に、運転上の不都合が心配される。 However, when the aromatic content is lowered, the rubber swelling property of the diesel fuel is remarkably lowered. Conventional diesel engine engines such as diesel automobiles are designed on the assumption that rubber swells due to diesel engine fuel using a synthetic rubber or the like for the fuel system. For this reason, when the rubber swelling property of diesel fuel is reduced, there is a concern about inconvenience in operation.
本発明は、このような課題に解決するものであり、硫黄分、芳香族分を低減しても、適度なゴム膨潤性を有するディーゼル燃料の提供を目的とする。 This invention solves such a subject, and it aims at provision of the diesel fuel which has moderate rubber swelling property, even if it reduces a sulfur content and an aromatic content.
本発明者らは、上記課題を解決するために鋭意研究した結果、軽油の多環芳香族分を低減し、芳香族含有量を所定の範囲とすることにより、ゴム膨潤性が維持できることを見出した。さらに、芳香族はその置換基によりゴム膨潤性への影響が大きく影響することを見出し、これらの結果から本発明に想到した。 As a result of intensive studies to solve the above problems, the present inventors have found that the rubber swelling property can be maintained by reducing the polycyclic aromatic content of light oil and making the aromatic content within a predetermined range. It was. Furthermore, it has been found that aromatics have a great influence on rubber swellability due to their substituents, and the present invention has been conceived from these results.
すなわち、本発明によるディーゼルエンジン用燃料組成物は、(a)硫黄分が10質量ppm以下、(b)30℃における動粘度が3.0〜4.6mm2/s、(c)10%留出温度が200〜250℃、(d)引火点が60℃以上、(e)密度が0.82g/cm3〜0.84g/cm3、(f)全芳香族分が10容量%以上、24容量%以下、(g)二環以上の芳香族分が3容量%以下、及び(h)全芳香族分に含まれる全水素に占める芳香族環に由来する水素の割合(質量%)Ha、全芳香族分に含まれる全水素に占める芳香族環の置換基のα位炭素に結合する水素の割合Hα、同β位炭素に結合する水素の割合Hβ、同γ位以上の炭素に結合する水素の割合Hγの(Ha、Hα、Hβ、Hγ)が、(15.6、33.1、37.0、14.3)、(15.4、36.9、35.5、12.2)、(15.4、30.7、39.0、14.9)又は(15.5、37.3、35.4、11.8)のものである。特に、炭素数9の芳香族分が2容量%以上であることが好ましい。
That is, the fuel composition for a diesel engine according to the present invention has (a) a sulfur content of 10 mass ppm or less, (b) a kinematic viscosity at 30 ° C. of 3.0 to 4.6 mm 2 / s, and (c) a 10% retention. Outlet temperature is 200 to 250 ° C., (d) Flash point is 60 ° C. or more, (e) Density is 0.82 g / cm 3 to 0.84 g / cm 3 , (f) Total aromatic content is 10% by volume or more, 24% by volume or less, (g) 3% by volume or less of the aromatic content of two or more rings, and (h) the proportion (% by mass) of hydrogen derived from the aromatic ring in the total hydrogen contained in the total aromatic content. , The proportion Hα of hydrogen bonded to the α-position carbon of the substituent of the aromatic ring in the total hydrogen contained in the total aromatic content, the proportion Hβ of hydrogen bonded to the β-position carbon, and the bond to the carbon at the γ-position or higher (Ha, Hα, Hβ, Hγ) of the hydrogen ratio Hγ is (15.6, 33.1, 37.0, 14.3), (15.4, 36.9, 35. , 12.2), is of the (15.4,30.7,39.0,14.9) or (15.5,37.3,35.4,11.8). In particular, the aromatic content of 9 carbon atoms is preferably 2% by volume or more.
本発明によれば、極性指数などを所定の範囲に設定したので、硫黄分10質量ppm以下と超低硫黄分であり、かつ、二環以上の芳香族分が4容量%以下とした場合にも、適度なゴム膨潤性を有するディーゼルエンジン用燃料組成物を得ることができ、従来用いられてきたディーゼルエンジン機関に用いても、その燃料系に支障をきたすことがない。 According to the present invention, since the polarity index and the like are set in a predetermined range, when the sulfur content is 10 mass ppm or less and the sulfur content is extremely low, and the aromatic content of two or more rings is 4 vol% or less. However, a fuel composition for a diesel engine having an appropriate rubber swelling property can be obtained, and even if it is used in a conventionally used diesel engine engine, the fuel system is not hindered.
〔密度〕 本発明によるディーゼルエンジン用燃料は、密度が0.82g/cm3以上であり、0.82〜0.84g/cm3が好ましい。
〔硫黄分〕 本発明によるディーゼルエンジン用燃料は、硫黄分が10質量ppm以下であり、6質量ppm以下が好ましい。
〔動粘度〕 本発明によるディーゼルエンジン用燃料は、30℃における動粘度が2.0〜4.7mm2/s、特には3.0〜4.6mm2/sが好ましい。
〔蒸留性状〕 本発明によるディーゼルエンジン用燃料の10%留出温度が190℃以上であり、190〜260℃、特には200〜250℃が好ましい。また、90%留出温度は、260〜360℃、特には280〜350℃が好ましい。220℃以下の留出量は、3%以上、特には5〜15%が好ましい。
〔引火点〕 また、本発明によるディーゼルエンジン用燃料の引火点は60℃以上である。
〔芳香族分〕 本発明によるディーゼルエンジン用燃料は、全芳香族分が10〜24容量%、好ましくは15〜24容量%である。二環以上の芳香族分は4容量%以下、好ましくは3容量%以下である。三環以上の芳香族分は1容量%以下、特には0.6容量%以下が好ましい。また、炭素数9の芳香族分が2容量%以上、特には2〜6容量%であることが好ましい。
〔極性指数〕
本発明によるディーゼルエンジン用燃料は、極性指数PIが202〜208であり、好ましくは204〜206である。ここで、PI=0.2×(全芳香族分)+3.2×Ha+1.8×Hα+1.9×Hβ+1.4×Hγであり、Haは全芳香族分に含まれる全水素に占める芳香族環に由来する水素の割合(質量%)、Hα、Hβ、Hγは全芳香族分に含まれる全水素に占める芳香族環の置換基に由来する水素の割合であり、それぞれ置換基のα位、β位、γ位以上の炭素に結合する水素の割合に対応する。
[Density] fuel for diesel engines according to the present invention has a density of 0.82 g / cm 3 or more, preferably 0.82~0.84g / cm 3.
[Sulfur content] The diesel engine fuel according to the present invention has a sulfur content of 10 ppm by mass or less, preferably 6 ppm by mass or less.
[Kinematic Viscosity] The diesel engine fuel according to the present invention preferably has a kinematic viscosity at 30 ° C. of 2.0 to 4.7 mm 2 / s, particularly 3.0 to 4.6 mm 2 / s.
[Distillation Properties] The diesel engine fuel according to the present invention has a 10% distillation temperature of 190 ° C. or higher, preferably 190 to 260 ° C., particularly preferably 200 to 250 ° C. The 90% distillation temperature is preferably 260 to 360 ° C, particularly preferably 280 to 350 ° C. The distillation amount at 220 ° C. or lower is preferably 3% or more, particularly 5 to 15%.
[Flash point] The flash point of the diesel engine fuel according to the present invention is 60 ° C or higher.
[Aromatic Content] The diesel engine fuel according to the present invention has a total aromatic content of 10 to 24% by volume, preferably 15 to 24% by volume. The aromatic content of two or more rings is 4% by volume or less, preferably 3% by volume or less. The aromatic content of three or more rings is preferably 1% by volume or less, particularly preferably 0.6% by volume or less. Moreover, it is preferable that the aromatic component having 9 carbon atoms is 2% by volume or more, particularly 2 to 6% by volume.
[Polarity index]
The diesel engine fuel according to the present invention has a polarity index PI of 202-208, preferably 204-206. Here, PI = 0.2 × (total aromatic content) + 3.2 × Ha + 1.8 × Hα + 1.9 × Hβ + 1.4 × Hγ, and Ha is the aromatic that occupies the total hydrogen contained in the total aromatic content. The proportion of hydrogen derived from the ring (mass%), Hα, Hβ, and Hγ are the proportion of hydrogen derived from the substituent of the aromatic ring in the total hydrogen contained in the total aromatic content, and each of the α positions of the substituent , Corresponding to the proportion of hydrogen bonded to carbon at the β-position and γ-position or higher.
Ha、Hα、Hβ、Hγの一般的な算出方法は、プロトン・磁気共鳴スペクトル(NMR)による。全芳香族分中の芳香族環、並びに芳香族環置換基のα位、β位、γ位以上の炭素に結合する水素のピークがそれぞれ、9.2〜6.0ppm、4.17〜2.00ppm、2.00〜1.00ppm及び1.00〜0.50ppmに現れる。そこで、Ha、Hα、Hβ、Hγは、各々の積分値を用いて、以下の関係式に従って、各部位の水素割合を%として計算することが可能である。 A general calculation method of Ha, Hα, Hβ, and Hγ is based on a proton / magnetic resonance spectrum (NMR). The peaks of hydrogen bonded to the aromatic ring in the total aromatic component and carbons at the α-position, β-position, and γ-position or higher of the aromatic ring substituent are 9.2 to 6.0 ppm and 4.17 to 2, respectively. Appears at .00 ppm, 2.00 to 1.00 ppm and 1.00 to 0.50 ppm. Therefore, Ha, Hα, Hβ, and Hγ can be calculated by using the respective integral values as a percentage of hydrogen at each site according to the following relational expression.
Ha=(芳香族環由来の積分値)/(全積分値)×100
Hα=(芳香族環からα位の積分値)/(全積分値)×100
Hβ=(芳香族環からβ位の積分値)/(全積分値)×100
Hγ=(芳香族環からγ位以上の積分値)/(全積分値)×100
〔燃料の特性〕
一般的に、軽油は、少なくともJIS K 2204「軽油」を満たす品質を有するものでなければならず、本発明によるディーゼルエンジン用燃料も、上記のように特定した性状に加えて、JIS K 2269「原油及び石油製品の流動点並びに石油製品曇り点試験方法」による流動点、JIS K 2288「軽油−目詰まり点試験方法」による目詰まり点、JIS K 2270「原油及び石油製品−残留炭素分試験方法」による残留炭素分、及びJIS K 2280「石油製品−燃料油−オクタン価及びセタン価試験方法並びにセタン指数算出方法」によるセタン指数などの特性も上記のJIS K 2204における規定を満たすものであることが好ましい。
〔燃料の製造方法〕
本発明のディーゼルエンジン用燃料組成物の調製に用いられる基材は、原油の常圧蒸留装置から得られる直留軽油、減圧蒸留装置から得られる減圧軽油の他、これらに原油の常圧蒸留装置から得られる直留灯油、接触分解装置から得られる接触分解軽油、重油間接脱硫装置から得られる間脱軽油、重油直接脱硫装置から得られる直脱軽油などでもよく、またこれらの基材をさらに水素化脱硫、異性化、脱ろうなどの精製処理した基材が好ましい。石油精製工程から得られた複数の基材を混合して用いることもできる。さらに、基材として、天然ガス、石炭などを原料としてFischer-Tropsch法により合成された炭化水素に由来する基材を用いることもできる。
Ha = (integrated value derived from aromatic ring) / (total integrated value) × 100
Hα = (integral value of α position from aromatic ring) / (total integrated value) × 100
Hβ = (integral value of β-position from aromatic ring) / (total integrated value) × 100
Hγ = (integral value of γ position or more from the aromatic ring) / (total integrated value) × 100
[Characteristics of fuel]
In general, the light oil must have a quality satisfying at least JIS K 2204 “light oil”, and the fuel for the diesel engine according to the present invention is added to the above-specified properties in addition to JIS K 2269 “ Pour point of crude oil and petroleum product and pour point of petroleum product cloud point ", clogging point of JIS K 2288" light oil-clogging point test method ", JIS K 2270" crude oil and petroleum product-residual carbon content test method " And the properties of cetane index, etc. according to JIS K 2280 “Petroleum products—fuel oil—octane number and cetane number test method and cetane index calculation method” may also satisfy the above JIS K 2204 regulations. preferable.
[Method for producing fuel]
The base material used for preparing the fuel composition for a diesel engine of the present invention includes a straight-run gas oil obtained from a crude oil atmospheric distillation device, a vacuum gas oil obtained from a vacuum distillation device, and a crude oil atmospheric distillation device. Straight-run kerosene obtained from a catalytic cracker, catalytically cracked diesel oil obtained from a catalytic cracker, degasified oil obtained from a heavy oil indirect desulfurizer, direct degasified diesel oil obtained from a heavy oil direct desulfurizer, etc. Substrates subjected to purification treatment such as hydrodesulfurization, isomerization and dewaxing are preferred. A plurality of base materials obtained from the petroleum refining process can be mixed and used. Furthermore, as a base material, a base material derived from a hydrocarbon synthesized by Fischer-Tropsch method using natural gas, coal or the like as a raw material can be used.
硫黄分、全芳香族分、二環以上の芳香族分、極性指数は、それぞれの基材を測定することで複数の基材が配合された場合の値を計算することができる。特に、軽油留分に炭素数9の芳香族炭化水素を2〜10容量%、特には3〜7容量%を配合したものであることが好ましい。これに用いる軽油留分は、10%留出温度が200〜270℃、特には240〜270℃が好ましく、また、90%留出温度が300〜350℃、特には310〜340℃が好ましい。 The sulfur content, the total aromatic content, the aromatic content of two or more rings, and the polarity index can calculate values when a plurality of base materials are blended by measuring each base material. In particular, it is preferable that 2 to 10% by volume, particularly 3 to 7% by volume of an aromatic hydrocarbon having 9 carbon atoms is blended in the light oil fraction. The light oil fraction used for this has a 10% distillation temperature of 200 to 270 ° C, particularly preferably 240 to 270 ° C, and a 90% distillation temperature of 300 to 350 ° C, particularly 310 to 340 ° C.
本発明のディーゼルエンジン用燃料を調製するために、他の軽油基材として、さらに植物油メチルエステルなども用いることができる。また、ディーゼルエンジン用燃料への添加剤としては、低温流動性向上剤、耐摩耗性向上剤、セタン価向上剤、酸化防止剤、金属不活性剤、腐食防止剤等の公知の燃料添加剤を添加してもよい。低温流動性向上剤としては、エチレン共重合体などを用いることができるが、特には、酢酸ビニル、プロピオン酸ビニル、酪酸ビニルなどの飽和脂肪酸のビニルエステルが好ましく用いられる。耐摩耗性向上剤としては、長鎖(例えば、炭素数12〜24)脂肪酸または脂肪酸エステルが好ましく用いられる。10〜500質量ppm、好ましくは50〜150質量ppmの添加量で十分に耐摩耗性が向上する。 In order to prepare the diesel engine fuel of the present invention, vegetable oil methyl ester or the like can be used as another light oil base. In addition, as fuel additives for diesel engines, known fuel additives such as low-temperature fluidity improvers, wear resistance improvers, cetane number improvers, antioxidants, metal deactivators, and corrosion inhibitors are used. It may be added. As the low temperature fluidity improver, an ethylene copolymer or the like can be used, and in particular, a vinyl ester of a saturated fatty acid such as vinyl acetate, vinyl propionate or vinyl butyrate is preferably used. As the wear resistance improver, a long chain (for example, having 12 to 24 carbon atoms) fatty acid or fatty acid ester is preferably used. Abrasion resistance is sufficiently improved with an addition amount of 10 to 500 ppm by mass, preferably 50 to 150 ppm by mass.
以下に本発明を実施例及び比較例により具体的に説明するが、本発明はこれらの例によって何ら限定されるものではない。
〔軽油基材1〜4〕
以下の実施例及び比較例において、表1に示す性状の軽油基材1〜4を用いた。
The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.
[Light oil base 1 to 4]
In the following examples and comparative examples, light oil bases 1 to 4 having properties shown in Table 1 were used.
軽油基材1は、中東系原油を常圧蒸留して得た直留軽油留分と接触分解軽油留分との混合油を、触媒としてNi、Mo及びPを担持した市販触媒HOP−467(登録商標、ART K.K.製)を用い、反応温度380℃、反応圧力5.0MPa、水素/オイル比250NL/L、LHSV 2.0hr-1で水素化精製を行い、軽油留分を分留したものである。 The light oil base material 1 is a commercial catalyst HOP-467 (supporting Ni, Mo and P as a catalyst) using a mixed oil of a straight-run light oil fraction obtained by atmospheric distillation of Middle Eastern crude oil and a catalytic cracked light oil fraction as a catalyst. (Registered trademark, manufactured by ART K.K.) was used for hydrorefining at a reaction temperature of 380 ° C., a reaction pressure of 5.0 MPa, a hydrogen / oil ratio of 250 NL / L, and LHSV of 2.0 hr −1 to separate a light oil fraction. It is a thing that was retained.
軽油基材2は、中東系原油を常圧蒸留して得た直留灯油留分を、触媒としてNi、Mo及びPを担持した市販触媒HOP−461(登録商標、ART K.K.製)を用い、反応温度300℃、反応圧力3.5MPa、水素/オイル比170NL/L、LHSV 4.0hr-1で水素化精製を行い、灯油留分を分留したものである。 The light oil base material 2 is a commercially available catalyst HOP-461 (registered trademark, manufactured by ART K.K.) carrying Ni, Mo and P as catalysts from a straight-run kerosene fraction obtained by atmospheric distillation of Middle Eastern crude oil. The kerosene fraction was fractionated by hydrorefining at a reaction temperature of 300 ° C., a reaction pressure of 3.5 MPa, a hydrogen / oil ratio of 170 NL / L, and LHSV of 4.0 hr −1 .
軽油基材3は、中東系原油を常圧蒸留して得た直留軽油留分を、触媒としてNi、Mo及びPを担持した市販触媒HOP−414(登録商標、ART K.K.製)を用い、反応温度330℃、反応圧力6.5MPa、水素/オイル比350NL/L、LHSV 1.0hr-1で水素化精製を行い、軽油留分を分留したものである。 The light oil base material 3 is a commercially available catalyst HOP-414 (registered trademark, manufactured by ART K.K.) carrying Ni, Mo and P as catalysts from a straight-run light oil fraction obtained by atmospheric distillation of Middle Eastern crude oil. The gas oil fraction is fractionated by hydrorefining at a reaction temperature of 330 ° C., a reaction pressure of 6.5 MPa, a hydrogen / oil ratio of 350 NL / L, and LHSV of 1.0 hr −1 .
軽油基材4は、中東系原油を常圧蒸留して得た直留軽油留分と熱分解軽油留分との混合油を、触媒としてNi、Mo及びPを担持した市販触媒HOP−414(登録商標、ART K.K.製)を用い、反応温度310℃、反応圧力6.5MPa、水素/オイル比350NL/L、LHSV 0.5hr-1で水素化精製を行い、軽油留分を分留したものである。 The light oil base material 4 is a commercially available catalyst HOP-414 (supporting Ni, Mo and P as a catalyst) using a mixed oil of a straight-run light oil fraction obtained by atmospheric distillation of Middle Eastern crude oil and a pyrolysis light oil fraction as a catalyst. (Registered trademark, manufactured by ART K.K.) was used for hydrorefining at a reaction temperature of 310 ° C., a reaction pressure of 6.5 MPa, a hydrogen / oil ratio of 350 NL / L, and a LHSV of 0.5 hr −1 to separate a light oil fraction. It is a thing that was retained.
プロピルベンゼンは、市販試薬を用いた。 A commercially available reagent was used for propylbenzene.
また、炭素数9の芳香族分は、GCMS法(GC−MS装置:HP−6890(Agilent Technology社製))により定性分析・定量分析を行なった。 Further, the aromatic component having 9 carbon atoms was subjected to qualitative analysis / quantitative analysis by a GCMS method (GC-MS apparatus: HP-6890 (manufactured by Agilent Technology)).
なお、各物性について、密度はJIS K 2249、硫黄分はJIS K 2541、動粘度(30℃)はJIS K 2283、蒸留性状はJIS K 2254、引火点はJIS K 2265、芳香族分は石油学会法JPI−5S−49−97、ゴム膨潤特性である体積変化率は、ゴムとしてNBRを用いJIS K 6258により測定した。 In addition, as for each physical property, the density is JIS K 2249, the sulfur content is JIS K 2541, the kinematic viscosity (30 ° C.) is JIS K 2283, the distillation property is JIS K 2254, the flash point is JIS K 2265, and the aromatic content is the Japan Petroleum Institute. Method JPI-5S-49-97, the volume change rate, which is a rubber swelling property, was measured according to JIS K 6258 using NBR as rubber.
各軽油中の全芳香族分については、オープンカラムクロマト法により抽出した。抽出条件は以下の通りである。
〔抽出条件〕
シリカゲル:グレード 923(富士シリシア化学株式会社)
140℃×5時間エージング
試料 20gをn−ヘキサン 20mlに溶解させたものを上記シリカゲルに展開させた後、n−ヘキサン 200mlを用いて飽和分を除去させた。さらに塩化メチレン 200mlを用いて全芳香族分を抽出させた。得られた抽出溶液を60℃のバスで窒素パージしながら溶媒除去し、全芳香族分を得た。
The total aromatic content in each light oil was extracted by open column chromatography. The extraction conditions are as follows.
〔Extraction condition〕
Silica gel: Grade 923 (Fuji Silysia Chemical Ltd.)
140 ° C. × 5 hours Aging sample 20 g dissolved in 20 ml of n-hexane was developed on the silica gel, and then the saturated content was removed using 200 ml of n-hexane. Further, the total aromatic content was extracted using 200 ml of methylene chloride. The solvent was removed from the obtained extracted solution while purging with a 60 ° C. bath with nitrogen to obtain a total aromatic content.
また、Ha、Hα、Hβ、Hγは、オープンカラムクロマト法により抽出した全芳香族分をプロトンNMR(日本電子(株)製、GSX-270型NMR装置、270MHz)により測定を行なって算出した。 Ha, Hα, Hβ, and Hγ were calculated by measuring the total aromatic content extracted by open column chromatography using proton NMR (manufactured by JEOL Ltd., GSX-270 type NMR apparatus, 270 MHz).
〔実施例1〜3、比較例1〜2〕
これらの軽油基材1〜4およびプロピルベンゼンを表2の上部に示す配合量で配合し、実施例1〜3、比較例1〜2の軽油を調製した。調製された軽油の性状を表2に併せて示す。
[Examples 1-3, Comparative Examples 1-2]
These light oil base materials 1 to 4 and propylbenzene were blended in the blending amounts shown in the upper part of Table 2, and light oils of Examples 1 to 3 and Comparative Examples 1 to 2 were prepared. The properties of the prepared light oil are shown together in Table 2.
実施例1〜4のように極性指数を204〜205とすることで、ゴム膨潤性における体積変化率を6〜9容量%とすることができることがわかる。比較例1では極性指数が212、かつ引火点が60℃以下となり、また、比較例2、3では極性指数が各々201となりゴム膨潤性が悪化することがわかる。
It turns out that the volume change rate in rubber swellability can be made 6-9 volume% by making a polarity index into 204-205 like Examples 1-4. It can be seen that Comparative Example 1 has a polarity index of 212 and a flash point of 60 ° C. or lower, and Comparative Examples 2 and 3 each have a polarity index of 201, which deteriorates rubber swellability.
本発明によれば、極性指数などを所定の範囲に設定したので、硫黄分10質量ppm以下と超低硫黄分であり、かつ、二環以上の芳香族分が4容量%以下とした場合にも、適度なゴム膨潤性を有するディーゼルエンジン用燃料組成物を得ることができ、従来用いられてきたディーゼルエンジン機関に用いても、その燃料系に支障をきたすことがない。
According to the present invention, since the polarity index and the like are set in a predetermined range, when the sulfur content is 10 mass ppm or less and the sulfur content is extremely low, and the aromatic content of two or more rings is 4 vol% or less. However, a fuel composition for a diesel engine having an appropriate rubber swelling property can be obtained, and even if it is used in a conventionally used diesel engine engine, the fuel system is not hindered.
Claims (2)
(A) Sulfur content is 10 mass ppm or less, (b) Kinematic viscosity at 30 ° C. is 3.0 to 4.6 mm 2 / s, (c) 10% distillation temperature is 200 to 250 ° C., (d) Flash point. There 60 ° C. or higher, (e) density of 0.82g / cm 3 ~0.84g / cm 3 , (f) a total aromatic content of 10 vol% or more, 24% by volume, (g) a bicyclic or more aromatic 3% by volume or less of the group and (h) the proportion of hydrogen derived from the aromatic ring in the total hydrogen contained in the total aromatic content (mass%) Ha, the fragrance in the total hydrogen contained in the total aromatic content The ratio Hα of hydrogen bonded to the α-position carbon of the substituent of the group ring, the ratio Hβ of hydrogen bonded to the β-position carbon, the ratio Hγ of hydrogen bonded to carbons of the γ-position and higher (Ha, Hα, Hβ, Hγ) is (15.6, 33.1, 37.0, 14.3), (15.4, 36.9, 35.5, 12.2), (15.4, 30.7, 39). 0.0, 14.9) or ( 15.5, 37.3, 35.4, 11.8) fuel composition for diesel engines.
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Citations (6)
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JPH1150067A (en) * | 1997-08-05 | 1999-02-23 | Cosmo Sogo Kenkyusho:Kk | Fuel oil composition for diesel engine |
JP2000328078A (en) * | 1999-03-16 | 2000-11-28 | Nippon Mitsubishi Oil Corp | Gas oil composition |
JP2001055587A (en) * | 1999-06-09 | 2001-02-27 | Idemitsu Kosan Co Ltd | High-calorie fuel oil |
JP2001303072A (en) * | 2000-04-20 | 2001-10-31 | Nippon Mitsubishi Oil Corp | Gas oil composition |
JP2001303073A (en) * | 2000-04-20 | 2001-10-31 | Nippon Mitsubishi Oil Corp | Gas oil composition |
JP2005520032A (en) * | 2001-10-19 | 2005-07-07 | シェブロン ユー.エス.エー. インコーポレイテッド | Distillate fuel mixture with improved seal swellability from Fischer-Tropsch product |
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JPH1150067A (en) * | 1997-08-05 | 1999-02-23 | Cosmo Sogo Kenkyusho:Kk | Fuel oil composition for diesel engine |
JP2000328078A (en) * | 1999-03-16 | 2000-11-28 | Nippon Mitsubishi Oil Corp | Gas oil composition |
JP2001055587A (en) * | 1999-06-09 | 2001-02-27 | Idemitsu Kosan Co Ltd | High-calorie fuel oil |
JP2001303072A (en) * | 2000-04-20 | 2001-10-31 | Nippon Mitsubishi Oil Corp | Gas oil composition |
JP2001303073A (en) * | 2000-04-20 | 2001-10-31 | Nippon Mitsubishi Oil Corp | Gas oil composition |
JP2005520032A (en) * | 2001-10-19 | 2005-07-07 | シェブロン ユー.エス.エー. インコーポレイテッド | Distillate fuel mixture with improved seal swellability from Fischer-Tropsch product |
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