JP2004244628A - Gas oil with reduced sulfur content and its manufacturing process - Google Patents

Gas oil with reduced sulfur content and its manufacturing process Download PDF

Info

Publication number
JP2004244628A
JP2004244628A JP2004010716A JP2004010716A JP2004244628A JP 2004244628 A JP2004244628 A JP 2004244628A JP 2004010716 A JP2004010716 A JP 2004010716A JP 2004010716 A JP2004010716 A JP 2004010716A JP 2004244628 A JP2004244628 A JP 2004244628A
Authority
JP
Japan
Prior art keywords
gas oil
volume
base material
content
low sulfur
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.)
Pending
Application number
JP2004010716A
Other languages
Japanese (ja)
Inventor
Yasushi Akimoto
恭志 秋元
Masahiro Seo
昌裕 瀬尾
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Idemitsu Kosan Co Ltd
Original Assignee
Idemitsu Kosan Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Idemitsu Kosan Co Ltd filed Critical Idemitsu Kosan Co Ltd
Priority to JP2004010716A priority Critical patent/JP2004244628A/en
Publication of JP2004244628A publication Critical patent/JP2004244628A/en
Pending legal-status Critical Current

Links

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas oil with a reduced sulfur content, of a low environmental burden with not more than 10 mass ppm of a sulfur content, which causes no rubber shrinkage, and also to provide a manufacturing method of the same. <P>SOLUTION: The gas oil with a reduced sulfur content comprises 0-80 volume% of desulfurized kerosene base material, 10-100 volume% of a dewaxed gas oil base material and 0-60 volume% of a hydrocracked gas oil base material, and is characterized by having 10 mass ppm or less of the sulfur content. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

本発明は、低硫黄軽油及び低硫黄軽油の製造方法に関し、詳しくは特定の性状を有する脱硫灯油基材、脱ろう軽油基材及び水素化分解軽油基材を特定量含有してなる軽油であって、硫黄含有量が１０質量ｐｐｍ以下であり、低温流動性が良好な低硫黄軽油及び該低硫黄軽油の製造方法に関する。   The present invention relates to a low-sulfur gas oil and a method for producing the low-sulfur gas oil, and more particularly to a gas oil containing a specific amount of a desulfurized kerosene base material, a dewaxed gas oil base material and a hydrocracked gas oil base material having specific properties. The present invention also relates to a low sulfur gas oil having a sulfur content of 10 mass ppm or less and excellent low-temperature fluidity, and a method for producing the low sulfur gas oil.

近年、環境低負荷燃料として、低硫黄軽油が要求されており、欧州では既に、硫黄分１０質量ｐｐｍの軽油が市販されている。
しかしながら、一般に軽油中の硫黄分を水素化処理等によって低減する場合には、同時に芳香族化合物も水素化により低減されるが、燃料油中の芳香族分の減少に伴ってディーゼルエンジンにおける噴射ポンプ内のゴムが収縮し、安定性に問題が生じる可能性がある。 In recent years, low sulfur gas oil has been required as a low environmental load fuel, and gas oil having a sulfur content of 10 mass ppm has already been marketed in Europe.
However, in general, when the sulfur content in light oil is reduced by hydrotreating or the like, aromatic compounds are also reduced by hydrogenation at the same time, but the injection pump in diesel engines is reduced with the decrease in aromatic content in fuel oil. The rubber inside may shrink, causing stability problems.

軽油中の硫黄含有量を低減する方法としては、例えば直留軽油留分を深度脱硫することにより、軽油留分中の硫黄含有量を１０質量ｐｐｍ以下に低減することが可能であるが、深度脱硫した場合には脱硫触媒に与えるダメージが大きく、該脱硫触媒の触媒寿命が大きく低下する。このため、直留軽油留分の脱硫率の増加に伴って、コストが大幅に増大するという問題があった。
また軽油中の硫黄含有量を低減させる方法として、脱硫した直留軽油留分（ＤＧＯ）と灯油留分をブレンドする方法があるが、灯油の密度がＤＧＯと比較して低いことから、燃料の密度が低下し、出力の低下および燃費が悪化するという問題があった。さらに、脱硫灯油（ＤＫ）とＤＧＯにより製造した軽油は低温流動性に問題のある場合があり、高密度で流動点が十分低く、ディーゼルエンジン用として高い出力を与えることのできる脱ろう脱硫軽油基材を含む軽油組成物が提案されているが（例えば特許文献１参照）、硫黄含有量については現状求められているものにまで達していなかった。 As a method for reducing the sulfur content in gas oil, for example, by deep desulfurization of a straight gas oil fraction, it is possible to reduce the sulfur content in the gas oil fraction to 10 mass ppm or less. In the case of desulfurization, damage to the desulfurization catalyst is large, and the catalyst life of the desulfurization catalyst is greatly reduced. For this reason, there has been a problem that the cost is greatly increased as the desulfurization rate of the straight gas oil fraction is increased.
As a method of reducing the sulfur content in gas oil, there is a method of blending a desulfurized straight gas oil fraction (DGO) and a kerosene fraction. However, since the density of kerosene is lower than that of DGO, the fuel There has been a problem that the density is reduced, the output is reduced, and the fuel efficiency is deteriorated. In addition, gas oil produced from desulfurized kerosene (DK) and DGO may have problems with low-temperature fluidity, and has a high density, a sufficiently low pour point, and a dewaxed desulfurized gas oil base that can provide high output for diesel engines. Although a light oil composition containing a material has been proposed (see, for example, Patent Document 1), the sulfur content has not reached the level currently required.

また、軽油中の硫黄含有量を著しく低減した場合には潤滑性能が低下し、燃料噴射ポンプの各部の摩耗が生じることが予測され、これまで軽油に添加剤を加えることにより対処する方法が提案されている（例えば、特許文献２及び３参照）。しかしながら、さらに低硫黄の軽油組成物においては、添加剤の処方のみでは限界があった。   Also, if the sulfur content in light oil is significantly reduced, it is predicted that lubrication performance will deteriorate and wear of each part of the fuel injection pump will occur, and a method to address this by adding additives to light oil has been proposed. (For example, see Patent Documents 2 and 3). However, in low-sulfur gas oil compositions, there is a limit only in the formulation of additives.

特開平８−１５７８３９号公報JP-A-8-1557839 特開平８−２５９９６４号公報JP-A-8-259964 特開２００１−２００２７５号公報JP 2001-200275 A

本発明は、このような状況下で、硫黄含有量が１０質量ｐｐｍ以下と低環境負荷であり、かつ、密度、芳香族分含有量を従来の軽油と同等に維持することで、ゴムの収縮を生じず、低温流動性が高く、さらに高い潤滑性能をも有する低硫黄軽油及び該低硫黄軽油の製造方法を提供することを目的とするものである。   Under such circumstances, the present invention has a low environmental load such as a sulfur content of 10 mass ppm or less, and maintains a density and an aromatic content equal to those of a conventional light oil, thereby reducing rubber shrinkage. It is an object of the present invention to provide a low-sulfur gas oil having no low-temperature fluidity and high lubricity, and a method for producing the low-sulfur gas oil.

本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、特定の性状を有する脱硫灯油基材０〜８０容量％、脱ろう軽油基材１０〜１００容量％及び水素化分解軽油基材０〜６０容量％を含有してなる軽油であって、硫黄含有量が１０質量ｐｐｍ以下とした低硫黄軽油が上記目的を達成し得ることを見出した。本発明は、かかる知見に基づいて完成したものである。   The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that a desulfurized kerosene base material having specific properties of 0 to 80% by volume, a dewaxed light oil base material of 10 to 100% by volume, and hydrocracked gas oil The present inventors have found that a low-sulfur gas oil containing 0 to 60% by volume of a base material and having a sulfur content of 10 mass ppm or less can achieve the above object. The present invention has been completed based on such findings.

すなわち、本発明は、
（１）脱硫灯油基材０〜８０容量％、脱ろう軽油基材１０〜１００容量％及び水素化分解軽油基材０〜６０容量％を含有してなる軽油であって、硫黄含有量が１０質量ｐｐｍ以下であることを特徴とする低硫黄軽油、
（２）前記脱硫灯油基材の硫黄含有量が１０質量ｐｐｍ以下、１５℃における密度が０．７８０〜０．８１０ｇ／ｃｍ3、セタン指数が４０〜６０であり、前記脱ろう軽油基材の硫黄含有量が１０質量ｐｐｍ以下、１５℃における密度が０．８２０〜０．８６０ｇ／ｃｍ3、セタン指数が５０〜７０であり、かつ前記水素化分解軽油基材の硫黄含有量が１０質量ｐｐｍ以下、１５℃における密度が０．８００〜０．８５０ｇ／ｃｍ3、セタン指数が５５〜７８であることを特徴とする前記（１）記載の低硫黄軽油、
（３）前記水素化分解軽油基材の芳香族化合物含有量が７．０〜１９．５容量％であることを特徴とする前記（１）又は（２）に記載の低硫黄軽油、
（４）前記芳香族化合物が一環芳香族化合物７．０〜１５．０容量％、二環芳香族化合物０．０〜４．０容量％及び三環以上の芳香族化合物０．０〜０．５容量％含有することを特徴とする前記（３）記載の低硫黄軽油、
（５）前記低硫黄軽油の１５℃における密度が０．８０２〜０．８３８ｇ／ｃｍ3であることを特徴とする前記（１）〜（４）のいずれかに記載の低硫黄軽油、
（６）前記低硫黄軽油中の芳香族化合物含有量が１５．０容量％以上である前記（１）〜（５）のいずれかに記載の低硫黄軽油、
（７）前記低硫黄軽油中の多環芳香族化合物含有量が４．５容量％以下である前記（１）〜（６）のいずれかに記載の低硫黄軽油、
（８）前記低硫黄軽油の曇り点が−７℃以下であることを特徴とする前記（１）〜（７）のいずれかに記載の低硫黄軽油、
（９）前記低硫黄軽油の曇り点が−１１℃以下であることを特徴とする前記（１）〜（７）のいずれかに記載の低硫黄軽油、
（１０）脱硫灯油基材０〜８０容量％、脱ろう軽油基材１０〜１００容量％及び水素化分解軽油基材０〜６０容量％を混合することを特徴とする硫黄含有量１０質量ｐｐｍ以下の低硫黄軽油の製造方法、
を提供するものである。 That is, the present invention
(1) A light oil comprising 0 to 80% by volume of a desulfurized kerosene base material, 10 to 100% by volume of a dewaxed light oil base material, and 0 to 60% by volume of a hydrocracked light oil base material, wherein the sulfur content is 10%. Low sulfur gas oil characterized by being not more than ppm by mass,
(2) The desulfurized kerosene base material has a sulfur content of 10 mass ppm or less, a density at 15 ° C. of 0.780 to 0.810 g / cm 3 , a cetane index of 40 to 60, and A sulfur content of 10 mass ppm or less, a density at 15 ° C. of 0.820 to 0.860 g / cm 3 , a cetane index of 50 to 70, and a sulfur content of the hydrocracked gas oil base material of 10 mass ppm The low sulfur gas oil according to the above (1), wherein the density at 15 ° C. is 0.800 to 0.850 g / cm 3 and the cetane index is 55 to 78.
(3) The low sulfur gas oil according to the above (1) or (2), wherein the content of the aromatic compound in the hydrocracked gas oil base is 7.0 to 19.5% by volume.
(4) The aromatic compound is a linear aromatic compound 7.0 to 15.0% by volume, a bicyclic aromatic compound 0.0 to 4.0% by volume, and a tricyclic or higher aromatic compound 0.0 to 0.0. Low sulfur gas oil according to the above (3), characterized in that it contains 5% by volume;
(5) The low sulfur gas oil according to any of (1) to (4), wherein the density of the low sulfur gas oil at 15 ° C. is 0.802 to 0.838 g / cm 3 .
(6) The low sulfur gas oil according to any of (1) to (5), wherein the content of the aromatic compound in the low sulfur gas oil is 15.0% by volume or more.
(7) The low sulfur gas oil according to any one of (1) to (6), wherein the content of the polycyclic aromatic compound in the low sulfur gas oil is 4.5% by volume or less,
(8) The low sulfur gas oil according to any one of (1) to (7), wherein the low sulfur gas oil has a cloud point of −7 ° C. or less.
(9) The low sulfur gas oil according to any of (1) to (7), wherein the low sulfur gas oil has a cloud point of -11 ° C or lower.
(10) A sulfur content of 10 mass ppm or less characterized by mixing 0 to 80% by volume of a desulfurized kerosene base material, 10 to 100% by volume of a dewaxed light oil base material, and 0 to 60% by volume of a hydrocracked gas oil base material. Low sulfur gas oil production method,
Is provided.

本発明によれば、環境負荷が小さく、かつ、ゴムの収縮を生じない低硫黄軽油が得られる。   ADVANTAGE OF THE INVENTION According to this invention, the environmental load is small and the low sulfur gas oil which does not generate | occur | produce rubber shrinkage is obtained.

本発明は、脱硫灯油基材０〜８０容量％、脱ろう軽油基材１０〜１００容量％及び水素化分解軽油基材０〜６０容量％を含有してなる軽油であって、硫黄含有量が１０質量ｐｐｍ以下であることを特徴とする。
前記脱硫灯油基材とは、常圧蒸留装置から留出する直留灯油留分を脱硫触媒にて脱硫した留分をいい、硫黄含有量は１０質量ｐｐｍ以下であることが好ましい。脱硫は通常行われる方法で行うことができ、例えば固定床流通反応装置を用いて、Ｃｏ−Ｍｏ／アルミナ触媒、Ｎｉ−Ｍｏ／アルミナ触媒等の脱硫触媒の存在下、３０〜１００ｋｇ／ｃｍ2Ｇの圧力下、好ましくは５０〜７０ｋｇ／ｃｍ2Ｇの圧力下、３００〜４００℃、好ましくは３３０〜３６０℃の温度で、液空間速度（ＬＨＳＶ）０．５〜５ｈ-1、好ましくは１〜２ｈ-1の条件で深度脱硫反応を行い、その後ストリッパーで硫化水素とナフサ留分を除去して脱硫灯油（ＤＫ）を得るものである。 The present invention is a gas oil comprising 0 to 80% by volume of a desulfurized kerosene base material, 10 to 100% by volume of a dewaxed gas oil base material and 0 to 60% by volume of a hydrocracked gas oil base material, wherein the sulfur content is It is not more than 10 mass ppm.
The desulfurized kerosene base is a fraction obtained by desulfurizing a straight kerosene fraction distilled from an atmospheric distillation apparatus with a desulfurization catalyst, and preferably has a sulfur content of 10 mass ppm or less. Desulfurization can be carried out in a conventional method carried out, for example using a fixed bed flow reactor, Co-Mo / alumina catalyst, the presence of a desulfurization catalyst, such as Ni-Mo / alumina catalyst, 30~100kg / cm 2 G , Preferably at a pressure of 50 to 70 kg / cm 2 G, at a temperature of 300 to 400 ° C, preferably 330 to 360 ° C, and a liquid hourly space velocity (LHSV) of 0.5 to 5 h -1 , preferably 1 to 1 A deep desulfurization reaction is carried out under the condition of 2h -1 , and then hydrogen sulfide and a naphtha fraction are removed by a stripper to obtain desulfurized kerosene (DK).

また、ＤＫの１５℃における密度は０．７８０〜０．８１０ｇ／ｃｍ3の範囲であることが好ましく、さらには０．７９０〜０．８００ｇ／ｃｍ3の範囲であることが好ましい。この範囲であると出力及び燃費の悪化を抑制することができ、脱硫が容易になるという利点がある。さらに、ＤＫの３０℃における粘度が１．３０〜１．５５ｍｍ2／ｓｅｃの範囲であることが好ましい。また、セタン指数が４０〜６０の範囲であることが好ましく、さらには４３〜６０の範囲であることが好ましい。この範囲であると着火性が良好となる。その他蒸留性状等が第１表に示す性状を有することが好ましい。 It is preferable that a density at 15 ℃ of DK ranges from 0.780~0.810g / cm 3, it is further preferably in the range of 0.790~0.800g / cm 3. Within this range, there is an advantage that deterioration of output and fuel efficiency can be suppressed, and desulfurization becomes easy. Further, the viscosity of the DK at 30 ° C. is preferably in the range of 1.30 to 1.55 mm 2 / sec. Further, the cetane index is preferably in the range of 40 to 60, and more preferably in the range of 43 to 60. Within this range, the ignitability will be good. In addition, it is preferable that the distillation properties and the like have the properties shown in Table 1.

本発明における脱ろう軽油基材（ＤＷＧＯ）とは軽油基材からワックス分を除去したものであり、具体的には炭素数２０以上のノルマルパラフィン成分を１５容量％以下としたものが好ましく、さらには１２容量％以下、特には１０容量％以下であることが好ましい。炭素数２０以上のノルマルパラフィン成分が上記範囲を超えると、製品軽油の低温流動性が不十分となり、曇り点や流動点が十分低下しない場合がある。また、曇り点は−２０℃〜−５℃の範囲であることが好ましい。脱ろう処理の方法としては、特に限定されず、例えばゼオライト系等の脱ろう触媒を用い、３１０〜３８０℃の範囲で３０〜７０ｋｇ／ｃｍ2Ｇの圧力下、１．０〜２．０ｈｒ-1の液空間速度（ＬＨＳＶ）で行うことができる。 The dewaxed light oil base material (DWGO) in the present invention is obtained by removing a wax component from a light oil base material. Specifically, it is preferable that a normal paraffin component having 20 or more carbon atoms be 15% by volume or less. Is preferably 12% by volume or less, particularly preferably 10% by volume or less. When the normal paraffin component having 20 or more carbon atoms exceeds the above range, the low-temperature fluidity of the product gas oil becomes insufficient, and the cloud point and the pour point may not be sufficiently reduced. Further, the cloud point is preferably in the range of -20C to -5C. The method of the dewaxing treatment is not particularly limited. For example, a dewaxing catalyst such as a zeolite-based catalyst is used at a temperature of 310 to 380 ° C under a pressure of 30 to 70 kg / cm 2 G for 1.0 to 2.0 hr − It can be performed at a liquid hourly space velocity (LHSV) of 1 .

ＤＷＧＯはさらに脱硫処理されていることが好ましく、その硫黄含有量は１０質量ｐｐｍ以下であることが好ましい。脱硫方法としては、通常の脱硫処理によることができ、例えば、Ｃｏ−Ｍｏ／アルミナ触媒、Ｎｉ−Ｍｏ／アルミナ触媒等の脱硫触媒の存在下、３０〜１００ｋｇ／ｃｍ2Ｇの圧力下、好ましくは５０〜７０ｋｇ／ｃｍ2Ｇの圧力下、３００〜４００℃、好ましくは３３０〜３６０℃の温度で、液空間速度（ＬＨＳＶ）０．５〜５ｈ-1、好ましくは１〜２ｈ-1の条件で深度脱硫反応を行うことでなされる。
また、ＤＷＧＯの１５℃における密度は０．８２０〜０．８６０ｇ／ｃｍ3の範囲であることが好ましく、さらには０．８２０〜０．８５０ｇ／ｃｍ3の範囲であることが好ましい。この範囲であると製品軽油の密度が低下し、排出ガス中の粒子状物質（ＰＭ）が低減するなど、排出ガス性状が良好となる。次に３０℃における粘度は２．０〜６．０ｍｍ2／ｓｅｃの範囲であることが好ましく、またセタン指数が５０〜７０の範囲であることが好ましい。その他蒸留性状等が第１表に示す性状を有することが好ましい。 DWGO is preferably further desulfurized, and its sulfur content is preferably 10 ppm by mass or less. The desulfurization method can be a usual desulfurization treatment. For example, in the presence of a desulfurization catalyst such as a Co-Mo / alumina catalyst or a Ni-Mo / alumina catalyst, under a pressure of 30 to 100 kg / cm 2 G, preferably Under a pressure of 50 to 70 kg / cm 2 G, a temperature of 300 to 400 ° C., preferably 330 to 360 ° C., and a liquid hourly space velocity (LHSV) of 0.5 to 5 h −1 , preferably 1 to 2 h −1 . This is performed by performing a deep desulfurization reaction.
It is preferable that a density at 15 ℃ of DWGO ranges from 0.820~0.860g / cm 3, it is further preferably in the range of 0.820~0.850g / cm 3. Within this range, the properties of the exhaust gas are improved, for example, the density of the product light oil is reduced and the particulate matter (PM) in the exhaust gas is reduced. Next, the viscosity at 30 ° C. is preferably in the range of 2.0 to 6.0 mm 2 / sec, and the cetane index is preferably in the range of 50 to 70. In addition, it is preferable that the distillation properties and the like have the properties shown in Table 1.

本発明における水素化分解軽油基材（ＨＣＧＯ）とは、重質軽油（ＨＧＯ）、減圧軽油（ＶＧＯ）あるいはこれらの混合油を触媒の存在下で水素化分解し、当該分解生成油を蒸留分離して得られたものであり、その蒸留性状としては第１表に示すものであることが好ましい。従来、軽油基材として用いられているＨＣＧＯは、硫黄含有量が０．０００１〜０．２質量％のものが一般的であったが、本発明においてはＨＣＧＯの硫黄含有量が１０質量ｐｐｍ以下のものを使用することが好適である。ＨＣＧＯの硫黄含有量を１０質量ｐｐｍ以下とすることによって、環境負荷の小さい本発明の目的とする軽油が製造できる。以上の観点からＨＣＧＯの硫黄含有量は好ましくは７質量ｐｐｍ以下、さらには５質量ｐｐｍ以下であることが特に好ましい。   The hydrocracked gas oil base material (HCGO) in the present invention refers to a hydrocracked heavy gas oil (HGO), a vacuum gas oil (VGO) or a mixed oil thereof in the presence of a catalyst, and the cracked oil is separated by distillation. The distillation properties are preferably those shown in Table 1. Conventionally, HCGO used as a light oil base material generally has a sulfur content of 0.0001 to 0.2% by mass, but in the present invention, HCGO has a sulfur content of 10% by mass or less. It is preferred to use By setting the sulfur content of HCGO to 10 mass ppm or less, a light oil which is a target of the present invention and has a small environmental load can be produced. In view of the above, the sulfur content of HCGO is preferably 7 ppm by mass or less, more preferably 5 ppm by mass or less.

次に、本発明におけるＨＣＧＯの１５℃における密度は０．８００〜０．８５０ｇ／ｃｍ3の範囲であることが好ましい。密度が、０．８００ｇ／ｃｍ3未満であると燃費が悪化する場合があり、一方０．８５０ｇ／ｃｍ3を超えると排出ガス性状が悪化する場合がある。以上の観点から、ＨＣＧＯの密度は０．８１５〜０．８４０ｇ／ｃｍ3の範囲であることが好ましい。 Next, the density of HCGO at 15 ° C. in the present invention is preferably in the range of 0.800 to 0.850 g / cm 3 . If the density is less than 0.800 g / cm 3 , fuel efficiency may be deteriorated, while if it is more than 0.850 g / cm 3 , the properties of exhaust gas may be deteriorated. From the above viewpoint, the density of HCGO is preferably in the range of 0.815 to 0.840 g / cm 3 .

本発明におけるＨＣＧＯはその芳香族化合物含有量が７．０〜１９．５容量％であることが好ましい。芳香族化合物含有量が７．０容量％未満であると製品軽油中の芳香族含有量が小さくなり、ポンプ等に使用するゴムが縮むといった問題が発生する場合があり、一方１９．５容量％を超えると製品軽油中の芳香族分が増加し、排出ガス中の粒子状物質（ＰＭ）が増加するといった問題が発生する場合がある。以上の観点から、ＨＣＧＯの芳香族化合物含有量は８．０〜１５．０容量％の範囲であることが好ましく、１０．０〜１５．０容量％の範囲であることがさらに好ましい。
また、芳香族化合物は一環芳香族化合物と二環以上の多環芳香族化合物があるが、本発明におけるＨＣＧＯにおいては、一環芳香族化合物の含有量が７．０〜１５．０容量％の範囲であることが好ましく、さらには８．０〜１５．０容量％の範囲であることが好ましい。一環芳香族化合物がこの範囲であるとポンプ等に使用されるゴムの収縮がなく、また排出ガス中の粒子状物質（ＰＭ）を低減できる。一方、二環芳香族化合物の含有量は０．０〜４．０容量％の範囲であることが好ましく、さらには０．０〜３．０容量％の範囲であることが好ましい。二芳香族化合物の含有量がこの範囲であると排出ガス中の粒子状物質（ＰＭ）を低減できる。さらに、三環以上の芳香族化合物の含有量は０．０〜０．５容量％の範囲であることが好ましく、さらには０．０〜０．３容量％の範囲であることが好ましい。三環以上の芳香族化合物の含有量がこの範囲であると排出ガス中の粒子状物質（ＰＭ）を低減できる。 HCGO in the present invention preferably has an aromatic compound content of 7.0 to 19.5% by volume. When the content of the aromatic compound is less than 7.0% by volume, the content of aromatics in the product light oil becomes small, and a problem such as shrinkage of a rubber used for a pump or the like may occur. On the other hand, 19.5% by volume. If it exceeds 300, there may be a problem that the aromatic content in the product gas oil increases and the particulate matter (PM) in the exhaust gas increases. From the above viewpoints, the content of the aromatic compound in HCGO is preferably in the range of 8.0 to 15.0% by volume, and more preferably in the range of 10.0 to 15.0% by volume.
Further, the aromatic compound includes a single aromatic compound and a polycyclic aromatic compound having two or more rings. In the HCGO of the present invention, the content of the single aromatic compound is in the range of 7.0 to 15.0% by volume. And more preferably in the range of 8.0 to 15.0% by volume. When the partial aromatic compound is in this range, rubber used for a pump or the like does not shrink, and particulate matter (PM) in exhaust gas can be reduced. On the other hand, the content of the bicyclic aromatic compound is preferably in the range of 0.0 to 4.0% by volume, and more preferably in the range of 0.0 to 3.0% by volume. When the content of the diaromatic compound is within this range, the particulate matter (PM) in the exhaust gas can be reduced. Further, the content of the aromatic compound having three or more rings is preferably in the range of 0.0 to 0.5% by volume, and more preferably in the range of 0.0 to 0.3% by volume. When the content of the aromatic compound having three or more rings is in this range, the particulate matter (PM) in the exhaust gas can be reduced.

さらに、本発明におけるＨＣＧＯはそのセタン指数が５５〜７８の範囲であることが好ましく、さらには５７〜７８の範囲であることが好ましい。この範囲であると燃焼性が良く、排出ガス性状が良好となる。   Further, the cetane index of HCGO in the present invention is preferably in the range of 55 to 78, and more preferably in the range of 57 to 78. Within this range, the combustibility is good and the properties of the exhaust gas are good.

Figure 2004244628
Figure 2004244628

本発明では、上記特徴を有する脱硫灯油基材、脱ろう軽油基材及び水素化分解軽油基材をそれぞれ０〜８０容量％、１０〜１００容量％、０〜６０容量％の範囲で含有することを特徴とする。
さらには、上記各基材の含有量はそれぞれの基材の組合せ方法によって、その最適な含有量は変化し、より具体的には以下の態様とすることが好ましい。
（１）脱硫灯油基材０〜６０容量％、脱ろう軽油基材３０〜１００容量％及び水素化分解軽油基材０〜６０容量％、
（２）脱硫灯油基材０〜７０容量％、脱ろう軽油基材２０〜９０容量％及び水素化分解軽油基材０〜４０容量％。
また、本発明では、脱硫灯油基材、脱ろう軽油基材及び水素化分解軽油基材を上記範囲で含有すれば、他の基材については特に限定されず、通常軽油を製造するのに用いられる留分、例えば脱硫した直留軽油留分（ＤＧＯ），軽質直留軽油，重質直留軽油，接触分解軽油，間接脱硫軽油等を混合して本発明に係る低硫黄軽油を製造することができる。 In the present invention, the desulfurized kerosene base material, the dewaxed gas oil base material, and the hydrocracked gas oil base material having the above characteristics are contained in the ranges of 0 to 80% by volume, 10 to 100% by volume, and 0 to 60% by volume, respectively. It is characterized by.
Furthermore, the optimal content of each of the above-mentioned base materials varies depending on the method of combining the respective base materials, and more specifically, the following embodiments are preferable.
(1) Desulfurized kerosene base material 0 to 60% by volume, dewaxed light oil base material 30 to 100% by volume, and hydrocracked gas oil base material 0 to 60% by volume,
(2) Desulfurized kerosene base material 0 to 70% by volume, dewaxed light oil base material 20 to 90% by volume, and hydrocracked gas oil base material 0 to 40% by volume.
In the present invention, if the desulfurized kerosene base material, the dewaxed light oil base material and the hydrocracked light oil base material are contained in the above range, the other base materials are not particularly limited, and are usually used for producing light oil. A low-sulfur gas oil according to the present invention by mixing the fractions obtained, for example, desulfurized straight gas oil fraction (DGO), light straight gas oil, heavy straight gas oil, catalytic cracking gas oil, indirect desulfurized gas oil, etc. Can be.

本発明の低硫黄軽油は、硫黄含有量が１０質量ｐｐｍ以下であることを特徴とする。硫黄含有を１０質量ｐｐｍ以下とすることで、燃焼排出ガス中のＳＯｘ濃度を減少さることができ、さらには排出ガス浄化触媒への負担を小さくすることによって、該触媒の寿命を延長させることができる。また排出ガス中の粒子状物質（ＰＭ）に含まれる硫酸塩の含有量を減少させることができる。
また、該低硫黄軽油の１５℃における密度は０．８０２〜０．８３８ｇ／ｃｍ3であることが好ましい。この範囲であると、現在用いられる軽油と同等の燃費が得られるとともに、エンジンの出力低下を生じさせることもない。 The low sulfur gas oil of the present invention is characterized in that the sulfur content is 10 ppm by mass or less. By setting the sulfur content to 10 mass ppm or less, the concentration of SOx in the combustion exhaust gas can be reduced, and the life of the exhaust gas purification catalyst can be extended by reducing the burden on the exhaust gas purification catalyst. it can. Further, the content of the sulfate contained in the particulate matter (PM) in the exhaust gas can be reduced.
The density of the low sulfur gas oil at 15 ° C. is preferably 0.802 to 0.838 g / cm 3 . Within this range, fuel economy equivalent to that of currently used light oil can be obtained, and the output of the engine does not decrease.

また、該低硫黄軽油中の芳香族化合物の含有量は１５．０容量％以上であることが好ましく、さらには１８．０〜２０．０容量％の範囲であることが好ましい。この条件をとることにより、燃料ポンプに使用されるゴムの収縮をさらに抑制させることができ、また排出ガス触媒による排出ガスの浄化性能を向上させることができる。
該芳香族化合物の中でも二環以上の多環芳香族化合物については、４．５容量％以下であることが好ましく、さらには３．０容量％以下であることが好ましい。この条件をとることにより、排出ガスの浄化性能を向上させることができ、特に排出ガス中の粒子状物質（ＰＭ）濃度を低減することができる。
また、該低硫黄軽油のセタン価は５０．０〜６０．０の範囲であることが好ましい。この範囲をとることによって、既存の内燃機関にそのまま使用することができ、さらには排出ガスの浄化性能を向上させることができる。
さらに、該低硫黄軽油の曇り点は−７℃以下であることが好ましく、−１１℃以下であることがさらに好ましい。曇り点をこれらの条件とすることにより、低温時のエンジン始動性及びエンジン始動直後の加速性が良好となる。 Further, the content of the aromatic compound in the low sulfur gas oil is preferably 15.0% by volume or more, and more preferably in the range of 18.0 to 20.0% by volume. By adopting this condition, the shrinkage of rubber used for the fuel pump can be further suppressed, and the performance of purifying the exhaust gas by the exhaust gas catalyst can be improved.
Among the aromatic compounds, the content of the polycyclic aromatic compound having two or more rings is preferably 4.5% by volume or less, and more preferably 3.0% by volume or less. By taking this condition, the purification performance of the exhaust gas can be improved, and in particular, the particulate matter (PM) concentration in the exhaust gas can be reduced.
The cetane number of the low sulfur gas oil is preferably in the range of 50.0 to 60.0. By adopting this range, it can be used as it is for an existing internal combustion engine, and the purification performance of exhaust gas can be improved.
Further, the cloud point of the low sulfur gas oil is preferably -7 ° C or lower, more preferably -11 ° C or lower. By setting the cloud point under these conditions, the engine startability at a low temperature and the acceleration immediately after the engine start are improved.

本発明に係る低硫黄軽油は通常軽油に用いられる添加剤を使用することができ、適宜必要に応じて、流動性向上剤、潤滑性向上剤、酸化防止剤等を添加することができる。その好ましい添加量は、流動性向上剤であれば０〜５００質量ｐｐｍ、潤滑性向上剤であれば５０〜２００質量ｐｐｍ、酸化防止剤であれば０〜２０質量ｐｐｍである。   The low-sulfur gas oil according to the present invention can use additives usually used in gas oils, and can optionally include a fluidity improver, a lubricity improver, an antioxidant, and the like, if necessary. The preferable addition amount is 0 to 500 mass ppm for a fluidity improver, 50 to 200 mass ppm for a lubricity improver, and 0 to 20 mass ppm for an antioxidant.

次に、本発明を実施例により、さらに詳細に説明するが、本発明はこれらの例によってなんら限定されるものではない。
＜評価方法＞
１．密度；ＪＩＳ Ｋ２２４９に準じ、振動式密度試験方法にて測定した。
２．蒸留性状；ＪＩＳ Ｋ ２２５４に準じ、測定した。
３．硫黄含有量；電量紫外蛍光法により測定した。
４．粘度；ＪＩＳ Ｋ ２２８３に準じ、測定した。
５．引火点;ＪＩＳ Ｋ ２２６５に準じ、測定した。
６．流動点；ＪＩＳ Ｋ ２２６９に準じ、測定した。尚、ＪＩＳでは２．５℃毎に測定するが試験精度向上のため１℃毎に測定した。
７．目詰まり点；ＪＩＳ Ｋ ２２８８に準じ、測定した。
８．曇り点；ＪＩＳ Ｋ ２２６９に準じ、測定した。
９．セタン指数；ＪＩＳ Ｋ ２２０４に準じ、測定した。
１０．組成分析；飽和分含有量、不飽和分含有量、芳香族化合物含有量、一環芳香族化合物含有量、二環芳香族化合物含有量及び三環以上芳香族化合物含有量は高速液体クロマトグラフ（ＨＰＬＣ）法により測定した。
１１．排出ガス試験；以下に示すエンジンを用いて、１０、１５モード試験を行い、排出ガス中の粒子状物質（ＰＭ）の質量によって評価した。排出ガス中のＰＭは堀場製作所製「ダイリューショントンネル」を用いてフィルター上に捕集した。ＰＭの捕集量は以下のような基準で評価した。
〇 ； ６７ｍｇ／Ｎｍ3以下
△ ； ＰＭが６７ｍｇ／Ｎｍ3より多い
（供試エンジン；エンジン４気筒、排気量２９８２ｃｃ、噴射方式は直噴予混合、
噴射ポンプはコモンレール、ＥＧＲ有り、過給機付（ターボ、インタークーラー））
１２．潤滑性試験；石油学会法ＪＰＩ−５Ｓ−５０−９８「軽油−潤滑性試験方法」に準拠して、ＨＦＲＲ試験における摩耗痕径を測定し、以下の基準で評価した。
〇 ； 摩耗痕が４６０μｍ以下
× ； 摩耗痕が４６０μｍを越える
１３．出力・燃費試験
排出ガス試験と同様のエンジンを用いて、ＪＩＳ Ｄ １００１に準じて、全負荷状態における最大出力、最大トルク及び最小燃料消費率を測定した。最大出力、最大トルクについては、エンジンの仕様値と比較して、±３％未満の場合を良好とした。 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
<Evaluation method>
1. Density: Measured by a vibration-type density test method according to JIS K2249.
2. Distillation properties: Measured according to JIS K 2254.
3. Sulfur content: measured by coulometric ultraviolet fluorescence method.
4. Viscosity: Measured according to JIS K 2283.
5. Flash point; measured according to JIS K 2265.
6. Pour point: measured according to JIS K 2269. In addition, according to JIS, it is measured every 2.5 ° C., but it is measured every 1 ° C. to improve the test accuracy.
7. Clogging point: measured according to JIS K2288.
8. Cloud point; measured according to JIS K 2269.
9. Cetane index: measured according to JIS K 2204.
10. Composition analysis; Saturated content, unsaturated content, aromatic compound content, partial aromatic compound content, bicyclic aromatic compound content, and tricyclic or higher aromatic compound content were determined by high performance liquid chromatography (HPLC ) Method.
11. Exhaust gas test: A 10- and 15-mode test was performed using the following engine, and evaluation was made based on the mass of particulate matter (PM) in the exhaust gas. PM in the exhaust gas was collected on a filter using a “dilution tunnel” manufactured by Horiba, Ltd. The amount of PM collected was evaluated based on the following criteria.
〇: 67 mg / Nm 3 or less △: PM is more than 67 mg / Nm 3 (test engine: 4 cylinders of engine, displacement of 2982 cc, injection method is direct injection premix,
Injection pump is common rail, with EGR, with turbocharger (turbo, intercooler)
12. Lubricity test: The wear scar diameter in the HFRR test was measured in accordance with the Petroleum Institute of Japan method JPI-5S-50-98 "Light oil-lubricity test method", and evaluated according to the following criteria.
〇: Wear mark is not more than 460 μm. ×: Wear mark exceeds 460 μm. Output / Fuel Consumption Test Using the same engine as in the exhaust gas test, the maximum output, the maximum torque, and the minimum fuel consumption rate in a full load state were measured according to JIS D1001. Regarding the maximum output and the maximum torque, when the value was less than ± 3% as compared with the specification value of the engine, it was regarded as good.

実施例１〜４、比較例１〜４
第２表に示す性状を有する各種基材を第３表に示す割合で混合し、軽油を製造した。各種評価結果を第３表に示す。 Examples 1-4, Comparative Examples 1-4
Various base materials having the properties shown in Table 2 were mixed in the proportions shown in Table 3 to produce light oil. Table 3 shows various evaluation results.

Figure 2004244628
＊１ Ｔ１０は全留分の１０容量％が留出する温度、以下Ｔｎはｎ容量％量が留出する温度を示す。
Figure 2004244628
 * 1 T10 is the temperature at which 10% by volume of the entire fraction is distilled, and Tn is the temperature at which n% by volume is distilled out.

Figure 2004244628
Figure 2004244628

Figure 2004244628
＊２ 潤滑性向上剤として、三洋化成工業社製「サンフリックＦＭ−６」を使用した
Figure 2004244628
 * 2 "SANFRIC FM-6" manufactured by Sanyo Chemical Industries, Ltd. was used as a lubricity improver.

Claims (10)

脱硫灯油基材０〜８０容量％、脱ろう軽油基材１０〜１００容量％及び水素化分解軽油基材０〜６０容量％を含有してなる軽油であって、硫黄含有量が１０質量ｐｐｍ以下であることを特徴とする低硫黄軽油。 A gas oil comprising 0 to 80% by volume of a desulfurized kerosene base material, 10 to 100% by volume of a dewaxed light oil base material, and 0 to 60% by volume of a hydrocracked gas oil base material, and has a sulfur content of 10 mass ppm or less. A low sulfur gas oil characterized by the following. 前記脱硫灯油基材の硫黄含有量が１０質量ｐｐｍ以下、１５℃における密度が０．７８０〜０．８１０ｇ／ｃｍ3、セタン指数が４０〜６０であり、前記脱ろう軽油基材の硫黄含有量が１０質量ｐｐｍ以下、１５℃における密度が０．８２０〜０．８６０ｇ／ｃｍ3、セタン指数が５０〜７０であり、かつ前記水素化分解軽油基材の硫黄含有量が１０質量ｐｐｍ以下、１５℃における密度が０．８００〜０．８５０ｇ／ｃｍ3、セタン指数が５５〜７８であることを特徴とする請求項１記載の低硫黄軽油。 The sulfur content of the desulfurized kerosene base material is 10 mass ppm or less, the density at 15 ° C. is 0.780 to 0.810 g / cm 3 , the cetane index is 40 to 60, and the sulfur content of the dewaxed light oil base material is Is 10 mass ppm or less, the density at 15 ° C. is 0.820 to 0.860 g / cm 3 , the cetane index is 50 to 70, and the sulfur content of the hydrocracked gas oil base material is 10 mass ppm or less, 15 mass ppm or less. density at ℃ is 0.800~0.850g / cm 3, low sulfur diesel fuel according to claim 1, wherein the cetane index is characterized by a 55 to 78. 前記水素化分解軽油基材の芳香族化合物含有量が７．０〜１９．５容量％であることを特徴とする請求項１又は２に記載の低硫黄軽油。 The low sulfur gas oil according to claim 1 or 2, wherein the hydrocracked gas oil base material has an aromatic compound content of 7.0 to 19.5% by volume. 前記芳香族化合物が一環芳香族化合物７．０〜１５．０容量％、二環芳香族化合物０．０〜４．０容量％及び三環以上の芳香族化合物０．０〜０．５容量％含有することを特徴とする請求項３記載の低硫黄軽油。 The aromatic compound is a partial aromatic compound 7.0 to 15.0% by volume, a bicyclic aromatic compound 0.0 to 4.0% by volume, and a tricyclic or higher aromatic compound 0.0 to 0.5% by volume. The low sulfur gas oil according to claim 3, which is contained. 前記低硫黄軽油の１５℃における密度が０．８０２〜０．８３８ｇ／ｃｍ3であることを特徴とする請求項１〜４のいずれかに記載の低硫黄軽油。 The low sulfur gas oil according to any one of claims 1 to 4, wherein the density of the low sulfur gas oil at 15 ° C is 0.802 to 0.838 g / cm 3 . 前記低硫黄軽油中の芳香族化合物含有量が１５．０容量％以上である請求項１〜５のいずれかに記載の低硫黄軽油。 The low sulfur gas oil according to any one of claims 1 to 5, wherein the content of the aromatic compound in the low sulfur gas oil is 15.0% by volume or more. 前記低硫黄軽油中の多環芳香族化合物含有量が４．５容量％以下である請求項１〜６のいずれかに記載の低硫黄軽油。 The low sulfur gas oil according to any one of claims 1 to 6, wherein the content of the polycyclic aromatic compound in the low sulfur gas oil is 4.5% by volume or less. 前記低硫黄軽油の曇り点が−７℃以下であることを特徴とする請求項１〜７のいずれかに記載の低硫黄軽油。 The low sulfur gas oil according to any one of claims 1 to 7, wherein the low sulfur gas oil has a cloud point of -7C or less. 前記低硫黄軽油の曇り点が−１１℃以下であることを特徴とする請求項１〜７のいずれかに記載の低硫黄軽油。 The low sulfur gas oil according to any one of claims 1 to 7, wherein the low sulfur gas oil has a cloud point of -11 ° C or lower. 脱硫灯油基材０〜８０容量％、脱ろう軽油基材１０〜１００容量％及び水素化分解軽油基材０〜６０容量％を混合することを特徴とする硫黄含有量１０質量ｐｐｍ以下の低硫黄軽油の製造方法。


Low sulfur having a sulfur content of 10 mass ppm or less, characterized by mixing 0 to 80% by volume of a desulfurized kerosene base material, 10 to 100% by volume of a dewaxed gas oil base and 0 to 60% by volume of a hydrocracked gas oil base. Manufacturing method of light oil.


JP2004010716A 2003-01-20 2004-01-19 Gas oil with reduced sulfur content and its manufacturing process Pending JP2004244628A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2004010716A JP2004244628A (en) 2003-01-20 2004-01-19 Gas oil with reduced sulfur content and its manufacturing process

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003011330 2003-01-20
JP2004010716A JP2004244628A (en) 2003-01-20 2004-01-19 Gas oil with reduced sulfur content and its manufacturing process

Publications (1)

Publication Number Publication Date
JP2004244628A true JP2004244628A (en) 2004-09-02

Family

ID=33031915

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2004010716A Pending JP2004244628A (en) 2003-01-20 2004-01-19 Gas oil with reduced sulfur content and its manufacturing process

Country Status (1)

Country Link
JP (1) JP2004244628A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008088243A (en) * 2006-09-29 2008-04-17 Idemitsu Kosan Co Ltd Gas oil composition
JP2009040856A (en) * 2007-08-08 2009-02-26 Nippon Oil Corp Gas oil composition
JP2011052199A (en) * 2009-08-07 2011-03-17 Idemitsu Kosan Co Ltd Gas oil composition
JP2015166435A (en) * 2014-03-04 2015-09-24 Ｊｘ日鉱日石エネルギー株式会社 Dewaxing gas oil base material, and gas oil composition intended for cold district blended with the same
JP2015166434A (en) * 2014-03-04 2015-09-24 Ｊｘ日鉱日石エネルギー株式会社 Hydrogenation isomerization dewaxing gas oil base material, and gas oil composition intended for cold district blended with the same
JP2016148007A (en) * 2015-02-13 2016-08-18 出光興産株式会社 Diesel fuel oil composition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08157839A (en) * 1994-12-07 1996-06-18 Idemitsu Kosan Co Ltd Fuel composition
JP2000265180A (en) * 1999-03-17 2000-09-26 Jomo Technical Research Center:Kk Light oil with reduced foamability
JP2000328078A (en) * 1999-03-16 2000-11-28 Nippon Mitsubishi Oil Corp Gas oil composition
JP2001279272A (en) * 2000-03-30 2001-10-10 Jomo Technical Research Center:Kk Heavy fuel oil a

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08157839A (en) * 1994-12-07 1996-06-18 Idemitsu Kosan Co Ltd Fuel composition
JP2000328078A (en) * 1999-03-16 2000-11-28 Nippon Mitsubishi Oil Corp Gas oil composition
JP2000265180A (en) * 1999-03-17 2000-09-26 Jomo Technical Research Center:Kk Light oil with reduced foamability
JP2001279272A (en) * 2000-03-30 2001-10-10 Jomo Technical Research Center:Kk Heavy fuel oil a

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008088243A (en) * 2006-09-29 2008-04-17 Idemitsu Kosan Co Ltd Gas oil composition
JP2009040856A (en) * 2007-08-08 2009-02-26 Nippon Oil Corp Gas oil composition
JP2011052199A (en) * 2009-08-07 2011-03-17 Idemitsu Kosan Co Ltd Gas oil composition
JP2015166435A (en) * 2014-03-04 2015-09-24 Ｊｘ日鉱日石エネルギー株式会社 Dewaxing gas oil base material, and gas oil composition intended for cold district blended with the same
JP2015166434A (en) * 2014-03-04 2015-09-24 Ｊｘ日鉱日石エネルギー株式会社 Hydrogenation isomerization dewaxing gas oil base material, and gas oil composition intended for cold district blended with the same
JP2016148007A (en) * 2015-02-13 2016-08-18 出光興産株式会社 Diesel fuel oil composition

Similar Documents

Publication Publication Date Title
JP6941584B2 (en) Fuel oil composition and its manufacturing method
JP4460200B2 (en) Fuel oil base and light oil composition containing the same
JP3990225B2 (en) Light oil composition
JP2008138144A (en) Fuel oil composition for diesel engine
WO2009080673A2 (en) Fuel compositions
JP2011105958A (en) Method for producing gas oil composition
JP2004244628A (en) Gas oil with reduced sulfur content and its manufacturing process
JP4620381B2 (en) Light oil composition
JP2005220329A (en) Gas oil composition
JP2011213888A (en) Gas oil composition
JP2005220330A (en) Gas oil composition
JP4052773B2 (en) Light oil composition
JP2001158890A (en) Fuel composition
JP4119190B2 (en) Light oil composition and method for producing the same
JP5084583B2 (en) Method for producing light oil composition
JP5537961B2 (en) Light oil composition
JP5094071B2 (en) Fuel oil composition
JP5437193B2 (en) Light oil composition
JP3866510B2 (en) Diesel diesel oil composition
JP4555027B2 (en) Light oil composition
JP6448686B2 (en) Method of using fuel oil in an internal combustion engine
JP5154813B2 (en) Fuel oil composition
JP5052176B2 (en) Fuel oil composition
JP6448687B2 (en) Method of using fuel oil in an internal combustion engine
JP5094072B2 (en) Fuel oil composition

Legal Events

Date Code Title Description
A621 Written request for application examination

Effective date: 20060801

Free format text: JAPANESE INTERMEDIATE CODE: A621

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20100331

A131 Notification of reasons for refusal

Effective date: 20100406

Free format text: JAPANESE INTERMEDIATE CODE: A131

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20100604

A02 Decision of refusal

Effective date: 20100824

Free format text: JAPANESE INTERMEDIATE CODE: A02