JP2005023136A - Gas oil composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas oil composition which can simultaneously reduce particle-like substances, fine particles and nitrogen oxides exhausted from engines, can improve fuel consumption, little affects members, and has an excellent low temperature starting performance. <P>SOLUTION: This gas oil composition satisfying the JIS 1 gas oil standard is characterized by compounding the below-described hydrogenation-purified oil with a specific fatty acid alkyl ester in a prescribed rate and having a volume modulus of 1,350 to 1,550 MPa and a total insoluble content of ≤2.0 mg/100 mL after an oxidation stability test. The above-described hydrogenation-purified oil has a sulfur content of ≤8 mass ppm, a monocyclic naphthene content of ≥10 vol.%, a monocyclic aromatic compound content of ≤20 vol.%, a 90% distillation temperature of 280 to 350°C, and a difference of 50 to 150°C between a 80% distillation temperature and a 20% distillation temperature. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００９７】
【表２】

【００９８】
実施例および比較例で使用した軽油組成物は、表２に示すとおり、水素化精製油と脂肪酸アルキルエステル混合物を特定の配合割合で調合したものである。
表２から明らかなように、９０％留出温度（Ｔ９０）、８０％留出温度と２０％留出温度の差（Ｔ８０−Ｔ２０）、硫黄分含有量、１環ナフテン分含有量、１環芳香族分含有量およびエステル係数（Ｃ）が、いずれも本発明で規定される範囲内である水素化精製油と脂肪酸アルキルエステル混合物を、本発明で規定される範囲内で配合した実施例１〜６においては、ＪＩＳ規格１号軽油の性状を満足し、かつ体積弾性率が１３５０ＭＰａ以上１５５０ＭＰａ以下、酸化安定性試験後の全不溶解分が２．０ｍｇ／１００ｍＬ以下である軽油組成物を容易にかつ確実に得ることができた。一方、上記特定の水素化精製油および脂肪酸アルキルエステル混合物を用いずに軽油組成物を調製した比較例１においては、本発明の目的とする軽油組成物は必ずしも得られない。
【００９９】
次に実施例１〜６及び比較例１の各軽油組成物を用いて、以下に示す各種試験を行った。全ての試験結果を表３に示す。表３の結果から分かるように、実施例１〜６の軽油組成物は、比較例１の軽油組成物に比べ、ＰＭおよび粒子個数が少なく、窒素酸化物が少なく、燃費が良好であり、低温始動性が良好であり、かつゴム膨潤性能に優れていることが明らかである。
【０１００】
なお、車両試験に係わる試験方法は、同別添２７「ディーゼル自動車１０・１５モード排出ガス測定の技術基準」に準拠している。
【０１０１】
（車両排ガス試験、燃費試験）
下記に示すディーゼルエンジン搭載車両（車両１）を用いて、ＰＭ、窒素酸化物及び燃費の測定を行った。ＰＭは全量希釈トンネルにて希釈した排ガスを炭化フッ素被膜ガラス繊維フィルタで捕集し、分析した。試験モードは、図２に示す実走行を模擬した過渡運転モードで行い、排ガス成分は試験モード１ｋｍあたりの排出量として算出し、比較例１の燃料を供試した場合の結果を１００として、各結果を相対的に比較、定量化した。燃費は試験モード中に消費した燃料容積流量を燃料温度補正し、重量値に置き換えた値について、比較例１の燃料を供試した場合の結果を１００として、各結果を相対的に比較、定量化した。
【０１０２】
（車両諸元）：車両１
エンジン種類：インタークーラー付過給直列４気筒ディ−ゼル
排気量 ：３Ｌ
圧縮比 ：１８．５
最高出力 ：１２５ｋＷ／３４００ｒｐｍ
最高トルク：３５０Ｎｍ／２４００ｒｐｍ
規制適合 ：平成９年度排ガス規制適合
車両重量 ：１９００ｋｇ
ミッション：４ＡＴ
排ガス後処理装置：酸化触媒
【０１０３】
（微小粒子測定）
粒子数の測定の際には、図３に示す走査型モビリティ粒径分析装置を使用し、粒子の粒径ごとに分離と粒子数の検出を行った。すなわち、図３に示した装置において、希釈された排ガスサンプルを通す流路には、その上流から順に、荷電分布制御部ａ、分級部ｂ、粒子数計測部ｃが設けられている。希釈された排ガス中の微小粒子は、荷電分布制御部ａで平衡荷電分布状態となり、分級部ｂで粒子それぞれの電気移動度に従い分級（分離）される。そして、粒子数計測部ｃにおいて、粒径ごとに分離された粒子が計測される。
試験は、排ガス試験と同様に車両１を図２に示す試験モードで運転し、上記装置にて試験期間中に捕集された粒子を、総粒子数と直径１００ｎｍ以下の粒子（ナノ粒子）とに区分し、比較例１の燃料を供試した場合の結果を１００として、各結果を相対的に比較、定量化した。
【０１０４】
（低温始動性）
車両１を用い、環境温度の制御が可能なシャーシダイナモメータ上で、室温で、▲１▼供試ディーゼル自動車の燃料系統を評価燃料でフラッシング（洗浄）、▲２▼フラッシング燃料の抜き出し、▲３▼メインフィルタの新品への交換、▲４▼燃料タンクに評価燃料の規定量（供試車両の燃料タンク容量の１／２）の張り込みを行う。その後、▲５▼環境温度を室温から５℃まで急冷し、▲６▼５℃で１時間保持した後、▲７▼１℃／ｈの冷却速度で所定の温度（−３℃）に達するまで徐冷し、▲８▼所定の温度で１時間保持した後、エンジンを始動させる。１０秒間のクランキングを３０秒間隔で２回繰り返しても始動しない場合は不可（×）、クランキングを２回繰り返す間でエンジンが始動した場合は可（◯）とした。
【０１０５】
（ゴム膨潤試験）
エンジン部品のＯ−リング等で使用されているゴム部材に対する影響を確認するため、以下に示す手順で浸せき試験を行った。ゴムを構成している化合物の１つであるアクリロニトリルが結合アクリロニトリル質量中心値として、全体の２５％以上３５％以下であるニトリルゴム（中ニトリルゴム）を評価対象のゴム部材とし、ＭＩＬ Ｒ６８５５に準拠して試験燃料を１００℃に加熱、保持し、その中に試験ゴム部材を７０時間浸せきさせる。評価は７０時間後の試験ゴム部材の体積変化で比較、定量化する。判定は試験前後における体積変化率絶対値が±２０％以上の場合を不合格（×）とし、±１０％以上±２０％以内の場合をボーダーライン（△）、±１０％以内の場合を合格（○）とする。
【０１０６】
【表３】

【図面の簡単な説明】
【図１】軽油組成物の体積弾性率の測定に使用される装置の一例を示す概略構成図である。
【図２】排ガス試験における試験モードを示す図である。
【図３】粒子数の測定に使用する走査型モビリティ粒径分析装置の概略図である。
【符号の説明】
１ 定容容器
２ 供給弁
３ 排出弁
４ 温度センサ
５ 圧力センサ
６ ピストン
１００ 軽油組成物
ａ 荷電分布制御部
ｂ 分級部
ｃ 粒子数計測部[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a light oil composition having a low sulfur content and containing a fatty acid alkyl ester. More specifically, it relates to a light oil composition that reduces particulate matter (PM) discharged from the engine and fine particles and nitrogen oxides at the same time, improves fuel efficiency, has little effect on components, and has excellent low-temperature startability. is there.
[0002]
[Prior art]
Conventionally, as the base material for light oil, straight-run gas oil obtained from crude oil atmospheric distillation equipment is hydrorefined or hydrodesulfurized, and straight-run kerosene obtained from crude oil atmospheric distillation equipment is hydrogenated. Those subjected to hydrorefining treatment or hydrodesulfurization treatment are known. Conventional gas oil compositions are produced by blending one or more of the above gas oil base and kerosene base. Moreover, additives, such as a cetane number improver and a detergent, are mix | blended with these light oil compositions as needed (for example, refer nonpatent literature 1).
[0003]
[Non-Patent Document 1]
Seiichi Konishi, “Introduction to Fuel Engineering”, Suikabo, March 1991, p. 136-144
[0004]
[Problems to be solved by the invention]
By the way, in recent years, reduction of sulfur content and aromatic content in light oil, which is a fuel for internal combustion engines, has been demanded with the aim of urgently improving the air environment and reducing the environmental load. At the same time, in order to cope with the global warming problem, there is a need for fuel properties that contribute to further improving fuel efficiency and reduce carbon dioxide. One of the solutions is biofuels such as synthetic fuels and renewable energy. The use of diesel fuel (hereinafter also referred to as BDF) as an alternative fuel is being studied.
[0005]
The conventional gas oil base contains an aromatic content of about 40% by volume at maximum, and about 20% by volume on average. In addition, the gas oil fraction contains several percent of polycyclic aromatic components having two or more rings, which are considered to have a large ability to generate particulate matter (hereinafter also referred to as PM). In general, the aromatic content cannot be sufficiently reduced by hydrorefining or hydrodesulfurization treatment, so it is necessary to introduce a dearomatic process. However, existing equipment may not provide the desired light oil base material. Refining costs will increase significantly.
In general, the kerosene base material has a lower aromatic content than the light oil base material (up to about 30% by volume, and on average about 15% by volume). By mixing with the material, the aromatic content can be reduced. However, the light oil composition simply obtained in this manner is low in density and very light, which causes a deterioration in fuel consumption and a decrease in output. Furthermore, the mixing of the light oil base material and the kerosene base material also reduces the kinematic viscosity of the composition, which easily causes problems on the lubrication surface of the fuel injection pump and the like.
[0006]
Synthetic fuels are attracting attention as synthetic light oil and synthetic kerosene made from natural gas, asphalt, coal and the like. These fuel base materials are characterized by containing almost no aromatic content or sulfur content. However, in view of the influence on the members used in the fuel injection system, when such a fuel is used, particularly in an aged car, the rubber member used is rather contracted, resulting in fuel leakage ( (Leakage) may occur. In addition, since it is a base material mainly composed of paraffin, there is a concern that the precipitation of wax during start-up at low temperatures and the deterioration of fuel consumption due to low density are concerned.
[0007]
On the other hand, BDF is mainly a mixture of fatty acid alkyl esters made from vegetable oil, which contains almost no aromatics or sulfur, and is itself an oxygen-containing compound with oxygen in the molecule. It is attracting attention as a promising candidate for fuel. In addition, because it is derived from plants, it is positioned as renewable energy, so the international carbon dioxide reduction protocol concluded in 1997, the so-called Kyoto Protocol, rules that carbon dioxide derived from BDF is not counted as emissions. The BDF also has a policy merit.
[0008]
However, depending on the composition of the fatty acid alkyl ester contained, there are those that are solid at room temperature and those that have a very heavy boiling point, so when used simply as a substitute for light oil, flow performance at low temperatures and unburned carbonization are used. Hydrogen emissions and nitrogen oxide emissions will deteriorate. The fatty acid alkyl ester itself is a chemically stable substance, but the fatty acid glyceride, alkyl alcohol, and by-product glycerin mixture, which are raw materials for refining the fatty acid ester, have an adverse effect on engine members and the fuel injection system. It is extremely concerned. Therefore, when using BDF as an alternative to light oil, it is natural to pay attention to the properties of BDF itself, but in addition to that, BDF can be replaced with light oil or mixed with light oil at a high blending ratio. There are problems to do and you must avoid it.
[0009]
Therefore, regarding the provision of a light oil composition that reduces harmful exhaust components, particularly particulate matter (PM) and fine particles and nitrogen oxides at the same time, improves fuel efficiency, has little effect on components, and has excellent low-temperature startability. These performance improvements cannot be achieved at the same time by using only existing refining methods or simply replacing them with alternative fuels. Furthermore, because these engine performances are closely related to other fuel properties, it is very difficult to design high-quality fuels that can simultaneously achieve these required performances at a high level, and are required as commercial fuel oils. There are no examples or knowledge based on the examination of practical manufacturing methods that satisfy the various performances.
[0010]
The present invention has been made in view of such a situation, and its purpose is to reduce particulate matter (PM) and fine particles and nitrogen oxides discharged from the engine simultaneously when used as diesel fuel, An object of the present invention is to provide a light oil composition that improves fuel efficiency, has little effect on members, and has excellent performance at low temperature startability.
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention has a sulfur content of 8 mass ppm or less, a 1-ring naphthene content of 10 vol% or more, a 1-ring aromatic content of 20 vol% or less, a 90% distillation temperature of 280 ° C or more. A hydrorefined oil having a difference of 350 ° C. or lower and a difference between 80% distillation temperature and 20% distillation temperature of 50 ° C. or higher and 150 ° C. or lower is selected from myristic acid alkyl ester, palmitic acid alkyl ester and stearic acid alkyl ester Any one of fatty acid alkyl esters (B) containing any one or more of fatty acid alkyl esters (A) and selected from lauric acid alkyl esters, oleic acid alkyl esters, linoleic acid alkyl esters, and linolenic acid alkyl esters The total of the mass content of the fatty acid alkyl ester (A) / fatty acid alkyl ester ( ) And the average molecular weight of the fatty acid alkyl ester mixture is 500 or less, the total acid value is 1.0 mgKOH / g or less, and the sulfur content is 5 mass ppm or less. The volume modulus of elasticity is 1350 MPa or more and 1550 MPa or less, and the total insoluble matter after the oxidation stability test is 2.0 mg / 100 mL or less. It relates to a light oil composition that satisfies the JIS No. 1 light oil standard.
RBDF = (− 6 × C × FAME + HDS × (2 × PA + PN)) / 100
0 ≦ RBDF ≦ 10
RBDF: BDF index
C: Sum of mass content of fatty acid alkyl ester (A) / sum of mass content of fatty acid alkyl ester (B)
FAME: Fatty acid alkyl ester mixture content (volume%)
HDS: Hydrorefined oil content (volume%)
PA: Aromatic content of 2 or more rings in hydrorefined oil (volume%)
PN: Content of naphthene in two or more rings in hydrorefined oil (volume%)
[0011]
In the light oil composition, the density at 15 ° C. is 800 kg / m.³850 kg / m or more³It is preferable that the cetane number is 52 or more and the HFRR wear scar diameter (WS1.4) is 410 μm or less.
Moreover, in the said light oil composition, it is preferable to mix | blend the fatty-acid alkylester mixture which used vegetable oil as the raw material, and is a water content of 300 volume ppm or less.
[0012]
According to the present invention, it is difficult to realize with a conventional light oil composition by using a light oil composition containing the hydrorefined oil having the above specific properties and the fatty acid alkyl ester having the above specific properties. Diesel substances (PM) and fine particles and nitrogen oxides discharged from the engine were reduced at the same time, fuel efficiency was improved, there was little influence on the members, and the light oil composition with excellent low temperature startability performance Provided.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
As a constituent of the light oil composition of the present invention, the sulfur content is 8 ppm by mass or less, the monocyclic naphthene content is 10% by volume or more, and the monocyclic aromatic content is 20% by volume or less, 90% distillate. A hydrorefined oil having a temperature of 280 ° C. or higher and 350 ° C. or lower and a difference between 80% distillation temperature and 20% distillation temperature of 50 ° C. or higher and 150 ° C. or lower is used.
[0014]
The hydrorefined oil according to the present invention is a low sulfur gas oil fraction, a kerosene fraction, or a mixture thereof obtained by hydrotreating a predetermined raw material oil.
[0015]
As the raw oil of the light oil fraction, straight-run gas oil obtained from an atmospheric distillation apparatus of crude oil, straight-run heavy oil obtained from an atmospheric distillation apparatus and residual oil obtained by treating the crude oil with a vacuum distillation apparatus Catalytic cracked diesel oil or hydrocracked diesel oil obtained by catalytic cracking or hydrocracking diesel oil, vacuum heavy diesel oil or desulfurized heavy oil, hydrorefined diesel oil obtained by hydrorefining these petroleum hydrocarbons or hydrogenated Examples include desulfurized light oil.
[0016]
The hydrorefining of the petroleum hydrocarbon can be performed using a hydrodesulfurization apparatus common in petroleum refining. Generally, the reaction temperature is 300 to 380 ° C., the hydrogen pressure is 3 to 8 MPa, and the LHSV is 0.3 to 2 h.^-1The hydrogen / oil ratio is 100 to 500 NL / L.
As a catalyst used for hydrorefining, a general hydrodesulfurization catalyst can be applied. As the active metal, normally, Group 6A and Group 8 metals of the periodic table are preferably used, and examples thereof include Co—Mo, Ni—Mo, Co—W, and Ni—W. As the carrier, a porous inorganic oxide mainly composed of alumina is used. These conditions and the catalyst are not particularly limited as long as the properties of the raw material oil are satisfied.
[0017]
Moreover, the hydrorefined oil of this invention can use what hydrotreated the above-mentioned raw material oil in presence of a hydrogenation catalyst. The hydrotreating conditions are: reaction temperature 170-320 ° C., hydrogen pressure 2-10 MPa, LHSV 0.1-2 h^-1The hydrogen / oil ratio is 100 to 800 NL / L. Preferably, the reaction temperature is 175 to 300 ° C., the hydrogen pressure is 2.5 to 8 MPa, and the LHSV is 0.2 to 1.5 h.^-1The hydrogen / oil ratio is 150 to 600 NL / L, more preferably the reaction temperature is 180 ° C. to 280 ° C., the hydrogen pressure is 3 to 7 MPa, and the LHSV is 0.3 to 1.2 h.^-1The hydrogen / oil ratio is 150 to 500 NL / L. The lower the reaction temperature, the more advantageous for the hydrogenation reaction, but not for the desulfurization reaction. The higher the hydrogen pressure and the hydrogen / oil ratio, the more the desulfurization and hydrogenation reactions are promoted, but there is an optimal point economically. The lower the LHSV, the better the reaction, but if it is too low, it is disadvantageous because it requires an extremely large reaction column volume and excessive capital investment.
[0018]
The apparatus for hydrotreating the feedstock may be of any configuration, the reaction towers may be used alone or in combination, and hydrogen may be additionally injected between the reaction towers, gas-liquid separation operation or hydrogen sulfide. You may have the removal equipment.
A fixed bed system is preferably employed as the reaction mode of the hydrotreating apparatus. Hydrogen can take either a countercurrent or cocurrent flow with respect to the feedstock, and may have a plurality of reaction towers and a combination of countercurrent and cocurrent. As a general format, it is a down flow, and a gas-liquid twin parallel flow format is preferable. Hydrogen gas may be injected into the middle stage of the reaction tower as a quench for the purpose of removing reaction heat or increasing the hydrogen partial pressure.
[0019]
The catalyst used for the hydrotreatment is a catalyst in which a hydrogenation active metal is supported on a porous carrier. An inorganic oxide is mentioned as a porous support | carrier. Specific inorganic oxides include alumina, titania, zirconia, boria, silica, or zeolite. In the present invention, at least one of titania, zirconia, boria, silica, and zeolite is composed of alumina. Things are good. The production method is not particularly limited, but any preparation method can be employed using raw materials in various sols, salt compounds, and the like corresponding to each element. Furthermore, once the composite hydroxide or composite oxide such as silica alumina, silica zirconia, alumina titania, silica titania, and alumina boria is prepared, the preparation process in the state of alumina gel and other hydroxides or in an appropriate solution state It may be prepared by adding at any step. The ratio of alumina to other oxides can be any ratio with respect to the porous carrier, but preferably alumina is 90% by mass or less, more preferably 60% by mass or less, and more preferably 40% by mass or less. .
[0020]
Zeolite is a crystalline aluminosilicate, such as faujasite, pentasil, mordenite, etc., which is ultra-stabilized by a predetermined hydrothermal treatment and / or acid treatment, or one whose alumina content in the zeolite is adjusted is used. be able to. Preferably, faujasite and mordenite, particularly preferably Y type and beta type are used. The Y-type is preferably ultra-stabilized, and the ultra-stabilized zeolite by hydrothermal treatment forms new pores in the range of 20 to 100% in addition to the original pore structure called micropores of 20 cm or less. . Known conditions can be used for the hydrothermal treatment conditions.
[0021]
The active metal of the catalyst used for the hydrotreatment is at least one metal selected from Group 8 metals of the periodic table. Preferably, it is at least one selected from Ru, Rd, Ir, Pd and Pt, more preferably Pd or / and Pt. The active metal may be a combination of these metals. For example, Pt-Pd, Pt-Rh, Pt-Ru, Ir-Pd, Ir-Rh, Ir-Ru, Pt-Pd-Rh, Pt-Rh-Ru , Ir-Pd-Rh, Ir-Rh-Ru, etc. can be employed. As the metal source, a general inorganic salt or a complex salt compound can be used, and as a supporting method, any method of a supporting method used in an ordinary hydrogenation catalyst such as an impregnation method or an ion exchange method can be used. When a plurality of metals are supported, they may be supported simultaneously using a mixed solution, or may be sequentially supported using a single solution. The metal solution may be an aqueous solution or an organic solvent.
[0022]
Metal loading may be performed after the completion of the entire preparation process of the porous support, or after further preloading on an appropriate oxide, composite oxide, zeolite in the intermediate process of porous support preparation, Heat concentration and kneading may be performed.
The amount of the active metal supported is not particularly limited, but is 0.1 to 10% by mass, preferably 0.15 to 5% by mass, and more preferably 0.2 to 3% by mass with respect to the catalyst mass.
The catalyst is preferably used after a preliminary reduction treatment in a hydrogen stream. In general, when a gas containing hydrogen is circulated and heat of 200 ° C. or higher is applied according to a predetermined procedure, the active metal on the catalyst is reduced, and hydrogenation activity is exhibited.
[0023]
In the present invention, in addition to the hydrorefined oil of the light oil fraction, unrefined oil and / or hydrorefined oil is used as a raw material oil, and the reaction temperature is 220 to 350 ° C. in the presence of a hydrogenation catalyst, and the hydrogen pressure is 1 to 6MPa, LHSV 0.1-10h^-1, Sulfur content obtained by hydrogenation at a hydrogen / oil ratio of 10 to 300 NL / L: 8 mass ppm or less, Total aromatic content: 20 vol% or less, Bicyclic or higher aromatic content: 1 volume %, A naphthene content of 10% by volume or more, and a low-sulfur kerosene fraction having a boiling point range of 140 to 300 ° C. can be used.
[0024]
Such a low sulfur kerosene fraction is a kerosene fraction obtained by hydrotreating a predetermined feedstock. The raw oil is mainly straight-run kerosene obtained by atmospheric distillation of crude oil, but hydrocracked kerosene produced together with hydrocracked light oil and hydrogen obtained by hydrotreating the above kerosene fraction. Examples include chemical kerosene, natural gas, asphalt, and synthetic kerosene made from coal.
[0025]
The feedstock oil as the hydrorefined oil kerosene fraction is obtained by hydrorefining a petroleum hydrocarbon using a general hydrodesulfurization apparatus in petroleum refining. Usually, reaction temperature 220-350 ° C., hydrogen pressure 1-6 MPa, LHSV 0.1-10 h^-1The hydrogen / oil ratio is 10 to 300 NL / L.
A general hydrodesulfurization catalyst can be applied as the catalyst. As the active metal, Group 6A and Group 8 metals of the periodic table are usually used, and examples thereof include Co—Mo, Ni—Mo, Co—W, and Ni—W. As the carrier, a porous inorganic oxide mainly composed of alumina is used. These conditions and the catalyst are not particularly limited as long as the properties of the raw material oil are satisfied.
[0026]
The hydrorefined oil kerosene fraction of the present invention can be obtained by hydrotreating (desulfurizing and refining) the above-described raw material oil in the presence of a hydrogenation catalyst.
The hydrotreating conditions are: reaction temperature 220-350 ° C., hydrogen pressure 1-6 MPa, LHSV 0.1-10 h^-1The hydrogen / oil ratio is 10 to 300 NL / L. Preferably, the reaction temperature is 250 ° C. to 340 ° C., the hydrogen pressure is 2 to 5 MPa, and the LHSV is 1 to 10 h.^-1The hydrogen / oil ratio is 30 to 200 NL / L, more preferably the reactivity is 270 ° C. to 330 ° C., the hydrogen pressure is 2 to 4 MPa, LHSV 2 to 10 h.^-1The hydrogen / oil ratio is 50 to 200 NL / L. The lower the reaction temperature, the more advantageous for the hydrogenation reaction, but not for the desulfurization reaction. The higher the hydrogen pressure and the hydrogen / oil ratio, the more the desulfurization and hydrogenation reactions are promoted, but there is an optimal point economically. The lower the LHSV, the more advantageous for the reaction. However, if the LHSV is too low, a very large reaction tower volume is required, resulting in an excessive capital investment.
[0027]
The apparatus for hydrotreating the feedstock may be of any configuration, the reaction towers may be used alone or in combination, and hydrogen may be additionally injected between the reaction towers, gas-liquid separation operation or hydrogen sulfide. You may have the removal equipment.
A fixed bed system is preferably employed as the reaction mode of the hydrotreating apparatus. Hydrogen can take either a countercurrent or cocurrent flow with respect to the feedstock, and may have a plurality of reaction towers and a combination of countercurrent and cocurrent. As a general format, it is a down flow, and a gas-liquid twin parallel flow format is preferable. Hydrogen gas may be injected into the middle stage of the reaction tower as a quench for the purpose of removing reaction heat or increasing the hydrogen partial pressure.
[0028]
The catalyst used for the hydrotreatment is a catalyst in which a hydrogenation active metal is supported on a porous carrier. An inorganic oxide is mentioned as a porous support | carrier. Specific inorganic oxides include alumina, titania, zirconia, boria, silica, or zeolite. In the present invention, at least one of titania, zirconia, boria, silica, and zeolite is composed of alumina. Things are good. The production method is not particularly limited, but any preparation method can be employed using raw materials in various sols, salt compounds, and the like corresponding to each element. Furthermore, once the composite hydroxide or composite oxide such as silica alumina, silica zirconia, alumina titania, silica titania, and alumina boria is prepared, the preparation process in the state of alumina gel and other hydroxides or in an appropriate solution state It may be prepared by adding at any step. The ratio of alumina to other oxides can be any ratio with respect to the porous carrier, but preferably alumina is 90% by mass or less, more preferably 60% by mass or less, and more preferably 40% by mass or less. .
[0029]
Zeolite is a crystalline aluminosilicate, such as faujasite, pentasil, mordenite, etc., which is ultra-stabilized by a predetermined hydrothermal treatment and / or acid treatment, or one whose alumina content in the zeolite is adjusted is used. be able to. Preferably, faujasite and mordenite, particularly preferably Y type and beta type are used. The Y-type is preferably ultra-stabilized, and the ultra-stabilized zeolite by hydrothermal treatment forms new pores in the range of 20 to 100% in addition to the original pore structure called micropores of 20 cm or less. . Known conditions can be used for the hydrothermal treatment conditions.
[0030]
The active metal of the catalyst used for the hydrotreatment is at least one metal selected from Group 6A metals of the periodic table. Preferably, it is at least one selected from Mo and W. The active metal may be a combination of a Group 6A metal and a Group 8 metal, specifically, a combination of Mo or W and Co or Ni. For example, Co—Mo, Co—W, Ni—Mo, Combinations such as Ni-W, Co-Ni-Mo, and Co-Ni-W can be employed. As the metal source, a general inorganic salt or a complex salt compound can be used, and as a supporting method, any method of a supporting method used in an ordinary hydrogenation catalyst such as an impregnation method or an ion exchange method can be used. When a plurality of metals are supported, they may be supported simultaneously using a mixed solution, or may be sequentially supported using a single solution. The metal solution may be an aqueous solution or an organic solvent.
[0031]
Metal loading may be performed after the completion of the entire preparation process of the porous support, or after further preloading on an appropriate oxide, composite oxide, zeolite in the intermediate process of porous support preparation, Heat concentration and kneading may be performed.
The amount of the active metal supported is not particularly limited, but is 0.1 to 10% by mass, preferably 0.15 to 5% by mass, and more preferably 0.2 to 3% by mass with respect to the catalyst mass.
The catalyst is preferably used after a preliminary reduction treatment in a hydrogen stream. In general, when a gas containing hydrogen is circulated and heat of 200 ° C. or higher is applied according to a predetermined procedure, the active metal on the catalyst is reduced, and hydrogenation activity is exhibited.
[0032]
The hydrorefined oil according to the present invention needs to satisfy predetermined properties by using at least one of the above-described light oil fraction and kerosene fraction. Moreover, the hydrorefined oil in this invention can be comprised by mix | blending a some light oil fraction base material and a kerosene fraction base material in the category which satisfy | fills a predetermined condition. Examples of the light oil fraction base material include hydrorefined light oil, hydrodesulfurized light oil, hydrocracked light oil, natural gas, asphalt, synthetic light oil synthesized from coal, and the like. Examples of the kerosene fraction base material include hydrorefined kerosene, hydrodesulfurized kerosene, hydrocracked kerosene, natural gas, asphalt, and synthetic kerosene synthesized from raw materials such as coal.
[0033]
The sulfur content of the hydrorefined oil according to the present invention needs to be 8 mass ppm or less, preferably 7 mass ppm from the viewpoint of reducing harmful exhaust components discharged from the engine and improving the performance of the exhaust gas aftertreatment device. Below, more preferably 6 ppm by mass or less, still more preferably 5 ppm by mass or less, still more preferably 3 ppm by mass or less, and most preferably 1 ppm by mass or less. In addition, the sulfur content here means the mass content of the sulfur content based on the total amount of the light oil composition measured by JIS K2541 “Sulfur content test method”.
[0034]
The monocyclic naphthene content of the hydrorefined oil according to the present invention needs to be 10% by volume or more, preferably 15% by volume or more, and more preferably 20% by volume or more. When the content of monocyclic naphthene in the hydrorefined oil is within the above range, the properties defined in the light oil composition of the present invention can be achieved more easily and reliably, and with the fatty acid alkyl ester mixture Synergy can be achieved. Here, the content of 1-ring naphthene is measured in accordance with ASTM D2786 “Standard Test Method for Hydrocarbon Types Analysis of Gas-Oil Saturates Fractions by HighSaturation V (Capacity%).
[0035]
The monocyclic aromatic content of the hydrorefined oil according to the present invention needs to be 20% by volume or less, preferably 17% by volume or less, more preferably 15% by volume or less, More preferably, it is 12 volume% or less. When the aromatic content of the hydrorefined oil is within the above range, the properties defined in the light oil composition of the present invention can be achieved more easily and reliably and synergistic with the fatty acid alkyl ester mixture. The action can be achieved. The monocyclic aromatics content here is measured in accordance with JPI-5S-49-97 “Hydrocarbon Type Test Method—High Performance Liquid Chromatograph Method” published by the Japan Petroleum Institute. It means the volume percentage (volume%) of the content of monocyclic aromatics.
[0036]
The 90% distillation temperature (hereinafter also referred to as T90) of the hydrorefined oil according to the present invention is 280 ° C. or higher in order to suppress adverse effects on operating performance and the like associated with excessive lightening of distillation properties. It is necessary to be, preferably 290 ° C. or higher, more preferably 300 ° C. or higher. The T90 needs to be 350 ° C. or less, preferably 340 ° C. or less, more preferably 330 ° C. or less, from the viewpoint of suppressing an increase in particulate matter (PM) discharged from the engine. The 90% distillation temperature here means a value measured by JIS K 2254 “Petroleum product-distillation test method”.
[0037]
The difference between the 80% distillation temperature (hereinafter also referred to as T80) and the 20% distillation temperature (hereinafter also referred to as T20) of the hydrorefined oil according to the present invention is synergistic with the fatty acid alkyl ester mixture. Is required to be 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and further preferably 80 ° C. or higher. Similarly, the difference between T80 and T20 needs to be 150 ° C. or less, preferably 140 ° C. or less, more preferably 130 ° C. or less, and further preferably 120 ° C. or less. Here, the 80% distillation temperature and the 20% distillation temperature mean values measured by JIS K 2254 “Petroleum products-distillation test method”.
[0038]
In the present invention, it is necessary to mix an appropriate amount of a fatty acid alkyl ester mixture containing a specific fatty acid alkyl ester compound with the above-described hydrorefined oil.
As the fatty acid alkyl ester mixture, a glyceride compound (animal oil, vegetable oil) composed of fatty acid and glycerin produced from animal lipid parts and plant seeds as raw materials is generally used under an alkali catalyst (sodium methylate, caustic soda, etc.). And a mixture of fatty acid alkyl ester compounds obtained by separating and removing the remaining raw materials and by-products such as glycerin, catalyst, and the like. In the present invention, fatty acid alkyl ester compounds obtained by other chemical synthesis techniques can also be used.
[0039]
Examples of the raw material of the animal lipid part include beef tallow, milk lipid (butter), pork tallow, sheep fat, whale oil, fish oil, liver oil, and the like. Then, it is desirable to use vegetable oil as a raw material.
Examples of the vegetable oil raw material include coconut palm, palm palm, olive, Benibana, rapeseed (rapeseed flower), rice bran, sunflower, cottonseed, corn, soybean seeds, sesame seeds and other parts.
Moreover, in this invention, the waste oil which used these animal oils and vegetable oils for consumer use, industrial use, food use etc. can also be used as a raw material after adding the removal process of miscellaneous matters.
[0040]
A typical composition of the fatty acid portion of the glyceride compound contained in these raw materials is butyric acid (C) which is a fatty acid having no unsaturated bond in the molecular structure called saturated fatty acid.₃H₇COOH), caproic acid (C₅H₁₁COOH), caprylic acid (C₇H₁₅COOH), capric acid (C₉H₁₉COOH), lauric acid (C₁₁H₂₃COOH), myristic acid (C₁₃H₂₇COOH), palmitic acid (C₁₅H₃₁COOH), stearic acid (C₁₇H₃₅COOH) and oleic acid (C), an unsaturated fatty acid having one or more unsaturated bonds₁₇H₃₃COOH), linoleic acid (C₁₇H₃₁COOH), linolenic acid (C₁₇H₂₉COOH), ricinolenic acid (C₁₇H₃₂(OH) COOH) and the like. Although the hydrocarbon part of these fatty acids in natural substances is generally linear, it is used in the present invention even if it has a structure having side chains, that is, an isomer, as long as the properties defined in the present invention are satisfied. be able to. In addition, the position of the unsaturated bond in the molecule of the unsaturated fatty acid is not limited to those generally confirmed in nature as long as the properties defined in the present invention are satisfied in the present invention. The set one can also be used.
[0041]
The above-mentioned raw material oils (animal oil, vegetable oil) have one or more of these fatty acids, and the fatty acids they have differ depending on the raw material. For example, coconut oil has a relatively large amount of saturated fatty acids such as lauric acid and myristic acid, while soybean oil has a large amount of unsaturated fatty acids such as oleic acid and linoleic acid.
[0042]
In the present invention, the method for producing the fatty acid alkyl ester mixture is not particularly limited. As a typical example, stirring is performed at 70 ° C. for about 1 hour in the presence of an alkali catalyst (sodium methylate, caustic soda, etc.) Fatty acid by hydrolyzing raw material oil in a method of obtaining ester compound by directly reacting with alcohol (transesterification reaction) or high temperature and high pressure process (50-60 atm, 250-260 ° C, reaction for 2-3 hours, no catalyst) And glycerin, and the resulting fatty acid is reacted with an alkyl alcohol in the presence of an acid catalyst (sulfuric acid, PTS) to obtain an ester compound (esterification reaction).
[0043]
As the alkyl alcohol compound, methanol (CH₃OH), ethanol (C₂H₅OH), propanol (C₃H₇OH), butanol (C₄H₉OH), hexanol (C₅H₁₁OH) and the like, and these isomers can also be used, but it is preferable to use methanol and ethanol mainly from the viewpoint of economy and property stabilization upon esterification.
[0044]
Examples of the methyl ester compound obtained by the above production method include butyric acid methyl ester (C₃H₇COOCH₃), Caproic acid methyl ester (C₅H₁₁COOCH₃), Caprylic acid methyl ester (C₇H₁₅COOCH₃), Capric acid methyl ester (C₉H₁₉COOCH₃), Methyl laurate (C₁₁H₂₃COOCH₃), Myristic acid methyl ester (C₁₃H₂₇COOCH₃), Palmitic acid methyl ester (C₁₅H₃₁COOCH₃), Stearic acid methyl ester (C₁₇H₃₅COOCH₃), Oleic acid methyl ester (C₁₇H₃₃COOCH₃), Linoleic acid methyl ester (C₁₇H₃₁COOCH₃), Linolenic acid methyl ester (C_{1 7}H₂₉COOCH₃), Ricinolenic acid methyl ester (C₁₇H₃₂(OH) COOCH₃) And the like, and ethyl ester compounds include butyric acid ethyl ester (C₃H₇COOC₂H₅), Caproic acid ethyl ester (C₅H₁₁COOC₂H₅), Caprylic acid ethyl ester (C₇H₁₅COOC₂H₅), Capric acid ethyl ester (C₉H₁₉COOC₂H₅), Lauric acid ethyl ester (C₁₁H₂₃COOC₂H₅), Myristic acid ethyl ester (C₁₃H₂₇COOC₂H₅), Palmitic acid ethyl ester (C₁₅H₃₁COOC₂H₅), Stearic acid ethyl ester (C₁₇H₃₅COOC₂H₅), Ethyl oleate (C₁₇H₃₃COOC₂H₅), Linoleic acid ethyl ester (C₁₇H₃₁COOC₂H₅), Linolenic acid ethyl ester (C₁₇H₂₉COOC₂H₅), Ricinolenic acid ethyl ester (C₁₇H₃₂(OH) COOC₂H₅) And the like.
[0045]
Quantification of these fatty acid alkyl ester compounds and raw fatty acids can be performed using a gas chromatograph. Analytical conditions are shown below. By using a free fatty acid type column (FFAP), these substances can be easily and accurately quantified.
Column: FFAP (φ0.32mm × 25m)
Carrier gas: He (26 psi)
Detector: FID
Injection temperature: 280 ° C
Detector temperature: 300 ° C
Oven temperature: 100-260 ° C (10 minutes)
Temperature increase rate: 5 ° C / min
Injection volume: 0.4 μL (methanol solution)
[0046]
In the present invention, it is necessary to blend an appropriate amount of a fatty acid alkyl ester mixture having at least two kinds of specific fatty acid alkyl ester compounds and satisfying predetermined properties into the hydrorefined oil. Specifically, among the fatty acid alkyl ester compounds described above, one or more of fatty acid alkyl ester compounds (A) selected from myristic acid alkyl esters, palmitic acid alkyl esters, and stearic acid alkyl esters must be contained. Moreover, it must contain at least one of fatty acid alkyl ester compounds (B) selected from lauric acid alkyl esters, oleic acid alkyl esters, linoleic acid alkyl esters and linolenic acid alkyl esters. At this time, the value (C) obtained by dividing the total mass content of the three fatty acid alkyl ester compounds (A) by the total mass content of the four fatty acid alkyl ester compounds (B) described below, that is, , C = total mass content of fatty acid alkyl ester (A) / total mass content of fatty acid alkyl ester (B) needs to be 0.1 or more. This value is an index that represents the overall characteristics of the fatty acid alkyl ester mixture. If this value is small, the fluidity at low temperatures will deteriorate. Since this gas oil composition is required to have a performance corresponding to JIS standard No. 1 gas oil, this value needs to be 0.1 or more, preferably 0.2 or more. It is more preferably 3 or more, and further preferably 0.4 or more. Further, if this value is excessively large, the exhaust gas performance deteriorates, and in order to have a fluidity improving effect in the category of JIS standard No. 1 light oil, it is necessary to be 2.0 or less, 1.8 Or less, more preferably 1.6 or less, and even more preferably 1.4 or less.
[0047]
The average molecular weight of the fatty acid alkyl ester mixture blended in the light oil composition of the present invention needs to be 500 or less. The average molecular weight means an average molecular weight obtained by multiplying the content ratio of the contained compound and the molecular weight. If this value is excessively large, the fluidity tends to deteriorate at low temperatures, so it is necessary that it is 500 or less, preferably 450 or less, and more preferably 400 or less.
[0048]
Moreover, the total acid value of the fatty acid alkyl ester mixture blended in the light oil composition of the present invention is required to be 1.0 mgKOH / g or less. Since the total acid value indicates the amount of free fatty acid in the mixture, if this value is large, there is a concern that the acidic compound may adversely affect the member. Therefore, the total acid value needs to be 1.0 mgKOH / g or less, desirably 0.9 mgKOH / g or less, and more preferably 0.8 mgKOH / g or less. The total acid value as used herein means the total acid value measured according to JIS K 2501 “Petroleum products and lubricating oils—neutralization number test method”.
[0049]
The sulfur content of the fatty acid alkyl ester mixture blended in the light oil composition of the present invention is required to be 5 mass ppm or less. If the sulfur content is high, the exhaust gas after-treatment device installed in the engine will have a significant adverse effect, and since there is no sulfur content in the esterification reaction, contamination with multiple components is considered. The amount must be 5 ppm by mass or less, preferably 4 ppm by mass or less, more preferably 3 ppm by mass or less, still more preferably 2 ppm by mass or less, and 1 ppm by mass or less. Most preferably. In addition, the sulfur content here means the mass content of the sulfur content based on the total amount of the mixture measured by JIS K2541 “Sulfur content test method”.
[0050]
The light oil composition in the present invention can be obtained by blending an appropriate amount of the hydrorefined oil having the predetermined properties and the fatty acid alkyl ester mixture having the predetermined properties. The blending ratio of both must satisfy the following formula.
RBDF = (− 6 × C × FAME + HDS × (2 × PA + PN)) / 100
0 ≦ RBDF ≦ 10
RBDF: BDF index
C: Sum of mass content of fatty acid alkyl ester (A) / sum of mass content of fatty acid alkyl ester (B)
FAME: Fatty acid alkyl ester mixture content (volume%)
HDS: Hydrorefined oil content (volume%)
PA: Aromatic content of 2 or more rings in hydrorefined oil (volume%)
PN: Content of naphthene in two or more rings in hydrorefined oil (volume%)
[0051]
Here, the RBDF is referred to as a BDF index. The BDF index is a relational expression found by the present inventors through a number of experiments, and displays the following contents.
Although it is well known that aromatic compounds having two or more rings in the fuel (polycyclic aromatic components) adversely affect PM, nitrogen oxides (NOx), etc., they are heavy naphthenic compounds having two or more rings (polyhydric compounds). The present inventors have grasped that the amount of ring naphthene is also an adverse factor. At the same time, when the influence on the low-temperature flow performance was taken into consideration, the degree of influence was the ratio of the polycyclic naphthene content 1 to the polycyclic aromatic content 2.
On the other hand, since the fatty acid alkyl ester mixture is an oxygen-containing compound and has a structure that easily undergoes thermal decomposition, it has the effect of suppressing PM generation and improving combustion, and improving fuel efficiency and output. On the other hand, it has factors that cause deterioration of NOx emissions and low temperature fluidity. The present inventors have grasped that these phenomena are largely caused by the influence of the fatty acid structure of the fatty acid alkyl ester mixture and the content ratio of the specific saturated fatty acid and the specific unsaturated fatty acid. At the same time, the content ratio has a great influence on the low-temperature flow performance. Although lauric acid is a saturated fatty acid, the present inventors have found that these behaviors are similar to those of unsaturated fatty acids. Therefore, lauric acid is treated as an unsaturated fatty acid and is not useful when calculating the content ratio. We decided to rate the sum of saturated fatty acids and lauric acid.
[0052]
As a result of examining the influence of the polycyclic aromatic component and the polycyclic naphthene and the degree of influence of the fatty acid alkyl ester mixture, the present inventors have found that these have a first-order correlation. In view of exhaust gas performance, fuel efficiency performance, low-temperature flow performance, etc., the degree of influence of these three factors is: fatty acid alkyl ester mixture: −6 × (content of specific saturated fatty acid alkyl ester / (unsaturated fatty acid alkyl ester and laurin The total content of acid alkyl esters)), polycyclic aromatic content: 2, polycyclic naphthene content: 1 was found. That is, this relational expression has been found that by performing production at this ratio, it is possible to obtain fuel quality that simultaneously improves exhaust gas performance, fuel efficiency performance, low temperature performance, etc., and PM, NOx and fuel efficiency performance Can be improved at the same time.
[0053]
This means that the fatty acid alkyl ester compound, the polycyclic aromatic compound, and the polycyclic naphthene compound have a large influence on the exhaust gas and fuel consumption, and that the direction works in reverse. That is, the fatty acid alkyl ester compound, which is an oxygen-containing compound, has PM improving ability, but also has NOx deterioration ability and fuel consumption deterioration ability. On the other hand, the polycyclic aromatic compound and the polycyclic naphthene compound have the PM deterioration ability and the slight NOx deterioration ability, but have the fuel efficiency improvement ability.
[0054]
In the light oil composition according to the present invention, the properties and effects defined in the light oil composition of the present invention can be achieved more easily and reliably, and a synergistic action with the fatty acid alkyl ester mixture is achieved. The RBDF represented by the formula needs to be 0 or more, preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and even more preferably 4 or more. Preferably, 5 or more is most preferable. For the same reason, the RBDF represented by the above formula needs to be 10 or less, preferably 9 or less, and more preferably 8 or less.
[0055]
In the present invention, the amount of the fatty acid alkyl ester mixture is not limited as long as the above-mentioned conditions are satisfied, but in order to easily and surely obtain the properties and effects of the present invention, 3% by volume or more Is preferably 5% by volume or more, more preferably 7% by volume or more, and particularly preferably 10% by volume or more. Similarly, the amount of the fatty acid alkyl ester mixture is preferably 50% by volume or less, more preferably 45% by volume or less, and further preferably 40% by volume or less. When the blended amount of the fatty acid alkyl ester mixture is extremely large, a problem arises in the oxidation stability of the fuel and the predetermined effect cannot be exhibited.
[0056]
In the light oil composition of the present invention, the bulk modulus needs to be 1350 MPa or more and 1550 MPa or less.
In general, when a high pressure is applied to a compressible fluid such as light oil, the fluid itself is compressed according to the temperature and pressure at that place, and the density (volume per flow rate) changes. The compression elastic modulus of this object is defined as the bulk elastic modulus (unit: MPa). Assuming diesel fuel injection, the volume modulus of elasticity for the fuel fluid changes at a constant rate according to the physical characteristics and composition of the fuel itself as well as the temperature and pressure of the atmosphere in which the fuel is placed. Therefore, in an injection system having high-pressure and high-precision injection characteristics, such as an electronically controlled fuel injection pump, in order to maintain the fuel injection amount and injection rate as set, the volume elastic modulus shows a stable value. Fuel is needed. The stabilization of this value leads to the reduction of NOx, PM, fine particles and the like. Therefore, in the light oil composition of the present invention, the volume modulus of elasticity needs to be 1350 MPa or more and 1550 MPa or less, and preferably 1370 MPa or more and 1500 MPa or less.
[0057]
Note that the bulk modulus is not governed by a single fuel physical property or composition, but is defined as a result of multiple effects of multiple physical properties and compositions. From the technical point of view, it is reasonable to think of it as a fuel characteristic that should be considered in parallel with the composition.
There is no officially determined method for measuring the bulk modulus at this time, but the outline will be described with reference to FIG. The fuel to be measured is sealed in a constant volume container made of a material and structure that can prove that the volume change of the container itself due to temperature and pressure changes is sufficiently small with respect to the fuel volume change in the same environmental change. . At this time, the container needs to be filled only with the fuel to be measured. A constant volume piston made of a material and a structure capable of demonstrating that the volume change of the piston itself due to changes in temperature and pressure is sufficiently small with respect to the volume change of the fuel in the same environmental change is inserted into this constant volume container, Change the container volume. Since the fuel to be measured is compressed according to its compression elastic characteristic, the pressure in the container changes as a result. By measuring this pressure, the bulk modulus is calculated.
[0058]
In the light oil composition of the present invention, from the viewpoint of storage stability, the total insoluble content after the oxidation stability test needs to be 2.0 mg / 100 mL or less, and is 1.5 mg / 100 mL or less. Is more preferable, 1.0 mg / 100 mL or less is further preferable, and 0.5 mg / 100 mL or less is even more preferable. The oxidation stability test here is conducted under conditions of 95 ° C. and oxygen bubbling for 16 hours in accordance with ASTM D2274-94. The total insoluble matter after the oxidation stability test here means a value measured in accordance with the oxidation stability test.
[0059]
In the light oil composition of the present invention, the peroxide value after the oxidation stability test is preferably 10 ppm by mass or less, more preferably 5 ppm by mass or less, and further preferably from the viewpoint of storage stability and compatibility with members. Is 2 ppm by mass or less, and more preferably 1 ppm by mass or less. Here, the peroxide value means a value measured in accordance with the Petroleum Institute Standard JPI-5S-46-96.
To the light oil composition of the present invention, additives such as an antioxidant and a metal deactivator can be appropriately added in order to reduce the total insoluble matter and the peroxide value.
[0060]
The light oil composition in the present invention must satisfy the JIS No. 1 light oil standard. The JIS No. 1 diesel oil standard is a standard that satisfies “Class No. 1” defined in JIS K 2204 “Diesel Oil”. Specifically, the flash point is 50 ° C. or higher, the 90% distillation temperature is 360 ° C. or lower, and the pour point. −2.5 ° C. or less, clogging point (CFPP) −1 ° C. or less, 10% residual oil residual carbon content of 0.1% by mass or less, cetane index of 50 or more, kinematic viscosity at 30 ° C. 2.7 mm²/ S or more and a sulfur content of 0.05% by mass or less. In addition, the light oil composition in the present invention is preferably used in accordance with the No. 1 light oil usage guideline shown in “Guideline for Using Light Oil” shown in the explanation of JIS K 2204-1996.
[0061]
The flash point of the light oil composition of the present invention must satisfy JIS No. 1 light oil standard of 50 ° C. or higher. When the flash point is less than 50 ° C., it cannot be handled as a light oil composition for safety reasons. For the same reason, the flash point is preferably 54 ° C. or higher, more preferably 58 ° C. or higher. The flash point in the present invention is a value measured by JIS K 2265 “Crude oil and petroleum product flash point test method”.
[0062]
The cetane index of the light oil composition of the present invention needs to satisfy 50 or more which is JIS No. 1 light oil standard. When the cetane index is less than 50, the concentration of PM, aldehydes, or NOx in the exhaust gas tends to increase. For the same reason, the cetane index is more preferably 52 or more. The cetane index referred to in the present invention is defined by “Calculation method of cetane index using 8.4 variable equations” in JIS K 2280 “Petroleum products-fuel oil-octane number and cetane number test method and cetane index calculation method”. It means the calculated value. Here, the cetane index in the JIS standard is generally applied to light oil to which a cetane number improver is not added, but in the present invention, the above-mentioned " Applying “8.4 Calculation Method of Cetane Index Using Variable Equation”, a value calculated by the calculation method is expressed as a cetane index.
[0063]
The cetane number in the light oil composition of the present invention is preferably 52 or more, more preferably 54 or more, and further preferably 55 or more. When the cetane number is less than 52, the concentrations of NOx, PM and aldehydes in the exhaust gas tend to be high. Further, from the viewpoint of reducing black smoke in the exhaust gas, the cetane number is preferably 80 or less, more preferably 75 or less, and further preferably 70 or less. The cetane number referred to here is a cetane number measured in accordance with “7. Cetane number test method” in JIS K 2280 “Petroleum products—Fuel oil—Octane number and cetane number test method and cetane index calculation method”. Means.
[0064]
In the light oil composition of the present invention, if necessary, an appropriate amount of a cetane number improver can be blended to improve the cetane number of the resulting light oil composition.
As the cetane number improver, various compounds known as light oil cetane number improvers can be arbitrarily used, and examples thereof include nitrate esters and organic peroxides. These cetane number improvers may be used alone or in combination of two or more.
[0065]
In the present invention, it is preferable to use a nitrate ester among the cetane number improvers described above. Such nitrate esters include 2-chloroethyl nitrate, 2-ethoxyethyl nitrate, isopropyl nitrate, butyl nitrate, primary amyl nitrate, secondary amyl nitrate, isoamyl nitrate, primary hexyl nitrate, Various nitrates such as secondary hexyl nitrate, n-heptyl nitrate, n-octyl nitrate, 2-ethylhexyl nitrate, cyclohexyl nitrate, and ethylene glycol dinitrate are included. An alkyl nitrate of 6-8 is preferred.
[0066]
The content of the cetane improver is preferably 500 ppm by mass or more based on the total amount of the composition, more preferably 600 ppm by mass or more, further preferably 700 ppm by mass or more, and 800 ppm by mass or more. Even more preferably, it is most preferably 900 ppm by mass or more. When the content of the cetane number improver is less than 500 ppm by mass, a sufficient cetane number improving effect cannot be obtained, and PM, aldehydes, and further NOx in diesel engine exhaust gas tend not to be sufficiently reduced. Further, the upper limit of the content of the cetane number improver is not particularly limited, but is preferably 1400 mass ppm or less, more preferably 1250 mass ppm or less, based on the total amount of the light oil composition, and 1100 mass ppm or less. It is more preferable that it is 1000 mass ppm or less.
[0067]
As the cetane number improver, one synthesized according to a conventional method may be used, or a commercially available product may be used. In addition, what is marketed as a cetane number improver is usually obtained in a state where an active ingredient contributing to cetane number improvement (that is, cetane number improver itself) is diluted with an appropriate solvent. When preparing the light oil composition of this invention using such a commercial item, it is preferable that content of the said active ingredient in a light oil composition becomes in the above-mentioned range.
[0068]
In the light oil composition of the present invention, additives other than the cetane number improver can be blended as necessary, and in particular, a lubricity improver and / or a detergent is preferably blended.
As the lubricity improver, for example, one or more of carboxylic acid-based, ester-based, alcohol-based, and phenol-based lubricity improvers can be arbitrarily used. Among these, carboxylic acid-based and ester-based lubricity improvers are preferable.
Examples of the carboxylic acid-based lubricity improver include linoleic acid, oleic acid, salicylic acid, palmitic acid, myristic acid, hexadecenoic acid and a mixture of two or more of the above carboxylic acids.
Examples of ester-based lubricity improvers include carboxylic acid esters of glycerin. The carboxylic acid constituting the carboxylic acid ester may be one kind or two or more kinds, and specific examples thereof include linoleic acid, oleic acid, salicylic acid, palmitic acid, myristic acid, hexadecenoic acid and the like. There is.
[0069]
The blending amount of the lubricity improver is not particularly limited as long as the HFRR wear scar diameter (WS1.4) is within a preferable range described later, but is preferably 35 ppm by mass or more based on the total amount of the composition, and 50 ppm by mass. More preferably. When the blending amount of the lubricity improver is within the above range, the effectiveness of the blended lubricity improving agent can be effectively extracted. For example, in a diesel engine equipped with a distributed injection pump, An increase in driving torque can be suppressed and pump wear can be reduced. Further, the upper limit of the blending amount is preferably 150 mass ppm or less on the basis of the total amount of the composition, and more preferably 105 mass ppm or less because an effect commensurate with the addition amount cannot be obtained even if it is added more. preferable.
[0070]
Examples of the detergent include imide compounds; alkenyl succinimides such as polybutenyl succinimides synthesized from polybutenyl succinic anhydrides and ethylene polyamines; polyhydric alcohols such as pentaerythritol and polybutyls. Succinic acid esters such as polybutenyl succinic acid ester synthesized from tenyl succinic anhydride; copolymer polymers such as dialkylaminoethyl methacrylate, polyethylene glycol methacrylate, vinyl pyrrolidone and alkyl methacrylate copolymers, carboxylic acids and amines Ashless detergents such as reaction products of alkenyl succinic acid imide and reaction products of carboxylic acid and amine are preferred. These detergents can be used alone or in combination of two or more.
[0071]
Examples of using an alkenyl succinimide include a case where an alkenyl succinimide having a molecular weight of about 1000 to 3000 is used alone, an alkenyl succinimide having a molecular weight of about 700 to 2000, and an alkenyl succinimide having a molecular weight of about 10,000 to 20000. May be used in combination.
The carboxylic acid constituting the reaction product of the carboxylic acid and the amine may be one type or two or more types. Specific examples thereof include fatty acids having 12 to 24 carbon atoms and carbon atoms having 7 to 24 carbon atoms. An aromatic carboxylic acid etc. are mentioned. Examples of the fatty acid having 12 to 24 carbon atoms include linoleic acid, oleic acid, palmitic acid, myristic acid and the like, but are not limited thereto. In addition, examples of the aromatic carboxylic acid having 7 to 24 carbon atoms include benzoic acid and salicylic acid, but are not limited thereto. Moreover, the amine which comprises the reaction product of carboxylic acid and an amine may be 1 type, or may be 2 or more types. The amine used here is typically oleylamine, but is not limited thereto, and various amines can be used.
[0072]
The blending amount of the cleaning agent is not particularly limited, but in order to bring out the effect of blending the cleaning agent, specifically, the effect of suppressing clogging of the fuel injection nozzle, the blending amount of the cleaning agent is 30 mass ppm based on the total amount of the composition. It is preferable to set it as the above, It is more preferable to set it as 60 mass ppm or more, It is further more preferable to set it as 80 mass ppm or more. Even if an amount less than 30 ppm by mass is added, the effect may not appear. On the other hand, if the amount is too large, an effect commensurate with that cannot be expected, and conversely, NOx, PM, aldehydes, etc. in the diesel engine exhaust gas may increase, so the amount of detergent contained is 300 mass. It is preferably not more than ppm, and more preferably not more than 180 mass ppm.
[0073]
As in the case of the above cetane improver, those commercially available as lubricity improvers or detergents are in a state where the active ingredients contributing to lubricity improvement or cleaning are diluted with an appropriate solvent, respectively. It is usually obtained at When such a commercial product is blended in the light oil composition of the present invention, the content of the active ingredient in the light oil composition is preferably within the above range.
[0074]
Further, for the purpose of further improving the performance of the light oil composition in the present invention, other known fuel oil additives (hereinafter referred to as “other additives” for convenience) described later may be added alone or in combination of several kinds. it can. Other additives include, for example, low-temperature fluidity improvers such as ethylene-vinyl acetate copolymer and alkenyl succinic acid amide; antioxidants such as phenols and amines; metal deactivators such as salicylidene derivatives; Anti-icing agents such as polyglycol ethers; corrosion inhibitors such as aliphatic amines and alkenyl succinic acid esters; antistatic agents such as anionic, cationic and amphoteric surfactants; colorants such as azo dyes; Antifoaming agents and the like.
The addition amount of other additives can be arbitrarily determined, but the addition amount of each additive is preferably 0.5% by mass or less, more preferably 0.2% by mass or less, based on the total amount of the light oil composition. is there.
[0075]
Further, the density at 15 ° C. of the light oil composition according to the present invention is 800 kg / m 2 from the viewpoint of securing the calorific value.³Or more, preferably 805 kg / m³More preferably, 810 kg / m³The above is more preferable. In addition, the density is 850 kg / m from the point of reducing NOx and PM emissions.³Or less, preferably 845 kg / m³The following is more preferable, 840 kg / m³The following is more preferable. In addition, the density here means the density measured by JIS K 2249 “Density test method and density / mass / capacity conversion table of crude oil and petroleum products”.
[0076]
The light oil composition of the present invention desirably has a lubricating performance such that the HFRR wear scar diameter (WS1.4) is preferably 410 μm or less, more preferably 380 μm or less. When the HFRR wear scar diameter (WS1.4) exceeds 410 μm, especially in a diesel engine equipped with a distribution type injection pump, it causes an increase in the driving torque of the pump during operation and an increase in wear of each part of the pump. The engine itself may be destroyed as well as the performance deterioration. In addition, in an electronically controlled fuel injection pump capable of high-pressure injection, there is a concern about wear on the sliding surface.
The HFRR wear scar diameter (WS1.4) as used in the present invention is a value measured by the Petroleum Institute Standard JPI-5S-50-98 “Diesel Oil-Lubricity Test Method” issued by the Japan Petroleum Institute. Means.
[0077]
The sulfur content in the light oil composition of the present invention is not particularly limited as long as the hydrorefined oil and the fatty acid alkyl ester mixture satisfy a predetermined value, but in order to enhance the environmental load reduction effect, it is 8 mass ppm or less. Preferably, 5 mass ppm or less is more preferable, 3 mass ppm or less is more preferable, and 1 mass ppm or less is still more preferable. The sulfur content here means the sulfur content based on the total amount of the light oil composition, measured by JIS K 2541 “Sulfur Content Test Method”.
[0078]
The aromatic content in the gas oil composition of the present invention is not particularly limited as long as the hydrorefined oil and the fatty acid alkyl ester mixture satisfy a predetermined value. However, the environmental load reduction effect is enhanced, and NOx and PM are reduced. From the viewpoint, it is preferably 20% by volume or less, more preferably 15% by volume or less, and still more preferably 10% by volume or less. The aromatic content needs to be 3% by volume or more, preferably 5% by volume or more. If the aromatic content is less than 3% by volume, there is a concern about the influence on the material used for the injection pump.
[0079]
The naphthene compound content in the light oil composition of the present invention is not particularly limited as long as the hydrorefined oil and the fatty acid alkyl ester mixture satisfy a predetermined value, but in order to enhance the environmental impact reduction effect, the naphthene compound content The amount is preferably 95% by volume or less, more preferably 90% by volume or less, still more preferably 85% by volume or less, and most preferably 80% by volume or less. In addition, the naphthene compound content needs to be 10% by volume or more from the viewpoint of fuel efficiency and output improvement, preferably 20% by volume or more, and more preferably 30% by volume or more. Also, the naphthene compound content in the present invention is measured according to ASTM D2786 “Standard Test Method for Hydrocarbon Types Analysis of Gas-Oil Saturates Fraction by High Migrate Vs. ).
[0080]
In the present invention, the water content is preferably 300 ppm by volume or less, more preferably 250 ppm by volume or less, from the viewpoint of adverse effects on the member to the fuel tank and the like and suppression of hydrolysis of the ester compound. More preferably, it is 200 ppm by volume or less. In addition, the water | moisture content here is the water prescribed | regulated by JISK2275 "moisture test method (crude oil and petroleum products)."
[0081]
The clogging point (CFPP) of the light oil composition of the present invention must satisfy the JIS No. 1 light oil standard of −1 ° C. or lower. Furthermore, it is preferably −3 ° C. or lower and more preferably −5 ° C. or lower from the viewpoint of preventing the pre-filter blockage of the diesel vehicle. Here, the clogging point refers to a clogging point measured according to JIS K 2288 “Light oil—clogging point test method”.
[0082]
Moreover, the pour point in the light oil composition of this invention needs to satisfy | fill -2.5 degrees C or less which is a JIS1 light oil specification. Furthermore, from the viewpoint of low temperature startability or low temperature drivability, and from the viewpoint of maintaining injection performance in the electronically controlled fuel injection pump, it is preferably −5 ° C. or lower, and more preferably −7.5 ° C. or lower. Here, the pour point means a pour point measured by JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.
[0083]
As the distillation property in the light oil composition of the present invention, it is necessary that the hydrorefined oil and the fatty acid alkyl ester mixture satisfy a predetermined value and satisfy a 90% distillation temperature of 360 ° C. or less which is JIS No. 1 light oil standard. Preferably it is 350 degrees C or less, More preferably, it is 340 degrees C or less, More preferably, it is 330 degrees C or less. When the 90% distillation temperature exceeds the upper limit, the amount of PM and fine particles discharged tends to increase. The 90% distillation temperature is preferably 280 ° C. or higher, more preferably 285 ° C. or higher, further preferably 290 ° C. or higher, even more preferably 295 ° C. or higher, and most preferably 300 ° C. or higher. If the 90% distillation temperature is less than the lower limit, the fuel efficiency improvement effect becomes insufficient and the engine output tends to decrease. Although there is no restriction | limiting in particular in 10% distillation temperature, Preferably it is 250 degrees C or less, More preferably, it is 240 degrees C or less, More preferably, it is 230 degrees C or less, More preferably, it is 220 degrees C or less. If the 10% distillation temperature exceeds the upper limit, the exhaust gas performance tends to deteriorate. The 10% distillation temperature is preferably 160 ° C or higher, more preferably 170 ° C or higher, and further preferably 180 ° C or higher. If the 10% distillation temperature is less than the lower limit, engine output and startability at high temperatures tend to deteriorate. The 10% distillation temperature and 90% distillation temperature here mean values measured by JIS K 2254 “Petroleum product-distillation test method”.
[0084]
The kinematic viscosity at 30 ° C. of the diesel oil composition of the present invention is 2.7 mm, which is a JIS No. 1 diesel oil standard, with the hydrorefined oil and fatty acid alkyl ester mixture satisfying a predetermined value.²/ S or more, 3.0 mm²/ S or more, preferably 3.2 mm²/ S or more is more preferable. The kinematic viscosity is 2.7 mm²If it is less than / s, the fuel injection timing control on the fuel injection pump side tends to be difficult, and the lubricity in each part of the fuel injection pump mounted on the engine may be impaired. The kinematic viscosity at 30 ° C. of the light oil composition of the present invention is 5 mm.²/ S or less, preferably 4.7 mm²/ S or less is more preferable, 4.5 mm²/ S or less is more preferable. The kinematic viscosity is 5mm²If it exceeds / s, the resistance inside the fuel injection system increases, the injection system becomes unstable, and the concentrations of NOx and PM in the exhaust gas increase. In addition, kinematic viscosity here means kinematic viscosity measured by JISK2283 "crude oil and petroleum products-kinematic viscosity test method and viscosity index calculation method".
[0085]
The residual carbon content of 10% residual oil in the light oil composition of the present invention needs to satisfy 0.1% by mass or less, which is JIS No. 1 light oil standard. Furthermore, it is preferably 0.08% by mass or less and more preferably 0.06% by mass or less from the viewpoint of reducing fine particles and PM and maintaining the performance of the exhaust gas aftertreatment device mounted on the engine. preferable. The residual carbon content of 10% residual oil here means the residual carbon content of 10% residual oil measured by JIS K 2270 “Crude oil and petroleum products—residual carbon content test method”.
[0086]
In the light oil composition of the present invention, the ash content is preferably less than 0.01% by mass. If the ash content exceeds the upper limit, the ash becomes the core of PM during the combustion process in the engine, and the total amount of PM and the amount of nanoparticles increase. Further, even when the ash is discharged as it is, the ash is deposited on the exhaust gas post-processing device, and the performance of the post-processing device may be deteriorated. Furthermore, an adverse effect on the fuel injection system can be considered.
The ash content in the present invention means a value measured by JIS K 2272 “Crude oil and petroleum product ash content and sulfate ash test method”.
[0087]
Moreover, although the electrical conductivity in the light oil composition in this invention is not specifically limited, From the point of safety, it is preferable that it is 50 pS / m or more.
In order to improve the electrical conductivity, an antistatic agent or the like can be appropriately added to the light oil composition of the present invention. Here, the conductivity means a value measured in accordance with JIS K 2276 “Petroleum products—aviation fuel oil test method”.
[0088]
【The invention's effect】
As described above, the light oil composition of the present invention is a light oil composition in which an appropriate amount of the hydrorefined oil having the above specific properties and the fatty acid alkyl ester mixture having the above specific properties are mixed to satisfy the predetermined properties. By reducing the particulate matter (PM) and fine particles and nitrogen oxides discharged from the engine, which has been difficult to achieve with conventional light oil compositions, the fuel consumption is improved and the impact on the components is reduced. There are few, and it can have the performance excellent in low temperature startability.
[0089]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, this invention is not limited to these Examples at all.
[0090]
(Examples 1-6 and Comparative Example 1)
Additives were blended with the hydrorefined oil and fatty acid alkyl ester mixture having the properties shown in Table 1 to prepare light oil compositions shown in Table 2 (Examples 1 to 6 and Comparative Example 1).
In addition, the additive used was as follows.
Cetane number improver: 2-ethylhexyl nitrate
Lubricant improver: Carboxylic acid mixture based on linoleic acid
Detergent: Reaction product of oleic amine and carboxylic acid mixture based on oleic acid
Low temperature fluidity improver: ethylene-vinyl acetate copolymer
[0091]
The blending ratio of the blended diesel oil composition, and the blended diesel oil composition, density at 15 ° C., kinematic viscosity at 30 ° C., flash point, sulfur content, distillation properties, cetane number and cetane index, pour point Table 2 shows the results of measurement of clogging point, residual carbon content of 10% residual oil, volume modulus of elasticity, ash content, moisture, total insoluble matter after oxidation stability test, peroxide value, conductivity, and wear scar diameter. Shown in
[0092]
The properties of the fuel oil were measured by the following method.
The density refers to a density measured according to JIS K 2249 “Determination method of density of crude oil and petroleum products and density / mass / capacity conversion table”.
The kinematic viscosity refers to a kinematic viscosity measured according to JIS K 2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.
The sulfur content refers to the mass content of the sulfur content based on the total amount of light oil composition measured by JIS K2541 “Sulfur content test method”.
[0093]
All the distillation properties are values measured by JIS K 2254 "Petroleum products-Distillation test method".
The aromatic content and the aromatic content of two or more rings are determined by the Petroleum Institute Method JPI-5S-49-97 “Hydrocarbon Type Test Method—High Performance Liquid Chromatograph Method” published by the Japan Petroleum Institute. It means the volume percentage (volume%) of the aromatic content that has been observed and complied with.
Naphthenic compound content is measured in accordance with ASTM D2786 “Standard Test Method for Hydrocarbon Types Analysis of Gas-Oil Saturates Fractions by High Ionizing Volt.
Moisture means the moisture specified by JIS K 2275 “Moisture test method (crude oil and petroleum products)”.
The flash point indicates a value measured according to JIS K 2265 “Crude oil and petroleum product flash point test method”.
The total acid value means the total acid value measured according to JIS K 2501 “Petroleum products and lubricating oils—neutralization number test method”.
[0094]
The cetane index refers to a value calculated according to “Method for calculating cetane index using 8.4 variable equation” in JIS K 2280 “Petroleum products—fuel oil—octane number and cetane number test method and cetane index calculation method”. The cetane index in the JIS standard is not applied to the cetane number improver added, but the cetane index of the cetane index added with the cetane number improver also uses the above “8.4 variable equation”. It shall represent the value calculated by “Calculating method of cetane index”.
The cetane number means a cetane number measured according to “7. Cetane number test method” of JIS K 2280 “Petroleum products—fuel oil—octane number and cetane number test method and cetane index calculation method”.
[0095]
Lubrication performance and HFRR wear scar diameter (WS1.4) refer to the lubrication performance measured by the Petroleum Institute Standard JPI-5S-50-98 “Diesel Oil-Lubricity Test Method” issued by the Japan Petroleum Institute. .
The clogging point refers to a clogging point measured by JIS K 2288 “Light oil—clogging point test method”.
The pour point refers to a pour point measured according to JIS K 2269 “Crude point of petroleum and petroleum products and a cloud point test method of petroleum products”.
The residual carbon content of 10% residual oil means the residual carbon content of 10% residual oil as measured by JIS K 2270 “Crude oil and petroleum products—residual carbon content test method”.
Ash content means a value measured by JIS K 2272 “Crude oil and petroleum product ash and sulfate ash test method”.
The total insoluble matter after the oxidation stability test means a value measured under conditions of 95 ° C. and oxygen bubbling for 16 hours in accordance with ASTM D2274-94.
The peroxide value means a value measured according to the Petroleum Institute Standard JPI-5S-46-96.
The conductivity means a value measured in accordance with JIS K 2276 “Petroleum product-aviation fuel oil test method”.
[0096]
[Table 1]

[0097]
[Table 2]

[0098]
As shown in Table 2, the light oil compositions used in the examples and comparative examples are prepared by blending a hydrorefined oil and a fatty acid alkyl ester mixture at a specific blending ratio.
As is apparent from Table 2, 90% distillation temperature (T90), difference between 80% distillation temperature and 20% distillation temperature (T80-T20), sulfur content, 1-ring naphthene content, 1-ring Example 1 in which a mixture of a hydrorefined oil and a fatty acid alkyl ester, each having an aromatic content and an ester coefficient (C) within the range defined by the present invention, was blended within the range defined by the present invention. ~ 6, the light oil composition satisfying the properties of JIS standard No. 1 light oil and having a bulk modulus of 1350 MPa to 1550 MPa and a total insoluble content after an oxidation stability test of 2.0 mg / 100 mL or less is easy. I was able to get it reliably and reliably. On the other hand, in Comparative Example 1 in which a light oil composition was prepared without using the above-mentioned specific hydrorefined oil and fatty acid alkyl ester mixture, the light oil composition targeted by the present invention was not necessarily obtained.
[0099]
Next, various tests shown below were performed using the light oil compositions of Examples 1 to 6 and Comparative Example 1. All test results are shown in Table 3. As can be seen from the results in Table 3, the light oil compositions of Examples 1 to 6 have fewer PMs and fewer particles, less nitrogen oxides, better fuel efficiency, and lower temperature than the light oil composition of Comparative Example 1. It is clear that the startability is good and the rubber swelling performance is excellent.
[0100]
The test method related to the vehicle test conforms to the attachment 27 “Technical standard for diesel vehicle 10/15 mode exhaust gas measurement”.
[0101]
(Vehicle exhaust gas test, fuel consumption test)
PM, nitrogen oxides and fuel consumption were measured using a diesel engine-equipped vehicle (vehicle 1) shown below. PM collected the exhaust gas diluted in the whole dilution tunnel with a fluorocarbon-coated glass fiber filter and analyzed it. The test mode is performed in a transient operation mode that simulates the actual driving shown in FIG. 2, the exhaust gas component is calculated as an emission amount per 1 km of the test mode, and the result when the fuel of Comparative Example 1 is tested is set to 100. The results were relatively compared and quantified. For fuel consumption, the fuel volume flow rate consumed during the test mode is corrected for fuel temperature, and the weight value is replaced with the result when the fuel of Comparative Example 1 is used as 100. Turned into.
[0102]
(Vehicle specifications): Vehicle 1
Engine type: Supercharged inline 4-cylinder diesel with intercooler
Displacement: 3L
Compression ratio: 18.5
Maximum output: 125kW / 3400rpm
Maximum torque: 350Nm / 2400rpm
Compliance with regulations: 1997 emissions regulations compliance
Vehicle weight: 1900kg
Mission: 4AT
Exhaust gas aftertreatment device: oxidation catalyst
[0103]
(Measurement of fine particles)
When measuring the number of particles, a scanning mobility particle size analyzer shown in FIG. 3 was used to separate and detect the number of particles for each particle size. That is, in the apparatus shown in FIG. 3, a charge distribution control unit a, a classifying unit b, and a particle number measuring unit c are provided in order from the upstream side of the flow path through which the diluted exhaust gas sample passes. The fine particles in the diluted exhaust gas are in an equilibrium charge distribution state in the charge distribution control unit a, and are classified (separated) in accordance with the electric mobility of each particle in the classification unit b. And the particle | grain count part c measures the particle | grains isolate | separated for every particle size.
In the test, the vehicle 1 is operated in the test mode shown in FIG. 2 in the same manner as the exhaust gas test, and the particles collected during the test period by the above apparatus are classified into the total number of particles and particles having a diameter of 100 nm or less (nanoparticles) The results when the fuel of Comparative Example 1 was used as a test were set as 100, and the results were relatively compared and quantified.
[0104]
(Low temperature startability)
On the chassis dynamometer that can control the environmental temperature using the vehicle 1, at room temperature, (1) flush the fuel system of the test diesel vehicle with the evaluation fuel, (2) extract the flushing fuel, (3) ▼ Replace the main filter with a new one, and ④Put the specified amount of evaluation fuel (1/2 of the fuel tank capacity of the vehicle under test) into the fuel tank. Thereafter, (5) the ambient temperature is rapidly cooled from room temperature to 5 ° C, (6) held at 5 ° C for 1 hour, and (7) until a predetermined temperature (-3 ° C) is reached at a cooling rate of 1 ° C / h. Slowly cool and hold (8) at a predetermined temperature for 1 hour, and then start the engine. If the engine does not start even after 10 seconds of cranking is repeated twice at 30 second intervals, it is not possible (x), and if the engine is started between two times of cranking is repeated (◯).
[0105]
(Rubber swelling test)
In order to confirm the influence on the rubber member used in the O-ring or the like of the engine part, a soaking test was performed according to the following procedure. Acrylonitrile, one of the compounds composing rubber, has a combined acrylonitrile mass center value of nitrile rubber (medium nitrile rubber) that is 25% or more and 35% or less of the total as a rubber member to be evaluated, and conforms to MIL R6855 Then, the test fuel is heated and held at 100 ° C., and the test rubber member is immersed in it for 70 hours. Evaluation is made by comparing and quantifying the volume change of the test rubber member after 70 hours. Judgment is that the volume change rate absolute value before and after the test is ± 20% or more is rejected (x), the case of ± 10% or more and within ± 20% is borderline (△), and the case is within ± 10% (○).
[0106]
[Table 3]

[Brief description of the drawings]
FIG. 1 is a schematic configuration diagram showing an example of an apparatus used for measuring the bulk modulus of a gas oil composition.
FIG. 2 is a diagram showing a test mode in an exhaust gas test.
FIG. 3 is a schematic view of a scanning mobility particle size analyzer used for measuring the number of particles.
[Explanation of symbols]
1 constant volume container
2 Supply valve
3 Discharge valve
4 Temperature sensor
5 Pressure sensor
6 Piston
100 Light oil composition
a Charge distribution controller
b Classifier
c Particle Count Unit

Claims (3)

Sulfur content is 8 mass ppm or less, 1-ring naphthene content is 10 volume% or more, 1-ring aromatic content is 20 volume% or less, 90% distillation temperature is 280 ° C. or more and 350 ° C. or less, and 80 Fatty acid alkyl ester (A) selected from hydrolyzed refined oil having a difference between% distillation temperature and 20% distillation temperature of 50 ° C. or higher and 150 ° C. or lower selected from myristic acid alkyl ester, palmitic acid alkyl ester and stearic acid alkyl ester Any one or more of fatty acid alkyl ester (B) selected from lauric acid alkyl ester, oleic acid alkyl ester, linoleic acid alkyl ester and linolenic acid alkyl ester, Total mass content of alkyl ester (A) / total mass content of fatty acid alkyl ester (B) A fatty acid alkyl ester mixture having an average molecular weight of 500 or less, a total acid value of 1.0 mgKOH / g or less, and a sulfur content of 5 mass ppm or less. JIS No. 1 diesel oil characterized by having a volume modulus of 1350 MPa or more and 1550 MPa or less, and a total insoluble content after an oxidation stability test of 2.0 mg / 100 mL or less, blended in a volume ratio represented by the following formula: Gas oil composition that meets the standards.
RBDF = (− 6 × C × FAME + HDS × (2 × PA + PN)) / 100
0 ≦ RBDF ≦ 10
RBDF: BDF index C: sum of mass content of fatty acid alkyl ester (A) / sum of mass content of fatty acid alkyl ester (B) FAME: blending amount of fatty acid alkyl ester mixture (volume%)
HDS: Hydrorefined oil content (volume%)
PA: Aromatic content of 2 or more rings in hydrorefined oil (volume%)
PN: Content of naphthene in two or more rings in hydrorefined oil (volume%) The light oil composition according to claim 1, wherein the density at 15 ° C is 800 kg / m ³ or more and 850 kg / m ³ or less, the cetane number is 52 or more, and the HFRR wear scar diameter (WS 1.4) is 410 µm or less. Stuff. The light oil composition according to claim 1 or 2, wherein a mixture of fatty acid alkyl esters using vegetable oil as a raw material is blended, and the water content is 300 ppm by volume or less.

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