JP4103218B2 - Light oil composition - Google Patents
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- JP4103218B2 JP4103218B2 JP35600798A JP35600798A JP4103218B2 JP 4103218 B2 JP4103218 B2 JP 4103218B2 JP 35600798 A JP35600798 A JP 35600798A JP 35600798 A JP35600798 A JP 35600798A JP 4103218 B2 JP4103218 B2 JP 4103218B2
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Description
【0001】
【発明の属する技術分野】
本発明は、ジーゼルエンジンの燃料とする軽油であって気温の高い季節に使用するものにおいて、軽油のもつ潤滑性能を向上させ、それによって燃料ポンプなどの摩耗を軽減した低硫黄軽油組成物に関する。
【0002】
【従来の技術】
環境への硫黄酸化物の放出量を低減するため、軽油の低硫黄化が進められている。しかし、この目的で軽油基材に高度の脱硫処理を施すと、軽油の潤滑性能が低下する。このことは、日本に先行して軽油中の硫黄分の規制(0.05質量%以下)が行なわれるようになった欧米において、ディーゼルエンジンに燃料を供給する分配型燃料噴射ポンプの作動性や耐久性が、低硫黄軽油の使用により低下したことから明らかになった。分配型燃料噴射ポンプは、主に小〜中型のディーゼルエンジン車に搭載されているポンプであり、軽油自身のもつ潤滑性能によりポンプ内部の可動部分の潤滑を行なうものであるから、軽油の潤滑性能の低下はポンプの作動性や耐久性の低下に直結する。
【0003】
軽油の低硫黄化に伴ってその潤滑性能が低下するのは、軽油中の潤滑性能に寄与する微量成分が、軽油を高度に脱硫処理することによって、分解もしくは変質し、または除去されることが原因と考えられている。
【0004】
この問題に対処し、低硫黄軽油の潤滑性能を維持向上させるための努力がなされており、出願人も、低硫黄分原油の常圧蒸留で得た軽油を配合すること(特許第2754462号)、特定のアルキルアミンまたはアルキレンジアミンのカルボン酸塩を潤滑性向上剤として添加すること(特開平8−134476号)、潤滑性向上剤と少量の直留軽油をあわせて添加すること、などの対策を提案している。
【0005】
軽油の潤滑性能の試験には、通常、HFRR試験器[High Frequency Reciprocating Rig]が使用されており、潤滑性能はWSD(Wear Scar Diameter、試験球に生じる摩耗痕径)により評価されている。ところが、既知の潤滑性向上剤の添加によるWSDの改善効果は不安定な場合があり、いきおい多量の潤滑性向上剤を添加しなければならない。これはもちろん、経済的に不利であるから、改善が要望されていた。
【0006】
【発明が解決しようとする課題】
本発明者らは、このような技術の現状を打開することを意図して研究の結果、低硫黄化軽油に特定の潤滑性向上剤を添加する場合、それとともに流動性向上剤を極微量添加することにより、HFRR試験におけるWSDが十分に、かつ安定的に改善されることを見出した。
【0007】
従って本発明の目的は、本発明者らが得たこの新しい知見を活用し、高い潤滑性能を有し、機器の摩耗を軽減する低硫黄軽油組成物を提供することにある。
【0008】
【課題を解決するための手段】
本発明の低硫黄軽油組成物は、硫黄分含有量が0.05質量%以下であって、曇り点と流動点の温度差が10℃以内である軽油に対して、
(A)オレイン酸とリノール酸との1:1(質量基準)混合物のグリセリンエステルであって、モノ置換エステル、ジ置換エステルおよびトリ置換エステルからなる潤滑性向上剤25〜200容量ppmと、
(B)アルケニルコハク酸アミド、エチレン−酢酸ビニル共重合体、エチレン−アルキルアクリレート共重合体、塩素化ポリエチレンおよびポリアルキルアクリレートから選んだ少なくとも1種の流動性向上剤1〜50容量ppmとを、
両者の合計量が30〜250容量ppmとなるように添加してなることを特徴とする。
【0009】
軽油は一般に、使用する温度条件によって、その曇り点と流動点との温度差が10℃以内である「夏場の」軽油と、10℃を超える「冬場の」軽油とに分けられる。冬場の軽油は、低温流動性を確保するために流動性向上剤が比較的多量(100ppm以上)添加されているのが通常である。潤滑性向上剤とともに流動性向上剤を添加した冬場の軽油においては、WSDが十分に改善されている場合が多い。一方、夏場の軽油は低温流動性能を考慮する必要がないために、流動性向上剤は添加しないのが常である。このような夏場の軽油において、潤滑性向上剤とともに極微量の流動性向上剤をあわせ添加することによってWSDが顕著に改善されるという、流動性向上剤が本来もつ効果とは異なる効果を見出したことが、本発明の意義である。
【0010】
【発明の実施の形態】
本発明の軽油組成物の基材とする硫黄分含有量0.05質量%以下の軽油としては、深度脱硫軽油、直接脱硫軽油、間接脱硫軽油、脱硫灯油、直留灯油、直留軽油などが使用できる。ここで、「深度脱硫軽油」、「直接脱硫軽油」および「間接脱硫軽油」とは、それぞれ下記の軽油を意味する。
深度脱硫軽油:原油の常圧蒸留により得られる軽油留分を、水素化脱硫処理により高度に脱硫したもの
直接脱硫軽油:原油の常圧蒸留の残渣を直接水素化脱硫処理する際に、一部が水素化分解されるために得られる軽油留分
間接脱硫軽油:原油の常圧蒸留の残渣を減圧蒸留する際に得られる減圧軽油を、水素化脱硫処理して得られる軽油。
【0011】
本発明で使用する潤滑性向上剤としては、高級脂肪酸、ことに炭素数10〜30、好ましくは12〜22の高級脂肪酸のアルコールとのエステル化合物が、有利に使用できる。高級脂肪酸の例を挙げれば、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘン酸、オレイン酸、エライジン酸、パルミトレイン酸、ペトロセリン酸、リシノレイン酸、エレオステアリン酸、リノール酸、リノレン酸、エイコサン酸、ガロレイン酸、エルカ酸、ヒポガエン酸等の飽和または不飽和カルボン酸が適切であり、アルコールの例は、とりわけ、グリセリンのような多価アルコールである。グリセリンのエステルは、モノ−、ジ−、トリ−エステルなど、部分エステルと、完全エステルとの混合物が好ましい。具体的には、上記したオレイン酸とリノール酸との1:1(質量基準)混合物のグリセリンエステルであって、モノ置換エステル、ジ置換エステルおよびトリ置換エステルからなるものが、潤滑性向上剤として最適である。
【0012】
潤滑性向上剤の添加量は、25〜200ppmの範囲から、好ましくは50〜100ppmの範囲から選ぶ。25ppmより少ない添加量では、HFRR試験におけるWSDの十分な改善が得られない。一方、200ppmより多く添加しても、それ以上の効果は認められず、経済上不利である。
【0013】
本発明で使用する流動性向上剤として適切なものの例を挙げれば、アルケニルコハク酸アミド、エチレン−酢酸ビニル共重合体、エチレン−アルキルアクリレート共重合体などの共重合系ポリマー、塩素化ポリエチレン、ポリアルキルアクリレートなどのポリマーがある。好ましいのは、エチレン−酢酸ビニル共重合体である。流動性向上剤は、1種単独で用いても、2種以上を併用しても差し支えないことは、潤滑性向上剤と同様である。
【0014】
流動性向上剤の添加量は、1〜50ppmの範囲から、好ましくは5〜30ppmの範囲から選ぶ。1ppmに満たない微量では、HFRR試験におけるWSDの十分な改善が得られず、50ppmより多くても、効果はそれ以上には高まらず、不経済になる。
【0015】
潤滑性向上剤と流動性向上剤とは、両者の合計の添加量を、30〜250ppmの範囲から、好ましくは50〜200ppmの範囲から選ぶる。30ppmに達しない添加量では、HFRR試験におけるWSDの十分な改善が得られず、250ppmより多くても、、効果が飽和してしまうから、多量に添加する意味が乏しい。
【0016】
潤滑性向上剤に微量の流動性向上剤をあわせて添加した場合に、潤滑性向上剤によるWSD改善効果が増強される理由については、推測の域を出ないが、流動性向上剤の存在が境界潤滑領域における潤滑性向上剤の膜形成を安定化させているものと、発明者らは考えている。
【0017】
本発明の軽油組成物には、潤滑性向上剤および流動性向上剤以外の各種添加剤、たとえば上記した以外の潤滑性向上剤、防腐剤、防錆剤、消泡剤、清浄剤、酸化防止剤、色相安定剤、セタン価向上剤などを添加してもよい。
【0018】
【実施例】
以下に、本発明を実施例、比較例および参考例により具体的に説明する。ただし本発明は、これらの例によってら制限されるものではない。「ppm」は容量基準である。
【0019】
潤滑性向上剤としては、長鎖脂肪酸のエステルを使用した。その組成は、オレイン酸とリノール酸との1:1(質量基準)混合物のグリセリンエステルであって、モノ置換エステル:50質量%、ジ置換エステル:45質量%、トリ置換エステル:5質量%である。
【0020】
流動性向上剤としては、実施例1〜3および比較例3ではエチレン−酢酸ビニル共重合体を、実施例4および5ではアルケニルコハク酸アミドを使用した。
【0021】
表1に示す組成と特性値をもつ軽油組成物を製造し、それらについて、潤滑性能を評価した。試験は、HFRR試験器(PCS Instruments社製)を用い、JPI−5S−50−97に準拠した軽油−潤滑性試験を実施し、摩耗痕径(WSD)を測定することにより行なった。試験温度は60℃。WSDの値は、小さいほど軽油の潤滑性能が高いことを示す。表1の曇り点および流動点は、JIS K−2269に定める方法に準拠して測定した。
表 1
参考例は、潤滑性向上剤も流動性向上剤も添加してない、低硫黄軽油そのものの特性を示す。比較例1および2はこれに潤滑性向上剤だけを添加したものであるが、それによるWSD値の改善幅はあまり大きくない。比較例3は流動性向上剤を配合しただけであり、WSD値の改善は認められない。これらに対し、実施例1〜5に示すように潤滑性向上剤を添加し、あわせて流動性向上剤を極微量添加した軽油組成物は、優れた潤滑性能を示し、摩耗を軽減する能力があることがわかる。
【0022】
【発明の効果】
本発明の低硫黄軽油組成物は、低硫黄軽油に対し潤滑性向上剤とともに極微量の流動性向上剤を添加することにより、HFRR試験における摩耗痕径(WSD)で評価される潤滑性能を十分に、かつ安定的に改善し、軽油を取り扱う機器の摩耗を軽減することができる。従って、ポンプなどの作動性を損なうことなく、硫黄酸化物の排出量を減らすことに寄与することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a low-sulfur diesel oil composition that improves the lubrication performance of diesel oil and thereby reduces the wear of fuel pumps, etc., in diesel oil used as a fuel for diesel engines and used in high-temperature seasons.
[0002]
[Prior art]
In order to reduce the amount of sulfur oxides released to the environment, low-sulfur gas oil is being promoted. However, if the light oil base material is subjected to a high degree of desulfurization treatment for this purpose, the lubricating performance of the light oil decreases. This is because in Europe and the United States, where sulfur regulation in diesel oil (0.05% by mass or less) has been implemented prior to Japan, the operability of the distributed fuel injection pump that supplies fuel to diesel engines It became clear from the fact that the durability decreased due to the use of low sulfur gas oil. The distribution type fuel injection pump is a pump that is mainly mounted on small to medium-sized diesel engine cars, and lubricates the moving parts inside the pump by the lubrication performance of diesel oil itself. A decrease in the pressure directly leads to a decrease in pump operability and durability.
[0003]
The lubrication performance of diesel oil decreases with the reduction of sulfur, because the trace components that contribute to the lubrication performance of diesel oil are decomposed, altered, or removed by highly desulfurizing diesel oil. It is thought to be the cause.
[0004]
Efforts have been made to address this problem and maintain and improve the lubrication performance of low-sulfur diesel oil, and the applicant should also blend diesel oil obtained by atmospheric distillation of low-sulfur crude oil (Patent No. 2754462). Addition of a specific alkylamine or alkylenediamine carboxylate as a lubricity improver (Japanese Patent Laid-Open No. 8-134476), addition of a lubricity improver and a small amount of straight-run gas oil Has proposed.
[0005]
A HFRR tester [High Frequency Reciprocating Rig] is usually used for testing the lubrication performance of light oil, and the lubrication performance is evaluated by WSD (Wear Scar Diameter, wear scar diameter generated on a test ball). However, the improvement effect of WSD due to the addition of a known lubricity improver may be unstable, and a large amount of lubricity improver must be added. Of course, this is economically disadvantageous, so improvement has been demanded.
[0006]
[Problems to be solved by the invention]
As a result of research aimed at overcoming the current state of such technology, the present inventors have added a very small amount of fluidity improver together with a specific lubricity improver added to low-sulfurized diesel oil. By doing this, it was found that WSD in the HFRR test was sufficiently and stably improved.
[0007]
Accordingly, an object of the present invention is to utilize this new knowledge obtained by the present inventors, and to provide a low-sulfur gas oil composition having high lubricating performance and reducing equipment wear.
[0008]
[Means for Solving the Problems]
The low sulfur gas oil composition of the present invention has a sulfur content of 0.05% by mass or less, and a gas oil whose temperature difference between the cloud point and the pour point is within 10 ° C.,
(A) A glycerin ester of a 1: 1 (mass basis) mixture of oleic acid and linoleic acid, 25 to 200 ppm by volume of a lubricity improver comprising a mono-substituted ester, a di-substituted ester and a tri-substituted ester ,
(B) 1 to 50 ppm by volume of at least one fluidity improver selected from alkenyl succinic acid amide, ethylene-vinyl acetate copolymer, ethylene-alkyl acrylate copolymer, chlorinated polyethylene and polyalkyl acrylate ,
It is characterized by being added so that the total amount of both is 30 to 250 ppm by volume.
[0009]
Light oil is generally divided into “summer” light oil whose temperature difference between the cloud point and pour point is within 10 ° C. and “winter” light oil exceeding 10 ° C., depending on the temperature conditions used. In winter light oil, a relatively large amount (100 ppm or more) of a fluidity improver is usually added to ensure low temperature fluidity. In winter light oil to which a fluidity improver is added together with a lubricity improver, WSD is often sufficiently improved. On the other hand, since it is not necessary to consider low-temperature fluidity in summer light oil, it is usual not to add a fluidity improver. In such summer light oil, we found an effect different from the original effect of the fluidity improver that WSD is remarkably improved by adding a trace amount of fluidity improver together with the lubricity improver. That is the significance of the present invention.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the light oil having a sulfur content of 0.05% by mass or less as the base material of the light oil composition of the present invention include deep desulfurized light oil, direct desulfurized light oil, indirect desulfurized light oil, desulfurized kerosene, straight-run kerosene, straight-run light oil, and the like. Can be used. Here, “deep desulfurized light oil”, “direct desulfurized light oil” and “indirect desulfurized light oil” mean the following light oils, respectively.
Deep desulfurization gas oil: A gas oil fraction obtained by atmospheric distillation of crude oil is highly desulfurized by hydrodesulfurization process. Direct desulfurization gas oil: Part of direct hydrodesulfurization treatment of crude oil atmospheric distillation residue Gas oil fraction indirect desulfurization gas oil obtained by hydrocracking of oil: A gas oil obtained by hydrodesulfurization treatment of vacuum gas oil obtained when the residue of crude oil at atmospheric distillation is distilled under reduced pressure.
[0011]
The lubricity improver used in the present invention, higher fatty acids, in particular 10 to 30 carbon atoms, preferably an ester compound of an alcohol of the higher fatty acid of 12 to 22 can be advantageously used. Examples of higher fatty acids include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, elaidic acid, palmitoleic acid, petroceric acid, ricinoleic acid, eleostearic acid, linoleic acid, linolenic acid Saturated or unsaturated carboxylic acids such as acids, eicosanoic acid, galloic acid, erucic acid, hypogaenoic acid are suitable , and examples of alcohols are, among others, polyhydric alcohols such as glycerin . The ester of glycerin is preferably a mixture of a partial ester such as mono-, di-, and tri-ester and a complete ester. Specifically, a glycerin ester of a 1: 1 (mass basis) mixture of oleic acid and linoleic acid, which is composed of a mono-substituted ester, a di-substituted ester, and a tri-substituted ester, serves as a lubricity improver. Is optimal.
[0012]
The addition amount of the lubricity improver is selected from the range of 25 to 200 ppm, preferably from 50 to 100 ppm. If the addition amount is less than 25 ppm, sufficient improvement of WSD in the HFRR test cannot be obtained. On the other hand, adding more than 200 ppm is not economical because no further effect is observed.
[0013]
Examples of suitable flow improvers for use in the present invention include copolymer polymers such as alkenyl succinic acid amide, ethylene-vinyl acetate copolymer, ethylene-alkyl acrylate copolymer, chlorinated polyethylene, poly There are polymers such as alkyl acrylates. Preference is given to ethylene-vinyl acetate copolymers. As with the lubricity improver, the fluidity improver may be used alone or in combination of two or more.
[0014]
The addition amount of the fluidity improver is selected from the range of 1 to 50 ppm, preferably from the range of 5 to 30 ppm. If the amount is less than 1 ppm, sufficient improvement of WSD in the HFRR test cannot be obtained, and if it is more than 50 ppm, the effect does not increase any more and becomes uneconomical.
[0015]
The total addition amount of the lubricity improver and the fluidity improver is selected from the range of 30 to 250 ppm, preferably from the range of 50 to 200 ppm. If the addition amount does not reach 30 ppm, sufficient improvement of WSD in the HFRR test cannot be obtained, and if it exceeds 250 ppm, the effect is saturated, so that it is not meaningful to add a large amount.
[0016]
The reason why the WSD improvement effect by the lubricity improver is enhanced when a small amount of the fluidity improver is added to the lubricity improver is not speculated, but the existence of the fluidity improver The inventors consider that the film formation of the lubricity improver in the boundary lubrication region is stabilized.
[0017]
In the light oil composition of the present invention, various additives other than the lubricity improver and the fluidity improver, for example, lubricity improvers other than those described above, preservatives, rust preventives, antifoaming agents, detergents, antioxidants An agent, a hue stabilizer, a cetane number improver and the like may be added.
[0018]
【Example】
Hereinafter, the present invention will be specifically described with reference to Examples, Comparative Examples, and Reference Examples. However, the present invention is not limited by these examples. “Ppm” is based on volume.
[0019]
As the lubricity improver, an ester of a long chain fatty acid was used. The composition is a glycerin ester of a 1: 1 (mass basis) mixture of oleic acid and linoleic acid, mono-substituted ester: 50% by mass, di-substituted ester: 45% by mass, tri-substituted ester: 5% by mass is there.
[0020]
As a fluidity improver, ethylene-vinyl acetate copolymer was used in Examples 1 to 3 and Comparative Example 3, and alkenyl succinic acid amide was used in Examples 4 and 5.
[0021]
Light oil compositions having the compositions and characteristic values shown in Table 1 were produced, and the lubricating performance was evaluated for them. The test was performed by performing a light oil-lubricity test based on JPI-5S-50-97 using an HFRR tester (manufactured by PCS Instruments) and measuring the wear scar diameter (WSD). The test temperature is 60 ° C. The smaller the value of WSD, the higher the lubricating performance of light oil. The cloud point and pour point in Table 1 were measured according to the method defined in JIS K-2269.
Table 1
The reference example shows the characteristics of the low sulfur gas oil itself, to which neither a lubricity improver nor a fluidity improver is added. In Comparative Examples 1 and 2, only the lubricity improver is added to this, but the improvement in the WSD value is not so large. In Comparative Example 3, only a fluidity improver was blended, and no improvement in the WSD value was observed. On the other hand, as shown in Examples 1 to 5, a light oil composition to which a lubricity improver is added and a flow improver is added in a very small amount exhibits excellent lubrication performance and the ability to reduce wear. I know that there is.
[0022]
【The invention's effect】
The low sulfur gas oil composition of the present invention has sufficient lubrication performance evaluated by the wear scar diameter (WSD) in the HFRR test by adding a very small amount of fluidity improver together with the lubricity improver to the low sulfur gas oil. In addition, it can improve stably and reduce wear of equipment handling light oil. Therefore, it can contribute to reducing the discharge amount of sulfur oxide without impairing the operability of the pump or the like.
Claims (2)
(A)オレイン酸とリノール酸との1:1(質量基準)混合物のグリセリンエステルであって、モノ置換エステル、ジ置換エステルおよびトリ置換エステルからなる潤滑性向上剤25〜200容量ppmと、
(B)アルケニルコハク酸アミド、エチレン−酢酸ビニル共重合体、エチレン−アルキルアクリレート共重合体、塩素化ポリエチレンおよびポリアルキルアクリレートから選んだ少なくとも1種の流動性向上剤1〜50容量ppmとを、
両者の合計量が30〜250容量ppmとなるように添加してなることを特徴とする低硫黄軽油組成物。For light oil having a sulfur content of 0.05% by mass or less and a temperature difference between the cloud point and the pour point within 10 ° C.,
(A) A glycerin ester of a 1: 1 (mass basis) mixture of oleic acid and linoleic acid, 25 to 200 ppm by volume of a lubricity improver comprising a mono-substituted ester, a di-substituted ester and a tri-substituted ester ,
(B) 1 to 50 ppm by volume of at least one fluidity improver selected from alkenyl succinic acid amide, ethylene-vinyl acetate copolymer, ethylene-alkyl acrylate copolymer, chlorinated polyethylene and polyalkyl acrylate ,
A low sulfur gas oil composition, which is added so that the total amount of both is 30 to 250 ppm by volume.
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JP35600798A JP4103218B2 (en) | 1998-12-15 | 1998-12-15 | Light oil composition |
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JP35600798A JP4103218B2 (en) | 1998-12-15 | 1998-12-15 | Light oil composition |
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JP4103218B2 true JP4103218B2 (en) | 2008-06-18 |
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Families Citing this family (5)
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DE10155774B4 (en) * | 2001-11-14 | 2020-07-02 | Clariant Produkte (Deutschland) Gmbh | Additives for low sulfur mineral oil distillates, comprising an ester of alkoxylated glycerin and a polar nitrogen-containing paraffin dispersant |
DE10155747B4 (en) * | 2001-11-14 | 2008-09-11 | Clariant Produkte (Deutschland) Gmbh | Low sulfur mineral oil distillate additives comprising an ester of an alkoxylated polyol and an alkylphenol-aldehyde resin |
CA2431749C (en) * | 2002-07-09 | 2010-12-14 | Clariant Gmbh | Oxidation-stabilized lubricant additives for highly desulfurized fuel oils |
JP4754773B2 (en) * | 2002-07-09 | 2011-08-24 | クラリアント・プロドゥクテ・(ドイチュラント)・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | Oily liquids stabilized against oxidation based on vegetable or animal oils |
JP6544712B2 (en) * | 2015-06-16 | 2019-07-17 | 日油株式会社 | Fuel oil lubricity improver and fuel oil composition |
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