JP5191146B2 - Fuel oil composition - Google Patents
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- JP5191146B2 JP5191146B2 JP2007060106A JP2007060106A JP5191146B2 JP 5191146 B2 JP5191146 B2 JP 5191146B2 JP 2007060106 A JP2007060106 A JP 2007060106A JP 2007060106 A JP2007060106 A JP 2007060106A JP 5191146 B2 JP5191146 B2 JP 5191146B2
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- 239000000295 fuel oil Substances 0.000 title claims description 52
- 239000000203 mixture Substances 0.000 title claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
- 150000001448 anilines Chemical class 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 15
- 150000001336 alkenes Chemical class 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000003350 kerosene Substances 0.000 description 14
- 239000000446 fuel Substances 0.000 description 13
- 230000006866 deterioration Effects 0.000 description 11
- 239000010779 crude oil Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- -1 alkyl anilines Chemical class 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000003009 desulfurizing effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- KWVPRPSXBZNOHS-UHFFFAOYSA-N 2,4,6-Trimethylaniline Chemical compound CC1=CC(C)=C(N)C(C)=C1 KWVPRPSXBZNOHS-UHFFFAOYSA-N 0.000 description 2
- CZZZABOKJQXEBO-UHFFFAOYSA-N 2,4-dimethylaniline Chemical compound CC1=CC=C(N)C(C)=C1 CZZZABOKJQXEBO-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- VVAKEQGKZNKUSU-UHFFFAOYSA-N 2,3-dimethylaniline Chemical compound CC1=CC=CC(N)=C1C VVAKEQGKZNKUSU-UHFFFAOYSA-N 0.000 description 1
- AOPBDRUWRLBSDB-UHFFFAOYSA-N 2-bromoaniline Chemical compound NC1=CC=CC=C1Br AOPBDRUWRLBSDB-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- OAPDPORYXWQVJE-UHFFFAOYSA-N 4-propylaniline Chemical compound CCCC1=CC=C(N)C=C1 OAPDPORYXWQVJE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical class C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000005608 naphthenic acid group Chemical class 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
本発明は、燃料油組成物に関し、更に詳しくは、色相及び熱安定性に優れた航空機用燃料油組成物に関する。 The present invention relates to a fuel oil composition, and more particularly to an aircraft fuel oil composition excellent in hue and thermal stability.
燃料油の中でも、航空機用燃料、特に航空タ−ビン用燃料は、航空機の翼中に貯蔵され、エンジンへの供給に際してエンジンからの排熱と熱交換することにより効率を上げると共に、エンジンの冷却も担っている。従って、航空機用燃料は、高温度に長時間さらされることになり、その結果、変色及び分解が生じて可溶性の着色物質や、ガム分、粒状物質のような不溶性物質を生成する場合があるため、航空機用燃料において熱安定性は重要な要求項目である。また、航空機用燃料において、着色物質の生成による色相の悪化は、外観上好ましくないことに加え、将来分解が起こる可能性があることを示唆する現象であり、この色相の悪化を抑制することは熱安定性を改善する意味においても重要である Among fuel oils, aviation fuel, particularly aviation turbine fuel, is stored in the wings of an aircraft and increases efficiency by exchanging heat with exhaust heat from the engine when it is supplied to the engine. Also bears. Therefore, aviation fuel is exposed to high temperatures for a long time, and as a result, discoloration and decomposition may occur, producing soluble colored substances, insoluble substances such as gums and granular substances. Thermal stability is an important requirement for aviation fuels. In aircraft fuels, hue deterioration due to the formation of colored substances is a phenomenon that suggests that there is a possibility that decomposition may occur in the future in addition to undesirable appearance. Also important to improve thermal stability
従来から、航空機用燃料の色相悪化の原因物質としては、フェノ−ル、ナフテン酸塩、硫黄化合物等が知られており、その他、ピロ−ル類、インド−ル類などＮ−Ｈ含有複素環式芳香族化合物が熱安定性に悪影響を及ぼすので、それらを低減することも知られている（特許文献１参照）。
また、航空機用燃料の熱安定性を向上させるための方法として、ヒドロキシルアミンなどを添加することにより高温での分解に対し安定化させることが知られている（特許文献２参照）。
更にまた、航空機用燃料には、２,６−ｄｉｔｅｒｔｉａｒｙ−ｂｕｔｙｌ−ｐｈｅｎｏｌや２,６−ｄｉｔｅｒｔｉａｒｙ−ｂｕｔｙｌ−４−ｍｅｔｙｌ−ｐｈｅｎｏｌなどのフェノ−ル系の酸化防止剤が一般に添加されることになっている（非特許文献１参照）。
As a method for improving the thermal stability of aircraft fuel, it is known to stabilize against decomposition at high temperatures by adding hydroxylamine or the like (see Patent Document 2).
Furthermore, phenolic antioxidants such as 2,6-diaryary-butyl-phenol and 2,6-ditert-butyl-4-methyl-phenol are generally added to aviation fuels. (See Non-Patent Document 1).
しかしながら、上記のような色相悪化や熱安定性に悪影響を及ぼす原因物質の低減を図ったり、上記のような熱安定性向上剤や酸化防止剤を添加した場合においても、従来の航空機用燃料においては、輸送や燃料タンク貯蔵中にしばしば変色が生じるなど課題が残されている。
本発明の目的は、貯蔵中の色相悪化を抑制した色相及び熱安定性に優れた燃料油組成物を提供することである。
However, even when reducing the causative substances that adversely affect the hue deterioration and thermal stability as described above, or when adding the above thermal stability improver or antioxidant, However, problems remain, such as frequent discoloration during transportation and storage of fuel tanks.
The objective of this invention is providing the fuel oil composition excellent in the hue and thermal stability which suppressed the hue deterioration during storage.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、燃料油組成物に含有される原油由来の窒素分、特にアニリン類が燃料油組成物の色相に大きな影響を与えることを見出し、この含有量を特定値以下に制御することにより、色相の劣化が少なく熱安定性にも優れる燃料油組成物が得られ、上記目的が達成できることを見出して、本発明を完成した。
すなわち、本発明は、次の色相及び熱安定性に優れる燃料油組成物を提供するものである。
（１）アニリン類の含有量が０．５質量ｐｐｍ以下であり、窒素分の含有量が２質量ｐｐｍ以下であり、硫黄分の含有量が０．３質量％以下であり、引火点が４０〜６０℃、セ−ボルト色が＋１５以上、芳香族分の含有量が２５容量％以下、オレフィン分の含有量が５容量％以下であることを特徴とする航空タービン用燃料油組成物。
（２）前記アニリン類が、アルキル基の総炭素数が１〜３であるアルキルアニリンであることを特徴とする上記（１）に記載の航空タービン用燃料油組成物。
As a result of intensive studies to achieve the above object, the present inventors have found that crude oil-derived nitrogen contained in the fuel oil composition, particularly anilines, has a great influence on the hue of the fuel oil composition. The present inventors have found that a fuel oil composition having excellent hue and little thermal degradation can be obtained by controlling the content below a specific value, and the present invention has been completed.
That is, this invention provides the fuel oil composition excellent in the following hue and thermal stability.
(1) An aniline content is 0.5 mass ppm or less, a nitrogen content is 2 mass ppm or less, a sulfur content is 0.3 mass% or less, and a flash point is 40. A fuel oil composition for aviation turbines, characterized in that it has a temperature of -60 ° C, a Sevolt color of +15 or more, an aromatic content of 25 vol% or less, and an olefin content of 5 vol% or less.
(2) The fuel oil composition for an aviation turbine according to (1), wherein the aniline is an alkylaniline having a total carbon number of 1 to 3 in an alkyl group .
本発明によれば、色相の劣化を抑制し、色相の安定性及び熱安定性に優れた燃料油組成物を提供することができ、特に航空機用燃料油組成物として有用である。 ADVANTAGE OF THE INVENTION According to this invention, the deterioration of a hue can be suppressed and the fuel oil composition excellent in the stability of a hue and thermal stability can be provided, and it is especially useful as a fuel oil composition for aircrafts.
以下、本発明の内容を更に詳しく説明する。
本発明の燃料油組成物において、アニリン類の含有量は０.５質量ｐｐｍ以下であり、好ましくは０.３質量ｐｐｍ以下である。アニリン類とは、アニリン、およびアニリン中のベンゼン環の水素原子をアルキル基もしくはハロゲンで置換した化合物、すなわちアルキルアニリンもしくはハロゲン化アニリンを指す。これらのアニリン類は、光や熱などで変色し、着色する性質があり、燃料油に対して色相の劣化を生じさせることがある。そこで、アニリン類の含有量が０.５質量ｐｐｍ以下ならば、燃料油への着色の影響が少ないため、長期タンクに貯蔵していても色相劣化が顕著になることがなく、色相の安定性が図れる。なお、本発明の燃料油組成物におけるアニリン類の含有量は、少ないほど好ましく、０質量ｐｐｍが最も好ましい。
Hereinafter, the contents of the present invention will be described in more detail.
In the fuel oil composition of the present invention, the content of anilines is 0.5 mass ppm or less, preferably 0.3 mass ppm or less. The anilines refer to aniline and compounds in which the hydrogen atom of the benzene ring in aniline is substituted with an alkyl group or halogen, that is, alkylaniline or halogenated aniline. These anilines have the property of being discolored and colored by light, heat, or the like, and may cause deterioration of the hue of fuel oil. Therefore, if the content of aniline is 0.5 mass ppm or less, the influence of coloring on the fuel oil is small, so that hue deterioration does not become noticeable even when stored in a long-term tank, and the stability of the hue. Can be planned. The content of anilines in the fuel oil composition of the present invention is preferably as small as possible, and most preferably 0 mass ppm.
アニリン類の具体例としては、Ｎ−メチルアニリン、Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ，Ｎ−トリメチルアニリン、Ｎ−エチルアニリン、ｐ−プロピルアニリン等のアルキル基を側鎖に持つアルキルアニリン、およびｏ−クロロアニリン、ｏ−ブロモアニリン等のハロゲン化アニリンなどが挙げられる。アニリン類の中でも、アルキルアニリンは燃料油基材中に含有されるケ−スが多いため、本発明の燃料油組成物では、これらのアルキルアニリンの低減が特に重要となる。なお、アルキルアニリン中のアルキル基の総炭素数は１〜３であることが好ましい。またベンゼン環におけるアルキル基の置換位置や数は特に制限されるものではない。アルキル基の総炭素数が１である場合とは、１つのメチル基が置換している状態を意味し、総炭素数が２もしくは３である場合とは、１つのエチル基もしくはプロピル基が置換している状態、または２〜３個のメチル基が置換している状態を意味する。アルキルアニリンの具体例としては、２−メチルアニリン、３−メチルアニリン、２，３−ジメチルアニリン、２，４−ジメチルアニリン、２，４，６−トリメチルアニリン等が挙げられる。
上記アニリン類の含有量は、ＧＣ−ＮＣＤ（ガスクロマトグラフ／化学発光窒素検出器）分析やＧＣ−ＭＳ（ガスクロマトグラフ／質量分析計）分析によって定量することができる。
Specific examples of anilines include alkyl anilines having an alkyl group in the side chain such as N-methylaniline, N, N-dimethylaniline, N, N, N-trimethylaniline, N-ethylaniline, p-propylaniline, And halogenated anilines such as o-chloroaniline and o-bromoaniline. Among anilines, alkyl anilines are often contained in the fuel oil base material, and therefore reduction of these alkyl anilines is particularly important in the fuel oil composition of the present invention. In addition, it is preferable that the total carbon number of the alkyl group in alkylaniline is 1-3. The substitution position and number of alkyl groups in the benzene ring are not particularly limited. When the total carbon number of the alkyl group is 1, it means that one methyl group is substituted, and when the total carbon number is 2 or 3, one ethyl group or propyl group is substituted. Or a state in which 2 to 3 methyl groups are substituted. Specific examples of the alkylaniline include 2-methylaniline, 3-methylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,4,6-trimethylaniline and the like.
The content of the anilines can be quantified by GC-NCD (gas chromatograph / chemiluminescence nitrogen detector) analysis or GC-MS (gas chromatograph / mass spectrometer) analysis.
本発明の燃料油組成物において、窒素分は、２質量ｐｐｍ以下であり、好ましくは１質量ｐｐｍ以下である。窒素分が２質量ｐｐｍ以下であれば、色相の安定性が図れて、また、熱による安定性悪化を低減できる。また、窒素分の含有量は、少ないほど好ましく、０質量ｐｐｍが最も好ましい。
なお、窒素分は、ＪＩＳ Ｋ ２６０９「原油及び石油製品−窒素分試験方法」によって定量できる。
In the fuel oil composition of the present invention, the nitrogen content is 2 mass ppm or less, preferably 1 mass ppm or less. If the nitrogen content is 2 ppm by mass or less, the hue stability can be achieved, and the deterioration of stability due to heat can be reduced. The nitrogen content is preferably as small as possible, and most preferably 0 mass ppm.
The nitrogen content can be quantified according to JIS K 2609 “Crude oil and petroleum products—nitrogen content test method”.
本発明の燃料油組成物において、硫黄分は０.３質量％以下であり、好ましくは０.１質量％以下である。硫黄分が０.３質量％以下であれば、燃焼時に亜硫酸ガスが発生しにくくなり、燃焼系統の腐食を低減できるため好ましい。
なお、硫黄分は、ＪＩＳ Ｋ ２５４１「原油及び石油製品−硫黄分試験方法」によって定量できる。
In the fuel oil composition of the present invention, the sulfur content is 0.3% by mass or less, preferably 0.1% by mass or less. A sulfur content of 0.3% by mass or less is preferable because sulfurous acid gas is less likely to be generated during combustion and corrosion of the combustion system can be reduced.
The sulfur content can be quantified according to JIS K 2541 “Crude oil and petroleum products—sulfur content test method”.
本発明の燃料油組成物において、引火点は４０℃以上であり、好ましくは４０℃以上６０℃以下、更に好ましくは４２℃以上６０℃以下である。引火点が４０℃以上ならば、常温で可燃性蒸気が発生することがなく、静電気などで着火する危険性が低減できるため好ましい。
なお、引火点は、ＪＩＳ Ｋ ２２６５「原油及び石油製品−引火点試験方法」によって測定できる。
In the fuel oil composition of the present invention, the flash point is 40 ° C. or higher, preferably 40 ° C. or higher and 60 ° C. or lower, more preferably 42 ° C. or higher and 60 ° C. or lower. A flash point of 40 ° C. or higher is preferable because flammable vapor is not generated at room temperature and the risk of ignition due to static electricity can be reduced.
The flash point can be measured by JIS K 2265 “Crude oil and petroleum products—flash point test method”.
本発明の燃料油組成物において、セ−ボルト色は+１５以上であり、好ましくは+１５以上+３０以下、更に好ましくは+２０以上+３０以下である。セ−ボルト色が+１５以上ならば、品質上の面、外観、貯蔵劣化によるスラッジ生成などの問題が発生しにくく好ましい。
なお、セ−ボルト色は、ＪＩＳ Ｋ ２５８０「石油製品−色試験方法」によって測定できる。
In the fuel oil composition of the present invention, the Sebolt color is +15 or more, preferably +15 or more and +30 or less, more preferably +20 or more and +30 or less. If the bolt color is +15 or more, problems such as quality, appearance, and sludge generation due to storage deterioration are less likely to occur.
The Sebolt color can be measured according to JIS K 2580 “Petroleum products—color test method”.
本発明の燃料油組成物において、芳香族分は２５容量％以下であり、好ましくは５容量％以上２５容量％以下、更に好ましくは５容量％以上２０容量％以下である。芳香族分が２５容量％以下ならば、燃焼性やエンジン始動性の悪化を防止し、吹き消え（ブロ−アウト）が起こる危険性を低減できる。
なお、芳香族分は、ＪＰＩ−５Ｓ−４９−９７「石油製品−炭化水素タイプ試験方法−高速液体クロマトグラフ法（ＨＰＬＣ）」に基づいて定量できる。
In the fuel oil composition of the present invention, the aromatic content is 25% by volume or less, preferably 5% by volume or more and 25% by volume or less, more preferably 5% by volume or more and 20% by volume or less. When the aromatic content is 25% by volume or less, deterioration of combustibility and engine startability can be prevented, and the risk of blow-out can be reduced.
The aromatic content can be quantified based on JPI-5S-49-97 “Petroleum products—Hydrocarbon type test method—High performance liquid chromatograph method (HPLC)”.
本発明の燃料油組成物において、オレフィン分は５容量％以下であり、好ましくは３容量％以下である。オレフィン分が５容量％以下ならば、熱による安定性悪化を防止できるため好ましい。
なお、オレフィン分は、ＪＰＩ−５Ｓ−４９−９７「石油製品−炭化水素タイプ試験方法−高速液体クロマトグラフ法（ＨＰＬＣ）」に基づいて定量できる。
また、オレフィン分の含有量は少ないほど好ましく、０質量ｐｐｍが最も好ましい。
In the fuel oil composition of the present invention, the olefin content is 5% by volume or less, preferably 3% by volume or less. If the olefin content is 5% by volume or less, it is preferable because stability deterioration due to heat can be prevented.
The olefin content can be quantified based on JPI-5S-49-97 “Petroleum products—Hydrocarbon type test method—High performance liquid chromatograph method (HPLC)”.
Further, the smaller the olefin content, the better, and 0 mass ppm is most preferable.
本発明の燃料油組成物は、最終的に得られる燃料油組成物が本発明で規定する性状、特にアニリン類を本発明で規定する範囲内になるよう、一種又は二種以上の燃料油基材を配合して、製造することができる。 The fuel oil composition of the present invention comprises one or more fuel oil bases so that the finally obtained fuel oil composition falls within the properties defined in the present invention, particularly anilines within the range defined in the present invention. It can be manufactured by blending materials.
本発明で用いる燃料油基材としては、原油を常圧蒸留して得られるナフサ留分、灯油留分及びそれらを脱硫した脱硫ナフサ、脱硫灯油を用いることができる。また、灯油留分を脱蝋処理した留分や、水素化脱硫装置や水素化分解装置、接触分解装置、熱分解装置などから得られるナフサから灯油までの留分を用いることもできるし、それらを直接水素化処理した基材や、処理原油を常圧蒸留して得られるナフサから灯油までの留分を混合したものを更に脱硫処理などした基材も利用できる。更に、各種原料をガス化して得られる合成ガス（ＣＯと水素）からＦＴ反応により合成したナフサ、灯油留分なども利用できて、本発明の燃料油組成物の製造には各種燃料油基材を任意に用いることができる。 As the fuel oil base material used in the present invention, a naphtha fraction obtained by atmospheric distillation of kerosene, a kerosene fraction, a desulfurized naphtha obtained by desulfurizing them, and a desulfurized kerosene can be used. In addition, a fraction obtained by dewaxing a kerosene fraction, a fraction from naphtha to kerosene obtained from hydrodesulfurization equipment, hydrocracking equipment, catalytic cracking equipment, thermal cracking equipment, etc. can be used. It is also possible to use a base material obtained by directly hydrotreating the above, or a base material obtained by further desulfurizing a mixture of naphtha to kerosene obtained by atmospheric distillation of the treated crude oil. Furthermore, naphtha synthesized by FT reaction from synthesis gas (CO and hydrogen) obtained by gasifying various raw materials, kerosene fraction, etc. can be used, and various fuel oil base materials are used for the production of the fuel oil composition of the present invention. Can be used arbitrarily.
さらに、より好ましい製造方法としては、アニリン類を除去するため、燃料油基材を酸系の吸着剤、例えば、モレキュラ−シ−ブに通油させる方法がある。この操作を実施することで、アニリン類のない燃料油基材を得ることができる。 Furthermore, as a more preferable production method, there is a method in which the fuel oil base is passed through an acid-based adsorbent, for example, a molecular sieve, in order to remove anilines. By performing this operation, a fuel oil base material free of anilines can be obtained.
また、本発明の燃料油組成物には、必要に応じて、各種の添加剤を適宜配合することができる。このような添加剤としては、氷結防止剤、酸化防止剤、金属不活性剤、静電気防止剤、潤滑性向上剤、など公知の燃料添加剤を用いることができる。これらの添加剤は、一種又は数種を組み合わせて添加することができる。 Moreover, various additives can be suitably mix | blended with the fuel oil composition of this invention as needed. As such an additive, known fuel additives such as an anti-icing agent, an antioxidant, a metal deactivator, an antistatic agent, and a lubricity improver can be used. These additives can be added singly or in combination.
以下に本発明の内容を実施例及び比較例により更に詳しく説明するが、本発明はこれらによって制限されるものではない。 The content of the present invention will be described in more detail with reference to Examples and Comparative Examples below, but the present invention is not limited thereto.
〔窒素化合物含有量の測定〕
窒素化合物の含有量は、試料をヘキサン、クロロホルム、アセトンの順で固相抽出をし、アセトンの溶出液を濃縮して、ＧＣ−ＮＣＤ、ＧＣ−ＭＳで分析を実施することで定量した。ＧＣ−ＮＣＤの測定には、ＧＣ−２０１０ (島津製作所製)と７０９０Ｎ (ＡＮＴＥＫ社製)を用いた。 ＧＣ−ＭＳの測定には、Ａｇｉｌｅｎｔ ６８９０Ｎ及びＡｇｉｌｅｎｔ ５９７３ 四重極質量分析計（いずれもＡｇｉｌｅｎｔ社製）を用いた。各分析条件を表１および表２に示す。
[Measurement of nitrogen compound content]
The content of the nitrogen compound was quantified by subjecting the sample to solid-phase extraction in the order of hexane, chloroform, and acetone, concentrating the acetone eluate, and performing analysis with GC-NCD and GC-MS. For measurement of GC-NCD, GC-2010 (manufactured by Shimadzu Corporation) and 7090N (manufactured by ANTEK) were used. For the measurement of GC-MS, an Agilent 6890N and an Agilent 5973 quadrupole mass spectrometer (both manufactured by Agilent) were used. Each analysis condition is shown in Tables 1 and 2.
〔燃料油組成物の製造〕
実施例１
原油を常圧蒸留することで得られた直留灯油留分を用いて、表３に示す性状の航空機用燃料油組成物（ジェット燃料・ＪＥＴ（１））を得た。なお、表３において、Ａｎｉｌｉｎｅ+Ｃ１〜Ｃ３とは、アルキル基の総炭素数が１〜３であるアルキルアニリンの意味である（以下の表においても同様）。
[Manufacture of fuel oil composition]
Example 1
Using a straight kerosene fraction obtained by atmospheric distillation of crude oil, aircraft fuel oil compositions (jet fuel / JET (1)) having the properties shown in Table 3 were obtained. In Table 3, “Anyline + C1 to C3” means an alkylaniline in which the total carbon number of the alkyl group is 1 to 3 (the same applies to the following tables).
実施例２
原油を常圧蒸留することで得られた直留灯油留分を脱硫処理して得られた脱硫灯油留分を用いて、表３に示す性状の航空機用燃料油組成物（ジェット燃料・ＪＥＴ（２））を得た。
Example 2
Using a desulfurized kerosene fraction obtained by desulfurizing a straight kerosene fraction obtained by atmospheric distillation of crude oil, an aircraft fuel oil composition (jet fuel / JET ( 2)) was obtained.
比較例１
実施例１で得たと同様の、原油を常圧蒸留することで得られた直留灯油留分を用いて得た航空機用燃料油組成物に、Ａｎｉｌｉｎｅ+Ｃ３（アルキル基の総炭素数が３であるアルキルアニリン）である２,４,６−トリメチルアニリンを添加し、表４に示す性状の、アルキルアニリンを含むアニリン類の含有量が本発明の範囲から逸脱した、航空機用燃料油組成物（ジェット燃料・ＪＥＴ（３））を得た。
Comparative Example 1
Similar to that obtained in Example 1, an aircraft fuel oil composition obtained by using a straight-run kerosene fraction obtained by atmospheric distillation of crude oil was combined with Anilein + C3 (total carbon number of alkyl group was 3 2,4,6-trimethylaniline, and the content of anilines containing alkylaniline having the properties shown in Table 4 deviated from the scope of the present invention. (Jet fuel / JET (3)) was obtained.
比較例２
原油を常圧蒸留することで得られた直留灯油留分を用いて、表４に示す性状の、窒素分、アルキルアニリンを含むアニリン類の含有量と、セ−ボルト色が本発明の範囲から逸脱した、航空機用燃料油組成物（ジェット燃料・ＪＥＴ（４））を得た。
Comparative Example 2
Using straight-run kerosene fraction obtained by atmospheric distillation of crude oil, the content of anilines including nitrogen content and alkylaniline, and the Cevolt color, as shown in Table 4, are within the scope of the present invention. An aircraft fuel oil composition (jet fuel / JET (4)) deviating from the above was obtained.
比較例３
実施例２で得たと同様の、原油を常圧蒸留することで得られた直留灯油留分を脱硫処理して得られた脱硫灯油留分に、流動接触分解装置より得られた沸点範囲が５５〜２００℃である留分を添加し、表４に示す性状の、窒素分、アルキルアニリンを含むアニリン類、セ−ボルト色、オレフィン分、アロマ分の含有量が本発明の範囲から逸脱した、航空機用燃料油組成物（ジェット燃料・ＪＥＴ（５））を得た。
Comparative Example 3
The desulfurized kerosene fraction obtained by desulfurizing the straight-run kerosene fraction obtained by atmospheric distillation of the crude oil similar to that obtained in Example 2 has a boiling point range obtained from the fluid catalytic cracker. A fraction having a temperature of 55 to 200 ° C. was added, and the contents shown in Table 4, contents of nitrogen, anilines including alkylaniline, cebold color, olefin content, and aroma content deviated from the scope of the present invention. An aircraft fuel oil composition (jet fuel / JET (5)) was obtained.
〔燃料油組成物の評価試験〕
（試験方法）
ほう珪酸ガラス製の５００ｍＬ瓶に、燃料油組成物の試料３００ｍＬとＳＰＣＣ鋼片（１×２０×５０ｍｍ）を入れ、気相部を酸素で置換し、瓶を遮光する。そして、１００℃のオイルバスに設置し、２０時間経過した試料について色相（セ−ボルト色変化）や安定性（パ−オキサイド生成量）について評価した。この方法は、燃料油組成物のタンク貯蔵１年間をシミュレ−トする方法である。
[Evaluation test of fuel oil composition]
(Test method)
A 500 mL bottle of borosilicate glass is charged with 300 mL of a fuel oil composition sample and SPCC steel pieces (1 × 20 × 50 mm), the gas phase is replaced with oxygen, and the bottle is shielded from light. And it installed in the oil bath of 100 degreeC, and evaluated the hue (seol bolt color change) and stability (peroxide production amount) about the sample which passed for 20 hours. This method is a method of simulating the tank storage of the fuel oil composition for one year.
（試験結果）
実施例で得た航空機用燃料油組成物の試験結果および比較例で得た航空機用燃料油組成物の試験結果を表５に示す。
(Test results)
Table 5 shows the test results of the aircraft fuel oil compositions obtained in the examples and the test results of the aircraft fuel oil compositions obtained in the comparative examples.
表５から明らかなように、実施例１、２で得た、本発明の規定を満たす燃料油組成物は、試験後、色相の変化がなく、パ−オキサイドは生成しなかった。比較例１で得た、アルキルアニリンを含むアニリン類の含有量が本発明の範囲から逸脱した燃料油組成物は、試験後、色相が５ポイント低下したが、パ−オキサイドは生成しなかった。
比較例２で得た、窒素分、アルキルアニリンを含むアニリン類の含有量と、セ−ボルト色が本発明の範囲から逸脱した燃料油組成物は、試験後、色相が４ポイント低下し、パ−オキサイドが１質量ｐｐｍ生成した。
比較例３で得た、窒素分、アルキルアニリンを含むアニリン類、オレフィン分、アロマ分の含有量と、セ−ボルト色が本発明の範囲から逸脱した燃料油組成物は、試験後、セ−ボルト色が２９ポイント低下し、パ−オキサイドが３３７質量ｐｐｍ生成した。
これらのことから、窒素分、アルキルアニリンを含むアニリン類、硫黄分、オレフィン分、芳香族分の含有量や、引火点や、セ−ボルト色を本発明の規定の範囲内にすることで、色相及び熱安定性に優れた燃料油組成物を提供することができることは、明らかである。
As is apparent from Table 5, the fuel oil compositions obtained in Examples 1 and 2 that satisfy the provisions of the present invention did not change in hue after the test, and no peroxide was produced. The fuel oil composition obtained in Comparative Example 1 in which the content of anilines including alkylaniline deviated from the scope of the present invention decreased in hue by 5 points after the test, but no peroxide was produced.
The fuel oil composition obtained in Comparative Example 2 in which the content of anilines containing nitrogen and alkyl aniline and the sebolt color deviated from the scope of the present invention decreased in hue by 4 points after the test. -1 mass ppm of oxide was produced.
The fuel oil composition obtained in Comparative Example 3 having a nitrogen content, an aniline containing an alkylaniline, an olefin content, and an aroma content, and a sebolt color deviating from the scope of the present invention, The bolt color was reduced by 29 points, and 337 mass ppm of peroxide was generated.
From these, by making the content of nitrogen, anilines including alkyl aniline, sulfur content, olefin content, aromatic content, flash point, and Cevolt color within the prescribed range of the present invention, It is clear that a fuel oil composition having excellent hue and thermal stability can be provided.
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