JP4881662B2 - LIGHT OIL COMPOSITION AND METHOD FOR PRODUCING LIGHT OIL COMPOSITION - Google Patents
LIGHT OIL COMPOSITION AND METHOD FOR PRODUCING LIGHT OIL COMPOSITION Download PDFInfo
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- JP4881662B2 JP4881662B2 JP2006170359A JP2006170359A JP4881662B2 JP 4881662 B2 JP4881662 B2 JP 4881662B2 JP 2006170359 A JP2006170359 A JP 2006170359A JP 2006170359 A JP2006170359 A JP 2006170359A JP 4881662 B2 JP4881662 B2 JP 4881662B2
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- oil composition
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- light oil
- gas oil
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- 239000000203 mixture Substances 0.000 title claims description 69
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000003921 oil Substances 0.000 claims description 112
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 47
- 229910052717 sulfur Inorganic materials 0.000 claims description 47
- 239000011593 sulfur Substances 0.000 claims description 47
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 24
- 238000004821 distillation Methods 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 23
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 14
- 239000010779 crude oil Substances 0.000 claims description 14
- 239000003350 kerosene Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 150000003464 sulfur compounds Chemical class 0.000 claims description 11
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- 238000000034 method Methods 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 229910003296 Ni-Mo Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 40
- 239000000446 fuel Substances 0.000 description 28
- -1 alkyl sulfides Chemical class 0.000 description 25
- 238000002347 injection Methods 0.000 description 23
- 239000007924 injection Substances 0.000 description 23
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- 230000007797 corrosion Effects 0.000 description 17
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- 238000011156 evaluation Methods 0.000 description 3
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- 125000004432 carbon atom Chemical group C* 0.000 description 2
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- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
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- 239000005022 packaging material Substances 0.000 description 2
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- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
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- PWNBRRGFUVBTQG-UHFFFAOYSA-N 1-n,4-n-di(propan-2-yl)benzene-1,4-diamine Chemical compound CC(C)NC1=CC=C(NC(C)C)C=C1 PWNBRRGFUVBTQG-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- RURPJGZXBHYNEM-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]propyliminomethyl]phenol Chemical compound C=1C=CC=C(O)C=1C=NC(C)CN=CC1=CC=CC=C1O RURPJGZXBHYNEM-UHFFFAOYSA-N 0.000 description 1
- DPJQIIJHCSOAOB-UHFFFAOYSA-N 2-chloroethyl nitrate Chemical compound [O-][N+](=O)OCCCl DPJQIIJHCSOAOB-UHFFFAOYSA-N 0.000 description 1
- GDNQXPDYGNUKII-UHFFFAOYSA-N 2-ethoxyethyl nitrate Chemical compound CCOCCO[N+]([O-])=O GDNQXPDYGNUKII-UHFFFAOYSA-N 0.000 description 1
- NKRVGWFEFKCZAP-UHFFFAOYSA-N 2-ethylhexyl nitrate Chemical group CCCCC(CC)CO[N+]([O-])=O NKRVGWFEFKCZAP-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- NTHGIYFSMNNHSC-UHFFFAOYSA-N 3-methylbutyl nitrate Chemical compound CC(C)CCO[N+]([O-])=O NTHGIYFSMNNHSC-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
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- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
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- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 150000003862 amino acid derivatives Chemical class 0.000 description 1
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- 125000003277 amino group Chemical group 0.000 description 1
- HSNWZBCBUUSSQD-UHFFFAOYSA-N amyl nitrate Chemical compound CCCCCO[N+]([O-])=O HSNWZBCBUUSSQD-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- HLYOOCIMLHNMOG-UHFFFAOYSA-N cyclohexyl nitrate Chemical group [O-][N+](=O)OC1CCCCC1 HLYOOCIMLHNMOG-UHFFFAOYSA-N 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
本発明は、軽油組成物に関する。詳しくは、主にディーゼルエンジンの燃料に用いられる軽油組成物に関する。さらに詳しくは、燃料噴射系統の腐食を抑制し、環境への影響を低減するための精密な運転制御を、より長期間持続することを可能にする軽油組成物に関する。 The present invention relates to a light oil composition. In detail, it is related with the light oil composition mainly used for the fuel of a diesel engine. More specifically, the present invention relates to a light oil composition that enables precise operation control for suppressing corrosion of a fuel injection system and reducing environmental impact to be maintained for a longer period of time.
ディーゼル自動車の排出ガス規制は年々厳しくなっており、自動車メーカーは様々な技術で規制値をクリアしようとしている。これらの技術の中で、最も多く採用されているのが、コモンレール式燃料噴射装置と呼ばれる蓄圧装置を備えた燃料高圧噴射である。この装置は、高圧噴射での軽油液滴の微粒化による粒子状物質の低減ばかりではなく、1サイクル中に燃料噴射を複数回行うことが可能であり、最適な噴射時期と噴射回数などが精密に電子制御されている。
しかし、コモンレール式燃料噴射装置では、蓄圧装置で燃料が高圧になることと、蓄圧装置自体がエンジンに直結されているため、燃料温度がかなり上昇する。さらに従来の機械式噴射装置と比較して、噴射されずに燃料タンクへ戻る燃料量がかなり多いことから、燃料タンク内での燃料温度も上昇する(非特許文献1)。
燃料温度が上昇すると、軽油の熱安定性が問題となる可能性があり、長期間使用する間に燃料噴射弁や燃料ポンプなどの劣化が生じ、電子制御による精密な燃料噴射が不可能になる恐れがある。
However, in the common rail fuel injection device, the fuel temperature rises considerably because the pressure is increased by the pressure accumulator and the accumulator itself is directly connected to the engine. Furthermore, since the amount of fuel returned to the fuel tank without being injected is considerably larger than that of the conventional mechanical injection device, the fuel temperature in the fuel tank also rises (Non-Patent Document 1).
When the fuel temperature rises, the thermal stability of light oil may become a problem, and the fuel injection valve, fuel pump, etc. will deteriorate during long-term use, making precise fuel injection by electronic control impossible There is a fear.
軽油組成物の安定性や腐食性を規定するJIS規格は存在しないが、一般的には安定性は色相で管理されており、酸価等も転用できると考えられる。また、軽油組成物のエンジン材質に対する腐食性を評価する手法としては、ガソリンや灯油に使用する50℃で3時間の銅板腐食が転用できると考えられる。しかし、これらの評価方法は、従来の機械式燃料噴射装置の時代に開発されたものであり、コモンレール式燃料噴射装置のように燃料温度が上昇するケースに対しては精度の点で必ずしも十分とはいえない。また、上記指標に基づいて良好な安定性を有すると評価された軽油組成物であっても、ディーゼルエンジンの長期間の使用に伴い燃料噴射装置の運転が不安定になる可能性がある。これは、上記指標は軽油組成物の性状を評価するものであって、軽油組成物の安定性や腐食性に関与する直接の要因を見極めたものではないためである。 Although there is no JIS standard that regulates the stability and corrosivity of light oil compositions, in general, the stability is controlled by hue, and it is considered that the acid value and the like can also be diverted. Further, as a method for evaluating the corrosiveness of the light oil composition to the engine material, it is considered that the copper plate corrosion for 3 hours at 50 ° C. used for gasoline and kerosene can be diverted. However, these evaluation methods were developed in the era of conventional mechanical fuel injection devices, and are not necessarily sufficient in terms of accuracy for cases where the fuel temperature rises as in common rail fuel injection devices. I can't say that. Moreover, even if it is a light oil composition evaluated as having favorable stability based on the said parameter | index, operation | movement of a fuel-injection apparatus may become unstable with a long-term use of a diesel engine. This is because the above index evaluates the properties of the light oil composition and does not identify direct factors involved in the stability and corrosivity of the light oil composition.
本発明は、ディーゼルエンジンをより長期間安定的に運転するための軽油組成物であり、燃料噴射装置により燃料温度が上昇しても腐食性を極力抑制することができ、精密な燃焼制御をより長期間可能にする軽油組成物を提供することを目的とする。 The present invention is a light oil composition for stably operating a diesel engine for a longer period of time, and can suppress corrosion as much as possible even when the fuel temperature rises by a fuel injection device, and more precise combustion control can be achieved. It aims at providing the light oil composition which makes possible for a long term.
本発明者らは、上記従来技術の問題点を解決し、上記目的を達成すべく鋭意研究した結果、軽油中の硫黄分の中でも、メルカプタン類の硫黄分と、n−デシルメルカプタン(1−デカンチオール)より重質でジベンゾチオフェンより軽質な硫黄化合物の硫黄分とが、ディーゼルエンジンの燃料噴射系統における腐食作用に影響を及ぼしうることを知見し、これら硫黄分を特に選択的に低減することによって、燃料油の温度が上昇しても腐食性を低減できて上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above-mentioned problems of the prior art and to achieve the above-mentioned object, the present inventors have found that, among the sulfur content in light oil, the sulfur content of mercaptans and n-decyl mercaptan (1-decane). The sulfur content of sulfur compounds heavier than dithiothiophene and lighter than dibenzothiophene can affect the corrosive action in diesel engine fuel injection systems, and by selectively reducing these sulfur contents The inventors have found that even if the temperature of the fuel oil rises, the corrosivity can be reduced and the above object can be achieved, and the present invention has been completed.
すなわち本発明は、下記(1)〜(5)を特徴としている。
(1)原油から常圧蒸留により得た直留軽油を含む基材を、水素化処理を行うことにより得られた脱硫軽油組成物を含有し、以下の(a)〜(c)の性状を満たすことを特徴とする軽油組成物。
(a)全硫黄分が3〜10質量ppm
(b)全硫黄分の内、メルカプタン類の硫黄分が0.4〜2質量ppm
(c)全硫黄分の内、n−デシルメルカプタン(1−デカンチオール)より重質でジベンゾチオフェンより軽質な硫黄化合物の硫黄分が0.4質量ppm以下
(2)前記基材が、さらに、脱硫灯油、軽質減圧軽油及び接触分解軽油から選択される少なくとも1種を含むことを特徴とする上記(1)に記載の軽油組成物。
(3)前記基材が、さらに、脱硫灯油を含むことを特徴とする上記(1)に記載の軽油組成物。
(4)前記基材を、Co−Mo、Ni−Mo、Ni−Co−Mo触媒により、330〜400℃の温度の条件で水素化処理を行うことを特徴とする上記(1)〜(3)のいずれか1項に記載の軽油組成物。
(5)原油から常圧蒸留により得た直留軽油を含む基材を、Co−Mo、Ni−Mo、Ni−Co−Mo触媒により、330〜400℃の温度の条件で水素化処理し、
(a)全硫黄分が3〜10質量ppm
(b)全硫黄分の内、メルカプタン類の硫黄分が0.4〜2質量ppm
(c)全硫黄分の内、n−デシルメルカプタン(1−デカンチオール)より重質でジベンゾチオフェンより軽質な硫黄化合物の硫黄分が0.4質量ppm以下
である軽油組成物を得ることを特徴する軽油組成物の製造方法。
That is, the present invention is characterized by the following (1) to (5).
(1) A desulfurized gas oil composition obtained by subjecting a base material containing straight run gas oil obtained from crude oil by atmospheric distillation to a hydrogenation treatment, and having the following properties (a) to (c): A gas oil composition characterized by satisfying.
(A) 3-10 mass ppm of total sulfur content
(B) Among the total sulfur content, the sulfur content of mercaptans is 0.4-2 mass ppm.
(C) Among the total sulfur content, the sulfur content of the sulfur compound heavier than n-decyl mercaptan (1-decanethiol) and lighter than dibenzothiophene is 0.4 mass ppm or less.
(2) The gas oil composition as described in (1) above, wherein the base material further contains at least one selected from desulfurized kerosene, light vacuum gas oil, and catalytic cracked gas oil.
(3) The light oil composition as described in (1) above, wherein the base material further contains desulfurized kerosene.
(4) The base material is subjected to a hydrogenation treatment at a temperature of 330 to 400 ° C. with a Co—Mo, Ni—Mo, or Ni—Co—Mo catalyst. The gas oil composition according to any one of the above.
(5) A base material containing straight run gas oil obtained from crude oil by atmospheric distillation is hydrotreated with a Co—Mo, Ni—Mo, Ni—Co—Mo catalyst at a temperature of 330 to 400 ° C.,
(A) 3-10 mass ppm of total sulfur content
(B) Among the total sulfur content, the sulfur content of mercaptans is 0.4-2 mass ppm.
(C) Among the total sulfur content, the sulfur content of the sulfur compound heavier than n-decyl mercaptan (1-decanethiol) and lighter than dibenzothiophene is 0.4 mass ppm or less.
A process for producing a light oil composition, characterized in that the light oil composition is obtained.
本発明の、全硫黄分、該全硫黄分の内のメルカプタン類の硫黄分、及びn−デシルメルカプタン(1−デカンチオール)より重質でジベンゾチオフェンより軽質な硫黄化合物の硫黄分をそれぞれ一定値以下に管理した軽油組成物は、ディーゼルエンジンにおいて、燃料噴射装置により燃料温度が上昇しても、より長期間腐食性を抑制できる。その結果、より長期間精密な燃焼制御を可能にし、燃焼状態や排出ガス組成への悪影響を極力低減できて、ディーゼルエンジンをより長期間安定的に運転することができる。 The total sulfur content, the sulfur content of mercaptans in the total sulfur content of the present invention, and the sulfur content of sulfur compounds heavier than n-decyl mercaptan (1-decanethiol) and lighter than dibenzothiophene are each a constant value. The diesel oil composition managed below can suppress the corrosivity for a longer period in a diesel engine even if the fuel temperature is increased by the fuel injection device. As a result, precise combustion control can be performed for a longer period of time, adverse effects on the combustion state and exhaust gas composition can be reduced as much as possible, and the diesel engine can be stably operated for a longer period of time.
以下に、本発明を詳細に説明する。
本発明の軽油組成物の全硫黄分含有量は、PM排出量の抑制、及び特に排出ガス後処理装置を装着したエンジンにおける環境負荷の低減効果を長期間保持するために、10質量ppm以下とする(PMとはParticle Matterの略で、ディーゼルエンジンの排気ガス起源の粒子状物質をいう)。なお、本発明でいう全硫黄分とは、JIS K2541に準拠して測定した値である。また、ここでいう全硫黄分とは、例えば硫化水素、メルカプタン類、硫化アルキル類、環状硫化物、チオフェン類等の軽油組成物に含有されている全ての硫黄分を意味する。
The present invention is described in detail below.
The total sulfur content of the light oil composition of the present invention is 10 mass ppm or less in order to suppress the PM emission amount, and particularly to maintain the effect of reducing the environmental load in an engine equipped with an exhaust gas aftertreatment device for a long period of time. (PM is an abbreviation for Particle Matter, which means particulate matter originating from exhaust gas of diesel engines). In addition, the total sulfur content as used in the field of this invention is the value measured based on JISK2541. The total sulfur content here means all sulfur content contained in light oil compositions such as hydrogen sulfide, mercaptans, alkyl sulfides, cyclic sulfides, and thiophenes.
また、本発明の軽油組成物では、メルカプタン類の硫黄分は、2質量ppm以下、好ましくは1質量ppm以下である。本発明でいうメルカプタン類の硫黄分とは、本出願人の出願に係る特願2005−265598号の明細書に記載の方法により測定した値である。この方法は、石油系燃料油中のメルカプタン硫黄分の濃度を定量分析するための電位差滴定によるメルカプタン硫黄分試験方法において、用いる硝酸銀滴定液の濃度を0.0005〜0.005mol/Lとし、且つ試料のはかり採り量を50〜500mLとして電位差滴定を行い、該電位差滴定で測定された前記硝酸銀滴定液の滴定量からメルカプタン硫黄分の濃度を算出する石油系燃料油のメルカプタン硫黄分試験方法である。
本発明の軽油組成物においては、メルカプタン類の硫黄分は少ないほど好ましいが、メルカプタン類の硫黄分が2質量ppm以下であれば、燃料噴射系統で腐食が発生する可能性が低下する。その結果、環境への影響を低減するための精密な運転制御をより長時間持続することが可能になる。なお、ここでいう燃料噴射系統とは、燃料タンク、燃料フィルター、燃料ポンプ、コモンレール、燃料噴射弁、及びこれらを繋ぐ配管の総称である。
Moreover, in the light oil composition of this invention, the sulfur content of mercaptans is 2 mass ppm or less, Preferably it is 1 mass ppm or less. The sulfur content of the mercaptans referred to in the present invention is a value measured by the method described in the specification of Japanese Patent Application No. 2005-265598 according to the application of the present applicant. This method is a mercaptan sulfur content test method by potentiometric titration for quantitative analysis of the concentration of mercaptan sulfur in petroleum fuel oil. The concentration of silver nitrate titrant used is 0.0005 to 0.005 mol / L, and This is a method for testing a mercaptan sulfur content of a petroleum-based fuel oil by performing potentiometric titration with a sample weighing of 50 to 500 mL and calculating a mercaptan sulfur content from a titration amount of the silver nitrate titrant measured by the potentiometric titration. .
In the light oil composition of the present invention, the lower the sulfur content of mercaptans, the better. However, if the sulfur content of the mercaptans is 2 ppm by mass or less, the possibility of corrosion occurring in the fuel injection system is reduced. As a result, precise operation control for reducing the environmental impact can be continued for a longer time. The fuel injection system here is a general term for a fuel tank, a fuel filter, a fuel pump, a common rail, a fuel injection valve, and a pipe connecting them.
さらに、本発明の軽油組成物では、n−デシルメルカプタン(1−デカンチオール)より重質でジベンゾチオフェンより軽質な硫黄化合物の硫黄分は、0.4質量ppm以下、好ましくは0.1質量ppm以下である。本発明でいうn−デシルメルカプタン(1−デカンチオール)より重質でジベンゾチオフェンより軽質な硫黄化合物の硫黄分は、化学発光によって硫黄化合物を選択的に検出、定量するANTEK製硫黄化学発光検出器を備えた島津製作所製ガスクロマトグラフ装置を用いて、ガスクロマトグラフ法で測定される。ここで、n−デシルメルカプタンとジベンゾチオフェンを標準硫黄化合物として、硫黄分が検出されないHPLC用イソオクタンに溶解したものを予め測定し、ピークの位置を求めておく。その後、試料を測定し、n−デシルメルカプタンとジベンゾチオフェンのピークの位置の中間にあるピークの総面積で定量した。
ガスクロマトグラフの測定条件は、40℃で1分保持した後、10℃/分で300℃まで昇温し、300℃で3分保持した。また、使用したカラムは、ポリジメチルシロキサンをコーティングしたキャピラリータイプで、長さ30m、内径0.32mm、膜厚1.0μmを使用した。
n−デシルメルカプタン(1−デカンチオール)より重質でジベンゾチオフェンより軽質な硫黄化合物の硫黄分が、0.4質量ppm以下であれば、コモンレール式の燃料噴射系統で腐食が発生する可能性が低下し、環境への影響を低減するための精密な運転制御をより長期間持続することが可能になる。
Furthermore, in the light oil composition of the present invention, the sulfur content of the sulfur compound heavier than n-decyl mercaptan (1-decanethiol) and lighter than dibenzothiophene is 0.4 mass ppm or less, preferably 0.1 mass ppm. It is as follows. Sulfur chemiluminescence detector manufactured by ANTEK, which selectively detects and quantifies sulfur compounds by chemiluminescence, which is heavier than n-decyl mercaptan (1-decanethiol) and lighter than dibenzothiophene in the present invention. Is measured by a gas chromatograph method using a Shimadzu gas chromatograph apparatus. Here, n-decyl mercaptan and dibenzothiophene are used as standard sulfur compounds, and those dissolved in isooctane for HPLC in which no sulfur content is detected are measured in advance to determine the position of the peak. Then, the sample was measured and quantified by the total area of the peaks in the middle of the peak positions of n-decyl mercaptan and dibenzothiophene.
The measurement conditions of the gas chromatograph were maintained at 40 ° C. for 1 minute, then raised to 300 ° C. at 10 ° C./minute, and held at 300 ° C. for 3 minutes. The column used was a capillary type coated with polydimethylsiloxane and had a length of 30 m, an inner diameter of 0.32 mm, and a film thickness of 1.0 μm.
If the sulfur content of the sulfur compound heavier than n-decyl mercaptan (1-decanethiol) and lighter than dibenzothiophene is 0.4 ppm by mass or less, corrosion may occur in the common rail fuel injection system. Therefore, it is possible to maintain precise operation control for a longer period of time to reduce the environmental impact.
本発明の軽油組成物は、JIS K2204でいう所謂、特1号、1号、2号、3号、特3号軽油全般に適合させることができる。 The light oil composition of the present invention can be adapted to the so-called Special No. 1, No. 2, No. 2, No. 3 and Special No. 3 light oils generally referred to in JIS K2204.
本発明の軽油組成物の色相、酸価、50℃で3時間の銅板腐食等の、軽油組成物の安定性や腐食性の評価に転用できる性状は、従来の軽油組成物の性状と同等であっても差支えない。本発明の軽油組成物におけるこれらの各性状は、一般に、色相は−16以上(セーボルト色、JIS K2580)、または1.5以下(ASTM色、JIS K2580)、酸価は0.02以下(中和価、JIS K2501)、50℃、3時間での銅板腐食は2未満(銅板腐食、JIS K2513)であることが好ましい。本発明の軽油組成物はさらに、149℃で24時間の銅板腐食試験の判定値が4未満であることが好ましい。かかる試験は、過熱浴の温度を149℃に設定し、試料と銅板を加熱浴に浸す時間を24時間とする以外はJIS K2513に準拠した値である。従来のJIS K2513の50℃、3時間での銅板腐食よりも苛酷な条件とする事で、エンジン上部に設置されて、輻射熱で100℃を超えると考えられる環境下にあるコモンレール内での軽油組成物の腐食性を、加速的に評価したものである。 The properties of the light oil composition of the present invention that can be diverted to the evaluation of the stability and corrosivity of the light oil composition, such as the hue, acid value, and copper plate corrosion at 50 ° C. for 3 hours, are the same as the properties of the conventional light oil composition. It doesn't matter if it exists. Each of these properties in the light oil composition of the present invention generally has a hue of -16 or more (Saebold color, JIS K2580) or 1.5 or less (ASTM color, JIS K2580), and an acid value of 0.02 or less (medium It is preferable that the copper plate corrosion at 3 hours at 50 ° C. is less than 2 (copper plate corrosion, JIS K2513). The light oil composition of the present invention preferably further has a judgment value of less than 4 in a copper plate corrosion test at 149 ° C. for 24 hours. This test is a value based on JIS K2513 except that the temperature of the overheating bath is set to 149 ° C. and the time for immersing the sample and the copper plate in the heating bath is 24 hours. Light oil composition in a common rail in an environment where it is installed at the top of the engine and is considered to exceed 100 ° C due to radiant heat by making the conditions more severe than the conventional copper plate corrosion at 50 ° C for 3 hours of JIS K2513 This is an accelerated evaluation of the corrosivity of objects.
本発明の軽油組成物の製造方法は、前記した性状を満足する限り特に制限されない。例えば、本発明の軽油組成物は、直留軽油(LGO)及び/又は軽質減圧軽油(LVGO)を、Co−Mo、Ni−Mo、Ni−Co−Mo触媒等の触媒の存在下で、3〜12MPa、好ましくは7〜10MPaの圧力下、300〜400℃、好ましくは330〜360℃の温度で、液空間速度(LHSV)0.1〜5h-1、好ましくは0.5〜1.5h-1の条件で、水素化処理した後、必要に応じて流動性向上剤等を配合して得られる。
また、他の軽油基材を用いて、前記した性状を満たすように適宜配合することにより任意の方法で調製することができる。この際の軽油基材としては、例えば、脱硫灯油(UFT−KERO)、水素化分解軽油(HCGO)、接触分解軽油(LCO)、脱硫重質ナフサ(DHN)、脱ろう脱硫軽油(DWDLGO)、直脱軽油(DSGO)、間脱軽質軽油(VHLGO)、特開平6−158058号に代表される公報に記載されたフィッシャー・トロプッシュ合成により製造される灯油留分及び軽油留分などが挙げられる。これらの基材を1 種又は2 種以上を混合して製造できるし、また直留軽油(LGO)及び/又は軽質減圧軽油(LVGO)にこれらの基材を1 種又は2 種以上を混合してから、上記の条件で水素化処理して製造してもよい。
The method for producing the light oil composition of the present invention is not particularly limited as long as the above properties are satisfied. For example, the light oil composition of the present invention comprises a straight-run gas oil (LGO) and / or a light vacuum gas oil (LVGO) in the presence of a catalyst such as a Co-Mo, Ni-Mo, or Ni-Co-Mo catalyst. Liquid space velocity (LHSV) 0.1-5 h −1 , preferably 0.5-1.5 h at a temperature of 300-400 ° C., preferably 330-360 ° C. under a pressure of ˜12 MPa, preferably 7-10 MPa. It is obtained by blending a fluidity improver or the like as necessary after hydrogenation under the condition of -1 .
Moreover, it can prepare by arbitrary methods by mix | blending suitably so that the above-mentioned property may be satisfy | filled using another light oil base material. Examples of the light oil base at this time include desulfurized kerosene (UFT-KERO), hydrocracked light oil (HCGO), catalytic cracked light oil (LCO), desulfurized heavy naphtha (DHN), dewaxed desulfurized light oil (DWDLGO), Direct degassing light oil (DSGO), intermediate delighted light oil (VHLGO), kerosene fraction and gas oil fraction produced by Fischer-Tropsch synthesis described in JP-A-6-1558058 . These base materials can be produced by mixing one or more kinds, and one or two or more kinds of these base materials are mixed with straight-run gas oil (LGO) and / or light vacuum gas oil (LVGO). Then, it may be produced by hydrotreating under the above conditions.
本発明の軽油組成物には、曇り点、流動点の改善や含有するワックスの含有率を減少させるために、脱硫灯油(UFT−KERO)を配合することもできる。脱硫灯油は、常圧蒸留装置から得られた灯油留分を水素化脱硫処理したものである。脱硫灯油は、好ましくは直留軽油及び軽質減圧軽油から得られた組成物に対して5〜70容量%、より好ましくは10〜40容量% 配合される。 In the light oil composition of the present invention, desulfurized kerosene (UFT-KERO) can be blended in order to improve the cloud point and pour point and to reduce the content of wax contained. Desulfurized kerosene is obtained by hydrodesulfurizing a kerosene fraction obtained from an atmospheric distillation apparatus. The desulfurized kerosene is preferably blended in an amount of 5 to 70% by volume, more preferably 10 to 40% by volume, based on the composition obtained from straight-run gas oil and light vacuum gas oil.
本発明の軽油組成物には、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。この添加剤としては、流動性向上剤、セタン価向上剤、清浄剤、防錆剤、消泡剤、酸化防止剤、金属不活性化剤、色相安定剤などが挙げられる。
流動性向上剤としては、種々の低温流動性向上剤が使用でき、例え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、ポリエチレングリコール誘導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などが挙げられる。中でも、エチレン−酢酸ビニル共重合体が好ましい。これらの流動性向上剤は、1種単独で用いてもよいし、2種以上を組合せて用いてもよい。流動性向上剤の配合量は、流動性向上剤の機能が適切に発現する観点、及び流動性向上剤自体が自動車のフィルターを閉塞する不具合を避ける観点から、軽油組成物中に好ましくは100〜1000容量ppm、より好ましくは300〜600容量ppm含有される量である。
Various additives can be appropriately blended in the light oil composition of the present invention as necessary. Examples of the additive include a fluidity improver, a cetane number improver, a detergent, a rust inhibitor, an antifoaming agent, an antioxidant, a metal deactivator, and a hue stabilizer.
As the fluidity improver, various low temperature fluidity improvers can be used. For example, copolymer polymers such as alkenyl succinic acid amide, ethylene-vinyl acetate copolymer, ethylene-alkyl acrylate copolymer, polyethylene glycol derivative, Examples thereof include polymers such as chlorinated polyethylene and polyalkyl acrylate. Among these, an ethylene-vinyl acetate copolymer is preferable. These fluidity improvers may be used individually by 1 type, and may be used in combination of 2 or more type. The blending amount of the fluidity improver is preferably 100 to 100 in the light oil composition from the viewpoint of appropriately expressing the function of the fluidity improver and avoiding the problem that the fluidity improver itself blocks the automobile filter. The amount contained is 1000 ppm by volume, more preferably 300 to 600 ppm by volume.
セタン価向上剤としては、種々のセタン価向上剤が使用でき、例えば2−クロロエチルナイトレート、2−エトキシエチルナイトレート、イソプロピルナイトレート、ブチルナイトレート、第一アミルナイトレート、第二アミルナイトレート、イソアミルナイトレート、第一ヘキシルナイトレート、第二ヘキシルナイトレート、n−ヘプチルナイトレート、n−オクチルナイトレート、2−エチルヘキシルナイトレート、シクロヘキシルナイトレート、エチレングリコールジナイトレートなどの種々のナイトレートやジ−t−ブチルペルオキシドなど種々の過酸化物が挙げられ、好ましくは炭素数6 又は8のアルキルナイトレートが挙げられる。これらのセタン価向上剤は、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。セタン価向上剤の配合量は、適宜選定すれば良いが、軽油組成物に対して100〜1000容量ppm配合することが好ましい。 Various cetane number improvers can be used as the cetane number improver, such as 2-chloroethyl nitrate, 2-ethoxyethyl nitrate, isopropyl nitrate, butyl nitrate, first amyl nitrate, and second amylite. Various nights such as rate, isoamyl nitrate, primary hexyl nitrate, secondary hexyl nitrate, n-heptyl nitrate, n-octyl nitrate, 2-ethylhexyl nitrate, cyclohexyl nitrate, ethylene glycol dinitrate Examples include various peroxides such as a rate and di-t-butyl peroxide, and preferably an alkyl nitrate having 6 or 8 carbon atoms. These cetane number improvers may be used individually by 1 type, and may be used in combination of 2 or more type. The blending amount of the cetane number improver may be appropriately selected, but it is preferably blended with 100 to 1000 ppm by volume with respect to the light oil composition.
清浄剤としては、種々の清浄剤が使用でき、例えばイミド系化合物; ポリブテニルコハク酸無水物とエチレンポリアミン類とから合成されるポリブテニルコハク酸イミドなどのアルケニルコハク酸イミド; ペンタエリスリトールなどの多価アルコールとポリブテニルコハク酸無水物から合成されるポリブテニルコハク酸エステルなどのコハク酸エステル;ジアルキルアミノエチルメタクリレート、ポリエチレングリコールメタクリレート、ビニルピロリドンなどとアルキルメタクリレートとのコポリマーなどの共重合系ポリマーなどの無灰清浄剤などが挙げられ、好ましくはアルケニルコハク酸イミドである。これらの清浄剤は、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。清浄剤の配合量は、適宜選定すれば良いが、軽油組成物に対して450〜2000容量ppm配合することが好ましい。 Various detergents can be used as the detergent, for example, imide compounds; alkenyl succinimides such as polybutenyl succinimide synthesized from polybutenyl succinic anhydride and ethylene polyamines; pentaerythritol, etc. Succinic acid esters such as polybutenyl succinic acid esters synthesized from polyhydric alcohols of polybutenyl succinic anhydrides; copolymers of dialkylaminoethyl methacrylate, polyethylene glycol methacrylate, vinyl pyrrolidone, etc. and alkyl methacrylate copolymers An ashless detergent such as a polymer is exemplified, and alkenyl succinimide is preferable. These detergents may be used individually by 1 type, and may be used in combination of 2 or more type. The blending amount of the detergent may be appropriately selected, but it is preferable to blend 450 to 2000 volume ppm with respect to the light oil composition.
防錆剤としては、種々の防錆剤が使用でき、例えばステアリン酸などのモノカルボン酸、アルキル又はアルケニルコハク酸などのジカルボン酸などのカルボン酸; 脂肪酸、ナフテン酸、アビエチン酸、ラノリン脂肪酸、アルケニルコハク酸、アミノ酸誘導体などのカルボン酸のアルカリ土類金属塩、アルミニウム、亜鉛、鉛などの各種金属元素塩、アミン塩などのカルボン酸塩; 石油スルホン酸、ジノニルナフタレンスルホン酸、重質アルキルベンゼンスルホン酸などのスルホン酸のアルカリ金属塩、アルカリ土類金属塩、アミン塩などのスルホン酸塩; ソルビトール、ペンタエリスリトール、ショ糖、グリセリンなどの多価アルコールとオレイン酸、ラウリル酸などのカルボン酸との部分エステルなどのカルボン酸エステル; 高級脂肪族アルコールなどのアルコール; シクロヘキシルアミン、モルホリン、アルコキシフェニルアミン、ジエタノールアミン誘導体、アミノアルコール、ロジンアミンのエチレンオキサイド付加物などのアミン; リン酸などの極性基を主あるいは副極性基として有する油溶性界面活性剤などが挙げられる。これらの防錆剤の内、好ましいものは、無灰タイプのアミノ基を有するものである。これらの防錆剤は、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。防錆剤の配合量は、適宜選定すれば良いが、軽油組成物に対して2〜100容量ppm配合することが好ましい。 As the rust preventive agent, various rust preventive agents can be used, for example, monocarboxylic acid such as stearic acid, carboxylic acid such as dicarboxylic acid such as alkyl or alkenyl succinic acid; fatty acid, naphthenic acid, abietic acid, lanolin fatty acid, alkenyl Alkaline earth metal salts of carboxylic acids such as succinic acid and amino acid derivatives, various metal element salts such as aluminum, zinc and lead, carboxylates such as amine salts; petroleum sulfonic acid, dinonylnaphthalene sulfonic acid, heavy alkylbenzene sulfone Sulfonic acid salts such as alkali metal salts, alkaline earth metal salts and amine salts of sulfonic acids such as acids; polyhydric alcohols such as sorbitol, pentaerythritol, sucrose and glycerin and carboxylic acids such as oleic acid and lauric acid Carboxylic esters such as partial esters; higher aliphatics Alcohols such as alcohols; Amines such as cyclohexylamine, morpholine, alkoxyphenylamines, diethanolamine derivatives, amino alcohols, ethylene oxide adducts of rosinamines; oil-soluble surfactants having polar groups such as phosphoric acid as main or subpolar groups Is mentioned. Among these rust preventives, preferred are those having an ashless type amino group. These rust preventives may be used alone or in combination of two or more. Although the compounding quantity of a rust preventive agent should just be selected suitably, it is preferable to mix | blend 2-100 volume ppm with respect to a light oil composition.
消泡剤としては、種々の消泡剤が使用でき、例えばポリジメチルシロキサン、ジメチルシロキサンとトリフルオロプロピルメチルシロキサンとの共重合物、ジメチルシロキサンとオキシエチレンとの共重合物などのシリコーンポリマーが挙げられ、好ましくはジメチルシロキサンとオキシエチレンとの共重合物が挙げられる。これらの消泡剤は、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。消泡剤の配合量は、適宜選定すれば良いが、軽油組成物に対して3〜20容量ppm配合することが好ましい。 Various antifoaming agents can be used as the antifoaming agent, and examples thereof include silicone polymers such as polydimethylsiloxane, a copolymer of dimethylsiloxane and trifluoropropylmethylsiloxane, and a copolymer of dimethylsiloxane and oxyethylene. Preferably, a copolymer of dimethylsiloxane and oxyethylene is used. These antifoaming agents may be used individually by 1 type, and may be used in combination of 2 or more type. The blending amount of the antifoaming agent may be appropriately selected, but it is preferable to blend 3 to 20 ppm by volume with respect to the light oil composition.
酸化防止剤としては、種々の酸化防止剤が使用でき、例えばN,N ’−ジイソプロピル−p−フェニレンジアミン、N,N ’−ジ−sec−ブチル−p− フェニレンジアミンのようなアミン;2,6−ジ−tert−ブチル−4−メチルフェノール、2,4−ジメチル−6−tert−ブチルフェノール、2,6−ジ−tert−ブチルフェノールのようなフェノールなどが挙げられる。これらの酸化防止剤は、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。酸化防止剤の配合量は、適宜選定すれば良いが、軽油組成物に対して10〜60容量ppm配合することが好ましい。 As the antioxidant, various antioxidants can be used, for example, amines such as N, N′-diisopropyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine; Examples thereof include phenols such as 6-di-tert-butyl-4-methylphenol, 2,4-dimethyl-6-tert-butylphenol, and 2,6-di-tert-butylphenol. These antioxidants may be used individually by 1 type, and may be used in combination of 2 or more type. The blending amount of the antioxidant may be selected as appropriate, but it is preferable to blend 10 to 60 ppm by volume with respect to the light oil composition.
金属不活性化剤としては、種々の金属不活性化剤が使用でき、例えばN,N ’−ジサリチリデン−1,2−ジアミノプロパンなどが挙げられる。これらの金属不活性化剤は、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。金属不活性化剤の配合量は、適宜選定すれば良いが、軽油組成物に対して2〜20容量ppm配合することが好ましい。 As the metal deactivator, various metal deactivators can be used, and examples thereof include N, N'-disalicylidene-1,2-diaminopropane. These metal deactivators may be used alone or in combination of two or more. Although the compounding quantity of a metal deactivator should just be selected suitably, it is preferable to mix | blend 2-20 volume ppm with respect to a light oil composition.
色相安定剤としては、種々の色相安定剤が使用でき、例えば清浄剤としての機能をも有するアルケニルコハク酸イミドや、その他アントラキノン、ヒドラジンなどが挙げられる。これらの色相安定剤は、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。色相安定剤の配合量は、適宜選定すれば良いが、軽油組成物に対して10〜1000容量ppm配合することが好ましい。 As the hue stabilizer, various hue stabilizers can be used, and examples thereof include alkenyl succinimide having a function as a detergent, other anthraquinones, hydrazine, and the like. These hue stabilizers may be used individually by 1 type, and may be used in combination of 2 or more type. The blending amount of the hue stabilizer may be appropriately selected, but it is preferable to blend 10 to 1000 ppm by volume with respect to the light oil composition.
以下、実施例及び比較例によりさらに具体的に本発明を説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to a following example.
実施例1
中東系の原油から常圧蒸留により得た軽油留分(直留軽油、蒸留カットレンジ170〜370℃)を原料油とし、該原料油を水素化脱硫触媒として市販触媒(Co−Mo系)を用いて水素化処理して、脱硫軽油組成物を得た。その諸性状を表1に示した。
Example 1
A gas oil fraction (straight-run gas oil, distillation cut range 170 to 370 ° C.) obtained from Middle Eastern crude oil by atmospheric distillation is used as a raw material oil, and a commercial catalyst (Co-Mo system) is used as the hydrodesulfurization catalyst. The resulting mixture was hydrotreated to obtain a desulfurized gas oil composition. The properties are shown in Table 1.
実施例2
中東系の原油(ただし実施例1とは原油種が異なる)から常圧蒸留により得た軽油留分(直留軽油、蒸留カットレンジ170〜380℃)を原料油とし、該原料油を水素化脱硫触媒として市販触媒(Co−Mo系)を用いて水素化処理して、脱硫軽油組成物を得た。その諸性状を表1に示した。
Example 2
A gas oil fraction (straight-run gas oil, distillation cut range 170-380 ° C.) obtained by atmospheric distillation from Middle Eastern crude oil (however, the crude oil type is different from Example 1) is used as a raw oil, and the raw oil is hydrogenated. Hydrogenation treatment was performed using a commercially available catalyst (Co—Mo system) as a desulfurization catalyst to obtain a desulfurized light oil composition. The properties are shown in Table 1.
実施例3
実施例1で得た脱硫軽油組成物に、中東系の原油から常圧蒸留により得た灯油留分(直留灯油、蒸留カットレンジ160〜370℃)を原料油として、該原料油を水素化脱硫触媒として市販触媒(Co−Mo系)を用いて水素化処理して得られた脱硫灯油(蒸留カットレンジ150〜350℃)を10容量%混合して、脱硫軽油組成物を得た。その諸性状を表1に示した。
Example 3
The desulfurized gas oil composition obtained in Example 1 was kerosene fraction (straight-run kerosene, distillation cut range 160-370 ° C.) obtained by atmospheric distillation from Middle Eastern crude oil, and the raw oil was hydrogenated. A desulfurized gas oil composition was obtained by mixing 10% by volume of desulfurized kerosene (distillation cut range 150 to 350 ° C.) obtained by hydrogenation using a commercially available catalyst (Co—Mo system) as a desulfurization catalyst. The properties are shown in Table 1.
実施例4
中東系の原油から常圧蒸留により得た軽油留分(直留軽油、蒸留カットレンジ160〜370℃)に、中東系の原油から減圧蒸留により得た軽油留分(軽質減圧軽油、蒸留カットレンジ160〜370℃)を10容量%混合したものを原料油とし、該原料油を水素化脱硫触媒として市販触媒(Co−Mo系)を用いて水素化処理して、脱硫軽油組成物を得た。その諸性状を表1に示した。
Example 4
Gas oil fraction obtained from Middle Eastern crude oil by atmospheric distillation (straight-run gas oil, distillation cut range 160-370 ° C) and light oil fraction obtained by vacuum distillation from Middle East crude oil (light vacuum gas oil, distillation cut range) 160% to 370 ° C) was mixed with 10% by volume as a raw material oil, and the raw material oil was hydrotreated using a commercially available catalyst (Co-Mo system) as a hydrodesulfurization catalyst to obtain a desulfurized gas oil composition. . The properties are shown in Table 1.
実施例5
中東系の原油から常圧蒸留により得た軽油留分(直留軽油、蒸留カットレンジ170〜360℃)に、中東系原油から常圧蒸留により得た軽油留分以上の高沸点留分を接触分解して得られた接触分解軽油(LCO)を10容量%混合したものを原料油とし、該原料油を水素化脱硫触媒として市販触媒(Co−Mo系)を用いて水素化処理して、脱硫軽油組成物を得た。その諸性状を表1に示した。
Example 5
Contact a light oil fraction obtained by atmospheric distillation from Middle Eastern crude oil (straight-run diesel oil, distillation cut range 170-360 ° C) with a higher boiling point fraction higher than that obtained by atmospheric distillation from Middle Eastern crude oil A mixture obtained by mixing 10% by volume of catalytic cracking light oil (LCO) obtained by cracking is used as a raw material oil, and the raw material oil is hydrotreated using a commercially available catalyst (Co-Mo system) as a hydrodesulfurization catalyst, A desulfurized gas oil composition was obtained. The properties are shown in Table 1.
参考例1
中東系の原油から常圧蒸留により得た軽油留分(直留軽油、蒸留カットレンジ170〜
370℃)を原料油とし、該原料油を水素化脱硫触媒として市販触媒(Co−Mo系)を
用い水素化処理して得られた脱硫軽油に、フィッシャー・トロプシュ合成により得た炭素
数30以上のワックス分を水素化分解触媒として市販触媒(Pt系)を用いて水素化分解
した後、蒸留して得た軽油留分(蒸留カットレンジ200〜350℃)を10容量%混合
して、脱硫軽油組成物を得た。その諸性状を表1に示した。
Reference example 1
Gas oil fraction obtained from Middle Eastern crude oil by atmospheric distillation (straight-run gas oil, distillation cut range 170 ~
370 ° C.) as raw material oil, desulfurized light oil obtained by hydrotreating the raw material oil as a hydrodesulfurization catalyst using a commercially available catalyst (Co—Mo system), and having 30 or more carbon atoms obtained by Fischer-Tropsch synthesis After hydrocracking the wax content of the catalyst using a commercially available catalyst (Pt system) as a hydrocracking catalyst, 10% by volume of a light oil fraction (distillation cut range 200-350 ° C.) obtained by distillation is mixed to desulfurize A light oil composition was obtained. The properties are shown in Table 1.
比較例1
中東系の原油から常圧蒸留により得た軽油留分(直留軽油、蒸留カットレンジ170〜360℃)を原料油とし、該原料油を水素化脱硫触媒として市販触媒(Co−Mo系)を用い水素化処理して、脱硫軽油組成物を得た。その諸性状を表1に示した。
Comparative Example 1
A gas oil fraction (straight-run gas oil, distillation cut range 170 to 360 ° C.) obtained from Middle Eastern crude oil by atmospheric distillation is used as a raw material oil, and a commercial catalyst (Co-Mo system) is used as the hydrodesulfurization catalyst. Hydrogenation treatment was performed to obtain a desulfurized gas oil composition. The properties are shown in Table 1.
比較例2
参考例1で得た脱硫軽油組成物に、n−ドデシルメルカプタン(東京化成工業製、市販
試薬)を所定量添加し、メルカプタン類の硫黄分を2.2質量ppmに調整した脱硫軽油
組成物を得た。その諸性状を表1に示した。
Comparative Example 2
A desulfurized gas oil composition obtained by adding a predetermined amount of n-dodecyl mercaptan (manufactured by Tokyo Chemical Industry Co., Ltd., commercially available reagent) to the desulfurized gas oil composition obtained in Reference Example 1 and adjusting the sulfur content of the mercaptans to 2.2 mass ppm. Obtained. The properties are shown in Table 1.
上記実施例、参考例及び比較例で調製した軽油組成物について、50℃で3時間の銅板腐食試験及び149℃で24時間の銅板腐食試験を行った。その結果を表1に示した。
50℃で3時間の銅板腐食試験結果が、2以上であるか、又は149℃で24時間の銅板腐食試験結果が4以上であると、燃料噴射系統で腐食が発生し、環境への影響を低減するための精密な運転制御を長期間持続することが不可能になる恐れがある。
About the light oil composition prepared by the said Example, reference example, and the comparative example, the copper plate corrosion test for 3 hours at 50 degreeC and the copper plate corrosion test for 24 hours at 149 degreeC were done. The results are shown in Table 1.
If the copper plate corrosion test result for 3 hours at 50 ° C is 2 or more, or if the copper plate corrosion test result for 24 hours at 149 ° C is 4 or more, corrosion will occur in the fuel injection system, which may affect the environment. It may become impossible to maintain precise operation control for reduction for a long time.
表1から明らかなように、n−デシルメルカプタン(1−デカンチオール)より重質でジベンゾチオフェンより軽質な硫黄化合物の硫黄分が0.4質量ppmを超える比較例1では、149℃で24時間の銅板腐食試験が4に悪化する。また、メルカプタン類の硫黄分が2質量ppmを超える比較例2でも、149℃で24時間の銅板腐食試験が4に悪化することがわかる。 As is clear from Table 1, in Comparative Example 1 in which the sulfur content of the sulfur compound heavier than n-decyl mercaptan (1-decanethiol) and lighter than dibenzothiophene exceeds 0.4 mass ppm, it is 24 hours at 149 ° C. The copper plate corrosion test worsens to 4. Moreover, it turns out that the copper plate corrosion test of 24 hours at 149 degreeC deteriorates to 4 also in the comparative example 2 in which the sulfur content of mercaptans exceeds 2 mass ppm.
Claims (5)
(a)全硫黄分が3〜10質量ppm
(b)全硫黄分の内、メルカプタン類の硫黄分が0.4〜2質量ppm
(c)全硫黄分の内、n−デシルメルカプタン(1−デカンチオール)より重質でジベンゾチオフェンより軽質な硫黄化合物の硫黄分が0.4質量ppm以下 It contains a desulfurized gas oil composition obtained by subjecting a base material containing straight-run gas oil obtained from crude oil by atmospheric distillation to hydrogenation treatment, and satisfies the following properties (a) to (c) A light oil composition.
(A) 3-10 mass ppm of total sulfur content
(B) Among the total sulfur content, the sulfur content of mercaptans is 0.4-2 mass ppm.
(C) Among the total sulfur content, the sulfur content of the sulfur compound heavier than n-decyl mercaptan (1-decanethiol) and lighter than dibenzothiophene is 0.4 mass ppm or less.
(a)全硫黄分が3〜10質量ppm (A) 3-10 mass ppm of total sulfur content
(b)全硫黄分の内、メルカプタン類の硫黄分が0.4〜2質量ppm (B) Among the total sulfur content, the sulfur content of mercaptans is 0.4-2 mass ppm.
(c)全硫黄分の内、n−デシルメルカプタン(1−デカンチオール)より重質でジベンゾチオフェンより軽質な硫黄化合物の硫黄分が0.4質量ppm以下 (C) Among the total sulfur content, the sulfur content of the sulfur compound heavier than n-decyl mercaptan (1-decanethiol) and lighter than dibenzothiophene is 0.4 mass ppm or less.
である軽油組成物を得ることを特徴する軽油組成物の製造方法。A process for producing a light oil composition, characterized in that the light oil composition is obtained.
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