JP5128632B2 - Kerosene composition - Google Patents
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- JP5128632B2 JP5128632B2 JP2010098813A JP2010098813A JP5128632B2 JP 5128632 B2 JP5128632 B2 JP 5128632B2 JP 2010098813 A JP2010098813 A JP 2010098813A JP 2010098813 A JP2010098813 A JP 2010098813A JP 5128632 B2 JP5128632 B2 JP 5128632B2
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- 239000003350 kerosene Substances 0.000 title claims description 118
- 239000000203 mixture Substances 0.000 title claims description 112
- 238000004821 distillation Methods 0.000 claims description 71
- 229910052717 sulfur Inorganic materials 0.000 claims description 43
- 239000011593 sulfur Substances 0.000 claims description 43
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 41
- 125000003118 aryl group Chemical group 0.000 claims description 41
- 238000009835 boiling Methods 0.000 claims description 19
- 239000010779 crude oil Substances 0.000 claims description 14
- 150000002790 naphthalenes Chemical class 0.000 claims description 11
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 239000000295 fuel oil Substances 0.000 claims description 7
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims description 7
- 238000005194 fractionation Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 238000004817 gas chromatography Methods 0.000 claims 1
- 238000004811 liquid chromatography Methods 0.000 claims 1
- 238000004949 mass spectrometry Methods 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 description 14
- 230000023556 desulfurization Effects 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- 238000003860 storage Methods 0.000 description 11
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 235000019645 odor Nutrition 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 125000002619 bicyclic group Chemical group 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- -1 alkaline earth metal salts Chemical class 0.000 description 3
- 239000003747 fuel oil additive Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003556 thioamides Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、灯油組成物、特に石油ストーブなどに用いる灯油組成物に関し、詳しくは、酸化安定性に優れる低硫黄灯油組成物に関する。 The present invention relates to a kerosene composition, particularly a kerosene composition used for petroleum stoves, and more particularly to a low-sulfur kerosene composition having excellent oxidation stability.
現在石油ストーブに使用されている灯油の種類と規格は、日本工業規格（ＪＩＳ Ｋ２２０３）に示されており、その中でも１号灯油は、家庭用の暖房機器等に広く用いられている。灯油留分は主に、原油を常圧蒸留により所定の蒸留性状となるように分留することで得られる。そして、一般に、次いで水素化脱硫装置により硫黄分が所定量以下となるように水素化精製され、更に灯油製造過程において、ストリッパにより軽質分を蒸発させることにより引火点が４０℃以上となるように調整される。 The types and standards of kerosene currently used in oil stoves are shown in the Japanese Industrial Standard (JIS K2203), and among these, No. 1 kerosene is widely used for household heating equipment and the like. The kerosene fraction is mainly obtained by fractionating crude oil by atmospheric distillation so as to have a predetermined distillation property. In general, the hydrodesulfurization unit is then hydrorefined so that the sulfur content becomes a predetermined amount or less, and further, in the kerosene production process, the light component is evaporated by a stripper so that the flash point becomes 40 ° C. or higher. Adjusted.
このようにして得られる灯油の品質は、前述したようにＪＩＳ Ｋ２２０３に示される規格に基づき管理されているが、実用面では規格外の品質として酸化安定性も、長期間劣化することなく安定して貯蔵（備蓄）するためなどの観点から、重要である。そして、灯油の酸化安定性を向上させる方法として、酸化防止剤を添加する技術が知られている（例えば、特許文献１、特許文献２参照）。しかし、この技術は、酸化防止剤の作用に依存するものであって、灯油そのもの自体の酸化安定性の改善が望まれる。また、灯油の臭気や燃焼性を良好にする技術に関する提案もあるが（例えば、特許文献３、特許文献４参照）、この提案も灯油そのもの自体の酸化安定性の向上には至っていない。
また、近年、環境保全の観点から、環境負荷の少ない低硫黄の灯油が求められるようになっている。
The quality of kerosene obtained in this way is managed based on the standard shown in JIS K2203 as described above. However, in practical use, oxidation stability is stable without deterioration for a long time as quality outside the standard. It is important from the viewpoint of storing (stocking). And the technique of adding antioxidant is known as a method of improving the oxidation stability of kerosene (for example, refer to patent documents 1 and patent documents 2). However, this technique relies on the action of the antioxidant, and it is desired to improve the oxidation stability of the kerosene itself. There are also proposals regarding techniques for improving the odor and combustibility of kerosene (see, for example, Patent Document 3 and Patent Document 4), but this proposal has not improved the oxidation stability of kerosene itself.
In recent years, low sulfur kerosene with low environmental impact has been demanded from the viewpoint of environmental conservation.
本発明の目的は、上記従来の状況に鑑み、灯油組成物自体の酸化安定性を改善した低硫黄灯油組成物を提供することにある。 An object of the present invention is to provide a low-sulfur kerosene composition in which the oxidation stability of the kerosene composition itself is improved in view of the above-described conventional situation.
本発明者は、上記目的を達成するために鋭意検討を行った結果、硫黄分が１０質量ｐｐｍ以下の超低硫黄灯油に、特定の組成を有する脱硫率が低い灯油留分を特定量配合することにより、これら灯油留分が酸化防止剤と同様の機能を発現し、酸化安定性が大きく向上した灯油組成物が得られるという知見を得て本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventor blends a specific amount of a kerosene fraction having a specific composition and a low desulfurization rate into an ultra-low sulfur kerosene having a sulfur content of 10 mass ppm or less. Thus, the present inventors have completed the present invention by obtaining the knowledge that these kerosene fractions exhibit the same function as the antioxidant and can provide a kerosene composition with greatly improved oxidation stability.
すなわち、本発明は、上記目的を達成するために、初留点１３５〜１７０℃、５０％留出温度１６５〜２２０℃、７０％留出温度１７０〜２４０℃、９０％留出温度２１５〜２６５℃、９５留出温度２３０〜２７０℃の蒸留性状を有し、硫黄分５〜１０質量ｐｐｍである灯油組成物Ａと、原油を常圧蒸留して得られる灯油留分であって、初留点１３５〜１７０℃、５０％留出温度１６５〜２２０℃、７０％留出温度１７０〜２４０℃、９０％留出温度２１５〜２６５℃、９５％留出温度２５６〜２７０℃の蒸留性状を有し、芳香族分含有量が２．０〜１９．７容量％であり、その内２環芳香族分含有量が１．５〜５．０容量％であり、３環以上芳香族分含有量が０．５容量％以下である組成を有し、高速液体クロマトグラフ法（ＨＰＬＣ）により燃料油組成物を芳香族分と飽和分に分画採取した後、ガスクロマトグラフ法−質量分析法（ＧＣ−ＭＳ）で分析した芳香族分を、ＡＳＴＭＤ３２３９に従って解析することにより算出される、芳香族分中のナフテンベンゼン類含有割合が１５容量％以下、高速液体クロマトグラフ法（ＨＰＬＣ）により燃料油組成物を芳香族分と飽和分に分画採取した後、ガスクロマトグラフ−質量分析法（ＧＣ−ＭＳ）で分析した芳香族分を、ＡＳＴＭＤ３２３９に従って解析することにより算出される、芳香族分中のナフタレン類割合を、ＪＰＩ−５Ｓ−４９−９７により求めた芳香族分割合に乗ずることで、灯油組成物中のナフタレン類割合を求め、更にＪＰＩ−５Ｓ−４９−９７により求めた２環芳香族類割合で除する事で算出される、２環芳香族分中のナフタレン類含有割合が９５容量％以上であり、硫黄分が０．０５〜０．４質量％である灯油組成物Ｂを前記灯油組成物Ａに対して０．１〜５容量％とを含有し、硫黄分が８０質量ｐｐｍ以下であることを特徴とする灯油組成物を提供する。 That is, in order to achieve the above object, the present invention has an initial boiling point of 135 to 170 ° C, a 50% distillation temperature of 165 to 220 ° C, a 70% distillation temperature of 170 to 240 ° C, and a 90% distillation temperature of 215 to 265. ° C., has a distillation property of 95 distillation temperature 230 to 270 ° C., and kerosene composition a is a sulfur content of 5 to 10 wt pp m, a kerosene fraction obtained by atmospheric distillation of crude oil, first Distillation properties of a boiling point of 135 to 170 ° C, a 50% distillation temperature of 165 to 220 ° C, a 70% distillation temperature of 170 to 240 ° C, a 90% distillation temperature of 215 to 265 ° C, and a 95% distillation temperature of 256 to 270 ° C. Having an aromatic content of 2.0 to 19.7 % by volume, of which the bicyclic aromatic content is 1.5 to 5.0% by volume, and containing 3 or more rings of aromatic content the amount has the composition is less than 0.5 volume%, high-performance liquid chromatography (HPLC) After fractionation collected more fuel oil composition saturates the aromatic component, gas chromatography - mass spectrometry aromatic fraction was analyzed by (GC-MS), it is calculated by analyzing according to ASTMD3239, aromatic After the naphthenebenzene content in the group is 15% by volume or less and the fuel oil composition is fractionated into an aromatic component and a saturated component by high performance liquid chromatography (HPLC), gas chromatography-mass spectrometry (GC -MS) by multiplying the aromatic fraction determined by JPI-5S-49-97, calculated by analyzing the aromatic content analyzed in accordance with ASTM D3239, by the ratio of naphthalenes in the aromatic content, seeking naphthalenes proportion of kerosene composition, it is calculated by further dividing the 2 ring aromatics fraction determined by JPI-5S-49-97, 2 TamakiKaoru The kerosene composition B having a naphthalene content in the group of 95% by volume or more and a sulfur content of 0.05 to 0.4% by mass is 0.1 to 5% by volume with respect to the kerosene composition A. And a kerosene composition characterized by having a sulfur content of 80 ppm by mass or less.
本発明の灯油組成物は、酸化安定性に優れ、例えば４３℃で１３週間貯蔵してもパーオキサイドが発生せず、長期間劣化することなく安定して貯蔵することができ、また低硫黄であって、実用上有用である。 The kerosene composition of the present invention is excellent in oxidation stability, for example, does not generate peroxide even when stored at 43 ° C. for 13 weeks, can be stored stably without deterioration for a long time, and has low sulfur. And practically useful.
以下、本発明を詳細に説明する。
まず、本発明で用いる灯油組成物Ａについて説明する。本発明で用いる灯油組成物Ａは、超低硫黄灯油組成物であって、含まれる硫黄分は１０質量ｐｐｍ以下、好ましくは９質量ｐｐｍ以下である。硫黄分が１０質量ｐｐｍ以下であることは、脱硫率が低い灯油組成物Ｂを配合した際にも、硫黄分に由来する臭気等を抑制することができる。
Hereinafter, the present invention will be described in detail.
First, the kerosene composition A used in the present invention will be described. The kerosene composition A used in the present invention is an ultra-low sulfur kerosene composition, and the contained sulfur content is 10 ppm by mass or less, preferably 9 ppm by mass or less. When the sulfur content is 10 ppm by mass or less, the odor derived from the sulfur content can be suppressed even when the kerosene composition B having a low desulfurization rate is blended.
なお、本発明において、硫黄分は、ＪＩＳ Ｋ２５４１の微量電量滴定式酸化法により測定される。 In the present invention, the sulfur content is measured by a microcoulometric titration method according to JIS K2541.
本発明で用いる灯油組成物Ａの蒸留性状は、初留点１３５〜１７０℃、５０％留出温度１６５〜２２０℃、７０％留出温度１７０〜２４０℃、９０％留出温度２１５〜２６５℃、９５％留出温度２３０〜２７０℃であり、好ましくは、初留点１４０〜１６５℃、５０％留出温度１７０〜２２０℃、７０％留出温度１７５〜２４０℃、９０％留出温度２２０〜２６５℃、９５％留出温度２３５〜２７０℃である。初留点が１７０℃以内であることで着火性が優れる。初留点が１３５℃以上であれば、引火点が高く保て、ＪＩＳ Ｋ２２０３で定められる灯油の引火点規格値である４０℃を下回る可能性が低い。 The distillation properties of the kerosene composition A used in the present invention are as follows: initial boiling point 135 to 170 ° C., 50% distillation temperature 165 to 220 ° C., 70% distillation temperature 170 to 240 ° C., 90% distillation temperature 215 to 265 ° C. 95% distillation temperature 230-270 ° C., preferably initial distillation point 140-165 ° C., 50% distillation temperature 170-220 ° C., 70% distillation temperature 175-240 ° C., 90% distillation temperature 220 ~ 265 ° C, 95% distillation temperature 235-270 ° C. When the initial boiling point is within 170 ° C., the ignitability is excellent. If the initial boiling point is 135 ° C. or higher, the flash point is kept high, and there is a low possibility that the flash point will fall below 40 ° C., which is the flash point standard value of kerosene defined in JIS K2203.
また、５０％留出温度が２２０℃以内、７０％留出温度が２４０℃以内、９０％留出温度が２６５℃以内、９５％留出温度が２７０℃以内であれば、着火しやすいため定常燃焼に至るまでに時間がかからない。また、５０％留出温度が１６５℃以上、７０％留出温度が１７０℃以上、９０％留出温度が２１５℃以上、９５％留出温度が２３０℃以上であれば、芯式・放射形石油ストーブ使用時において、炎を燃焼筒の上部から出さずに、燃焼筒を赤熱した状態に保つという安定した燃焼状態を保つことができ、また消火の際も鎮火しやすい。 Also, if the 50% distillation temperature is within 220 ° C, the 70% distillation temperature is within 240 ° C, the 90% distillation temperature is within 265 ° C, and the 95% distillation temperature is within 270 ° C, it is easy to ignite, so that it is steady. It takes no time to reach combustion. If the 50% distillation temperature is 165 ° C or higher, the 70% distillation temperature is 170 ° C or higher, the 90% distillation temperature is 215 ° C or higher, and the 95% distillation temperature is 230 ° C or higher, the core type / radial type When using an oil stove, it is possible to maintain a stable combustion state in which the combustion cylinder is kept in a red-heated state without emitting a flame from the upper part of the combustion cylinder, and it is easy to extinguish the fire.
なお、本発明において、蒸留性状は、ＪＩＳ Ｋ２２５４の常圧法蒸留試験により測定される。 In the present invention, the distillation property is measured by the atmospheric pressure distillation test of JIS K2254.
本発明で用いる灯油組成物Ａの製造方法は、特に制限されるものではなく種々の製造方法によることができて、市販溶剤の混合、あるいは本発明で灯油組成物Ａの性状として規定する性状を有するように種々の原料を精製することなどで得ることができる。例えば、この灯油組成物Ａの製造に、原油を常圧蒸留して得られる灯油留分やそれらを脱硫した脱硫灯油を用いることができる。更に、直接脱硫装置から得られる直接脱硫灯油留分、及び重油や残油の水素化分解により得られる灯油留分等が使用可能であり、その原料は特に限定されない。 The production method of the kerosene composition A used in the present invention is not particularly limited, and can be produced by various production methods. The properties specified as the properties of the kerosene composition A in the present invention can be mixed or mixed with a commercially available solvent. It can be obtained by purifying various raw materials so as to have it. For example, a kerosene fraction obtained by atmospheric distillation of crude oil or a desulfurized kerosene obtained by desulfurizing them can be used for the production of the kerosene composition A. Furthermore, a direct desulfurized kerosene fraction obtained from a direct desulfurization apparatus, a kerosene fraction obtained by hydrocracking heavy oil or residual oil, and the like can be used, and the raw materials thereof are not particularly limited.
次に、本発明で用いる灯油組成物Ｂについて説明する。
本発明で用いる灯油組成物Ｂの蒸留性状は、初留点１３５〜１７０℃、５０％留出温度１６５〜２２０℃、７０％留出温度１７０〜２４０℃、９０％留出温度２１５〜２６５℃、９５％留出温度２３０〜２７０℃であり、好ましくは、初留点１４０〜１６５℃、５０％留出温度１７０〜２２０℃、７０％留出温度１７５〜２４０℃、９０％留出温度２２０〜２６５℃、９５％留出温度２３５〜２７０℃である。灯油組成物Ｂの蒸留性状が、灯油組成物Ａの蒸留性状と同様の上記範囲以内にあれば、この灯油組成物Ｂを灯油組成物Ａに配合した際に、得られる配合物の蒸留性状を、前述の灯油組成物Ａの蒸留性状の適正範囲に収めることが可能となる。
Next, the kerosene composition B used in the present invention will be described.
The distillation properties of the kerosene composition B used in the present invention are as follows: initial boiling point 135 to 170 ° C., 50% distillation temperature 165 to 220 ° C., 70% distillation temperature 170 to 240 ° C., 90% distillation temperature 215 to 265 ° C. 95% distillation temperature 230-270 ° C., preferably initial distillation point 140-165 ° C., 50% distillation temperature 170-220 ° C., 70% distillation temperature 175-240 ° C., 90% distillation temperature 220 ~ 265 ° C, 95% distillation temperature 235-270 ° C. If the distillation property of the kerosene composition B is within the above range similar to the distillation property of the kerosene composition A, when the kerosene composition B is blended with the kerosene composition A, the distillation property of the resulting composition is It becomes possible to be within the proper range of the distillation properties of the above-mentioned kerosene composition A.
本発明で用いる灯油組成物Ｂの組成は、芳香族分含有量が１．５〜３０容量％、好ましくは２．０〜２５容量％である。芳香族分が３０容量％以内であれば、灯油組成物Ａに配合した際に、得られる配合物の芳香族分が多くなることを防ぎ、その燃焼性が良好になる。また、芳香族分が１．５容量％以上であれば、灯油組成物Ａに配合した際に、得られる配合物の酸化安定性を向上させる効果が大きくなる。
なお、本発明において、芳香族分の含有割合（組成割合）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）」に基づいて求められる。
The composition of the kerosene composition B used in the present invention has an aromatic content of 1.5 to 30% by volume, preferably 2.0 to 25% by volume. When the aromatic content is within 30% by volume, when blended with the kerosene composition A, the aromatic content of the resulting blend is prevented from increasing, and its combustibility is improved. Moreover, if an aromatic content is 1.5 volume% or more, when mix | blending with the kerosene composition A, the effect of improving the oxidation stability of the compound obtained will become large.
In addition, in this invention, the content rate (composition rate) of aromatic content is calculated | required based on JPI-5S-49-97 "petroleum product-hydrocarbon type test method-high performance liquid chromatograph method (HPLC)".
本発明で用いる灯油組成物Ｂは、２環芳香族分含有量が、上記芳香族分１．５〜３０容量％の内の１．５〜５．０容量％、好ましくは２．０〜４．０容量％である。そして、３環以上芳香族分含有量が、上記芳香族分１．５〜３０容量％の内の０．５容量％以下である。２環芳香族分含有量が５．０容量％以内、３環以上芳香族分含有量が０．５容量％以内ならば、灯油組成物Ａに配合した際に、得られる配合物の多環芳香族分が多くなることを防ぎ、その燃焼性が良好となる。また、２環芳香族分が１．５容量％以上ならば、灯油組成物Ａに配合した際に、得られる配合物の酸化安定性を向上させる効果が大きくなる。 The kerosene composition B used in the present invention has a bicyclic aromatic content of 1.5 to 5.0% by volume of the aromatic content of 1.5 to 30% by volume, preferably 2.0 to 4%. 0.0% by volume. And 3 ring or more aromatic content is 0.5 volume% or less in said aromatic content 1.5-30 volume%. If the content of bicyclic aromatics is within 5.0% by volume, and the content of aromatics of 3 or more rings is within 0.5% by volume, when blended with kerosene composition A, the resulting polycyclic The aromatic content is prevented from increasing and the combustibility is improved. Further, when the bicyclic aromatic content is 1.5% by volume or more, when blended with the kerosene composition A, the effect of improving the oxidation stability of the resulting blend is increased.
なお、本発明において、２環芳香族分及び３環以上芳香族分の含有割合は、ＪＰＩ−５Ｓ−４９−９７に基づいて求められる。 In addition, in this invention, the content rate of 2 ring aromatic content and 3 or more ring aromatic content is calculated | required based on JPI-5S-49-97.
本発明で用いる灯油組成物Ｂは、芳香族分中のナフテンベンゼン類含有割合が１５容量％以下、好ましくは１３容量％以下であり、２環芳香族分中のナフタレン類含有割合が９５容量％以上、好ましくは９７容量％以上である。芳香族分中のナフテンベンゼン類含有割合が１５容量％以下、２環芳香族分中のナフタレン類含有割合が９５容量％以上であれば、灯油組成物Ａに配合した際に、得られる配合物の酸化安定性を向上させる効果が大きくなる。 The kerosene composition B used in the present invention has a naphthenebenzene content in the aromatic content of 15% by volume or less, preferably 13% by volume or less, and a naphthalene content in the bicyclic aromatic content of 95% by volume. Above, preferably 97% by volume or more. A blend obtained when blended with kerosene composition A if the naphthenebenzene content in aromatics is 15% by volume or less and the naphthalene content in bicyclic aromatics is 95% by volume or more The effect of improving the oxidation stability of is increased.
なお、本発明において、芳香族分中のナフテンベンゼン類及びナフタレン類含有割合は、高速液体クロマトグラフ法（ＨＰＬＣ）により燃料油組成物を芳香族分と飽和分に分画採取した後、芳香族分をガスクロマトグラフ法−質量分析法（ＧＣ−ＭＳ）で分析し、ＡＳＴＭＤ ３２３９に従って解析することにより算出される。そして、ここで得られた芳香族分中のナフタレン類割合を、ＪＰＩ−５Ｓ−４９−９７により求めた芳香族分割合に乗ずることで、灯油組成物中のナフタレン類割合を求め、更にＪＰＩ−５Ｓ−４９−９７により求めた２環芳香族類割合で除することで、２環芳香族中のナフタレン類割合が算出される。 In the present invention, the content of naphthenebenzenes and naphthalenes in the aromatic component is determined after the fuel oil composition is fractionated into an aromatic component and a saturated component by high performance liquid chromatography (HPLC). The minute is analyzed by gas chromatography-mass spectrometry (GC-MS) and calculated according to ASTM D 3239. Then, the ratio of naphthalenes in the aromatic content obtained here is multiplied by the aromatic content ratio determined according to JPI-5S-49-97, so that the ratio of naphthalenes in the kerosene composition is determined. By dividing by the ratio of the bicyclic aromatics determined by 5S-49-97, the ratio of naphthalenes in the bicyclic aromatics is calculated.
ここで言うナフテンベンゼン類とは、テトラリン及びそのアルキル置換基誘導体や、インダン及びそのアルキル置換基誘導体等を示し、ナフタレン類とは、ナフタレン及びそのアルキル置換基誘導体等を示す。 The naphthenebenzenes mentioned here refer to tetralin and its alkyl substituent derivatives, indane and its alkyl substituent derivatives, and the like, and the naphthalenes refer to naphthalene and its alkyl substituent derivatives and the like.
本発明で用いる灯油組成物Ｂの製造方法は、特に制限されるものではなく種々の製造方法によることができるが、主に原油を常圧蒸留して得られる灯油留分やそれらを脱硫した脱硫灯油を用いて製造することができる。更に、直接脱硫装置から得られる直接脱硫灯油留分、及び重油や残油の水素化分解により得られる灯油留分等が使用可能であり、その原料は特に限定されない。 The production method of the kerosene composition B used in the present invention is not particularly limited and can be based on various production methods. The kerosene fraction obtained mainly by atmospheric distillation of crude oil and desulfurization obtained by desulfurizing them. It can be manufactured using kerosene. Furthermore, a direct desulfurized kerosene fraction obtained from a direct desulfurization apparatus, a kerosene fraction obtained by hydrocracking heavy oil or residual oil, and the like can be used, and the raw materials thereof are not particularly limited.
但し、本発明で用いる灯油組成物Ｂは、脱硫率が低い方が好ましく、硫黄分が０．０５〜０．４質量％、好ましくは０．１０〜０．４質量％である。脱硫率が低く、硫黄分が０．０５質量％以上であれば、灯油組成物Ａに配合した際に、得られる配合物の酸化安定性を向上させる効果が大きくなる。一方、硫黄分が０．４質量％以内ならば、灯油組成物Ａに配合した際に、得られる配合物の硫黄分の増加を抑制でき、硫黄分に由来する臭気等を抑制することができる。 However, the kerosene composition B used in the present invention preferably has a lower desulfurization rate and has a sulfur content of 0.05 to 0.4 mass%, preferably 0.10 to 0.4 mass%. When the desulfurization rate is low and the sulfur content is 0.05% by mass or more, the effect of improving the oxidative stability of the resulting blend when blended with the kerosene composition A is increased. On the other hand, if the sulfur content is within 0.4% by mass, an increase in the sulfur content of the resulting composition can be suppressed when blended with the kerosene composition A, and odors derived from the sulfur content can be suppressed. .
本発明に係る灯油組成物は、上記の灯油組成物Ａに灯油組成物Ｂを、灯油組成物Ａ基準で０．１〜５．０容量％、好ましくは０．３〜４．０容量％配合して調製される。灯油組成物Ａに灯油組成物Ｂを０．１容量％以上配合することにより、所期の酸化安定性向上効果が得られ、配合量を５容量％以下にすることにより、硫黄分の増加を抑制し、硫黄分に由来する臭気等を抑制することができる。本発明に係る灯油組成物の調製に際しての灯油組成物Ｂの灯油組成物Ａへの配合は、灯油組成物Ａと灯油組成物Ｂとを任意の手段で混合することによって行うことができる。 The kerosene composition according to the present invention contains the kerosene composition B in the kerosene composition A described above in an amount of 0.1 to 5.0% by volume, preferably 0.3 to 4.0% by volume, based on the kerosene composition A. Prepared. By blending kerosene composition B with kerosene composition A in an amount of 0.1% by volume or more, the desired effect of improving oxidative stability can be obtained. It can suppress and the odor etc. which originate in a sulfur content can be suppressed. In the preparation of the kerosene composition according to the present invention, the kerosene composition B can be blended into the kerosene composition A by mixing the kerosene composition A and the kerosene composition B by any means.
本発明に係る灯油組成物の硫黄分は、８０質量ｐｐｍ以下であり、５０質量ｐｐｍ以下であることが好ましい。これにより、硫黄分に由来する臭気等を抑制することができる。 The sulfur content of the kerosene composition according to the present invention is 80 ppm by mass or less, and preferably 50 ppm by mass or less. Thereby, the odor etc. which originate in a sulfur content can be suppressed.
また、本発明に係る灯油組成物においては、必要に応じて種々の燃料油添加剤を適宜添加することができる。この燃料油添加剤としては、シッフ型化合物やチオアミド型化合物等の金属不活性剤、有機りん系化合物等の表面着火防止剤、琥珀酸イミド、ポリアルキルアミン、ポリエーテルアミン等の清浄分散剤、多価アルコール及びそのエーテル等の氷結防止剤、有機酸のアルカリ金属やアルカリ土類金属塩、高級アルコールの硫酸エステル等の助燃剤、アニオン系界面活性剤、カチオン系界面活性剤、両性界面活性剤等の帯電防止剤、アルケニル琥珀酸エステル等の錆止め剤等の公知の燃料油添加剤が挙げられる。また、本発明に係る灯油組成物は、前述のとおり酸化防止剤を添加するまでもなく酸化安定性に優れるものであるが、必要に応じてフェノール系、アミン系等の公知の酸化防止剤を添加することを妨げるものではない。上記各種添加剤は、１種添加することも複数種組み合わせて添加することもできる。また、これらの添加剤の添加量は必要に応じて適宜設定することができる。 Moreover, in the kerosene composition which concerns on this invention, various fuel oil additives can be added suitably as needed. Examples of the fuel oil additive include metal deactivators such as Schiff type compounds and thioamide type compounds, surface ignition preventives such as organophosphorus compounds, detergent dispersants such as succinimide, polyalkylamine, and polyetheramine. Anti-icing agents such as polyhydric alcohols and ethers thereof, organic metal alkali metal and alkaline earth metal salts, auxiliary alcohols such as higher alcohol sulfates, anionic surfactants, cationic surfactants, amphoteric surfactants And known fuel oil additives such as antistatic agents such as alkenyl succinate and the like. In addition, the kerosene composition according to the present invention is excellent in oxidation stability without adding an antioxidant as described above, but if necessary, a known antioxidant such as a phenol type or an amine type may be used. It does not prevent the addition. The above various additives can be added singly or in combination. Moreover, the addition amount of these additives can be suitably set as needed.
本発明に係る灯油組成物は、所謂民生用暖房機器、例えば各種石油ストーブ類、石油ファンヒーター類、あるいは石油式給湯器等に好ましく用いることができ、更には直火式の食品乾燥用燃料、工業用燃料、石油発動機用燃料、ソルベント等各種用途にも好ましく使用できる。 The kerosene composition according to the present invention can be preferably used for so-called consumer heaters, for example, various petroleum stoves, petroleum fan heaters, petroleum-type water heaters, and the like. It can be preferably used for various uses such as industrial fuel, petroleum engine fuel, and solvent.
次に、本発明を実施例、比較例により更に具体的に説明する。なお、本発明は、これらの例によって何ら制限されるものではない。 Next, the present invention will be described more specifically with reference to examples and comparative examples. In addition, this invention is not restrict | limited at all by these examples.
以下の実施例、比較例において、引火点、蒸留性状、硫黄分、煙点は、ＪＩＳ Ｋ２２０３に定められる方法に準拠して測定を行なった。 In the following examples and comparative examples, the flash point, distillation properties, sulfur content, and smoke point were measured according to the method defined in JIS K2203.
貯蔵試験は下記条件で行った。
試験温度：４３℃
試料量：６５０ｍｌ
容器材質：ほう珪酸ガラス
容器容量：１０００ｍｌ
雰囲気：大気開放
光の有無：暗所、
鋼片（ＳＰＣＣ）：１×２０×５０ｍｍを１枚入れる
試験期間：１３週間
貯蔵試験後のパーオキサイド測定：ＪＰＩ−５Ｓ−４６−９６に準拠
The storage test was conducted under the following conditions.
Test temperature: 43 ° C
Sample volume: 650ml
Container material: Borosilicate glass Container capacity: 1000 ml
Atmosphere: Open to air Presence of light: Dark place,
Steel slab (SPCC): 1x20x50mm is put in. Test period: 13 weeks Peroxide measurement after storage test: Conforms to JPI-5S-46-96
飽和分、芳香族分の割合と、芳香族分の環数別割合は、ＪＰＩ−５Ｓ−４９−９７に基づいて測定を行った。ＨＰＬＣの装置構成及び分析条件を以下に示す。 The ratio of the saturated component, the aromatic component, and the aromatic component according to the number of rings were measured based on JPI-5S-49-97. The apparatus configuration and analysis conditions of HPLC are shown below.
装置：Ａｇｉｌｅｎｔ １１００ Ｓｅｒｉｅｓ（ＡＬＳ：Ｇ１３２９Ａ，Ｂｉｎ Ｐｕｍｐ：Ｇ１３１２Ａ，Ｄｅｇａｓｓｅｒ：Ｇ１３７９Ａ，Ｒｉｄ：Ｇ１３６２Ａ，Ｃｏｌｃｏｍ：Ｇ１３１６Ａ）
移動相：ｎ−ヘキサン
流量：１．０ｍｌ／ｍｉｎ
カラム：硝酸銀含浸シリカカラム（４．６ｍｍｌ．Ｄ．＊７０ｍｍＬ．センシュー科学製 ＡｇＮＯ３−１０７１−Ｙ）：アミン修飾カラム（４．０ｍｍｌ．Ｄ．＊２５０ｍｍＬ．２本 センシュー科学製 ＬＩＣＨＲＯＳＯＲＢ−ＮＨ２）
カラム温度：３５℃
試料濃度：１０ｖｏｌ％
注入量：５μｌ
Equipment: Agilent 1100 Series (ALS: G1329A, Bin Pump: G1312A, Degasser: G1379A, Rid: G1362A, Colcom: G1316A)
Mobile phase: n-hexane Flow rate: 1.0 ml / min
Column: Silver nitrate impregnated silica column (4.6 ml. D. * 70 mm L. Senshu Scientific AgNO 3 -1071-Y): Amine modified column (4.0 ml. D. * 250 mm L. 2 Senshu Scientific LICHROSORB-NH 2 )
Column temperature: 35 ° C
Sample concentration: 10 vol%
Injection volume: 5 μl
また、飽和分、芳香族分のタイプ分析は下記方法で行なった。
まず、試料をＨＰＬＣにより飽和分と芳香族分に分画後、飽和分、芳香族分それぞれについて、ＧＣ−ＭＳによりタイプ分析を行なった。ここで得られた分析結果を基に、飽和分はＡＳＴＭＤ ２７８６に、芳香族分はＡＳＴＭ Ｄ ３２３９に従って解析を行い、飽和分中のナフテン類割合と環数別ナフテン類割合、及び芳香族分中のナフテンベンゼン類割合とナフタレン類割合を求めた。分析条件を以下に示す。
Moreover, the type analysis of the saturated content and the aromatic content was performed by the following method.
First, after fractionating the sample into a saturated component and an aromatic component by HPLC, type analysis was performed on each of the saturated component and the aromatic component by GC-MS. Based on the analysis results obtained here, the saturation content was analyzed according to ASTM D 2786, the aromatic content was analyzed according to ASTM D 3239, the naphthene ratio in the saturation content and the naphthene ratio by number of rings, and the aromatic content. The ratio of naphthenebenzenes and naphthalenes was determined. The analysis conditions are shown below.
装置：ＨＰ−６８９０ ＨＰ５９７３ 四重極質量分析計
カラム：ＤＢ−１：３０ｍ×０．２５ｍｍＩ．Ｄ．×０．２５μｍ
オーブン温度：４０℃（１ｍｉｎ）→１０℃／ｍｉｎ→２８０℃（５ｍｉｎ）
注入口温度：４３℃ Ｏｖｅｎ ｔｒａｃｋ ｍｏｄｅ ＯＮ
インターフェース温度：３００℃
キャリアーガス：Ｈｅ：５５ＫＰａ Ｃｏｎｓｔａｎｔ ｆｌｏｗ ｍｏｄｅ ＯＮ
Ｓｏｌｖｅｎｔ Ｄｅｌａｙ：４．５ｍｉｎ
質量範囲：５０〜５００ Ｔｈｒｅｓｈｏｌｄ＝１００ Ｓａｍｐｌｉｎｇ♯３
イオン化電圧：７０ｅＶ
注入方法：オンカラム注入 ３．０μｌ（芳香族分）、１．０μｌ（飽和分）
Apparatus: HP-6890 HP5973 Quadrupole mass spectrometer Column: DB-1: 30 m × 0.25 mm I.D. D. × 0.25μm
Oven temperature: 40 ° C. (1 min) → 10 ° C./min→280° C. (5 min)
Inlet temperature: 43 ° C. Even track mode ON
Interface temperature: 300 ° C
Carrier gas: He: 55 KPa Constant flow mode ON
Solvent Delay: 4.5min
Mass range: 50-500 Threshold = 100 Sampling # 3
Ionization voltage: 70 eV
Injection method: On-column injection 3.0 μl (aromatic content), 1.0 μl (saturated content)
実施例１
原油を常圧蒸留することで得られた沸点範囲１４９〜２７１℃の灯油留分を、反応温度（ＷＡＢＴ）３２０℃、水素分圧４．５ＭＰａ、液空間速度（ＬＨＳＶ）５．２ｈ−１の条件下で脱硫処理して、沸点範囲１４９〜２６９℃、硫黄分９質量ｐｐｍの灯油組成物Ａを得た。そして、それに、原油を常圧蒸留することで得た沸点範囲１４９〜２７１℃、硫黄分０．１９質量％の灯油組成物Ｂを１容量％配合することにより灯油組成物を得た。灯油組成物Ａ、Ｂの性状、及び得られた灯油組成物の硫黄分含有量と、貯蔵試験結果を表１に示す。
Example 1
A kerosene fraction having a boiling range of 149 to 271 ° C. obtained by subjecting crude oil to atmospheric distillation was reacted at a reaction temperature (WABT) of 320 ° C., a hydrogen partial pressure of 4.5 MPa, and a liquid space velocity (LHSV) of 5.2 h −1 . A desulfurization treatment was performed under conditions to obtain a kerosene composition A having a boiling range of 149 to 269 ° C. and a sulfur content of 9 mass ppm. And the kerosene composition was obtained by mix | blending 1 vol% of kerosene composition B with a boiling-point range 149-271 degreeC obtained by carrying out atmospheric pressure distillation of crude oil and 0.19 mass% of sulfur content to it. Table 1 shows the properties of the kerosene compositions A and B, the sulfur content of the obtained kerosene composition, and the storage test results.
実施例２
原油を常圧蒸留することで得られた沸点範囲１３９〜２８９℃の直留灯油留分を、反応温度（ＷＡＢＴ）３１５℃、水素分圧５．５ＭＰａ、液空間速度（ＬＨＳＶ）３．０ｈ−１の条件下で脱硫処理して、沸点範囲１４６〜２９１℃、硫黄分５質量ｐｐｍの灯油組成物Ａを得た。そして、それに、原油を常圧蒸留することで得た沸点範囲１４０〜２８２℃、硫黄分０．１５質量％の灯油組成物Ｂを３容量％配合することにより灯油組成物を得た。灯油組成物Ａ、Ｂの性状、及び得られた灯油組成物の硫黄分含有量と、貯蔵試験結果を表１に示す。
Example 2
A straight-run kerosene fraction having a boiling point range of 139 to 289 ° C. obtained by atmospheric distillation of crude oil was converted into a reaction temperature (WABT) of 315 ° C., a hydrogen partial pressure of 5.5 MPa, and a liquid space velocity (LHSV) of 3.0 h − The kerosene composition A having a boiling point range of 146 to 291 ° C. and a sulfur content of 5 mass ppm was obtained by desulfurization treatment under the condition 1 . And the kerosene composition was obtained by mix | blending 3 vol% kerosene composition B with a boiling point range 140-282 degreeC obtained by carrying out atmospheric pressure distillation of crude oil and 0.15 mass% of sulfur content to it. Table 1 shows the properties of the kerosene compositions A and B, the sulfur content of the obtained kerosene composition, and the storage test results.
比較例１
原油を常圧蒸留することで得られた沸点範囲１３９〜２８９℃の直留灯油留分を、反応温度（ＷＡＢＴ）３１５℃、水素分圧５．５ＭＰａ、液空間速度（ＬＨＳＶ）３．０ｈ−１の条件下で脱硫処理して、沸点範囲１４６〜２９１℃、硫黄分５質量ｐｐｍの灯油組成物Ａを得た。そして、それに灯油組成物Ｂは配合しなかった。灯油組成物Ａの性状、及び灯油組成物Ａの貯蔵試験結果を表２に示す。
Comparative Example 1
A straight-run kerosene fraction having a boiling point range of 139 to 289 ° C. obtained by atmospheric distillation of crude oil was converted into a reaction temperature (WABT) of 315 ° C., a hydrogen partial pressure of 5.5 MPa, and a liquid space velocity (LHSV) of 3.0 h − The kerosene composition A having a boiling point range of 146 to 291 ° C. and a sulfur content of 5 mass ppm was obtained by desulfurization treatment under the condition 1 . And kerosene composition B was not mix | blended with it. Table 2 shows the properties of the kerosene composition A and the storage test results of the kerosene composition A.
比較例２
原油を常圧蒸留することで得られた沸点範囲１３９〜２８９℃の直留灯油留分を、反応温度（ＷＡＢＴ）３１５℃、水素分圧５．５ＭＰａ、液空間速度（ＬＨＳＶ）３．０ｈ−１の条件下で脱硫処理して、沸点範囲１４６〜２９１℃、硫黄分５質量ｐｐｍの灯油組成物Ａを得た。そして、それに、原油を常圧蒸留することで得た沸点範囲１４０〜２８２℃、硫黄分０．１５質量％の灯油組成物Ｂを８容量％配合することにより灯油組成物を得た。
灯油組成物Ａ、Ｂの性状、及び得られた灯油組成物の硫黄分含有量と、貯蔵試験結果を表２に示す。
Comparative Example 2
A straight-run kerosene fraction having a boiling point range of 139 to 289 ° C. obtained by atmospheric distillation of crude oil was converted into a reaction temperature (WABT) of 315 ° C., a hydrogen partial pressure of 5.5 MPa, and a liquid space velocity (LHSV) of 3.0 h − The kerosene composition A having a boiling point range of 146 to 291 ° C. and a sulfur content of 5 mass ppm was obtained by desulfurization treatment under the condition 1 . And the kerosene composition was obtained by mix | blending 8 vol% of kerosene composition B with the boiling-point range 140-282 degreeC obtained by carrying out the atmospheric pressure distillation of crude oil, and 0.15 mass% of sulfur content.
Table 2 shows the properties of the kerosene compositions A and B, the sulfur content of the obtained kerosene composition, and the storage test results.
比較例３
原油を常圧蒸留することで得られた沸点範囲１３９〜２８９℃の直留灯油留分を、反応温度（ＷＡＢＴ）３１５℃、水素分圧５．５ＭＰａ、液空間速度（ＬＨＳＶ）３．０ｈ−１の条件下で脱硫処理して、沸点範囲１４６〜１９１℃、硫黄分５質量ｐｐｍの灯油組成物Ａを得た。そして、それに、原油を常圧蒸留次いで脱硫処理することにより得られた、沸点範囲１５０〜２８９℃、硫黄分５０質量ｐｐｍの灯油組成物Ｂを１容量％配合することにより灯油組成物を得た。灯油組成物Ａ、Ｂの性状、及び得られた灯油組成物の硫黄分含有量と、貯蔵試験結果を表２に示す。
Comparative Example 3
A straight-run kerosene fraction having a boiling point range of 139 to 289 ° C. obtained by atmospheric distillation of crude oil was converted into a reaction temperature (WABT) of 315 ° C., a hydrogen partial pressure of 5.5 MPa, and a liquid space velocity (LHSV) of 3.0 h − The kerosene composition A having a boiling point range of 146 to 191 ° C. and a sulfur content of 5 mass ppm was obtained by desulfurization treatment under the condition 1 . And the kerosene composition was obtained by mix | blending 1 vol% kerosene composition B with a boiling point range of 150-289 degreeC and a sulfur content of 50 mass ppm obtained by carrying out the atmospheric pressure distillation and desulfurization process of crude oil to it. . Table 2 shows the properties of the kerosene compositions A and B, the sulfur content of the obtained kerosene composition, and the storage test results.
上記表１、２に示すとおり、灯油組成物Ｂを配合しない比較例１は、４３℃×１３週間の貯蔵試験後にパーオキサイドが発生した。灯油組成物Ｂを８容量％と多く配合した比較例２は、貯蔵試験後にパーオキサイドは発生しないが、硫黄分が多くなった。そして、灯油組成物Ｂとして、硫黄分０．００５質量％まで超深度脱硫を行なったものを使用した比較例３は、酸化安定性向上効果が小さく、貯蔵試験後においてパーオキサイドが発生した。 As shown in Tables 1 and 2, in Comparative Example 1 in which the kerosene composition B was not blended, peroxide was generated after a storage test at 43 ° C. × 13 weeks. In Comparative Example 2 in which the kerosene composition B was blended as much as 8% by volume, peroxide was not generated after the storage test, but the sulfur content increased. And the comparative example 3 which used what carried out ultra deep desulfurization to 0.005 mass% of sulfur content as the kerosene composition B had little oxidation stability improvement effect, and the peroxide generate | occur | produced after the storage test.
一方、灯油組成物Ｂの性状及び配合量が本発明に規定する範囲を満たす実施例１、２は、硫黄分を抑えつつ、酸化安定性向上効果が大きく、４３℃×１３週間の貯蔵試験後においてパーオキサイドは発生しなかった。 On the other hand, Examples 1 and 2 in which the properties and blending amount of the kerosene composition B satisfy the range defined in the present invention have a large effect of improving the oxidation stability while suppressing the sulfur content, and after a storage test at 43 ° C. for 13 weeks. No peroxide was generated.
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| US10494579B2 (en) | 2016-04-26 | 2019-12-03 | Exxonmobil Research And Engineering Company | Naphthene-containing distillate stream compositions and uses thereof |
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