JP2001019978A - A-fuel oil composition - Google Patents
A-fuel oil compositionInfo
- Publication number
- JP2001019978A JP2001019978A JP11191906A JP19190699A JP2001019978A JP 2001019978 A JP2001019978 A JP 2001019978A JP 11191906 A JP11191906 A JP 11191906A JP 19190699 A JP19190699 A JP 19190699A JP 2001019978 A JP2001019978 A JP 2001019978A
- Authority
- JP
- Japan
- Prior art keywords
- naphthene
- oil
- present
- composition
- fuel oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、Ａ重油組成物に関
する。更に詳しくは、近年の高性能エンジンへ十分な性
能を持ち、かつ、優れた低温流動性を有するＡ重油組成
物に関する。[0001] The present invention relates to a fuel oil A composition. More specifically, the present invention relates to a fuel oil A composition having sufficient performance for a recent high-performance engine and having excellent low-temperature fluidity.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】Ａ重油
はボイラー燃料やディーゼルエンジン燃料として用いら
れているが、近年Ａ重油に使用されるエンジンの高出力
化及び低燃費化等に伴い、Ａ重油としては、より高性能
化の要望が年々高まっている。これら高性能エンジンの
燃料としてＡ重油を用いた場合、着火性の悪化や、煤の
発生が増大してバーナー及び炉内の清掃頻度が増えると
いった燃焼性に関する問題が生じることがある。一方、
Ａ重油としては、ガソリンや灯油に比べ重質分をより多
く含んでいるため、低温時のワックス析出が問題となる
ことがある。低温時におけるワックス析出は、燃料系統
中の夾雑物防止用のフィルターを閉塞させ、最悪の場合
燃料供給が不可能となる恐れがある。低温時のワックス
析出を抑える方法としては、流動性向上剤を添加する方
法が一般的であるが、実際の厳しい冬期の使用条件下で
は充分な効果が発揮できないのが現状である。また、従
来は低温時のフィルター目詰まり性の判断に、目詰まり
点による試験が用いられてきた。この試験方法では流動
性向上剤を添加することにより、低温流動性が改善され
るが、この試験方法は試料油の冷却速度が早く急冷（約
４０℃／時間）であるため、実際の使用条件下とは大き
く異なる。冷却速度が遅ければ遅いほど、析出するワッ
クスが大きくなりフィルターの目詰まりを起こすことが
知られており、目詰まり点による評価では不十分である
ことが分かっている。一般に、低温性能に優れたＡ重油
は、燃焼性が悪くなる場合が多く、これら全ての性能を
同時に満たすＡ重油が望まれている。本発明の目的は、
近年の高性能エンジンへの使用に耐え得り、かつ冬期に
おいてワックスによるフィルターの目詰まりを起こさな
いＡ重油組成物を提供することにある。2. Description of the Related Art Fuel oil A is used as boiler fuel and diesel engine fuel. However, in recent years, with the increase in output and fuel efficiency of engines used for fuel oil A, fuel oil A has been developed. As fuel oil, demands for higher performance are increasing year by year. When heavy fuel oil A is used as fuel for these high-performance engines, problems with flammability such as deterioration of ignitability and frequency of cleaning the burner and the furnace due to increased generation of soot may occur. on the other hand,
Heavy fuel oil A contains more heavy components than gasoline and kerosene, so that wax precipitation at low temperatures may become a problem. The deposition of wax at low temperatures may block the filter for preventing foreign substances in the fuel system, and in the worst case, make it impossible to supply fuel. As a method of suppressing wax deposition at low temperatures, a method of adding a fluidity improver is generally used, but at present, a sufficient effect cannot be exerted under actual severe winter use conditions. Conventionally, a test based on a clogging point has been used to determine filter clogging at low temperatures. In this test method, the low-temperature fluidity is improved by adding a fluidity improver. However, in this test method, the cooling rate of the sample oil is fast and rapid cooling (about 40 ° C./hour). Significantly different from below. It is known that the slower the cooling rate, the larger the amount of precipitated wax and clogging of the filter, and it has been found that the evaluation based on the clogging point is insufficient. In general, A fuel oil excellent in low-temperature performance often has poor flammability, and A fuel oil satisfying all these performances at the same time is desired. The object of the present invention is
An object of the present invention is to provide a fuel oil A composition that can withstand the use of recent high-performance engines and that does not cause clogging of filters by wax in winter.
【０００３】[0003]
【課題を解決するための手段】本発明者らは、上記課題
を解決するため鋭意研究を重ねた結果、ナフテン分を特
定の範囲とした場合に、燃焼性が高く、かつ、冬期にお
いてワックスによるフィルターの目詰まりを起こさない
ことを見出し本発明を完成させるに至った。つまり、本
発明のＡ重油組成物は、ナフテン分が４０質量％以上で
あることを特徴とする。また、本発明のＡ重油組成物
は、水素化分解軽油及びエキストラクトを用いて得られ
たものであることが好ましい。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, when the naphthene content is in a specific range, the flammability is high, and the wax is used in winter. They found that clogging of the filter did not occur, and completed the present invention. That is, the heavy oil composition A of the present invention is characterized in that the naphthene content is 40% by mass or more. Further, the heavy oil composition A of the present invention is preferably obtained using a hydrocracked light oil and an extract.
【０００４】[0004]
【発明の実施の形態】以下に、本発明をさらに詳細に説
明する。本発明のＡ重油組成物は、ナフテン分が４０質
量％以上であることが必要である。ナフテン分は、燃焼
性、冬期においてワックスによるフィルターの目詰まり
の防止などの点を、全て同時に満たすことができ、かつ
これらの効果により優れることから、Ａ重油組成物全量
基準でナフテン分が４０質量％以上であることが必要で
あり、４５質量％以上であることが好ましく、５０質量
％以上であることがより好ましく、５５質量％以上であ
ることが最も好ましい。ナフテン分には、一環ナフテン
分、二環ナフテン分、三環以上の多環ナフテン分が含ま
れ、これらここの成分の含有量については特に制限はな
い。しかしながら、燃焼性、冬期においてワックスによ
るフィルターの目詰まりの防止などの点を、全て同時に
満たすことができ、かつこれらの効果にさらにより優れ
ることから、このうち一環ナフテン分がＡ重油組成物全
量基準で２５質量％以上であることが好ましく、３０質
量％以上であることがより好ましく、３５質量％以上で
あることが最も好ましい。本発明において、ナフテン分
および一環ナフテン分とは、ＡＳＴＭ Ｄ２７８６「質
量分析法」に準拠して得られたＡ重油全量を基準とした
値を表すものを意味している。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The heavy oil composition A of the present invention needs to have a naphthene content of 40% by mass or more. The naphthene component can simultaneously satisfy all aspects such as flammability and prevention of clogging of the filter by the wax in winter, and is more excellent by these effects. Therefore, the naphthene component is 40 mass% based on the total amount of the heavy oil A composition. % Or more, preferably 45% by mass or more, more preferably 50% by mass or more, and most preferably 55% by mass or more. The naphthene component includes a mononaphthene component, a bicyclic naphthene component, and a tricyclic or higher polycyclic naphthene component, and the content of these components is not particularly limited. However, all aspects such as combustibility and prevention of filter clogging due to wax in winter can be satisfied at the same time, and these effects are even more excellent. Is preferably 25% by mass or more, more preferably 30% by mass or more, and most preferably 35% by mass or more. In the present invention, the term “naphthene component” and “partial naphthene component” mean a value representing a value based on the total amount of heavy oil A obtained in accordance with ASTM D2786 “Mass Spectrometry”.
【０００５】また、本発明のＡ重油の飽和分、芳香族分
については特に制限はない。しかしながら、燃焼性、冬
期においてワックスによるフィルターの目詰まりの防止
等の点から、飽和分が５５容量％以上であることが好ま
しく、６０％容量以上であることがより好ましく、６５
容量％以上であることがさらにより好ましく、７０％容
量以上であることが特に好ましく、７５容量％以上であ
ることが最も好ましい。また、燃焼性の低減等の点か
ら、芳香族分が４５容量％以下であることが好ましく、
３５容量％以下であることがより好ましく、３０容量％
以下であることがさらにより好ましく、２５容量％以下
であることが最も好ましい。本発明において、飽和分及
び芳香族分とは、ＪＰＩ−５Ｓ−４９−９７「炭化水素
タイプ試験方法−高速液体クロマトグラフ法」に準拠し
て測定された値を表すものを意味している。また、飽和
分にはノルマルパラフィンが含まれるが、この量につい
ても特に制限はない。しかしながら、低温時のワックス
析出を減少させる点から、ノルマルパラフィンは２０質
量％以下であることが好ましく、１５質量％以下である
ことがより好ましい。本発明において、ノルマルパラフ
ィン分は、以下に示すガスクロマトグラフィー法により
定量されるＡ重油組成物全量を基準としたノルマルパラ
フィン分の含有量を表すものを意味している。 １）カラム：ステンレス製 内径０．２５ｍｍ、長さ２
５ｍ ２）インジェクション温度：３６０℃ ３）キャリアーガス：ヘリウム ４）検出器：水素炎イオン化方式（ＦＩＤ） ５）カラム温度速度：８℃／ｍｉｎ（１４０−３５５
℃） また、本発明において、Ａ重油組成物のセタン指数、セ
タン価については特に制限はないが、燃焼性により優れ
る点から、セタン指数が５８以上であることが好まし
く、６０以上であることがより好ましく、セタン価が５
８以上であることが好ましく、６０以上であることがよ
り好ましく、６２以上であることが最も好ましい。本発
明において、セタン指数はＪＩＳ Ｋ ２２０４−１９
９２「軽油」に準拠して得られた値を表すものを意味し
ている。つまり次の式によって算出する。 セタン指数（Ｃ）＝0.49083＋1.06577（Ｘ）−0.001052
2（Ｘ）2 Ｘ＝97.833（ｌｏｇＡ）2＋2.2088ＢｌｏｇＡ＋0.01247
Ｂ2−423.51ｌｏｇＡ−4.7808Ｂ＋419.59 Ａ：（9/5）［101.3ｋＰａ（760ｍｍＨｇ）における50
％留出温度（℃）］＋32 Ｂ：ＡＰＩ度 （101.3ｋＰａ（760ｍｍＨｇ）における50％留出温度
（℃）は、ＪＩＳ Ｋ２２５４「石油製品−蒸留試験方
法」によって測定し、ＡＰＩ度は、ＪＩＳＫ ２２４９
「原油及び石油製品−密度試験方法及び密度・質量・容
量換算表」によって１５℃の密度から換算して求め
る。） また、セタン価とは、ＪＩＳ Ｋ ２２８０「石油製品
−燃料油−オクタン価及びセタン価試験方法並びにセタ
ン指数算出方法」に準拠して得られた値を表すものを意
味している。また、本発明において、Ａ重油組成物の曇
り点については、燃料系統中の夾雑物阻止用のフィルタ
ーを閉塞させる低温時のワックス析出を減少させる点か
ら、−８℃以下であることが好ましく、−１０℃以下で
あることがより好ましく、−１２℃以下であることがさ
らにより好ましく、−１５℃以下であることが最も好ま
しい。本発明のＡ重油組成物は、流動点については特に
制限はないが、低温時のワックス析出を減少させる点か
ら、−１５℃以下であることが好ましい。本発明におい
て、曇り点及び流動点とは、ＪＩＳ Ｋ ２２６９「原
油及び石油製品の流動点並びに石油製品曇り点試験方
法」に準拠して得られた値を表すものを意味している。[0005] There is no particular limitation on the saturated content and aromatic content of the heavy oil A of the present invention. However, from the viewpoints of flammability, prevention of clogging of the filter by wax in winter, etc., the saturated content is preferably 55% by volume or more, more preferably 60% by volume or more, and 65% by volume or more.
Even more preferably, it is at least 70% by volume, particularly preferably at least 70% by volume, most preferably at least 75% by volume. Further, from the viewpoint of reducing flammability, the aromatic content is preferably 45% by volume or less,
More preferably 35% by volume or less, 30% by volume
Is still more preferred, and most preferably 25% by volume or less. In the present invention, the saturated component and the aromatic component refer to values measured in accordance with JPI-5S-49-97 "Test Method for Hydrocarbon Type-High Performance Liquid Chromatography". Further, normal paraffin is contained in the saturated component, but the amount is not particularly limited. However, normal paraffin is preferably 20% by mass or less, and more preferably 15% by mass or less, from the viewpoint of reducing wax precipitation at low temperatures. In the present invention, the normal paraffin content means a content representing a normal paraffin content based on the total amount of the heavy fuel oil composition A determined by the gas chromatography method described below. 1) Column: stainless steel, inner diameter 0.25 mm, length 2
5m 2) Injection temperature: 360 ° C 3) Carrier gas: helium 4) Detector: Flame ionization (FID) 5) Column temperature rate: 8 ° C / min (140-355)
In the present invention, the cetane index and the cetane number of the heavy oil composition A are not particularly limited, but from the viewpoint of excellent flammability, the cetane index is preferably 58 or more, and more preferably 60 or more. More preferably, the cetane number is 5
It is preferably 8 or more, more preferably 60 or more, and most preferably 62 or more. In the present invention, the cetane index is JIS K 2204-19.
92 means a value obtained based on “light oil”. That is, it is calculated by the following equation. Cetane index (C) = 0.49083 + 1.06577 (X)-0.001052
2 (X) 2 X = 97.833 (logA) 2 + 2.2088BlogA + 0.01247
B 2 -423.51 log A-4.7808B + 419.59 A: (9/5) [50 at 101.3 kPa (760 mmHg)
% Distillation Temperature (° C.)] + 32 B: API Degree The 50% distilling temperature (° C.) at 101.3 kPa (760 mmHg) is measured according to JIS K2254 “Petroleum Product-Distillation Test Method”, and the API degree is JIS K 2249.
It is determined by converting from the density at 15 ° C according to “Crude oil and petroleum products-Density test method and density / mass / volume conversion table”. In addition, the cetane number means a value obtained according to JIS K 2280 "Petroleum products-fuel oil-Octane number and cetane number test method and cetane index calculation method". Further, in the present invention, the cloud point of the heavy fuel oil composition A is preferably -8 ° C or less from the viewpoint of reducing wax deposition at a low temperature that blocks a filter for preventing impurities in a fuel system, The temperature is more preferably -10C or lower, still more preferably -12C or lower, and most preferably -15C or lower. The heavy oil composition A of the present invention has no particular limitation on the pour point, but is preferably -15 ° C or lower from the viewpoint of reducing wax precipitation at low temperatures. In the present invention, the cloud point and the pour point refer to values obtained in accordance with JIS K 2269 "Test methods for pour point of crude oil and petroleum products and cloud point of petroleum products".
【０００６】また、本発明のＡ重油組成物のＣＦＰＰ
（目詰まり点）については特に制限はないが、冬期にお
いてワックスによるフィルター目詰まりの防止の点によ
り優れることから、−１０℃以下であることが好まし
く、−１２℃以下であることがより好ましく、−１５℃
以下であることが最も好ましい。本発明において、ＣＦ
ＰＰとは、ＪＩＳ Ｋ ２２８８「軽油−目詰まり点試
験方法」に準拠して得られた値を表すものを意味してい
る。また、本発明のＡ重油組成物の−１０℃におけるワ
ックス含有量については特に制限はないが、冬期におい
てワックスによるフィルター目詰まりの防止の点により
優れることから、１．０質量％以下であることが好まし
く、０．５質量％以下であることがより好ましく、０．
３質量％以下であることが最も好ましい。本発明におい
て、−１０℃におけるワックス含有量とは、メンブラン
フィルター、メチルエチルケトン−アセトン混合溶剤及
び試料を−１０℃まで冷却し、試料１７ｇを、目開き
５．０μｍのメンブランフィルターで吸引ろ過し、フィ
ルター上のワックスをメチルエチルケトン−アセトン混
合溶剤３０ｍｌで洗浄した後、フィルターに捕集したワ
ックス量を測り、試料全量に対するワックス量を表すも
のを意味している。また、本発明のＡ重油組成物の硫黄
分、窒素分については特に制限はないが、排ガス中の有
害物質を低減するには、硫黄分は０．５質量％以下であ
ることが好ましく、０．３質量％以下であることがより
好ましく、０．２質量％以下であることが最も好まし
い。窒素分は０．０２質量％以下であることが好まし
く、０．０１５質量％以下であることがより好ましく、
０．０１質量％以下であることが最も好ましい。本発明
において、硫黄分、窒素分とは、それぞれ、ＪＩＳ Ｋ
２５４１「原油及び石油製品−硫黄分試験方法」、Ｊ
ＩＳ Ｋ ２６０９「原油及び石油製品−窒素分試験方
法」に準拠して得られた値を表すものを意味している。
本発明のＡ重油組成物の１０％残留炭素分は０．２重量
％以上であり、好ましくは０．２〜１．０重量％であ
る。この範囲より小さい場合、１０％残留炭素分が０．
２重量％以上というＡ重油の免税条件を満たさなくな
る。また、１０％残留炭素分が好ましい範囲より多くな
った場合、色相が悪くなり商品のイメージが悪くなる、
ドライスラッジが増え、常温でフィルターに目詰まりを
起こしやすくなる、低温流動性に悪影響を及ぼす等の恐
れがある。本発明において、１０％残留炭素分とは、Ｊ
ＩＳ Ｋ ２２７０「原油及び石油製品−残留炭素分試
験方法」に準拠して得られた値を表すものを意味してい
る。本発明のＡ重油の色相については特に制限はない
が、商品のイメージ及び常温及び低温時のフィルター目
詰まりの点から、７．０以下であることが好ましく、
６．０以下であることがより好ましく、５．０以下であ
ることが最も好ましい。本発明において、色相とは、Ｊ
ＩＳ Ｋ ２５８０「石油製品−色試験方法」に準拠し
て得られる「ＡＳＴＭ色」を表すものを意味している。
本発明のＡ重油組成物のアスファルテン分は特に制限は
ないが、色相やドライスラッジによる常温でのフィルタ
ー目詰まり、低温流動性等の点から、０．０１質量％以
下であることが好ましく、０．００５質量％以下である
ことがより好ましく、０．００２質量％以下であること
が最も好ましい。本発明において、アスファルテン分と
は、ＩＰ１４３「アスファルテン分試験方法」に準拠し
て得られた値を表すものを意味している。本発明のＡ重
油組成物のドライスラッジ量については特に制限はない
が、常温でのフィルター目詰まりが起こり難くなる点か
ら、２．０ｍｇ／１００ｍｌ以下であることが好まし
く、１．５ｍｇ／１００ｍｌ以下であることがより好ま
しく、１．０ｍｇ／１００ｍｌ以下であることが最も好
ましい。本発明において、ドライスラッジ量とは、常温
において、試料を目開き１．２μｍのフィルターで吸引
ろ過し、ろ過後のフィルター及びフィルター上の残留物
をｎ−ヘプタンで洗浄し乾燥後残留物の質量から、試料
１００ｍｌ当りの残留物の質量で表される値を意味して
いる。また、本発明のＡ重油組成物の蒸留性状について
は何ら制限はないが、通常は下記性状を満たすものが用
いられる。 蒸留初留点： １３０〜２１０℃ Ｔ１０： １８０〜２６０℃ Ｔ５０： ２５０〜３３０℃ Ｔ９０： ３００〜３８０℃ 本発明において、上記蒸留性状は、ＪＩＳ Ｋ ２２５
４「石油製品−蒸留試験方法」に準拠して得られる値を
意味している。本発明のＡ重油組成物の動粘度について
は特に制限はないが、通常３０℃で３〜５ｍｍ2／ｓ、
５０℃で２〜３．５ｍｍ2／ｓのものが用いられる。本
発明において、動粘度とは、ＪＩＳ Ｋ ２２８３「原
油及び石油製品−動粘度試験方法及び粘度指数算出方
法」に準拠して得られた値を表すものを意味している。
本発明のＡ重油組成物の引火点については特に制限はな
いが、通常５０〜１２０℃のものが用いられる。本発明
において、引火点とは、ＪＩＳ Ｋ ２２６５「原油及
び石油製品−引火点試験方法」に準拠して得られた値を
表すものを意味している。本発明のＡ重油組成物の総発
熱量については特に制限はないが、通常３５０００〜５
００００Ｊ／ｇのものが用いられる。本発明において、
総発熱量とは、ＪＩＳ Ｋ ２２７９「原油及び石油製
品−発熱量試験方法及び計算による推定方法」に準拠し
て得られた値を表すものを意味している。本発明のＡ重
油組成物の水分含有量については特に制限はないが、通
常０．０５容量％以下のものが用いられる。本発明にお
いて、水分含有量とは、ＪＩＳ Ｋ ２２７５「原油及
び石油製品−水分試験方法」に準拠して得られた値を表
すものを意味している。本発明のＡ重油組成物の密度に
ついては特に制限はないが、通常０．８〜０．９２ｇ／
ｃｍ3のものが用いられる。本発明において、密度と
は、ＪＩＳ Ｋ ２２４９「原油及び石油製品−密度試
験方法及び密度・質量・容量換算表」に準拠して得られ
た値を表すものを意味している。Further, CFPP of the heavy oil composition A of the present invention
The (clogging point) is not particularly limited, but is preferably -10 ° C or less, more preferably -12 ° C or less, because it is more excellent in preventing filter clogging with wax in winter. -15 ° C
It is most preferred that: In the present invention, CF
PP means a value obtained in accordance with JIS K 2288 "Diesel oil-clogging point test method". The wax content at -10 ° C of the heavy oil composition A of the present invention is not particularly limited, but is preferably 1.0% by mass or less because it is more excellent in preventing filter clogging with wax in winter. Is preferably 0.5% by mass or less, more preferably 0.5% by mass or less.
Most preferably, it is 3% by mass or less. In the present invention, the wax content at −10 ° C. means that a membrane filter, a methyl ethyl ketone-acetone mixed solvent and a sample are cooled to −10 ° C., and 17 g of the sample is suction-filtered through a 5.0 μm-aperture membrane filter. After washing the above wax with 30 ml of a mixed solvent of methyl ethyl ketone-acetone, the amount of wax collected on a filter is measured to indicate the amount of wax relative to the total amount of the sample. Further, the sulfur content and the nitrogen content of the heavy oil composition A of the present invention are not particularly limited. However, in order to reduce harmful substances in exhaust gas, the sulfur content is preferably 0.5% by mass or less. It is more preferably at most 0.3 mass%, most preferably at most 0.2 mass%. The nitrogen content is preferably 0.02% by mass or less, more preferably 0.015% by mass or less,
Most preferably, it is 0.01% by mass or less. In the present invention, the sulfur content and the nitrogen content refer to JIS K, respectively.
2541 "Crude oil and petroleum products-Test method for sulfur content", J
Means a value obtained in accordance with IS K 2609 "Crude oil and petroleum products-Test method for nitrogen content".
The 10% residual carbon content of the heavy oil composition A of the present invention is 0.2% by weight or more, preferably 0.2 to 1.0% by weight. If it is smaller than this range, the 10% residual carbon content is 0.1%.
2% by weight or more will not meet the tax exemption condition for Fuel Oil A. If the 10% residual carbon content exceeds the preferred range, the hue becomes worse and the image of the product becomes worse.
Dry sludge may increase, and the filter may be easily clogged at room temperature, and may adversely affect low-temperature fluidity. In the present invention, the 10% residual carbon content is J
It means a value obtained in accordance with IS K 2270 "Crude oil and petroleum products-Test methods for residual carbon content". The hue of the heavy oil A of the present invention is not particularly limited, but is preferably 7.0 or less from the viewpoint of image of the product and clogging of the filter at normal temperature and low temperature,
It is more preferably 6.0 or less, and most preferably 5.0 or less. In the present invention, the hue is J
It refers to an "ASTM color" obtained according to IS K 2580 "Petroleum products-Color test method".
The asphaltene content of the heavy oil composition A of the present invention is not particularly limited, but is preferably 0.01% by mass or less from the viewpoint of hue, filter clogging at room temperature due to dry sludge, low-temperature fluidity, and the like. The content is more preferably 0.005% by mass or less, and most preferably 0.002% by mass or less. In the present invention, the asphaltene content means a value that is obtained in accordance with IP143 “Asphaltene content test method”. The amount of dry sludge of the heavy oil composition A of the present invention is not particularly limited, but is preferably 2.0 mg / 100 ml or less, and is preferably 1.5 mg / 100 ml or less from the viewpoint that clogging of the filter at room temperature is unlikely to occur. Is more preferable, and most preferably 1.0 mg / 100 ml or less. In the present invention, the amount of dry sludge refers to the mass of a residue at normal temperature, which is obtained by suction-filtering a sample with a filter having an aperture of 1.2 μm, washing the filter after filtration and the residue on the filter with n-heptane, and drying. Means the value represented by the mass of the residue per 100 ml of the sample. The distillation properties of the heavy oil composition A of the present invention are not particularly limited, but usually those satisfying the following properties are used. Initial distillation point: 130 to 210 ° C. T10: 180 to 260 ° C. T50: 250 to 330 ° C. T90: 300 to 380 ° C. In the present invention, the above-mentioned distillation properties are JIS K225.
4 means a value obtained in accordance with "Petroleum products-distillation test method". The kinematic viscosity of the heavy oil composition A of the present invention is not particularly limited, but is usually 3 to 5 mm 2 / s at 30 ° C.
Those having a temperature of 50 ° C. and 2 to 3.5 mm 2 / s are used. In the present invention, the kinematic viscosity means a value representing a value obtained in accordance with JIS K 2283 "Crude oil and petroleum products-Kinematic viscosity test method and viscosity index calculation method".
The flash point of the heavy oil composition A of the present invention is not particularly limited, but one having a temperature of 50 to 120 ° C is usually used. In the present invention, the flash point means a value obtained based on JIS K 2265 "Crude oil and petroleum products-flash point test method". The total calorific value of the heavy oil composition A of the present invention is not particularly limited, but is usually 35,000 to 5
0000 J / g is used. In the present invention,
The total calorific value means a value obtained based on JIS K 2279 "Crude oil and petroleum products-Calorific value test method and estimation method by calculation". The water content of the heavy oil composition A of the present invention is not particularly limited, but is usually 0.05% by volume or less. In the present invention, the term “water content” means a value obtained in accordance with JIS K 2275 “Crude Oil and Petroleum Products—Moisture Testing Method”. The density of the heavy oil composition A of the present invention is not particularly limited, but is usually 0.8 to 0.92 g /.
cm 3 is used. In the present invention, the density means a value obtained in accordance with JIS K 2249 "Crude oil and petroleum products-Density test method and density / mass / volume conversion table".
【０００７】本発明のＡ重油組成物の製造方法は特に限
定されず従来周知の任意の方法を用いることができ、通
常Ａ重油基材に残留炭素付与用基材を混合し、必要に応
じて添加剤を配合して製造される。Ａ重油基材として
は、常圧蒸留装置より得られる直留灯油（又は脱硫処理
した灯油）、直留軽質軽油（又は脱硫処理した軽質軽
油）、直留重質軽油（又は脱硫処理した重質軽油）、流
動接触分解装置及び／又は残渣流動接触分解装置より得
られる軽質サイクル油、減圧蒸留装置より得られる減圧
軽油を水素化脱硫した水素化脱硫減圧軽油、水素化分解
装置より得られる水素化分解軽油、直接Ａ重油脱硫装置
より得られる直脱軽油等が挙げられる。これらの中の１
種のみを使用しても良く、２種以上を混合しても良い。
これらの中でも、燃焼性、冬期においてワックスによる
フィルターの目詰まりの防止等の点を、全て同時に満た
すことができ、かつこれらの効果により優れることか
ら、水素化分解軽油を使用することが好ましい。ここで
いう、水素化分解軽油とは、水素化分解装置から得られ
る、軽油留分である。具体的には、その蒸留性状とし
て、５０％留出点が２５０〜３５０℃であり、１５℃の
密度が０．８１０〜０．８８０ｇ／ｃｍ3の範囲であ
る。水素化分解装置は、重質軽油等をアモルファス系Ｎ
ｉ−Ｍｏ触媒等の触媒条件下で、８〜１５ＭＰａの運転
水素圧力下、３３０〜４５０℃の運転反応温度で、液空
間速度０．１〜１．０／ｈの条件で水素化分解と同時に
脱硫及び脱窒素を行う。また、残留炭素分付与用基材と
しては、常圧残油、直脱残油、減圧残油、エキストラク
ト、スラリー油等が挙げられる。これらの中の１種のみ
を使用しても良く、２種以上を混合しても良い。これら
の中でも、エキストラクトを使用することが好ましい。
特に、Ａ重油基材として水素化分解軽油を使用した場合
には、色相やドライスラッジ生成によるフィルター目詰
まりの点から、エキストラクトを使用することが好まし
い。ここでいうエキストラクトとは、フルフラール等の
溶剤を用いて潤滑油中の芳香族分を除く工程で副生する
高芳香族分の油であり、具体的には、その性状として、
１５℃の密度が０．９５〜１．０５ｇ／ｃｍ3、１００
℃における動粘度が５〜１００ｍｍ2／ｓ、硫黄分が
０．５〜５．０質量％である。本発明のＡ重油組成物は
上記した通り、水素化分解軽油及びエキストラクトを使
用することが好ましいが、両者の配合量については特に
制限はない。しかしながら、その効果を十分に発揮させ
るためには、水素化分解軽油をＡ重油組成物全量基準で
５０％以上使用することが好ましく、７５％以上使用す
ることがより好ましく、８５％以上使用することがさら
により好ましく、９０％以上使用することが最も好まし
い。また、残留炭素分についての免税条件を満たすため
に、通常は９９．５容量％以下、好ましくは９９容量％
以下で使用される。また、残留炭素分についての免税条
件を満たすために、エキストラクトは通常Ａ重油組成物
全量基準で０．５容量％以上、好ましくは１容量％以上
で使用される。また、ドライスラッジによる常温でのフ
ィルター目詰まり、低温流動性等を考慮すると、５容量
％以下で使用されることが好ましく、３容量％以下で使
用されることがより好ましい。また、添加剤としては、
セタン価向上剤、酸化防止剤、安定化剤、分散剤、金属
不活性化剤、微生物殺菌剤、助燃剤、帯電防止剤、識別
剤、着色剤等の各種添加剤が挙げられ、これら添加剤を
適宜加えることができる。これらの中でも、冬期におい
てワックスによるフィルター目詰まりを防止する効果に
より優れることから、流動性向上剤を添加することが好
ましい。流動性向上剤としては、たとえばエチレン−酢
酸ビニル共重合体、エチレン−α−オレフィン共重合体
等のポリマー型添加剤、油溶性分散剤型添加剤及びアル
ケルコハク酸等を用いることが出来る。また、流動性向
上剤の添加量については何ら制限はないが、Ａ重油組成
物全量基準で０．００１〜０．１容量％であることが好
ましく、０．０１〜０．０３質量％であることがより好
ましい。The method for producing the heavy oil A composition of the present invention is not particularly limited, and any conventionally known method can be used. Usually, a base material for imparting residual carbon is mixed with the heavy oil A base material, and if necessary, It is manufactured by blending additives. A heavy oil base material includes straight-run kerosene (or desulfurized kerosene), straight-run light gas oil (or desulfurized light gas oil), straight-run heavy gas oil (or desulfurized heavy oil) obtained from an atmospheric distillation unit. Gas oil), light cycle oil obtained from a fluid catalytic cracking unit and / or residue fluid catalytic cracking unit, hydrodesulfurized vacuum gas oil obtained by hydrodesulfurizing vacuum gas oil obtained from a vacuum distillation unit, hydrogenation obtained from a hydrocracking unit Crude gas oil, direct gas oil obtained from a direct A heavy oil desulfurization unit, and the like. One of these
Only a kind may be used and two or more kinds may be mixed.
Among them, it is preferable to use hydrocracked gas oil because it can simultaneously satisfy the flammability, prevention of clogging of the filter by wax in winter, and the like, and are more excellent in these effects. Here, the hydrocracked gas oil is a gas oil fraction obtained from the hydrocracking unit. Specifically, as the distillation properties, the 50% distillation point is 250 to 350 ° C., and the density at 15 ° C. is in the range of 0.810 to 0.880 g / cm 3 . Hydrocracking equipment converts heavy gas oil into amorphous N
Simultaneously with hydrocracking, under catalytic conditions such as i-Mo catalyst, under an operating hydrogen pressure of 8 to 15 MPa, an operating reaction temperature of 330 to 450 ° C., and a liquid hourly space velocity of 0.1 to 1.0 / h Perform desulfurization and denitrification. In addition, examples of the base material for imparting residual carbon include residual oil under normal pressure, residual oil directly removed, residual oil under reduced pressure, extract, and slurry oil. One of these may be used alone, or two or more thereof may be mixed. Among them, it is preferable to use an extract.
In particular, when a hydrocracked gas oil is used as the heavy oil A base, it is preferable to use an extract from the viewpoint of hue and filter clogging due to generation of dry sludge. The extract referred to here is a high aromatic oil produced as a by-product in the process of removing aromatic components in a lubricating oil using a solvent such as furfural, and specifically, as its properties,
The density at 15 ° C. is 0.95 to 1.05 g / cm 3 , 100
The kinematic viscosity at 5 ° C. is 5 to 100 mm 2 / s, and the sulfur content is 0.5 to 5.0% by mass. As described above, the heavy oil composition A of the present invention preferably uses a hydrocracked gas oil and an extract, but there is no particular limitation on the blending amounts of both. However, in order to sufficiently exhibit the effect, it is preferable to use the hydrocracked gas oil in an amount of 50% or more, more preferably 75% or more, and more preferably 85% or more based on the total amount of the heavy fuel oil composition A. Is even more preferable, and 90% or more is most preferably used. Further, in order to satisfy the tax exemption condition for the residual carbon content, it is usually 99.5% by volume or less, preferably 99% by volume.
Used in: Further, in order to satisfy the tax exemption condition for the residual carbon content, the extract is generally used in an amount of 0.5% by volume or more, preferably 1% by volume or more based on the total amount of the heavy fuel oil composition A. Also, in consideration of filter clogging at room temperature due to dry sludge, low-temperature fluidity, and the like, it is preferably used at 5% by volume or less, more preferably at 3% by volume or less. Also, as an additive,
Various additives such as a cetane improver, an antioxidant, a stabilizer, a dispersant, a metal deactivator, a microbial bactericide, a flame retardant, an antistatic agent, a discriminating agent, a coloring agent, and the like. Can be added as appropriate. Among these, it is preferable to add a fluidity improver because it is more excellent in the effect of preventing clogging of the filter by wax in winter. As the fluidity improver, for example, a polymer type additive such as an ethylene-vinyl acetate copolymer and an ethylene-α-olefin copolymer, an oil-soluble dispersant type additive, and an alkyl succinic acid can be used. The amount of the fluidity improver is not particularly limited, but is preferably 0.001 to 0.1% by volume, preferably 0.01 to 0.03% by mass, based on the total weight of the heavy oil composition A. Is more preferable.
【０００８】[0008]
【実施例】以下、実施例により本発明をさらに詳細に説
明するが、本発明はこれらによってなんら限定されるも
のではない。実施例１〜３及び比較例１ 表１に示す性状を有する各基材（水素化分解軽油、直留
軽油、分解軽油、エキストラクト）を表２の各例に示す
ような容量比で混合し、実施例１〜３及び比較例１のＡ
重油組成物を調製し、これら調整した各組成物の性状を
表２に記載した。各試料油（各組成物）について、低温
流動性性能評価及び燃焼性性能評価を下記の方法により
行った。その結果を表２に併記した。低温流動性性能評価 以下の方法により、低温時における燃料フィルター前後
での負圧の大きさを測定し低温流動性の性能評価を行っ
た。試験器としては、ビニールハウス栽培の加温用に使
用されている暖房機のバーナー部分と、それに付帯する
燃料フィルター（１００メッシュ）からなる低温流動性
試験器を用いて行った。試験条件は冬期の厳しい外気温
度変化をもとに、冷却速度０．５℃／ｈ、冷却開始温度
５℃、ソーキングは試験温度で５時間とした。判定は燃
料フィルター前後で負圧を１時間測定し、測定時間中負
圧が７００ｍｍＨｇ以下である場合を合格とし、測定時
間中に負圧が７００ｍｍＨｇより大きくなることがあっ
た場合を不合格とした。負圧測定が合格となる最低温度
を表２に示した。燃焼性性能評価 以下の方法により、着火遅れを測定することにより燃焼
性の性能評価を行った。着火遅れは、エンジン性能、排
ガスに悪影響を与え、特に近年の高性能エンジンにおけ
るトラブルの主要原因となる。燃焼室の容積が１リット
ルである燃料着火性試験機を用い、圧力４５バーレル、
温度４５０℃の空気中に燃料を噴射して、噴射から着火
するまでの時間を測定した。その結果を表２に示した。The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the invention thereto. Examples 1 to 3 and Comparative Example 1 Each base material (hydrocracked gas oil, straight-run gas oil, cracked gas oil, extract) having the properties shown in Table 1 was mixed at a volume ratio as shown in each example of Table 2. A of Examples 1 to 3 and Comparative Example 1
The heavy oil compositions were prepared, and the properties of each of these adjusted compositions are shown in Table 2. For each sample oil (each composition), low-temperature fluidity performance evaluation and flammability performance evaluation were performed by the following methods. The results are shown in Table 2. Evaluation of low-temperature fluidity performance The low pressure fluidity performance was evaluated by measuring the magnitude of the negative pressure before and after the fuel filter at low temperatures by the following method. As a test device, a low-temperature fluidity test device including a burner portion of a heater used for heating greenhouse cultivation and a fuel filter (100 mesh) attached to the burner portion was used. The test conditions were based on severe outdoor temperature changes in winter, with a cooling rate of 0.5 ° C./h, a cooling start temperature of 5 ° C., and a soaking test temperature of 5 hours. The judgment was made by measuring the negative pressure for 1 hour before and after the fuel filter, and when the negative pressure was 700 mmHg or less during the measurement time, it was judged as pass, and when the negative pressure was sometimes larger than 700 mmHg during the measurement time, it was judged as reject. . Table 2 shows the minimum temperature at which the negative pressure measurement was accepted. Flammability performance evaluation The flammability performance was evaluated by measuring the ignition delay by the following method. The ignition delay adversely affects the engine performance and exhaust gas, and is a major cause of trouble particularly in recent high-performance engines. Using a fuel ignitability tester having a combustion chamber volume of 1 liter, a pressure of 45 barrels,
Fuel was injected into air at a temperature of 450 ° C., and the time from injection to ignition was measured. The results are shown in Table 2.
【０００９】[0009]
【表１】 [Table 1]
【００１０】[0010]
【表２】 [Table 2]
【００１１】表２の結果から明らかなように、本発明に
かかる実施例１〜３のＡ重油組成物は、いずれも着火性
がよく燃焼性に優れ、近年の高性能エンジンへ十分な性
能を持ち、かつ優れた低温流動性を有することが分か
る。これに対して、ナフテン分が規定値未満の比較例１
は低温流動性及び燃焼性が悪い。As is clear from the results shown in Table 2, the fuel oil compositions A of Examples 1 to 3 according to the present invention all have good ignitability and excellent flammability, and have sufficient performance for recent high-performance engines. It can be seen that it has excellent low-temperature fluidity. In contrast, Comparative Example 1 in which the naphthene content was less than the specified value
Has poor low-temperature fluidity and flammability.
【００１２】[0012]
【発明の効果】以上要するに本発明によれば、燃焼性が
高く、近年の高性能エンジンへの使用に耐え得り、か
つ、冬期においてワックスによるフィルターの目詰まり
を起こさないＡ重油組成物が得られる。In summary, according to the present invention, there is provided a fuel oil A composition which has high flammability, can withstand the use in recent high-performance engines, and does not cause clogging of filters by wax in winter. Can be
フロントページの続き (72)発明者 清水 和夫 神奈川県横浜市中区千鳥町８番地 日石三 菱株式会社中央技術研究所内 (72)発明者 上原 淳 東京都港区西新橋一丁目３番12号 日石三 菱株式会社内 Ｆターム(参考） 4H013 CB02 Continued on the front page (72) Inventor Kazuo Shimizu 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Pref. Nishiishi Mitsui Co., Ltd. Central Research Laboratory (72) Inventor Atsushi Uehara 1-3-12 Nishishinbashi, Minato-ku, Tokyo Nishiishi Mitsubishi Co., Ltd. F-term (reference) 4H013 CB02
Claims (2)
油組成物。1. A fuel oil A composition having a naphthene content of 40% by mass or more.
いて得られた請求項１記載のＡ重油組成物。2. The heavy oil A composition according to claim 1, which is obtained by using a hydrocracked light oil and an extract.
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| JP3999911B2 JP3999911B2 (en) | 2007-10-31 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7695610B2 (en) | 2005-07-18 | 2010-04-13 | Oiltreid Limited Liabilities Company | Light fuel oil |
| US7708876B2 (en) | 2005-07-18 | 2010-05-04 | Oiltreid Limited Liabilities Company | Heavy fuel oil |
| JP2017190410A (en) * | 2016-04-14 | 2017-10-19 | Ｊｘｔｇエネルギー株式会社 | Hydrocarbon oil and method for producing hydrocarbon oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10550341B2 (en) | 2015-12-28 | 2020-02-04 | Exxonmobil Research And Engineering Company | Sequential deasphalting for base stock production |
| US10550335B2 (en) | 2015-12-28 | 2020-02-04 | Exxonmobil Research And Engineering Company | Fluxed deasphalter rock fuel oil blend component oils |
| US10590360B2 (en) | 2015-12-28 | 2020-03-17 | Exxonmobil Research And Engineering Company | Bright stock production from deasphalted oil |
| US10494579B2 (en) | 2016-04-26 | 2019-12-03 | Exxonmobil Research And Engineering Company | Naphthene-containing distillate stream compositions and uses thereof |
| WO2019005009A1 (en) | 2017-06-27 | 2019-01-03 | Exxonmobil Research And Engineering Company | Fuel components from hydroprocessed deasphalted oils |
-
1999
- 1999-07-06 JP JP19190699A patent/JP3999911B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7695610B2 (en) | 2005-07-18 | 2010-04-13 | Oiltreid Limited Liabilities Company | Light fuel oil |
| US7708876B2 (en) | 2005-07-18 | 2010-05-04 | Oiltreid Limited Liabilities Company | Heavy fuel oil |
| JP2017190410A (en) * | 2016-04-14 | 2017-10-19 | Ｊｘｔｇエネルギー株式会社 | Hydrocarbon oil and method for producing hydrocarbon oil |
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