JP2019151761A - Property improvement method of light oil - Google Patents
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Abstract
Description
本発明は軽油の性状改善方法に関する。 The present invention relates to a method for improving the properties of light oil.
軽油は沸点範囲がおよそ１７０〜３７０℃の炭化水素成分で構成されており、着火性向上（セタン化向上）に有効なパラフィンのほか、ナフテン、単環芳香族化合物、２環芳香族及び３環以上の芳香族化合物が含まれている。軽油中の芳香族化合物が増加するとパティキュレート（微小粒子状物質）の排出量が増加する可能性があるとも言われており、特に２環以上の多環芳香族化合物がパティキュレート生成に関与する傾向がみられるといわれている（非特許文献１）。 Light oil is composed of hydrocarbon components with a boiling range of approximately 170-370 ° C. In addition to paraffin, which is effective in improving ignitability (improving cetaneation), naphthene, monocyclic aromatic compounds, bicyclic aromatic compounds and tricyclic rings The above aromatic compounds are contained. It is said that the emission of particulates (microparticulate matter) may increase when the aromatic compounds in light oil increase, and in particular, polycyclic aromatic compounds with two or more rings are involved in the generation of particulates. It is said that there is a tendency (Non-Patent Document 1).
排出ガスのクリーン化の観点から、軽油中の多環芳香族化合物の削減が求められており、これに対応する技術として、メタンを主成分とする天然ガスを改質反応で一酸化炭素と水素を含む合成ガス(syngas)に変換し、これをフィッシャー・トロプシュ（FT）反応で増炭することによって、芳香族や硫黄分をほとんど含まない軽油等の中間留分を合成するジーティーエル（GTL(gas to liquid)）プラント技術の開発も行われてきている（非特許文献２）。しかし、GTLプラントは天然ガス田の近傍で比較的大規模なプラントを設置する必要があるほか、従来の原油由来の中間留分の処理には適用できない難しさがある。 From the viewpoint of cleaner exhaust gas, there is a need to reduce polycyclic aromatic compounds in light oil, and as a corresponding technology, natural gas mainly composed of methane is reformed with carbon monoxide and hydrogen. GTL (GTL) that synthesizes middle distillates such as light oils that contain almost no aromatics and sulfur by converting to syngas containing gas and augmenting it with the Fischer-Tropsch (FT) reaction (gas to liquid)) Plant technology has also been developed (Non-Patent Document 2). However, the GTL plant needs to have a relatively large plant in the vicinity of the natural gas field, and it is difficult to apply it to the conventional middle distillate derived from crude oil.
市販軽油の中には比較的無色透明のものから、淡黄色や淡黄緑色など呈するものもある。このように呈色する軽油は主に波長３８０以上７８０ｎｍ以下の範囲での紫外・可視光線の吸収と関係がある。一般的に、ベンゼン環を複数持っている多環芳香族化合物は共役二重結合を有することで紫外・可視領域の光を吸収し、さらに電子の共役系が大きくなるとその吸収波長は長波長側にシフトする。たとえば、ナフタレン（２環）の主な吸収波長は２４５〜２８５ｎｍなのに対し、アントラセン（３環）の主な吸収波長は３００〜３８０ｎｍ、フェナントレン（３環）は２６０〜３８０ｎｍ、ピレン（４環）は２５０ｎｍ〜３８０ｎｍ、ナフタセン（４環）は３００ｎｍ〜５００ｎｍとなっている。このように、芳香族が紫外可視光吸収を示すことを応用して、高速液体クロマトグラフィー（ＨＰＬＣ）における芳香族の検出に紫外吸収検出器が用いられている（非特許文献３）。このような知見から、市販軽油の中で淡黄色や淡黄緑色を呈するものにあっては、多環芳香族を含む可能性があるものと思われる。 Some commercially available light oils are relatively colorless and transparent, and light yellow or light yellowish green. The light oil thus colored is mainly related to the absorption of ultraviolet and visible light in the wavelength range of 380 to 780 nm. In general, polycyclic aromatic compounds having multiple benzene rings have a conjugated double bond that absorbs light in the ultraviolet and visible regions, and when the conjugated system of electrons becomes larger, the absorption wavelength is longer. Shift to. For example, the main absorption wavelength of naphthalene (2 rings) is 245 to 285 nm, whereas the main absorption wavelength of anthracene (3 rings) is 300 to 380 nm, phenanthrene (3 rings) is 260 to 380 nm, and pyrene (4 rings) is 250 nm to 380 nm and naphthacene (4 rings) are 300 nm to 500 nm. Thus, an ultraviolet absorption detector is used for the detection of aromatics in high performance liquid chromatography (HPLC) by applying the fact that aromatics exhibit ultraviolet visible light absorption (Non-patent Document 3). From such knowledge, it is considered that a commercially available light oil that exhibits light yellow or light yellow green may contain a polycyclic aromatic.
軽油中の多環芳香族化合物を除去する方法としては、軽油を水素化精製処理して芳香族化合物を低減させる軽油留分の製造方法（特許文献１）が開示されている。また、軽油を脱色する方法としては、着色した軽油留分を活性炭と接触させて着色原因物質を吸着除去する方法（特許文献２）、蛍光色などの着色がない軽油基材を製造する方法（特許文献３）が開示されている。 As a method for removing polycyclic aromatic compounds in light oil, a method for producing a light oil fraction (Patent Document 1) in which light oil is hydrorefined to reduce aromatic compounds is disclosed. In addition, as a method for decolorizing light oil, a method in which a colored light oil fraction is brought into contact with activated carbon to remove the color-causing substances by adsorption (Patent Document 2), and a method for producing a light oil base material without coloring such as fluorescent color ( Patent Document 3) is disclosed.
しかし上記の先行技術は、多環芳香族化合物または着色成分どちらか一方を除去対象とする処理技術であり、両者を同時に除去することは考慮されていない。 However, the above-described prior art is a treatment technique for removing either the polycyclic aromatic compound or the coloring component, and it is not considered to remove both at the same time.
本発明はかかる事情に鑑みてなされたものであり、原油由来の軽油に関し芳香族化合物及び呈色物質を同時に低減する軽油の性状改善技術を提供する。特に波長３６０ｎｍ以上７８０ｎｍ以下の紫外可視光を吸収するような多環芳香族化合物及び呈色物質の低減に関し好ましい方法を提供できる。 This invention is made | formed in view of this situation, and provides the property improvement technique of the light oil which reduces simultaneously an aromatic compound and a colored substance regarding the light oil derived from crude oil. In particular, it is possible to provide a preferable method for reducing polycyclic aromatic compounds and colored substances that absorb ultraviolet visible light having a wavelength of 360 nm or more and 780 nm or less.
本発明者らは鋭意研究を重ねた結果、（１）軽油槽において、軽油１０００ｍｌに対し、酸性白土を温度８０℃以上２５０℃以下、空気流通下で３時間以上１０時間以下処理して得た熱処理白土を３０ｇ以上１５０ｇ以下添加することを特徴とする軽油の性状改善方法であり、（２）軽油槽の温度が１５℃以上５０℃以下であることを特徴とする（１）記載の軽油の性状改善方法であり、（３）軽油槽における熱処理白土と軽油との接触時間が２時間以上７２時間以下であることを特徴とする（１）、または（２）記載の軽油の性状改善方法であり、（４）軽油槽が遮光されていることを特徴とする（１）、（２）、または（３）記載の軽油の性状改善方法であり、（５）遮光が不完全な軽油槽において、軽油の液面と当該槽との空間部分を二酸化炭素、アルゴン、窒素、ブタンおよびハイドロフルオロカーボン類から選ばれる少なくとも一種で置換することを特徴とする（１）、（２）、または（３）記載の軽油の性状改善方法を見出し、本発明を完成するに至った。 As a result of intensive research, the present inventors have obtained (1) in a light oil tank, acid clay was treated at a temperature of 80 ° C. or more and 250 ° C. or less for 3 hours or more and 10 hours or less with respect to 1000 ml of light oil. A method for improving the properties of light oil characterized by adding 30 g or more and 150 g or less of heat-treated clay. (2) The temperature of the light oil tank is 15 ° C. or more and 50 ° C. or less. (3) The method for improving the properties of light oil according to (1) or (2), wherein the contact time between the heat-treated clay and the light oil in the light oil tank is 2 hours or more and 72 hours or less. (4) The method for improving the properties of light oil according to (1), (2) or (3), characterized in that the light oil tank is shielded from light, and (5) in a light oil tank where light shielding is incomplete. The space between the oil level and the tank The method for improving the properties of gas oil according to (1), (2), or (3), characterized by substituting with at least one selected from carbon oxide, argon, nitrogen, butane and hydrofluorocarbons, It came to be completed.
以上、本発明によれば軽油中の多環芳香族化合物を除去することができ、さらに呈色を低減できる。 As described above, according to the present invention, the polycyclic aromatic compound in the light oil can be removed, and coloration can be further reduced.
以下に本発明の実施形態について具体的に説明するが、本発明の技術内容をより具体的に説明するためのものであり、本発明の範囲を限定するものではない。 Embodiments of the present invention will be specifically described below, but are intended to more specifically describe the technical contents of the present invention and do not limit the scope of the present invention.
（処理対象軽油）
処理対象の軽油に特に制限はない。すなわち、軽油のＪＩＳ規格（ＪＩＳ Ｋ ２２０４）による特１号、１号、２号、３号及び特３号軽油に対し、好ましく用いることができる。特に高沸点成分が多く、呈色する傾向が強いと思われる１号軽油に対し好ましく用いることができる。
(Light oil to be treated)
There is no particular limitation on the light oil to be treated. That is, it can be preferably used for Special No. 1, No. 2, No. 2, No. 3 and Special No. 3 diesel oil according to JIS standard (JIS K 2204). In particular, it can be preferably used for No. 1 diesel oil, which has many high-boiling components and seems to have a strong tendency to color.
（酸性白土）
酸性白土のＳｉ／Ａｌモル比（ケイバン比）は３以上７以下、比表面積は特に限定されないが、２０以上２００ｍ２／ｇ以下のものを好ましく用いることができる。
(Acid clay)
The Si / Al molar ratio (Kayban ratio) of the acid clay is 3 or more and 7 or less, and the specific surface area is not particularly limited, but 20 or more and 200 m2 / g or less can be preferably used.
（酸性白土の熱処理条件）
酸性白土は、空気流通下で熱処理して水分等吸着物質を除去することで活性化することができる。酸性白土を空気流通下で熱処理して熱処理白土を得るときの温度は８０℃以上２５０℃以下が好ましく、１２０℃以上２３０℃以下がより好ましく、１３０℃以上２００℃以下が最も好ましい。この範囲未満では酸性白土中に水分が残留する傾向があり活性不十分な面がある。またこの範囲を超過すると酸性白土の構造が変化して軽油に対する性状改善効果が低下する傾向がある。また、前記熱処理の時間は３時間以上１０時間以下が好ましく、４時間以上８時間以下がより好ましく、５時間以上６時間以下が最も好ましい。この範囲未満では熱処理白土と軽油との接触が十分に行われない傾向がある。熱処理時間は生産性の観点から６時間以下に抑えることが実用的である。
(Heat treatment conditions for acid clay)
Acidic clay can be activated by heat treatment under air flow to remove adsorbed substances such as moisture. The temperature at which the acid clay is heat-treated under air flow to obtain the heat-treated clay is preferably 80 ° C. or higher and 250 ° C. or lower, more preferably 120 ° C. or higher and 230 ° C. or lower, and most preferably 130 ° C. or higher and 200 ° C. or lower. Below this range, there is a tendency for moisture to remain in the acid clay and there is a surface with insufficient activity. Moreover, when this range is exceeded, the structure of acid clay will change and the property improvement effect with respect to light oil tends to fall. The heat treatment time is preferably 3 hours or more and 10 hours or less, more preferably 4 hours or more and 8 hours or less, and most preferably 5 hours or more and 6 hours or less. If it is less than this range, there is a tendency that the contact between the heat-treated clay and the light oil is not sufficiently performed. It is practical to suppress the heat treatment time to 6 hours or less from the viewpoint of productivity.
（軽油槽への熱処理白土の添加量）
軽油槽への熱処理白土の添加量は軽油１０００ｍｌに対して３０ｇ以上１５０ｇ以下が好ましく、６０ｇ以上１３０ｇ以下がより好ましく、８０ｇ以上１１０ｇ以下が最も好ましい。この範囲未満では十分な性状改善効果が得られない傾向がある。この範囲を超過すると、性状改善効果が頭打ちとなり不経済な面がある。
(Amount of heat-treated white clay added to the light oil tank)
The amount of heat-treated clay added to the light oil tank is preferably 30 g or more and 150 g or less, more preferably 60 g or more and 130 g or less, and most preferably 80 g or more and 110 g or less with respect to 1000 ml of light oil. If it is less than this range, there is a tendency that sufficient property improving effect cannot be obtained. If this range is exceeded, the effect of improving the properties will reach its peak, which is uneconomical.
（軽油槽）
軽油と酸性白土を接触処理するときに用いる軽油槽は内部に光が透過しないように遮光されていることが好ましいが、軽油槽の遮光が不完全な場合、軽油槽空間部分は不活性ガスまたは非酸化性ガスで置換することが好ましい。不活性ガスまたは非酸化性ガスには二酸化炭素、アルゴン、窒素、ブタン及びハイドロフルオロカーボン類を好ましく、二酸化炭素、アルゴン、窒素及びハイドロフルオロカーボン類をより好ましく、二酸化炭素、アルゴン及びハイドロフルオロカーボン類を最も好ましく用いることができる。これらの非酸化性ガスは一種単独で用いることができるほか、二種以上を任意の割合で混合することができる。
(Light oil tank)
The light oil tank used when the light oil and acid clay are contact-treated is preferably shielded from light so that light does not pass through the inside. However, if the light oil tank is not fully shielded, the light oil tank space portion is inert gas or Replacement with a non-oxidizing gas is preferred. Carbon dioxide, argon, nitrogen, butane and hydrofluorocarbons are preferred for the inert gas or non-oxidizing gas, carbon dioxide, argon, nitrogen and hydrofluorocarbons are more preferred, and carbon dioxide, argon and hydrofluorocarbons are most preferred. Can be used. These non-oxidizing gases can be used alone or in a combination of two or more.
（軽油槽の温度及び接触処理時間）
軽油槽の温度は１５℃以上５０℃以下が好ましく、１７℃以上４０℃以下がより好ましく、２０℃以上３０℃以下が最も好ましい。接触処理時間は２時間以上７２時間以下が好ましく、６時間以上６０時間以下がより好ましく、１２時間以上４８時間以下が最も好ましい。また、図１のように軽油槽内を攪拌することは、熱処理白土と軽油との接触が促進されるので好ましい。
(Light oil tank temperature and contact treatment time)
The temperature of the light oil tank is preferably 15 ° C or higher and 50 ° C or lower, more preferably 17 ° C or higher and 40 ° C or lower, and most preferably 20 ° C or higher and 30 ° C or lower. The contact treatment time is preferably from 2 hours to 72 hours, more preferably from 6 hours to 60 hours, and most preferably from 12 hours to 48 hours. Further, stirring in the light oil tank as shown in FIG. 1 is preferable because the contact between the heat treated clay and the light oil is promoted.
以下に実施例を示し、本発明をより詳細に開示する。また、これらの実施例及び比較例は表１及び表２に概要をまとめた。しかしながら、実施例等は本発明の本質を説明するためのものであり、これらによって本発明の範囲を限定的に解釈してはならない。 The following examples illustrate the present invention in more detail. These examples and comparative examples are summarized in Tables 1 and 2. However, the examples and the like are for explaining the essence of the present invention, and the scope of the present invention should not be construed as being limited thereto.
＜軽油の性状改善評価方法＞
軽油の性状改善評価は紫外可視吸収スペクトルにより行う。紫外可視吸収スペクトルは、光の波長（ｎｍ）と吸光度の関係で表され、吸光度が減少するほど無色に近づくことを意味する。本発明では、波長３６０ｎｍ以上７８０ｎｍ以下の吸光度の積分値を単に吸光度積分値と呼び、前記吸光度積分値を性状改善の指標とする。なお、吸光度は無次元量なので吸光度積分値の単位はｎｍとなる。軽油の吸光度積分値が３０ｎｍ未満であれば、見た目ではほぼ無色である。従って、以下の実施例および比較例における軽油の性状改善評価は、吸光度積分値が３０未満を適、３０以上を否とする。
<Light oil property improvement evaluation method>
The property improvement evaluation of light oil is performed by UV-visible absorption spectrum. The UV-visible absorption spectrum is represented by the relationship between the wavelength of light (nm) and the absorbance, and it means that it becomes more colorless as the absorbance decreases. In the present invention, the integrated value of absorbance at wavelengths of 360 nm or more and 780 nm or less is simply referred to as absorbance integrated value, and the absorbance integrated value is used as an index for improving properties. Since the absorbance is a dimensionless quantity, the unit of the absorbance integrated value is nm. If the integrated value of absorbance of light oil is less than 30 nm, it is almost colorless in appearance. Accordingly, the light oil property improvement evaluation in the following examples and comparative examples is appropriate when the absorbance integral value is less than 30 and not more than 30.
＜実施例１＞
処理対象の軽油には市販のJIS１号軽油の中から黄色に呈色していたものを用いた。前記軽油について紫外可視吸収スペクトルを測定したところ、吸光度積分値は５２．９ｎｍであった。処理剤の酸性白土は空気中８０℃で１０時間熱処理することで熱処理白土１を得た。次に図１の装置を用い遮光された軽油槽内に前記軽油１０００ｍｌとともに熱処理白土１を１５０ｇ加え、前記軽油槽の空間部分を窒素で置換した。次に前記軽油槽を４０℃に保ち槽内を２時間攪拌して軽油と熱処理白土１を接触処理したところ、軽油はほぼ無色に性状改善された。処理前及び処理後の軽油の紫外可視吸収スペクトルを図２に示す。吸光度積分値は５２．９ｎｍから２７．８ｎｍに減少した。このように可視領域の吸光度が減少して無色に近くなり、本実施例による軽油の性状改善評価は適であった。なお、実施例２以降は、実施例１と同様に吸光度積分値を算出し性状改善評価を行った。
<Example 1>
As the light oil to be treated, a commercially available JIS No. 1 light oil that was colored yellow was used. When the ultraviolet visible absorption spectrum was measured about the said light oil, the absorbance integrated value was 52.9 nm. The acid clay of the treating agent was heat-treated at 80 ° C. for 10 hours in air to obtain heat-treated
＜実施例２＞
酸性白土を空気中１２０℃で８時間熱処理することで熱処理白土２を得た。次に遮光された軽油槽内に実施例１と同じ市販軽油１０００ｍｌとともに熱処理白土２を１３０ｇ加え、前記軽油槽の空間部分をブタンで置換した。次に前記軽油槽を３０℃に保ち槽内を１２時間攪拌して軽油と熱処理白土２を接触処理したところ、軽油の呈色は減少し、吸光度積分値は２５．６ｎｍに減少した。よって、本実施例による軽油の性状改善評価は適であった。
<Example 2>
The heat-treated clay 2 was obtained by heat-treating the acid clay at 120 ° C. in air for 8 hours. Next, 130 g of heat-treated white clay 2 was added together with 1000 ml of the same commercially available light oil as in Example 1 in the light oil tank protected from light, and the space portion of the light oil tank was replaced with butane. Next, when the light oil tank was kept at 30 ° C. and the inside of the tank was stirred for 12 hours and the light oil and the heat-treated clay 2 were contact-treated, the coloration of the light oil decreased and the integrated absorbance value decreased to 25.6 nm. Therefore, the property improvement evaluation of the light oil by a present Example was suitable.
＜実施例３＞
酸性白土を空気中２００℃で５時間熱処理することで熱処理白土３を得た。次に遮光された軽油槽内に実施例１と同じ市販軽油１０００ｍｌとともに熱処理白土３を８０ｇ加え、前記軽油槽の空間部分を置換せず空気のままとした。次に室温（２０℃）において前記軽油槽内を６時間攪拌して軽油と熱処理白土３を接触処理したところ、軽油の呈色は減少し、吸光度積分値は２７．０ｎｍに減少した。よって、本実施例による軽油の性状改善評価は適であった。
<Example 3>
The heat-treated clay 3 was obtained by heat-treating the acid clay at 200 ° C. for 5 hours in the air. Next, 80 g of heat-treated clay 3 was added into the light oil tank protected from light and 1000 ml of the same commercially available light oil as in Example 1, and the space portion of the light oil tank was not replaced but left as air. Next, when the inside of the light oil tank was stirred for 6 hours at room temperature (20 ° C.) and the light oil and the heat-treated clay 3 were subjected to contact treatment, the coloration of the light oil decreased, and the absorbance integrated value decreased to 27.0 nm. Therefore, the property improvement evaluation of the light oil by a present Example was suitable.
＜実施例４＞
酸性白土を空気中１３０℃で６時間熱処理することで熱処理白土４を得た。次に遮光された軽油槽内に実施例１と同じ市販軽油１０００ｍｌとともに熱処理白土４を１１０ｇ加え、前記軽油槽の空間部分を二酸化炭素で置換した。次に室温（１７℃）において前記軽油槽内を４８時間攪拌して軽油と熱処理白土４を接触処理したところ、軽油の呈色は減少し、吸光度積分値は２５．８ｎｍに減少した。よって、本実施例による軽油の性状改善評価は適であった。
<Example 4>
The heat-treated clay 4 was obtained by heat-treating the acid clay at 130 ° C. in air for 6 hours. Next, 110 g of heat treated clay 4 was added to the light oil tank protected from light and 1000 ml of the same commercially available light oil as in Example 1, and the space portion of the light oil tank was replaced with carbon dioxide. Next, when the inside of the light oil tank was stirred for 48 hours at room temperature (17 ° C.) and the light oil and the heat-treated clay 4 were contact-treated, the coloration of the light oil decreased and the integrated value of absorbance decreased to 25.8 nm. Therefore, the property improvement evaluation of the light oil by a present Example was suitable.
＜実施例５＞
酸性白土を空気中２３０℃で４時間熱処理することで熱処理白土５を得た。次に遮光された軽油槽内に実施例１と同じ市販軽油１０００ｍｌとともに熱処理白土５を６０ｇ加え、前記軽油槽の空間部分をアルゴンで置換した。次に前記軽油槽を１５℃に保ち槽内を６０時間攪拌して軽油と熱処理白土５を接触処理したところ、軽油の呈色は減少し、吸光度積分値は２７．５ｎｍに減少した。よって、本実施例による軽油の性状改善評価は適であった。
<Example 5>
The heat-treated clay 5 was obtained by heat-treating the acid clay at 230 ° C. for 4 hours in the air. Next, 60 g of heat-treated clay 5 was added together with 1000 ml of the same commercially available light oil as in Example 1 in the light oil tank protected from light, and the space portion of the light oil tank was replaced with argon. Next, when the light oil tank was kept at 15 ° C. and the inside of the tank was stirred for 60 hours and the light oil and the heat-treated white clay 5 were contact-treated, the coloration of the light oil decreased and the absorbance integrated value decreased to 27.5 nm. Therefore, the property improvement evaluation of the light oil by a present Example was suitable.
＜実施例６＞
酸性白土を空気中２５０℃で３時間熱処理することで熱処理白土６を得た。次に遮光された軽油槽内に実施例１と同じ市販軽油１０００ｍｌとともに熱処理白土３を３０ｇ加え、前記軽油槽の空間部分をジフルオロメタンで置換した。次に前記軽油槽を５０℃に保ち槽内を７２時間攪拌して軽油と熱処理白土６を接触処理したところ、軽油の呈色は減少し、吸光度積分値は２９．１ｎｍに減少した。よって、本実施例による軽油の性状改善評価は適であった。
<Example 6>
The heat-treated clay 6 was obtained by heat-treating the acid clay at 250 ° C. in air for 3 hours. Next, 30 g of heat-treated clay 3 was added to the light oil tank protected from light and 1000 ml of the same commercial light oil as in Example 1, and the space portion of the light oil tank was replaced with difluoromethane. Next, when the light oil tank was kept at 50 ° C. and the inside of the tank was stirred for 72 hours and the light oil and the heat-treated clay 6 were contact-treated, the coloration of the light oil decreased, and the absorbance integrated value decreased to 29.1 nm. Therefore, the property improvement evaluation of the light oil by a present Example was suitable.
＜実施例７＞
酸性白土を空気中１８０℃で５時間熱処理することで熱処理白土７を得た。次に透明な軽油槽内に実施例１と同じ市販軽油１０００ｍｌとともに熱処理白土７を１４０ｇ加え、前記軽油槽の空間部分を二酸化炭素で置換した。次に前記軽油槽を１６℃に保ち槽内を７２時間攪拌して軽油と熱処理白土７を接触処理したところ、軽油の呈色は減少し、吸光度積分値は２７．１ｎｍに減少した。よって、本実施例による軽油の性状改善評価は適であった。
<Example 7>
The heat-treated clay 7 was obtained by heat-treating the acid clay at 180 ° C. for 5 hours in the air. Next, 140 g of heat-treated white clay 7 was added together with 1000 ml of the same commercially available light oil as in Example 1 in a transparent light oil tank, and the space portion of the light oil tank was replaced with carbon dioxide. Next, when the light oil tank was kept at 16 ° C. and the inside of the tank was stirred for 72 hours to contact the light oil and the heat-treated white clay 7, the coloration of the light oil decreased and the integrated value of absorbance decreased to 27.1 nm. Therefore, the property improvement evaluation of the light oil by a present Example was suitable.
＜実施例８＞
酸性白土を空気中１６０℃で５時間熱処理することで熱処理白土８を得た。次に透明な軽油槽内に実施例１と同じ市販軽油１０００ｍｌとともに熱処理白土８を１２０ｇ加え、前記軽油槽の空間部分をジフルオロメタンで置換した。次に室温（２２℃）において前記軽油槽内を３６時間攪拌して軽油と熱処理白土８を接触処理したところ、軽油の呈色は減少し、吸光度積分値は２７．４ｎｍに減少した。よって、本実施例による軽油の性状改善評価は適であった。
<Example 8>
The acid clay was heat-treated in air at 160 ° C. for 5 hours to obtain heat-treated clay 8. Next, 120 g of heat-treated clay 8 together with 1000 ml of the same commercially available light oil as in Example 1 was added into a transparent light oil tank, and the space portion of the light oil tank was replaced with difluoromethane. Next, when the inside of the light oil tank was stirred for 36 hours at room temperature (22 ° C.), the light oil and the heat-treated clay 8 were subjected to contact treatment. As a result, the coloration of the light oil decreased and the absorbance integrated value decreased to 27.4 nm. Therefore, the property improvement evaluation of the light oil by a present Example was suitable.
＜実施例９＞
酸性白土を空気中１４０℃で６時間熱処理することで熱処理白土９を得た。次に透明な軽油槽内に実施例１と同じ市販軽油１０００ｍｌとともに熱処理白土９を１００ｇ加え、前記軽油槽の空間部分をアルゴンで置換した。次に前記軽油槽を２５℃に保ち槽内を２４時間攪拌して軽油と熱処理白土９を接触処理したところ、軽油の呈色は減少し、吸光度積分値は２７．８ｎｍに減少した。よって、本実施例による軽油の性状改善評価は適であった。
<Example 9>
The heat-treated clay 9 was obtained by heat-treating the acid clay at 140 ° C. for 6 hours in the air. Next, 100 g of heat-treated clay 9 was added together with 1000 ml of the same commercially available light oil as in Example 1 in a transparent light oil tank, and the space portion of the light oil tank was replaced with argon. Next, when the light oil tank was kept at 25 ° C. and the inside of the tank was stirred for 24 hours and the light oil and the heat-treated clay 9 were contact-treated, the coloration of the light oil decreased, and the absorbance integrated value decreased to 27.8 nm. Therefore, the property improvement evaluation of the light oil by a present Example was suitable.
＜実施例１０＞
酸性白土を空気中２２０℃で４時間熱処理することで熱処理白土１０を得た。次に透明な軽油槽内に実施例１と同じ市販軽油１０００ｍｌとともに熱処理白土１０を９０ｇ加え、前記軽油槽の空間部分をブタンで置換した。次に室温（１８℃）において前記軽油槽内を６０時間攪拌して軽油と熱処理白土１０を接触処理したところ、軽油の呈色は減少し、吸光度積分値は２７．２ｎｍに減少した。よって、本実施例による軽油の性状改善評価は適であった。
<Example 10>
The heat-treated clay 10 was obtained by heat-treating the acid clay at 220 ° C. for 4 hours in the air. Next, 90 g of heat-treated white clay 10 was added into a transparent light oil tank together with 1000 ml of the same commercially available light oil as in Example 1, and the space portion of the light oil tank was replaced with butane. Next, when the inside of the light oil tank was stirred at room temperature (18 ° C.) for 60 hours and the light oil and the heat-treated clay 10 were contact-treated, the coloration of the light oil decreased and the integrated value of absorbance decreased to 27.2 nm. Therefore, the property improvement evaluation of the light oil by a present Example was suitable.
＜実施例１１＞
酸性白土を空気中１１０℃で８時間熱処理することで熱処理白土１１を得た。次に透明な軽油槽内に実施例１と同じ市販軽油１０００ｍｌとともに熱処理白土１１を５０ｇ加え、前記軽油槽の空間部分を窒素で置換した。次に３０℃において前記軽油槽内を８時間攪拌して軽油と熱処理白土１１を接触処理したところ、軽油の呈色は減少し、吸光度積分値は２９．４ｎｍに減少した。よって、本実施例による軽油の性状改善評価は適であった。
<Example 11>
The heat-treated white clay 11 was obtained by heat-treating the acid white clay in air at 110 ° C. for 8 hours. Next, 50 g of the heat-treated clay 11 was added to a transparent light oil tank together with 1000 ml of the same commercially available light oil as in Example 1, and the space portion of the light oil tank was replaced with nitrogen. Next, when the inside of the light oil tank was stirred for 8 hours at 30 ° C. and the light oil and the heat-treated clay 11 were contact-treated, the coloration of the light oil decreased and the integrated value of absorbance decreased to 29.4 nm. Therefore, the property improvement evaluation of the light oil by a present Example was suitable.
＜比較例１＞
実施例３において、透明な軽油槽を用いた以外は同条件で熱処理白土３と軽油との接触処理を行った。処理後の軽油は黄色味を帯びており、吸光度積分値は４２．７ｎｍであった。よって、軽油の性状改善評価は否であった。本比較例は、軽油槽空間部分が空気である場合、軽油槽を遮光しないと十分な性状改善効果が得られないことを示す例である。
<Comparative Example 1>
In Example 3, the heat treatment clay 3 and light oil were contacted under the same conditions except that a transparent light oil tank was used. The light oil after the treatment was yellowish and the integrated value of absorbance was 42.7 nm. Therefore, the property improvement evaluation of light oil was no. This comparative example is an example showing that when the light oil tank space is air, a sufficient property improving effect cannot be obtained unless the light oil tank is shielded from light.
＜比較例２＞
実施例２において、熱処理白土と軽油との接触時間を１時間とした以外は同条件で熱処理白土２と軽油との接触処理を行った。処理後の軽油の呈色は黄色味を帯びており、吸光度積分値は３５．５ｎｍであった。よって、性状改善評価は否であった。本比較例は、熱処理白土と軽油との接触時間が好適な範囲を満たさない場合には、所望の性状改善効果が得られないことを示す例である。
<Comparative example 2>
In Example 2, the contact treatment between the heat-treated clay 2 and light oil was performed under the same conditions except that the contact time between the heat-treated clay and light oil was 1 hour. The color of the light oil after the treatment was yellowish, and the absorbance integrated value was 35.5 nm. Therefore, the property improvement evaluation was no. This comparative example is an example showing that the desired property improving effect cannot be obtained when the contact time between the heat-treated clay and the light oil does not satisfy a suitable range.
＜比較例３＞
実施例３において、熱処理白土と軽油との接触時間を１時間とした以外は同条件で熱処理白土３と軽油との接触処理を行った。処理後の軽油の呈色は黄色味を帯びており、吸光度積分値は３６．２ｎｍであった。よって性状改善評価は否であった。本比較例は、軽油槽空間部分のガスが空気であって遮光された軽油槽を用いた場合でも熱処理白土と軽油との接触時間が好適な範囲を満たさない場合には、所望の性状改善効果が得られないことを示す例である。
<Comparative Example 3>
In Example 3, the contact treatment between the heat treated white clay 3 and the light oil was performed under the same conditions except that the contact time between the heat treated white clay and the light oil was set to 1 hour. The color of the light oil after the treatment was yellowish, and the absorbance integrated value was 36.2 nm. Therefore, the property improvement evaluation was no. In this comparative example, even when a gas oil tank in which the gas in the light oil tank space is air and is shielded from light is used, if the contact time between the heat-treated white clay and the light oil does not satisfy the preferred range, the desired property improvement effect This is an example showing that cannot be obtained.
＜比較例４＞
実施例４において、熱処理白土の添加量を１０ｇとした以外は同条件で熱処理白土４と軽油との接触処理を行った。処理後の軽油の呈色は黄色味を帯びており、吸光度積分値は３７．５ｎｍであった。よって性状改善評価は否であった。本比較例は、熱処理白土の添加量が好適な範囲を満たさない場合には、所望の性状改善効果が得られないことを示す例である。
<Comparative example 4>
In Example 4, the contact treatment of the heat treated clay 4 and light oil was performed under the same conditions except that the amount of the heat treated clay added was 10 g. The color of the light oil after the treatment was yellowish, and the integrated absorbance was 37.5 nm. Therefore, the property improvement evaluation was no. This comparative example is an example showing that a desired property improving effect cannot be obtained when the amount of heat-treated clay added does not satisfy the preferred range.
＜比較例５＞
実施例５において、軽油槽の温度を５℃に保持した以外は同条件で熱処理白土５と軽油との接触処理を行った。処理後の軽油の呈色は黄色味を帯びており、吸光度積分値は３３．１ｎｍであった。よって性状改善評価は否であった。本比較例は、軽油槽の温度が好適な範囲を満たさない場合には、所望の性状改善効果が得られないことを示す例である。
<Comparative Example 5>
In Example 5, the heat treatment clay 5 and the light oil were subjected to contact treatment under the same conditions except that the temperature of the light oil tank was maintained at 5 ° C. The color of the light oil after the treatment was yellowish, and the absorbance integrated value was 33.1 nm. Therefore, the property improvement evaluation was no. This comparative example is an example showing that the desired property improving effect cannot be obtained when the temperature of the light oil tank does not satisfy the preferred range.
＜比較例６＞
酸性白土を空気中５０℃で５時間熱処理することで熱処理白土１０６を得た。実施例３において、熱処理白土３の代わりに熱処理白土１０６を用いて軽油との接触処理を行った。処理後の軽油の呈色は黄色味を帯びており、吸光度積分値は３７．４ｎｍであった。よって性状改善評価は否であった。本比較例は、酸性白土の熱処理温度が好適な範囲を満たさない場合には、所望の性状改善効果が得られないことを示す例である。
<Comparative Example 6>
The acid clay was heat-treated in air at 50 ° C. for 5 hours to obtain a heat-treated clay 106. In Example 3, the heat treatment white clay 106 was used in place of the heat treated white clay 3 to perform contact treatment with light oil. The color of the light oil after the treatment was yellowish, and the absorbance integrated value was 37.4 nm. Therefore, the property improvement evaluation was no. This comparative example is an example showing that the desired property improving effect cannot be obtained when the heat treatment temperature of the acid clay does not satisfy a suitable range.
＜比較例７＞
酸性白土を空気中１３０℃で１時間熱処理することで熱処理白土１０７を得た。実施例４において、熱処理白土４の代わりに熱処理白土１０７を用いて軽油との接触処理を行った。処理後の軽油の呈色は黄色味を帯びており、吸光度積分値は３４．９ｎｍであった。よって性状改善評価は否であった。本比較例は、酸性白土の熱処理時間が好適な範囲を満たさない場合には、所望の性状改善効果が得られないことを示す例である。
<Comparative Example 7>
The heat-treated white clay 107 was obtained by heat-treating the acid white clay in air at 130 ° C. for 1 hour. In Example 4, the heat treatment white clay 107 was used in place of the heat treated white clay 4, and contact treatment with light oil was performed. The color of the light oil after the treatment was yellowish, and the absorbance integrated value was 34.9 nm. Therefore, the property improvement evaluation was no. This comparative example is an example showing that the desired property improving effect cannot be obtained when the heat treatment time of the acid clay does not satisfy a suitable range.
＜比較例８＞
酸性白土を空気中３８０℃で５時間熱処理することで熱処理白土１０８を得た。実施例８において、熱処理白土８の代わりに熱処理白土１０８を用いて軽油との接触処理を行った。処理後の軽油の呈色は黄色味を帯びており、吸光度積分値は３９．０ｎｍであった。よって性状改善評価は否であった。本比較例は、酸性白土の熱処理温度が好適な範囲を超過した場合には、所望の性状改善効果が得られないことを示す例である。
<Comparative Example 8>
The heat-treated white clay 108 was obtained by heat-treating the acid white clay at 380 ° C. for 5 hours in the air. In Example 8, the heat treatment white clay 108 was used in place of the heat treated white clay 8 to perform contact treatment with light oil. The color of the light oil after the treatment was yellowish, and the absorbance integrated value was 39.0 nm. Therefore, the property improvement evaluation was no. This comparative example is an example showing that the desired property improving effect cannot be obtained when the heat treatment temperature of the acid clay exceeds a suitable range.
酸性白土を熱処理して得られる熱処理白土と軽油を接触処理することにより、多環芳香族化合物及び呈色が少ない性状に優れた軽油を得ることができるようになる。 By heat-treating heat-treated clay obtained by heat-treating acid clay and light oil, it becomes possible to obtain light oil excellent in properties with less polycyclic aromatic compounds and coloration.
１ 軽油槽
２ 処理対象軽油
３ 酸性白土
４ 攪拌手段
1 Light oil tank 2 Light oil to be treated 3 Acid clay 4 Stirring means
Claims (5)
In the light oil tank where light shielding is incomplete, the space between the liquid surface of the light oil and the tank is replaced with at least one selected from carbon dioxide, argon, nitrogen, butane and hydrofluorocarbons. 4. The method for improving the properties of light oil according to any one of 3
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| US20030150780A1 (en) * | 2001-12-10 | 2003-08-14 | India Oil Corporation Limited | Process and an apparatus for preparation of petroleum hydrocarbon solvent with improved color stability from nitrogen rich crude oil |
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