JP4994327B2 - Kerosene composition and method for producing the same - Google Patents
Kerosene composition and method for producing the same Download PDFInfo
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
本発明は、灯油組成物に関する。詳しくは、石油ストーブや石油ファンヒーター等の暖房機器などに用いられる灯油組成物に関する。 The present invention relates to a kerosene composition. Specifically, the present invention relates to a kerosene composition used in heating equipment such as an oil stove and an oil fan heater.
環境問題への関心が社会的に高まる中、室内暖房機器の分野では、暖房機器から排出される臭気物質(炭化水素等)や汚染物質(SOx等)を低減する技術が検討されている。例えば臭気物質の低減方法としては、暖房機器の燃焼部の改善、排出ガス浄化装置の装着等が提案されている(例えば、特許文献1参照)。 While interest in environmental issues is socially increasing, in the field of indoor heating equipment, technologies for reducing odorous substances (such as hydrocarbons) and pollutants (such as SOx) discharged from heating equipment are being studied. For example, as a method for reducing odorous substances, improvement of a combustion part of a heating device, installation of an exhaust gas purification device, and the like have been proposed (see, for example, Patent Document 1).
一方、暖房機器の燃料としては、例えばn−パラフィンおよびi−パラフィン類よりなる灯油の使用が提案されている(例えば、特許文献2参照)。
しかし、上記従来の灯油は、燃焼部の改善や排出ガス浄化装置の装着が施されていない既存の暖房機器の燃料としては十分とはいえない。また、従来の灯油を燃焼部の改善や排出ガス浄化装置の装着が施された暖房機器に用いる場合も、長期にわたってクリーンな燃焼を持続させることは必ずしも容易でない。 However, the above-mentioned conventional kerosene is not sufficient as a fuel for existing heating equipment that has not been improved in the combustion section or fitted with an exhaust gas purification device. In addition, even when conventional kerosene is used in a heating device having an improved combustion section or an exhaust gas purification device, it is not always easy to maintain clean combustion over a long period of time.
本発明は、このような実情に鑑みてなされたものであり、暖房機器を長期にわたって安定的に運転することが可能な灯油組成物及びその製造方法を提供することを目的とする。 This invention is made | formed in view of such a situation, and it aims at providing the kerosene composition which can drive | operate a heating apparatus stably over a long period of time, and its manufacturing method.
本発明者らは、上記目的を達成すべく鋭意検討を重ねた結果、特定の深度水素化処理が施された灯油基材であって、蒸留性状、ナフテン分、全芳香族分、二環以上の芳香族分、ナフテン分/全芳香族分の容量比、硫黄分、並びに密度が特定条件を満たす灯油組成物を暖房機器の燃料として用いた場合に上記課題が解決されることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the inventors of the present invention are kerosene base materials that have been subjected to a specific deep hydrogenation treatment, and include distillation properties, naphthene content, total aromatic content, two or more rings. It was found that the above-mentioned problems can be solved when a kerosene composition satisfying specific conditions of the aromatic content, naphthene content / total aromatic content volume ratio, sulfur content, and density is used as a fuel for heating equipment. The invention has been completed.
すなわち、本発明の灯油組成物は、未精製油及び水素化精製油から選ばれる少なくとも1種を含む原料油を、水素化触媒存在下、反応温度100〜350℃、水素圧力1〜6MPa、液空間速度0.1〜4h−1、水素/油比70〜500NL/Lで深度水素化処理して得られる灯油基材であって、蒸留性状における初留点が140℃以上、終点が300℃以下、30容量%留出温度が189〜210℃、50容量%留出温度が190〜230℃、70容量%留出温度が220〜250℃であり、ナフテン分が20容量%以上、全芳香族分が15容量%以下、二環以上の芳香族分が1容量%以下、ナフテン分/全芳香族分の容量比が2.0以上、硫黄分が10質量ppm以下、15℃における密度が770〜820kg/m3である灯油基材を含有し、全芳香族分が15容量%以下であることを特徴とする。 That is, the kerosene composition of the present invention comprises a raw material oil containing at least one selected from unrefined oil and hydrorefined oil in the presence of a hydrogenation catalyst, reaction temperature of 100 to 350 ° C., hydrogen pressure of 1 to 6 MPa, liquid A kerosene base material obtained by deep hydrogenation treatment at a space velocity of 0.1 to 4 h −1 and a hydrogen / oil ratio of 70 to 500 NL / L, having an initial boiling point of 140 ° C. or higher and an end point of 300 ° C. in distillation properties. Hereinafter, the 30 vol% distillation temperature is 189 to 210 ° C, the 50 vol% distillation temperature is 190 to 230 ° C, the 70 vol% distillation temperature is 220 to 250 ° C, and the naphthene content is 20 vol% or more. 15% by volume or less of aromatics, 1% by volume or less of aromatics having two or more rings, a volume ratio of naphthene / total aromatics of 2.0 or more, sulfur content of 10 mass ppm or less, and a density at 15 ° C. 770~820kg / m 3 a is kerosene based on Containing, total aromatic content is equal to or less than 15 volume%.
本発明では、原料油を特定条件で深度水素化処理し、蒸留性状、ナフテン分、全芳香族分、二環以上の芳香族分、ナフテン分/全芳香族分の容量比、硫黄分、並びに密度が特定条件を満たす灯油基材を得る。本発明の灯油組成物は当該灯油基材を含有するものであり、これにより、灯油組成物の燃焼性を飛躍的に改善することができ、さらに高水準の燃焼性を長期間維持することができる。また、本発明の灯油組成物は、安定性、引火性、安全性、並びに暖房機器の燃焼部や排ガス浄化装置に対する適合性にも優れる。従って、本発明の灯油組成物を暖房機器に用いることにより、燃費の向上、臭気物質及び汚染物質の排出量の低減、暖房機器への負荷の低減などが実現可能となり、その結果、暖房機器を長期にわたって安定的に運転することが可能となる。 In the present invention, raw oil is subjected to deep hydrotreating under specific conditions, distillation properties, naphthene content, total aromatic content, aromatic content of two or more rings, naphthene content / total aromatic content ratio, sulfur content, and A kerosene base material whose density satisfies a specific condition is obtained. The kerosene composition of the present invention contains the kerosene base material, which can drastically improve the combustibility of the kerosene composition and can maintain a high level of combustibility for a long period of time. it can. Moreover, the kerosene composition of the present invention is excellent in stability, flammability, safety, and adaptability to a combustion part of a heating device and an exhaust gas purification device. Therefore, by using the kerosene composition of the present invention for heating equipment, it becomes possible to improve fuel efficiency, reduce the emission of odorous substances and pollutants, reduce the load on the heating equipment, etc. It becomes possible to operate stably over a long period of time.
本発明の灯油組成物の全芳香族分が10容量%以下であることが好ましい。 The total aromatic content of the kerosene composition of the present invention is preferably 10% by volume or less.
また、深度水素化処理に用いられる原料油は、その蒸留性状における初留点が140℃以上、終点が310℃以下であることが好ましい。 In addition, the raw oil used for the deep hydrogenation treatment preferably has an initial boiling point of 140 ° C. or higher and an end point of 310 ° C. or lower in the distillation properties.
また、本発明の灯油組成物の製造方法は、未精製油及び水素化精製油から選ばれる少なくとも1種を含む原料油を、水素化触媒存在下、反応温度100〜350℃、水素圧力1〜6MPa、LHSV0.1〜4h−1、水素/油比70〜500NL/Lで深度水素化処理し、蒸留性状における初留点が140℃以上、終点が300℃以下、50容量%留出温度が190〜230℃であり、ナフテン分が20容量%以上、全芳香族分が15容量%以下、二環以上の芳香族分が1容量%以下、ナフテン分/全芳香族分の容量比が2.0以上、硫黄分が10質量ppm以下、15℃における密度が770〜820kg/m3である灯油基材を得る工程を有することを特徴とする。 In the method for producing a kerosene composition of the present invention, a raw material oil containing at least one selected from unrefined oil and hydrorefined oil is prepared in the presence of a hydrogenation catalyst at a reaction temperature of 100 to 350 ° C., a hydrogen pressure of 1 Deep hydrogenation treatment is performed at 6 MPa, LHSV 0.1 to 4 h −1 , hydrogen / oil ratio 70 to 500 NL / L, the initial distillation point in distillation properties is 140 ° C. or higher, the end point is 300 ° C. or lower, and the 50% by volume distillation temperature is 190 to 230 ° C., naphthene content of 20% by volume or more, total aromatic content of 15% by volume or less, bicyclic or higher aromatic content of 1% by volume or less, naphthene content / total aromatic content volume ratio is 2 It is characterized by having a step of obtaining a kerosene base material having a sulfur content of 0.0 or more, a sulfur content of 10 mass ppm or less, and a density at 15 ° C. of 770 to 820 kg / m 3 .
上記製造方法によれば、暖房機器を長期にわたって安定的に運転することが可能な本発明の灯油組成物を容易に且つ確実に得ることができる。 According to the said manufacturing method, the kerosene composition of this invention which can drive | operate a heating apparatus stably over a long period of time can be obtained easily and reliably.
本発明によれば、暖房機器を長期にわたって安定的に運転することが可能な灯油組成物及びその製造方法を提供することが可能となる。 ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the kerosene composition which can drive a heating apparatus stably over a long period of time, and its manufacturing method.
以下、本発明の好適な実施形態について詳細に説明する。 Hereinafter, preferred embodiments of the present invention will be described in detail.
(灯油基材)
本発明にかかる灯油基材は、未精製油及び水素化精製油から選ばれる少なくとも1種を含む原料油に特定の深度水素化処理を施すことにより得られる。
(Kerosene base material)
The kerosene base material according to the present invention is obtained by subjecting a raw oil containing at least one selected from unrefined oil and hydrorefined oil to a specific deep hydrogenation treatment.
未精製油及び水素化精製油としては、具体的には例えば、原油の常圧蒸留装置から得られる直留灯油、直留灯油を水素化精製して得られる水素化脱硫灯油、常圧蒸留装置から得られる直留重質油や残査油を減圧蒸留装置で処理して得られる減圧軽油留分を水素化精製して得られる水素化精製灯油、減圧軽油留分を水素化分解した水素化分解灯油、減圧軽油留分あるいは脱硫重油を接触分解して得られる接触分解灯油、直留重質油を熱分解して得られる熱分解灯油、熱分解灯油を水素化精製して得られる水素化脱硫灯油、残査油を水素化精製して得られる水素化脱硫灯油等が挙げられる。これらの原料油は1種を単独で又は2種以上を組み合わせて用いることができる。 Specific examples of unrefined oil and hydrorefined oil include straight-run kerosene obtained from a crude oil atmospheric distillation device, hydrodesulfurized kerosene obtained by hydrorefining straight-run kerosene, and atmospheric distillation device. Hydrocracked kerosene obtained by hydrorefining a vacuum gas oil fraction obtained by treating straight-run heavy oil and residual oil obtained from the above with a vacuum distillation unit, and hydrogenation obtained by hydrocracking a vacuum gas oil fraction Hydrogenation obtained by hydrocracking pyrolysis kerosene, pyrolysis kerosene obtained by thermal cracking of cracked kerosene, vacuum gas oil fraction or desulfurized heavy oil, catalytic cracked kerosene obtained by pyrolyzing heavy oil Examples include desulfurized kerosene and hydrodesulfurized kerosene obtained by hydrorefining residual oil. These feedstocks can be used alone or in combination of two or more.
原料油は、得られる灯油基材が本発明で規定する条件を満たせば、未精製油及び/又は水素化精製油のみからなるものであってもよく、また、他の成分をさらに含有していてもよい。他の成分としては、直留灯油または水素化脱硫灯油または水素化精製灯油の抽出によりノルマルパラフィン分を除去した残分である脱ノルマルパラフィン灯油、天然ガス等を一酸化炭素と水素に分解した後にF−T(Fischer−Tropsch)合成で得られるGTL(Gas to Liquids)の灯油留分及び/又はその水素化分解物などが挙げられる。原料油がこれらの成分を含有する場合、未精製油及び水素化精製油の合計量は、50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、70容量%以上であることがさらに好ましい。 The raw material oil may be composed of only unrefined oil and / or hydrorefined oil as long as the obtained kerosene base material satisfies the conditions specified in the present invention, and further contains other components. May be. Other components include demineralized kerosene, which is a residue obtained by removing normal paraffin by extraction of straight-run kerosene, hydrodesulfurized kerosene, or hydrorefined kerosene, after decomposing natural gas into carbon monoxide and hydrogen. Examples include kerosene fractions of GTL (Gas to Liquids) obtained by FT (Fischer-Tropsch) synthesis and / or hydrocracked products thereof. When the raw material oil contains these components, the total amount of unrefined oil and hydrorefined oil is preferably 50% by volume or more, more preferably 60% by volume or more, and 70% by volume or more. More preferably it is.
また、原料油の蒸留性状は特に制限されないが、その初留点は140℃以上であることが好ましい。また、原料油の終点は、好ましくは310℃以下、より好ましくは305℃以下、さらに好ましくは300℃以下である。かかる蒸留性状を有する原料油を用いることで、本発明にかかる灯油基材を確実に得ることができる。また、原料油の蒸留性状が上記条件を満たすことで、より高い脱硫効果を得ることができる。 The distillation property of the raw material oil is not particularly limited, but the initial boiling point is preferably 140 ° C. or higher. The end point of the raw material oil is preferably 310 ° C. or lower, more preferably 305 ° C. or lower, and further preferably 300 ° C. or lower. By using the raw material oil having such distillation properties, the kerosene base material according to the present invention can be reliably obtained. Moreover, the higher desulfurization effect can be acquired because the distillation property of raw material oil satisfy | fills the said conditions.
原料油の深度水素化処理は、反応温度100〜350℃、水素圧力1〜6MPa、液空間速度0.1〜4h−1、水素/油比70〜500NL/Lの条件下で行われる。 The raw material oil is deeply hydrogenated under the conditions of a reaction temperature of 100 to 350 ° C., a hydrogen pressure of 1 to 6 MPa, a liquid space velocity of 0.1 to 4 h −1 , and a hydrogen / oil ratio of 70 to 500 NL / L.
深度水素化処理における反応温度は、100〜350℃であり、好ましくは130〜320℃である。反応温度が100℃未満であると十分な水素化反応速度が得られず、一方、350℃を超えると水素化反応が反応平衡の点で不十分となる。 The reaction temperature in the deep hydrogenation treatment is 100 to 350 ° C, preferably 130 to 320 ° C. When the reaction temperature is less than 100 ° C., a sufficient hydrogenation reaction rate cannot be obtained. On the other hand, when the reaction temperature exceeds 350 ° C., the hydrogenation reaction becomes insufficient in terms of reaction equilibrium.
深度水素化処理における水素圧力は、1〜6MPaであり、好ましくは2〜6MPaである。また、水素/油比は、70〜500NL/Lであり、好ましくは90〜400NL/Lである。水素圧力が1MPa未満の場合、及び水素/油比が70NL/L未満の場合には、脱硫反応又は水素化反応の促進効果が不十分となる。また、水素圧力が6MPaを超える場合、及び水素/油比が500NL/Lを超える場合には、製造コストが増大してしまう。 The hydrogen pressure in the deep hydrogenation treatment is 1 to 6 MPa, preferably 2 to 6 MPa. The hydrogen / oil ratio is 70 to 500 NL / L, preferably 90 to 400 NL / L. When the hydrogen pressure is less than 1 MPa and the hydrogen / oil ratio is less than 70 NL / L, the effect of promoting the desulfurization reaction or hydrogenation reaction is insufficient. In addition, when the hydrogen pressure exceeds 6 MPa and when the hydrogen / oil ratio exceeds 500 NL / L, the manufacturing cost increases.
深度水素化処理における液空間速度(Liquid Hourly Space Velocity、以下「LHSV」という)は0.1〜4h−1であり、好ましくは0.2〜3h−1である。LHSVは低いほど反応に有利であるが、0.1h−1未満の場合には、極めて大きな反応塔容積が必要となる。 The liquid space velocity (Liquid Hourly Space Velocity, hereinafter referred to as “LHSV”) in the deep hydrogenation treatment is 0.1 to 4 h −1 , preferably 0.2 to 3 h −1 . A lower LHSV is advantageous for the reaction, but if it is less than 0.1 h −1 , a very large reaction column volume is required.
深度水素化処理に用いる触媒は、特に限定されるものではないが、例えば水素化活性金属を多孔質担体に担持したものが挙げられる。多孔質担体としては無機酸化物が好ましく用いられる。具体的な無機酸化物としては、アルミナ、チタニア、ジルコニア、ボリア、シリカ、あるいはゼオライトが挙げられ、このうちチタニア、ジルコニア、ボリア、シリカ、ゼオライトのうち少なくとも1種類とアルミナによって構成されているものが本発明において好適に用いられる。 The catalyst used for the deep hydrogenation treatment is not particularly limited, and examples thereof include a catalyst in which a hydrogenation active metal is supported on a porous carrier. An inorganic oxide is preferably used as the porous carrier. Specific examples of the inorganic oxide include alumina, titania, zirconia, boria, silica, and zeolite. Among these, at least one of titania, zirconia, boria, silica, and zeolite and an alumina is used. It is suitably used in the present invention.
深度水素化処理に用いる触媒の活性金属としては周期律表第6族及び/または第8族金属から選ばれる少なくとも1種類の金属であることが好ましい。より好ましくはRu,Rd,Ir,Pd,Pt,Ni,Co,Mo,Wから選ばれる少なくとも1種類である。活性金属としてはこれらの金属を組み合わせたものでもよく、例えばPt−Pd,Pt−Rh,Pt−Ru,Ir−Pd,Ir−Rh,Ir−Ru,Pt−Pd−Rh,Pt−Rh−Ru,Ir−Pd−Rh,Ir−Rh−Ru,Co−Mo,Ni−Mo,Ni−Wなどの組み合わせを採用することができる。活性金属の担持量は特に限定されないが、触媒質量に対し金属量合計で0.1〜30質量%であることが望ましい。 The active metal of the catalyst used for the deep hydrogenation treatment is preferably at least one metal selected from Group 6 and / or Group 8 metals in the periodic table. More preferably, it is at least one selected from Ru, Rd, Ir, Pd, Pt, Ni, Co, Mo, and W. The active metal may be a combination of these metals, for example, Pt-Pd, Pt-Rh, Pt-Ru, Ir-Pd, Ir-Rh, Ir-Ru, Pt-Pd-Rh, Pt-Rh-Ru. , Ir-Pd-Rh, Ir-Rh-Ru, Co-Mo, Ni-Mo, Ni-W, and the like can be employed. Although the amount of active metal supported is not particularly limited, it is desirable that the total amount of metal is 0.1 to 30% by mass with respect to the catalyst mass.
触媒は水素または硫化水素気流下において予備還元処理を施した後に用いるのが好ましい。一般的には水素または硫化水素を含むガスを流通し、200℃以上の熱を所定の手順に従って与えることにより触媒上の活性金属が還元され、水素化活性を発現することになる。 The catalyst is preferably used after pre-reduction treatment in a hydrogen or hydrogen sulfide stream. In general, when a gas containing hydrogen or hydrogen sulfide is circulated and heat of 200 ° C. or higher is applied according to a predetermined procedure, the active metal on the catalyst is reduced, and hydrogenation activity is exhibited.
上記の深度水素化処理により得られる本発明にかかる灯油基材は、蒸留性状、ナフテン分、全芳香族分、二環以上の芳香族分、ナフテン分/全芳香族分の容量比、硫黄分、並びに密度が特定条件を満たすものである。以下、灯油基材の諸性状について詳述する。 The kerosene base material according to the present invention obtained by the above-described deep hydrogenation treatment has a distillation property, naphthene content, total aromatic content, aromatic content of two or more rings, naphthene content / total aromatic content volume ratio, sulfur content. As well as the density, a specific condition is satisfied. Hereinafter, various properties of the kerosene base material will be described in detail.
(蒸留性状)
灯油基材の蒸留性状における初留点は140℃以上であり、終点は300℃以下であり、50容量%留出温度は190〜230℃である。
(Distillation properties)
The initial distillation point in the distillation properties of the kerosene base material is 140 ° C. or higher, the end point is 300 ° C. or lower, and the 50 vol% distillation temperature is 190 to 230 ° C.
灯油基材の初留点は、引火点低下による安全性への影響から、140℃以上であることが必要であり、143℃以上であることが好ましく、145℃以上であることがさらに好ましい。一方、低温時の着火特性維持の点から170℃以下であることが好ましく、165℃以下であることがより好ましい。 The initial boiling point of the kerosene base material needs to be 140 ° C. or higher, preferably 143 ° C. or higher, and more preferably 145 ° C. or higher because of the influence on safety caused by the reduction of the flash point. On the other hand, the temperature is preferably 170 ° C. or lower, more preferably 165 ° C. or lower, from the viewpoint of maintaining ignition characteristics at low temperatures.
灯油基材の終点は、300℃以下であることが必要であり、290℃以下であることが好ましく、280℃以下であることがより好ましい。終点が300℃を超える場合は点火時にススが発生しやすく、芯式ストーブに使用した場合には芯にタールが付着しやすくなる。 The end point of the kerosene base material needs to be 300 ° C. or less, preferably 290 ° C. or less, and more preferably 280 ° C. or less. When the end point exceeds 300 ° C., soot is likely to be generated at the time of ignition, and when used in a core-type stove, tar tends to adhere to the core.
灯油基材の50容量%留出温度(以下、「T50」という)は190℃以上であることが必要であり、195℃以上であることが好ましく、200℃以上であることがより好ましい。T50が190℃未満の場合は燃料消費率が悪化する。一方、燃焼性の点から、T50は、230℃以下であることが必要であり、225℃以下であることが好ましい。 The 50 vol% distillation temperature (hereinafter referred to as “T50”) of the kerosene base material is required to be 190 ° C. or higher, preferably 195 ° C. or higher, and more preferably 200 ° C. or higher. When T50 is less than 190 ° C., the fuel consumption rate deteriorates. On the other hand, from the viewpoint of combustibility, T50 needs to be 230 ° C. or lower, and is preferably 225 ° C. or lower.
灯油基材のその他の蒸留性状は特に制限されないが、下記性状を満たしていることが望ましい。 Other distillation properties of the kerosene base material are not particularly limited, but desirably satisfy the following properties.
30容量%留出温度(以下、「T30」という)は、給油時の臭気低減および発熱量の点から、170℃以上であることが好ましく、175℃以上であることがより好ましく、180℃以上であることがさらに好ましい。一方、低温時の着火性の点から、T30は210℃以下であることが好ましく、205℃以下であることがより好ましく、200℃以下であることがさらに好ましい。 The 30% by volume distillation temperature (hereinafter referred to as “T30”) is preferably 170 ° C. or higher, more preferably 175 ° C. or higher, more preferably 180 ° C. or higher, from the viewpoints of odor reduction and heat generation during refueling. More preferably. On the other hand, from the viewpoint of ignitability at low temperatures, T30 is preferably 210 ° C. or lower, more preferably 205 ° C. or lower, and further preferably 200 ° C. or lower.
70容量%留出温度(以下、「T70」という)は、発熱量の点から、220℃以上であることが好ましく、225℃以上であることがより好ましい。一方、燃焼性の点から、T70は、250℃以下であることが好ましく、245℃以下であることがより好ましい。 The 70 vol% distillation temperature (hereinafter referred to as “T70”) is preferably 220 ° C. or higher, and more preferably 225 ° C. or higher, from the viewpoint of heat generation. On the other hand, from the viewpoint of combustibility, T70 is preferably 250 ° C. or lower, and more preferably 245 ° C. or lower.
95容量%留出温度(以下、「T95」という)は、燃焼性の点から、270℃以下であることが好ましく、268℃以下であることがより好ましい。 The 95% by volume distillation temperature (hereinafter referred to as “T95”) is preferably 270 ° C. or less, and more preferably 268 ° C. or less from the viewpoint of combustibility.
本発明でいう初留点、T30、T50、T70、T95、終点とは、それぞれJIS K 2254「石油製品−蒸留試験方法」により測定される値を意味する。 The initial boiling point, T30, T50, T70, T95, and end point in the present invention mean values measured by JIS K 2254 “Petroleum products-distillation test method”, respectively.
(ナフテン分)
灯油基材のナフテン分は、20容量%以上であることが必要であり、好ましくは25容量%以上、より好ましくは28容量%以上である。ナフテン分が20容量%未満の場合には単位容量当たりの発熱量が不十分となる。
(For naphthenic)
The naphthene content of the kerosene base material needs to be 20% by volume or more, preferably 25% by volume or more, and more preferably 28% by volume or more. When the naphthene content is less than 20% by volume, the amount of heat generated per unit capacity is insufficient.
本発明でいうナフテン分とは、ASTM D2425(Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry)に順ずる方法にて測定されるナフテン系炭化水素の含有量(単位:容量%)を意味する。 The naphthene content in the present invention refers to ASTM D 2425 (Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry). .
(芳香族分)
灯油基材の全芳香族分は、燃焼性の点から、15容量%以下であることが必要であり、好ましくは10容量%以下、より好ましくは8容量%以下である。
(Aromatic content)
The total aromatic content of the kerosene base material is required to be 15% by volume or less, preferably 10% by volume or less, more preferably 8% by volume or less from the viewpoint of combustibility.
本発明でいう全芳香族分とは、石油学会法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」で測定される全芳香族分の値を意味する。 The total aromatic content as used in the field of this invention means the value of the total aromatic content measured by Petroleum Institute method JPI-5S-49-97 "petroleum product-hydrocarbon type test method-high performance liquid chromatograph".
また、上記全芳香族分のうち二環以上の芳香族分は、1容量%以下であることが必要であり、好ましくは0.8容量%以下、より好ましくは0.5容量%以下である。二環以上の芳香族分が1容量%を超えると燃焼性が著しく低下する。 In addition, the aromatic content of two or more rings in the total aromatic content needs to be 1% by volume or less, preferably 0.8% by volume or less, more preferably 0.5% by volume or less. . When the aromatic content of two or more rings exceeds 1% by volume, the flammability is significantly reduced.
本発明でいう二環以上芳香族分とは、石油学会法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」で測定される二環芳香族分および三環以上芳香族分の総和を意味する。 The term “bicyclic or higher aromatics” as used in the present invention refers to bicyclic aromatics and tricyclics measured by the Petroleum Institute method JPI-5S-49-97 “Petroleum products—hydrocarbon type test method—high performance liquid chromatograph”. This means the sum of aromatic content.
(ナフテン/全芳香族分の容量比)
灯油基材のナフテン分/全芳香族分の容量比は、燃料消費率と燃焼性とのバランスの点から、2.0以上であることが必要であり、好ましくは3.0以上である。
(Naphthene / total aromatic content ratio)
The volume ratio of the naphthene content / total aromatic content of the kerosene base material needs to be 2.0 or more, preferably 3.0 or more, from the viewpoint of the balance between the fuel consumption rate and the combustibility.
ここでいうナフテン分及び全芳香族分は上述のナフテン分及び全芳香族分と同一の内容であり、それぞれASTM D2425(Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry)、石油学会法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」に準拠して求められる値を意味する。 The naphthene content and the total aromatic content here are the same as the above-mentioned naphthene content and the total aromatic content, respectively, ASTM D2425 (Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectral Method). It means a value determined in accordance with 5S-49-97 “Petroleum Products—Hydrocarbon Type Test Method—High Performance Liquid Chromatograph”.
(硫黄分)
灯油基材の硫黄分は、燃焼排出ガス中の硫黄酸化物抑制、及び暖房用機器に装着されている排ガス後処理用触媒の寿命の点から、10質量ppm以下であることが必要であり、好ましくは5質量ppm以下、より好ましくは1質量ppm以下である。
(Sulfur content)
The sulfur content of the kerosene base material must be 10 mass ppm or less from the viewpoint of sulfur oxide suppression in the combustion exhaust gas and the life of the exhaust gas aftertreatment catalyst attached to the heating equipment, Preferably it is 5 mass ppm or less, More preferably, it is 1 mass ppm or less.
本発明でいう硫黄分とは、JIS K 2541「硫黄分試験方法」により測定される値を意味する。 The sulfur content in the present invention means a value measured by JIS K 2541 “Sulfur content test method”.
(密度)
灯油基材の15℃における密度は、燃料消費率の点から770Kg/m3以上であることが必要であり、好ましくは780Kg/m3以上である。一方、燃焼性の点から、820Kg/m3以下であることが必要であり、好ましくは810Kg/m3以下である。本発明でいう15℃における密度とは、JIS K2249「原油及び石油製品−密度試験方法並びに密度・質量・容量換算表」で測定される値である。
(density)
Density at 15 ℃ kerosene base material, it is necessary in terms of the fuel consumption rate is 770 kg / m 3 or more, preferably 780 kg / m 3 or more. On the other hand, from the viewpoint of flammability, it must be at 820 kg / m 3 or less, preferably 810Kg / m 3 or less. The density at 15 ° C. in the present invention is a value measured by JIS K2249 “Crude oil and petroleum products—density test method and density / mass / capacity conversion table”.
(動粘度)
灯油基材の動粘度は特に制限されないが、芯式ストーブにおける芯への染み込み性の点から、30℃で1.7mm2/s未満であることが望ましい。一方、芯式ストーブにおける消火後の余熱による芯からの染み出し防止の点から、30℃で1.0mm2/s以上であることが望ましい。
(Kinematic viscosity)
The kinematic viscosity of the kerosene base material is not particularly limited, but is preferably less than 1.7 mm 2 / s at 30 ° C. from the viewpoint of penetration into the core of the core stove. On the other hand, it is desirable that it is 1.0 mm < 2 > / s or more at 30 degreeC from the point of prevention of the seepage from the core by the residual heat after fire extinguishing in a core type stove.
本発明でいう30℃における動粘度とは、JIS K2283「原油及び石油製品−動粘度試験方法」で測定される値を意味する。 The kinematic viscosity at 30 ° C. in the present invention means a value measured by JIS K2283 “Crude oil and petroleum products—Kinematic viscosity test method”.
(引火点)
灯油基材の引火点は特に制限されないが、取り扱い上の安全性の点から40℃以上であることが望ましい。
(Flash point)
The flash point of the kerosene base material is not particularly limited, but is preferably 40 ° C. or higher from the viewpoint of safety in handling.
本発明でいう引火点とは、JIS K2265「原油及び石油製品−引火点試験方法」のタグ密閉式で測定される値を意味する。 The flash point as used in the field of this invention means the value measured by the tag sealing type | formula of JISK2265 "Crude oil and petroleum products-Flash point test method."
(煙点)
灯油基材の煙点は特に制限されないが、芯式ストーブにおけるスス発生や不完全燃焼防止の点から、21mm以上であることが望ましい。
(Smoke point)
The smoke point of the kerosene base material is not particularly limited, but is preferably 21 mm or more from the viewpoint of soot generation and incomplete combustion prevention in the core type stove.
本発明でいう煙点とは、JIS K2537「石油製品−航空タービン燃料油及び灯油−煙点試験方法」で測定される値を意味する。 The smoke point as used in the field of this invention means the value measured by JISK2537 "Petroleum products-Aviation turbine fuel oil and kerosene-Smoke point test method".
(セーボルト色)
灯油基材の色は特に制限されないが、不純物の識別等安全性への影響を考慮し、セーボルト色で+25以上であることが望ましい。
(Saebold color)
The color of the kerosene base material is not particularly limited, but it is desirable that the Saybolt color be +25 or more in consideration of the influence on safety such as identification of impurities.
ここでいうセーボルト色とは、JIS K2580「石油製品−色試験方法」中のセーボルト色試験方法で測定される値である。 The Saebold color here is a value measured by the Saebold color test method in JIS K2580 “Petroleum products-color test method”.
本発明の灯油組成物は、上記の灯油基材のみからなるものであってもよく、また、必要に応じて、後述する各種添加剤を含有してもよい。なお、本発明の灯油組成物が添加剤を含有する場合、組成物全体で、灯油基材について規定された条件を満たすことが好ましい。 The kerosene composition of the present invention may be composed only of the above-mentioned kerosene base material, and may contain various additives described later as necessary. In addition, when the kerosene composition of this invention contains an additive, it is preferable that the conditions prescribed | regulated about the kerosene base material are the whole composition.
すなわち、灯油組成物の蒸留性状における初留点は、好ましくは140℃以上、より好ましくは143℃以上、さらに好ましくは145℃以上である。また、当該初留点は、好ましくは170℃以下、より好ましくは165℃以下である。また、灯油組成物の終点は、好ましくは300℃以下、より好ましくは290℃以下、さらに好ましくは280℃以下である。また、灯油組成物のT50は、好ましくは190℃以上、より好ましくは195℃以上、さらに好ましくは200℃以上である。また、当該T50は、好ましくは230℃以下、より好ましくは225℃以下である。また、灯油組成物のT30は、好ましくは170℃以上、より好ましくは175℃以上、さらに好ましくは180℃以上である。また、当該T30は、好ましくは210℃以下、より好ましくは205℃以下、さらに好ましくは200℃以下である。また、灯油組成物のT70は、好ましくは220℃以上、より好ましくは225℃以上である。また、当該T70は、好ましくは250℃以下、より好ましくは245℃以下である。また、灯油組成物のT95は、好ましくは270℃以下、より好ましくは268℃以下である。 That is, the initial boiling point in the distillation properties of the kerosene composition is preferably 140 ° C. or higher, more preferably 143 ° C. or higher, and further preferably 145 ° C. or higher. The initial boiling point is preferably 170 ° C. or lower, more preferably 165 ° C. or lower. The end point of the kerosene composition is preferably 300 ° C. or lower, more preferably 290 ° C. or lower, and further preferably 280 ° C. or lower. Moreover, T50 of a kerosene composition becomes like this. Preferably it is 190 degreeC or more, More preferably, it is 195 degreeC or more, More preferably, it is 200 degreeC or more. The T50 is preferably 230 ° C. or lower, more preferably 225 ° C. or lower. Moreover, T30 of a kerosene composition becomes like this. Preferably it is 170 degreeC or more, More preferably, it is 175 degreeC or more, More preferably, it is 180 degreeC or more. The T30 is preferably 210 ° C. or lower, more preferably 205 ° C. or lower, and further preferably 200 ° C. or lower. Moreover, T70 of a kerosene composition becomes like this. Preferably it is 220 degreeC or more, More preferably, it is 225 degreeC or more. Moreover, the T70 is preferably 250 ° C. or lower, more preferably 245 ° C. or lower. Moreover, T95 of a kerosene composition becomes like this. Preferably it is 270 degrees C or less, More preferably, it is 268 degrees C or less.
また、灯油組成物のナフテン分は、好ましくは20容量%以上、より好ましくは25容量%以上、さらに好ましくは28容量%以上である。また、当該全芳香族分は、好ましくは15容量%以下、より好ましくは10容量%以下、さらに好ましくは8容量%以下である。また、当該全芳香族分のうち二環以上の芳香族分は、好ましくは1容量%以下、より好ましくは0.8容量%以下、さらに好ましくは0.5容量%以下である。また、灯油基材のナフテン分/全芳香族分の容量比は、好ましくは2.0以上であることが必要であり、好ましくは3.0以上である。また、灯油組成物の硫黄分は、好ましくは10質量ppm以下、より好ましくは5質量ppm以下、さらに好ましくは1質量ppm以下である。 The naphthene content of the kerosene composition is preferably 20% by volume or more, more preferably 25% by volume or more, and still more preferably 28% by volume or more. The total aromatic content is preferably 15% by volume or less, more preferably 10% by volume or less, and still more preferably 8% by volume or less. The aromatic content of two or more rings in the total aromatic content is preferably 1% by volume or less, more preferably 0.8% by volume or less, and still more preferably 0.5% by volume or less. Further, the volume ratio of the naphthene content / total aromatic content of the kerosene base material is preferably 2.0 or more, and preferably 3.0 or more. The sulfur content of the kerosene composition is preferably 10 ppm by mass or less, more preferably 5 ppm by mass or less, and further preferably 1 ppm by mass or less.
また、灯油組成物の15℃における密度は、好ましくは770Kg/m3以上、より好ましくは780Kg/m3以上である。また、当該密度は、好ましくは820Kg/m3以下、より好ましくは810Kg/m3以下である。また、灯油組成物の30℃における動粘度は、好ましくは1.0mm2/s以上1.7mm2/s未満である。 The density of the kerosene composition at 15 ° C. is preferably 770 Kg / m 3 or more, more preferably 780 Kg / m 3 or more. The density is preferably 820 Kg / m 3 or less, more preferably 810 Kg / m 3 or less. The kinematic viscosity of the kerosene composition at 30 ° C. is preferably 1.0 mm 2 / s or more and less than 1.7 mm 2 / s.
また、灯油組成物の引火点は、好ましくは40℃以上であり、煙点は、好ましくは21mm以上である。さらに、灯油組成物の色は、セーボルト色で+25以上であることが望ましい。
(添加剤)
本発明の灯油組成物は、必要に応じて、2,6−ジ−tert−ブチル−p−クレゾール等のフェノール系化合物、N,N‘−ジ−sec−ブチル−p−フェニレンジアミン等のアミン系化合物などの酸化防止剤、シッフ型、チオアミド型化合物などの金属不活性剤、有機リン系化合物などの表面着火剤、コハク酸アミド、ポリアルキルアミン、ポリエーテルアミンなどの清浄分散剤、多価アルコールおよびそのエーテルなどの氷結防止剤、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、1−メトキシ−2−アセトキシプロパンなどの助燃剤、アニオン系界面活性剤、カチオン系界面活性剤、両性界面活性剤などの帯電防止剤およびアゾ染料などの着色剤など、公知の燃料油添加剤を1種または数種組み合わせて添加してもよい。これら燃料油添加剤の添加量は任意であるが、通常その合計添加量が、0.5質量%以下であることが好ましく、0.05質量%以下であることがより好ましい。
The flash point of the kerosene composition is preferably 40 ° C. or higher, and the smoke point is preferably 21 mm or higher. Furthermore, it is desirable that the kerosene composition has a Saybolt color of +25 or more.
(Additive)
The kerosene composition of the present invention may be prepared by using a phenolic compound such as 2,6-di-tert-butyl-p-cresol and an amine such as N, N′-di-sec-butyl-p-phenylenediamine, if necessary. Antioxidants such as Schiff compounds, metal deactivators such as Schiff and thioamide compounds, surface igniters such as organophosphorus compounds, detergents and dispersants such as succinic amides, polyalkylamines and polyetheramines, polyvalent Anti-icing agent such as alcohol and its ether, alkali metal or alkaline earth metal salt of organic acid, sulfuric acid ester of higher alcohol, auxiliary combustor such as 1-methoxy-2-acetoxypropane, anionic surfactant, cationic interface One or a combination of known fuel oil additives such as activators, amphoteric surfactants and other antistatic agents, and azo dyes and other colorants May be added. The addition amount of these fuel oil additives is arbitrary, but the total addition amount is usually preferably 0.5% by mass or less, and more preferably 0.05% by mass or less.
上述の添加剤は、常法に従い合成したものを用いてもよく、また市販の添加剤を用いてもよい。なお、市販されている添加剤は、その添加剤が目的としている効果に寄与する有効成分を適当な溶剤で希釈している場合もある。有効成分が希釈されている市販添加剤を使用する場合には、灯油組成物中の当該有効成分の含有量が上述の範囲になるように市販添加剤を添加することが好ましい。 As the above-mentioned additive, one synthesized according to a conventional method may be used, or a commercially available additive may be used. In addition, the additive currently marketed may have diluted the active ingredient which contributes to the effect which the additive aimed at with the appropriate solvent. When using a commercially available additive in which the active ingredient is diluted, it is preferable to add the commercially available additive so that the content of the active ingredient in the kerosene composition falls within the above range.
上記構成を有する本発明の灯油組成物は引火性、燃焼性、安全性、並びに暖房機器に対する適合性の全てがバランスよく高められたものであり、暖房機器を長期にわたって安定的に運転することが可能なものである。従って、本発明の灯油組成物は、石油ストーブ(例えば芯式ストーブ)や石油ファンヒーター等の暖房機器に使用される暖房用燃料組成物として非常に有用である。 The kerosene composition of the present invention having the above-described configuration has a well-balanced increase in flammability, flammability, safety, and suitability for heating equipment, and can stably operate the heating equipment for a long period of time. It is possible. Therefore, the kerosene composition of the present invention is very useful as a heating fuel composition used in heating equipment such as a petroleum stove (for example, a core-type stove) and a petroleum fan heater.
以下、実施例及び比較例に基づき本発明をさらに具体的に説明するが、本発明は以下の実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.
[実施例1〜3、比較例1〜4]
実施例1〜3及び比較例1〜3においては、未成製油又は水素化精製油を表1、2に示す条件で水素化処理して灯油基材を得た。各灯油基材の諸性状を表1、2に示す。
[Examples 1 to 3, Comparative Examples 1 to 4]
In Examples 1 to 3 and Comparative Examples 1 to 3, a crude oil or hydrorefined oil was hydrotreated under the conditions shown in Tables 1 and 2 to obtain a kerosene base material. Various properties of each kerosene base are shown in Tables 1 and 2.
実施例1、2及び比較例1、2では、得られた灯油基材をそのまま試料油として以下の試験に供した。また、実施例3及び比較例3では、得られた灯油基材にフェノール系酸化防止剤(2,6−ジ−tert−ブチル−p−クレゾール)を20質量ppm添加し、得られた灯油組成物を試料油とした。また、比較例4では、F−T合成で得られるGTLの灯油留分を水素化分解したものを試料油として用いた。 In Examples 1 and 2 and Comparative Examples 1 and 2, the obtained kerosene base material was directly used as a sample oil for the following tests. In Example 3 and Comparative Example 3, 20 mass ppm of phenolic antioxidant (2,6-di-tert-butyl-p-cresol) was added to the obtained kerosene base material, and the resulting kerosene composition was obtained. The product was used as sample oil. In Comparative Example 4, a hydrocracked GTL kerosene fraction obtained by FT synthesis was used as sample oil.
[燃焼試験]
次に、実施例1〜3及び比較例1〜4の各試料油を用いて燃焼試験を行った。具体的には、試験用暖房機器として、芯上下式ストーブ(開放式石油ストーブ芯式自然通気形、排ガス浄化装置あり、コロナ製 SX−E261Y)、及び石油ファンヒーター(開放式石油ストーブ気化式強制通気形、排ガス浄化装置なし、三菱電機製 KD−F32C)に試料油を充填し、点火−5時間の定常運転−消火を1サイクルとし、これらの工程を100サイクル繰り返した。
[Combustion test]
Next, a combustion test was performed using the sample oils of Examples 1 to 3 and Comparative Examples 1 to 4. Specifically, as heating equipment for testing, a core up-and-down stove (open type oil stove core type natural ventilation type, with exhaust gas purifier, SX-E261Y manufactured by Corona), and an oil fan heater (open type oil stove vaporization type forced Ventilation type, no exhaust gas purification device, KD-F32C manufactured by Mitsubishi Electric) was filled with sample oil, ignition—5 hours of steady operation—extinguishing was taken as one cycle, and these steps were repeated 100 cycles.
本試験においては、1回目のサイクル後のTHC(Total HydroCarbon)濃度(以下、「THC濃度1」という)、並びに100回目のサイクル後のTHC濃度(以下、「THC濃度2」という)及びSOx濃度を測定した。具体的には、各サイクルの消火から30秒経過時までの間、暖房機器からの排出ガスをJIS S 3031法に準拠したX字管を用いて捕集し、排出ガス中のTHC濃度あるいはさらにSOx濃度を測定した。THC濃度1、2及びSOx濃度の測定の際には、分析計としてそれぞれ堀場製作所製 FIA−510H及び堀場製作所製 PG−200シリーズを用いた。得られた結果を表3、4に示す。表3、4中のTHC濃度1、2は全て比較例1のTHC濃度1を100としたときの相対値である。同様に、表3、4中のSOx濃度は比較例1のSOx濃度を100としたときの相対値である。THC濃度1、2は臭気物質の排出量の指標となり、SOx濃度は汚染物質の排出量の指標となる。 In this test, the THC (Total HydroCarbon) concentration after the first cycle (hereinafter referred to as “THC concentration 1”), the THC concentration after the 100th cycle (hereinafter referred to as “THC concentration 2”), and the SOx concentration. Was measured. Specifically, the exhaust gas from the heating equipment is collected using an X-tube conforming to the JIS S 3031 method from the extinction of each cycle until 30 seconds elapse, and the THC concentration in the exhaust gas or further The SOx concentration was measured. When measuring the THC concentrations 1 and 2 and the SOx concentration, FIA-510H manufactured by HORIBA, Ltd. and PG-200 series manufactured by HORIBA, respectively were used as analyzers. The obtained results are shown in Tables 3 and 4. The THC concentrations 1 and 2 in Tables 3 and 4 are relative values when the THC concentration 1 of Comparative Example 1 is 100. Similarly, the SOx concentrations in Tables 3 and 4 are relative values when the SOx concentration in Comparative Example 1 is 100. The THC concentrations 1 and 2 are indicators of odorous substance emissions, and the SOx concentration is an indicator of pollutant emissions.
また、本試験においては、1回目のサイクルにおける燃料消費率(以下、「燃料消費率1」という)、並びに最終サイクルにおける燃料消費率(以下、「燃料消費率2」という)を測定し、両者の差Δ(燃料消費率1−燃料消費率2)を求めた。得られた結果を表3、4に示す。燃料消費率1、2は比較例1の燃料消費率1を100としたときの相対値で示した。燃料消費率1は値が大きいほど燃費が悪いことを意味する。また、サイクル数が増加すると、燃焼部への固着物(例えば酸化劣化物)の付着等により暖房効率が悪化するため、通常、燃料消費率2は燃料消費率1よりも小さくなる。両者の差Δ(燃料消費率1−燃料消費率2)は、燃焼部への固着物の付着量及びTHC濃度(すなわち臭気物質の排出量)の指標となる。 In this test, the fuel consumption rate in the first cycle (hereinafter referred to as “fuel consumption rate 1”) and the fuel consumption rate in the final cycle (hereinafter referred to as “fuel consumption rate 2”) were measured. Difference Δ (fuel consumption rate 1−fuel consumption rate 2). The obtained results are shown in Tables 3 and 4. The fuel consumption rates 1 and 2 are shown as relative values when the fuel consumption rate 1 of Comparative Example 1 is 100. The larger the value of the fuel consumption rate 1, the worse the fuel consumption. In addition, when the number of cycles increases, the heating efficiency deteriorates due to adhesion of fixed substances (for example, oxidized deterioration substances) to the combustion part, and therefore the fuel consumption rate 2 is usually smaller than the fuel consumption rate 1. The difference Δ (fuel consumption rate 1−fuel consumption rate 2) is an index of the amount of sticking matter adhering to the combustion part and the THC concentration (that is, the amount of odorous substance discharged).
表3に示したように、実施例1〜3においてはいずれも、良好な燃焼性を示し、また、排出ガス中の臭気物質及び汚染物質の発生が十分に抑制されていることが確認された。さらに、100サイクル時の燃料消費率の低下及びTHC濃度の増加の度合いが小さく、燃焼部分への酸化劣化物の固着が十分に抑制されていることが示唆された。 As shown in Table 3, it was confirmed that all of Examples 1 to 3 showed good flammability, and the generation of odorous substances and pollutants in the exhaust gas was sufficiently suppressed. . Furthermore, the decrease in the fuel consumption rate and the increase in the THC concentration during 100 cycles were small, suggesting that sticking of oxidative degradation products to the combustion portion was sufficiently suppressed.
これに対して、比較例1〜3の場合はTHC濃度1及びSOx濃度が高かった。また、Δ(燃料消費率1−燃料消費率2)が大きく、100サイクル後の暖房機器の燃焼部には酸化劣化物による固着物が多量付着していた。一方、比較例4の場合は、燃料消費率が大きい値を示し、THC排出量が多かった。 On the other hand, in Comparative Examples 1 to 3, the THC concentration 1 and the SOx concentration were high. Further, Δ (fuel consumption rate 1−fuel consumption rate 2) was large, and a large amount of adhering matter due to oxidative degradation adhered to the combustion portion of the heating equipment after 100 cycles. On the other hand, in the case of Comparative Example 4, the fuel consumption rate showed a large value, and the amount of THC emission was large.
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