JP5154982B2 - A heavy oil composition - Google Patents
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- JP5154982B2 JP5154982B2 JP2008059990A JP2008059990A JP5154982B2 JP 5154982 B2 JP5154982 B2 JP 5154982B2 JP 2008059990 A JP2008059990 A JP 2008059990A JP 2008059990 A JP2008059990 A JP 2008059990A JP 5154982 B2 JP5154982 B2 JP 5154982B2
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- 239000000295 fuel oil Substances 0.000 title claims description 74
- 239000000203 mixture Substances 0.000 title claims description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 10
- 238000012417 linear regression Methods 0.000 claims description 4
- 239000003921 oil Substances 0.000 description 46
- 239000001993 wax Substances 0.000 description 18
- 238000010998 test method Methods 0.000 description 16
- 239000010779 crude oil Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 238000004821 distillation Methods 0.000 description 12
- 239000000446 fuel Substances 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 11
- 239000003350 kerosene Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000003209 petroleum derivative Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008264 cloud Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
本発明は、Ａ重油組成物に関する。更に詳しくは、寒冷地におけるボイラー、ディーゼル機器、ガスタービン等の燃焼機器に用いられるＪＩＳ１種重油規格を満たすＡ重油組成物に関する。 The present invention relates to an A heavy oil composition. More specifically, the present invention relates to an A heavy oil composition that satisfies the JIS Class 1 heavy oil standard used for combustion equipment such as boilers, diesel equipment, gas turbines, etc. in cold regions.
従来、Ａ重油組成物の基材としては、原油の常圧蒸留装置から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、重質軽油、分解装置から得られる接触分解軽油、直接脱硫装置から得られる直脱軽油などが知られている。従来のＡ重油組成物は上記基材を１種または２種以上配合し、その他に残留炭素基材として、常圧残油、直脱残油、減圧残油などを１種または２種以上付与することにより製造されている。また、これらのＡ重油組成物には、必要に応じてセタン価向上剤や低温流動性向上剤等の添加剤が配合される（例えば、非特許文献１参照。）。
Ａ重油組成物は、ボイラー等の外燃機器燃料、小型漁船や建設機械等のオフロード用ディーゼルエンジン機器燃料、ガスタービン機器燃料などとして広く用いられている。
Ａ重油組成物を用いる各種燃焼機器には、燃料油中の異物を除去する目的で、燃料系統に目開き５〜２５０μｍのフィルターが設けられている。しかし、このような燃焼機器を冬季に使用すると、Ａ重油組成物から析出したワックスなどにより、フィルターの閉塞が起こりやすくなる。
A fuel oil composition is widely used as fuel for external combustion equipment such as boilers, diesel engine equipment fuel for off-road use such as small fishing boats and construction machinery, and gas turbine equipment fuel.
Various combustion devices using the A heavy oil composition are provided with a filter having an opening of 5 to 250 μm in the fuel system for the purpose of removing foreign substances in the fuel oil. However, when such a combustion device is used in winter, the filter is likely to be clogged with wax precipitated from the A heavy oil composition.
そこで、かかる問題を解決すべく、Ａ重油組成物の低温流動性を改善するための検討が行われており、低温流動性能の改善には灯油留分の増量、脱ろう基材の活用、重質油の配合（特許文献１）、残渣油の増量（特許文献２）、低温流動性向上剤の添加（非特許文献２）等が提案されている。
しかし、上述の各方法で得られるＡ重油組成物はそれぞれ次の点で改善の余地があり、いずれもＡ重油組成物として実用に供し得るには未だ十分とは言えない。すなわち、寒冷地仕様のＡ重油を製造するために灯油留分を配合すると、配合量が多すぎて引火点が障害となり安全上有効ではない。脱ろう基材を活用しても寒冷地で使用するにはワックス量が多く、低温性能を満足することはできない。重質油の増配合はワックス析出点（曇り点）の悪化につながる。残渣油の増量は燃焼ガス中の煤塵量が多くなる。また低温流動性向上剤の性能は、使用基材との相性によるところが多く、単に添加するだけでは寒冷地向けＡ重油の低温性能を向上させることはできない。
However, the A heavy oil composition obtained by the above-described methods has room for improvement in the following points, and none of them is still sufficient to be put to practical use as the A heavy oil composition. That is, when kerosene fraction is blended to produce A heavy oil for cold district specifications, the blending amount is too large and the flash point becomes an obstacle, which is not effective from a safety standpoint. Even if a dewaxing base material is used, the amount of wax is too large to be used in a cold region, and the low temperature performance cannot be satisfied. Increased blending of heavy oil leads to deterioration of the wax precipitation point (cloud point). Increasing the amount of residual oil increases the amount of dust in the combustion gas. In addition, the performance of the low temperature fluidity improver depends largely on the compatibility with the substrate used, and the low temperature performance of A heavy oil for cold regions cannot be improved simply by adding it.
ＪＩＳ１種重油規格を満たすＡ重油組成物は、ボイラー燃料やオフロード用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重油組成物に使用されるボイラーの高出力化及び低燃費化等に伴い、異物を除去するために用いられているフィルターの目が細かくなり、Ａ重油組成物は、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可能性が高まっている。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。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（例えば、非特許文献３を参照。）。
本発明の目的は、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。 An object of the present invention is to provide an A heavy oil composition that does not cause clogging of a filter by wax in winter.
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、Ａ重油組成物の直鎖飽和炭化水素分および曇り点を特定の範囲とした場合に、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。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have clogged the filter with wax in winter when the straight chain saturated hydrocarbon content and cloud point of the A heavy oil composition are in a specific range. The inventors have found that the problem does not occur and have completed the present invention.
すなわち、本発明は、炭素数２７の直鎖飽和炭化水素分量が０．００５質量％以上０．０５０質量％以下であり、かつ、曇り点が−６℃以上０℃以下であることを特徴とする低温性能に優れるＡ重油組成物に関する。 That is, the present invention is characterized in that the amount of linear saturated hydrocarbon having 27 carbon atoms is 0.005% by mass or more and 0.050% by mass or less, and the cloud point is −6 ° C. or more and 0 ° C. or less. It is related with A heavy oil composition which is excellent in the low-temperature performance to do.
本発明のＡ重油組成物は、炭素数１８から２３の直鎖飽和炭化水素分量から求めた線形回帰直線の傾きが０．４５以下であることが望ましい。 The A heavy oil composition of the present invention preferably has a slope of a linear regression line obtained from a linear saturated hydrocarbon content having 18 to 23 carbon atoms of 0.45 or less.
また本発明のＡ重油組成物は、修正目詰まり点が−１５℃以下であることが望ましい。 Moreover, as for the A heavy oil composition of this invention, it is desirable that a correction | amendment clogging point is -15 degrees C or less.
本発明によれば、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。 According to the present invention, it is possible to obtain an A heavy oil composition that does not cause clogging of the filter by wax in winter.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明のＡ重油組成物は炭素数２７の直鎖飽和炭化水素分量が０．００５質量％以上、０．０５０質量％以下であることが必要であり、０．０１０質量％以上、０．０４０質量％以下であることが好ましい。炭素数２７の直鎖飽和炭化水素分量が０．００５質量％より少ない場合、低温性能が著しく悪化し、冬期においてワックスによるフィルターの目詰まりが起こりやすくなる。また、炭素数２７の直鎖飽和炭化水素分量が０．０５０質量％より多い場合も、低温性能が著しく悪化し、冬期においてワックスによるフィルターの目詰まりが起こりやすくなる。
本発明において、炭素数２７の直鎖飽和炭化水素分量は、ＧＣ−ＦＩＤを用いて測定される値（質量％）である。すなわち、カラムにはメチルシリコンのキャピラリーカラム（ＵＬＴＲＡＡＬＬＯＹ−１）、キャリアガスにはヘリウムを、検出器には水素イオン検出器（ＦＩＤ）を用い、カラム長３０ｍ、キャリアガス流量１．０ｍＬ／ｍｉｎ、分割比１：７９、試料注入温度３６０℃、カラム昇温条件１４０℃→（８℃／ｍｉｎ）→３５５℃、検出器温度３６０℃の条件で測定された値である。
A heavy oil composition of the present invention requires that the amount of linear saturated hydrocarbon having 27 carbon atoms is 0.005% by mass or more and 0.050% by mass or less, and is 0.010% by mass or more and 0.040% by mass. It is preferable that it is below mass%. When the amount of the linear saturated hydrocarbon having 27 carbon atoms is less than 0.005% by mass, the low-temperature performance is remarkably deteriorated and the filter is easily clogged with wax in winter. Further, when the amount of the linear saturated hydrocarbon having 27 carbon atoms is more than 0.050% by mass, the low temperature performance is remarkably deteriorated, and the filter is easily clogged with wax in winter.
In the present invention, the amount of linear saturated hydrocarbon having 27 carbon atoms is a value (mass%) measured using GC-FID. That is, a capillary column of methyl silicon (ULTRAALLOY-1) is used for the column, helium is used for the carrier gas, a hydrogen ion detector (FID) is used for the detector, a column length of 30 m, a carrier gas flow rate of 1.0 mL / min, and a splitting. It is a value measured under the conditions of ratio 1:79, sample injection temperature 360 ° C., column temperature rising condition 140 ° C. → (8 ° C./min)→355° C., detector temperature 360 ° C.
本発明のＡ重油組成物の曇り点は、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、−６℃以上０℃以下であることが必要であり、−５℃以上−２℃以下であることが好ましい。
本発明において、曇り点とは、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。
The cloud point of the heavy oil composition A of the present invention needs to be −6 ° C. or more and 0 ° C. or less in order to reduce wax precipitation at a low temperature that clogs the filter for preventing contaminants in the fuel system. It is preferable that it is -5 degreeC or more and -2 degreeC or less.
In the present invention, the cloud point means a value obtained in accordance with JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.
本発明のＡ重油組成物は炭素数１８から２３の直鎖飽和炭化水素分量から求めた線形回帰直線の傾きが０．４５以下となることが望ましい。炭素数１８から２３の線形回帰直線の傾きが０．４５より大きい場合は低温性能が悪化し、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りやすくなる。 In the A heavy oil composition of the present invention, the slope of the linear regression line determined from the amount of linear saturated hydrocarbon having 18 to 23 carbon atoms is preferably 0.45 or less. When the slope of the linear regression line having 18 to 23 carbon atoms is larger than 0.45, the low-temperature performance is deteriorated, and the filter is easily clogged with wax in winter.
本発明のＡ重油組成物の修正目詰まり点は−１５℃以下であることが好ましい。Ａ重油組成物の修正目詰まり点が−１５℃より高い場合は、冬期においてワックスによるフィルターの目詰まりが起こりやすくなる。
本発明において、修正目詰まり点とは、石油学会規格 ＪＰＩ−５S−４７−９６「Ａ重油の低温流動性試験方法」の解説に記載の修正法４で測定される値を意味する。
The corrected clogging point of the A heavy oil composition of the present invention is preferably −15 ° C. or lower. When the corrected clogging point of the A heavy oil composition is higher than −15 ° C., the filter is easily clogged with wax in winter.
In the present invention, the corrected clogging point means a value measured by the correction method 4 described in the explanation of the Petroleum Institute standard JPI-5S-47-96 “Testing method for low temperature fluidity of A heavy oil”.
本発明で用いるＡ重油基材としては、常圧蒸留装置より得られる直留軽油留分またはその脱硫軽油留分、直留灯油留分またはその脱硫灯油留分、水素化分解軽油、水素化分解灯油、残油脱硫軽油留分、水素化脱硫軽油留分または水素化精製軽油留分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軽油留分、重質軽油留分、減圧軽油を脱硫した軽油、流動接触分解灯油などが挙げられる。本発明においては、これらを１種または２種以上を併用しても良い。 A heavy oil base material used in the present invention includes a straight-run gas oil fraction obtained from an atmospheric distillation apparatus or a desulfurized gas oil fraction thereof, a straight-run kerosene fraction or a desulfurized kerosene fraction thereof, hydrocracked gas oil, hydrocracking. Kerosene, residual oil desulfurized gas oil fraction, hydrodesulfurized gas oil fraction or hydrorefined gas oil fraction is the residue from which normal paraffin content has been removed, denormalized paraffin gas oil fraction, heavy gas oil fraction, vacuum gas oil And diesel oil desulfurized, fluid catalytic cracking kerosene and the like. In the present invention, these may be used alone or in combination of two or more.
本発明のＡ重油組成物には残留炭素基材が含有されていても良い。
残留炭素基材の種類は特に限定するものではないが、常圧残油、残油脱硫重油、減圧残油、スラリー油、エキストラクト油等が挙げられ、これらを単独、もしくは２種以上併用して用いることができる。ここで常圧残油とは、常圧蒸留装置で原油を常圧において蒸留して得られる残油である。残油脱硫重油とは、残油脱硫装置において常圧残油または減圧残油を脱硫したときに得られる重油である。減圧残油とは、減圧蒸留装置で常圧残油を減圧下で蒸留して得られる残油である。スラリー油とは、流動接触分解装置から得られる残油である。エキストラクト油とは、潤滑油原料用減圧蒸留装置からの留分を、溶剤抽出法により抽出分離したもののうち潤滑油に適さない芳香族成分のことである。
The A heavy oil composition of the present invention may contain a residual carbon base material.
The type of the residual carbon base material is not particularly limited, and examples thereof include atmospheric residual oil, residual oil desulfurized heavy oil, vacuum residual oil, slurry oil, and extract oil. These may be used alone or in combination of two or more. Can be used. Here, the atmospheric residual oil is a residual oil obtained by distilling crude oil at atmospheric pressure using an atmospheric distillation apparatus. The residual oil desulfurized heavy oil is a heavy oil obtained when a normal pressure residual oil or a vacuum residual oil is desulfurized in a residual oil desulfurization apparatus. The vacuum residue is a residue obtained by distilling atmospheric residue under reduced pressure using a vacuum distillation apparatus. Slurry oil is residual oil obtained from a fluid catalytic cracker. Extract oil is an aromatic component that is not suitable for lubricating oil among the fractions extracted from the vacuum distillation apparatus for lubricating oil raw material by solvent extraction.
本発明のＡ重油組成物は、ＪＩＳ１種重油規格を満たすことが必要である。ＪＩＳ１種重油規格とは、ＪＩＳ Ｋ ２２０５「重油」に規定された「１種」を満足させる規格であり、具体的には引火点６０℃以上、流動点５℃以下、残留炭素分４質量％以下、５０℃における動粘度２０ｍｍ２／ｓ以下、硫黄分２．０質量％以下、水分０．３容量％以下、灰分０．０５質量％以下であることが必要である。 The A heavy oil composition of the present invention needs to satisfy JIS Class 1 heavy oil standards. The JIS Class 1 heavy oil standard is a standard that satisfies “Class 1” defined in JIS K 2205 “Heavy oil”. Specifically, the flash point is 60 ° C. or higher, the pour point is 5 ° C. or lower, and the residual carbon content is 4% by mass. Hereinafter, it is necessary that the kinematic viscosity at 50 ° C. is 20 mm 2 / s or less, the sulfur content is 2.0 mass% or less, the water content is 0.3 volume% or less, and the ash content is 0.05 mass% or less.
本発明のＡ重油組成物の引火点は、ＪＩＳ１種重油規格の６０℃以上であることが必要であり、６２℃以上であることが好ましい。Ａ重油組成物の引火点が６０℃より低い場合、取り扱い時の安全性に問題が発生しやすくなる。
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。
The flash point of the heavy oil composition A of the present invention needs to be 60 ° C. or higher of JIS Class 1 heavy oil standard, and preferably 62 ° C. or higher. When the flash point of A heavy oil composition is lower than 60 ° C., a problem is likely to occur in safety during handling.
In the present invention, the flash point means a value obtained in accordance with JIS K 2265 “Crude oil and petroleum products—flash point test method”.
本発明のＡ重油組成物の流動点は、ＪＩＳ１種重油規格である５℃以下を満たす必要がある。さらに、低温流動性の観点から、２．５℃以下であることが好ましい。ここで流動点とは、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」により測定される流動点を意味する。 The pour point of the heavy oil composition A of the present invention needs to satisfy JIS Class 1 heavy oil standard of 5 ° C. or lower. Furthermore, it is preferable that it is 2.5 degrees C or less from a viewpoint of low-temperature fluidity | liquidity. Here, the pour point means a pour point measured by JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.
本発明のＡ重油組成物における残留炭素分は、ＪＩＳ１種重油規格である４質量％以下を満たす必要がある。さらに、微小粒子やＰＭ低減の観点、並びにエンジンに搭載される排ガス後処理装置の性能維持の観点から、３質量％以下であることが好ましく、２質量％以下であることがより好ましい。ここでいう残留炭素分とは、ＪＩＳ Ｋ ２２７０「原油及び石油製品−残留炭素分試験方法」により測定される残留炭素分を意味する。 The residual carbon content in the heavy oil composition A of the present invention needs to satisfy 4 mass% or less, which is a JIS class 1 heavy oil standard. Furthermore, it is preferably 3% by mass or less, more preferably 2% by mass or less, from the viewpoint of reducing fine particles and PM and maintaining the performance of the exhaust gas aftertreatment device mounted on the engine. The residual carbon content here means a residual carbon content measured by JIS K 2270 “Crude oil and petroleum products—residual carbon content test method”.
本発明のＡ重油組成物の５０℃における動粘度は３．０ｍｍ２／ｓ以下であることが好ましく、２．８ｍｍ２／ｓ以下であることがより好ましい。５０℃における動粘度が３．０ｍｍ２／ｓより大きい場合、燃料噴射システム内部の抵抗が増加して噴射系が不安定化し、排出ガス中のＮＯｘ、ＰＭの濃度が高くなってしまう。ここでいう動粘度とは、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」により測定される動粘度を意味する。 The kinematic viscosity at 50 ° C. of the A heavy oil composition of the present invention is preferably 3.0 mm 2 / s or less, and more preferably 2.8 mm 2 / s or less. When the kinematic viscosity at 50 ° C. is greater than 3.0 mm 2 / s, the resistance inside the fuel injection system increases, the injection system becomes unstable, and the concentrations of NOx and PM in the exhaust gas increase. The kinematic viscosity here means the kinematic viscosity measured by JIS K 2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.
本発明のＡ重油組成物における硫黄分は、ＪＩＳ１種重油規格である２質量％以下を満たす必要がある。さらに、微小粒子やＰＭ低減の観点、並びにエンジンに搭載される排ガス後処理装置の性能維持の観点から、１．５質量％以下であることが好ましく、１質量％以下であることがより好ましい。ここでいう硫黄分とは、ＪＩＳ Ｋ ２５４１「原油及び石油製品−硫黄分試験方法」により測定される残留炭素分を意味する。 The sulfur content in the heavy oil composition A of the present invention needs to satisfy 2% by mass or less, which is a JIS class 1 heavy oil standard. Furthermore, from the viewpoint of reducing fine particles and PM, and from the viewpoint of maintaining the performance of the exhaust gas aftertreatment device mounted on the engine, it is preferably 1.5% by mass or less, and more preferably 1% by mass or less. A sulfur content here means the residual carbon content measured by JISK2541 "crude oil and petroleum products-sulfur content test method".
本発明のＡ重油成物においては、水分の含有量はＪＩＳ１種重油規格である０．３容量％以下を満たす必要がある。さらに、部材への悪影響の観点から、０．２容量％以下であることが好ましく、０．１容量％以下であることがより好ましい。なお、本発明でいう水分とは、ＪＩＳ Ｋ ２２７５「水分試験方法（原油および石油製品）」によって測定される値を意味する。 In the heavy oil A composition of the present invention, the moisture content needs to satisfy 0.3% by volume or less, which is a JIS Class 1 heavy oil standard. Furthermore, from the viewpoint of adverse effects on the member, it is preferably 0.2% by volume or less, and more preferably 0.1% by volume or less. In addition, the water | moisture content said by this invention means the value measured by JISK2275 "moisture test method (crude oil and petroleum products)".
本発明のＡ重油成物においては、灰分の含有量はＪＩＳ１種重油規格である０.０５質量％以下を満たす必要がある。さらに、微小粒子やＰＭ低減の観点から、０．０４質量％以下であることが好ましく、０．０３質量％以下であることがより好ましい。なお、本発明でいう灰分とは、ＪＩＳ Ｋ ２２７２「原油及び石油製品の灰分並びに硫酸灰分試験方法」によって測定される値を意味する。 In the heavy oil A composition of the present invention, the ash content needs to satisfy 0.05 mass% or less, which is a JIS class 1 heavy oil standard. Furthermore, from the viewpoint of reducing fine particles and PM, the content is preferably 0.04% by mass or less, and more preferably 0.03% by mass or less. The ash content in the present invention means a value measured by JIS K 2272 “Crude oil and petroleum product ash content and sulfate ash test method”.
本発明のＡ重油組成物の１０％残留炭素分については特に制限はないが、税法上のＡ重油の免税条件である「１０％残油の残留炭素分０．２質量％以上」の点から０．２質量％以上であることが要望されている。しかし、スラッジによるフィルター目詰まり防止の点から、０．８質量％以下が好ましく、０．６質量％以下がより好ましい。ここでいう１０％残留炭素分とは、ＪＩＳ Ｋ ２２７０「原油及び石油製品−残留炭素分試験方法」により測定される残留炭素分を意味する。 Although there is no restriction | limiting in particular about the 10% residual carbon content of the A heavy oil composition of this invention, From the point of "the residual carbon content of 10% residual oil 0.2 mass% or more" which is a tax exemption condition of A heavy oil on tax law It is desired to be 0.2% by mass or more. However, 0.8 mass% or less is preferable and 0.6 mass% or less is more preferable from the point of prevention of filter clogging due to sludge. The 10% residual carbon content here means the residual carbon content measured by JIS K 2270 “Crude oil and petroleum products—residual carbon content test method”.
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、８００ｋｇ／ｍ３以上、９１０ｋｇ／ｍ３以下であることが好ましい。Ａ重油組成物の密度が８００ｋｇ／ｍ３より小さい場合、容量当りの発熱量が小さくなり、さらに、冬期においてワックスによるフィルターの目詰まりが起こりやすくなる。また、Ａ重油組成物の密度が９１０ｋｇ／ｍ３より大きい場合、外燃機器用ボイラーにおいて着火性の悪化や、煤の発生が増大しやすくなる。
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。
Although there is no restriction | limiting in particular about the density of A heavy oil composition of this invention, It is preferable that they are 800 kg / m < 3 > or more and 910 kg / m < 3 > or less. When the density of the A heavy oil composition is less than 800 kg / m 3 , the calorific value per capacity becomes small, and the filter is easily clogged with wax in winter. Moreover, when the density of A heavy oil composition is larger than 910 kg / m < 3 >, in the boiler for external combustion equipment, deterioration of ignitability and generation of soot are likely to increase.
In the present invention, the density means a value obtained based on JIS K 2249 “Crude oil and petroleum products—density test method and density / mass / capacity conversion table”.
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好ましい。
１０容量％留出温度（Ｔ１０）： １８０〜２８０℃
５０容量％留出温度（Ｔ５０）： ２４０〜３４０℃
９０容量％留出温度（Ｔ９０）： ２８０〜３８０℃
本発明において、上記蒸留性状は、ＪＩＳ Ｋ ２２５４「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。
Although there is no restriction | limiting about the distillation property of A heavy oil composition of this invention, Usually, what satisfy | fills the following property is preferable.
10 vol% distillation temperature (T10): 180-280 ° C
50 volume% distillation temperature (T50): 240-340 degreeC
90 volume% distillation temperature (T90): 280-380 degreeC
In the present invention, the distillation property means a value obtained according to JIS K 2254 “Petroleum products—Distillation test method”.
本発明のＡ重油組成物のセタン指数については特に制限はないが、セタン指数は燃焼性の点から、３０以上であることが好ましく、３５以上であることがより好ましい。
本発明において、セタン指数はＪＩＳ Ｋ ２２０４−１９９２「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）−0.0010522（Ｘ）2
[Ｘ＝97.833（ｌｏｇＡ）2＋2.2088ＢｌｏｇＡ＋0.01247Ｂ2−423.51ｌｏｇＡ−4.7808Ｂ＋419.59]
Ａ：（9/5）［101.3ｋＰａ（760ｍｍＨｇ）における50容量％留出温度（℃）］＋32
Ｂ：ＡＰＩ度
（101.3ｋＰａ（760ｍｍＨｇ）における５０容量％留出温度（℃）は、ＪＩＳ Ｋ ２２５４「石油製品−蒸留試験方法」によって測定し、ＡＰＩ度は、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」によって１５℃の密度から換算して求める。）
Although there is no restriction | limiting in particular about the cetane index of A heavy oil composition of this invention, From the point of combustibility, it is preferable that it is 30 or more, and it is more preferable that it is 35 or more.
In the present invention, the cetane index means a value obtained in accordance with JIS K 2204-1992 “light oil”. That is, it is calculated by the following formula.
Cetane index (C) = 0.49083 + 1.06577 (X)-0.0010522 (X) 2
[X = 97.833 (log A) 2 +2.2088 B log A + 0.01247 B 2 −423.51 log A−4.7808 B + 419.59]
A: (9/5) [50% by volume distillation temperature (° C.) at 101.3 kPa (760 mmHg)] + 32
B: API volume (50 volume% distillation temperature (° C.) at 101.3 kPa (760 mmHg) is measured according to JIS K 2254 “Petroleum products-distillation test method”, and the API degree is JIS K 2249 “crude oil and petroleum products— Calculated from the density at 15 ° C. by “density test method and density / mass / capacity conversion table”)
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防止の点により優れることから、−３℃以下であることが好ましく、−５℃以下であることがより好ましく、−７℃以下であることが最も好ましい。
本発明において、ＣＦＰＰ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。
Although there is no restriction | limiting in particular about CFPP (clogging point) of A heavy oil composition of this invention, Since it is excellent by the point of the filter clogging prevention by wax in winter, it is preferable that it is -3 degrees C or less, and -5 degreeC It is more preferable that the temperature is -7 ° C or less.
In the present invention, CFPP means a value obtained in accordance with JIS K 2288 “Diesel Oil—Clogging Point Test Method”.
本発明のＡ重油組成物の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、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。
本発明において窒素分とは、ＪＩＳ 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。
Although there is no restriction | limiting in particular about the nitrogen content of A heavy oil composition of this invention, In order to reduce the harmful substance in waste gas, it is preferable that it is 0.02 mass% or less, and it is 0.015 mass% or less. Is more preferable, and it is most preferable that it is 0.01 mass% or less.
In the present invention, the nitrogen content means a value representing a value obtained according to JIS K 2609 “Crude oil and petroleum products—nitrogen content test method”.
また、本発明のＡ重油組成物には、必要に応じて添加剤を配合することができる。ここでいう添加剤としては、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質量％であることが好ましく、０．０１〜０．０５質量％であることがより好ましい。 Moreover, an additive can be mix | blended with the A heavy oil composition of this invention as needed. Various additives such as cetane number improvers, antioxidants, stabilizers, dispersants, metal deactivators, microbial disinfectants, auxiliary agents, antistatic agents, discriminating agents, colorants, etc. These additives can be added as appropriate. Among these, it is preferable to add a fluidity improver because it is excellent in the effect of preventing filter clogging by wax in winter. As the fluidity improver, for example, polymer-type additives such as ethylene-vinyl acetate copolymer and ethylene-α-olefin copolymer, oil-soluble dispersant-type additives, and alkersuccinic acid can be used. Moreover, although there is no restriction | limiting about the addition amount of a fluid improvement agent, it is preferable that it is 0.001-0.1 mass% on the basis of A heavy oil composition whole quantity, and is 0.01-0.05 mass%. It is more preferable.
以下、実施例により本発明をさらに具体的に説明するが、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。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
［実施例１〜２及び比較例１〜２］
実施例１〜２及び比較例１〜２のＡ重油組成物の性状を表１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を下記の方法により行った。その結果を表２に記した。
[Examples 1-2 and Comparative Examples 1-2]
Table 1 shows the properties of the A heavy oil compositions of Examples 1-2 and Comparative Examples 1-2. About each sample oil (each composition), low temperature fluidity performance evaluation was performed by the following method. The results are shown in Table 2.
（低温流動性性能評価）
試料容器として、２０Ｌペール缶を用意し、ペール缶の上面に試料吸引管を差し込む穴を設けた。穴の形成位置は、上面の中心と外周上の点とを結ぶ直線の中点とした。一方、試料吸引管として外径１０ｍｍの銅管を用意し、その一端をシリコンゴム管を介してフィルター（ネポン株式会社製、コードＮｏ．１２０２６７）の入口に接続した。また、フィルターの出口を銅管を介して吸引ポンプに接続した。吸引ポンプは、通油量を１〜１０Ｌ／ｈｒの範囲内で調節可能なものを用いた。
次に、温度が２０〜２５℃の試料（Ａ重油組成物）約１５Ｌを上記のペール缶に入れ、ペール缶の上面の穴に試料吸引管付き蓋をした後、ペール缶とフィルターとを低温恒温槽内に収容し、ポンプを駆動させ、通油量が９．５±０．２Ｌ／ｈｒとなるようにポンプ圧力を調整した。低温恒温槽としては、プログラム温度調節機能を備え、温度精度±０．５℃以内で−３０℃以下まで冷却可能な恒温槽を用いた。ペール缶とフィルターとを低温恒温槽に収容した後、低温恒温槽内を所定の温度プロファイルで冷却し、吸引ポンプを駆動させた。より具体的には、試料の曇り点より８℃高い温度から冷却速度１℃／ｈｒで所定の温度まで冷却した。その温度で３時間保持し、圧力計で圧力を測定して通油限界を判定した。通油限界の判定は、保持温度で６０分間通油中に差圧が３３ｋＰａ（２５０ｍｍＨｇ）以下である場合を合格、３３ｋＰａを超えた場合を不合格とし、不合格となるまで１℃間隔で保持温度を低くして試験を繰り返した。 判定が不合格となった最高温度（目詰まり温度）を低温性能の評価の指標とした。なお、試料は試験ごとに新油に取り替えた。目詰まり温度が−１５℃以下を良好（○）、−１４℃以上を不良（×）と判断した。得られた結果を表２に示す。
(Low temperature fluidity performance evaluation)
A 20 L pail can was prepared as a sample container, and a hole into which the sample suction tube was inserted was provided on the top surface of the pail can. The hole was formed at the midpoint of a straight line connecting the center of the upper surface and the point on the outer periphery. On the other hand, a copper tube having an outer diameter of 10 mm was prepared as a sample suction tube, and one end of the copper tube was connected to the inlet of a filter (Nepon Corporation, code No. 120267) via a silicon rubber tube. Moreover, the outlet of the filter was connected to a suction pump through a copper tube. As the suction pump, a pump capable of adjusting the oil flow rate within a range of 1 to 10 L / hr was used.
Next, about 15 L of a sample (A heavy oil composition) having a temperature of 20 to 25 ° C. is put in the above-mentioned pail can, a lid with a sample suction tube is put in the hole on the top surface of the pail can, and then the pail can and the filter are cooled to a low temperature. The pump was accommodated in a thermostat, the pump was driven, and the pump pressure was adjusted so that the oil flow rate was 9.5 ± 0.2 L / hr. As the low-temperature thermostat, a thermostat equipped with a program temperature adjusting function and capable of cooling to −30 ° C. or less within a temperature accuracy of ± 0.5 ° C. was used. After the pail can and the filter were accommodated in the low-temperature thermostatic chamber, the inside of the low-temperature thermostatic chamber was cooled with a predetermined temperature profile, and the suction pump was driven. More specifically, the sample was cooled from a temperature 8 ° C. higher than the cloud point of the sample to a predetermined temperature at a cooling rate of 1 ° C./hr. The temperature was held for 3 hours, and the oil passage limit was determined by measuring the pressure with a pressure gauge. Judgment of the oil passage limit is accepted when the differential pressure is 33 kPa (250 mmHg) or less during oil passage for 60 minutes at the holding temperature, and is rejected when it exceeds 33 kPa, and held at 1 ° C intervals until it fails. The test was repeated at a lower temperature. The highest temperature (clogging temperature) at which the judgment was rejected was used as an index for evaluating the low temperature performance. In addition, the sample was replaced with new oil for each test. A clogging temperature of −15 ° C. or lower was judged good (◯), and a temperature of −14 ° C. or higher was judged bad (x). The obtained results are shown in Table 2.
表２の結果から明らかなように、本発明にかかる実施例１〜２のＡ重油組成物は、低温時のフィルター通油性能に優れることが分かる。 As is clear from the results in Table 2, it can be seen that the A heavy oil compositions of Examples 1 and 2 according to the present invention are excellent in filter oil passing performance at low temperatures.
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