JP4885568B2 - Heavy oil composition - Google Patents
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本発明は、重油組成物に関し、詳しくは、ボイラー等の燃料として使用した場合、発熱量が高く、排出ガス中の煤濃度を低減できる重油組成物（Ａ重油組成物）に関する。 The present invention relates to a heavy oil composition, and more particularly to a heavy oil composition (A heavy oil composition) that has a high calorific value and can reduce the soot concentration in exhaust gas when used as a fuel such as a boiler.
一般にＡ重油は、軽質軽油、重質軽油、灯油など比較的軽質な留分と共に、残留炭素分が軽油取引税の対象外となるように重質かつ高硫黄分の常圧残油や減圧残油等の留分を残留炭素付与剤として配合し、１０％残留炭素分が０．２質量％を越えるようにして製造されている。
このような重油をボイラー用燃料として使用すると、燃焼性が低下するため燃焼排出ガス中の煤が多くなり、バーナーが汚れやすくなることがあって、環境対策上好ましくない。
また、燃料油の発熱量が高い基材として、流動接触分解装置から得られるライトサイクルオイル（ＬＣＯ）が知られているが、該ＬＣＯは芳香族分が高いため、その混合比率が高い燃料を使用すると、ボイラー使用時に着火不良、煤の発生など燃焼不良が一層深刻化することがある。このようなことから、煤の発生を抑制する燃料油の製造においては、ＬＣＯを配合することは回避されることが多い。その結果、ＬＣＯは、余剰の基材として扱われているという問題がある。
In general, A heavy oil is a heavy and high sulfur atmospheric pressure residue or reduced pressure residue so that the residual carbon content is not subject to the light oil transaction tax, along with relatively light fractions such as light diesel oil, heavy diesel oil, and kerosene. A fraction such as oil is blended as a residual carbon imparting agent, so that the 10% residual carbon content exceeds 0.2% by mass.
When such heavy oil is used as a fuel for boilers, the combustibility is lowered, so that soot in the combustion exhaust gas increases and the burner is likely to become dirty, which is not preferable in terms of environmental measures.
In addition, light cycle oil (LCO) obtained from fluid catalytic cracking equipment is known as a base material with high calorific value of fuel oil, but since LCO has a high aromatic content, a fuel with a high mixing ratio is used. Then, when using the boiler, poor combustion such as poor ignition and generation of soot may become more serious. For this reason, blending LCO is often avoided in the production of fuel oil that suppresses the generation of soot. As a result, there is a problem that LCO is handled as an excess base material.
一方、酸素含有化合物は、燃料油の燃焼性を改善し、排気ガスを清浄化する試みが多数報告されている。例えば、ガソリンについてエタノールやエチルターシャリーブチルエーテルを配合しＰＭ等の発生を抑制するもの（例えば、特許文献１、２参照）、軽油について特定の脂肪酸アルキルエステルを配合しＰＭ等の発生を抑制するもの（例えば、特許文献３〜５参照）などがあり、いずれも酸素含有化合物が燃料油の燃焼性を高めることを利用したものである。
しかしながら、これらはいずれもガソリン、軽油など軽質油を対象とするものであり、重油のような燃焼性が劣る重質油に対する燃焼排出ガスに対するものはない。
そのため、重油のような重質油について、しかも、燃焼排出ガスの煤濃度を低減するという環境対策に不利となるＬＣＯを含有する重油であっても、燃料油において、基本的に要求される発熱量を高く保ち、かつボイラーの燃焼排出ガス中の煤の発生を抑制しうる燃料油が必要とされている。
On the other hand, many attempts have been reported for oxygen-containing compounds to improve the combustibility of fuel oil and to purify exhaust gas. For example, gasoline containing ethanol or ethyl tertiary butyl ether to suppress the generation of PM, etc. (for example, see Patent Documents 1 and 2), diesel oil containing a specific fatty acid alkyl ester to suppress the generation of PM, etc. (For example, refer to Patent Documents 3 to 5) and the like, which utilize the fact that an oxygen-containing compound enhances the combustibility of fuel oil.
However, all of these are intended for light oils such as gasoline and light oil, and there is no combustion exhaust gas for heavy oils such as heavy oils with poor combustibility.
Therefore, even with heavy oil such as heavy oil, and even with heavy oil containing LCO, which is disadvantageous for environmental measures to reduce the soot concentration of combustion exhaust gas, heat generation basically required in fuel oil There is a need for a fuel oil that can keep the amount high and can suppress the generation of soot in the combustion exhaust gas of the boiler.
本発明は、このような状況下でなされたもので、ボイラー等の燃料として使用した場合、発熱量が高く、燃焼排出ガス中の煤濃度を低減できる重油組成物（Ａ重油組成物）を提供することを目的とするものである。 The present invention has been made under such circumstances, and provides a heavy oil composition (A heavy oil composition) that has a high calorific value and can reduce the soot concentration in combustion exhaust gas when used as a fuel for a boiler or the like. It is intended to do.
本発明者らは、重油及び酸素含有化合物の組成と燃焼排出ガス中の煤濃度との関係について鋭意研究した結果、特定の組成を有する重油（基材）に特定の脂肪酸アルキルエステルを配合した重油組成物がその目的を達成できることを見出した。本発明はかかる知見に基づいて完成したものである。 As a result of diligent research on the relationship between the composition of heavy oil and oxygen-containing compounds and the soot concentration in combustion exhaust gas, the present inventors have mixed heavy oil (base material) having a specific composition with a specific fatty acid alkyl ester. It has been found that the composition can achieve its purpose. The present invention has been completed based on such findings.
すなわち、本発明は、
１．（ａ）ライトサイクルオイル、（ｂ）炭素数８〜２２の脂肪酸と炭素数１〜４のアルキルアルコールを反応して得られる脂肪酸アルキルエステル、及び（ｃ）残留炭素付与剤を配合してなり、前記（ａ）成分と（ｂ）成分の配合割合が、（ａ）成分と（ｂ）成分の合計量基準で、（ａ）成分が１０〜４０容量％、（ｂ）成分が９０〜６０容量％であり、１５℃における密度が０．８８〜０．９５ｇ／ｃｍ3、１０％残留炭素分が０．２１〜１．０質量％、芳香族分が３０〜９０容量％であって、酸素含有量（ｐ質量％）が芳香族分（ｑ容量％）と下記の式（１）を満たす範囲であることを特徴とする重油組成物、
ｐ／ｑ ＝ ０．０１〜０．２０ ・・・（１）
２.脂肪酸アルキルエステルの脂肪酸が、炭素数８〜２２の脂肪酸を２以上含む混合脂肪酸であり、該混合脂肪酸が炭素数１８の不飽和脂肪酸を５０質量％以上含有する混合脂肪酸である前記１に記載の重油組成物、
３.脂肪酸アルキルエステルが脂肪酸のメチルエステルである前記２又は３に記載の重油組成物、
を提供するものである。
That is, the present invention
1. (A) a light cycle oil, (b) a fatty acid alkyl ester obtained by reacting a fatty acid having 8 to 22 carbon atoms with an alkyl alcohol having 1 to 4 carbon atoms, and (c) a residual carbon imparting agent, The blending ratio of the component (a) and the component (b) is based on the total amount of the component (a) and the component (b), the component (a) is 10 to 40% by volume, and the component (b) is 90 to 60% by volume. , and the 15 density at ℃ is 0.88~0.95g / cm 3, 10% carbon residue is from 0.21 to 1.0 wt%, aromatics content comprising 30 to 90 volume%, oxygen content A heavy oil composition characterized in that the amount (p% by mass) is in a range satisfying the aromatic content (q% by volume) and the following formula (1):
p / q = 0.01-0.20 (1)
2. Fatty acid alkyl ester is a mixed fatty acids containing 2 or more fatty acids having 8 to 22 carbon atoms, the 1 is a mixed fatty acid which the mixed fatty acid contains more than 50 wt% of unsaturated fatty acids of 18 carbon atoms The heavy oil composition as described,
3. The heavy oil composition according to 2 or 3 above, wherein the fatty acid alkyl ester is a methyl ester of a fatty acid,
Is to provide.
本発明の重油組成物は、ボイラー等の燃料として使用した場合、発熱量が高く、ボイラーの燃焼排出ガス中の煤濃度を低減できる。また、燃焼排出ガスの煤濃度を低減する場合に不利となるＬＣＯを含有する重油であっても、燃焼排出ガス中の煤濃度の低減が可能である。したがって、環境汚染対策に貢献できる重油として有効に活用することができる。 The heavy oil composition of the present invention has a high calorific value when used as a fuel for a boiler or the like, and can reduce the soot concentration in the combustion exhaust gas of the boiler. Moreover, even if it is the heavy oil containing LCO which becomes disadvantageous when reducing the soot concentration of combustion exhaust gas, the soot concentration in combustion exhaust gas can be reduced. Therefore, it can be effectively utilized as heavy oil that can contribute to environmental pollution countermeasures.
本発明の重油組成物は、１５℃における密度が０．８８〜０．９５ｇ／ｃｍ3、１０％残留炭素分が０．２１〜１．０質量％、芳香族分が３０〜９０容量％であって、酸素含有量（ｐ質量％）が芳香族分（ｑ容量％）と前記式（１）を満たす範囲であることを特徴とする。
ｐ／ｑ ＝ ０．０１〜０．２０ ・・・・（１）
The heavy oil composition of the present invention has a density at 15 ° C. of 0.88 to 0.95 g / cm 3 , 10% residual carbon content of 0.21 to 1.0% by mass, and aromatic content of 30 to 90% by volume. The oxygen content (p% by mass) is within a range satisfying the aromatic content (q% by volume) and the above formula (1).
p / q = 0.01 to 0.20 (1)
本発明の重油組成物の１５℃における密度は、０．８８〜０．９５ｇ／ｃｍ3、好ましくは０．８９〜０．９３ｇ／ｃｍ3であることが必要である。１５℃における密度は、０．８８ｇ／ｃｍ3未満であれば発熱量が低下する恐れがあり、また１５℃における密度が０．９５ｇ／ｃｍ3を越えると燃焼排出ガス中の煤濃度が著しく増大する恐れがある。なお、ここでいう密度は、ＪＩＳ Ｋ ２２４９によって測定した値である。 Density at 15 ℃ of fuel oil composition of the present invention, 0.88~0.95g / cm 3, preferably must be a 0.89~0.93g / cm 3. If the density at 15 ° C. is less than 0.88 g / cm 3 , the calorific value may decrease, and if the density at 15 ° C. exceeds 0.95 g / cm 3 , the soot concentration in the combustion exhaust gas will increase significantly. There is a fear. The density here is a value measured according to JIS K 2249.
本発明の重油組成物の１０％残留炭素分は、０．２１〜１．０質量％、好ましく、０．２１〜０．８質量％、より好ましく、０．２１〜０．５質量％であることが必要である。１０％残留炭素分は、０．２１質量％未満では、Ａ重油の免税条件を満たすことができなくなり、また、１０％残留炭素分が１．０質量％を越えると、燃焼排出ガス中の煙濃度が増大することが多い。
なお、ここでいう１０％残留炭素分は、ＪＩＳ Ｋ ２２７０「原油および石油製品−残留炭素分試験方法」により測定した値である。
The 10% residual carbon content of the heavy oil composition of the present invention is 0.21 to 1.0 mass%, preferably 0.21 to 0.8 mass%, more preferably 0.21 to 0.5 mass%. It is necessary. If the 10% residual carbon content is less than 0.21% by mass, it will not be possible to satisfy the tax exemption condition of heavy oil A. If the 10% residual carbon content exceeds 1.0% by mass, the smoke in the combustion exhaust gas The concentration often increases.
In addition, the 10% residual carbon content here is a value measured by JIS K 2270 “Crude oil and petroleum products—residual carbon content test method”.
また、本発明の重油組成物の芳香族分は、３０〜９０容量％、好ましくは４０〜８０容量％であることが必要である。重油組成物の芳香族分が３０容量％未満では、低発熱量となって好ましくなく、また一方、重油組成物の芳香族分が９０容量％を越えると燃焼排出ガス中の煤濃度が著しく増大する恐れがある。
なお、ここでいう芳香族分は、石油学会規格ＪＰＩ−５Ｓ−４９−９７「石油製品−炭化水素タイプ試験方法−高速液体クロマトグラフ法」によって測定した値である。
The aromatic content of the heavy oil composition of the present invention is required to be 30 to 90% by volume, preferably 40 to 80% by volume. If the aromatic content of the heavy oil composition is less than 30% by volume, a low calorific value is not preferable. On the other hand, if the aromatic content of the heavy oil composition exceeds 90% by volume, the soot concentration in the combustion exhaust gas is remarkably increased. There is a fear.
Here, the aromatic content is a value measured by the Petroleum Institute Standard JPI-5S-49-97 “Petroleum Products—Hydrocarbon Type Test Method—High Performance Liquid Chromatograph Method”.
さらに、本発明の重油組成物の酸素含有量（ｐ質量％）が芳香族分（ｑ容量％）と下記の式（１）を満たす範囲であることが必要である。
ｐ／ｑ ＝ ０．０１〜０．２０ ・・・（１）
このｐ／ｑの値は、重油組成物の燃焼性と発熱量とのバランスを表す。その値が０．０１未満の場合は、燃焼排出ガス中の煤濃度の低減効果が不充分であり、一方ｐ／ｑが０．２０を越えると、燃焼性は良好であるが、低発熱量となって良好な重油は得られない。
なお、ここでいう酸素含有量は、２００４年石油製品討論会要旨集第１９〜２３頁に記載のガスクロマトグラフ法（検出器：ＡＥＤ）に準拠して測定した値である。
Furthermore, the oxygen content (p% by mass) of the heavy oil composition of the present invention needs to be in a range satisfying the aromatic content (q% by volume) and the following formula (1).
p / q = 0.01-0.20 (1)
The value of p / q represents the balance between the combustibility and the calorific value of the heavy oil composition. If the value is less than 0.01, the effect of reducing the soot concentration in the combustion exhaust gas is insufficient. On the other hand, if p / q exceeds 0.20, the combustibility is good, but the low calorific value is low. As a result, good heavy oil cannot be obtained.
In addition, oxygen content here is the value measured based on the gas chromatograph method (detector: AED) as described in the 19th to 23rd pages of abstracts of 2004 petroleum product discussion meeting.
本発の明重油組成物の酸素含有量は、脂肪酸アルキルエステルを配合しその配合量によって調整することが好ましい。
前記脂肪酸アルキルエステルは、炭素数８〜２２の脂肪酸と炭素数１〜４のアルキルアルコールから得られるエステルが好ましい。
炭素数８〜２２の脂肪酸としては、飽和脂肪酸であっても不飽和脂肪酸であってもよい。このような脂肪酸の具体例としては、例えば、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、パルミトレイン酸、ステアリン酸、オレイン酸、リノール酸、リノレン酸、アラキン酸、エイコセン酸、アラキドン酸、エイコサペンタエン酸、ベヘン酸、エルカ酸、ドコサペンタエン酸、ドコサヘキサエン酸などが挙げられる。
これらの脂肪酸のいずれかを１種以上用いた脂肪酸アルキルエステルが好ましい。
The oxygen content of the present light heavy oil composition is preferably adjusted by blending a fatty acid alkyl ester and the blending amount.
The fatty acid alkyl ester is preferably an ester obtained from a fatty acid having 8 to 22 carbon atoms and an alkyl alcohol having 1 to 4 carbon atoms.
The fatty acid having 8 to 22 carbon atoms may be a saturated fatty acid or an unsaturated fatty acid. Specific examples of such fatty acids include, for example, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, eicosenoic acid, arachidonic acid Eicosapentaenoic acid, behenic acid, erucic acid, docosapentaenoic acid, docosahexaenoic acid and the like.
Fatty acid alkyl esters using one or more of these fatty acids are preferred.
本発明においては、脂肪酸として炭素数８〜２２の脂肪酸を２以上含む混合脂肪酸を用いることが好ましい。
このような混合脂肪酸は、動物油や植物油などの油脂を原料とし、それから得られる脂肪酸は大量に入手することができるため好適である。この原料動物油としては、牛脂、豚脂、羊脂、鯨油、魚油、肝油等が、原料植物油としては、アマニ油、サフラワー油、ひまわり油、大豆油、コーン油、綿実油、ゴマ油、オリーブ油、ヒマシ油、落花生油、ココヤシ油、パーム核油、菜種油、米ぬか油等が挙げられる。
In the present invention, it is preferable to use a mixed fatty acid containing two or more fatty acids having 8 to 22 carbon atoms as the fatty acid.
Such a mixed fatty acid is suitable because it can be obtained in a large amount from fats and oils such as animal oils and vegetable oils. The raw animal oils include beef tallow, lard, sheep oil, whale oil, fish oil, liver oil, etc., and the raw vegetable oils include linseed oil, safflower oil, sunflower oil, soybean oil, corn oil, cottonseed oil, sesame oil, olive oil, castor oil. And oil, peanut oil, coconut oil, palm kernel oil, rapeseed oil, rice bran oil, and the like.
本発明においては、特に、脂肪酸が炭素数８〜２２の脂肪酸を２以上含む混合脂肪酸であるとともに、該混合脂肪酸が炭素数１８の不飽和脂肪酸を５０質量％以上、好ましくは７０質量％以上含有する混合脂肪酸であることが好ましい。このような混合脂肪酸の脂肪酸アルキルエステルは、性状が安定しているため安定した燃焼をすることができ、燃焼排出ガス中の煤濃度の低減効果が一層優れるものである。
炭素数１８の不飽和脂肪酸の具体例としては、例えば、オレイン酸、リノール酸、リノレン酸などがあげられる。
このような混合脂肪酸は、前記した各種油脂のうち、例えば、アマニ油、サフラワー油、ひまわり油、大豆油、コーン油、綿実油、ゴマ油、オリーブ油、ヒマシ油、落花生油、菜種油など植物油から得られる脂肪酸を用いればよい。
In the present invention, in particular, the fatty acid is a mixed fatty acid containing 2 or more fatty acids having 8 to 22 carbon atoms, and the mixed fatty acid contains 50% by mass or more, preferably 70% by mass or more of unsaturated fatty acids having 18 carbon atoms. It is preferable that it is a mixed fatty acid. Such a fatty acid alkyl ester of a mixed fatty acid has stable properties, so that stable combustion can be achieved, and the effect of reducing soot concentration in the combustion exhaust gas is further excellent.
Specific examples of the unsaturated fatty acid having 18 carbon atoms include oleic acid, linoleic acid, linolenic acid, and the like.
Such mixed fatty acids are obtained from vegetable oils such as linseed oil, safflower oil, sunflower oil, soybean oil, corn oil, cottonseed oil, sesame oil, olive oil, castor oil, peanut oil, and rapeseed oil among the various oils described above. Fatty acids may be used.
一方、脂肪酸アルキルエステルを形成する炭素数１〜４のアルキルアルコールの具体例としては、メタノール、エタノール、直鎖又は分岐鎖を有するプロパノール、直鎖又は分岐鎖を有するブタノールが挙げられる。これらの中で、製造の容易性の観点からメタノール及びエタノールが好ましく、特にメタノールが好ましい。 On the other hand, specific examples of the alkyl alcohol having 1 to 4 carbon atoms forming the fatty acid alkyl ester include methanol, ethanol, propanol having a linear or branched chain, and butanol having a linear or branched chain. Among these, methanol and ethanol are preferable from the viewpoint of ease of production, and methanol is particularly preferable.
脂肪酸アルキルエステルは、上記脂肪酸とアルキルアルコールとを公知の方法で、例えば、苛性ソーダ等のアルカリ触媒の存在下で、エステル化反応すればよい。 The fatty acid alkyl ester may be esterified with the above fatty acid and alkyl alcohol by a known method, for example, in the presence of an alkali catalyst such as caustic soda.
脂肪酸アルキルエステルの好適な具体例としては、前記炭素数８〜２２の飽和又は不飽和脂肪酸メチルエステル及び植物油から得られる混合脂肪酸のメチルエステルが挙げられ、中でも、炭素数１８の不飽和脂肪酸を全脂肪酸の５０質量％以上含有するアマニ油、サフラワー油、ひまわり油、大豆油、コーン油、綿実油、ゴマ油、オリーブ油、ヒマシ油、落花生油、菜種油から選ばれた１種以上の植物油から得られる混合脂肪酸のメチルエステルが挙げられる。 Preferable specific examples of fatty acid alkyl esters include saturated or unsaturated fatty acid methyl esters having 8 to 22 carbon atoms and methyl esters of mixed fatty acids obtained from vegetable oils. Mixture obtained from one or more vegetable oils selected from linseed oil, safflower oil, sunflower oil, soybean oil, corn oil, cottonseed oil, sesame oil, olive oil, castor oil, peanut oil and rapeseed oil containing 50% by weight or more of fatty acids And methyl esters of fatty acids.
本発明の重油組成物に配合される脂肪酸アルキルエステルは、全酸価は１．０ｍｇＫＯＨ／ｇ以下であること好ましい。全酸価が１．０ｍｇＫＯＨ／ｇ以下であれば、重油の性状を悪化させる恐れがなく、機器に悪影響を及ぼす恐れもない。この全酸価とは、ＪＩＳ Ｋ ２５０１「石油製品及び潤滑油−中和価試験方法」により測定した値である。 The fatty acid alkyl ester blended in the heavy oil composition of the present invention preferably has a total acid value of 1.0 mgKOH / g or less. If the total acid value is 1.0 mgKOH / g or less, there is no possibility of deteriorating the properties of heavy oil, and there is no possibility of adversely affecting the equipment. The total acid value is a value measured according to JIS K 2501 “Petroleum products and lubricants—neutralization number test method”.
本発明の重油組成物は、さらに以下の条件を満たすことが好ましい。
本発明の重油組成物の硫黄分は、０．５質量％以下であることが好ましく、０．３質量％であることがより好ましい。重油組成物の硫黄分が０．５質量％以下であれば、燃焼排出ガス中の煤濃度が増大することを抑制できる場合がある。なお、ここでいう硫黄分は、ＪＩＳ Ｋ２５４１「硫黄分試験方法」によって測定した値である。
また、本発明の重油組成物の５０℃における動粘度は、１．８〜４．５ｍｍ2／ｓであることが好ましく、１．８〜３．５ｍｍ2／ｓであることがより好ましい。５０℃における動粘度が１．８〜４．５ｍｍ2／ｓであれば、燃料の供給に支障がなく、
しかも、燃焼状態を良好に保つことができる。
The heavy oil composition of the present invention preferably further satisfies the following conditions.
The sulfur content of the heavy oil composition of the present invention is preferably 0.5% by mass or less, and more preferably 0.3% by mass. If the sulfur content of the heavy oil composition is 0.5% by mass or less, it may be possible to suppress an increase in the soot concentration in the combustion exhaust gas. In addition, the sulfur content here is a value measured by JIS K2541 “Sulfur content test method”.
Moreover, it is preferable that it is 1.8-4.5 mm < 2 > / s, and, as for the kinematic viscosity in 50 degreeC of the heavy oil composition of this invention, it is more preferable that it is 1.8-3.5 mm < 2 > / s. If the kinematic viscosity at 50 ° C. is 1.8 to 4.5 mm 2 / s, there is no hindrance to the fuel supply,
Moreover, the combustion state can be kept good.
本発明の重油組成物は、９０％留出温度（Ｔ９０）が３３０〜４００℃であることが好ましい。Ｔ９０が３３０℃以上であれば、エンジン内で良好な噴霧を形成でき、燃焼状態を良好に保ち、出力の低下やセタン価の低下を回避することができる。一方、Ｔ９０が４００℃以下であれば燃焼状態を良好に保つことができる。なお、Ｔ９０は、ＪＩＳ Ｋ ２２５４に基づいて測定した蒸留性状から求めた値である。
本発明の重油組成物の蒸留性状は、上記と同様の理由から、さらに５０％留出温度（Ｔ５０）が２８０〜３３０℃であることが好ましい。
The heavy oil composition of the present invention preferably has a 90% distillation temperature (T90) of 330 to 400 ° C. If T90 is 330 ° C. or higher, a good spray can be formed in the engine, the combustion state can be kept good, and a decrease in output and a decrease in cetane number can be avoided. On the other hand, if T90 is 400 ° C. or lower, the combustion state can be kept good. T90 is a value obtained from the distillation properties measured based on JIS K 2254.
The distillation property of the heavy oil composition of the present invention is preferably such that the 50% distillation temperature (T50) is 280 to 330 ° C. for the same reason as described above.
本発明の重油組成物は、任意の方法で得ることができる。例えば、次に示す重油基材を適宜選択して配合し、さらに、いわゆる残留炭素分付与剤を配合することにより調製することができる。
その重油基剤としては、例えば、直留灯油（又は脱硫灯油）、直留軽質軽油、（又は脱硫軽質軽油）、直留重質軽油（又は脱硫重質軽油）、ライトサイクルオイル（軽質サイクル油）、水素化脱硫減圧軽油、水素化分解軽油、直脱軽油等が挙げられる。これらの基材を１種又は２種以上を配合して調整すればよい。これらの基材のうち、本発明においては、特に燃焼排気ガス中の煤濃度の抑制に不利なライトサイクルオイルを主成分の基材として使用する態様を含むものである。
The heavy oil composition of the present invention can be obtained by any method. For example, it can be prepared by appropriately selecting and blending the following heavy oil base and further blending a so-called residual carbon content-imparting agent.
Examples of the heavy oil base include straight-run kerosene (or desulfurized kerosene), straight-run light light oil, (or desulfurized light light oil), straight-run heavy light oil (or desulfurized heavy light oil), and light cycle oil (light cycle oil). , Hydrodesulfurized vacuum gas oil, hydrocracked gas oil, direct degassing gas oil and the like. What is necessary is just to mix | blend 1 type or 2 types or more of these base materials. Among these base materials, the present invention includes an embodiment in which light cycle oil, which is particularly disadvantageous for suppressing soot concentration in the combustion exhaust gas, is used as the base material.
また、残留炭素分付与剤としては、常圧残油、減圧残油、脱硫残油、スラリーオイル、エキストラクトなどが挙げられる。これらの残留炭素分付与剤は、１種単独で、又は２種以上を組み合わせて配合する。この残留炭素分付与剤の配合量は、重油組成物の１０％残留炭素分が０．２１〜１．０質量％になるように調整して配合する。 Examples of the residual carbon content-imparting agent include atmospheric residual oil, vacuum residual oil, desulfurized residual oil, slurry oil, and extract. These residual carbon content imparting agents are blended singly or in combination of two or more. The blending amount of the residual carbon content imparting agent is adjusted and blended so that the 10% residual carbon content of the heavy oil composition is 0.21 to 1.0 mass%.
本発明の重油組成物には、必要に応じてセタン価向上剤、流動性向上剤、酸化防止剤、清浄剤、金属不活性化剤、防錆剤、腐食防止剤、帯電防止剤等各種添加剤を配合することができる。これらの添加剤は１種又は２種以上添加することができる。また、その添加量は状況に応じて適宜選定すればよいが、通常は添加剤の合計量として軽油組成物に対して０．５質量％以下とすることが好ましい。 Various additives such as a cetane number improver, a fluidity improver, an antioxidant, a detergent, a metal deactivator, a rust inhibitor, a corrosion inhibitor, and an antistatic agent are added to the heavy oil composition of the present invention as necessary. An agent can be blended. These additives can be added alone or in combination of two or more. Moreover, the addition amount may be appropriately selected according to the situation, but it is usually preferable that the total amount of the additive is 0.5% by mass or less based on the light oil composition.
次に実施例により本発明を詳しく説明するが、本発明はこれらの例によって何ら制限されるものではない。なお、重油組成物の性状及び性能は次の方法に従って求めた。
〔重油組成物の性状と組成〕
・密度
ＪＩＳ Ｋ ２２４９に準拠して測定した。
・セタン価
ＪＩＳ Ｋ ２２８０に準拠して測定した。
・硫黄分
ＪＩＳ Ｋ ２５４１に準拠して測定した。
・１０％残留炭素分
ＪＩＳ Ｋ ２２７０に準拠して測定した。
・蒸留性状
ＪＩＳ Ｋ ２５４１により測定した。
・芳香族分
石油学会規格ＪＰＩ−５Ｓ−４９−９７により測定した。
・酸素含有量
２００４年石油製品討論会要旨集第１９〜２３頁に記載のガスクロマトグラフ法（検出器：ＡＥＤ）に準拠して測定した。
・発熱量
ＪＩＳ Ｋ２２７９により測定した。
EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not restrict | limited at all by these examples. The properties and performance of the heavy oil composition were determined according to the following method.
[Properties and composition of heavy oil composition]
-Density Measured according to JIS K 2249.
-Cetane number Measured according to JIS K 2280.
-Sulfur content Measured according to JIS K2541.
-10% residual carbon content Measured according to JIS K 2270.
-Distillation property It measured by JISK2541.
-Measured according to Aromatics Petroleum Institute Standard JPI-5S-49-97.
-Oxygen content It measured based on the gas chromatograph method (detector: AED) as described in pages 19-23 of abstracts of 2004 petroleum product discussion.
-Calorific value Measured according to JIS K2279.
〔重油組成物の性能〕
・ボイラーの排出ガス実験
下記の暖房給湯用小型温水ボイラーを用いて各燃料を燃焼し、その際のスモーク（煙）濃度をスモークスケール（バッカラッカ社製スモークメーター）で測定し，ＪＩＳ Ｂ ８４０７−１９７９の規定に基づいてスモークナンバーを求めた。なお、実験は室温で行った。
（ボイラーの仕様）
バーナーの種類 ：ガーンタイプバーナー式（ノズルヒーターなし）
噴霧の形式 ：油圧式
熱出力 ：１００、０００ｋｃａｌ／ｈ
[Performance of heavy oil composition]
・ Boiler exhaust gas experiment Each fuel was burned using the following small hot water boiler for heating and hot water supply, and the smoke (smoke) concentration at that time was measured with a smoke scale (baccarat company smoke meter), and JIS B 8407-1979. The smoke number was calculated based on The experiment was performed at room temperature.
(Boiler specifications)
Burner type: Gurn type burner type (no nozzle heater)
Spray type: Hydraulic heat output: 100,000 kcal / h
実施例１〜４及び比較例１
重油基材として第２表に示す性状のＬＣＯを用い、これに第１表に示す組成を有し第２表に示す性状の菜種油のメチルエステル化物（炭素数１８の脂肪酸の含有割合＝８８．９質量％）及び、残留炭素分付与剤として、常圧残油を用いて第３表に示す性状の実施例１〜３の重油組成物を調製した。比較例１は、ＬＣＯであり、比較例２は市販Ａ重油である。それらの重油組成物の性状及び性能を第３表に示す。なお、残留炭素分付与剤である常圧残油は、１５℃における密度が０．９９９ｇ／ｃｍ3，硫黄分３．２質量％、残留炭素分１４．８質量％のものを用いた。
Examples 1 to 4 and Comparative Example 1
LCO having the properties shown in Table 2 was used as the heavy oil base material, and the methyl esterified product of rapeseed oil having the composition shown in Table 1 and properties shown in Table 2 (content ratio of fatty acids having 18 carbon atoms = 88. 9 mass%) and heavy oil compositions of Examples 1 to 3 having the properties shown in Table 3 using atmospheric residual oil as residual carbon content-imparting agents. Comparative Example 1 is LCO, and Comparative Example 2 is a commercial A heavy oil. Table 3 shows the properties and performance of these heavy oil compositions. The atmospheric residual oil, which is a residual carbon content-imparting agent, was used with a density at 15 ° C. of 0.999 g / cm 3 , a sulfur content of 3.2% by mass, and a residual carbon content of 14.8% by mass.
本発明の重油組成物によれば、ボイラー等の燃料として使用した場合、発熱量が高く、ボイラーの燃焼排出ガス中の煤濃度を低減できる。また、燃焼排出ガスの煤濃度を低減する場合に不利となるＬＣＯを含有する重油であっても、排出ガス中の煤濃度の低減が可能である。したがって、環境汚染対策に貢献できる重油として有効に活用することとともに、ＬＣＯの有効活用にも貢献することができる。 According to the heavy oil composition of the present invention, when used as fuel for a boiler or the like, the calorific value is high, and the soot concentration in the combustion exhaust gas of the boiler can be reduced. Moreover, even if it is the heavy oil containing LCO which becomes disadvantageous when reducing the soot concentration of combustion exhaust gas, the soot concentration in exhaust gas can be reduced. Therefore, it can be effectively used as heavy oil that can contribute to environmental pollution countermeasures, and can also contribute to the effective use of LCO.
Claims (3)
ｐ／ｑ ＝ ０．０１〜０．２０ ・・・（１） (A) a light cycle oil, (b) a fatty acid alkyl ester obtained by reacting a fatty acid having 8 to 22 carbon atoms with an alkyl alcohol having 1 to 4 carbon atoms, and (c) a residual carbon imparting agent, The blending ratio of the component (a) and the component (b) is based on the total amount of the component (a) and the component (b), the component (a) is 10 to 40% by volume, and the component (b) is 90 to 60% by volume. , and the 15 density at ℃ is 0.88~0.95g / cm 3, 10% carbon residue is from 0.21 to 1.0 wt%, aromatics content comprising 30 to 90 volume%, oxygen content A heavy oil composition characterized in that the amount (p% by mass) is within a range satisfying the aromatic content (q% by volume) and the following formula (1).
p / q = 0.01-0.20 (1)
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