JP2007254664A - Environmentally responsive high-octane gasoline composition and method for producing the same - Google Patents
Environmentally responsive high-octane gasoline composition and method for producing the same Download PDFInfo
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- JP2007254664A JP2007254664A JP2006083143A JP2006083143A JP2007254664A JP 2007254664 A JP2007254664 A JP 2007254664A JP 2006083143 A JP2006083143 A JP 2006083143A JP 2006083143 A JP2006083143 A JP 2006083143A JP 2007254664 A JP2007254664 A JP 2007254664A
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- 239000006078 metal deactivator Substances 0.000 description 1
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
本発明は、環境への影響に配慮しつつ十分な運転特性を確保した高オクタン価環境対応型ガソリン組成物及びその製造方法に関する。 The present invention relates to a high octane number environment-friendly gasoline composition and a method for producing the same, in which sufficient operating characteristics are ensured while taking into consideration the influence on the environment.
地球温暖化ガスの一つと考えられている二酸化炭素の排出量を削減するために、ガソリンのリサーチ法オクタン価（ＲＯＮ）を高めることが有効であることが報告されている。一方、石油化学製品の海外需要増加により石油化学製品の生産量が増大し、石油化学原料の一つである芳香族基材製造装置の接触改質ガソリン製造装置の稼動が上がり、これに伴い副産物である重質芳香族基材が余剰化している。この重質芳香族基材は硫黄分をほとんど含まずＲＯＮが高い利点があるが、沸点が高いためガソリン混合後の揮発性を一定範囲にする為には一定比率以上の低硫黄軽質基材を混合することが必要である。 It has been reported that it is effective to increase the research octane number (RON) of gasoline in order to reduce the emission of carbon dioxide, which is considered as one of the global warming gases. On the other hand, the production volume of petrochemical products increased due to an increase in overseas demand for petrochemical products, and the operation of the catalytic reforming gasoline production equipment of the aromatic base material production equipment, which is one of the petrochemical raw materials, increased. The heavy aromatic base material is surplus. This heavy aromatic base material has the advantage that it contains almost no sulfur and has a high RON, but since it has a high boiling point, a low sulfur light base material with a certain ratio or more must be used in order to keep the volatility after gasoline mixing within a certain range. It is necessary to mix.
ＪＩＳ Ｋ ２２０２には、ＲＯＮが９６.０以上の１号自動車ガソリンと８９.０以上の２号自動車ガソリンが規定されており、前者は高性能なプレミアムガソリンとして、後者はレギュラーガソリンとして市販されている。従来、プレミアムガソリンは、接触改質ガソリン基材、メチル−ｔ−ブチルエーテル（ＭＴＢＥ）のような１００以上のＲＯＮをもつ基材、アルキレートガソリン基材、接触分解ガソリン軽質分のような９３以上のＲＯＮをもつ基材を中心に、各種の基材を配合して製造されている。また、レギュラーガソリンは、接触分解ガソリン基材を中心に、アロマ留分やＲＯＮの低い脱硫直留ナフサ等が添加され製造されている。 JIS K 2202 stipulates No. 1 automobile gasoline with RON of 96.0 or more and No. 2 automobile gasoline with 89.0 or more. The former is marketed as high-performance premium gasoline and the latter as regular gasoline. Yes. Conventionally, premium gasoline has a catalytic reforming gasoline base, a base with more than 100 RON such as methyl-t-butyl ether (MTBE), an alkylate gasoline base, a catalytic cracking gasoline lighter than 93 Manufactured by blending various base materials, mainly base materials with RON. Regular gasoline is produced by adding an aroma fraction, a desulfurized straight naphtha having a low RON, etc. to a catalytic cracked gasoline base material.
また、一般的に接触分解ガソリンや各種の分解ガソリンなどの分解ナフサ留分には多くのオレフィン類が含まれており、ＲＯＮの向上に大きく寄与している（非特許文献１参照）。これまでは、ＲＯＮが比較的低いパラフィン類は、ガソリン基材としては好まれず削減される方向であった。
その反面、ＲＯＮが高い化合物として広く使用されているオレフィン化合物は、光化学的に不安定であること、貯蔵安定性に問題があることから、スラッジ分などの固体状化合物を析出させてしまう欠点が問題視されている。
In general, cracked naphtha fractions such as catalytically cracked gasoline and various cracked gasolines contain a large amount of olefins, greatly contributing to the improvement of RON (see Non-Patent Document 1). Until now, paraffins with a relatively low RON were not preferred as a gasoline base material and were in the direction of reduction.
On the other hand, olefin compounds that are widely used as compounds with high RON are photochemically unstable and have problems with storage stability, and therefore have the disadvantage of precipitating solid compounds such as sludge. It is regarded as a problem.
また、オレフィン分のうち比較的低分子の物については、ＲＯＮは高いものの蒸気圧も高い傾向があるが、夏季ガソリン基材としては比較的沸点が低く、蒸気圧の低い基材が必要とされる傾向にある。 In addition, although RON is high in the olefin content, the vapor pressure tends to be high, but as a summer gasoline base material, a base material having a relatively low boiling point and a low vapor pressure is required. Tend to.
これに対して、アルキレートガソリンを多く使用してオレフィン分やアロマ分を削減したガソリン組成物に関する開示がある（特許文献１参照）が、これらＲＯＮの高い基材を低減させているためＲＯＮが不十分であり、かつ蒸留性状を調整するため軽質分を多く添加させる必要からリード蒸気圧（ＲＶＰ）が６５ｋＰａを超えており、依然として環境に配慮したガソリンと言えるレベルでは無かった。
また、オレフィン含有量を削減し含酸素化合物を添加することでＲＯＮを高めたガソリン組成物を製造する方法も開示されている（特許文献２参照）が、オレフィン分が６〜１５容量％と依然として多く、含酸素化合物にＲＯＮを依存しているため、燃費の悪い含酸素化合物を多く含むガソリン組成物となってしまい、環境負荷を低減した燃料とは言えなかった。
同様に、含酸素化合物を添加することでＲＯＮを高めたガソリン組成物を製造する方法も開示されている（特許文献３参照）が、含酸素化合物以外のガソリン構成基材の製造方法に関する開示が無く、現実的に製造し、実施できる技術とは言えなかった。
さらに、オレフィン分布を制御したガソリン組成物についても開示されている（特許文献４参照）が、全オレフィン含有量は２０容量％と依然として高く、高いＲＯＮを維持しながら、オレフィン分を低減できる方法はこれまで無かった。
On the other hand, there is a disclosure relating to a gasoline composition in which a large amount of alkylate gasoline is used to reduce the olefin content and aroma content (see Patent Document 1). Reed vapor pressure (RVP) exceeded 65 kPa because it was insufficient, and it was necessary to add a small amount of light in order to adjust the distillation properties, and it was still not at a level that could be said to be environmentally friendly gasoline.
Moreover, although the method of manufacturing the gasoline composition which raised RON by reducing olefin content and adding an oxygen-containing compound is also disclosed (refer patent document 2), olefin content is still 6-15 volume%. In many cases, since RON depends on oxygen-containing compounds, it becomes a gasoline composition containing a large amount of oxygen-containing compounds with poor fuel consumption, and cannot be said to be a fuel with reduced environmental load.
Similarly, a method for producing a gasoline composition in which RON is increased by adding an oxygen-containing compound is also disclosed (see Patent Document 3). However, there is disclosure relating to a method for producing a gasoline-constituting substrate other than oxygen-containing compounds. It was not a technology that could actually be manufactured and implemented.
Furthermore, although a gasoline composition with controlled olefin distribution is also disclosed (see Patent Document 4), the total olefin content is still as high as 20% by volume, and a method that can reduce the olefin content while maintaining a high RON is disclosed. Never before.
以上の状況を考慮しつつガソリン製造の実態に目を向けると、重質な石油留分を分解することによって製造される分解ガソリン基材は、他のガソリン基材に比べて経済的に製造できるという利点がある一方、硫黄分を多く含んでいる。その結果、上述のようにして製造されるガソリン中の硫黄分の大部分は、分解ガソリン基材に由来している。分解ガソリン基材に含まれる硫黄分は、高圧水素と触媒の共存下で水素化精製するという公知技術を用いて容易に低減できる。しかし、その場合は、接触分解ガソリン基材中に多く含まれ、高いＲＯＮをもつオレフィン分が水素化されて当該基材のＲＯＮが低下してしまうため、それを配合して十分な運転性能を有するガソリンを得ることは難しいという問題点があった。 Looking at the actual situation of gasoline production in consideration of the above situation, cracked gasoline bases produced by cracking heavy petroleum fractions can be produced more economically than other gasoline bases. On the other hand, it contains a lot of sulfur. As a result, most of the sulfur content in the gasoline produced as described above is derived from the cracked gasoline base material. The sulfur content contained in the cracked gasoline base material can be easily reduced using a known technique of hydrotreating in the presence of high-pressure hydrogen and a catalyst. However, in that case, a large amount of catalytic cracking gasoline base material is contained, and the olefin component having high RON is hydrogenated to decrease the RON of the base material. There was a problem that it was difficult to obtain gasoline.
レギュラーガソリンで使用されている直留ナフサは、原油の蒸留から得られるため経済的に製造することができるが、ＲＯＮが低いため多く用いることは難しい。 Straight-run naphtha used in regular gasoline can be produced economically because it is obtained from distillation of crude oil, but it is difficult to use many because of low RON.
オレフィンに代わるＲＯＮの高い化合物として、イソパラフィン分が挙げられる。イソパラフィン分を優先的に製造してＲＯＮを向上させる方法として、炭化水素の骨格異性化技術が知られている（非特許文献２参照）。しかしながら、このような骨格異性化反応も、適切な触媒やプロセスを使用しなければ十分な効果は得られず、また、ブレンド基材を最終的に適切な組み合わせをしない限り、満足できるガソリン製品を得ることは難しい。また、一般的に異性化油はその原料となるナフサ留分と比較すると沸点が軽くなるため、異性化油をあまり多用すると製品ガソリンのＲＶＰが高くなってしまう欠点もあった。 A compound having a high RON instead of an olefin includes an isoparaffin component. A hydrocarbon skeletal isomerization technique is known as a method for preferentially producing an isoparaffin component to improve RON (see Non-Patent Document 2). However, such a skeletal isomerization reaction cannot be fully effective unless an appropriate catalyst or process is used, and a satisfactory gasoline product can be obtained unless the blend base is finally combined appropriately. Difficult to get. In addition, since isomerized oil generally has a lighter boiling point than the naphtha fraction used as a raw material, there is a drawback that RVP of product gasoline increases when isomerized oil is used too much.
異性化反応と同様にイソパラフィン分を選択的に製造する方法として、アルキレーション反応を用いるプロセスがある。アルキレーション反応は、硫酸などの酸触媒を使用して、主に炭素数４のオレフィンとイソパラフィンとを反応させて炭素数８のイソパラフィン（ｉ−Ｃ８）を製造する反応であり、既に多くの装置が世界中で稼動している（非特許文献３参照）。しかし、その反応の特徴ゆえ、生成物として炭素数８の多分岐イソパラフィンが多く得られるものの、炭素数が８より少ない多分岐のイソパラフィンを得ることは難しかった。アルキレートガソリンは高沸点成分で構成されているため蒸留性状の制約から、また、原料として比較的高価な炭素数４の化合物を使用しなければならないため供給量やコストの制約から、あまり大量には製造すること、及び使用することができなかった。
オレフィン分が５．０容量％以下、硫黄分が１０質量ｐｐｍ以下と低く、かつ、ＲＯＮが高く十分な実用性能を確保した環境対応型ガソリン及びその製造方法は未だ確立されていない。このような状況下で、本発明は、オレフィン分を５．０容量％以下、硫黄分を１０質量ｐｐｍ以下、好ましくは１質量ｐｐｍ以下に低減し、かつ、特定のガソリン成分を含有することにより、十分な運転特性を確保した高オクタン価の環境対応型ガソリン組成物及びその製造方法を提供することを目的とするものである。 An environment-friendly gasoline having a low olefin content of 5.0 vol% or less, a sulfur content of 10 mass ppm or less, a high RON and ensuring sufficient practical performance, and a method for producing the same have not yet been established. Under such circumstances, the present invention reduces the olefin content to 5.0% by volume or less, the sulfur content to 10 mass ppm or less, preferably 1 mass ppm or less, and contains a specific gasoline component. An object of the present invention is to provide an environment-friendly gasoline composition having a high octane number and sufficient production characteristics, and a method for producing the same.
本発明者らは、上記課題を解決するために鋭意研究した結果、低沸点成分の異性化油と高沸点成分のアロマ分を適切に組み合わせたガソリンは運転性、加速性とも良好であり、加えてＲＯＮが高いため燃費が改善されて環境負荷が低減されることを見出した。さらに、環境負荷の少ないイソパラフィン類、特に炭素数６の二分岐以上のイソパラフィンを比較的多く含有するガソリン組成物は、オレフィン分を多く使用しなくても、蒸留性状とリード蒸気圧（ＲＶＰ）の良好なバランスを保持しながら、高いＲＯＮ、低硫黄の環境対応型ガソリンを得ることができることを見出した。例えば、炭素数６で二分岐イソパラフィンである２，３-ジメチルブタンは、ＲＯＮが１０３、ＲＶＰが５１ｋＰａ、沸点が５８℃であり、ガソリン基材として理想的な性状を有しており、このような化合物が多く含まれるガソリンほど、環境負荷の少ないガソリンであると言える。このように、本発明者らは、高いＲＯＮを有し、かつＲＶＰも低く蒸留性状も好ましい特定化合物を見出し、その含有量を制御することで、高いＲＯＮを維持したまま硫黄分を低減した環境対応型ガソリン組成物が得られることを見出し、かかる知見に基づいて本発明を完成した。 As a result of diligent research to solve the above problems, the inventors of the present invention have good operability and acceleration performance of gasoline in which an isomerized oil having a low boiling point component and an aroma component having a high boiling point component are appropriately combined. It has been found that since RON is high, fuel efficiency is improved and environmental load is reduced. Furthermore, a gasoline composition containing a relatively large amount of isoparaffins having a low environmental impact, in particular, an isoparaffin having 6 or more carbon atoms, has a distillation property and a lead vapor pressure (RVP) even without using a large amount of olefin. It has been found that high RON, low sulfur environment-friendly gasoline can be obtained while maintaining a good balance. For example, 2,3-dimethylbutane, which has 6 carbon atoms and is a bifurcated isoparaffin, has an RON of 103, an RVP of 51 kPa, a boiling point of 58 ° C., and has ideal properties as a gasoline base material. Gasoline containing a lot of chemical compounds can be said to be gasoline with less environmental impact. As described above, the present inventors have found a specific compound having a high RON, a low RVP and a preferable distillation property, and controlling the content thereof, thereby reducing the sulfur content while maintaining a high RON. The present inventors have found that a corresponding gasoline composition can be obtained, and have completed the present invention based on such knowledge.
すなわち、本発明は、ＲＯＮが９６以上、オレフィン分が５．０容量％以下、アロマ分が２０容量％以上４０容量％以下、イソパラフィン分が４０容量％以上８０容量％以下、及び硫黄分が１０質量ｐｐｍ以下であり、かつ、含酸素化合物の含有量が０〜１５容量％である高オクタン価の環境対応型ガソリン組成物である。 That is, the present invention has a RON of 96 or more, an olefin content of 5.0% by volume or less, an aroma content of 20% to 40% by volume, an isoparaffin content of 40% to 80% by volume, and a sulfur content of 10%. This is an environment-friendly gasoline composition having a high octane number and having a mass ppm or less and an oxygen-containing compound content of 0 to 15% by volume.
該ガソリン組成物は、５０容量％留出温度が９８℃以下、炭素数６のイソパラフィン（ｉ−Ｃ６）の含有量が１０容量％以上、２,３−ジメチルブタンの含有量が１.５容量％以上、（炭素数６のイソパラフィン）／（炭素数６のノルマルパラフィン（ｎ−Ｃ６））容量比（ｉ−Ｃ６／ｎ−Ｃ６容量比）が５．０以上、及び（炭素数６のイソパラフィン）／（炭素数６のオレフィン（Ｃ６＝））容量比（ｉ−Ｃ６／Ｃ６＝容量比）が３．０以上であることが好ましく、さらに硫黄分が１質量ｐｐｍ以下、炭素数８のイソパラフィンが２０容量％以下、リード蒸気圧（ＲＶＰ）が６５ｋＰａ以下であることが好ましい。 The gasoline composition has a 50 volume% distillation temperature of 98 ° C. or less, a carbon number 6 isoparaffin (i-C6) content of 10 volume% or more, and a 2,3-dimethylbutane content of 1.5 volume. % Or more, (C6-C normal paraffin (n-C6)) volume ratio (i-C6 / n-C6 volume ratio) is 5.0 or more, and (C6-C6 isoparaffin) ) / (Olefin having 6 carbon atoms (C6 = )) The volume ratio (i-C6 / C6 = volume ratio) is preferably 3.0 or more, and further, the sulfur content is 1 mass ppm or less and the carbon number is 8 isoparaffin. Is preferably 20% by volume or less, and the Reid vapor pressure (RVP) is preferably 65 kPa or less.
また、本発明は、
（１）１０容量％留出温度が２５〜６０℃、かつ９０容量％留出温度が５５〜８０℃であるナフサ留分の一部または全量を、水素加圧下、固体酸触媒を用いて骨格異性化して異性化生成油を得る異性化工程、及び
（２）前記（１）の異性化工程で得られた異性化生成油を異性化ガソリン基材として他のガソリン基材と混合するブレンド工程
を含む、前記の高オクタン価の環境対応型ガソリン組成物の製造方法である。
The present invention also provides:
(1) A part or all of a naphtha fraction having a 10% by volume distillation temperature of 25 to 60 ° C. and a 90% by volume distillation temperature of 55 to 80 ° C. using a solid acid catalyst under hydrogen pressure An isomerization step for isomerization to obtain an isomerized product oil, and (2) a blending step in which the isomerized product oil obtained in the isomerization step of (1) is mixed with another gasoline base as an isomerized gasoline base. A process for producing an environmentally friendly gasoline composition having a high octane number.
さらに、本発明の環境対応型ガソリン組成物の製造方法は、異性化工程で得られた異性化生成油を高オクタン価化合物と低オクタン価化合物とに分離し、得られた高オクタン価化合物を異性化ガソリン基材として用い、さらに、低オクタン価化合物を再度異性化工程に送って処理することが好ましく、また、異性化反応の原料に用いるナフサ留分としては、原油を蒸留し脱硫して得られた脱硫直留ナフサを用いることが好ましい。 Furthermore, the method for producing an environmentally friendly gasoline composition of the present invention separates the isomerized product oil obtained in the isomerization step into a high octane compound and a low octane compound, and the obtained high octane compound is isomerized gasoline. It is preferably used as a base material, and it is preferable to send the low octane compound again to the isomerization process for treatment, and as a naphtha fraction used as a raw material for the isomerization reaction, desulfurization obtained by distilling crude oil and desulfurizing it It is preferable to use straight-run naphtha.
発明者らが着目したガソリン成分は炭素数が６でかつ分岐状の脂肪族飽和炭化水素であり、とりわけ２,３−ジメチルブタンは、ＲＯＮが１０３と高く、３７．８℃におけるＲＶＰが５１ｋＰａ、沸点が５８℃であり、ガソリン基材には最適な性能を有している。しかも、従来から広く用いられている分解反応等では、２,３−ジメチルブタンのような多分岐状イソパラフィンを多く得ることは難しかったが、固体酸触媒存在下でナフサに異性化反応を施すことにより可能となった。さらにこれにより、本発明の環境対応型ガソリン組成物に対して、従来のガソリン組成物では考えられない性状、すなわち、オレフィン分を５．０容量％以下、かつ硫黄分を１０質量ｐｐｍ以下、さらには１質量ｐｐｍ以下まで減じても、満足するＲＯＮ、蒸留性状およびＲＶＰを付与することが可能となった。本発明により、かかる格別の性状を有する高オクタン価の環境対応型ガソリン組成物が提供できる。 The gasoline component that the inventors have focused on is a branched aliphatic saturated hydrocarbon having 6 carbon atoms, in particular 2,3-dimethylbutane has a high RON of 103, an RVP at 37.8 ° C. of 51 kPa, The boiling point is 58 ° C., and it has optimal performance for gasoline base materials. In addition, it has been difficult to obtain a large amount of multi-branched isoparaffins such as 2,3-dimethylbutane in the conventionally widely used decomposition reactions, but isomerization reaction is performed on naphtha in the presence of a solid acid catalyst. Made possible. Furthermore, this makes it possible for the environment-friendly gasoline composition of the present invention to have properties unthinkable in conventional gasoline compositions, that is, an olefin content of 5.0% by volume or less and a sulfur content of 10 mass ppm or less, Even if it reduced to 1 mass ppm or less, it became possible to provide satisfactory RON, distillation properties and RVP. According to the present invention, it is possible to provide an environmentally friendly gasoline composition having such a special property and having a high octane number.
なお、本発明から得られるガソリン組成物については、イソパラフィン分（分岐状の脂肪族飽和炭化水素）の含有量が多いことから、ガソリンエンジン用燃料としてはもちろんのこと、これに加えて燃料電池用の燃料としてもエネルギー効率の高い性能を有しており、共用ガソリンとしても使用することができる。 In addition, the gasoline composition obtained from the present invention has a high isoparaffin content (branched aliphatic saturated hydrocarbon), so as a fuel for a gasoline engine, in addition to this, for a fuel cell. As a fuel, it has high energy efficiency and can be used as a common gasoline.
〔環境対応型ガソリン組成物〕
環境対応型ガソリン組成物に含まれる炭化水素化合物のうち、芳香環を有するものをアロマ、アロマ以外で不飽和結合を有するものをオレフィン、非芳香環を有するものをナフテン、それ以外をパラフィンとする。また、パラフィンの内、直鎖状のものをノルマルパラフィン、分岐を有するものをイソパラフィンと分類する。
本発明の高オクタン価環境対応型ガソリン組成物を、以下に詳しく説明する。
[Environmentally friendly gasoline composition]
Of the hydrocarbon compounds contained in the environmentally friendly gasoline composition, those having aromatic rings are aroma, those having unsaturated bonds other than aroma are olefins, those having non-aromatic rings are naphthenes, and others are paraffins. . Moreover, among paraffins, linear paraffins are classified as normal paraffins, and those having branches are classified as isoparaffins.
The high octane number environment-friendly gasoline composition of the present invention will be described in detail below.
〔オクタン価〕
本発明による環境対応型ガソリン組成物のリサーチ法オクタン価（ＲＯＮ）は９６以上であり、好ましくは９８以上、さらには１００以上が好ましい。ＲＯＮが９６未満の場合は、とりわけ登坂加速時のノッキングや加速不良を起こす恐れがある他、燃費悪化の懸念から好ましくない。
[Octane number]
The research octane number (RON) of the environmentally friendly gasoline composition according to the present invention is 96 or more, preferably 98 or more, more preferably 100 or more. When RON is less than 96, there is a risk that knocking or acceleration failure may occur, particularly during uphill acceleration, and there is a concern about deterioration of fuel consumption.
〔硫黄分〕
本発明による環境対応型ガソリン組成物の硫黄分は１０質量ｐｐｍ以下、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。ガソリン中の硫黄分は、排気ガス中で硫黄酸化物となり、エンジン排ガスを浄化する窒素酸化物除去触媒を被毒して触媒活性を低下させる。被毒した窒素酸化物除去触媒は、還元雰囲気下で再生されて活性を回復するが、このとき還元雰囲気を形成するために燃料が使用され、その分燃費が悪化する原因となっている。したがって、ガソリン中の硫黄分が少ないほど燃費は向上する。さらに、ガソリン車両の燃料タンク液面計に銀が一部使用されていることから、硫黄化合物等による燃料系統の腐食を防止するため、銀板腐食が1以下であることが望ましい。
[Sulfur content]
The sulfur content of the environment-friendly gasoline composition according to the present invention is 10 ppm by mass or less, preferably 5 ppm by mass or less, more preferably 1 ppm by mass or less. The sulfur content in gasoline becomes sulfur oxides in the exhaust gas, poisoning the nitrogen oxide removal catalyst that purifies the engine exhaust gas and reducing the catalytic activity. The poisoned nitrogen oxide removing catalyst is regenerated in a reducing atmosphere and recovers its activity. At this time, fuel is used to form a reducing atmosphere, which causes a deterioration in fuel consumption. Therefore, the fuel efficiency improves as the sulfur content in gasoline decreases. Furthermore, since some silver is used in the fuel tank level gauge of gasoline vehicles, it is desirable that the corrosion of the silver plate is 1 or less in order to prevent corrosion of the fuel system due to sulfur compounds and the like.
〔オレフィン含有量〕
本発明による環境対応型ガソリン組成物のオレフィン分は、光安定性及び貯蔵安定性の観点から少ない方が好ましく、５．０容量％以下、より好ましくは４．６容量％以下、さらに好ましくは４．４容量％以下である。
[Olefin content]
The olefin content of the environment-friendly gasoline composition according to the present invention is preferably smaller from the viewpoint of light stability and storage stability, and is 5.0% by volume or less, more preferably 4.6% by volume or less, and still more preferably 4%. .4% by volume or less.
〔パラフィン含有量〕
本発明による環境対応型ガソリン組成物のイソパラフィンの含有量は４０容量％以上８０容量％以下、好ましくは４５容量％以上８０容量％以下、さらに好ましくは５０容量％以上８０容量％以下であり、ノルマルパラフィンの含有量は９.０容量％以下が好ましく、より好ましくは７.０容量％以下、さらに好ましくは５．５容量％以下である。ここで、イソパラフィンの含有量が４０容量％以下の場合やノルマルパラフィンの含有量が９.０容量％を超える場合、従来通りの蒸留性状、蒸気圧及びオクタン価を維持するために、環境に悪影響を与える可能性があるオレフィン分を多く含む基材多く使用せざるを得ない結果となってしまうので好ましくない。
[Paraffin content]
The content of isoparaffin in the environment-friendly gasoline composition according to the present invention is 40% by volume to 80% by volume, preferably 45% by volume to 80% by volume, more preferably 50% by volume to 80% by volume. The content of paraffin is preferably 9.0% by volume or less, more preferably 7.0% by volume or less, and still more preferably 5.5% by volume or less. Here, when the content of isoparaffin is 40% by volume or less, or when the content of normal paraffin exceeds 9.0% by volume, there is an adverse effect on the environment in order to maintain the conventional distillation properties, vapor pressure and octane number. This is not preferable because a large amount of a base material containing a large amount of olefin that may be given is used.
〔炭素数６のイソパラフィン含有量〕
本発明による環境対応型ガソリン組成物は、ｉ−Ｃ６の含有量が１０容量％以上であることが好ましく、より好ましくは１１容量％以上、さらに好ましくは１２容量％以上であり、２,３−ジメチルブタンの含有量が１.５容量％以上であることが好ましく、より好ましくは２．０容量％以上、さらに好ましくは２.３容量％以上であり、ｉ−Ｃ６／ｎ−Ｃ６比（容量）は５.０以上が好ましく、さらに好ましくは７.０以上であり、特に好ましくは１０.０以上である。これらは、ＲＯＮ維持の観点から多い方が好ましい。また、ｉ−Ｃ６／Ｃ６＝比（容量）は、光安定性及び貯蔵安定性の観点から３．０以上が好ましく、さらに好ましくは５．０以上であり、特に好ましくは１０.０以上である。
ここで、ｉ−Ｃ６の含有量が１０容量％以上、かつ、２,３−ジメチルブタンの含有量が１.５容量％以上、ｉ−Ｃ６／ｎ−Ｃ６比が５．０以上、ｉ−Ｃ６／Ｃ６＝比が３．０以上のガソリン組成物でない場合、前記と同様、従来通りの蒸留性状、蒸気圧及びオクタン価を維持するために、環境に悪影響を与える可能性があるオレフィン分を多く含む基材多く使用せざるを得ない結果となってしまうので好ましくない。
[Content of isoparaffin having 6 carbon atoms]
The environment-friendly gasoline composition according to the present invention preferably has an i-C6 content of 10% by volume or more, more preferably 11% by volume or more, and still more preferably 12% by volume or more. The content of dimethylbutane is preferably 1.5% by volume or more, more preferably 2.0% by volume or more, still more preferably 2.3% by volume or more, and the i-C6 / n-C6 ratio (capacity ) Is preferably 5.0 or more, more preferably 7.0 or more, and particularly preferably 10.0 or more. A larger number of these is preferable from the viewpoint of maintaining RON. Further, i-C6 / C6 = ratio (capacity) is preferably 3.0 or more, more preferably 5.0 or more, and particularly preferably 10.0 or more, from the viewpoint of light stability and storage stability. .
Here, the content of i-C6 is 10% by volume or more, the content of 2,3-dimethylbutane is 1.5% by volume or more, the i-C6 / n-C6 ratio is 5.0 or more, i- C6 / C6 = If the ratio is not a gasoline composition of 3.0 or more, as in the case described above, in order to maintain the conventional distillation properties, vapor pressure, and octane number, the olefin content that may adversely affect the environment is increased. Since it will be a result which must use many base materials to contain, it is unpreferable.
〔炭素数８のイソパラフィン含有量〕
本発明による環境対応型ガソリン組成物は、炭素数８のイソパラフィン（イソオクタン又はｉ−Ｃ８）は２０容量％以下が好ましく、さらには１９容量％以下であり、特に好ましくは１８容量％以下である。ｉ−Ｃ８のうち、トリメチルペンタン類のように分岐数の多いイソパラフィンはＲＯＮが高いものの、他の分岐数の少ないイソオクタン類はＲＯＮが比較的低く、しかも、ｉ−Ｃ８は全体的に沸点が１００℃を超えるものがほとんどであるため、あまり多く使用しない方が好ましい。
[Content of isoparaffin having 8 carbon atoms]
In the environment-friendly gasoline composition according to the present invention, the carbon number 8 isoparaffin (isooctane or i-C8) is preferably 20% by volume or less, more preferably 19% by volume or less, and particularly preferably 18% by volume or less. Among i-C8, isoparaffins with a large number of branches such as trimethylpentanes have a high RON, but other isooctanes with a small number of branches have a relatively low RON, and i-C8 has an overall boiling point of 100. Since most of them exceed ℃, it is preferable not to use much.
〔アロマ含有量〕
本発明による環境対応型ガソリン組成物において、アロマ分は２０容量％以上４０容量％以下であり、好ましくは２３容量％以上３５容量％以下、より好ましくは２５容量％以上３０容量％以下である。環境保全（排気ガス性状）や低温運転性維持の観点からアロマ分は少ない方が好ましいが、ＲＯＮを維持するため及び燃費悪化防止の点から２０容量％以上が好ましい。また、アロマ分が４０容量％を超えると燃焼室デポジットが増加し、点火プラグのくすぶりが発生したり、排ガス中のベンゼン濃度が高くなる恐れがある。また、ベンゼン含有量は１．０容量％以下、さらには０．１容量％以下が好ましい。
[Aroma content]
In the environment-friendly gasoline composition according to the present invention, the aroma content is 20% to 40% by volume, preferably 23% to 35% by volume, more preferably 25% to 30% by volume. From the viewpoint of environmental preservation (exhaust gas properties) and maintaining low temperature driving performance, it is preferable that the amount of aroma is small. However, 20% by volume or more is preferable for maintaining RON and preventing deterioration of fuel consumption. Further, if the aroma content exceeds 40% by volume, the combustion chamber deposit increases, which may cause smoldering of the spark plug or increase the concentration of benzene in the exhaust gas. The benzene content is preferably 1.0% by volume or less, more preferably 0.1% by volume or less.
〔密度〕
本発明による環境対応型ガソリン組成物において、本発明のガソリン組成物の密度は、０．７０ｇ／ｃｍ３以上０．７８ｇ／ｃｍ３以下が好ましいが、より好ましくは０．７１ｇ／ｃｍ３以上０．７６ｇ／ｃｍ３以下、さらに好ましくは０．７２ｇ／ｃｍ３以上０．７５ｇ／ｃｍ３以下である。密度が０．７０ｇ／ｃｍ３未満では、出力が低下するとともにガソリン消費量が多大となる。一方、０．７８ｇ／ｃｍ３を越えると熱効率が悪くなるため、やはり出力が低下する。
〔density〕
In environmentally friendly gasoline composition according to the present invention, the density of the gasoline composition of the present invention, 0.70 g / cm 3 or more 0.78 g / cm 3 but less preferred, more preferably 0.71 g / cm 3 or more 0 .76g / cm 3, more preferably not more than 0.72 g / cm 3 or more 0.75 g / cm 3. When the density is less than 0.70 g / cm 3 , the output is reduced and the gasoline consumption is increased. On the other hand, if it exceeds 0.78 g / cm 3 , the thermal efficiency is deteriorated, so that the output is also lowered.
〔蒸留性状〕
本発明による環境対応型ガソリン組成物において、５０％留出温度は７５℃以上９８℃以下であることが好ましく、より好ましくは７５℃以上９６℃以下、さらに好ましくは７５℃以上９４℃以下である。５０％留出温度が７５℃に満たない場合は、燃費の観点から好ましくなく、９８℃を超える場合は、常温運転性の観点から好ましくない。１０％留出温度は２５℃以上６０℃以下であることが好ましく、より好ましくは２７℃以上５０℃以下、さらに好ましくは３０℃以上４０℃以下である。９０％留出温度は１４０℃以上２００℃以下であることが好ましく、より好ましくは１５０℃以上１９５℃以下、さらに好ましくは１５５℃以上１９０℃以下である。
[Distillation properties]
In the environmentally friendly gasoline composition according to the present invention, the 50% distillation temperature is preferably 75 ° C or higher and 98 ° C or lower, more preferably 75 ° C or higher and 96 ° C or lower, and further preferably 75 ° C or higher and 94 ° C or lower. . When the 50% distillation temperature is less than 75 ° C., it is not preferable from the viewpoint of fuel consumption, and when it exceeds 98 ° C., it is not preferable from the viewpoint of normal temperature drivability. The 10% distillation temperature is preferably 25 ° C or higher and 60 ° C or lower, more preferably 27 ° C or higher and 50 ° C or lower, and further preferably 30 ° C or higher and 40 ° C or lower. The 90% distillation temperature is preferably 140 ° C. or higher and 200 ° C. or lower, more preferably 150 ° C. or higher and 195 ° C. or lower, and still more preferably 155 ° C. or higher and 190 ° C. or lower.
〔ＲＶＰ〕
本発明による環境対応型ガソリン組成物において、ＲＶＰは６５ｋＰａ以下が好ましく、より好ましくは６２ｋＰａ以下、さらに好ましくは６０ｋＰａ以下である。ＲＶＰが高いと蒸発損失の増加、ベーパーロックの懸念、危険性の増加などの問題が起こりやすい。
[RVP]
In the environment-friendly gasoline composition according to the present invention, RVP is preferably 65 kPa or less, more preferably 62 kPa or less, and further preferably 60 kPa or less. When the RVP is high, problems such as an increase in evaporation loss, a concern about vapor lock, and an increase in danger are likely to occur.
〔環境対応型ガソリン組成物の製造方法〕
本発明の環境対応型ガソリン組成物の製造方法を、以下に詳しく説明する。
[Method for producing environmentally friendly gasoline composition]
The method for producing the environment-friendly gasoline composition of the present invention will be described in detail below.
〔ナフサ留分〕
本発明において、異性化反応の原料となるナフサ留分は、少なくとも６０〜７０℃、さらには３５〜８０℃の沸点成分を含む留分であることが好ましい。ナフサ留分の蒸留性状は、１０容量％留出温度が２５〜６０℃、９０容量％留出温度が５５〜８０℃であり、好ましくは９５容量％留出温度が６０〜８５℃である。場合によっては、この留分の一部を蒸留分離して使用することもできる。また、この軽質留分のアロマ含有量は、０〜１.０容量％が好ましい。必要に応じて、ベンゼンなどのアロマ分をスルフォラン抽出法に代表される溶剤抽出法などにより除去する。
[Naphtha fraction]
In the present invention, the naphtha fraction used as the raw material for the isomerization reaction is preferably a fraction containing a boiling point component of at least 60 to 70 ° C., more preferably 35 to 80 ° C. The distillation properties of the naphtha fraction have a 10% by volume distillation temperature of 25 to 60 ° C, a 90% by volume distillation temperature of 55 to 80 ° C, and preferably a 95% by volume distillation temperature of 60 to 85 ° C. In some cases, a part of this fraction can be distilled and used. Further, the aroma content of this light fraction is preferably 0 to 1.0% by volume. If necessary, aroma such as benzene is removed by a solvent extraction method typified by sulfolane extraction method.
ナフサ留分は特に限定されるものではないが、具体的には原油の常圧蒸留装置から留出する直留ナフサ、アロマ分を抽出した際に生成する抽出ラフィネートのナフサ留分、熱分解装置や接触分解装置等の各種分解装置から生成する分解ナフサ、さらには天然ガス、バイオガスなどに由来する一酸化炭素と水素の合成ガスからのＦＴ（Fischer Tropsch）合成反応およびその分解反応から得られるＧＴＬナフサなどが挙げられ、以上の中では直留ナフサまたは抽出ラフィネートのナフサ留分が好ましい。なお、これらナフサには硫黄分等の不純物が多く含まれる場合があるので、必要に応じて水素化処理や脱硫処理を行なう。ここでは直留ナフサを脱硫処理して得られたものを脱硫直留ナフサ（留分）と称する。 Although the naphtha fraction is not particularly limited, specifically, a straight-run naphtha distilled from an atmospheric distillation unit of crude oil, a naphtha fraction of extracted raffinate produced when an aroma is extracted, and a pyrolysis unit Obtained from FT (Fischer Tropsch) synthesis reaction and decomposition reaction from synthesis gas of carbon monoxide and hydrogen derived from natural gas, biogas, etc. GTL naphtha and the like can be mentioned. Among them, straight-run naphtha or naphtha fraction of extracted raffinate is preferable. Since these naphthas may contain a large amount of impurities such as sulfur, hydrogenation or desulfurization is performed as necessary. Here, what was obtained by desulfurizing straight run naphtha is referred to as desulfurization straight run naphtha (fraction).
〔脱硫直留ナフサ留分〕
本発明の環境対応型ガソリン組成物の原料である脱硫直留ナフサを製造するプロセスは、原料油、蒸留装置、運転条件を特に限定するものでなく、公知の任意の製造工程を採用できる。
例えば、原油の常圧蒸留工程から得られた直留ナフサ留分を水素存在下、ニッケルやモリブデンなどを含む触媒を用いて脱硫処理することで得られる。反応条件を反応温度２５０〜４００℃、反応圧力１.０〜８.０ＭＰａ、ＬＨＳＶ０.５〜５ｈ−１とすることにより、チオフェン類やスルフィド類が水素化脱硫される。前記の反応条件の中でも特に好ましい反応条件としては、例えば、反応温度２５０〜３５０℃、反応圧力２.０〜４.０ＭＰａ、ＬＨＳＶ１.０〜４.０ｈ−１である。
[Desulfurized straight naphtha fraction]
The process for producing the desulfurized straight-run naphtha, which is the raw material of the environment-friendly gasoline composition of the present invention, does not particularly limit the feedstock oil, the distillation apparatus, and the operating conditions, and any known production process can be employed.
For example, it can be obtained by desulfurizing a straight-run naphtha fraction obtained from the atmospheric distillation process of crude oil in the presence of hydrogen, using a catalyst containing nickel, molybdenum or the like. By setting the reaction conditions to a reaction temperature of 250 to 400 ° C., a reaction pressure of 1.0 to 8.0 MPa, and LHSV of 0.5 to 5 h −1 , thiophenes and sulfides are hydrodesulfurized. Among the above reaction conditions, particularly preferable reaction conditions are, for example, a reaction temperature of 250 to 350 ° C., a reaction pressure of 2.0 to 4.0 MPa, and LHSV of 1.0 to 4.0 h −1 .
〔異性化工程〕
上記ナフサ留分、例えば脱硫直留ナフサ留分を水素雰囲気下で固体酸触媒を用いて異性化処理し、異性化ガソリン基材を製造する。この異性化処理によりノルマルパラフィンがイソパラフィンに変換される。異性化方法は特に限定されないが、触媒として周期律表第ＶＩＩＩ族の元素を含有する固体酸触媒が挙げられる。固体酸としては、ゼオライト、ヘテロポリ酸、アルミナに塩素を担持した塩素化アルミナ、ジルコニアと硫酸分を含む硫酸ジルコニア類やジルコニアとタングステンの酸化物成分を含むタングステン酸ジルコニア類などに代表される固体超強酸等を使用することができる。上記固体酸触媒は１種のみで用いても良いし、２種以上を組み合わせて用いても良い。
[Isomerization process]
The naphtha fraction, for example, a desulfurized straight naphtha fraction, is isomerized using a solid acid catalyst in a hydrogen atmosphere to produce an isomerized gasoline base material. By this isomerization treatment, normal paraffin is converted to isoparaffin. Although the isomerization method is not particularly limited, examples of the catalyst include a solid acid catalyst containing an element of Group VIII of the periodic table. Solid acids such as zeolite, heteropoly acid, chlorinated alumina with chlorine supported on alumina, zirconia sulfate containing zirconia and sulfuric acid, and zirconia tungstate containing oxide components of zirconia and tungsten, etc. A strong acid or the like can be used. The said solid acid catalyst may be used only by 1 type, and may be used in combination of 2 or more type.
本発明において異性化工程で使用する固体酸触媒は、周期律表第ＶＩＩＩ族の元素からなる群から選ばれる１種以上の元素を含有する固体酸触媒が好ましい。周期律表第ＶＩＩＩ族の元素としては、白金（Ｐｔ）、パラジウム（Ｐｄ）、ルテニウム（Ｒｕ）、ロジウム（Ｒｈ）、イリジウム（Ｉｒ）、オスミウム（Ｏｓ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）などが挙げられる。このうち、白金、パラジウム、及びルテニウムが好ましく、特に白金を好ましく用いることができる。 In the present invention, the solid acid catalyst used in the isomerization step is preferably a solid acid catalyst containing one or more elements selected from the group consisting of Group VIII elements of the Periodic Table. As elements of Group VIII of the periodic table, platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), iridium (Ir), osmium (Os), iron (Fe), cobalt (Co) And nickel (Ni). Among these, platinum, palladium, and ruthenium are preferable, and platinum can be particularly preferably used.
周期律表第ＶＩＩＩ族の元素の割合（当該元素含有量の平均値）は、当該元素として、０．０１〜１０質量％、好ましくは０．０５〜５質量％、特には０．１〜３質量％である。周期律表第ＶＩＩＩ族の元素の含有量が少なすぎると、触媒性能向上効果が低く好ましくない。この元素の含有量が多すぎると、触媒の比表面積や細孔容積の低下を引き起こすため好ましくない。 The ratio of elements in Group VIII of the periodic table (average value of the element content) is 0.01 to 10% by mass, preferably 0.05 to 5% by mass, particularly 0.1 to 3% as the element. % By mass. If the content of the Group VIII element in the periodic table is too small, the catalyst performance improving effect is low, which is not preferable. If the content of this element is too large, the specific surface area and pore volume of the catalyst are reduced, which is not preferable.
異性化工程で使用する触媒に用いるゼオライト、ヘテロポリ酸、塩素化アルミナ、固体超強酸については、特に限定されないが、酸性度が高いものが好ましい。具体的には、ゼオライトとしては、Ａ型、Ｌ型、Ｘ型、Ｙ型、ＺＳＭ−５型（ＭＦＩ型）、ベータ型、ペンタシル型ゼオライト、モルデナイト、フェリエライト、などが用いられるが、特にベータ型が好ましい。また、各種ゼオライトにおいて、陽イオンは、プロトンの他、ナトリウム（Ｎａ）、カリウム（Ｋ）などのアルカリ金属、マグネシウム（Ｍｇ）、カルシウム（Ｃａ）などのアルカリ土類金属が好ましいが、遷移金属でも良い。遷移金属としては、具体的には、銀（Ａｇ）、白金（Ｐｔ）、ルテニウム（Ｒｕ）、ロジウム（Ｒｈ）、ニッケル（Ｎｉ）、銅（Ｃｕ）等が挙げられる。これら触媒の形状は、粉末状、ペレット状、タブレット状、又はビーズ状であることが好ましい。 Zeolite, heteropolyacid, chlorinated alumina, and solid superacid used for the catalyst used in the isomerization step are not particularly limited, but those having high acidity are preferable. Specifically, as zeolite, A type, L type, X type, Y type, ZSM-5 type (MFI type), beta type, pentasil type zeolite, mordenite, ferrierite, etc. are used. A mold is preferred. In various zeolites, the cation is preferably an alkali metal such as sodium (Na) or potassium (K), or an alkaline earth metal such as magnesium (Mg) or calcium (Ca) in addition to protons. good. Specific examples of the transition metal include silver (Ag), platinum (Pt), ruthenium (Ru), rhodium (Rh), nickel (Ni), copper (Cu), and the like. These catalysts are preferably in the form of powder, pellets, tablets, or beads.
ヘテロポリ酸とは、２種類以上の無機系オキシ酸が互いに縮合している酸を意味する。本発明に用いられるヘテロポリ酸はＫｅｇｇｉｎ型、Ｄａｗｓｏｎ型、Ａｎｄｅｒｓｏｎ型など特定の構造に限定されるものではないが、安定性、合成の容易さの点からＫｅｇｇｉｎ型構造のものが好ましい。具体的には一般式Ｈ３ＡＢ１２Ｏ４０で表される化合物である。これらの化合物の中心元素（Ａ原子）はリン（Ｐ）、ケイ素（Ｓｉ）、ホウ素（Ｂ）、ゲルマニウム（Ｇｅ）、ヒ素（Ａｓ）、セレン（Ｓｅ）、チタン（Ｔｉ）およびジルコニウム（Ｚｒ）より成る群から選択できる。これらの酸の配位元素（B原子）としてはモリブデン（Ｍｏ）、タングステン（Ｗ）、バナジウム（Ｖ）、マンガン（Ｍｎ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、銅（Ｃｕ）、亜鉛（Ｚｎ）、ニオブ（Ｎｂ）および鉄（Ｆｅ）の様なイオンが使用できる。中でも、Ａ原子としてはＰが好ましく、Ｂ原子としてはＷまたはＭｏが好ましい。 The heteropolyacid means an acid in which two or more kinds of inorganic oxyacids are condensed with each other. The heteropolyacid used in the present invention is not limited to a specific structure such as Keggin type, Dawson type, and Anderson type, but a Keggin type structure is preferable from the viewpoint of stability and ease of synthesis. Specifically, it is a compound represented by the general formula H 3 AB 12 O 40 . The central elements (A atoms) of these compounds are phosphorus (P), silicon (Si), boron (B), germanium (Ge), arsenic (As), selenium (Se), titanium (Ti) and zirconium (Zr). It can be selected from the group consisting of: These acid coordination elements (B atoms) include molybdenum (Mo), tungsten (W), vanadium (V), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), zinc ( Ions such as Zn), niobium (Nb) and iron (Fe) can be used. Among them, P is preferable as the A atom, and W or Mo is preferable as the B atom.
塩素化アルミナは、アルミナ担体に無機塩素化合物あるいは有機塩素化合物を担持することにより得ることができる。無機塩素化合物としては、塩化水素、塩化アンモニウム、過塩素酸、塩素酸ナトリウム、亜塩素酸ナトリウム、次亜塩素酸ナトリウム、等が挙げられ、有機塩素化合物としては、四塩化炭素、クロロホルム、ジクロロメタン、ジクロロエタン等が挙げられる。触媒中の塩素含有量としては、塩素元素として０．５〜２０.０質量％、より好ましくは１.０〜１５.０質量％、更に好ましくは３.０〜１０.０質量％である。塩素量が少なすぎると異性化反応に必要な酸強度が不十分なため効果的な異性化活性が得られず、一方、塩素量が多すぎると反応系内および生成油中に塩素化合物が多量に存在してしまい、配管などの腐食を起こしたり生成油の安定性を悪化させたりするため好ましくない。 Chlorinated alumina can be obtained by supporting an inorganic chlorine compound or an organic chlorine compound on an alumina carrier. Examples of inorganic chlorine compounds include hydrogen chloride, ammonium chloride, perchloric acid, sodium chlorate, sodium chlorite, sodium hypochlorite, etc., and examples of organic chlorine compounds include carbon tetrachloride, chloroform, dichloromethane, Examples include dichloroethane. As chlorine content in a catalyst, it is 0.5-20.0 mass% as a chlorine element, More preferably, it is 1.0-15.0 mass%, More preferably, it is 3.0-10.0 mass%. If the amount of chlorine is too small, the acid strength required for the isomerization reaction is insufficient, so that effective isomerization activity cannot be obtained. On the other hand, if the amount of chlorine is too large, a large amount of chlorine compound is present in the reaction system and in the product oil. This is undesirable because it may cause corrosion of piping and the like, or deteriorate the stability of the product oil.
硫酸ジルコニア類は、チタン、ジルコニウムおよびハフニウム（Ｈｆ）から選ばれるＩＶ族金属成分の１種と硫酸分を含むものである。ＩＶ族金属成分としてはジルコニウムが好ましい。ジルコニウム元素として２０〜７２質量％、特には３０〜６０質量％含むことが好ましい。また、触媒中に占める硫酸分の割合は、硫黄元素として０.７〜７質量％、好ましくは１〜６質量％、特には２〜５質量％である。 Zirconia sulfates contain one type IV metal component selected from titanium, zirconium and hafnium (Hf) and a sulfuric acid content. Zirconium is preferred as the group IV metal component. It is preferable to contain 20 to 72 mass%, particularly 30 to 60 mass% as the zirconium element. Moreover, the ratio of the sulfuric acid content which occupies in a catalyst is 0.7-7 mass% as a sulfur element, Preferably it is 1-6 mass%, Especially 2-5 mass%.
タングステン酸ジルコニア類は、チタン、ジルコニウムおよびハフニウムから選ばれるＩＶ族金属成分の１種とタングステンおよびモリブデンから選ばれるＶＩ族金属成分の１種とを金属成分として含むものである。ＩＶ族金属成分としてはジルコニウムが好ましく、ＶＩ族金属成分としてはタングステンが好ましい。触媒中にＩＶ族金属成分を金属元素として１０〜７２質量％、特には２０〜６０質量％含むことが好ましい。また、触媒中にＶＩ族金属成分を金属元素として２〜３０質量％、特に５〜２５質量％、さらには１０〜２０質量％含むことが好ましい。
硫酸ジルコニア類及びタングステン酸ジルコニア類等のジルコニア部分は、実質的に正方晶ジルコニアからなることが好ましい。
Tungstic acid zirconia contains one type IV metal component selected from titanium, zirconium and hafnium and one type VI metal component selected from tungsten and molybdenum as metal components. Zirconium is preferred as the group IV metal component, and tungsten is preferred as the group VI metal component. The catalyst preferably contains a group IV metal component as a metal element in an amount of 10 to 72% by mass, particularly 20 to 60% by mass. Moreover, it is preferable to contain 2-30 mass%, especially 5-25 mass%, further 10-20 mass% as a group VI metal component as a metal element in a catalyst.
The zirconia portion such as zirconia sulfate and zirconia tungstate is preferably substantially composed of tetragonal zirconia.
ゼオライト触媒、ヘテロポリ酸触媒及び固体超強酸触媒を使用する場合、触媒中のアルミナ含有量はアルミニウム元素として２〜４０％が好ましく、より好ましくは５〜３０質量％、特に好ましくは８〜２５質量％である。 When a zeolite catalyst, a heteropolyacid catalyst and a solid superacid catalyst are used, the alumina content in the catalyst is preferably 2 to 40%, more preferably 5 to 30% by mass, particularly preferably 8 to 25% by mass as an aluminum element. It is.
固体酸触媒の比表面積は５０〜１０００ｍ２／ｇが好ましく、より好ましくは１００〜８００ｍ２／ｇ、特には１２０〜５００ｍ２／ｇである。比表面積は通常知られているＢＥＴ法によって測定できる。本発明の固体酸触媒の細孔構造は、細孔直径０.００２〜０.０５μｍの範囲については窒素吸着法、細孔直径０.０５〜１０μｍの範囲は水銀圧入法により測定できる。細孔直径０.００２〜１０μｍの細孔容積は０.１ｃｍ３／ｇ以上が好ましく、より好ましくは０.３ｃｍ３／ｇ以上、特には０.３５〜１.５ｃｍ３／ｇである。 The specific surface area of the solid acid catalyst is preferably 50 to 1000 m 2 / g, more preferably 100 to 800 m 2 / g, and particularly preferably 120 to 500 m 2 / g. The specific surface area can be measured by a commonly known BET method. The pore structure of the solid acid catalyst of the present invention can be measured by a nitrogen adsorption method for a pore diameter range of 0.002 to 0.05 μm and by a mercury intrusion method for a pore diameter range of 0.05 to 10 μm. Pore volume of pores having a pore diameter 0.002~10μm is preferably 0.1 cm 3 / g or more, more preferably 0.3 cm 3 / g or more, particularly a 0.35~1.5cm 3 / g.
固体酸触媒の形状は特に限定されるものではなく、粉末状、ペレット状、タブレット状、ビーズ状などどのような形状でもかまわないが、粉体でなく、成形された形状が好ましい。例えば、押出し成形で容易に得ることができる断面が円の円柱状や、クローバ型などの異形の柱状（平均径約１．５ｍｍ、長さ約４．０ｍｍ）のペレットあるいはエクストゥルード（extrude）と呼ばれる形態の固体酸触媒を好ましく用いることができる。 The shape of the solid acid catalyst is not particularly limited, and may be any shape such as powder, pellet, tablet, and bead, but is preferably not a powder but a molded shape. For example, a pellet or an extrude having a circular cross section that can be easily obtained by extrusion molding, or an irregular columnar shape such as a clover type (average diameter: about 1.5 mm, length: about 4.0 mm) Is preferably used.
異性化工程において、反応条件を反応温度１００〜４００℃、反応圧力０.５〜５.０ＭＰａ、Ｈ２／油比０.１〜１０.０ｍｏｌ／ｍｏｌ、ＬＨＳＶ０.１〜１０.０ｈ−１とすることにより、アロマ分やナフテン分の一部または全量が開環、水素化され、同時にノルマルパラフィンが異性化されてイソパラフィンが増加する。イソパラフィンも分岐する位置が変わったり、分岐数の多いものに変換される。前記の反応条件の中でも特に好ましい反応条件としては、例えば、反応温度１２０〜３００℃、反応圧力１.８〜３.２ＭＰａ、Ｈ２／油比０.３〜５.０ｍｏｌ／ｍｏｌ、ＬＨＳＶ１.０〜３.０ｈ−１である。異性化生成油はそのまま異性化ガソリン基材として他のガソリン基材と混合して本発明の環境対応型ガソリン組成物を製造することができる。さらに、異性化生成油の重質分、未反応分、低オクタン価化合物等（総称して単に低オクタン価化合物という。）を、蒸留、分離膜、吸着剤等により分離した残りの留分（総称して単に高オクタン価化合物という。）は、より高いオクタン価を有しているため、異性化ガソリン基材としてより使い勝手よく用いることができる。分離した低オクタン価化合物は、異性化工程にリサイクルして再度反応させ、より高オクタン価の異性化生成油（高オクタン価化合物）に変換してもよく、また、石油化学品原料用として用いることもできる。 In the isomerization step, the reaction conditions are as follows: reaction temperature 100 to 400 ° C., reaction pressure 0.5 to 5.0 MPa, H 2 / oil ratio 0.1 to 10.0 mol / mol, LHSV 0.1 to 10.0 h −1 . As a result, a part or all of the aroma and naphthene are ring-opened and hydrogenated, and at the same time, normal paraffins are isomerized to increase isoparaffins. Isoparaffins are also converted into ones with different branching positions or with many branches. Among the above reaction conditions, particularly preferable reaction conditions include, for example, a reaction temperature of 120 to 300 ° C., a reaction pressure of 1.8 to 3.2 MPa, an H 2 / oil ratio of 0.3 to 5.0 mol / mol, and an LHSV of 1.0. ~ 3.0h- 1 . The isomerized product oil can be directly mixed with another gasoline base as an isomerized gasoline base to produce the environment-friendly gasoline composition of the present invention. Furthermore, the remaining fraction (generally referred to as the heavy fraction, unreacted fraction, low octane compound, etc. (collectively referred to simply as the low octane compound) of the isomerized product oil separated by distillation, separation membrane, adsorbent, etc. Simply having a high octane number) can be used more conveniently as an isomerized gasoline base material. The separated low octane compound may be recycled to the isomerization step and reacted again to convert it to a higher octane isomerization product oil (high octane compound), or it can be used as a petrochemical raw material. .
〔ブレンド工程〕
本発明の環境対応型ガソリン組成物は、上記のように処理して得られた本発明の異性化ガソリン基材と他のガソリン基材とを適宜の割合でブレンドすることによって製造することができる。
他のガソリン基材とは、本発明の環境対応型ガソリン組成物を調製するに際して異性化ガソリン基材とともに用いる各種基材を指し、従来のガソリン製造に用いられているガソリン基材が挙げられる。具体的には、直留ナフサ留分を水素化脱硫後、その軽質分を蒸留分離することにより得た脱硫直留軽質ナフサ留分（ＤＳＬＧ）、ブチレン留分とイソブタン留分をアルキル化して得たアルキレートガソリン（ＡＬＫＧ）、接触分解ナフサ留分あるいはそれを脱硫処理した脱硫接触分解ナフサ留分、接触分解ナフサ留分を蒸留して得た軽質留分の接触分解軽質ナフサ留分（ＦＬ）、脱硫重質ナフサを固体改質触媒により改質して得た改質ガソリン、及び改質ガソリンを蒸留して得られたベンゼン分を殆ど含有しない炭素数７を主成分とする留分（ＡＣ７）、同じく炭素数８を主成分とする留分（ＡＣ８）、あるいは炭素数９以上を主成分とする留分（ＡＣ９）、各種の石油精製工程や石油化学の工程から副生されるガソリン留分、さらに、単離されたブタン、ペンタンや、いわゆるＢＴＸなどのアロマ化合物などが挙げられる。さらに、エタノールなどのアルコールや、アルコールからの誘導体であるエーテル類やエステル類の、いわゆる「含酸素化合物」を使用しても良い。
[Blend process]
The environment-friendly gasoline composition of the present invention can be produced by blending the isomerized gasoline base material of the present invention obtained by the treatment as described above and another gasoline base material at an appropriate ratio. .
Other gasoline base materials refer to various base materials used together with isomerized gasoline base materials in preparing the environment-friendly gasoline composition of the present invention, and include gasoline base materials used in conventional gasoline production. Specifically, after hydrodesulfurization of straight-run naphtha fraction, desulfurized straight-run light naphtha fraction (DSLG) obtained by distillation separation of the light fraction, alkylation of butylene fraction and isobutane fraction is obtained. Alkylate gasoline (ALKG), catalytic cracked naphtha fraction or desulfurized catalytic cracked naphtha fraction, and catalytic cracked light naphtha fraction (FL) of light fraction obtained by distillation of catalytic cracked naphtha fraction , A reformed gasoline obtained by reforming desulfurized heavy naphtha with a solid reforming catalyst, and a fraction containing only 7 carbon atoms (AC7) containing almost no benzene obtained by distillation of the reformed gasoline ), A fraction mainly composed of 8 carbon atoms (AC8), a fraction mainly composed of 9 or more carbon atoms (AC9), and a gasoline fraction by-produced from various petroleum refining and petrochemical processes. Min, further isolation The butane, pentane and, aroma compounds, such as so-called BTX and the like. Furthermore, so-called “oxygen compounds” of alcohols such as ethanol, ethers and esters which are derivatives from alcohols may be used.
この含酸素化合物としては、例えば、炭素数２〜５のアルコール類、炭素数４〜８のエーテル類が好適であり、具体的には、エタノール、プロピルアルコール類、ブチルアルコール類などのアルコールや、アルコール類からの誘導体であるエーテル類やエステル類、例えば、エチルイソプロピルエーテル、エチルターシャリーブチルエーテル（ＥＴＢＥ）、エチルセカンダリーブチルエーテル（ＥＳＢＥ）、ジイソプロピルエーテル、ターシャリーアミルエチルエーテル（ＴＡＥＥ）や、酢酸エチル、プロピオン酸エチル等が挙げられる。 As the oxygen-containing compound, for example, alcohols having 2 to 5 carbon atoms and ethers having 4 to 8 carbon atoms are suitable. Specifically, alcohols such as ethanol, propyl alcohols, butyl alcohols, Ethers and esters which are derivatives from alcohols such as ethyl isopropyl ether, ethyl tertiary butyl ether (ETBE), ethyl secondary butyl ether (ESBE), diisopropyl ether, tertiary amyl ethyl ether (TAEE), ethyl acetate, And ethyl propionate.
これらの含酸素化合物は、全ガソリン組成物基準で、０〜１５容量％、好ましくは３〜１２容量％、より好ましくは、５〜１０容量％使用される。これは、少なすぎると添加効果が少なく、また、多すぎると水分等の不純物を同伴してしまい、配管やシール材の腐食等のトラブルを引き起こすためである。例えば、エタノールは水を際限なく溶解することから、燃料中に多く含まれる場合、自動車燃料タンク内で水分が濃縮され、蓄積して悪影響を与える可能性がある。さらに、燃料油中に含酸素化合物が多い場合、例えば１５容量％を超える量が含まれると、既存エンジンの空気／燃料比最適値から外れて酸素過剰気味となることから、排ガス中の窒素酸化物（ＮＯｘ）量が増加してしまう欠点がある。また、含酸素化合物は他のガソリン基材と比較すると発熱量が総じて低く、燃費を下げてしまうことがあるため、あまり多く使用することは好ましくない。 These oxygenated compounds are used in an amount of 0 to 15% by volume, preferably 3 to 12% by volume, more preferably 5 to 10% by volume, based on the total gasoline composition. This is because if the amount is too small, the effect of addition is small, and if the amount is too large, impurities such as moisture are accompanied, causing troubles such as corrosion of pipes and sealing materials. For example, since ethanol dissolves water infinitely, if it is contained in a large amount in fuel, water may be concentrated and accumulated in an automobile fuel tank, which may have an adverse effect. Furthermore, if the fuel oil contains a large amount of oxygen-containing compounds, for example, if the amount exceeds 15% by volume, it will deviate from the optimum value of the air / fuel ratio of the existing engine, resulting in an excess of oxygen. There is a drawback that the amount of substances (NOx) increases. Further, since oxygen-containing compounds generally have a lower calorific value than other gasoline base materials and may reduce fuel consumption, it is not preferable to use too much.
〔添加剤〕
本発明の環境対応型ガソリン組成物の好ましい態様として、必要に応じて公知の燃料添加剤を配合することができる。これらの配合量は適宜選べるが、通常は添加剤の合計量として０.１質量％以下とすることが好ましい。本発明の環境対応型ガソリン組成物で使用可能な添加剤を例示すれば、アミン系、フェノール系、アミノフェノール系などの酸化防止剤、シッフ型化合物、チオアミド型化合物などの金属不活性化剤、有機リン系化合物などの表面着火防止剤、コハク酸イミド、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、多価アルコールやそのエーテルなどの氷結防止剤、有機酸のアルカリ金属塩やアルカリ土類金属塩、高級アルコールの硫酸エステルなどの助燃剤、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、アルケニルコハク酸エステルなどのさび止め剤、キニザリン、クマリンなどの識別剤、アゾ染料などの着色剤を挙げることができる。
〔Additive〕
As a preferred embodiment of the environment-friendly gasoline composition of the present invention, a known fuel additive can be blended as necessary. Although these compounding quantities can be selected suitably, it is usually preferable to set it as 0.1 mass% or less as a total amount of an additive. Examples of additives that can be used in the environment-friendly gasoline composition of the present invention include amine-based, phenol-based, aminophenol-based antioxidants, Schiff-type compounds, metal deactivators such as thioamide-type compounds, Surface ignition inhibitors such as organic phosphorus compounds, detergents and dispersants such as succinimides, polyalkylamines and polyetheramines, anti-icing agents such as polyhydric alcohols and ethers, alkali metal salts and alkaline earths of organic acids Auxiliary agents such as metal salts, higher alcohol sulfates, anionic surfactants, cationic surfactants, amphoteric surfactants, rust inhibitors such as alkenyl succinates, quinizarin, coumarins, etc. Examples thereof include colorants such as discriminating agents and azo dyes.
以下に、実施例により本発明をより具体的に説明するが、本発明はこれらの例により何ら制限されるものではない。 Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples.
（異性化工程）
反応器に後述のようにして調製した白金塩素化アルミナ触媒を充填し、原料油の脱硫直留軽質ナフサ（ＤＳＬＧ）と３００容量ｐｐｍに相当する四塩化炭素を混合して反応器に通油して異性化反応を実施して、異性化生成油Ａを得た。反応条件は、反応温度：１４０℃、反応圧力：３．０ＭＰａ、ＬＨＳＶ：１.５ｈ-1、Ｈ２／Ｏｉｌ：０.２ｍｏｌ／ｍｏｌとした。
なお、白金塩素化アルミナ触媒は以下のようにして調製した。ガンマアルミナを直径１．６ｍｍのダイスにより押出し成形した。空気下での予備焼成後、ＨＣｌの存在下、塩化白金酸を前記成形アルミナに担持した。このように調製した触媒前駆体を空気下で焼成後、水素流通下にて６００℃で還元した。次いで、２５０℃の温度条件下、四塩化炭素を注入しで塩素化を行った。触媒は、外径約１.５ｍｍ、長さ約４．０ｍｍのペレット状で、白金を０.３質量％、塩素を７.０質量％含有するものであった。
表１に原料の脱硫直留軽質ナフサと異性化生成油Ａの性状を示す。オクタン価は、原料の脱硫直留軽質ナフサの６４．８から異性化反応により８５．３へ向上した。
(Isomerization process)
The reactor was filled with a platinum chlorinated alumina catalyst prepared as described below, and the raw oil desulfurized straight-run light naphtha (DSLG) and carbon tetrachloride equivalent to 300 ppm by volume were mixed and passed through the reactor. The isomerization reaction was carried out to obtain isomerization product oil A. The reaction conditions were as follows: reaction temperature: 140 ° C., reaction pressure: 3.0 MPa, LHSV: 1.5 h −1 , H 2 / Oil: 0.2 mol / mol.
The platinum chlorinated alumina catalyst was prepared as follows. Gamma alumina was extruded with a 1.6 mm diameter die. After preliminary calcination under air, chloroplatinic acid was supported on the shaped alumina in the presence of HCl. The catalyst precursor thus prepared was calcined in air and then reduced at 600 ° C. under a hydrogen flow. Next, chlorination was performed by injecting carbon tetrachloride under a temperature condition of 250 ° C. The catalyst was in the form of a pellet having an outer diameter of about 1.5 mm and a length of about 4.0 mm, and contained 0.3% by mass of platinum and 7.0% by mass of chlorine.
Table 1 shows the properties of raw desulphurized straight-run light naphtha and isomerized product oil A. The octane number was improved from 64.8 of the raw desulphurization straight-run light naphtha to 85.3 by isomerization reaction.
（蒸留分離工程）
次いで、得られた異性化生成油Ａを、東京特殊金網株式会社製の充填物、ＧＯＯＤＲＯＬＬ ＴＹＰＥ Ｄ（ＳＵＳ３０４製）を充填した塔高４２００ｍｍＨ、塔径４２.８ｍｍφの蒸留塔を用いて、還流比３／１〜５／１（理論段数８５段）、設定圧力を０.１ＭＰａで蒸留し、塔頂温度が２５℃までの留分（ガス分）、２５〜６０℃の留分（軽質分、すなわち高オクタン価化合物Ｂ）、そして残りの６０℃以上の留分（重質分、すなわち低オクタン価化合物Ｃ）を得た。それぞれの収率は、ガス分が５.０容量％、高オクタン価化合物Ｂが７１．５容量％、低オクタン価化合物Ｃが２３．５容量％であった。上記蒸留分離後の高オクタン価化合物Ｂ及び低オクタン価化合物Ｃの性状を、蒸留前の異性化生成油Ａの性状とともに表１に示す。
(Distillation separation process)
Next, the obtained isomerization product oil A was refluxed using a distillation tower having a tower height of 4200 mmH and a tower diameter of 42.8 mmφ filled with a packing made by Tokyo Special Wire Mesh Co., Ltd. and GOODROLL TYPE D (made by SUS304). 3 / 1-5 / 1 (theoretical plate number: 85 plates), distillation at a set pressure of 0.1 MPa, fraction with a top temperature of 25 ° C. (gas component), fraction with 25-60 ° C. (light component, That is, a high octane compound B) and the remaining fraction of 60 ° C. or higher (heavy fraction, ie, low octane compound C) were obtained. The yields were 5.0% by volume for the gas, 71.5% by volume for the high octane compound B, and 23.5% by volume for the low octane compound C, respectively. The properties of the high octane compound B and the low octane compound C after the distillation separation are shown in Table 1 together with the properties of the isomerized product oil A before distillation.
次いで、上記のようにして得られた低オクタン価化合物Ｃを、再度反応器に通して異性化反応を実施した。その結果得られた異性化生成油Ｄと、上記の蒸留分離で得た軽質分の高オクタン価化合物Ｂとをそれぞれ得られた量の割合で混合し分離異性化ガソリン基材Ｅ（ＩＳＯ−Ｅ）を得た。 Next, the low octane compound C obtained as described above was passed through the reactor again to carry out the isomerization reaction. The resulting isomerized product oil D and the light-weight high-octane compound B obtained by the above-mentioned distillation separation are mixed in the proportions of the obtained amounts, respectively, and separated isomerized gasoline base E (ISO-E) Got.
異性化工程、更には分離工程を経て得た表１に記載の各留分から、高オクタン価化合物Ｂ及び分離異性化ガソリン基材Ｅは、十分高いオクタン価を有しており、極めて良好なガソリン基材であると判断される。異性化生成油Ａ及び異性化生成油Ｄも比較的高いオクタン価を有しており、良好なガソリン基材である。なお、高オクタン価化合物Ｂをガソリン基材として使用することは、利用価値の低い低オクタン価化合物Ｃの生産を伴う。したがって、低オクタン価化合物Ｃを再度異性化して得た異性化生成油Ｄと高オクタン価化合物Ｂを混合して得た分離異性化ガソリン基材Ｅは、良好な性状に加えて、無駄となる製品を副生しないことから特に好ましいガソリン基材と考えられる。 From each fraction shown in Table 1 obtained through the isomerization step and further the separation step, the high octane compound B and the separated isomerized gasoline base E have a sufficiently high octane number and are extremely good gasoline bases. It is judged that. Isomerized oil A and isomerized oil D also have relatively high octane numbers and are good gasoline bases. In addition, using the high octane compound B as a gasoline base material is accompanied by the production of a low octane compound C having a low utility value. Therefore, the separated isomerized gasoline base E obtained by mixing the isomerization product oil D obtained by isomerization of the low octane compound C again and the high octane compound B is not only good properties but also a waste product. Since it is not a by-product, it is considered to be a particularly preferable gasoline base material.
表２に示す性状のガソリン基材を、表３の上部に示す配合割合でブレンドして実施例１〜４及び比較例１〜４のガソリン組成物を調合した。比較例は、従来ガソリンの基材組成をもとに構成基材中の接触分解ナフサ比率を下げてオレフィン量を低減したものであり、それに対して、実施例は、比較例の基材組成をもとに異性化ガソリンを使用して多分岐イソパラフィン含有率を高めることにより、オレフィン分削減によるオクタン価低下分を補ったものである。なお、使用したガソリン基材は、次のようにして調製されたものである。 The gasoline bases having the properties shown in Table 2 were blended at the blending ratio shown in the upper part of Table 3 to prepare gasoline compositions of Examples 1 to 4 and Comparative Examples 1 to 4. In the comparative example, the amount of olefin is reduced by lowering the catalytic cracking naphtha ratio in the constituent base material based on the base material composition of conventional gasoline. Originally, isomerized gasoline is used to increase the content of multi-branched isoparaffin to compensate for the decrease in octane number due to olefin content reduction. In addition, the gasoline base material used was prepared as follows.
イソペンタン留分（ｉＣ５）
イソペンタンを多く含む炭素数５が主体の留分である。脱硫重質ナフサの接触改質で副生する軽質留分と脱硫軽質ナフサ留分とを蒸留分離することにより、純度９５％以上の炭素数５のイソパラフィン留分を得た。
Isopentane fraction (iC5)
This fraction is mainly composed of 5 carbon atoms rich in isopentane. A light fraction produced as a by-product of catalytic reforming of desulfurized heavy naphtha and a desulfurized light naphtha fraction were separated by distillation to obtain an isoparaffin fraction having a carbon number of 5% having a purity of 95% or more.
アルキレートガソリン（ＡＬＫＧ）
ブチレンを主成分とする留分とイソブタンを主成分とする留分を硫酸触媒により反応させて、イソパラフィン分の高い炭化水素を得た。
Alkylate gasoline (ALKG)
A fraction containing butylene as a main component and a fraction containing isobutane as a main component were reacted with a sulfuric acid catalyst to obtain a hydrocarbon having a high isoparaffin content.
接触分解軽質ナフサ留分（ＦＬ）
脱硫軽油あるいは脱硫重油を原料に用い、固体触媒存在下、流動床式反応装置での接触分解反応によりオレフィン分の高い接触分解ナフサ留分（ＦＣＣＧ）を得、このＦＣＣＧを軽質留分と重質留分に蒸留分離して得た軽質留分（ＦＬ）である。
Catalytic cracking light naphtha fraction (FL)
Desulfurized light oil or desulfurized heavy oil is used as a raw material, and in the presence of a solid catalyst, a catalytic cracking reaction in a fluidized bed reactor is used to obtain a catalytic cracking naphtha fraction (FCCG) with a high olefin content. It is a light fraction (FL) obtained by distillation separation into a fraction.
改質ガソリン（ＡＣ７、ＡＣ９）
脱硫重質ナフサを固体改質触媒により移動床式反応装置を用いて反応させることにより、アロマ含量の多い炭化水素に改質して改質ガソリンを得る。改質ガソリンはそのまま使用することもできるが、ここでは蒸留分離することにより炭素数７及び炭素数９の炭化水素をそれぞれ８５％以上含有する留分（ＡＣ７及びＡＣ９）を得た。
Reformed gasoline (AC7, AC9)
Desulfurized heavy naphtha is reacted with a solid reforming catalyst using a moving bed reactor to reform to a hydrocarbon with a high aroma content to obtain reformed gasoline. The reformed gasoline can be used as it is, but here, fractions (AC7 and AC9) containing 85% or more of C7 and C9 hydrocarbons were obtained by distillation separation.
エタノール（ＥｔＯＨ）
市販の発酵エタノール（９９度１級、日本アルコール販売（株）製）を使用した。
Ethanol (EtOH)
Commercially available fermented ethanol (99 degrees first grade, manufactured by Nippon Alcohol Sales Co., Ltd.) was used.
エチルターシャリーブチルエーテル（ＥＴＢＥ）
イオン交換樹脂触媒（Ａｍｂｅｒｌｙｓｔ-１５）を用いてエタノールとイソブチレンとを反応させ、次いで蒸留法により精製し、純度９５％以上のＥＴＢＥを得た。
Ethyl tertiary butyl ether (ETBE)
Ethanol and isobutylene were reacted using an ion exchange resin catalyst (Amberlyst-15) and then purified by distillation to obtain ETBE having a purity of 95% or more.
実施例１〜４、比較例１〜４のガソリン組成物の性状を表３の下部に示す。なお、ガソリン基材及び調製したガソリン組成物の性状は、次の方法により測定した。
密度はＪＩＳ Ｋ ２２４９の振動式密度試験方法、リード法蒸気圧（ＲＶＰ）はＪＩＳ Ｋ ２２５８のリード法蒸気圧試験方法、蒸留性状はＪＩＳ Ｋ ２２５４の常圧法蒸留試験方法によって測定した。硫黄分は、ＪＩＳ Ｋ ２５４１の硫黄分試験方法によって測定した。銀板腐食はＪＩＳ Ｋ２５１３（石油製品−銅板腐食試験方法：対応 ＡＳＴＭ Ｄ１３０）のボンベ法（ジェット燃料）で、銅板の代わりにＪＩＳ Ｋ２２７６（石油製品−航空燃料油試験方法）の「１４．銀板腐食試験方法」に用いる銀板を使用して評価した。アロマ分、オレフィン分、パラフィン分等の各種炭化水素化合物の成分組成はＪＩＳ Ｋ ２５３６のガスクロマトグラフ法による全成分試験方法により測定した。リサーチ法オクタン価（ＲＯＮ）はヒューレッドパッカード社製ＰＩＯＮＡ装置を用いて、ガスクロマトグラフ法によって測定した。
Properties of the gasoline compositions of Examples 1 to 4 and Comparative Examples 1 to 4 are shown in the lower part of Table 3. In addition, the property of the gasoline base material and the prepared gasoline composition was measured by the following method.
The density was measured by the vibration type density test method of JIS K 2249, the Reed method vapor pressure (RVP) was measured by the Reed method vapor pressure test method of JIS K 2258, and the distillation properties were measured by the atmospheric pressure distillation test method of JIS K 2254. The sulfur content was measured by the sulfur content test method of JIS K2541. Silver plate corrosion is the cylinder method (jet fuel) of JIS K2513 (Petroleum products-Copper plate corrosion test method: corresponding ASTM D130). Instead of the copper plate, “14. Silver plate of JIS K2276 (Petroleum product-Aviation fuel oil test method)” The silver plate used in the “corrosion test method” was evaluated. The component composition of various hydrocarbon compounds such as aroma, olefin, and paraffin was measured by the all component test method based on the gas chromatograph method of JIS K2536. The research method octane number (RON) was measured by a gas chromatograph method using a PIONA manufactured by Hured Packard.
表３から、実施例１〜４の環境対応型ガソリンは比較例１〜４の従来型ガソリンと比較して、脱硫直留軽質ナフサ留分を異性化処理して得た分離異性化ガソリン基材（ＩＳＯ）を用いることにより、ノルマルパラフィン含有量が少ない代わりにイソパラフィンの含有量が多く、２,３−ジメチルブタンおよびｉ−Ｃ６の含有量が多く、ｉ−Ｃ６／ｎ−Ｃ６比が高く、さらにｉ−Ｃ６／Ｃ６＝比が高いため、同程度までオレフィン分を低減したにもかかわらずＲＯＮが高い。すなわち、実施例１〜４の環境対応型ガソリンは、比較例１〜４と硫黄分やアロマ分が同程度であっても、良好な蒸留性状およびＲＶＰで、かつ高いＲＯＮであり、優れた実用性能を有することがわかる。 From Table 3, the environmentally friendly gasolines of Examples 1 to 4 were separated and isomerized gasoline base materials obtained by isomerization of the desulfurized straight-run light naphtha fraction as compared with the conventional gasolines of Comparative Examples 1 to 4. By using (ISO), the content of isoparaffin is high instead of the low content of normal paraffin, the content of 2,3-dimethylbutane and i-C6 is high, and the i-C6 / n-C6 ratio is high, Furthermore, since i-C6 / C6 = ratio is high, RON is high despite the olefin content being reduced to the same extent. That is, the environmentally friendly gasolines of Examples 1 to 4 have good distillation properties and RVP, and high RON, even if the sulfur content and aroma content are the same as those of Comparative Examples 1 to 4, and are excellent in practical use. It can be seen that it has performance.
Claims (9)
（２）前記（１）の異性化工程で得られた異性化生成油を異性化ガソリン基材として他のガソリン基材と混合するブレンド工程を含む、請求項１〜５いずれかに記載の高オクタン価の環境対応型ガソリン組成物の製造方法。 (1) A part or all of a naphtha fraction having a 10% by volume distillation temperature of 25 to 60 ° C. and a 90% by volume distillation temperature of 55 to 80 ° C. using a solid acid catalyst under hydrogen pressure An isomerization step for isomerization to obtain an isomerized product oil, and (2) a blending step in which the isomerized product oil obtained in the isomerization step of (1) is mixed with another gasoline base as an isomerized gasoline base. The manufacturing method of the environment-friendly gasoline composition of the high octane number in any one of Claims 1-5 containing these.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006083143A JP4916742B2 (en) | 2006-03-24 | 2006-03-24 | High octane number environment-friendly gasoline composition and method for producing the same |
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| JP2020510742A (en) * | 2017-03-01 | 2020-04-09 | アルベマール ヨーロッパ エスアールエル | Alkylation process with improved octane number |
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| JP2020510742A (en) * | 2017-03-01 | 2020-04-09 | アルベマール ヨーロッパ エスアールエル | Alkylation process with improved octane number |
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