JP4801342B2 - Gasoline composition, method for producing gasoline base material, and method for producing gasoline composition - Google Patents
Gasoline composition, method for producing gasoline base material, and method for producing gasoline composition Download PDFInfo
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- 239000003502 gasoline Substances 0.000 title claims description 53
- 239000000203 mixture Substances 0.000 title claims description 27
- 239000000463 material Substances 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000004821 distillation Methods 0.000 claims description 23
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 21
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- XTDQDBVBDLYELW-UHFFFAOYSA-N 2,2,3-trimethylpentane Chemical compound CCC(C)C(C)(C)C XTDQDBVBDLYELW-UHFFFAOYSA-N 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 9
- RLPGDEORIPLBNF-UHFFFAOYSA-N 2,3,4-trimethylpentane Chemical compound CC(C)C(C)C(C)C RLPGDEORIPLBNF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 3
- 239000002585 base Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000001282 iso-butane Substances 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- -1 alkali metal salt Chemical class 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- 239000003747 fuel oil additive Substances 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- ZRLNBWWGLOPJIC-CMCGXILPSA-N 21alpha(H)-A'-Neogammacerane Chemical compound C([C@]1(C)[C@H]2CC[C@H]34)CCC(C)(C)[C@@H]1CC[C@@]2(C)[C@]4(C)CC[C@@H]1[C@]3(C)CC[C@H]1C(C)C ZRLNBWWGLOPJIC-CMCGXILPSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
本発明は、ガソリン組成物、ガソリン基材の製造方法及び当該ガソリン基材を配合するガソリン組成物の製造方法に関する。 The present invention relates to a gasoline composition, a method for producing a gasoline base material, and a method for producing a gasoline composition containing the gasoline base material.
地球温暖化対策が世界的な課題になっており、二酸化炭素の削減方法として、自動車の燃費改善のためガソリンのオクタン価を上げることが要望されている。
このオクタン価を上げる方法として、トルエン等の芳香族分やオレフィン分、その他重質留分の配合割合を増やすことが一般的であるが、芳香族分や重質留分はオクタン価は高いが、燃焼性が悪く、エンジン内のデポジットの原因になることが知られている。また、オレフィン分もオクタン価が高いが、安定性が悪く、ガム状物質を増加させ、インジェクターを詰まらせる等の不具合が発生する可能性があると指摘されている。
Global warming countermeasures have become a global issue, and as a carbon dioxide reduction method, it is desired to increase the octane number of gasoline in order to improve the fuel efficiency of automobiles.
As a method of increasing the octane number, it is common to increase the blending ratio of aromatics such as toluene, olefins, and other heavy fractions, but the aromatics and heavy fractions have a high octane number, but combustion It is known that it causes poor deposits in the engine. Moreover, although the octane number is high also in the olefin content, it has been pointed out that there is a possibility of problems such as poor stability, increased gum-like substances, and clogging the injector.
一方、エタノールやその誘導体であるエチルターシャリーブチルエーテル（ETBE）、或いはメチルターシャリーブチルエーテル（MTBE）の含酸素化合物を配合することにより、重質留分をある程度低減させてもオクタン価を維持できるとしたガソリンが提案されている（例えば、特許文献１〜３参照）。したがって、重質留分をある程度含有させたまま含酸素化合物を配合することによってオクタン価の高いガソリンを得ることはできる。
しかし、含酸素化合物を添加するためには、タンクや混合設備等、これに対応する新たな設備を設ける必要であるし、また、含酸素化合物は燃料基材としては価格が高い等の問題がある。 However, in order to add an oxygen-containing compound, it is necessary to provide a new facility corresponding to this, such as a tank and a mixing facility, and the oxygen-containing compound has a problem that it is expensive as a fuel base material. is there.
本発明者は、上記課題を解決するために鋭意研究を重ねた結果、２,２,４−トリメチルペンタンを特定量含有させることにより高オクタン価ガソリンが得られること、また重質化を防ぐためにアルキレートの重質部分をカットした軽質アルキレートがガソリン基材として好適で、これを配合することにより、比較的安いコストで、重質留分を含まなくて高オクタン価ガソリンが製造できるという知見を得、本発明に想到した。 As a result of intensive studies to solve the above problems, the present inventor has obtained a high octane gasoline by adding a specific amount of 2,2,4-trimethylpentane, and in order to prevent heaviness. A light alkylate with a heavy portion of the chelate cut is suitable as a gasoline base material, and by combining it, we have obtained the knowledge that high octane gasoline can be produced without a heavy fraction at a relatively low cost. The present invention has been conceived.
本発明の第１の態様によるガソリン組成物は、蒸気圧が６５kPa以下、１５℃における密度が０.７０〜０.７８g/cm3及び５０％留出温度が７５〜１００℃であり、硫黄分を１０質量ppm以下、ベンゼン分を１容量％以下及び２,２,４−トリメチルペンタンを１〜１０容量％含み、２,２,４−トリメチルペンタン／２,２,３−トリメチルペンタンの容積比が３０以上、２,２,４−トリメチルペンタン／２,３,４−トリメチルペンタンの容積比が３０以上のリサーチ法オクタン価が９２〜９６からなるもので、好ましくは銀板腐食が１以下のものである。 The gasoline composition according to the first aspect of the present invention has a vapor pressure of 65 kPa or less, a density at 15 ° C. of 0.70 to 0.78 g / cm 3, a 50% distillation temperature of 75 to 100 ° C., and a sulfur content. 10 mass ppm or less, 1% by volume or less of benzene and 1 to 10% by volume of 2,2,4-trimethylpentane, and a volume ratio of 2,2,4-trimethylpentane / 2,2,3-trimethylpentane 30 or more, 2,2,4-trimethylpentane / 2,3,4-trimethylpentane with a volume ratio of 30 or more and a research octane number of 92 to 96, preferably with silver plate corrosion of 1 or less It is.
本発明の第２の態様によるガソリン基材の製造方法は、初留点が２５℃以上、終点が２２０℃以下及び１５℃における密度が０.７２g/cm3以下のアルキレートを、２０段から４０段のトレイからなる蒸留塔で、還流比２〜３、運転圧力０.０５〜０.１５MPaの条件で蒸留分離することにより、初留点が２５℃以上、終点が１２０℃以下、１５℃における密度が０.６８g/cm3以下で、かつ２,２,４−トリメチルペンタンを４０容量％以上、２,２,３−トリメチルペンタンが３容量％以下、２,３,４−トリメチルペンタンが３容量％以下含有する軽質アルキレートを得ることからなるものである。
In the method for producing a gasoline base material according to the second aspect of the present invention, an alkylate having an initial boiling point of 25 ° C. or more, an end point of 220 ° C. or less, and a density at 15 ° C. of 0.72 g / cm 3 or less is obtained from 20 stages. In a distillation column comprising 40 trays , the initial boiling point is 25 ° C. or higher, the end point is 120 ° C. or lower, 15 ° C. by distillation separation under conditions of a reflux ratio of 2 to 3 and an operating pressure of 0.05 to 0.15 MPa. The density is 0.668 g / cm 3 or less, and 2,2,4-trimethylpentane is 40% by volume or more, 2,2,3-trimethylpentane is 3% by volume or less, and 2,3,4-trimethylpentane is 2,4,4-trimethylpentane. It consists of obtaining a light alkylate containing 3% by volume or less.
本発明の第３の態様のガソリン組成物の製造方法は、上記第２の態様の方法で得られたガソリン基材を配合して上記第１の態様のガソリン組成物を得ることからなる。 The method for producing a gasoline composition according to the third aspect of the present invention comprises blending the gasoline base material obtained by the method according to the second aspect to obtain the gasoline composition according to the first aspect.
本発明は、現在市販のレギュラーグレードガソリンよりリサーチオクタン価（RON）を高くできるので、燃費が向上でき、二酸化炭素の削減に有効であり、かつ芳香族分、オレフィン分、その他の重質留分の含有量を低減できるので、燃焼性が良好となり、エンジン内でのデポジットの生成を抑制できるとともに、安定性も良好となり、ガム状物質の生成によるインジェクター閉塞等の不具合発生の可能性がなくなる等、格別の効果を奏する。また、エタノールやETBEといった含酸素化合物を含有させることがないので、新たな設備を設ける必要がなく、安価にガソリン組成物を製造できるという格別の効果を奏する。 Since the present invention can increase the research octane number (RON) compared to the regular grade gasoline currently on the market, it can improve fuel efficiency, is effective in reducing carbon dioxide, and has an aromatic content, olefin content, and other heavy fractions. Since the content can be reduced, the flammability is good, the formation of deposits in the engine can be suppressed, the stability is also good, and there is no possibility of problems such as injector clogging due to the production of gum-like substances, etc. There is a special effect. In addition, since no oxygen-containing compounds such as ethanol and ETBE are contained, there is no need to install new equipment, and a special effect that a gasoline composition can be produced at low cost is achieved.
本発明によるガソリン組成物は、リサーチ法オクタン価（以下、単に「ＲＯＮ」ともいう）が９２〜９６、好ましくは９４〜９６、特に好ましくは９５〜９６のものである。このリサーチ法オクタン価は、ＪＩＳ Ｋ ２２８０に規定される方法により測定されるものである。RONをこの範囲にすることにより、自動車の燃費をより向上させ、二酸化炭素の排出を削減できる。 The gasoline composition according to the present invention has a research octane number (hereinafter also simply referred to as “RON”) of 92 to 96, preferably 94 to 96, particularly preferably 95 to 96. This research octane number is measured by a method defined in JIS K 2280. By setting RON within this range, it is possible to further improve the fuel efficiency of automobiles and reduce carbon dioxide emissions.
本発明のガソリン組成物は、低温始動性やベーパーロックなどによる運転性の不具合防止の点から、蒸気圧が３７.８℃の蒸気圧が６５kPa以下、好ましくは４４〜６０ｋPaのものである。この蒸気圧は、ＪＩＳ Ｋ ２２５８に規定された方法で測定されるものである。 The gasoline composition of the present invention has a vapor pressure of 37.8 ° C. and a vapor pressure of 65 kPa or less, preferably 44 to 60 kPa, from the viewpoint of preventing problems of drivability due to low temperature startability and vapor lock. This vapor pressure is measured by a method defined in JIS K 2258.
また、１５℃における密度が０.７０〜０.７８g/cm3、好ましくは０.７１〜０.７６g/cm3、特に好ましくは０.７２〜０.７５g/cm3のものである。この密度が０.７０g/cm3以上であると燃費が良く、また０.７８g/cm3以下にすると加速性能が良く、プラグのくすぶりを生じることがない。
この密度は、ＪＩＳ Ｋ ２２４９で規定された方法により測定されるものである。
The density at 15 ° C. is 0.70 to 0.78 g / cm 3 , preferably 0.71 to 0.76 g / cm 3 , and particularly preferably 0.72 to 0.75 g / cm 3 . When this density is 0.70 g / cm 3 or more, fuel economy is good, and when it is 0.78 g / cm 3 or less, acceleration performance is good and plug smoldering does not occur.
This density is measured by a method defined in JIS K 2249.
さらに、良好な始動性及び加速性を得るためには５０％留出温度が７５〜１００℃、好ましくは８７〜９８℃のものである。留出温度はＪＩＳ Ｋ ２２５４に規定された方法により測定されるものである。 Furthermore, in order to obtain good startability and acceleration, the 50% distillation temperature is 75 to 100 ° C, preferably 87 to 98 ° C. The distillation temperature is measured by the method defined in JIS K 2254.
本発明によるガソリン組成物は、排ガス浄化触媒への影響の抑制及び環境汚染防止の観点から、硫黄分を１０質量ppm以下、好ましくは５質量ppm以下、より好ましくは２質量ppm以下含むものである。この硫黄分は、ＪＩＳ Ｋ ２５４１に規定された方法により測定されるものである。 The gasoline composition according to the present invention contains a sulfur content of 10 mass ppm or less, preferably 5 mass ppm or less, more preferably 2 mass ppm or less, from the viewpoint of suppressing the influence on the exhaust gas purification catalyst and preventing environmental pollution. This sulfur content is measured by the method defined in JIS K2541.
また、大気中へのベンゼン排出量を抑制するために、ガソリン組成物中のベンゼン量は１容量％、好ましくは０.５容量％以下とする。このベンゼン含有量は、ＪＩＳ Ｋ ２５３６に規定された方法により測定されるものである。 In order to suppress the amount of benzene discharged into the atmosphere, the amount of benzene in the gasoline composition is 1% by volume, preferably 0.5% by volume or less. This benzene content is measured by the method specified in JIS K2536.
さらに、２,２,４−トリメチルペンタンを１〜１０容量％、好ましくは３〜６容量％含むものである。この２,２,４−トリメチルペンタンは、沸点が低く、オクタン価が高いため、ガソリン組成物の成分として優れたものである。この成分が１容量％以下であれば、オクタン価を高めることはできない。また更に２,２,４−トリメチルペンタン／２,２,３−トリメチルペンタンの容積比が３０以上、好ましくは４０以上，更に好ましくは５０以上、２,２,４−トリメチルペンタン／２,３,４−トリメチルペンタンの容積比が３０以上、好ましくは４０以上，更に好ましくは５０以上とする。これらの範囲外であれば、蒸留性状を重質化させないでRONを上げることが難しくなる。 Further, it contains 1 to 10% by volume, preferably 3 to 6% by volume of 2,2,4-trimethylpentane. Since 2,2,4-trimethylpentane has a low boiling point and a high octane number, it is excellent as a component of a gasoline composition. If this component is 1% by volume or less, the octane number cannot be increased. Furthermore, the volume ratio of 2,2,4-trimethylpentane / 2,2,3-trimethylpentane is 30 or more, preferably 40 or more, more preferably 50 or more, 2,2,4-trimethylpentane / 2,3, The volume ratio of 4-trimethylpentane is 30 or more, preferably 40 or more, more preferably 50 or more. If it is outside these ranges, it will be difficult to increase RON without increasing the distillation properties.
なお、本発明のガソリン組成物は、活性硫黄による車両の燃料センターゲージの不具合を防ぐために、銀板腐食が1以下であることが好ましく、さらには０であることがより好ましい。この銀板腐食は、英国石油協会規格ＩＰ−２２７に規定された方法により測定されるものである。 In the gasoline composition of the present invention, the corrosion of the silver plate is preferably 1 or less, and more preferably 0, in order to prevent malfunction of the vehicle fuel center gauge due to active sulfur. This silver plate corrosion is measured by the method prescribed in British Petroleum Institute Standard IP-227.
上記本発明のガソリン組成物は、流動接触分解ガソリン基材、接触改質ガソリン基材、直留ナフサを脱硫処理した基材などを配合して製造できるが、この場合、２,２,４-トリメチルペンタンを１〜１０容量％含むように配合する。
この２,２,４-トリメチルペンタンは、イソブタンとブテンを、硫酸、フッ化水素、塩化アルミニウム等の酸触媒の存在下に反応させて得られるアルキレート中に多く含まれるので、このアルキレートを配合することにより調製できるが、このアルキレート中には、２,２,３−トリメチルペンタンや２,３,４−トリメチルペンタンも多く含まれている。したがって、アルキレートをこのまま配合するとガソリン組成物が重質化するため、この２,２,３−トリメチルペンタンや２,３,４−トリメチルペンタンを除いたものを配合する必要がある。
The gasoline composition of the present invention can be produced by blending a fluid catalytic cracking gasoline base material, a catalytic reformed gasoline base material, a base material obtained by desulfurizing straight-run naphtha, etc. In this case, 2,2,4- It mix | blends so that 1-10 volume% of trimethylpentane may be included.
This 2,2,4-trimethylpentane is contained in a large amount in the alkylate obtained by reacting isobutane and butene in the presence of an acid catalyst such as sulfuric acid, hydrogen fluoride, and aluminum chloride. Although it can be prepared by blending, this alkylate contains a large amount of 2,2,3-trimethylpentane and 2,3,4-trimethylpentane. Therefore, if the alkylate is blended as it is, the gasoline composition becomes heavier. Therefore, it is necessary to blend those excluding 2,2,3-trimethylpentane and 2,3,4-trimethylpentane.
ところで、２,２,４−トリメチルペンタンの沸点は９９.４℃、２,２,３−トリメチルペンタンの沸点は１１０.０℃、２,３,４−トリメチルペンタンの沸点は１１３.８℃であるので、アルキレートを蒸留分離することにより、２,２,４-トリメチルペンタンに富む留分を得ることができる。この２,２,４-トリメチルペンタンに富む留分、すなわち、軽質アルキレートを上記で特定した量及び比率の範囲になるように配合することで、本発明のガソリン組成物を簡便に製造することができる。 By the way, the boiling point of 2,2,4-trimethylpentane is 99.4 ° C, the boiling point of 2,2,3-trimethylpentane is 110.0 ° C, and the boiling point of 2,3,4-trimethylpentane is 113.8 ° C. Therefore, a fraction rich in 2,2,4-trimethylpentane can be obtained by distilling away the alkylate. The gasoline composition of the present invention can be easily produced by blending the fraction rich in 2,2,4-trimethylpentane, that is, the light alkylate so as to be in the range of the amount and ratio specified above. Can do.
この軽質アルキレートを用いた場合の好ましい配合量は、流動接触分解ガソリン基材を３０〜８５容量％、特には５０〜８５容量％、接触改質ガソリン基材を０〜２０容量％、特には０〜１５容量％、軽質アルキレートを２〜２０容量％、特には６〜１５容量％である。 The preferred blending amount when this light alkylate is used is 30 to 85% by volume, especially 50 to 85% by volume of fluid catalytic cracking gasoline base, and 0 to 20% by volume of catalytic reforming gasoline base, particularly 0 to 15% by volume, 2 to 20% by volume of light alkylate, particularly 6 to 15% by volume.
上記の軽質アルキレートは、イソブタンとブテンを、硫酸、フッ化水素、塩化アルミニウム等の酸触媒の存在下に反応させて得られる、初留点が２５℃以上、好ましくは３０〜４０℃、終点が２２０℃以下、好ましくは１９０〜２１０℃、及び１５℃における密度が０.７２g/cm3以下、好ましくは０．６９〜０．７１g/cm3のアルキレートを蒸留分離することにより、初留点が２５℃以上、好ましくは３０〜４０℃終点が１２０℃以下、好ましくは１００〜１１０℃、１５℃における密度が０.６８g/cm3以下、好ましくは０.６６〜０.６７g/cm3で、かつ２,２,４−トリメチルペンタンを４０容量％以上、好ましくは４５〜５５容量％、２,２,３−トリメチルペンタンが３容量％以下、好ましくは１容量％以下、２,３,４−トリメチルペンタンが３容量％以下、好ましくは１容量％以下含有するようにすることにより、好適なガソリン基材を得ることができる。 The above light alkylate is obtained by reacting isobutane and butene in the presence of an acid catalyst such as sulfuric acid, hydrogen fluoride, and aluminum chloride. The initial boiling point is 25 ° C. or higher, preferably 30 to 40 ° C., and the end point. There 220 ° C. or less, preferably by the density at 190 to 210 ° C., and 15 ℃ is 0.72 g / cm 3 or less, preferably distillation using alkylate 0.69~0.71g / cm 3, first fraction The point is 25 ° C. or more, preferably 30 to 40 ° C. The end point is 120 ° C. or less, preferably 100 to 110 ° C., and the density at 15 ° C. is 0.68 g / cm 3 or less, preferably 0.66 to 0.67 g / cm 3. And 2,2,4-trimethylpentane is 40% by volume or more, preferably 45 to 55% by volume, and 2,2,3-trimethylpentane is 3% by volume or less, preferably 1% by volume or less. 4-volume trimethylpentane % Or less, preferably 1% by volume or less, a suitable gasoline base material can be obtained.
この蒸留分離においては、２０段から４０段のトレイ、好ましくは３０段からなる蒸留塔で、還流比は２〜３、好ましくは２.４、運転圧力は０.０５〜０.１５MPa、好ましくは０.１MPaの条件により、比較的簡便に上記に記載した範囲の軽質成分（軽質アルキレート）を分留することができる。 In this distillation separation, a 20 to 40 tray, preferably a 30 distillation column, with a reflux ratio of 2-3, preferably 2.4, and an operating pressure of 0.05-0.15 MPa, preferably Under the condition of 0.1 MPa, the light component (light alkylate) in the above-described range can be fractionated relatively easily.
なお、上述の本発明のガソリン組成物には、当業界で公知の燃料油添加剤の１種又は２種以上を必要に応じて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配合量を０.１質量％以下にすることが好ましい。
本発明のガソリン組成物で使用可能な燃料油添加剤を例示すれば、フェノール系、アミン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、多価アルコール又は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又は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、アゾ染料などの着色剤を挙げることができる。
In addition, 1 type, or 2 or more types of a fuel oil additive well-known in this industry can be mix | blended with the gasoline composition of this invention mentioned above as needed. Although these compounding quantities can be selected suitably, it is preferable to make the total compounding quantity of an additive into 0.1 mass% or less normally.
Examples of fuel oil additives that can be used in the gasoline composition of the present invention include phenol-based and amine-based antioxidants, Schiff-type compounds, metal deactivators such as thioamide-type compounds, and organic phosphorus-based compounds. Surface ignition inhibitor, detergent dispersants such as succinimide, polyalkylamine, polyetheramine, anti-icing agent such as polyhydric alcohol or its ether, alkali metal salt or alkaline earth metal salt of organic acid, higher alcohol And a colorant such as an azo dye, an antistatic agent such as an anionic surfactant, a cationic surfactant and an amphoteric surfactant.
以下に、本発明を実施例に基づいてより詳細に説明するが、本発明は、これらに限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
なお、本実施例では蒸留性状はＪＩＳ Ｋ ２２５４に規定された方法により測定した。 In this example, the distillation property was measured by the method defined in JIS K 2254.
表１に示すガソリン基材を用意した。各基材は、次の方法で用意した。
ＤＳ−ＬＧ：直留ガソリンであり、中東系原油の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。
The gasoline base material shown in Table 1 was prepared. Each substrate was prepared by the following method.
DS-LG: straight-run gasoline, obtained by hydrodesulfurizing a naphtha fraction of Middle Eastern crude oil, and distilling and separating the lighter fraction.
ＦＣＣＧ：接触分解ガソリンを分留して５％留出温度が２５〜４３℃であって、かつ９５％留出温度が５５〜８０℃である軽質接触分解ガソリンを得る。また、５％留出温度が８０.０〜１２０℃であって、かつ９５％留出温度が１７０〜２１０℃である重質接触分解ガソリンを水素化脱硫によって硫黄分を低減した後、スイートニング処理でチオール低減処理を行い、前記の軽質接触分解ガソリンとを１：１の割合（容量比）で混合したものである。 FCCG: catalytically cracked gasoline is fractionated to obtain light catalytically cracked gasoline having a 5% distillation temperature of 25 to 43 ° C and a 95% distillation temperature of 55 to 80 ° C. Further, after reducing sulfur content by hydrodesulfurization of heavy catalytic cracked gasoline having a 5% distillation temperature of 80.0 to 120 ° C and a 95% distillation temperature of 170 to 210 ° C, sweetening A thiol reduction treatment is performed in the treatment, and the light catalytic cracking gasoline is mixed at a ratio (volume ratio) of 1: 1.
ＡＬＫＧ：アルキレートガソリンであり、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。９０％留出温度が１３０℃以下になる様に、蒸留分離により重質留分をカットした。 ALKG: alkylate gasoline, 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. The heavy fraction was cut by distillation separation so that the 90% distillation temperature was 130 ° C. or lower.
L-ALKG：ALKGを３０段のトレイで２,２,４−トリメチルペンタンを５０％以上、２,３,４−トリメチルペンタンを１％以下になるように重質分をカットした。 L-ALKG: A heavy portion was cut so that ALKG was 30 trays and 2,2,4-trimethylpentane was 50% or more and 2,3,4-trimethylpentane was 1% or less.
ＡＣ−７留分：軽質改質ガソリンであり、重質ナフサを固体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、芳香族分の高い炭化水素に改質し、蒸留分離することにより得た炭素数７の炭化水素を９５％以上含有する留分である。
ＡＣ−９留分：重質改質ガソリンであり、重質ナフサを固体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、芳香族分の高い炭化水素に改質し、蒸留分離することにより得た炭素数９以上の炭化水素を９５％以上含有する留分である。
AC-7 fraction: Light reformed gasoline, by reacting heavy naphtha with a solid catalyst using a moving bed reactor, reforming it into a hydrocarbon with a high aromatic content, and separating it by distillation. This is a fraction containing 95% or more of the obtained hydrocarbon having 7 carbon atoms.
AC-9 fraction: Heavy reformed gasoline, reforming heavy naphtha with a solid catalyst using a moving bed reactor, reforming it into a hydrocarbon with high aromatic content, and separating it by distillation. Is a fraction containing 95% or more of the hydrocarbon having 9 or more carbon atoms obtained by the above.
表１で示したガソリン基材を表２の比率で配合して、実施例１〜３となるガソリンを調製した。調整したガソリンの性状、特性を表２に併せて示す。 The gasoline bases shown in Table 1 were blended at the ratios shown in Table 2 to prepare gasolines that would be Examples 1-3. Table 2 shows the properties and characteristics of the adjusted gasoline.
この結果から明らかなように、本発明のガソリン組成物とすることにより、５０％留出温度が低い、すなわち重質留分の含有量が少なくても、オクタン価を高くできることが分かる。 As is apparent from these results, it can be seen that by using the gasoline composition of the present invention, the octane number can be increased even when the 50% distillation temperature is low, that is, the content of the heavy fraction is small.
本発明は、含酸素化合物を配合することなく、しかも蒸留性状を重質化させずにオクタン価の高いガソリン組成物とすることができる。 The present invention can provide a gasoline composition having a high octane number without blending an oxygen-containing compound and without increasing the distillation properties.
Claims (4)
The method for producing a gasoline composition according to claim 1 or 2, wherein a light alkylate obtained by the method according to claim 3 is blended.
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