WO2005044959A1 - Lead-free gasoline composition and method for production thereof - Google Patents

Lead-free gasoline composition and method for production thereof Download PDF

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Publication number
WO2005044959A1
WO2005044959A1 PCT/JP2004/016115 JP2004016115W WO2005044959A1 WO 2005044959 A1 WO2005044959 A1 WO 2005044959A1 JP 2004016115 W JP2004016115 W JP 2004016115W WO 2005044959 A1 WO2005044959 A1 WO 2005044959A1
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gasoline
sulfur
naphtha fraction
cracked naphtha
gasoline composition
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PCT/JP2004/016115
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French (fr)
Japanese (ja)
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Yasuhiro Araki
Katsuaki Ishida
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Japan Energy Corporation
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/04Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/06Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1037Hydrocarbon fractions
    • C10G2300/104Light gasoline having a boiling range of about 20 - 100 °C
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1037Hydrocarbon fractions
    • C10G2300/1044Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • C10G2300/202Heteroatoms content, i.e. S, N, O, P
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/30Physical properties of feedstocks or products
    • C10G2300/301Boiling range
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/30Physical properties of feedstocks or products
    • C10G2300/305Octane number, e.g. motor octane number [MON], research octane number [RON]
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02Gasoline

Abstract

A method for producing a lead-free gasoline composition having a sulfur content of 1 mass ppm or less and a research method octane number of 89.0 or more, which comprises a step of subjecting a cracked naphtha fraction exhibiting a temperature for 5 vol % distillation of 25°C or higher and a temperature for 95 vol % distillation of 210°C or lower, having an olefin content of 5 mass % or more and a diene number of 0.3 g/100 g or less to a desulfurization treatment, and a step of a blending step of mixing the above resultant desulfurized cracked naphtha fraction with another gasoline base material; and a lead-free gasoline composition which has a research method octane number of 89.0 or more, exhibits a temperature for 50 vol % distillation of 105°C or lower, has an olefin content of 10 vol % or more and a total sulfur content of 1 mass ppm or less, and has a percentage of a thiophene type sulfur compound in the total sulfur content of 50 mass % or more in terms of sulfur. The above lead-free gasoline composition has a sulfur content of 1 mass % or less and also retains satisfactory driving characteristics.

Description

Specification

Unleaded gasoline composition and a method of manufacturing the same

Technical field

[0001] The present invention includes a method for manufacturing the same unleaded gasoline composition with reduced environmental impact.

In particular, by reducing the sulfur content to below 1 mass ppm, unleaded gasoline composition to ensure sufficient OPERATION characteristics while considering the impact on the environment and a manufacturing method thereof.

BACKGROUND

[0002] In recent years, along with the high performance of the automobile, the demand for high-performance gasoline with a high driving performance is energizing!]. On the other hand, environmental pollution due to motor fuels and their combustion exhaust gas has been One Do a social problem. Therefore, while maintaining a high driving performance, less automotive fuels environmental impact has been desired. In particular, from the viewpoint of exhaust gas Kiyoshii spoon and fuel economy improvement, further reduction of the sulfur content has been desired.

The [0003] JIS K 2202 is, Research Octane Number (RON) are 96.0 or more 1 No. automobile gasoline and 89.0 or more 2 No. motor gasoline is defined, the former as a high-performance premium gasoline, the latter It is commercially available as regular gasoline. Conventionally, Premium moth sled down is catalytically reformed gasoline base material, methyl substrate with more than 100 RON, such as t-butyl ether (MTBE), alkylate gasoline base material, 93 or more RON such as catalytic cracking gasoline components mainly substrate with, is produced by blending a variety of substrates! , Ru.

Cracked gasoline base material which is produced by decomposing [0004] The heavier petroleum fractions as compared to other gasoline base material, while there is an advantage that can be economically produced, contain high sulfur It was. As a result, most of the sulfur content in gasoline is produced as described above, it was derived from the degradation gasoline base material.

[0005] sulfur reduction of cracked gasoline base material is readily possible with the known art that purified hydrogenated in the presence of high pressure hydrogen and a catalyst. However, in that case, be included in many of catalytically cracked gasoline base material, high, since the Orefin fraction having a RON decreases the RON of hydrogenated in the substrate, sufficient driving performance in gasoline blended with it is such obtained, and, cormorants problems in flashing. [0006] On the other hand, a hydrocarbon oil, under certain conditions, desorption and process of contacting with the adsorbent Ru adsorbed sulfur I 匕合 product, the sulfur compounds from the adsorbent by venting hydrogen to the adsorbent by repeating about Surue to suppress unwanted reactions such as hydrogenation of Orefin, a method of continuously reducing the sulfur content in the hydrocarbon oil as the base material of the gasoline it has been proposed (Patent documents reference 1). While with force, a method of using such adsorbents also probably because due to certain hydrocarbon compounds containing organic in feedstock, the adsorption capacity of sulfur is inhibited to reduce the sulfur content efficiently «continue to it can not, such is necessarily a satisfactory way ChikaraTsuta. Patent Document 1: JP 2003- 277768 JP

Disclosure of the Invention

Problems that the Invention is to you'll solve

[0007] sulfur content of 1 mass ppm or less and Teigukatsu, sufficient practical performance to ensure the environmental gasoline, and a manufacturing method thereof has not been established yet. The present invention is, under such circumstances, to reduce the sulfur content, and it is an object to provide a lead-free gasoline composition and a manufacturing method thereof ensuring a sufficient driving characteristics.

Means for Solving the Problems

[0008] The present inventors have carried out an extensive study to solve the above problems, the Gen content perform desulfurization treatment other than hydrorefining using a fraction low V ヽ cracked naphtha, high! ヽ RON while maintaining the heading to be able to efficiently reduce sulfur and by using thus obtained substrate, we found that you unleaded gasoline composition ensuring a sufficient driving characteristics can be obtained, and she conceived the unleaded gasoline composition and the manufacturing method thereof of the present invention.

[0009] That is, the manufacturing method of the sulfur content of 1 mass ppm or less, and a research octane number (RO N) is unleaded gasoline composition is 89.0 or higher according to the present invention,

(1) 5 vol% distillation temperature of above 25 ° C, and 95 vol% distillation temperature of 210 ° C or less, Orefu in content of 5 vol% or more, a fraction cracked naphtha or less Zhen value of 0.3gZl00g desulfurization step of desulfurization treatment and,

(2) wherein (1) a blend mixing desulfurization cracked naphtha fraction obtained with other gasoline components in the desulfurization step of

including. [0010] Preferably, (1) in the step of advance Jen reduction processing through the Gen value is used 0.3GZl OOG following cracked naphtha fraction. That is, manufacturing method of unleaded gasoline composition of the present invention, compared cracked naphtha fraction of the feedstock, it is preferred to include a step of performing a pre-Jen reduction process. At this time, Jen reduction process, Group 8 elements when preferably be brought into contact with the catalyst device this comprising between periodic table cracked naphtha fraction of the feedstock, Jen reduction catalytic force cobalt or nickel force chosen at least: arbitrary is preferable that the invention will include L species.

[0011] Furthermore, the method for producing an unleaded gasoline composition of the present invention, (1) in the desulfurization process of decomposition naphthoquinone porous desulfurization agent having a vulcanized KiOsamuchaku function under a hydrogen partial pressure of IMPa following hydrogen coexist when it is preferred instrument this is in contact desulfurized with sub fraction, porous desulfurizing agent, copper, zinc, preferably contains at least one selected nickel and Tetsukakara.

In blending step (2), it is preferred to mix a 10 90 Capacity 0/0 desulfurizing cracked naphtha fraction and 90- 10 capacity% other gasoline components.

[0012] Further, the method for producing an unleaded gasoline composition of the present invention is more octane high ,, e.g. Li search RON of 93.0 or more, particularly in order to obtain the unleaded gasoline composition such 96.0 or higher, cracked naphtha fraction minute, 5 volume% distillation temperature of 25-43 ° C, and 95 vol% distillation temperature of 55- 100 ° C, Orefin content of 5 vol% or more, light cracked naphtha Gen value is less than 0.3gZl00g it is preferable to use a fraction in the desulfurization step (1).

Such light cracked naphtha fraction, even those obtained by fractionating the cracked naphtha fraction of the feedstock after Gen reduction process, or to fractionate the cracked naphtha fraction of the feedstock Jen even those obtained by reduction treatment, or fractionation and Jen reduction processing, even those obtained by performing at the same time, after.

In addition, before performing the fractionation to obtain a cracked naphtha fraction of light, or fractionated simultaneously with cracked naphtha fraction of the feedstock or Gen reduction processing was cracked naphtha fraction of the feedstock to, for containing Murrell sulfur compounds What child stranded 〖be folly Shi preferred that previously subjected to a pretreatment to increase the molecular weight, it is possible to sulfur contained in the light cracked naphtha fraction keep easily reduced.

[0013] A preferred method for producing the unleaded gasoline composition of the present invention, after the desulfurization treatment in such a light cracked naphtha fraction the above (1) step, in the blending process of the above (2), 10- 60 combined mixing and volume percent lighter desulfurized cracked naphtha fraction and 90- 40% by volume of other gasoline components, is a method for producing the unleaded gasoline composition is RON of 93.0 or more

[0014] unleaded gasoline composition according to the invention has a RON of 89.0 or more, 50 vol% distillation temperature of 105 ° C or less, Orefin content of 10 vol% or more, the total sulfur content of 1 mass ppm or less under, and proportion of Chiofen such sulfur compounds to the total sulfur content is not less than 50 wt% as sulfur.

Also preferably unleaded gasoline composition of the present invention has a RON is on 93.0 or more. More preferably, Orefi down fraction boiling range 35- 100 ° C in the total Orefuin content of 90 vol% or more, the proportion of coupling weighing Chiofen and 2-methylthiophene in the total sulfur content of more than 50 wt% as sulfur , and Z or, the content of thiols is 0.1 mass ppm or less as a sulfur content.

Effect of the invention

[0015] Particularly cracked naphtha fraction such as catalytically cracked gasoline and various cracked gasoline, Zhen compound is contained inevitably. When Jen acids are included, Te processing smell by porous desulfurization agent, Jen acids are preferentially adsorbed to the porous desulfurizing agent, the ability to adsorb (sorb) sulfur is impaired inhibitory. On the other hand, according to the present invention, pre-Jen performs processing for reducing, since the limit below 0. 3GZl00g Gen value, as possible out to long-lasting high sulfur sorption function. That is, the contact after the Gen removed cracked gasoline, under slight hydrogen coexistence, and desulfurized cracked naphtha fraction obtained by treating a porous desulfurizing agent having a sulfate KiOsamuchaku function, a sulfur content less 10 ppm by weight by mixing with other gasoline components, it is possible to produce a sulfur content of 1 mass p pm following unleaded gasoline composition. Since it is possible to also remove Chiofen such sulfur I 匕合 of cracked naphtha fraction in such catalytic cracking gasoline, light cracked naphtha fraction desulfurization processes such as cracked naphtha fraction containing a large amount of Chiofu E emissions such sulfur compounds it is possible. Further, Orefin component contained much in the light cracked naphtha fraction such as catalytically cracked light gasoline Do almost hydrogenated, so avoiding octane loss associated with the desulfurization process. Therefore, it is possible to reduce only the sulfur content to less than 1 ppm by mass without also unleaded gasoline composition forces are conventionally obtained changing the other properties photo command.

BEST MODE FOR CARRYING OUT THE INVENTION

[0016] The present invention, desulfurization step desulfurization process a cracked naphtha fraction having a specific properties, and the desulfurized cracked naphtha fraction obtained, the sulfur content including blending step of mixing with other gasoline components 1 mass ppm or less, and a research octane number is a manufacturing method of unleaded gasoline sets formed product is 89.0 or more. In the following description, the cracked naphtha fraction, will be described with proactively citing so-called Ru fluidized catalytic cracking gasoline (FCC gasoline), the present invention is Nag other at limited to F CC gasoline processes such as petroleum refining and petrochemical products obtained also device power, etc. intermediate products, such as thermal decomposition naphtha also generate pyrolyzer force, dewaxed naphtha to produce dewaxing unit power, cracked naphtha to produce naphtha cracker force or the like can be used as a cracked naphtha fraction. In short, 5 volume% distillation temperature of 2 5 ° C or more and 95 vol% distillation temperature of 210 ° C or less, Orefin content of 5 vol% or more, cracked naphtha di E emissions value is less than 0.3 g / 100 g it may be a fraction. Therefore, in addition to the cracked naphtha fraction of the so-called halls (whole), which was further fractionated by light cracked naphtha fraction obtained, or even heavy cracked naphtha fraction, the condition it is sufficient to satisfy. Note that these cracked naphtha 5 vol% distillation temperature of fraction 25-130 ° C, and 95 vol% distillation temperature is preferably from 55- 210 ° C. Further, in order to Gen value is used the following 0.3GZl00g, cracked naphtha fraction is processed facilities to reduce Jen detailing advance below, it is preferred to use those having the Gen value.

[0017] [Jen reduction processing]

Production method Nio unleaded gasoline composition of the present invention Te, previously performed Gen reducing process for cracked naphtha fraction such as FCC gasoline, Gen value to obtain a fraction cracked naphtha or less 0.3GZl00g. When Gen value is less than O. lgZlOOg, even more preferred. When Jefferies emissions value exceeds 0.3GZl00g, reduces the desulfurization performance of the multi-porous desulfurizing agent with sulfur sorption function used in the subsequent desulfurization step, in particular desulphurization of Chiofen such sulfur 匕合 product is difficult ing. Lowering of desulfurization performance can be known by an increase in the regeneration frequency of porous desulfurizing agent for retaining reduction in desulfurization rate in a unit processing amount, or a predetermined desulfurization rate. It was but connexion, it is good preferable to provide the force next desulfurization step is pretreated to reduce Jeni 匕合 thereof. However, in this Gen reduction process, because Orefin octane number is significantly decreased when Utati spoon to paraffin in the hydrogenation, preferably that Orefin to selective Gen reduction processing so as not to be hydrogenated.

[0018] Note that the Gen value here is a value measured by UOP326- 82.

Further, in Jen reduction process, by selecting the catalyst and the conditions used, the sulfur content may be reduced at the same time. That way, it is possible to extend the life of the porous desulfurization agent having a sorption function.

[0019] The method of Jen reduction process comprises contacting a catalytic cracking naphtha fraction and Jen reduction catalyst in the presence of hydrogen, to convert Zhen to Monoorefin, or the sulfides by reacting a sulfur compound to coexist with Gen Utati spoon way to the preferred U ヽ. Jen catalyst supporting at least one kind of periodic table Group 8 metal on an inorganic porous carrier such as alumina is preferably used as a reducing catalyst. Further, there is resistance to feedstock containing sulfur - catalysts comprising Tsu Kell or cobalt is still time so preferred. The reaction conditions, Jen number of contact decomposition naphtha fraction in is not more than 0.3gZlOOg and it is necessary to set the Orefin hydrogenation rate becomes 2 0% or less. Here, the Orefin hydrogenation rate, in the case where the Orefuin content of pretreatment with 100%, the reduction rate of Orefin content after treatment! Still, catalytic cracking naphtha fraction and Jen reduction catalyst hydrogen preferred have reaction conditions are contacted in the coexistence, the reaction temperature 40- 300 ° C, the reaction pressure 0.0- 4.0MPa (gauge pressure), LHSV 1.0- / OIL ratio of 1

Is one 100NL / L.

[0020] In the conventional power petroleum refining, have been carried out with selective hydrotreating child Gen in Orefin can be applied as a method for reducing the stringency in the present invention. Specifically [or, IFP Selective Hydrogenation process, Hules Selective Hydrogenation such process is preferably used (petroleum Gakkai petroleum refining process, p.62, Kodansha Saien Tifuiku, 1998, see).

In addition, as a method for reducing the stringency in the present invention, SHU process (21st JPI Petroleum Renning Conrerence 'Recent Progress in Petroleum Process Technology ", 37 (2002)) and CD Hydro process (NPRA 2001 Annual Meeting, AM- 01-39) it can be also used.

[0021] [catalytic cracking gasoline]

Te manufacturing method Nio ヽ unleaded gasoline composition of the present invention, catalytically cracked gasoline typically used as described above as a cracked naphtha fraction. Process for producing the catalytic cracking gasoline, catalytic cracking units, feedstocks may be employed any known manufacturing process Nag in limited in particular operating conditions. Straight catalytic cracking apparatus, amorphous silica-alumina, by using a catalyst such as Zeoraito, other petroleum fractions from gas oil to vacuum gas oil, de-gas oil while derived from heavy oil indirect desulfurization unit, obtained from the heavy oil direct desulfurization unit de heavy oil, which is then catalytically cracking etc. atmospheric Residue oil to obtain the high-octane gasoline base unit. For example, UOP catalytic cracking process that is listed in Petroleum Institute ed., "New oil refining process", flexi-cracking process, Ultra 'ortho-flow method, fluid catalytic cracking process, such as Texaco fluid catalytic cracking process, RCC method, residual, such as HOC method oils and the like fluidized catalytic cracking process.

[0022] In order to reduce the sulfur I 匕合 of cracked naphtha fraction in the feedstock and to petroleum fractions from gas oil to vacuum gas oil catalytic cracking unit, in particular the sulfur content 4000 ppm by mass or less, more preferably ί or 2000 ppm by weight or less, further [this ί or 1000 ppm by mass or less, it is preferable to use a fraction with reduced due hydrotreating below Japanese [this ί or 500 ppm by weight.

[0023] [desulfurization step]

In the desulfurization step in the method for producing the unleaded gasoline composition of the present invention, Jen titer was desulfurized fraction cracked naphtha or less 0.3 g ZlOOg, obtain desulfurization cracked naphtha fraction to be subjected to subsequent blending step. The sulfur content of the desulfurized cracked naphtha fraction obtained in the desulfurization step, 2 mass ppm preferably be desulfurized to less tool 1 mass ppm or less, further still more preferably can be below 0.5 ppm by weight. In the desulfurization step, since Chiofen such sulfur I 匕合 product of sulfur compounds is most likely to remain sulfur I 匕合 was Chiofu emissions such sulfur I in the total sulfur content of the desulfurized decomposition naphthoquinone in Sa fraction 匕合proportion of things 50 mass% or more sulfur, more preferably less than 70% by mass. Here, the Yo Chiofen such sulfur compounds, Chiofen, 2-methylthiophene, 2, is that the sulfur I 匕合 containing Chiofen skeleton in the molecule, such as 5-dimethyl-thiophene. Further, Orefuin content of desulfurized catalytically cracked gasoline is 5- 60 volume 0/0, and particularly preferably from 20- 40 volume%. The method of desulfurization process in [0024] the desulfurization step, a method of contacting a cracked naphtha fraction and desulfurization agent having a sorption function in the presence of hydrogen Shi preferred ヽ. In the presence of a hydrodesulfurization catalyst and hydrogen, in the method of hydrotreating processes cracked naphtha fraction, Orefin is the RON of the gasoline base material that is obtained is hydrogenated to produce by then and immediately or hydrodesulfurization reduction硫I 匕水 element is ease regenerate thiols react with Orefuin, therefore, is unsuitable because sufficiently desulfurized be a V ヽ. Since no sulfur is removed from the organic sulfur compounds when used desulfurizing agent having a sorption features regenerate react with Orefin immobilized on desulfurizing agent thiols preferred.

[0025] As the desulfurizing agent in the case of using a method of contacting a cracked naphtha fraction and desulfurizing agent having a sorption function of the sulfur is not particularly limited as long as it has a sorption function to sulfur I 匕合 product . Copper, zinc, porous desulfurizing agent containing at least one selected from nickel and iron are preferably used. Preferred desulfurizing agent, the metal component such as copper 0.5 85% by weight, particularly contains 1 one 80 wt%. Method for producing a desulfurizing agent is not particularly limited, component of the yo una porous carrier of alumina impregnated with a metal component such as copper, and manufacturing method of firing carrying, such as a metal component and an aluminum or copper by coprecipitation shaped precipitated bets, production method via a process such as baking may be mentioned as a preferable method. Further, molding, further metal components in the calcined de agents impregnated, carries, may be fired. Desulfurizing agent, to the fired also of the may be used as it is, may be used after treated in a hydrogen atmosphere. Specific surface area of the desulfurizing agent is preferably 30 m 2 Zg more, particularly 50- 600m 2 Zg. How the composition or manufacturing desulfurizing agent is not particularly limited, exemplified by the ヽ ones favored Japanese Patent No. 3324746, is disclosed in Japanese Patent No. 3230864 Patent Gazette and JP-A-11-61154 Ru such desulfurizing agent It is.

[0026] The porous desulfurization agent having a sulfur sorption function of the present invention, is fixed into desulfurizing agent sulfur atom in the organic sulfur compounds, hydrocarbon residues other than the sulfur atom in the organic sulfur compounds for a porous desulfurizing agent having a function to desorb the desulfurizing agent by cleaving the carbon-sulfur bonds in organosulfur I 匕合 thereof, earthenware pots. The hydrocarbon residue upon desorption, the carbon bond is cleaved with sulfur added is hydrogen present in the system. It was it would connexion, hydrocarbon compound organosulfur I 匕合 product force sulfur atom has been removed is obtained as product. However, the hydrocarbon compound having sulfur atom is removed is, may even be given further hydrogenation, isomerization, the products undergo reaction such as decomposition. Meanwhile, sulfur is to be immobilized on the desulfurizing agent, unlike the hydrotreating does not generate sulfur I 匕合 of such hydrogen sulfide as a product.

[0027] desulfurization, be carried out in Bruno Tutsi formula, Do may be performed by the flow method, but be carried out by circulating a cracked naphtha fraction to a fixed-bed desulfurizer packed with desulfurizing agent, desulfurization It preferred because agents desulfurization cracked naphtha fraction separation obtained with it conveniently. The temperature at which desulfurization treatment is 0- 40 0 ​​range force ° C can also be chosen, may preferably also select range force of 20- 380 ° C. Only contacted with the desulfurizing agent to facilitate desulfurization hardly desulfurized Chiofen acids, it may be performed desulfurization process coexist hydrogen. However, Orefin is hydrogenated, since the RON of the resulting gasoline base material to avoid a decrease, the hydrogen partial pressure is preferably less than 0.6MPa the gesture et preferred to less than IMPa. If a fixed-bed flow by contacting a cracked naphtha fraction and desulfurizing agent performs desulfurization process, LHSV is preferably selected from 0.01- lOOOOhr- 1 of range.

[0028] When producing the premium gasoline, gasoline base material used is high, and is desirable this with octane number. Also, the gasoline base material having a high octane number, even when the blend manufacturing a regular gasoline, preferable in widening the flexibility of the blend. By decomposition naphtha fraction further fractionated, a relatively high octane number of cracked naphtha fraction of light, di E emission reduction processing described above, a material obtained by desulfurization of the present invention is mixed with other gasoline components it is possible to produce unleaded gasoline set formed products.

[0029] light cracked naphtha fraction after fractionation and Jen reduction process, 5 volume% distillation temperature of 25 one 43 ° C, and 95 vol% distillation temperature of 55- 100 ° C, it is Orefin fraction 5 vol% or more, di-E emission value of the preferred device the light cracked naphtha fraction that is located below 0.3gZl00g, even those obtained by fractionation after Gen reduction processing, and fractionated Jen be those obtained by reduction treatment, or Jen reduction processing and fractionating may be of a obtained by performing simultaneously after. The movement, in advance of or fractionated to a fractionation, the previously subjected to a pretreatment to increase the molecular weight of the sulfur compounds, sulfur became large molecular weight to heavier decomposition naphtha fraction having a high boiling point , it is possible to without low sulfur content light cracked naphtha fraction in a simple operation. Hereinafter, the fractionation steps, and will be described in detail step of the pretreatment you increase the molecular weight of the sulfur I 匕合 thereof.

[0030] [fractional distillation process]

The fractionation step in the manufacturing method of the unleaded gasoline composition of the present invention, there is provided a 5 volume percent distillation temperature fractionating the catalytic cracking gasoline is 25.0- 43.0 ° C, and 95 vol% distillation temperature of 55.0 - obtain a cracked naphtha fraction of light, such as catalytically cracked light gasoline is 100.0 ° C. When 5 vol% distillation temperature is less than 25.0 ° C, the vapor pressure of the unleaded gasoline composition is increased. 95 vol% distillation temperature of 80.0 ° C, especially more than 100.0 ° C, the sulfur content of the desulfurized catalytically cracked light gasoline is high. 5 volume% distillation temperature or exceed 43.0 ° C, the 95 vol% distillation temperature or less than 55.0 ° C, or the One difficulty adjusting the distillation properties of the unleaded gasoline composition, in the fractional distillation step yield ratio of catalytically cracked light gasoline obtained or summer high cost of reduced unleaded gasoline composition.

[0031] catalytically cracked light gasoline obtained in the fractional distillation step preferably includes the Chiofen such sulfur compounds as a sulfur content 0.1 50 mass ppm. 20 mass ppm or less, further still more preferably is not more than 10 mass ppm. Chiofen such sulfur 匕合 product, because after a residual easily sulfur I 匕合 was the desulfurized catalytically cracked light gasoline obtained in the desulfurization treatment in the process, is catalytically cracked light gasoline obtained in the fractional distillation step , as containing Chi Ofen such sulfur I 匕合 was more than 50 ppm by mass as the sulfur content, the desulfurization step, undesirable operation cycle of the desulfurizing agent is shortened. Catalytically cracked light gasoline obtained in the fractional distillation step, Do contains Chiofen by force of less than 0.1 ppm by weight as sulfur, the rubbing 〖as, as it reduces the yield ratio of the catalytically cracked light gasoline is not preferable.

[0032] Further, in the fractionation step obtains a cracked naphtha fraction a light fractionating the catalytically cracked gasoline, of course, will also be produced relatively heavy cracked naphtha fraction. In this case, the present invention is intended to eliminate the fraction of heavy cracked naphtha 5 vol% distillation temperature of Nag is above 25 ° C, preferably 25-130 ° C, and 95 vol% distillation temperature of 210 ° C or less, preferably 55- 210 ° C, O Refuin content of 5 mass% or more, if Gen value is satisfies the following 0.3GZlOOg, unleaded gasoline composition of the present invention, the production of particularly relatively low-octane gasoline composition at low cost, it can be preferably used. Usually, catalytic cracking when heavy gasoline sulfur of the sulfur content multi instrument particularly catalytic cracking heavy gasoline than catalytically cracked light gasoline is 50 mass ppm, only the removed Jen, under coexistence of hydrogen When performing the processing by the desulfurizing agent having a sorption function, the life of the desulfurizing agent is considerably shortened. The contact for cracked heavy gasoline relatively Orefin small amount, if up to the sulfur content of about 5 ppm by weight in the hydrodesulfurization in the presence of hydrogen pressure, can desulfurization without compromising the relatively Okuta down titer loss it is. Therefore, the hydrodesulfurization in the hydrogen presence of high pressure, the Orefin hydrogenation rate of 20% or less, preferably the sulfur content in the catalytic cracking heavy gasoline while keeping 10% or less 20 mass ppm or less, preferably 10 mass pp m or less, more after reducing below 5 mass ppm, it is preferred to desulfurize performs processing by desulfurizing agent having a sorption function in the presence of hydrogen. Note that the reduction of Jen amount, during hydrodesulfurization can be carried out desulfurization and at the same time. Preferably in order to suppress the adverse effect of water hydrodesulfurization catalyst and hydrodesulfurization apparatus according Jen polymerization, it may be carried out in advance Jen reduction process.

[0033] Among other Chiofen such sulfur I 匕合 was Chiofen such sulfur compounds having at the 2-position an alkyl group, ease of most remaining desulfurized catalytically cracked light gasoline obtained in the desulfurization step, a sulfur compound. In catalytically cracked light gasoline in mainly Chiofen as Chiofen such sulfur I 匕合 thereof, 2-methylthiophene, as Chiofen such sulfur I 匕合 product with a force 2-position alkyl group include 3-methylthiophene 2 - methyl thiophene you relevant. Accordingly, in the fractional distillation step, not preferred is that you reduce the 2-methylthiophene. For this purpose, 95 vol% distillation temperature of 100.0 ° C at the time of fractionation, in particular 85.0 ° C, more preferably not more than 75 ° C. Since the 3-methylthiophene well below the gel and the 2-methylthiophene of 95 vol% distillation temperature during distillation to below 75 ° C is also not included almost catalytically cracked light gasoline, Chiofen metals contained this time sulfur it 匕合 was mainly a switch Ofen. Therefore, when 95 volume% distillation temperature of less than 75 ° C during fractionation, ease most remaining desulfurized catalytically cracked light gasoline obtained in the desulfurization step! /, Sulfur compounds becomes Chiofen.

[0034] [process before increasing the molecular weight of the sulfur compounds]

Catalytic cracking gasoline Nitsu to be subjected to a fractionation process! / ヽ Te, the molecular weight of the sulfur compound or subjected to a fractionation step is pretreated to greatly, or fractionation and it is preferable to perform a pretreatment to increase the molecular weight of the sulfur compounds simultaneously contained. By selectively increasing the molecular weight of the sulfur I 匕合 of such thiols, since the boiling point of the sulfur-containing Qiao 匕合 product is high, in partial cut step, catalytic cracking sulfur-containing Kyi 匕合 product can migrate to heavy gasoline, it is possible to reduce the sulfur content of the catalytically cracked light gasoline obtained in the fractional distillation process. Specifically, more preferred when the following total 0.1 pp m a content of thiols in catalytically cracked light gasoline sulfur.

[0035] In the conventional force oil refining, known ways scan Itoyungu is made to deodorize the product by treating the thiols, to convert the oxidation or oxidative extraction method, thiols to disulfide compounds It is applicable to the present invention us, Te as how to increase the molecular weight of the sulfur I 匕合 thereof. Specifically, Maalox method, a doctor method Ru are preferably used (Sangyo Tosho, oil refining technology Handbook third edition, 1981, see).

[0036] Further, as a method for increasing the molecular weight of the sulfur 匕合 product in the present invention, a method of reacting a sulfur I 匕合 product and Orefin metals contained in the cracked naphtha fraction also preferably used. In concrete terms, (see JP 2001-55584 Patent Gazette) a method of reacting the thiols and Orefin compound Ya thiols Ya Chiofen such a method of reacting with Orefuin acids ( "Production of Low bulfur Gasoline and Diesel Fuels :. Tier 2 and Beyond, Petroleum Refining Technology Seminar August 2001, 11- 18, reference), etc. also, particularly preferred good to use a process that can be molecular weight increasing treatment and Jen reduction processing of sulfur compounds at the same time . Specifically, said SHU process Ru preferably used. further, while fractionation, when so is preferred to use a process that can handle the Gen low reduction process simultaneously to increase the molecular weight of the sulfur compounds . Specifically, it said CD Hydro process is preferably used.

[0037] [Other gasoline base material used in the blending step]

Other gasoline base material which is mixed with a blend step, catalytically reformed gasoline base material, alkylate gasoline components, desulfurized treated substrate of virgin naphtha, isomer I spoon gasoline base material, produced from naphtha cracker naphtha substrate, toluene, xylene and MTBE, Echiru t Buchi ether (ETBE), t chromatography § mill E chill ether (TAEE), ethanol, the oxygen-containing gasoline components such as methanol, may be a known gasoline components . Other gasoline base material which is mixed with a blend step, the sulfur content is not more than 10 mass ppm, preferably 3 ppm by mass or less, more than 1 mass ppm, particularly preferably not more than 0.5 mass ppm. When the sulfur content of another gasoline base material exceeds 10 mass ppm, the amount of a blend step of the gasoline base material is restricted, it is not preferred.

[0038] A preferred amount is described for each research octane number. For example, a preferred blending amount in the case of research octane number is 96 102, a fraction desulfurized cracked naphtha 25 8 0% by volume, in particular 30 to 50 volume%, a catalytically reformed gasoline base material 25 50 volume% , especially 30 to 45 volume 0/0 of catalytically reformed gasoline, and 10 40 volume 0/0, especially from 15 30 volume 0/0.

The blending amount in the case of research octane number is 93- 96, the desulfurized cracked naphtha fraction 50 to 90 volume% and particularly 60- 80 volume%, contacting the reformate substrate 5 35% by volume, Japanese 10- 25 vol. 0/0 of catalytically reformed gasoline, and 10 25 volume 0/0, and particularly a 5-15 capacity%.

The blending amount in the case of research octane number is 89- 93, the desulfurized cracked naphtha fraction 55- 90% by volume, in particular 65 - 85 volume%, a catalytically reformed gasoline base material 0 20% by volume, in particular 5- 15% by volume of catalytically reformed gasoline, and 0-15% by volume, in particular at 0 10% by volume.

[0039] [Additives]

Furthermore, the gasoline composition of the present invention may be blended as required one or more known fuel oil additives in the art. These amounts are preferably the appropriate choice force normal to keep the total amount of the additives below 0.1 wt%. To exemplify fuel oil additive can be used in gasoline of the present invention, phenol-based, Sani 匕防 sealant such as an amine, Schiff type compounds, metal deactivators such as thioamide-type compounds, organophosphate surface ignition inhibitors such as compounds, succinimides, polyalkyl § Min, polyether § Min of any detergent-dispersant, anti-icing agents such as polyhydric alcohols or ethers thereof, § alkali metal salt or aralkyl force of an organic acid combustion aid such as Li earth metal salts, sulfuric esters of higher alcohols, Anion-based surfactants, cationic surfactants, antistatic agents such as amphoteric surfactants, there may be mentioned a colorant such as § zone dyes it can.

[0040] [unleaded gasoline composition]

Unleaded gasoline composition of the present invention has a RON of 89.0 or more, with 50 vol% distillation temperature of less 105 ° C, Orefin content of 10 vol% or more, the total sulfur content of 1 mass ppm or less under the total sulfur content proportion of Chiofu emissions such sulfur I 匕合 was occupied in is 50- 100 mass% as sulfur. Preferably, the lower limit of the RON of 93.0 or more, particularly 96.0 than on, the upper limit is usually 102.0 hereinafter Orefu in partial boiling range 35- 100 ° C in the total Orefuin content of 90 vol% or more, the total sulfur content It accounted Chiofen and 2-methyl ratio of coupling metering thiophene 50 mass% or more sulfur, more than 70 mass%, the content of thiols is below 0.1 mass ppm as a sulfur content.

[0041] Hereinafter, the present invention will be described more in detail with reference to Examples, the present invention is not intended to be limited to the following examples.

Adjustment of gasoline a certain material

After硫I匕Temperature: 300 ° C or with a solution of 2 wt%溶力the Jimechirujisuru Fuido catalyst 5 cm 3 carrying 20 mass% of nickel n- heptane alumina, reaction temperature 250 ° C, the reaction pressure atmospheric pressure , liquid hourly space velocity (LHSV) 4hr- under the condition of H ZOil ratio 340NLZL, Middle

2

Obtained by Tsuyu the resulting catalytically cracked gasoline A with the fluid catalytic cracking Gen reduction processing line ヽ, the catalytic cracking gasoline B to a vacuum gas oil fraction of the system oil that treated hydrotreating a main feed oil It was. Copper-zinc-aluminum composite Sani匕物prepared by coprecipitation (copper content 35% by mass, zinc content 35 mass%, aluminum content 5 mass%) was filled with 5 cm 3 in the reaction tube, to which hydrogen gas the 5 cm 3 Zmin, was 16hr circulation at a temperature of 200 ° C, was subjected to reduction treatment. Thereafter, the catalytically cracked gasoline B in the reaction tube, the reaction temperature 100 ° C, the reaction pressure atmospheric pressure, LHSV2.0hr- H ZOil ratio sorption features and based on 20 hours through oil conditions 0.06NLZL

2

To obtain a desulfurized catalytically cracked gasoline C was desulfurized by the desulfurization agent having. Properties of catalytically cracked gasoline A, catalytically cracked gasoline B and desulfurized catalytically cracked gasoline C were as shown in Table 1.

[0042] The density ί Contact IS K 2249, the vapor pressure ί Contact IS K 2258, distillation property ί Contact IS K 2254, Jen value was measured in accordance with UOP326- 82. Sulfur content was measured in accordance with ASTM D 5453 (ultraviolet fluorescence method). The content of sulfur compounds (sulfur equivalent), selectively detect by the chemiluminescent connexion sulfur compounds, using a Shimadzu gas chromatograph equipped with a ANTEK manufactured sulfur chemiluminescence detector to quantify, by gas chromatography It was measured. Hydrocarbon component composition and RON, using the Hewlett Packard PIONA device was measured by gas chromatography.

[0043] [Table 1]

[0044] catalytically cracked gasoline A the force catalytically cracked gasoline B was Jen value 0.6 g / 100 g is Jefferies down value of the O.lgZlOOg next Jen was substantially removed. Catalytically cracked gasoline B is desulfurized catalytically cracked gasoline C sulfur content 0.2 wt ppm was obtained by treatment with a force desulfurization agent contained sulfur content 5.0 mass ppm. The resulting desulfurized catalytically cracked gasoline C, such includes a force other sulfur I 匕合 product contained Chiofen acids 0.2 mass ppm ChikaraTsuta.

[0045] Preparation of gasoline certain material 2

The catalytically cracked gasoline D of another lot obtained from Likewise Middle East crude oil Preparation 1 of the gasoline components fractionated into light fraction and a heavy fraction, to obtain a catalytically cracked light gasoline E. Using this catalytically cracked light gasoline E, reaction temperature 200 ° C, except that the LHSV 2Hr- 1 and performs similarly Zhen reduction processing and preparation 1 of the gasoline base material, to obtain a catalytically cracked light gasoline F . Then, exactly the same procedure as in Preparation 1 of a gasoline base material, under the conditions to obtain a desulfurized catalytically cracked light gasoline G catalytically cracked light gasoline F and desulfurization. Catalytically cracked gasoline D, catalytically cracked light gasoline E, Characteristics of the catalytically cracked light gasoline F and desulfurized catalytically cracked light gasoline G was Table 2 Noto cage.

[Table 2] desulfurization

Catalytic cracking catalytic cracking catalytic cracking catalytic cracking

Gasoline light gasoline light gasoline light gasoline

DEFG

Density (1 5 ° C) [g / cm 3] 0.741 1 0.6704 0.6703 0.6700

Vapor pressure (37.8 ° C) [kPa] 58.0 96.0 95.0 94.5

Carbide 7 Ingredient Composition [% by volume]

Saturates 45.7 47.1 46.8 47.1

Orefin min 32.8 51.1 51.3 51.0

Aromatic content 21.5 1.8 1.9 1.9

RON 92.0 93.9 93.9 93.9

Jen value [gZ100g] 1.6 1.6 0.1 0.1 District

Sulfur content [wt ppm] 73 21 14 0.2

The content of sulfur compounds

[Terms of sulfur weight ppm]

Chiofen 4.9 7.2 6.9 0.0

2-methylthiophene 3.8 1.4 1.6 0.2

3-methylthiophene 4.3 1.5 1.6 0.0

C2 substituted one or more Chiofen 17.5 0.0 0.0 0.0

Benzochi old Fen class 24.9 0.0 0.0 0.0

C1 one Chio Ichiru 0.1 0.1 0.0 0.0

C2- thiol 3.5 5.2 0.0 0.0

C3- thiol 2.0 2.8 0.0 0.0

C4- thiol 0.7 0.5 0.0 0.0

C5 or more over Ji old Lumpur 7.3 0.0 0.3 0.0

Sulfides such 3.2 0.5 0.3 0.0

Disulfide compounds 0.0 0.0 0.0 0.0

Distillation characteristics [° C]

Initial boiling point 38.0 32.5 32.5 32.5

5 vol% distillation temperature 50.0 39.5 39.0 39.0

1 0 vol% distillation temperature 55.0 41.0 40.5 41.0

50 vol% distillation temperature 97.5 50.0 50.0 49.5

90 vol% distillation temperature 174.0 76.0 76.0 76.0

95 vol% distillation temperature 186.5 86.5 86.0 86.5

End point 204.0 121.0 121.5 120.5 [0047] catalytically cracked light gasoline E is Jen value 1.6 g, 100 g and a force catalytically cracked light gasoline F is Jen titer is O. lg / LOOG next Jen was substantially removed. Catalytically cracked light gasoline F is desulfurized catalytically cracked light gasoline G of sulfur 0.2 mass ppm is obtained by treatment with a force desulfurization agent contained sulfur content of 14 mass ppm. The resulting desulfurized catalytically cracked light gasoline G is 2-methyl-thiophene contained 0.2 mass ppm force Chiofen and 3-methylation thiophene comprise! / Was not.

[0048] Preparation of gasoline certain material 3

The catalytically cracked gasoline D to give a sweet and Jung treated catalytically cracked gasoline H. The catalytic cracking gasoline H fractionated into light fraction and a heavy fraction, to obtain a catalytically cracked light gasoline I. By the same method as Preparation 2 of gasoline components, it performs Gen reduction processing on the catalytically cracked light gasoline I, to obtain a catalytically cracked light gasoline J. The catalytically cracked light gasoline J, using copper-zinc composite Sani 匕物 prepared in Preparation 1 of a gasoline base material performs desulfurization under the same conditions as in Preparation 1 of a gasoline base material, desulfurized catalytically cracked light gasoline K It was obtained. 'Properties of catalytically cracked gasoline H, catalytically cracked light petrol I, catalytically cracked to remove Gen light petrol J and desulfurized catalytically cracked light gasoline K was as in Table 3.

[0049] [Table 3]

Catalytic cracking catalytic cracking catalytic cracking desulfurization catalytic cracking

Gasoline light gasoline light gasoline light gasoline

HIJK

Density (15 ° C) [g / cm 3] 0.741 1 0.6704 0.6704 0.6704

Vapor pressure (37.8 ° C) [kPa] 58.0 96.0 96.5 96.0

Hydrocarbon component composition [% by volume]

Saturates 45.7 47.0 47.1 46.9

Orefin min 32.8 51.2 50.9 51.1

Aromatic content 21.5 1.8 2.0 2.0

RON 92.0 93.9 93.9 93.9

Jen value [g / 100g] 1.6 1.6 0.1 0.1 District

Sulfur [Shitsusato ppm] 73 1 1 1 1 0.2

The content of sulfur compounds *

Chiofen 4.9 7.8 7.5 0.0

2-methylthiophene 3.8 1.4 1.5 0.2

3-methylthiophene 4.3 1.5 1.5 0.0

C2 substituted one or more Chiofen 17.5 0.0 0.0 0.0

Benzochiofen such 24.9 0.0 0.0 0.0

C1- thiol 0.0 0.0 0.0 0.0

C2- Chio Ichiru 0.0 0.0 0.0 0.0

C3- thiol 0.0 0.0 0.0 0.0

C4- thiol 0.0 0.0 0.0 0.0

C5 more - Chio - - Le 0.0 0.0 0.0 0.0

Sulfides such 3.2 0.5 0.2 0.0

Disulfide compounds 13.7 0.0 0.0 0.0

Distillation characteristics [° C]

Initial boiling point 38.0 32.5 32.5 32.0

5% by volume of distillate 50.0 39.5 39.5 39.0

1 0 vol% distillation temperature 55.0 41.0 41.0 41.0

50 vol% distillation temperature 97.5 50.0 50.0 49.5

90 vol% distillation temperature 174.0 76.5 76.0 75.5

95 vol% distillation temperature 186.5 86.0 86.0 86.5

The end 204.0 121.0 121.5 120.0

* The content of the sulfur compound is a sulfur-converted value (mass ppm).

Light thiols were included in the catalytically cracked gasoline D is a suite Jung processing Te cowpea, were Utati匕 the higher molecular weight disulfide compounds. Catalytically cracked light gasoline I is Jen value 1.6gZl00g a a force catalytically cracked light gasoline J is Jen titer O.lgZlOOg next Jen was substantially removed. Catalytically cracked light gasoline J, which had Nde contains sulfur of 11 ppm by weight, by treatment with a desulfurizing agent, the desulfurizing catalytically cracked light petrol K sulfur content 0.2 mass ppm was obtained. The resulting desulfurized catalytically cracked light gasoline K had a 2- Mechiruchiofue emissions 0.2 mass ppm comprise a! /, Were, but include Chiofen and 3-methylthiophene! /, Tsuta Naka. Thiols by suite Jung before fractional distillation to shift to heavies becomes disulfide, sulfur content of catalytically cracked light gasoline can be reduced to 11 mass ppm compared to 21 ppm by weight when no suite Jung. Accordingly, it is possible to reduce the load of the sorbent is believed that the sorbent can long life.

[0051] Preparation of gasoline certain material 4

Using copper zinc complex Sani 匕物 the catalytically cracked gasoline A and catalytically cracked light gasoline E were each hand prepared Preparation 1 of a gasoline base material performs desulfurization treatment under the same conditions as in Preparation 1 of a gasoline base material, desulfurization to obtain a catalytic cracking gasoline L and desulfurized catalytically cracked light gasoline M. Characteristics of the desulfurization contact touch cracked gasoline L and desulfurized catalytically cracked light gasoline M were as shown in Table 4.

[0052] [Table 4]

Desulfurization contact desulfurization catalytic cracking

Cracked gasoline L light gasoline M

Density (1 5 ° C) [g / cm 3] 0.7325 0.6704

Vapor pressure (37.8 ° C> [kPa] 72.0 96.0

Hydrocarbons off K Ingredient Composition [% by volume]

Saturated components 53.8 50.5

Orefin min 23.1 48.0

Aromatic content 23.1 1.5

RON 91.3 93.8

Jen flE [g / 100g] 0.6 1.6

Sulfur content [wt ppm] 3.6 11

The content of sulfur 1!匕合products

[[Delta] Yellow reduced mass ppm]

Chiofen class 3.6 10.7

Chiofen 0.6 7.8

2-methylthiophene 0.5 1.4

3-methylthiophene 0.5 1.5

C2 substituted one or more Chiofen 2.0 0.0

Benzochiofen class 0.0 0.0

Thiols 0.0 0.0

C1 Chioru 0.0 0.0

C2- thiol 0.0 0.0

C3- thiol 0.0 0.0

C4- thiol 0.0 0.0

C5 more - thiol 0.0 0.0

Sulfides such 0.0 0.0

Disulfide compounds 0.0 0.0

Distillation characteristics [° C]

Initial boiling point 31.5 32.5

5 vol% distillation temperature 40.0 39.0

1 0 vol% distillation temperature 45.0 41.5

50 vol% distillation temperature 89.5 50.0

90 vol% distillation temperature 166.0 76.0

95 vol% distillation temperature 178.0 86.5

The end 207.5 122.0

[0053] The desulfurized catalytically cracked gasoline L includes a 3.6 mass ppm sulfur, also desulfurized contact touch cracked light gasoline M are included sulfur 11 ppm by weight, both not removed Gen in it it is clear that the removal of the particular Doing sorption process Chiofen such sulfur I 匕合 product is difficult.

[0054] Preparation of gasoline certain material 5

As gasoline base obtained by known techniques other than catalytic cracking, desulfurization virgin naphtha N, contacting the reformed fuel oil 0, catalytically reformed heavy oil P, alkylate gasoline Q, there is ETBE substrate R, As a properties are shown in Table 5. Fuel oil O in catalytic reforming, a catalytically reformed gasoline, is obtained by distillation of a fraction rich in Torr E down. Catalytically reformed heavy oil P from catalytic reforming of gasoline, is obtained by distillation of aromatic than 11 A at 9 or more carbon atoms.

[Table 5]

* The content of the sulfur compound is a sulfur-converted value (mass ppm).

Example 1

The desulfurized straight run naphtha N 10.0 volume%, contacting the reformed fuel oil O 5.0% by volume, catalytically reformed heavy oil P 5.0 volume 0/0, and 5.0% by volume alkylate gasoline Q, of gasoline components preparation 1 desulfurized catalytically cracked gasoline C and 75.0 volume% formulation according, to prepare the unleaded gasoline composition S. Further, as additives, a coloring agent (Shiradi 匕学 manufactured CL-53) 2mg / L, an antioxidant (manufactured by Sumitomo Chemical Co., Ltd. Sumiraiza one 4ML) 20 mg / L, detergent-dispersant (BASF made Keropur A P-95) 100mg / L were each added mosquitoes 卩. The addition of the additive was carried out in exactly the same way even Nio, preparation of unleaded gasoline compositions of Examples and Comparative Examples below. Properties of the prepared unleaded gasoline composition S shown in Table 6.

Example 2 [0057] Further, desulfurized straight run naphtha N to 3.5 volume%, contacting the reformed fuel oil O 19.0% by volume, catalytically reformed heavy oil P 15.0 capacitance 0/0, the alkylate gasoline Q 23.0 and volume%, the desulfurized catalytically cracked light gasoline K preparation 3, wherein the gasoline base material is 39.5 volume% formulation was prepared unleaded gasoline composition T. The properties of the unleaded gasoline composition T shown in Table 6.

Example 3

[0058] desulfurization straight run naphtha N 6.0% by volume, contact the reformed fuel oil O 8.0% by volume, catalytically reformed heavy oil P 5.0 capacity 0/0, alkylate gasoline Q 8.0 capacity 0/0, and 6.0% by volume ETBE substrate R, the desulfurized catalytically cracked gasoline C of preparation 1, wherein the gasoline base material blended 67.0 volume% to prepare a lead-free gasoline compositions U. The properties of the unleaded gasoline composition U shown in Table 6.

Example 4

[0059] desulfurized straight run naphtha N 6.0 volume%, contacting the reformed fuel oil O 9.0% by volume, catalytically reformed heavy oil P 8.0% by volume, and 10.0% by volume alkylate gasoline Q, gasoline components desulfurized catalytically cracked gasoline C 57.0% by volume of preparation 1 Symbol placement of the desulfurized catalytically cracked light gasoline K preparation 3, wherein the gasoline base material 10.0 volume% formulation was prepared unleaded gasoline composition V. The properties of the unleaded gasoline composition V shown in Table 6.

[0060] [Table 6]

Comparative Example 1

Instead of using desulfurized catalytically cracked gasoline C, except for using the catalytically cracked gasoline A, in exactly the same formulation as in the actual Example 1 of unleaded gasoline composition S, and, prepare unleaded gasoline composition W. The properties of the unleaded gasoline composition W shown in Table 6. Comparative Example 2

[0062] Instead of using desulfurized catalytically cracked light gasoline K Preparation 3, wherein the gasoline base material, except for using the catalytically cracked light gasoline I Preparation 3, wherein the gasoline base material, unleaded gasoline composition of Example 2 in exactly the same formulation as in the object T, it was prepared unleaded gasoline composition X. The properties of the unleaded gasoline composition X shown in Table 6.

According to [0063] Table 6, unleaded gasoline composition S provided by the present invention, as compared to the unleaded gasoline composition W provided Te cowpea in the prior art, substantially changing the other properties Kotonagu sulfur it is clear that can reduce min below 1 mass ppm. Also, unleaded gasoline composition T that is provided by the present invention as compared to the corresponding unleaded gasoline composition X, the sulfur content Nag little altering other properties can be reduced to less than 1 mass ppm. Unleaded gasoline composition U that is provided by the present invention, V is also a sulfur can be reduced to less than 1 mass ppm.

[0064] Preparation of gasoline certain material 6

After suite Jung treated catalytically cracked gasoline AA obtained by processing similarly Middle Eastern crude different lots Preparation 1 of a gasoline base material with Preparation 1 above gasoline base material, a light fraction and a heavy fraction fractionated, was obtained as the heavies contact cracked heavy gasoline BB. Cobalt catalytic cracking heavy gasoline BB, catalyst supporting molybdenum and phosphorus on an alumina (cobalt-containing Yuryou 2.4 wt%, molybdenum content 9.4 wt%, phosphorus content 2.0 wt%) was used, reaction temperature 220 ° C , reaction pressure 1.0 MPa, under conditions of ZOil ratio 307NLZL

At performs Zhen reduction process, Gen value to remove Jen obtain catalytically cracked heavy gasoline CC below O.LgZl 200 g from 0.6GZl00g. This, Jen removing catalytic cracking heavy gasoline CC, exactly the same procedure as in Preparation 1 of a gasoline base material except for using 0.18NLZL the H ZOil ratio

2

, Desulfurized under the conditions to obtain a desulfurized catalytically cracked heavy gasoline DD sulfur content 0.9 wt ppm. The properties of the gasoline (catalytic cracking gasoline AA- desulfurized catalytically cracked heavy gasoline DD) shown in Table 7.

[0065] Preparation of gasoline certain material 7

Catalytically cracked heavy gasoline BB as preparation 6 of the gasoline base material, quite the same as in Preparation 1 of a gasoline base material except for a Kotonagu H / OU ratio performing Jen reduction processing was 0.18NL / L

2

Flip method, desulfurized under the conditions to obtain a desulfurized catalytically cracked heavy gasoline EE. The properties of the desulfurized catalytically cracked heavy gasoline EE shown in Table 7. [0066] [Table 7]

Example 5

[0067] desulfurized straight run naphtha N 10.0 volume%, contacting the reformed fuel oil O 7.0% by volume, catalytic reforming and 6.0% by volume of the heavy oil P 5.0 Capacity 0 alkylate gasoline Q, of gasoline components preparation 3 37.0% by volume desulfurized catalytically cracked light gasoline K description, and desulfurization catalytic cracking heavy gasoline DD preparation 6, wherein the gasoline base material is 35.0 volume% formulation was prepared Υ unleaded gasoline composition . The properties of the unleaded gasoline composition Υ shown in Table 6.

Comparative Example 3

[0068] except for using desulfurized catalytically decomposition heavy gasoline EE Preparation 7, wherein the gasoline base material in place of the desulfurization catalytic cracking heavy gasoline DD, prepared unleaded gasoline composition Z in the same manner as in Example 5 did. The properties of the unleaded gasoline composition Z shown in Table 6.

In [0069] Table 7 is compared with the desulfurized catalytically cracked heavy gasoline EE desulfurizing catalytically cracked heavy gasoline DD and adjustment made 7 gasoline base material preparation 6 of gasoline components, high Gen value, high sulfur content it can be seen or to sulfur be desulfurized by the desulfurization agent having a sorption function 1 mass ppm or less up is very difficult. Thus, the desulfurized catalytically cracked heavy gasoline DD was desulfurized by the desulfurization agent having a sorption capability after the Zhen reduction process, used in conjunction with a gasoline base material of other low sulfur, a sulfur content of 1 mass ppm or less in, can be easily prepared unleaded gasoline composition retained sufficient operating characteristics are as shown in the Table 6 and unleaded gasoline composition Y.

[0070] [Reference Example]

The same copper-zinc-aluminum composite as that described for preparation 1 of a gasoline base Sani匕物(copper content 35% by mass, zinc content 35 mass%, aluminum content 5 mass%) was filled with 5 cm 3 into the reaction tube , which was 16hr circulated at 5 cm 3 Zmin conditions the hydrogen gas, the reduction treatment having conducted. Thereafter, the containing toluene solution (100 ppm by mass of sulfur content) 263 ppm by weight Chiofen to the reaction tube, the reaction temperature 100 ° C, the reaction pressure atmospheric pressure, / Oil ratio

And based communication oil conditions 0.18NLZL, to give the product shown in Table 8.

[0071] The selectivity of Table 8 product

[Mol% of raw materials Chiofen Criteria

Hydrogen sulfide <0.1

Carbide 7l element

1-butene 76

cis- 2- butene 14

trans- 2- butene 7

n- butane 3

Chiofen tool 0.1

[0072] From Table carbide by treatment with copper-zinc-aluminum composite Sani 匕物 in presence of hydrogen, Chiofen force sulfur in the feedstock is removed, derived from hydrocarbon residues other than the sulfur atom in Chiofen while hydrogen is obtained as the product, not to produce hydrogen sulfide, it is clear that acts copper-zinc-aluminum composite Sani 匕物 is a porous desulfurizing agent having a sulfur sorption function of the present invention .

Industrial Applicability

[0073] The present invention is, after Gen remove cracked gasoline fraction, under slight hydrogen coexistence, was treated by a porous desulfurizing agent with sulfur sorption function, reduce sulfur content, leaving Orefin min, and desulfurized cracked naphtha fraction obtained by avoiding octane loss associated with the desulfurization process is the sulfur content of the sulfur content of 1 mass ppm or less of lead-free gasoline compositions for mixing the following other gasoline components 10 ppm by weight . Thus, it was possible to reduce only the sulfur content to less than 1 ppm by mass without changing photo command unleaded gasoline composition force other properties which have been obtained conventionally. Therefore, unleaded gasoline composition of the present invention is to maintain a high operating performance, it is useful as low V ヽ motor fuel environmental impact.

Claims

The scope of the claims
[1] 5 volume% distillation temperature of above 25 ° C, and 95 vol% distillation temperature of 210 ° C or less, Orefin content of 5 mass% or more, the desulfurization of a fraction cracked naphtha or less Zhen value of 0.3gZlOOg a desulfurization step to be processed, and the desulfurized cracked naphtha fraction obtained, and a blending step for mixing with other gasoline components, unleaded gasoline sulfur content is 1 mass ppm or less, and RON of 89.0 or more Processes for making compositions.
[2] to cracked naphtha fraction of the feedstock, the method for producing the unleaded gasoline composition of claim 1 comprising the step of performing Gen reduction processing by contacting the pre-Jen reduction catalyst.
[3] Jen reduction catalyst, method for producing the unleaded gasoline composition of claim 2 comprising at least one metal selected Group 8 elements in the periodic table force.
[4] at least one metal contained in Gen reduction catalyst, method for producing the unleaded gasoline composition according to claim 3, wherein the nickel or cobalt.
[5] desulfurization process, a porous desulfurizing agent cracked naphtha fraction and a hydrogen partial pressure with a sulfur sorption function
Method for producing the unleaded gasoline composition according to any one of claims 1 one 4 IMPa is to contact in the presence of the following hydrogen.
[6] The porous desulfurizing agent, copper, zinc, method for producing the unleaded gasoline composition of claim 5 which contains at least one selected nickel and Tetsuryoku.
[7] In the blending step, 10- 90 vol 0/0 desulfurizing cracked naphtha fraction and 90- 10 volume 0/0 mixed with other gasoline components of claim 1 one 6 unleaded according to any one of method for producing a gasoline composition.
[8] cracked naphtha fraction, 5 volume% distillation temperature of 25-43 ° C, and 95 vol% distillation temperature of 5 5-100 ° C, Orefin content of 5 mass% or more, Jen value of 0.3gZl00g manufacturing method according to claim 1 one 7 unleaded gasoline composition according to any one of a cracked naphtha fraction of light or less.
[9] light cracked naphtha fraction, is a force in which the cracked naphtha fraction of the feedstock obtained by fractionation after Gen reduction process, the fractionated said cracked naphtha fraction of the feedstock force and those obtained by Jen reduction processing after or unleaded gasoline composition according to claim 8 wherein in which fractionation and Jen reduction process cracked naphtha fraction in the feedstock was obtained by performing the same time the method of production.
[10] Before performing fractional distillation to obtain a cracked naphtha fraction of light, or fractionated simultaneously with cracked naphtha fraction of the feedstock or Gen reduction processing was cracked naphtha fraction of the feedstock to, sulfur compounds contained method for producing the unleaded gasoline composition of claim 9 for pretreatment to increase the molecular weight.
[11] In the blending step, mixing the 10-to 60 percent by volume of the lighter desulfurized cracked naphtha fraction and 90- 40 capacity% of other gasoline components, claim research octane number is 93.0 or more
Method of any 〖This unleaded gasoline composition according 8-10.
[12] RON of 89.0 or more, 50 vol% distillation temperature of 105 ° C or less, Orefin content of 10 vol% or more, the total sulfur content of less than 1 mass ppm, Chiofen such sulfur I in the total sulfur content 匕合unleaded gasoline composition ratio of the object is not less than 50 wt% as sulfur.
[13] RON of unleaded gasoline composition according to claim 12 is 93.0 or more.
[14] Orefuin content unleaded gasoline composition according to claim 13 Ru der 90 volume 0/0 or more boiling range 35- 100 ° C in the total Orefuin minute.
[15] unleaded gasoline composition of claim 13 percentage of the total amount of Chiofen and 2-methylthiophene in the total sulfur content is not less than 50% by mass as a sulfur content.
[16] unleaded gasoline composition according to any claim 12 15 Neu shift the content of thiols is below 0.1 mass ppm as a sulfur content.
PCT/JP2004/016115 2003-11-07 2004-10-29 Lead-free gasoline composition and method for production thereof WO2005044959A1 (en)

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