WO2005044959A1

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

Info

Publication number: WO2005044959A1
Application number: PCT/JP2004/016115
Authority: WO
Inventors: Yasuhiro Araki; Katsuaki Ishida
Original assignee: Japan Energy Corporation
Priority date: 2003-11-07
Filing date: 2004-10-29
Publication date: 2005-05-19
Also published as: EP1686166A4; JP2008156663A; CA2543953A1; JPWO2005044959A1; EP1686166A1; JP4932257B2; JP5024884B2; CA2543953C; KR20060113721A; US20070068849A1; KR101114742B1

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

Lead-free gasoline composition and method for producing the same

Technical field

The present invention relates to a lead-free gasoline composition with reduced impact on the environment and a method for producing the same.

In particular, the present invention relates to a lead-free gasoline composition having a sulfur content reduced to 1 ppm by mass or less and ensuring sufficient operation characteristics while considering the effect on the environment, and a method for producing the same.

Background art

[0002] In recent years, demand for high-performance gasoline having high driving performance has been increasing with the advancement of high-performance automobiles!]. On the other hand, environmental pollution caused by automobile fuel and its combustion exhaust gas has become a social problem. Therefore, there is a demand for a vehicle fuel that maintains high driving performance and has a low environmental impact. In particular, further reduction of sulfur content is desired from the viewpoints of exhaust gas purification and fuel efficiency improvement.

[0003] JIS K 2202 stipulates car gasoline No. 1 with a research octane number (RON) of 96.0 or more and gasoline No. 2 with a gasoline of 89.0 or more.The former is a high-performance premium gasoline, and the latter is gasoline. Commercially available as regular gasoline. Traditionally, premium gasoline has been used in catalytic reforming gasoline bases, bases with more than 100 RON, such as methyl tbutyl ether (MTBE), alkylate gasoline bases, and catalytic cracking gasoline bases, with more than 93 RONs. Manufactured by blending various base materials, centered on base materials with RU

[0004] Cracked gasoline bases produced by cracking heavy petroleum fractions have the advantage of being more economical to produce than other gasoline bases, but contain high sulfur content. Was. As a result, most of the sulfur content in gasoline produced as described above was derived from the cracked gasoline base material.

[0005] The sulfur content of the cracked gasoline base material can be easily reduced by a known technique of hydrorefining in the presence of high-pressure hydrogen and a catalyst. However, in that case, the catalytic cracking gasoline base material contains a large amount, and the high RON containing olefins are hydrogenated and the RON of the base material is reduced. If you can't get rid of the problem, you'll need to clarify the problem. [0006] On the other hand, a step of contacting a hydrocarbon oil with an adsorbent under specific conditions to adsorb the sulfur-containing compound, and desorbing sulfur compounds from the adsorbent by passing hydrogen through the adsorbent. By repeating the steps described above, a method has been proposed in which unnecessary reactions such as hydrogenation of olefins are suppressed, and the sulfur content in hydrocarbon oil as a base material of gasoline is continuously reduced (Patent Document 1). However, the method using such an adsorbent also reduces the sulfur content efficiently and continuously, probably because of the specific hydrocarbon compounds contained in the feedstock oil. I couldn't do it, and it wasn't always a satisfactory way. Patent Document 1: Japanese Patent Application Laid-Open No. 2003-277768

Disclosure of the invention

Problems to be solved by the invention

[0007] An environmentally friendly gasoline with a low sulfur content of 1 mass ppm or less and sufficient practical performance, and a method for producing the same have not yet been established. An object of the present invention is to provide a lead-free gasoline composition that reduces sulfur content and ensures sufficient operating characteristics under such circumstances, and a method for producing the same.

Means for solving the problem

[0008] The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems. As a result, when a desulfurization treatment other than hydrorefining is performed using a low-V ヽ cracked naphtha fraction, a high ヽ content is obtained. It has been found that sulfur content can be reduced efficiently while maintaining the above, and that a lead-free gasoline composition with sufficient operating characteristics can be obtained by using the base material thus obtained. A lead-free gasoline composition of the present invention and a method for producing the same have been conceived.

That is, the method for producing a lead-free gasoline composition having a sulfur content of 1 mass ppm or less and a research octane number (RON) of 89.0 or more according to the present invention comprises:

(1) Decomposed naphtha fraction having a 5% by volume distillation temperature of 25 ° C or more, a 95% by volume distillation temperature of 210 ° C or less, an olefin content of 5% by volume or more, and a Jen value of 0.3gZl00g or less. A desulfurization step for desulfurization, and

(2) A blending step of mixing the desulfurized cracked naphtha fraction obtained in the desulfurizing step (1) with another gasoline base material

including. [0010] Preferably, in the step (1), a decomposed naphtha fraction having a Gen value of 0.3 gZlOOg or less, which has been subjected to a Gen reduction treatment in advance, is used. That is, it is preferable that the method for producing a lead-free gasoline composition of the present invention includes a step of subjecting a crude oil of a cracked naphtha fraction to a Gen reduction treatment in advance. At this time, it is preferable to contact the feedstock oil of the cracked naphtha fraction with a catalyst containing an element of Group 8 of the periodic table. At least selected: preferably containing L species.

Further, in the method for producing a lead-free gasoline composition of the present invention, in the desulfurization step (1), a porous desulfurizing agent having a sulfur sorption function is decomposed in the presence of hydrogen having a hydrogen partial pressure of IMPa or less. In this case, desulfurization treatment is preferably performed by contacting with a sulfur fraction, and the porous desulfurizing agent preferably contains at least one selected from copper, zinc, nickel and iron.

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] In addition, the method for producing a lead-free gasoline composition of the present invention has a high octane number, for example, a research-method octane number of 93.0 or more, particularly 96.0 or more. Light naphtha has a 5% by volume distillation temperature of 25-43 ° C, a 95% by volume distillation temperature of 55-100 ° C, an olefin component of 5% by volume or more, and a Gen value of 0.3gZl00g or less. The fraction is preferably used in the desulfurization step (1).

Such a light cracked naphtha fraction may be obtained by subjecting the cracked naphtha fraction to a feedstock oil after the gen reduction treatment and then fractionating the crude cracked naphtha fraction, or may be a fractionated fraction of the cracked naphtha fraction. It may be obtained by performing a Gen reduction process later, or by performing a fractionation and a Gen reduction process simultaneously.

Further, before performing the fractionation to obtain a light cracked naphtha fraction, or simultaneously with the fractionation, the raw material oil of the cracked naphtha fraction or the raw oil of the cracked naphtha fraction that has been subjected to the gen reduction treatment is used to reduce the sulfur compounds contained therein. It is preferable to perform a pretreatment for increasing the molecular weight, so that the sulfur content in the light cracked naphtha fraction can be easily reduced.

[0013] A preferable method for producing the unleaded gasoline composition of the present invention is such a light cracked naphtha. After the fraction is desulfurized in the step (1), in the blending step (2), the light desulfurized cracked naphtha fraction of 10 to 60% by volume and another gasoline base material of 90 to 40% by volume are mixed. Is a method for producing unleaded gasoline compositions with a octane number of 93.0 or higher.

The unleaded gasoline composition according to the present invention has a research octane number of 89.0 or more, a 50% by volume distillation temperature of 105 ° C. or less, an olefin content of 10% by volume or more, a total sulfur content of 1 mass ppm or less, and The ratio of thiophene sulfur compounds to the total sulfur content is 50% by mass or more as the sulfur content.

Preferably, the unleaded gasoline composition of the present invention has a research octane number of 93.0 or more. More preferably, the olefin content in the boiling range of 35-100 ° C in the total olefin content is 90% by volume or more, and the total amount of thiophene and 2-methylthiophene in the total sulfur content is 50% by mass or more as the sulfur content. , And the content of Z or thiols is 0.1 mass ppm or less as sulfur content.

The invention's effect

[0015] Particularly, cracked naphtha fractions, such as catalytic cracked gasoline and various cracked gasolines, inevitably contain gens. When the gens are contained, the gens preferentially adsorb to the porous desulfurization agent in the treatment with the porous desulfurization agent, and the function of adsorbing (sorbing) sulfur is hindered. On the other hand, according to the present invention, since a process for reducing the Gen is performed in advance and the Gen value is limited to 0.3 gZ100 g or less, a high sulfur sorption function can be maintained for a long time. That is, after removing the catalytic cracking gasoline, the desulfurization cracked naphtha fraction obtained by treating with a porous desulfurizing agent having a sulfur sorption function in the presence of a small amount of hydrogen and a sulfur content of 10 mass ppm or less By mixing with another gasoline base material, it becomes possible to produce a lead-free gasoline composition having a sulfur content of 1 mass ppm or less. It is also possible to remove thiophene-sulfur disulfides in cracked naphtha fractions such as catalytic cracked gasoline, so desulfurization of light cracked naphtha fractions such as cracked naphtha fractions rich in thiophene-sulfur compounds is also possible. Is possible. In addition, since the olefin component contained in the light cracked naphtha fraction such as catalytic cracked light gasoline is hardly hydrogenated, octane loss due to desulfurization treatment can be avoided. Therefore, the power of the unleaded gasoline composition obtained in the past is almost the same as other properties. It is possible to reduce only the sulfur content to less than 1 ppm by mass with little change.

BEST MODE FOR CARRYING OUT THE INVENTION

[0016] The present invention provides a desulfurization step of desulfurizing a cracked naphtha fraction having a specific property, and a blending step of mixing the obtained desulfurized cracked naphtha fraction with another gasoline base material. This is a method for producing a lead-free gasoline composition with a octane number of 19.0 ppm or less and a research octane number of 89.0 or more. In the following description, as the cracked naphtha fraction, so-called fluid catalytic cracking gasoline (FCC gasoline) will be mainly cited and described, but the present invention is not limited to FCC gasoline and other Processes such as petroleum refining and petrochemicals, products that can obtain equipment power, and intermediate products, for example, thermal decomposition naphtha that also generates pyrolysis equipment power, dewaxing equipment power that generates dewaxing naphtha, and naphtha cracker power that generates cracking naphtha Can be used as a cracked naphtha fraction. In short, a decomposed naphtha with a 5% by volume distillation temperature of 25 ° C or more, a 95% by volume distillation temperature of 210 ° C or less, an olefin component of 5% by volume or more, and a Jen number of 0.3g / 100g or less. Any fraction may be used. Therefore, in addition to the so-called whole cracked naphtha fraction, a light cracked naphtha fraction obtained by further fractionating it or a heavy cracked naphtha fraction is also subject to the above conditions. You only have to satisfy. The 5% by volume distillation temperature of these cracked naphtha fractions is preferably 25 to 130 ° C, and the 95% by volume distillation temperature is preferably 55 to 210 ° C. Further, in order to use those having a Gen value of 0.3 gZl00 g or less, it is preferable to use a decomposed naphtha fraction which has been subjected to a process for reducing the Gen described below in detail and has the Gen value.

[Gen reduction processing]

According to the method for producing the lead-free gasoline composition of the present invention, a cracked naphtha fraction such as FCC gasoline is subjected in advance to a gen reduction treatment to obtain a cracked naphtha fraction having a gen value of 0.3 gZl00 g or less. It is even more preferred that the Gen value be less than O.lgZlOOg. If the gender value exceeds 0.3 g / 100 g, the desulfurization performance of the porous desulfurizing agent having a sulfur sorption function used in the subsequent desulfurization step will be reduced, and it will be particularly difficult to desulfurize thiophene sulfur conjugates. The decrease in the desulfurization performance can be known from the decrease in the desulfurization rate in the unit treatment amount or the increase in the frequency of regeneration of the porous desulfurization agent for maintaining the predetermined desulfurization rate. Therefore, it is preferable to perform a pre-treatment for reducing the amount of the jenny-dangling product and provide it to the subsequent desulfurization step. Good. However, in this jen reduction treatment step, if the olefin is hydrogenated and converted into paraffin, the octane number is greatly reduced. Therefore, it is preferable to perform a selective gen reduction treatment so that the olefin is not hydrogenated.

[0018] The Gen value here is a value measured by UOP326-82.

In addition, in the gen reduction treatment, the sulfur content can be reduced at the same time by selecting the catalyst and conditions to be used. By doing so, it is possible to extend the life of the porous desulfurizing agent having a sorption function.

[0019] In the method of the treatment for reducing gen, a gen-reducing catalyst is contacted with a catalytic cracking naphtha fraction in the presence of hydrogen to convert gen to monoolefin or to react sulfide with a sulfur compound coexisting to form sulfide. U ヽ is preferred. As the gen reduction catalyst, a catalyst in which at least one metal belonging to Group 8 of the periodic table is supported on an inorganic porous carrier such as alumina is preferably used. Furthermore, catalysts containing nickel or cobalt that are resistant to feedstocks containing sulfur are even more preferred. The reaction conditions must be set so that the Gen value in the catalytically-decomposed naphtha fraction is 0.3 gZlOOg or less and the olefin hydrogenation rate is 20% or less. Here, the hydrogenation rate of the olefin is the reduction rate of the olefin content after the treatment, assuming that the olefin content before the treatment is 100%. Preferred reaction conditions for contacting in the coexistence are reaction temperature 40-300 ° C, reaction pressure 0.0-4.0MPa (gauge pressure), LHSV 1.0- / OIL ratio 1

One is 100NL / L.

Conventionally In petroleum refining, the hydrogen in olefins is selectively hydrorefined, and the present invention can be applied as a method for reducing gen. Specifically, the IFP Selective Hydrogenation process and the Hules Selective Hydrogenation process are preferably used (see Petroleum Refining Process, edited by The Japan Petroleum Institute, p.62, Kodansha Sientifik, 1998).

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

[Catalytic cracking gasoline]

In the method for producing a lead-free gasoline composition of the present invention, as described above, catalytic cracking gasoline is typically used as a cracked naphtha fraction. The process for producing this catalytic cracking gasoline can employ any known production process that does not particularly limit the catalytic cracking device, the feedstock, and the operating conditions. The catalytic cracking unit uses catalysts such as amorphous silica alumina and zeolite to separate petroleum fractions from gas oil to vacuum gas oil, as well as direct gas oil obtained from heavy oil indirect desulfurization unit and direct oil desulphurization unit obtained from heavy oil direct desulfurization unit. This equipment obtains high octane gasoline base material by catalytic cracking of heavy oil, residual oil at normal pressure, etc. For example, UOP catalytic cracking, flexicracking, ultra-ortho-flow, Texaco fluid catalytic cracking and other fluid catalytic cracking methods, RCC method, HOC method, etc. There is an oil fluidized catalytic cracking method and the like.

[0022] In order to reduce the sulfur sulfide in the cracked naphtha fraction, a petroleum fraction from gas oil to reduced pressure gas oil, particularly the sulfur content of 4000 mass ppm or less, is used as the feed oil for the catalytic cracking unit. It is preferable to use a fraction reduced to 2,000 mass ppm or less, 1000 mass ppm or less, and especially 500 mass ppm or less by hydrorefining or the like.

[Desulfurization step]

In the desulfurization step in the method for producing a lead-free gasoline composition of the present invention, a cracked naphtha fraction having a Gen value of 0.3 g ZlOOg or less is desulfurized to obtain a desulfurized cracked naphtha fraction to be subjected to the next blending step. The sulfur content of the desulfurized cracked naphtha fraction obtained in the desulfurization step is desirably desulfurized to 2 mass ppm or less, more preferably 1 mass ppm or less, and even more preferably 0.5 mass ppm or less. In the desulfurization step, the thiophene-based sulfur conjugate is the most likely to remain among the sulfur compounds, and thus the thiophene-based sulfur conjugate included in the total sulfur in the desulfurized cracked naphtha fraction. The proportion of the substance is preferably 50% by mass or more, more preferably 70% by mass or more as a sulfur content. Here, the dithiophene sulfur compound means a sulfur-containing compound having a thiophene skeleton in a molecule such as thiophene, 2-methylthiophene, and 2,5-dimethylthiophene. Further, Orefuin content of desulfurized catalytically cracked gasoline is 5- 60 volume ^_0/0, and particularly preferably from 20- 40 volume%. [0024] The desulfurization method in the desulfurization step is preferably a method in which a desulfurizing agent having a sorption function and a cracked naphtha fraction are brought into contact in the presence of hydrogen. In the method of hydrorefining the cracked naphtha fraction in the presence of a hydrodesulfurization catalyst and hydrogen, the RON of the gasoline base material obtained by hydrogenation of olefins is reduced, and the RON is formed again immediately after hydrodesulfurization. Hydrogen sulfate reacts with olefin to easily regenerate thiols, which is not suitable because V ヽ cannot be sufficiently desulfurized. It is preferable to use a desulfurizing agent having a sorption function, since sulfur removed from the organic sulfur compound is immobilized on the desulfurizing agent and does not react with olefin to regenerate thiols.

[0025] In the case of using a method in which a desulfurizing agent having a sulfur sorbing function is brought into contact with a decomposed naphtha fraction, the desulfurizing agent is not particularly limited as long as it has a sorbing function for the sulfur-containing compound. . A porous desulfurizing agent containing at least one selected from copper, zinc, nickel and iron is preferably used. Preferred desulfurizing agents contain 0.5 to 85% by weight, especially 118 to 80% by weight of a metal component such as copper. The production method of the desulfurizing agent is not particularly limited, but a production method in which a porous carrier such as alumina is impregnated with a metal component such as copper and supported and fired, or a metal component such as copper and a component such as aluminum are coprecipitated. Is preferable as a production method of precipitating and subjecting to steps such as molding and baking. Further, the metal component may be further impregnated and supported on the shaped and fired desulfurizing agent and fired. As the desulfurizing agent, the fired one may be used as it is, or may be used after being treated in a hydrogen atmosphere. The specific surface area of the desulfurizing agent is preferably 30 m ² Zg or more, particularly 50 to 600 m ² Zg. The composition and production method of the desulfurizing agent are not particularly limited, but desulfurizing agents such as those disclosed in Japanese Patent Nos. 3324746, 3230864 and JP-A-11-61154 are preferred. Can be

[0026] The porous desulfurizing agent having a sulfur sorbing function of the present invention refers to a method of immobilizing a sulfur atom in an organic sulfur compound to a desulfurizing agent, and a method of removing a hydrocarbon residue other than a sulfur atom in the organic sulfur compound. As for the above, a porous desulfurizing agent having a function of releasing from a desulfurizing agent by cleavage of a carbon-sulfur bond in the organic sulfur conjugate is used. When the hydrocarbon residue is eliminated, hydrogen existing in the system is added to the carbon in which the bond with sulfur has been cleaved. As a result, hydrocarbon compounds from which sulfur atoms have been removed are obtained as products. Will be done. However, the hydrocarbon compound from which the sulfur atom has been removed may give a product that has undergone a reaction such as hydrogenation, isomerization, or decomposition. On the other hand, sulfur is immobilized in the desulfurizing agent, so unlike sulfur refining, it does not generate sulfur sulfides such as hydrogen sulfide as products.

[0027] The desulfurization treatment may be performed by a notch type or a flow type. However, the desulfurization treatment may be performed by flowing the decomposed naphtha fraction through a fixed-bed desulfurization tower filled with a desulfurizing agent. This is preferable because the agent and the desulfurized cracked naphtha fraction obtained can be easily separated. As the temperature for the desulfurization treatment, a force in a range of 0 to 400 ° C can be selected, and a force in a range of 20 to 380 ° C is preferably selected. In order to promote the desulfurization of thiophenes that are difficult to be desulfurized only by contacting with a desulfurizing agent, desulfurization treatment may be performed in the presence of hydrogen. However, the hydrogen partial pressure is preferably less than IMPa, and more preferably less than 0.6 MPa, in order to avoid the olefin being hydrogenated and the RON of the resulting gasoline substrate being reduced. When the desulfurization treatment is carried out by bringing the desulfurizing agent and the decomposed naphtha fraction into contact with each other in a fixed bed flow system, the LHSV is preferably selected from the range of 0.01 to 100 hr- ¹ .

When producing premium gasoline, it is desirable that the gasoline base material used has a high octane number. In addition, a gasoline base material having a high octane number is also preferable for blending for producing regular gasoline in order to increase the flexibility of the blend. The cracked naphtha fraction is further fractionated, and the light cracked naphtha fraction having a relatively high octane number is mixed with the above-mentioned gen reduction treatment and desulfurized product with another gasoline base material. Unleaded gasoline compositions can be produced.

[0029] The lightly decomposed naphtha fraction after the fractionation and the Gen reduction treatment has a 5% by volume distillation temperature of 25 to 43 ° C, a 95% by volume distillation temperature of 55 to 100 ° C, and an olefin component of 5%. It is preferable that the light cracked naphtha fraction, which preferably has a volume percentage of not less than 0.3 g and a value of not more than 0.3 g of Z00 g, is fractionated, even if it is obtained by fractionation after the treatment of reducing gen. It may be obtained by performing a Gen reduction process later, or may be obtained by performing a Gen reduction process and a fractionation simultaneously. If a pretreatment is performed to increase the molecular weight of the sulfur compound prior to or during fractionation, the sulfur with a higher molecular weight moves into the heavy naphtha fraction with a higher boiling point. The amount of sulfur in the light cracked naphtha fraction by simple operation. Can be eliminated. Hereinafter, the fractionation step and the pretreatment step for increasing the molecular weight of the sulfur conjugate will be described in more detail.

[Fractionation step]

In the fractionation step in the method for producing a lead-free gasoline composition of the present invention, the catalytic cracking gasoline is fractionated to have a 5% by volume distillation temperature of 25.0 to 43.0 ° C and a 95% by volume distillation temperature of 55.0%. — Obtain a light cracked naphtha fraction such as catalytic cracked light gasoline at 100.0 ° C. If the 5% by volume distillation temperature is less than 25.0 ° C, the vapor pressure of the unleaded gasoline composition will increase. When the 95% by volume distillation temperature exceeds 80.0 ° C, especially 100.0 ° C, the sulfur content of desulfurized catalytically cracked light gasoline increases. If the 5% by volume distilling temperature exceeds 43.0 ° C or the 95% by volume distilling temperature is less than 55.0 ° C, it becomes difficult to adjust the distillation properties of the unleaded gasoline composition, or in the fractionation process. The yield of the resulting catalytic cracked light gasoline is reduced, and the cost of unleaded gasoline compositions is increased.

[0031] The catalytic cracking light gasoline obtained in the fractionation step preferably contains 0.1 to 50 mass ppm of thiophene sulfur compounds as sulfur. Even more preferably, it is at most 20 ppm by mass, more preferably at most 10 ppm by mass. Since the thiophene sulfur ligated product is a sulfur ligated gasoline easily remaining in the desulfurized catalytically cracked light gasoline obtained in the desulfurization treatment in the subsequent step, the catalytically cracked light gasoline obtained in the fractionation process is used. If the thiophene sulfur conjugate having a sulfur content exceeding 50 ppm by mass is contained, the operation cycle of the desulfurizing agent in the desulfurization step is undesirably short. It is not preferable that the catalytically cracked light gasoline obtained in the fractionation step does not contain thiophene having a sulfur content of less than 0.1 ppm by mass, since the yield of the catalytically cracked light gasoline is reduced.

[0032] Further, if a catalytically cracked gasoline is fractionated in the fractionation step to obtain a lightly cracked naphtha fraction, naturally a relatively heavy cracked naphtha fraction is also produced. At this time, the present invention does not exclude a heavy cracked naphtha fraction. The 5% by volume distillation temperature is 25 ° C or more, preferably 25 to 130 ° C, and the 95% by volume distillation temperature is 210 ° C. Below, preferably 55-210 ° C, if the olefin content is 5% by mass or more and the Gen value is 0.3gZlOOg or less, the production of the unleaded gasoline composition of the present invention, particularly the gasoline composition having a relatively low octane number, is recommended. It can be suitably used at low cost. Normally, catalytic cracking heavy gasoline has a higher sulfur content than catalytic cracking light gasoline.Especially, when the sulfur content in catalytic cracking heavy gasoline is 50 mass ppm or more, only gen is removed and hydrogen is removed in the presence of hydrogen. Treatment with a sorbent desulfurizing agent significantly shortens the life of the desulfurizing agent. Since catalytic cracking heavy gasoline has a relatively small amount of olefin, desulfurization can be performed without impairing octane number loss even in the case of hydrodesulfurization in the presence of high-pressure hydrogen, up to a sulfur content of about 5 ppm by mass. It is. Therefore, by hydrodesulfurization in the presence of high-pressure hydrogen, the sulfur content in catalytically cracked heavy gasoline is reduced to 20 mass ppm or less, preferably 10 mass pp while keeping the olefin hydrogenation rate at 20% or less, preferably 10% or less. After reducing to less than m, more preferably less than 5 mass ppm, desulfurization is preferably carried out by treatment with a desulfurizing agent having a sorption function in the presence of hydrogen. The amount of gen can be reduced simultaneously with desulfurization in hydrodesulfurization. Preferably, in order to suppress adverse effects on the hydrodesulfurization catalyst and the hydrodesulfurization device due to the gen polymerization or the like, it is preferable to perform a gen reduction treatment in advance.

Among the thiophene sulfur conjugates, the thiophene sulfur compound having an alkyl group at the 2-position is the sulfur compound most likely to remain in the desulfurized catalytically cracked light gasoline obtained in the desulfurization step. In catalytically cracked light gasoline, thiophenes, which mainly contain thiophene, 2-methylthiophene, and 3-methylthiophene, are contained as thiophenes. —Methylthiophene is applicable. Therefore, it is preferable to reduce 2-methylthiophene in the fractionation step. For this purpose, the 95% by volume distillation temperature during fractionation is preferably 100.0 ° C, particularly 85.0 ° C, and more preferably 75 ° C or less. If the 95% by volume distillation temperature during the fractionation is reduced to 75 ° C or less, not only 2-methylthiophene but also 3-methylthiophene is hardly contained in the catalytically cracked light gasoline, so the thiophenes contained at this time The sulfur-based compound is mainly chioffen. Therefore, if the 95% by volume distillation temperature during fractional distillation is 75 ° C or less, it is most likely to remain in the desulfurized catalytically cracked light gasoline obtained in the desulfurization process! /, And the sulfur compound is thiophene.

[Pretreatment for Increasing Molecular Weight of Sulfur Compound]

About catalytic cracking gasoline for fractionation process! / Increase the molecular weight of the sulfur compounds contained It is preferable to perform a pretreatment to increase the molecular weight of the sulfur compound at the same time as the fractionation. Since the boiling point of the sulfur-containing compound is increased by selectively increasing the molecular weight of the sulfur-containing compound such as thiols, the sulfur-containing compound is catalytically decomposed in the fractionation step. It can be transferred into heavy gasoline and the sulfur content of catalytically cracked light gasoline obtained in the fractionation process can be reduced. Specifically, it is more preferable that the total content of thiols in the catalytic cracking light gasoline be 0.1 mass ppm or less in terms of sulfur content.

Conventional Power In petroleum refining, sweet jung is used to treat thiols to deodorize the product. A known method for converting thiols into disulfides by an oxidation method or an oxidative extraction method is known. Can be applied to the present invention as a method for increasing the molecular weight of the sulfur conjugate. Specifically, the Marlox method, the doctor method, and the like are preferably used (see Sangyo Tosho Co., Ltd., Petroleum Refining Technology Handbook, 3rd edition, 1981).

[0036] In the present invention, as a method for increasing the molecular weight of the sulfur-containing compound, a method of reacting the sulfur-containing compound and the olefins contained in the decomposed naphtha fraction is also suitably used. Specifically, a method of reacting thiols and olefins (see Japanese Patent Application Laid-Open No. 2001-55584) ゃ a method of reacting thiols ゃ thiophenes with olefins (“Production of Low bulfur Gasoline and Diesel Fuels”) : Tier 2 and Beyond, Petroleum Refining Technology Seminar August 2001, 11-18), and it is particularly preferable to use a process that can simultaneously increase the molecular weight of sulfur compounds and reduce gen. Specifically, the above-mentioned SHU process is preferably used, and it is more preferable to use a process that can simultaneously perform a process of increasing the molecular weight of the sulfur compound and a process of reducing the gen while performing fractionation. Specifically, the aforementioned CD Hydro process is preferably used.

[Other Gasoline Base Material Used in Blending Step]

Other gasoline base materials to be mixed in the blending process include a catalytic reforming gasoline base material, an alkylate gasoline base material, a base material obtained by desulfurizing a straight-run naphtha, a isomeride gasoline base material, and a naphtha formed from a naphtha cracker. Base material, toluene, xylene and MTBE, ethyl t-butyl ether (ETBE), t-amyl ethyl ether (TAEE), ethanol, methanol, etc. A known gasoline base material such as an oxygen-containing gasoline base material can be used. The other gasoline base material mixed in the blending step has a sulfur content of 10 mass ppm or less, preferably 3 mass ppm or less, more preferably 1 mass ppm or less, and particularly preferably 0.5 mass ppm or less. If the sulfur content of another gasoline base exceeds 10 ppm by mass, the amount of the gasoline base in the blending step is undesirably limited.

[0038] Preferable blending amounts will be described for each research octane number. For example, when the octane number of the research method is 96-102, the preferred compounding amount is 25-80% by volume, particularly 30-50% by volume of the desulfurized cracked naphtha fraction, and 25-50% by volume of the catalytic reforming gasoline base material. , especially 30 to 45 volume ^_0/0 of catalytically reformed gasoline, and 10 40 volume ^_0/0, especially from 15 30 volume ^_0/0.

When the octane number of the research method is 93-96, the preferred compounding amount is 50-90% by volume, particularly 60-80% by volume of the desulfurized cracked naphtha fraction, and 5-35% by volume of the catalytic reforming gasoline base material. 10- 25 vol. ^_0/0 of catalytically reformed gasoline, and 10 25 volume ^_0/0, and particularly a 5-15 capacity%.

When the octane number of the research method is 89-93, the preferred compounding amount is 55-90% by volume, particularly 65-85% by volume of the desulfurized cracked naphtha fraction, and 0-20% by volume of the catalytic reforming gasoline base material. 5-15% by volume, alkylate gasoline base material is 0-15% by volume, especially 0-10% by volume.

[Additive]

Further, one or more fuel oil additives known in the art can be added to the gasoline composition of the present invention as needed. The amount of these additives can be appropriately selected. Usually, it is preferable to maintain the total amount of additives at 0.1% by mass or less. Examples of fuel oil additives that can be used in the gasoline of the present invention include phenol-based and amine-based antioxidants, metal deactivators such as Schiff-type compounds and thioamide-type compounds, and organic phosphorus-based additives. Surface ignition inhibitors such as compounds, detergents and dispersants such as succinimide, polyalkylamines and polyetheramines, antifreeze agents such as polyhydric alcohols or their ethers, alkali metal salts of organic acids or alkaline acids Antistatic agents such as lithium earth metal salts, sulfuric esters of higher alcohols, etc., anionic surfactants, cationic surfactants, amphoteric surfactants, etc. Coloring agents such as blocking agents and azo dyes can be mentioned.

[Lead-free gasoline composition]

The unleaded gasoline composition of the present invention has a research octane number of 89.0 or more, a 50% by volume distillation temperature of 105 ° C or less, an olefin content of 10% by volume or more, a total sulfur content of 1 mass ppm or less, and a total sulfur content of The ratio of thiophene-based sulfur conjugates in the total is 50-100% by mass in terms of sulfur content. Preferably, the lower limit of the octane number of the research method is 93.0 or more, particularly 96.0 or more, the upper limit is usually 102.0 or less, the boiling point occupying 35 to 100 ° C in the total olefin content is 90% by volume or more, and the total sulfur content is 90% or more. Of the total weight of thiophene and 2-methylthiophene in sulfur is 50% by mass or more, more preferably 70% by mass or more, and the content of thiols is 0.1% by mass or less as sulfur.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the following examples.

Gasoline material

A catalyst containing 20% by mass of nickel on alumina, 5 cm ³ of a solution of 2% by mass of dimethyl disulphide in n-heptane, was filtered at 300 ° C, and then the reaction temperature was 250 ° C and the reaction pressure was normal pressure. , Liquid hourly space velocity (LHSV) 4hr— H ZOil ratio 340NLZL, Middle East

2

The catalytic cracking gasoline A obtained by fluid catalytic cracking using the hydrorefining of the vacuum gas oil fraction of the crude oil as the main feed oil is passed through the oil to perform the gen reduction treatment to obtain catalytic cracking gasoline B. Was. A reaction tube was charged with 5 cm ³ of copper-zinc-aluminum composite oxide (copper content 35% by mass, zinc content 35% by mass, aluminum content 5% by mass) prepared by a coprecipitation method, and hydrogen gas was added thereto. Was flowed under the conditions of 5 cm ³ Zmin and a temperature of 200 ° C. for 16 hours to perform a reduction treatment. After that, catalytic cracking gasoline B is passed through this reaction tube for 20 hours under the conditions of a reaction temperature of 100 ° C, a reaction pressure of normal pressure, and an LHSV of 2.0 hours—HZOil ratio of 0.06NLZL for 20 hours for sorption function.

2

Catalytically cracked gasoline C desulfurized with a desulfurizing agent having Table 1 shows the properties of catalytic cracking gasoline A, catalytic cracking gasoline B, and desulfurizing catalytic cracking gasoline C.

[0042] The density ί ISK 2249, the vapor pressure ί IS K 2258, the distillation properties ί IS K 2254, and the Gen value were measured in accordance with UOP326-82. The sulfur content was measured according to ASTM D 5453 (ultraviolet fluorescence method). The sulfur compound content (sulfur conversion) is determined by chemiluminescence. Then, using a gas chromatograph made by Shimadzu Corporation equipped with an ANTEK sulfur chemiluminescence detector for selectively detecting and quantifying sulfur compounds, the measurement was carried out by gas chromatography. The hydrocarbon component composition and RON were measured by gas chromatography using a PIONA apparatus manufactured by Hewlett-Packard Company.

[Table 1]

[0044] Catalytic cracking gasoline A had a Gen value of 0.6g / 100g. Catalytic cracking gasoline B had a Gen value of O.lgZlOOg, and almost all of the Gen was removed. Catalytic cracking gasoline B had a sulfur content of 5.0 mass ppm and was treated with a force desulfurizing agent to obtain desulfurization catalytic cracking gasoline C with a sulfur content of 0.2 mass ppm. The resulting desulfurized catalytic cracking gasoline C had a power containing 0.2 mass ppm of thiophenes and no other sulfur-containing compounds.

[0045] Preparation of certain materials for gasoline 2

Contact of another lot obtained from Middle Eastern crude oil in the same manner as in preparation of the gasoline base material 1 Cracked gasoline D was fractionated into light and heavy fractions to obtain catalytic cracked light gasoline E. Using this catalytic cracked light gasoline E, the reaction temperature was set to 200 ° C and the LHSV was set to 2 hours- ^1. Gen reduction treatment was performed in the same manner as in Preparation 1 of the gasoline base material, to obtain catalytic cracked light gasoline F. . Next, catalytic cracking light gasoline F was desulfurized under exactly the same method and conditions as in preparation 1 of gasoline base material to obtain desulfurized catalytic cracking light gasoline G. Table 2 shows the properties of catalytic cracking gasoline D, catalytic cracking light gasoline E, catalytic cracking light gasoline F, and desulfurizing catalytic cracking light gasoline G.

[Table 2] Desulfurization

Catalytic cracking catalytic cracking catalytic cracking catalytic cracking

Gasoline Light gasoline Light gasoline Light gasoline

D E F G

Density ( ¹⁵ ° 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

Composition of elemental carbon carbide [% by volume]

Saturation 45.7 47.1 46.8 47.1

Orefin 32.8 51.1 51.3 51.0

Aromatic 21.5 1.8 1.9 1.9

RON 92.0 93.9 93.9 93.9

Gen value [gZ100g] 1.6 1.6 0.1

Sulfur content [mass ppm] 73 21 14 0.2

Sulfur compound content

[Sulfur conversion mass ppm]

Zofen 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 or more Thiophene 17.5 0.0 0.0 0.0

Benzothiable phens 24.9 0.0 0.0 0.0

C1 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 higher 7.3 0.0 0.3 0.0

Sulfides 3.2 0.5 0.3 0.0

Disulfides 0.0 0.0 0.0 0.0

Distillation properties [° C]

First stop 38.0 32.5 32.5 32.5

5% by volume distillation temperature 50.0 39.5 39.0 39.0

10% by volume distillation temperature 55.0 41.0 40.5 41.0

50% by volume distillation temperature 97.5 50.0 50.0 49.5

90% by volume distillation temperature 174.0 76.0 76.0 76.0

95% by volume distillation temperature 186.5 86.5 86.0 86.5

End point 204.0 121.0 121.5 120.5 [0047] Catalytic cracking light gasoline E had a Gen value of 1.6g and 100g. Catalytic cracking light gasoline F had a Gen value of O.lg / lOOg and almost all of the Gen was removed. Catalytic cracked light gasoline F contained 14 mass ppm of sulfur. Treatment with a force desulfurizing agent yielded desulfurized catalytically cracked light gasoline G with a sulfur content of 0.2 mass ppm. The resulting desulfurized catalytic cracking light gasoline G did not contain thiophene and 3-methylthiophene which contained 0.2 mass ppm of 2-methylthiophene! /.

[0048] Preparation of certain materials for gasoline 3

Catalytic cracking gasoline D was subjected to sweet Jung treatment to obtain catalytic cracking gasoline H. Catalytic cracking gasoline H was fractionated into light and heavy fractions to obtain catalytic cracking light gasoline I. In the same manner as in preparation of gasoline base material 2, catalytic cracking light gasoline I was subjected to gen reduction treatment to obtain catalytic cracking light gasoline J. This catalytic cracked light gasoline J was subjected to desulfurization treatment using the copper-zinc composite oxidized product prepared in gasoline base material preparation 1 under the same conditions as in gasoline base material preparation 1. Got. Table 3 shows the properties of catalytic cracking gasoline H, catalytic cracking light gasoline I, catalytic cracking light gasoline J without gen, and desulfurization catalytic cracking light gasoline K.

[Table 3]

Catalytic cracking catalytic cracking catalytic cracking desulfurization catalytic cracking

Gasoline Light gasoline Light gasoline Light gasoline

H I J K

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]

Saturation 45.7 47.0 47.1 46.9

Orefin 32.8 51.2 50.9 51.1

Aromatic 21.5 1.8 2.0 2.0

RON 92.0 93.9 93.9 93.9

Gen value [g / 100g] 1.6 1.6 0.1

Sulfur content [ppm] 73 1 1 1 1 0.2

Sulfur compound content *

Zofen 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 or more Thiophene 17.5 0.0 0.0 0.0

Benzothiophenes 24.9 0.0 0.0 0.0

C1—Thiol 0.0 0.0 0.0 0.0

C2—Chill 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 or higher—Chain-0.0 0.0 0.0 0.0

Sulfides 3.2 0.5 0.2 0.0

Disulfides 13.7 0.0 0.0 0.0

Distillation properties [° C]

First stop 38.0 32.5 32.5 32.0

5 volume% distillation 50.0 39.5 39.5 39.0

10% by volume distillation temperature 55.0 41.0 41.0 41.0

50% by volume distillation temperature 97.5 50.0 50.0 49.5

90% by volume distillation temperature 174.0 76.5 76.0 75.5

95% by volume distillation temperature 186.5 86.0 86.0 86.5

End point 204.0 121.0 121.5 120.0

* Sulfur compound content is the value in terms of sulfur (ppm by mass).

Light thiols contained in catalytic cracking gasoline D were converted to higher molecular weight disulfides by sweet Jung treatment. Catalytic cracking light gasoline I had a Gen value of 1.6gZl00g. Catalytic cracking light gasoline J had a Gen value of O.lgZlOOg, and gen was almost completely removed. Catalytically cracked light gasoline J contained 11 mass ppm of sulfur, but by treatment with a desulfurizing agent, desulfurized catalytically cracked light gasoline K with a sulfur content of 0.2 mass ppm was obtained. The resulting desulfurized catalytically cracked light gasoline K contains 0.2 mass ppm of 2-methylthiophene! /, But contains thiophene and 3-methylthiophene! / I got it. By performing sweet jung before fractionation, thiols become disulfides and transfer to heavy components, so that the sulfur content in catalytically cracked light gasoline can be reduced to 11 mass ppm compared to 21 mass ppm without sweet jung. As a result, the load of the sorbent can be reduced, and the life of the sorbent can be extended.

[0051] Preparation of certain materials for gasoline 4

Catalytic cracking gasoline A and catalytic cracking light gasoline E were each desulfurized using the copper-zinc composite oxide prepared in gasoline base preparation 1 under the same conditions as gasoline base preparation 1. Catalytic cracking gasoline L and desulfurization catalytic cracking light gasoline M were obtained. Table 4 shows the properties of desulfurized catalytic cracked gasoline L and desulfurized catalytic cracked light gasoline M.

[Table 4]

Desulfurization contact Desulfurization catalytic decomposition

Cracked gasoline L Light gasoline M

Density ( ¹⁵ ° C) [g / cm ³ ] 0.7325 0.6704

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

K element composition [volume%]

Saturation 53.8 50.5

Orefin 23.1 48.0

Aromatic content 23.1 1.5

RON 91.3 93.8

Gen flE [g / 100g] 0.6 1.6

Sulfur content [mass ppm] 3.6 11

Sulfur ¹ ! The content of the compound

[δ yellow equivalent mass ppm]

Thiophenes 3.6 10.7

Zofen 0.6 7.8

2-Methylthiophene 0.5 1.4

3-methylthiophene 0.5 1.5

C2 substituted or higher thiophene 2.0 0.0

Benzothiophenes 0.0 0.0

Thiols 0.0 0.0

C1-thiol 0.0 0.0

C2-thiol 0.0 0.0

C3—thiol 0.0 0.0

C4—Thiol 0.0 0.0

C5 or higher—thiol 0.0 0.0

Sulfides 0.0 0.0

Disulphides 0.0 0.0

Distillation properties [° C]

First stop 31.5 32.5

5% by volume distillation temperature 40.0 39.0

10% by volume distillation temperature 45.0 41.5

50% by volume distillation temperature 89.5 50.0

90% by volume distillation temperature 166.0 76.0

95% by volume distillation temperature 178.0 86.5

End point 207.5 122.0

[0053] The desulfurized catalytic cracking gasoline L contains 3.6 mass ppm of sulfur, and the desulfurized catalytic cracking light gasoline M contains 11 mass ppm of sulfur, and neither removes gen. It is clear that it is difficult to remove the thiophene sulfur conjugate particularly when the sorption treatment is performed.

[0054] Preparation of certain materials for gasoline 5

Gasoline base materials obtained by known techniques other than catalytic cracking include desulfurized straight-run naphtha N, catalytically modified medium oil 0, catalytically modified heavy oil P, alkylated gasoline Q, and ETBE substrate R. The properties are as shown in Table 5. Catalytic reforming medium oil O is obtained by distilling off a fraction rich in toluene from catalytic reforming gasoline. The catalytically modified heavy oil P is obtained by distilling and separating aromatics having 9 or more carbon atoms and less than 11 carbon atoms from catalytically modified gasoline.

[Table 5]

* Sulfur compound content is a value (mass ppm) converted to sulfur.

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 75.0% by volume of the desulfurized catalytic cracking gasoline C described in Preparation 1 was blended to prepare a lead-free gasoline composition S. In addition, as an additive, a coloring agent (CL-53, manufactured by Shiradio Kagaku) 2 mg / L, an antioxidant (Sumilyzer-1 4ML, manufactured by Sumitomo Chemical Co., Ltd.) 20 mg / L, a detergent and dispersant (Keropur A P-95, manufactured by BSF) 100 mg / L each was added. The addition of this additive was carried out in exactly the same manner as in the preparation of the lead-free gasoline compositions of the following Examples and Comparative Examples. Table 6 shows the properties of the prepared unleaded gasoline composition S.

Example 2 [0057] Further, the desulfurized straight run naphtha N 3.5 volume%, contacting the reformed fuel oil O 19.0% by volume, catalytically reformed heavy oil P 15.0 capacitance ^_0/0, and 23.0 volume% alkylate gasoline Q Preparation of Gasoline Base Material 39.5% by volume of desulfurized catalytic cracking light gasoline K described in 3 was blended to prepare a lead-free gasoline composition T. Table 6 shows the properties of unleaded gasoline composition T.

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, 6.0% by volume of ETBE base material R and 67.0% by volume of desulfurized catalytic cracking gasoline C described in Preparation of gasoline base material 1 were blended to prepare lead-free gasoline composition U. Table 6 shows the properties of unleaded gasoline composition U.

Example 4

[0059] Gasoline base material: 6.0% by volume of desulfurized straight-run naphtha N, 9.0% by volume of catalytic reforming medium oil O, 8.0% by volume of catalytic reforming heavy oil P, and 10.0% by volume of alkylated gasoline Q Preparation of desulfurized catalytically cracked gasoline C described in 1 above, 57.0% by volume of gasoline base material, and 10.0% by volume of desulfurized catalytically cracked light gasoline K described in 3 were blended to prepare a lead-free gasoline composition V. Table 6 shows the properties of lead-free gasoline composition V.

[Table 6]

Comparative Example 1

An unleaded gasoline composition W was prepared with exactly the same formulation as in the unleaded gasoline composition S of Example 1, except that catalytic cracking gasoline A was used instead of desulfurized catalytic cracking gasoline C. Table 6 shows the properties of unleaded gasoline composition W. Comparative Example 2

[0062] Preparation of gasoline base material The lead-free gasoline composition of Example 2 was used except that the catalytically cracked light gasoline I described in Preparation 3 of Gasoline was used instead of using the desulfurized catalytically cracked light gasoline K described in 3 An unleaded gasoline composition X was prepared with exactly the same formulation as in the case of the composition. Table 6 shows the properties of the lead-free gasoline composition X.

[0063] According to Table 6, the unleaded gasoline composition S provided by the present invention is compared with the unleaded gasoline composition W provided by the prior art, and has almost no change in other properties. It is clear that the fraction can be reduced to less than 1 ppm by mass. In addition, the unleaded gasoline composition T provided by the present invention can reduce the sulfur content to 1 mass ppm or less without substantially changing other properties as compared with the corresponding unleaded gasoline composition X. The unleaded gasoline compositions U and V provided by the present invention can also reduce the sulfur content to 1 ppm by mass or less.

[0064] Preparation of certain materials for gasoline 6

Catalytic cracking gasoline AA obtained by treating a Middle Eastern crude oil different from the above-mentioned gasoline base material preparation 1 in the same manner as gasoline base material preparation 1 and then subjecting it to sweet jung processing is converted to light and heavy components. The heavy fraction was obtained as catalytic cracking heavy gasoline BB. The catalytic cracking heavy gasoline BB was used at a reaction temperature of 220 ° C using a catalyst in which cobalt, molybdenum and phosphorus were supported on alumina (cobalt content 2.4% by mass, molybdenum content 9.4% by mass, phosphorus content 2.0% by mass). , Reaction pressure 1.0MPa, ZOil ratio 307NLZL

, To remove the jen to obtain a catalytic cracked heavy gasoline CC having a jen value of 0.6 gZl00 g to less than O.lgZl00 g. Exactly the same method as in gasoline-based preparation 1 except that the heavy gasoline CC,

2

Under the same conditions to obtain a desulfurized catalytic cracking heavy gasoline DD having a sulfur content of 0.9 mass ppm. Table 7 shows the properties of each gasoline (catalytically cracked gasoline AA—desulfurized catalytically cracked heavy gasoline DD).

[0065] Preparation of certain materials for gasoline 7

Exactly the same as gasoline base material preparation 1 except that the catalytic cracking heavy gasoline BB used in the above gasoline base material preparation 6 was changed to an H / OU ratio of 0.18 NL / L without performing the Gen reduction treatment.

2

Desulfurization was performed using the same method and conditions to obtain desulfurized catalytic cracking heavy gasoline EE. Table 7 shows the properties of desulfurization catalytic cracking heavy gasoline EE. [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 of desulfurized catalytically cracked light gasoline K and 35.0% by volume of desulfurized catalytically cracked heavy gasoline DD described in Preparation of gasoline base 6 were blended to prepare a lead-free gasoline composition Υ. Table 6 shows the properties of unleaded gasoline composition Υ.

Comparative Example 3

Preparation of Gasoline Base in Place of Desulfurized Catalytic Cracked Heavy Gasoline DD Unleaded gasoline composition Z was prepared in exactly the same manner as in Example 5, except that the desulfurized catalytic cracked heavy gasoline EE described in 7 was used. did. Table 6 shows the properties of unleaded gasoline composition Z.

[0069] In Table 7, comparing the desulfurization catalytic cracking heavy gasoline DD of gasoline base material preparation 6 with the desulfurization catalytic cracking heavy gasoline EE of gasoline base material preparation 7, a high Gen value and a high sulfur content It can be seen that it is extremely difficult to reduce the sulfur content to 1 ppm by mass or less even when desulfurizing with a desulfurizing agent having a sorption function. Therefore, the desulfurization catalytic cracking heavy gasoline DD, desulfurized with a desulfurizing agent having a sorption function after performing the Gen reduction treatment, is used together with other low-sulfur gasoline base materials, and the sulfur content is 1 mass ppm or less. As shown in Table 6, as a lead-free gasoline composition Y, a lead-free gasoline composition having sufficient operating characteristics can be easily prepared.

[0070] [Reference example]

Preparation of gasoline base material 5 cm ³ of the same copper-zinc-aluminum composite oxide (copper content 35% by mass, zinc content 35% by mass, aluminum content 5% by mass) as described in 1 was filled in a reaction tube. Then, hydrogen gas was circulated under the condition of 5 cm ³ Zmin for 16 hours to perform a reduction treatment. Then, a toluene solution containing 263 mass ppm of thiophene (100 mass ppm as sulfur content) was placed in the reaction tube at a reaction temperature of 100 ° C, a reaction pressure of normal pressure, and an / Oil ratio.

The oil was passed under the conditions of 0.18NLZL to obtain the products shown in Table 8.

[0071] [Table 8] Product selectivity

[Mol% based on raw material thiophene]

Hydrogen sulfide <0.1

7L carbonized

1—butene 76

cis—2-butene 14

trans—2—butene 7

n—butane 3

Chioffen tick 0.1

[0072] From the table, it can be seen from the table that the treatment with the copper-zinc-aluminum composite oxide in the co-presence of hydrogen removes the thiophene power and sulfur in the feedstock oil and removes carbon derived from hydrocarbon residues other than sulfur atoms in thiophene. While hydrogen was obtained as a product, no hydrogen sulfide was generated, and it is clear that the copper-zinc-aluminum composite oxide served as the porous desulfurizing agent having the sulfur sorption function of the present invention. .

Industrial applicability

According to the present invention, after the cracked gasoline fraction is removed with a gen, it is treated with a porous desulfurizing agent having a sulfur sorbing function in the presence of a small amount of hydrogen to reduce the sulfur content and leave the olefin component. A lead-free gasoline composition with a sulfur content of 1 mass ppm or less, which is obtained by mixing a desulfurization cracked naphtha fraction obtained by avoiding octane loss due to desulfurization treatment with another gasoline base material with a sulfur content of 10 mass ppm or less . Therefore, it was possible to reduce only the sulfur content to 1 mass ppm or less without changing the properties of the conventional unleaded gasoline composition and other properties. Therefore, the unleaded gasoline composition of the present invention is useful as a V-vehicle fuel with low environmental load while maintaining high driving performance.

Claims

The scope of the claims

[1] Desulfurization of decomposed naphtha fractions with a 5% by volume distillation temperature of 25 ° C or higher, a 95% by volume distillation temperature of 210 ° C or lower, an olefin component of 5% by mass or more, and a Gen value of 0.3gZlOOg or less Unleaded gasoline with a sulfur content of 1 mass ppm or less and a research octane number of 89.0 or more, including a desulfurization step of treating and a blending step of mixing the obtained desulfurized cracked naphtha fraction with another gasoline base material A method for producing the composition.

2. The method for producing a lead-free gasoline composition according to claim 1, comprising a step of bringing a feed oil of the cracked naphtha fraction into contact with a gen reduction catalyst in advance to perform a gen reduction treatment.

[3] The method for producing a lead-free gasoline composition according to claim 2, wherein the gen reduction catalyst contains at least one metal selected from Group 8 elemental forces of the periodic table.

[4] The method for producing a lead-free gasoline composition according to claim 3, wherein the at least one metal contained in the gen reduction catalyst is nickel or cobalt.

[5] The desulfurization treatment converts the porous desulfurizing agent with a sulfur sorption function and the cracked naphtha fraction to hydrogen partial pressure.

15. The method for producing a lead-free gasoline composition according to claim 14, wherein the contacting is performed in the presence of hydrogen having a pressure of IMPa or less.

6. The method for producing a lead-free gasoline composition according to claim 5, wherein the porous desulfurizing agent contains at least one selected from copper, zinc, nickel, and iron.

[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 A method for producing a gasoline composition.

[8] Decomposed naphtha fraction, 5% by volume distillation temperature is 25-43 ° C, 95% by volume distillation temperature is 55-100 ° C, olefin content is 5% by mass or more, Gen value is 0.3gZl00g 18. The method for producing a lead-free gasoline composition according to claim 17, which is a light cracked naphtha fraction as follows.

[9] The light cracked naphtha fraction is a fraction obtained by subjecting the cracked naphtha fraction to a feedstock oil that has been subjected to a gen reduction treatment and then fractionating the crude cracked naphtha fraction. 9. The unleaded gasoline according to claim 8, wherein the gas is obtained by performing a gen reduction treatment after the separation, or by simultaneously performing the fractionation of the feed oil of the cracked naphtha fraction and the gen reduction treatment. A method for producing the composition.

[10] Before performing the fractionation to obtain a light cracked naphtha fraction, or at the same time as the fractionation, the feedstock oil of the cracked naphtha fraction or the feedstock oil of the cracked naphtha fraction that has been subjected to the gen-reduction treatment is reduced 10. The method for producing a lead-free gasoline composition according to claim 9, wherein a pretreatment for increasing the molecular weight is performed.

[11] In the blending step, a light desulfurized cracked naphtha fraction of 10-60% by volume is mixed with 90-40% by volume of another gasoline base material, and the octane number of the research method is 93.0 or more.

8. The method for producing a lead-free gasoline composition according to any one of 8 to 10.

[12] Research method: Octane number of 89.0 or more, 50% by volume Distilling temperature: 105 ° C or less, Olefin content: 10% by volume or more, Total sulfur content: 1 mass ppm or less, Thiophenes in total sulfur content An unleaded gasoline composition having a sulfur content of 50% by mass or more.

[13] The unleaded gasoline composition according to claim 12, which has a research octane number of 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. The unleaded gasoline composition according to claim 13, wherein the ratio of the total amount of thiophene and 2-methylthiophene to the total sulfur content is 50% by mass or more as the sulfur content.

[16] The unleaded gasoline composition according to any one of claims 12 to 15, wherein the content of thiols is 0.1 mass ppm or less in terms of sulfur content.