JP2004105963A - Catalyst for converting aromatic hydrocarbon compound and conversion method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst, which has high activity, reduced in catalytic deterioration and has high selectivity, suitable for reacting benzene and a ≥9 C aromatic hydrocarbon compound to convert them to toluene and an 8 C aromatic hydrocarbon compound useful as base materials of gasoline, and a conversion method. <P>SOLUTION: The catalyst is obtained by supporting a metal selected from a metal of the group VIII and a metal of the group VIA or a compound thereof on a carrier containing zeolite having micropores with the maximum pore size of 0.6-1.0 nm and an SiO<SB>2</SB>/Al<SB>2</SB>O<SB>3</SB>ratio of 50 or more. This catalyst is used to convert benzene and the ≥9 C aromatic hydrocarbon compound in raw material oil with a specific boiling point range to toluene and the 8 C aromatic hydrocarbon compound in the presence of hydrogen. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to a catalyst for converting aromatic hydrocarbon compounds, and more specifically, by reacting benzene with an aromatic hydrocarbon compound having 9 or more carbon atoms, these compounds are more useful as a gasoline base material. The present invention relates to a catalyst suitable for converting to toluene and an aromatic hydrocarbon compound having 8 carbon atoms. The present invention also relates to a method for converting aromatic hydrocarbon compounds, and more particularly, to reacting benzene with an aromatic hydrocarbon compound having 9 or more carbon atoms to make these compounds more useful as a gasoline base material. The present invention relates to a method suitable for converting to toluene and an aromatic hydrocarbon compound having 8 carbon atoms.

芳香 Aromatic hydrocarbon compounds contained in gasoline base materials are generally excellent as gasoline base materials in that they have a high octane number and a large calorific value. Furthermore, among them, toluene and aromatic hydrocarbon compounds having 8 carbon atoms have a high octane number and are excellent in drivability, and it is desired to increase their contents. Particularly, a method of directly converting benzene and an aromatic hydrocarbon compound having 9 or more carbon atoms in a gasoline fraction into toluene and an aromatic hydrocarbon compound having 8 carbon atoms is significant.

(4) The reaction of converting aromatic hydrocarbon compounds into aromatic hydrocarbon compounds having different carbon numbers includes a transalkylation reaction and a disproportionation reaction of aromatic hydrocarbon compounds. The transalkylation reaction is a reaction using a plurality of different aromatic hydrocarbon compounds as reactants, and the disproportionation reaction of the aromatic hydrocarbon compounds is a reaction in which two molecules of the same aromatic hydrocarbon compound react. A well known process for these reactions is the production of benzene and xylene by the disproportionation of toluene. Further, as an application of this reaction, there is a method in which an aromatic hydrocarbon compound having 9 or more carbon atoms is added to a raw material to cause a transalkylation reaction to increase the yield of xylene. However, in this process, it is necessary to use toluene, which is itself useful as a gasoline base material, instead of benzene as a raw material. In addition, high-purity raw materials are used for the purpose of synthesizing chemical industrial raw materials, and other compounds, particularly gasoline fractions, which are mixtures of various hydrocarbon compounds including aliphatic hydrocarbon compounds, are used as raw materials. That was not considered at all.

US Pat. No. 5,347,061 (Patent Document 1) discloses that benzene and an aromatic hydrocarbon compound having 9 or more carbon atoms in a gasoline fraction are directly converted into toluene and an aromatic hydrocarbon compound having 8 carbon atoms. A method is disclosed. This is a benzene-rich hydrocarbon compound fraction obtained by distillation of reformed gasoline and having a carbon number of 6, and a fraction of a mixture of an aromatic hydrocarbon compound having 9 or more carbon atoms and a non-aromatic hydrocarbon compound, The present invention relates to a process for producing a toluene and an aromatic hydrocarbon compound having 8 carbon atoms by causing a transalkylation reaction, an alkylation reaction, and a decomposition reaction in the presence of an acidic metallosilicate catalyst. As the acidic metallosilicate catalyst, a zeolite catalyst such as ZSM-5 is exemplified, but there is no detailed description about the pore diameter or the loading of the metal.
US Patent No. 5,347,061

An object of the present invention is to convert these compounds into toluene and an aromatic hydrocarbon compound having 8 carbon atoms, which are more useful as a gasoline base, by reacting benzene with an aromatic hydrocarbon compound having 9 or more carbon atoms. It is an object of the present invention to provide a catalyst which exhibits high activity, is low in catalyst deterioration, and has high selectivity. Further, an object of the present invention is to convert these compounds into toluene and an aromatic hydrocarbon compound having 8 carbon atoms, which are more useful as a gasoline base material, by reacting benzene with an aromatic hydrocarbon compound having 9 or more carbon atoms. It is to provide a method.

By reacting benzene with an aromatic hydrocarbon compound having 9 or more carbon atoms, the present inventors have proposed a novel method for converting directly into toluene and an aromatic hydrocarbon compound having 8 carbon atoms, which is more preferable as a gasoline base material. As a result of diligent research on various catalysts, catalysts in which a specific metal is supported on a zeolite-containing support having a large maximum micropore diameter and a large SiO ₂ / Al ₂ O ₃ ratio have a specific boiling point range. In the case of using a raw material oil having the following formulas, it was found that the catalyst exhibited high activity, small catalyst deterioration and high selectivity, and completed the present invention.

That is, the present invention provides a support containing a zeolite having a maximum micropore diameter of 0.6 to 1.0 nm and an SiO ₂ / Al ₂ O ₃ ratio of 50 or more, comprising a Group VIII metal and a A catalyst obtained by supporting at least one metal selected from the group VIA metals or a compound thereof, wherein the benzene and the aromatic carbon having 9 or more carbon atoms are contained in a feed oil having a boiling range of 30 to 210 ° C. An object of the present invention is to provide a catalyst for converting an aromatic hydrocarbon compound used in a method for converting a hydrogen compound into toluene and an aromatic hydrocarbon compound having 8 carbon atoms in the presence of hydrogen.

Further, the present invention provides a support containing a zeolite having a maximum micropore diameter of 0.6 to 1.0 nm and an SiO ₂ / Al ₂ O ₃ ratio of 50 or more, comprising a group VIII metal and a group VIII metal of the periodic table. Using a catalyst obtained by supporting at least one metal selected from Group VIA metals or a compound thereof, in the presence of hydrogen, benzene and carbon number contained in a feed oil having a boiling point range of 30 to 210 ° C. An object of the present invention is to provide a method for converting an aromatic hydrocarbon compound of 9 or more into toluene and an aromatic hydrocarbon compound having 8 carbon atoms. Hereinafter, the present invention will be described in detail.

The catalyst of the present invention reacts benzene with an aromatic hydrocarbon compound having 9 or more carbon atoms to convert these compounds into toluene and an aromatic hydrocarbon compound having 8 carbon atoms which are more useful as a gasoline base material. It is suitable, shows high activity, has small catalyst deterioration, and has high selectivity. Further, by the conversion method of the present invention, benzene is reacted with an aromatic hydrocarbon compound having 9 or more carbon atoms, and these compounds are efficiently converted into toluene and an aromatic hydrocarbon compound having 8 carbon atoms, which are more useful as a gasoline base material. Can be converted.

The catalyst of the present invention comprises a support containing zeolite having a maximum micropore diameter of 0.6 to 1.0 nm and an SiO ₂ / Al ₂ O ₃ ratio of 50 or more; At least one metal selected from Group VIA metals or a compound thereof is supported.

The pore structure of a porous catalyst material is generally classified into flow channels, macropores (pore diameters exceeding 50 nm), mesopores (pore diameters of 2 to 50 nm), and micropores (pore diameters of less than 2 nm). Is done. Further, some porous catalyst materials have two or more types of micropores having different sizes. In the present invention, the maximum pore size of the micropore is defined as the maximum pore size of these micropores. It refers to the pore entrance diameter, which needs to be 0.6 to 1.0 nm. In addition, such a micropore usually has a ring forming a pore entrance formed of a 12-membered oxygen ring. Hereinafter, in the present invention, when the pores are not a perfect circle but an ellipse, the major axis is defined as the pore diameter.

最大 The maximum pore diameter of the micropores of the zeolite used in the present invention needs to be 0.6 to 1.0 nm, preferably 0.6 to 0.8 nm. When the thickness is less than 0.6 nm, the activity of the conversion reaction from benzene and an aromatic hydrocarbon compound having 9 or more carbon atoms to toluene and an aromatic hydrocarbon compound having 8 carbon atoms decreases, and the activity of the aliphatic hydrocarbon compound decreases. It is not preferable because the selectivity of the decomposition reaction is increased.

Examples of the zeolite used in the present invention include mordenite, X-type zeolite, Y-type zeolite, offretite, β-type zeolite, L-type zeolite, Ω-type zeolite and the like, among which mordenite and Y-type zeolite are preferable, and furthermore Preferably, it is mordenite. These zeolites may be synthetic or natural. In the present invention, one kind of zeolite may be used, or two or more kinds of zeolites may be used in combination as needed.

The SiO ₂ / Al ₂ O ₃ ratio (molar ratio) of the zeolite used in the present invention is preferably larger from the viewpoint of the activity of the catalyst, the deterioration of the catalyst, and the stability during regeneration of the catalyst. The SiO ₂ / Al ₂ O ₃ ratio needs to be 50 or more, preferably 80 or more, more preferably 100 to 300, and most preferably 150 to 250. Such SiO ₂ / Al ₂ O ₃ ratio is large zeolite may but be synthesized by appropriately adjusting the ratio of raw materials during the synthesis so that if the desired value, SiO ₂ / Al ₂ O _{3 It} is obtained by synthesizing a zeolite having a small ratio and subjecting it to a dealumination treatment by a known method such as steaming treatment or acid treatment.

In general, zeolites have a negative charge in the crystal framework, and there is a counter cation to compensate for it. The counter cation of the zeolite used in the present invention is optional, but is preferably a hydrogen ion or a mixture of a hydrogen ion and an alkali metal ion and / or an alkaline earth metal ion, more preferably a hydrogen ion and an alkali metal ion and / or Mixtures with alkaline earth metal ions are preferred. The ratio of the hydrogen ion to the total counter cation is preferably 20% or more, more preferably 30% or more, and most preferably 40 to 90%, as the ion equivalent. Further, the ratio of the alkali metal ion and / or the alkaline earth metal ion to the whole counter cation is preferably 80% or less, more preferably 70% or less, and particularly preferably 10 to 60% in terms of ion equivalent. Is desirable. As counter cations, K ⁺ and Na ⁺ are preferable for alkali metal ions, and Mg ²⁺ and Ca ²⁺ are preferable for alkaline earth metal ions.

In order to prepare a zeolite having an alkali metal ion and / or an alkaline earth metal ion as a counter cation as described above, when the counter cation of the zeolite as a raw material is almost a hydrogen ion, a part of the hydrogen ion is used. Is exchanged with an alkali metal ion and / or an alkaline earth metal ion. When the counter cation of the zeolite used as the raw material is almost an alkali metal ion and / or an alkaline earth metal ion, the zeolite may be exchanged with hydrogen ions so as to leave a part of these ions. After exchanging with ions, it may be exchanged again with alkali metal ions and / or alkaline earth metal ions. In order to exchange the counter cation for hydrogen ions, a method of directly exchanging for hydrogen ions or a method of exchanging for ammonium ions and then calcination to convert to hydrogen ions can be adopted as is known.

際 When preparing the catalyst of the present invention, the order of loading and molding of the metal may be performed in any order, but it is preferable to mold the carrier before loading the metal. For the molding, a commonly used molding method can be used. For example, extrusion molding, tablet molding, oil drop method and the like can be mentioned. Among these, extrusion molding is preferred. In molding, a binder may be used as necessary.

The binder is not particularly limited, and any one of metal oxides such as alumina, titania and silica-alumina and clay minerals can be used. Alumina, silica and clay minerals are preferred, and alumina is particularly preferred. Further, two or more binders may be used as needed. Although the amount of the binder is not limited, it is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, based on the total amount of the carrier including the binder. If the amount of the binder is too large, the catalytic performance may be reduced, and if the amount is small, molding may be difficult.

金属 The metal supported on the catalyst used in the present invention is at least one metal selected from Group VIII metals or Group VIA metals of the periodic table. The Group VIII metal of the periodic table is specifically Co, Fe, Ni, Ru, Rh, Pd, Os, Ir, or Pt. Preferred are Co, Fe, Ni, Ru, Rh, Pd, Ir, and Pt, more preferred are Ni, Pd, and Ir, and particularly preferred are Ni and Pd. The Group VIA metal of the periodic table is specifically Cr, Mo, W. Mo and W are preferred, and Mo is more preferred. These metals may be used alone or in combination of two or more.

法 There is no particular limitation on the metal supporting method, and a normal supporting method can be applied. For example, an impregnation method, a CVD (Chemical Vapor Deposition) method, and the like can be mentioned, but the impregnation method is preferable. Further, among the impregnation methods, an adsorption method, an ion exchange method, an evaporation to dryness method, an incipient wetness method, and a spray method are preferable.

In addition, as a raw material of the metal to be supported, any commonly used material can be used. For example, chloride, nitrate, sulfate and the like can be mentioned. An ammine complex such as Pd (NH ₃ ) ₄ Cl ₂ or Pd (NH ₃ ) ₄ (NO ₃ ) can also be used. In the catalyst used in the present invention, the metal may be supported as a metal atom, or may be supported as a compound such as a sulfide or an oxide. It is preferably carried as sulfide.

The catalyst of the present invention comprises at least one metal selected from Group VIII metals and Group VIA metals of the periodic table supported on the above-described carrier. The activity is lowered, and the catalyst is apt to deteriorate, which is not preferable.

The amount of such a metal supported is appropriately selected depending on the type of the metal, the reaction conditions, and the like, and is not particularly limited. However, based on the total amount of the catalyst including the supported metal, Ru, Rh, Pd , Os, Ir, and Pt are preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and most preferably 0.1 to 1% by mass. Co, Fe, Ni, Cr, Mo, and W are preferably 0.1 to 15% by mass, more preferably 0.3 to 10% by mass, and most preferably 0.5 to 5% by mass.

触媒 The catalyst of the present invention is preferably subjected to a calcination treatment after preparation. The firing temperature is usually from 200 to 600 ° C, preferably from 300 to 500 ° C. Before the start of the reaction, a reduction treatment or a sulfurization treatment is preferably performed as a pretreatment. Hydrogen reduction using a gas containing hydrogen is preferable for the reduction treatment, and the reduction temperature is usually 100 to 600 ° C, preferably 200 to 500 ° C. It is preferable to use a sulfurizing agent such as hydrogen sulfide, carbon disulfide, and dimethyl disulfide (DMDS) in the co-presence of a gas containing hydrogen gas for the sulfurization treatment. More preferably, it is 200 to 400 ° C.

れ ば When the catalyst of the present invention is used, hydrogenation of an aromatic ring, which is a side reaction, rarely occurs. However, depending on the type of metal, reaction conditions, and the like, this side reaction may be significant, and in this case, it is more preferable to perform a sulfidation treatment as a pretreatment.

In the present invention, the above-mentioned catalyst is obtained by converting benzene and an aromatic hydrocarbon compound having 9 or more carbon atoms contained in a feed oil having a boiling range of 30 to 210 ° C. into toluene and an aromatic hydrocarbon compound having 8 carbon atoms. It is used for the method of converting to

に お い て In the present invention, as the raw material oil, one having a boiling point range of 30 to 210 ° C, preferably 30 to 200 ° C, more preferably 30 to 195 ° C according to the measurement method specified in ASTM D86 is used. If the boiling point exceeds 210 ° C., coking is likely to occur and the life of the catalyst may be shortened.

原料 Further, the feedstock oil used in the present invention needs to satisfy the above boiling point range and contain benzene and an aromatic hydrocarbon compound having 9 or more carbon atoms. Here, the contents of benzene and the aromatic hydrocarbon compound having 9 or more carbon atoms in the feedstock are arbitrary, but from the viewpoint of reaction efficiency, it is preferable that both are large. In the present invention, the content of benzene is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more based on the total amount of the feed oil, and the content of the aromatic hydrocarbon compound having 9 or more carbon atoms. Is at least 1% by mass, preferably at least 30% by mass, more preferably at least 50% by mass, based on the total amount of the feedstock oil. Further, as the raw material oil used in the present invention, the content of the aromatic hydrocarbon compound having 9 carbon atoms is 1% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more based on the total amount of the raw material oil. It is desirable that

Further, the ratio of the aromatic hydrocarbon compound having 9 or more carbon atoms to benzene (the number of moles of the aromatic hydrocarbon compound having 9 or more carbon atoms / the number of moles of benzene) in the feedstock is preferably in the range of 0.5 to 10. , 1 to 5 are more preferable. If this ratio is too low, the conversion of benzene will decrease. If this ratio is too large, the conversion of aromatic hydrocarbon compounds having 9 or more carbon atoms will decrease, resulting in inefficiency. As the raw material oil used in the present invention, any oil can be used as long as it satisfies the above boiling point range and contains benzene and an aromatic hydrocarbon compound having 9 or more carbon atoms.

Such a raw material oil may be a pure product such as a chemical industrial raw material, but usually, the raw material oil used in the present invention is a mixture with other compounds, and specifically, for example, crude oil Of petroleum distillate obtained by distilling the same, and those obtained by subjecting petroleum distillate to various treatments. Among them, reformed gasoline obtained from a catalytic reformer, catalytic cracked gasoline obtained from a fluid catalytic cracker, and the like are preferably used, and reformed gasoline rich in aromatic components is particularly preferably used.

{Circle around (4)} The mixture as described above usually contains toluene, which is a product of the reaction according to the present invention, and an aromatic hydrocarbon compound having 8 carbon atoms. In the present invention, these compounds may be used as a raw material oil, but it is preferable to remove these compounds by distillation or the like to obtain a raw material oil from the viewpoint of reaction efficiency. That is, a fraction containing benzene, a fraction containing toluene and an aromatic hydrocarbon compound having 8 carbon atoms, and a fraction containing an aromatic hydrocarbon compound having 9 or more carbon atoms are obtained by distilling a reformed gasoline or the like. It is preferable that the fraction containing benzene and the fraction containing an aromatic hydrocarbon compound having 9 or more carbon atoms are mixed to obtain a feedstock oil. In addition, the toluene and the aromatic hydrocarbon compound having 8 carbon atoms removed here may be used as a gasoline base material, respectively, or as a raw material in the chemical industry. If necessary, the benzene-containing fraction is separated by distillation or the like, and high-purity benzene separated therefrom by a known method such as sulfolane extraction is used to contain an aromatic hydrocarbon compound having 9 or more carbon atoms. It may be used as a raw material oil by mixing with a fraction to be used.

When the conversion reaction of an aromatic hydrocarbon is carried out using the catalyst of the present invention, it is necessary to carry out the reaction in the presence of hydrogen. In the present invention, the ratio of the hydrogen gas to the base oil (volume of hydrogen in a standard state at 0 ° C. and 1 atm / volume of the base oil) is not particularly limited, but is preferably 50 to 2000 Nm ³ / m ³ , More preferably, the range is 500 to 1500 Nm ³ / m ³ . If the ratio of the hydrogen gas to the feed oil is too small, the life of the catalyst is significantly shortened. It is not economical if the ratio of hydrogen gas to feed oil is too large.

When the catalyst of the present invention is used, the reaction may be performed in the presence of hydrogen, and other reaction conditions may be appropriately selected depending on the activity of the catalyst, the composition of the raw material oil and the product oil, and the like. There are no restrictions on the liquid space velocity or the like. However, the reaction is usually carried out at a pressure of 0.1 to 6 MPa, preferably 2 to 4 MPa. Also, the reaction temperature is usually in the range of 200 to 550 ° C, preferably 250 to 500 ° C, more preferably 350 to 500 ° C. If the reaction temperature is too low, the conversion will decrease. If the reaction temperature is too high, the dealkylation reaction occurs preferentially, and the conversion of benzene decreases. The LHSV is preferably in the range of 0.1 to 10 ^-1, more preferably 0.5~5h ^-1.

に お い て In the present invention, the type of the reactor may be any of a fixed bed, a fluidized bed and an expanded bed, but a fixed bed is preferred. The contact between the feedstock, hydrogen and the catalyst may be any of parallel upward flow, parallel downward flow, and countercurrent. The reaction may be performed by a flow method or a batch method, but the flow method is preferred.

In the method of the present invention, when benzene and an aromatic hydrocarbon compound having 9 or more carbon atoms are converted into toluene and an aromatic hydrocarbon compound having 8 carbon atoms, the conversion rate is high, and unreacted benzene in the product oil is high. And the content of the aromatic hydrocarbon compound having 9 or more carbon atoms is small. Therefore, it is not always necessary to mix the produced oil with the base oil and recycle and react again. However, recycling may be performed to increase the efficiency of the reaction. In the case of recycling, a part of the produced oil may be directly mixed with the base oil, or only a specific fraction of the generated oil may be taken out by distillation or the like and mixed with the base oil. Recycling of a benzene-containing fraction promotes the decomposition of coexisting aliphatic hydrocarbon compounds having 6 to 7 carbon atoms into lighter components of lower value, thereby reducing the yield as a gasoline base material. Therefore, it is preferable not to recycle when the benzene concentration in the produced oil is low.

FIG. 1 shows a simple example of a process for recycling using the catalyst of the present invention. The feed oil containing benzene and the aromatic hydrocarbon compound having 9 or more carbon atoms supplied from the conduit 1 contains the aromatic hydrocarbon compound having 9 or more carbon atoms recycled from the distillation column (4) via the conduit 5. The waste fraction is sent from the conduit 2 to the reactor (3). The product oil is sent to the distillation column (4) via the conduit 6, and the gas fraction from the conduit 7, the benzene-containing fraction from the conduit 8, and the toluene and toluene-containing aromatic hydrocarbon compound having 8 carbon atoms from the conduit 9. And a fraction containing the aromatic hydrocarbon compound having 9 or more carbon atoms from the conduit 10, and at least a part of the fraction containing the aromatic hydrocarbon compound having 9 or more carbon atoms is recycled from the conduit 5. .

FIG. 2 illustrates another preferred example of a process for recycling using the catalyst of the present invention. The feed oil supplied from the conduit 11 contains a fraction containing benzene (conduit 13), a fraction containing toluene (conduit 14), and an aromatic hydrocarbon compound having 8 or more carbon atoms by the distillation column (12). It is divided into fractions (conduit 15). A fraction (conduit 17) containing an aromatic hydrocarbon compound having 8 carbon atoms is separated from a fraction containing an aromatic hydrocarbon compound having 8 or more carbon atoms (conduit 15 and conduit 24) by a distillation column (16). After that, at least a part (conduit 18) of a fraction (conduit 19) containing an aromatic hydrocarbon compound having 9 or more carbon atoms is sent to a reactor (20) together with a fraction containing benzene (conduit 13). . A fraction containing benzene and toluene (conduit 23) is separated from the product oil (conduit 21) by a distillation column (22), and a fraction containing an aromatic hydrocarbon compound having 8 or more carbon atoms (conduit 24) is distilled. Sent to the tower (16).

The present invention will be described more specifically with reference to examples and comparative examples below, but the present invention is not limited to these examples.

Maximum pore diameter of the micropores is _{0.70nm, SiO 2 / Al 2 O} 3 ratio of 203 hydrogen ion type mordenite [HSZ690HOA, Tosoh Corporation] on, with the addition of boehmite peptized with dilute nitric acid kneaded , Extrusion molding, drying and calcination to prepare a catalyst carrier. The amount of boehmite was adjusted so that the alumina binder was 30% by mass based on the total amount of the carrier. The carrier was loaded with 3% by mass (based on the total amount of the catalyst) of Ni in terms of Ni metal using an aqueous solution of nickel nitrate by an incipient wetness method, dried and calcined to prepare a catalyst. Next, before performing the following reaction, the catalyst was subjected to sulfuration treatment with hydrogen gas containing 1% by volume of hydrogen sulfide. A reaction experiment was carried out using a pressurized flow type reaction apparatus having a capacity of 20 ml and using a raw material oil having the properties and compositions shown in Table 1. This feedstock is obtained by mixing benzene with a fraction (boiling point range: 150 to 190 ° C.) mainly containing an aromatic hydrocarbon compound having 9 carbon atoms, which is obtained by distilling and separating reformed gasoline obtained from a catalytic reformer. It is obtained by doing. The reaction was carried out at a pressure of 3.0 MPa, a temperature of 390 ° C., an LHSV of 1.5 h ⁻¹ , a hydrogen / oil ratio of 800 Nm ³ / m ³ , and a molar ratio of aromatic hydrocarbon compound having 9 or more carbon atoms / benzene of 1.9. Table 1 shows the reaction results 72 hours and 360 hours after the start of the reaction.

In place of the feedstock oil used in Example 1, the reformed gasoline obtained from the catalytic reforming unit was distilled to separate a fraction containing benzene and a fraction containing an aromatic hydrocarbon compound having 9 carbon atoms. Then, a catalyst preparation and a reaction experiment were carried out in the same manner as in Example 1 except that a feedstock oil obtained by mixing both of them as it was was used. This feedstock contains a considerable amount of aliphatic hydrocarbon compounds having 6 and 7 carbon atoms. The molar ratio of the aromatic hydrocarbon compound having 9 or more carbon atoms / benzene was 2.9. Table 1 shows the results.

Instead of the hydrogen ion type mordenite having a maximum micropore diameter of 0.70 nm and an SiO ₂ / Al ₂ O ₃ ratio of 203 used in Example 1, Na ion exchange was carried out in the following manner. A catalyst preparation and a reaction experiment were performed in the same manner as in Example 1 except that the catalyst was used. Table 2 shows the results.
(Method of exchanging Na ion) Mordenite was placed in an aqueous solution of NaCl, stirred at 90 ° C. for 14 hours, filtered, and washed with ion-exchanged water. Then, it was dried and fired. The ion exchange rate was 50%.

Instead of the hydrogen ion type mordenite having a maximum pore diameter of 0.70 nm and an SiO ₂ / Al ₂ O ₃ ratio of 203 used in Example 1, the maximum pore diameter of the micro pores was 0.74 nm, and _A catalyst preparation and a reaction experiment were performed in the same manner as in Example 1 except that a hydrogen ion type ultra-stable Y-type zeolite [HSZ390HUA, Tosoh Corporation] having a ₂ / Al ₂ O ₃ ratio of 240 was used. Table 2 shows the results.

(Comparative Example 1)
When distilling the reformed gasoline obtained from the catalytic reforming unit instead of the feedstock oil used in Example 1, the boiling point range of the fraction containing the aromatic hydrocarbon compound having 9 carbon atoms was 150 to 230 ° C. A catalyst preparation and a reaction experiment were performed in the same manner as in Example 1 except that a mixture of the obtained fraction and pure benzene was used. Table 3 shows the results.

(Comparative Example 2)
Instead of the hydrogen ion type mordenite having a maximum pore diameter of 0.70 nm and an SiO ₂ / Al ₂ O ₃ ratio of 203 used in Example 1, the maximum pore diameter of the micropores was 0.54 nm, and the SiO ₂ / Al ₂ O ₃ ratio was 203. _A catalyst preparation and a reaction experiment were performed in the same manner as in Example 1 except that a hydrogen ion type ZSM-5 having a ₂ / Al ₂ O ₃ ratio of 26 was used. Table 3 shows the results.

(Comparative Example 3)
Instead of the hydrogen ion type mordenite having a maximum pore diameter of 0.70 nm and an SiO ₂ / Al ₂ O ₃ ratio of 203 used in Example 2, the maximum pore diameter of the micro pores was 0.54 nm, and _A catalyst preparation and a reaction experiment were conducted in the same manner as in Example 2 except that a hydrogen ion type ZSM-5 having a ₂ / Al ₂ O ₃ ratio of 26 was used. Table 3 shows the results.

(Comparative Example 4)
Instead of the hydrogen ion type mordenite having a maximum pore diameter of 0.70 nm and an SiO ₂ / Al ₂ O ₃ ratio of 203 used in Example 1, the maximum pore diameter of the micro pores was 0.70 nm, and the SiO ₂ / Al ₂ O ₃ ratio was 203. _A catalyst preparation and a reaction experiment were performed in the same manner as in Example 1 except that a hydrogen ion type mordenite [HSZ640HOA, Tosoh Corporation] having a ₂ / Al ₂ O ₃ ratio of 20 was used. Table 4 shows the results.

(Comparative Example 5)
Instead of the hydrogen ion type mordenite having a maximum pore diameter of 0.70 nm and an SiO ₂ / Al ₂ O ₃ ratio of 203 used in Example 1, the maximum pore diameter of the micro pores was 0.74 nm, and _A catalyst preparation and a reaction experiment were performed in the same manner as in Example 1 except that a hydrogen ion type ultrastable Y-type zeolite [HSZ370HUA, Tosoh Corporation] having a ₂ / Al ₂ O ₃ ratio of 26 was used. Table 4 shows the results.

(Comparative Example 6)
A reaction experiment was carried out in the same manner as in Example 1 except that the catalyst used in Example 1 was replaced with a catalyst in which no metal was supported on the same catalyst carrier as in Example 1. Table 4 shows the results.

As is clear from the results in Tables 1 and 2, in the examples, the conversion of benzene and aromatic hydrocarbon compounds having 9 or more carbon atoms was high 72 hours after the start of the reaction, and the conversion was 360 hours after the start of the reaction. It can be seen that the deterioration of the catalyst is small. On the other hand, as is evident from Table 3, in the comparative example using a feed oil having a boiling point exceeding the range specified in the present invention, the conversion after 360 hours is low, and the catalyst deteriorates greatly. In addition, as shown in Table 3, in Comparative Example 2 using a zeolite having a maximum micropore diameter of less than 0.6 nm, the conversion of an aromatic hydrocarbon compound having 9 or more carbon atoms after 72 hours from the start of the reaction. And especially the conversion of trimethylbenzene is low. Furthermore, the conversion is small 360 hours after the start of the reaction, and the catalyst deteriorates greatly. In Comparative Example 3 using the same catalyst as Comparative Example 2 and using a raw oil containing a substantial amount of an aliphatic hydrocarbon compound having 6 or 7 carbon atoms as the raw oil, the amount of hexane in the produced oil was particularly small, It is understood that the decomposition of the group hydrocarbon compound is large. Further, as shown in Table 4, in Comparative Examples 4 and 5 in which zeolites having a small SiO ₂ / Al ₂ O ₃ ratio were used, the conversion was low and the deterioration of the catalyst was large. In Comparative Example 6 using a catalyst that does not support a metal, the conversion of benzene and an aromatic hydrocarbon compound having 9 or more carbon atoms is extremely low.

It is a flowchart for explaining the manufacturing method of the gasoline base material using the catalyst of the present invention. FIG. 4 is a process chart for explaining another method for producing a gasoline base material using the catalyst of the present invention.

Explanation of reference numerals

1,11 feed oil supply conduit 3,20 reaction column 4,12,16,22 distillation column

Claims (8)

Maximum pore diameter of the micropores 0.6～1.0Nm, carriers which SiO ₂ / Al ₂ O ₃ ratio contains a Y-type zeolite is 50 or more, Group VIII metals and Group VIA metals A catalyst obtained by supporting at least one metal selected from the group consisting of benzene and an aromatic hydrocarbon compound having 9 or more carbon atoms in the presence of hydrogen in the presence of hydrogen. And a catalyst for conversion of an aromatic hydrocarbon compound used in a method of converting into an aromatic hydrocarbon compound having 8 carbon atoms. The catalyst according to claim 1, wherein the boiling point of the feedstock is 30 to 210 ° C. The catalyst according to claim 1, wherein the feedstock is selected from reformed gasoline or catalytic cracking gasoline. Claim 1, wherein the catalyst SiO ₂ / Al ₂ O ₃ ratio of Y-type zeolite is 100 to 300. Maximum pore diameter of the micropores 0.6～1.0Nm, carriers which SiO ₂ / Al ₂ O ₃ ratio contains a Y-type zeolite is 50 or more, Group VIII metals and Group VIA metals Benzene and an aromatic hydrocarbon compound having 9 or more carbon atoms contained in a feed oil in the presence of hydrogen using a catalyst obtained by supporting at least one metal selected from And an aromatic hydrocarbon compound having 8 carbon atoms. 6. The conversion method according to claim 5, wherein the boiling point range of the feed oil is 30 to 210C. 6. The conversion method according to claim 5, wherein the feed oil is selected from reformed gasoline or catalytic cracking gasoline. The method of conversion according to claim 5, wherein SiO ₂ / Al ₂ O ₃ ratio of Y-type zeolite is 100 to 300.

Images