JP2000117112A - Hydrodesulfurization catalyst for gasoline fraction, method for producing the same, and gasoline composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst capable of desulfurization while maintaining the performance of gasoline, and to provide a method for hydrodesulfurization of a gasoline fraction using the catalyst, a desulfurized gasoline and a gasoline composition. SOLUTION: The catalyst is a catalyst in which a metal belonging to Group 8 of the periodic table and phosphorus are supported on alumina, or a catalyst wherein a metal belonging to Group 8 of the periodic table, a group 6B metal in the periodic table and phosphorus are supported on alumina. Catalyst having a surface area of 280 m ² / g or more, a pore diameter of 50 ° or more and a pore volume of 0.5 cc / g or more, a hydrodesulfurization treatment method using the same, a desulfurized gasoline obtained by the desulfurization treatment, and a gasoline composition object.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel catalyst used in the field of gasoline production, a method for producing the same, a method for hydrodesulfurizing a gasoline base material using the catalyst, a desulfurized gasoline and a gasoline composition.

[0002]

2. Description of the Related Art At present, there is an increasing need for a reduction in environmental load worldwide, and a reduction in the sulfur content of gasoline is required. As a desulfurization method for gasoline production, an alkaline cleaning method such as the Marlox method has been known for a long time. However, this desulfurizes mainly mercaptans, and there is a limit in reducing the sulfur content in desulfurized gasoline. In addition, hydrodesulfurization treatment using a naphtha catalyst is widely performed, and it is known that a catalyst composition in which molybdenum and nickel or cobalt are supported on an alumina carrier is generally effective for this catalyst (Japanese Patent Laid-Open Publication No. 6-2265
No. 72). A method for producing a hydrodesulfurization catalyst for hydrocarbon oils using aluminum alkoxide is also known (Japanese Patent Application Laid-Open No. Hei 5-76766). It is a special catalyst containing metal as sulfide. Therefore, the desulfurization reaction of the catalysts produced by these methods proceeds sufficiently, but at the same time, hydrogenation reaction of olefins and the like occurs, and no consideration has been given to side reactions such as reduction of octane number. For this reason, there is a case where there is a problem in using desulfurized gasoline as it is as a gasoline base material.

On the other hand, it is known that a catalyst in which phosphorus is supported on an active alumina carrier is effective for hydrodesulfurization (Japanese Patent Publication No. 2-18136, Japanese Patent Publication No. 6-61464).
No.). Although the effect of adding phosphorus has not been fully elucidated, it is said that the effect is to improve the dispersibility of the active metal component and to optimize the reactivity and selectivity of the catalyst by combining with the active metal component. Have been done. As a technique for further improving the dispersibility of the active metal component, it has been proposed to add the metal component and phosphorus at the stage of producing alumina (JP-A-63-123448, JP-A-3-123448).
No. 275142). However, since phosphorus usually shows high reactivity with alumina, most of the phosphorus binds to the alumina and does not work effectively, and when a large amount of phosphorus is added, the aggregation of metal components is rather caused. There was a problem that it was not preferable.

Furthermore, it has recently been shown that a specific hydrogenation selectivity can be obtained when phosphorus and a Group 8 metal are combined in a special state (Journal of Catalysis).
s, vol. 161, p. 539, 1966). However, in the case of an alumina carrier, there is a problem that it is extremely difficult to produce an effective catalyst by a usual preparation method due to the strong reactivity between phosphorus and alumina. Therefore, as a catalyst for hydrotreating heavy oil, which requires high reactivity and durability, there is a report as described above, but highly selective hydrogen for gasoline base material production, which emphasizes properties such as octane number. The use of phosphorus as a hydrodesulfurization catalyst has not been studied.

[0005]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a novel catalyst exhibiting an effective hydrodesulfurization ability for a hydrodesulfurization treatment for producing a gasoline base material. Another object of the present invention is to provide a method for producing a catalyst that can easily and practically produce the catalyst of the present invention.

The present invention further provides a method for advantageously performing hydrodesulfurization of various gasoline fractions, especially cracked gasoline, using the novel catalyst of the present invention, and provides a high-performance method. It is another object to provide a gasoline base material and a gasoline composition using the same.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, aluminum alkoxide was prepared in the presence of alcohol or ether.
Prepare an alumina carrier from the gel obtained by mixing with water,
It has been found that a catalyst produced by adding phosphorus, a metal of Group 6B of the Periodic Table and a metal of Group 8 of the Periodic Table to this carrier is effective as a desulfurization catalyst for gasoline fractions.

[0008] Further, 5 to 30% by weight of phosphorus is contained,
An alumina-supported catalyst carrying a Group 8 metal of the Periodic Table or a Group 8B metal of the Periodic Table and a Group 6B metal of the Periodic Table;
It has been found that a catalyst having a specific surface area of 280 m ² / g or more, a pore diameter of 50 ° or more and a pore volume of 0.5 cc / g or more is effective as a desulfurization catalyst for gasoline fraction, and completed the present invention. .

That is, the gist of the present invention is as follows. (1) An alumina carrier catalyst containing 5 to 30% by weight of phosphorus and supporting a metal of Group 8 of the periodic table or a metal of Group 6B of the periodic table, and having a specific surface area of A hydrodesulfurization catalyst for a gasoline fraction having a pore size of at least 280 m ² / g, a pore diameter of at least 50 ° and a pore volume of at least 0.5 cc / g.

(2) The content of the metal of Group VIII of the periodic table is 1
The hydrodesulfurization catalyst according to (1), which is 0 to 30% by weight. (3) The content of the Group 6B metal in the Periodic Table is 8 in the Periodic Table.
The hydrodesulfurization catalyst according to (1) or (2), which has a content of a group metal or less. (4) Phosphorus and periodicity are added to an alumina carrier obtained from a gel formed by mixing aluminum alkoxide with water in the presence of alcohol or ether, or a carrier obtained from a mixture obtained by adding a molding binder to the gel. The method for producing a hydrodesulfurization catalyst according to any one of (1) to (3), further comprising including a Group 8 metal of Table 8 and a Group 6B metal of Periodic Table as necessary.

(5) Mixing aluminum alkoxide, a phosphorus compound, a Group 8 metal compound of the Periodic Table and, if necessary, a Group 6B metal compound with water in the presence of an alcohol or ether. Features (1)-
The method for producing a hydrodesulfurization catalyst according to any one of (3). (6) The method for producing a hydrodesulfurization catalyst according to (4) or (5), wherein the alcohol is an aliphatic polyhydric alcohol having two or more hydroxyl groups.

(7) The alcohol is a second alcohol having 5 or more carbon atoms.
The method for producing a hydrodesulfurization catalyst according to any one of (4) to (6), which is a secondary or tertiary alcohol. (8) The method for producing a hydrodesulfurization catalyst according to any one of (4) to (7), wherein the alcohol or ether has a molecular weight of 100 or more. (9) A method for hydrodesulfurizing a gasoline fraction using the hydrodesulfurization catalyst according to any one of (1) to (3).

(10) The hydrodesulfurization method according to (9), wherein the gasoline fraction is cracked gasoline. (11) Obtained by the hydrodesulfurization method according to (9) or (10), has a sulfur content of 50 ppm or less, a research octane value of 86 or more, and a distillation property of 30 to 220 ° C.
Gasoline base material that is in the range. (12) The gasoline base material according to (11), wherein the olefin content is in a range of 15 to 50% by volume.

(13) The gasoline base material according to (11) or (12), and at least one gasoline base material among a reformed gasoline, an alkylated gasoline, and an oxygen-containing gasoline base material, and having a sulfur content of Is 50 ppm or less, the research octane number is 90 or more, and the distillation property is 30 to
A gasoline composition having a temperature in the range of 220 ° C. and a vapor pressure in the range of 50 to 80 kPa.

[0015]

Embodiments of the present invention will be described below. The catalyst of the present invention is an alumina-supported catalyst containing 5 to 30% by weight of phosphorus and supporting a Group 8 metal of the Periodic Table or a Group 8B metal of the Periodic Table and a Group 6B metal of the Periodic Table. The amount of phosphorus contained in alumina, which is a carrier of the catalyst of the present invention having a specific surface area of 280 m ² / g or more, a pore diameter of 50 ° or more, and a pore volume of 0.5 cc / g or more, is based on the weight of the catalyst. And 5 to 30% by weight, preferably 5 to 25% by weight, as atoms. If the phosphorus content is less than 5% by weight, the hydrogenation activity of the catalyst is too strong, and undesired hydrogenation reactions, such as hydrogenation of olefins having a high octane number, are not preferred. If it exceeds 30% by weight, phosphorous aggregation may occur, which is not preferable. In addition, the phosphorus contained in the catalyst includes those supported on an alumina carrier and those bonded to alumina to form a carrier component.

Further, the catalyst of the present invention needs to support a metal of Group 8 of the periodic table, or a metal and a metal of Group 6B of the periodic table, in addition to the phosphorus content. Examples of the metals of Group 8 of the periodic table that constitute the catalyst of the present invention include iron, cobalt, and nickel, and at least one of them is used. Preferably, they are cobalt and nickel. The amount of the metal to be supported is 10 to 30% by weight, preferably 10 to 25% by weight of the metal based on the weight of the catalyst. If the amount of the supported metal is less than 10% by weight, a sufficient hydrogenation effect may not be obtained, and if it exceeds 30% by weight, metal aggregation may occur, which is not preferable.

Further, as the catalyst of the present invention, Periodic Table 6
In the case where a Group B metal is further supported, chromium, molybdenum, tungsten, and the like are given as Group 6B metals of the periodic table, and at least one of them is used. Molybdenum and tungsten are preferred. The content of the group 6B metal in the periodic table is preferably not more than the content of the group 8 metal in the periodic table, calculated as a metal based on the weight of the catalyst. If the content of the Group 6B metal in the Periodic Table is too large, the hydrogenation activity of the catalyst will be too strong, and undesirable hydrogenation reactions, such as hydrogenation of olefins having a high octane number, will occur. A reaction occurs, which is not preferable. Further, the periodic table No. 6
The content of the group B metal is 30% by weight or less, preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, calculated as a metal based on the weight of the catalyst. If it exceeds 30% by weight, metal aggregation may occur, which is not preferable.

The catalyst of the present invention has a specific surface area of 280 m.
^Two/ G or more, a pore diameter of 50 ° or more and a pore volume of 0.5
cc / g or more. Specific surface area is normal hydrocarbon oil water
280 m^Two/ G or more,
Preferably 280-380m ^Two/ G. 280m^Two
If it is less than / g, the reactivity will decrease. Pore diameter
Is 50 ° or more, preferably 50 to 100 °. 50
If it is smaller than Å, the reactivity will rapidly decrease. Fine
The pore volume is 0.5 cc / g or more, preferably 0.5 to 1.
5 cc / g, preferably 0.55 to 1.0 cc / g
You. If the pore volume is too small, the hydrogenation activity will decrease.
U.

Next, a preferred method for producing the catalyst of the present invention will be described. An alumina carrier obtained from a gel formed by mixing aluminum alkoxide with water in the presence of an alcohol or an ether, or a carrier obtained from a mixture of the gel and a binder for molding, contains phosphorus and Group 8 of the periodic table. Metal or phosphorus, said metal and Periodic Table 6
This is a method of containing (or carrying) a Group B metal. The addition of a molding binder during the production of the carrier has the meaning of improving moldability. In the present invention, it is important to mix the aluminum alkoxide with water in the presence of alcohol or ether to form a gel, and to prepare a carrier therefrom. In this step, the specific surface area, pore diameter and pore volume of the catalyst are substantially determined. Thereafter, the phosphorus compound and a metal compound of Group 8 of the periodic table, or a metal compound of Group 6B of the periodic table are supported or contained in the carrier. Usually, this is dried and calcined by a usual method to obtain the catalyst of the present invention. The shaping may be performed at the stage of the carrier or after supporting the metal. When a molding binder is not added, it is preferable to add it at a stage before molding.

As another production method of the present invention, an aluminum alkoxide, a phosphorus compound, a metal compound of Group VIII of the periodic table, or a compound of the group 6B and the periodic table VIII can be used.
There is a method for producing a catalyst in which a substance containing a group metal compound is mixed with water in the presence of an alcohol or ether to form a gel substance, which is then dehydrated, dried and calcined. When molding is desired, molding can be facilitated by further using a molding binder.

The raw materials used for producing the catalyst of the present invention will be described sequentially. Although it does not specifically limit as aluminum alkoxide, For example, aluminum n-butoxide, aluminum sec-butoxide, aluminum tert-butoxide, aluminum iso
-Propoxide, etc., which are used alone or in combination. In addition, these aluminum alkoxides can be diluted with an organic solvent such as hydrocarbons such as acetone and toluene for adjusting the viscosity.

The phosphorus compound is not particularly restricted but includes, for example, aqueous phosphoric acid, phosphoric anhydride, phosphorus pentoxide,
Examples thereof include ammonium salts and the like, which are used alone or in combination. As the Group 8 metal compound of the periodic table, chlorides, nitrates, sulfates, acetates, ammonium salts, carbonates, hydroxides and the like are used. Specific examples include nickel nitrate, cobalt nitrate, nickel carbonate, cobalt carbonate, nickel acetate, cobalt acetate, nickel chloride, nickel sulfate, nickel hydroxide, cobalt chloride, cobalt sulfate and the like. You.

As the Group 6B metal compound of the periodic table, chlorides, oxides, ammonium salts and the like are used. Specifically, ammonium paramolybdate, ammonium paratungstate, ammonium metamolybdate, ammonium metatungstate, molybdenum trioxide, tungsten trioxide, molybdenum chloride, tungsten chloride, etc., may be used alone or as a mixture. You.

As the alcohol, any alcohol may be used, such as an aliphatic polyhydric alcohol having two or more hydroxyl groups, a secondary or tertiary alcohol having 5 or more carbon atoms, or an alcohol having a molecular weight of 100 or more. It is desirable. Further, any ether may be used, but it is preferable that the ether has a molecular weight of 100 or more.

The aliphatic polyhydric alcohol having two or more hydroxyl groups is not particularly restricted but includes, for example, propanediol, glycerin, butanediol,
Examples thereof include butanetriol, erythritol, pentanediol, and sorbitol, which are used alone or in combination. Among them, 1,2-propanediol;
2,4-butanetriol; 1,3-butanediol;
Among the two or more hydroxyl groups such as 1,2-pentanediol, those in which at least one hydroxyl group is bonded to other than the terminal carbon atom are preferable, and among them, 1,3-butanediol; Those having a boiling point of 120 ° C. or higher such as pentanediol are more preferred.

The secondary or tertiary alcohol having 5 or more carbon atoms includes 5-methyl-1 hexanol, isoamyl alcohol, (3-methyl-1-butanol),
Methyl-2 butanol, isoundecylene alcohol,
Isooctanol, isopentanol, isogellanol, isohexyl alcohol, 2,4 dimethyl-1-pentanol, 2,4,4 dimethyl-1-pentanol and the like can be mentioned.

The alcohol or ether having a molecular weight of 100 or more is preferably water-soluble. This is because there is a mixing step with water. Examples of these include polyethylene glycol, polyoxyethylene phenyl ether, ether-containing water-soluble polymers such as polyoxyethylene octyl phenyl ether and alcoholic water-soluble polymers such as polyvinyl alcohol, saccharose, various sugars such as glucose, methyl cellulose, There are water-soluble polysaccharides such as water-soluble starch or derivatives thereof. The above alcohols and ethers can be used alone or in combination of two or more.

Although any binder may be used for the molding, boehmite, alumina gel, silica gel, titania gel and the like prepared from inorganic salts are preferably used, and alumina gel obtained from an inorganic aluminum salt is particularly preferable. As the inorganic salts, inorganic salts such as aluminum, silicon and titanium, that is, chlorides, nitrates, sulfates, acetates, sodium salts and the like can be used. A gel may be formed by adding an alkali or an acid to at least one or more of these salts. Note that it is preferable to remove residual salts and the like by washing with water or the like.

An example of a method for producing the catalyst of the present invention using the above raw materials will be described. First, the step of forming a gel from aluminum alkoxide will be described. The ratio of alcohol or ether to alkoxide (ratio of number of alcohol or ether molecules / number of alkoxide molecules) is 0.05 to
5, preferably 0.1 to 3, and a water / alkoxide ratio (ratio of the number of water molecules / the number of alkoxide molecules) of 1 to 50, preferably 2 to 40, and 50 to 100 ° C, preferably 60 to 100 ° C. Mix at a temperature of ９０90 ° C. and hydrolyze to form a gel. If the conditions are out of the above range, an undesired reaction may proceed and the yield of the catalyst may be reduced.

The order of mixing the above-mentioned raw materials is not particularly limited, but it is preferable to carry out the mixing under conditions that the alkoxide does not react and gel before hydrolysis. One way is to
A method is preferred in which the above-mentioned alcohol or ether, an active metal component and a phosphorus compound are added to alkoxide diluted with an organic solvent such as alcohol, and water is further added to carry out hydrolysis. At the time of mixing, it is necessary to take care not to react with moisture in the air. The gel obtained by hydrolysis may be effectively aged for several hours in some cases. Usually, the obtained gel is dehydrated,
What is necessary is just to shape | mold, dry and bake, and to make it into a catalyst. In molding, it is preferable to use a molding binder.

Another method for producing the catalyst of the present invention is as follows.
The above alcohol or ether is added to alkoxide diluted with an organic solvent such as alcohol, and water is further added to hydrolyze. It is also effective to subject the gel obtained by hydrolysis to aging for several hours in some cases as described above. Usually, this is dehydrated, molded, dried, and calcined to prepare a carrier, and the active metal component and the phosphorus compound are supported on the carrier, and then dried and calcined to form a catalyst. Also in this case, it is preferable to use a molding binder at the time of molding. The molding may be carried out after supporting the metal or the like.

Dehydration is performed for convenience of molding and drying. The catalyst is usually molded and subjected to the reaction, but the molding is often performed before calcination. There is also a method of increasing the strength by firing and then firing again after firing. When carrying a metal component or the like after preparing the carrier, the carrier before loading may be molded,
The catalyst after carrying the metal component or the like may be molded.
As the molding method, general molding methods such as tablet molding, kneading, kneading and extrusion molding can be used. The binder does not need to be used during molding, but it is preferable to use the above-mentioned boehmite, alumina gel, silica gel, titania gel, or the like, and particularly preferable is an alumina gel obtained from an inorganic aluminum salt.

The shape of the molding is not particularly limited, but is generally spherical or columnar. In the case of an extruded product, its cross section is preferably circular, trilobal, or quadrilobular from the viewpoint of pressure loss when a catalyst is used and contact efficiency with a feedstock oil. In the case of molding after firing, it is preferable to perform drying and firing again after molding from the viewpoint of strength. In this case, it is preferable to carefully perform drying at 50 to 250 ° C, preferably 100 to 200 ° C, in dry air so as not to crack the catalyst.
Calcination in dry air at 300-700 ° C, preferably 3
What is necessary is just to perform on conditions of 50-600 degreeC.

As a method for drying the gel obtained from the alkoxide, general drying methods such as drying under reduced pressure, drying under normal pressure, and freeze-drying can be used, and they may be used alone or in combination. The drying condition is not particularly limited, but may be a condition under which water and an organic solvent for dilution are sufficiently removed and a material which can be easily fired in the next firing step is used. Usually, drying temperature 4
The temperature may be 0 to 200 ° C. and the drying time is 0.5 to 24 hours.

The firing step is a step which affects the pore structure of the catalyst after the gel formation step. As the firing method, a general firing method such as a flow-type firing furnace, a muffle furnace, and a rotary kiln can be used. It is desirable to carry out the reaction in the presence of a sufficient amount of air in order to remove organic substances and unnecessary crystallization water. The firing temperature is usually 400 to 700 ° C, preferably 450 to 600 ° C. Outside this range, the removal of organic substances and unnecessary crystallization water may be incomplete, or a catalyst having a desired pore structure may not be obtained,
The yield of the desired catalyst composition may decrease. The firing time is not particularly limited, but it is necessary to sufficiently perform dehydration, removal of organic substances, and the like. Usually, it is 0.5 to 24 hours.

Next, a method for hydrodesulfurization of a gasoline fraction using the catalyst of the present invention will be described. First, prior to hydrodesulfurization of the gasoline fraction, the catalyst of the present invention must undergo a sulfidation treatment. The sulfuration method may be carried out by bringing into contact with a sulfur-containing compound having a theoretical sulfuration amount equal to or more than the metal compound of Group 8 of the periodic table and the metal compound of Group 6B of the periodic table in the presence of hydrogen. The sulfurization temperature is usually from 200 to 450 ° C, preferably from 250 to 450 ° C. If it is too low, sulfuration may be insufficient, and if it is too high, aggregation of metal components may occur. The sulfurizing agent is not particularly limited, but various sulfur compounds such as hydrogen sulfide, dimethyl disulfide, carbon disulfide, and petroleum fractions such as gasoline fractions containing sulfur can be used.

As the gasoline fraction used in the hydrodesulfurization treatment, those containing sulfur to be desulfurized, containing useful olefins, and having a relatively high octane number, such as cracked gasoline such as catalytic cracked gasoline, are preferable. is there. This is because the catalyst of the present invention selectively performs desulfurization of a gasoline fraction, has a low hydrogenation activity for olefin components, and has an effect of suppressing a decrease in octane number. Normally, catalytic cracking gasoline has a boiling point of 30
Suitable raw materials include those of light catalytic cracking gasoline (boiling point of 30 to 140 ° C.), heavy catalytic cracking gasoline (boiling point of 70 to 220 ° C.), etc. It is.

The reaction conditions for the hydrodesulfurization treatment of the present invention vary depending on the type of the target feed oil and the properties of the target desulfurized gasoline, but the reaction temperature is usually 200 to 400.
C, preferably in the range of 250 to 380C. The reaction pressure is usually from normal pressure to 20 kg / cm ² ,
It is preferable to select the range of ^{2 to} 25 kg / cm ² . The reaction system is not particularly limited, but usually a flow system using a fixed bed is suitably adopted.

In the case of a fixed bed distribution system, LHS
V (liquid hourly space velocity) is ¹ to 20 h ^-1 , preferably 2 to 18 h ^-1 .
It is better to select within the range of h- ¹ . The supply ratio (hydrogen / hydrocarbon oil ratio) of hydrogen gas and hydrocarbon oil is usually 10 to 20.
0 Nm ³ / kl, preferably 12 to 180 Nm ³ / kl
It is preferable to select within the range.

By subjecting various gasoline fractions to hydrodesulfurization treatment using the catalyst of the present invention by the above-described method, desulfurized gasoline having a sufficiently low sulfur content and excellent properties such as octane number can be obtained in good yield. be able to. In addition, the amount of hydrogen consumed is reduced by the amount that the olefin is not hydrogenated. The resulting desulfurized gasoline is used as a base material for a gasoline composition (gasoline as a commercial product), and its properties are preferably adjusted as follows,
It can be manufactured by appropriately selecting the conditions of the above method.

Desulfurized gasoline has a sulfur content of 50 ppm
Or less (by weight), an octane value of 86 or more (research octane number), a distillation property in the range of 30 to 200 ° C., and an olefin content in desulfurized gasoline of 15 to 50%
(Capacity basis). Further, by adding at least one of reformed gasoline, alkylated gasoline, and oxygen-containing gasoline base material to the above desulfurized gasoline, the sulfur content is 50 ppm or less, the research octane number is 90 or more, and the distillation property is 30 or more. ~
A gasoline composition having a temperature in the range of 200 ° C. and a vapor pressure in the range of 50 to 80 kPa can be obtained. Moreover,
With the same base material configuration as above, its properties are 30% sulfur content.
It is possible to obtain a gasoline composition having a ppm or lower, a research octane number of 90 or higher, a distillation property in the range of 30 to 200 ° C, a 50% distillation temperature of 100 ° C or lower, and a vapor pressure in the range of 50 to 80 kPa. Further, with the same base material constitution as described above, the properties are as follows: the sulfur content is 10 ppm or less, the octane number is 90 or more, the distillation property is 30 to 200 ° C.,
% Distillation temperature 100 ° C or less, and vapor pressure 50-80 kPa
, And a gasoline composition in the range of In addition, commonly used additives such as detergents can be added to these gasoline compositions. These can be suitably used as high-performance gasoline compositions for automobile engines and the like.

[0042]

(Production of catalyst)

Example 1 150 cc of aluminum sec-butoxide, 100 cc of 1,3-butanediol (boiling point: 203 ° C.), and cobalt nitrate 6 in a flask equipped with a temperature controller maintained at 85 ° C.
41 g of water salt and 16 g of phosphoric anhydride were added. Further, 100 cc of distilled water was added at 85 ° C., and the mixture was stirred for 1 hour to obtain a gel. The gelled product was subjected to a rotary evaporator under reduced pressure at 60 ° C. for 1 hour,
After drying at 0 ° C. for 15 hours, it was calcined in air at 550 ° C. for 3 hours to obtain Catalyst 1. Table 1 shows the amount of metal carried on catalyst 1 and the like.
Table 2 shows the physical properties. The amount of metal carried is represented by weight% as metal or phosphorus. Example 2 A catalyst was prepared under the same conditions as in Example 1 except that polyethylene glycol (molecular weight: 400) was used instead of 1,3-butanediol. Table 1 shows the amount of metal supported on the catalyst 2 and the like, and Table 2 shows physical properties thereof.

Example 3 A catalyst was prepared under the same conditions as in Example 1 except that 2-hexanol was used in place of 1,3-butanediol. Table 1 shows the amount of metal supported on the catalyst 3 and Table 2 shows the physical properties.
Shown in Example 4 A catalyst was prepared under the same conditions as in Example 1 except that 1,2,4-butanetriol (boiling point 150 ° C.) was used instead of 1,3-butanediol. Table 1 shows the amount of metal supported on the catalyst 4 and the like, and Table 2 shows physical properties thereof.

Example 5 A catalyst was prepared under the same conditions as in Example 1 except that isohexyl alcohol (boiling point: 153 ° C.) was used instead of 1,3-butanediol. Table 1 shows the amount of metal carried on the catalyst 5 and the like, and Table 2 shows physical properties thereof. Example 6 A catalyst was prepared under the same conditions as in Example 1 except that 1-propanol was used instead of 1,3-butanediol, and a catalyst 6 was obtained. Table 1 shows the amount of metal supported on the catalyst 6 and Table 2 shows the physical properties.
Shown in

Example 7 Nickel nitrate hexahydrate instead of cobalt nitrate hexahydrate
A catalyst was prepared under the same conditions as in Example 1 except that 1 g was used, whereby Catalyst 7 was obtained. Table 1 shows the amount of metal carried on the catalyst 7 and the like, and Table 2 shows physical properties thereof. Example 8 A catalyst was prepared under the same conditions as in Example 7 except that 1-butanol was used instead of 1,3-butanediol.
I got Table 1 shows the amount of metal supported on the catalyst 8 and the like, and Table 2 shows physical properties thereof.

Example 9 150 cc of aluminum sec-butoxide, 100 cc of 1,3-butanediol (boiling point: 203 ° C.), cobalt nitrate 6 in a flask equipped with a temperature controller maintained at 85 ° C.
41 g of water salt, 2 g of ammonium molybdate tetrahydrate, and 16 g of phosphoric anhydride were added. Further, 100 cc of distilled water was added while maintaining the temperature at 85 ° C., and the mixture was stirred for 1 hour to obtain a gel. The gelled product was dried at 60 ° C. for 1 hour under reduced pressure using a rotary evaporator and at 120 ° C. for 15 hours using a blow dryer, and then calcined in air at 550 ° C. for 3 hours to obtain Catalyst 9. Table 3 shows the amount of metal supported on the catalyst 9 and Table 4 shows physical properties.
Shown in

Example 10 A catalyst was prepared in the same manner as in Example 9 except that 1,2,4-butanetriol (boiling point: 150 ° C.) was used instead of 1,3-butanediol. . Table 3 shows the amount of supported metal of the catalyst 10 and the like, and Table 4 shows physical properties thereof. Example 11 A catalyst was prepared in the same manner as in Example 9 except that ethanol was used instead of 1,3-butanediol, and a catalyst 11 was obtained. Table 3 shows the amount of metal carried on the catalyst 11 and Table 4 shows the physical properties.
Shown in

Example 12 150 cc of aluminum sec-butoxide and 100 cc of 1,3-butanediol (boiling point: 203 ° C.) were added to a flask equipped with a temperature controller maintained at 85 ° C.
While maintaining the temperature at 85 ° C., 10 cc of distilled water was added thereto.
After stirring for an hour, a gel was obtained. This gel was dried at 60 ° C. for 1 hour under reduced pressure by a rotary evaporator and at 120 ° C. for 15 hours by a blow dryer, and then dried in air at 500 ° C.
For 3 hours to obtain a carrier. 30 g of this carrier was impregnated with 41 g of cobalt nitrate hexahydrate and 16 g of phosphoric anhydride dissolved in distilled water at normal pressure. After leaving this for one hour,
After drying at 120 ° C. for 15 hours with a blast dryer, the mixture was calcined in air at 550 ° C. for 3 hours to obtain Catalyst 12. Table 3 shows the amount of metal carried on the catalyst 12 and the like, and Table 4 shows physical properties thereof.

Example 13 A catalyst was prepared in the same manner as in Example 12, except that 1-propanol was used instead of 1,3-butanediol, to obtain a catalyst 13. Table 3 shows the amount of metal supported on the catalyst 13 and the like, and Table 4 shows physical properties thereof. Comparative Example 1 41 g of nickel nitrate hexahydrate and 16 g of phosphoric anhydride were dissolved in distilled water to form an activated alumina carrier (specific surface area: 200 m ^2).
/ G) 30 g was impregnated at normal pressure. After leaving this to stand for 1 hour, it was dried at 120 ° C. for 3 hours, and dried at 500 ° C. with air for 3 hours.
After calcining for a time, catalyst 14 was obtained. Table 3 shows the amount of metal supported on the catalyst 14 and the like, and Table 4 shows physical properties thereof.

COMPARATIVE EXAMPLE 2 19 g of ammonium molybdate tetrahydrate, 16 g of nickel nitrate hexahydrate and 1.5 g of phosphoric anhydride were dissolved in distilled water to form an activated alumina carrier (specific surface area: 200 m ² / g).
g was impregnated at normal pressure. After allowing this to stand for 1 hour, 12
The catalyst was dried at 0 ° C. for 3 hours and calcined at 500 ° C. for 3 hours in air to obtain a catalyst 15. Table 3 shows the amount of metal supported on the catalyst 15 and the like, and Table 4 shows physical properties thereof.

Comparative Example 3 A catalyst was prepared in the same manner as in Comparative Example 1 except that the activated alumina carrier was not impregnated with phosphoric anhydride, and a catalyst 16 was obtained. Table 3 shows the amount of metal carried on the catalyst 16 and the like, and Table 4 shows physical properties thereof. Comparative Example 4 A catalyst was prepared in the same manner as in Comparative Example 2, except that the activated alumina carrier was not impregnated with phosphoric anhydride, thereby obtaining Catalyst 17. Table 3 shows the amount of metal carried on the catalyst 17 and the like, and Table 4 shows physical properties thereof.

Comparative Example 5 A catalyst was prepared in the same manner as in Example 11 except that phosphoric anhydride was not used, and a catalyst 18 was obtained. Table 3 shows the amount of metal carried on the catalyst 18 and the like, and Table 4 shows physical properties thereof. [Production of Desulfurized Gasoline] Example 14 Each of the catalysts was prepared at a temperature of 400 ° C. in a hydrogen sulfide / hydrogen stream as a pretreatment for desulfurization for producing desulfurized gasoline.
After being sulfurized for a time, it was used for hydrodesulfurization treatment.

The catalysts 1 to 15 were subjected to hydrodesulfurization using a catalytic cracking gasoline as a raw material in a fixed bed flow reactor to obtain a desulfurized gasoline. Table 5 shows the properties of the raw material catalytic cracking gasoline, Table 6 shows the hydrodesulfurization treatment conditions, Table 7 shows the properties of the desulfurized gasoline obtained by the treatment with the catalyst 1, and the sulfur content of the desulfurized gasoline obtained by the treatment with each catalyst. Tables 8 and 9 show the minutes and the like.

[Production of Gasoline Composition] Example 15, Comparative Example 6 A gasoline composition was prepared from the desulfurized gasoline obtained by the treatment with the catalyst 1 of Example 14 and the gasoline base material shown in Table 7 at a mixing ratio shown in Table 10. Was manufactured. Table 10 shows the properties of the obtained gasoline composition.

[0055]

[Table 1]

[0056]

[Table 2]

[0057]

[Table 3]

[0058]

[Table 4]

[0059]

[Table 5]

[0060]

[Table 6]

[0061]

[Table 7]

[0062]

[Table 8]

[0063]

[Table 9]

[0064]

[Table 10]

As shown in Tables 7 to 9, the sulfur content of desulfurized gasoline is lower than that of raw gasoline, but the octane number and olefin content are hardly reduced. Further, as shown in Table 10, the gasoline composition based on this desulfurized gasoline has a lower sulfur content than the gasoline composition based on the conventional base, and is suitable as a high-performance gasoline composition for automobile engines and the like. It turns out that it can be used.

[0066]

The hydrodesulfurization treatment catalyst for gasoline fractions using the catalyst composition of the present invention does not hydrogenate olefins, does not lower the octane number, The desulfurization treatment can be performed efficiently, whereby a high-performance gasoline base material with significantly reduced sulfur content and the like can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C10G 45/08 C10G 45/08 A C10L 1/04 C10L 1/04 F term (Reference) 4G069 AA01 BA01A BC28A BC66A BC67A BC68A BC70A BC71A BC72A BC73A BC74A BC75A BD07A BD08A BD09A BD10A CC02 EC03X EC04X EC05X EC07X EC08X EC14X EC15X EC16X EC17X 4H029 CA00 DA00

Claims (13)

[Claims] 1. A phosphoric acid containing 5 to 30% by weight of phosphorus, a metal belonging to Group 8 of the periodic table, a metal belonging to Group 8 of the periodic table, and a metal belonging to Group 6 of the periodic table.
Hydrodesulfurization of a gasoline fraction having a specific surface area of 280 m ² / g or more, a pore diameter of 50 ° or more, and a pore volume of 0.5 cc / g or more, which is an alumina carrier catalyst carrying a Group B metal. catalyst. 2. The content of Group 8 metal of the periodic table is 10 to 3
The hydrodesulfurization catalyst according to claim 1, which is 0% by weight. 3. The hydrodesulfurization catalyst according to claim 1, wherein the content of the Group 6B metal of the periodic table is not more than the content of the Group 8 metal of the periodic table. 4. An alumina carrier obtained from a gel formed by mixing aluminum alkoxide with water in the presence of alcohol or ether, or a carrier obtained from a mixture obtained by adding a molding binder to the gel, phosphorus, The method for producing a hydrodesulfurization catalyst according to any one of claims 1 to 3, further comprising a Group 8 metal of the periodic table and, if necessary, a Group 6B metal of the periodic table. 5. A method comprising mixing an aluminum alkoxide, a phosphorus compound, a metal compound of Group 8 of the Periodic Table, and optionally a metal compound of Group 6B of the Periodic Table with water in the presence of an alcohol or ether. The method for producing a hydrodesulfurization catalyst according to claim 1. 6. The alcohol according to claim 4, wherein the alcohol is an aliphatic polyhydric alcohol having two or more hydroxyl groups.
A method for producing the hydrodesulfurization catalyst according to the above. 7. The method for producing a hydrodesulfurization catalyst according to claim 4, wherein the alcohol is a secondary or tertiary alcohol having 5 or more carbon atoms. 8. The alcohol or ether having a molecular weight of 1
The method for producing a hydrodesulfurization catalyst according to any one of claims 4 to 7, which is at least 00. 9. A method for hydrodesulfurizing a gasoline fraction using the hydrodesulfurization catalyst according to claim 1. Description: 10. The hydrodesulfurization method according to claim 9, wherein the gasoline fraction is cracked gasoline. 11. A hydrodesulfurization method according to claim 9 or 10, having a sulfur content of 50 ppm or less, a research octane value of 86 or more, and a distillation property of 30 to 22.
Gasoline base material in the range of 0 ° C. 12. An olefin content of 15 to 50% by volume.
The gasoline base material according to claim 11, which is in the range of: 13. A gasoline base material according to claim 11 or at least one of a reformed gasoline, an alkylated gasoline and an oxygenated gasoline base material, wherein the sulfur content is 50 ppm or less. A gasoline composition having a research octane number of 90 or more, a distillation property in the range of 30 to 220 ° C., and a vapor pressure in the range of 50 to 80 kPa.