JP3113912B2 - Method for hydroisomerizing aromatic hydrocarbons contained in aromatic hydrocarbons or hydrocarbons containing aromatic hydrocarbons, and catalyst used in the hydroisomerization method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for hydroisomerizing aromatic hydrocarbons contained in aromatic hydrocarbons and hydrocarbons including aromatic hydrocarbons, and a method for hydroisomerizing the same. Regarding the catalyst.

[0002]

2. Description of the Related Art In the production of gasoline in the petroleum refining industry, it is common practice to carry out contact reforming in which a hydrocarbon of a naphtha fraction is brought into contact with a catalyst under hydrogen pressure.
This catalytic reforming reaction is a complicated reaction including various reactions such as decomposition, dehydrogenation, isomerization, alkylation, and cyclization. This catalytic reforming reaction can improve the octane number of the obtained gasoline, and is widely used as a reaction for producing gasoline. By the way, the gasoline thus obtained contains aromatic hydrocarbons. In addition to gasoline, diesel fuels include aromatic hydrocarbons such as naphthalene. However, it has been pointed out that when these fuels are used, aromatic hydrocarbons such as benzene are emitted as unburned components and become air pollutants. Therefore, benzene is contained in hydrocarbons for fuel. It is desired not to contain. In the petrochemical industry, aromatic hydrocarbons such as benzene and toluene are obtained, but in these industries, the purpose of using benzene and toluene is limited, and in some cases, it is desired to use more. It needs to be converted to a cyclocyclic hydrocarbon or an aliphatic hydrocarbon. Conventionally, in such a case, a hydrogenation reaction of an aromatic hydrocarbon has been used, and a catalyst in which a group IVb metal and a group VIII metal are supported on a refractory inorganic oxide has been used as a catalyst ( JP 6
JP-A-116570, JP-A-6-500148). However, according to these methods, the hydrogenation reaction is achieved but the isomerization reaction is not sufficiently achieved, and when the obtained product is used as a fuel oil, satisfactory results cannot be obtained. . In the reforming reaction, sulfuric acid, aluminum chloride, antimony trichloride, hydrogen fluoride, and the like are used. However, hydrocarbons treated with these contain components that corrode the apparatus, so that they are used. There is a need to remove acids associated with exhaust gases and products. As a method of performing the reforming reaction while preventing such unfavorable effects, there is known a method of treating a metal oxide or hydroxide of Group IV of the periodic table with an aqueous solution containing a sulfate group and then using a fired catalyst. (JP-B-59-6181, JP-A-Heisei 143).
348, JP-A-4-187239). The purpose of this method is to perform a reforming reaction as described above, in which a hydrocarbon containing an aromatic hydrocarbon obtained by the reforming treatment is hydrogenated to hydrogenate the aromatic hydrocarbon. Is not taken into account. Methods for hydrogenating and isomerizing hydrocarbons including benzene are described in JP-A-9-188633 and JP-A-9-346.
No. 0 is known, but this method is a two-stage method in which a hydrogenation reaction of benzene is performed and then an isomerization reaction is performed. As a method performed in one stage, Japanese Patent Laid-Open No. 7-2
No. 78569 and Japanese Patent Application Laid-Open No. 9-3449 are known, and this method is applied to a specific aluminosilicate with VI.
A catalyst supporting a Group II metal is used.In addition to the isomerization of hydrocarbons, a decomposition reaction produces a large amount of by-product gas, and satisfactory results have not been obtained. It was in a state where it had not been done.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to hydrogenate aromatic hydrocarbons contained in aromatic hydrocarbons or hydrocarbons containing aromatic hydrocarbons by hydrogenation and isomerization. To provide a hydroisomerization method for producing an alicyclic hydrocarbon in which an alicyclic hydrocarbon is isomerized, and a catalyst used in the hydroisomerization method.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on the above-mentioned problems, and as a result, have conducted a hydrogenation treatment on a hydrocarbon containing an aromatic hydrocarbon so that the aromatic hydrocarbon is hydrogenated and isomerized at the same time. When the catalyst is used by supporting a group VIII metal on a support made of a specific solid acid, the hydrogenation of aromatic hydrocarbons can be promoted, and the isomerization reaction of the obtained alicyclic hydrocarbons can also be performed. They have found that they can proceed at the same time, and have completed the present invention. That is, according to the present invention, a hydrocarbon containing an aromatic hydrocarbon,
Tungsten zirconia supported on high surface area silica ?
In the presence of a Group VIII metal catalyst supported on a solid acid comprising
Hydrogenation of aromatic hydrocarbons by contacting them with hydrogen under pressure to produce alicyclic hydrocarbons and isomerized alicyclic hydrocarbons. Hydrotreating method, supported on solid acid consisting of tungsten zirconia supported on high surface area silica
Provided is a catalyst for hydroisomerization of an aromatic hydrocarbon or an aromatic hydrocarbon containing an aromatic hydride, characterized by comprising a selected Group VIII metal.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The hydrocarbon to be treated in the present invention is an aromatic hydrocarbon or a hydrocarbon containing an aromatic hydrocarbon. The hydrocarbon containing an aromatic hydrocarbon is a hydrocarbon of a gasoline fraction containing an aromatic hydrocarbon, and has a boiling point range of a gasoline fraction. Specifically, it contains an aliphatic hydrocarbon and an alicyclic hydrocarbon in addition to the aromatic hydrocarbon. The content of hydrocarbons other than aromatic hydrocarbons can be in any range as long as the reaction is not hindered. In addition, the hydrocarbon fraction used as a solvent can also be treated if it contains aromatic hydrocarbons. For example, a cleaning solvent (140 to 200)
C), solvents such as paints, insecticides and inks (200-3
20 ° C.). Hydrocarbons produced from the petrochemical process include hydrocarbons containing benzene, toluene, xylene, etc., and may be a mixture of these or a single component consisting of only individual components. No problem. Hydrocarbon products including benzene, toluene or xylene in petrochemicals can be mentioned.

The hydroisomerization catalyst of the present invention is a solid acid catalyst supporting a Group VIII metal. Many catalysts such as zeolite, mordenite, and silica alumina are known as solid acid catalysts. The solid acid catalyst used in the present invention is tungsten zirconia supported on high surface area silica. These solid acid catalysts are produced as follows. Tungsten zirconia is obtained after preparing a suspension containing each of tungsten and zirconia, mixing these to form a suspension of tungsten zirconia, and heating the water to separate and remove water by evaporation or the like. Specifically, it is manufactured as follows. After adding an alkali to a tungsten hydrate to form a suspension, and mixing an aqueous solution containing a metal salt of zirconium with an alkali to form a suspension of a hydroxide, the mixture is heated. The water is evaporated, dried, heated and fired. The solid acid is supported on silica having a high surface area by adding silica to a suspension of solid acid (tungsten zirconia) and sufficiently adsorbing the solid acid on silica. The high surface area silica used in the present invention has a large specific surface area and is 200 m ² / g, preferably 270 m ² / g.
m ² / g.

[0007] The present invention has the hydroisomerization function,
The solid acid supporting the Group VIII metal is the catalyst VI described below.
Group II metals include platinum, nickel, cobalt, palladium, rhodium, iridium, ruthenium, and the like. Among these, when platinum and nickel are used, good results can be obtained. The group VIII metal is supported on the solid acid as follows. An aqueous solution composed of a salt of a Group VIII metal is prepared so as to have a required concentration, and the solution before baking of the solid acid is added to the aqueous solution, mixed well, dried, and heated and calcined. Alternatively, after the solid acid after firing is immersed in an aqueous solution of a group VIII metal having a required concentration to allow the solid acid to adsorb the group VIII metal, drying and heating can be performed in the same manner as described above. The ratio of the transition metal to the carrier can be changed at an arbitrary ratio. Generally, it is supported on the carrier in a range of about 0.5 to 5% by weight.

[0008] The catalyst thus produced is 100
Dried in an air stream heated to about 200 ° C.,
The activation treatment is performed at 850 ° C, preferably 500-600 ° C. The catalyst can be used in the form of granules, tablets, pellets and the like.

In the method of the present invention, an aromatic hydrocarbon such as benzene or a hydrocarbon containing an aromatic hydrocarbon such as benzene and hydrogen are treated in the presence of a solid acid catalyst supporting the aforementioned group VIII metal. And hydrogenating an aromatic hydrocarbon to form an alicyclic hydrocarbon, and simultaneously performing isomerization of the alicyclic hydrocarbon. This hydroisomerization treatment can be performed in one stage, but can also be performed in two stages. In the two-stage process, the reaction material is subjected to the hydrogenation / isomerization treatment in the preceding stage, and then to the product containing the hydrogenated product,
The isomerization treatment is performed. Hydrogen is introduced separately into two reaction zones, a first stage and a second stage. The catalyst used is
It is also possible to use a solid acid catalyst carrying the Group VIII metal in the preceding and subsequent stages, or use a solid acid catalyst carrying the Group VIII metal in the preceding stage and a catalyst comprising the solid acid catalyst in the later stage be able to. In some cases, another hydrogenation catalyst may be used in the first step, and a solid acid catalyst supporting the group VIII metal may be used in the second step. The method of the present invention is performed under the following conditions. The reaction temperature is 190-3
It is in the range of 00C, preferably 200-250C. The reaction pressure is 20 to 100 kg / cm ² , preferably 25
８０80 kg / cm ² . This pressure indicates the hydrogen partial pressure. Hydrocarbon supply (liquid hourly space velocity, HSV)
Is 0.2 to 4.0 h ^-1 , preferably 0.2 to 3.0
h- ¹ . The hydrogen / oil ratio is preferably 200
0-5000 scf / bbl—raw material, preferably 25
00 to 3500 scf / bbl-range of raw material.

According to the present invention, an aromatic hydrocarbon such as benzene contained in a raw material hydrocarbon is hydrogenated to an alicyclic hydrocarbon, and at the same time, the alicyclic hydrocarbon is isomerized. You. As a result, benzene can be converted to methylcyclopentane by the isomerization that occurs simultaneously with the hydrogenation, resulting in a hydrocarbon mixture having an improved octane number. Therefore, when using the obtained product as a fuel, preferable gasoline can be obtained. Further, since this fuel no longer contains aromatic hydrocarbons such as benzene, even when the fuel is burned, no adverse effects are caused by the aromatic hydrocarbons, and the environment can be maintained in a favorable state. Further, since the hue-deteriorating substance contained in the hydrocarbon is hydrogenated, it can be converted to a hydrotreated oil having a good hue and light resistance. In addition, aromatic hydrocarbons such as benzene, toluene and xylene by-produced can be converted into other hydrogenated hydrocarbons in the petrochemical industry and the like. In toluene and xylene, benzene is produced by a dealkylation reaction, and then cyclohexene is produced by a hydrogenation reaction of benzene to produce methylcyclopentane.

[0011]

EXAMPLES Specific examples of the present invention will be shown below as examples. The content of the present invention is not limited to this. Example 1 (Preparation of the catalyst of the present invention and a platinum catalyst supported on tungsten zirconia or sulfate zirconia as comparative examples) ZrOCl ₂ was hydrolyzed (aqueous ammonia) to obtain Zr (OH) ₄ with 1N sulfuric acid. Contact, filter, dry at 110 ° C., Zr
(OH) ₄ / H ₂ SO ₄ was obtained. In the case of tungsten zirconia, 4138.91 g of Zr (OH) is added in 200 g of water at 60 ° C. for 1 hour at 300 r.
Stirred at pm. Ammonium metatungsten hydrate
[(NH4) 6 (H2W12O40)] 57.6 g of an aqueous solution of
Was adjusted to 10 and stirred for 50 minutes. After leaving this for 10 minutes,
To the suspension of Zr (OH) 4 was added dropwise with stirring (100 drops /
Min) and heated to dryness in a hot water bath (75-80 ° C.) for 15 hours. Then, dried in a dryer at 110 ° C for 24 hours, [(NH4) 6
(H2W12O40)] / Zr (OH) 4 was obtained. In addition, a zirconium hydroxide solution is adsorbed on silica having a high surface area of 270 m ² / g or more, and after drying, 57.6 g of an aqueous solution of [(NH4) 6 (H2W12O40)] is contacted and adsorbed. A zirconia catalyst precursor (before firing) was prepared.
The catalyst precursors thus obtained were all 500
Sintered zirconia, tungsten zirconia, and silica-supported tungsten zirconia (tungsten zirconia supported on SiO ₂ having a high surface area) were prepared by air calcination at 800800 ° C. When carrying the metal having a hydrogenating function, chloroplatinic acid hexahydrate _{(H 2 PtCl 6 · 6H 2} O) , which corresponds to the supported amount, nickel nitrate hexahydrate (N
An aqueous solution of i (NO ₃ ) ₂ .6H ₂ O) was added to the precursor before calcination and mixed well. This was air-dried at room temperature for 24 hours and then dried at 110 ° C. for 36 hours in a drier. The resulting H ₂ Pt
Using an electric furnace, hold the precursor adsorbed with Cl ₆ or Ni (NO ₃ ) ₂ at a temperature rise of 1 ° C./min and 200 ° C. for 1 hour.
Baking was performed at a temperature of 500 to 800 ° C. for 3 hours. Thus, a metal-supported solid superacid composite catalyst was obtained. The catalyst particle size was adjusted to 26 to 42 mesh using a molding machine.

Comparative Examples 1 and 2 (Preparation of Catalysts of Comparative Examples Other Than Platinum Catalyst Supported on Tungsten Zirconia or Sulfate Zirconia) A conventional catalyst, Y-type zeolite or mordenite catalyst was used as a comparative example catalyst JRC-HY Catalyst Reference Catalyst
5.6. What carried platinum on JRC-Z-HM10 was used.

Example 2 (Hydrogenation / isomerization reaction of benzene) Using 150 g of a stainless steel autoclave, 3 g of benzene, 1 g of the catalyst produced in Example 1 and 11 g of a solvent (pentanes) were used. The reaction conditions were as follows. Reaction temperature 250 ° C, hydrogen initial pressure 3.5MPa, heating rate 15 ° C /
Minutes, retention time 60 minutes. Prior to the reaction, the catalyst was heated at 350 ° C.
And exhausted for 20 minutes. The analysis of the reaction product was performed by GC. Comparing with the isomerization rate to methylcyclopentane from benzene, not in Pt / In ZrO ₂ completely _{proceed, Pt / SiO 2 / Al 2} O 3 in 3
%, 5.6% for Pt / HY, and about 1 for Pt / HM10
It was 0%. Pt _/ ^SO 4 2- _/ ZrO ₂ in 47%
And a remarkably high result was obtained as compared with other catalysts. The results of the hydroisomerization of benzene are shown in FIGS.

From the above results, the following has been found. According to the catalyst of the present invention, methylcyclopentane, which is a product of the hydroisomerization reaction, can be obtained at a good ratio. Then, as shown in FIG. 1, unreacted benzene did not exist in any case, and almost all disappeared, indicating that the reaction rate was high.

[0015]

According to the method of the present invention, the aromatic hydrocarbon contained in the hydrocarbon to be treated can be hydroisomerized, so that the hydrocarbon obtained by the present invention is used as a fuel. No adverse effects due to aromatic hydrocarbons occur during the combustion treatment, and the environment can be maintained in a favorable state. In addition, by performing the above reaction using the catalyst of the present invention, a hydroisomerization product as a reaction product can be obtained, and good results can be obtained. Also,
By subjecting a hydrocarbon used for a solvent or the like to a treatment similar to that described above, an aromatic hydrocarbon-free hydrocarbon can be obtained, so that a solvent satisfying environmental regulations and regulations for humans can be obtained. Further, the aromatic hydrocarbon obtained in the petrochemical process can be an alicyclic hydrocarbon.

[Brief description of the drawings]

FIG. 1 is a diagram showing the hydroisomerization rate of benzene with a catalyst in which platinum is supported on a solid acid catalyst.

FIG. 2 shows the hydroisomerization of a benzene fraction from petroleum refinery treated with metal-supported tungsten zirconia.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C10G 35/06 C10G 35/085 B01J 23/652 B01J 23/85

Claims (2)

(57) [Claims] 1. An aromatic hydrocarbon or a hydrocarbon containing an aromatic hydrocarbon is added to hydrogen in the presence of a group VIII metal catalyst supported on a solid acid comprising tungsten zirconia supported on high surface area silica. Aromatic hydrocarbons or hydrocarbons containing aromatic hydrocarbons, characterized in that aromatic hydrocarbons are hydrogenated to alicyclic hydrocarbons by treating under reduced pressure, and are simultaneously isomerized to produce alicyclic hydrocarbons. A method for hydroisomerizing hydrogen. 2. An aromatic hydrocarbon or a hydrocarbon containing an aromatic hydrocarbon, comprising a group VIII metal supported on a solid acid comprising tungsten zirconia supported on silica having a high surface area. Hydroisomerization catalyst.