JPS62179593A - Production of aromatic-rich fraction - Google Patents

Abstract

PURPOSE:To enhance the conversion into or selectivity for an aromatic, by bringing a hydrocarbon having a low aromatic content into contact with gallium- contg. crystalline aluminosilicate. CONSTITUTION:The following starting hydrocarbon (I) is brought into contact with gallium-contg. crystalline aluminosilicate (II). Component (I): starting hydrocarbon composed mainly of at least one hydrocarbon having at least two carbon atoms selected from among paraffinic hydrocarbon, olefinic hydrocarbon, acetylenic hydrocarbon, cyclic paraffinic hydrocarbon, and cyclic olefinic hydrocarbon. Component (II): gallium-contg. crystalline aluminosilicate of the formula aGa2O3.bAl2O3.cSiO2.dGeO2.mM-2/nO [wherein M is H, alkali metal or alkaline earth metal; n is a valency of M; a, b, c, and d are respectively a>0, b>0, c>0, and d>=0, provided that a+b<=20, a/b=100/1-1/100, and c+d=100; and m is 0<=m<=3(a+b)].

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a fraction rich in aromatics, and more specifically, the present invention relates to a method for producing a fraction rich in aromatic components, and more specifically, the present invention relates to a method for producing a fraction rich in aromatic components, and more specifically, the present invention relates to a method for producing a fraction rich in aromatic components, and more specifically, the present invention relates to a method for producing a fraction rich in aromatic components. This invention relates to a method for efficiently producing the main ingredient.

[Prior art and problems to be solved by the invention] Conventionally, there has been a method for producing hydrocarbons rich in aromatic hydrocarbons (aromatic content) from raw material hydrocarbons containing non-aromatic hydrocarbons as the main component. Various methods using crystalline aluminosilicate such as ZSM-5 have been proposed, but none of these methods can be said to have sufficient selectivity for aromatic components. For example, JP-A No. 53-92717 discloses a method using an aluminosilicate ion-exchanged with gallium ions, but since the activity of this aluminosilicate is not high, the aromatic content is not recovered. The problem is that the rate is low. Furthermore, according to Inui et al., a method using gallosilicate has been announced (8th Intern,
Congr, Catal, Berlin, 1984
Even with this method, the selectivity for aromatic components is not sufficient.

Therefore, the present inventor conducted extensive research in order to solve the problems of the above-mentioned conventional techniques and to develop a method with a high conversion rate and selectivity to aromatic components.

[Means for solving problems]

As a result, they discovered that the object could be achieved by using a specific gallium-containing crystalline aluminosilicate as a catalyst, and the present invention was completed.

That is, the present invention mainly uses at least one hydrocarbon having two or more carbon atoms selected from the group consisting of paraffinic hydrocarbons, olefinic hydrocarbons, acetylenic hydrocarbons, cyclic paraffinic hydrocarbons, and cyclic olefinic hydrocarbons. The raw material hydrocarbon as a component is expressed by the general formula % formula % [wherein M represents hydrogen, an alkali metal or an alkaline earth metal, and n represents the valence of M].

Also, a, b, c, d are a > Q + b > O+
C>0.

d≧0, and a+b≦20. a/b=LOO/
1 to 1/100, c + d = 100
It is. m is 0≦m≦3 (a+b). ] (hereinafter referred to as "general formula (I)").The present invention provides a method for producing a fraction rich in aromatic components, which comprises bringing the fraction into contact with a gallium-containing crystalline aluminosilicate represented by the formula (hereinafter referred to as "general formula (I)").

In the method of the present invention, the gallium-containing crystalline aluminosilicate represented by the above general formula (1) acts as a catalyst. In this general formula (1), M, n, m
, a, b, c, and d are as described above, but in particular, a/
b=10/1 to 1/10 is preferable. There are no particular limitations on the crystal structure of this gallium-containing crystalline aluminosilicate, but those having the X'-ray diffraction pattern shown in Table 1 are preferred.

Table 1 Table 1 (Continued) The gallium-containing crystalline aluminosilicate represented by the general formula (1) basically has a basic octopus skeleton consisting of Si and AI, with part of the AI replaced by Ga. However, a part of Si may be replaced with Ge.

There are various methods for preparing this gallium-containing crystalline aluminosilicate, but in general, various silicon sources, aluminum sources, gallium sources and crystallizing agents, and if necessary, germanium sources are added to an aqueous medium. It can be prepared by a hydrothermal reaction.

In the method of the present invention, a gallium-containing crystalline aluminosilicate represented by the above general formula (1) is used as a catalyst, and a hydrocarbon with a low aromatic content, specifically paraffinic hydrocarbons, olefinic hydrocarbons, acetylene The raw material is a hydrocarbon having at least 2 carbon atoms selected from the group consisting of hydrocarbons, cyclic paraffin hydrocarbons, and cyclic olefin hydrocarbons.

There are various types of raw material hydrocarbons, but those with an aromatic content of 15% by weight or less, such as propane, butane-butylene fraction (BB fraction), ethylene, propylene, or naphtha, are preferred. used. Other paraffinic hydrocarbons include n-pentane, n-hexane, methylpentane, n-hebutane, methylhexane, dimethylpentane, n-octane, etc., and olefinic hydrocarbons include pentene and hexene.

Examples of the acetylene hydrocarbon include methylpentene, heptene, methylhexene, dimethylpentene, and octene. Examples of the acetylene hydrocarbon include hexyne, heptyne, and octyne. Furthermore, examples of cyclic paraffinic hydrocarbons include methylcyclopenkune, cyclohexane, methylcyclohexane, dimethylcyclohexane, etc., and examples of cyclic olefinic hydrocarbons include methylcyclopentene, cyclohexene, methylcyclohexene, dimethylcyclohexene, etc.

The method of the present invention proceeds by bringing the above-mentioned raw material hydrocarbon into contact with the above-mentioned gallium-containing crystalline aluminosilicate, and there are no particular restrictions on the conditions at that time. However, in order to get good results, the temperature should be 200-8
00℃, preferably 400-650℃, pressure 0-30
kg/cm"G, preferably 0-10 kg/am"G
, weight hourly space velocity (WH5V) 0, 1~l 00 hr-
', preferably from 1.0 to 10 hr-'. Note that the reaction system can also be diluted by introducing an inert gas.

〔Effect of the invention〕

According to the method of the present invention, aromatic-rich fractions (hydrocarbons) can be obtained from various non-aromatic hydrocarbons or aromatic-poor hydrocarbons with high conversion and selectivity. Moreover, since the catalyst activity can be maintained at a high level for a long period of time, the yield of aromatic components is extremely high even if continuous operation is performed for a long period of time.

Therefore, the method of the present invention can be widely and effectively utilized in fields such as the petrochemical industry that produces or uses aromatic hydrocarbons and the petroleum industry that produces high octane fuel.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 (1) Preparation of gallium-containing crystalline aluminosilicate Aluminum sulfate (All (S 04) 3.18H2
0) 7.5g, gallium nitrate (Ga(NOz): + ・
A solution prepared by dissolving 9.2 g of 6HzO) and 26.3 g of tetrapropylammonium bromide in 250 ml of water, and water glass (SiO2: 37.6% by weight, NazO
: 17.5% by weight) dissolved in 300 mj2 of water, and 122 mf of water with sodium chloride (
Solution C was prepared by adding 79 g of NaCl).

Next, the above liquids A and B were added to C at the same time using a dropping funnel.
It was added dropwise and mixed into the liquid little by little. After the dropwise addition, 1 normal sulfuric acid was added to adjust the pH to 9.5, and the reaction was carried out at 170°C for 2 hours in an autoclave under self-pressure (6.5 kg/cm" G). After cooling, precipitation occurred. The material was separated, washed five times with water, and then dried at 120'C.The dried precipitate was then treated with 1N ammonium nitrate (NH,N03
)' solution and stirred for 24 hours. After that, a new standard of ammonium nitrate (NH4NO,
) solution and further stirred for 24 hours. Next, the obtained precipitate was washed with 100 times the amount of distilled water, filtered,
It was dried at 120°C and then fired at 550°C.

When the obtained fired product was analyzed, S + Oz /
A I t Ox (molar ratio) = 73, Gaz
It was found to be a gallium-containing crystalline aluminosilicate with an O* content of 562% by weight. Moreover, the results of X-ray diffraction of this product are shown in FIG.

(2) Conversion reaction The gallium-containing crystalline aluminosilicate prepared in (1) above was filled into a glass tube with an inner diameter of 7 mm and a length of 5 CI11 to serve as a catalyst, and the n- Conversion reaction was carried out by introducing hexane at a rate of WH3V 2hr-'. The results are shown in Table 2.

Comparative Example 1 (1) Preparation of gallium-containing ZSM-5 S i Ot / A l z O3 (molar ratio) = 73
of proton type 23M-5 zeolite with 2.2% by weight of Ga! Gallium nitrate (Ga
(NO*):+) Vacuum impregnation with aqueous solution, drying at 120°C, and further baking at 550°C to obtain gallium-containing ZSM-
5 was prepared.

(2) Conversion reaction Gallium-containing ZSM obtained in Comparative Example 1 (1)
Example 1 (2) except that -5 was used as a catalyst
The conversion reaction was carried out under the same conditions.

The results are shown in Table 2.

Comparative Example 2 (1) Preparation of gallium-containing ZSM-5 5iOz/AhOz (mole ratio) = 73 proton type 2
5.5% by weight of G az O in 3M-5 zeolite
Gallium nitrate (G a (N O3
) 3) A gallium-containing ZSM-5 was prepared by vacuum impregnation with an aqueous solution, drying at 120°C, and further baking at 550°C.

(2) Conversion reaction Gallium-containing ZSM-5 obtained in Comparative Example 2 (1) above
The conversion reaction was carried out under the same conditions as in Example 1 (2) except that the following was used as a catalyst.

The results are shown in Table 2.

Comparative Example 3 (1) Preparation of gallium-containing ZSM-5 Gallium nitrate (Ga(No.
:+)i) The aqueous solution was ion-exchanged at 95°C, washed with water, dried at 120°C, and further calcined at 550°C to prepare gallium-containing ZSM-5.

As a result of elemental analysis, this material contained 1.1% by weight of Ga and O.
, was found to be supported.

(2) Conversion reaction The gallium-containing ZSM obtained in Comparative Example 3 (1)
The conversion reaction was carried out under the same conditions as in Example 1 (2) except that No. 5 was used as a catalyst.

The results are shown in Table 2.

Example 2 In Example 1 (2), n-hexane was replaced with n-
The conversion reaction was carried out under the same conditions as in Example 1 (2) except that pentane was used. The results are shown in Table 2.

Comparative Example 4 In Example 1 (2), Comparative Example 3 (1) was used as a catalyst.
The conversion reaction was carried out under the same conditions as in Example 1 (2), except that the gallium-containing ZSM-5 prepared in Example 1 (2) was used, and n-pentane was used instead of n-hexane. The results are shown in Table 2.

Example 3 In Example 1 (2), #= instead of n-hexane
The conversion reaction was carried out under the same conditions as in Example 1 (2) except that fluorine was used and the temperature was 535°C. The results are shown in Table 2.

Example 4 (1) Preparation of gallium-containing crystalline aluminosilicate In Example 1 (1), gallium nitrate (Ga(N
Sing was carried out in the same manner as in Example 1 (1) except that 12.6 g of Oz) + 6 H2O) was used.
/AhO:+ (molar ratio) = 73, Ga202
A gallium-containing crystalline aluminosilicate with a content of 6.1% by weight was obtained.

(2) Conversion reaction Example 1 (2) was carried out under the same conditions as in Example 1 (2) except that the gallium-containing crystalline aluminosilicate obtained in Example 4 (1) above was used as a catalyst. A conversion reaction was carried out. The results are shown in Table 2.

Example 5 (1) Preparation of gallium-containing crystalline aluminosilicate In Example 1 (1), gallium nitrate (Ga(N
The same operation as in Example 1 (1) was performed to obtain S i O
t/ A h O3 (molar ratio) = 73 + Ga
A gallium-containing crystalline aluminosilicate with an O3 content of 2.6% by weight was obtained.

(2) Conversion reaction Example 1 (2) was carried out under the same conditions as in Example 1 (2) except that the gallium-containing crystalline aluminosilicate obtained in Example 4 (1) above was used as a catalyst. A conversion reaction was carried out. The results are shown in Table 2.

Example 6 A conversion reaction was carried out under the same conditions as in Example 1 (2) except that WH3V was changed to 10 hr. The results are shown in Table 2.

Comparative Example 5 In Example 3, a conversion reaction was carried out under the same conditions as in Example 3, except that the gallium-containing ZSM-5 prepared in Comparative Example 3 (1) was used as a catalyst. The results are shown in Table 2.

Comparative Example 6 (1) Preparation of gallium-containing ZSM-5 Sing/AhO:+C molar ratio) = 40 proton type 23M-5 zeolite, 2% by weight of G az O:
Gallium nitrate (G a (N O3
) z) A gallium-containing ZSM-5 was prepared by vacuum impregnation with an aqueous solution, drying at 120°C, and further firing at 550°C.

(2) Conversion reaction The gallium-containing ZSM obtained in Comparative Example 6 (1)
The conversion reaction was carried out under the same conditions as in Example 3, except that No. 5 was used as a catalyst. The results are shown in Table 2.

Comparative Example 7 (1) Preparation of gallosilicate In Example 1 (1), aluminum sulfate (Ah
(Son)s・18HzO) was performed in the same manner as in Example 1 (1) except that 5iOzO) was not used.
/GazO:+ (molar ratio) = 55 gallosilicate was obtained.

(2) Conversion reaction A conversion reaction was carried out under the same conditions as in Example 3, except that the gallosilicate obtained in Comparative Example 7 (1) above was used as a catalyst. The results are shown in Table 2.

Comparative Example 8 A conversion reaction was carried out under the same conditions as in Example 6, except that the gallosilicate prepared in Comparative Example 7 (1) above was used as a catalyst. The results are shown in Table 2.

Comparative Example 9 (1) Preparation of gallium-containing crystalline aluminosilicate In Example 1 (1), gallium nitrate (Ga(No.
5iOz/Al
2O3 (molar ratio) = 70 + G az A gallium-containing crystalline aluminosilicate with an O3 content of 0.8% by weight was obtained.

(2) Conversion reaction Example 1 (2) was carried out under the same conditions as in Example 1 (2) except that the gallium-containing crystalline aluminosilicate obtained in Comparative Example 9 (1) above was used as a catalyst. A conversion reaction was carried out. The results are shown in Table 2.

Comparative Example 10 In Example 3, a conversion reaction was carried out under the same conditions as in Example 3, except that proton type 23M-5 zeolite with a 5ioz/A1zO3Cmo)Lt ratio of 73 was used as a catalyst. The results are shown in Table 2.

Comparative Example 11 In Example 3, a conversion reaction was carried out under the same conditions as in Example 3, except that the gallium-containing ZSM5 obtained in Comparative Example 3 (1) was used as a catalyst. The results are shown in Table 2.

Comparative Example 12 In Example 1 (2), S i Oz/A h
The conversion reaction was carried out under the same conditions as in Example 1 (2) except that proton type ZSM-5 with O3 (molar ratio) = 73 was used as a catalyst. The results are shown in Table 2.

[Brief explanation of drawings]

FIG. 1 shows the X-ray diffraction pattern of the gallium-containing crystalline aluminosilicate obtained in Example 1 (1). In the figure, θ indicates the Bragg angle.

Claims (1)

[Claims] (1) Paraffinic hydrocarbons, olefinic hydrocarbons,
A raw material hydrocarbon whose main component is at least one type of hydrocarbon having 2 or more carbon atoms selected from the group consisting of acetylenic hydrocarbons, cyclic paraffinic hydrocarbons, and cyclic olefinic hydrocarbons is expressed by the general formula aGa_2O_3・bAl_2O_3・cSiO_2・
dGeO_2・mM_2_/_nO [where M is hydrogen,
Indicates an alkali metal or alkaline earth metal, n is M
Indicates the valence of Also, a, b, c, d are a>0, b>0, c>0, d≧
0, and a+b≦20, a/b=100/1~1
/100, c+d=100. m is 0≦m≦3(a
+b). ] A method for producing a fraction rich in aromatics, which comprises bringing the fraction into contact with a gallium-containing crystalline aluminosilicate represented by: