JPS6010068B2 - Aromatization method for terpene compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Consideration is being given to using substances obtained from living organisms to replace energy sources or chemical raw materials that have conventionally been produced from fossil resources.

The present invention relates to obtaining a raw material for gasoline or pure aromatic hydrocarbons containing aromatic hydrocarbons as a main component from a mixture containing terbene compounds as a main component. This paper relates to the aromatization of refined oil.

Eucalyptus, a plant that grows extremely quickly and is suitable for any soil type, is attracting attention because it contains about 1 to 4% by weight of so-called eucalyptus oil, which is composed of terbenes, etc., although it varies depending on the type.

As an example of the properties of eucalyptus oil, specific gravity (15/400) 0.
9202, octane number (research method) 98.1 real gum (unwashed) 9/100' of 136', boiling point 168-19
4℃, flash point 51℃, kinematic viscosity (30qo) 2.35th order s
Although the specific gravity is equivalent to that of automobile oil, the boiling point is only at the higher end of the boiling point range of commercially available automobile gasoline. Since it has a high octane number, when using it, consider both the actual gum and the boiling point, and it is possible to mix it into gasoline at a concentration of a few percent or less. and,
If only eucalyptus oil is used as fuel, the gasoline engine will not start and acceleration will be difficult. As a result of our earnest efforts to solve these problems, the present inventors have obtained aromatized oil with a yield or quality comparable to or superior to that of gasoline or aromatic hydrocarbon production raw materials obtained from petroleum. I was able to find a way. The method will be explained below. An example of the composition of eucalyptus oil is cineole (C, P, 80) 88. % by weight, Qpinene (C,.

Day, 6) 5.9% by weight, Pcymene (C, Rainbow, 4) 2.1
Weight %, Pinocarbegal (C, oH, 60) 1. % by weight of the box and 1.9% by weight of the others. As long as the raw material is a terbene compound, it does not have to be a hydrocarbon such as Q-pinene, or may be an oxygen-containing compound such as cineole. Terbene compounds obtained from plants or rarely from animals generally have multiples of five carbon atoms. Compounds with a high number of carbon atoms are not preferred because they produce precipitates or coke when reacted with the catalyst, and require purification treatment such as hydrogenation treatment. As the reaction bed for aromatization, a fixed bed may be used if the amount of coke produced on the catalyst is small.

If a large amount of coke is produced, consider catalyst regeneration and choose a fluidized bed. A catalyst containing Y zeolite in an alumina or silica alumina carrier is used, and the activity of the Y zeolite is manipulated to work effectively. The content of aluminosilicate Y zeolite is 5 to 5% by weight, preferably 10 to 3% by weight.
% by weight. The shape of the catalyst should be determined by the catalyst bed. That is, in the case of a fixed bed, a cylindrical or spherical catalyst is used, and in the case of a fluidized bed, a powdered catalyst is used. The reaction temperature is between 35,000 and 600 pm, preferably 4 pm.
00qo to 50000, and the reaction pressure is 10kg
/ below, and usually below 2k9/c fins. in some cases,
Inert gas or hydrogen may be applied to facilitate the reaction. In the case of a fixed bed, the ratio of oil passing through the catalyst to the liquid hourly space velocity is 0.5 to -1, preferably 1 to water -1, and in the case of a fluidized bed, the ratio of the weight of the catalyst to the weight of oil is 3 to 12. , preferably 8-10. Among these conditions, it is noteworthy that the
There is no need for a high hydrogen pressure of 0k9/s or higher, and the aromatization reaction proceeds with a catalyst composition that does not contain noble metals. The reaction product is separated into gas, liquid oil, coke and water, and the liquid oil is distilled to 200°C from the initial boiling point.
The yield so far was used as gasoline for yield measurement and quality property tests.

The present invention will be explained in more detail below with reference to Examples.

Example 1 Eucalyptus oil was placed in a reaction tube filled with Y zeolite/alumina catalyst (cylindrical molded product, diameter 1.5 ribs, length 3 bars) at a liquid hourly space velocity of 1. Apply oil at section-1.

The reaction temperature is 450 qo. The situation and results are shown in Example 1 in Table 1. The yield of aromatized oil is 6% by weight.
The properties of aromatized oil are superior to catalytically reformed gasoline in petroleum refining, with both aromatic content and octane number being higher. Example 2 In the Example 2 column of Table 1, the same eucalyptus oil as in Example 1 was used as a catalyst with a different carrier, namely a Y zeolite silica alumina catalyst (cylindrical molded product, diameter 1.5 side,
This is an example in which aromatization was performed using a length of 3 cm).

Compared to Example 1, the yield of aromatized oil and the aromatic content are slightly superior. Example 3 In order to remove the actual gum of eucalyptus oil, a flow-through high-pressure reactor filled with a cobalt-molybdenum-alumina catalyst was used at a hydrogen pressure of 30 k9/g, a reaction temperature of 380 oo, and a liquid hourly space velocity of 1. Example 3 in Table 1 shows an example in which eucalyptus oil treated with Blood-1 was aromatized under the conditions of Example 1.

The aromatized oil yield and the aromatic content of the aromatized oil are as shown in Example 1.
The price is higher in the case of . Comparative Example 1 As a comparative example of aromatization, Comparative Example 1 in Table 1 shows an example in which Middle Eastern automotive naphtha was catalytically reformed using a platinum/alumina catalyst.

Although the reaction temperature is high and high pressure hydrogen of 30k9/m is used, the yield of aromatized oil, its aromatic content, and octane number are all rather low. However, since this aromatized oil is used as a raw material for automobile gasoline, etc., the aromatized oils of Examples 1 to 3, which are of superior quality, can be satisfactorily used for similar purposes. ship

Claims (1)

[Scope of Claims] 1. A method for converting a terpene compound into a light oil containing aromatic hydrocarbons as a main component using a catalyst having an alumina or alumina-silica carrier containing crystalline aluminosilicate Y zeolite. 2. A method of applying the conversion method according to claim 1 to eucalyptus oil or its refined oil.