JPS6033153B2 - gasoline manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of gasoline from biomass.

More specifically, the present invention relates to producing usable automobile gasoline by catalytically cracking glycerin esters of higher fatty acids obtained as vegetable oils using a catalyst containing crystalline aluminosilicate Y zeolite. Generally, higher fatty acid glycerol ester has a high molecular weight,
It has a boiling point so high that it does not fall within the range of about 12,000 or less than normal temperature, which is the boiling point of gasoline.

Therefore, thermal cracking, catalytic cracking, or hydrocracking methods are used to lighten these materials. However, as a fuel for driving current gasoline engines, it is also necessary to satisfy the octane number, distillation properties, and freedom from impurities as specified in the Japanese Industrial Standard JISK2202 Automotive Gasoline. It is. Attempts have been made in the past to break down biological oils to obtain petroleum or similar substances. for example,
“Lubricating oil and grease” by Hiroshi Horiguchi (June 1, 1971,
Published by Sankyo Publishing ■, 281 pages) and P. B. Weiez et al.
An example of this can be found in Science, No. 206, Gotoji (published October 5, 197g). however,
It is difficult to accept it as it is because it has poor distillation properties, contains corrosive or odoriferous substances, and when a catalyst is used, the activity is significantly reduced. As a result of various studies to solve these problems, the present inventors succeeded in obtaining gasoline of the desired quality by the method described below.

That is, the present invention produces gasoline by catalytic cracking using a mixture of glycerin esters of higher fatty acids having 6 to 36 carbon atoms as a raw material.

Fatty acids may be saturated or unsaturated, and although they may have to be hydrogenated for normal use, unhydrogenated raw materials may be used as raw materials for the present invention. Examples of glycerin esters of saturated fatty acids include terracotta oil, and examples of glycerin esters mainly composed of unsaturated fatty acids include South Sea oil. The catalyst contains crystalline aluminosilicate Y zeolite in an alumina or alumina silica carrier.

The content of aluminosilicate Y zeolite is 5-5% by weight
, preferably 10-3% cloud cover. The shape of the catalyst should be determined by the catalyst bed. That is, in the case of a fluidized bed catalyst, a powdered one is used, and in the case of a fixed bed catalyst, a cylindrical or spherical one is used. The reaction conditions for decomposition into gasoline using a catalyst include adding less than 10 kg/kg of reaction pressure to make the reaction proceed smoothly.
Usually it is 2k9/c digits or less.

The reaction temperature is from 350°C to 650q0, preferably 450
30 to 550 qo. In the case of a fluidized bed, the ratio of catalyst and higher fatty acid glycerine ester is 3:1 to 12:1.
(catalyst weight vs. higher fatty acid glycerin ester weight),
Preferably it is 8:1 to 10:1 (weight to weight). Further, in the case of a fixed bed, the liquid hourly space velocity is 1 to -1, preferably 1 to -1. When the reaction is carried out under such conditions, gas, water, and coke are produced along with oil. Distill the oil, use the distillate from room temperature to 20,000 as gasoline, and after washing with caustic soda, meet the Japanese Industrial Standards JISK2.
The quality is confirmed using the test method specified in 202. EXAMPLES The present invention will be specifically described below with reference to Examples. Example
1 Example 1 in Table 1 shows an example of obtaining gasoline from unrefined bamboo shoot oil using saturated fatty acid glycerin ester as a raw material.

When catalytic cracking is performed in a fluidized bed reactor using Y zeolite, silica, and alumina powder catalyst, and gasoline is obtained by distilling the resulting oil, the gasoline yield obtained by one contact with the catalyst is 34wt%, the quality is 94 octane,
The properties, including distillation properties, are such that it can be used as automotive gasoline. In normal catalytic cracking, the residual oil from cracking is re-cracked, so the yield can be further improved. Example 2 As an example in which highly saturated higher fatty acid glycerine ester was used as a raw material, hydrogenated bamboo shoot oil was catalytically cracked in the same manner as in Example 1 to obtain gasoline, and the results shown in Table 1 were used. This is shown in Example 2.

This is a good result that is almost the same as in Example 1. Example 3 Example 3 in Table 1 shows an example of both fluidized bed and fixed bed catalytic cracking using South Sea tung oil as an example in which unsaturated fatty acid glycerine ester is the main component.

In the case of a fluidized bed, the method is the same as in Example 1, but in the case of a fixed bed, a cylindrical (diameter 1.5 fence, length 3 sides) Y zeolite/alumina catalyst is packed into a reaction tube, and the reaction temperature is 5000
0, and the catalytic cracking was carried out at a liquid hourly space velocity of 1.2 h-1.
The obtained gasoline has an octane number of 91 or 93, impurities including distillation properties can be removed by simple washing with caustic soda, and it can be used practically as a gasoline engine fuel. Comparative Example As a comparative example, Comparative Example 1 shows the results when gasoline was brought into contact with a catalyst once in the same fluidized bed reactor as in the example when gasoline was obtained by catalytic cracking from vacuum gas oil in petroleum refining.

The octane number of gasoline is 91. ship

Claims (1)

[Claims] 1 Using glycerin ester of higher fatty acid as a raw material, by contacting it with a catalyst having alumina or alumina silica as a carrier containing crystalline aluminosilicate Y zeolite,
A method for producing gasoline with an octane number of 90 or higher.