JPS5936193A - Method for catalytic cracking of hydrocarbon - Google Patents

Abstract

PURPOSE:To obtain a gasoline with a high content of aromatics and a high octane number, by catalytically cracking a mixture of a specific unsaturated hydrocarbon with a light oil in the presence of a specified catalyst consisting of a crystalline silicate and an inorganic parent material. CONSTITUTION:(A) A mixture of usually 1-50wt% 2-4C unsaturated hydrocarbon with a light oil is catalytically cracked in the presence of (B) a catalyst consisting of (i) 1-60wt% crystalline silicate, e.g. ZSM-5, and (ii) 99-40wt% inorganic parent material, e.g. a metal or glass, usually under conditions of 450-600 deg.C under ordinary pressure -5kg/cm<2> at 2-20 weight ratio between the catalyst and the raw material. Light gaseous materials formed as a by-product in the reaction can be recycled for the reaction. EFFECT:A small amount of coke, etc. is formed, and the yield of the gasoline fraction is very high.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for catalytic cracking of hydrocarbons, and more specifically, a mixture of an unsaturated hydrocarbon having 2 to 4 carbon atoms with a low added value and light oil is used as a raw material, and this is processed into crystalline silicate. The present invention relates to a method for catalytic cracking of hydrocarbons, which can efficiently produce a gasoline fraction rich in aromatic components by contacting the hydrocarbons with a catalyst consisting of an inorganic matrix and an inorganic matrix.

Generally, in petroleum refining, in order to produce automatic RLT gasoline, a method is adopted in which a light oil fraction obtained by atmospheric distillation or vacuum distillation of crude oil is catalytically cracked using a silica-alumina catalyst. However, the gasoline distillate obtained in this case has a relatively low content of aromatic hydrocarbons and has a disadvantage that the octane number is lower than that of gasoline obtained by catalytic reforming of petroleum naphtha. In addition, the gas component obtained by catalytic cracking of light oil has a high content of unsaturated hydrocarbons. For example, the butane-butene fraction contains about 50% unsaturated hydrocarbons, making it unsuitable as a commercial fuel. Currently, most of the oil is consumed as in-house fuel at refineries. Moreover,
In the above-mentioned catalytic cracking process of light oil fraction, there is a problem that a considerable amount of coke is produced and the gasoline yield is low.

Therefore, the inventors of the present invention have conducted extensive research in order to eliminate the drawbacks of the above-mentioned conventional techniques. As a result, diesel oil as a raw material has carbon numbers of 2 to 2.
When a mixture of unsaturated hydrocarbons of 4 is used,
The inventors discovered that the object could be achieved by using a mixture of crystalline silicate and an inorganic matrix in a fixed ratio as a catalyst, leading to the completion of the present invention.

That is, the present invention catalytically cracks a mixture of an unsaturated hydrocarbon having 2 to 4 carbon atoms and light oil using a catalyst consisting of 1 to 60% crystalline silicate and 99 to 40% inorganic matrix. The present invention provides a method for catalytic cracking of hydrocarbons characterized by the following.

In the method of the present invention, a mixture of an unsaturated hydrocarbon having a Mu prime number of 2 to 4 and light oil as described above is used as a raw material. Here, examples of unsaturated hydrocarbons having 2 to 4 carbon atoms that are one component of the raw material include ethylene and propylene.

Examples include butene or a mixture thereof. Note that this unsaturated hydrocarbon having 2 to 4 carbon atoms includes methane, ethane,
There is no problem even if saturated hydrocarbons having 4 or less carbon atoms, such as propane and butane, are included. Specific examples include butane-butene mixed gas, '/s, propane-propylene mixed gas, etc. obtained during petroleum refining.

The other component of the above raw materials, gas oil, is obtained by atmospheric distillation or vacuum distillation of crude oil, and either light gas oil, heavy gas oil, or vacuum gas oil can be used.Usually, A fraction having a boiling point of 200 to 650°C (under normal pressure), preferably a fraction having a boiling point of 250 to 580°C (under normal pressure) is used.

In the method of the present invention, a mixture of the above-mentioned unsaturated hydrocarbon having 2 to 4 carbon atoms and light oil is used as a raw material, or there is no particular restriction on the mixing ratio of the two, depending on the properties of the desired product and the gas oil used. It may be determined as appropriate depending on the type of catalyst, etc. but,
Usually, carbon dioxide (2 to 4 unsaturated hydrocarbons) is added to 1 to 5 U, 1 M%, preferably 5 to 40
The weight should be selected within the range of 111%. If the mixing ratio of the unsaturated hydrocarbon having 2 to 4 carbon atoms exceeds 50% by weight based on the mixture, the production efficiency of the gasoline fraction will decrease, which is not preferable.

Further, in the method of the present invention, crystalline silicates 1 to 1 are used as catalysts.
It is necessary to use a material consisting of 60% free weight and 99-40% inorganic matrix. As the crystalline silicate, it is preferable to use ZSM-5 or a zeolite having a similar crystal structure. This ZSM-5 or a zeolite similar to this refers to one whose X-ray diffraction pattern is the same or similar to ZSM-5, and it may be aluminum as the metal or a zeolite containing other things in υ instead, Further, it may be a material containing other elements together with aluminum. Specifically, ZSM-5
, ZSM-8, 78M-11, crystalline borosilicate ψ described in JP-A-55-55500, crystalline titanosilicate described in JP-A-56-96720, and JP-A-56-96720; Publication No. 55-162419 1, Samurai Publication No. 56-22625 and Japanese Patent Publication No. 56-596
Examples include the crystalline metallosilicate described in Publication No. +9, and all of these are H-type or metal 1n
I can stay once a month as a replacement.

There are various types of inorganic matrix, such as metal, glass, asbestos, and silicon carbide.

Aggregate, pumice, brick, diatomaceous earth, alumina, silica
Examples include alumina.

In the method of the present invention, as described above, a mixed catalyst in which the crystalline silicate and the inorganic matrix are combined, dispersed, or intimately mixed is used as a catalyst, and the content of the crystalline silicate is 1 to 60% of the total 1 h. The heavy forging percentage should be 10 to 50 claws Kt%. If the content of crystalline silikenite exceeds 60% by weight, although the catalyst activity is improved, there is a risk that the catalyst will become finely powdered and the operability will be reduced.

The method of the present invention is carried out by using a mixture of an unsaturated hydrocarbon having 2 to 4 carbon atoms and light oil as a raw material, and bringing the first mixture into contact with a mixed catalyst of crystalline silicate and an inorganic matrix. The reaction conditions at this time are usually normal pressure to 5 k
y/cpi, preferably normal pressure to 5 y/cpi, and a temperature of 450 to 600°C, preferably 450 to 5 y/cpi.
The temperature should be 50°C, and the catalyst/raw material ratio should be 2.
-20, preferably 5-15.

According to the method G of the present invention, which contains a large amount of aromatic compounds and an octane number, it is possible to efficiently produce carbonaceous gas with a large amount of aromatic compounds and a high octane number, and with a small amount of coke etc. expensive. Moreover, the number of carbon atoms is 2~
Compared to the case where unsaturated hydrocarbons or light oil (4) are used alone as raw materials, it is possible to obtain gasoline with a significantly higher aromatic content, resulting in a so-called synergistic effect. Note that the light gas that is produced as a by-product at this time can also be recycled and used for [11 degrees 1; f), :.

Therefore, the method of the present invention provides oil 't+1'J! + Can be widely used in the petrochemical industry, and can be effectively used for iR octane gasoline and aromatic compounds 'J':4 fj'j.

Next, the present invention will be explained in more detail using examples.

Example (11 Preparation of crystalline silicate Aluminum sulfate (18 water ti;',) 7.52
F-, sulfuric acid (97%) + 7.6f and water 250 ml
Solution (1) consisting of water glass (Sin, !+7.
671 (1'A % l Na2017, 5 sections 0. Water 4
49 weight 1 company%) +6251- and a solution consisting of 500 ml of water 01), sodium chloride 791 and water 12
Solutions consisting of 2 ml (110 each) were prepared.

Next, the solution (Il) and the solution αD were simultaneously added to the above-mentioned solution Il and solution αD while stirring at room temperature to obtain a mixture.

Subsequently, powdered mordenite 1y- was added to this mixture, the pH was adjusted to 100], the mixture was placed in a 1-ton autoclave, stirred at 170°C at 200 rpm, and reacted for 20 hours under autogenous pressure. I let it happen. The reaction mixture was then cooled and washed 5 times with 1 t of water. Then for filtration, l:
When the solid content was separated and dried at 120"C for 3 hours, a crystalline silicate of 40, sy was obtained. This crystalline silicate was confirmed by X-ray diffraction and was found to be ZSM-5. ZSM-5 has the following composition in molar ratio:

α9 Nano -6U Sin, -1,0At20
゜5 ml per y of ZSM-5 caught using the above method
Ion exchange twice with 1N ammonium nitrate of L, 120
After drying at 550°C for 6 hours in the air,
It was set as type Il.

(2) Preparation of mixed catalyst Commercially available silica-alumina gel (Rlumina content: A50%
) was added with the H-type crystalline silicate obtained by +13 to 55% by weight.

Next, water was added, and the mixture was thoroughly mixed using a kneader, and then dried and pulverized. This finely powdered mixed catalyst is prepared as follows (3
) in 100% steam before being used in the catalytic cracking reaction.
It was treated at 70'C for 6 hours.

(3) From the catalytic cracking reaction raw material 1°C to the vacuum distillation apparatus, a mixture of vacuum gas oil and gas containing the unsaturated hydrocarbons shown in Table 1 at a ratio of 77:25 (ton/injection ratio) of the former to the latter was prepared. 2 raw materials and
In (2) above, using the +4 mixed catalyst, the pressure is 2 kP/c++! G % ya Iu: 5 [1
0”C, catalyst/raw material jr<F ratio 10.Steam/
Moxibustion of raw material nail fit ratio o1 (fluid contact amount πii under ll
I did 14:.

The results are shown in Table 2.

Comparative Example Example (3) except that only light oil was used as the reaction raw material.
) A catalytic cracking reaction was carried out in the same manner as in . The results are shown in Table 2.

Chapter 1 Table

Claims (1)

[Scope of Claims] 0) A mixture of an unsaturated hydrocarbon having 2 to 4 carbon atoms and light oil is mixed with 1 to 60% by weight of crystalline silicate and 99% by weight of an inorganic matrix.
t1! Catalytic cracking using a catalyst consisting of ~40% by weight and 11%! Catalytic cracking method for hydrocarbons with J character. (2) The catalytic cracking method J according to claim 1, wherein the mixing ratio of the unsaturated hydrocarbon having 2 to 4 carbon atoms is 1 to 50% by weight based on the entire mixture. (3) The crystalline silicate is , ZSM=5 or similar % i'r Catalytic cracking process according to claim 1.