JPS58217589A - Conversion of hydrocarbon - Google Patents

Abstract

PURPOSE:To obtain liquid hydrocarbon containing aromatic components, by bringing stock hydrocarbon formed by mixing a 2-4C olefin and light naphtha into contact with a ZXM-5 type crystalline aluminosilicate zeolite catalyst. CONSTITUTION:A 2-4C olefin (A) (e.g., ethylene, propylene) and light naphtha (B) which is a 5C or higher fraction with a b.p. of 100 deg.C or below, substantially containing no aromatic components or olefin components and containing hydrocarbon based on saturated components, especially, paraffin components as a main component, are mixed so as to bring the wt. ratio of the component A to the component B to 0.05-19/1. Subsequently, the obtained stock hydrocarbon is brought into contact with a ZSM-5 type crystalline aluminosilicate zeolite catalyst at about 200-550 deg.C under pressure of about atmospheric pressure -50kg/ cm<2> to be converted into liquid hydrocarbon containing aromatic components.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for converting hydrocarbons, and more specifically, uses a hydrocarbon mixture of a specific olefin and light naphtha in a fixed ratio as a raw material and converts it into an aromatic material by contacting it with a ZSM-5 catalyst. The present invention relates to a method for efficiently producing liquid hydrocarbons containing group compounds.

Traditionally, olefins, paraffins, or mixtures of these are used as catalysts. Several methods have been developed for converting hydrocarbons into aromatic-containing hydrocarbons.

For example, (1) a method of converting olefins having 2 to 4 carbon atoms, paraffins, and mixtures thereof into aromatic compounds Jl/+ by contacting them with crystalline zeolite (US Patent No. 5760
(Specification No. 024), (method of converting a liquid hydrocarbon having 5 or more carbon atoms with a 2+ aromatic content of 15% by weight or less into an aromatic compound by contacting it with a ZSM-5 zeolite (
Japanese Unexamined Patent Publication No. 49-41522 2% Publication No. 56-4265
No. 9, U.S. Pat. No. 5,756,942).

Alternatively, (3) ethylene - a hydrocarbon with a temperature below 204°C is brought into contact with ZSM-5 type zeolite, and then zsM
A method is known in which the zeolite is converted into an aromatic compound by bringing it into contact with a mixed catalyst of an s-type zeolite and a second molecular sieve zeolite having a pore diameter of 45 to 6.7 λ (Japanese Patent Application Laid-Open No. 1983-4029).

However, these conventional methods have various drawbacks, such as a low conversion rate to aromatic components and the need to carry out the reaction in two stages.

Therefore, the inventors of the present invention have made extensive efforts to overcome the drawbacks of the prior art described above, to develop a method for converting hydrocarbons that has a high conversion rate to aromatic components and can be performed with simple operations. As a result, when using ZSM-5 zeolite as a catalyst, L
, /i4 It was discovered that the object could be achieved by using a mixture of a constant olefin and light naphtha in a constant ratio as the entire raw material, and the present invention was completed.

That is, the present invention combines (French) olefins having 2 to 4 carbon atoms and CB) light naphtha, which is a fraction with a carbon number of 5 or more and a boiling point of 100'C or less and is mainly unsaturated, to (4) olefins/
(B) Raw material hydrocarbons mixed at a ratio of light naphtha = 005 to 19 (heavy weight ratio) are brought into contact with a ZSM-5 crystalline aluminosilicate zeolite catalyst to convert them into liquid hydrocarbons containing aromatic components. The present invention provides a method for converting hydrocarbons characterized by the following.

In the method of the present invention, as described above, (A) olefin and (
B) A mixture of light naphtha is used as feedstock. here(
A) The olefin that is the component is carbon 77i.2~
4, ethylene, propylene, butene, or a mixture thereof. Note that the olefin as component (A) may contain paraffins having 4 or less carbon atoms such as methane, ethane, propane, butane. Specifically, examples include bunone-butene mixed gas and propane-propylene mixed gas obtained during Ishi 7111 refining.

On the other hand, light naphtha, which is component (B), is a distillate with a carbon number of 5 or more and a boiling point of jOQ''C or less, and contains substantially no aromatic content or olefin content, and contains unsaturated, especially paraffinous,
It is a hydrocarbon mainly composed of carbon.

This is also obtained during oil refining.

In the method of the present invention, a mixture of the above-mentioned (A) component olefin and (B) component light naphtha is used as a raw material, and the mixture of both is (Al olefin/CB).
Light naphtha should be 0.05 to +9 (R1 ratio), better < jrJ-01B to 5.7 (Tsume ratio).

Further, in the method of the present invention, ZSM-5 crystalline anominosilicate zeolite is used as a catalyst in the ventricle. As this ZSM-5 series zeolite, ZSM-5
, ZSM-8, ZSMll and other zeolites exhibiting similar behavior.

f; When using ZSM-5 type zeolite, alumina or the like can be used together as a binder.

The method of the present invention uses a mixture of component (4) and ψ component as a raw material as described above, and brings it into contact with a ZSM-5 crystalline aluminosilicate zeolite catalyst, and the reaction conditions at this time are as follows: Usually always LF.

~50kliI/cr! G pressure, preferably normal pressure ~ 2
゜kg/c++! The pressure is a, the temperature is 200-550
"C, preferably 550-450°C 1 d space velocity (WH3V) (L 1-50 hr-', preferably 05-10 hr-1.

According to the method of the present invention as described above, it is possible to efficiently obtain a liquid hydrocarbon containing an aromatic content in a single step. When a certain olefin or a light naphtha (CB) component is used alone as the 19 material, the aromatic content is 11:P and the aromatic content is 11M.
The ratio is extremely high, and a great synergistic effect can be achieved by mixing the two.

Therefore, the method of the present invention involves the following steps:
It can be widely used in various chemical industries.

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

Implementation 111 +11 Preparation of catalyst Sulfuric acid 7. Aluminum (18 hydroxide) 7,529. value penalty (
Solution (I) consisting of 1.7.6f) (97%) and 250m of water, 'water glass (5in257.6% Na2
017.5 weight 10%, water 44.9 weight fit%) +627
A solution (5) consisting of 500 rpm of water and a solution qUD consisting of 791 M of sodium cyclide and 122 M of water were prepared, respectively.

2 big Jlic! Solution CI>
and solution (II) were added dropwise at the same time to the mixture while stirring in the room Y' and λ.Subsequently, 1 g of powdered mordenite was added to this mixture, and the pH was adjusted to 100. The reaction mixture was placed in a 1 t autoclave, stirred at 170° C. with a rotational speed of 200 rllll, and reacted for 20 hours under autogenous pressure.Then, the reaction mixture was cooled and washed 5 times with 1 t of water. Blowing Dorokin 11G Koyori I
, 'il type fraction was dried at 120"C for 5 hours to obtain a crystalline aluminosilicate zeolite of 40.57. This crystalline aluminosilicate zeolite was confirmed by xlJ diffraction and was found to be ZSM. -5.This ZSM-5 has the following composition in terms of molar ratio.

II 9 Na, 0 : 6 OSin, : 1
．． OA40°
5 per 1 was added to form H type.

(2) Conversion reaction quartz strand; tube (this is the H-type ZSM obtained in (1) above)
-5 was charged, and this was filled with butane-5 having the composition shown in Table 1.
Butene mixed gas (BB) and desulfurized light naphtha with the composition shown in Table 2 (C vine boiling point: 100°C, does not contain olefins and aromatics) (DLN)
A conversion reaction was carried out at 400° C. by passing raw materials mixed at a ratio of DLN = 5/70. The results are shown in Table 3.

Example 2 In Example 1 (2), BB/DLN =
The same operation as in Example 1 (2) was carried out except that the mixture was passed through the 575 offshore. The results are shown in Table 5.

Comparative Example 1 The fact that only BB was used as the raw material was compared to Practical Example 1 (2).
) and Doho L:? ) operation was performed. The results are shown in Table 5.

Comparative Example 2 Example 11 except that only DLN was passed as the raw material
The same operation as (2) was performed. °Results are shown in Table 5O Table 1 Table 2 Table 5 - Expected values based on the results of Comparative Examples 1 and 2 are shown.

Claims (1)

[Scope of Claims] (11(A) ole7-yne having 2 to 4 carbon atoms and (B)
Feedstock hydrocarbons are made by mixing light naphtha, which is a distillate with a carbon number of 5 or more and a boiling point of 100°C or less and is mainly saturated, in a ratio of (A) olefin/(B) light naphtha = 005 to 19 (weight ratio). A method for converting hydrocarbons, the method comprising converting hydrocarbons into liquid hydrocarbons containing aromatic components by contacting them with a ZSM-5 crystalline aluminosilicate zeolite catalyst. (21) The method according to claim 1, wherein the weight ratio of (A) olefin/(B) light naphtha is α18 to 5.7. The method according to claim 1, which contains the following paraffins: