JPS59219387A - Preparation of hydrocarbon - Google Patents

Abstract

PURPOSE:To prepare hydrocarbon with a high conversion over a long period, by using a catalyst consisting of a specified crystalline silicate. CONSTITUTION:An aqueous mixt. of (A) silica source, (B) alumina source, (C) alkali (alkaline earth) metal source, (D) tetra(1-4C alkyl)ammonium salt and (E) methanol in which A/B is 10 or higher, E/water is 0.1-10, E/A is 5-100, hydroxy ion/A is 0.01-0.5 (excluding hydroxy ion from the organic base) and D/A is 0.01-1.0 by mol, is made to undergo crystallization reaction at 110-300 deg.C for 5hr-10 days. The reaction product is washed with water and dried at around 120 deg.C to obtain a catalyst consisting of a crystalline silicate which is shown by the molar ratio equation [where M is H or an alkali (alkaline earth) metal; n is the valency of M; p is 0.3-3.0 and q is 10 or higher] and has an X-ray diffraction pattern of the table when burned at 550 deg.C in the air. Then an oxygen-contg. compd., e.g. methanol, is brought into contact with the catalyst at 250-600 deg.C under normal or high pressure at a weight space velocity of 0.1-50hr<-1>.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing hydrocarbons.
This invention relates to a method for efficiently producing various hydrocarbons from oxygen-containing compounds such as alcohols by using a crystalline silicate with a completely new crystal structure called I-3 as a catalyst.

Traditionally, liquid hydrocarbons used in gasoline are produced from petroleum. In recent years, there has been much talk of oil depletion, and expectations are high for methods of obtaining gasoline from raw materials other than oil, such as coal-based biomass. To date, methanol, tahadimethyl ether, and ZSM-5
A method has been proposed in which hydrocarbons are produced by passing them over molded aluminosilicate (Japanese Unexamined Patent Publication No. 52-8005).

However, such conventional methods have drawbacks such as an insufficient yield of liquid hydrocarbons.

Therefore, the present inventors have conducted extensive research in order to develop a method for producing hydrocarbons in a simple process and with a high conversion rate over a long period of time using oxygen-containing compounds obtained from coal, biomass, and other sources as raw materials. Layered. As a result, it was found that hydrocarbons can be efficiently obtained by using a crystalline silicate with a completely new structure called 15I-3 (Japanese Patent Application No. 130629/1988), which was developed earlier, as a catalyst. The present invention was completed based on this knowledge.

That is, in the present invention, when producing hydrocarbons from oxygen-containing compounds in the presence of a catalyst, the composition expressed in molar ratio after calcining at 550°C in air is as follows: 9M2/n 0-Al203 ・q Si
Oz・−=−(I) (where M represents hydrogen, an alkali metal and/or an alkaline earth metal, and n represents the valence of M. Ru.

0.3-<p3.0, q≦10) and whose X-ray diffraction pattern is shown in Table 1. The present invention provides a method.

Table 1 Irradiation: Cu-Kcz; Wavelength: 1.5418 In the method of Ohki's invention, as mentioned above, any oxygen-containing compound can be used as a raw material without any particular restriction. Here, examples of the oxygen-containing compound include alcohols having 1 to 4 carbon atoms, ethers, aldehydes, carboxylic acids, and the like. Specifically, methanol and ethanol.

Gropanol, butanol, dimethyl ether.

Examples include diethyl ether, acetaldehyde, propylaldehyde, acetic acid, propionic acid, and methanol is particularly preferred.

As mentioned above, the catalyst used in the present invention is
The composition expressed in molar ratio after firing in 00 is represented by the general formula (I) and the X-ray diffraction pattern is the first
Represented in the table is the π1t ricade (l5I-3). In addition, the alkali metals and alkaline earth metals such as strium contained in the production of this crystalline silicate can be ion-exchanged by various methods and used as H-type or metal ion exchange type. Note that this crystalline silicate (ISI
-3) In producing (a) silica source, (
b) an alumina source, (C) an alkali metal and/or alkaline earth metal source, (d) a tetraalkylammonium salt having an alkyl group having 4 to 6 carbon atoms, and (e) methanol, and the mole of each component. 1 is: Silica/Alumina≦10 Methanol/Water=0.1-10 Methanol/Silica-5-100 Hydroxide ion/Silica=0.01-0.5 (excluding hydroxide ions from organic bases) .) Te) Dialkyl ammonium salt/silica-0,01~
1.0 and the aqueous mixture at 100-300'C! The reaction may be carried out until a small amount of crystalline silicate is formed.

More specific reaction conditions at this time include a reaction temperature of 100
The reaction may be carried out at ~300°C, preferably from 120 to 200°C, for about 5 hours to 10 days, preferably about 10 hours to 5 days. There are no particular restrictions on the pressure, and it is usually carried out under autogenous pressure. Further, the reaction system is usually kept under stirring, and the atmosphere may be replaced with an inert gas if necessary. The pH of the reaction system is neutral to alkaline, usually 7.5 to 1.
1.0, preferably in the range of pl[8.0 to 10.5.

After the crystallization reaction described in Section 2, washing with water and drying at about 120°C results in the composition represented by the general formula (I).
The X-ray diffraction pattern of I-3 is shown in Table 2.

Table 2 Table 2 (continued) Irradiation Cu K (z: wavelength 1.54.1-s'
A: The relative intensity was determined as follows, with the intensity at a lattice spacing of 3.87±01 kyu as a factor of 100.

Very strong: 90-100 degrees strong, 70-90% somewhat strong, 40-70 degrees moderate, 20-40 degrees weak, θ~20% The method of the present invention uses oxygen-containing compounds as raw materials as described above. The reaction is carried out by contacting with the above-mentioned crystalline silicate catalyst, and the reaction conditions at this time are usually normal pressure or increased pressure, and the temperature is 250-600'C, preferably 3oo to 5oC. .

Ocl Weight Hourly Space Velocity (WHSV) 0.1-50
hr-'preferably should be 0.5-10 hr'.

As described above, according to the method of the present invention, liquid hydrocarbons used for ganoline can be obtained in high yield from oxygen-containing compounds obtained from raw materials other than petroleum, such as coal, biomass, and others. In addition, xylene is also produced, and the proportion of P-xylene in the produced xylene is high.

Therefore, the present invention is useful in the chemical industry for the production of Kashirin, P.
- Can be effectively used in the production of xylene, etc.

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

Example 1 (1) Preparation of catalyst Aluminum sulfate (18 hydrate) 9.7 r, sulfuric acid (
A solution consisting of 17.6 F (97%), 25.2 F of tetrabutylammonium bromide and 100 ml of water was used as liquid A, and water glass (5 iOz 29.0 wt.
%.

NazO9.4wt% + water 61.6wt%) 21
1? A solution consisting of 96 g of water and 96 g of water was designated as Solution B. water 5
(Liquid A and Solution B were gradually mixed dropwise at the same time into 3 ml, then 13.0 g of 50% sulfuric acid was added to adjust the pH to 8.5, and 376 ml of methanol was further added and mixed. The aqueous mixture was placed in a 1 volume autoclave, and the reaction was carried out at 170°C under 2 autoclave with stirring for 20 hours.After cooling the reaction mixture, the product was
．． Washed 5 times with 5 tons of water. The solid content was then separated by p-filtration and dried at 120°C for 6 hours. Of crystalline silicate Cl5I-3) was obtained. The composition (molar ratio) of this product is 0.16NazO0,82(TBA)
It was zOAt20a61.7 SiC2・4.8H20. TBA here refers to a tetrabutylammonium group. Moreover, the X-ray diffraction pattern of this crystalline silicate is shown in FIG.

Further, this crystalline silica) (5I-3) was calcined in air at 550°C for 6 hours, and then calcined with 1 g of silikenite for 6 hours to obtain an H type. Furthermore, as alumina, 3
Alumina sol corresponding to 5% by weight was added as a binder, extrusion molded, and calcined in air at 55° 0 C for 6 hours to obtain a catalyst.

(2) Production of hydrocarbons The catalyst 2.51 obtained in the above (1) was charged into a flow reactor, and methanol was passed through it for 37 ooc at normal pressure.

The reaction was carried out under conditions of WHSV 2.1 hr-'. The results are shown in Table 3.

Comparative Example 1 In Example 1 (2), crystalline aluminonolicade zeolite ZSM-5 (JP-A-50-5335) was used as a catalyst.
The reaction was carried out in the same manner as in Example 1(2) except that 2.51 (produced in Example 8 of the publication) was used. The results are shown in Table 3.

[Brief explanation of the drawing]

FIG. 1 shows the X-ray diffraction pattern of the crystalline silicate obtained on the real stream side 1. Here, θ indicates the angle of incidence. Procedural amendment (voluntary) June 12, 1980 Commissioner of the Japan Patent Office Kazuo Wakasugi 1. Indication of the case Patent application 1982-94068 2. Name of the invention Process for producing hydrocarbons 3. Person making the amendment Related: Patent applicant: New Fuel Oil Development Technology Research Association 4, Agent ■104 Address: 1-1-10-5 Kyobashi, Chuo-ku, Tokyo Column for detailed description of the invention in the specification subject to amendment (1) Description box On page 11, lines 12-13, "Kashirin" is corrected to "gasoline". (2) "Incident angle" in the third line of page 15 is corrected to "glancing angle." (or more) - hair

Claims (1)

[Claims] (1) Calcination U5 at 550'C in air for producing hydrocarbons from oxygen-containing compounds using a catalyst.
After that, the composition expressed in molar ratio is - General formula 1) MV,
0-At203 qS 1O2 (wherein M represents hydrogen, alkali metal and alkaline earth metal, n
indicates the valence of M. p and q are selected from the following range. 0.3p3.0, q≦10), and the X-ray diffraction pattern has a relative intensity of 1.1.20 on the −4=4− side. 2
Moderate 10.06±0.2
Slightly strong 3.87 +0.10 Very strong 3
．． 8. ll ni 0.10 strong 3.
77 +0.10 Moderate lattice spacing d(A
) -Loquat-1i-Kenichiro□3.73 +0.1.
0 Slightly strong 3.66±0.10
1. A process for producing hydrocarbons, characterized in that a crystalline silicate of medium type is used as a catalyst. (2) The X-ray diffraction pattern of crystalline silicate is 1
],,20 ten 0.2 moderate 10.06
02 Slightly strong 7.48± 0.2
Weak 6.74 High 0.15
Weak 6.39± 0.15
Weak 6.02±0.15 Weak 5.74± 0.15 Weak
5.59±0.15 Weak 5.0
1±0.15 weak 4.63±0,
15 Weak 4.3 8, :f: 0.1. 5
Weak 4.28±0.10 Weak 4.02 +0.10 Weak 3.87±0
,10 very strong 3.83±0.10
Strong 3.77±0.10 Moderate 3.73±0.10 Slightly strong 3.66±0.
10 Moderate 3.50±0.07 Weak 3.45
± 0.07 Weak 3.32 ±
0.07 weak 3.06±O1
07 Weak 2.99± 0.07 Weak 2.
95±0.07 weak. The method according to claim 1. (3) Alcohol whose oxygen-containing compound has 1 to 4 carbon atoms. The method according to claim 1, wherein the ether, aldehyde or carboxylic acid is used. (4) The method according to claim 1, wherein the oxygen-containing compound is methanol.