JPS60166628A - Production of lower olefin - Google Patents

Abstract

PURPOSE:To produce a lower olefin such as ethylene, propylene, etc. from methanol, dimethyl ether, etc., in high efficiency, by using a catalyst comprising a crystalline aluminosilicate containing iron and a bivalent metal and having a specific composition. CONSTITUTION:A lower olefin is produced from methanol and/or dimethyl ether by using a catalyst comprising a crystalline aluminosilicate having the composition of formula (M<1> is alkali metal or H; M<2> is Cu, Ca, Cd or Ni; 0.1<a<2.0; b>0; c>0; d>0; c+d=1; e>20; 0<n<30). The above catalyst can be prepared by the hydrothermal reaction of the sources of SiO2, Fe2O3, Al2O3, alkali metal ion and bivalent metal ion in an aqueous medium in the presence of a crystallization modifier such as n-butanol.

Description

Detailed Description of the Invention The present invention relates to a method for producing lower olefins, and more specifically, a method for efficiently producing lower olefins such as ethylene and propylene from methanol and dimethyl ether by using a specific crystalline aluminosilicate-1 as a catalyst. Regarding.

Conventionally, methods for producing hydrocarbons from methanol or dimethyl ether using various crystalline silicates as catalysts have been known. For example, ZSM by Mopil Oil
-5 zeolite is made from methanol and has 10 carbon atoms.
It is excellent for synthesizing hydrocarbons, mainly from gasoline fractions up to is inappropriate. However, ZSM-34 zeolite exhibits high selectivity to ethylene, propylene, etc. during the catalytic process for producing lower olefins from methanol, but its activity decreases extremely quickly and cannot be said to be of practical use. . Moreover, these ZSM-based zeolites I require the use of expensive organic amines as crystallization modifiers during the preparation process.
The disadvantage is that the manufacturing cost is high.

The present inventors have conducted extensive research in order to develop a method for efficiently producing lower olefins such as ethyl/propylene and propylene using methanol and dimethyl ether as raw materials. As a result, they discovered that the desired lower olefins can be produced efficiently with high selectivity by using crystalline aluminosilicate with a specific composition containing iron and divalent metals as a catalyst. The present invention was completed based on this knowledge. That is, in the present invention, when producing lower olefins from methanol and/or dimethyl ether using a catalyst, the composition formula % formula % () (where Ml is the alkali metal dimension or hydrogen 1M2 is copper, calcium, cadmium and Indicates one or more divalent metals selected from the group consisting of nickel.-!ta,
0.1 < a < 2.0.

1)>O, c)0, d:)>0, ci d=I
, e>20, 0<n<30. ) Divalent metal-containing extracrystalline iron aluminosilicate-1
This invention provides a method for producing lower olefins, which is characterized by using as a catalyst.

The composition formula <1 used as a catalyst in the method of the present invention
Divalent metal-containing extracrystalline iron aluminosilicates, denoted by +, can be prepared in various ways, including:
Usually 5i02, Fe2O3, Af! ,203,
It is produced by subjecting sources of alkali metal ions and divalent metal ions to a hydrothermal reaction in an aqueous medium.

In this case, it is preferable to add an alcohol, particularly n-butanol, as a crystallization regulator to the aqueous medium.

The 5i02 source used in preparing the crystalline alumino/liquid-1 described in Section 2 is water glass and silica sol.

Although silica gel or silica can be used, water glass and silica sol are particularly preferred. Manoζ, Fe2O
Water-soluble ferric salts can be used as the three sources, and preferred examples include ferric nitrate and ferric ammonium sulfate. As the Al2O2 source, sodium aluminate, aluminum sulfate, alumina sol, alumina, etc. can be used, but sodium aluminate and aluminum sulfate are preferred. On the other hand, as the alkali metal ion source, for example, sthorium oxide, sodium aluminate, sthrium hydroxide, etc. in water glass are used. Further, divalent metal sources include compounds of copper, calcium, cadmium and nickel, specifically copper acetate, copper nitrate, cupric chloride, calcium acetate, calcium nitrate, calcium chloride, cadmium acetate, cadmium nitrate.

Cadmium chloride, nickel acetate, nickel nitrate.

Examples include nickel chloride, and these may be used alone or in combination. In addition, as a crystallization regulator, alcohols, preferably straight chain alcohols having 1 to 8 carbon atoms, specifically n-propanol, n -Butanol, especially n-butanol, is most preferred.

The composition of the reaction mixture for carrying out the hydrothermal reaction is preferably prepared in the following proportions.

5i02/Fe203 (mol J7): 25-200
0. More preferably 50-500°5i02/ALO3 (mole ratio)'25-500. More preferably 40-400゜OH-/SiO2(7)㐋hi): 0.05-1.0
．． More preferably 0.1-0.5°H2Q10n- (molar ratio), 10-300. More preferably 50-250°M20/SiO2 (mole ratio): 0.001-0.0
5, more preferably 0.002 to 0.02 alcohol/S i O3 (molar ratio): O, 1 to 5,
Furthermore, in order to obtain a mixture having a composition in this range, the above-mentioned compounds are added, and in order to adjust the pH, an acid such as hydrochloric acid, sulfuric acid, nitric acid, or an alkali metal hydroxide is added as appropriate. It is also effective to add it.

The mixture thus obtained was heated under autogenous pressure to 120
~220°C, preferably about 1-2 at 150-190°C
The mixture may be heated and stirred in a closed container for 5 to 50 hours. The reaction product is separated by filtration or centrifugation, and washed with water to remove excess ionic substances.
- Then dry.

In this way, a divalent metal-containing extracrystalline iron alumino 7-liquid 1. is obtained, which is of an alkali metal salt type (Ml in m is an alkali metal). This alkali metal salt-type divalent metal-containing crystal +/1 iron aluminosilicate is reacted with an inorganic acid such as hydrochloric acid, sulfuric acid, or nitric acid, an organic acid such as formic acid or acetic acid, or with an ammonium salt by a conventional method. By performing a treatment such as heating and then firing, a part or all of the alkali metal can be replaced with protons (H+), thereby converting it into a hydrogen type divalent metal-containing extracrystalline iron aluminosilicate. When used as a catalyst, iron aluminosilicate synthesized using n-butanol as a crystallizing agent is added with I of the Synchronous Table of Elements.
A, TB, TTA, TIB, HA.

ITTB, R'A, Th'B, VA, VB
, VIB, ■B, ■1 insert belonging to group ■ and rare earth -4
- may be modified by an ion exchange method or an impregnation method.

Divalent metal-containing crystalline iron aluminosilicate obtained here
1 is represented by the above-mentioned formula (I) as a compositional formula, and the X-ray diffraction pattern showing the crystal structure is shown in the table in the specification of JP-A-58-1, No. 10421, which has already been filed. These are basically the same as those shown in Table 1 and Table 2. This is considered to be because in the iron aluminosilicate-1 of the present invention, divalent metals are bonded in an ion-exchange manner, so that they have almost no effect on the skeleton of the crystal structure itself.

In order to prepare a divalent metal-containing extracrystalline iron aluminone ricade having the above compositional formula and X-ray diffraction pattern, it is preferable to proceed with the reaction in the presence of an alcohol, especially n-butanol, as described above. Ugly, ZSM-
Even if organic amines are used to prepare Zeolite I.5, the desired aluminosilicate I. cannot be obtained.

In the method of the present invention, lower olefins such as ethylene and propylene are produced from a raw material consisting of methanol and/or dimethyl ether using the thus obtained divalent metal-containing extracrystalline iron aluminosilicate as a catalyst. The conversion reaction of methanol and/or dimethyl ether at this time may be carried out in any reaction form as long as these raw materials are supplied as a gas and can be brought into sufficient contact with a solid catalyst, such as a fixed bed reaction method or a fluidized bed reaction method. Examples include a reaction method and a moving bed reaction method. In addition, this conversion reaction is
It can be carried out under various conditions, for example, reaction temperature 2
50-500℃, weight hourly space velocity (WH3V) 0
．． 1-20 hr-', preferably 1-10 hr-'
, total pressure 0.1 to 100 atm, preferably 0.5 to 1
Kokichi can be performed under conditions of 0 atmospheric pressure.

According to the method of the present invention, lower olefins can be produced from methanol or dimethyl ether in a stable state with high selectivity and high yield. Note that even if the raw materials methanol and dimethyl ether are used as they are without being diluted with steam or the like, lower olefins can be produced with sufficiently high selectivity and yield. Furthermore, the catalyst used in the method of the present invention can be prepared by using an inexpensive alcohol such as n-butanol as a crystallization modifier instead of an expensive organic amine. can be said to be very advantageous.

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

Preparation Examples 1 to 5 (Preparation of Catalyst) A predetermined amount of the metal salt shown in Table 1 was dissolved in 86F water to prepare liquid A, and No. 4 water glass (5I0224%, Na206.
5%) 61.1! was dissolved in 64 y of water and used as liquid B. Add liquid B to liquid A while stirring vigorously, then add 24 ml of a 2.5 N sulfuric acid aqueous solution, and further add 16.2 F of n-butanol, and continue stirring for about 10 minutes after the addition is complete. This was continued for 1 minute to obtain an aqueous gel mixture. next,
This aqueous gel mixture was charged into an autoclave with an internal volume of 300 m6, and stirred at 180°C for 20 hours under autogenous pressure (50 m6).
Hydrothermal treatment was carried out at 0r, pm, )L. The reaction mixture is separated into a solid component and a solution part using a centrifuge.
The solid components were thoroughly washed with water and further dried at 120°C.

here? Crystalline iron aluminosilicate-1 containing 4% divalent metal was treated in air at 530°C for 5 hours.

Next, 13 ml of a 0.6N hydrochloric acid aqueous solution was added to this fired crystalline iron aluminosilicate containing divalent metal 1.1y.
The mixture was mixed at a ratio of 1, and stirred at room temperature for 24 hours to exchange sodium ions with pro). After that, it was thoroughly washed with water at room temperature, dried at 120°C, and then dried at 50°C.
Calcination was performed in air at 0° C. for 3 hours to convert it into a hydrogen form. Table 1 shows the molar ratio of each component in the hydrogen type divalent metal-containing crystalline iron aluminosilicate obtained.

11- Examples 1 to 5 2 ml of the hydrogen type divalent metal-containing extracrystalline iron aluminium non-liquid obtained in Preparation Examples 1 to 5! was packed in a fixed bed flow reactor with a catalyst and 1 to 1, and the pressure was normal pressure and the temperature was 290 = -3.
The conversion reaction was carried out under the conditions of 20° C. and LH5V 2 hr'-' by supplying methanol to the above reactor at a rate of 4 me/hr and argon as an internal standard gas at a rate of 40 m#/min. The results are shown in Table 2.

Comparative Example 1 Using tetraprobylammonium bromide, molar ratio SiO2/AR20a = 180, SiO,
The conversion reaction was carried out under the same conditions as in Example 1, except that 25M5-like iron-aluminosilicate obtained by hydrothermal synthesis at 160° C. for 16 hours under autogenous pressure at /Fe203=90 was used as a catalyst. The results are shown in Table 2.

Comparative Example 2 Comparative Example 1 except that the crystalline iron aluminosilicate-1 (hereinafter referred to as "5hell catalyst") prepared in Example 1 of JP-A-53-76199 was used as a catalyst.
The conversion reaction was carried out under the same conditions. The results are shown in Table 2.

Comparative Example 3 Crystalline method aluminosilicate prepared in Example 1 of JP-A-57-7820 (hereinafter referred to as "Mitsubishi catalyst")
A conversion reaction was carried out under the same conditions as in Comparative Example 1, except that the following was used as a catalyst. The results are shown in Table 2.

Claims (1)

[Claims] (1) In producing lower olefins from methanol and/or dimethyl ether using a catalyst, the composition formula % formula % (where Ml is an alkali metal or hydrogen 9M'' is selected from the group consisting of copper, calcium, cadmium and nickel) is used. Indicates one or more divalent metals.Also, 0
．． 1<a<2. o. 1) ) O+ c ) 0 + d ) 0 + c
Divalent metal-containing crystalline iron aluminosilicate-1 expressed as 10d=1+e)20.0(n(30)
A method for producing a lower olefin, characterized by using as a catalyst.