JP3510406B2 - Methanol synthesis catalyst - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst for synthesizing methanol from a gas containing hydrogen (H ₂ ) and carbon monoxide (CO) as main components.

[0002]

2. Description of the Related Art The research and development of a methanol synthesis catalyst has been conducted for a long time, and a catalyst having a composition such as zinc oxide-chromium oxide or copper oxide-zinc oxide is prepared by a coprecipitation method or the like. In particular, a ternary or quaternary catalyst composed of copper oxide-zinc oxide-aluminum oxide and / or chromium oxide has high methanol synthesis activity and is widely used. On the other hand, methanol is expected to be in increasing demand as a raw material for the production of MTBE (methyl tertiary butyl ether), gasoline, petrochemical intermediate products, hydrogen, carbon monoxide, city gas, etc. Large-scale methanol synthesis plants are expected to be built all over the world. In addition, methanol is currently produced by using a gas containing hydrogen and carbon monoxide as main components, which is produced by a steam reforming reaction of natural gas, as a raw material and bringing it into contact with the above-mentioned three-way or four-way catalyst.

In addition to the above-mentioned three-way or four-way system catalyst, a catalyst comprising copper oxide-zinc oxide-manganese oxide (Japanese Patent Publication No. 56-56).
-9376), a catalyst composed of copper oxide-zinc oxide-silicon oxide (JP-B-63-39287), and a catalyst composed of copper oxide-zinc oxide-gallium oxide (JP-A-6-3).
However, since it is hard to say that the methanol synthesis activity is low and the life is sufficient, development of a high-performance methanol synthesis catalyst has been awaited.

[0004]

A catalyst comprising copper oxide-zinc oxide-aluminum oxide and / or chromium oxide has a high methanol synthesis activity, but has a problem that the activity decreases with time. As described above, the catalyst comprising manganese oxide, copper oxide-zinc oxide-silicon oxide, and copper oxide-zinc oxide-gallium oxide has a problem that the methanol synthesis activity is low and the life cannot be said to be sufficient. . In view of the above technical level, the present invention is to provide a methanol synthesis catalyst having high activity and excellent durability.

[0005]

[Means for Solving the Problems] As a result of earnestly carrying out research and development of a catalyst that exceeds the performance of existing methanol synthesis catalysts, the present inventors have highly dispersed copper, which plays the most important role in methanol synthesis activity, Moreover, they have found a methanol synthesis catalyst with a small decrease in activity, and have completed the present invention. That is, the present invention has the following configurations. (1) At least copper, zinc, aluminum and zirconium
Containing each oxide of gallium, gallium, manganese,
Containing one or more metal oxides of indium, C
u: Zn: Al: Zr: (Ga, Mn and / or In)
The composition ratio of is 100: 10 to 200: 1 to 20: in atomic ratio.
1-20: 1-20 methanol
Synthetic catalyst ( hereinafter referred to as the first invention ) . (2) At least copper, zinc, aluminum, zirconium
Characterized by containing oxides of aluminum and indium
And a methanol synthesis catalyst (hereinafter referred to as the second invention).

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The composition ratio (atomic ratio) of the methanol synthesis catalyst of the first invention is Cu: Zn: Al: Zr: α = 10.
It is 0:10 to 200: 1 to 20: 1 to 20: 1 to 20. Here, α represents one or more metals of Ga, Mn, and In. Preferred composition ratio (atom of the second invention of the methanol synthesis catalyst)
Ratio) is Cu: Zn: Al: Zr: In = 100: 10.
It is 200: 1 to 20: 1 to 20: 1 to 20.

Hereinafter, an example of the method for producing the methanol synthesis catalyst of the present invention will be described in more detail. First, the precipitating agent aqueous solution is kept warm: Ga, Mn, In in the first invention while stirring.
One or more metals , In and Al in the second invention ,
An aqueous solution containing each metal salt of Zn and Zr is dropped to deposit a precipitate, and after the dropping, an aqueous solution containing a Cu salt is dropped to form a precipitate. When the pH at the end of dropping is 4 or more, almost all the dropped metal ions are deposited as a precipitate.

The precipitant aqueous solution is an alkaline solution,
Usually 0.1 to 10M concentration of Na₂CO ₃Aqueous solution, NaH
CO₃Aqueous solution, NaOH aqueous solution, K₂CO₃Aqueous solution, N
H₃Aqueous solution is used, especially Na₂CO₃Water soluble
Liquids are preferred. In addition, the temperature of the solution when forming the precipitate
It is preferable to keep the temperature in the range of 15 to 90 ° C.

Further, Cu, Zn, Al, Zr and the first
In the invention, metal salts of Ga, Mn, and In, second invention
In, the metal salt of In is used in the form of nitrate, chloride, sulfate, or acetate as an aqueous solution having a concentration of 0.01 to 1.0 M, and is particularly preferably used as nitrate. Further, the dropping time and the aging time have no particular influence on the methanol synthesis activity of the catalyst, but they may be the conditions under which the metal ions are uniformly dispersed and the precipitate is deposited. Usually, the dropping time: 1 minute to 3 hours, the aging time It is carried out for 1 minute to 3 hours. The obtained precipitate has various crystal species, but after sufficiently removing alkali metal ions and anions by washing, 200 to 400
A methanol synthesis catalyst is obtained by calcination in the range of ° C.

By using the catalyst of the present invention, a gas containing H ₂ and CO or a gas containing H ₂ , CO and CO ₂ is used as a synthesis gas as a raw material for a methanol synthesis reaction, and pressure:
It is possible to synthesize methanol with long-term and stable performance at a temperature of 200 kg / cm ² G or less and a temperature of 100 to 300 ° C.

[0011]

EXAMPLES The present invention will be described in more detail with reference to the following examples, and the effects of the catalyst of the present invention will be clarified. However, the description of the examples is not limited unless the essence of the present invention is impaired. is not.

(Example 1) Sodium carbonate: 2.5 mo
1 is dissolved in 2 liters of water and kept warm at 60 ° C. This alkaline aqueous solution is referred to as solution A. Zinc nitrate: 0.18mo
1 and aluminum nitrate: 0.03 mol, zirconium oxynitrate: 0.015 mol and gallium nitrate: 0.
Dissolve 015 mol in water: 600 cc, keep the temperature at 60 ° C., and use this acidic solution as solution B. In addition, copper nitrate:
0.3 mol of water is dissolved in 300 cc of water and kept at 60 ° C., and this acidic solution is referred to as solution C.

First, the solution B is added to the solution A with stirring 30 times.
A uniform suspension is added dropwise over a minute to obtain a suspension. Next, solution C
Was added dropwise to the suspension at a constant rate over 30 minutes, and
Get the item. After dropping, aging for 2 hours, then deposit
Filtration and Na ion, NO ₃Ions are not detected
To wash. Dry at 100 ° C for 24 hours, then 3
Methanol synthesis catalyst by calcining at 00 ° C for 3 hours
To get This catalyst is referred to as catalyst 1.

(Example 2) Zinc nitrate in solution B: 0.3 mo
1, aluminum nitrate: 0.05 mol, zirconium oxynitrate: 0.03 mol, indium nitrate: 0.0
A methanol synthesis catalyst was prepared by the same preparation method as in Example 1 except that 3 mol was used. This catalyst is referred to as catalyst 2. Further, in the liquid B, zinc nitrate: 0.15 mol, aluminum nitrate: 0.015 mol, zirconium oxynitrate: 0.015 mol, manganese nitrate: 0.015 mo
In addition, in liquid B, zinc nitrate: 0.15 mol, aluminum nitrate: 0.006 mol, zirconium oxynitrate: 0.006 mol, gallium nitrate: 0.006 mo.
Prepared as in Example 1 but using 1
Catalyst 4 was obtained.

Example 3 Example 1 was repeated except that the solutions A, B and C having the same composition as the catalyst 1 of Example 1 were used and the mixed solution of the solutions B and C was added dropwise to the solution A. Catalyst 5 was obtained in the same manner.

(Example 4) Zinc nitrate in solution B: 0.15 m
ol, aluminum nitrate: 0.009 mol, zirconium oxynitrate: 0.006 mol, gallium nitrate:
A methanol synthesis catalyst was prepared by the same preparation method as in Example 1 except that 0.006 mol and manganese nitrate: 0.006 mol were used. This catalyst is referred to as catalyst 6. Further, in the liquid B, zinc nitrate: 0.15 mol, aluminum nitrate: 0.009 mol, zirconium oxynitrate: 0.
A methanol synthesis catalyst was prepared by the same preparation method as in Example 1 except that 006 mol, manganese nitrate: 0.006 mol, and indium nitrate: 0.006 mol were used.
This catalyst is referred to as catalyst 7.

(Comparative Example) In the preparation method of Example 1,
By the same method except that no zirconium oxynitrate was added and no gallium nitrate or aluminum nitrate was added, the composition was CuO—ZnO—Al ₂ O ₃ (C
u: Zn: Al = 100: 60: 10) catalyst 8 and Cu
_{O-ZnO-Ga 2 O 3} (Cu: Zn: Ga = 100:
60:10) Catalyst 9 was prepared. Further, in the preparation method of Example 1, the composition was C except that silica sol or manganese nitrate was used instead of aluminum nitrate, zirconium oxynitrate and gallium nitrate.
_{uO-ZnO-SiO 2 (Cu} : Zn: Si = 100:
60:10) catalyst 10 and CuO-ZnO-MnOx
(Cu: Zn: Mn = 100: 60: 10) catalyst 11
Was prepared.

(Experimental Example 1) An activity evaluation test of the methanol synthesis reaction of the catalysts 1 to 11 obtained in Examples 1 to 4 and Comparative Example was conducted under the conditions shown in Table 1 below.

[0019]

[Table 1]

The catalyst was sized to 16 to 28 mesh, charged into a ₂ cc microreactor, subjected to a reduction treatment with H ₂ 3% / N ₂ base gas, and then a raw material gas was supplied for initial activity evaluation. Table 2 shows the results of evaluating the initial activity of each catalyst.

[0021]

[Table 2] The reaction products were all methanol and water. Table 2
As shown in FIG.
It was found that the methanol synthesis activity was higher than that of No. 11.

(Experimental Example 2) Catalyst 1 and catalyst 8 subjected to initial activity evaluation were used as durability test catalysts. The reaction conditions were the same as in Experimental Example 5 except for the reaction pressure, and the activity results are shown in Table 3.

[0023]

[Table 3] The reaction products were all methanol and water. Table 3
As shown in, it was found that the catalyst prepared according to the present invention has a higher methanol synthesis activity than the conventional catalyst and is excellent in durability.

[0024]

The methanol synthesis catalyst of the present invention has a high methanol synthesis activity and can maintain the activity for a long period of time, so that methanol can be efficiently synthesized.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-6-312138 (JP, A) JP-A-63-209754 (JP, A) JP-A-6-254414 (JP, A) International Publication 94/021376 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) B01J 21/00-38/74

Claims (2)

(57) [Claims] 1. A least copper, zinc, containing the oxides of aluminum and zirconium, Ri further gallium, manganese, Na <br/> contain one or more metal oxides of indium, Cu: Zn: Al : Zr: (Ga, Mn and / or
Has a composition ratio of In) of 100: 10 to 200: 1 in atomic ratio.
20: 1 to 20: 1 to 20 der methanol synthesis catalyst, characterized in Rukoto. 2. At least copper, zinc, aluminum and di
It contains ruconium and indium oxides.
And a methanol synthesis catalyst.