JPS60197633A - Preparation of oxygen-containing organic compound - Google Patents

Abstract

PURPOSE:To obtain an oxygen-containing organic compound from carbon monoxide and hydrogen efficiently, by using an easily obtainable catalyst having high activity prepared by adding an alkali metal and an alkaline earth metal in a solid state to a solid catalytic component containing specific plural metals. CONSTITUTION:In preparing an oxygen-containing organic compound such as alcohol, ether, etc. by reacting carbon monoxide with hydrogen in the presence of a catalyst, a mixture of the solid catalytic component A comprising (a) copper or zinc, (b) one or more elements selected from nickel, cobalt, and iron, and (c) one or more elements selected from Groups IIIb, IVb, Vb, VIb and VIIb, aluminum, gallium, and silicon, and the solic catalytic component B containing a solid alkali metal and/or alkaline earth metal is used as the catalyst, to obtain the desired compound useful as an alcohol for blending of gasolin for automobile, etc. industrially advantageously.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing oxygen-containing organic compounds, and more specifically, by using a specific catalyst, oxygen-containing organic compounds such as alcohols and ethers are efficiently produced from carbon oxide and hydrogen. Regarding the method.

Conventionally, various methods have been developed for producing oxygen-containing organic compounds using -carbon oxide and hydrogen as raw materials.

For example, Cu/Co/(Cr+Fe+V, M
n)/rare earth/(alkali metal or alkaline earth metal) method (JP-A-55-8553)
0), or C3+/Ti/(Cr, Mo,
A method using an alloy catalyst consisting of Mn+Rh, Co, PtlFe/(alkali metal or alkaline earth metal) (Japanese Unexamined Patent Publication No. 122045/1983) is known. However, in the former method, when preparing the catalyst, alkali metals and alkaline earth metals are added using a solution impregnation method, so the entire catalyst becomes alkaline, and as a result, the activity of the resulting catalyst is not sufficient. There is. Furthermore, since the latter method uses an alloy catalyst, its preparation requires time and effort, and the oxygen-containing organic compounds produced are concentrated in methanol and ethanol.

Therefore, the present inventors have conducted extensive research in order to overcome the drawbacks of the above-mentioned conventional techniques and to develop a highly efficient method for producing alcohol using a highly active and easily prepared catalyst. As a result, they found that the objective could be achieved by using a catalyst prepared by adding a component containing an alkali metal or an alkaline earth metal in solid form to a solid catalyst component containing a plurality of specific metals. The present invention was completed based on this knowledge.

That is, in producing an oxygen-containing organic compound by reacting carbon monoxide and hydrogen in the presence of a catalyst, the present invention provides the following methods: (a) copper or zinc; (b) one selected from nickel, cobalt, and iron; More than one element.

(c) Groups mb, IVb, and vb of the periodic table.

One or more elements selected from the Vtb group, ■b group, aluminum, gallium, and silicon.

Provided is a method for producing an oxygen-containing organic compound, which uses a catalyst formed by mixing a solid catalyst component A containing: and a solid catalyst component B containing a solid alkali metal and/or alkaline earth metal. It is something to do.

As mentioned above, the catalyst mixture used in the method of the present invention is a mixture of solid catalyst component A and solid catalyst component B. Here, the solid catalyst component A is the above-mentioned (a), (b), (
C) Contains component. Among these, component (a) is copper or zinc, but it is not limited to metallic steel or metallic zinc, and various compounds containing copper or zinc can be used.

Among them, water-soluble compounds are convenient for preparing the solid catalyst component A, and specifically, copper compounds such as copper nitrate, steel sulfate, and copper chloride, or zinc nitrate and zinc sulfate.

Examples include zinc compounds such as zinc chloride.

In addition, component (b) contains at least one element among nickel, cobalt, and iron, and includes metal powders, oxides, or salts of these metals, and preferred among them are water-soluble compounds, Examples include nitrates, sulfates, and chlorides of these metals.

In addition, as this (b) component, the said compound may be used individually, or may be used as a mixture of 2 or more types.

Furthermore, the component (C) includes groups mb, group IVb, and v of the periodic table.
Group b, Group ■b, aluminum, gallium.

It contains at least one type of silicon.

Indolium falls under these categories.

Lanthanum, actinium, titanium, zirconium.

Hafnium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, aluminum.

These include gallium and silicon. Component (C) may include these metal powders, oxides, or salts, but
Particularly preferred are water-soluble compounds, such as nitrates, sulfates, and chlorides of these metals.

Specifically, yttrium nitrate and lanthanum nitrate.

Titanium sulfate, titanium chloride, zirconium oxynitrate, zirconium oxychloride, zirconium chloride.

Hafnium chloride, vanadyl sulfate, niobium chloride, chromium nitrate, chromium sulfate, molybdenum chloride, tungsten chloride,
Vanadium chloride, ammonium molybdate, ammonium tungstate, manganese nitrate, manganese sulfate, aluminum nitrate, aluminum chloride, aluminum sulfate, gallium nitrate.

Examples include sodium silicate, and these may be used alone or in combination of two or more.

In order to prepare the solid catalyst component A containing the above components (a), (b), and (C), the above-mentioned (a) and (b) are prepared.

Using various compounds containing the metals of the components (c) as raw materials, these may be sufficiently mixed, various operations may be performed, and the resulting product may be subjected to appropriate treatments such as drying and firing. A specific method is to add each component (a), (b), and (C) to water to form an aqueous solution or suspension, and then add sodium carbonate, magnesium acetate, etc. to the solution or suspension at room temperature or while heating. A precipitate may be produced by adding a coprecipitant and causing coprecipitation. Thereafter, the precipitate may be aged if necessary, washed with water, dried and fired, and further may be subjected to reduction treatment, etc., if desired.

In addition to the coprecipitation method described above, it can also be prepared by a cross-wire method, an impregnation method, and the like. .

(a) and (b) in this solid catalyst component A.

(c) The blending ratio of the components is not particularly limited and varies depending on the type and purpose of use.
) component 5 to 70% by weight, (b) component 1 to 50% by weight, (
c) Component may be selected within the range of 1 to 70% by weight.

On the other hand, as solid catalyst component B, alkali metal and/or
Or solid materials containing alkaline earth metals, such as sodium carbonate, magnesium acetate, potassium carbonate, and sodium hydrogen carbonate.

Powders of potassium oxalate, magnesium oxalate, barium carbonate, barium oxalate, barium acetate, etc., or a mixture thereof may be used.

The catalyst used in the method of the present invention can be obtained by mixing the above-mentioned solid catalyst component A and solid catalyst component B, but the mixing at this time should be carried out so that both components A and B are in a solid state. It is particularly preferable to pulverize and mix in a dry manner without adding water, etc. After thoroughly mixing the solid catalyst components A and B, if desired, add a binder such as graphite and molding to obtain the desired catalyst. I can do it. Further, it is also effective to perform further reduction processing.

The mixing ratio of solid catalyst components A and H in the above catalyst is (a) and (b) in solid catalyst component A.

(C) It may be determined as appropriate depending on the type and content of the component, the type of oxygen-containing organic compound desired, and other conditions, and cannot be determined unambiguously, but usually the solid catalyst component A
85-99.9% by weight, solid catalyst component B 15-0.
It may be determined within a range of 1% by weight.

The method of the present invention is to produce an oxygen-containing organic compound from a mixed gas of hydrogen and carbon monoxide by using a catalyst prepared as described above. The ratio of hydrogen and carbon monoxide used as raw materials here is not particularly limited, but a mixed gas having a hydrogen/carbon monoxide molar ratio of 1/3 to 3/1 is generally suitable.

Further, other conditions for the method of the present invention may be appropriately selected depending on various situations, but the reaction temperature is 200 to 500°C, preferably 240 to 400°C, and the reaction pressure is relatively low. The gas hourly space velocity (GH3
V) is 500 to 100,000 hr-', preferably 10
It should be in the range of 00 to 50000 hr".

According to the method of the present invention as described above, a mixed alcohol containing methanol and more distinct alcohols, specifically mixed alcohols such as methanol, ethanol, propatool, butanol, etc., can be produced in high yield. ,
Dimethyl ether.

Various oxygenated organic compounds such as acetaldehyde, acetone, and methyl ethyl ketone are also produced.

In addition, a relatively low reaction pressure is sufficient at this time, and equipment costs, operating costs, etc. can be significantly reduced. Furthermore, since the obtained oxygen-containing organic compound contains a large proportion of methanol and higher alcohol than alcohol, it is suitable as an alcohol for blending into automobile gasoline or as a raw material for manufacturing various chemical products. This method is of extremely high industrial value.

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

Example 1 (1) Preparation of catalyst Copper nitrate (trihydrate) 29. (Ig, cobalt nitrate (6
water salt) 17.5g and aluminum nitrate (nase water salt)
Aqueous solution containing 45.0 g 1.5 j! was heated to 85°C. Separately, 1.51 g of an aqueous solution containing 71.7 g of sodium carbonate (anhydrous salt) was heated to 90°C. Then, these two aqueous solutions were quickly added to 1 liter of warm water at 85°C.

The mixture was mixed and kept at 85° C. for 2 hours while stirring at 300 r, p, m. Thereafter, the obtained precipitate was filtered and further washed with water in an amount approximately 100 times the amount of the precipitate.

After washing, the precipitate was filtered off, dried at 120°C for 10 hours, and further calcined at 450°C for 2 hours. After cooling to room temperature, 1/2 of the resulting calcined product was taken and added to it. 1.02 g of sodium carbonate (anhydrous salt) powder was added, pulverized and mixed in a dry method, graphite was further added to the mixture to give a concentration of 2% by weight, and the catalyst was then compressed into pellets using a tablet molding machine. . The composition of this catalyst was Cu:Co:Al:Na-2:1:2:0.64 (molar ratio).

(2) Synthesis gas conversion reaction The catalyst obtained in (1) above was heated in a stainless steel reaction tube (SU
3 reaction tubes) were filled with 1 lIl. Next, add C to this reaction tube.
o/Nt = 1/9 gas GH3V = 4000hr
-', while gradually raising the temperature to 240℃ for 20 minutes.
pretreated for hours. Thereafter, while flowing synthesis gas with CO/H snow = 1/2 at G HS V = 4000 hr-', the pressure was gradually increased to 61 Kg/cs+''G, and a conversion reaction of the synthesis gas was performed at a predetermined temperature.The results are as follows. The products shown in Table 1 were not condensed at the outlet of the reaction tube and were directly introduced into a gas chromatography system through a line heated to 200° C. for analysis.

Comparative Example 1 (1) Preparation of Catalyst To the remainder of the calcined product obtained in Example 1 (1) (i.e., 172 of the obtained calcined product), 9.6 m# of an aqueous sodium carbonate solution with a concentration of 1 mol H was added at 90°C. The mixture was impregnated on a water bath heated to 100°C, evaporated to dryness, and then dried at 120°C for 5 hours, after which graphite was added to a concentration of 2% by weight, and then compressed into pellets using a tablet machine. A catalyst was obtained. 3 The composition of this catalyst is Cu:Co:A1:Na=2:1:2:
It was 0.63 (molar ratio).

(2) Conversion reaction of synthesis gas A conversion reaction of synthesis gas was carried out in the same manner as in Example 1 (2) except that the catalyst obtained in (1) above was used. The results are shown in Table 1.

Example 2 (1) Preparation of catalyst 1.51 g of an aqueous solution containing 22.5 g of zinc nitrate (hexahydrate), 43.6 g of nickel nitrate (hexahydrate) and 24.2 g of zirconium oxychloride (octahydrate) was Warmed to ℃. Separately, 1.51 of an aqueous solution containing 47.7 g of sodium carbonate (anhydrous salt) was heated to 90°C. Then, these two aqueous solutions were quickly added to ljl of 85°C warm water.

The mixture was mixed and kept at 85° C. for 2 hours while stirring at 300 r, p, w. Thereafter, the obtained precipitate was filtered and further washed with water in an amount approximately 100 times the amount of the precipitate.

After washing, the precipitate was filtered off, dried at 120°C for 10 hours, and further calcined at 450°C for 2 hours. After cooling to room temperature, 1/2 of the resulting calcined product was taken and added to it. 1.33 g of potassium carbonate (anhydrous salt) powder was added, pulverized and mixed in a dry method, graphite was further added to the mixture to give a concentration of 2% by weight, and the catalyst was then compressed into pellets using a tablet molding machine. . The composition of this catalyst was Zn:Ni:Zr=1:2:1:0.13 (molar ratio).

(2) Synthesis gas conversion reaction The catalyst obtained in (1) above was heated in a stainless steel reaction tube (SU
3 reaction tube) was filled with 1 l. Then Co was added to this reaction tube.
/N, -1/! l) G H'S V= 4000
Pretreatment was carried out at 240°C for 20 hours while the temperature was gradually raised while flowing at hr-'. After that, GO/Hg −1
/ 2 synthesis gas was gradually increased in pressure to 61Kg/cm"G while flowing at GHSV-4000hr-凰,
The synthesis gas conversion reaction was carried out at 371°C. Results first
Shown in the table.

Comparative Example 2 9.6 mj of a potassium carbonate aqueous solution with a concentration of 1 mol/l was added to the remainder of the fired product obtained in Example 2 (1) (i.e., 172 of the obtained fired product)! Comparative Example 1 below
A catalyst was prepared in the same manner as in (1). The composition of this catalyst was Zn:Ni:Zr:-1:2:1:0.13 (molar ratio).

Subsequently, using this catalyst, a conversion reaction of synthesis gas was carried out in the same manner as in Example 1 (2). The results are shown in Table 1.

Example 3 (1) Preparation of catalyst 1.51 g of an aqueous solution containing 24.2 g of copper nitrate (trihydrate), 29.1 g of nickel nitrate (hexahydrate), and 80.0 g of an aqueous titanium nitrate solution with a concentration of 30χ was heated to 60°C. Warmed.

Separately, an aqueous solution 1.51 containing 66.3 g of sodium carbonate (anhydrous salt) was heated to 90°C.Next, these two aqueous solutions were quickly added to 85°C hot water 11, mixed, and heated at 300 r, p. 2 at 85°C while stirring with
Holds time.

Thereafter, a catalyst was prepared in the same manner as in Example 1 (1). The composition of this catalyst is Cu:Ni:Ti:Na=1:1:1:
It was 0.3B (molar ratio).

(2) Conversion reaction of synthesis gas A conversion reaction of synthesis gas was carried out in the same manner as in Example 1 (2) except that the catalyst obtained in (1) above was used. The results are shown in Table 1.

Comparative Example 3 9.6 mj of a sodium carbonate aqueous solution with a concentration of 1 mol/1 was added to the remainder of the fired product obtained in Example 3 (1) (that is, 172 of the obtained fired product)! Comparative Example 1 below
A catalyst was prepared in the same manner as in (1). The composition of this catalyst is Cu:Ni:Ti:Na=1+1:1:
It was 0.37 (molar ratio).

Subsequently, using this catalyst, a conversion reaction of synthesis gas was carried out in the same manner as in Example 1 (2). The results are shown in Table 1.

March 7, 1985 Manabu Shiga, Commissioner of the Patent Office 1. Indication of the case Patent application 1982-51100 2. Name of the invention Process for producing oxygen-containing organic compounds 3. Person making the amendment Relationship to the incident Patent applicant New Fuel Oil Development Technology Research Association 4, Agent ■104 5th floor Nishikan Building, 1-10 Kyobashi, Chuo-ku, Tokyo (7407) Patent attorney Kubo 1) Fujibe Telephone (275) No. 0721 No. 5, "Titanium nitrate" in column 6 of the detailed description of the invention in the specification subject to amendment, page 14, second line from the bottom of the specification of contents of the amendment, is corrected to "titanium sulfate."

(that's all)

Claims (1)

[Claims] (1) In producing an oxygen-containing organic compound by reacting carbon monoxide and hydrogen in the presence of a catalyst, (a) copper or zinc. (b) One or more elements selected from nickel, cobalt and iron. (C) Group mb, group IVb, and group vb of the periodic table. One or more elements selected from ■B group, ■B group, aluminum, gallium, and silicon. 1. A method for producing an oxygen-containing organic compound, which comprises using a catalyst obtained by mixing a solid catalyst component A containing: and a solid catalyst component B containing a solid alkali metal and/or alkaline earth metal.