JPS5935894B2 - How to convert carbon monoxide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for converting carbon monoxide, and more particularly to a method for producing lower hydrocarbons and/or lower alcohols from carbon monoxide and hydrogen.

Several methods have been proposed for producing hydrocarbons from carbon monoxide and hydrogen, including the Fischer-Tropschew method [for example, "Catalytic Reaction (Hydrogenation Catalyst Engineering Course 6", Vol. 121-182). Page, Jijin Shokan (19
65)], the carbon number distribution of the generated hydrocarbons is wide,
In addition, there are problems such as a large amount of carbon dioxide produced due to side reactions.

The first method for producing alcohol from carbon monoxide and hydrogen is methanol synthesis. According to current industrial production methods, such as Japanese Patent Publication No. 51-44715, methanol is selectively produced and useful as a chemical raw material. However, in order to use methanol as an energy source such as fuel, it is preferable that it contains an alcohol with two or more carbon atoms, and a method for synthesizing methanol suitable for such purposes has not been established industrially. Not there. Recently, a method for producing alcohol using a rhodium-based catalyst has been disclosed, for example, in Japanese Patent Publication No. 55-27891, but it has not been put to practical use because of the complexity in preparing or recovering the catalyst. The present inventors conducted intensive research to solve the problems in these conventional methods, and as a result, they arrived at the present invention. That is, the present invention is a method for converting carbon monoxide, which is characterized in that lower hydrocarbons and/or lower alcohols are obtained from carbon monoxide and hydrogen in the presence of a catalyst in which rhenium is supported on an iron-based carrier. .

The catalyst used in the present invention only needs to contain rhenium as a catalyst component, and this rhenium is used supported on an iron-based carrier. The rhenium source used as the catalyst component is not particularly limited, but metal rhenium, rhenium oxide, rhenium trichloride, rhenium pentachloride, ammonium perrhenate, and the like are usually preferably used.

Ammonium perrhenate is particularly preferred. The carrier may be any iron-based substance, and is not particularly limited, but iron oxide is preferably used. As the iron oxide, commercially available iron hydroxide calcined in a nitrogen stream is usually used, but other iron-based compounds may be used as the raw material. The supporting method may be normal;
Wet methods such as impregnation methods and precipitation methods, dry methods such as mixing methods, and ion exchange methods are employed.

Of these, the impregnation method is most preferred in practice. The amount of catalyst supported on the carrier is not particularly limited, but it is usually 0.5 wt% or more, preferably 1 to 20 wt% as rhenium oxide (Re2O7) based on the carrier.

For example, if rhenium is used as a carrier and Re2O2 is used, 10wt.
% supported catalyst, the support is immersed in a corresponding amount of ammonium perrhenate aqueous solution,
It can be supported.

The catalyst thus obtained is dried prior to the reaction,
It is preferable to use it after reduction firing. Drying conditions may be normal conditions, preferably 80 to 150°C, preferably 90 to 110°C.
℃ for 10 to 24 hours, preferably 12 to 18 hours.
In addition, the conditions for reduction firing may be normal conditions, and 200 to 30
The temperature is 0°C, preferably 250 to 300°C, for 1 to 5 hours, preferably 2 to 4 hours. The reaction conditions for the carbon monoxide conversion reaction may be any conventional method, and are usually as follows.

That is, the ratio of carbon monoxide and hydrogen supplied to the reaction system is not particularly limited, but in practice it is preferably 0.5 mole or more of hydrogen per 1 mole of carbon monoxide, and 1 to 7 moles of hydrogen.
Particularly preferred is 5 mol. The reaction pressure is not particularly limited, but in practice it is preferably in the range of normal pressure to 300k9/CTit, particularly preferably in the range of 10 to 150k9/CTit.

The reaction temperature is usually 180°C or higher, preferably 200-35°C.
It is 0°C.

The contact time with the catalyst varies depending on the reaction temperature and the like and can be selected as appropriate, but is preferably about 1000 to 5000 hr-1.

In addition, in the present invention, the conversion reaction of carbon monoxide can be carried out by a continuous method or a batch method.

In this way carbon monoxide is converted to lower hydrocarbons and/or lower alcohols. These lower hydrocarbons are mainly C1-4 aliphatic hydrocarbons, especially methane. Further, lower alcohols are mainly C1-4 aliphatic alcohols, and methanol and ethanol are particularly common. In the present invention, a catalyst that is easy to prepare and recover is used, and a lower alcohol and/or alcohol suitable as an energy source is used.
Or lower hydrocarbons can be easily obtained.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
Preparation of Example Catalyst: Commercially available ferric hydroxide was calcined at 450° C. for 2 hours in a nitrogen stream to obtain ferric oxide, which was used as a carrier.

1.5 ammonium perrhenate (99.9% purity)
101 cc of the 6 wt% aqueous solution was impregnated into the ferric oxide 139 described above, and after drying this at 100°C for 14 hours, 39 of the 6 wt% aqueous solution was soaked in SVl with a reducing gas of CO/H2-1/2.
"Catalyst C-2" was obtained by calcination reduction at 300° C. for 3 hours while flowing with OOOhr-1. In addition, this "catalyst C-2" was mixed with N2/H2-9/1 gas at SV3OOOOhr-
1.Heat at 250℃ for 10 hours to prepare "Catalyst C-4".
” was obtained.

Carbon monoxide conversion reaction: A carbon monoxide conversion reaction was carried out in a continuous manner using the above-mentioned "Catalyst C-2" and "Catalyst C-4" in a fixed bed format.

The reaction conditions for the carbon monoxide conversion reaction were as follows.

Reaction temperature: 250°C H2/CO molar ratio of raw material gas: 2/1 Pressure
201<g/? (Absolute) Space velocity of raw material gas (S■) 2500hr-1
Table 1 shows the results about 10 hours after the start of the reaction.

Claims (1)

[Claims] 1 In the presence of a catalyst in which rhenium is supported on an iron-based carrier,
A method for converting carbon monoxide, which comprises obtaining lower hydrocarbons and/or lower alcohols from carbon monoxide and hydrogen.