JP-7857300-B2 - Method and apparatus for producing carbon monoxide

JP7857300B2JP 7857300 B2JP7857300 B2JP 7857300B2JP-7857300-B2

Inventors

山内宏貴
上田翔太

Assignees

住友精化株式会社

Dates

Publication Date: 20260512
Application Date: 20220805
Priority Date: 20210818

Claims (7)

The process includes a step of generating carbon monoxide by the decomposition reaction of at least one of the raw materials, formic acid or alkyl formate, in the presence of a solid acid catalyst. The solid acid catalyst is a proton-type zeolite, A method for producing carbon monoxide, wherein the solid acid catalyst has a total pore volume of pores with a pore diameter of 2 nm or less that is 0.23 cm³ /g or less.
The method for producing carbon monoxide according to claim 1, wherein the total pore volume of the solid acid catalyst is 0.20 cm³ /g or less.
The method for producing carbon monoxide according to claim 2, wherein the total pore volume of the solid acid catalyst is 0.19 cm³ /g or less.
The method for producing carbon monoxide according to claim 1 , wherein the Si/Al atomic ratio of the proton-type zeolite is 1 to 200.
A method for producing carbon monoxide according to any one of claims 1 to 4 , wherein the decomposition reaction of the raw material is carried out at 100 to 300°C.
A carbon monoxide production apparatus that generates carbon monoxide by the decomposition reaction of at least one of formic acid or alkyl formate as a raw material in the presence of a solid acid catalyst, The reactor comprises a solid acid catalyst and a reactor that generates carbon monoxide by a decomposition reaction of the raw materials in the presence of the solid acid catalyst, The solid acid catalyst is a proton-type zeolite, A carbon monoxide production apparatus comprising the solid acid catalyst wherein the total pore volume of pores having a pore diameter of 2 nm or less is 0.23 cm³ /g or less.
The carbon monoxide production apparatus according to claim 6 , wherein the total pore volume of the solid acid catalyst is 0.20 cm³ /g or less.

Description

This disclosure relates to a method and apparatus for producing carbon monoxide. Conventionally, methods for producing carbon monoxide include methods of producing carbon monoxide by steam reforming natural gas, methods of producing carbon monoxide by contacting light hydrocarbons with oxygen in the presence of a partial oxidation catalyst, and methods of producing carbon monoxide by decomposing formic acid. Of these, the method of producing carbon monoxide by decomposing formic acid is advantageous because it can produce carbon monoxide with high selectivity. Methods for producing carbon monoxide by decomposing formic acid include methods using mineral acids and methods using solid acid catalysts. Among these, the method using solid acid catalysts is considered promising as a method that can produce carbon monoxide with a high conversion rate. For example, Patent Document 1 below discloses a method for producing carbon monoxide by decomposing formic acid using a solid acid catalyst, and then reducing the hydrogen concentration in the produced carbon monoxide by subjecting it to a purification process using a palladium catalyst or the like. Korean Published Patent Publication No. 2016-0173781 This is a schematic diagram showing one embodiment of a carbon monoxide production apparatus according to the present disclosure.This figure shows the relationship between the hydrogen concentration in Examples 1 to 3 and Comparative Example 1 and the total pore volume of pores with a pore diameter of 2 nm or less.This figure shows the relationship between the conversion rate of the raw materials and the total pore volume of pores having a pore diameter of 2 nm or less in Examples 1 to 3 and Comparative Example 1. The embodiments of this disclosure will be described in detail below. However, this disclosure is not limited to the embodiments described below. The carbon monoxide production method according to this disclosure includes a step of generating carbon monoxide by a decomposition reaction of at least one of formic acid or alkyl formate as a raw material in the presence of a solid acid catalyst. As the solid acid catalyst, a solid acid catalyst is used in which the total pore volume of pores having a pore diameter of 2 nm or less (hereinafter also referred to as "micropores") is 0.23 cm³ /g or less. The carbon monoxide production method according to this disclosure can be carried out, for example, by a carbon monoxide production apparatus equipped with a reactor that houses the above-mentioned solid acid catalyst and generates carbon monoxide by a decomposition reaction of raw materials in the presence of the solid acid catalyst. (solid acid catalyst) While the solid acid catalyst is not particularly limited, proton-type zeolites are preferably used as solid acid catalysts. Examples of proton-type zeolites include mordenite, ZSM-5, beta-type, Y-type, and US-Y-type zeolites. As a proton-type zeolite catalyst, for example, high-silica zeolite catalysts manufactured by Tosoh Corporation can be used. In the solid acid catalyst, the total pore volume of the micropores is 0.23 cm³ /g or less. When the total pore volume of the micropores in the solid acid catalyst is 0.23 cm³ /g or less, the hydrogen concentration in the produced carbon monoxide can be sufficiently reduced without a purification process to remove hydrogen, compared to when a solid acid catalyst with a total pore volume of micropores exceeding 0.23 cm³/g is used. Alternatively, the conversion rate of the raw materials can be improved compared to when the total pore volume of pores with a pore diameter of 2 nm or less in the solid acid catalyst exceeds 0.23 cm³ /g. Therefore, carbon monoxide can be produced efficiently according to the carbon monoxide production method of this disclosure. From the viewpoint of improving the conversion rate of raw materials and more sufficiently reducing the hydrogen concentration in the produced carbon monoxide without performing a purification process to remove hydrogen, the total pore volume of the micropores of the solid acid catalyst is preferably 0.20 cm³ /g or less, more preferably 0.19 cm³ /g or less, even more preferably 0.18 cm³ /g or less, and particularly preferably 0.15 cm³/g or less. However, in the solid acid catalyst, the total pore volume of the micropores is preferably 0.10 cm³ /g or more, and more preferably 0.12 cm³ /g or more. In the solid acid catalyst, when the total pore volume of the micropores is 0.10 cm³ / g or more, the decomposition reaction of the raw materials proceeds more easily, and as a result, the conversion rate of the raw materials tends to improve further. Pore diameter refers to the value dp obtained by analyzing the measurement results, which are obtained using the BELSORP-MAX analytical instrument (Microtrac-Bell) under the following conditions, using the SF method with the BELMaster analysis software (Microtrac-Bell). (conditions) Measurement temperature: -196℃ Adsorbate: Nitrogen