JP-2026075049-A - Catalysts and apparatus for synthesis gas production

Abstract

【assignment】 The present invention provides a catalyst for synthesis gas production that can suppress excessive heat generation during the reaction and exhibits excellent heat resistance and durability. [Solution] A catalyst for producing synthesis gas from hydrocarbons, which is represented by the following formula (1) and satisfies the following formula (2). M/A x B y O x + 2y (1) [In equation (1), M is Pt or Rh, A is at least one element selected from divalent metallic elements, B is at least one element selected from tetravalent metallic elements, O is oxygen, a real number satisfying 0 ≤ x ≤ 1, and a real number satisfying 0 < y ≤ 1.] R = S² / (S1 + S²) ≤ 0.1 (2) [In equation (2), S1: Peak area derived from Linear-CO adsorbed on Pt particles or Rh particles in CO-DRIFTS measurement, S2: Peak area derived from Bridge-CO adsorbed on Pt particles or Rh particles in CO-DRIFTS measurement.] [Selection Diagram] None

Inventors

• 真鍋 亮
• 下川 隆一
• 村田 和優
• 小池　正和
• 堤内 出
• 細川 三郎

Assignees

• 三菱ケミカル株式会社
• 国立大学法人京都工芸繊維大学

Dates

Publication Date

20260507

Application Date

20250908

Priority Date

20241021

Claims (8)

1. A catalyst for producing synthesis gas containing carbon monoxide and hydrogen from hydrocarbons, wherein the catalyst is represented by the following formula (1) and satisfies the following formula (2). M/A x B y O x+2y (1) [In equation (1), M is either Pt or Rh. A is at least one element selected from divalent metallic elements, B is at least one element selected from tetravalent metallic elements. O is oxygen, A real number satisfying 0 ≤ x ≤ 1, It is a real number satisfying the condition 0 < y ≤ 1. R=S2/(S1+S2)≦0.1 (2) [In equation (2), S1: Peak area derived from Linear-CO adsorbed on Pt particles or Rh particles in CO-DRIFTS measurement. S2: Peak area derived from Bridge-CO adsorbed on Pt particles or Rh particles in CO-DRIFTS measurement.
2. The catalyst according to claim 1, wherein in formula (1), A is at least one element selected from the group consisting of Ca, Sr, and Ba.
3. The catalyst according to claim 1, wherein in formula (1), B is at least one element selected from the group consisting of Zr and Ti.
4. The catalyst according to claim 1, wherein in equation (1), when x = 0, B is Zr.
5. The catalyst according to claim 1, wherein the amount of Pt or Rh supported in formula (1) is less than 1% by mass.
6. The catalyst according to claim 1, wherein M in formula (1) is Pt, and R ≤ 0.09 in formula (2).
7. The catalyst according to claim 1, wherein M in formula (1) is Rh, and in formula (2), 0 ≤ R ≤ 0.1.
8. A synthesis gas production apparatus comprising: a reactor through which a gas to be treated containing at least hydrocarbons flows; and a catalyst disposed inside the reactor at a position in contact with the gas to be treated, wherein the catalyst is the catalyst described in claim 1.

Description

This invention relates to a catalyst for synthesis gas production and a synthesis gas production apparatus. Synthesis gas is an important mixed gas used not only as a raw material for basic chemicals such as methanol and liquid hydrocarbons, but also in a wide range of chemical synthesis processes, including ammonia synthesis and oxo synthesis. Known methods for producing synthesis gas include steam reforming of hydrocarbons (Patent Document 1, Non-Patent Document 1), dry reforming (Patent Document 2, Non-Patent Document 1), and autothermal reforming (Patent Document 3). Steam reforming and dry reforming are endothermic reactions, and therefore require fuel to be used to heat the reaction chamber to allow the reaction to proceed sufficiently. These processes typically produce synthesis gas while maintaining a temperature of 800°C or higher. Autothermal reforming, on the other hand, is a synthesis gas production process that reduces fuel consumption by adding oxygen to hydrocarbons to induce an exothermic reaction, and then using that heat to carry out steam reforming or dry reforming. The reaction chamber in autothermal reforming reaches temperatures of around 2000°C due to the exothermic reaction. As mentioned above, steam reforming and dry reforming are endothermic reactions that use large amounts of fuel, resulting in high greenhouse gas (GHG) emissions and a significant environmental burden. On the other hand, autothermal reforming is an exothermic reaction that reaches temperatures of around 2000°C, raising concerns about the durability (heat resistance) of the catalysts used, as well as requiring expensive refractory materials for the reactor, which presents problems from an economic standpoint. As a method for producing synthesis gas, a catalytic partial oxidation (CPOx) process (Non-Patent Literature 2), in which hydrocarbons and oxygen are directly supplied to the catalyst layer, has also been proposed and investigated. The CPOx process utilizes a catalyst for the oxidation of hydrocarbons, and by initiating the reaction under mild conditions and controlling the exothermic rate, it is expected that heat can be controlled without external supply and the temperature distribution inside the reactor can be controlled. This can reduce environmental impact and reactor costs. Japanese Patent Publication No. 2018-135262Japanese Patent Publication No. 2023-104499Japanese Patent Publication No. 2004-043195 Han, B., Wang, F., Zhang, L. et al., “Syngas production from methane steam reforming and dry reforming reactions over sintering-resistant Ni@SiO2 catalyst”, Res. Chem. Intermed., 46, 1735-1748 (2020).Fazlikeshteli, S., Vendrell, X. Llorca, J., “Catalytic partial oxidation of methane over bimetallic Ru-Ni supported on CeO2 for syngas production”, International Journal of Hydrogen Energy Volume 51, Part A, 2 January 2024, Pages 1494-1507. The present invention will be described in detail below with reference to examples. However, the present invention is not limited in any way by the following examples. In the following examples, percentages are based on mass unless otherwise specified. The following items were evaluated. (1) Method for measuring FT-IR (CO-DRIFTS) The FT-IR (CO-DRIFTS) spectra of the Pt-supported catalyst or Rh-supported catalyst prepared in each example were measured using a Bruker Optics "Trade name: VERTEX 70v". The measurement conditions were as follows: resolution of 4 cm⁻¹ , wavenumber range of 600 to 7500 cm⁻¹ , MCT detector, and 32 integrations (data acquired at 1-minute intervals during continuous measurement). A Specac "Selector" and environmental chamber were used, and measurements were performed using the diffuse reflectance method. As a pretreatment, the sample was heated to 150°C at a rate of 10°C/min under degassing conditions, held for 30 minutes, and then cooled to 35°C. The background spectrum was measured at 35°C under degassing conditions after pretreatment. Subsequently, CO was introduced into the sample and held for 30 minutes, then degassed again, and the IR spectrum was obtained after 30 minutes of degassing. The analysis was baseline-corrected using an improved asymmetric reweighted least squares (IarPLS) method [Ye, J. et al., Applied Optics, 2020, 59, 10933-10943]. Baseline correction was performed in the range of 1600–2300 cm⁻¹ , with IARPLS parameters set to smoothing parameter λ = 1 × 10⁸ , difference order = 2, maximum iterations = 50, and convergence criterion = 1 × 10⁻³ . The baseline-corrected absorbance (Abs) spectra were fitted with Voigt functions for peaks with peak tops in 1700–1900 cm⁻¹ and 1900–2200 cm⁻¹ , respectively. When multiple peaks were observed, fitting was performed using multiple Voigt functions. S1 was calculated as the sum of the areas of Voigt functions with peak tops between 1900 and 2100 cm⁻¹ , and S2 was calculated as the sum of the areas of Voigt functions with peak tops between 1800 and 1900 cm⁻¹ . (2) Catalyst Activity Evaluation T