Search

EP-4735385-A1 - LIGHT ACTIVATED REVERSE BOUDOUARD PROCESS

EP4735385A1EP 4735385 A1EP4735385 A1EP 4735385A1EP-4735385-A1

Abstract

A light assisted photochemical process for converting carbonaceous materials and carbon dioxide to carbon monoxide under ambient operating conditions, and system therefor are disclosed.

Inventors

  • OZIN, GEOFFREY
  • VIASUS PEREZ, Camilo Javier
  • YE, JESSICA
  • NGUYEN, Nhat Truong

Assignees

  • Hydrofuel Canada Inc.
  • The Governing Council of the University of Toronto

Dates

Publication Date
20260506
Application Date
20240628

Claims (20)

  1. 1 . A process for the production of carbon monoxide comprising reacting one or more carbonaceous materials with a gaseous carbon dioxide feed stream, wherein the carbonaceous material is exposed to light concurrently with the contact of the carbonaceous material by the gaseous carbon dioxide source.
  2. 2. The process of claim 1 wherein the process is carried out at a temperature between ambient temperature and about 560-degrees C.
  3. 3. The process of claim 1 wherein the process is carried out at a temperature between ambient temperature and about 280-degrees C.
  4. 4. The process of any of claims 1 - 3 wherein the gaseous carbon dioxide source comprises carbon dioxide and an inert gas.
  5. 5. The process of claim 4 wherein the inert gas is argon.
  6. 6. The process of Claim 1 wherein the light is solar light.
  7. 7. The process of claim 1 wherein the light is from light emitting diodes.
  8. 8. The process of claim 1 , 6 or 7 where the intensity of the light as measured at the surface of the carbonaceous material is between 0.1 and 95 W cm -2 .
  9. 9. The process of claim 1 , 6 or 7 where the intensity of the light as measured at the surface of the carbonaceous material is between 1 .0 and 95 W cm -2 .
  10. 10. The process of claim 1 , 6 or 7 where the intensity of the light as measured at the surface of the carbonaceous material is between 1 .5 and 95 W cm -2 .
  11. 11 . The process of claim 1 , 6 or 7 where the intensity of the light as measured at the surface of the carbonaceous material is between about 10 and 95 W cm -2 .
  12. 12. The process of claim 1 , 6 or 7 where the intensity of the light as measured at the surface of the carbonaceous material is between 15 and 95 W cm’ 2 .
  13. 13. The process of any of claims 1 - 10 wherein the light source is amplified by optical or electronic means to achieve the desired intensities.
  14. 14. The process of any of claims 1 - 11 wherein the wavelength of the light to which the carbonaceous material is exposed is greater than about 420 nm.
  15. 15. The process of any of claims 1 - 11 wherein the wavelength of the light to which the carbonaceous material is exposed is greater than about 495 nm.
  16. 16. The process of any of claims 1 - 11 wherein the wavelength of the light to which the carbonaceous material is exposed is greater than 595 nm.
  17. 17. A process for the production of carbon monoxide comprising reacting one or more carbonaceous materials with a gaseous carbon dioxide feed stream, wherein: the carbonaceous material is irradiated with solar light at an intensity as measured at the surface of the carbonaceous material of at least 0.1 W cm’ 2 .
  18. 18. A process for the production of carbon monoxide comprising reacting one or more carbonaceous materials with a gaseous carbon dioxide feed stream, wherein: the carbonaceous material is irradiated with solar light at an intensity as measured at the surface of the carbonaceous material of at least 1 W cm’ 2 .
  19. 19. A process for the production of carbon monoxide comprising reacting one or more carbonaceous materials with a gaseous carbon dioxide feed stream, wherein: the carbonaceous material is irradiated with solar light at an intensity as measured at the surface of the carbonaceous material of at least 15 W cm’ 2 .
  20. 0. A process for the production of carbon monoxide comprising reacting one or more carbonaceous materials with a gaseous carbon dioxide feed stream, wherein: a. the carbonaceous material is irradiated with light from one or more light emitting diodes; and b. the intensity of the light as measured at the surface of the carbonaceous material is at least 15 W cm’ 2 1 .A process for the production of carbon monoxide comprising reacting one or more carbonaceous materials with a gaseous carbon dioxide feed stream, wherein: a. the carbonaceous material is irradiated with light from one or more light emitting diodes; and b. the intensity of the light as measured at the surface of the carbonaceous material is at least 15 W cm’ 2 ; and c. the wavelength of the light from the light emitting diodes is above about 400 nm.

Description

LIGHT ACTIVATED REVERSE BOUDOUARD PROCESS FIELD OF THE INVENTION [0001] The present invention relates to a process for the synthesis of a carbon monoxide from solid-state carbon and carbon dioxide gas using a light-driven reverse- Boudouard reaction. The process of the invention allows the reverse-Boudouard reaction to proceed under more sustainable and practicable conditions than those currently used by way of using sunlight and/or light-emitting diodes, which may be powered 24/7 by silicon photovoltaics, and/or lithium-ion batteries to provide the required light. The process of the present invention is adapted to utilize carbon dioxide and various forms of carbonaceous materials, including but not limited to various forms of carbon black, biochar, and carbonaceous waste to synthesize carbon monoxide in a practical and environmentally friendly way. BACKGROUND [0002] Syngas, or synthesis gas, is a fuel gas mixture consisting primarily of hydrogen (H2), carbon monoxide (CO), and potentially some carbon dioxide (CO2). It is used, for example, as an intermediate in the production of hydrocarbon fuels, such as diesel fuel and methanol, in creating synthetic natural gas and and in the production of industrial chemicals such as ammonia and methanol. Currently, the industrial production of syngas occurs via steam-methane reformation and/or coal or coke steam gasification. Syngas can also be obtained from pyrolysis initiated on residues, biomass, and waste. Both processes are highly energy consuming and carbon footprint-intensive. [0003] Previous attempts at more eco-friendly carbon monoxide production have utilized thermal steam-gasification of fossil fuels, biomass, and/or waste materials, usually through auto-combustion of the carbonaceous feedstock. Notably, the large-scale application of this technology has been limited by high temperatures required, ash melting, and tar contamination. In additional generally, thermal steam gasification generates a large carbon footprint, requires injections of pure oxygen, and produces combustion-related contaminants like dioxins and furans. [0004] The reverse-Boudouard reaction has been used to convert carbon and carbon dioxide to carbon monoxide under purely thermally-driven conditions at temperatures up to 900°C (according to the reaction expressed in equation 1 below). Such high temperatures present technical challenges associated with large-scale high-temperature energy-intensive operations, and these challenges limit the reaction’s utility. C + CO2 2 CO AH°298K = + 172 kJ/mol (1 ) While it has been shown that the use of alkali, alkali-earth, and transition metal catalysts can decrease the required reverse-Boudouard reaction temperature to a limited extent, reactor degradation from catalyst melting and deposition remain a problem for extent practical application. [0005] The global CO market is expected to reach USD 6.643 billion by the end of 2026, growing at a combined annual growth rate of 2.7% during 2021 -2026. SUMMARY OF THE INVENTION [0006] The present invention encompasses methods and apparatuses for the preparation of syngas containing carbon monoxide by a modified reverse Boudouard process while avoiding the very high operating temperatures required for the production of carbon monoxide under purely thermally-driven conditions. It has surprisingly been found that a light-driven reverse-Boudouard process, using sunlight or LED-based lighting, with or without additional heating, can effectively convert carbonaceous materials to carbon monoxide without the elevated temperatures of the prior art. The process of the present invention can be carried out in either batch or flow-type reactors where the solid carbonaceous material is contacted with a gaseous medium containing carbon dioxide in an environment where the interface between the solid carbonaceous material and the carbon dioxide is irradiated by light. The reaction occurs on the surface of the solid carbonaceous material and consumes both carbon and carbon dioxide in approximately equivalent molar amounts, resulting in the production of two carbon monoxides for every atom of carbon and every molecule of carbon dioxide consumed. [0007] While solar light can be used to reduce the heat requirements of the reaction, its intermittency has the potential to limit its effectiveness. The proposed solution of the present invention also permits the production of CO in light-driven reverse-Boudouard process, using light-emitting diodes (LEDs) instead of natural light; the LEDs may be powered using the energy and production storage capacity of silicon photovoltaics and lithium-ion batteries. This Photochemical Reverse Boudouard Reaction can facilitate 24- 7 CO production, under ambient operating conditions even in the absence of sunlight and continuous electrical power. [0008] The solar light and the LED light may be filtered to optimize the wavelengths of the light to which the carbonaceous material is exposed. The