The goal of this project is to develop a liquid phase photocatalytic process for direct conversion of methane into methanol so that, when applied to flared gas at a well site, the process can generate methanol using a direct photocatalytic route. The goal will be accomplished by completing several research objectives that include:

1. Develop a bifunctional catalyst using a semiconductor photocatalyst architecture to facilitate methane activation to directly convert methane into methanol. 
2. Develop a scalable reactor design to maximize mass transfer and methanol selectivity using an optimized photocatalyst. 
3. Develop a conceptual process design for a modular system for flare gas utilization. 
4. Conduct comprehensive techno-economic and commercial market assessments to position the technology for commercialization. 

Initially, the major focus of the project will be to develop and optimize the semiconductor catalyst for the effective conversion of photons into hydroxyl (•OH) radicals which support methane activation and a co-catalyst that selectively, and with high yield, converts the methyl radicals generated from methane activation into methanol and integrate these into a single bifunctional catalyst.  Stanford will then shift to process development focusing on testing to identify optimal operating conditions, completing long-term testing at realistic commercial conditions, testing with simulated natural gas compositions and intermittent operation involving on/off and varying flow conditions.   
 

Stanford University - Stanford, CA 94305
Susteon, Inc. - Cary, NC 27513
Casale SA - Lugano, Switzerland

The conversion of methane present in natural gas into a liquid or solid product that would enable flared, vented, or otherwise rejected gas to be monetized through conversion to transported, value-added products has the potential to produce a new revenue stream.  This project will focus on a process to convert methane to methanol (CH₃OH) as an attractive alternative to a wasted commodity.  Currently, methanol is synthesized from methane in an indirect, inefficient two-step syngas process requiring high temperature (800°C) and pressure (60 bar), which needs support from a large balance of plant systems that effectively prohibits small-scale and remote application.  Direct conversion of methane to methanol is highly desirable but, remains a fundamental challenge due to the large energy barriers required to activate the inert CH₄ molecules as well as the higher relative reactivity of the C-H bond in methanol compared to those in methane.  While liquid-phase methane conversion has been attempted at room temperature, methane solubility in water limits methane mass transfer to the catalyst surface, significantly lowering total methanol production rates below acceptable commercial rates.  Due to these issues, direct methane to methanol conversion remains a fundamental challenge.

This project aims to overcome this challenge by developing novel photocatalytic activation of methane at a gas-water interface such that methanol can be formed at room temperature.  Photons are used to excite hydroxyl (OH) radicals in aqueous media, which then excite methane to form methanol on a catalyst surface.  As part of this project, Stanford will design and use novel high-throughput screening to identify the best photocatalyst to achieve the highest selectivity and methane conversion efficiency. Based on these values, Stanford will design and build a new photoreactor system that can be modular and scalable for direct methane to methanol conversion.  So, when applied to flared gas at a well site, the process can generate methanol using a direct photocatalytic route.
 

The project offers a potential mechanism to reduce quantities of flared gas at oil and gas production sites, where gas transport options are insufficient or do not exist, by converting the gas to energy-dense liquid products. This process, if successfully developed and deployed, will reduce the volume of natural gas being flared to the atmosphere, thereby having a positive effect on the environment.

FY22 Q2: The focus of the Stanford/Susteon team was to further increase the methane conversion and liquid oxygenate yields by increasing reactor pressure and UV flux and study the structure-performance relationship. In Task 5, the team found the methane conversion and liquid product yields were significantly improved by UV light intensity and the total pressure. The team further performed the ¹³C isotope labeling experiments which confirmed that the produced oxygenates (including CH₃OH, CH₃OOH, HCOOH) were originated from methane precursors. Furthermore, we explored the catalytic role of Au and its loading effect on the performance in the composite catalysts.

FY22, Q1: The Stanford/Susteon team submitted SOPO modifications and costs for Tasks 9 and 10 that were added to the project following a project update between SU, NETL and Headquarters on 7/6/2021. The Technology Manager committed to $300K in additional funding for additional research that is to be obligated in FY22, Q2. Tasks 9 involves research into ways to utilize methane by creating OH radicals via different processes, such as photocatalysis and thermo-catalysis to increase the CH₄ conversion. Task 10 will be used to develop a preliminary basic engineering design package for a methane-to-methanol pilot test unit for a 1 bbl./day methanol production capacity.

FY21, Q4: Following a progress meeting with Headquarters and the Technology Manager, the Stanford/Susteon team made the case for additional funding to conduct more research into ways to utilize methane by creating various radicals via different processes.

FY21, Q3: Project progress was very good with Stanford ahead of schedule on several aspects of the research to convert methane to methanol via a novel photocatalytic process that essentially operates at room temperature. Stanford researchers have found the methane conversion and liquid product yields were significantly improved by integrating Au-Pd co-catalysts with TiO₂ composite oxides, as well as using H₂O₂ as an oxidizer. Using very conservative assumptions, the TEA, developed by Susteon, deems the process to be competitive with larger scale methane conversion processes in the current configuration. If water can be used to replace the H₂O₂ as an oxidizer, which generates hydroxyl radicals to form methanol, costs would be greatly reduced. Stanford showed great progress in replacing H₂O₂ with water and are optimistic about the cost reductions for the process.

The project started on October 1, 2020. Project activities were initiated on October 1, 2020 and an initial project kickoff meeting was held on October 23, 2020. The Technology Maturation plan was submitted on time. All milestones, including the Go/No-go decision point have been completed on time.

In the initial quarter of research, the project has developed and synthesized a series of photocatalysts containing TiO₂ as semiconductors and different metal co-catalysts (Au-Pd, Ru, Rh etc.), which is the milestone of Task 2.  The Stanford team also developed a multiplex fluorescence array for rapid measurement of •OH radicals on the as-synthesized catalysts. Stanford has investigated the effect of co-catalysts and reaction condition (H₂O₂ concentration), and we have successfully optimized the •OH radical production on the TiO₂ by loading Au-Pd as co-catalysts.

Catalytic testing was conducted in a high pressure photoreactor that was constructed on-site.  A proof-of-concept demonstration of the photocatalytic approach by using TiO₂ was performed.  The integration of Au-Pd on TiO₂ improves methanol yield by 5 times and methane conversion by 1.5 times.  Additionally, methanol selectivity of TiO₂ is improved by more than 10 times after growing an oxide layer to form a composite oxide.  Further integration of Au-Pd co-catalyst with this TiO₂ composite oxide increases the methane conversion and methanol selectivity simultaneously.  After preliminary reaction condition optimization, our current best performing catalysts Au-Pd/TiO₂composite oxides achieved 0.16% methane conversion and ~ 90% liquid product selectivity.

The Stanford/Susteon team successfully optimized the reaction conditions of the Au-Pd/TiO₂ composite oxides to further increase methane conversion and liquid product yields. After optimizing reaction conditions, including water amount, CH₄/O₂ ratios and light irradiation time, up to 1% CH₄ conversion wit 80% liquid oxygenates were achieved.

$1,300,000

$325,000

NETL – Bruce Brown (Bruce.Brown@netl.doe.gov or 412-386-5534)
Stanford – Dr. Arun Majumdar (amajumdar@stanford.edu or 650-725-4016)