Periodic Reporting for period 3 - C123 (Methane oxidative conversion and hydroformylation to propylene)
Okres sprawozdawczy: 2022-01-01 do 2023-06-30
C123 project’s main goal is validation in a relevant environment (TRL5) of an efficient and selective transformation of largely available, unexploited and cheap methane resources (e.g. stranded gas (CH4) and biogas (CH4+CO2)) to valuable C3 products propanal, propanol and propene. Specifically, C123 developed new catalytic materials in novel process configurations and related operating procedures via a two-step conversion of these CH4 resources to the C3 products. The first step, the Oxidative Conversion of Methane (OCoM), is a suite of reactions that will lead to a mixture of ethene, carbon monoxide, and hydrogen optimized for the second step, a common reaction known as hydroformylation (HF) into propanal and/or propanol. Propanol can then be dehydrated into propene. Propene is the basic building block of polypropene, a common plastic with a wide range of applications, and it is the fourth largest emitter of greenhouse gas emissions among the major chemical compounds. The C123 project aims to reduce these emissions.
C123 adopted an integrated approach, considering and optimising the process from a global perspective, through minimisation of recycling and separation steps, utilization of variable feedstocks, and increased resource and carbon efficiency. The process was evaluated and validated for the implementation both as decentralised localised units (~10 kt/y) – the modular route – and as an alternative implementation in existing large facilities (>140 kt/y) - the add-on route.
C123 has three overall objectives that will achieve the project's main goal. Objective 1 is the development, shaping and upscaling of innovative heterogeneous catalysts for both process steps. Catalyst development interacted closely with reactor development, so that product compositions were aligned with the best possible reactor configuration. Objective 2 is the development of novel catalytic routes and reactor designs that allow a comprehensive evaluation of the process performance and minimisation of by-products. This required an integrated reaction, reactor and process design that adapted and controlled the multiple reaction pathways that have different energy requirements, into an energy- and resource-efficient process. Objective 3 is the overall integration and validation of an economically viable, environmentally friendly and socially acceptable process in a relevant environment. Both process routes were validated individually and detailed Life Cycle and Techno-economic Analyses were performed to determine the impact of the C123 technology on the environment and future competitiveness of the European chemical industry.
C123 adopted an integrated approach, considering and optimising the process from a global perspective, through minimisation of recycling and separation steps, utilization of variable feedstocks, and increased resource and carbon efficiency. The process was evaluated and validated for the implementation both as decentralised localised units (~10 kt/y) – the modular route – and as an alternative implementation in existing large facilities (>140 kt/y) - the add-on route.
C123 has three overall objectives that will achieve the project's main goal. Objective 1 is the development, shaping and upscaling of innovative heterogeneous catalysts for both process steps. Catalyst development interacted closely with reactor development, so that product compositions were aligned with the best possible reactor configuration. Objective 2 is the development of novel catalytic routes and reactor designs that allow a comprehensive evaluation of the process performance and minimisation of by-products. This required an integrated reaction, reactor and process design that adapted and controlled the multiple reaction pathways that have different energy requirements, into an energy- and resource-efficient process. Objective 3 is the overall integration and validation of an economically viable, environmentally friendly and socially acceptable process in a relevant environment. Both process routes were validated individually and detailed Life Cycle and Techno-economic Analyses were performed to determine the impact of the C123 technology on the environment and future competitiveness of the European chemical industry.
The work performed and the main results from the project will be covered for each of the five technical Work Packages.
For WP2, first and second generation catalysts for OCoM have been scaled up and tested as both powders and single pellets to determine the optimal conditions for the optimal conversion to an equimolar concentration of ethene and CO. The optimal conditions consider that any ethane produced in the reaction will be converted to ethene in a downstream post-bed cracker. The chosen catalyst system was tested in a TRL 5 reactor. Modelling based on the intrinsic kinetic studies in the project showed that natural gas compositions with a naturally high concentration of C2 components provide the best feedstocks for realisation of a C123 process. Unfortunately, this concept is not useful for conversion of biogas since the CO2 in biogas cannot be converted in the process. Further increases in carbon conversion rates and higher reaction pressures are needed for commercialisation of the process.
For WP3, porous materials have been synthesized, scaled-up, shaped and tested as heterogeneous catalysts in gas phase HF. Of materials tested at TRL4, the one based on the Metal-organic Framework NU-1000 and post-modified with an appropriate phosphine and a homogeneous rhodium HF catalyst provided ethene conversion and propanal selectivity far beyond those previously observed for a heterogeneous, gas phase HF reaction. This catalyst was tested at TRL 5, but it did not work as well due to leaching and deactivation. A hindrance to commercialisation, beyond the technical challenges, is the high price of the material. More economic catalysts that demonstrate better stability will be needed for commercial viability. A kinetic model based on the gas phase testing data suggested that the same rate determining steps that were observed for the homogeneous catalyst also are relevant for the gas phase reaction.
For WP4, process models for both the add-on route and modular route were designed and validated. For the OCoM reaction, an innovative radial reactor design involving the addition of oxygen over multiple steps controls the large heat of reaction and provides the optimal C2:CO molar ratio. Because the add-on route was designed for integration into a larger petrochemical facility, it involves cryogenic distillations for recovery of hydrocarbon feedstocks from the recycle stream. Because of costs, a standard homogeneous HF reaction step was used. For the modular route, the process units must fit into containers, limiting size. Thus, cryogenic separations were avoided. The heterogeneous HF reaction was part of the modular process. Except for the OCoM and heterogenous HF reactions, all process steps were modifications of established technologies. Both processes, however, still have many steps and must operate at different pressure levels. The need for hydrogen not supplied from the reaction processes is also a challenge.
In WP5, TEAs and LCAs of the five different exploitation Scenarios were completed. Both the TEA and LCA confirm that the conversion of associated gas to propanol via the modular process (Scenario B2) was the most promising Scenario. Since associated gas is currently flared and has no significant value, conversion of this wasted carbon resource to a useful chemical is both economically beneficial and improves significantly the climate change impact. However, a reduced HF catalyst cost will improve the overall economics.
The project has thus far produced 13 scientific publications, been featured 40 times at conferences and workshops and provided 5 patents. A project video was also produced. For Scenario B2, an exploitation Roadmap for development to TRL 9 was created and a business survey illustrated the overall commercial interest in the concept, given the required process and economic improvements.
For WP2, first and second generation catalysts for OCoM have been scaled up and tested as both powders and single pellets to determine the optimal conditions for the optimal conversion to an equimolar concentration of ethene and CO. The optimal conditions consider that any ethane produced in the reaction will be converted to ethene in a downstream post-bed cracker. The chosen catalyst system was tested in a TRL 5 reactor. Modelling based on the intrinsic kinetic studies in the project showed that natural gas compositions with a naturally high concentration of C2 components provide the best feedstocks for realisation of a C123 process. Unfortunately, this concept is not useful for conversion of biogas since the CO2 in biogas cannot be converted in the process. Further increases in carbon conversion rates and higher reaction pressures are needed for commercialisation of the process.
For WP3, porous materials have been synthesized, scaled-up, shaped and tested as heterogeneous catalysts in gas phase HF. Of materials tested at TRL4, the one based on the Metal-organic Framework NU-1000 and post-modified with an appropriate phosphine and a homogeneous rhodium HF catalyst provided ethene conversion and propanal selectivity far beyond those previously observed for a heterogeneous, gas phase HF reaction. This catalyst was tested at TRL 5, but it did not work as well due to leaching and deactivation. A hindrance to commercialisation, beyond the technical challenges, is the high price of the material. More economic catalysts that demonstrate better stability will be needed for commercial viability. A kinetic model based on the gas phase testing data suggested that the same rate determining steps that were observed for the homogeneous catalyst also are relevant for the gas phase reaction.
For WP4, process models for both the add-on route and modular route were designed and validated. For the OCoM reaction, an innovative radial reactor design involving the addition of oxygen over multiple steps controls the large heat of reaction and provides the optimal C2:CO molar ratio. Because the add-on route was designed for integration into a larger petrochemical facility, it involves cryogenic distillations for recovery of hydrocarbon feedstocks from the recycle stream. Because of costs, a standard homogeneous HF reaction step was used. For the modular route, the process units must fit into containers, limiting size. Thus, cryogenic separations were avoided. The heterogeneous HF reaction was part of the modular process. Except for the OCoM and heterogenous HF reactions, all process steps were modifications of established technologies. Both processes, however, still have many steps and must operate at different pressure levels. The need for hydrogen not supplied from the reaction processes is also a challenge.
In WP5, TEAs and LCAs of the five different exploitation Scenarios were completed. Both the TEA and LCA confirm that the conversion of associated gas to propanol via the modular process (Scenario B2) was the most promising Scenario. Since associated gas is currently flared and has no significant value, conversion of this wasted carbon resource to a useful chemical is both economically beneficial and improves significantly the climate change impact. However, a reduced HF catalyst cost will improve the overall economics.
The project has thus far produced 13 scientific publications, been featured 40 times at conferences and workshops and provided 5 patents. A project video was also produced. For Scenario B2, an exploitation Roadmap for development to TRL 9 was created and a business survey illustrated the overall commercial interest in the concept, given the required process and economic improvements.
The C123 project has advanced the state-of-the-art within OCoM, showing how the reaction can be adapted to provide a suitable feedstock for HF. For this step, the project has developed an innovative reactor that efficiently controls the heat of reaction. The heterogeneous HF gas phase catalysts developed in the project showed a substantial improvement over the state-of-the-art. Technical challenges still remain prior to commercialisation, including better pressure management between the OCoM and HF steps and less expensive catalysts.
The conversion of currently flared associated gas to propanol was shown to have positive economic and environmental profiles and relevance for commercialisation. However, the political repercussions of the current Russia-Ukrainian conflict and the movement away from fossil to renewable energy and carbon sources as part of the European Green Deal sets additional requirements for further development.
The conversion of currently flared associated gas to propanol was shown to have positive economic and environmental profiles and relevance for commercialisation. However, the political repercussions of the current Russia-Ukrainian conflict and the movement away from fossil to renewable energy and carbon sources as part of the European Green Deal sets additional requirements for further development.