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Methane oxidative conversion and hydroformylation to propylene

Periodic Reporting for period 1 - C123 (Methane oxidative conversion and hydroformylation to propylene)

Reporting period: 2019-01-01 to 2020-08-31

C123 project’s main goal is validation in a relevant environment (TRL5) of an efficient and selective transformation of currently largely available, unexploited, cheap methane resources (such as stranded gas (CH4) and biogas (CH4+CO2)) to the C3 products propanal, propanol and propylene. Specifically, C123 is developing new catalytic materials in novel process configurations and related operating procedures via a two-step conversion of these methane resources to valuable C3 products. The first step is called the Oxidative Conversion of Methane (OCoM), a suite of reactions that will lead to a mixture of ethylene, carbon monoxide, and hydrogen optimized for the second step, a common reaction known as hydroformylation (HF) into propanal and/or propanol. Ultimately, propanol can be dehydrated into propylene, either in an integrated manner or as a stand-alone step. Propylene is the basic building block of polypropylene, 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 is adopting an integrated approach, considering and optimising the process from a global perspective, through minimisation of recycling and separation steps, utilization of variable feedstocks, and increasing resource and carbon efficiency. The process will be 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 (>200 kt/y) - the add-on route.
C123 has three overall objectives that, together, will achieve the project's main goal. Objective 1 is the development of innovative heterogeneous catalysts for both process steps. The research also includes shaping and upscaling of these catalysts. Catalyst development is interacting closely with reactor development, so that product compositions are 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 requires an integrated reaction, reactor and process design that will adapt and control 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. This work will validate both process routes individually and assess key societal, environmental and competitive aspects of the technology. Detailed Life Cycle and Techno-economic Analyses will certify the positive impact of the C123 technology on the environment and future competitiveness of the European chemical industry.
"The work performed and the main results will be covered for each of the five technical Work Packages.
For WP2, benchmark Oxidative Coupling of Methane (OCM) catalysts in powder form have been tested under OCoM conditions, specifically through the addition of CO2 and testing at higher pressures. The catalysts show different stabilities and selectivities, with the catalyst NaMnW/SiO2 particularly performing well under OCoM conditions. This catalyst also shows full O2 conversion, which is important for the process design. Shaped catalysts from these powders have been made using either SiC or Al2O3, different orders of deposition and different impregnation methods. The kinetic model for the OCoM process uses the individual gas phase and surface reaction steps, and it includes elementary reaction steps by simulating the various equilibria in the OCoM process in sub-units of the reactor. Four different OCoM processes were proposed and tested via stoichiometric analysis in Aspen Plus. Two of these proposals are particularly relevant for further elaboration.
For WP3, high throughput and traditional catalyst screening regimes have identified the preferred catalyst and ligand systems for the homogeneous hydroformylation of ethylene. Regardless of the amount of H2 that is present in the reactant gas, the only observed product is propanal. Since the production of propylene in the project scheme comes from the dehydration of propanol, the high selectivity to propanal may therefore require an extra hydrogenation step which may affect the C123 techno-economics. No measurable decrease in catalyst activity or selectivity was observed in the presence of CO2, which is an important positive development for the process concepts.
For WP4, the primary efforts have been on the development of the process and microkinetic models for the two steps of the C123 technology. For the process models, a toolbox of principle process topologies has led to the development of two process flow diagrams, a ""lean"" version with a minimum of separation steps and suitable for the modular route, and a large scale version with extensive recovery and recycle and a high carbon efficiency for the add-on route. Preliminary mass balance calculations show that high purities of propanol (modular route) and propylene (add-on route) can be expected. Development of the microkinetic engine for simulations and parameter estimations has thus far included model gas phase reactions, catalytic reactions on the catalyst surface and gas/liquid equilibria.
For WP5, five different baseline industrial different scenarios and associated KPIs have been developed for the techno-economic and sustainability assessments. For the former, the process concepts from WP4 have been studied to identify impacts of key technical parameters. One key finding is the need to limit the build-up of non-condensable gases in the recycling loop. Preliminary economic analyses show favorable opportunities for production of propanal or propanol via the modular route. For the latter, greenhouse gas emissions and the impact on human health have been shown thus far to be the lowest for the use of biogas as methane source.
For WP6, the project website and a LinkedIn page have been created. The project has produced and distributed two newsletters via these channels. The project organized its Winter School I2CM in February, 2020. Intellectual property rights and freedom-to-operate are continuously monitored in the project, and opportunities for the establishment of C123-based IPR have been identified."
Known OCM catalysts that have been tested for the C123 OCoM process are showing promising potential for further elaboration. NaMnW/SiO2 particularly responds well to the presence of CO2 and higher pressures while still providing full O2 conversion. For HF catalyst development, no effect of CO2 is observed on catalyst activity or product selectivity. Process development work has led to a new method for the separation of light components from propanal.
The project still expects to reduce the dependence on current fossil fuel resources, enhance European competitiveness, improve energy efficiency and reduce CO2 emissions. To that end, it is highly relevant that very high product selectivities are expected and that there are economic opportunities for the conversion of biogas to C3 products in small modular units. Eventual deployment of C123 technology could provide more economic opportunities and jobs for rural areas.
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