Periodic Reporting for period 3 - DECADE (DistributEd Chemicals And fuels production from CO2 in photoelectrocatalytic DEvices)
Reporting period: 2023-05-01 to 2025-01-31
Integrated devices for the distributed production of chemicals and fuels from CO2, H2O and solar energy are a key element for the transition to a low-carbon and more sustainable model of economic development. Efficient and integrated photoelectrocatalytic (PEC) devices are able to use directly solar energy to produce chemicals and energy vectors from small molecules such as CO2 and H2O.
Thus, double benefit is realized: 1) emitted CO2 becomes a raw C-source rather than a waste, thus responding to the concept of circularity, and 2) the reaction of CO2 conversion becomes an efficient way to introduce renewable energy in the process. There are thus many beneficial effects:
1) reduction of CO2 emissions with a functional closing of the carbon-cycle,
2) lowering of the carbon footprint (reuse of CO2 and substituting with renewable energy the fossil energy sources to produce the final products)
3) increasing process productivity and economics.
The overall objective of the DECADE project is to develop a novel photoelectrocatalytic (PEC) device that would use waste CO2 and bio-alcohols as feeding inputs to synthetize value-added products. The novel element of the designed PEC device would be the enhanced energy efficiency, as the device in designed to exploit both sides of the electro-catalytic cells to produce the same chemicals and integrates a PV cell to drive the reaction by sunlight. The target products, the production of which would be optimized, are ethyl acetate (EA) and ethyl formate (EF). These products are used as green solvents/chemicals or fuel additives (octane booster). As an alternative, the production of methyl formate (MF) from methanol would be investigated to lower the carbon footprint in methanol plants producing added-value chemicals.
The DECADE project concept is summarized in Figure 1.
Figure 1 DECADE project concept
Thus, double benefit is realized: 1) emitted CO2 becomes a raw C-source rather than a waste, thus responding to the concept of circularity, and 2) the reaction of CO2 conversion becomes an efficient way to introduce renewable energy in the process. There are thus many beneficial effects:
1) reduction of CO2 emissions with a functional closing of the carbon-cycle,
2) lowering of the carbon footprint (reuse of CO2 and substituting with renewable energy the fossil energy sources to produce the final products)
3) increasing process productivity and economics.
The overall objective of the DECADE project is to develop a novel photoelectrocatalytic (PEC) device that would use waste CO2 and bio-alcohols as feeding inputs to synthetize value-added products. The novel element of the designed PEC device would be the enhanced energy efficiency, as the device in designed to exploit both sides of the electro-catalytic cells to produce the same chemicals and integrates a PV cell to drive the reaction by sunlight. The target products, the production of which would be optimized, are ethyl acetate (EA) and ethyl formate (EF). These products are used as green solvents/chemicals or fuel additives (octane booster). As an alternative, the production of methyl formate (MF) from methanol would be investigated to lower the carbon footprint in methanol plants producing added-value chemicals.
The DECADE project concept is summarized in Figure 1.
Figure 1 DECADE project concept
The project is completed, and it was affected significantly by pandemic, which determined the need for a project extension compared to the initial planning.
The project main results was the realization of a prototype of the DECADE technology, which was tested and validated also in field, at the refinery site of one of the partners.
During the third and final RP3, the active WPs were all except WP1 (ended) and WP2-WP3 (minor activities to support the prototype development).
WP4 (Assessment and exploitation) realized in this RP3 the techno-economic, LCA and eco-design assessments, the market perspective and social impact evaluation and the exploitation strategy. The results of these studies indicate the need for a further improvement of the technologies. Alternative solutions were considered to solve the issues encountered in the development of the project.
WP5 (Scale up & Prototype) has designed, scale-up, engineered and manufactured the prototype and its components.
WP 6 (Validation) has validated the prototype using selected anode and cathode from WP1 and simulated and real sunlight. The system was also validated with real feedstocks at the refinery site. The integration of this PEC device within methanol production plant was analyzed.
WP7 (Benchmarking) has defined literature benchmarking results to compare the prototype or lab-scale apparatus results.
Finally, all activities related to WP8 (Project coordination and management) and WP9 (Ethics Requirements) were realized. Remarkable the about 30 scientific publications made on the results of the project.
The project main results was the realization of a prototype of the DECADE technology, which was tested and validated also in field, at the refinery site of one of the partners.
During the third and final RP3, the active WPs were all except WP1 (ended) and WP2-WP3 (minor activities to support the prototype development).
WP4 (Assessment and exploitation) realized in this RP3 the techno-economic, LCA and eco-design assessments, the market perspective and social impact evaluation and the exploitation strategy. The results of these studies indicate the need for a further improvement of the technologies. Alternative solutions were considered to solve the issues encountered in the development of the project.
WP5 (Scale up & Prototype) has designed, scale-up, engineered and manufactured the prototype and its components.
WP 6 (Validation) has validated the prototype using selected anode and cathode from WP1 and simulated and real sunlight. The system was also validated with real feedstocks at the refinery site. The integration of this PEC device within methanol production plant was analyzed.
WP7 (Benchmarking) has defined literature benchmarking results to compare the prototype or lab-scale apparatus results.
Finally, all activities related to WP8 (Project coordination and management) and WP9 (Ethics Requirements) were realized. Remarkable the about 30 scientific publications made on the results of the project.
DECADE project goes beyond the state-of-the-art, proposing a novel solution to overcome limitations in current, state-of-the-art PEC approaches. In addition to solve PEC limitations, the substitution of water as preferred electron and proton reservoir is also adding commercial value to the process. Instead of oxygen, the anodic reaction participates to the final product, increasing the commercial interest, but also the energy efficiency. Currently, most PEC strategies only contemplate water as sacrificial electron and proton donor, with no clear or convenient alternatives. Alternatives, such as chlorine production, would be very difficult to implement due to safety issues, particularly for distributed solutions.
There are several elements of innovation in the proposed DECADE approach, based on the identification of the critical issues in the current PEC approach. Further relevant advantages are:
- Integration of solar energy within (bio)refineries, combined with the reuse of CO2 emissions to converge on the production of high added-value chemicals (circular economy). We will test in our prototype the use of conventional refinery CO2 streams to lower carbon footprint and improve circular economy, evaluating also the use for biorefinery streams. Thus, there is a win-win solution of integrating renewable energy in (bio)refinery while lowering the carbon footprint and increasing the production of higher value products.
- Development of circular economy and low-carbon production concepts for large-scale chemical processes, with the analysis of the integration of the novel PEC solution into methanol plants to convert waste CO2 to chemicals and introduce solar energy within the methanol value chain.
- A step to the distributed production of chemicals, particularly green solvents and fuel additives for gasoline, which can be produced in a single integrated device with minimization of downstream separation costs.
- The flexible use of the products to either green chemicals or high-octane number fuel additives, with analysis of different cases of applications and with the involvement of companies addressing different possible uses of the technology.
DECADE project will reduce the environmental impact on society of energy/chemicals production (reducing its CO2 footprint and use of resources) by i) enabling a change from fossil based to advanced use of bio-based products (including their associated CO2 emissions) in combination with direct solar energy, ii) developing new routes for utilization waste CO2 produced in chemical processes, iii) offering new opportunities to implement concept of circular economy and iv) new possibilities for distributed production of green solvents at local/regional level, with thus also positive impact on territory and local economies.
There are several elements of innovation in the proposed DECADE approach, based on the identification of the critical issues in the current PEC approach. Further relevant advantages are:
- Integration of solar energy within (bio)refineries, combined with the reuse of CO2 emissions to converge on the production of high added-value chemicals (circular economy). We will test in our prototype the use of conventional refinery CO2 streams to lower carbon footprint and improve circular economy, evaluating also the use for biorefinery streams. Thus, there is a win-win solution of integrating renewable energy in (bio)refinery while lowering the carbon footprint and increasing the production of higher value products.
- Development of circular economy and low-carbon production concepts for large-scale chemical processes, with the analysis of the integration of the novel PEC solution into methanol plants to convert waste CO2 to chemicals and introduce solar energy within the methanol value chain.
- A step to the distributed production of chemicals, particularly green solvents and fuel additives for gasoline, which can be produced in a single integrated device with minimization of downstream separation costs.
- The flexible use of the products to either green chemicals or high-octane number fuel additives, with analysis of different cases of applications and with the involvement of companies addressing different possible uses of the technology.
DECADE project will reduce the environmental impact on society of energy/chemicals production (reducing its CO2 footprint and use of resources) by i) enabling a change from fossil based to advanced use of bio-based products (including their associated CO2 emissions) in combination with direct solar energy, ii) developing new routes for utilization waste CO2 produced in chemical processes, iii) offering new opportunities to implement concept of circular economy and iv) new possibilities for distributed production of green solvents at local/regional level, with thus also positive impact on territory and local economies.