Periodic Reporting for period 2 - CATCO2NVERS (Creating added-value chemicals from bio-industrial CO2 emissions using integrated catalytic technologies)
Reporting period: 2022-11-01 to 2024-04-30
The bio-based industries represent a great opportunity to implement CO2 reduction technologies to produce addedvalue chemicals and mitigate its emissions. Negative emissions technologies, as carbon capture, utilization and storage ones are currently a priority to explore, especially in non-exploited industrial sectors such as the bio-based industry as they significantly contribute to CO2 emissions. CATCO2NVERS will contribute to reduce GHG emissions from the bio-based industries developing 5 innovative and integrated technologies based on 3 catalytic methods (electrochemical, enzymatic and thermochemical). It will transform waste-CO2 (up to 90%) and residual biomass from 2 bio-based industries into 5 added-value chemicals (glyoxylic acid, lactic acid, furan dicarboxylic methyl ester, cyclic carbonated fatty acid methyl esters with production yields between 70-90%. Methanol which will not have an energetic use but will be used in CATCO2NVERS own technologies. These target chemicals will be used as building blocks and monomers to obtain biopolymers of 100% bio-origin. Industrial partners will validate the application of the obtained chemical building blocks on the most relevant markets. In addition, the waste-CO2 stream will be conditioned by removing potential inhibitors for the catalysts. CATCO2NVERS will explore an energy and resource efficient scenario following an industrial symbiosis model to ensure a biorefinery process along the CO2 valorization chain with zero or negative GHG emissions.
The work carried out in CATCO2NVERS during this second period (M19-M36), is in line with the description stated in the Annex 1 of the Grant Agreement and most of the objectives have been accomplished in due time with no deviations. Overall, the project is progressing adequately, and promising results have been obtained as result of the research work and testing performed so far.
In this period the research work has been focused on finishing the development of catalysts and establishing the processing conditions in each of the technologies posed for the conversion of CO2 towards the five foreseen chemicals at labscale.
The selected optimal conditions for each of the conversion processes have also been tested on some of the technologies with real gas mixtures according to the gas composition established previously in the first period.
In TEC1, during this period the focus was mainly on CO2 reduction reaction step to oxalate.
In TEC2, during this period the focus was mainly on increasing the efficiency of the biocatalysts for the conversion of acetaldehyde and CO2 to pyruvate for the screening of heterogeneous catalysts for the hydrogenation of NAD+ to NADH and its regeneration during lactate dehydrogenase-catalyzed reduction of pyruvate to lactate. PDC-20 was employed in combination with lactate dehydrogenase and glucose dehydrogenase to achieve the conversion of acetaldehyde and CO2 to lactate. Proof-of-principle was obtained for and integrated conversion of acetaldehyde to lactate and the oxidation of ethanol to acetaldehyde in a one-pot set-up.
In TEC3 the work has been focused on the development of efficient heterogeneous catalysts for the consecutive oxidation and carboxylation without isolating the intermediate, under mild conditions. The best conditions developed in TEC3 have been applied using the simulated gas mixtures from partner PERSEO. Also, some of the developed catalysts have also been tested in other catalytic applications.
In TEC4, during this period the focus was mainly on the development of a one-pot two steps process for the oxidation and carboxylation of vegetal oils to cyclic carbonates. The selected conditions have also been tested with real gas mixtures according to the gas composition established previously in the first period.
In the hydrogenation of CO2 to bio-methanol (TEC5) the influence of the synthesis procedure has been investigated, from the etching process to the impregnation procedure. Further optimization reactions were performed, varying parameters such as the addition of hydrotalcite as sorbent, variations in total inlet flow, composition of inlet stream, reaction temperature with the selected catalysts. In order to increase the overall conversion of CO2 and MeOH production, a recirculation system has been included in the set-up.
For each of the developed technologies independent and ad-hoc solutions have been designed and tested for the purification of each of the five chemicals aimed. After gathering the preliminary information from the partners for the different technologies in task 5.1 the basic engineering was carried out for the selected technologies.
During this period the consortium has also been very participative and active in other not exclusively technical activities such as the development of business plans for each of the CO2 valorization routes, the identification of Key Exploitable Results and exploitation strategies, together with the execution of dissemination activities (participating in conferences, diffusion of brochures, project presentation, posters, preparation of webpage, videos and newsletters, submission of papers, etc..)
In this period the research work has been focused on finishing the development of catalysts and establishing the processing conditions in each of the technologies posed for the conversion of CO2 towards the five foreseen chemicals at labscale.
The selected optimal conditions for each of the conversion processes have also been tested on some of the technologies with real gas mixtures according to the gas composition established previously in the first period.
In TEC1, during this period the focus was mainly on CO2 reduction reaction step to oxalate.
In TEC2, during this period the focus was mainly on increasing the efficiency of the biocatalysts for the conversion of acetaldehyde and CO2 to pyruvate for the screening of heterogeneous catalysts for the hydrogenation of NAD+ to NADH and its regeneration during lactate dehydrogenase-catalyzed reduction of pyruvate to lactate. PDC-20 was employed in combination with lactate dehydrogenase and glucose dehydrogenase to achieve the conversion of acetaldehyde and CO2 to lactate. Proof-of-principle was obtained for and integrated conversion of acetaldehyde to lactate and the oxidation of ethanol to acetaldehyde in a one-pot set-up.
In TEC3 the work has been focused on the development of efficient heterogeneous catalysts for the consecutive oxidation and carboxylation without isolating the intermediate, under mild conditions. The best conditions developed in TEC3 have been applied using the simulated gas mixtures from partner PERSEO. Also, some of the developed catalysts have also been tested in other catalytic applications.
In TEC4, during this period the focus was mainly on the development of a one-pot two steps process for the oxidation and carboxylation of vegetal oils to cyclic carbonates. The selected conditions have also been tested with real gas mixtures according to the gas composition established previously in the first period.
In the hydrogenation of CO2 to bio-methanol (TEC5) the influence of the synthesis procedure has been investigated, from the etching process to the impregnation procedure. Further optimization reactions were performed, varying parameters such as the addition of hydrotalcite as sorbent, variations in total inlet flow, composition of inlet stream, reaction temperature with the selected catalysts. In order to increase the overall conversion of CO2 and MeOH production, a recirculation system has been included in the set-up.
For each of the developed technologies independent and ad-hoc solutions have been designed and tested for the purification of each of the five chemicals aimed. After gathering the preliminary information from the partners for the different technologies in task 5.1 the basic engineering was carried out for the selected technologies.
During this period the consortium has also been very participative and active in other not exclusively technical activities such as the development of business plans for each of the CO2 valorization routes, the identification of Key Exploitable Results and exploitation strategies, together with the execution of dissemination activities (participating in conferences, diffusion of brochures, project presentation, posters, preparation of webpage, videos and newsletters, submission of papers, etc..)
The CATCO2NVERS project proposes five technologies to be applied for the conversion and/or use of emitted CO2:
TEC1: CO2 to glyoxylic acid (electrocatalysis) through oxalic acid intermediate using heterogeneous catalysts, mainly metallic and metal oxide nanoparticles free of toxic materials. Paired electrolysis (oxalic acid reduction and ethylene glycol oxidation to glyoxylic acid).
TEC2: CO2 to lactic acid (biocatalysis). The process is based on an efficient, low energy demanding multi-enzymatic cascade reaction system comprising selected enzymes working in synergy.
TEC3:CO2 to FDME (thermocatalysis) using porous heterogeneous catalysts that contain active sites such as ionic groups, metal catalytic sites (such as Co, Fe or Cu), and basic catalytic sites (such as Cs or K). Preferably, two of these active sites are expected to be in the same porous network. FDME will be produced from furfural and CO2, through an ester-type intermediate, in a one-pot two steps process.
TEC4: CO2 to CCFAMEs (thermocatalysis) using heterogeneous catalysts based on metal complexes of N-rich porous organic polymers such as poly(azomethine-pyridine)s (PAM-Py) networks as new materials for the CO2 oxidative carbonylation of FAMEs in multi-cyclic carbonates.
TEC5: CO2 to bio-methanol (thermocatalysis). The technology is based on the development of a new multimetallic catalyst over aluminum micro fibrous network structure/hydrotalcite adsorbent without noble metals at low pressure to increase the conversion rate of CO2 to MeO
TEC1: CO2 to glyoxylic acid (electrocatalysis) through oxalic acid intermediate using heterogeneous catalysts, mainly metallic and metal oxide nanoparticles free of toxic materials. Paired electrolysis (oxalic acid reduction and ethylene glycol oxidation to glyoxylic acid).
TEC2: CO2 to lactic acid (biocatalysis). The process is based on an efficient, low energy demanding multi-enzymatic cascade reaction system comprising selected enzymes working in synergy.
TEC3:CO2 to FDME (thermocatalysis) using porous heterogeneous catalysts that contain active sites such as ionic groups, metal catalytic sites (such as Co, Fe or Cu), and basic catalytic sites (such as Cs or K). Preferably, two of these active sites are expected to be in the same porous network. FDME will be produced from furfural and CO2, through an ester-type intermediate, in a one-pot two steps process.
TEC4: CO2 to CCFAMEs (thermocatalysis) using heterogeneous catalysts based on metal complexes of N-rich porous organic polymers such as poly(azomethine-pyridine)s (PAM-Py) networks as new materials for the CO2 oxidative carbonylation of FAMEs in multi-cyclic carbonates.
TEC5: CO2 to bio-methanol (thermocatalysis). The technology is based on the development of a new multimetallic catalyst over aluminum micro fibrous network structure/hydrotalcite adsorbent without noble metals at low pressure to increase the conversion rate of CO2 to MeO