Periodic Reporting for period 2 - CO2SMOS (Advanced chemicals production from biogenic CO2 emissions for circular bio-based industries)
Periodo di rendicontazione: 2022-11-01 al 2024-04-30
The use of biogenic CO2 emissions as feedstock allows to reduce its emissions by turning this pollutant into a valuable product. In this context, CO2SMOS aims at converting biogenic CO2 into added-value chemicals for their application into chemicals and polymers, with the challenge of developing biogenic CO2-based biorefinery processes with zero or negative greenhouse gas emissions.
The project tackles the primary conversion of CO2 into two platform bulk chemicals, syngas and acetate, and their latter conversion into seven chemicals (polyhydroxyalkanoates (mcl-PHA and PHB), 2,3-butanediol (2,3-BDO), long chain dicarboxylic acids (LcDCAs), BTEX, cyclic carbonates and hydroxycarboxylic acids (HCAs)) that can be integrated into the final biomaterials.
These conversions will be achieved through the following technologies:
1) Gas fermentation of CO2/H2 and CO2 derived syngas into acetate (T#1.1) and 2,3-BDO (T#1.2)
2) Electrocatalytic conversion of CO2/H2O into green syngas (T#2.1) and HCAs (T#2.2)
3) Chemical conversion of CO2 by organic catalysts into cyclic carbonates from renewable feedstocks (T#3)
4) Aerobic liquid fermentation for synthesis of mcl-PHA, PHB, LcDCAs and 2,3-BDO (T#4)
5) Catalytic membrane reactor for syngas conversion to BTEX and PX (T#5)
The technologies will be tested and validated from lab (TRL 3-4) to pilot scale (TRL 5), including the final applications in the formulation of high-performance biomaterials & renewable chemicals
The project tackles the primary conversion of CO2 into two platform bulk chemicals, syngas and acetate, and their latter conversion into seven chemicals (polyhydroxyalkanoates (mcl-PHA and PHB), 2,3-butanediol (2,3-BDO), long chain dicarboxylic acids (LcDCAs), BTEX, cyclic carbonates and hydroxycarboxylic acids (HCAs)) that can be integrated into the final biomaterials.
These conversions will be achieved through the following technologies:
1) Gas fermentation of CO2/H2 and CO2 derived syngas into acetate (T#1.1) and 2,3-BDO (T#1.2)
2) Electrocatalytic conversion of CO2/H2O into green syngas (T#2.1) and HCAs (T#2.2)
3) Chemical conversion of CO2 by organic catalysts into cyclic carbonates from renewable feedstocks (T#3)
4) Aerobic liquid fermentation for synthesis of mcl-PHA, PHB, LcDCAs and 2,3-BDO (T#4)
5) Catalytic membrane reactor for syngas conversion to BTEX and PX (T#5)
The technologies will be tested and validated from lab (TRL 3-4) to pilot scale (TRL 5), including the final applications in the formulation of high-performance biomaterials & renewable chemicals
WP1
Sources of biogenic CO2 were mapped and the scenarios required for CO2 utilization were set according to the stakeholders’ needs, indicators for process assessment and analysis of process value chains
WP2-WP3-WP4
T#1.1: Work covered from the modification of strains, to fermentative production of bio-acetate, and the downstream processing (DSP) of the broths, which turned them into cell-free acetate-containing media. Process was successfully scaled-up from lab-scale to 150 l bioreactor
T#1.2: Work lines were similar to T#1.1 but applied to 2,3-BDO. Lab-scale titer was below the target and at 150 l scale, the microorganism was able to grow but no diol was produced. An efficient DSP method for its purification from the broth was developed.
T#2.1: Work started separately on the HT-PEM, water extracting membrane and RWGS (reverse water gas shift) catalyst. Their integration was not possible because suitable high-temperature membranes for the PEM were not available, hence HT-PEM development is on-going with the available membranes. The extracting membrane and catalysts performed suitably but as their integration was ineffective, the next integration will proceed with ceramic membranes
T#2.2: Not-foreseen materials were probed as catalysts that did convert ethylene glycol to glycolic acid
T#3: Several catalyst formulations were tailored to carbonate all the targeted feedstocks with CO2. This search derived in conversions and selectivities above 95%. Scaling up of the process is under evaluation
T#4: Work lines were similar to T#1.1 but applied to different strains and liquid fermentation. Lab-scale results were excellent for PHA and good for PHB and 2,3-BDO, whereas LcDCAs need for further improvement. PHB production was scaled-up in a 150 l equipment and mcl-PHA and 2,3-BDO upscaling is on-going
T#5: The optimization of the catalysts led to outstanding performances. The research on the solid electrolyte O2 separator (SEOS) concluded with the selection of the materials for the next integration with the catalyst. Set-up for the scale-up validation is currently being built
WP5
Efforts focused on validating at lab-scale the (i) use of PHA, PHB and LcDCAs into biodegradable plastics, (ii) extrudability of biomaterials containing PHA and LcDCAs, (iii) carbonates as plasticizers, and (iv) use of 2,3-BDO in polyesters with high glass transition temperature. Typically, the activity started with benchmark materials but CO2-derived chemicals were also validated in some cases. The polymerization of CO2-derived carbonates to polycarbonates was unsuccessful
WP6-WP7-WP8
The first value chain out of the two expected to evaluate CO2SMOS replicability was defined upon the production of PHB and its analysis is about to be completed (HAZID analysis finished). KERs list was polished and adapted to CO2SMOS scenario by M36. The developing of business models has begun based on this list, and together with the replicability studies will be the foundation for the incoming TEA
The LCA and LCC analysis are on-going but the available data of CO2 to PHB and 2,3-BDO value chains point to negative carbon footprints
Social and dissemination aspects: recommendations are being developed after analyzing the relevant legislation and comparing it to CO2SMOS’ implications. A study was completed to determine users’ requirements and understand public reasoning and cognition regarding the CCU. CO2SMOS is being disseminated in different forums through scientific (4) and conference (43) papers, press releases (2) and organization of technical workshops (3), among others.
WP9
Financial, ethical and administrative coordination of the Project is on progress
Sources of biogenic CO2 were mapped and the scenarios required for CO2 utilization were set according to the stakeholders’ needs, indicators for process assessment and analysis of process value chains
WP2-WP3-WP4
T#1.1: Work covered from the modification of strains, to fermentative production of bio-acetate, and the downstream processing (DSP) of the broths, which turned them into cell-free acetate-containing media. Process was successfully scaled-up from lab-scale to 150 l bioreactor
T#1.2: Work lines were similar to T#1.1 but applied to 2,3-BDO. Lab-scale titer was below the target and at 150 l scale, the microorganism was able to grow but no diol was produced. An efficient DSP method for its purification from the broth was developed.
T#2.1: Work started separately on the HT-PEM, water extracting membrane and RWGS (reverse water gas shift) catalyst. Their integration was not possible because suitable high-temperature membranes for the PEM were not available, hence HT-PEM development is on-going with the available membranes. The extracting membrane and catalysts performed suitably but as their integration was ineffective, the next integration will proceed with ceramic membranes
T#2.2: Not-foreseen materials were probed as catalysts that did convert ethylene glycol to glycolic acid
T#3: Several catalyst formulations were tailored to carbonate all the targeted feedstocks with CO2. This search derived in conversions and selectivities above 95%. Scaling up of the process is under evaluation
T#4: Work lines were similar to T#1.1 but applied to different strains and liquid fermentation. Lab-scale results were excellent for PHA and good for PHB and 2,3-BDO, whereas LcDCAs need for further improvement. PHB production was scaled-up in a 150 l equipment and mcl-PHA and 2,3-BDO upscaling is on-going
T#5: The optimization of the catalysts led to outstanding performances. The research on the solid electrolyte O2 separator (SEOS) concluded with the selection of the materials for the next integration with the catalyst. Set-up for the scale-up validation is currently being built
WP5
Efforts focused on validating at lab-scale the (i) use of PHA, PHB and LcDCAs into biodegradable plastics, (ii) extrudability of biomaterials containing PHA and LcDCAs, (iii) carbonates as plasticizers, and (iv) use of 2,3-BDO in polyesters with high glass transition temperature. Typically, the activity started with benchmark materials but CO2-derived chemicals were also validated in some cases. The polymerization of CO2-derived carbonates to polycarbonates was unsuccessful
WP6-WP7-WP8
The first value chain out of the two expected to evaluate CO2SMOS replicability was defined upon the production of PHB and its analysis is about to be completed (HAZID analysis finished). KERs list was polished and adapted to CO2SMOS scenario by M36. The developing of business models has begun based on this list, and together with the replicability studies will be the foundation for the incoming TEA
The LCA and LCC analysis are on-going but the available data of CO2 to PHB and 2,3-BDO value chains point to negative carbon footprints
Social and dissemination aspects: recommendations are being developed after analyzing the relevant legislation and comparing it to CO2SMOS’ implications. A study was completed to determine users’ requirements and understand public reasoning and cognition regarding the CCU. CO2SMOS is being disseminated in different forums through scientific (4) and conference (43) papers, press releases (2) and organization of technical workshops (3), among others.
WP9
Financial, ethical and administrative coordination of the Project is on progress
T#1: new modifications in strains were checked and/or operation protocols were tailored to increase the process performance. The target acetate production titer was achieved
T#2.1: a water extracting membrane with a high-water permeability was developed as well as a RWGS catalyst without noble metals that met the foreseen selectivity to CO and showed the highest yield for CO production below 250 ºC
The programmed catalyst-membrane integration pursues an increased shift of the equilibrium, whereas the on-going work on HT-PEM at mild temperatures (110-140 ºC) with non-fluorinated membranes will provide new insights in the field
T#2.2: Pd-Ag combinations supported on Ni foams were probed to be efficient catalysts for the electro-oxidation of ethylene glycol to glycolic acid
The final integration of the PCEC will rely on the results of the on-going optimization of the anodic and cathodic reactions
T#3: Catalyst formulation was modified according to the requirements of each feedstock
T#4: The genetical modification and/or protocol optimization for the use of acetate as carbon source allowed to fulfil the expected PHA production titer and PHB productivity. 2,3-BDO production titer was close to the objective and may be achieved in the on-going pilot scale fermentations
T#5: Aromatization catalysts able to simultaneously fulfil 3 out of the 4 foreseen KPIs (PX in total xylenes, CO conversion, PX in total aromatics) were developed
The next integration of the catalysts with the SEOS aims at shifting the equilibrium and further improve the overall performance
Besides these milestones, the lab integration of CO2-derived PHA, PHB, carbonates and 2,3-BDO into the final formulation of biodegradable polyesters and polyesters with high glass transition temperature was already validated and is planned to be checked at pilot scale
The true techno-economic and environmental potential of CO2SMOS solutions will be disclosed in the next RP, although the already available LCA results about carbon footprint are encouraging.
T#2.1: a water extracting membrane with a high-water permeability was developed as well as a RWGS catalyst without noble metals that met the foreseen selectivity to CO and showed the highest yield for CO production below 250 ºC
The programmed catalyst-membrane integration pursues an increased shift of the equilibrium, whereas the on-going work on HT-PEM at mild temperatures (110-140 ºC) with non-fluorinated membranes will provide new insights in the field
T#2.2: Pd-Ag combinations supported on Ni foams were probed to be efficient catalysts for the electro-oxidation of ethylene glycol to glycolic acid
The final integration of the PCEC will rely on the results of the on-going optimization of the anodic and cathodic reactions
T#3: Catalyst formulation was modified according to the requirements of each feedstock
T#4: The genetical modification and/or protocol optimization for the use of acetate as carbon source allowed to fulfil the expected PHA production titer and PHB productivity. 2,3-BDO production titer was close to the objective and may be achieved in the on-going pilot scale fermentations
T#5: Aromatization catalysts able to simultaneously fulfil 3 out of the 4 foreseen KPIs (PX in total xylenes, CO conversion, PX in total aromatics) were developed
The next integration of the catalysts with the SEOS aims at shifting the equilibrium and further improve the overall performance
Besides these milestones, the lab integration of CO2-derived PHA, PHB, carbonates and 2,3-BDO into the final formulation of biodegradable polyesters and polyesters with high glass transition temperature was already validated and is planned to be checked at pilot scale
The true techno-economic and environmental potential of CO2SMOS solutions will be disclosed in the next RP, although the already available LCA results about carbon footprint are encouraging.