Community Research and Development Information Service - CORDIS

FP7

ECO2CO2 Report Summary

Project ID: 309701
Funded under: FP7-NMP
Country: Italy

Final Report Summary - ECO2CO2 (Eco-friendly biorefinery fine chemicals from CO2 photo-catalytic reduction)

Executive Summary:
The Eco2CO2 project aims at exploiting a photo-electro-chemical (PEC) CO2 conversion route for the synthesis of methanol as a key intermediate for the production of fine chemicals (fragrances, flavourings, adhesives, monomers,...) in a lignocellulosic biorefinery. A distinct improvement in the ecological footprint of the envisaged chemical industries will thus be achieved by: i) boosting the potential of lignocellulosic biorefineries by exploiting secondary by-products such as furfurals or lignin; ii) providing a small but non-negligible contribution to the reduction of CO2 release into the atmosphere by exploitation of sunlight as an energy source. The most crucial development in the project will be the development of a PEC reactor capable of converting CO2 into methanol by exploiting water and sun light with a targeted conversion efficiency exceeding 6%, with reference to wavelengths above 400 nm, and an expected durability of 10.000 h. The above specifications must be reached without using expensive noble metals or precious materials which should enable costs of the PEC panels lower than 60 Euro/m2 including the installation. Catalytic reactions of methanol and furfural to produce perfuming agents via partial oxidation or methylation, as well as of lignin or lignin depolymerisation derivatives to produce adhesives or monomers (e.g. p-xylene) will undergo a R&D programme to achieve cost effective production of green fine chemicals, proven by the end of the project via lab bench tests of at least 100 g/h production rates. Based on early calculations, if successful, the Eco2CO2 technologies should be capable of inducing avoided CO2 emissions by the year 2020 as high as 50 Mtons/year worldwide.

Project Context and Objectives:
The Eco2CO2 project aims at exploiting a photo-electro-chemical (PEC) CO2 conversion route to produce methanol as a key intermediate for the production of fine chemicals (fragrances, flavourings, cresol, adhesives,...) integrated with a lignocellulosic biorefinery. A distinct improvement in the ecological footprint of the envisaged chemical industries will thus be achieved by: i) boosting the potential of lignocellulosic biorefineries by exploiting secondary by-products such as furfurals or lignin; ii) providing a non-negligible contribution to the reduction of CO2 release into the atmosphere by exploitation of sunlight as an energy source.
The most challenging part of our proposal is to achieve a photochemical conversion of CO2 to methanol. For this reason Eco2CO2, will concentrate most efforts on this ambitious target. The key objective of the project will be to provide evidence that fine chemical products can be effectively produced in a cost-competitive way comparable to their synthesis from petroleum derivatives. Moreover, the “green label” of the Eco2CO2 fine chemicals will provide them with a competitive advantage. This will not only be demonstrated experimentally, but by economic projections performed by the key industrial partners. First targets for fine chemicals (i.e. methyl 2-furoate; p-xylene; lignin-based adhesives) have been selected in this proposal depending on the key partners' strategic needs. If the production of other fine chemicals prove to be cost effective during the course of the project then this may be considered sufficient for proof of concept of the Eco2CO2 technology.
The project originally proposes a platform approach around the concept of transforming CO2 to methanol via PEC reactor and then using methanol (or eventually byproducts in the reaction) to upgrade by-products from ligno-cellulosic 2G biorefinery according to a three-phases approach. In the second reporting period, this concept has evolved and, in such regard, modifications were requested in two amendments to the grant agreement. Actually, two routes of CO2 reduction were studied in the project: (1) Methanol direct synthesis by developing electrocatalysts for the CO2 reduction to methanol based on Covalent Triazine Frameworks (CTF) functionalized with Cu, Ir, Pt or Pd; and (2) Methanol indirect synthesis by developing electrocatalysis for the CO2 and H2O reduction to CO and H2 (syngas), which can be converted into methanol by traditional processes.

Project Results:
See a detailed description of the work performed and the main results in the attached report.
The main objectives (OB) and milestones of the project were substantially achieved, as specified in following:

OB1) The key objective of the project will be to provide evidence that fine chemical products can be effectively produced in a cost-competitive way comparable to their synthesis from petroleum derivatives. Production rates of 100 g product/h in pilot reactors will need to be attained for the following reactions:

OB1.1) Furfural methylation to methyl 2-furoate:
Partially achieved
-) The objective was to proof the feasibility of this reaction at the scale of 100 g/h in a small scale reactor, however, during the biannual project meeting in June 2014 AVT proposed to reduce this to 100 g/day, to increase the safety and reduce large volumes of chemical wastes, although the developed setup was designed to meet the criteria of the proposal.
-) AVT screened catalyst in batch reactor, using a feed of 10 wt% furfural in MeOH. Since yields of up to 30% were observed, AVT has designed a system with two reactors. The smaller reactor was designed to produce 1-10 g/h, the bigger reactor 10-100 g/h, assuming that the yield and weight hourly space velocity (WHSV) based on the batch experiments could be improved. With a flow rate of 10 ml/min, a feed of 20 wt% furfural and a yield of 90% a productivity of 100 g/h can be achieved.
However, 90% yield were only obtained with 0.5 wt% of furfural in the feed with a maximum of 15 g/day of product, thus only 15 % of the original productivity target.
-) Either higher furfural concentrations or inlet furfural flow rate (to increase the WHSV) caused fast catalyst deactivation. Therefore, target productivity was not achieved because of very fast substrate-related catalyst deactivation.

OB1.2) Adhesives from lignin methylation:
Partially achieved
-) Lignin samples from BioChemTech were pretreated, conditioned and characterized by IREC. Acid washings were done in order to reduce the carbohydrates content of the original lignin. Different method were employed for the recovery of lignin depolymerisation products (i.e. spray drying, water washing, lyophilisation and precipitation), being precipitation the selected one since it provide the highest Klason lignin and functional group (phenolic, aliphatic and methoxyl determined by NMR) contents.
-) Valuable products were extracted with methanol from bare and pre-treated Lignin by CTQC, being it more efficient (75% of soluble mass with respect to 25%) on Lignin pre-treated at 230 oC than on bare Lignin. Main extracted components (i.e. Phenol, Anisole, o-Cresol and Guaiacol determined by F-TIR and GC-MSD) were selected as model in order to perform methylation experiments in both Batch and Continuous reactors.
-) Reaction of lignin with formaldehyde (IREC) was effective for the production of partial substitutes of phenol for the production of resins. A considerable improvement in reactivity was observed on modified lignin’s and it increases in Lignins depolymerised at more severe conditions.
-) From batch tests in liquid phase: the highest guaiacol conversion (43%) was achieved with the a desilicated H-MFI-30 catalyst that produces up to 3.6 g conv/g cat h. This result indicates a feasible scalability of the process to achieve 100 g/h of productivity in a semi-continuous batch system operating with about 28 g of catalyst and a liquid volume of about 3 L, considering a catalyst/reactant ratio of 0.03 wt/wt and a methanol/guaiacol molar ratio of 2/1.
-) From the continuous system tests in vapor phase: activity, selectivity and stability depends on the catalyst and operative conditions. Preliminary test at atmospheric pressure shown a deactivation of the DESIL-H-MFI-30 catalyst after 30 min. However, by optimizing operative conditions (300 oC, 3.5bar) more stable operation and higher conversion were obtained. The most stable operation was achieved with the DESIL-H-MFI-30 catalyst on a 10 g bed, which exhibited a maximum substrate conversion of 8.3% for all the monitored process, which correspond to 1.6 mg conv/g catal·h). This result can be improved by increasing the residence time inside the reactor by implementing recirculation on the system, which is the typical way to achieve high conversions on industrial plant reactors.

OB2) A targeted efficiency exceeding 6% for this conversion process is set, calculated, per unit surface area exposed, as the ratio between the higher heating value of the produced methanol and the overall incoming solar power. Model calculations show that this concept has the potential to exceed 10% conversion efficiencies.
Achieved in 80%
-) Detailed modelling data are pointing at the way to go (D8.2 and D8.3) with the measured performances and show that 10% conversion is quite compatible with thermodynamic calculations but requires the development of appropriate electrocatalytic micro- and nano-structure.
-) The best results with a Co-catalysed Mo-doped BiVO4 photo-anode and a Ag NPs-based cathodic electro-catalyst in the Final ECO2CO2 prototype show up to 4.8% overall sunlight into syngas (STS) conversion efficiency.
This paves the way to full achievement of the ambitious goal of the project by:
-) More engineering efforts on reactor design to improve fluid-dynamics to limit mass-transfer and kinetics limitations phenomena, engineering of the PEC device (reduction of anode-cathode distance), improved integration of PEM with cathodic electrode (3 different versions of prototype device have already evolved during the ECO2CO2 project).

OB3) To allow the application of this technology on a large scale, the above specifications must be reached without using expensive noble metals or materials and must have the potential to be assembled using mass production procedures.
Achieved at 100%
-) Attention have been addressed in both water-splitting anode and CO2 reduction cathode of the PEC cell were noble metal catalysts are not present.
-) The synthesis techniques adopted for the anode based on BiVO4 and Co-catalysts as well as on the cathode made of Ag/C-cloth are amenable for mass production and were actually used to manufacture the final ECO2CO2 prototype.

OB4) The prospected system durability will exceed 10.000 h lifetime. The prototype will be manufactured and tested by the end of the project. The test duration will be at least 1000 h in the last six months of the project
Achieved at 100%
-) The prototype device have operated for about the expected 1000 h with a limited reduction of efficiency (about 5%) was noticed and a maximum of 4.8% STH efficiency with a quite stable CO/H2 ratio of about 3 have been measured.
Potential Impact:
The main objectives (OB) and milestones of the project were substantially achieved, as specified above.

The expected impacts listed in the call work programme were: (i) New industrial routes for using CO2; and (ii) Reduction of overall greenhouse gases emissions deriving from industrial processes in Europe. It is thus expected that the proposal addresses the problem of CO2 in terms of sustainability and process innovation, by contributing at once to the reduction of overall GHG emissions and the development of new industrial routes to high-added value fine chemicals based on CO2. The dilemma is that the market of fine chemicals is small to give a significant reduction of GHG emissions. Moreover, the conversion of CO2 requires energy or the use of reactants whose production may generate more CO2 than the CO2 incorporated in the final product. For example, the production of polycarbonate by reaction of propylene oxide with CO2 incorporates about 0.43 tons CO2 per ton polycarbonate, but about 2 tons of CO2 per ton of propylene oxide are needed to produce this last reactant! The unique idea of Eco2CO2 solves this dilemma by generating fine chemicals from CO2 within a 2nd generation biorefinery.

The Eco2CO2 project concept idea has been heavily influenced by the viewpoint of the industrial partners involved. These partners do all agree that fine chemicals have in general the highest chance of getting to a significant market penetration within the span of potential biorefinery products, also including monomers, commodity chemicals and fuels. This is in the spirit of the topic addressed and generally recognized by the Sustainable Chemistry Community (www.suschem.org). The SPIRE (Sustainable Process Industry through Resource and Energy Efficiency) PPP proposed by Cefic (European Federation of the Chemical Industries) and the European Technology Platform on Sustainable Chemistry (ETP SusChem) for Horizon 2020 regard chemical reuse of CO2 and bioeconomy as key pillars to achieve the goals of resource and energy efficiency in process industry. Hence, Eco2CO2 fits the key strategies outlines in the SPIRE roadmap “European Industrial Competitiveness through Resource Efficiency”.

A critical decision had to be taken by the within the Eco2CO2 partnership on two alternative routes exploiting photoelectrocatalytic (PEC) conversion: 1) Develop and study a PEC reactor capable of directly converting CO2 Eco2CO2 into a precise fine chemical; 2) Develop a PEC reactor transforming CO2 into a platform chemical, in this case methanol, which can then be employed in tailored catalytic reactors to produce fine chemicals with biorefinery sub-products. The partnership, mostly influenced by the industrial partners, clearly decided to undertake route number two. In addition, during the progress of the project it was decided to exploit an additional route of CO2 reduction for the production of Syngas hat can be exploited in different traditional technologies for the production of methanol or other fine chemicals.

Deliverable 9.400: “Final exploitation plan and market system reliability and economic performance study”, was completed. This contains a complete market analysis, considering the Eco2CO2 technological advancements and the fine chemicals (fragrances, flavourings, cresol, adhesives,...) produced by methanol and secondary by-products such lignin or furfural, deriving by biorefineries technologies of the Partners. In such study, a preliminary methanol market analysis has been conducted taking into consideration the petrochemical methanol and bio-methanol. Particularly has been explored the biomethanol market and main companies involved in the syngas conversion staring from non-traditional feedstock. The results show that the methanol is one of the most important and versatile chemical for industry. Eco2CO2 project have shown the potentiality to convert CO2 emission of a biorefinery to methanol reducing in this way the GHG output and producing a compound that represents an essential building block for the chemical industry.

It has been evaluated the perspective of converting CO2 emission from biorefineries, assuming to produce the whole amount of bio-ethanol that could satisfy the needs of the Renewable Energy Directive (RED). In the light of the Eco2CO2 potentialities, assuming of converting all the CO2 streams coming from the bioethanol production to respect the RED, it has been estimated that it could be possible to produce about the 5-7% of worldwide methanol demand.

Moreover, it was identified that at present, various factors influence the economics of Eco2CO2 technology:
• feedstock types and prices
• electricity generation fuel mix and prices
• scale of production capacity
• technology choice and investment costs
• desired grade of the final product
• price of conventional methanol.

The project results have been disseminated to the General Public and to the scientific community through (i) about 37 participation to international conferences (with at least 24 of them as oral communivations); (ii) about 26 papers have been published or just submitted to international peer-review international journals (at least 5 of them have been published in Open Access); (iii) at least 5 training events organized by the partners and (iv) the project website.

Training Events

➢ Claver, C., Today´s challenge: A biorefinery in Catalonia. Looking for strategies and answers, Attendance to meeting in Tarragona (Spain) 2 June, 2015.
➢ Claver, C., Participation as Management Committee Substitute Member (MC SM) in COST Action FP1306: Valorisation of lignocellulosic biomass to Chemicals, Materials and Fuels; Attendance to 2nd MC meeting in Belgrade (Serbia) 3-5 February, 2015.
➢ Prof. Carmen Claver gave a lecture on February 12th, 2016 at the Circe center: " Centro de investigación de recursos y consumos energéticos" in Zaragoza, Spain (http://www.fcirce.es/web/page.aspx?id=aboutcirce), with about 35 persons present to the event among pHD students, researcher and profesors, etc.. The title of her presentation was: “Nuevos retos en catálisis Eficiencia energética y desarrollo sostenible” and the work performed at CTQ regarding WP2 and WP7 of the Eco2CO2 project were disseminated. The slides related to the project are attached to this report in the Annex section.

➢ On February 15 to 17, 2016 was organized the 3° WINTER SCHOOL of the SINCHEM program, of which Politecnico di Torino is a partner (see: https://eventi.unibo.it/sinchem-school-2016). This event was exploited as an occasion to dissemination the results of the Eco2CO2 project to PhD students, researchers and scientists coming from different countries (about 60 attendants), in the facilities of the Department of Industrial Chemistry, Bologna University. Prof. Saracco gave a lecture entitled: “Toward a solar-driven green-chemistry web”, in which he presented the specific researches that are under development in the Eco2CO2 project.
➢ On 1st March 2016 CTQC organized in their facilities in Tarragona (Spain) a Symposium called: “Bio-based chemicals and electrochemistry: The future of chemistry?”, in which the outcomes of the Eco2CO2 project have been disseminated to scientists, researchers and visitors invited to this event.


List of Websites:
http://www.eco2co2.org/

contact details:

Guido Saracco, PhD

Professor of Chemistry
Chemistry Institute
Department of Applied Science and Technology (DISAT)
Politecnico di Torino
Corso Duca degli Abruzzi, 24
10129 Torino, Italy

Head of the Center for Sustainable Futures (CSF@POLITO)
Istituto Italiano di Tecnologia
Corso Trento 21,
10129, Torino

Phone +39 011 5091 963
Fax +39 011 5091 901
Mobile: +39-335-8737127
e-mail: guido.saracco@polito.it

Contact

Guido Saracco, (Head of Department)
Tel.: +39 010904618
Fax: +39 0110904699
E-mail
Record Number: 189364 / Last updated on: 2016-09-14