Insights into the European market for bio-based chemicals

Bio-based products can bring new functionalities to the market and make the EU economy more sustainable. According to this analysis, based on ten key chemical categories, the EU produces 4.7 Mt/a of bio-based chemicals which represents a bio-based share of about 3.0%, although the market is diverse and large differences can be found between product categories. Under a business-as-usual scenario, the overall bio-based share of the market is not expected to increase rapidly, with an estimated CAGR of 3.6%. Hurdles are still present in the development of the bio-based industry (e.g. production costs), but also big opportunities have been identified and new policy measures could help.JRC.D.4-Economics of Agricultur

ALIGNED: A framework for the LCA of bio-based products

The assessment of bio based products presents several challenges: from the definition of system boundaries and choice of system models, modeling competition for biomass and for land, to performing dynamic and time specific accounting, making scenarios and considering uncertainty. We present the background, methodology, and expected results of the Horizon-Europe-funded project “Aligning Life Cycle Assessment methods and bio-based sectors for improved environmental performance” (ALIGNED, grant number 101059430). Targeting five sectors namely woodworking, pulp and paper, biochemicals, construction and textiles, ALIGNED fulfils three research needs: 1) to improve, harmonize, and align LCA methodology for the assessment of bio-based products covering environmental and socio-economic aspects, 2) to demonstrate the harmonized methodology to improve the environmental performance of specific technology development cases in industries within the bio-based sectors 3) to inform and involve stakeholders, enabling an efficient methodological uptake.ALIGNED modelling framework does not intend to provide a new standard or guideline but instead to make available an ecosystem of science-based and open approaches and tools to ease the assessment of bio-based products. Key elements in such framework include: 1) A science and evidence-based approach: scientifically sound modelling as close as possible to reality, avoiding normative rules, and favoring models that can be validated and revised when new data become available as well as an ecosystem of interacting models and tools. 2) A lifecycle perspective: the assessment takes the full life cycle of bio-based products into account. 3) Relevance for decision-makers and usefulness for decision support: we focus on modelling what are the consequences of specific decisions. We explicitly consider uncertainty in the decision support. 4) Balancing model complexity and model applicability: we select and use in this framework models that are scientifically robust but also usable by practitioners to the largest extent, keeping in mind the trade-off between model complexity and applicability. 5) Adherence to open-science practices: models, tools, and their documentation are open, while data should be as open as possible. 6) Ensuring relevance for bio-based products: the modelling framework considers the specific challenges and issues that exist in the assessment of bio-based products

Biobased chemicals from polyhydroxybutyrate

Currently, most chemicals and materials are obtained from fossil resources. After use, these chemicals and materials are converted to CO2. As discussed in chapter 1, this causes a build-up of CO2 in the atmosphere, the main driving force of global warming. In order to reach a sustainable system, biomass could be used as a resource for chemicals and materials instead. A biorefinery approach, where all parts of biomass are used to its full potential is essential. Taking this into consideration, wastewater streams of current biobased processes could be an excellent source for chemicals and materials. However, wastewater is often dilute and heterogeneous of nature. To overcome these challenges, wastewater rich in carbon can be processed by microorganisms to obtain a biodegradable polyester, polyhydroxyalkanoate (PHA). However, the mechanical properties of this polymer make it unsuitable as polymeric material. Moreover, processing of PHA is challenging. To circumvent these issues, we propose a conversion of the inferior PHA to methyl acrylate and propylene (Figure 7.1) which can be used in current processing infrastructure. PHA rich cells are obtained from the purification of wastewater. The PHA obtained can be purified and converted to MC (Figure 7.1, chapter 2) or the PHA rich cells can be used directly (Figure 7.1, chapter 3). For the second step, the conversion of methyl crotonate (MC) to methyl acrylate and propylene, the catalyst was immobilised (Figure 7.1, chapter 4). The current state of ethenolysis reaction on biomass was reviewed (Figure 7.1, chapter 5). The conversion of PHA to methyl acrylate and propylene enables the use of carbon from wastewater streams without the disadvantages related to the direct use of PHA. In chapter 2, the first step of the conversion of PHA to methyl acrylate and propylene was investigated. Since PHA obtained from wastewater exists mostly as polyhydroxybutyrate (PHB), this was chosen as a starting material for our studies. It was shown that PHB could be converted to MC using methanol at 200 °C.. MC has the advantage of being immiscible with water, which aids its separation. In chapter 2, the pathway of the reaction was clarified, which was subsequently used to optimise the conditions of this conversion. The conversion of PHB to MC proceeds via a thermolysis to crotonic acid (CA), which is followed by an esterification to MC. The formation of CA is the rate determining step below 18 bar, where above 18 bar this changes to the esterification to MC. A selectivity of 60% to MC is obtained with a full conversion of PHB with 18 bar being the optimal pressure for the conversion. Microorganisms produce PHA within their cells, which poses challenges to the downstream processing of PHA as the material has to be isolated from within the cells and dried. The isolation and drying of PHB is costly and is responsible for a large part of the production costs of PHA. In order to reduce the costs of PHA for the production of biobased chemicals, the conversion of PHA to MC was tested using whole cells. In chapter 3, PHA rich cells were directly converted to MC using the optimised conditions found in chapter 2. The influence of fermentation salts, water and the presence of valerate monomers in the PHA were studied. It was found that the valerate monomers have no influence on the conversion. Fermentation salts do influence the conversion depending on the salt. Magnesium hydroxide catalyses the conversion of PHB to MC, where magnesium sulphate catalyses the formation of methyl 3-hydroxybutyrate as side product. The reaction tolerates up to 20% water, which means that the drying step in the downstream processing of PHA can be significantly reduced. The second step of the conversion of PHA to methyl acrylate and propylene involves an ethenolysis, a cross metathesis of MC with ethylene. This ethenolysis reaction requires a homogeneous catalyst. One of the most active catalysts for this conversion is the ruthenium based Hovey-Grubbs 2nd generation. However, the required high loading of this catalyst makes it an expensive part of the conversion. In order to enable reusing of the catalyst, immobilisation of the Hovey-Grubbs catalyst was investigated in chapter 4. The catalyst was immobilised inside a metal organic framework (MOF). For this purpose MIL-101-NH2(Al) was used for its large cavities connected by small openings. This allows the catalyst to reside inside the cavities, while the small openings prevent it from leaching out. The catalyst was successfully immobilised using a mechanochemical approach. This method can be applied on other catalysts as well, which was shown by the immobilisation of Zhan catalyst. Both immobilised catalysts show metathesis activity for multiple reaction cycles. It was found that the MOF, MIL-101-NH2(Al), partially undergoes a structural change to form MIL-53-NH2(Al). When MIL-53-NH2(Al) was used as starting MOF the catalyst was trapped but inactive. It was concluded that when starting from MIL-101-NH2(Al), the catalyst trapped in the parts of the material that was converted to MIL-53-NH2(Al) are catalytically inactive. To investigate the current state of the art of the use of ethenolysis on biomass, a literature review was performed in chapter 5. The results of the ethenolysis of methyl oleate (MO) were compared in order to investigate the most important parameters. It was found that the purity of the ethylene feed has the biggest influence on the turn over numbers (TONs) and that a higher purity ethylene has shown a larger impact on the ethenolysis of MO than the development of novel catalysts. When electron poor substrates are used, the highest TONs are obtained with the less stable Hoveyda-Grubbs 2nd generation. However, no studies were performed on the influence of ethylene purity on these reactions and higher TONs may be achieved using a higher purity ethylene. In chapter 6, the results and conclusions of the thesis are summarised. The implications of these findings are discussed and suggestions for further research within the field are given

Lignin Based Molecular Materials – a Zinc Vanillate with a Hydrogen Bonded 4- and 8-connected Net with a New Topology

Vanillic acid, C8H8O4, is a possible product from a future biorefinery with lignin as raw material. Two coordination compounds with this ligand in two different protonation states were prepared: 1 [Zn(C8H7O4)2(H2O)2] and 2 [Co2(C8H6O4)2(H2O)6] ⋅ 2H2O. Both compounds form extended 3D structures with strong hydrogen bonds. A high symmetry 8- and 4-connected network topology, jus, is found in 1. The dinuclear coordination entity in 2 hints at a potentially useful SBU for MOF synthesis from lignin based bridging ligands

Getting your hands dirty: A data digging exercise to unearth the EU's bio-based chemical sector

Under the auspices of the EU's new Circular Economy Action Plan and Bioeconomy Strategy, the usage of sustainably renewable biomass for bio-based chemicals is a part-solution for addressing the multidimensional challenges of (inter alia) growth and employment, food and energy security, climate change and biodiversity. Unfortunately, the lack of a formal system of European data classification and collection presents a major obstacle to measuring, monitoring and ex-ante modelling of the bio-based chemicals sector, which clouds the ability to make science-based policy and legislative judgements. Employing a combination of different data sources and plausible assumptions, this paper seeks to overcome some of these data gaps through the compilation of a meaningful set of economic and sustainability indicators for specific bio-based chemical activities and products. Due to the variety of data sources employed for each indicator, a data quality index is constructed, whilst rigorous comparisons with other studies and further critical discussion reaffirms the general observation of poor data quality. Subject to these data and methodological limitations, this paper analyses the performance of bio-based chemical industries. As long as official data sources lack adequate information systems, the current paper serves as a springboard for lowering the data ‘entry costs' behind this intricate sector, encouraging further knowledge-sharing and serving as a replication template for other regions.Publishe