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Periodic Report Summary 2 - GRAIL (Glycerol Biorefinery Approach for the Production of High Quality Products of Industrial Value)

Project Context and Objectives:
GRAIL is a glycerol-based biorefinery project aimed at providing high quality chemical products from cheap and abundant crude glycerol through highly integrated conversion technologies.
Why is glycerol an important bio-based chemical?
Crude glycerol is by far the most abundant bio-based chemical in the world economy. The reason is found in the current biodiesel manufacturing system where crude glycerol is generated as a major by-product. A total amount of 203 biodiesel plants are operational in Europe which account for a total capacity of 20.24 Mt/a for biodiesel and a concomitant 2.02 Mt/a capacity for crude glycerol. In addition to these plants there are 101 plants that are not in operation due to economic constraints, 11 under construction and 32 planned. It has been estimated that a crude glycerol potential of 828,000 t/a is realistic in the EU. Such a large production level exceeds the current consumption of glycerol in the market segment of highly valued chemicals.
The GRAIL biorefinery approach is based on highly integrated conversion processes that transform cheap and abundant crude glycerol into value added energy products and performance chemicals.
Biorefineries have been proposed as the most efficient chemical conversion system for biomass feedstocks. The possibility to transform cheap bio-based feedstocks, in the range of 30-300 €cent/kg, into a variety of chemical products in the range of thousands of €cent/kg is the defining feature of biorefineries. The GRAIL fundamental objective is to adopt the biorefinery concept for the conversion of crude glycerol into energy products and performance chemicals.
The first goal of GRAIL is to develop a cost-effective purification methodology that is able to generate a range of glycerol compositions that fit the windows of specifications for the manufacture of the GRAIL bioproducts. Furthermore, the conversion processes associated with the production of the GRAIL bioproducts will be designed in order to use the lowest possible quality of the glycerol compositions.
A central innovation of GRAIL is that the crude glycerol purification process can start in situ in the same biodiesel manufacturing plant. This is in contrast with the current industrial practices where crude glycerol is externally purified in dedicated glycerol refineries. Such integration of biodiesel manufacturing companies avoids environmental and economic costs due to transportation and eliminates the need for energy intensive, complex, and multi-step purification processes. The impact in the economic performance of biodiesel companies could be profound since they could benefit from the replacement of the low valued crude glycerol by a highly pure, more profitable by-product.
The GRAIL glycerol purification technology is partially based on a pre-existing process (T2) developed under EU project 2G-Biofuel. The T2 process couples the production of fatty acid methyl esters (FAME) with the production of pure glycerol acetals. It is a primary GRAIL objective to transform glycerol acetals into pure glycerol. The combined system opens the door for the first time to access an abundant source of cheap and high purity glycerol which can be utilized as a platform chemical for the synthesis of key chemical products and formulations.
GRAIL bioproducts range from biofuels, polymers, performance chemicals, and food ingredients.
GRAIL is aimed at developing robust and cost-effective glycerol transformation processes with impact in four different chemical market segments: energy chemicals, polymers, performance chemicals, and food ingredients. What these sectors have in common are the large volume of consumption, which is compatible with the large volume of crude glycerol production, and the need for strict quality specifications. Both the conceptual framework of GRAIL and the specific conversion technologies chosen have been carefully designed to fulfill the volume, price and quality needs of final consumers.

Project Results:
1: Characterization of crude glycerol production in the EU. Development of the purification process.
• Crude glycerol availability in Europe has been evaluated including the determination of hot spot regions (MS1.1, D1.1).
• Procurement of glycerol samples from representative biodiesel manufacturing sites has been done successfully.
• Development of the analytical methodologies to evaluate glycerol samples (crude and purified).
• Technical and economical requirements of glycerol for each end use have been set (D1.3).
• Two purification processes have been developed for crude glycerol in order to fulfill the needs of GRAIL partners who develop conversion processes. The two purificaction processes yield two different grades of purified glycerine:
o 1) Technical grade glycerin. Low salt –low organics crude glycerin used in fermentation reactions to prevent the inhibitory effect of crude glycerin impurities on microorganisms.
o 2) Pure glycerin up to 99.5%. Chemically purified glycerin which is used in the manufacture of resins and food ingredients. Both applications demand highly pure and cheap glycerin feedstocks.
2. Conversion of crude glycerol into biofuels
• A modified continuous fermentation process to obtain hydrogen and ethanol using mixed microbial culture (MMC) has been implemented showing the feasibility and the stability of the process (Deliverable 2.9). The methodology, upscaled to a 1o L reactor, overcomes two problems encountered previously, namely the lack of reproducibility and replicability when compared to reference data. Increased ethanol productivities were also found by using strict and stable microaerophilic conditions. The consequence of this finding is that the size, and therefore the capital costs, of the fermentation plants can be reduced.
• Studies on methane production from volatile fatty acid rich effluents from hydrogen production indicate that energy balances depend on the crude glycerin sources. The results suggest that an homogenized technical grade glycerin could stabilize the energy balance.
• The screening of suitable bacteria for glycerol conversion into butanol, and the optimization of the glycerol fermentation process has been performed (D2.3). Continuous or batch production systems have been found more efficient. The immobilization improved fermentation efficiency without any loss of product concentration. So far, results indicate even shorter fermentation time and therefore increased butanol productivity.
• A novel, genetically modified glycerol and alcohol resistant lipase derived from Proteus mirabilis for the production of FAGE has been over expressed successfully in E. coli BL21 (DE3). Nonetheless, the protein is presented as inclusion bodies, which severely restricted the industrial applications.
• As an alternative to use genetically modified lipases, commercial lipases were selected to perform the enzymatic synthesis of FAGE. Optimal reaction conditions were determined for the bioprocess leading to 95% yield.
3. Conversion of glycerol into monomers, polymers and performance chemicals
• 1,3-PD productivities reached as high as 5.7 g/l/h corresponding to 70.4 g/L concentration. The ionic liquid [P6,6,6,14][C8S] was found to be the most suitable extraction agent for real fermentation broths, achieving a 39.1 % extraction efficiency. In task 3.4, the selective production of a range of C3 and C6 aldehydes via homogeneous hydrogen transfer initiated dehydration (HTID) of 1,3-propanediol (1,3-PDO) in ionic liquids has been successfully achieved using an iridium complex as the catalyst. The HTID of 1,3-PDO in ionic liquids, using ridium complexes as the catalyst precursors, was also successfully driven, at different reaction conditions (in a closed reaction vessel), towards the production of the valuable C6 aldehyde 2-methyl-pentenal (yields up to 99 %; selectivity up to 86.6 %).
• Maleic resins, alkyd resins, and polyester resins are constituents of powder coatings. They have been prepared from glycerin samples purified from crude glycerin obtained from biodiesel plants and the sensitivity of their properties with glycerin quality has been evaluated showing that the resins can generally be produced with the same quality. The purity of glycerin used to make polyester resin needs to be highly pure.
• Two sequential batch reactors (SBR) have been used for the production of polyhydroxialkanoates (PHA) from fermented glycerol. From the two main substrates available (butyrate and 1,3-propanediol), PHA in preliminary experiments was only formed from butyrate. Nevertheless, experiments with and without nitrogen revealed that the culture had the capacity to produce PHA from 1,3-propanediol under nitrogen limiting conditions.
• The efficiency of FAGEs derived from olive, sesame and advocate oils as emollients in cosmetic formulations and as preservatives in biodiesel blends has been demonstrated.
4. Conversion of glycerol into food ingredients
• Several downstream processing protocols for the extraction of DHA produced by Schizochytrium limacinum; Vitamin B12 produced by Propionibacterium freudenreichii subsp. Shermanii and ß-carotene produced by Blaskelea trispora have been identified, selected, and successfully implemented. In addition, Schizochytrium limacinum and Propionibacterium freudenreichii subsp. Shermanii fermentation has been successfully up-scaled to 5L while Blaskelea trispora fermentation has been successfully up-scaled to 1L.
5. Techno-economic analysis and environmental credentials
• Block-diagrams have been developed for further demonstration of the viability of each process technology for the valorisation of glycerol (D5.1).
• Process simulations from laboratory data have been performed and indications for improvement have been delivered to research teams. Process engineers have identified opportunities for process integration, plant size minimization and material and energy efficiency.
• Data collected from R&D teams has been used to establish the goal and scope, the system boundaries, the methodology, the functional unit and the requirements to compare the environmental performance of the biorefinery based conversion processes (D6.1, D6.2).
6. Dissemination
• The second E-Newsletter was delivered in July 2015 and the third in February 2016.
• The GRAIL Open Day, held in Brussels on March 2016, offered the opportunity to interact with representatives from industry interested in GRAIL R&D outcomes. The event also served to create awareness about GRAIL among the global R&D community.
• Selected R&D results are regularly published in a variety of journals and events:
o 21 publications
o 20 articles on journals
o 47 dissemination events
• A Quality Assurance Committee and Quality Assurance procedure have been created.

Potential Impact:
Expected results
The expected result of GRAIL is the successful development of a variety of products and processes for the maximum valorization of crude glycerol with the minimum cost. The project will generate product dossiers with the relevant quality specifications as well as the engineering design for scale-up processes and pre-industrial batches. In addition, the technologies would be characterized for their life cycle impacts and compared with reference processes/products.
Potential socio-economic impacts
Impact on the biodiesel industry. A comparison of the conversion costs for biofuels for the time period until 2015 shows that no biofuel, conventional or advanced, can be produced competitively when compared to fossil fuel (68 €cent/L) under the assumption of a crude oil price of 100 €/barrel. However, with total production costs of 69 €cent/L and 84 €cent/L for biodiesel from waste oil and from palm oil, the gap towards fossil fuel is relatively small for these two types of biofuel. Correcting for the energy density, the gaps are 3 €cent and 19 €cent/L, respectively. Note that even under an extremely negative crude oil scenario of 200 €/barrel, the production costs for bioethanol (171 €cent/L) are far from competitive when compared to fossil fuels (131 €cent/L). Besides this, the production costs of hydrotreated vegetable oils (HVO) and biomass-to-liquid (BTL) fuels appear far more unfavourable in 2015 with 421 €cent/L and 171 €cent/L, respectively. The uncompetitive total production costs for HVO and BTL are mainly due to excessive conversion costs, which reflect that the scale and learning effects have not generated any impact on the conversion costs. Even when taking into account the scale and learning effects of the conversion costs for the time period until 2020, no biofuel can be produced competitively to fossil fuel at crude oil prices 50€/barrel. It is only when the crude oil price scenario escalates to 100 €/barrel that biodiesel from waste oil starts to be competitive with a production cost (55 €cent/L), lower than fossil fuel (68 €cent/L). Assuming a crude oil price of 150 €/barrel in 2020, only ethanol from lignocellulosic waste (91 €cent/L) and biodiesel from both, waste oil (64 €cent/L) and palm oil (98 €cent/L) can be produced competitively below the fossil fuel cost of 99 €cent/L.
The expected impact of performing crude glycerol purification within biodiesel manufacturing facilities on biodiesel production costs is that it may lead to a net credit gain. The credit gain may be even larger if advanced biofuels such as S-50 are co-manufactured in retro-fitted biodiesel plants. Therefore, it is expected that the combination of GRAIL technology with the existing biodiesel manufacturing process should, for the first time, close the gap between fossil diesel and biofuels even at the low crude oil price range within the time period until 2020.
Furthermore, biodiesel plants, if re-configured with GRAIL technology, would become between 5 to 20% more profitable. Such improvement in economic performance would overcome the financial tensions that caused the closure of 1/3 of the existing biodiesel plants. Reconversion of European non operational biodiesel plants would re-employ as far as 2000 direct jobs.
Impact on the chemical and food sector
The total EU consumption of alkyd resins is 500 000 tones/year. The glycerol content in these resins is at around 12% which gives a potential market of 60 000 tones for purified glycerol. A 10% reduction on the price of pure glycerol obtained with GRAIL technology would likely increase 25% the profit margin by reducing the cost of raw materials. Similar increases of profit margins are expected in a variety of other resins like rosin and maleic resins, and polyester resins.
Food ingredients would also benefit from less expensive raw materials, however the increase in profit margins could be less pronounced since a higher quality glycerol is required in this sector.

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