GRAIL – Publishable Summary of the first 18 months

Project context and main 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.

  1. 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.

  1. 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.

  1. 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.

Work performed

  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).
  • The chemical process for crude glycerol purification has been developed at laboratory scale and preliminary mass and energy balances performed.
  1. Conversion of crude glycerol into biofuels
  • Optimization of the fermentation processes, based on mixed microbial culture (MMC) biotechnology, to obtain simultaneously hydrogen and ethanol from crude glycerol streams has been performed (D2.1, D2.2). Methane production from volatile fatty acids has been improved.
  • The screening of suitable bacteria for glycerol conversion into butanol, and the optimization of the glycerol fermentation process has been performed (D2.3).
  • The screening and expression of novel glycerol and alcohol resistant enzymes (mostly lipases) derived from extremophile environments for the production of FAGE has been performed.
  1. Conversion of glycerol into monomers, polymers and performance chemicals
  • Screening of 1,3-propanediol producers and optimization of the glycerol fermentation process (D3.2). Extraction experiments of 1,3-propanediol from water solutions and fermentation broths (D3.3) and the transformation of 1,3-propanediol into added valued chemicals have been performed.
  • Studies on the impact of the use of purified crude glycerol as feedstock to alkyd resin, rosin esters and maleic resin properties have been performed.
  • The characterization and adaptation of several MMC to crude glycerol has been performed. The operation of continuous reactors in order to obtain butyric acid has been established.
  • The chemical synthesis and analytical characterization of FAGE at the kilo-lab scale and the first evaluation experiments as ingredient in paints and cosmetic formulations have been performed, indicating that the green chemical has an enormous potential in these applications.

4. Conversion of glycerol into food ingredients

  • Collection and cultivation of a variety of bacteria, microalgae and fungi providing cultures for production of Trehalose, Cyanocobalamin (Vitamin B12), ß-carotene and Docosahexaenoic acid (DHA) (MS4.1, D4.1).
  • Optimization of bacterial growth and yield of the targeted products at lab scale (MS4.2, D4.2).
  • Establishment of the appropriate downstream processing protocols to separate bacteria biomass from the target food compounds.

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).
  • First process simulations have been performed.
  • The collection of experimental data from both partners and literature has been performed in order 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 relevant dissemination elements have been established: Technology transfer plan,   project logo, website, project flyers, project slides layout, e-newsletter, and initial press note (D7.1, D7.2, D7.3).
  • A Quality Assurance Committee and Quality Assurance procedure have been created.
  • Initial identification of the envisaged scientific and technical knowledge, products and services generated from the project execution.

Expected final results and potential impacts

  1. 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.

  1. 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.

  1. 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.

The document is available here: GRAIL_Publishable summary RP1


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    May 2, 2017

    The article entitled: “Review of technical glycerol potential from biodiesel production and availability for improved cascading in Europe” has been published and is available online. Authors: André Brosowski (DBFZ), Stephanie Hauschild (DBFZ), Karin Naumann (DBFZ), Jens Hösel (DBFZ), Daniela Thrän (Helmholtz Centre for environmental research), Type of publication: Article – Research Paper Date: April 2017 Publication: […]


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    April 11, 2017

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    February 22, 2017

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