GRAIL
Publishable summary
RP1 - (M1-M18)
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.
2. 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.
3. 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
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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.
2. Conversion of crude glycerol into biofuels
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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).
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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.
3. Conversion of glycerol into monomers, polymers and performance chemicals
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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 1,3propanediol 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
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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
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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
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The relevant dissemination elements have been established: Technology
transfer plan, project logo, website, project flyers, project slides layout, enewsletter, 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.
2. 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.
3. 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.