GRAIL : GLYCEROL BIOREFINERY APPROACH FOR THE PRODUCTION OF HIGH QUALITY PRODUCTS OF INDUSTRIAL VALUE
GRAIL is a 48-months collaborative project funded by the European Commission, under the FP7 Programme for Knowledge Based Bio-Economy. The topic of GRAIL project is “Preventing and valorizing bio-waste in biorefineries optimal and cost-effective industrial biocatalysts”.
- Evaluation of raw material supply
- Biotransformation of glycerol to biofuels;
- Development of green chemicals from glycerol.
3rd YEAR ADVANCE MEETING – OCTOBER 12-14, 2016 – NORWAY
The communication and cooperation among partners is highly encouraged by the coordinating partner IUCT; therefore, technical workshops and meetings, as well as General Assembly meetings are considered the teamwork basis. With this aim, during the last semester of 2016, the Consortium met in Bergen (Norway), where the last results and achievements were discussed.
FUTURE EVENTS: FINAL CONFERENCE: September 20, 2017 in Barcelona (Spain).
Evaluation of raw material supply
Under the leadership of the Deutsches Biomasseforschungszentrum gemeinnützige GmbH (DBFZ), the project partners InKemia IUCT Group (IUCT) and Viomichania Rition Megaron Anastasios Fanis Anonymos Etairia (MEGARA) form a consistent basis for the investigations in the GRAIL project and continuously accompany the project course. In the first project years, the glycerol availability and quality in Europe was evaluated. A patent for a flexible purification procedure is pending in order to provide the required glycerol qualities for the projects’ conversion processes. Ongoing, mass and energy balances for selected glycerol processing plant concepts are investigated and optimized via flowsheet simulation.
Supply chains and the potential availability of glycerol in an European and global context is one of the crucial issues for the overall approach of the GRAIL project. In 2014, the DBFZ investigated the glycerol occurrence from biodiesel plants based on data from 2012 and 2013. Despite a feasible biodiesel capacity of about 22 million t y-1 in Europe (global around 50 million t y-1), 2013’s production was just about 8 million t y-1. That corresponds to roughly 0.8 million t y-1 of glycerol in different quality levels. Based on the theoretical potential of glycerol (European
biodiesel capacity) from operating biodiesel plants, a spatial analysis was conducted (Fig. 1). This serves as a basis for the selection of glycerol processing plant locations.
In this study, an accumulation of several biodiesel plants was considered and the transport distances of glycerol were varied (50, 100, 150 and 200 km). The coloration in different shades of grey and green represents the suitability of a specific area to provide an adequate amount of glycerol. Fig. 1 shows that the variety of a suitable plant location is decreasing the more glycerol is needed for the conversion plants. With regard to large-scale processes (> 200 kt y-1), the North Sea coast of Belgium and the Netherlands is the preferred area. The location of Rotterdam (The Netherlands) was finally chosen, which is surrounded by several biodiesel plants providing glycerol. In addition, Rotterdam seems to be favorable due to its good transport connection via port, road and rail as well as the connection to other industries in the surrounding industrial area.
Various Glycerol Quality
Several glycerol qualities are available on the European market. In 2014 and 2015, the DBFZ conducted an analytical screening of these glycerol qualities. 17 different samples were collected, classified by the producers as low, medium and high quality glycerol. Mostly, rapeseed oil was used as raw material for the biodiesel production. However, used cooking oil (UCO), palm and soybean oil as well as mixtures of these with rapeseed oil were also stated as feedstock. Various conversion routes or technology suppliers as Lurgi, Connemann and the procedure of Desmet Ballestra were entitled. The use of alcoholates as catalysts for the biodiesel production leads for all samples to a glycerol content above 80 %. The impurities were analyzed to be water and small amounts of methanol. Investigations regarding the use of raw glycerol shall therefore at least consider this feedstock composition. Furthermore, most of the samples were generated in biodiesel plants using sodium-based catalysts. Via ICP-OES analysis sodium, phosphorous and sulphur were found to be the main elements in the glycerol phase.
Two out of 17 glycerol samples were
provided by operators using potassiumbased catalysts in the biodiesel process; the detected main elements were potassium, sulphur, sodium and phosphorous (Fig.2).
Sulphur and phosphorous most likely originate from the vegetable oils themselves; plants absorb sulphur compounds during their growth phase and produce phospholipids especially for membrane construction.
The amounts and compositions of fatty acids, fatty acid methyl esters and soaps in the glycerol samples are directly affected by the fatty acid pattern of the feedstock. This was figured out by comparison of these samples’ parameters with their respective stated raw materials. The occurrence of soaps in the glycerol can have large influences on the microorganism performance within the fermentation processes. These compounds shall therefore be removed by water scrubbing. Additionally, it was verified that the presence of the trans-isomer of octadecenoic acid indicates the use of animal fats as a raw material for the biodiesel process. The origin of the glycerol, whether it is from vegetable or animal oils, is of particular interest within the food sector and the cosmetic industry. The detailed deliverable with regard to the European glycerol qualities will be available on the project website, soon.
BIOTRANSFORMATION OF GLYCEROL TO BIOFUELS
The overall objective concerns the use of a holistic approach for the valorisation of crude glycerol into biofuel using biological processes (mixed microbial culture, single strain) and into biocatalyst using enzymes. The optimization of the different processes has been achieved. The good improvement of ethanol and hydrogen productions from fed-batch fermentation was obtained by ENEA after the isolation of a more efficient microbial culture as a result of its adaption to the substrate. SINTEF is testing the gas stripping as a method for increasing the ethanol production. Moreover, SINTEF is involved in a new task with the aim of evaluating the positive effects on ethanol production of working under partial vacuum conditions during continuous fermentation. PUCV showed the feasibility of a two-step process that converts glycerol to produce hydrogen with a CSTR reactor and utilizes the effluent in the UASB reactor to produce methane. Overall, combining hydrogen generation from glycerol and CH4 produced from the fermented effluent, has resulted in a reasonable organic removal system, as well a reasonable system to produce a high amount of gaseous biofuel, compared to the one stage fermentation process. STUBA pointed out that batch or continuous mode of production are more useful than fed-batch for the butanol production, whose production was optimized by the cells immobilization. IUCT developed successfully the bioprocess for the FAGE production as biocatalyst using commercial lipases.
DEVELOPMENT OF GREEN CHEMICALS FROM GLYCEROL
Butyric acid production and optimization The enrichment and adaptation of MMCs at DTU proved to be a winning strategy to efficiently convert complex substrates, such as crude glycerol derived from animal fat (with no pretreatment). The adaptation allowed the bacteria to grow in CSTR on high feed concentration, performing a high glycerol consumption rate. 1.3 PDO turned out to be the dominant metabolite during steady state, followed by butyrate. The statistical optimization allowed to maximize productivity of PDO and butyric acid, with a 5-fold increase compared to steady state results in standard fermentation conditions prior to optimization. The results showed a model with a complex interaction between the key factors (pH, HRT and glycerol concentration), which implied a careful choice of operating parameters. The model further showed the need for a fine tuning of HRT in combination with the other parameters, in order to maximize productivities and avoid cells wash out. To avoid this problem, preliminary tests and kinetic characterization of the consortium turned out to be fundamental to choose the proper experimental range.
Production of polymers
MEGARA tested samples of Bio Glycerol supplied by IUCT, Cargill and ADM which were used for the synthesis of alkyd resins, maleic resins, rosin esters and saturated polyester resins for powder coatings. The derived bio-propylene glycol from vegetable oils, which was used for the synthesis of UPR, was supplied by Oleon. The formulations for the synthesis of the bio based resins were analogous to the formulations of the commercial products. By incorporating Bio Glycerol and Bio propylene glycol into the formulations of selected commercial polyester resins, the renewable content of polymers increases, while their carbon footprint decreases. Comparing the synthesized bio based resins with their analogous commercial products , it is evident that refined Bio Glycerol and Biopropylene glycol can successfully substitute the petrochemical based glycerol in the formulation of polyester resins for the production of a new
generation of resins without negatively affecting their final properties and overall performance.
1,3-PDO conversion to high value products
The process of extraction of 1,3- propanediol and its conversion to highvalue products by employing chemocatalysis has been targeted. Both high extraction efficiency and stability was achieved. QUB has shown that the hydrogen transfer initiated dehydration (HTID) of 1,3-PDO in ionic liquids allows the successful production of a range of C3 and C6 aldehydes as the value-added chemicals. Both propionaldehyde and 2-methylpentenal were produced with high conversions, yields and selectivities. The successful synthesis and isolation of valueadded chemicals out of the ionic liquid solutions of 1,3-PDO proves that the combination of HTID of 1,3-PDO in ionic liquids with bio-catalysis has the potential to allow the transformation of waste glycerol into valuable chemicals. This valorisation of waste to chemicals would add significant value and improve the economics of biomass waste utilization.
The process to produce value-added chemicals directly from glycerol will be ultimately tested.
PHA production and extraction
DTU has found that enrichment of PHA accumulating microorganisms on fermented crude glycerol (a mixture of 1,3-PDO and volatile Fatty Acids, VFA) led to a process where VFA were converted into PHA (up to 70% of the cells dry matter) and 1,3-PDO was recovered from the process (97% recovery). This novel strategy has the potential to be applied for a remarkably fast accumulation and production of VFA, while 1,3-PDO can be recovered as a high value product in a biorefinery scheme.
MASS AND ENERGY BALANCES OF GLYCEROL PROCESSING PLANT CONCEPTS
The preparation of mass and energy balances of the investigated processes within the project was divided between the project partners DBFZ, Processi Innovativi (PI) and STIFTELSEN SINTEF (SINTEF). The balances were conducted via process simulation using the software ASPEN Plus®. During the first project period mass and process energy balances were conducted by the DBFZ for the conversion routes from glycerol to 1,3-propanediol and n-butanol; both processes are examined by STUBA. In addition, the purification process of raw glycerol and the production of Fatty Acid Glycerol Esters (FAGE), processes invented by IUCT, were simulated in large-scale. For
the fermentation processes it was shown that the dilution rates of the fed glycerol lead to large amounts of water to be handled in the downstream processing.
Furthermore, the conversion rates were detected to be very low. Hence, the developed process cases were successively optimized with regard to these aspects and new experimental findings. For the 1,3-propanediol production, the initially proposed four-step water evaporation and two-step distillation were replaced by a reverse osmosis cascade with a subsequent distillation. The amount of membrane stages and their selectivity were significantly supported by calculations from SINTEF. In the n-butanol case, an in-situ gas stripping with nitrogen was considered. For this, the operation mode was adapted to a continuous process and the gas stripping takes place inside of the fermenter. In order to increase the butanol concentration in the stripped product, a reverse osmosis cascade was implemented in the upstream of a distillation step. The latter step was expanded to meet the requirements for the separation of an azeotropic mixture (butanol / ethanol / water), which was neglected during the base cases. The results will be underlined by a comparison of the optimized process routes with the base cases in terms of relevant economic and ecological aspects. These investigations will be conducted by DBFZ and VERTECH assisted by the calculation from PI. The most promising conversion routes and optimization approaches will be published at international conferences and in scientific journals.
At October 2016, the GRAIL project reached the month 36 of its life and now the project is living its last stage as FP7 project. Coordinating partner IUCT, as a bridge among the project and the European Commission, has led the consortium to a successful delivery of the Second Period Report. As future steps, IUCT is working towards the on-time delivery of the Final Report and future sets of Deliverables. Moreover, in closely collaboration with InBio, dissemination leader, the coordination team is organizing a final Dissemination Conference.
- C. Varrone, I.V. Skiadas and H.N. Gavala. (2016). Statistical optimization of operating parameters for CSTR bioprocesses: the case study of glycerol conversion. Abstract in Sustain ATV Conference 2016, Kgs. Lyngby, Denmark.
- A. Burniol-Figols, C. Varrone, A.E. Daugaard, I.V. Skiadas and H.N. Gavala. (2016). Polyhydroxyalkanoates (PHA) production from fermented crude glycerol by mixed microbial cultures. Abstract in Sustain ATV Conference 2016, Kgs. Lyngby, Denmark
- K. Pissaridi, Kalliopi Krassa. (2016). Glycerol Biorefinery Approach for the Production of High Quality Products of Industrial Value: Production of Bio-based Polymers, 11th Hellenic Polymer Society International Conference, Crete, Greece.
- F. Lorenzini, Y. Wang, Y. Ma, X. Liu, M. Rebros, A. C. Marr (2016). ‘Adding value to glycerol by combining chemo- and bio-catalysis: synthesis of aldehydes from 1,3- propanediol via hydrogen transfer catalysed by highly recyclable Cp*Ir(NHC) catalysts.’ CSC 2016 Conference and Exhibition, Halifax, NS, Canada. & UK Catalysis Conference, Loughborough. & 2nd EuGSC, 2nd EuCheMS Congress on Green and Sustainable Chemistry, Lisbon & 9th International Conference on Environmental Catalysis, Newcastle, New South Wales, Australia. (Oral presentations)
- A. C. Marr (2016) ‘Combining Bio- and Chemo-catalysis, Striving for a Greener Chemical Industry’. Faculty colloquium of the faculty of Bio- and Chemical Engineering, TU Dortmund. (Oral presentation.)
- A. C. Marr (2016). ‘Combining Bio- and Chemo-catalysis, Finding Greener Routes to Chemicals’. 43rd International Conference of Slovak Society Chemical Engineering. (Oralpresentation, plenary lecture.)
- Y.Y. Ma, H. Iqbal, Y.-M. Wang, M. Rebros, F. Lorenzini, A. C. Marr (2016). ‘Combining bio- and chemo-catalysis for the production of value-added chemicals from waste glycerol derived from biorefinery.’ Royal Society of Chemistry awards symposium,Belfast, N. Ireland, UK. (Poster presentation.)
1. Combining Bio- and Chemo-Catalysis for the Conversion of Bio-Renewable Alcohols:
Homogeneous Iridium Catalysed Hydrogen Transfer Initiated Dehydration of 1,3-
Propanediol to Aldehydes.
Authors : Y.M. Wang, F. Lorenzini,M. Rebros, G. C. Saunders, A. C. Marr.
2. Immobilization of cells and enzymes to LentiKats®
Authors : Krasňan V., Stloukal R., Rosenberg M., Rebroš M.
COOPERATION WITH AN ITALIAN BIODIESEL PRODUCER
The cooperation with the Italian biodiesel producer is going on. The process book of the pilot plant has been completed. The activities for the pilot plant construction can be started.
The GRAIL e-newsletter is available in pdf here: GRAIL_eNewsletter5