Search results for: biorefineries
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 12

Search results for: biorefineries

12 Comparative Techno-Economic Assessment and LCA of Selected Integrated Sugarcane-Based Biorefineries

Authors: Edgard Gnansounoua, Pavel Vaskan, Elia Ruiz Pachón

Abstract:

This work addresses the economic and environmental performance of integrated biorefineries based on sugarcane juice and residues in the context of Brazil. We have considered four multiproduct scenarios; two from existing Brazilian sugar mills and the others from ethanol autonomous distilleries. They are integrated biorefineries producing first (1G) and second (2G) generation ethanol, sugar, molasses (for animal feed) and electricity. We show the results for the analysis and comparison of the different scenarios using a techno-economic value-based approach and LCA methodology. We have found that all the analysed scenarios show positive values of Climate change and Fossil depletion reduction as compared to the reference systems. However the scenario producing only ethanol shows less efficiency in Human toxicity, Freshwater ecotoxicity and Freshwater eutrophication impacts. The best economic configuration is provided by the scenario with the largest ethanol production. On the other hand, the best environmental performance is presented by the scenario with full integration sugar – 1G2G ethanol production. The integration of 2G based residues in a 1G ethanol production plant leads to positive environmental impacts compared to the conventional 1G industrial plant but proves to be more expensive.

Keywords: sugarcane, biorefinery, 1G/2G bioethanol integration, LCA, Brazil

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11 Advanced Bio-Fuels for Biorefineries: Incorporation of Waste Tires and Calcium-Based Catalysts to the Pyrolysis of Biomass

Authors: Alberto Veses, Olga Sanhauja, María Soledad Callén, Tomás García

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The appropriate use of renewable sources emerges as a decisive point to minimize the environmental impact caused by fossil fuels use. Particularly, the use of lignocellulosic biomass becomes one of the best promising alternatives since it is the only carbon-containing renewable source that can produce bioproducts similar to fossil fuels and it does not compete with food market. Among all the processes that can valorize lignocellulosic biomass, pyrolysis is an attractive alternative because it is the only thermochemical process that can produce a liquid biofuel (bio-oil) in a simple way and solid and gas fractions that can be used as energy sources to support the process. However, in order to incorporate bio-oils in current infrastructures and further process in future biorefineries, their quality needs to be improved. Introducing different low-cost catalysts and/or incorporating different polymer residues to the process are some of the new, simple and low-cost strategies that allow the user to directly obtain advanced bio-oils to be used in future biorefineries in an economic way. In this manner, from previous thermogravimetric analyses, local agricultural wastes such as grape seeds (GS) were selected as lignocellulosic biomass while, waste tires (WT) were selected as polymer residue. On the other hand, CaO was selected as low-cost catalyst based on previous experiences by the group. To reach this aim, a specially-designed fixed bed reactor using N₂ as a carrier gas was used. This reactor has the peculiarity to incorporate a vertical mobile liner that allows the user to introduce the feedstock in the oven once the selected temperature (550 ºC) is reached, ensuring higher heating rates needed for the process. Obtaining a well-defined phase distribution in the resulting bio-oil is crucial to ensure the viability to the process. Thus, once experiments were carried out, not only a well-defined two layers was observed introducing several mixtures (reaching values up to 40 wt.% of WT) but also, an upgraded organic phase, which is the one considered to be processed in further biorefineries. Radical interactions between GS and WT released during the pyrolysis process and dehydration reactions enhanced by CaO can promote the formation of better-quality bio-oils. The latter was reflected in a reduction of water and oxygen content of bio-oil and hence, a substantial increase of its heating value and its stability. Moreover, not only sulphur content was reduced from solely WT pyrolysis but also potential and negative issues related to a strong acidic environment of conventional bio-oils were minimized due to its basic pH and lower total acid numbers. Therefore, acidic compounds obtained in the pyrolysis such as CO₂-like substances can react with the CaO and minimize acidic problems related to lignocellulosic bio-oils. Moreover, this CO₂ capture promotes H₂ production from water gas shift reaction favoring hydrogen-transfer reactions, improving the final quality of the bio-oil. These results show the great potential of grapes seeds to carry out the catalytic co-pyrolysis process with different plastic residues in order to produce a liquid bio-oil that can be considered as a high-quality renewable vector.

Keywords: advanced bio-oils, biorefinery, catalytic co-pyrolysis of biomass and waste tires, lignocellulosic biomass

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10 Isosorbide Bis-Methyl Carbonate: Opportunities for an Industrial Model Based on Biomass

Authors: Olga Gomez De Miranda, Jose R. Ochoa-Gomez, Stefaan De Wildeman, Luciano Monsegue, Soraya Prieto, Leire Lorenzo, Cristina Dineiro

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The chemical industry is facing a new revolution. As long as processes based on the exploitation of fossil resources emerged with force in the XIX century, Society currently demands a new radical change that will lead to the complete and irreversible implementation of a circular sustainable economic model. The implementation of biorefineries will be essential for this. There, renewable raw materials as sugars and other biomass resources are exploited for the development of new materials that will partially replace their petroleum-derived homologs in a safer, and environmentally more benign approach. Isosorbide, (1,4:3,6-dianhydro-d-glucidol) is a primary bio-based derivative obtained from the plant (poly) saccharides and a very interesting example of a useful chemical produced in biorefineries. It can, in turn, be converted to other secondary monomers as isosorbide bis-methyl carbonate (IBMC), whose main field of application can be as a key biodegradable intermediary substitute of bisphenol-A in the manufacture of polycarbonates, or as an alternative to the toxic isocyanates in the synthesis of new polyurethanes (non-isocyanate polyurethanes) both with a huge application market. New products will present advantageous mechanical or optical properties, as well as improved behavior in non-toxicity and biodegradability aspects in comparison to their petro-derived alternatives. A robust production process of IBMC, a biomass-derived chemical, is here presented. It can be used with different raw material qualities using dimethyl carbonate (DMC) as both co-reactant and solvent. It consists of the transesterification of isosorbide with DMC under soft operational conditions, using different basic catalysts, always active with the isosorbide characteristics and purity. Appropriate isolation processes have been also developed to obtain crude IBMC yields higher than 90%, with oligomers production lower than 10%, independently of the quality of the isosorbide considered. All of them are suitable to be used in polycondensation reactions for polymers obtaining. If higher qualities of IBMC are needed, a purification treatment based on nanofiltration membranes has been also developed. The IBMC reaction-isolation conditions established in the laboratory have been successfully modeled using appropriate software programs and moved to a pilot-scale (production of 100 kg of IBMC). It has been demonstrated that a highly efficient IBMC production process able to be up-scaled under suitable market conditions has been obtained. Operational conditions involved the production of IBMC involve soft temperature and energy needs, no additional solvents, and high operational efficiency. All of them are according to green manufacturing rules.

Keywords: biomass, catalyst, isosorbide bis-methyl carbonate, polycarbonate, polyurethane, transesterification

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9 Co-Hydrothermal Gasification of Microalgae Biomass and Solid Biofuel for Biogas Production

Authors: Daniel Fozer

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Limiting global warming to 1.5°C to the pre-industrial levels urges the application of efficient and sustainable carbon dioxide removal (CDR) technologies. Microalgae based biorefineries offer scalable solutions for the biofixation of CO2, where the produced biomass can be transformed into value added products by applying thermochemical processes. In this paper we report on the utilization of hydrochar as a blending component in hydrothermal gasification (HTG) process. The effects of blending ratio and hydrochar quality were investigated on the biogas yield and and composition. It is found that co-gasifying the hydrochar and the algae biomass can increase significantly the total gas yield and influence the biogas (H2, CH4, CO2, CO, C2H4, C2H6) composition. It is determined that the carbon conversion ratio, hydrogen and methane selectivity can be increased by influencing the fuel ratio of hydrochar via hydrothermal carbonization. In conclusion, it is found that increasing the synergy between hydrothermal technologies result in elevated conversion efficiency.

Keywords: biogas, CDR, Co-HTG, hydrochar, microalgae

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8 Lignin Valorization: Techno-Economic Analysis of Three Lignin Conversion Routes

Authors: Iris Vural Gursel, Andrea Ramirez

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Effective utilization of lignin is an important mean for developing economically profitable biorefineries. Current literature suggests that large amounts of lignin will become available in second generation biorefineries. New conversion technologies will, therefore, be needed to carry lignin transformation well beyond combustion to produce energy, but towards high-value products such as chemicals and transportation fuels. In recent years, significant progress on catalysis has been made to improve transformation of lignin, and new catalytic processes are emerging. In this work, a techno-economic assessment of two of these novel conversion routes and comparison with more established lignin pyrolysis route were made. The aim is to provide insights into the potential performance and potential hotspots in order to guide the experimental research and ease the commercialization by early identifying cost drivers, strengths, and challenges. The lignin conversion routes selected for detailed assessment were: (non-catalytic) lignin pyrolysis as the benchmark, direct hydrodeoxygenation (HDO) of lignin and hydrothermal lignin depolymerisation. Products generated were mixed oxygenated aromatic monomers (MOAMON), light organics, heavy organics, and char. For the technical assessment, a basis design followed by process modelling in Aspen was done using experimental yields. A design capacity of 200 kt/year lignin feed was chosen that is equivalent to a 1 Mt/y scale lignocellulosic biorefinery. The downstream equipment was modelled to achieve the separation of the product streams defined. For determining external utility requirement, heat integration was considered and when possible gasses were combusted to cover heating demand. The models made were used in generating necessary data on material and energy flows. Next, an economic assessment was carried out by estimating operating and capital costs. Return on investment (ROI) and payback period (PBP) were used as indicators. The results of the process modelling indicate that series of separation steps are required. The downstream processing was found especially demanding in the hydrothermal upgrading process due to the presence of significant amount of unconverted lignin (34%) and water. Also, external utility requirements were found to be high. Due to the complex separations, hydrothermal upgrading process showed the highest capital cost (50 M€ more than benchmark). Whereas operating costs were found the highest for the direct HDO process (20 M€/year more than benchmark) due to the use of hydrogen. Because of high yields to valuable heavy organics (32%) and MOAMON (24%), direct HDO process showed the highest ROI (12%) and the shortest PBP (5 years). This process is found feasible with a positive net present value. However, it is very sensitive to the prices used in the calculation. The assessments at this stage are associated with large uncertainties. Nevertheless, they are useful for comparing alternatives and identifying whether a certain process should be given further consideration. Among the three processes investigated here, the direct HDO process was seen to be the most promising.

Keywords: biorefinery, economic assessment, lignin conversion, process design

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7 Portuguese Pine Resin: The Economic and Activity Decline to a New Forestry and Biotechnology Approach

Authors: Carolina Nunes, Sónia Ribeiro, Hélio Faustinho, Hélia Sales, Rita Pontes, João Nunes

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Pine resin activity in Portugal was one of the most important and major non-wood forestry, representing a strategic natural resource for Portuguese Bioeconomy and an important social activity for rural regions. Pine forests representing a stock of atmospheric carbon, contributing to greenhouse effect mitigation and social and environmental important services returns. They are important sources of numerous useful products, including not only wood and cellulose but also nonwood products used by the chemical, food, and pharmaceutical industries, as well as for biorefineries. Portuguese pine forest area decreases from 1 million hectares to 400 mil hectares in the last 20 years. Portugal, in 80´s decade, was one of the world´s TOP 3 producers, with a middle annual production of 140 mil tones.year-1. With the pressure of the social desertification, forest fires, phytosanitary problems (e.g. nematode of the pine wood) and the decrease of economic value and competitivity of the Portuguese forest, the actual middle annual production is less than 10 mil tones.year-1 (lesser 92%). This significant decrease representing an annual economic loss of approximately 130-140 million Euros. year⁻¹ for forest primary sector in Portugal. The Biopinus project design new forestry approach and strategic biotechnologies knowledge to increase the economic value of Pine resin in Portugal, with an impact on the growth of the economic value of Pine resin from 1,1 to 1,5 Euros/kg.

Keywords: pine resin, bioeconomy, economic value, biotecnology

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6 An Enzyme Technology - Metnin™ - Enables the Full Replacement of Fossil-Based Polymers by Lignin in Polymeric Composites

Authors: Joana Antunes, Thomas Levée, Barbara Radovani, Anu Suonpää, Paulina Saloranta, Liji Sobhana, Petri Ihalainen

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Lignin is an important component in the exploitation of lignocellulosic biomass. It has been shown that within the next years, the yield of added-value lignin-based chemicals and materials will generate renewable alternatives to oil-based products (e.g. polymeric composites, resins and adhesives) and enhance the economic feasibility of biorefineries. In this paper, a novel technology for lignin valorisation (METNIN™) is presented. METNIN™ is based on the oxidative action of an alkaliphilic enzyme in aqueous alkaline conditions (pH 10-11) at mild temperature (40-50 °C) combined with a cascading membrane operation, yielding a collection of lignin fractions (from oligomeric down to mixture of tri-, di- and monomeric units) with distinct molecular weight distribution, low polydispersity and favourable physicochemical properties. The alkaline process conditions ensure the high processibility of crude lignin in an aqueous environment and the efficiency of the enzyme, yielding better compatibility of lignin towards targeted applications. The application of a selected lignin fraction produced by METNIN™ as a suitable lignopolyol to completely replace a commercial polyol in polyurethane rigid foam formulations is presented as a prototype. Liquid lignopolyols with a high lignin content were prepared by oxypropylation and their full utilization in the polyurethane rigid foam formulation was successfully demonstrated. Moreover, selected technical specifications of different foam demonstrators were determined, including closed cell count, water uptake and compression characteristics. These specifications are within industrial standards for rigid foam applications. The lignin loading in the lignopolyol was a major factor determining the properties of the foam. In addition to polyurethane foam demonstrators, other examples of lignin-based products related to resins and sizing applications will be presented.

Keywords: enzyme, lignin valorisation, polyol, polyurethane foam

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5 Multi-Criteria Decision Making Tool for Assessment of Biorefinery Strategies

Authors: Marzouk Benali, Jawad Jeaidi, Behrang Mansoornejad, Olumoye Ajao, Banafsheh Gilani, Nima Ghavidel Mehr

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Canadian forest industry is seeking to identify and implement transformational strategies for enhanced financial performance through the emerging bioeconomy or more specifically through the concept of the biorefinery. For example, processing forest residues or surplus of biomass available on the mill sites for the production of biofuels, biochemicals and/or biomaterials is one of the attractive strategies along with traditional wood and paper products and cogenerated energy. There are many possible process-product biorefinery pathways, each associated with specific product portfolios with different levels of risk. Thus, it is not obvious which unique strategy forest industry should select and implement. Therefore, there is a need for analytical and design tools that enable evaluating biorefinery strategies based on a set of criteria considering a perspective of sustainability over the short and long terms, while selecting the existing core products as well as selecting the new product portfolio. In addition, it is critical to assess the manufacturing flexibility to internalize the risk from market price volatility of each targeted bio-based product in the product portfolio, prior to invest heavily in any biorefinery strategy. The proposed paper will focus on introducing a systematic methodology for designing integrated biorefineries using process systems engineering tools as well as a multi-criteria decision making framework to put forward the most effective biorefinery strategies that fulfill the needs of the forest industry. Topics to be covered will include market analysis, techno-economic assessment, cost accounting, energy integration analysis, life cycle assessment and supply chain analysis. This will be followed by describing the vision as well as the key features and functionalities of the I-BIOREF software platform, developed by CanmetENERGY of Natural Resources Canada. Two industrial case studies will be presented to support the robustness and flexibility of I-BIOREF software platform: i) An integrated Canadian Kraft pulp mill with lignin recovery process (namely, LignoBoost™); ii) A standalone biorefinery based on ethanol-organosolv process.

Keywords: biorefinery strategies, bioproducts, co-production, multi-criteria decision making, tool

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4 Biorefinery as Extension to Sugar Mills: Sustainability and Social Upliftment in the Green Economy

Authors: Asfaw Gezae Daful, Mohsen Alimandagari, Kathleen Haigh, Somayeh Farzad, Eugene Van Rensburg, Johann F. Görgens

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The sugar industry has to 're-invent' itself to ensure long-term economic survival and opportunities for job creation and enhanced community-level impacts, given increasing pressure from fluctuating and low global sugar prices, increasing energy prices and sustainability demands. We propose biorefineries for re-vitalisation of the sugar industry using low value lignocellulosic biomass (sugarcane bagasse, leaves, and tops) annexed to existing sugar mills, producing a spectrum of high value platform chemicals along with biofuel, bioenergy, and electricity. Opportunity is presented for greener products, to mitigate climate change and overcome economic challenges. Xylose from labile hemicellulose remains largely underutilized and the conversion to value-add products a major challenge. Insight is required on pretreatment and/or extraction to optimize production of cellulosic ethanol together with lactic acid, furfural or biopolymers from sugarcane bagasse, leaves, and tops. Experimental conditions for alkaline and pressurized hot water extraction dilute acid and steam explosion pretreatment of sugarcane bagasse and harvest residues were investigated to serve as a basis for developing various process scenarios under a sugarcane biorefinery scheme. Dilute acid and steam explosion pretreatment were optimized for maximum hemicellulose recovery, combined sugar yield and solids digestibility. An optimal range of conditions for alkaline and liquid hot water extraction of hemicellulosic biopolymers, as well as conditions for acceptable enzymatic digestibility of the solid residue, after such extraction was established. Using data from the above, a series of energy efficient biorefinery scenarios are under development and modeled using Aspen Plus® software, to simulate potential factories to better understand the biorefinery processes and estimate the CAPEX and OPEX, environmental impacts, and overall viability. Rigorous and detailed sustainability assessment methodology was formulated to address all pillars of sustainability. This work is ongoing and to date, models have been developed for some of the processes which can ultimately be combined into biorefinery scenarios. This will allow systematic comparison of a series of biorefinery scenarios to assess the potential to reduce negative impacts on and maximize the benefits of social, economic, and environmental factors on a lifecycle basis.

Keywords: biomass, biorefinery, green economy, sustainability

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3 Techno-Economic Assessments of Promising Chemicals from a Sugar Mill Based Biorefinery

Authors: Kathleen Frances Haigh, Mieke Nieder-Heitmann, Somayeh Farzad, Mohsen Ali Mandegari, Johann Ferdinand Gorgens

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Lignocellulose can be converted to a range of biochemicals and biofuels. Where this is derived from agricultural waste, issues of competition with food are virtually eliminated. One such source of lignocellulose is the South African sugar industry. Lignocellulose could be accessed by changes to the current farming practices and investments in more efficient boilers. The South African sugar industry is struggling due to falling sugar prices and increasing costs and it is proposed that annexing a biorefinery to a sugar mill will broaden the product range and improve viability. Process simulations of the selected chemicals were generated using Aspen Plus®. It was envisaged that a biorefinery would be annexed to a typical South African sugar mill. Bagasse would be diverted from the existing boilers to the biorefinery and mixed with harvest residues. This biomass would provide the feedstock for the biorefinery and the process energy for the biorefinery and sugar mill. Thus, in all scenarios a portion of the biomass was diverted to a new efficient combined heat and power plant (CHP). The Aspen Plus® simulations provided the mass and energy balance data to carry out an economic assessment of each scenarios. The net present value (NPV), internal rate of return (IRR) and minimum selling price (MSP) was calculated for each scenario. As a starting point scenarios were generated to investigate the production of ethanol, ethanol and lactic acid, ethanol and furfural, butanol, methanol, and Fischer-Tropsch syncrude. The bypass to the CHP plant is a useful indicator of the energy demands of the chemical processes. An iterative approach was used to identify a suitable bypass because increasing this value had the combined effect of increasing the amount of energy available and reducing the capacity of the chemical plant. Bypass values ranged from 30% for syncrude production to 50% for combined ethanol and furfural production. A hurdle rate of 15.7% was selected for the IRR. The butanol, combined ethanol and furfural, or the Fischer-Tropsch syncrude scenarios are unsuitable for investment with IRRs of 4.8%, 7.5% and 11.5% respectively. This provides valuable insights into research opportunities. For example furfural from sugarcane bagasse is an established process although the integration of furfural production with ethanol is less well understood. The IRR for the ethanol scenario was 14.7%, which is below the investment criteria, but given the technological maturity it may still be considered for investment. The scenarios which met the investment criteria were the combined ethanol and lactic acid, and the methanol scenarios with IRRs of 20.5% and 16.7%, respectively. These assessments show that the production of biochemicals from lignocellulose can be commercially viable. In addition, this assessment have provided valuable insights for research to improve the commercial viability of additional chemicals and scenarios. This has led to further assessments of the production of itaconic acid, succinic acid, citric acid, xylitol, polyhydroxybutyrate, polyethylene, glucaric acid and glutamic acid.

Keywords: biorefineries, sugar mill, methanol, ethanol

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2 Safety Considerations of Furanics for Sustainable Applications in Advanced Biorefineries

Authors: Anitha Muralidhara, Victor Engelen, Christophe Len, Pascal Pandard, Guy Marlair

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Production of bio-based chemicals and materials from lignocellulosic biomass is gaining tremendous importance in advanced bio-refineries while aiming towards progressive replacement of petroleum based chemicals in transportation fuels and commodity polymers. One such attempt has resulted in the production of key furan derivatives (FD) such as furfural, HMF, MMF etc., via acid catalyzed dehydration (ACD) of C6 and C5 sugars, which are further converted into key chemicals or intermediates (such as Furandicarboxylic acid, Furfuryl alcohol etc.,). In subsequent processes, many high potential FD are produced, that can be converted into high added value polymers or high energy density biofuels. During ACD, an unavoidable polyfuranic byproduct is generated which is called humins. The family of FD is very large with varying chemical structures and diverse physicochemical properties. Accordingly, the associated risk profiles may largely vary. Hazardous Material (Haz-mat) classification systems such as GHS (CLP in the EU) and the UN TDG Model Regulations for transport of dangerous goods are one of the preliminary requirements for all chemicals for their appropriate classification, labelling, packaging, safe storage, and transportation. Considering the growing application routes of FD, it becomes important to notice the limited access to safety related information (safety data sheets available only for famous compounds such as HMF, furfural etc.,) in these internationally recognized haz-mat classification systems. However, these classifications do not necessarily provide information about the extent of risk involved when the chemical is used in any specific application. Factors such as thermal stability, speed of combustion, chemical incompatibilities, etc., can equally influence the safety profile of a compound, that are clearly out of the scope of any haz-mat classification system. Irrespective of the bio-based origin, FD has so far received inconsistent remarks concerning their toxicity profiles. With such inconsistencies, there is a fear that, a large family of FD may also follow extreme judgmental scenarios like ionic liquids, by ranking some compounds as extremely thermally stable, non-flammable, etc., Unless clarified, these messages could lead to misleading judgements while ranking the chemical based on its hazard rating. Safety is a key aspect in any sustainable biorefinery operation/facility, which is often underscored or neglected. To fill up these existing data gaps and to address ambiguities and discrepancies, the current study focuses on giving preliminary insights on safety assessment of FD and their potential targeted by-products. With the available information in the literature and obtained experimental results, physicochemical safety, environmental safety as well as (a scenario based) fire safety profiles of key FD, as well as side streams such as humins and levulinic acid, will be considered. With this, the study focuses on defining patterns and trends that gives coherent safety related information for existing and newly synthesized FD in the market for better functionality and sustainable applications.

Keywords: furanics, humins, safety, thermal and fire hazard, toxicity

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1 Physico-Chemical Characterization of Vegetable Oils from Oleaginous Seeds (Croton megalocarpus, Ricinus communis L., and Gossypium hirsutum L.)

Authors: Patrizia Firmani, Sara Perucchini, Irene Rapone, Raffella Borrelli, Stefano Chiaberge, Manuela Grande, Rosamaria Marrazzo, Alberto Savoini, Andrea Siviero, Silvia Spera, Fabio Vago, Davide Deriu, Sergio Fanutti, Alessandro Oldani

Abstract:

According to the Renewable Energy Directive II, the use of palm oil in diesel will be gradually reduced from 2023 and should reach zero in 2030 due to the deforestation caused by its production. Eni aims at finding alternative feedstocks for its biorefineries to eliminate the use of palm oil by 2023. Therefore, the ideal vegetable oils to be used in bio-refineries are those obtainable from plants that grow in marginal lands and with low impact on food-and-feed chain; hence, Eni research is studying the possibility of using oleaginous seeds, such as castor, croton, and cotton, to extract the oils to be exploited as feedstock in bio-refineries. To verify their suitability for the upgrading processes, an analytical protocol for their characterization has been drawn up and applied. The analytical characterizations include a step of water and ashes content determination, elemental analysis (CHNS analysis, X-Ray Fluorescence, Inductively Coupled Plasma - Optical Emission Spectroscopy, ICP– Mass Spectrometry), and total acid number determination. Gas chromatography coupled to flame ionization detector (GC-FID) is used to quantify the lipid content in terms of free fatty acids, mono-, di- and triacylglycerols, and fatty acids composition. Eventually, Nuclear Magnetic Resonance and Fourier Transform-Infrared spectroscopies are exploited with GC-MS and Fourier Transform-Ion Cyclotron Resonance to study the composition of the oils. This work focuses on the GC-FID analysis of the lipid fraction of these oils, as the main constituent and of greatest interest for bio-refinery processes. Specifically, the lipid component of the extracted oil was quantified after sample silanization and transmethylation: silanization allows the elution of high-boiling compounds and is useful for determining the quantity of free acids and glycerides in oils, while transmethylation leads to a mixture of fatty acid esters and glycerol, thus allowing to evaluate the composition of glycerides in terms of Fatty Acids Methyl Esters (FAME). Cotton oil was extracted from cotton oilcake, croton oil was obtained by seeds pressing and seeds and oilcake ASE extraction, while castor oil comes from seed pressing (not performed in Eni laboratories). GC-FID analyses reported that the cotton oil is 90% constituted of triglycerides and about 6% diglycerides, while free fatty acids are about 2%. In terms of FAME, C18 acids make up 70% of the total and linoleic acid is the major constituent. Palmitic acid is present at 17.5%, while the other acids are in low concentration (<1%). Both analyzes show the presence of non-gas chromatographable compounds. Croton oils from seed pressing and extraction mainly contain triglycerides (98%). Concerning FAME, the main component is linoleic acid (approx. 80%). Oilcake croton oil shows higher abundance of diglycerides (6% vs ca 2%) and a lower content of triglycerides (38% vs 98%) compared to the previous oils. Eventually, castor oil is mostly constituted of triacylglycerols (about 69%), followed by diglycerides (about 10%). About 85.2% of total FAME is ricinoleic acid, as a constituent of triricinolein, the most abundant triglyceride of castor oil. Based on the analytical results, these oils represent feedstocks of interest for possible exploitation as advanced biofuels.

Keywords: analytical protocol, biofuels, biorefinery, gas chromatography, vegetable oil

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