Search results for: humins

Authors: Pierluigi Tosi, Ed de Jong, Gerard van Klink, Luc Vincent, Alice Mija

Abstract:

During the last decades renewable and low-cost resources have attracted increasingly interest. Carbohydrates can be derived by lignocellulosic biomasses, which is an attractive option since they represent the most abundant carbon source available in nature. Carbohydrates can be converted in a plethora of industrially relevant compounds, such as 5-hydroxymethylfurfural (HMF) and levulinic acid (LA), within acid catalyzed dehydration of sugars with mineral acids. Unfortunately, these acid catalyzed conversions suffer of the unavoidable formation of highly viscous heterogeneous poly-disperse carbon based materials known as humins. This black colored low value by-product is made by a complex mixture of macromolecules built by covalent random condensations of the several compounds present during the acid catalyzed conversion. Humins molecular structure is still under investigation but seems based on furanic rings network linked by aliphatic chains and decorated by several reactive moieties (ketones, aldehydes, hydroxyls, …). Despite decades of research, currently there is no way to avoid humins formation. The key parameter for enhance the economic viability of carbohydrate conversion processes is, therefore, increasing the economic value of the humins by-product. Herein are presented new humins based polymeric materials that can be prepared starting from the raw by-product by thermal treatment, without any step of purification or pretreatment. Humins foams can be produced with the control of reaction key parameters, obtaining polymeric porous materials with designed porosity, density, thermal and electrical conductivity, chemical and electrical stability, carbon amount and mechanical properties. Physico chemical properties can be enhanced by modifications on the starting raw material or adding different species during the polymerization. A comparisons on the properties of different compositions will be presented, along with tested applications. The authors gratefully acknowledge the European Community for financial support through Marie-Curie H2020-MSCA-ITN-2015 "HUGS" Project.

Keywords: by-product, humins, polymers, valorization

Procedia PDF Downloads 117

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

Abstract:

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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Authors: Iris Vural Gursel, Jonathan Moncada, Ernst Worrell, Andrea Ramirez

Abstract:

In order to achieve the transition from a fossil to bio-based economy, biomass needs to replace fossil resources in meeting the world’s energy and chemical needs. This calls for development of biorefinery systems allowing cost-efficient conversion of biomass to chemicals. In biorefinery systems, feedstock is converted to key intermediates called platforms which are converted to wide range of marketable products. The C6 sugars platform stands out due to its unique versatility as precursor for multiple valuable products. Among the different potential routes from C6 sugars to bio-based chemicals, 1,3-butadiene and ε-caprolactam appear to be of great interest. Butadiene is an important chemical for the production of synthetic rubbers, while caprolactam is used in production of nylon-6. In this study, ex-ante techno-economic performance of 1,3-butadiene and ε-caprolactam routes from C6 sugars were assessed. The aim is to provide insight from an early stage of development into the potential of these new technologies, and the bottlenecks and key cost-drivers. Two cases for each product line were analyzed to take into consideration the effect of possible changes on the overall performance of both butadiene and caprolactam production. Conceptual process design for the processes was developed using Aspen Plus based on currently available data from laboratory experiments. Then, operating and capital costs were estimated and an economic assessment was carried out using Net Present Value (NPV) as indicator. Finally, sensitivity analyses on processing capacity and prices was done to take into account possible variations. Results indicate that both processes perform similarly from an energy intensity point of view ranging between 34-50 MJ per kg of main product. However, in terms of processing yield (kg of product per kg of C6 sugar), caprolactam shows higher yield by a factor 1.6-3.6 compared to butadiene. For butadiene production, with the economic parameters used in this study, for both cases studied, a negative NPV (-642 and -647 M€) was attained indicating economic infeasibility. For the caprolactam production, one of the cases also showed economic infeasibility (-229 M€), but the case with the higher caprolactam yield resulted in a positive NPV (67 M€). Sensitivity analysis indicated that the economic performance of caprolactam production can be improved with the increase in capacity (higher C6 sugars intake) reflecting benefits of the economies of scale. Furthermore, humins valorization for heat and power production was considered and found to have a positive effect. Butadiene production was found sensitive to the price of feedstock C6 sugars and product butadiene. However, even at 100% variation of the two parameters, butadiene production remained economically infeasible. Overall, the caprolactam production line shows higher economic potential in comparison to that of butadiene. The results are useful in guiding experimental research and providing direction for further development of bio-based chemicals.

Keywords: bio-based chemicals, biorefinery, C6 sugars, economic analysis, process modelling

Procedia PDF Downloads 126