• Energy Research

AbstractNew technology is needed to exploit the potential of lignin as a renewable feedstock for fuels, chemicals and performance products. Fast fluidized bed pyrolysis of different lignins at 400°C yields up to 21 wt% (d.b.) of a phenolic fraction containing 10 wt% (d.b.) of several phenols. Subsequent catalytic hydrotreating of this phenolic fraction with 100 bar of hydrogen in dodecane at 350°C yields mainly cycloalkanes, cyclohexanols and alkanes. For the production of monomeric phenols, it appears that the used ruthenium on carbon is a too active catalyst. However, cyclohexanols may be interesting products, e.g., for use as oxygenates in engine fuel. © 2009 American Institute of Chemical Engineers Environ Prog, 2009

AbstractBio‐based industries (pulp and paper and biorefineries) produce > 50 Mt/yr of lignin that results from fractionation of lignocellulosic biomass. Lignin is world's second biopolymer and a major potential source for production of performance materials and aromatic chemicals. Lignin valorization is a key‐issue for enhanced profitability of sustainable bio‐based industries. Despite a myriad of potential applications for lignin and decades of research, its heterogeneity and recalcitrance still preclude commercial value‐added applications. Most lignin is utilized for heat and power. Unconventional solutions are needed to better exploit lignin's potential. Organosolv lignins are especially suitable as feedstock for high‐value chemicals. AtECN, a lignin biorefinery approach (LIBRA) has been developed, involving a dedicated lignin pyrolysis protocol that is robust, continuous, and capable of processing different lignins. Typical product yields are 20% gas, 35% char, and 45% oil. The oil contains approximately 45% oligomeric phenolic substances, 23% monomeric phenols, and 33% water. The future perspective is scale‐up of the process to produce larger lignin pyrolysis oil samples for separation, purification, and industrial application tests. Presently, small lignin pyrolysis oil samples are investigated as feedstock for extracting high‐value chemicals, as a substitute for phenol in several applications, and as a feedstock for hydrotreating. The biochar is tested as growth enhancer and as substitute for carbon‐black in rubber. Regarding the large lignin side streams from (future) bio‐based industries, theLIBRApyrolysis technology has ample potential to increase the profitability of lignocellulosic biorefineries provided that for both the liquid product and the solid char value‐added applications are developed. © 2014 Society of Chemical Industry and John Wiley & Sons, Ltd

AbstractIncreased deployment of solar photovoltaic (PV) enables the transition to decarbonized energy systems, capable of tempering the dire consequences of global warming. Even though backsheets are very important regarding lifetime energy yield of the PV module, the environmental impacts of their production, use, and end‐of‐life (EoL) processing are largely neglected. As part of a recently finalized Dutch national project EXTENSIBLE (Energy yield assessment of neXT gENeration and SustaInaBLE backsheets), the environmental impacts for 7 different polymeric backsheets have been evaluated via a life cycle assessment (LCA). The selected backsheets include 3 traditional polyethylene terephthalate (PET)‐based backsheets with a fluorine containing outer layer (two white pigmented and one fully transparent). The other 4 backsheets are novel high‐performance polyolefin (PO)‐based backsheets, manufactured by Endurans Solar™, also including one transparent version. From results of the LCA, it is concluded that in comparison with PET‐based backsheets and fluoropolymer containing backsheets, PO‐based backsheets perform best in terms of energy yield, reliability, and environmental impacts. The production of fluoropolymer‐ and PET‐based backsheets cause substantial environmental impacts, especially regarding climate change and ozone depletion. This conclusion is corroborated by recent literature data. Regarding the EoL phase, it was shown from a theoretical assessment that pyrolysis of the spent backsheets potentially leads to much lower global warming potential (GWP) when compared to incineration, especially for the PO‐based backsheets. Incineration of the shredded and solid backsheet material causes direct emissions of CO2 with a limited heat recovery potential only. Deploying pyrolysis for spent PO‐based backsheets significantly improves their life‐time GWP per kWh produced. Pyrolysis offers the possibility to recover a large part of the PO as an usable pyrolysis oil that might serve as feedstock for chemicals or as transportable liquid fuel for the generation of process heat in recovery boilers, thereby avoiding the use of new fossil resources. EoL pyrolysis (or incineration) of fluoropolymer‐based backsheets is problematic due to the presence of fluorinated hydrocarbons, leading to corrosive and/or toxic products.

The need for green renewable sources is adamant because of the adverse effects of the increasing use of fossil fuels on our society. Biomass has been considered as a very attractive candidate for green energy carriers, chemicals and materials. The development of cheap and efficient fractionation technology to separate biomass into its main constituents is highly desirable. It enables treatment of each constituent separately, using dedicated conversion technologies to get specific target chemicals. The synergistic combination of aquathermolysis (hot pressurised water treatment) and pyrolysis (thermal degradation in the absence of oxygen) is a promising thermolysis option, integrating fractionation of biomass with production of valuable chemicals. Batch aquathermolysis in an autoclave and subsequent pyrolysis using bubbling fluidised bed reactor technology with beech, poplar, spruce and straw indicate the potential of this hybrid concept to valorise lignocellulosic biomass. Hemicellulose-derived furfural was obtained in yields that ranged from 2 wt% for spruce to 8 wt% for straw. Hydroxymethylfurfural from hemicellulose was obtained in yields from 0.3 wt% for poplar to 3 wt% for spruce. Pyrolysis of the aquathermolised biomass types resulted in 8 wt% (straw) to 11 wt% (spruce) of cellulose-derived levoglucosan. Next to the furfurals and levoglucosan, appreciable amounts of acetic acid were obtained as well from the aquathermolysis step, ranging from 1 wt% for spruce to 5 wt% for straw. To elucidate relations between the chemical changes occurring in the biomass during the integrated process and type and amount of the chemical products formed, a 13C-solid state NMR study has been conducted. Main conclusions are that aquathermolysis results in hemicellulose degradation to lower molecular weight components. Lignin ether bonds are broken, but apart from that, lignin is hardly affected by the aquathermolysis. Cellulose is also retained, although it seems to become more crystalline, probably due to a higher ordering of amorphous cellulose when the samples are cooled down after aquathermolysis. These NMR results are in agreement with thermogravimetric analyses results.

Non-purified lignins resulting from ethanol-based organosolv fractionation of wheat straw were characterized for the presence of impurities (carbohydrates and ash), functional groups (hydroxyl, carboxyl and methoxyl), phenyl-propanoid structural moieties, molar mass distribution and thermal behavior. In accordance with its herbaceous nature, the syringyl/guaiacyl-ratio of the wheat straw lignins was substantially lower than of Alcell lignin. In addition, the content of p-hydroxyphenyl and carboxyl groups is substantially higher for the wheat straw lignins. The non-purified organosolv lignins had a high purity with 0.4–5.2% carbohydrate impurities, both originating from lignin to carbohydrate complexes and residual organosolv liquor. The use of H2SO4 in the organosolv process improved the lignin yield, but at low acid doses increased the carbohydrate impurities. For applications where a low amount of carbohydrates is important, lignin from a high-temperature autocatalytic organosolv process was found to be preferred. The highest content of total hydroxyl groups was determined when lignins were produced using 30 mM H2SO4 as catalyst or 50% w/w aqueous ethanol as solvent for the organosolv process. Aliphatic hydroxyl groups, the most predominant type of hydroxyl groups present originating for a substantial part from residual carbohydrates, were found to decrease with reaction time and ethanol proportion of the organosolv solvent. The correlations between organosolv process conditions and lignin characteristics determined can facilitate the use of organosolv lignins in value-added applications such as in polymers and resins and as a feedstock for bio-based aromatics.

Fast pyrolysis is an efficient technology to convert lignocellulosic biomass to a liquid product. However, the high contents of oxygenated compounds and water hinder the direct utilization of pyrolysis oils. Here, we report an upgrading concept to obtain liquid products with improved product properties and enriched in valuable low molecular weight chemicals and particularly alkylphenols. It entails two steps, viz. i) pyrolysis with in-situ staged condensation at multiple kg scale followed by ii) a catalytic hydrotreatment of selected fractions using a Ru/C catalyst. Of all pyrolysis oil fractions after staged condensation, the product collected in a condenser equipped with an electrostatic precipitator (ESP) at 120 °C was identified as the most attractive for hydrotreatment when considering product yields and composition. The best hydrotreatment results (Ru/C, 350 °C, 100 bar H2, 4 h) were achieved using beechwood and walnut shells as feedstock, resulting in a high oil yield (about 64 wt% based on pyrolysis oil fraction intake) with a higher heating value of about 37 MJ/kg and enriched in alkylphenols (about 16 wt%). Overall, it was shown that the type of biomass (beech sawdust, walnut granulates, and pine/spruce sawdust) has a limited impact on liquid and alkylphenols yields which implies feedstock flexibility of this integrated concept.

The cost-effectiveness of a lignocellulose biorefinery may be improved by developing applications for lignin with a higher value than application as fuel. We have developed a pyrolysis based lignin biorefinery approach, called LIBRA, to transform lignin into phenolic bio-oil and biochar using bubbling fluidized bed reactor technology. The bio-oil is a potential source for value-added products that can replace petrochemical phenol in wood-adhesives, resins and polymer applications. The biochar can e.g. be used as a fuel, as soil-improver as solid bitumen additive and as a precursor for activated carbon. In this paper we applied the pyrolysis-based LIBRA concept for the valorisation of wheat straw-derived organosolv lignin. First, we produced lignin with a high purity from two wheat straw varieties, using an organosolv fractionation approach. Subsequently, we converted these lignins into bio-oil and biochar by pyrolysis. For comparison purposes, we also tested two reference lignins, one from soda-pulping of a mixture of wheat straw and Sarkanda grass (Granit) and one from Alcell organosolv fractionation of hardwoods. Results indicate that ~80 wt% of the dry lignin can be converted into bio-oil (with a yield of 40–60%) and biochar (30–40%). The bio-oil contains 25–40 wt% (based on the dry lignin weight) of a phenolic fraction constituting of monomeric (7–11%) and oligomeric (14–24%) components. The monomeric phenols consist of guaiacols, syringols, alkyl phenols, and catechols. 4-vinylguaiacol is the major phenolic monomer that is formed during the pyrolysis of the straw lignins in yields from 0.5–1 wt%. For the hardwood-lignin Alcell, the predominant phenol is 4-methylsyringol (1.2 wt%). The ratio guaiacols/syringols seems to be an indicative marker for the source of the lignin.

To assess the potential of acetic and formic acid organosolv fractionation of wheat straw as basis of an integral biorefinery concept, detailed knowledge on yield, composition and purity of the obtained streams is needed. Therefore, the process was performed, all fractions extensively characterized and the mass balance studied. Cellulose pulp yield was 48% of straw dry matter, while it was 21% and 27% for the lignin and hemicellulose-rich fractions. Composition analysis showed that 67% of wheat straw xylan and 96% of lignin were solubilized during the process, resulting in cellulose pulp of 63% purity, containing 93% of wheat straw cellulose. The isolated lignin fraction contained 84% of initial lignin and had a purity of 78%. A good part of wheat straw xylan (58%) ended up in the hemicellulose-rich fraction, half of it as monomeric xylose, together with proteins (44%), minerals (69%) and noticeable amounts of acids used during processing.