An overview of lignin pathways of valorization: from isolation to refining and conversion into value‑added products

ABSTRACT: The increasing demand for greener and sustainable alternatives to fossil-derived fuels, chemicals, and materials has attracted huge attention to lignin, the largest renewable source of aromatic building blocks on earth. This natural polymer accounts for 15 to 40% of all lignocellulosic biomass. As such, in the pulp and paper industries, for example, huge amounts of lignin are produced worldwide. However, most applications for these lignins are of low value, such as their burning for energy. Furthermore, with the introduction of second-generation ethanol biorefineries, the overall lignin production increased. To attain a circular bio-based economy, all side-streams of lignocellulosic biomass and, particularly, lignin should be valorized to as high of a value as possible. Lignin's rich structure has allowed achieving various high-value products over the years, not only in the production of biofuels but also regarding chemicals and materials. The present paper addresses a broad vision of the several stages of lignin valorization, from the isolation of lignin through pre-treatments of lignocellulosic biomass and the current industrial lignin production to fractionation methodologies that provide homogeneous lignins more adequate for valorization and the conversion of lignin into value-added products via chemical and biological routes.info:eu-repo/semantics/publishedVersio

Acute toxicity evaluation of several compounds involved in fossil fuels biodesulphurisation studies

The increasing use of fossil fuels has led to increased emissions of sulphur oxides into the air, which is a major cause of acid rain. Legislation already adopted in 2009 stipulates that the maximum level of sulphur allowed in fuels is only 10 ppm. The process of hydrodesulphurization (HDS) used in refineries is based on very expensive physico-chemical techniques, and has limitations in the removal of organic sulphur. As for stricter legislation on the maximum levels of sulphur in fossil fuels, the most HDS recalcitrant compounds needs to be removed. This implies an increase in the intensity of the physical-chemical treatment and inherently its associated costs. As a result, the recalcitrant compounds to HDS represent a significant barrier to the achievement of very low levels of sulphur in some petroleum fractions. The alternative to the physical-chemical treatment could be the use of biological processes (biodesulphurisation) which is more effective for the desulphurization of fossil fuels, especially as the removal of sulphur covalently bound to organic matrices. The biodesulphurisation (BDS) occurs in more mild conditions of operation under conditions of atmospheric pressure and temperature, giving greater specificity of reaction due to the nature of the biocatalysts, not requiring molecular hydrogen. Thus, in the last 15 years there has been an increase of studies involving the use of microorganisms with the ability to specifically remove the HDS recalcitrant sulphur compounds. Several model compounds such as dibenzothiophene (DBT), DBT sulphone or benzothiophene (BT) are used in BDS studies to characterise organic sulphur in coal, coal tars and crude oils. The desulphurising microorganisms are able to remove the sulphur atom from these compounds and use it in their metabolism. However, such compounds are very toxic to the cells. The aim of this work was to evaluate the toxicity of several compounds used in BDS studies, such as DBT and its derivatives and organic solvents used to dissolve these hydrocarbons, to two typical desulphurising strains, namely: Gordonia alkanivorans strain 1B and Rhodococcus eritropolis strain D1. The toxicity bioassays evaluated the inhibitory effect of the studied compounds to the described bacteria by measuring the respiration rate (mg O2/l) under defined conditions in the presence of different concentrations of those compounds. The inhibitory or toxic effect of each chemical at a specific concentration is expressed as a percent of the baseline respiration rate. From these results the several IC50s were estimated and are described in Table 1. These toxicity values showed that strain 1B was less sensitive for almost all of the hydrocarbons, which is an important advantage considering the desulphurisation of fossil fuels process. On the other hand, strain 1B was more sensitive to dimethylformamide (DMF), a typical solvent used in BDS studies. However, a good correlation can be observed between IC50-1B versus IC50-D1 (IC50-D1 = 0.504 x IC50-1B + 2.84; r2 = 0.908, p < 0.05)

Imidazole processing of wheat straw and eucalyptus residues: comparison of pre-treatment conditions and their influence on enzymatic hydrolysis

ABSTRACT: Biomass pre-treatment is a key step in achieving the economic competitiveness of biomass conversion. In the present work, an imidazole pre-treatment process was performed and evaluated using wheat straw and eucalyptus residues as model feedstocks for agriculture and forest-origin biomasses, respectively. Results showed that imidazole is an efficient pre-treatment agent; however, better results were obtained for wheat straw due to the recalcitrant behavior of eucalyptus residues. The temperature had a stronger effect than time on wheat straw pre-treatment but at 160 degrees C and 4 h, similar results were obtained for cellulose and hemicellulose content from both biomasses (ca. 54% and 24%, respectively). Lignin content in the pre-treated solid was higher for eucalyptus residues (16% vs. 4%), as expected. Enzymatic hydrolysis, applied to both biomasses after different pre-treatments, revealed that results improved with increasing temperature/time for wheat straw. However, these conditions had no influence on the results for eucalyptus residues, with very low glucan to glucose enzymatic hydrolysis yield (93% for wheat straw vs. 40% for eucalyptus residues). Imidazole can therefore be considered as a suitable solvent for herbaceous biomass pre-treatment.info:eu-repo/semantics/publishedVersio

Conceptual Design of an Autotrophic Multi-Strain Microalgae-Based Biorefinery: Preliminary Techno-Economic and Life Cycle Assessments

ABSTRACT: Microalgae represent a promising solution in addressing the impacts associated with the current agricultural and manufacturing practices which are causing irreparable environmental damage. Microalgae have considerable biosynthetic potential, being a rich source of lipids, proteins, and high-value compounds. Under the scope of the H2020-BBI MULTI-STR3AM project, an innovative large-scale production system of valuable commodities for the food, feed, and fragrance sectors is being developed on the basis of microalgae, reducing costs, increasing the scale of production, and boosting value chain sustainability. In this work, we aimed to create a process model that can mimic an industrial plant to estimate mass and energy balances, optimize scheduling, and calculate production costs for a large-scale plant. Three autotrophic microalgae strains (Nannochloropsis sp., Dunaliella sp. and Spirulina sp.) were considered for this assessment, as well as the use of locally sourced CO2 (flue gas). The developed process model is a useful tool for obtaining the data required for techno-economic analysis (TEA) and life cycle assessment (LCA) of industrial biorefinery-based processes. Nannochloropsis sp. was the most economic option, whereas Dunaliella sp. was the most expensive strain to produce due to its lower productivity. Preliminary environmental assessments of the climate change impact category revealed that water recirculation and the use of flue gas could lead to values of 5.6, 10.6, and 9.2 kgCO(2eq)center dot kg(AFDW)(-1) for Nannochloropsis sp., Dunaliella sp., and Spirulina sp., respectively, with electricity and NaCl as the main contributors. The obtained data allow for the quantification of the production costs and environmental impacts of the microalgal biomass fractions produced, which will be fundamental for future comparison studies and in determining if they are higher or lower than those of the replaced products. The process model developed in this work provides a useful tool for the evaluation and optimization of large-scale microalgae production systems.info:eu-repo/semantics/publishedVersio

Sustainable value methodology to compare the performance of conversion technologies for the production of electricity and heat, energy vectors and biofuels from waste biomass

ABSTRACT: The Sustainable Value methodology was used to compare and rank eight combinations of waste biomass types and conversion technologies on a common assessment basis to produce energy, energy vectors and advanced biofuels. The studied combinations included agricultural and agro-industrial residues, slurries and effluents, pulp and paper mill sludge, piggery effluents and organic fractions of municipal solid waste, to produce biodiesel by (trans)esterification, biogas by anaerobic digestion, ethanol by fermentation, hydrogen by dark fermentation, electricity and heat by combustion, biogas and synthesis gas by gasification, and bio-oils by pyrolysis or hydrothermal liquefaction. The numerator “Functional Performance” of the Sustainable Value indicator was estimated according to 14 criteria of process technology, material and energy inputs and outputs, and acceptance by the stakeholders. The performance of the technologies was classified based on the values of relative importance (φ) and level of satisfaction (S) attributed to each criterion. The gasification of residues from the olive-oil industry reached the highest “Functional Performance”, followed by anaerobic digestion of chestnut processing residues and pig-rearing effluents. The Sustainable Value denominator “Costs” depended mainly on the degree of maturity of the technologies, which penalised pyrolysis, hydrothermal liquefaction and dark fermentation. The final ranking of the Sustainable Value indicator was gasification> combustion> anaerobic digestion> (trans)esterification> pyrolysis and fermentation to ethanol> hydrothermal liquefaction> dark fermentation, respectively for the most adequate waste biomass types under study. Thermochemical conversions were mainly impacted by process and input criteria, while output and social acceptance criteria were more decisive for the biochemical conversions.info:eu-repo/semantics/publishedVersio