Efficient Extraction of Fermentation Inhibitors by Means of Green Hydrophobic Deep Eutectic Solvents.

The methods for hydrogen yield efficiency improvements, the gaseous stream purification in gaseous biofuels generation, and the biomass pretreatment are considered as the main trends in research devoted to gaseous biofuel production. The environmental aspect related to the liquid stream purification arises. Moreover, the management of post-fermentation broth with the application of various biorefining techniques gains importance. Chemical compounds occurring in the exhausted liquid phase after biomass pretreatment and subsequent dark and photo fermentation processes are considered as value-added by products. The most valuable are furfural (FF), 5-hydroxymethylfurfural (HMF), and levulinic acid (LA). Enriching their solutions can be carried with the application of liquid-liquid extraction with the use of a suitable solvent. In these studies, hydrophobic deep eutectic solvents (DESs) were tested as extractants. The screening of 56 DESs was carried out using the Conductor-like Screening Model for Real Solvents (COSMO-RS). DESs which exposed the highest inhibitory effect on fermentation and negligible water solubility were prepared. The LA, FF, and HMF were analyzed using FT-IR and NMR spectroscopy. In addition, the basic physicochemical properties of DES were carefully studied. In the second part of the paper, deep eutectic solvents were used for the extraction of FF, LA, and HMF from post-fermentation broth (PFB). The main extraction parameters, i.e., temperature, pH, and DES: PFB volume ratio (VDES:VPFB), were optimized by means of a Box-Behnken design model. Two approaches have been proposed for extraction process. In the first approach, DES was used as a solvent. In the second, one of the DES components was added to the sample, and DES was generated in situ. To enhance the post-fermentation broth management, optimization of the parameters promoting HMF, FF, and LA extraction was carried under real conditions. Moreover, the antimicrobial effect of the extraction of FF, HMF, and LA was investigated to define the possibility of simultaneous separation of microbial parts and denatured peptides via precipitation.

Methanolysis Fractionation and Catalytic Conversion of Poplar Wood toward Methyl Levulinate, Phenolics, and Glucose.

In the present study, methanolysis of poplar biomass was conducted for the selective transformation of hemicellulose and lignin, which leads to methyl glycosides (mainly C5 glycosides) and lignin fragments in the liquefied products that can be separated according to their difference in hydrophilicity. The distribution of methyl glycosides and delignification was dependent on the presence of acid catalysts and reaction temperatures. The obtained lignin fraction was separated into solid lignin fragments and liquid lignin oil according to their molecular weight distribution. Subsequently, directional conversion of methyl C5 glycosides into methyl levulinate was performed with dimethoxymethane/methanol as the cosolvent. A yield of 12-30% of methyl levulinate yield (based on the methyl glycoside) was achieved under these conditions. The remaining cellulose-rich substrate showed enhanced susceptibility to enzymatic hydrolysis, resulting in a yield of glucose of above 70%. Overall, the described strategy shows practical implications for the effective valorization of biomass.

Electrodialytic separation of levulinic acid catalytically synthesized from woody biomass for use in microbial conversion.

Levulinic acid (LA) is produced by the catalytic conversion of a variety of woody biomass. To investigate the potential use of desalting electrodialysis (ED) for LA purification, electrodialytic separation of levulinate from both reagent and cedar-derived LA solution (40-160 g L-1 ) was demonstrated. When using reagent LA solution with pH5.0-6.0, the recovery rates of levulinate ranged from 68 to 99%, and the energy consumption for recovery of 1 kg of levulinate ranged from 0.18 to 0.27 kWh kg-1 . With cedar-derived LA solution (pH6.0), good agreement in levulinate recovery (88-99%), and energy consumption (0.18-0.22 kWh kg-1 ) were observed in comparison to the reagent LA solutions, although a longer operation time was required due to some impurities. The application of desalting ED was favorable for promoting microbial utilization of cedar-derived LA. From 0.5 mol L-1 of the ED-concentrated sodium levulinate solution, 95.6% of levulinate was recovered as LA calcium salt dihydrate by crystallization. This is the first report on ED application for LA recovery using more than 20 g L-1 LA solutions (40-160 g L-1 ). © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 33:448-453, 2017.

One-pot synthesis of levulinic acid from cellulose in ionic liquids.

A simple and effective route for the production of levulinic acid (LA) from cellulose has been developed in SO3H-functionalized ionic liquids. The effects of ionic liquid structures, reaction conditions and combination of metal chlorides with ILs on the yield of LA were investigated, where the highest yield of 39.4% was obtained for 120 min in the presence of 1-(4-sulfonic acid) butyl-3-methylimidazolium hydrogen sulphate ([BSMim]HSO4) with addition of H2O. The catalytic activities of ionic liquids depended on the anions and decreased in the order: CF3SO3(-)>HSO4(-) > OAc(-), which was in good agreement with their acidity order. The ILs play a dual solvent-acid role for the cellulose conversion into LA and exhibited favorable catalytic activity over four repeated runs.

Morphology Tailoring of Sulfonic Acid Functionalized Organosilica Nanohybrids for the Synthesis of Biomass-Derived Alkyl Levulinates.

Morphology evolution of sulfonic acid functionalized organosilica nanohybrids (Si(Et)Si-Pr/ArSO3 H) with a 1D tubular structure (inner diameter of ca. 5 nm), a 2D hexagonal mesostructure (pore diameter of ca. 5 nm), and a 3D hollow spherical structure (shell thickness of 2-3 nm and inner diameter of ca. 15 nm) was successfully realized through P123-templated sol-gel cocondensation strategies and fine-tuning of the acidity followed by aging or a hydrothermal treatment. The Si(Et)Si-Pr/ArSO3 H nanohybrids were applied in synthesis of alkyl levulinates from the esterification of levulinic acid and ethanolysis of furfural alcohol. Hollow spherical Si(Et)Si-Pr/ArSO3 H and hexagonal mesoporous analogues exhibited the highest and lowest catalytic activity, respectively, among three types of nanohybrids; additionally, the activity was influenced by the -SO3 H loading. The activity differences are explained in terms of different Brønsted acid and textural properties, reactant/product diffusion, and mass transfer rate, as well as accessibility of -SO3 H sites to the reactant molecules. The reusability of the nanohybrids was also evaluated.

Separation of galactose, 5-hydroxymethylfurfural and levulinic acid in acid hydrolysate of agarose by nanofiltration and electrodialysis.

A two-stage membrane process for the separation of galactose, 5-hydroxymethylfurfural (5-HMF) and levulinic acid (LA) has been proposed. The first step of nanofiltration (NF) is to remove 5-HMF and LA from galactose solution obtained by the hydrolysis of agarose, the main component of red algal galactan for the reduction of its microbial toxicity. 5-HMF and LA are inhibitory to fermentation but at the same time useful compounds themselves with many applications. The second step of electrodialysis (ED) is to separate 5-HMF and LA in the permeate from NF. More than 91% of 5-HMF and up to 62% of LA could be removed from agarose hydrolysate, while galactose was almost completely retained by NF. Further removal of LA was expected to be possible with no loss of galactose by operating the NF process in a diafiltration mode. 5-HMF and LA could be effectively separated from each other by ED.

Detoxification of acidic catalyzed hydrolysate of Kappaphycus alvarezii (cottonii).

Red seaweed, Kappaphycus alvarezii, holds great promise for use in biofuel production due to its high carbohydrate content. In this study, we investigated the effect of fermentation inhibitors to the K. alvarezii hydrolysate on cell growth and ethanol fermentation. In addition, detoxification of fermentation inhibitors was performed to decrease the fermentation inhibitory effect. 5-Hydroxymethylfurfural and levulinic acid, which are liberated from acidic hydrolysis, was also observed in the hydrolysate of K. alvarezii. These compounds inhibited ethanol fermentation. In order to remove these inhibitors, activated charcoal and calcium hydroxide were introduced. The efficiency of activated charcoals was examined and over-liming was used to remove the inhibitors. Activated charcoal was found to be more effective than calcium hydroxide to remove the inhibitors. Detoxification by activated charcoal strongly improved the fermentability of dilute acid hydrolysate in the production of bioethanol from K. alvarezii with Saccharomyces cerevisiae. The optimal detoxifying conditions were found to be below an activated charcoal concentration of 5%.

Improvement in HPLC separation of acetic acid and levulinic acid in the profiling of biomass hydrolysate.

5-Hydroxymethylfurfural (HMF) and furfural could be separated by the Aminex HPX-87H column chromatography, however, the separation and quantification of acetic acid and levulinic acid in biomass hydrolysate have been difficult with this method. In present study, the HPLC separation of acetic acid and levulinic acid on Aminex HPX-87H column has been investigated by varying column temperature, flow rate, and sulfuric acid content in the mobile phase. The column temperature was found critical in resolving acetic acid and levulinic acid. The resolution for two acids increased dramatically from 0.42 to 1.86 when the column temperature was lowered from 60 to 30 °C. So did the capacity factors for levulinic acid that was increased from 1.20 to 1.44 as the column temperature dropped. The optimum column temperature for the separation was found at 45 °C. Variation in flow rate and sulfuric acid concentration improved not as much as the column temperature did.

Nest liquid resources of several cavity nesting bees in the genus Centris and the identification of a preservative, levulinic acid.

Twig-nesting species of bees in the genus Centris including C. bicornuta, C. analis, C. vittata, and C. nitida, found in the dry forest of Guanacaste Province of Costa Rica, provision their nests with pollen and nectar, rather than pollen and oil as reported for other Centris species. The liquid contents of the nests of these four species were found to contain sugars including 66-75% fructose, 25-33% glucose, and a trace of sucrose. The sugar concentration averaged 47.2%, slightly higher than most flower nectars. No tri-, di-, or monoglycerides, the main components of the flower oil of Byrsonima crassifolia, were detected in the nest provisions. Although these four Centris species are also known to collect oil from B. crassifolia, the oil appears to be used for activities other than nest provisioning. The liquid nest contents did have a slight goat-like odor, suggesting the presence of short-chain fatty acids, and were found to contain a small amount (less than 1%) of three fatty acids. Two of these, butanoic and octanoic acid, were found in trace amounts and are responsible for the goat-like odor. A third was identified as levulinic acid, which made up about 99% of the nest fatty acid contents. This fatty acid had little odor, but may be important as a fungicidal agent. Attempts to determine the source of the fatty acids, were not successful.