Hydrolysis characteristics and kinetics of waste hay biomass as a potential energy crop for fermentable sugars production using autoclave parr reactor system

The use of the organic fraction of municipal solid waste crops has received considerable attention as a sustainable feedstock that can replace fossil fuels for the production of renewable energy. Therefore, municipal bin-waste in the form of hay was investigated as a potential energy crop for fermentable sugars production. Hydrolysis of hay by dilute phosphoric acid was carried out in autoclave parr reactor, where reactor temperature (135-200 degrees c) and acid concentration (2.5-10% (w/w)) were examined. Analysis of the decomposition rate of hemicellulosic biomass was undertaken using HPLC of the reaction products. Xylose production reached a maximum value of 13.5 g/100 g dry mass corresponding to a yield of 67% at the best identified conditions of 2.5 wt% H3PO4, 175 degrees C, 10 min reaction time, and at 5 wt% H3PO4, 150 degrees C, and 5 min reaction time. For glucose, an average yield of 25% was obtained at 5 wt% H3PO4, 175 degrees C and 30 min. Glucose degradation to HMF was achieved at 10 wt% H3PO4 and 200 degrees C. The maximum yield for produced arabinose was an average of 3 g/100 g dry. mass corresponding to 100% of the total possible arabinose. The kinetic study of the acid hydrolysis was also carried out using the Saeman and the Two-fraction models. It was found for both models that the kinetic constants (k) depend on the acid concentration and temperature. For xylose and arabinose it was found that the rate of formation was more favoured than the rate of degradation. By contrast, for glucose it was found that glucose degradation was occurring faster than glucose formation. It can be concluded that dilute phosphoric acid hydrolysis of hay crop is feasible for the production of fermentable sugars which are essential for bioethanol synthesis. 

Lignocellulosics as a renewable feedstock for chemical industry : chemical hydrolysis and pretreatment processes

Lignocellulosic materials including agricultural, municipal and forestry residues, and dedicated bioenergy crops offer significant potential as a renewable feedstock for the production of fuels and chemicals. These products can be chemically or functionally equivalent to existing products that are produced from fossil-based feedstocks. To unlock the potential of lignocellulosic materials, it is necessary to pretreat or fractionate the biomass to make it amenable to downstream processing. This chapter explores current and developing technologies for the pretreatment and fractionation of lignocellulosic biomass for the production of chemicals and fuels.

A comprehensive mechanistic kinetic model for dilute acid hydrolysis of switchgrass cellulose to glucose, 5-HMF and levulinic acid

Switchgrass was treated by 1% (w/w) H₂SO₄in batch tube reactors at temperatures ranging from 140–220°C for up to 60 minutes. In this study, release patterns of glucose, 5-hydroxymethylfurfural (5-HMF), and levulinic acid from switchgrass cellulose were investigated through a mechanistic kinetic model. The predictions were consistent with the measured products of interest when new parameters reflecting the effects of reaction limitations, such as cellulose crystallinity, acid soluble lignin–glucose complex (ASL–glucose) and humins that cannot be quantitatively analyzed, were included. The new mechanistic kinetic model incorporating these parameters simulated the experimental data with R² above 0.97. Results showed that glucose yield was most sensitive to variations in the parameter regarding the cellulose crystallinity at low temperatures (140–180°C), while the impact of crystallinity on the glucose yield became imperceptible at elevated temperatures (200–220 °C). Parameters related to the undesired products (e.g. ASL–glucose and humins) were the most sensitive factors compared with rate constants and other additional parameters in impacting the levulinic acid yield at elevated temperatures (200–220°C), while their impacts were negligible at 140–180°C. These new findings provide a more rational explanation for the kinetic changes in dilute acid pretreatment performance and suggest that the influences of cellulose crystallinity and undesired products including ASL–glucose and humins play key roles in determining the generation of glucose, 5-HMF and levulinic acid from biomass-derived cellulose.

Organosolv pretreatment of plant biomass for enhanced enzymatic saccharification

The combination of dwindling petroleum reserves and population growth make the development of renewable energy and chemical resources more pressing than ever before. Plant biomass is the most abundant renewable source for energy and chemicals. Enzymes can selectively convert the polysaccharides in plant biomass into simple sugars which can then be upgraded to liquid fuels and platform chemicals using biological and/or chemical processes. Pretreatment is essential for efficient enzymatic saccharification of plant biomass and this article provides an overview of how organic solvent (organosolv) pretreatments affect the structure and chemistry of plant biomass, and how these changes enhance enzymatic saccharification. A comparison between organosolv pretreatments utilizing broadly different classes of solvents (i.e., low boiling point, high boiling point, and biphasic) is presented, with a focus on solvent recovery and formation of by-products. The reaction mechanisms that give rise to these by-products are investigated and strategies to minimize by-product formation are suggested. Finally, process simulations of organosolv pretreatments are compared and contrasted, and discussed in the context of an industrial-scale plant biomass to fermentable sugar process.

Kinetic model for the hydrolysis of lignocellulosic biomass in the ionic liquid, 1-ethyl-3-methyl-imidazolium chloride†

The kinetics of the acid-catalysed hydrolysis of cellobiose in the ionic liquid 1-ethyl-3-methylimidazolium chloride, [C(2)mim]Cl, was studied as a model for general lignocellulosic biomass hydrolysis in ionic liquid systems. The results show that the rate of the two competing reactions, polysaccharide hydrolysis and sugar decomposition, vary with acid strength, and that for acids with an aqueous pK(a) below approximately zero, the hydrolysis reaction is significantly faster than the degradation of glucose, thus allowing hydrolysis to be performed with a high selectivity in glucose. In tests with soluble cellulose, hemicellulose (xylan), and lignocellulosic biomass (Miscanthus grass), comparable hydrolysis rates were observed with bond scission occurring randomly along the biopolymer chains, in contrast to end-group hydrolysis observed with aqueous acids.

Dilute acid hydrolysis of Lignocellulosic biomass

The overall aim of this work was to establish the optimum conditions for acid hydrolysis of hemicellulosic biomass in the form of potato peel. The hydrolysis reaction was undertaken in a 1l high pressure pilot batch reactor using dilute phosphoric acid. Analysis of the decomposition rate of hemicellulosic biomass (namely Cellulose, Hemicellulose and lignin) was undertaken using HPLC of the reaction products namely, 5 and 6 carbon sugars. Process parameters investigated included, reactor temperature (from 135 degrees C to 200 degrees C) and acid concentration (from 2.5% (w/w) to 10% (w/w)). Analysis of the reactor products indicated that high conversion of cellulose to glucose was apparent although arabinose conversion was quite low due to thermally un-stability. However, an overall sugar yield is 82.5% was achieved under optimum conditions. This optimum yield was obtained at 135 degrees C and 10% (w/w) acid concentration. 55.2 g sugar/100 g dry potato peel is produced after a time of 8 min. The work indicates that the use of potato peel may be a feasible option as a feed material for the production of sugars for biofuel synthesis, due its low cost and high sugar yields. (C) 2009 Elsevier B.V. All rights reserved.

Acid-catalyzed hydrolysis of cellulose and cellulosic waste using a microwave reactor system

A microwave reactor system was investigated as a potential technique to maximize sugar yield for the hydrolysis of municipal solid waste for ethanol production. Specifically, dilute acid hydrolysis of a-cellulose and waste cellulosic biomass (grass clippings) with phosphoric acid was undertaken within the microwave reactor system. The experimental data and reaction kinetic analysis indicate that the use of a microwave reactor system can successfully facilitate dilute acid hydrolysis of cellulose and waste cellulosic biomass, producing high yields of total sugars in short reaction times. The maximum yield of reducing sugars was obtained at 7.5% (w/v) phosphoric acid and 160 degrees C, corresponding to 60% of the theoretical total sugars, with a reaction time of 5 min. When using a very low acid concentration (0.4% w/v) for the hydrolysis in the microwave reactor, it was found that 10 g of total sugars/100 g dry mass was produced, which is significant considering the low acid concentration. When hydrolyzing grass clippings using the microwave reactor, the optimum conditions were an acid concentration of 2.5% (w/v), 175 degrees C with a 15 min reaction time, giving 18 g/100 g dry mass of total sugars, with xylose being the sugar with the highest yield. It was observed that pentose sugars were more easily formed but also more easily degraded, these being significantly affected by increases in acid concentration and temperature. Kinetic modeling of the data indicated that the use of microwave heating may account for an increase in reaction rate constant, k(1), found in this study in comparison with conventional systems described in the literature.

“Studies on glucose tolerant β-glucosidases from a novel Byssochlamys fulva and their applications in biomass to ethanol conversion”

Beta-glucosidases are critical enzymes in biomass hydrolysis process and is important in creating highly efficient enzyme cocktails for the bio-ethanol industry. Among the two strategies proposed for overcoming the glucose inhibition of commercial cellulases, one is to use heavy dose of BGL in the enzyme blends and the second is to do simultaneous saccharification and fermentation where glucose is converted to alcohol as soon as it is being generated. While the former needs extremely high quantities of enzyme, the latter is inefficient since the conditions for hydrolysis and fermentation are different. This makes the process technically challenging and also in this case, the alcohol generation is lesser, making its recovery difficult. A third option is to use glucose tolerant β-glucosidases which can work at elevated glucose concentrations. However, there are very few reports on such enzymes from microbial sources especially filamentous fungi which can be cultivated on cheap biomass as raw material. There has been very less number of studies directed at this, though there is every possibility that filamentous fungi that are efficient degraders of biomass may harbor such enzymes. The study therefore aimed at isolating a fungus capable of secreting glucose tolerant β- glucosidase enzyme. Production, characterization of β-glucosidases and application of BGL for bioethanol production were attempted.

Enzymatic hydrolysis of pretreated sugar cane bagasse using Penicillium funiculosum and Trichoderma harzianum cellulases

In this study, we investigated the enzymatic hydrolysis of pretreated sugarcane bagasse using eight different enzymatic blends obtained from concentrated crude enzyme extracts produced by Penicillium funiculosum and Trichoderma harzianum as well as from the extracts in combination with a commercial enzymatic cocktail. The influence of different levels of biomass delignification, degree of crystallinity of lignicellulose, composition of enzymatic activities and BSA on enzymatic hydrolysis yields (HYs) was evaluated. Our X-ray diffraction studies showed that crystallinity of lignocellulose is not a key determinant of its recalcitrance toward enzymatic hydrolysis. In fact, under the experimental conditions of our study, an increase in crystallinity of lignocellulosic samples resulted in increased glucose release by enzymatic hydrolysis. Furthermore, under the same conditions, the addition of BSA had no significant effect on enzymatic hydrolysis. The most efficient enzyme blends were obtained by mixing a commercial enzymatic cocktail with P. funiculosum or T. harzianum cellulase preparations (HYs above 97%) followed by the concentrated extract of P. funiculosum alone (HY= 88.5%). Increased hydrolytic efficiencies appeared to correlate with having an adequate level of both beta-glucosidase and xylanase activities in the blends. (C) 2011 Elsevier Ltd. All rights reserved.

Evaluation of 316L Stainless Steel Corrosion Resistance in Solution Simulating the Acid Hydrolysis of Biomass

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Optimal control strategy for fed-batch enzymatic hydrolysis of lignocellulosic biomass based on epidemic modeling

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The effect of power-ultrasound on the pretreatment of acidified aqueous solutions of banana flower-stalk: Structural, chemical and statistical analysis

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Dilute Acid Hydrolysis of Sugar Cane Bagasse at High Temperatures: A Kinetic Study of Cellulose Saccharification and Glucose Decomposition. Part I: Sulfuric Acid as the Catalyst

The kinetics of sugar cane bagasse cellulose saccharification and the decomposition of glucose under extremely low acid (ELA) conditions, (0.07%), 0.14%, and 0.28% H2SO4, and at high temperatures were investigated using batch reactors. The first-order rate constants were obtained by weight loss, remaining glucose, and fitting glucose concentration profiles determined with HPLC using the Saeman model. The maximum glucose yields reached 67.6% (200 degrees C, 0.07% H2SO4, 30 min), 69.8% (210 degrees C, 0.14% H2SO4, 10 min), and 67.3% (210 degrees C, 0.28% H2SO4, 6 min). ELA conditions produced remarkable glucose yields when applied to bagasse cellulose. The first-order rate constants were used to calculate activation energies and extrathermodynamic parameters to elucidate the reaction mechanism under ELA conditions. The effect of acid concentration on cellulose hydrolysis and glucose decomposition was also investigated. The observed activation energies and reaction orders with respect to hydronium ion for cellulose hydrolysis and glucose decomposition were 184.9 and 124.5 kJ/mol and 1.27 and 0.75, respectively.

Adding value to the Brazilian sisal: acid hydrolysis of its pulp seeking production of sugars and materials

The present work is inserted into the broad context of the upgrading of lignocellulosic fibers. Sisal was chosen in the present study because more than 50% of the world's sisal is cultivated in Brazil, it has a short life cycle and its fiber has a high cellulose content. Specifically, in the present study, the subject addressed was the hydrolysis of the sisal pulp, using sulfuric acid as the catalyst. To assess the influence of parameters such as the concentration of the sulfuric acid and the temperature during this process, the pulp was hydrolyzed with various concentrations of sulfuric acid (30-50%) at 70 A degrees C and with 30% acid (v/v) at various temperatures (60-100 A degrees C). During hydrolysis, aliquots were withdrawn from the reaction media, and the solid (non-hydrolyzed pulp) was separated from the liquid (liquor) by filtering each aliquot. The sugar composition of the liquor was analyzed by HPLC, and the non-hydrolyzed pulps were characterized by viscometry (average molar mass), and X-ray diffraction (crystallinity). The results support the following conclusions: acid hydrolysis using 30% H2SO4 at 100 A degrees C can produce sisal microcrystalline cellulose and the conditions that led to the largest glucose yield and lowest decomposition rate were 50% H2SO4 at 70 A degrees C. In summary, the study of sisal pulp hydrolysis using concentrated acid showed that certain conditions are suitable for high recovery of xylose and good yield of glucose. Moreover, the unreacted cellulose can be targeted for different applications in bio-based materials. A kinetic study based on the glucose yield was performed for all reaction conditions using the kinetic model proposed by Saeman. The results showed that the model adjusted to all 30-35% H2SO4 reactions but not to greater concentrations of sulfuric acid. The present study is part of an ongoing research program, and the results reported here will be used as a comparison against the results obtained when using treated sisal pulp as the starting material.