Dissolving lignocellulosic biomass in a 1-butyl-3-methylimidazolium chloride-water mixture

An ionic liquid (IL)-water mixture employed to treat lignocellulosic biomass is promising. The addition of water decreases viscosity and process cost so as to improve the IL practical application. In this work, effects of temperature (50-170 °C), water content (0-80 wt%), treating duration (0.5-4 h) and pressure (0.1-3.2 MPa) on treating legume straw process using a 1-butyl-3-methylimidazolium chloride ([C₄mim]Cl)-water mixture were experimentally investigated. Legume straw was found to be partially dissolved, and the dissolved substances can be flocculated by adding the coagulating agent—water (equal to volume of the solution). For this process at 0.1 MPa, the maximum 29.1 wt% legume straw is dissolved in the [C₄mim]Cl-water mixture with water content of 20 wt% at 150 °C during 2 h, which is much higher than 9.8 wt% using pure [C₄mim]Cl. A hemicellulose-free lignin-rich material (64.0 wt% lignin and 35.3 wt% cellulose) is obtained by adding the water. Even for 0.5 h, 22.3 wt% of legume straw is dissolved in the case of water content of 20 wt%, 150 °C and 0.1 MPa. High pressure favors the dissolution of legume straw but lignin content in the residue has no obvious change. The addition of proper amount of water facilitates the dissolution of legume straw and a relative rapid dissolving rate can be achieved in a [C₄mim]Cl-water mixture. There are great differences in chemical and physical properties between legume straw and the obtained samples (residue and floc) due to the dissolution and reconstitution.     

Thermogravimetric analysis and the optimisation of bio-oil yield from fixed-bed pyrolysis of rice husk using response surface methodology (RSM)

The effects of pyrolysis temperature, heating rate, particle size, holding time, and gas flow rate were investigated to optimize bio-oil yield from rice husk pyrolysis. Thermogravimetric analysis showed thermal degradation of hemicellulose, cellulose and lignin, indicating faster decomposition of cellulose compared to lignin. The optimisation process was analysed by employing central composite design (CCD) in response surface methodology (RSM) using Design Expert Version 7.5.1 (StatEase, USA). A two-level fractional factorial was initially carried out and followed by RSM. The statistical analysis showed that pyrolysis temperature, heating rate, particle size and holding time significantly affected the bio-oil yield. By utilising response surface method, these four factors were investigated, analysed and optimal conditions were obtained at pyrolysis temperature of 473.37 °C, heating rate of 100 °C/min, particle size of 0.6 mm and holding time of 1 min. Confirmation runs gave 48.30% and 47.80% of bio-oil yield compared to 48.10% of predicted value. Furthermore, the pyrolytic bio-oils obtained from fixed-bed pyrolysis were examined using gas chromatographic/mass spectroscopy (GC/MS), Fourier transform infrared (FTIR) methods, elemental analyzer, pH probe and bomb calorimeter.     

Sequential extractions and structural characterization of lignin with ethanol and alkali from bamboo (Neosinocalamus affinis)

A sequential process with the combination of ethanol and alkali aqueous solutions was utilized to extract lignin from bamboo (Neosinocalamus affinis), a potential lignocellulosic material. In this case, the successive treatments of dewaxed bamboo with 70% ethanol at 80 °C, 0.2 and 0.5 M NaOH, 70% ethanol containing 0.6 M NaOH, and 1.0, 2.0, and 3.0 M NaOH at 50 °C, resulted in a total yield of acid-insoluble lignin fractions of 10.06%, corresponding to release of 62.25% original lignin from the cell walls. The lignin fractions obtained were then characterized by GPC, FT-IR, NMR spectroscopy, and sugar analysis. As compared to the alkali lignin fractions, the ethanol-soluble lignin fraction had a relatively higher molecular weight (2670 g/mol) and the content of carbohydrates primarily consisted of glucose 2.01% and xylose 1.90%. This suggested that the carbohydrate chains linked to lignin may increase the hydrodynamic volume of lignin and therefore increase the apparent molecular weight of the ethanol-soluble lignin. HSQC spectra analysis revealed that the alkali lignin fractions consisted mainly of β-O-4′ linkages combined with small amounts of β-β′, β-5′, β-1′ linkages, and p-hydroxycinnamyl alcohol end groups. Furthermore, minor amounts of esterified p-coumaric and ferulic acids were also detected in the lignins isolated.     

Characterization of depolymerized residues from extremely low acid hydrolysis (ELA) of sugarcane bagasse cellulose: Effects of degree of polymerization, crystallinity and crystallite size on thermal decomposition

Sugarcane bagasse cellulose was subjected to the extremely low acid (ELA) hydrolysis in 0.07% H₂SO₄ at 190, 210 and 225 °C for various times. The cellulose residues from this process were characterized by TGA, XRD, GPC, FTIR and SEM. A kinetic study of thermal decomposition of the residues was also carried out, using the ASTM and Kissinger methods. The thermal studies revealed that residues of cellulose hydrolyzed at 190, 210 and 225 °C for 80, 40 and 8 min have initial decomposition temperature and activation energy for the main decomposition step similar to those of Avicel PH-101. XRD studies confirmed this finding by showing that these cellulose residues are similar to Avicel in crystallinity index and crystallite size in relation to the 110 and 200 planes. FTIR spectra revealed no significant changes in the cellulose chemical structure and analysis of SEM micrographs demonstrated that the particle size of the cellulose residues hydrolyzed at 190 and 210 °C were similar to that of Avicel.     

Thermal transitions of the amorphous polymers in wheat straw

The thermal transitions of the amorphous polymers in wheat straw were investigated using dynamic mechanical thermal analysis (DMTA). The study included both natural and solvent extracted wheat straw, in moist (8-9% water content) and dry conditions, and was compared to spruce samples. Under these conditions two transitions arising from the glass transition of lignin and hemicelluloses have been identified. Key transitions attributed to softening of lignin were found at 53, 63 and 91 °C for moist samples of wheat straw, extracted straw and spruce, respectively. Transitions for hemicelluloses were determined at 2, −1 and 5 °C, respectively. Differences are likely due to different compositions of lignin and hemicelluloses from straw and spruce and structural differences between the raw materials. The high wax content in wheat straw resulted in a transition at about 40 °C which was absent in solvent extracted wheat straw samples and spruce. This specific transition was further investigated and confirmed by differential scanning calorimetry (DSC) of extracted wheat straw wax. Information about the thermal transitions is of great importance for the utilization of wheat straw in pelletizing, briquetting and fiber board manufacturing.     

Processing of Lespedeza stalks by pretreatment with low severity steam and post-treatment with alkaline peroxide

The steam pre-treatment with low severity preserves valuable biomass components, and further delignification with alkaline peroxide could improve hydrolysis. A combination of low severity steam pretreatment and alkaline peroxide post-treatment of Lespedeza stalks was investigated. The post-treatment of steam-pretreated Lespedeza stalks with alkaline peroxide significantly increased the cellulose content and changed the structure of the cellulose-rich fractions. A glucose yield of 503.5 mg g⁻¹ raw material from enzyme hydrolysis was obtained when the steam-pretreated material (184 °C for 4 min) was post-treated with 2% hydrogen peroxide at 60 °C for 24 h with a substrate concentration of 3.3%. Its hydrolysis yield is 88.8%, which is higher than that of samples processed by steam pretreatment alone (63.7%). The samples obtained by post-treatment with alkaline peroxide were found to have a smoother surface and looser structure in scanning electron microscopy images. The isolated lignin preparations had a yield range from 10.9 to 14.7 (% dry matter). The lignin was characterized by thermogravimetric analysis/differential thermal analysis, Fourier transform infrared spectroscopy, and gel permeation chromatography. Alkaline peroxide treatment increased the thermal stability of lignin, and decreased the amounts of all functional groups. Depolymerization and repolymerization occurred during the alkaline peroxide treatment.     

油料作物秸秆快速热解及其生物油特性的研究

以油菜秸秆、脱灰油菜秸秆、花生秸秆及芝麻秸秆等为原料,在小型流化床上进行了快速热解试验研究。从纤维素、半纤维素、木质素含量与灰分含量等原料品质方面,对热解产物分布以及生物油特性的影响进行了对比分析。结果表明,不同秸秆的纤维素、半纤维素、木质素的含量不同,其热解产物分布有所不同,纤维素与半纤维素含量高的秸秆,生物油产率较高。灰分对热解产物分布影响较大,脱除灰分有利于提高生物油的产率;脱除灰分对秸秆生物油品质有一定影响,其生物油的pH值、密度、运动粘度高于其它秸秆生物油。油菜秸秆、花生秸秆、芝麻秸秆生物油主要品质指标基本一致。     

Gorse (Ulex europæus) as a possible source of xylans by hydrothermal treatment

Autocatalytic hydrothermal process conditions were used to study Ulex europæus (Gorse) as a source of xylan compounds. The aim was to study the possibilities for using this unutilised biomass material to produce xylans. Ulex is an evergreen shrub that grows in the northwest of Spain and has no economic value. Therefore, Ulex is considered a promising candidate as a biomass source. Ulex showed a total xylose content of 12%, thus qualifying it as a suitable material to extract xylan-derived compounds. Autohydrolysis was applied to extract xylans from Ulex. To find the best conditions for xylan extraction, samples of Ulex were subjected to different temperatures and time conditions. Results indicate that autohydrolysis is a suitable method to selectively extract xylans at temperatures between 160 and 190 °C for 5-30 min, reaching a maximum xylan recovery of almost 63% of the initial xylan at 180 °C for 30 min, with only small effects on cellulose and lignin contents.     

Temperature-induced structural and chemical changes in cork from Quercus cerris

The effects of temperature on anatomical and chemical characteristics of Quercus cerris cork were examined. Cork samples were subjected to isothermal air heating between 150 °C and 400 °C and analyzed for mass loss, cellular structure and chemical composition.The thermal decomposition of Q. cerris cork is similar to that of Q. suber cork. Cork is thermally stable below 200 °C and after that degradation depended on temperature and heating time with increasing mass loss, i.e. 3% at 200 °C 10 min and 46% at 350 °C 60 min. With temperature and starting at 200 °C, cells expanded, cell wall thickness was reduced and corrugations were lost.Extractives degraded at lower temperatures, although aliphatic extractives were found to be more stable. Suberin from Q. cerris was more heat resistant than Q. suber suberin, while lignin showed similar resistance.These results provide a basis for studies on the production of Q. cerris bark expanded cork agglomerates for insulation purposes.     

Chemical characterization of various parts of nipa palm (Nypa fruticans)

The current study was initiated to characterize various parts of nipa palm (Nypa fruticans) to establish whole utilization of this biomass as potential raw material for fuels and chemicals. Nipa consisting of frond, shell, husk and leaf was chemically characterized for cellulose, hemicellulose, lignin, starch, protein, extractives and inorganic constituents for its each part. The total chemical composition showed that the cellulose and hemicellulose contents were in the range of 28.9-45.6 wt% and 21.8-26.4 wt%, respectively. The hemicellulose was rich with glucuronoxylan. The lignin content was 19.4-33.8 wt% with the highest lignin content found in leaf. The alkaline nitrobenzene oxidation products showed that nipa palm lignin mainly consists of guaiacyl and syringyl propane units with a small amount of p-hydroxyphenylpropane unit. Besides the main chemical components, starch, protein and extractives were also present in significant amounts from 2 to 8 wt%. Additionally, the ash content was high from 5.1 to 11.7 wt%, consisting of the major inorganic elements being Na, K and Cl with minor inorganic elements of Mg, Ca, Si, P, S and Al. Overall, each part of the nipa palm has its individual superior characteristics and could be exploited as lignocellulosic resources for fuels and chemicals.     

Effect of pre-extraction on soda-anthraquinone (AQ) pulping of rice straw

The effect of hot-water and alkaline pre-extraction of rice straw on soda-anthraquinone pulping was carried out. The pre-extraction with hot water at 150 °C for 1 h dissolved 34.7% biomass and the pre-extracted liquor comprised of 16.6% sugars, 6.7% lignin, 6.6% acetic acid and other unknown products. But the pre-extraction with 1% NaOH at 100 °C for 1 h dissolved 10.2% sugars, 5.1% lignin and 10% acetic acid from rice straw. Pre-extracted rice straw was cooked by soda-anthraquinone process with varying alkali charges. The pulp from pre-extracted rice straw was low in kappa number with reduced pulp yield. The drainage resistance (°SR) improved obviously on pre-extraction of rice straw. Pulp strength properties such as the tensile index and the burst index were found to be lower, but the tear index was higher both with hot-water and alkaline pre-extraction. After bleaching, the gaps of the overall pulp yield and strength properties between pre-extracted and non-extracted rice straw became narrower. The alkaline pre-extraction showed improved yield and properties compared with hot-water pre-extracted rice straw.     

Structural characterization and isolation of lignin and hemicelluloses from barley straw

Structural characterization and isolation of lignin and hemicelluloses from crops are very important for industrial utilization. In this paper, the sequential treatments of barley straw using 90% dioxane, 80% acidic dioxane, 100% dimethyl sulfoxide, and 8% NaOH released total 93% of original lignin and 87% of original hemicelluloses. The extractions with acidic dioxane and dimethyl sulfoxide produced the original hemicelluloses and high-condensed lignin mainly from the middle lamella. FT-IR and NMR analyses show that the hemicelluloses of barley straw contain acidic arabinxylans as the major polysaccharides, which are substituted by α-l-arabinofuranose, 4-O-methyl-glucuronic acid, acetyl group (DS = 0.13), and xylose at O-3 and/or O-2 of xylan, and lignin contains β-O-4′ as a predominant interunit linkage with high amounts of β-5′ and β-1′. The guaiacyl and syringyl units are more etherified, and the proportion of erythro-β-O-4′ is slightly higher than that of threo-β-O-4′ in the lignin of barley straw.     

Biorefining of perennial grasses: Development of visible and near infrared tools for assessing fineness of extracted fibre

The biorefining of grass offers an opportunity to integrate primary production agriculture with the extraction of fibre. The study was aimed at developing protocols for processing ryegrass to determine fibre content and to generate visible and near infrared reflectance (Vis-NIR) calibrations for estimating fibre fineness with the aid of a new reference airflow method. The method for determining fineness of processed fibres has been adapted from flax fibre protocols. A Vis-NIR calibration using partial least squares (PLS) regression method was employed to generate models with a calibration set consisting of 85 samples obtained from fresh and ensiled grasses. The PLS model was successfully validated with 21 independent samples with a prediction error of 1.26 dtex. An optimised PLS model (r² = 0.86) consisting of 106 samples has been developed. The quality assurance protocols could be used for assessing fibre content and quality of silage, hay and fresh grass.     

Kinetic modeling of enzymatic saccharification using wheat straw pretreated under autohydrolysis and organosolv process

The enzymatic saccharification kinetics of untreated wheat straw, pretreated solids obtained by a sequence of autohydrolysis (solubilization of hemicellulose) and organosolv (solubilization of lignin) were studied together with two pure cellulose model substrates, filter paper and Avicel. Two kinetic models for glucose production were compared and its kinetic constants calculated. According to the obtained results, enzymatic saccharification of the autohydrolysis pretreated solids (APS) proved to be more effective than when the organosolv pretreated solids (OPS) were used. The maximum extent of the enzymatic conversion of cellulose to glucose was 90.88% and 64.04%, for APS and OPS respectively, at 96 h. This result was probably due to an increase in accessible area for APS and a possible inhibition by phenolic acids deposited on the surface of OPS, acting as a barrier for enzymatic saccharification. Initial saccharification rate for APS and OPS was 0.47 g/(L h) and 0.34 g/(L h), respectively. Models based on first and second order cellulase deactivation kinetics satisfactory predicted the behavior of glucose production, however the second order model had a higher accuracy than the first order one. Visualization of structural modification induced by enzymatic saccharification at 12 h for the pretreated solids was done using scanning electron microscopy.     

Sugarcane bagasse whiskers: Extraction and characterizations

This work evaluates the use of sugarcane bagasse (SCB) as a source of cellulose to obtain whiskers. These fibers were extracted after SCB underwent alkaline peroxide pre-treatment followed by acid hydrolysis at 45 °C. The influence of extraction time (30 and 75 min) on the properties of the nanofibers was investigated. Sugarcane bagasse whiskers (SCBW) were analyzed by transmission electron microscopy (TEM), X-ray diffraction (XRD) and thermogravimetric analysis (TGA) in air atmosphere. The results showed that SCB could be used as source to obtain cellulose whiskers and they had needle-like structures with an average length (L) of 255 ± 55 nm and diameter (D) of 4 ± 2 nm, giving an aspect ratio (L/D) around 64. More drastic hydrolysis conditions (75 min) resulted in less thermally stable whiskers and caused some damage on the crystal structure of the cellulose as observed by XRD analysis.     

Jatropha curcas seed cake as substrate for production of xylanase and cellulase by Aspergillus niger FGSCA733 in solid-state fermentation

Jatropha curcas seed-cake was evaluated for use as a solid state fermentation substrate for production of cellulolytic and xylanolytic enzymes by Aspergillus niger. Supplementation of the seedcake with 10% thatch grass (Hyperrhaenia sp.) resulted in a fivefold increase in xylanase production. Ammonium chloride supplementation increased production of xylanase by 13%. Under the same conditions, cellulase production was not influenced by supplementation with grass or the nitrogen sources used. Maximum xylanase was produced at 25 °C whilst cellulase was maximally produced at 40 °C. Highest xylanase activity was obtained when the cultures had an initial pH of 3 whereas cellulase was maximally produced at an initial pH of 5. Under optimised conditions, 6087 U and 3974 U of xylanase and cellulase respectively were obtained per gram of substrate. Zymograms of crude enzyme extracts showed six active bands ranging from 20 kDa to 43 kDa for cellulase and a 31 kDa active band for xylanase.     

Optimization of ethanol production by Saccharomyces cerevisiae UFPEDA 1238 in simultaneous saccharification and fermentation of delignified sugarcane bagasse

Ethanol production by Saccharomyces cerevisiae UFPEDA1238 was performed in simultaneous saccharification and fermentation of delignified sugarcane bagasse. Temperature (32 °C, 37 °C), agitation (80; 100 rpm), enzymatic load (20 FPU/g cellulose and 10%, v/v β-glucosidase or 10 FPU/g cellulose and 5% β-glucosidase) and composition of culture medium were evaluated. Ethanol concentration, enzymatic convertibility of cellulose and volumetric productivity were higher than 25 g/L, 72% and 0.70 g/L h, respectively, after 30 h, when the culture medium 1 and 20 FPU/g cellulose/10%, v/v β-glucosidase or the culture medium 2 and 10 FPU/g cellulose/5% β-glucosidase were used in SSF at 37 °C and 80 rpm. In the SSF with culture medium 2 (supplemented with ammonium, phosphate, potassium and magnesium), 150 L ethanol/t bagasse was achieved, with minimum enzyme loading (10 FPU/g cellulose and 5%, v/v β-glucosidase) for 8%, w/v of solids, which is often an important requirement to provide cost-efficient second generation ethanol processes.     

Lignin content and briquette quality of different fibre hemp plant types and energy sunflower

Fibre hemp and energy sunflower are potential energy crops for production of solid biomass as renewable energy. The current study estimated (i) the lignin content of fibre hemp and energy sunflower plants grown on different nitrogen treatments and (ii) the quality of the briquettes made from different plant types of fibre hemp (i.e. monoecious and dioecious), energy sunflower and the combination of fibre hemp and energy sunflower. The monoecious and dioecious fibre hemp cultivars (Chameleon, Finola and Santhica-27, USO-31, respectively) and the energy sunflower cultivar Wielkopolski were grown in the experimental field in 2008-2010 on Stagnic Luvisol soil. The plants were grown on N treatments of N0, mineral nitrogen (100 kg N ha⁻¹), cattle slurry (100 kg N ha⁻¹), sewage sludge (100 kg N ha⁻¹) and vetch (100 kg N ha⁻¹). Calorific values (16.6-17.4 MJ kg⁻¹) of briquettes pressed from different materials did not differ significantly and had relatively low sulphur (<0.05%) and chlorine content (0.03-0.37%). Briquettes with higher compactness were made from the sunflower and the dioecious hemp. Dioecious hemp had significantly higher lignin content. The dioecious hemp needs lower GDD values for maturating, its stems lignin content was higher than of monoecious hemp by harvest time and therefore this plant type is more suitable for briquetting in Nordic climatic conditions. Comparison of the different N treatments indicated that application of sewage sludge decreased the emergence and density of the fibre hemp plants and the lignin content per kg of DM.     

Herbage production and quality of a range of secondary grass species at five rates of fertilizer nitrogen application

The productivity of ten grasses was measured under six cuts per annum for 3 years and three cuts for a fourth harvest year in comparison with a perennial ryegrass (Lolium perenne) control. The grasses were Yorkshire fog (Holcus lanatus), two red fescues (Festuca rubra), creeping bent (Agrostis stolonifera), bent (Agrostis castellana), bent (Agrostis capillaris), smooth meadow-grass (Poa pratensis), crested dogstail (Cynosurus cristatus), sweet vernal (Anthoxanthum odoratum) and timothy (Phleum bertolonii). Another grass sown, rough meadow-grass (Poa trivialis), did not persist after the first harvest year. Annual N rates were 0, 120, 240, 360 and 480 kg ha^?1. Classified by DM production, the grasses grouped into: high (perennial ryegrass, Yorkshire fog and red fescue), intermediate (creeping bent, bent (A. castellana), crested dogstail and smooth meadow-grass) and low (bent (A. capillaris), sweet vernal and timothy. With frequent cutting, production ranking interacted with N rate: Yorkshire fog. red fescue and creeping bent were more productive than ryegrass at the 0 N and 120 N rates but not at higher N rates; crested dogstail and sweet vernal outperformed ryegrass at 0 N; ryegrass and smooth meadow-grass performed relatively better at moderate to high N. DM production of ryegrass was matched or exceeded by some of the other grasses during different parts of the season particularly at low N rates. Notable features from the 3-cut regime were the outstanding DM production of Yorkshire fog at all N rates and the poor production of bent (A. capillaris) and crested dogstail. High DM response to applied N in both cutting regimes was given by perennial ryegrass. smooth meadow-grass, red fescue cv. Boreal, timothy, crested dogstail and Yorkshire fog. N concentrations were highest in less productive grasses such as the bents and lowest in highly productive ryegrass and Yorkshire fog. Ryegrass was superior in digestibility to the other grasses, but especially to the red fescues, bents and smooth meadow-grass. The other grasses, especially Yorkshire fog and bent (A. capillaris) were superior to ryegrass in P, K and Mg concentrations, but not Ca. It is concluded that the annual and/or seasonal production of some of the secondary grasses at low to moderate N rates, e.g. the performance of Yorkshire fog and red fescue, warrant a reconsideration of their poor reputation, particularly within the context of increasing grassland extensification. Breeding to improve selected characteristics, such as digestibility in red fescue, seems justified. Assessment of the grazing and ensiling qualities of secondary grasses require further study.     

Characteristics, composition and thermal stability of Acacia senegal (L.) Willd. seed oil

The chemical composition, main physicochemical properties and thermal stability of oil extracted from Acacia senegal seeds were evaluated. The oil, moisture and the ash contents of the seeds were 9.80%, 6.92% and 3.82%, respectively. Physicochemical properties of the oil were iodine value, 106.56 g/100 g of oil; saponification value, 190.23 mg KOH/g of oil; refractive index (25 °C), 1.471; unsaponifiable matter, 0.93%; acidity, 6.41% and peroxide value, 5.43 meq. O₂/kg of oil. The main fatty acids in the oil were oleic acid (43.62%) followed by linoleic acid (30.66%) and palmitic acid (11.04%). The triacylglycerols (TAGs) with equivalent carbon number ECN 44 (34.90%) were dominant, followed by TAGs ECN 46 (28.19%), TAGs ECN 42 (16.48%) and TAGs ECN 48 (11.23%). The thermal stability analysed in a normal oxidizing atmosphere showed that the oil decomposition began at 268.6 °C and ended at 618.5 °C, with two stages of decomposition at 401.5 °C and 576.3 °C. According to these results, A. senegal seed oil has physicochemical properties, fatty acids composition and thermal characteristics that may become interesting for specific applications in several segments of food and non-food industries.