Thermochemical characterisation of straws and high yielding perennial grasses

The research is concerned with thermochemical characterisation of straws and high yielding perennial grasses. Crops selected for this study include wheat straw (Triticum aestivum), rape straw (Brassica napus), reed canary grass (Phalaris arundinacea) and switch grass (Panicum virgatum). Thermogravimetric analysis (TGA) was used to examine the distribution of char and volatiles during pyrolysis up to 900 °C. Utilising multi-heating rate thermogravimetric data, the Friedman iso-conversional kinetic method was used to determine pyrolysis kinetic parameters. Light and medium volatile decomposition products were investigated using pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) up to 520 °C. The 22 highest yielding identifiable cellulose, hemicellulose and lignin biomass markers were semi-quantified taking into consideration peak areas from GC chromatograms. Notable differences can be seen in butanedioic acid, dimethyl ester (hemicelluloses decomposition products), 2-methoxy-4-vinylphenol (lignin marker) and levoglucosan (intermediate pyrolytic decomposition product of cellulose) content when comparing perennial grasses with straw. From results presented in this study, perennial grasses such as switch grass, have the most attractive properties for fast pyrolysis processing. This is because of the observed high volatile yield content of 82.23%, heating value of 19.64 MJ/kg and the relatively low inorganic content.     

Evaluation of grape stalks as a bioresource

The compositional characteristics of grape stalk in terms of lignin, sugars, ash, extractives and tannins contents were established. The biomass composition of grape stalk is 34% lignin, 36% cellulose, 24% hemicellulose and 6% tannins. The tannins, analysed by solution ¹³C NMR, were essentially of procyanidin type and the dichloromethane extractives fraction, characterized by GC-MS, was mainly composed of fatty acids. Different processes for the pretreatment of grape stalk were compared. Due to the high content of lignin and tannins, dilute sulfuric acid and ethanol organosolv pretreatments resulted in a low degree of delignification. However, a wet oxidation process permitted a significant reduction of the Klason lignin content of the pulp with a good carbohydrate recovery and improved enzymatic digestibility.     

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.     

Chemical characterization of barks from Picea abies and Pinus sylvestris after fractioning into different particle sizes

The composition of Norway spruce (Picea abies (L.) Karst.) and Scots pine (Pinus sylvestris L.) barks was studied after grinding and fractioning into different particles sizes.Both barks fractionated well and with similar fraction yield profile. The yield of fines was low and the major fractions were larger particles, i.e. 2.4% and 3.1% of particles under 0.425 mm and 66.0% and 50.3% of particles over 2 mm, respectively for spruce and pine bark.The chemical composition of spruce and pine barks, as a mass weighed average of all granulometric fractions was, respectively: ash 3.3 and 4.6%; total extractives 21.6 and 18.8% (hydrophilic extractives were dominant), lignin 27.9 and 33.7% and holocellulose 42.7 and 37.6%. Suberin accounted for 1.3% and 1.6% of spruce and pine bark, respectively. The non-cellulosic monosaccharides showed in both barks predominance of arabinose followed by xylose and mannose.Ash elemental composition showed that N represented about 35% of the total inorganics, Ca 35% and K 17%. Zn, Cu, Ni, Cr and Pb were present in both barks at levels under 1% of the total inorganics. Spruce bark had in average higher contents compared to pine bark, except for Pb and Cr.Size reduction of spruce and pine bark did not apply randomly to the different components and instead resulted into partial separation of the inorganic and organic matter into different size particles. Fine particles concentrated higher amounts of inorganic material and of extractives.     

Cell morphology and chemical characteristics of corn stover fractions

This paper investigated cell morphology, chemical components, lignin distribution and inorganic elements distribution of corn stover fractions. Corn stover fractions, classified as stalk rind, stalk pith and leaf, had different tissues, cell morphology and chemical compositions. Corn stalk rind had good fiber morphological characteristics for papermaking, while stalk pith, having short fibers and high contents of parenchyma and vessel, was not suitable for papermaking. Stalk rind had the highest lignin and cellulose content but the lowest hemicellulose content among all the fractions. The major ash-forming elements in corn stover fractions were potassium, chlorine, silica, calcium, magnesium and sulfur. Potassium and chlorine took more than 86% of total inorganic elements in stalk rind while silica content was much higher in leaf and stalk pith than that in stalk rind. Perivascular sclerenchyma and subepidermal sclerenchyma of stalk rind were more lignified than the other tissues. The highest lignin concentration existed in cell middle lamella and corner. All corn stover fractions could be good biorefinery feedstock based on their main chemical compositions, though they are obviously heterogeneous in aspects of cell morphology and chemical characteristics.     

不同生育期橡胶树幼茎细胞壁三要素的变化动态

对巴西橡胶树热研7-33-97半年生组培苗的木质部不同发育时期的木质素、纤维素和半纤维素含量进行测定分析,用Van Soes方法计算得到木质素、纤维素和半纤维素的含量。结果表明,木质素、纤维素和半纤维素在生长发育过程中的含量随着生长发育逐渐增加。其中木质素与纤维素的含量随着生长发育趋于稳定状态,而半纤维素的含量从GX期开始迅速增加,直到SX期也没有出现趋向稳定的趋势;木质素/纤维素的比值在发育过程中变化不大,木质素/半纤维素的比值及纤维素/半纤维素的比值在GX期均达最大。木质素与纤维素的相关性显著,积累是同步的。     

Basic properties of grain by-products and their viability in polypropylene composites

The objective was to study the potential of grain by-products (husk) of grains such as wheat (Triticum aestivum L; German name is Weizen) and rice (Oryza sativa) as reinforcements for thermoplastics as an alternative to or in combination with wood fibres. Prior to composites preparation, the chemical components of fibres such as cellulose, hemi-cellulose, lignin, starch, protein and fat were measured and the surface chemistry and functionality of grain by-products were studied using EDX and FT-IR. Structural constituents (cellulose, starch) were found in wheat husk (W) equal 42%, in rice husk 50% and in soft wood 42%, respectively. Thermal degradation characteristics, the bulk density, water absorption and the solubility index were also investigated. Wheat husk (W) and rice husk were found thermally stable at temperatures as low as 178 °C and 208 °C, respectively. The particle morphology and particle size were investigated using microscopy. Water absorption properties of the fibres were studied to evaluate the viability of these fibres as reinforcements. Polypropylene composites were fabricated using a high speed mixer and an ensuing injection moulding process with 40 wt% fibre. The tensile and Charpy impact strength of the resulting composites were investigated. The tensile elongation at break was found to 75% for wheat husk (W) composites and 23% for rice husk composites better than soft wood composites. Rice husk composites showed 13% better Charpy impact strength than soft wood composites. Due to coupling agent, tensile strength of composites found to improve 25% for soft wood, 35% for wheat husk (W) and 45% for rice husk.     

Digestibility of dietary fiber components in vegetarian men

Digestibility of fiber components namely neutral detergent fiber (total content of cellwall) cellulose, hemicellulose and lignin are estimated in 14 healthy vegetarian men during adlibitum feeding and at 3 energy levels namely 2526, 2868 and 3290 kcals/day. Values of digestibility for adlibitum experiments were 34.17±2.3 for neutral detergent fiber (NDF), 30.1±3.9 for cellulose and 53.4±3.0 for hemicellulose and 8.1±2.6 for lignin. There was a considerable variability in digestibility of fiber components between individuals.     

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.     

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。     

玉米茎秆纤维组分近红外反射光谱模型的建立

以200份玉米自交系作为试验材料,利用近红外反射光谱技术建立3种茎秆组分的近红外光谱模型,研究更快速、准确地测定玉米茎秆中木质素、纤维素和半纤维素的含量的方法。结果表明,在4 017.94～8 053.28、4 017.94～8 067.89和4 027.08～8 928.20谱区内建立的测定玉米茎秆木质素、纤维素和半纤维素含量的近红外光谱模型效果最好。利用偏最小二乘回归法建立校正模型,木质素、纤维素和半纤维素的校正相关系数分别为0.932 9、0.925 1和0.926 5,校正标准差分别为1.57、1.68和1.18。选取30份玉米茎秆样品作为检验集对模型进行验证,木质素、纤维素和半纤维素的外部相关系数分别为0.938 9、0.891 1和0.905 0,其预测标准差分别为1.57、2.14和1.49。同样选取30份茎秆样品对模型进行交叉验证,其相关系数分别为0.897 3、0.944 2和0.891 8,交叉验证标准差分别为1.87、2.32和1.43。研究结果表明,所建模型质量较好,能快速、准确测量玉米茎秆木质素、纤维素和半纤维素含量。     

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.     

Relationships involving several types of extractives of five native argentine wood species of genera Prosopis and Acacia

The relationships existing among the values obtained when extracting the wood of four Argentinean species of Prosopis (P. alba, P. kuntzei, P. nigra, and P. ruscifolia) and one of the Acacia (A. aroma) by several procedures were evaluated and discussed. The used methods were: extraction in toluene/ethanol and hot water; determination of tannic and non-tannic content; measurement of phenolic compounds. Additionally, liquid chromatography (HPLC) was also used in order to quantitatively evaluate the content of (−)-mesquitol, a relatively unusual flavonoid (flavanol type). The total amount of Oxidation Products was also measured. They result from oxidation and polymerization processes of phenolic compounds occurring during heartwood formation, and were not separated during chromatographic analysis. Data evidenced a linear trend (R² = 0.970) between organic and tannic extractives of all species, and a similar one (R² = 0.927) between total phenols and tannic (or organic) extractives in the case of heartwood of Prosopis species. Interestingly, for sapwood very different values of organic extracts, tannic content or Oxidation Products type compounds were measured in spite of a similar amount of phenolic substances. Moreover, the various species presented the same peaks in chromatograms, thus evidencing the chemical similarity of compounds but a different quantity between heartwood and sapwood and also among the various species. The observed similarity implied that the various methods of extraction did not really extract only a single class of substances, and that great care must be adopted when using some specific procedures for extractions.Furthermore, the existing relationships between extractives and selected technological properties, namely specific volumetric shrinkage coefficient (BSvol) and natural durability (evaluated in terms of mass loss after fungal attacks in laboratory conditions), were given. It appeared that in heartwood BSvol was well correlated to organic extractives (R² = 0.984), thus evidencing the microimpregnation of cell walls by extractives, but the fitting quality of the correlation was dependent on the type of extractives used. Analogously, a good relationship between mass loss and phenolic compounds existed (R² = 0.764), and in this case the value of R² was even more dependent on the considered extracts. Moreover, the availability of quantitative data on several Prosopis species allowed to consistently evaluate the bioactivity of (−)-mesquitol on the resistance against fungal attack, and the logarithmic form of the relationship between mass loss and (−)-mesquitol content suggested a direct fungicidal activity of this compound. On the other hand, data also evidenced that neither phenolic compounds nor (−)-mesquitol can be considered as the unique and definite factor able to determine the durability of the considered species.     

Composite materials of thermoplastic starch and fibers from the ethanol-water fractionation of bagasse

The aim of this study was to evaluate the potential of the fibrous material obtained from ethanol-water fractionation of bagasse as reinforcement of thermoplastic starches in order to improve their mechanical properties. The composites were elaborated using matrices of corn and cassava starches plasticized with 30 wt% glycerin. The mixtures (0, 5, 10 and 15 wt% bagasse fiber) were elaborated in a rheometer at 150 °C. The mixtures obtained were pressed on a hot plate press at 155 °C. The test specimens were obtained according to ASTM D638. Tensile tests, moisture absorption tests for 24 days (20-23 °C and 53% RH, ASTM E104), and dynamic-mechanical analyses (DMA) in tensile mode were carried out. Images by scanning electron microscopy (SEM) and X-ray diffraction were obtained. Fibers (10 wt% bagasse fiber) increased tensile strength by 44% and 47% compared to corn and cassava starches, respectively. The reinforcement (15 wt% bagasse fiber) increased more than fourfold the elastic modulus on starch matrices. The storage modulus at 30 °C (E_30 °C′) increased as the bagasse fiber content increased, following the trend of tensile elastic modulus. The results indicate that these fibers have potential applications in the development of biodegradable composite materials.     

Relationship of physicochemical characteristics and hydrolyzed hydroxycinnamic acid profile of barley varieties and nutrient availability in ruminants

The objectives of this study were to (1) investigate the relationship between physicochemical characteristics (mean/median particle sizes, physical hull content) and hydrolyzed hydroxycinnamic acid profile (ferulic acid (FA), para-coumaric acid (pCA), and their ratio) of barley varieties and in situ rumen degradability in dairy cattle; and (2) investigate rumen degradation kinetics of FA and pCA of CDC barley varieties grown in western Canada. Barley variety had a significant effect (P < 0.05) on rumen undegradable fraction of DM, FA, pCA, neutral (NDF) and acid detergent fiber (ADF) at 12 and/or 24 h of rumen incubation. FA in barley grain was more degradable than the pCA (P < 0.05). There were no differences (P > 0.05) in effective degradability of DM (EDDM) and EDFA, but significant differences in EDpCA (P < 0.05). Barley hull was strongly correlated to NDF, ADF, ADL, hemicellulose and cellulose (R > 0.78, P < 0.001) and correlated to FA (R = 0.57, P < 0.05) but not to pCA (R = 0.42, P > 0.05) in original samples. FA and pCA were highly and positively correlated to NDF, ADF, ADL, hemicellulose, cellulose, mean/median particle sizes, and rumen indigestible DM, NDF and ADF at either 12 or 24 h (P < 0.05). Mean/median particle size of barley grain positively influenced the rumen indigestible DM, but not others (FA, pCA). The results implied that reduction of barley hull, FA and pCA contents could increase the degradability of barley grain in rumen. Multi-regression with best model variable selection analysis revealed that FA was the factor most inhibiting to DM degradability of barley in rumen, and was the most effective factor to predict DM degradability, while hull was the most effective factor to determine NDF degradability in rumen. Both hull and FA affected ADF degradability in the rumen. The results indicate that breeding or identifying barley varieties with lower hull and FA contents would result in higher degradability, higher energy density and higher quality barley and improve nutrient availability of barley.     

玉米秸秆能量指标的测定和利用研究

通过对15个杂交种及其22个亲本自交系的茎秆热值及其化学组分的测定,结果表明:秸秆热值与秸秆产量和子粒产量关系密切;不同材料间、同一材料不同部位间的热值及半纤维素、纤维素、木质素含量存在差异;同一材料的热值及纤维素、木质素含量从上部到下部逐渐增多,半纤维素含量逐渐减少;热值与纤维素、木质素含量间有密切相关回归关系,其回归方程为Y=10 523.6+13 273.4X₁+15 908.9X₂,初步确定纤维素、木质素作为秸秆的主要能量指标;根据热值、产量性状结果,认     

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.     

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.     

Improving the barrier and mechanical properties of corn starch-based edible films: Effect of citric acid and carboxymethyl cellulose

The films produced from pure starch are brittle and difficult to handle. Chemical modifications (e.g. cross-linking) and using a second biopolymer in the starch based composite have been studied as strategies to produce low water sensitive and relatively high strength starch based materials. A series of corn starch films with varying concentrations (0-20%, W/W) of citric acid (CA) and carboxymethyl cellulose (CMC) were produced by casting method. The effects of CA and CMC on the water vapor permeability (WVP), moisture absorption, solubility and tensile properties were investigated. The water vapor barrier property and the ultimate tensile strength (UTS) were improved significantly (p < 0.05) as the CA percentage increased from 0 to 10% (W/W). At the level of 15% (W/W) CMC, the starch films showed the lowest WVP values (2.34 × 10⁻⁷ g Pa⁻¹ h⁻¹ m⁻¹) and UTS increased from 6.57 MPa for the film without CMC to 16.11 MPa for that containing 20% CMC.