Fractional extraction and physico-chemical characterization of hemicelluloses and cellulose from sugar beet pulp

Four hemicelluloses and cellulose fractions were extracted with 10% KOH or 7.5% NaOH at 15°C for 16 h and with 24% KOH or 17.5% NaOH at 15°C for 2 h from defatted, protein and pectin free, lignified or delignified sugar beet pulp (SBP). There was no significant difference in the yield and sugar composition of isolated hemicelluloses and cellulose obtained from four different procedures. 7.5% NaOH extraction at 15°C for 16 h from lignified SBP gave a slightly higher yield of hemicelluloses (10.96%), while 24% KOH extraction at 15°C for 2 h from delignified SBP produced the highest yield of cellulose (18.35%). Molecular-average weights ranged from 88 850 to 91 330 Da for the hemicelluloses obtained from lignified SBP, and 21 620–21 990 Da for the hemicelluloses isolated from delignified SBP. The neutral sugar composition of the hemicelluloses consisted of glucose, arabinose, galactose, xylose, and minor quantities of rhamnose and mannose. The infrared spectra showed an absorption band at 900 cm⁻¹, indicating some amounts of β-linked polysaccharides. Besides ferulic and p-coumaric acids, six other phenolics were also identified in the mixture of alkaline nitrobenzene oxidation of associated lignin in the isolated hemicelluloses and cellulose fractions.     

Multiple response optimization of alkaline pretreatment of sisal fiber (Agave sisalana) assisted by ultrasound

A procedure for the alkaline pretreatment of sisal fiber assisted by ultrasound was optimized to obtain a higher solubilization of hemicellulose and the removal of lignin with cellulose fraction maintenance. A full factorial design 2³ was used for the evaluation of the effects of the variables (sonication time, NaOH concentration, and sonication amplitude) on the pretreatment. The optimal values for the variables using the Doehlert matrix for the sonication time, NaOH concentration, and sonication amplitude were 27 min, 4.1% (m/v), and 50%, respectively. The X-ray diffractometry and scanning electron microscopy analyses, after pretreatment, showed changes in chemical structure and morphology due to the removal of 82% of hemicellulose and 86% of lignin from sisal fiber. The soft reaction conditions and relatively short times demonstrated the effectiveness of the combined action of ultrasound with alkaline pretreatment to improve the accessibility to cellulose in this important step of the ethanol production process from biomass.     

Modification of corn cob meal with quarternary ammonium groups

Corn cob meal was modified with quarternary ammonium groups and subsequently extracted with 80% ethanol, water, and 5% NaOH. The fractions obtained had lower polydispersities, values, and yields than unmodified material. The yields are lower than those obtained on bagasse under the same conditions. The modification caused the drastic degradation of the ethanol-lignin (EL) fraction. The one-step extraction with NaOH/H₂O₂ gave 28·8% yield of material (calculated on the starting material) which contained 12·0% Klason lignin, and had the highest polydispersity (4·3, ). The water-soluble fractions consisted of arabinoglucuronoxylan and alkali-soluble fractions of xylan without other sugar moieties. The water-soluble fraction from NaOH/H₂O₂ extraction contained arabinoglucuronoxylan with modified arabinose and acid units. By this method higher yields could be obtained than on bagasse treated by the sequential extraction.     

Gelation mechanism of agarose

The non-Newtonian behavior and dynamic viscoelasticity of a series of aqueous solutions of agarose were measured with a rheogoniometer. The flow curve, at 25°, of agarose solution approximated to plastic behavior at 0.1, 0.13, and 0.15% concentrations. Gelation occurred at concentration of 0.13% at low temperature (0°). The dynamic modulus of agarose showed a very high value at low temperature, and increased with an increase in temperature, showing a maximum value at 30°, then it decreased. In the presence of NaCl, KCl, CaCl₂, and MgCl₂ for a solution of agarose at 0.08% concentration, the transition temperature, at which dynamic modulus decreased rapidly, was observed at 60°. Gelation was also observed at low temperature (0°) in acid and alkaline range after reaching pH values of 2.3 and 9.5, respectively, by addition of 100m HCl, H₂SO₄, NaOH, and Ca(OH)₂ to a 0.08% agarose solution. A possible mode of intra- and inter-molecular hydrogen bonding within and between the agarose molecules in aqueous solution is proposed.     

Enhanced enzymatic hydrolysis of spruce by alkaline pretreatment at low temperature

Alkaline pretreatment of spruce at low temperature in both presence and absence of urea was studied. It was found that the enzymatic hydrolysis rate and efficiency can be significantly improved by the pretreatment. At low temperature, the pretreatment chemicals, either NaOH alone or NaOH-urea mixture solution, can slightly remove lignin, hemicelluloses, and cellulose in the lignocellulosic materials, disrupt the connections between hemicelluloses, cellulose, and lignin, and alter the structure of treated biomass to make cellulose more accessible to hydrolysis enzymes. Moreover, the wood fiber bundles could be broken down to small and loose lignocellulosic particles by the chemical treatment. Therefore, the enzymatic hydrolysis efficiency of untreated mechanical fibers can also be remarkably enhanced by NaOH or NaOH/urea solution treatment. The results indicated that, for spruce, up to 70% glucose yield could be obtained for the cold temperature pretreatment (-15 degrees C) using 7% NaOH/12% urea solution, but only 20% and 24% glucose yields were obtained at temperatures of 23 degrees C and 60 degrees C, respectively, when other conditions remained the same. The best condition for the chemical pretreatment regarding this study was 3% NaOH/12% urea, and -15 degrees C. Over 60% glucose conversion was achieved upon this condition.     

Isolation and characterisation of cellulose obtained by a two-stage treatment with organosolv and cyanamide activated hydrogen peroxide from wheat straw

Seven wheat straw cellulose preparations were isolated by a two-stage acidic organosolv treatment followed by cyanamide activated hydrogen peroxide bleaching. The effects of concentration of acetic and formic acids on the yield of cellulose and degradation of lignin and non-cellulose polysaccharides were investigated. Organic acids were more effective than alcohols on the degradation of lignin and hemicelluloses. Formic acid/acetic acid/water (30/60/10, v/v/v) system was found to be the most effective in delignification and removal of non-cellulose polysaccharides from the straw and did not have any undesirable effects on cellulose properties such as its intrinsic viscosity. In this case, the treatment removed 94.1% of the original lignin and 76.5% of the original hemicelluloses using 0.1% HCl as a catalyst at 85 °C for 4 h. Cyanamide activated hydrogen peroxide bleaching degraded substantial amounts of residual hemicelluloses and lignin, produced the cellulose samples having a relatively high purity. Under a best condition, a cellulose relatively free of lignin (0.7%) and with intrinsic viscosity of 393 ml g⁻¹ and favourable molar mass (213,940 g mol⁻¹) was obtained. Both unbleached and bleached cellulose preparations were further characterised by FT-IR and CP/MAS ¹³C NMR spectroscopy, and thermal stability.     

Ethanol production from cotton-based waste textiles

Ethanol production from cotton linter and waste of blue jeans textiles was investigated. In the best case, alkali pretreatment followed by enzymatic hydrolysis resulted in almost complete conversion of the cotton and jeans to glucose, which was then fermented by Saccharomyces cerevisiae to ethanol. If no pretreatment applied, hydrolyses of the textiles by cellulase and beta-glucosidase for 24 h followed by simultaneous saccharification and fermentation (SSF) in 4 days, resulted in 0.140-0.145 g ethanol/g textiles, which was 25-26% of the corresponding theoretical yield. A pretreatment with concentrated phosphoric acid prior to the hydrolysis improved ethanol production from the textiles up to 66% of the theoretical yield. However, the best results obtained from alkali pretreatment of the materials by NaOH. The alkaline pretreatment of cotton fibers were carried out with 0-20% NaOH at 0 degrees C, 23 degrees C and 100 degrees C, followed by enzymatic hydrolysis up to 4 days. In general, higher concentration of NaOH resulted in a better yield of the hydrolysis, whereas temperature had a reverse effect and better results were obtained at lower temperature. The best conditions for the alkali pretreatment of the cotton were obtained in this study at 12% NaOH and 0 degrees C and 3 h. In this condition, the materials with 3% solid content were enzymatically hydrolyzed at 85.1% of the theoretical yield in 24 h and 99.1% in 4 days. The alkali pretreatment of the waste textiles at these conditions and subsequent SSF resulted in 0.48 g ethanol/g pretreated textiles used.     

Liquid hot water and alkaline pretreatment of soybean straw for improving cellulose digestibility

Soybean straw was pretreated with either liquid hot water (LHW) (170-210 °C for 3-10 min) or alkaline soaking (4-40 g NaOH/100 g dry straw) at room temperature to evaluate the effects on cellulose digestibility. Nearly 100% cellulose was recovered in pretreated solids for both pretreatment methods. For LHW pretreatment, xylan dissolution from the raw material increased with pretreatment temperature and time. Cellulose digestibility was correlated with xylan dissolution. A maximal glucose yield of 70.76%, corresponding to 80% xylan removal, was obtained with soybean straw pretreated at 210 °C for 10 min. NaOH soaking at ambient conditions removed xylan up to 46.37% and the subsequent glucose yield of pretreated solids reached up to 64.55%. Our results indicated LHW pretreatment was more effective than NaOH soaking for improving cellulose digestibility of soybean straw.     

Pretreatment and enzymic saccharification of water hyacinth cellulose

Water hyacinth was pretreated, under variable conditions, with NaOH, alkaline H₂O₂, peracetic acid and sodium chlorite. Combined pretreatments included sodium chlorite with each of NaOH, alkaline H₂O₂ and peracetic acid. Combined pretreatment with 0.1% NaClO₂ for 1 h at 100 °C and peracetic acid at 100 °C for 15 min afforded the most promising sample. The recovered lignin, cellulose and hemicellulose of this sample was 2.56%, 96.69%, and 81.38%, respectively. The same sample, by cellulase hydrolysis showed the highest cellulose conversion (80.8%) and 90% saccharification using 200 FPU/g substrate. Some ambient factors affecting saccharification of pretreated water hyacinth were investigated. Enzymic saccharification after 6 h was about 50% of that at 48 h, indicating a slow hydrolysis rate by time. Addition of 8% glucose at the beginning of the enzymic hydrolysis decreased the saccharification to about its half while addition of 8% ethanol brought about complete inhibition of the enzyme. Addition of cellobiase to the reaction mixture increased cellulose conversion and saccharification by 10%.     

Cellulose and hemicelluloses recovery from grape stalks

In this work, two mild chemical fractionation procedures were compared to separate and recover lignocellulosic components from grape stalks. The first method consisted of mild acid hydrolysis for hemicelluloses separation, followed by an alkaline/oxidative step for lignin solubilization, while in the second method the acid hydrolysis was preceded by an alkali steeping phase. Influence of the length of the first step of both methods (from 2 to 24 h) on monosaccharides and cellulose yields was investigated. The first method allowed a higher sugar recovery for longer times, and a slightly lower amount of cellulose. Cellulose residues from both the methods were comparable for cellulose content and thermal profile (studied by differential scanning calorimetry). Acid hydrolysis of the first step was carried out also in autoclave, showing that xylan degradation could be described by a first order kinetics where at higher temperature the presence of a fast reaction and a slow reacting fraction must be accounted for.     

A comparison of chemical pretreatment methods for improving saccharification of cotton stalks

The effectiveness of sulfuric acid (H(2)SO(4)), sodium hydroxide (NaOH), hydrogen peroxide (H(2)O(2)), and ozone pretreatments for conversion of cotton stalks to ethanol was investigated. Ground cotton stalks at a solid loading of 10% (w/v) were pretreated with H(2)SO(4), NaOH, and H(2)O(2) at concentrations of 0.5%, 1%, and 2% (w/v). Treatment temperatures of 90 degrees C and 121 degrees C at 15 psi were investigated for residence times of 30, 60, and 90 min. Ozone pretreatment was performed at 4 degrees C with constant sparging of stalks in water. Solids from H(2)SO(4), NaOH, and H(2)O(2) pretreatments (at 2%, 60 min, 121 degrees C/15 psi) showed significant lignin degradation and/or high sugar availability and hence were hydrolyzed by Celluclast 1.5L and Novozym 188 at 50 degrees C. Sulfuric acid pretreatment resulted in the highest xylan reduction (95.23% for 2% acid, 90 min, 121 degrees C/15 psi) but the lowest cellulose to glucose conversion during hydrolysis (23.85%). Sodium hydroxide pretreatment resulted in the highest level of delignification (65.63% for 2% NaOH, 90 min, 121 degrees C/15 psi) and cellulose conversion (60.8%). Hydrogen peroxide pretreatment resulted in significantly lower (p相似文献   

Mild alkaline pretreatment can achieve high hydrolytic and fermentation efficiencies for rice straw conversion to bioethanol

Abstract

Mild alkaline pretreatment was evaluated as a strategy for effective lignin removal and hydrolysis of rice straw. The pretreatment efficiency of different NaOH concentrations (0.5, 1.0, 1.5 or 2.0% w/w) was assessed. Rice straw (RS) pretreated with 1.5% NaOH achieved better sugar yield compared to other concentrations used. A cellulose conversion efficiency of 91% (45.84?mg/ml glucose release) was attained from 1.5% NaOH pretreated rice straw (PRS), whereas 1% NaOH pretreated rice straw yielded 35.10?mg/ml of glucose corresponding to a cellulose conversion efficiency of 73.81%. The ethanol production from 1% and 1.5% NaOH pretreated RS hydrolysates was similar at ～3.3% (w/v), corresponding to a fermentation efficiency of 86%. The non-detoxified hydrolysate was fermented using the novel yeast strain Saccharomyces cerevisiae RPP-03O without any additional supplementation of nutrients.     

Enzymatic hydrolysis of chemithermomechanically pretreated sugarcane bagasse and samples with reduced initial lignin content

Chemithermomechanical (CTM) processing was used to pretreat sugarcane bagasse with the aim of increasing cell wall accessibility to hydrolytic enzymes. Yields of the pretreated samples were in the range of 75-94%. Disk refining and alkaline-CTM and alkaline/sulfite-CTM pretreatments yielded pretreated materials with 21.7, 17.8, and 15.3% of lignin, respectively. Hemicellulose content was also decreased to some extent. Fibers of the pretreated materials presented some external fibrillation, fiber curling, increased swelling, and high water retention capacity. Cellulose conversion of the alkaline-CTM- and alkaline/sulfite-CTM-pretreated samples reached 50 and 85%, respectively, after 96 h of enzymatic hydrolysis. Two samples with low initial lignin content were also evaluated after the mildest alkaline-CTM pretreatment. One sample was a partially delignified mill-processed bagasse. The other was a sugarcane hybrid selected in a breeding program. Samples with lower initial lignin content were hydrolyzed considerably faster in the first 24 h of enzymatic digestion. For example, enzymatic hydrolysis of the sample with the lowest initial lignin content (14.2%) reached 64% cellulose conversion after only 24 h of hydrolysis when compared with the 30% observed for the mill-processed bagasse containing an initial lignin content of 24.4%.     

Dilute acid pretreatment, enzymatic saccharification and fermentation of wheat straw to ethanol

Wheat straw consists of 48.57 ± 0.30% cellulose and 27.70 ± 0.12% hemicellulose on dry solid (DS) basis and has the potential to serve as a low cost feedstock for production of ethanol. Dilute acid pretreatment at varied temperature and enzymatic saccharification were evaluated for conversion of wheat straw cellulose and hemicellulose to monomeric sugars. The maximum yield of monomeric sugars from wheat straw (7.83%, w/v, DS) by dilute H₂SO₄ (0.75%, v/v) pretreatment and enzymatic saccharification (45 °C, pH 5.0, 72 h) using cellulase, β-glucosidase, xylanase and esterase was 565 ± 10 mg/g. Under this condition, no measurable quantities of furfural and hydroxymethyl furfural were produced. The yield of ethanol (per litre) from acid pretreated enzyme saccharified wheat straw (78.3 g) hydrolyzate by recombinant Escherichia coli strain FBR5 was 19 ± 1 g with a yield of 0.24 g/g DS. Detoxification of the acid and enzyme treated wheat straw hydrolyzate by overliming reduced the fermentation time from 118 to 39 h in the case of separate hydrolysis and fermentation (35 °C, pH 6.5), and increased the ethanol yield from 13 ± 2 to 17 ± 0 g/l and decreased the fermentation time from 136 to 112 h in the case of simultaneous saccharification and fermentation (35 °C, pH 6.0).     

Bioethanol production from barley hull using SAA (soaking in aqueous ammonia) pretreatment

Barley hull, a lignocellulosic biomass, was pretreated using aqueous ammonia, to be converted into ethanol. Barley hull was soaked in 15 and 30 wt.% aqueous ammonia at 30, 60, and 75 °C for between 12 h and 11 weeks. This pretreatment method has been known as “soaking in aqueous ammonia” (SAA). Among the tested conditions, the best pretreatment conditions observed were 75 °C, 48 h, 15 wt.% aqueous ammonia and 1:12 of solid:liquid ratio resulting in saccharification yields of 83% for glucan and 63% for xylan with 15 FPU/g-glucan enzyme loading. Pretreatment using 15 wt.% ammonia for 24–72 h at 75 °C removed 50–66% of the original lignin from the solids while it retained 65–76% of the xylan without any glucan loss.

Addition of xylanase along with cellulase resulted in synergetic effect on ethanol production in SSCF (simultaneous saccharification and co-fermentation) using SAA-treated barley hull and recombinant E. coli (KO11). With 3% w/v glucan loading and 4 mL of xylanase enzyme loadings, the SSCF of the SAA treated barley hull resulted 24.1 g/L ethanol concentration at 15 FPU cellulase/g-glucan loading, which corresponds to 89.4% of the maximum theoretical yield based on glucan and xylan.

SEM results indicated that SAA treatment increased surface area and the pore size. It is postulated that these physical changes enhance the enzymatic digestibility in the SAA treated barley hull.     

Single cell protein production from bagasse pith pretreated with sodium hydroxide at room temperature

Summary Previous publications have revealed that a pretreatment of lignocellulosic wastes is necessary if they are to be employed as the hydrocarbon source of single cell protein production. A hot alkaline treatment is the most common.We have treated sugar cane bagasse pith with 1% NaOH solution at room temperature, at a NaOH/pith ratio of 10%. Different contact times were used in the experiments. The shortest contact period required for maximum protein production was 24 h at 25° C. A mixed culture of Cellulomonas sp. and Bacillus subtilis was used in the experiments. The values obtained for hemicellulose and cellulose in the treated pith did not differ greatly from those of untreated pith, in contrast the amount of lignin was 33% lower in the treated pith. The effect of reutilization of the alkaline liquor used for the pretreatment of pith upon protein production was also investigated. With four recyclings, there was a NaOH saving of 34.4 kg per 100 kg produced protein as compared to when the liquor was only used once.The quality of the resulting effluents, as measured by the chemical oxygen demand (COD), proved to be very similar for both types of treatment.     

Optimization of alkaline pretreatment of coffee pulp for production of bioethanol

The use of lignocellulosic raw materials in bioethanol production has been intensively investigated in recent years. However, for efficient conversion to ethanol, many pretreatment steps are required prior to hydrolysis and fermentation. Coffee stands out as the most important agricultural product in Brazil and wastes such as pulp and coffee husk are generated during the wet and dry processing to obtain green grains, respectively. This work focused on the optimization of alkaline pretreatment of coffee pulp with the aim of making its use in the alcoholic fermentation. A central composite rotatable design was used with three independent variables: sodium hydroxide and calcium hydroxide concentrations and alkaline pretreatment time, totaling 17 experiments. After alkaline pretreatment the concentration of cellulose, hemicellulose, and lignin remaining in the material, the subsequent hydrolysis of the cellulose component and its fermentation of substrate were evaluated. The results indicated that pretreatment using 4% (w/v) sodium hydroxide solution, with no calcium hydroxide, and 25 min treatment time gave the best results (69.18% cellulose remaining, 44.15% hemicelluloses remaining, 25.19% lignin remaining, 38.13 g/L of reducing sugars, and 27.02 g/L of glucose) and produced 13.66 g/L of ethanol with a yield of 0.4 g ethanol/g glucose. © 2013 American Institute of Chemical Engineers Biotechnol. Prog., 30:451–462, 2014     

Mild pretreatment of yellow poplar biomass using sequential dilute acid and enzymatically-generated peracetic acid to enhance cellulase accessibility

Biomass contains cellulose, xylan and lignin in a complex interwoven structure that hinders enzymatic hydrolysis of the cellulose. To separate these components in yellow poplar biomass, we sequentially pretreated with dilute sulfuric acid and enzymatically-generated peracetic acid. In the first step, the dilute acid with microwave heating (140°C, 5 min) hydrolyzed 90% of xylan. The xylose yield in hydrolysate after dilute acid pretreatment was 83.1%. In the second step, peracetic acid (60°C, 6 h) removed up to 80% of lignin. This sequential pretreatment fractionated biomass into xylan and lignin, leaving a solid residue enriched in cellulose (~80%). The sequential pretreatment enhanced enzymatic digestibility of the cellulase by removal of the other components in biomass. The glucose yield after enzymatic hydrolysis was 90.5% at a low cellulase loading (5 FPU/g of glucan), which is 1.6 and 18 times higher than for dilute acid-pretreated biomass and raw biomass, respectively. This novel sequential pretreatment with dilute acid and peracetic acid efficiently separates the three major components of yellow poplar biomass, and reduces the amount of cellulase needed.     

Fractional and structural characterization of hemicelluloses isolated by alkali and alkaline peroxide from barley straw

Eight hemicellulosic fractions were obtained by sequential treatment of dewaxed barley straw with 0.1 M NaOH at 45 °C for 3 h, 0.25, 0.5, 1.0, 1.5, 2.0, and 3.0% H₂O₂ at 45 °C for 3 h at pH 11.5, and 10% KOH–1% Na₂B₄O₇·10H₂O at 28 °C for 15 h under continuous agitation. The yields of the fractions were 8.0, 3.1, 3.3, 3.3, 2.2, 2.0, 2.0, and 9.9%, respectively, of the initial amount of barley straw, corresponding to the dissolution of 21.6, 8.4, 8.9, 8.9, 5.9, 5.4, 5.4, and 26.7% of the original hemicelluloses. Meanwhile, the successive treatment also solubilized 29.1, 15.8, 14.6, 10.8, 4.5, 3.2, 2.7, and 3.7% of the original lignin, respectively. This sequential extraction together resulted in dissolution of 91.1% of the original hemicelluloses and 84.8% of the original lignin. The 0.1 M NaOH-soluble hemicellulosic fraction contained mainly xylose, glucose, and arabinose, 44.2, 15.7, and 15.2%, respectively, while the 10% KOH–1% Na₂B₄O₇·10H₂O-soluble fraction predominated in xylose, 75.0%. The six alkaline peroxide-soluble fractions were composed of 50.3–54.4% xylose, 14.7–16.9% arabinose, 6.8–10.7% glucose, 6.8–8.5% glucuronic acid or 4-O-methyl- -glucuronic acid, 0.4–1.5% mannose, and 0.3–1.2% rhamnose. All the hemicellulosic fractions contained substantial amounts of glucuronoarabinoxylans and noticeable quantities of β-glucans. In comparison, the six hemicellulosic fractions, isolated with alkaline peroxide, had much higher molecular weights (56,890–63,810 g mol⁻¹) than those of the two hemicellulosic preparations (28,000–29,080 g mol⁻¹), isolated with alkali in the absence of hydrogen peroxide. The thermal stability of the hemicelluloses increased with an increment of their molar mass.     

Fast and efficient alkaline peroxide treatment to enhance the enzymatic digestibility of steam-exploded softwood substrates.

The enzymatic digestibility of steam-exploded Douglas-fir wood chips (steam exploded at 195 degrees C, 4.5 min, and 4.5% (w/w) SO(2)) was significantly improved using an optimized alkaline peroxide treatment. Best hydrolysis yields were attained when the steam-exploded material was post-treated with 1% hydrogen peroxide at pH 11.5 and 80 degrees C for 45 min. This alkaline peroxide treatment was applied directly to the water-washed, steam-exploded material eliminating the need for independent alkali treatment with 0.4% NaOH, which has been traditionally used to post-treat wood samples to try to remove residual lignin. Approximately 90% of the lignin in the original wood was solubilized by this novel procedure, leaving a cellulose-rich residue that was completely hydrolyzed within 48 h, using an enzyme loading of 10 FPU/g cellulose. About 82% of the originally available polysaccharide components of the wood could be recovered. The 18% of the carbohydrate that was not recovered was lost primarily to sugar degradation during steam explosion.