Impact of dilute acid pretreatment on the structure of bagasse for bioethanol production

Dilute acid pretreatment is a commonly used pretreatment method in the course of producing bioethanol from lignocellulosics and the structure variation of the lignocellulosics is highly related to the pretreatment process. To understand the impact of dilute acid pretreatment on the structure of bagasse, four different pretreatment conditions by varying heating time are considered where the bagasse and the pretreated materials are examined using a variety of analysis methods. The obtained results indicate that the thermogravimetric analysis (TGA) is able to provide a useful insight into the recognition of lignocellulosic structure. Specifically, the peak of the TGA of the pretreated materials moves toward the low temperature region, revealing that the lignocellulosic structure is loosened. However, the characteristic of crystal structure of cellulose remains in the pretreated materials. Increasing heating time enhances the pretreatment procedure; as a result, the average particle size of the investigated materials increases with heating time. This swelling behavior may be attributed to the enlarged holes inside the particles in that the surface area decreases with increasing heating time. In addition, when the heating time is increased to a certain extent (e.g. 15 min), some fragments are found at the surface and they tend to peel off from the surface. It follows that the dilute acid pretreatments have a significant effect on the bagasse structure. Copyright © 2009 John Wiley & Sons, Ltd.     

Microwave-assisted alkali pretreatment of rice straw to promote enzymatic hydrolysis and hydrogen production in dark- and photo-fermentation

Rice straw was pretreated by microwave-assisted alkali to improve saccharification in enzymatic hydrolysis and hydrogen yield in combined dark- and photo-fermentation in this paper. A maximum reducing sugar yield of 69.3 g/100 g TVS was obtained when 50 g/l rice straw was pretreated by microwave heating for 15 min at 140 °C in 0.5% NaOH solution and then enzymatically hydrolyzed for 96 h. When hydrolyzed rice straw was used for hydrogen production by anaerobic bacteria in dark-fermentation, a maximum hydrogen yield of 155 ml/g TVS was obtained. The residual solution (mainly acetate and butyrate) from dark-fermentation was reutilized for hydrogen production by immobilized photosynthetic bacteria in photo-fermentation. By combination of dark- and photo-fermentation, the maximum hydrogen yield was greatly enhanced to 463 ml/g TVS, which is 43.2% of the theoretical hydrogen yield.     

Efficient sugar production from sugarcane bagasse by microwave assisted acid and alkali pretreatment

Sugarcane bagasse represents one of the best potential feedstocks for the production of second generation bioethanol. The most efficient method to produce fermentable sugars is by enzymatic hydrolysis, assisted by thermochemical pretreatments. Previous research was focused on conventional heating pretreatment and the pretreated biomass residue characteristics. In this work, microwave energy is applied to facilitate sodium hydroxide (NaOH) and sulphuric acid (H₂SO₄) pretreatments on sugarcane bagasse and the efficiency of sugar production was evaluated on the soluble sugars released during pretreatment. The results show that microwave assisted pretreatment was more efficient than conventional heating pretreatment and it gave rise to 4 times higher reducing sugar release by using 5.7 times less pretreatment time. It is highlighted that enrichment of xylose and glucose can be tuned by changing pretreatment media (NaOH/H₂SO₄) and holding time. SEM study shows significant delignification effect of NaOH pretreatment, suggesting a possible improved enzymatic hydrolysis process. However, severe acid conditions should be avoided (long holding time or high acid concentration) under microwave heating conditions. It led to biomass carbonization, reducing sugar production and forming ‘humins’. Overall, in comparison with conventional pretreatment, microwave assisted pretreatment removed significant amount of hemicellulose and lignin and led to high amount of sugar production during pretreatment process, suggesting microwave heating pretreatment is an effective and efficient pretreatment method.     

The effect of heat pretreatment temperature on fermentative hydrogen production using mixed cultures

The effect of heat treatment at different temperatures on two types of inocula, activated sludge and anaerobically digested sludge, was investigated in batch cultures. Heat treatments were conducted at 65, 80 and 95 °C for 30 min. The untreated inocula produced less amount of hydrogen than the pretreated inocula, with lactic acid as the main metabolite. The maximum yields of 2.3 and 1.6 mol H₂/mol glucose were achieved for the 65 °C pretreated anaerobically digested and activated sludges, respectively. Approximately a 15% decrease in yield was observed with increasing pretreatment temperature from 65 to 95 °C concomitant with an increase in butyrate/acetate ratio from 1.5 to 2.4 for anaerobically digested sludge. The increase of pretreatment temperature of activated sludge to 95 °C suppressed the hydrogen production by lactic acid fermentation. DNA analysis of the microbial community showed that the elevated pretreatment temperatures reduced the species diversity.     

Biohydrogen production from pure and natural lignocellulosic feedstock with chemical pretreatment and bacterial hydrolysis

Pretreatment and saccharification of lignocellulosic materials is the key technology affecting the efficiency of cellulosic biohydrogen production. In this work, two pure cellulosic materials (i.e., carboxymethyl-cellulose (CMC) and xylan) were directly hydrolyzed (without pretreatment) by a cellulolytic isolate Cellulomonas uda E3-01 able to release extracellular cellulolytic enzymes. Natural cellulosic feedstock (i.e., sugarcane bagasse) was chemically pretreated prior to the bacterial hydrolysis.A temperature-shift strategy (35 °C for cellulolytic enzymes production and 45 °C for hydrolysis reaction) was used to increase the production of reducing sugars during the bacterial hydrolysis. The hydrolysates of CMC, xylan, and bagasse were efficiently converted to H₂ via dark fermentation with Clostridium butyricum CGS5. The maximum hydrogen yield was 8.80 mmol H₂/g reducing sugar (i.e., 1.58 mol H₂/mol hexose) for CMC, 6.03 mmol H₂/g reducing sugar (i.e., 0.91 mol H₂/mol pentose) for xylan, and 6.01 mmol H₂/g reducing sugar for bagasse.     

Acidified glycerol pretreatment for enhanced ethanol production from rice straw

Rice straw was pretreated using an industrial grade glycerol for ethanol production. The pretreatment was conducted at 130–210 °C for 1–24 h with 5% solid loading. The glucan content in the regenerated rice straw increased with increasing pretreatment temperature and time. The production of fermentable sugars initially increased as the pretreatment temperature and reaction time increased, but then decreased somewhat at the higher temperatures and with longer reaction duration. The highest amount of reducing sugar produced by the enzymatic hydrolysis was achieved at 190 °C for 10 h with 5% solid loading, optimal condition for the glycerol pretreatment of rice straw. Furthermore, it was observed that glycerol pretreatment with the addition of HCl improved the digestibility of fermentable sugars by 4–5 times that of untreated samples. Fermentation of hydrolysates resulted in an ethanol yield of 0.44 g/g sugar, corresponding to a theoretical yield of 84.3%. It was concluded that acidified glycerol is one of the good candidates of the organic solvent for the pretreatment of lignocellulosic biomass.     

Step-change flow rate liquid hot water pretreatment of sweet sorghum bagasse for enhancement of total sugars recovery

A step-change flow rate liquid hot water (SCFLHW) process was developed with the objective of improving the total sugars recovery including xylose and glucose from sweet sorghum bagasse (SSB). Total xylose yield increased from 60% for batch system (4.25% w/v, 18 min, 184 °C) to about 80% at an initial flow rate of 20 ml/min for 8 min, followed by a rate of 10 ml/min for 10 min. It was hypothesized that the flowing water could enhance the mass transfer and improves the sugars recovery. Although little lignin was removed, the 72 h enzymatic digestibility of treated sample was enhanced by the increase of flow rate. The lignin droplet redeposited on the surface of residual solids might play a crucial role in determining the enzymatic digestibility. The total recovery of sugars from SSB, after the pretreatment (first with the flow rate of 20 ml/min for 8 min, then 10 ml/min for 10 min) and 72 h enzymatic digestion, reached 83.7%, which is superior to the recovery using the SO₂-steam pretreatment or ammonia fiber expansion.     

Production of ethyl ester from esterified crude palm oil by microwave with dry washing by bleaching earth

The production of ethyl ester from a feed material of esterified crude palm oil with 1.7 wt% of free fatty acid (FFA) content using microwave heating was investigated. Parametric studies were carried out to investigate the optimum conditions for the transesterification process (amount of ethanol, amount of catalyst and reaction time). As a result, optimum reaction parameters for the transesterification process aided by microwave heating have been identified: a molar ratio of oil to ethanol of 1:8.5, 1.5 wt% of KOH/oil, a reaction time of 5 min and a microwave power of 70 W. Glycerin from the ester phase was separated by adding 10 wt% of pure glycerin. The ethyl ester was purified with 1.2 wt% of bleaching earth to remove the residual catalyst and residual glycerin. This transesterification process provided a yield of 85 wt% with an ester content of 98.1 wt%. The final ethyl ester product met the specifications stipulated by ASTM D6751-02.     

Enhancement of biohydrogen producing using ultrasonication

Ultrasonication was evaluated as a pretreatment for biological hydrogen production from glucose in batch studies, in comparison with heat-shock pretreatment, acid pretreatment, and base pretreatment. The optimized sonication energy for hydrogen production using anaerobic digester sludge was 79 kJ/gTS. Sonication with temperature control (less than 30 °C) increased volumetric hydrogen production by 120% over the untreated sludge, and by 40% over the heat-shock and acid pretreated sludge, with a marginal (∼10%) increase in hydrogen production rate. Upon comparing the molar hydrogen yield in sonicated sludge with and without temperature control, the deleterious effect of heat on some hydrogen producers as reflected by a 30% decrease in yield to 1.03 mol H₂/mol glucose is evident. Sonication with temperature control affected a 45% increase in molar hydrogen yield to 1.55 mol H₂/mol glucose over heat-shock pretreatment at 70 °C for 30 min and acidification to pH 3.0 for 24 h at 4 °C. Sonication with temperature control produced a biomass yield of 0.13 g VSS/g COD, as compared to 0.24 g VSS/g COD for the untreated sludge. The hydrogen yield increased linearly with the molar acetate to butyrate ratio and decreased linearly with the biomass yield.     

Thermal pre-treatment of wet microalgae harvest for efficient hydrocarbon recovery

Botryococcus braunii, a green colonial microalga, is an unusually rich renewable source of hydrocarbons. In this study, wet microalgae harvest was thermally pretreated to enhance hydrocarbon recovery using a solvent extraction process. Samples containing a mixture of B. braunii and water were kept below 100 °C for 10 min. The observed hydrocarbon recovery was 97.8% at 90 °C. The extraction results suggest that the energy-intensive concentration and drying processes of the harvest could be eliminated. The proposed thermal pretreatment would revolutionize the conventional downstream processes.     

Utilization of pineapple stem juice to enhance enzyme-hydrolytic efficiency for sugarcane bagasse after an optimized pre-treatment with alkaline peroxide

The enzymatic hydrolysis of sugarcane bagasse was investigated by treating a peroxide–alkaline bagasse with a pineapple stem juice, xylanase and cellulase. Pre-treatment procedures of sugarcane bagasse with alkaline hydrogen peroxide were evaluated and compared. Analyses were performed using 2⁴ factorial designs, with pre-treatment time, temperature, magnesium sulfate and hydrogen peroxide concentration as factors. The responses evaluated were the yield of cellobiose and glucose released from pretreated bagasse after enzymatic hydrolysis. The results show that the highest enzymatic conversion was obtained for bagasse using 2% hydrogen peroxide at 60 °C for 16 h in the presence of 0.5% magnesium sulfate. Bagasse (5%) was treated with pineapple stem extract, which contains mixtures of protease and esterase, in combination with xylanase and cellulase. It was observed that the amount of glucose and cellobiose released from bagasse increased with the mixture of enzymes. It is believed that the enzymes present in pineapple extracts are capable of hydrolyze specific linkages that would facilitate the action of digesting plant cell walls enzymes. This increases the amount of glucose and other hexoses that are released during the enzymatic treatment and also reduces the amount of cellulase necessary in a typical hydrolysis.     

Microwave assisted synthesis of surfactant stabilized platinum/carbon nanotube electrocatalysts for direct methanol fuel cell applications

Platinum electrocatalysts deposited on multi-walled carbon nanotubes (CNT) with high loading were prepared using a microwave-assisted polyol reduction method and employed for direct methanol fuel cells (DMFC). A zwitterionic surfactant was used as a stabilizing agent for the formation of Pt nanoparticles. A uniform and narrow size distribution of highly dispersed Pt nanoparticles could be achieved by adjusting the weight ratio of surfactant to Pt precursor allowing for Pt loadings of up to 60 wt%. The heating time and the temperature for the ethylene glycol (EG) oxidation were found to be the key factors for depositing Pt nanoparticles homogeneously on carbon nanotubes. The smallest average particle diameter of 1.8 nm was obtained through microwave heating to 140 °C in 50 s. The structure, amount and morphology of the electrocatalysts were characterized with XRD, TGA, and TEM, respectively. Single cell DMFC measurements were performed in a membrane-electrode assembly (MEA) with 5 cm² active area and very low catalyst loading (0.25 mg cm⁻² of noble metal on both anode and cathode). The DMFC performance of the surfactant stabilized cathode catalyst obtained by the new method described here revealed that the power density was three times higher than for a commercial catalyst used for comparison and two times higher than for an unstabilized CNT supported catalyst.     

Enzymatic saccharification of dilute acid pretreated saline crops for fermentable sugar production

Four saline crops [athel (Tamarix aphylla L), eucalyptus (Eucalyptus camaldulensis), Jose Tall Wheatgrass (Agropyron elongatum), and Creeping Wild Ryegrass (Leymus triticoides)] that are used in farms for salt uptake from soil and drainage irrigation water have the potential for fuel ethanol production because they don’t take a large number of arable lands. Dilute sulfuric acid pretreatment and enzymatic hydrolysis were conducted to select the optimum pretreatment conditions and the best saline crop for further enzymatic hydrolysis research. The optimum dilute acid pretreatment conditions included T = 165 °C, t = 8 min, and sulfuric acid concentration = 1.4% (w/w). Creeping Wild Ryegrass was decided to be the best saline crop. Solid loading, cellulase and β-glucosidase concentrations had significant effects on the enzymatic hydrolysis of dilute acid pretreated Creeping Wild Ryegrass. Glucose concentration increased by 36 mg/mL and enzymatic digestibility decreased by 20% when the solid loading increased from 4 to 12%. With 8% solid loading, enzymatic digestibility increased by over 30% with the increase of cellulase concentration from 5 to 15 FPU/g-cellulose. Under given cellulase concentration of 15 FPU/g-cellulose, 60% increase of enzymatic digestibility of pretreated Creeping Wild Ryegrass was obtained with the increase of β-glucosidase concentration up to 15 CBU/g-cellulose. With a high solid loading of 10%, fed-batch operation generated 12% and 18% higher enzymatic digestibility and glucose concentration, respectively, than batch process.     

Bioconversion of corncob to hydrogen using anaerobic mixed microflora

Biohydrogen production from corncob using natural anaerobic microflora was reported for the first time. The optimum pretreatment condition for the corncob was determined to be 100 °C, 30 min, and 1% HCl (w/w). The maximum hydrogen yield of 107.9 ml/g-TVS and hydrogen production rate of 4.20 ml/g-TVS h⁻¹ was obtained under the condition of 10 g/l substrate concentration and initial pH 8.0. Butyrate and acetate were the dominant metabolic by-products of hydrogen fermentation. Chemical composition analysis, Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) were used to study the mechanism of degrading corncob for hydrogen production. The amorphous domains of cellulose and hemicellulose were hydrolyzed into fermentable saccharides through acid pretreatment and the microorganisms had a devastating effect on the crystallinity of the cellulose. The hydrogen yield from pretreated corncob was much higher than from raw corncob. Therefore, the acid pretreatment played a crucial role on hydrogen production from corncob.     

Effects of pretreatment methods on solubilization of beet-pulp and bio-hydrogen production yield

Sugar processing wastewater and beet-pulp are two major waste streams of sugar-beet processing plants. Contrary to wastewater, beet-pulp is generally used as animal feed in cattle-raising industry. However, it can serve as a substrate for bio-hydrogen production which corresponds to a higher valorization of beet-pulp. Moreover, pretreatment of lignocellulosic materials like beet-pulp is needed in order to improve overall energy efficiency and enable economic feasibility of bio-hydrogen production. Therefore, the effect pretreatment methods (alkaline, thermal, microwave, thermal-alkaline and microwave-alkaline) on bio-hydrogen production from sugar beet-pulp through dark fermentation were investigated in this study. Reactors pretreated with alkaline, microwave-alkaline and thermal-alkaline methods yielded significant solubilization of beet-pulp compared to others. Therefore, in the second phase of the study, they were used to pretreat the beet-pulp which was then subjected to dark fermentation for bio-hydrogen production. Maximum bio-hydrogen production yield of 115.6 mL H₂/g COD was observed in reactor which contained alkaline pretreated beet-pulp.     

Lipid production from sweet sorghum bagasse through yeast fermentation

Cryptococcus curvatus has great potential in fermenting unconditioned hydrolysates of sweet sorghum bagasse. With hydrolysates obtained by enzymatic hydrolysis of the solid pretreated by microwave with lime, the maximal yeast cell dry weight and lipid content were 10.83 g/l and 73.26%, respectively. For hydrolysates obtained in the same way but without lime, these two parameters were 15.50 g/l and 63.98%, respectively. During yeast fermentation, glucose and xylose were consumed simultaneously while cellobiose was released from the residual bagasse. The presence of lime, on one hand, made cellulose more accessible to enzymes as evidenced by higher total reducing sugar release compared to that without during enzymatic hydrolysis step; on the other hand, it caused the degradation of sugars to non-sugar chemicals during pretreatment step. As a result, higher lipid yield of 0.11 g/g bagasse or 0.65 ton/hectare of land was achieved from the pathway of microwave pretreatment and enzymatic hydrolysis while 0.09 g/g bagasse or 0.51 ton/hectare of land was attained from the process of lime-assisted microwave pretreatment followed by the same enzymatic saccharification.     

Improved hydrogen production via thermophilic fermentation of corn stover by microwave-assisted acid pretreatment

A microwave-assisted acid pretreatment (MAP) strategy has been developed to enhance hydrogen production via thermophilic fermentation of corn stover. Pretreatment of corn stover by combining microwave irradiation and acidification resulted in the increased release of soluble substances and made the corn stover more accessible to microorganisms when compared to thermal acid pretreatment (TAP). MAP showed obvious advantages in short duration and high efficiency of lignocellulosic hydrolysis. Analysis of the particle size and specific surface area of corn stover as well as observation of its cellular microstructure were used to elucidate the enhancement mechanism of the hydrolysis process by microwave assistance. The cumulative hydrogen volume reached 182.2 ml when corn stover was pretreated by MAP with 0.3 N H₂SO₄ for 45 min, and the corresponding hydrogen yield reached 1.53 mol H₂/mol-glucose equivalents converted to organic end products. The present work demonstrates that MAP has potential to enhance the bioconversion efficiency of lignocellulosic waste to renewable biofuel.     

Effects of rapid process on the conductivity of multiple elements doped ceria-based electrolyte

The citric acid-based combustion technique (SV) for powder preparation and the rapid microwave sintering (MW) process are used to lower the synthesizing temperature and to shorten the processing time then to modify the grain boundary resistance and oxygen vacancies mobility in multiple elements doped ceria-based electrolyte (LSBC). Nanoparticles of less than 50 nm with a pure fluorite structure are prepared by SV method at a low temperature of 600 °C. Microwave sintering lowers the sintering temperature to 1400 °C from the conventional sintering (CS) temperature of 1500 °C needed for solid-state (SS) prepared LSBC, and requires only 15 min of sintering time. The SV sample conventionally sintered at 1400 °C-6 h reaches a conductivity of 0.006 S cm⁻¹. When the SV samples are microwave sintered at 1400 °C-15 min, they achieve a conductivity as high as 0.01 S cm⁻¹ measured at 600 °C. Microwave sintering reduces the grain boundary resistance of both SS and SV samples. The migration enthalpy (H_m) of 0.66 eV in the SS-MW and SV-MW samples is similar to that of the fully densified SS-CS sample. The Schottky barrier height can be adjusted by SV powder preparation and by the MW process using a slightly lower sintering temperature and with a shorter processing time for multiple elements doped solid electrolyte.     

Waste biomass to liquids: Low temperature conversion of sugarcane bagasse to bio-oil. The effect of combined hydrolysis treatments

This article describes the influence of different sugarcane bagasse hydrolysis pretreatments on modifications to biomass feedstock and the characteristics of the resultant pyrolysis products. Sugarcane bagasse was pretreated with acid, alkaline or sequential acid/alkaline solutions and pretreated samples were then subjected to a low temperature conversion (LTC) process under He or O₂/He atmospheres at 350-450 °C. Both pretreated samples and sugarcane bagasse in natura were analyzed by determination of their chemical composition and by thermogravimetric, FTIR and SEM analyses. The gases yielded during LTC were monitored on-line by quadrupole mass spectrometry, and the liquid fractions obtained were characterized by FTIR and ¹H and ¹³C NMR. Irrespective of the sugarcane bagasse pretreatment applied, the main bio-oil component obtained was levoglucosan. However, the LTC yield of bio-oil depended on the hydrolysis treatment of the biomass and decreased in the presence of O₂. The acid hydrolysis pretreatment increased the LTC bio-oil yield notably.