Pretreatment and Fractionation of Corn Stover by Soaking In Ethanol and Aqueous Ammonia

A new process for pretreatment of lignocellulosic biomass, designated the soaking in ethanol and aqueous ammonia (SEAA) process, was developed to improve hemicellulose preservation in solid form. In the SEAA process, an aqueous ammonia solution containing ethanol is used. Corn stover was treated with 15 wt.% ammonia at 1:9 solid–liquid ratio (by weight) at 60 °C for 24 h with ethanol added at 1, 5, 20, and 49 wt.% (balance was water). The extents by which xylan was solubilized with no ethanol and with ethanol added at 1, 5, 20, and 49 wt.% of the total liquid were 17.2%, 16.7%, 14.5%, 10.4%, and 6.3% of the original xylan, respectively. Thus, at the highest ethanol concentration used the loss of hemicellulose to the liquid phase was reduced by 63%. The digestibility of glucan and xylan in the pretreated corn stover samples by cellulase was not affected by ethanol addition of up to 20 wt.%. The enzymatic digestibility of the corn stover treated with 49 wt.% ethanol added was lower than the digestibility of the sample treated with no ethanol addition. Thus, based on these results, 20 wt.% was found to be the optimum ethanol concentration for use in the SEAA process for pretreatment of corn stover.     

Hydrolyzabilities of Different Corn Stover Fractions After Aqueous Ammonia Pretreatment

The effect of aqueous ammonia pretreatment on the hydrolysis of different corn stover fractions (rind, husk, leaf, and pith) by xylanase (XYL) with cellulases (CELs) was evaluated. The aqueous ammonia pretreatment had excellent delignification ability (above 66 %) for different corn stover fractions. The corn rind exhibited the lowest susceptibility to aqueous ammonia pretreatment. The pretreated rind showed the lowest hydrolyzability by CEL and XYL, which was supported by a high content of crystalline cellulose in the hydrolyzed residues of rind, as confirmed by X-ray diffraction (XRD). With the addition of 1 mg XYL/g dry matter, a high glucose yield (above 90 %) could be obtained from the pretreated rind by CEL. The results revealed that a high hydrolyzate yield of corn rind after aqueous ammonia pretreatment could be obtained with 1 mg xylanase/g dry matter, showing that aqueous ammonia pretreatment and xylanase addition to cellulases have great potential for the efficient hydrolysis of corn stover without previous fractionation.     

Enhancement of Enzymatic Hydrolysis and Klason Lignin Removal of Corn Stover Using Photocatalyst-Assisted Ammonia Pretreatment

Photocatalyst-assisted ammonia pretreatment was explored to improve lignin removal of the lignocellulosic biomass for effective sugar conversion. Corn stover was treated with 5.0–12.5 wt.% ammonium hydroxide, two different photocatalysts (TiO₂ and ZnO) in the presence of molecular oxygen in a batch reactor at 60 °C. Various solid-to-liquid ratios (1:20–1:50) were also tested. Ammonia pretreatment assisted by TiO₂-catalyzed photo-degradation removed 70 % of Klason lignin under the optimum condition (12.5 % ammonium hydroxide, 60 °C, 24 h, solid/liquid?=?1:20, photocatalyst/biomass?=?1:10 with oxygen atmosphere). The enzymatic digestibilities of pretreated corn stover were 85 % for glucan and 75 % for xylan with NH₃-TiO₂-treated solid and 82 % for glucan and 77 % for xylan with NH₃-ZnO-treated solid with 15 filter paper units/g-glucan of cellulase and 30 cellobiase units/g-glucan of β-glucosidase, a 2–13 % improvement over ammonia pretreatment alone.     

Bio-detoxification Bacteria Isolated from Dye-Polluted Soils Promote Lactic Acid Production from Ammonia Pretreated Corn Stover

Agro-stovers are the most abundant substrates for producing lactic acid, which has great potential application in the production of biodegradable and biocompatible polylactic acid polymers. However, chemical pretreatments on agro-stovers generate inhibitors that repress the subsequent lactic acid fermentation. In this study, three bacterial strains (Enterococcus faecalis B101, Acinetobacter calcoaceticus C1, and Pseudomonas aeruginosa CS) isolated from dye-polluted soils could utilize phenolic inhibitor mimics (vanillin, 4- hydroxybenzaldehyde, or syringaldehyde) from alkaline pretreated corn stovers as a sole carbon source. Lactic acid titer increased from 27.42 g/L (Bacillus coagulans LA204 alone) to 44.76 g/L (CS and LA204) using 50 g/L glucose with 1 g/L 4-hydroxybenzaldehyde added. Lactic acid production from 50 g/L ammonia pretreated corn stover was increased nearly twofold by inoculating phenolic degradation bacteria and lactic acid bacteria (C1& Lactobacillus pentosus FL0421). In the control (FL0421 alone), only 16.98 g/L of lactic acid was produced. The isolated and identified strains degraded the phenolic compounds and increased the lactic acid production from glucose and ammonia pretreated corn stover. These characteristics of the strains support industrial application with efficient in situ detoxification of phenolic compounds during lactic acid production from agro-stovers using simultaneous saccharification and fermentation (SSF).

     

Fermentation of Acid-pretreated Corn Stover to Ethanol Without Detoxification Using Pichia stipitis

In this work, the effect of adaptation on P. stipitis fermentation using acid-pretreated corn stover hydrolyzates without detoxification was examined. Two different types of adaptation were employed, liquid hydrolyzate and solid state agar adaptation. Fermentation of 12.5% total solids undetoxified acid-pretreated corn stover was performed in shake flasks at different rotation speeds. At low rotation speed (100 rpm), both liquid hydrolyzate and solid agar adaptation highly improved the sugar consumption rate as well as ethanol production rate compared to the wild-type strains. The fermentation rate was higher for solid agar-adapted strains compared to liquid hydrolyzate-adapted strains. At a higher rotation speed (150 rpm), there was a faster sugar consumption and ethanol production for both the liquid-adapted and the wild-type strains. However, improvements in the fermentation rate between the liquid-adapted and wild strains were less pronounced at the high rotation speed.     

Fermentation of Reactive-Membrane-Extracted and Ammonium-Hydroxide-Conditioned Dilute-Acid-Pretreated Corn Stover

Acid-pretreated biomass contains various compounds (acetic acid, etc.) that are inhibitory to fermentative microorganisms. Removing or deactivating these compounds using detoxification methods such as overliming or ammonium hydroxide conditioning (AHC) improves sugar-to-ethanol yields. In this study, we treated the liquor fraction of dilute-acid-pretreated corn stover using AHC and a new reactive membrane extraction technique, both separately and in combination, and then the sugars in the treated liquors were fermented to ethanol with the glucose–xylose-fermenting bacterium, Zymomonas mobilis 8b. We performed reactive extraction with mixtures of octanol/Alamine 336 or oleyl alcohol/Alamine 336. The best ethanol yields and rates were achieved for oleyl alcohol-extracted hydrolysates followed by AHC hydrolysates, while octanol-extracted hydrolysates were unfermentable because highly toxic octanol was found in the hydrolysate. Adding olive oil significantly improved yields for octanol-extracted hydrolysate. Additional work is underway to determine if this technology is a cost-effective alternative to traditional hydrolysate conditioning processes.     

Fungal Cellulase/Xylanase Production and Corresponding Hydrolysis Using Pretreated Corn Stover as Substrates

Three pretreated corn stover (ammonia fiber expansion, dilute acid, and dilute alkali) were used as carbon source to culture Trichoderma reesei Rut C-30 for cellulase and xylanase production. The results indicated that the cultures on ammonia fiber expansion and alkali pretreated corn stover had better enzyme production than the acid pretreated ones. The consequent enzymatic hydrolysis was performed applying fungal enzymes on pretreated corn stover samples. Tukey’s statistical comparisons exhibited that there were significant differences on enzymatic hydrolysis among different combination of fungal enzymes and pretreated corn stover. The higher sugar yields were achieved by the enzymatic hydrolysis of dilute alkali pretreated corn stover.     

Fractionation of Corn Fiber Treated by Soaking in Aqueous Ammonia (SAA) for Isolation of Hemicellulose B and Production of C5 Sugars by Enzyme Hydrolysis

A process was developed to fractionate and isolate the hemicellulose B component of corn fiber generated by corn wet milling. The process consisted of pretreatment by soaking in aqueous ammonia followed by enzymatic cellulose hydrolysis, during which the hemicellulose B was solubilized by cleavage into xylo-oligosaccharides and subsequently recovered by precipitation with ethanol. The pretreatment step resulted in high retention of major sugars and improvement of subsequent enzymatic hydrolysis. The recovered hemicellulose B was hydrolyzed by a cocktail of enzymes that consisted of β-glucosidase, pectinase, xylanase, and ferulic acid esterase (FAE). Xylanase alone was ineffective, demonstrating yields of less than 2% of xylose and arabinose. The greatest xylose and arabinose yields, 44% and 53%, respectively, were obtained by the combination of pectinase and FAE. A mass balance accounted for 87% of the initially present glucan, 91% of the xylan, and 90% of the arabinan. The developed process offered a means for production of corn fiber gum as a value-added co-product and C5 sugars, which could be converted to other valuable co-products through fermentation in a corn wet-milling biorefinery.     

秸秆生产乙醇预处理关键技术

乙醇是一种很有希望替代有限石油的燃料。目前燃料乙醇已在我国部分省市得到应用。我国目前燃料乙醇生产的主要原料是陈化粮,但我国陈化粮可用于燃料乙醇生产的量十分有限。真正可大量转化乙醇的应是纤维质材料。纤维质材料转化乙醇的挑战性问题是产量偏低、成本偏高。纤维质材料的预处理是转化乙醇过程中的关键步骤,该步骤的优化可明显提高纤维素的水解率,进而降低乙醇的生产成本。本文总结了纤维质材料预处理的各种方法,对各种方法的优缺点进行了综述和分析,并对生物质预处理技术发展的前景进行了展望。     

Production of Terephthalic Acid from Corn Stover Lignin

Funneling and functionalization of a mixture of lignin‐derived monomers into a single high‐value chemical is fascinating. Reported herein is a three‐step strategy for the production of terephthalic acid (TPA) from lignin‐derived monomer mixtures, in which redundant, non‐uniform substitutes such as methoxy groups are removed and the desired carboxy groups are introduced. This strategy begins with the hydro‐treatment of corn‐stover‐derived lignin oil over a supported molybdenum catalyst to selectively remove methoxy groups. The generated 4‐alkylphenols are converted into 4‐alkylbenzoic acids by carbonylation with carbon monoxide. The Co‐Mn‐Br catalyst then oxidizes various alkyl chains into carboxy groups, transforming the 4‐alkylbenzoic acid mixture into a single product: TPA. For this route, the overall yields of TPA based on lignin content of corn stover could reach 15.5 wt %, and importantly, TPA with greater than 99 % purity was obtained simply by first decanting the reaction mixture and then washing the solid product with water.     

秸秆生产乙醇预处理关键技术

乙醇是一种很有希望替代有限石油的燃料.目前燃料乙醇已在我国部分省市得到应用.我国目前燃料乙醇生产的主要原料是陈化粮,但我国陈化粮可用于燃料乙醇生产的量十分有限.真正可大量转化乙醇的应是纤维质材料.纤维质材料转化乙醇的挑战性问题是产量偏低、成本偏高.纤维质材料的预处理是转化乙醇过程中的关键步骤,该步骤的优化可明显提高纤维素的水解率,进而降低乙醇的生产成本.本文总结了纤维质材料预处理的各种方法,对各种方法的优缺点进行了综述和分析,并对生物质预处理技术发展的前景进行了展望.     

Rapid Determination of Cellulose and Hemicellulose Contents in Corn Stover Using Near-Infrared Spectroscopy Combined with Wavelength Selection

The contents of cellulose and hemicellulose (C and H) in corn stover (CS) have an important influence on its biochemical transformation and utilization. To rapidly detect the C and H contents in CS by near-infrared spectroscopy (NIRS), the characteristic wavelength selection algorithms of backward partial least squares (BIPLS), competitive adaptive reweighted sampling (CARS), BIPLS combined with CARS, BIPLS combined with a genetic simulated annealing algorithm (GSA), and CARS combined with a GSA were used to select the wavelength variables (WVs) for C and H, and the corresponding regression correction models were established. The results showed that five wavelength selection algorithms could effectively eliminate irrelevant redundant WVs, and their modeling performance was significantly superior to that of the full spectrum. Through comparison and analysis, it was found that CARS combined with GSA had the best comprehensive performance; the predictive root mean squared errors of the C and H regression model were 0.786% and 0.893%, and the residual predictive deviations were 3.815 and 12.435, respectively. The wavelength selection algorithm could effectively improve the accuracy of the quantitative analysis of C and H contents in CS by NIRS, providing theoretical support for the research and development of related online detection equipment.     

Effects of Low Moisture Anhydrous Ammonia (LMAA) Pretreatment at Controlled Ammoniation Temperatures on Enzymatic Hydrolysis of Corn Stover

Corn stover was treated using low-moisture anhydrous ammonia (LMAA) at controlled ammoniation temperature. Moisturized corn stover (50 % moisture) was contacted with anhydrous ammonia (0.1 g NH₃/g-biomass) in a batch reactor at various temperatures (ambient to 150 °C). After ammoniation at elevated and controlled temperature, ammoniated corn stover was pretreated at various temperatures (60–150 °C) for 72–144 h. Change in composition was marginal at low pretreatment temperature but was relatively severe with pretreatment at high temperature (130–150 °C). The latter resulted in low enzymatic digestibility. It was also observed that extreme levels (either high or low) of residual ammonia affected enzymatic digestibility, while residual ammonia improved by 1.0–1.5 %. The LMAA method enhanced enzymatic digestibility compared to untreated corn stover (29.8 %). The highest glucan and xylan digestibility (84.1 and 73.6 %, respectively) was obtained under the optimal LMAA conditions (i.e., ammoniation at 70 °C for 20 min, followed by pretreatment at 90 °C for 48 h).     

Extraction of Proteins from Switchgrass Using Aqueous Ammonia within an Integrated Biorefinery

Switchgrass (Panicum vergatum) is a potential feedstock for future cellulosic biorefineries. Such a feedstock may also provide protein, most likely for use as an animal feed. In this paper, we present a potential scheme for integrating fiber processing with extractions to obtain both sugar and protein products from switchgrass pretreated using Ammonia Fiber Expansion (AFEX). Solutions of 3% aqueous ammonia at pH 10.5 provided optimal extraction of proteins. Addition of the nonionic surfactant Tween-80 improved protein recovery for AFEX-treated materials. It was determined that an extraction following AFEX solubilized approximately 40% of the protein, while a subsequent hydrolysis solubilized much of the remaining protein while producing 325 g sugar per kg biomass. The remaining insoluble residue contained very little protein or ash, making it ideal for heat and power production. In contrast, an extraction following hydrolysis solubilized only 68% of the original protein in the biomass, while obtaining slightly higher sugar yields.     

Enzymatic Conversion of Xylan Residues from Dilute Acid-Pretreated Corn Stover

Enzymatic conversion of oligomeric xylose and insoluble xylan remaining after effective pretreatment offers significant potential to improve xylan-to-xylose yields while minimizing yields of degredation products and fermentation inhibitors. In this work, a commercial enzyme cocktail is demonstrated to convert up to 70?% of xylo-oligomers found in dilute acid-pretreated hydrolyzate liquor at varying levels of dilution when supplemented with accessory enzymes targeting common side chains. Commercial enzyme cocktails are also shown to convert roughly 80?% of insoluble xylan remaining after effective high-solids, dilute acid pretreatment.     

Direct Synthesis of Nitriles from Aldehydes Using Chloramine-T/KI in Aqueous Ammonia

A convenient method for direct conversion of aldehydes into nitriles has been developed using chloramine-T/KI in aqueous ammonia.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource: Full experimental and spectral details.]     

Two-Stage Fractionation of a Mixture of Pesticides by Micropreparative TLC and HPLC

JPC – Journal of Planar Chromatography – Modern TLC - A ten-component mixture of pesticides was applied to the edge of the layer in ‘frontal + elution’ mode for preliminary...     

秸秆稀酸水解液中抑制物的研究

采用气相色谱/质谱(GC/MS)法对秸秆稀酸水解液中主要抑制物进行分析与鉴定,得到主要抑制物为乙酸、糠醛、乙酰丙酸和5-羟甲基糠醛.用气相色谱法定量乙酸、糠醛、乙酰丙酸和5-羟甲基糠醛的线性范围分别为0.07～0.51、0.05～0.351、0.11～0.85、0.08～0.63 mg/mL,相关系数大于0.995.对秸秆稀酸水解液进行测定的结果表明,不同温度下木糖和葡萄糖降解有着不同变化规律,为秸秆稀酸水解工艺的改进提供了参考.