Efficiency of acetic acid and formic acid as a catalyst in catalytical and mechanocatalytical pretreatment of barley straw

In this study, the potential of organic acids (formic acid, acetic acid) in a catalytical and mechanocatalytic conversion of lignocellulosic barley straw to valuable sugars is explored using sulfuric acid as a reference. Acid-catalyzed hydrolysis has been carried out with acid-impregnated samples as well as unmodified barley straw. In the mechanocatalytical approach, pretreatment consists of impregnation with the acid catalyst and mechanical treatment by ball milling following chemical hydrolysis. Straw samples and residues were analyzed by Fourier transform infrared spectrometry (FT-IR) whereas hydrolysate analysis was based on total reducing sugar (TRS) determination following the DNS method and capillary electrophoresis (CE) analysis. The results indicated that acetic acid and formic acid are rather mild acids yielding low TRS levels compared to the reference acid. Mechanocatalytical pretreatment slightly increased TRS yields, but not significantly. Strikingly, sulfuric acid showed an efficient conversion efficiency yielding almost 45% of TRS. Furthermore, this study provided evidence for the acetylation of straw components when acetic acid was used as catalyst. Alkali hydrolysis induced the de-esterification, but revealed no significant increase of TRS yields.     

Mesophilic biohydrogen production from calcium hydroxide treated wheat straw

The use of Ca(OH)₂ pre-treatment to improve fermentative biohydrogen yields, from wheat straw was investigated. Wheat straw was pre-treated with 7.4% (w/w) Ca(OH)₂ at ambient temperature (20 °C) for 2, 5, 8, and 12 days, prior to 35 °C fermentation with sewage sludge inoculum. Biohydrogen yields were evaluated during dark fermentation and simultaneous saccharification fermentation (SSF) of total pre-treated straw material and compared to those from separated solid and hydrolysate fractions. Ca(OH)₂ pre-treatment followed by SSF, exhibited a synergetic relationship. On average, 58.78 mL-H₂ g-VS⁻¹ was produced from SSF of pre-treated and filtered solids. This was accompanied by approximately a 10-fold increase in volatile fatty acid production, compared to the untreated control. By omitting pre-treatment hydrolysate liquors from SSF, H₂ production increased on average by 35.8%, per VS of harvested straw. Additional inhibition studies indicated that CaCO₃, formed as a result of pre-treatment pH control, could promote homoacetogenesis and reduce biohydrogen yields.     

The effect of alkali treatment on rice husk moisture content and drying kinetics

The utilization of rice husks for energy production is often problematic due to their high ash content. A simple method for silica ash removal is the treatment of the husks with sodium hydroxide solutions. The alkali treatment can induce other changes to the husks which need to be investigated. Here, the effects of alkali treatment on the moisture content and drying kinetics of the samples were investigated. The alkali treatment is shown to result in an increase in moisture retention by the as-prepared biomass. Response surface methodology (RSM) using a Box–Behnken design (BBD) is employed to investigate the effects of various input parameters, namely reaction temperature, duration, and alkali mass ratio on moisture uptake of the rice husk. In addition, the drying kinetics of the as-prepared samples are modeled and compared to raw husk prior to treatment. The results show a small increase in the effective diffusivity and a significant decrease in the activation energy required for drying the treated samples.     

Biogas production from reed biomass: Effect of pretreatment using different steam explosion conditions

Biogas production often competes with food and feed production for the raw materials and cropland required for cultivation. Common reed offers an alternative source of biomass for biogas production, alleviating this conflict. Effective microbiological conversion of this type of lignocellulosic biomass requires a pretreatment process. This study aims to determine the specific methane yields of steam-exploded reed as well as to identify how pretreatment conditions influence its physico-chemical characteristics. For this purpose, reed was pretreated with steam explosion at severity factors ranging from 2.47 to 4.83. The effects on methane yields were analyzed in batch experiments. Scanning electron microscopy (SEM) images were captured and detailed chemical analyses of the substrates carried out. Results show that the digestibility of reed biomass improved remarkably after pretreatment. Compared to the untreated sample, steam explosion increased the specific methane yield up to 89% after pretreatment at 200 °C for 15 min. However, methane yield decreased under harsher conditions, which may be due to the formation of degradation compounds during the pretreatment.     

Comparison of steam-alkali-chemical and microwave-alkali pretreatment for enhancing the enzymatic saccharification of oil palm trunk

This paper demonstrates two different pretreatment protocols for oil palm trunks (OPT); steam-alkali-chemical (SAC) and microwave-alkali (Mw-A) method. The composition, morphology, structure and crystallinity of OPT before and after pretreatment were analyzed. The effectiveness of the pretreated methods was investigated by performing enzymatic saccharification on the OPT. The physiochemical factors namely: enzyme ratio (cellulase to β-glucosidase), pH, temperature and substrate loading (w/v) on enzymatic saccharification were also investigated. The pre-determined optimal conditions were then used for further enzymatic hydrolysis of raw and pretreated OPT substrates. The results revealed a huge degree of reduction in lignin, up to 89% for SAC treated OPT and at least 15% for Mw-A treated OPT sample as compared to untreated ones. High glucose accumulation (79.4%) was obtained after 72 h saccharification for both pretreated OPT samples.     

Purified Butanol from Lignocellulose – Solvent-Impregnated Resins for an Integrated Selective Removal

In traditional microbial biobutanol production, the solvent must be recovered during fermentation process for a sufficient space-time yield. Thermal separation is not feasible due to the boiling point of n-butanol. As an integrated and selective solid-liquid separation alternative, solvent impregnated resins (SIRs) were applied. Two polymeric resins were evaluated and an extractant screening was conducted. Vacuum application with vapor collection in fixed-bed column as bioreactor bypass was successfully implemented as butanol desorption step. In course of further increasing process economics, fermentation with renewable lignocellulosic substrates was conducted using Clostridium acetobutylicum. Utilization of SIR was shown to be a potential strategy for solvent removal from fermentation broth, while application of a bypass column allows for product removal and recovery at once.     

Improving physicochemical characteristics and anaerobic digestion performance of rice straw via ammonia pretreatment at varying concentrations and moisture levels

Rice straw physicochemical characteristics and anaerobic digestion(AD) performance via ammonia pretreatment at varying ammonia concentrations(2%, 4%, and 6%) and moisture contents(30%, 50%, 70%, and 90%)under a mild condition were investigated. The results showed that the ammonia pretreatment effectively damaged the rice straw structure, increased the soluble organic concentration, and improved rice straw hydrolysis and AD performance. After pretreatment, the ester bond and ether bond were ruptured in lignocellulose and the volatile fatty acids(VFAs) were within the range of 1457.81–1823.67 mg·L~(-1). In addition, ammonia pretreatment had high selectivity on lignin removal, resulting in a maximum lignin removal rate of 50.80%. The highest methane yield of rice straw was 250.34 ml·(g VS)~(-1) at a 4% ammonia concentration coupled with a 70% moisture content, which was 28.55% higher than that of the control. The result showed that ammonia pretreatment of rice straw is technically suitable to enhance AD performance for further application.     

Current Trends in Pretreatment and Fractionation of Lignocellulose as Reflected in Industrial Patent Activities

The pretreatment process to disintegrate lignocellulose and to fractionate its three main components hemicellulose, cellulose, and lignin, is a crucial step to enable sustainable and economic value chains based on biomass feedstock. This review provides an overview of the recent patenting activities on pretreatment. Most of these activities focus on optimization of different known processes to improve economics, such as increased catalyst efficiency, effluents recirculation, or lignin valorization. However, also a number of patents and demonstration activities based on emerging concepts for pretreatments are observed.     

Pyrolysis of sugarcane bagasse pretreated with sulfuric acid

Pyrolysis is a promising technique for the recovery of useful gas, tar, and solid products from biomass waste. However, the low tar yields obtained from lignocellulosic biomass are a significant drawback. To enhance tar yields, sugarcane bagasse, which is the most abundant agricultural waste in Fiji, was pretreated at ambient temperature and atmospheric pressure using various sulfuric acid (H₂SO₄) concentrations. Here, the ether bonds of cellulose, hemicellulose, and lignin were partially hydrolyzed. The pretreated samples were then pyrolyzed at 500 °C, and it was confirmed that H₂SO₄-pretreatment disrupted the bagasse cell structure, with the thermogravimetry and differential thermogravimetry results confirming that decomposition occurred at lower temperatures after pretreatment. In addition, tar yields were significantly enhanced from 5.6 wt% to 13.4 wt% for the untreated and 3 M H₂SO₄-pretreated samples respectively. The main components detected in this tar product were levoglucosan, andcellulose-and hemicellulose-derived products, whose proportions were increased following pretreatment. Thus, our work demonstrates that dilute acid pretreatment enhances tar production from sugarcane bagasse due to the production of shorter chain components via the partial hydrolysis of ether bonds.     

Optimal control of dilute acid pretreatment and enzymatic hydrolysis for processing lignocellulosic feedstock

Lignocellulosic feedstock is one of the potential renewable sources for producing ethanol for transportation. The process steps viz., acid pretreatment and enzymatic hydrolysis in bio-chemical process route are intended to produce fermentable sugars, which can be readily fermented for producing ethanol. However, the dilute acid pre-treatment and enzymatic hydrolysis process steps are found to be economically inefficient. The present work aims at optimizing these process steps for improving the process performance. Such optimization is expected to increase conversion, reduce energy or material requirement, thereby improving the economics. The kinetic models of acid pretreatment and enzymatic hydrolysis for lignocellulosic feedstock processing are adapted from literature. Subsequently, these kinetic models are augmented by associated mass and energy balances, to develop a batch reactor model and fed-batch reactor model for dilute acid pretreatment and enzymatic hydrolysis processes, respectively. Optimal control with Pontryagin's maximum principle has been implemented to determine the optimal time dependent profiles of heating and cooling fluid flow rates and operating temperatures for acid pretreatment and substrate feed rate profile for enzymatic hydrolysis to optimize the respective processes performance. Different objective functions such as maximizing concentration of desired product, minimizing the batch time, and maximizing profit have been considered. The simulation results yielded an increase of 6.7% and 8.8% in final concentration of desired product; 43% and 42.5% reduction in batch processing time for pretreatment and enzymatic hydrolysis processes, respectively. Finally, the simulation results have also provided optimal operating policies which have increased the profit of pretreatment by 124% and enzymatic hydrolysis by 150%, thereby improving the techno-economic feasibility for processing lignocellulosic feedstock.