Two-stage Pretreatment Research Articles

Optimized Furfural Production Using the Acid Catalytic Conversion of Xylan Liquor from Organosolv-Fractionated Rice Husk

This study determined the optimal production of furfural (FuR) from liquid hydrolysate xylan liquor obtained through a two-stage pretreatment process using NaOH for de-ashing and EtOH for the delignification of raw rice husk (RH). The de-ashing pretreatment was conducted at 150 °C, with 6.0% (w/v) NaOH and a reaction time of 40 min. The optimal conditions for delignification pretreatment, performed using an organosolv fractionation method with EtOH, were a reaction temperature of 150 °C, 60% (v/v) EtOH, 0.25% (w/v) H2SO4, and a reaction time of 90 min. Through a two-stage pretreatment process, a liquid hydrolysate in the form of xylan liquor was obtained, which was subjected to an acid catalytic conversion process to produce FuR. The process conditions were varied, with reaction temperatures of 130–170 °C, H2SO4 catalyst concentrations of 1.0–3.0 wt.%, and reaction times of 0–90 min. The Response Surface Methodology tool was used to identify the optimal FuR yield from xylan liquor. Ultimately, the optimal process conditions for the acid catalytic conversion were found to be a substrate-to-catalyst ratio of 2:8, a reaction temperature of 168.9 °C, a catalyst concentration of 1.9 wt.%, and a reaction time of 41.24 min, achieving an FuR yield of 67.31%.

Analysis of Energy Potential of Switchgrass Biomass

In this research, the energy potential of switchgrass (SG) was analyzed to find promising directions for producing bioenergy from this biomass. The first direction is determining the thermal energy of bioethanol extracted from SG biomass after its pretreatment, enzymatic hydrolysis (saccharification), and fermentation of the resulting glucose. It was established that after a two-stage pretreatment of 1 ton of SG with dilute solutions of nitric acid and alkali, the largest amount of bioethanol can be extracted with an energy potential of 4.9 GJ. It is also shown that by the utilization of solid and liquid waste, the production cost of bioethanol can be reduced. On the other hand, the direct combustion of 1 ton of the initial SG biomass used as a solid biofuel provides an increased amount of thermal energy of 18.3 GJ, which is 3.7 times higher than the energy potential of the resulting bioethanol extracted from 1 ton of this biomass. Thus, if the ultimate goal is to obtain the maximum energy amount, then another direction for obtaining bioenergy from biomass should be implemented, namely, direct combustion, preferably after pelletizing. Studies have shown that fuel characteristics of SG pellets such as the gross thermal energy and density of thermal energy are lower than those of wood pellets, but they can be improved if the SG biomass is densified into pellets together with binders made from polymer waste.

Preparation of Cellulose Fiber from Cattail Using Two-Stage Pretreatment and Choline Chloride-Oxalic Acid Deep Eutectic Solvent Extraction for Oil Adsorption

Preparation of Cellulose Fiber from Cattail Using Two-Stage Pretreatment and Choline Chloride-Oxalic Acid Deep Eutectic Solvent Extraction for Oil Adsorption

Development of complete hydrometallurgical processes for gold recovery from ICs and CPUs using ionic liquids

Integrated circuits (ICs) and central processing units (CPUs), essential components of electrical and electronic equipment (EEE), are complex composite materials rich in recyclable high-value strategic and critical metals, with many in concentrations higher than in their natural ores. With gold the most valuable metal present, increase in demand for gold for EEE and its limited availability have led to a steep rise in the market price of gold, making gold recycling a high priority to meet demand. To overcome the limitations associated with conventional technologies for recycling e-waste, the use of greener technologies (ionic liquids (ILs) as leaching agents), offers greater potential for the recovery of gold from e-waste components. While previous studies have demonstrated the efficiency and feasibility of using ILs for gold recovery, these works predominantly concentrate on the extraction stage and often utilise simulated solutions, lacking the implementation of a complete process validated with real samples to effectively assess its overall effectiveness. In this work, a simulated Model Test System was used to determine the optimal leaching and extraction conditions before application to real samples. With copper being the most abundant metal in the e-waste fractions, to access the gold necessitated a two-stage pre-treatment (nitric acid leaching followed by aqua regia leaching) to ensure complete removal of copper and deliver a gold-enriched leach liquor. Gold extraction from the leach liquor was achieved by liquid-liquid extraction using Cyphos 101 (0.1 M in toluene with an O:A = 1:1, 20 °C, 150 rpm, and 15 min) and as a second process by sorption extraction with loaded resins (Amberlite XAD-7 with 300 mg of Cyphos 101/g of resins at 20 °C, 150 rpm and 3 h). In both processes, complete stripping and desorption of gold was achieved (0.5 M thiourea in 0.5 M HCl) and gold recovered, as nanoparticles of purity ≥95%, via a reduction step using a sodium borohydride solution (0.1 M NaBH4 in 0.1 M NaOH). These two hydrometallurgical processes developed can achieve overall efficiencies of ≥95% for gold recovery from real e-waste components, permit the reuse of the IL and resins up to five consecutive times, and offer a promising approach for recovery from any e-waste stream rich in gold.

Efficacy and Functional Mechanisms of a Two-Stage Pretreatment Approach Based on Alkali and Ionic Liquid for Bioconversion of Waste Medium-Density Fiberboard.

A novel pretreatment strategy utilizing a combination of NaOH and 1-Butyl-3-methylimidazolium chloride ([Bmim]Cl) was proposed to enhance the enzymatic hydrolysis of abandoned Medium-density fiberboard (MDF). The synergistic effect of NaOH and [Bmim]Cl pretreatment significantly improved the glucose yield, reaching 445.8 mg/g within 72 h, which was 5.04 times higher than that of the untreated samples. The working mechanism was elucidated according to chemical composition, as well as FTIR, 13C NMR, XRD, and SEM analyses. The combined effects of NaOH and [Bmim]Cl led to lignin degradation, hemicellulose removal, the destruction and erosion of crystalline regions, pores, and an irregular microscopic morphology. In addition, by comparing the enzymatic hydrolysis sugar yield and elemental nitrogen content of untreated MDF samples, eucalyptus, and hot mill fibers (HMF), it was demonstrated that the presence of adhesives and additives in waste MDF significantly influences its hydrolysis process. The sugar yield of untreated MDF samples (88.5 mg/g) was compared with those subjected to hydrothermal pretreatment (183.2 mg/g), Ionic liquid (IL) pretreatment (406.1 mg/g), and microwave-assisted ionic liquid pretreatment (MWI) (281.3 mg/g). A long water bath pretreatment can reduce the effect of adhesives and additives on the enzymatic hydrolysis of waste MDF. The sugar yield produced by the combined pretreatment proposed in this study and the removal ability of adhesives and additives highlight the great potential of our pretreatment technology in the recycling of waste fiberboard.

EFFECTS OF COMBINED CHEMICAL AND HYDROTHERMAL PRETREATMENT ON PAPYRUS CELLULOSE STRUCTURE

"Papyrus (Cyperus papyrus L.) is a lignocellulosic plant suitable for many applications when properly pretreated. This study explores the potential of a two-stage pretreatment (combining hydrothermal and chemical methods) on the characteristics of cellulose fibers derived from papyrus. One-stage and two-stage pretreatments were compared, utilizing sodium hydroxide (NaOH) and ferric chloride (FeCl3) chemical solutions at a 3% (w/v) concentration. Chemical pretreatment was employed for one-stage processing, while hydrothermal pretreatment was introduced prior to chemical pretreatment. As the liquid hot-water process intensified, significant changes in chemical composition and morphology occurred. Hydrothermal pretreatment partially eliminates hemicelluloses and lignin, while increasing the cellulose content and enhancing fiber crystallinity. Following the pulping and bleaching stages, it was determined that the FeCl3-based two-stage pretreatment exhibited the greatest potential for cellulose recovery and hemicelluloses and lignin removal, yielding the highest crystallinity index."

Two-Stage Pretreatment of Jerusalem Artichoke Stalks with Wastewater Recycling and Lignin Recovery for the Biorefinery of Lignocellulosic Biomass

Jerusalem artichoke (Helianthus tuberosus L.) is emerging as one of the energy plants considered for biofuel production. Alkali and alkali-involved pretreatment methods have been widely used for the bioconversion of cellulosic materials due to their high sugar yield and low inhibitor release. However, the recovery and treatment of wastewater (black liquor) have been poorly studied. Here, we present a novel two-stage pretreatment process design for recycling black liquor. Jerusalem artichoke stalk (JAS) was first treated with 2% (w/v) NaOH, after which lignin was recovered by H2SO4 at pH 2.0 from the black liquor. The recycled solutions were subsequently used to treat the NaOH-pretreated JAS for the second time to dissolve hemicellulose. CO-pretreated JAS, hydrolysates, and acid-insoluble lignin were obtained after the above-mentioned two-stage pretreatment. A reducing sugar yield of 809.98 mg/g Co-pretreated JAS was achieved after 48 h at 5% substrate concentration using a cellulase dosage of 25 FPU/g substrate. In addition, hydrolysates containing xylose and acid-insoluble lignin were obtained as byproducts. The pretreatment strategy described here using alkali and acid combined with wastewater recycling provides an alternative approach for cellulosic biorefinery.

Technoeconomic evaluation of recent process improvements in production of sugar and high-value lignin co-products via two-stage Cu-catalyzed alkaline-oxidative pretreatment

BackgroundA lignocellulose-to-biofuel biorefinery process that enables multiple product streams is recognized as a promising strategy to improve the economics of this biorefinery and to accelerate technology commercialization. We recently identified an innovative pretreatment technology that enables of the production of sugars at high yields while simultaneously generating a high-quality lignin stream that has been demonstrated as both a promising renewable polyol replacement for polyurethane applications and is highly susceptible to depolymerization into monomers. This technology comprises a two-stage pretreatment approach that includes an alkaline pre-extraction followed by a metal-catalyzed alkaline-oxidative pretreatment. Our recent work demonstrated that H2O2 and O2 act synergistically as co-oxidants during the alkaline-oxidative pretreatment and could significantly reduce the pretreatment chemical input while maintaining high sugar yields (~ 95% glucose and ~ 100% xylose of initial sugar composition), high lignin yields (~ 75% of initial lignin), and improvements in lignin usage.ResultsThis study considers the economic impact of these advances and provides strategies that could lead to additional economic improvements for future commercialization. The results of the technoeconomic analysis (TEA) demonstrated that adding O2 as a co-oxidant at 50 psig for the alkaline-oxidative pretreatment and reducing the raw material input reduced the minimum fuel selling price from $1.08/L to $0.85/L, assuming recoverable lignin is used as a polyol replacement. If additional lignin can be recovered and sold as more valuable monomers, the minimum fuel selling price (MFSP) can be further reduced to $0.73/L.ConclusionsThe present work demonstrated that high sugar and lignin yields combined with low raw material inputs and increasing the value of lignin could greatly increase the economic viability of a poplar-based biorefinery. Continued research on integrating sugar production with lignin valorization is thus warranted to confirm this economic potential as the technology matures.

A Comparative Study of Various Pretreatment Approaches for Bio-Ethanol Production from Willow Sawdust, Using Co-Cultures and Mono-Cultures of Different Yeast Strains.

The effect of different pretreatment approaches based on alkali (NaOH)/hydrogen peroxide (H2O2) on willow sawdust (WS) biomass, in terms of delignification efficiency, structural changes of lignocellulose and subsequent fermentation toward ethanol, was investigated. Bioethanol production was carried out using the conventional yeast Saccharomyces cerevisiae, as well as three non-conventional yeasts strains, i.e., Pichia stipitis, Pachysolen tannophilus, Wickerhamomyces anomalus X19, separately and in co-cultures. The experimental results showed that a two-stage pretreatment approach (NaOH (0.5% w/v) for 24 h and H2O2 (0.5% v/v) for 24 h) led to higher delignification (38.3 ± 0.1%) and saccharification efficiency (31.7 ± 0.3%) and higher ethanol concentration and yield. Monocultures of S. cerevisiae or W. anomalus X19 and co-cultures with P. stipitis exhibited ethanol yields in the range of 11.67 ± 0.21 to 13.81 ± 0.20 g/100 g total solids (TS). When WS was subjected to H2O2 (0.5% v/v) alone for 24 h, the lowest ethanol yields were observed for all yeast strains, due to the minor impact of this treatment on the main chemical and structural WS characteristics. In order to decide which is the best pretreatment approach, a detailed techno-economical assessment is needed, which will take into account the ethanol yields and the minimum processing cost.

Insight into understanding sequential two-stage pretreatment on modifying lignin physiochemical properties and improving holistic utilization of renewable lignocellulose biomass

The key to obtain the full benefits of renewable lignocellulosic biomass is to develop sustainable and economical fractionation technology of lignocellulosic components. Acidic pretreatment usually solubilizes the majority of hemicellulose, but also aggravates lignin repolymerization which would intensify lignin inhibition on cellulose hydrolysis. Thus, in this work, two approaches were utilized to modify the lignin physiochemical properties and synergistically improve holistic utilization of lignocellulose biomass. Firstly, the addition of 2-naphthol in dilute acid (DA) pretreatment largely suppressed lignin repolymerization and mitigated lignin inhibition, resulting in increased cellulose hydrolysis yield from 46.81% to 55.74%. Secondly, it was found that the phenolic groups of lignin played a pivotal role in determining the ease of cellulose hydrolysis, thus a second-stage treatment with acid-chlorite (CHL) or poly(ethylene glycol) diglycidyl ether (PEE) was introduced to selectively oxidize/block phenolic groups of lignin, which further improved cellulose hydrolysis to theoretically maximum yield. In addition to enhanced cellulose hydrolysis, the lignin residues recovered after PEE modification and enzymatic hydrolysis could be used as high-capacity adsorbents for lead ions removal from wastewater, while xylose was utilized for xylonic acid production. Results showed that the biorefinery process based on DA pretreatment and PEE post-treatment could enable a holistic utilization of renewable lignocellulosic biomass.

Comparative study of single stage and two-stage pretreatments on corn stover: A kinetic assessment

The effects of two-stage pretreatment consisting of tepid water (first stage) and FeCl3 (second stage) pretreatments on hemicellulose hydrolysis were investigated. A kinetic comparison between the single stage (FeCl3-only pretreatment) and the two-stage pretreatment was evaluated. Compared with single stage pretreatment, the two-stage pretreatment decreased the activation energy Ea of hemicellulose hydrolysis by 38.3% and decreased the optimal reaction time by 34.8%. Besides, the xylose content increased by 14.9% and the catalyst dosage decreased by 31.9% in the two-stage pretreatment. This study provided an efficient pretreatment process for hemicellulose hydrolysis.

Sustainable Second-Generation Ethanol Production from Switchgrass Biomass via Co-fermentation of Pentoses and Hexoses Using Novel Wild Yeasts

The production of second-generation (2G) ethanol remains an interesting proposition for the implementation of sustainable and net carbon–neutral energy systems. To be economically viable, 2G biorefineries must make use of all processing streams, including the less desirable pentose (C5) sugar stream. In this work, a strategy of sequential dilute acid and alkaline pretreatment of the lignocellulosic feedstock, switchgrass, was implemented for improving the fermentable sugar yield. The hemicellulose-enriched hydrolysate obtained after dilute acid pretreatment was fermented by a newly isolated wild Scheffersomyces parashehatae strain—UFMG-HM-60.1b; the corresponding ethanol yield (YPS) and volumetric productivity (QP) were 0.19 g/g and 0.16 g/L h, respectively. The remaining switchgrass cellulignin fraction was subjected to optimized alkaline delignification at 152 ºC for 30 min. Then, the delignified solid fraction was subjected to contiguous enzymatic saccharification and fermentation releasing a glucose (C6) sugar stream. The control yeast strain, Saccharomyces cerevisiae 174, displayed an ethanol YPS of 0.46 g/g and QP of 0.70 g/L h for the C6 sugar stream, whereas the above-mentioned wild strain presented YPS and QP of 0.29 g/g and 0.38 g/L h, respectively. Upon combining the conversion of hemicellulose (37%) and cellulose-derived sugars (57%), the wild S. parashehatae strain provided higher yield (94%) than the generic S. cerevisiae (90%). Henceforth, our sequential two-stage pretreatment and fermentation of C5 and C6 sugar streams provides a pathway for maximum utilization of switchgrass carbohydrates for 2G ethanol production.

Production of biogas and fermentable sugars from spent brewery grains: Evaluation of one- and two-stage thermal pretreatment in an integrated biorefinery

In this study, the production of fermentable sugars and biogas from thermally pretreated brewer’s spent grains (BSGs) was investigated. There were two autohydrolysis conditions (C1-1S: 180 ºC, 30 min, 5 mLH2O gBSG−1 and C2-1S: 180 ºC, 60 min, 5 mLH2O gBSG−1) which were evaluated, with and without a previous low severity pretreatment (80 ºC, 10 min, 10 mLH2O gBSG−1). The highest specific methane production (302.4 NLCH4 kgCOD−1) and enzymatic hydrolysis yield (EHY of 98%, 50 FPU gBSG−1) were obtained from the two-stage pretreatment, with the second stage operated at 180 °C for 60 min, 5 mLH2O gBSG−1. However, in the integrated process, the two-stage pretreatment with the second stage performed at 180 °C for 30 min, and 5 mLH2O gBSG−1 was the best condition to produce fermentable sugars from enzymatic hydrolysis of pretreated BSGs, using a lower enzyme loading (EHY of 93%, 25 FPU gBSG−1). The burning of biogas produced from an anaerobic digestion of liquid fractions (hydrolysates) generated after two-stage thermal pretreatment in a combined heat and power system can produce a net thermal energy of 1.71 MJ kgBSG dry basis−1 and electrical energy of 0.392 kW h kgBSG dry basis−1.

Pilot scale demonstration of a two-stage pretreatment and bioethanol fermentation process for cotton gin trash

A two-stage dilute acid and steam explosion (SE) pretreatment process was developed and evaluated at pilot scale for ethanol production from cotton gin trash (CGT). Optimal conditions for CGT processing were defined as 1:6 solids to liquids ratio with 9% H2SO4 wt. on solids at 180 °C for 15 min. during stage 1 with ensuing pressed fibres successively exposed to SE at 200 °C for 5 min during stage 2. SE fibres were highly acquiescent to enzyme hydrolysis (76%) in the presence of PEG 6000, yielding 381 g glucose kg−1 fibre. Simultaneous saccharification and fermentation (SSF) trials validated the selected process option and additional fed-batch SSFs confirmed titres above the minimum 4% ww-1 benchmark for economically viable distillation. The practicality of converting CGT to ethanol was demonstrated at pilot scale with titres above 4% ww-1 and a conversion efficiency of 60% t−1 dry GCT.

Optimization of two-stage pretreatment for maximizing ethanol production in 1.5G technology

Two-stage pretreatment conditions were optimized to convert corn fiber, separated from whole stillage in a corn dry grind ethanol plant, to fermentable sugars via hydrolysis. Liquid hot water pretreatment (25% solids) at 180 °C for 10 min, followed by three cycles of disk milling, provided maximum glucose, xylose, and arabinose yields of 88.5%, 41.0%, and 30.4% respectively after hydrolysis with Cellulase I. The glucose, xylose, and arabinose yields with Cellulase II at optimum conditions were 94.9%, 74.2%, and 66.3%, respectively. SSF of corn fiber using engineered yeast, with both Cellulase I and II, provided maximum ethanol concentrations of 2.13% and 2.73% (v/v). The protein content in the residual solid after fermentation was 47.95% and 52.05% for Cellulase I and II, respectively. This technology provides additional ethanol in a dry grind plant by converting corn fiber into ethanol and increases the protein content of DDGS, thereby improving the quality.

Self-standardization of quality of bacterial cellulose produced by Medusomyces gisevii in nutrient media derived from Miscanthus biomass

Bacterial cellulose (BC) was synthesized from biomass of Miscanthus grown in West Siberia. Miscanthus biomass was pretreated at atmospheric pressure with 4 wt.% solutions of HNO3 and NaOH in one and two stages. The effect of four methods of the pretreatment of the feedstock on BC yield and properties was examined. The resultant pulps were subjected to enzymatic hydrolysis with commercial CelloLux-A and BrewZyme BGX enzymes. Biosynthesis of BC was run under static and non-sterile conditions using Medusomyces gisevii Sa-12. The two-stage pretreatment of Miscanthus biomass gave a 20 % increase in BC production compared to the single-stage pretreatment. The resultant BC exhibited a high crystallinity index (88–93 %) and an extraordinarily high content of allomorph Iα (99–100 %), irrespective of the pretreatment method; therefore, it has been revealed for the first time that the Medusomyces gisevii Sa-12 symbiotic culture is capable of self-standardization against the quality of produced BC.

Effect of two-stage sodium hydroxide pretreatment on the composition and structure of Napier grass (Pakchong 1) (Pennisetum purpureum)

ABSTRACT Sodium hydroxide is ideal in removing lignin from lignocellulosic materials at an effective operational cost. Two-stage NaOH pretreatment was employed herein to investigate lignin and hemicellulose removal and understand the morphology of Napier grass (Pakchong 1) (Pennisetum purpureum), which is considered lignocellulosic due to its high carbohydrate content. NaOH was used at different concentrations (0, 1, 2, 3, and 4 wt.%) and presoak times (1, 2, 3, and 4 h). The results demonstrated that 3 wt.% NaOH at 121°C without presoak resulted in 83.5% lignin removal, with a cellulose to lignin ratio of 3.0. Moreover, the treated samples showed cracking and irregular patterns at optimal conditions.

Two-Stage Pretreatment with Steam Explosion and Chemical Treatment of Reed (Phragmites Australis) to Enhance its Glucose Conversion for Bioethanol Production

Two-Stage Pretreatment with Steam Explosion and Chemical Treatment of Reed (Phragmites Australis) to Enhance its Glucose Conversion for Bioethanol Production

An integrated approach to obtain xylo-oligosaccharides from sugarcane straw: From lab to pilot scale

Sugarcane straw (SS) is a widely available agricultural processing feedstock with the potential to produce 2nd generation bioethanol and bioproducts, in addition to the more conventional use for heat and/or electrical power generation. In this study, we investigated the operational parameters to maximize the production of xylo-oligosaccharides (XOS) using mild deacetylation, followed by hydrothermal pretreatment. From the laboratory to the pilot-scale, the optimized two-stage pretreatment promoted 81.5% and 70.5% hemicellulose solubilization and led to XOS yields up to 9.8% and 9.1% (w/w of initial straw), respectively. Moreover, different fungal xylanases were also tested to hydrolyze XOS into xylobiose (X2) and xylotriose (X3). GH10 from Aspergillus nidulans performed better than GH11 xylanases and the ratio of the desired products (X2 + X3) increased to 72% due to minimal monomeric sugar formation. Furthermore, a cellulose-rich fraction was obtained, which can be used in other high value-added applications, such as for the production of cello-oligomers.

Hydrothermal pretreatment and acid hydrolysis of coconut pulp residue for fermentable sugar production

Coconut pulp residue is the waste generated after the extraction of milk and oil. This material became an interest as feedstock for the production of biofuels and other bioproducts in a biorefinery context. The present study aimed to improve the release of sugar from coconut pulp residue through the optimization of sequential hydrothermal and acid pretreatment. An experimental design was constructed with the central composite design (CCD) response surface method using factors of the hydrothermal residence time of 20, 40, 60min and post-acid treatment concentration of 1%, 2% and 3% (v/v) in constant temperature and time of 121°C and 20min. Total sugar yields of 32.47, 27.51 and 26.72g/L were observed after hydrothermal pretreatment time of 20, 40 and 60min, respectively. Furthermore, when the pretreated solid residues were subjected to acid pretreatment, the results revealed an increment of 90% on reducing sugars after reaction with 1%, 2% and 3% H2SO4. Statistically, the optimum condition for the two-stage hydrolysis of coconut pulp residue was 60min hydrothermal pretreatment followed by 3% H2SO4 acid hydrolysis with maximal reducing sugar release of 120.71g/L. In addition, the degree of polymerization achieved was 1.2, indicating no further hydrolysis required. The current study demonstrates that two-stage pretreatment improves saccharification and provide sufficient sugars for the fermentation process.