Physical and chemical characterizations of corn stover and poplar solids resulting from leading pretreatment technologies

In order to investigate changes in substrate chemical and physical features after pretreatment, several characterizations were performed on untreated (UT) corn stover and poplar and their solids resulting pretreatments by ammonia fiber expansion (AFEX), ammonia recycled percolation (ARP), controlled pH, dilute acid, flowthrough, lime, and SO₂ technologies. In addition to measuring the chemical compositions including acetyl content, physical attributes determined were biomass crystallinity, cellulose degree of polymerization, cellulase adsorption capacity of pretreated solids and enzymatically extracted lignin, copper number, FT-IR responses, scanning electron microscopy (SEM) visualizations, and surface atomic composition by electron spectroscopy of chemical analysis (ESCA). Lime pretreatment removed the most acetyl groups from both corn stover and poplar, while AFEX removed the least. Low pH pretreatments depolymerized cellulose and enhanced biomass crystallinity much more than higher pH approaches. Lime pretreated corn stover solids and flowthrough pretreated poplar solids had the highest cellulase adsorption capacity, while dilute acid pretreated corn stover solids and controlled pH pretreated poplar solids had the least. Furthermore, enzymatically extracted AFEX lignin preparations for both corn stover and poplar had the lowest cellulase adsorption capacity. ESCA results showed that SO₂ pretreated solids had the highest surface O/C ratio for poplar, but for corn stover, the highest value was observed for dilute acid pretreatment with a Parr reactor. Although dependent on pretreatment and substrate, FT-IR data showed that along with changes in cross linking and chemical changes, pretreatments may also decrystallize cellulose and change the ratio of crystalline cellulose polymorphs (Iα/Iβ).     

Features of promising technologies for pretreatment of lignocellulosic biomass

Cellulosic plant material represents an as-of-yet untapped source of fermentable sugars for significant industrial use. Many physio-chemical structural and compositional factors hinder the enzymatic digestibility of cellulose present in lignocellulosic biomass. The goal of any pretreatment technology is to alter or remove structural and compositional impediments to hydrolysis in order to improve the rate of enzyme hydrolysis and increase yields of fermentable sugars from cellulose or hemicellulose. These methods cause physical and/or chemical changes in the plant biomass in order to achieve this result. Experimental investigation of physical changes and chemical reactions that occur during pretreatment is required for the development of effective and mechanistic models that can be used for the rational design of pretreatment processes. Furthermore, pretreatment processing conditions must be tailored to the specific chemical and structural composition of the various, and variable, sources of lignocellulosic biomass. This paper reviews process parameters and their fundamental modes of action for promising pretreatment methods.     

木质纤维素预处理及高值化技术研究进展

木质纤维素生物质是地球上最丰富的可再生生物资源.随着化石能源的消耗及环境的污染,以取代石化燃料为目标的由生物质向生物燃料的转化受到了广泛的关注.木质纤维素有很强的天然抗降解屏障,需先通过物理、化学及微生物等手段进行预处理,进而以更低的成本和更高的效率转化为生物燃料及其他高附加值产品.本文在总结酸碱等传统预处理方法优缺点...     

Application of high throughput pretreatment and co‐hydrolysis system to thermochemical pretreatment. Part 1: Dilute acid

Because conventional approaches for evaluating sugar release from the coupled operations of pretreatment and enzymatic hydrolysis are extremely time and material intensive, high throughput (HT) pretreatment and enzymatic hydrolysis systems have become vital for screening large numbers of lignocellulosic biomass samples to identify feedstocks and/or processing conditions that significantly improve performance and lower costs. Because dilute acid pretreatment offers many important advantages in rendering biomass highly susceptible to subsequent enzymatic hydrolysis, a high throughput pretreatment and co‐hydrolysis (HTPH) approach was extended to employ dilute acid as a tool to screen for enhanced performance. First, a single‐step neutralization and buffering method was developed to allow effective enzymatic hydrolysis of the whole pretreated slurry. Switchgrass and poplar were then pretreated with 0.5% and 1% acid loadings at a 5% solids concentration, the resulting slurry conditioned with the buffering approach, and the entire mixture enzymatically hydrolyzed. The resulting sugar yields demonstrated that single‐step neutralizing and buffering was capable of adjusting the pH as needed for enzymatic saccharification, as well as overcoming enzyme inhibition by compounds released in pretreatment. In addition, the effects of pretreatment conditions and biomass types on susceptibility of pretreated substrates to enzymatic conversion were clearly discernible, demonstrating the method to be a useful extension of HTPH systems. Biotechnol. Bioeng. 2013; 110: 754–762. © 2012 Wiley Periodicals, Inc.     

Biomass pretreatment strategies via control of rheological behavior of biomass suspensions and reactive twin screw extrusion processing

Twin screw extrusion based pretreatment of biomass is an attractive option due to its flexibility to carry out chemical reactions under relatively high stresses, temperatures and pressures. However, extrusion processes are rarely utilized in biomass pretreatment because such processing is constrained by rheological behavior of typical biomass suspensions. Without the manipulation of their rheological behavior, biomass suspensions become unprocessable within the extruder at modest biomass concentrations. Here it is demonstrated that gelation agents can render biomass suspensions processable. Specifically, carboxy methyl cellulose, CMC, could be used in conjunction with alkaline pretreatment of hardwood-type biomass and enabled separation of lignin from cellulose fibers. Furthermore, recycled black liquor, obtained upon pretreatment, was determined to be as effective as CMC for rendering biomass suspensions flowable by again facilitating the concomitant application of high shearing stresses and chemical treatment for the pretreatment of the biomass in the twin screw extruder.     

Cunninghamella elegans biomass optimisation for textile wastewater biosorption treatment: an analytical and ecotoxicological approach

The effect of pre-treatments on the composition of Cunninghamella elegans biomass and on its biosorption yields in the treatment of simulated textile wastewaters was investigated. The inactivated biomass was subjected to physical treatments, such as oven drying and lyophilisation, and chemical treatments using acid or alkali. The wastewater colour, COD and toxicity variations were evaluated. The lyophilisation sped up the biosorption process, whereas the chemical pre-treatment changed the affinity of biomass for different dyes. The alkali per-treated biomass achieved the highest COD reduction in the treatment of alkali wastewaters, probably because no release of alkali-soluble biomass components occurred under the alkaline pH conditions. Accordingly, only the acid pre-treated biomass decreased the COD of the acidic effluent. The ecotoxicity test showed significant toxicity reduction after biosorption treatments, indicating that decolourisation corresponds to an actual detoxification of the treated wastewaters. Fourier transform infrared spectroscopy, differential scanning calorimetry and thermogravimetric analyses of biomasses allowed highlighting their main chemical and physical properties and the changes induced by the different pre-treatments, as well as the effect of the chemical species adsorbed from wastewaters.     

Cellulase digestibility of pretreated biomass is limited by cellulose accessibility

Attempts to correlate the physical and chemical properties of biomass to its susceptibility to enzyme digestion are often inconclusive or contradictory depending on variables such as the type of substrate, the pretreatment conditions and measurement techniques. In this study, we present a direct method for measuring the key factors governing cellulose digestibility in a biomass sample by directly probing cellulase binding and activity using a purified cellobiohydrolase (Cel7A) from Trichoderma reesei. Fluorescence-labeled T. reesei Cel7A was used to assay pretreated corn stover samples and pure cellulosic substrates to identify barriers to accessibility by this important component of cellulase preparations. The results showed cellulose conversion improved when T. reesei Cel7A bound in higher concentrations, indicating that the enzyme had greater access to the substrate. Factors such as the pretreatment severity, drying after pretreatment, and cellulose crystallinity were found to directly impact enzyme accessibility. This study provides direct evidence to support the notion that the best pretreatment schemes for rendering biomass more digestible to cellobiohydrolase enzymes are those that improve access to the cellulose in biomass cell walls, as well as those able to reduce the crystallinity of cell wall cellulose.     

Effects of the pelleting conditions on chemical composition and sugar yield of corn stover,big bluestem,wheat straw,and sorghum stalk pellets

Pelleting of biomass can increase their bulk density and thus improve storability and reduce transportation costs. The objective of this research was to determine the effects of the pelleting conditions on chemical composition and fermentable sugar yield of the biomass. Corn stover, wheat straw, big bluestem, and sorghum stalks were used for this study. Dilute sulfuric acid was used for biomass pretreatment. Accellerase 1500™ was used for cellulose hydrolysis. Effects of mill screen size, die thickness, and L/D ratio of die on chemical compositions and sugar yield were determined. Glucan content of the biomass was positively affected by die thickness and negatively affected by mill screen size. Opposite trend was observed for xylan content. Wheat straw pellets had the highest sugar yield (92.5–94.1%) and big bluestem pellets had the lowest sugar yield (83.6–91.1%). Optimum pelleting condition is 6.5 mm screen size and 44.5 mm die thickness.     

Fungal pretreatment of lignocellulosic biomass

Pretreatment is a crucial step in the conversion of lignocellulosic biomass to fermentable sugars and biofuels. Compared to thermal/chemical pretreatment, fungal pretreatment reduces the recalcitrance of lignocellulosic biomass by lignin-degrading microorganisms and thus potentially provides an environmentally-friendly and energy-efficient pretreatment technology for biofuel production. This paper provides an overview of the current state of fungal pretreatment by white rot fungi for biofuel production. The specific topics discussed are: 1) enzymes involved in biodegradation during the fungal pretreatment; 2) operating parameters governing performance of the fungal pretreatment; 3) the effect of fungal pretreatment on enzymatic hydrolysis and ethanol production; 4) efforts for improving enzymatic hydrolysis and ethanol production through combinations of fungal pretreatment and physical/chemical pretreatment; 5) the treatment of lignocellulosic biomass with lignin-degrading enzymes isolated from fungal pretreatment, with a comparison to fungal pretreatment; 6) modeling, reactor design, and scale-up of solid state fungal pretreatment; and 7) the limitations and future perspective of this technology.     

低温等离子体生物质炼制技术

生物质炼制是世界各国的战略性研究方向。目前,主要有汽爆、酸、碱等炼制技术,而低温等离子体因具有独特的化学活性和高能量等优势而倍受青睐。本论文系统阐述了基于低温等离子体技术的生物质预处理、降解制糖、选择性功能改性、液化、气化等炼制技术的研究进展,并探讨了低温等离子体生物质炼制的机理及其今后研究发展方向。     

Reducing acid in dilute acid pretreatment and the impact on enzymatic saccharification

Dilute acid pretreatment is a leading pretreatment technology for biomass to ethanol conversion due to the comparatively low chemical cost and effective hemicellulose solubilization. The conventional dilute acid pretreatment processes use relatively large quantities of sulfuric acid and require alkali for pH adjustment afterwards. Significant amounts of sulfate salts are generated as by-products, which have to be properly treated before disposal. Wastewater treatment is an expensive, yet indispensable part of commercial level biomass-to-ethanol plants. Therefore, reducing acid use to the lowest level possible would be of great interest to the emerging biomass-to-ethanol industry. In this study, a dilute acid pretreatment process was developed for the pretreatment of corn stover. The pretreatment was conducted at lower acid levels than the conventional process reported in the literature while using longer residence times. The study indicates that a 50% reduction in acid consumption can be achieved without compromising pretreatment efficiency when the pretreatment time was extended from 1–5 min to 15–20 min. To avoid undesirable sugar degradation and inhibitor generation, temperatures should be controlled below 170°C. When the sulfuric acid-to-lignocellulosic biomass ratio was kept at 0.025 g acid/g dry biomass, a cellulose-to-glucose conversion of 72.7% can be achieved at an enzyme loading of 0.016 g/g corn stover. It was also found that acid loading based on total solids (g acid/g dry biomass) governs the pretreatment efficiency rather than the acid concentration (g acid/g pretreatment liquid). While the acid loading on lignocellulosic biomass may be achieved through various combinations of solids loading and acid concentration in the pretreatment step, this work shows that it is unlikely to reduce acid use without undermining pretreatment efficiency simply by increasing the solid content in pretreatment reactors, therefore acid loading on biomass is indicated to be the key factor in effective dilute acid pretreatment.     

Surface and ultrastructural characterization of raw and pretreated switchgrass

The US Department of Energy-funded Biomass Refining CAFI (Consortium for Applied Fundamentals and Innovation) project has developed leading pretreatment technologies for application to switchgrass and has evaluated their effectiveness in recovering sugars from the coupled operations of pretreatment and enzymatic hydrolysis. Key chemical and physical characteristics have been determined for pretreated switchgrass samples. Several analytical microscopy approaches utilizing instruments in the Biomass Surface Characterization Laboratory (BSCL) at the National Renewable Energy Laboratory (NREL) have been applied to untreated and CAFI-pretreated switchgrass samples. The results of this work have shown that each of the CAFI pretreatment approaches on switchgrass result in different structural impacts at the plant tissue, cellular, and cell wall levels. Some of these structural changes can be related to changes in chemical composition upon pretreatment. There are also apparently different structural mechanisms that are responsible for achieving the highest enzymatic hydrolysis sugar yields.     

An economic assessment of algal turf scrubber technology for treatment of dairy manure effluent

Controlling the input of nitrogen (N) and phosphorus (P) from dairies and other livestock operations into the surrounding air- and water-sheds poses both technical and economic challenges to the agricultural community. The purpose of this paper is to assess the economics of algal turf scrubber treatment technology at the farm-scale for a hypothetical 1000-cow dairy. Costs were developed for farms with and without anaerobic pretreatment. The majority of capital costs were due to land preparation, installation of liner material, and engineering fees. The majority of operational costs were due to energy requirements for biomass drying, pumping water, and repayment of capital investment. On farms using anaerobic pretreatment, waste heat from burning of biogas could be used to offset the energy requirements of biomass drying. In addition, biogas combustion exhaust gas could then be recycled back to the algal system to supply dissolved inorganic carbon for optimal algal production and pH control. Under the best case (algal system coupled with anaerobic digestion pretreatment), the yearly operational costs per cow, per kg N, per kg P, and per kg of dried biomass were $454, $6.20, $31.10, and $0.70, respectively. Without anaerobic digestion pretreatment, the yearly operational costs were 36% higher, amounting to $631 per cow, $8.70 per kg N, $43.20 per kg P, and $0.97 per kg of dried biomass. For perspective, a recent survey of 36 Maryland dairy farms found long-term annual profits of about $500 per cow. As no market currently exists for manure grown algal biomass, our cost analysis does not include any value of the biomass generated during manure treatment. In addition, there are a variety of potential uses for the algal biomass from manure treatment that could defray treatment costs. Future opportunities for dairies to participate in nutrient trading approaches to watershed nutrient management may also become important.     

High-throughput screening for ionic liquids dissolving (ligno-)cellulose

The recalcitrance of lignocellulosic biomass poses a major challenge for its sustainable and cost-effective utilization. Therefore, an efficient pretreatment is decisive for processes based on lignocellulose. A green and energy-efficient pretreatment could be the dissolution of lignocellulose in ionic liquids. Several ionic liquids were identified earlier which are capable to dissolve (ligno-)cellulose. However, due to their multitude and high costs, a high-throughput screening on small scale is essential for the determination of the most efficient ionic liquid. In this contribution two high-throughput systems are presented based on extinction or scattered light measurements. Quasi-continuous dissolution profiles allow a direct comparison of up to 96 ionic liquids per experiment in terms of their dissolution kinetics. The screening results indicate that among the ionic liquids tested EMIM Ac is the most efficient for dissolving cellulose. Moreover, it was observed that AMIM Cl is the most effective ionic liquid for dissolving wood chips.     

Fatty acid from the renewable sources: A promising feedstock for the production of biofuels and biobased chemicals

With the depletion of the nonrenewable petrochemical resources and the increasing concerns of environmental pollution globally, biofuels and biobased chemicals produced from the renewable resources appear to be of great strategic significance. The present review described the progress in the biosynthesis of fatty acid and its derivatives from renewable biomass and emphasized the importance of fatty acid serving as the platform chemical and feedstock for a variety of chemicals. Due to the low efficient conversions of lignocellulosic biomass or carbon dioxide to fatty acid, we also put forward that rational strategies for the production of fatty acid and its derivatives should further derive from the consideration of whole bioprocess (pretreatment, saccharification, fermentation, separation), multiscale analysis and interdisciplinary combinations (omics, kinetics, metabolic engineering, synthetic biology, fermentation and so on).     

Front-end recovery of protein from lignocellulosic biomass and its effects on chemical pretreatment and enzymatic saccharification

Front-end protein recovery from biomass at different maturities, and its effects on chemical pretreatment and enzyme hydrolysis of partially deproteinized fiber were investigated. The protein recovery from alfalfa and switchgrass biomass using sodium dodecyl sulfate and potassium hydroxide treatments was ~50–65 % of initial biomass protein. When hot water was used as extraction media, the protein recovery was 52.9 and 43.7 % of total protein in switchgrass and alfalfa, respectively. For any treatment, relative protein recovery was higher from switchgrass than from alfalfa. Only approximately half the total protein was recovered from relatively mature (early fall) biomass compared with midsummer harvested biomass. When protein was recovered partially using sodium dodecyl sulfate or potassium hydroxide, and leftover fiber pretreated, aqueous ammonia pretreatment removed 58.5–60.1 % of lignin and retained more cellulose in the fiber compared with acid pretreatment (nearly no lignin removal). Protein removal was helpful in the enzyme digestibility of fibers. Delignification of ammonia pretreated partially deproteinized alfalfa fiber was in the range of 34.4–45 %, while dilute sulfuric acid did not remove lignin effectively. Overall, the higher delignification and enzyme digestibilities were observed in aqueous ammonia pretreated partially deproteinized alfalfa fibers regardless of biomass type.     

Interspecific evolutionary relationships of alpha-glucuronidase in the genus Aspergillus

The increased availability and production of lignocellulosic agroindustrial wastes has originated proposals for their use as raw material to obtain biofuels (ethanol and biodiesel) or derived products. However, for biomass generated from lignocellulosic residues to be successfully degraded, in most cases it requires a physical (thermal), chemical, or enzymatic pretreatment before the application of microbial or enzymatic fermentation technologies (biocatalysis). In the context of enzymatic technologies, fungi have demonstrated to produce enzymes capable of degrading polysaccharides like cellulose, hemicelluloses and pectin. Because of this ability for degrading lignocellulosic material, researchers are making efforts to isolate and identify fungal enzymes that could have a better activity for the degradation of plant cell walls and agroindustrial biomass. We performed an in silico analysis of alpha-glucoronidase in 82 accessions of the genus Aspergillus. The constructed dendrograms of amino acid sequences defined the formation of 6 groups (I, II, III, IV, V, and VI), which demonstrates the high diversity of the enzyme. Despite this ample divergence between enzyme groups, our 3D structure modeling showed both conservation and differences in amino acid residues participating in enzyme–substrate binding, which indicates the possibility that some enzymes are functionally specialized for the specific degradation of a substrate depending on the genetics of each species in the genus and the condition of the habitat where they evolved. The identification of alpha-glucuronidase isoenzymes would allow future use of genetic engineering and biocatalysis technologies aimed at specific production of the enzyme for its use in biotransformation.     

Minimising biomass accumulation in biotrickling filters

Various approaches can minimize biomass accumulation in biotricking filters (BTF), which can be classified as: (1) physical, (2) chemical and (3) biological. Other approaches include (4) improvement of the bioreactor design and (5) modification of the mode and operational parameters. All of these methods involve either reduction in biomass growth or removal of excess biomass and each method has unique advantages and disadvantages as far as biomass reduction capability, sustainability and ease of integration to the system are concerned, which are compared and contrasted in this review. A careful comparison and analysis of these methods is a requisite to an optimum operation of a BTF system.     

Production of xylitol by a Coniochaeta ligniaria strain tolerant of inhibitors and defective in growth on xylose

In conversion of biomass to fuels or chemicals, inhibitory compounds arising from physical–chemical pretreatment of the feedstock can interfere with fermentation of the sugars to product. Fungal strain Coniochaeta ligniaria NRRL30616 metabolizes the furan aldehydes furfural and 5‐hydroxymethylfurfural, as well as a number of aromatic and aliphatic acids and aldehydes. Use of NRRL30616 to condition biomass sugars by metabolizing the inhibitors improves their fermentability. Wild‐type C. ligniaria has the ability to grow on xylose as sole source of carbon and energy, with no accumulation of xylitol. Mutants of C. ligniaria unable to grow on xylose were constructed. Xylose reductase and xylitol dehydrogenase activities were reduced by approximately two thirds in mutant C8100. The mutant retained ability to metabolize inhibitors in biomass hydrolysates. Although C. ligniaria C8100 did not grow on xylose, the strain converted a portion of xylose to xylitol, producing 0.59 g xylitol/g xylose in rich medium and 0.48 g xylitol/g xylose in corn stover dilute acid hydrolysate. 2016 American Institute of Chemical Engineers Biotechnol. Prog., 2016 © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:606–612, 2016     

Conversion of rice straw to bio-based chemicals: an integrated process using Lactobacillus brevis

Commercialization of lignocellulosic biomass as a feedstock for bio-based chemical production is problematic due to the high processing costs of pretreatment and saccharifying enzymes combined with low product yields. Such low product yield can be attributed, in large part, to the incomplete utilization of the various carbohydrate sugars found in the lignocellulosic biomass. In this study, we demonstrate that Lactobacillus brevis is able to simultaneously metabolize all fermentable carbohydrates in acid pre-processed rice straw hydrolysate, thereby allowing complete utilization of all released sugars. Inhibitors present in rice straw hydrolysate did not affect lactic acid production. Moreover, the activity of exogenously added cellulases was not reduced in the presence of growing cultures of L. brevis. These factors enabled the use of L. brevis in a process termed simultaneous saccharification and mixed sugar fermentation (SSMSF). In SSMSF with L. brevis, sugars present in rice straw hydrolysate were completely utilized while the cellulase maintained its maximum activity due to the lack of feedback inhibition from glucose and/or cellobiose. By comparison to a sequential hydrolysis and fermentation process, SSMSF reduced operation time and the amount of cellulase enzyme necessary to produce the same amount of lactic acid.