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At least 577 records · Page 32

In Situ Catalytic Fast Pyrolysis using Red Mud Catalyst: Impact of catalytic fast pyrolysis temperature and biomass feedstocks

Catalytic fast pyrolysis (CFP) has been considered as a very promising approach for converting lignocellulosic biomass into higher-quality bio-oils followed by hydrotreating to produce fuelrange products. A reactive, robust, and low-cost catalyst is required to drive the CFP process. Red mud, a side-product produced during the refining of bauxite to alumina, appears to be an effective catalyst for in situ CFP of biomass. In this paper, we report the impact of CFP reaction temperature on the conversion of a pinyon juniper feedstock to bio-oils using red mud as the catalyst and then to fuel-range hydrocarbons by hydrotreating of the produced bio-oil. The yield and quality of the CFP bio-oil produced and the yield and quality of hydrotreated final products were determined. When the CFP process temperature was lowered from 450 to 400ºC, the bio-oil yield increased with minimal differences in the oxygen content, hydrogen-to-carbon ratio, water content, etc. In addition, CFP bio-oils at both temperatures were processed in a single-stage continuous hydrotreater without reactor plugging during the testing period (i.e., ~100 hours on stream). The yield of CFP bio-oil produced at 400ºC was lower than the yield at 450ºC. However, the overall yield, from biomass to hydrocarbon fuel, was still higher for CFP processing at 400ºC than for processing at 450ºC. This indicates the potential for enhancing overall carbon efficiency, including CFP processing and hydrotreating, by employing red mud catalysts for biomass pyrolysis and tuning the CFP parameters. Detailed analysis of bio-oil and hydrotreated products showed a lower content of lignin-derived species in both samples. Furthermore, CFP processing of three different biomass feedstocks corroborated red mud catalyst development for producing improved quality bio-oil and, when combined with hydrotreating, for the production of fuel range hydrocarbons.

Santosa, Daniel M.↗

Insight into the Catalytic Mechanism of GH11 Xylanase: Computational Analysis of Substrate Distortion Based on a Neutron Structure

The reaction mechanism of biomass decomposition by xylanases remains the subject of debate. Here, to clarify the mechanism, we investigated the glycosylation step of GH11 xylanase, an enzyme that catalyzes the hydrolysis of lignocellulosic hemicellulose (xylan). Making use of a recent neutron crystal structure, which revealed the protonation states of relevant residues, we used ab initio quantum mechanics/molecular mechanics (QM/MM) calculations to determine the detailed reaction mechanism of the glycosylation step. In particular, our focus is on the controversial question of whether or not an oxocarbenium ion intermediate is formed on the reaction pathway. The calculations support the validity of a basic retaining mechanism within a double-displacement scheme. The estimated free energy barrier of this reaction is ~18 kcal/mol with QM/MM-CCSD(T)/6-31(+)G**//MP2/6-31+G**/AMBER calculations, and the rate-determining step of the glycosylation is scission of the glycosidic bond after proton transfer from the acidic Glu177. The estimated lifetime of the oxocarbenium ion intermediate (on the order of tens of ps) and the secondary kinetic isotope effect suggest that there is no accumulation of this intermediate on the reaction path, although the intermediate can be transiently formed. In the enzyme–substrate (ES) complex, the carbohydrate structure of the xylose residue at the -1 subsite has a rather distorted (skewed) geometry, and this xylose unit at the active site has an apparent half-chair conformation when the oxocarbenium ion intermediate is formed. The major catalytic role of the protein environment is to orient residues that take part in the initial proton transfer. Because of a fine alignment of catalytic residues, the enzyme can accelerate the glycosylation reaction without paying a reorganization energy penalty.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancing Hydrogen Production from Bioenergy Crops via Photoreforming

Photoreforming perennial bioenergy crops (willow, Miscanthus , and poplar) has the potential to produce H 2 with reduced environmental impacts. To understand the compositional effects of the biomass on the average rate of H 2 production over the first 30 min of reaction ( r H 2 ), the r H 2 values of model biomass component (i.e., cellulose, hemicellulose, and lignin) mixtures were compared with those from the raw biomass. The higher cellulose or hemicellulose content in multicomponent mixtures resulted in higher r H 2 , whereas lignin reduced the hydrogen production rate. However, with raw biomass, the ratio of biomass components alone did not determine the r H 2 via photoreforming, with rates of hydrogen production for different varieties of willow ranging between 1.9 μmol h -1 and 12.3 μmol h -1 , 11.8 μmol h -1 for a poplar, and 6.8 μmol h -1 for a miscanthus biomass. In addition, comparable r H 2 values of raw poplar and its extracted cellulose via an IonoSolv treatment indicated the possibility of using raw biomass materials without delignification for generating H 2 via photoreforming. Importantly, r H 2 was positively correlated with the interaction between water and the biomass, as assessed by NMR relaxation via an examination of the T 1 /T 2 ratio. A stronger water-biomass interaction resulted in a higher r H 2 . Genetic modification of biomass has been suggested as a putative way to improve the r H 2 of biomass with an enhanced interaction with water. This research enhances the understanding of factors influencing H 2 production from lignocellulosic biomass by photoreforming and supports the breeding and management of perennial biomass crops to maximize H 2 yields while minimizing land area requirements.

biomass↗

Understanding the Competition between Alcohol Formation and Dimerization during Electrochemical Reduction of Aromatic Carbonyl Compounds

The electrochemical reductive dimerization of small aromatic carbonyl compounds derived from lignocellulosic biomass is a crucial C−C coupling reaction for upgrading small molecules to longchain hydrocarbons, particularly in the synthesis of drop-in sustainable aviation fuels. Although other electrochemical reduction reactions of these reactants (i.e., hydrogenation and hydrogenolysis) have undergone extensive mechanistic investigation, the understanding of dimerization remains relatively underdeveloped. Most importantly, there is a lack of understanding of the selectivity-determining step between dimerization and monomer reduction and critical factors that can affect this step. In this study, we provide a comprehensive mechanistic model to explain the competition between dimerization and monomer reduction of benzaldehyde under various conditions. Our model proposes that the selectivity between dimerization and monomer reduction depends on the competition between desorption of a ketyl radical from the electrode, necessary for dimerization, and further reduction of the ketyl radical to an alcohol on the electrode by proton-coupled electron transfer (PCET). Computationally comparing the adsorption/desorption energy and PCET activation barrier energy is challenging because conventional DFT calculations substantially underestimate the PCET kinetic barriers. In this study, we employed constrained DFTbased configuration interaction (CDFT-CI) to obtain a reliable comparison of these energies. Our mechanistic model was tested and supported by experimental results obtained with four electrodes (Cu, Pb, Bi, graphite), three pH conditions (acidic, neutral, basic), and three potentials. Our study offers a coherent mechanistic foundation that can explain how each of these conditions impacts the desorption and PCET processes and the selectivities for dimerization and alcohol production.

09 BIOMASS FUELS↗

Native Architecture of Wheat Straw Cell Walls: A Unified Model from X-ray Scattering and Solid-State NMR

Plant secondary cell walls constitute the dominant reservoir of renewable biomass, comprising tightly packed cellulose, hemicellulose, and lignin at the nanoscale. Recent advances in solid-state NMR spectroscopy and the availability of small-angle X-ray scattering for biomass characterization have led to an accumulation of experimental data on cell wall organization, yet no explicit structure model has simultaneously satisfied both Xray and NMR observations. Using wheat straw as a model system, we propose a structural framework consistent with current knowledge of cellulose biosynthesis, X-ray scattering data, and one- and two-dimensional 13 C solid-state NMR spectra. In this model, 18-chain elementary fibrils align in parallel and populate the cross-section at random. Arabinose-substituted xylan shows no conformational dependence for cellulose-binding in wheat, and only a minor fraction of 2-fold xylan appears in close proximity to cellulose, unlike in Arabidopsis, where xylan is more tightly attached to the cellulose surface. While NMR data cannot unambiguously resolve the internal arrangement of the 18 glucan chains, X-ray scattering profiles uniquely constrain the fibril size and exclude the possibility of tight bundling in the intact walls. The specific interaction between the matrix polymers and the cellulose elementary fibrils must be reconsidered in light of the small interfibril spaces, which bring the matrix components into spatial proximity with cellulose even in the absence of attractive interactions. These findings provide fundamental molecular-level insight into cellulose fibril architecture and matrix−polymer interactions, resolving longstanding discrepancies between spectroscopic and scattering data and advancing our understanding of biopolymer assembly into structurally and functionally versatile lignocellulosic biomaterials.

Carbohydrates↗

Tailoring poplar lignin without yield penalty by combining a null and haploinsufficient CINNAMOYL-CoA REDUCTASE2 allele

Lignin causes lignocellulosic biomass recalcitrance to enzymatic hydrolysis. Engineered low-lignin plants have reduced recalcitrance but often exhibit yield penalties, offsetting their gains in fermentable sugar yield. Here, CRISPR/Cas9-generated CCR2(–/*) line 12 poplars have one knockout CCR2 allele while the other contains a 3-bp deletion, resulting in a 114I115A-to-114T conversion in the corresponding protein. Despite having 10% less lignin, CCR2(–/*) line 12 grows normally. On a plant basis, the saccharification efficiency of CCR2(–/*) line 12 is increased by 25–41%, depending on the pretreatment. Analysis of monoallelic CCR2 knockout lines shows that the reduced lignin amount in CCR2(–/*) line 12 is due to the combination of a null and the specific haploinsufficient CCR2 allele. Analysis of another CCR2(–/*) line shows that depending on the specific CCR2 amino-acid change, lignin amount and growth can be affected to different extents. Furthermore, our findings open up new possibilities for stably fine-tuning residual gene function in planta.

59 BASIC BIOLOGICAL SCIENCES↗

A grass-specific cellulose–xylan interaction dominates in sorghum secondary cell walls

Abstract Sorghum ( Sorghum bicolor L. Moench) is a promising source of lignocellulosic biomass for the production of renewable fuels and chemicals, as well as for forage. Understanding secondary cell wall architecture is key to understanding recalcitrance i.e. identifying features which prevent the efficient conversion of complex biomass to simple carbon units. Here, we use multi-dimensional magic angle spinning solid-state NMR to characterize the sorghum secondary cell wall. We show that xylan is mainly in a three-fold screw conformation due to dense arabinosyl substitutions, with close proximity to cellulose. We also show that sorghum secondary cell walls present a high ratio of amorphous to crystalline cellulose as compared to dicots. We propose a model of sorghum cell wall architecture which is dominated by interactions between three-fold screw xylan and amorphous cellulose. This work will aid the design of low-recalcitrance biomass crops, a requirement for a sustainable bioeconomy.

59 BASIC BIOLOGICAL SCIENCES↗

Complete and efficient conversion of plant cell wall hemicellulose into high-value bioproducts by engineered yeast

Abstract Plant cell wall hydrolysates contain not only sugars but also substantial amounts of acetate, a fermentation inhibitor that hinders bioconversion of lignocellulose. Despite the toxic and non-consumable nature of acetate during glucose metabolism, we demonstrate that acetate can be rapidly co-consumed with xylose by engineered Saccharomyces cerevisiae . The co-consumption leads to a metabolic re-configuration that boosts the synthesis of acetyl-CoA derived bioproducts, including triacetic acid lactone (TAL) and vitamin A, in engineered strains. Notably, by co-feeding xylose and acetate, an enginered strain produces 23.91 g/L TAL with a productivity of 0.29 g/L/h in bioreactor fermentation. This strain also completely converts a hemicellulose hydrolysate of switchgrass into 3.55 g/L TAL. These findings establish a versatile strategy that not only transforms an inhibitor into a valuable substrate but also expands the capacity of acetyl-CoA supply in S. cerevisiae for efficient bioconversion of cellulosic biomass.

59 BASIC BIOLOGICAL SCIENCES↗

Emergence of lignin-carbohydrate interactions during plant stem maturation visualized by solid-state NMR

Lignification waterproofs and strengthens secondary plant cell walls but increases the energy cost of sugar release for biofuels. The physical association between lignin and the carbohydrate scaffold that accommodates lignin polymerization, along with the distinct roles of lignin units and carbohydrate partners during lignification, remain unclear. Here, we map lignin-carbohydrate spatial proximity by solid-state NMR in 13 C-labeled Arabidopsis inflorescence stems during secondary cell wall formation. Analyses include wild-type plants and mutants that selectively or globally disrupt lignin biosynthesis. Mature walls in basal regions show enrichment of S-lignin and dense carbohydrate-lignin packing. Acetylated xylan predominantly associates with S-lignin, while methylated pectin unexpectedly interacts with G-lignin during early-stage lignification. The importance of S-lignin in stabilizing the carbohydrate-lignin interface is highlighted by weak lignin-carbohydrate contacts and compromised mechanical properties in the low-S fah1 mutant, whereas the ref3 mutant, despite reduced lignin content, remains unaffected due to a high S/G ratio. Thus, molecular mixing patterns, rather than lignin content, critically determine the structure and properties of lignocellulosic materials.

59 BASIC BIOLOGICAL SCIENCES↗

Phylogenomics and genetic analysis of solvent-producing Clostridium species

Abstract The genus Clostridium is a large and diverse group within the Bacillota (formerly Firmicutes), whose members can encode useful complex traits such as solvent production, gas-fermentation, and lignocellulose breakdown. We describe 270 genome sequences of solventogenic clostridia from a comprehensive industrial strain collection assembled by Professor David Jones that includes 194 C. beijerinckii , 57 C. saccharobutylicum , 4 C. saccharoperbutylacetonicum , 5 C. butyricum , 7 C. acetobutylicum , and 3 C. tetanomorphum genomes. We report methods, analyses and characterization for phylogeny, key attributes, core biosynthetic genes, secondary metabolites, plasmids, prophage/CRISPR diversity, cellulosomes and quorum sensing for the 6 species. The expanded genomic data described here will facilitate engineering of solvent-producing clostridia as well as non-model microorganisms with innately desirable traits. Sequences could be applied in conventional platform biocatalysts such as yeast or Escherichia coli for enhanced chemical production. Recently, gene sequences from this collection were used to engineer Clostridium autoethanogenum , a gas-fermenting autotrophic acetogen, for continuous acetone or isopropanol production, as well as butanol, butanoic acid, hexanol and hexanoic acid production.

59 BASIC BIOLOGICAL SCIENCES↗

A novel d-xylose isomerase from the gut of the wood feeding beetle Odontotaenius disjunctus efficiently expressed in Saccharomyces cerevisiae

Carbohydrate rich substrates such as lignocellulosic hydrolysates remain one of the primary sources of potentially renewable fuel and bulk chemicals. The pentose sugar d-xylose is often present in significant amounts along with hexoses. Saccharomyces cerevisiae can acquire the ability to metabolize d-xylose through expression of heterologous d-xylose isomerase (XI). This enzyme is notoriously difficult to express in S. cerevisiae and only fourteen XIs have been reported to be active so far. We cloned a new d-xylose isomerase derived from microorganisms in the gut of the wood-feeding beetle Odontotaenius disjunctus. Although somewhat homologous to the XI from Piromyces sp. E2, the new gene was identified as bacterial in origin and the host as a Parabacteroides sp. Expression of the new XI in S. cerevisiae resulted in faster aerobic growth than the XI from Piromyces on d-xylose media. The d-xylose isomerization rate conferred by the new XI was also 72% higher, while absolute xylitol production was identical in both strains. Interestingly, increasing concentrations of xylitol (up to 8 g L –1 ) appeared not to inhibit d-xylose consumption. The newly described XI displayed 2.6 times higher specific activity, 37% lower KM for d-xylose, and exhibited higher activity over a broader temperature range, retaining 51% of maximal activity at 30 °C compared with only 29% activity for the Piromyces XI.

59 BASIC BIOLOGICAL SCIENCES↗

Growth-uncoupled propanediol production in a Thermoanaerobacterium thermosaccharolyticum strain engineered for high ethanol yield

Abstract Cocultures of engineered thermophilic bacteria can ferment lignocellulose without costly pretreatment or added enzymes, an ability that can be exploited for low cost biofuel production from renewable feedstocks. The hemicellulose-fermenting species Thermoanaerobacterium thermosaccharolyticum was engineered for high ethanol yield, but we found that the strains switched from growth-coupled production of ethanol to growth uncoupled production of acetate and 1,2-propanediol upon growth cessation, producing up to 6.7 g/L 1,2-propanediol from 60 g/L cellobiose. The unique capability of this species to make 1,2-propanediol from sugars was described decades ago, but the genes responsible were not identified. Here we deleted genes encoding methylglyoxal reductase, methylglyoxal synthase and glycerol dehydrogenase. Deletion of the latter two genes eliminated propanediol production. To understand how carbon flux is redirected in this species, we hypothesized that high ATP levels during growth cessation downregulate the activity of alcohol and aldehyde dehydrogenase activities. Measurements with cell free extracts show approximately twofold and tenfold inhibition of these activities by 10 mM ATP, supporting the hypothesized mechanism of metabolic redirection. This result may have implications for efforts to direct and maximize flux through alcohol dehydrogenase in other species.

09 BIOMASS FUELS↗

Generation of ionic liquid tolerant Pseudomonas putida KT2440 strains via adaptive laboratory evolution

Although the use of ionic liquids (ILs) for the pretreatment of lignocellulosic biomass has been limited due to high costs, recent efforts to develop low-cost protic ILs show promise for achieving cost-effectiveness for biorefineries. However, an additional challenge remains in that ILs present in biomass hydrolysates are toxic to most microbial hosts, resulting in poor growth phenotypes. To address this issue, we applied an adaptive laboratory evolution (ALE) approach for tolerizing Pseudomonas putida KT2440, an industrially relevant bacterial host, to two low-cost ILs (triethanolammonium acetate [TEOH][OAc] and triethylammonium hydrogen sulfate [TEA][HS]). After continuous cultivations with gradually increased IL levels, we obtained evolved strains showing significant improvements in their growth performance under high concentrations of the ILs (maximum 4% [TEOH][OAc] and 8% [TEA][HS], in w/v) at which the wild-type strain cannot grow. Sequencing of evolved strains revealed multiple regions where mutations were associated with improved performance in minimal media conditions (relA, gacS, oprB/PP_1446, fleQ, tktA, and uvrY/PP_4100) and in IL-specific conditions (PP_5350, PP_4929/emrE, oprD, and PP_5324). We further validated the causality of the PP_5350 and emrE genes for improved IL tolerance via reverse engineering and transcriptomic analysis. Here, a common mutation in the PP_5350 gene, encoding a RpiR family transcriptional regulator, was shown to significantly upregulate the glyoxylate cycle for efficient acetate catabolism. In addition, it was suggested that the emrE gene encodes an efflux pump which can export [TEA][HS]. Finally, the cultivation of two of the best performing evolved strains with IL-treated biomass hydrolysates demonstrated their considerable potential to be used as platform strains. Taken as a whole, this work provides strains for utilization of IL-treated biomass and a mechanistic understanding that could be further leveraged to develop efficient microbial bioprocesses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solvent-induced membrane stress in biofuel production: molecular insights from small-angle scattering and all-atom molecular dynamics simulations

The disruptive effect of organic solvents on microbial membranes represents a significant challenge to the economical production of green fuels and value-added chemicals from lignocellulosic feedstocks. One route to overcoming this challenge is to engineer microbes with membranes capable of resisting organic solvent stresses. In this regard, it is useful to understand the mechanisms by which organic solvents disrupt typical biomembranes. In this study, molecular dynamics (MD) simulation, complemented by small-angle X-ray and neutron scattering (SANS/SAXS), provide a molecular-scale view of the disruption of a microbial model membrane by 1-butanol and tetrahydrofuran (THF), two common water–organic cosolvent mixtures of importance in biofuel production. Solvent interactions at the interface between the head-group and fatty acid tail regions lead to more dramatic membrane changes than interactions solely at the head-groups or tails. Although both organic solvents are found to partition into the membrane, the depth of solvent penetration into the membrane is quite different. Specifically, 1-butanol localizes near the interface between the lipid heads and tails at low concentrations, but partitions into both the head and tail regions at high concentrations. In contrast, THF, overall, partitions less than 1-butanol and prefers the lipid tail regions. Importantly, the presence of 1-butanol near the head/tail interface introduces drastic membrane changes not seen with THF. The organic solvent interactions with the lipids lead to membrane thinning and fluidization, but more so for 1-butanol than for THF. These results suggest that an aim for the future engineering of robust membranes could be to design lipid head groups that reduce the accumulation of organic solvents at the head–tail interface and that rational designs need also be cognizant of the different solvent-specific mechanisms responsible for membrane disruption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thiol-promoted catalytic synthesis of high-performance furan-containing lubricant base oils from biomass derived 2-alkylfurans and ketones

About 97% of lubricant base oils are currently sourced from petroleum and the majority of the rest is produced from vegetable oils. We demonstrate a promising catalytic route to produce base oils from lignocellulosic biomass-derived 2-alkylfurans and ketones via carbon–carbon coupling in neat conditions. Among several homogeneous and heterogeneous acid catalysts tested, a perfluorinated sulfonic acid (Aquivion PW79S) exhibits the best catalytic performance and yields up to 90% renewable furan-containing base oils with the use of a thiol promotor. The effects of the acid strength of the catalysts, molecular size and structure of thiols and ketones, and fraction of thiols are studied. Electronic structure calculations elucidate the reaction pathway and indicate that the thiol reduces the barrier of the rate-determining dehydration step. The structure and properties of base oils can be tuned by using different synthons. Here, these base oils have excellent properties and can be competitive with or surpass the commercial synthetic alkylnaphthalene and furan-containing bio-ester base oils.

09 BIOMASS FUELS↗

Enhancing the multi-functional properties of renewable lignin carbon fibers via defining the structure–property relationship using different biomass feedstocks

Lignin has been explored extensively as a renewable precursor for carbon materials, considering its abundance as a major component of plant cell walls and its sustainability as a byproduct of both lignocellulosic biorefinery and the paper-making industry. Despite the extensive efforts to define the process–property relationship, it remains largely unknown how lignin biosynthesis and its chemistry would impact the resultant carbon fiber properties, for both mechanical and electroconductive performances. Such inadequate understanding fundamentally limits feedstock design and selection to improve carbon fiber properties toward broader commercial applications. Using lignin from a broad range of biomass feedstocks for carbon fiber manufacturing, we have fundamentally explored the structure–function relationship between lignin chemistry and carbon fiber performance. Specifically, lignin extracted from hardwood (sugar maple), softwood (loblolly pine and red cedar), and herbaceous plants (corn stover and switchgrass) was used for carbon fiber manufacturing, considering the very different lignin structures from these feedstocks. Linear regression models were established to define the relationship between carbon fiber mechanical properties and lignin structural characteristics. The results highlighted that the content of β-O-4 linkages correlates significantly with the tensile strength and elastic modulus of lignin carbon fibers, indicating that more linear β-O-4 linkages would promote the carbon fiber mechanical performance. Moreover, electroconductive properties are essential for broader energy device application of lignin-based carbon fibers, yet the mechanisms controlling their electroconductivity are largely unknown. Furthermore, we hereby demonstrated that a higher β-O-4 content also promotes the electroconductivity of lignin carbon fibers. Microstructure analysis further revealed that the crystallite size and content of the pre-graphitic turbostratic carbon structure in lignin-based carbon fibers were enhanced as the β-O-4 linkages increased. The content of β-O-4 linkages has shown a strong correlation with the crystallite content in a linear regression model. This study thus revealed the underlying mechanisms regarding how the lignin structure in planta defines the resultant carbon fiber properties. Moreover, the study also highlighted the correlation between the mechanical and electroconductive properties of lignin-based carbon fibers, both of which were defined by the lignin structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Double bonus: surfactant-assisted biomass pelleting benefits both the pelleting process and subsequent enzymatic saccharification of the pretreated pellets

Pelleting overcomes the utilization limitation of lignocellulosic biomass due to its low density and related processing costs. Efficiently combining biomass pelleting and enzymatic saccharification is a challenge for applying biomass with low density in a biorefinery. In this study, we propose a novel biomass processing approach involving the addition of surfactant during pelleting and using the pellets for pretreatment and enzymatic saccharification. Here, we investigated the effects of polyethylene glycol (PEG) 6000 assisted pelleting on pelleting specific energy consumption and friction, and on subsequent pretreatment as well as on enzymatic saccharification of the pretreated pellets. The results showed that PEG 6000 assisted pelleting decreased the total pelleting specific energy consumption by about 14% for wheat straw and 18% for pine, and reduced the maximum friction during ejection of pellets by about 34% for wheat straw and 29% for pine. PEG 6000 assisted pelleting enhanced subsequent enzymatic sugar yield effectively for both acid and alkaline pretreated wheat straw and pine, especially for acid-treated pine pellets, where a 256% increase in glucose yield was obtained. The results suggest that PEG 6000 decreases the cleavage of β-O-4' linkages during pretreatment and thus hinders the formation of phenolic hydroxyl groups, contributing to the enhanced sugar yield in enzymatic saccharification. As surfactants were found to have beneficial effects on both biomass pelleting and the sugar yield obtained from the enzymatic saccharification of the pretreated pellets, it would be advantageous to add surfactants during pelletizing when the pellets are intended for application in a biorefinery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sustainable production of 5-hydroxymethyl furfural from glucose for process integration with high fructose corn syrup infrastructure

5-Hydroxymethyl furfural (HMF) is a platform chemical, which can be derived from lignocellulosic biomass, and used for production of liquid fuels and polymers. We demonstrate a process for production of HMF using sequential enzymatic and catalytic reactions of glucose to synthesize HMF, and simulated-moving-bed (SMB) separation to purify HMF. The adsorption thermodynamic parameters of glucose, fructose, and HMF on a commercial chromatography resin are experimentally determined for modeling the SMB-based HMF production process. The experimental data are used to develop a rigorous process model and then estimate the cost of production. Chromatographic separation of HMF has 16% lower operating costs compared to an extraction-based process and has a minimum selling price of approximately $1478 per ton. We demonstrate that the HMF process can be integrated with the high fructose corn syrup (HFCS) process, and we performed analyses considering two systems including construction of a new integrated facility and retrofitting an existing HFCS facility to produce HMF. Our analyses suggest that the latter approach is a promising short-term low-risk strategy to advance the HMF production technology to commercial scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗