Conversion of acetone and mixed ketones to hydrocarbons using HZSM-5 catalyst in the carboxylate platform.

In this study, two different feeds were treated to produce hydrocarbons: (1) reagent-grade acetone, and (2) mixed ketones obtained from lignocellulosic biomass via the carboxylate platform. Acetone and mixed ketones underwent catalytic self-condensation over HZSM-5. For acetone, HZSM-5(80) was used, and the experiments were conducted in two sets: (1) vary temperature (305-415°C) at P = 101 kPa (abs) and weight hourly space velocity (WHSV) = 1.3 h-1; (2) vary WHSV (1.3-7.9 h-1) at T = 350 and 415°C, and P = 101 kPa (abs). For acetone over HZSM-5(280), the experiments were conducted in two sets: (1) vary WHSV (1.3-6.5 h-1) at T = 415°C, and P = 101 kPa (abs); and (2) vary WHSV (1.3-11.8 h-1) at P = 790 kPa (abs) and T = 415°C. For mixed ketones, HZSM-5(280) was used at WHSV = 1.9 h-1, T = 430-590°C, and P = 101 kPa (abs). For acetone at higher temperatures, the conversion was 100% and the liquid products were aromatics centered on C8. At low temperatures, conversion was less and the carbon liquid distribution was centered on C9 (mainly mesitylene). For mixed ketones, catalyst deactivation was higher causing product concentrations to change over time, and the highest conversion reached was 40%.

Microbial communities for valorizing biomass using the carboxylate platform to produce volatile fatty acids: A review.

The carboxylate platform employs a diverse microbial consortium of anaerobes in which the methanogens are inhibited. Nearly all biomass components are digested to a mixture of C1-C8 monocarboxylic acids and their corresponding salts. The methane-arrested anaerobic digestion proceeds readily without needing to sterilize biomass or equipment. It accepts a wide range of feedstocks (e.g., agricultural residues, municipal solid waste, sewage sludge, animal manure, food waste, algae, and energy crops), and produces high product yields. This review highlights several important aspects of the platform, including its thermodynamic underpinnings, influences of inoculum source and operating conditions on product formation, and downstream chemical processes that convert the carboxylates to hydrocarbon fuels and oxygenated chemicals. This review further establishes the carboxylate platform as a viable and economical route to industrial biomass utilization.

Energy Portfolio Assessment Tool (EPAT): Sustainable energy planning using the WEF nexus approach - Texas case.

The paper introduces a holistic framework that identifies the links between energy and other systems (water, land, environment, finance, etc.), and measures the impact of energy portfolios, to offer a solid foundation for the best sustainable decision making in energy planning. The paper presents a scenario-based holistic nexus tool, Energy Portfolio Assessment Tool (EPAT) that provides a platform for energy stakeholders and policymakers to create and evaluate the sustainability of various scenarios based on the water-energy-food (WEF) nexus approach. The tool is applied to a case study in Texas, USA. Scenarios considered are set by the U.S. Energy Information Administration (EIA): EIA Reference Case - 2015, EIA Clean Power Plan (CPP) & Reference Case - 2030, and EIA No-CPP & Reference Case - 2030. In the presence of the CPP, total water withdrawal is expected to decrease significantly, while total water consumption is projected to experience a slight decrease due to the increase in water consumption in electricity generation caused by the new electricity mix. The CPP is successful in decreasing emissions, but is accompanied by tradeoffs, such as increased water consumption and land use by electricity generation. The absence of the CPP will lead to an extreme surge in total water withdrawn and consumed, and in emissions. Therefore, conservation policies should move from the silo to the nexus mentality to avoid unintended consequences that result in improving one part of the nexus while worsening the other parts.

Assessment of Shock Pretreatment of Corn Stover Using the Carboxylate Platform.

Corn stover was pretreated with lime and shock, a mechanical process that uses a shockwave to alter the biomass structure. Two pretreatments (lime-only and lime + shock) were evaluated using enzymatic hydrolysis, batch mixed-culture fermentations, and continuous countercurrent mixed-culture fermentation. In a 120-h enzymatic hydrolysis, shock pretreatment increased the glucan digestibility of submerged lime pretreatment (SLP) corn stover by 3.5 % and oxidative lime pretreatment (OLP) corn stover by 2.5 %. The continuum particle distribution model (CPDM) was used to simulate a four-stage continuous countercurrent mixed-culture fermentation using empirical rate models obtained from simple batch experiments. The CPDM model determined that lime + shock pretreatment increased the total carboxylic acids yield by 28.5 % over lime-only pretreatment in a countercurrent fermentation with a volatile solids loading rate (VSLR) of 12 g/(L/day) and liquid retention time (LRT) of 30 days. In a semi-continuous countercurrent fermentation performed in the laboratory for 112 days with a VSLR of 1.875 g/(L day) and LRT of 16 days, lime + shock pretreatment increased the total carboxylic acid yield by 14.8 %. The experimental results matched closely with CPDM model predictions (4.05 % error).

Evaluating the performance of carboxylate platform fermentations across diverse inocula originating as sediments from extreme environments.

To test the hypothesis that microbial communities from saline and thermal sediment environments are pre-adapted to exhibit superior fermentation performances, 501 saline and thermal samples were collected from a wide geographic range. Each sediment sample was screened as inoculum in a 30-day batch fermentation. Using multivariate statistics, the capacity of each community was assessed to determine its ability to degrade a cellulosic substrate and produce carboxylic acids in the context of the inoculum sediment chemistry. Conductance of soils was positively associated with production of particular acids, but negatively associated with conversion efficiency. In situ sediment temperature and conversion efficiency were consistently positively related. Because inoculum characteristics influence carboxylate platform productivity, optimization of the inoculum is an important and realistic goal.

Comparison of three screening methods to select mixed-microbial inoculum for mixed-acid fermentations.

Using a mixed culture of microorganisms, the carboxylate platform converts biomass into hydrocarbons and chemicals. To develop a method that identifies the highest performing inoculum for carboxylate fermentations, five bacterial communities were screened and ranked by three fermentation performance tests: (1) 30-day batch screen, (2) 28-day continuum particle distribution model (CPDM), and (3) 5-month continuous countercurrent fermentation trains. To screen numerous inocula sources, these tests were used sequentially in an aseptic environment. For the batch-fermentation screen, Inoculum 1 achieved the highest conversion. For the CPDM evaluation, the operating map for Inoculum 1 had the highest performance. For the continuous countercurrent fermentation, the train resulting from Inoculum 1 was among the best performers. This study suggests that the three screens are a useful and predictive method for choosing optimal inocula sources. The bacterial community with optimal performance in these three screens could be considered for use in commercial-scale fermentations.

Short-term oxidative lime pretreatment of palm pruning waste for use as animal feedstuff.

BACKGROUND: Oxidative lime pretreatment (OLP) is an effective pretreatment for highly recalcitrant lignocellulosic materials. This experiment was conducted to investigate the effect of short-term OLP on fermentative gas production kinetics of date palm prunings. Rachis and petiole were pretreated with excess lime (0.5 g Ca(OH)2 g(-1) dry matter) in a reactor charged with 10 bar pure oxygen pressure at different times and temperatures. RESULTS: Lignin removal was greatly affected by OLP, whereas cellulose was well preserved even after severe pretreatment. After 72 h fermentation, the cumulative gas production was 321.2 mL gas g(-1) organic matter (OM) for the most severe pretreatment, compared to 73.6 mL g(-1) OM for the untreated rachis. For the petiole pretreated at 120 °C for 280 min, 268 mL gas was produced compared to 59 mL gas g(-1) OM for the untreated petiole. Scanning electron microscope images showed the formation of pores (average diameter of 10-12 µm) and carbonate calcium deposits on the surface of treated biomass. An increase in biomass crystallinity was observed in pretreated samples resulting from cellulose enrichment. CONCLUSIONS: The results suggest that OLP improves the ruminal digestibility of date palm prunings, which may have potential for inclusion in the ruminant diet at low cost.

Propagated fixed-bed mixed-acid fermentation: effect of volatile solid loading rate and agitation at near-neutral pH.

To increase conversion and product concentration, mixed-acid fermentation can use a countercurrent strategy where solids and liquids pass in opposite directions through a series of fermentors. To limit the requirement for moving solids, this study employed a propagated fixed-bed fermentation, where solids were stationary and only liquid was transferred. To evaluate the role of agitation, continuous mixing was compared with periodic mixing. The periodically mixed fermentation had similar conversion, but lower yield and selectivity. Increasing volatile solid loading rate from 1.5 to 5.1g non-acid volatile solids/(L(liq)·d) and increasing liquid retention time decreased yield, conversion, selectivity, but increased product concentrations. Compared to a previous study at high pH (~9), this study achieved higher performance at near neutral pH (~6.5) and optimal C-N ratios. Compared to countercurrent fermentation, propagated fixed-bed fermentations have similar selectivities and produce similar proportions of acetic acid, but have lower yields, conversion, productivities, and acid concentrations.

Mesophilic and thermophilic conditions select for unique but highly parallel microbial communities to perform carboxylate platform biomass conversion.

The carboxylate platform is a flexible, cost-effective means of converting lignocellulosic materials into chemicals and liquid fuels. Although the platform's chemistry and engineering are well studied, relatively little is known about the mixed microbial communities underlying its conversion processes. In this study, we examined the metagenomes of two actively fermenting platform communities incubated under contrasting temperature conditions (mesophilic 40°C; thermophilic 55 °C), but utilizing the same inoculum and lignocellulosic feedstock. Community composition segregated by temperature. The thermophilic community harbored genes affiliated with Clostridia, Bacilli, and a Thermoanaerobacterium sp, whereas the mesophilic community metagenome was composed of genes affiliated with other Clostridia and Bacilli, Bacteriodia, γ-Proteobacteria, and Actinobacteria. Although both communities were able to metabolize cellulosic materials and shared many core functions, significant differences were detected with respect to the abundances of multiple Pfams, COGs, and enzyme families. The mesophilic metagenome was enriched in genes related to the degradation of arabinose and other hemicellulose-derived oligosaccharides, and the production of valerate and caproate. In contrast, the thermophilic community was enriched in genes related to the uptake of cellobiose and the transfer of genetic material. Functions assigned to taxonomic bins indicated that multiple community members at either temperature had the potential to degrade cellulose, cellobiose, or xylose and produce acetate, ethanol, and propionate. The results of this study suggest that both metabolic flexibility and functional redundancy contribute to the platform's ability to process lignocellulosic substrates and are likely to provide a degree of stability to the platform's fermentation processes.

Comparison of mixed-acid fermentations inoculated with six different mixed cultures.

The MixAlco™ process biologically converts biomass to carboxylate salts that may be converted to a variety of chemicals and fuels. This study examines the fermentation performance of six different mixed cultures, and how the performance was affected by the bacterial composition of each community. All six countercurrent fermentations had very similar performance, but were dissimilar in microbial community composition. The acid concentrations varied by only 12% between fermentation trains and the conversions varied only by 6%. The microbial communities were profiled using 16S rRNA tag-pyrosequencing, which revealed the presence of dynamic communities that were dominated by bacteria resembling Clostridia, but they shared few taxa in common. Yue-Clayton similarity calculations of the communities revealed that they were extremely different. The presence of different but functionally similar microbial communities in this study suggests that it is the operating parameters that determine the fermentation end-products.

Influence of carbon-to-nitrogen ratio on the mixed-acid fermentation of wastewater sludge and pretreated bagasse.

In mixed-acid fermentation, carbon and nitrogen are critical nutrients for cell synthesis, growth, and metabolism. To study the effect of C/N ratio on the yield of carboxylic acids, wastewater sludge was co-digested with pretreated bagasse; the amount of sludge was varied from 0% to 100% (dry weight basis). Fermentation was performed at 55°C at a solids concentration of 50 g dry solids/L, and Iodoform was used to inhibit methane formation. It was observed that C/N ratio significantly affects yield, especially at extreme ratios. The highest carboxylic acid yield (0.36 g acids/g VS fed) was obtained for C/N ratios ranging from 13 to 25 g C/g N. C/N ratio also affected the composition profile of carboxylic acids. In all mixtures, acetic acid was the major fraction, followed by butyric acid. However, i-butyric, valeric acid, and i-valeric acid increased with increasing sludge content, which likely resulted from protein degradation.

Propagated fixed-bed mixed-acid fermentation: Part I: Effect of volatile solid loading rate and agitation at high pH.

Countercurrent fermentation is a high performing process design for mixed-acid fermentation. However, there are high operating costs associated with moving solids, which is an integral component of this configuration. This study investigated the effect of volatile solid loading rate (VSLR) and agitation in propagated fixed-bed fermentation, a configuration which may be more commercially viable. To evaluate the role of agitation on fixed-bed configuration performance, continuous mixing was compared with periodic mixing. VSLR was also varied and not found to affect acid yields. However, increased VSLR and liquid retention time did result in higher conversions, productivity, acid concentrations, but lower selectivities. Agitation was demonstrated to be important for this fermentor configuration, the periodically-mixed fermentation had the lowest conversion and yields. Operating at a high pH (∼9) contributed to the high selectivity to acetic acid, which might be industrially desirable but at the cost of lower yield compared to a neutral pH.

Thermodynamic prediction of hydrogen production from mixed-acid fermentations.

The MixAlco™ process biologically converts biomass to carboxylate salts that may be chemically converted to a wide variety of chemicals and fuels. The process utilizes lignocellulosic biomass as feedstock (e.g., municipal solid waste, sewage sludge, and agricultural residues), creating an economic basis for sustainable biofuels. This study provides a thermodynamic analysis of hydrogen yield from mixed-acid fermentations from two feedstocks: paper and bagasse. During batch fermentations, hydrogen production, acid production, and sugar digestion were analyzed to determine the energy selectivity of each system. To predict hydrogen production during continuous operation, this energy selectivity was then applied to countercurrent fermentations of the same systems. The analysis successfully predicted hydrogen production from the paper fermentation to within 11% and the bagasse fermentation to within 21% of the actual production. The analysis was able to faithfully represent hydrogen production and represents a step forward in understanding and predicting hydrogen production from mixed-acid fermentations.

Process and technoeconomic analysis of leading pretreatment technologies for lignocellulosic ethanol production using switchgrass.

Six biomass pretreatment processes to convert switchgrass to fermentable sugars and ultimately to cellulosic ethanol are compared on a consistent basis in this technoeconomic analysis. The six pretreatment processes are ammonia fiber expansion (AFEX), dilute acid (DA), lime, liquid hot water (LHW), soaking in aqueous ammonia (SAA), and sulfur dioxide-impregnated steam explosion (SO(2)). Each pretreatment process is modeled in the framework of an existing biochemical design model so that systematic variations of process-related changes are consistently captured. The pretreatment area process design and simulation are based on the research data generated within the Biomass Refining Consortium for Applied Fundamentals and Innovation (CAFI) 3 project. Overall ethanol production, total capital investment, and minimum ethanol selling price (MESP) are reported along with selected sensitivity analysis. The results show limited differentiation between the projected economic performances of the pretreatment options, except for processes that exhibit significantly lower monomer sugar and resulting ethanol yields.

Comparative data on effects of leading pretreatments and enzyme loadings and formulations on sugar yields from different switchgrass sources.

Dilute sulfuric acid (DA), sulfur dioxide (SO(2)), liquid hot water (LHW), soaking in aqueous ammonia (SAA), ammonia fiber expansion (AFEX), and lime pretreatments were applied to Alamo, Dacotah, and Shawnee switchgrass. Application of the same analytical methods and material balance approaches facilitated meaningful comparisons of glucose and xylose yields from combined pretreatment and enzymatic hydrolysis. Use of a common supply of cellulase, beta-glucosidase, and xylanase also eased comparisons. All pretreatments enhanced sugar recovery from pretreatment and subsequent enzymatic hydrolysis substantially compared to untreated switchgrass. Adding beta-glucosidase was effective early in enzymatic hydrolysis while cellobiose levels were high but had limited effect on longer term yields at the enzyme loadings applied. Adding xylanase improved yields most for higher pH pretreatments where more xylan was left in the solids. Harvest time had more impact on performance than switchgrass variety, and microscopy showed changes in different features could impact performance by different pretreatments.

Comparative study on enzymatic digestibility of switchgrass varieties and harvests processed by leading pretreatment technologies.

Feedstock quality of switchgrass for biofuel production depends on many factors such as morphological types, geographic origins, maturity, environmental and cultivation parameters, and storage. We report variability in compositions and enzymatic digestion efficiencies for three cultivars of switchgrass (Alamo, Dacotah and Shawnee), grown and harvested at different locations and seasons. Saccharification yields of switchgrass processed by different pretreatment technologies (AFEX, dilute sulfuric acid, liquid hot water, lime, and soaking in aqueous ammonia) are compared in regards to switchgrass genotypes and harvest seasons. Despite its higher cellulose content per dry mass, Dacotah switchgrass harvested after wintering consistently gave a lower saccharification yield than the other two varieties harvested in the fall. The recalcitrance of upland cultivars and over-wintered switchgrass may require more severe pretreatment conditions. We discuss the key features of different pretreatment technologies and differences in switchgrass cultivars and harvest seasons on hydrolysis performance for the applied pretreatment methods.

WITHDRAWN: Comparative Data on Effects of Leading Pretreatments and Enzyme Loadings and Formulations on Sugar Yields from Different Switchgrass Sources.

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Application of cellulase and hemicellulase to pure xylan, pure cellulose, and switchgrass solids from leading pretreatments.

Accellerase 1000 cellulase, Spezyme CP cellulase, ß-glucosidase, Multifect xylanase, and beta-xylosidase were evaluated for hydrolysis of pure cellulose, pure xylan, and switchgrass solids from leading pretreatments of dilute sulfuric acid, sulfur dioxide, liquid hot water, lime, soaking in aqueous ammonia, and ammonia fiber expansion. Distinctive sugar release patterns were observed from Avicel, phosphoric acid swollen cellulose (PASC), xylan, and pretreated switchgrass solids, with accumulation of significant amounts of xylooligomers during xylan hydrolysis. The strong inhibition of cellulose hydrolysis by xylooligomers could be partially attributed to the negative impact of xylooligomers on cellulase adsorption. The digestibility of pretreated switchgrass varied with pretreatment but could not be consistently correlated to xylan, lignin, or acetyl removal. Initial hydrolysis rates did correlate well with cellulase adsorption capacities for all pretreatments except lime, but more investigation is needed to relate this behavior to physical and compositional properties of pretreated switchgrass.

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.

Oxidative lime pretreatment of Alamo switchgrass.

Previous studies have shown that oxidative lime pretreatment is an effective delignification method that improves the enzymatic digestibility of many biomass feedstocks. The purpose of this work is to determine the recommended oxidative lime pretreatment conditions (reaction temperature, time, pressure, and lime loading) for Alamo switchgrass (Panicum virgatum). Enzymatic hydrolysis of glucan and xylan was used to determine the performance of the 52 studied pretreatment conditions. The recommended condition (110°C, 6.89 bar O(2), 240 min, 0.248 g Ca(OH)(2)/g biomass) achieved glucan and xylan overall yields (grams of sugar hydrolyzed/100 g sugar in raw biomass, 15 filter paper units (FPU)/g raw glucan) of 85.9 and 52.2, respectively. In addition, some glucan oligomers (2.6 g glucan recovered/100 g glucan in raw biomass) and significant levels of xylan oligomers (26.0 g xylan recovered/100 g xylan in raw biomass) were recovered from the pretreatment liquor. Combining a decrystallization technique (ball milling) with oxidative lime pretreatment further improved the overall glucan yield to 90.0 (7 FPU/g raw glucan).