Target Cultivation and Financing Parameters for Sustainable Production of Fuel and Feed from Microalgae.

Production of economically competitive and environmentally sustainable algal biofuel faces technical challenges that are subject to high uncertainties. Here we identify target values for algal productivity and financing conditions required to achieve a biocrude selling price of $5 per gallon and beneficial environmental impacts. A modeling framework--combining process design, techno-economic analysis, life cycle assessment, and uncertainty analysis--was applied to two conversion pathways: (1) "fuel only (HTL)", using hydrothermal liquefaction to produce biocrude, heat and power, and (2) "fuel and feed", using wet extraction to produce biocrude and lipid-extracted algae, which can substitute components of animal and aqua feeds. Our results suggest that with supporting policy incentives, the "fuel and feed" scenario will likely achieve a biocrude selling price of less than $5 per gallon at a productivity of 39 g/m(2)/day, versus 47 g/m(2)/day for the "fuel only (HTL)" scenario. Furthermore, if lipid-extracted algae are used to substitute fishmeal, the process has a 50% probability of reaching $5 per gallon with a base case productivity of 23 g/m(2)/day. Scenarios with improved economics were associated with beneficial environmental impacts for climate change, ecosystem quality, and resource depletion, but not for human health.

Quantitative uncertainty analysis of Life Cycle Assessment for algal biofuel production.

As a result of algae's promise as a renewable energy feedstock, numerous studies have used Life Cycle Assessment (LCA) to quantify the environmental performance of algal biofuels, yet there is no consensus of results among them. Our work, motivated by the lack of comprehensive uncertainty analysis in previous studies, uses a Monte Carlo approach to estimate ranges of expected values of LCA metrics by incorporating parameter variability with empirically specified distribution functions. Results show that large uncertainties exist at virtually all steps of the biofuel production process. Although our findings agree with a number of earlier studies on matters such as the need for wet lipid extraction, nutrients recovered from waste streams, and high energy coproducts, the ranges of reported LCA metrics show that uncertainty analysis is crucial for developing technologies, such as algal biofuels. In addition, the ranges of energy return on (energy) invested (EROI) values resulting from our analysis help explain the high variability in EROI values from earlier studies. Reporting results from LCA models as ranges, and not single values, will more reliably inform industry and policy makers on expected energetic and environmental performance of biofuels produced from microalgae.

Two-temperature stage biphasic CO2-H2O pretreatment of lignocellulosic biomass at high solid loadings.

Most biomass pretreatment processes for monosaccharide production are run at low-solid concentration (<10 wt%) and use significant amounts of chemical catalysts. Biphasic CO(2) -H(2) O mixtures could provide a more sustainable pretreatment medium while using high-solid contents. Using a stirred reactor for high solids (40 wt%, biomass water mixture) biphasic CO(2)-H(2) O pretreatment of lignocellulosic biomass allowed us to explore the effects of particle size and mixing on mixed hardwood and switchgrass pretreatment. Subsequently, a two-temperature stage pretreatment was introduced. After optimization, a short high-temperature stage at 210°C (16 min for hardwood and 1 min for switchgrass) was followed by a long low-temperature stage at 160°C for 60 min. Glucan to glucose conversion yields of 83% for hardwood and 80% for switchgrass were obtained. Total molar sugar yields of 65% and 55% were obtained for wood and switchgrass, respectively, which consisted of a 10% points improvement over those obtained during our previous study despite a 10-fold increase in particle size. These yields are similar to those obtained with other major pretreatment technologies for wood and within 10% of major technologies for switchgrass despite the absence of chemical catalysts, the use of large particles (0.95 cm) and high solid contents (40 wt%).

Moving toward a framework for electricity and heat equivalence in energy systems analysis.

Sustaining, maintaining, and upgrading the electricity grid, while meeting decarbonization goals is a challenge facing policymakers, regulators, grid operators, and investors. Simultaneously meeting demands for future capacity, retiring older inefficient technologies, and addressing externalities from energy production and use requires more diverse and inclusive technologies to avoid constraints and shortfalls in grid capability. Changing the energy production paradigm by encouraging alternative technologies was a key driver for FERC Order 2222. This stimulus for developing new small-scale generation will complement and supplement the existing fleet only if it attracts new investment. This investment must reflect technology that goes beyond the energy-only characteristics of traditional generation, creating systems where suites of energy-equivalent outputs are enhanced by environmental quality benefits and offsets. We use energy system designs to highlight the contribution that measuring and accounting for equivalency values provides net increases in capacity, electricity, and alternative fuels while simultaneously reducing carbon waste impacts.

Hydrothermal carbonization of anaerobic digestate and manure from a dairy farm on energy recovery and the fate of nutrients.

Hydrothermal carbonization (HTC) of raw and anaerobically digested (AD) manure with either water or whey was studied, with the goal of recovering energy and nutrients. Specifically, the impacts of HTC reaction temperature (180-240 °C), solid feedstock, and type of liquid on hydrochar quality and aqueous phase properties were tested. Of the hydrochars produced, the calorific value of whey-based hydrochar was the highest, (19.4 and 16.0 MJ/kg for manure and digestate, respectively). Overall, the net energy gain was higher for HTC of manure with whey (7.4-8.3 MJ/kg dry feedstock) and water (4.4-5.1 MJ/kg) compared to the combined AD-HTC process with whey (4.4-5.3 MJ/kg) and water (2.3-2.9 MJ/kg). Digestate-derived hydrochar contained up to 1.8% P, higher than manure-derived hydrochar (≤1.5%). Using whey as a liquid for HTC increased the aqueous-phase N-P-K concentrations up to 3,200, 410, and 7,900 mg/L, respectively, suggesting its potential use as a liquid fertilizer.

High-solids biphasic CO2-H2O pretreatment of lignocellulosic biomass.

A high pressure (200 bar) CO(2)-H(2)O process was developed for pretreating lignocellulosic biomass at high-solid contents, while minimizing chemical inputs. Hardwood was pretreated at 20 and 40 (wt.%) solids. Switchgrass, corn stover, big bluestem, and mixed perennial grasses (a co-culture of big bluestem and switchgrass) were pretreated at 40 (wt.%) solids. Operating temperatures ranged from 150 to 250 degrees C, and residence times from 20 s to 60 min. At these conditions a biphasic mixture of an H(2)O-rich liquid (hydrothermal) phase and a CO(2)-rich supercritical phase coexist. Following pretreatment, samples were then enzymatically hydrolyzed. Total yields, defined as the fraction of the theoretical maximum, were determined for glucose, hemicellulose sugars, and two degradation products: furfural and 5-hydroxymethylfurfural. Response surfaces of yield as a function of temperature and residence time were compared for different moisture contents and biomass species. Pretreatment at 170 degrees C for 60 min gave glucose yields of 77%, 73%, and 68% for 20 and 40 (wt.%) solids mixed hardwood and mixed perennial grasses, respectively. Pretreatment at 160 degrees C for 60 min gave glucan to glucose yields of 81% for switchgrass and 85% for corn stover.

Combining anaerobic digestion and hydrothermal liquefaction in the conversion of dairy waste into energy: A techno economic model for New York state.

There is increasing global interest and policies being enacted to lower greenhouse gas emissions, especially from the agricultural sector. In the U.S. for example, states with large dairy operations may combine proven manure valorization technologies, such as anaerobic digestion and hydrothermal liquefaction. Sustainable manure treatment would increase the recovery of energy and other useful co-products, namely biogas, biocrude oil and hydro-char as well as lower the environmental impacts. In this study, the economic feasibility of implementing a centralized bioenergy system in New York State was investigated. The feasibility of this transformation depends on many factors, including capital costs, discount rates, and other financing arrangements, electricity selling prices, incentives and farm sizes and locations. For a large-scale implementation in New York State accounting for nearly 50% of the state's dairy farms, our model of a distributed, hybrid anaerobic/hydrothermal system was shown to treat 590 million liters of wet manure per day, producing 607 million kWh of electricity, 162,000 L of biocrude oil and 117,000 kg of hydro-char per day. Electricity selling price is a critical factor. Increasing the electricity selling price from wholesale ($0.06/kWh) to retail ($0.18/kWh) increased the net present value from $395 million to $1.5 billion (considering a 40-year project lifetime).

Synthesis of amides and lactams in supercritical carbon dioxide.

Supercritical carbon dioxide can be employed as an environmentally friendly alternative to conventional organic solvents for the synthesis of a variety of carboxylic amides. The addition of amines to ketenes generated in situ via the retro-ene reaction of alkynyl ethers provides amides in good yield, in many cases with ethylene or isobutylene as the only byproducts of the reaction. Reactions with ethoxy alkynes are performed at 120-130 degrees C, whereas tert-butoxy derivatives undergo the retro-ene reaction at 90 degrees C. With the exception of primary, unbranched amines, potential side reactions involving addition of the amines to carbon dioxide are not competitive with the desired C-N bond-forming reaction. The amide synthesis is applicable to the preparation of beta-hydroxy and beta-amino amide derivatives, as well as amides bearing isolated carbon-carbon double bonds. Preliminary experiments aimed at developing an intramolecular variant of this process to afford macrolactams suggest that the application of CO(2)/co-solvent mixtures may offer advantages for the synthesis of large-ring compounds.

A Quantitative Metric for the Design of Selective Supercritical CO2 Extraction of Lithium from Geothermal Brine.

As demand grows for lithium, its recovery from geothermal brines provides an attractive alternative to slow mining. One promising extraction method uses crown ethers as extractants in supercritical carbon dioxide with cation exchangers to facilitate extraction from brine. Molecular dynamics modeling is used to understand the mechanism of binding between lithium (or sodium) and combinations of 14-crown-4 ethers and cation exchangers, and the predictive capability of computational modeling to test lithium selectivity is established for four combinations of crown ethers [methylene-14-crown-4 (M14C4) and a fluorinated 14-crown-4 (F14C4)] and cation exchangers [di(2-ethyl-hexyl)phosphoric acid (HDEHP) and tetraethylammonium perfluoro-1-octanesulfonate (TPFOS)]. Binding free energies (given in kcal mol-1 ) of lithium and sodium, respectively, to crown ether-cation exchangers are 85 and 71 for M14C4-HDEHP, 90 and 71 for F14C4-HDEHP, 93 and 80 for M14C4-TPFOS, and 104 and 93 for F14C4-TPFOS. Good agreement is found between computational predictions and supercritical carbon dioxide extraction experiments at 60 °C and 250 bar. Binding free energy gives a suitable metric to describe extraction efficiency. Differences in the binding free energies of sodium and lithium to crown ethers determine the extraction selectivity. Fluorine groups are found to exert a positive influence to optimize extraction efficiency. Of the systems studied, F14C4 with TPFOS offers the most selective and efficient extraction system.

Path sampling calculation of methane diffusivity in natural gas hydrates from a water-vacancy assisted mechanism.

Increased interest in natural gas hydrate formation and decomposition, coupled with experimental difficulties in diffusion measurements, makes estimating transport properties in hydrates an important technological challenge. This research uses an equilibrium path sampling method for free energy calculations [Radhakrishnan, R.; Schlick, T. J. Chem. Phys. 2004, 121, 2436] with reactive flux and kinetic Monte Carlo simulations to estimate the methane diffusivity within a structure I gas hydrate crystal. The calculations support a water-vacancy assisted diffusion mechanism where methane hops from an occupied "donor" cage to an adjacent "acceptor" cage. For pathways between cages that are separated by five-membered water rings, the free energy landscape has a high barrier with a shallow well at the top. For pathways between cages that are separated by six-membered water rings, the free energy calculations show a lower barrier with no stable intermediate. Reactive flux simulations confirm that many reactive trajectories become trapped in the shallow intermediate at the top of the barrier leading to a small transmission coefficient for these paths. Stable intermediate configurations are identified as doubly occupied off-pathway cages and methane occupying the position of a water vacancy. Rate constants are computed and used to simulate self-diffusion with a kinetic Monte Carlo algorithm. Self-diffusion rates were much slower than the Einstein estimate because of lattice connectivity and methane's preference for large cages over small cages. Specifically, the fastest pathways for methane hopping are arranged in parallel (nonintersecting) channels, so methane must hop via a slow pathway to escape the channel. From a computational perspective, this paper demonstrates that equilibrium path sampling can compute free energies for a broader class of coordinates than umbrella sampling with molecular dynamics. From a technological perspective, this paper provides one estimate for an important transport property that has been difficult to measure. In a hydrate I crystal at 250 K with nearly all cages occupied by methane, we estimate D approximately 7 x 10(-15) X m(2)/s where X is the fraction of unoccupied cages.

Coupling hydrothermal liquefaction and membrane distillation to treat anaerobic digestate from food and dairy farm waste.

Increased demand for water, energy and food requires new ways to produce fertilizers, fuels and reusable water. Recovery of resources from wastes could lead to an additional source of energy and nutrients, and also reduce the waste to be disposed. In this work, we used hydrothermal liquefaction to produce a biocrude oil product, followed by membrane distillation of the aqueous effluents to concentrate a nutrient-rich stream that can be used as fertilizer. The motivation for this work is that residual heat from the hydrothermal liquefaction process could be utilized to drive the membrane distillation process, which would improve the efficiency and reduce the cost of the distillation process. The membrane distillation system was demonstrated to be able to recover 75% of the water. The membrane distillation retentate had very high ammonium and phosphate concentrations, making it suitable as a fertilizer. Membrane permeate contained high concentrations of volatile organics.

Integrating electrochemical, biological, physical, and thermochemical process units to expand the applicability of anaerobic digestion.

Anaerobic digestion (AD) is a mature biotechnology-production platform with millions of installations at homes, farms, and industrial/municipal settings. Large-scale industrial, agricultural, and municipal waste-treatment systems may observe novel integration with electrochemical, biological, physical, and thermochemical process units to make AD more attractive. Without governmental subsidies, AD has often only a relatively low economic return or none at all. Diversification of products besides methane in biogas may help to change this. Here, several sections discuss different process units to: 1) upgrade biogas into biomethane; 2) convert carbon dioxide in biogas to more biomethane; 3) generate cooling power from process heat; 4) produce bio-crude oil (bio-oil) from organic matter; and 5) produce a liquid biochemical product from organic matter. This is not meant to be an exhaustive list, but rather a selection of particularly promising process units from a technological view, which are already integrated with AD or close to full-scale integration.

Coupling hydrothermal liquefaction and anaerobic digestion for energy valorization from model biomass feedstocks.

Hydrothermal liquefaction converts food waste into oil and a carbon-rich hydrothermal aqueous phase. The hydrothermal aqueous phase may be converted to biomethane via anaerobic digestion. Here, the feasibility of coupling hydrothermal liquefaction and anaerobic digestion for the conversion of food waste into energy products was examined. A mixture of polysaccharides, proteins, and lipids, representing food waste, underwent hydrothermal processing at temperatures ranging from 200 to 350°C. The anaerobic biodegradability of the hydrothermal aqueous phase was examined through conducting biochemical methane potential assays. The results demonstrate that the anaerobic biodegradability of the hydrothermal aqueous phase was lower when the temperature of hydrothermal processing increased. The chemical composition of the hydrothermal aqueous phase affected the anaerobic biodegradability. However, no inhibition of biodegradation was observed for most samples. Combining hydrothermal and anaerobic digestion may, therefore, yield a higher energetic return by converting the feedstock into oil and biomethane.

Prospects for energy recovery during hydrothermal and biological processing of waste biomass.

Thermochemical and biological processes represent promising technologies for converting wet biomasses, such as animal manure, organic waste, or algae, to energy. To convert biomass to energy and bio-chemicals in an economical manner, internal energy recovery should be maximized to reduce the use of external heat and power. In this study, two conversion pathways that couple hydrothermal liquefaction with anaerobic digestion or catalytic hydrothermal gasification were compared. Each of these platforms is followed by two alternative processes for gas utilization: 1) combined heat and power; and 2) combustion in a boiler. Pinch analysis was applied to integrate thermal streams among unit processes and improve the overall system efficiency. A techno-economic analysis was conducted to compare the feasibility of the four modeled scenarios under different market conditions. Our results show that a systems approach designed to recover internal heat and power can reduce external energy demands and increase the overall process sustainability.

Application of the cell potential method to predict phase equilibria of multicomponent gas hydrate systems.

We present the application of a mathematical method reported earlier by which the van der Waals-Platteeuw statistical mechanical model with the Lennard-Jones and Devonshire approximation can be posed as an integral equation with the unknown function being the intermolecular potential between the guest molecules and the host molecules. This method allows us to solve for the potential directly for hydrates for which the Langmuir constants are computed, either from experimental data or from ab initio data. Given the assumptions made in the van der Waals-Platteeuw model with the spherical-cell approximation, there are an infinite number of solutions; however, the only solution without cusps is a unique central-well solution in which the potential is at a finite minimum at the center to the cage. From this central-well solution, we have found the potential well depths and volumes of negative energy for 16 single-component hydrate systems: ethane (C2H6), cyclopropane (C3H6), methane (CH4), argon (Ar), and chlorodifluoromethane (R-22) in structure I; and ethane (C2H6), cyclopropane (C3H6), propane (C3H8), isobutane (C4H10), methane (CH4), argon (Ar), trichlorofluoromethane (R-11), dichlorodifluoromethane (R-12), bromotrifluoromethane (R-13B1), chloroform (CHCl3), and 1,1,1,2-tetrafluoroethane (R-134a) in structure II. This method and the calculated cell potentials were validated by predicting existing mixed hydrate phase equilibrium data without any fitting parameters and calculating mixture phase diagrams for methane, ethane, isobutane, and cyclopropane mixtures. Several structural transitions that have been determined experimentally as well as some structural transitions that have not been examined experimentally were also predicted. In the methane-cyclopropane hydrate system, a structural transition from structure I to structure II and back to structure I is predicted to occur outside of the known structure II range for the cyclopropane hydrate. Quintuple (L(w)-sI-sII-L(hc)-V) points have been predicted for the ethane-propane-water (277.3 K, 12.28 bar, and x(eth,waterfree) = 0.676) and ethane-isobutane-water (274.7 K, 7.18 bar, and x(eth,waterfree) = 0.81) systems.

Carbon nanotube formation and growth via particle-particle interaction.

Carbon nanotubes are observed to form under a wide range of temperatures, pressures, reactive agents, and catalyst metals. In this paper we attempt to rationalize this body of observations reported in the literature in terms of fundamental processes driving nanotube formation. Many of the observed effects can be attributed to the interaction of three key processes: surface catalysis and deposition of carbon, diffusive transport of carbon, and precipitation effects. A new nanotube formation mechanism is proposed that describes the nanotube structures observed experimentally in a premixed flame and can account for certain shortcomings of the prevailing mechanism that has been repeatedly applied to explain nanotube formation in nonflame environments. The interacting particle model (IPM) attributes the initiation of nanotube growth to the physical interaction between catalyst particles. Coalescence of two (or more) catalyst particles leads to partial blocking of the particle surface, causing a disparity in carbon deposition over the particle surface. The resulting concentration gradient generates a net diffusive flux toward the interparticle contact point. Dimers that separate in this condition can support continuous nanotube growth between the particles. The model can also be extended to multiple particles to account for more complex morphologies. The IPM is consistent with many of the structures observed in the flame-produced material. The validity of the model is evaluated through analysis of diffusion dynamics and a force analysis of particle binding and separation. The IPM is also discussed in relation to identifying the requirements and best conditions to support nanotube growth in the premixed flame. The formation of nanotubes between particles as described by the IPM indicates that a single mechanism cannot completely describe nanotube synthesis; more likely, multiple pathways exist with varying rates that depend on specific process conditions.

Pictet-Spengler reactions in multiphasic supercritical carbon dioxide/CO2-expanded liquid media. In situ generation of carbamates as a strategy for reactions of amines in supercritical carbon dioxide.

Acyl-Pictet-Spengler cyclizations can be achieved in scCO2/CO2-expanded liquid media via the in situ formation of carbamate derivatives of beta-arylethylamines.

Ultrasonic cavitation for disruption of microalgae.

Challenges with mid-stream fractionation steps in proposed microalgae biofuel pathways arise from the typically dilute cell density in growth media, micron scale cell sizes, and often durable cell walls. For microalgae to be a sustainable source of biofuels and co-products, efficient fractionation by some method will be necessary. This study evaluates ultrasonic cell disruption as a processing step that fractionates microalgae. A range of species types with different sizes and cell wall compositions were treated. The initial seconds of sonication offered the most significant disruption, even for the more durable Nannochloropsis cells. Following this initial period, diminishing effectiveness was attributed, by acoustic measurements, to attenuation of the ultrasound in the ensuing cloud of cavitating bubbles. At longer exposure times, differences between species were more pronounced. Processing higher concentrations of Isochrysis slowed cell disintegration only marginally, making the expenditure of energy more worthwhile.

Hydrothermal gasification of waste biomass: process design and life cycle asessment.

A process evaluation methodology is presented that incorporates flowsheet mass and energy balance modeling, heat and power integration, and life cycle assessment Environmental impacts are determined by characterizing and weighting (using CO2 equivalents, Eco-indicator 99, and Eco-scarcity) the flowsheet and inventory modeling results. The methodology is applied to a waste biomass to synthetic natural gas (SNG) conversion process involving a catalytic hydrothermal gasification step. Several scenarios are constructed for different Swiss biomass feedstocks and different scales depending on logistical choices: large-scale (155 MW(SNG)) and small-scale (5.2 MW(SNG)) scenarios for a manure feedstock and one scenario (35.6 MW(SNG))for a wood feedstock. Process modeling shows that 62% of the manure's lower heating value (LHV) is converted to SNG and 71% of wood's LHV is converted to SNG. Life cycle modeling shows that, for all processes, about 10% of fossil energy use is imbedded in the produced renewable SNG. Converting manure and replacing it, as a fertilizer, with the process mineral byproduct leads to reduced N20 emissions and an improved environmental performance such as global warming potential: -0.6 kg(CO2eq)/MJ(SNG) vs. -0.02 kg(CO2eq)/MJ(SNG) for wood scenarios.