Corinne D. Scown

Grand Challenges for Life-Cycle Assessment of Biofuels

Biofuels are widely touted as viable, albeit not straightforward, alternatives to petroleum-derived fuels. To best determine their utilization, many practitioners turn to life-cycle assessment (LCA) to ascertain the “environmental footprint”. Although parameters such as resource and land use, along with infrastructure, can be incorporated into LCA algorithms, many have noted that the methodological approach still needs careful attention. In this Feature, McKone et al. outline seven grand challenges that need to be engaged and surmounted to provide the best way forward for biofuel use.

Water footprint of u.s. transportation fuels.

In the modern global economy, water and energy are fundamentally connected. Water already plays a major role in electricity generation and, with biofuels and electricity poised to gain a significant share of the transportation fuel market, water will become significantly more important for transportation energy as well. This research provides insight into the potential changes in water use resulting from increased biofuel or electricity production for transportation energy, as well as the greenhouse gas and freshwater implications. It is shown that when characterizing the water impact of transportation energy, incorporating indirect water use and defensible allocation techniques have a major impact on the final results, with anywhere between an 82% increase and a 250% decrease in the water footprint if evaporative losses from hydroelectric power are excluded. The greenhouse gas impact results indicate that placing cellulosic biorefineries in areas where water must be supplied using alternative means, such as desalination, wastewater recycling, or importation can increase the fuels total greenhouse gas footprint by up to 47%. The results also show that the production of ethanol and petroleum fuels burden already overpumped aquifers, whereas electricity production is far less dependent on groundwater.

Life-cycle net energy assessment of large-scale hydrogen production via photoelectrochemical water splitting

Here we report a prospective life-cycle net energy assessment of a hypothetical large-scale photoelectrochemical (PEC) hydrogen production facility with energy output equivalent to 1 GW continuous annual average (1 GW HHV = 610 metric tons of H2 per day). We determine essential mass and energy flows based on fundamental principles, and use heuristic methods to conduct a preliminary engineering design of the facility. We then develop and apply a parametric model describing system-wide energy flows associated with the production, utilization, and decommissioning of the facility. Based on these flows, we calculate and interpret life-cycle net energy metrics for the facility. We find that under base-case conditions the energy payback time is 8.1 years, the energy return on energy invested (EROEI) is 1.7, and the life-cycle primary energy balance over the 40 years projected service life of the facility is +500 PJ. The most important model parameters affecting the net energy metrics are the solar-to-hydrogen (STH) conversion efficiency and the life span of the PEC cells; parameters associated with the balance of systems (BOS), including construction and operation of the liquid and gas handling infrastructure, play a much smaller role.

Transforming biomass conversion with ionic liquids: process intensification and the development of a high-gravity, one-pot process for the production of cellulosic ethanol

Producing concentrated sugars and minimizing water usage are key elements in the economics and environmental sustainability of advanced biofuels. Conventional pretreatment processes that require a water-wash step can result in losses of fermentable sugars and generate large volumes of wastewater or solid waste. To address these problems, we have developed high gravity biomass processing with a one-pot conversion technology that includes ionic liquid pretreatment, enzymatic saccharification, and yeast fermentation for the production of concentrated fermentable sugars and high-titer cellulosic ethanol. The use of dilute bio-derived ionic liquids (a.k.a. bionic liquids) enables one-pot, high-gravity bioethanol production due to their low toxicity to the hydrolytic enzyme mixtures and microbes used. We increased biomass digestibility at >30 wt% loading by understanding the relationship between ionic liquid and biomass loading, yielding 41.1 g L−1 of ethanol (equivalent to an overall yield of 74.8% on glucose basis) using an integrated one-pot fed-batch system. Our technoeconomic analysis indicates that the optimized one-pot configuration provides significant economic and environmental benefits for cellulosic biorefineries by reducing the amount of ionic liquid required by ∼90% and pretreatment-related water inputs and wastewater generation by ∼85%. In turn, these improvements can reduce net electricity use, greenhouse gas-intensive chemical inputs for wastewater treatment, and waste generation. The result is an overall 40% reduction in the cost of cellulosic ethanol produced and a reduction in local burdens on water resources and waste management infrastructure.

Lifecycle greenhouse gas implications of US national scenarios for cellulosic ethanol production

The Energy Independence and Security Act of 2007 set an annual US national production goal of 39.7 billion l of cellulosic ethanol by 2020. This paper explores the possibility of meeting that target by growing and processing Miscanthus giganteus. We define and assess six production scenarios in which active cropland and/or Conservation Reserve Program land are used to grow to Miscanthus. The crop and biorefinery locations are chosen with consideration of economic, land-use, water management and greenhouse gas (GHG) emissions reduction objectives. Using lifecycle assessment, the net GHG footprint of each scenario is evaluated, providing insight into the climate costs and benefits associated with each scenario’s objectives. Assuming that indirect land-use change is successfully minimized or mitigated, the results suggest two major drivers for overall GHG impact of cellulosic ethanol from Miscanthus: (a) net soil carbon sequestration or emissions during Miscanthus cultivation and (b) GHG offset credits for electricity exported by biorefineries to the grid. Without these factors, the GHG intensity of bioethanol from Miscanthus is calculated to be 11‐13 g CO2-equivalent per MJ of fuel, which is 80‐90% lower than gasoline. Including soil carbon sequestration and the power-offset credit results in net GHG sequestration up to 26 g CO2-equivalent per MJ of fuel.

Novel pathways for fuels and lubricants from biomass optimized using life-cycle greenhouse gas assessment

Significance The development of renewable liquid fuels and bioproducts is critical to reducing global reliance on petroleum and mitigating climate change, particularly for applications where few low-carbon alternatives exist. We combine chemical catalysis with life-cycle greenhouse gas (GHG) modeling to create a new platform for producing biobased aviation fuel and automotive lubricant base oils. The recyclable catalysts we developed are capable of converting sugar and biomass-derived alkyl methyl ketones into cyclic enones via condensation reactions. These products can subsequently be hydrodeoxygenated to create a new class of aviation fuel and lubricant candidates with superior cold flow properties, density, and viscosity that substantially reduce GHG emissions relative to conventional petroleum. Decarbonizing the transportation sector is critical to achieving global climate change mitigation. Although biofuels will play an important role in conventional gasoline and diesel applications, bioderived solutions are particularly important in jet fuels and lubricants, for which no other viable renewable alternatives exist. Producing compounds for jet fuel and lubricant base oil applications often requires upgrading fermentation products, such as alcohols and ketones, to reach the appropriate molecular-weight range. Ketones possess both electrophilic and nucleophilic functionality, which allows them to be used as building blocks similar to alkenes and aromatics in a petroleum refining complex. Here, we develop a method for selectively upgrading biomass-derived alkyl methyl ketones with >95% yields into trimer condensates, which can then be hydrodeoxygenated in near-quantitative yields to give a new class of cycloalkane compounds. The basic chemistry developed here can be tailored for aviation fuels as well as lubricants by changing the production strategy. We also demonstrate that a sugarcane biorefinery could use natural synergies between various routes to produce a mixture of lubricant base oils and jet fuels that achieve net life-cycle greenhouse gas savings of up to 80%.

Upgrading Lignocellulosic Products to Drop‐In Biofuels via Dehydrogenative Cross‐Coupling and Hydrodeoxygenation Sequence

Life-cycle analysis (LCA) allows the scientific community to identify the sources of greenhouse gas (GHG) emissions of novel routes to produce renewable fuels. Herein, we integrate LCA into our investigations of a new route to produce drop-in diesel/jet fuel by combining furfural, obtained from the catalytic dehydration of lignocellulosic pentose sugars, with alcohols that can be derived from a variety of bio- or petroleum-based feedstocks. As a key innovation, we developed recyclable transition-metal-free hydrotalcite catalysts to promote the dehydrogenative cross-coupling reaction of furfural and alcohols to give high molecular weight adducts via a transfer hydrogenation-aldol condensation pathway. Subsequent hydrodeoxygenation of adducts over Pt/NbOPO4 yields alkanes. Implemented in a Brazilian sugarcane biorefinery such a process could result in a 53-79% reduction in life-cycle GHG emissions relative to conventional petroleum fuels and provide a sustainable source of low carbon diesel/jet fuel.

Life-cycle implications and supply chain logistics of electric vehicle battery recycling in California

Plug-in electric vehicle (PEV) use in the United States (US) has doubled in recent years and is projected to continue increasing rapidly. This is especially true in California, which makes up nearly one-third of the current US PEV market. Planning and constructing the necessary infrastructure to support this projected increase requires insight into the optimal strategies for PEV battery recycling. Utilizing life-cycle perspectives in evaluating these supply chain networks is essential in fully understanding the environmental consequences of this infrastructure expansion. This study combined life-cycle assessment and geographic information systems (GIS) to analyze the energy, greenhouse gas (GHG), water use, and criteria air pollutant implications of end-of-life infrastructure networks for lithium-ion batteries (LIBs) in California. Multiple end-of-life scenarios were assessed, including hydrometallurgical and pyrometallurgical recycling processes. Using economic and environmental criteria, GIS modeling revealed optimal locations for battery dismantling and recycling facilities for in-state and out-of-state recycling scenarios. Results show that economic return on investment is likely to diminish if more than two in-state dismantling facilities are constructed. Using rail as well as truck transportation can substantially reduce transportation-related GHG emissions (23–45%) for both in-state and out-of-state recycling scenarios. The results revealed that material recovery from pyrometallurgy can offset environmental burdens associated with LIB production, namely a 6–56% reduction in primary energy demand and 23% reduction in GHG emissions, when compared to virgin production. Incorporating human health damages from air emissions into the model indicated that Los Angeles and Kern Counties are most at risk in the infrastructure scale-up for in-state recycling due to their population density and proximity to the optimal location.

CO2 enabled process integration for the production of cellulosic ethanol using bionic liquids

There is a clear and unmet need for a robust and affordable biomass conversion technology that can process a wide range of biomass feedstocks and produce high yields of fermentable sugars and biofuels with minimal intervention between unit operations. The lower microbial toxicity of recently-developed renewable ionic liquids (ILs), or bionic liquids (BILs), helps overcome the challenges associated with the integration of pretreatment with enzymatic saccharification and microbial fermentation. However, the most effective BILs known to date for biomass pretreatment form extremely basic pH solutions in the presence of water, and therefore require neutralization before the pH range is acceptable for the enzymes and microbes used to complete the biomass conversion process. Neutralization using acids creates unwanted secondary effects that are problematic for efficient and cost-effective biorefinery operations using either continuous or batch modes. We demonstrate a novel approach that addresses these challenges through the use of gaseous carbon dioxide to reversibly control the pH mismatch. This approach enables the realization of an integrated biomass conversion process that eliminates the need for intermediate washing and/or separation steps. A preliminary technoeconomic analysis indicates that this integrated approach could reduce production costs by 50–65% compared to previous IL biomass conversion methods studied.

From Sugars to Wheels: The Conversion of Ethanol to 1,3‐Butadiene over Metal‐Promoted Magnesia‐Silicate Catalysts

1,3-Butadiene (1,3-BD) is a high-value chemical intermediate used mainly as a monomer for the production of synthetic rubbers. The ability to source 1,3-BD from biomass is of considerable current interest because it offers the potential to reduce the life-cycle greenhouse gas (GHG) impact associated with 1,3-BD production from petroleum-derived naphtha. Herein, we report the development and investigation of a new catalyst and process for the one-step conversion of ethanol to 1,3-BD. The catalyst is prepared by the incipient impregnation of magnesium oxide onto a silica support followed by the deposition of Au nanoparticles by deposition-precipitation. The resulting Au/MgO-SiO2 catalyst exhibits a high activity and selectivity to 1,3-BD and low selectivities to diethyl ether, ethylene, and butenes. Detailed characterization of the catalyst shows that the desirable activity and selectivity of Au/MgO-SiO2 are a consequence of a critical balance between the acidic-basic sites associated with a magnesium silicate hydrate phase and the redox properties of the Au nanoparticles. A process for the conversion of ethanol to 1,3-BD, which uses our catalyst, is proposed and analyzed to determine the life-cycle GHG impact of the production of this product from biomass-derived ethanol. We show that 1,3-BD produced by our process can reduce GHG emissions by as much as 155 % relative to the conventional petroleum-based production of 1,3-BD.